(Davies, Michael Scott, P.J.B.) Guide To The Use

GUIDE TO THE USE
OF MATERIALS IN WATERS
MICHAEL DAVIES
AND
P.J.B. SCOTT
NACE International
The Corrosion Society
1440 South Creek Drive
Houston, Texas 77084
NACE International
The Corrosion Society
02003 by NACE International

Library of Congress Catalog Number 200211 5801
ISBN 1575901471
Printed in the United States of America. All rights reserved. This book, or parts thereof,
may not be reproduced in any form without permission of the copyright owners.
Neither NACE International, its officers, directors, or members thereof accept any re-
sponsibility for the use of the methods and materials discussed herein. The information
is advisory only and the use of the materials and methods is solely at the risk of the user.
NACE International
1440 South Creek Drive
Houston, Texas 77084
http://www.nace.org
Manager, NACE Press: Neil Vaughan
About the Cover

Emerging from the background of a breaking wave are illustrations of some of the uses of
materials in waters. They are (clockwise from top left): a heat exchanger, an oil platform
in a tropical sea, a biofouled pier, the massive cooling towers of a power plant, and an
old water wheel. (All photos courtesy of CARIAD Consultants.)
Cover Design: P.J.B. Scott and Michael Davies with assistance by Michele Sandusky,
NACE Graphics Department
Contents
List of Tables xvii

About the Authors xxi
Chapter 1 Introduction 1
Chapter 2 Oceanography and Limnology 5

2.1 Fresh Water 7
2.1.1 Potable Water 7
2.1.2 Lakes and Rivers 8
2.1.3 Chemistry 8
2.1.4 Freshwater Biology 12
2.1.5 Turnover 14
2.2 Estuaries and Brackish Water 14
2.2.1 Types of Estuaries 15
2.2.2 Biology and Chemistry of Estuaries 15
2.2.3 Corrosion in Estuaries 16
2.3 Seawater 17
2.3.1 Physical Properties 17
2.3.2 Chemistry 17
2.3.3 Oxygen and Carbon Dioxide 17
2.3.4 Nutrients 21
2.3.5 Sediments 22
2.3.6 Circulation 22
2.3.7 Waves 24
2.3.8 Tides 24
2.3.9 Coasts and Beaches 25
2.3.10 Marine Biology 26
2.3.11 Corrosion in Seawater 29
iii
2.4 Pollution 31
2.4.1 Pollution and Corrosion 33
2.4.2 Pollution and Fouling 33
2.4.3 Pollution and Biodeterioration 34
2.5 Introduced Species 34
2.6 References 36
Chapter 3 Standards and Specifications 41

3.1 Metals and Alloys 41
3.2 Nonmetallic Materials 43
3.3 References 44
Chapter 4 Corrosion Mechanisms 45

4.1 General Corrosion 45
4.2 Localized Corrosion 45
4.2.1 Crevice Corrosion 45
4.2.2 Underdeposit Corrosion 46
4.2.3 Tuberculation 47
4.2.4 Filiform Corrosion 47
4.2.5 Pitting Corrosion 47
4.2.6 Microbiologically Influenced Corrosion 48
4.3 Environmentally Assisted Cracking 49
4.3.1 Stress Corrosion Cracking 50
4.3.2 Hydrogen Effects 50
4.3.3 Corrosion Fatigue 52
4.4 Velocity-Influenced Corrosion 52
4.4.1 Erosion Corrosion 56
4.4.2 Cavitation 56
4.4.3 Fretting Corrosion 56
4.5 Galvanic Attack 57
4.6 Intergranular Corrosion 64
4.7 Dealloying or SelectiveAttack 64
4.8 References 64
Chapter 5 Metals and Alloys 67

5.1 Ferrous Metals-Carbon, Low Alloy Steels, and Cast Irons 67
5.1.1 Carbon and Low Alloy Steels 69
5.1.1.1 Corrosion Behavior 70
5.1.1.1.1 Stress Corrosion Cracking 71
5.1.1.1.2 Microbiologically Influenced Corrosion 72
5.1.2 Cast Irons 72
5.1.2.1 Corrosion Behavior 73
5.1.2.1.1 Pitting and Crevice Corrosion 73
5.1.2.1.2 Stress Corrosion Cracking 74
Contents V
5.1.2.1.3 Erosion Corrosion 74

5.1.2.1.4 Graphitic Corrosion 74
5.1.2.1.5 Microbiologically Influenced Corrosion 75
5.1.3 Corrosion of Carbon Steel and Cast Irons in Fresh Waters 75
5.1.4 Corrosion of Carbon Steel and Cast Irons in Seawater 76
5.1.5 Biodeterioration of Steel and Cast Iron 78
5.1.6 Standards and Specifications-Steels and Cast Irons 78
5.1.6.1 ASTM 78
5.1.6.2 EN 79
5.2 Stainless Steels 79
5.2.1 Wrought Stainless Steels 80
5.2.1.1 Martensitic Stainless Steels 80
5.2.1.2 Precipitation Hardening Stainless Steels 81
5.2.1.3 Ferritic Stainless Steels 81
5.2.1.4 Austenitic Stainless Steels 82
5.2.1.5 Duplex Stainless Steels 84
5.2.2 Cast Stainless Steels 85
5.2.3 Corrosion Behavior 85
5.2.3.1 Crevice Corrosion 86
5.2.3.2 Pitting Corrosion 87
5.2.3.2.1 Pitting Resistance Equivalent
of Stainless Steels 88
5.2.3.3 Stress Corrosion Cracking 90
5.2.3.4 Intergranular Corrosion 91
5.2.3.4.1 Weld Decay 91
5.2.3.4.2 Knife Line Attack 92
5.2.3.5 MicrobiologicallyInfluenced Corrosion 92
5.2.4 Corrosion of Stainless Steels in Waters 93
5.2.4.1 Effect of Biofilms and Chlorination
in Seawater 94
5.2.5 Standards and Specifications-Stainless Steels 97
5.2.5.1 ASTM 97
5.2.5.2 EN 97
5.3 Nickel Alloys 98
5.3.1 Wrought Nickel Alloys 98
5.3.1.1 Alloy 200-Nickel 99
5.3.1.2 Ni / Cu All0ys-Monels 99
5.3.1.3 Ni/Mo Alloys-B Hastelloys 99
5.3.1.4 Ni/Cr/Mo Alloys< Hastelloys 99
5.3.1.5 Ni/Cr/Fe Alloys-Incoloys and Inconels 100
5.3.2 Cast Nickel Alloys 100
5.3.3.1 Localized Corrosion 101
5.3.3.4 Microbiologically Influenced Corrosion 103
5.3.4 Corrosion of Nickel Alloys in Fresh Water 103
5.3.5 Corrosion of Nickel Alloys in Seawater 104
5.3.6 Standards and Specifications-Nickel Alloys 107
5.3.6.1 ASTM 107
5.3.6.2 EN 107
5.4 Copper Alloys 107
5.4.1 Alloys of Copper 108
5.4.2.3 Selective Leaching or Dealloying 111
5.4.3 Corrosion of Copper Alloys in Fresh Waters and Condensates 112
5.4.4 Corrosion of Copper Alloys in Seawater 113
5.4.4.1 Effect of Temperature 113
5.4.4.2 Effect of Oxygen 114
5.4.4.3 Effect of Sulfides 114
5.4.4.4 Effect of Chlorination 116
5.4.4.5 Effect of Velocity 116
5.4.5 Standards and Specifications-Copper Alloys 117
5.4.5.1 ASTM 117
5.4.5.2 ENand I s 0 118
5.5 Aluminum Alloys 119
5.5.1.1 Pitting 121
5.5.1.2 Crevice Corrosion 122
5.5.1.3 Galvanic Corrosion 122
5.5.1.4 Deposition Corrosion 122
5.5.1.6 Exfoliation 123
5.5.1.8 Corrosion Fatigue 123
5.5.2 Corrosion of Aluminum Alloys in Fresh Water 124
5.5.3 Corrosion of Aluminum Alloys in Seawater 125
5.5.4 Standards and Specifications-Aluminum Alloys 127
5.5.4.1 AA and UNS 127
5.5.4.2 ASTM 128
5.5.4.3 EN 128
5.6 Titanium and Its Alloys 129
Contents vii
5.6.1.2 Hydrogen Effects 131

5.6.1.4 MicrobiologicallyInfluenced Corrosion of Titanium
and Other Transition Metals 132
5.6.2 Corrosion of Titanium in Waters 132
5.6.3 Standards and Specifications-Titanium Alloys 133
5.6.3.1 ASTM 133
5.7 Zirconium 134
5.7.2 Corrosion of Zirconium in Waters 135
5.7.3 Standards and Specifications-Zirconium Alloys 135
5.7.3.1 ASTM 135
5.8 Lead 136
5.8.1.1 MicrobiologicallyInfluenced Corrosion 137
5.8.2 Corrosion of Lead in Waters 137
5.8.3 Standards and Specifications-Lead Alloys 138
5.8.3.1 ASTM 138
5.9 References 139
Chapter 6 Nonmetallic Materials 149

6.1 Plastics 149
6.1.1 Thermoplastics 149
6.1.1.1 Polyvinyl Chloride 149
6.1.1.2 Polyolefines-Polyethylene, Polypropylene,
and Polybutylene 150
6.1.1.3 Fluorocarbons 151
6.1.1.4 Other Thermoplastics 152
6.1.2 Thermosets 153
6.1.2.1 Polyester Resins 153
6.1.2.2 Vinyl Ester Resins 154
6.1.2.3 Epoxy Resins 154
6.1.2.4 Other Thermosetting Resins 154
6.1.3 Fiber-Reinforced Plastics 154
6.1.3.1 Dual Laminate Construction 157
6.1.4 Elastomers 157
6.1.5 Degradation of Plastics 159
6.1.5.1 Environmental 159
6.1.5.2 Biodeteriorationof Plastics and Rubber 162
6.1.5.2.1 Organisms That Attack Plastics 162
6.1.5.2.2 Materials Attacked 163
6.1.5.2.3 Remedial Measures 164
6.1.6 The Use of Plastics in Waters 165
viii Contents
6.1.7 Standards and Specifications-Plastics 168

6.1.7.1 ASTM 168
6.2 Concrete and Ceramics - 169
6.2.1 Concrete 169
6.2.2 Reinforced Concrete 171
6.2.3 Prestressed Concrete 172
6.2.4 Deterioration of Concrete in Waters 174
6.2.4.1 Corrosion of Reinforcement 177
6.2.4.2 Reinforcement Materials Other Than Carbon Steel 180
6.2.4.2.1 Stainless and Low Alloy Steels 180
6.2.4.2.2 Coated Rebar 183
6.2.4.2.3 Nonmetallic Rebar 186
6.2.4.3 Modifymg the Concrete M i x 186
6.2.4.3.1 Inhibitors 187
6.2.4.4 Cathodic Protection of Reinforced Concrete 190
6.2.4.5 Coating Concrete 193
6.2.4.6 Repair and Remediation of Existing Concrete 194
6.2.5 Ceramics, Bricks, Stone, and Related Materials 196
6.2.6 Biodeterioration of Concrete and Stone 198
6.2.6.1 Organisms That Attack Concrete and Stone 199
6.2.6.2 Structures Attacked 202
6.2.6.3 Remedial Measures 203
6.2.7 Standards and Specificationsxoncrete and Reinforcement 204
6.2.7.1 ASTM 204
6.2.7.2 NACE 204
6.2.7.3 EN 205
6.3 Coatings and Linings 205
6.3.1 Coatings 206
6.3.1.1 Thermal Spray 208
6.3.1.2 Plating 209
6.3.1.3 Hot Dipping 209
6.3.2 Linings 209
6.3.2.1 Thermoplastics 209
6.3.2.2 Thermosets 212
6.3.2.3 Rubber 212
6.3.2.4 Cement and Concrete 213
6.3.2.5 Metals 213
6.3.3 Biodeterioration of Coatings and Linings 214
6.3.4 Standards and Specifications-Coatingsand Linings 214
6.3.4.1 NACE 214
6.3.4.2 EN 215
6.4 Wood 215
6.4.1 Degradation of Wood 217
6.4.1.1 Environment 217
Contents ix
6.4.1.2 Biodeterioration 218

6.4.1.2.1 Organisms That Degrade Wood 218
6.4.1.2.2 Structures Attacked 221
6.4.1.2.3 Remedial Measures 222
6.4.2 Standards and Specifications-Wood 223
6.4.2.1 ASTM 223
6.5 References 224
Chapter 7 Biofouling and Biodeterioration 235

7.1 Biofilms and Biofouling 235
7.1.1 Problems Caused by Biofilms and Biofouling 239
7.1.2 Biofilm Development 240
7.1.3 Microbiofouling 241
7.1.3.1 Bacteria 241
7.1.3.2 Algae 242
7.1.3.3 Fungi 243
7.1.4 Macrobiofouling and Biodeterioration 244
7.1.4.1 Macrofouling Organisms 246
7.1.4.2 Factor Affecting Macrofouling and Bioerosion 247
7.2 Microbiologically Influenced Corrosion 251
7.2.1 Organisms Implicated in MIC 255
7.2.1.1 Bacteria 255
7.2.1.2 Algae 257
7.2.1.3 Fungi 258
7.2.2 Metals Susceptible to MIC 258
7.3 References 258
Chapter 8 Monitoring 269

8.1 Techniques Used to Monitor Corrosion 270
8.1.1 Operating Conditions 270
8.1.1.1 Chemical Composition 270
8.1.1.2 Physical Conditions 270
8.1.1.3 Operating Equipment 271
8.1.1.4 Inspection 272
8.1.1.4.1 Inspection Protocol 273
8.1.1.5 Failure Analysis 273
8.1.2 Corrosion Monitors 274
8.1.2.1 Corrosion Coupons 274
8.1.2.2 Electrical Resistance Method 276
8.1.2.3 Inductive Resistance Method 277
8.1.2.4 Hydrogen Probes 277
8.1.2.5 Acoustic Emission 278
8.1.2.6 Sand/Erosion Monitors 278
8.1.2.7 Sentinel Holes 279
X Contents
8.1.3 Electrochemical Corrosion Monitoring Techniques 279

8.1.3.1 Linear Polarization Resistance 279
8.1.3.2 Zero Resistance Ammeter or Galvanic 280
8.1.3.3 Alternating Current Impedance 280
8.1.3.4 Other Techniques 280
8.2 Corrosion Monitoring of Reinforced Concrete Structures 281
8.2.1 Half-Cell Potentials 281
8.2.1.1 Macrocell Current Measurements 282
8.2.2 Linear Polarization Measurements 282
8.2.2.1 Surface Surveys of Concrete 282
8.2.3 Concrete Resistance and Resistivity Measurements 283
8.2.4 Acoustic Emission Monitoring of Prestressing Steel 283
8.2.5 Eddy Current 284
8.3 Monitoring of Biofouling 285
8.4 Monitoring of MIC 285
8.4.1 Early MIC Detection 286
8.4.2 Water Monitoring 287
8.4.3 Bacterial Monitoring 287
8.4.3.1 Planktonic Bacteria 288
8.4.3.2 Sulfate-Reducing Bacteria 289
8.4.3.3 Sessile Bacteria 290
8.4.3.4 Microbial Sampling of Equipment Surfaces 291
8.4.4 Biocide Monitoring 291
8.4.4.1 Biocide Quantity 291
8.4.4.2 Biocide Efficacy 292
8.4.5 MIC Diagnosis and Failure Analysis 294
8.5 Standards and Specifications-Monitoring 298
8.5.1 ASTM 298
8.5.2 NACE 298
8.5.3 EN 299
8.6 References 299
Chapter 9 Corrosion Control 305

9.1 Materials Selection 305
9.1.1 Corrosion Testing 307
9.1.1.1 Immersion Testing 310
9.1.1.2 Electrochemical Techniques 311
9.1.1.2.1 Potentiostatic and Potentiodynamic
Polarization 311
9.1.1.2.1.1 General Corrosion 311
9.1.1.2.1.2 Localized Corrosion 312
9.1.1.2.2 Electrochemical Impedance
spectroscopy 314
9.1.1.2.3 Electrochemical Noise 316
9.1.1.2.4 Zero Resistance Ammeter (ZRA) 316
9.1.1.2.5 Scanning Electrode Techniques 316
9.1.2 Standards and Specifications-Corrosion Testing 316
9.1.2.1 ASTM 316
9.1.2.2 NACE 318
9.1.2.3 EN 319
9.2 Design Features 320
9.3 Modification of Operating Conditions 321
9.4 Anodic Protection of Metals 321
9.5 Cathodic Protection 322
9.5.1 Sacrificial Anode Protection 322
9.5.2 Impressed Current Systems 324
9.5.3 Requirements for Cathodic Protection 324
9.5.4 Practice of Cathodic Protection 326
9.5.5 Standards and Specifications-CathodicProtection 328
9.5.5.1 NACE 328
9.5.5.2 EN 328
9.6 References 329
Chapter 10 Water Systems 333

10.1 Cooling Water Systems 333
10.1.1 Heat Exchangers 334
10.1.1.1 Startup/Lay-Up Procedures 343
10.1.2 Once-Through Freshwater Cooling Systems 344
10.1.2.1 Tanks, Screens, and Filters 345
10.1.2.2 Piping 345
10.1.2.3 Pumps 345
10.1.2.4 Valves 346
10.1.3 Once-Through Seawater Cooling Systems 346
10.1.3.1 Seawater Exchangers 346
10.1.3.1.1 Tubing 347
10.1.3.1.2 Tubesheets 349
10.1.3.1.3 Waterboxes 349
10.1.3.2 Intakes and Strainers 350
10.1.3.3 Seawater Piping 354
10.1.3.3.1 Carbon Steel and Cast Iron 355
10.1.3.3.2 Cement-Lined Pipe 356
10.1.3.3.3 Copper Alloys 356
10.1.3.3.4 Stainless Steels and Nickel Alloys 357
10.1.3.3.5 Titanium 357
10.1.3.3.6 Plastics 357
10.1.3.3.7 Rubber or Other Polymeric-Lined Pipe 358
10.1.3.4 Pumps 359
10.1.3.5 Valves 362
xii Contents
10.1.4 Recirculating Water 364

10.1.4.1 Cooling Tower Types 364
10.1.4.2 Cooling Tower Materials 365
10.2 Cooling Water Treatment 367
10.2.1 Inorganic Fouling and Deposit Control 367
10.2.1.1 Design and Operation 368
10.2.1.2 Filtration 369
10.2.1.3 Dispersants and Coagulants 369
10.2.2 Scaling Control 370
10.2.2.1 Scaling Indices 371
10.2.2.1.1 Langelier Saturation Index 371
10.2.2.1.2 Ryznar Stability Index 372
10.2.2.1.3 Puckorius Scaling Index 373
10.2.2.1.4 Stiff-Davis Index 374
10.2.2.1.5 Oddo-Tomson Index 374
10.2.2.1.6 Larson-Skold Index 374
10.2.3 Corrosion Control by Inhibitors 375
10.2.3.1 Inhibitors and Biofilms 377
10.2.4 Biofouling Control 378
10.2.4.1 Nonchemical Methods 378
10.2.4.2 Chemical Methods 379
10.2.4.3 Antifouling Coatings 380
10.2.5 MIC Control 383
10.2.5.1 Biocides 385
10.2.5.1.1 Oxidizing Biocides 386
10.2.5.1.2 Nonoxidizing Biocides 391
10.2.5.1.3 Biocide Resistance 392
10.2.5.1.4 Biocide Application 393
10.2.5.1.4.1 Biocide Selection 393
10.2.5.1.4.2 Determine Minimum
Effective Concentration
and Dosage Rate 393
10.2.5.1.4.3 Monitor Application and
Effectiveness 394
10.2.6 Combined Treatment Programs 394
10.2.7 Standards and Specifications-Cooling Water 396
10.2.7.1 ASTM 396
10.2.7.2 NACE 396
10.3 References 396
Chapter 11 Applications 405

11.1 Ships and Boats 405
11.1.1 Wood 405
11.1.1.1 Copper Bottoms 407
Contents xiii
11.1.2 Iron and Steel 409

11.1.2.1 CP of Steel Ships 413
11.1.2.2 Coatings 414
11.1.3 Aluminum 416
11.1.4 Copper-Nickel Alloy 417
11.1.5 Titanium and Its Alloys 419
11.1.6 Plastics 420
11.1.7 Concrete or Ferrocement Boats 422
11.1.7.1 Ferrocement and Epoxy/GRP Combinations 423
11.2 Propellers, Shafts, and Fittings 423
11.3 Shipboard Equipment 425
11.3.1 Marine Tankers 425
11.3.2 Marine Fasteners 426
11.3.3 Condensers and Heat Exchangers 427
11.3.4 Multieffect Desalination Evaporators 427
11.3.5 Naval Centrifugal Pumps 428
11.3.6 Marine Valves 428
11.3.7 Ferry Decks 428
11.4 Docks, Piers, and Other Aquatic Structures 429
11.4.1 Wood 429
11.4.2 Stone 430
11.4.3 Concrete 431
11.4.4 Steel 435
11.4.5 Alloy Sheathing 436
11.4.6 Plastics 437
11.4.7 Coatings 438
11.5 Dams and Barriers 440
11.5.1 Dams 440
11.5.1.1 Dam Failures 444
11.5.2 Barrages and Barriers 445
11.5.3 Man-Made Rivers 446
11.6 Potable Water Handling 448
11.6.1 Treatment of Potable Water 448
11.6.2 Potable Water Distribution 451
11.6.2.1 Potable Water Tanks 452
11.6.2.2 Potable Water Piping 453
11.6.2.2.1 Cast Iron 453
11.6.2.2.2 Steel and Galvanized Steel 454
11.6.2.2.3 Concrete 455
11.6.2.2.4 Asbestos Cement 456
11.6.2.2.5 Stainless Steel 457
11.6.2.2.6 Copper 460
11.6.2.2.7 Plastics 461
11.6.3 Electrochemical Protection of Domestic Water Systems 462
xiv Contents
11.7 Wastewater Handling 462

11.7.1 Treatment Plants 463
11.7.1.1 Stainless Steels 465
11.7.1.2 Galvanized Steel 466
11.7.1.3 Concrete 466
11.7.1.4 Vitrified Clay 467
11.7.1.5 Corrosion Protection 467
11.7.2 Sewers and Wastewater Piping 468
11.7.2.1 Concrete 468
11.7.2.2 Asbestos Cement 470
11.7.2.3 Vitrified Clay 470
11.7.2.4 Plastics 471
11.7.2.5 Steel and Cast Iron 472
11.7.2.6 Coatings 474
11.7.3 Standards and Specifications-Water
and Waste Water 474
11.7.3.1 AWWA/ANSI 474
11.7.3.1.1 Ductile-Iron Pipe and Fittings 474
11.7.3.1.2 Steel Pipe and Tanks 475
11.7.3.1.3 Concrete and A/C Pipe and Tanks 476
11.7.3.1.4 Plastic Pipe 476
11.7.3.2 ASTM 477
11.7.3.3 EN 478
11.8 Oil and Gas 479
11.8.1 Oil Rigs and Other Offshore Structures 480
11.8.1.1 Cathodic Protection 481
11.8.1.2 Cladding 484
11.8.1.3 Coatings and Linings 485
11.8.2 Seawater Handling Systems 487
11.8.2.1 Carbon Steels 491
11.8.2.2 Stainless Steels 492
11.8.2.3 Titanium 494
11.8.2.4 FRP Piping 495
11.8.2.5 Copper Alloy Piping 496
11.8.3 Injection Systems for Secondary Recovery 496
11.8.4 Standards and Specifications4 and Gas 498
11.8.4.1 NACE 498
11.8.4.2 NORSOK 499
11.9 Petroleum Refining 500
11.9.1 Refinery Waste Water 501
11.9.2 Sour Water Corrosion 503
11.9.3 Wet H2S Cracking 506
11.9.4 Standards and Specifications-Petroleum Refining 507
11.9.4.1 NACE 507
Contents xv
11.10 Chemical Process Plants 507

11.10.1 Cooling Water Systems 508
11.lo.1.1 Once-Through Seawater 509
11.10.1.2 Once-Through Fresh Water 518
11.10.1.3 Recirculating Water Systems 518
11.10.2 Hydro Testing and Storage 519
11.11 Pulp and Paper Mills 520
11.11.1 Pulp Mills 522
11.11.2 Mechanical Pulping 522
11.11.3 Chemical Pulping 523
11.11.4 Hybrid Pulping Processes 524
11.11.5 Bleaching 524
11.11.6 Paper Machines 526
11.11.7 Water Treatment 527
11.12 Power Plants 528
11.12.1 Fossil Fuel and Nuclear Plants 528
11.12.1.1 Cooling with Fresh Water 528
11.12.1.1.1 Feedwater Heaters 529
11.12.1.1.2 Condensers 529
11.12.1.1.3 Moderator Heat Exchangers 530
11.12.1.1.4 Shutdown, Bleed, and Recirculation
Coolers 531
11.12.1.2 Cooling with Brackish and Seawater 531
11.12.2 Power Generated from Alternative Energy Sources 533
11.12.2.1 Hydroelectric 533
11.12.2.2 Tides 534
11.12.2.3 Offshore Wind 535
11.12.2.4 Ocean Thermal Energy Conversion 535
11.13 Steam Systems 537
11.14 Desalination 540
11.14.1 Thermal Desalination Processes 541
11.14.1.1 Multistage Flash 541
11.14.1.2 Other Distillation Processes 548
11.14.2 Membrane Desalination Processes 548
11.14.2.1 Electrodialysis 548
11.14.2.2 Reverse Osmosis 549
11.14.3 Waste Water from Desalination 551
11.14.4 Standards and Specifications-Desalination 552
11.14.4.1 ASTM 552
11.15 Mining 552
11.16 Fish Farming 553
11.17 Swimming Pools 555
11.18 References 557
rvi Contents
Appendix A Nominal Composition of Alloys 575
Appendix B Approximate Equivalent Grade of Some Cast and Wrought Alloys 579
Index 581
Color Plates follow p . 234.
Chapter I
Introduction
Water is everywhere. Some places have too much and worry about floods; others have
too little and are concerned with providing sufficient amounts for people, animals, and
crops. Everyone knows what water is, but in the context of this book the term includes
a wide range of fluids-from ultrapure H20 through seawater, to waste waters from
human and industrial sources.
Most materials used by man have some application in aqueous environments. Some
are highly successful, such as water and wastewater piping dating back to Roman or
pre-Roman times and still in use today. Other applications are less long-lived, such as
badly maintained ships (Figure1.1).Much is known about the way that materials behave
in these types of environments. This book is intended to summarize the state of the art
in terms of materials properties, biological factors, and effects of water properties and
composition. It also includes descriptions of all the major applications of materials in
waters, with details of experience gained and methods used to produce equipment that
will have a long life in this sometimes very aggressive medium.
Over the past 20 years or so the technology available for producing and treating
materials has improved dramatically. This has led to the availability of a whole new
range of stainless steels, exotic alloys, and plastics. At the same time the demand for
better materials for use in more arduous aqueous environmentshas also increased. This
demand has come mainly from oil and gas production, chemical process industries, pulp
and paper, and desalination. The available information about these changes is spread
throughout many sources, often with interests in specific materials. For example, the
Nickel Development Institute (NiDI) provides information on the use of nickel-based
alloys and stainless steels; the Copper Development Association (CDA)provides similar
information on the use of copper-based alloys; the National Association of Corrosion
Engineers (NACE) provides information on corrosion behavior and prevention in all
environments. There is no one source that includes all the available alloys and materials
and compares their uses in waters. This book attempts to fill this gap by providing an
impartial summary of the uses of materials in aqueous environments. It deals with the
subject in a practical way intended for people involved in specifymg and using materials
in these demanding water systems.
1
Figure 1.1 The effect of lack of maintenance of steel in water is illustrated
by these sunken and sinking ships. (See color plate.) (Photo courtesy of
CARIAD Consultants.)
Introduction 3
The book covers all constructional materials used in these applicationsand describes
their relevant properties. Materials that are included are, for example, wood (for boats,
yachts, and piers), plastics (for piping and tanks), concrete (for piers and cooling towers),
structural steels (for oil platforms), aluminum (for boats and motors), stainless steels,
and copper- and nickel-based alloys (for water-cooled heat exchangers, piping, pumps,
and valves).
Chapters are devoted to describing aqueous environments, giving the basic practical
information on those aspects that are relevant to specifymg construction materials for
use in them. The areas of water treatment, monitoring, and control are given detailed
treatment because problems in these areas cost industry millions of dollars annually.
Mechanical and corrosion resistance properties, fabricability, and advantages and
disadvantages of the materials in specific aquatic environments are covered in depth.
The information provided is intended to be detailed enough to allow readers to make
informed decisions in specific cases and also provides complete references to the lat-
est journals, standards and specifications, Web sites, and other information sources for
follow-up research if required.
Throughout the book metals and alloys are identified by their Unified Numbering
System (UNS)numbers, with trade names or genericnames where this aids identification.
Trade names are also used where they provide more specific information on the material
under discussion. Lists of selected standards and specifications are included at the end of
major sections.These are not intended to be completebut to indicate those standards and
specifications most relevant to those materials or their use in the specific applications.
The composition of the metals and alloys in general use in waters is contained in
Appendix A. Appendix B provides lists of equivalent wrought and cast grades of some
of the alloys. Inevitably, some aspects of the this complex subject are dealt with in a
number of different sections. Where this happens other chapters containing relevant
information are referred to in the text.
Chapter 2
Oceanography and Limnology
A basic understanding of water is important to its users. This chapter looks at the physi-
cal, chemical, and biological properties of waters as they relate to our use of it as a coolant
or an environment in which we operate.
Water is a unique material covering 70% of the Earth's surface. Without it life could
not exist. The only substance to occur naturally in all three phases on Earth (solid ice,
liquid water, and gaseous vapor), it has many unusual properties that make it ideal
as a major component of the Earth and living organisms. Water is a universal sol-
vent and the large variety of salts, compounds, and gases that dissolve in water is
crucial in physical, chemical, and biological processes on Earth. Water has high trans-
parency and low compressibility, permitting biological processes to occur deep in ocean
waters.
Almost all liquids increase in density as their temperature declines toward freezing.
Water is the exception to this rule. While pure water has a freezing point of 0°C it
reaches a maximum density of 1 g/cm3 at 3.98"C. This unique feature has extremely
important consequences for the biology and circulation of water bodies and these are
discussed below. The density of seawater is significantly higher, 1.025 g/cm3 at 15°C.
The temperature of maximum density of seawater decreases as salinity increases.
Studies of related compounds suggest that theoretically, water should freeze at
-150°C and boil at -1OO"C, not 0 and 100°C, respectively. The heat capacity of water
is the highest of all commonly encountered solids and liquids, preventing extremes of
climate in both the oceans and atmosphere. The top 3 m of the ocean has the same ther-
mal capacity as the entire atmosphere. In a Cday period the planet's oceans absorb an
amount of thermal energy from the sun and kinetic energy from the wind equivalent
to all of the world's known oil reserves.' The latent heat of fusion and vaporization are
also the highest of all common substances, which have a major influence on heat transfer
from the oceans to the atmosphere.
Many complex physical, chemical, and biological processes are occurring contin-
uously in all natural waters and these processes have important consequences for us
when we use waters. Disasters and expensive failures occur when man does not take
these factors into consideration.
5
6 Oceanography and Limnolonv
Waters can be classified according to composition; e.g., fresh contains less than
1,000 ppm chlorides, brackish has 1,000 to 10,OOO ppm chlorides, seawater has 2.5 to
3.5% sodium chloride, and brines have stiU higher concentrations of chlorides. Other
classificationsare based on the content of salts, such as calcium and magnesium, which
have an effect on scaling and corrosion.
The dominant consideration for our use of steels in water is its corrosivity. In fresh
water, water quality strongly influences its corr~sivity?~ The corrosive nature of waters
varies considerably depending largely on their composition and on the alloy exposed
to the aqueous environment. One factor of prime concern in fresh water is its hardness,
usually expressed as calcium carbonatecontent. Hardness varies considerably in natural
waters. Other factors of importance are pH, temperature, conductivity,dissolved oxygen
concentration, chloride content, dissolved and suspended solids,velocity, and biological
activity.
In seawater, by definition,there are always significant quantities of chloridespresent
in the dissolved salts and conductivityis high. Other factors that influence corrosivity of
seawater are similar to those in fresh water, i.e., physical and chemical factors, such as
pH, temperature, dissolved oxygen concentration, and dissolved and suspended solids.
Figure 2.1 Human activities have a marked influence on coastal waters. In developed areas
large quantities of nutrients from sewage and toxic substances from industrial activity change
the quality and constituents of the natural water. (Photo courtesy of CAIUAD Consultants.)
2.1 Fresh Water 7
Also very important in many cases is the biological activity of myriad aquatic organisms,
whose metabolic products are directly or indirectly corrosive to many metals.
For nonmetallic materials, biological considerations are often paramount. A vast
spectrumof organisms, bacteria, algae, fungi, sponges, mollusks, polychaeteworms, and
others degradesboth natural and man-made materials. Theseorganisms and their effects
will be discussed in detail in Chapters 6, “Nonmetallic Materials,” and 7, ”Biofouling
and Biodeterioration.”
Most of our activities occur in the surface waters of lakes and oceans, particularly in
coastalareas (Figure2.1). Nearshore, shallow water conditionsare more variable in all the
physical, chemical,and biological variables than open waters and waters at great depths.
In this chapter we will discuss natural waters from the point of view of their relevance
to us as water users when we build in or near waters or use them for industrial purposes.
Although many basic featuresof the subject will be covered where they are relevant to this
book, this is not meant to be a general introductory text to oceanography and limnology.
The relevance of the information for our use of waters is outlined in thischapter but will
recur later under specific headings, such as Chapter 4, ”Corrosion Mechanisms” and
Chapter 11, ”Applications.”
2.1 FRESH WATER
The term ”fresh water” covers a whole range of aqueous environmentsbut is generally
used to differentiate it from waters with higher chloride contents, i.e., brackish and
seawater. Fresh water is generally more benign to metals than waters containing large
amounts of chlorides or other salts. The dissolved salts, particularly cations, in fresh
waters can increase corrosion or reduce it by forming protective deposits. Dissolved
gases such as oxygen, carbon dioxide, and hydrogen sulfide generally increase corrosion
of most metals.
Fresh waters tend tobe lower in pH and the pH tends to fluctuate more than seawater.
The effect of pH on corrosion depends on the metal, e.g., corrosion of iron increases as
pH drops below about 4, is steady between 4 and 10, and decreases rapidly at pH greater
than 10. Aluminum and zinc show increased corrosion rates as pH increases above 9.4
Because these effects are metal dependent, corrosion in fresh waters is discussed under
the sections for specific alloys in Chapter 5, “Metals and Alloys.”
2.1.1 Potable Water
Potable water is water that is low in salts and safe for drinking. Its conductivity is
generally in the range of 50 to 1,500 pnihos/cm. Raw water normally requires treatment
to make it potable. In general, this is done by public water utilities that are responsible
for the treatment and distribution of water to communities. Although in developed
countries less than 1%of potable water is consumed, all water delivered to homes for
8 OceanoaraDhv and Limnoloav
food preparation, bathing, washing, watering gardens, heating, and cooling is treated to
potable standards.
Water has been treated for thousands of years, but only when the connection be-
tween bacteria in sewage and severe epidemics was made were procedures developed
for safe water in the 19th century. Today the World Health Organization (WHO), Euro-
pean Union (EU), and the United States Environmental Protection Agency (U.S. EPA),
along with many other organizations, have a well-defined set of limits and standards for
microorganisms and toxic substances in drinking water. One gets the impression, how-
ever, that the rate of development of new toxins greatly exceeds the rate of development
of standards for testing them and regulations for limits.
Drinking water quality varies but most bodies agree on the main principles, the
WHO standards being representative. They include standards for color, taste, odor, tur-
bidity, total dissolved solids, pH, oxygen, microorganisms, and organic and inorganic
constituents.
Water intended for drinking and household purposes must not contain water-borne
pathogens. The most numerous and the most specific bacterial indicator of fecal pol-
lution from humans and animals is Escherichiu coli. E. coli (or thermo-tolerant coliform
organisms) must, therefore, not be present in 100-mL samples of any water intended for
drinking? The U.S. EPA quality limit for bacteria is 1 coliform colony/100 mL and the
action limit is 4 coliform colonies/100 mL. Because disinfection and other water quality
standards are usually stringent, potable water is normally free or nearly free of bacteria
and other microorganisms. As a result most industrial users of potable water do not have
to worry about microbiological corrosion unless the water becomes contaminated from
other sources, such as open cooling towers.
WHO limits for some inorganic constituents (Table2.1) and disinfectants (Table 2.2)
are given below. At levels permitted in drinking water, many potential corrodentsare not
a sigruficantconcern. Iron and manganese bacteria can convert ferrous and manganese
bicarbonate to ferric hydrate and hydrated manganese oxide, both of which can be
important sources of deposits in potable water systems?
2.1.2 Lakes and Rivers
The most obvious difference between seawater and fresh water is the salt content. Fresh
water is usually defined as tasting sweet,with a salinity of less than 0.5%. Fresh water can
be divided into to two distinct habitats, non-flowing waters such as lakes, and flowing
waters such as rivers. In industry fresh water may be used as raw river or lake water,
natural water treated with softeners, biocides, etc., or condensate, condensed steam.
2.1.3 Chemistry
Silicates and some trace elements, such as thorium and cerium, are usually higher in
natural river water than seawater. Industrial activity also increases the concentration of
2.1 Fresh Water 9
Table 2.1 WHO Limits for Inorganic Constituents of

Health Sigruficancein Drinking Waters
Element Guideline Value (mg/L)
Antimony 0.005 (P)
Arsenic 0.01 (P)
Barium 0.7
Boron 0.5 (P)
Cadmium 0.003
chromium 0.05 (P)
Copper 2 (PI
Cyanide 0.07
Fluoride 1.5
Lead 0.01
Manganese 0.5 (P)
Mercury (total) 0.001
Molybdenum 0.07
Nickel 0.02 (P)
Nitrate (as NO;) 50 (acute)
Nitrite (as NO;) 3 (acute) 0.2 (P) (chronic)
Selenium 0.01
Uranium 0.002 (P)
(P): Provisional guideline value.
Table 2.2 WHO Limits for Disinfectants and Disinfectant By-products in DrinkingWaters
Chemical Compound Guideline Value (mg/L)
Disinfectants
Monochloramine 3
Di- and trichloramine Inadequate data
Chlorine 5; for effective disinfection there should be a residual concentration of
free chlorine of 0.5 mg/L after at least 30 min contact time at pH t8.0
Chlorine dioxide A guideline value has not been established because of the rapid
breakdown of chlorinedioxideand because the chloriteguidelinevalue
is adequately protective for potential toxicity from chlorine dioxide
Iodine Inadequate data
Disinfectant by-products
Bromate 25 (PI
Chlorate Inadequate data
Chlorite 200 (P)
(P):Provisional guideline value.
Note: At concentrationspermitted for drinking water chlorine and chlorine residuals may damage
some stainless steels.
10 Oceanoeraohv and Limnoloev
Table 2.3 The Average Composition of Soluble

Materials in Rivers7
Constituent %byWeight
Carbonate 35.15
Calcium (Ca2+) 20.39
Sulfate (SO,'-) 12.14
Silica (SiO2) 11.67
sodium (Na+) 5.79
Chloride (Cl-) 5.68
Magnesium (Me) 3.41
Oxides [(Fe,A1)203] 2.75
Potassium (K+) 2.12
Nitrate (NO,-) 0.90
heavy metals such as copper, lead, and mercury. The total dissolved organic constituents
are also usually higher in rivers than in the sea.
The composition of soluble material in fresh water (Table 2.3) is different from that
of seawater (Table 2.5). Since river-borne salts are the primary source of sea salts it is
a mystery why they are so different. One theory is that the more soluble salts, such
as NaC1, have leached out of rocks over geological time and have already contributed
their components to seawater. The land is now being leached of less soluble materials.
Unfortunately it is not possible to test this theory.
Because of the variety of sources and treatments of industrial fresh water, its quality
varies enormously and hence its effect on materials (seeTable 2.4 for examples of waters
used in industry).
Sulfates add to the solids content of water and may combine with calcium to form
scale. Nitrates also add to solid content and provide an important nutrient for microor-
ganism, which may lead to microbiologically influenced corrosion (MIC). Chlorides,
even in small quantities, may cause localized or general corrosion of many metals. Iron
and silica may form deposits, leading to underdeposit corrosion. Oxygen, hydrogen
sulfide, and ammonia all cause corrosion in various materials.
Conductivity gives a measure of water's dissolved mineral content, an approximate
measure of the degree of impurities in the water. It is related to total dissolved solids
and, when high, causes process interference and foaming in boilers. Suspended solids
may drop out of the bulk water in areas of low velocity and cause problems of scaling
and deposit formation.
"Hardness," an old-fashioned term related to the difficulty of producing soap suds,
measures the calcium and magnesium in water. Hardness is an important factor in
the susceptibility to scaling, which reduces heat transfer efficiency and increases the
probability of underdeposit corrosion. For ease of calculation, hardness is usually ex-
pressed in terms of calcium carbonate (CaCO3). Hardness may range from zero to
Table 2.4 Some Chemical Analyses of Variou Fresh Waters
Conductivity Alkalinity Total Dissolved Total Hardness Chloride SO4 NO3
Source (Wnhos/cm) (ppm) Solids (ppm) (ppm) PH (ppm) (ppm) (ppm)
Distilled water 0.5-3
Potable water (general) 50-1500
Well water, Crete, potable 1150-1440 - - 176430 7.7-8.0 - 170
and residential useE
Potable makeup cooling 32 89 - 109 7.9 16 36
water, Sasolburg, South
Africa9
Industrial well water, - 146 495 303 7.8 71 165
Georgia'O
Lake Huron" 21.0 7.8 5.0 15.0
Squaw Creek Reservoir, 2200-2800 115 1434 373 7.4-8.2 590 250
Tx'2
Lake Ontario, intake for 365 115 309 126 8.7 30.0 75
Pickering Nuclear
Power Station13
Raw cooling and boiler - 30 75 28 6.7 25 -
water, Port Arthur, TX14
Raw cooling and boiler - 120 307 188 7.5 48 84
water, New Orleans,
LA14
Lake Gatun, PanamaI5 0.091-0.12 - 69-165 - 6.9-8.0 0-12.5 0-7.2
hundreds of milligrams per liter and may be expressed in several different ways. It
is measured by titration.16 Total hardness is defined as the sum of calcium and mag-
nesium concentrations, expressed as CaC03 in mg/L or ppm. This is the normal way
of reporting hardness as a measure of industrial water quality. When the hardness is
greater than the sum of carbonate and bicarbonate alkalinity, the amount of hardness
that is equivalent to the total alkalinity is called “carbonate hardness” and the rest is
called ”noncarbonate hardness.” When the hardness is less than or equal to the sum of
carbonate and bicarbonate alkalinity, all hardness is carbonate hardness.
Hardness is related to alkalinity, which is caused by dissolved bicarbonate salts. When
carbon dioxide (C02) dissolves in water it reacts with it to form carbonic acid (H2C03).
Carbon dioxide (carbonic acid) dissolves carbonates (limestone, dolomite) to produce
hardness and alkalinity. Alkalinity buffers water, moderating pH changes. Most natural
waters contain bicarbonate alkalinity and are less than pH 8.4. At higher pH, bicarbonate
(HCO,) is converted to bound C02, or carbonate (COi2).17Alkalinity may embrittle
some steels and in hot environments, such as boilers, carbonate and bicarbonate break
down to form carbon dioxide, which causes corrosion.
Because scale is an important problem in industry there have been several attempts
to predict the susceptibility of systems to scale formation, e.g., Ryznar and Langelier
Indices (see Chapter 10, Section 10.2.2, ”Scaling Control”).
2.1.4 Freshwater Biology
In general, freshwater ecosystems are more varied in plant life and more restricted in
animal forms than marine ecosystems. In the water column planktonic algae (phyto-
plankton) include diatoms, blue-green algae, and green algae (including single-celled
forms and filamentous forms called ”pond scum”). Duckweeds, which are seed plants,
may also form sheets on the surface. Phytoplankton are more abundant in still waters
than in rivers.
River and lake bottoms are often covered with larger weeds and more diverse
families of higher plant life. Along the edge but rooted in the water are cattails
(T’ha), bulrushes (Scirpus), arrowheads (Sugitturiu), bur reeds (Spurguniurn), spike
rushes (Eleocharis), and pickerelweeds (Pontederiu).In deeper waters many plants are
rooted on the bottom and mostly submerged. These include pond weeds (Potamoget-
onaceae), which are more common in warm climates, where they can choke waterways
and clog boat motors and intakes. The most famous example is the water hyacinth,
Eichhorniu crassipes, which grows extremely quickly and has taken over tropical lakes,
canals, and rivers all over the world, clogging them (see Section 2.5, “Introduced
Species”).
Microorganisms, such as bacteria and fungi (often the same families and species
as in the sea), are also present and important components of the biology. These mi-
croorganisms present the same risk factors for corrosion as in any other aquatic
environment.
2.1 Fresh Water 13
Algae, both planktonic and bottom dwelling,are the most important primary produc-
ers, converting carbon dioxide into simple sugars. As in the sea, primary productivity
depends on light and essential nutrients. In contrast to the sea, however, oxygen and
carbon dioxide concentrations are often limiting in the freshwater environment.Nitrates
and phosphates are also often limiting.
Lakes may be naturally eutrophic (rich in nutrients such as nitrates and phosphates)
or oligotrophic (nutrient poor). Eutrophication, however, is more often associated with
artificial introduction of pollutants such as sewage. Eutrophication is commonly as-
sociated with higher corrosion levels of steel. Eutrophic lakes are generally shallow
and have high productivity because the algae have large amounts of nutrients avail-
able. Oxygen levels are generally more variable and can be very low during plankton
blooms.
Where nutrients are excessive algal blooms may occur. About 50% of the time algal
blooms are toxic.18Toxic algae in fresh water obviously have serious consequences for
potable water, but in addition they may kill off fish and other life (whichthen decompose,
consuming oxygen) and increase bacterial populations.
Oligotrophiclakes are deeper and clearer with higher, more stable oxygen levels. With
human intervention, especially near sewage outfalls and heavily fertilized farmlands,
lakes may be artificially enhanced in nutrients, resulting in eutrophic conditions in an
otherwise oligotrophic lake.
Fresh water generally contains far fewer biofouling animal species than marine envi-
ronments. Most freshwater fouling takes the form of plant fouling. Among the animals,
mollusks (clams, mussels, and snails), aquatic insects (which are rarely found in the sea),
crustaceans (copepods, isopods, crabs, crayfish),and fish are the dominant groups in the
water, although planktonic animals, such as protozoans, rotifers, and burrowing annelid
worms, are also found.
The most economically important animals in fresh water are bivalve mollusks, which
include fouling mussels. Clams and mussels have been introduced to North American
subtropical and temperatewaters, respectively,where they have done considerabledam-
age. Larger animals that live at least partly in fresh water are the amphibiousvertebrates:
frogs, salamanders, turtles, crocodiles, alligators, and water snakes; all are more common
in fresh water than marine environmentsbut none are a serious problem for water users
in industry (except possibly for those people actually in the water).
One characteristic unique to freshwater habitats affects the number and distribu-
tion of living organisms. This is the isolation of freshwater bodies, which results in
dispersal problems for organisms. They may be prevented by land barriers from get-
ting to environments that would be favorable places for them to live. This is mostly a
problem for larger organisms such as fish. Small species such as algae and bacteria fre-
quently hitch a ride with the wind or on the bodies of birds and other more migratory
organisms.
Another method introduced more recently by man to aid in the distribution of fresh-
water (and marine) organisms is the practice of dumping ballast water. This is now a very
common method for the dispersion of larger organisms to remote parts of the world.
14 Oceanographyand Limnology
2.1.5 Turnover
Natural waters have large seasonal variations in physical, chemical,and biological char-
acteristics.Oxygen, nutrients, pH, and other factors important for fouling and corrosion
vary on a more or less predictable schedule during what is known as the "turnover."
Any monitoring program that does not consider these changes will have an incomplete
picture of the biology and chemistry of the system.
Temperate lakes vary in temperature from 0 to about 20°C. During the summer a
stable layer of warm, less dense water overlies the cold, dense layer. During the autumn
the warm layer cools and sinks until it reaches either the colder layer or the bottom of
the lake. This sinking is called the "autumn overturn" and it permits mixing of the lake
water and the distribution of nutrients to the upper layers. If the surface cools further,
to below the maximum density of water at 4"C, it once again becomes less dense than
the depths and overturn ceases. Eventually, if it is not too deep, the entire lake may cool
below 4°C as heat is conducted upward through the ice to the atmosphere. Because this
process of heat conduction is slow, however, lakes rarely freeze completely, allowing
organisms a refuge of liquid water at depths where they can survive the winter. During
the spring warming the surface temperature increases to PC, becoming denser than the
bottom water, and the spring turnover occurs, often suddenly. As the surface warms
above the temperature of maximum density the summer stable layer is reestablished
and mixing ceases. In deeper lakes the bottom waters may never cool below 4°C and
thus only become mixed during very large storms.
Subtropical lakes that never drop below the density maximum of 4°C generally have
a stable temperature gradient from top to bottom, but turn over once a year in winter.
Tropical lakes with small seasonal changes in temperature have stable thermal gradients
all year round. In these lakes mixing may occur only during major storms. In deep
tropical lakes the bottom layer (below the level of storm influence) may never be mixed.
2.2 ESTUARIES AND BRACKISH WATER
Brackish waters are usually encountered in estuaries where seawater mixes with fresh
water from a river. An estuary is defined as a semienclosed coastal body of water with
free connection to the sea. It is strongly affected by tidal action. The seawater in it is
diluted by fresh water from the land and salinity fluctuationsare large. Brackish waters
have a salinity of approximately2 to 18%.They may also carry high levels of dissolved
salts from agricultural runoff, e.g., sulfates, phosphates, and nitrates. River mouths,
coastal bays, tidal marshes, and the water behind barrier beaches are some examples of
estuaries.
Although we tend to think of estuaries as transitional between rivers and oceans,
many of the biological and physical characteristics of estuaries are, in fact, unique. Many
estuarine species are distinct, rather than remnants of marine or freshwater ecosystems.
This distinct biology and chemistry creates unique challenges in avoiding problems
2.2 Estuaries and Brackish Water 15
with materials and, therefore, estuaries should be considered separately from rivers
and the sea.
The degree of dilutionof seawater is a critical feature of estuaries, resulting in brackish
water (i.e., salinity is usually intermediate between fresh and salt).Water circulation and
stratificationpattern are the most important features in classifymg estuaries.
2.2.1 Types of Estuaries
There are several types of estuaries, with characteristic patterns of salinity, temperature,
and flow. As these factors are all important when using water, for example, as a coolant,
we will describe the types and their important characteristics.
In a salt-wedge estuary the river flow is dominant over tidal action and the water is
strongly stratified. A wedge of salty bottom water may extend considerable distances
upstream. There is usually a sharp halocline (salinity gradient).The best example is the
Mississippi River. The greatest estuary in the world, the Amazon River, with 20% of the
world’s fresh water input into the oceans, is also a salt-wedge estuary, but the volumes
of water are so large that the salt wedge cannot penetrate past the river mouth.
Where tidal and river flows are more or less equal, mixing results from turbulence,
caused by tidal periodicity. The halocline is less marked and there may be a complex
pattern of layers and water masses. ChesapeakeBay, United Statesand the Mersey River,
England are two examples of these slightly stratified estuaries.
Where the tidal action is dominant the estuary tends to be well mixed and generally
higher in salinity.Salinity variations are more often horizontal than vertical. Fresh water
will usually flow along the right shore (as you face the sea) in the Northern Hemisphere,
because of the Coriolisforce. In addition,salinityincreases graduallyas you move toward
the sea. This type of estuary is less common in nature but the Bay of Fundy, Canada,
with the largest tidal range in the world, is an example.
Inverse estuaries are a feature of hot, arid climates. They are “inverse”because high
evaporation rates and minimal freshwater input result in salinities that are higher than
the open sea. Evaporation leads to a salinity increase in the surface water at the inner
end of the estuary. The associated density increase causes the water to sink and flow out
toward the sea near the bottom. The result is a sharp halocline with two-layer circulation
but in the opposite direction to a salt-wedgeestuary, i.e., Ocean water enters the estuary in
the upper layer and hypersaline estuary water leaves in the lower layer. Inverse estuaries
may be shallow regions with a large surface area such as hypersaline lagoons or larger
gulfs of significant depth and extent. An example is Spencer Gulf, Australia.
2.2.2 Biology and Chemistry of Estuaries
An important feature of estuaries is that they are the agents for introducing terrestrial
material into the sea. In estuaries the cations carried in solution in river water meet chlo-
rides and other anions present in seawater and form colloids. Colloids are a dispersion of
16 OceanoeraDhv and Limnoloev
ultrafine particles, between dissolved and suspended. The electrical charge of colloidal
particles causes them to attract additional molecules which flocculate,becoming larger
and denser as they move toward waters with increased salinity.
Because of terrestrial runoff, estuaries and their adjacent seas are usually nutrient-
rich environments. The back-and-forth movement of an estuary tends to trap nutrients
there. Physical conditionsare often stressful for organisms. Fluctuating salinity and tem-
perature, large amounts of suspended and resuspended sediments, storm activity, and
tidal variations all contribute to the stressful environment. The combination of nutrient-
rich and stressful factors results in estuaries having fewer species than marine coastal
environments, but the total biomass is high with higher productivity than the sea on one
side and the fresh water on the other. In other words, there is a lot of what there is. This
may be bad news if the species happens to be a nuisance species.
Estuarine material includes soil, dissolved rock, organic matter, domestic and agri-
cultural runoff, hydrocarbons, heavy metals, and industrial pollution. Sediments trans-
ported downstream are kept in suspension by the turbulence of river flow. When these
suspended sediments reach the estuary they meet tidal forces, which vary the flow rates
between high and low tides, coming to rest as the tides turn.Thus, heavy sediments have
a chance to settle out at this interface. As colloids flocculatethey also become denser and,
thus, settle faster.
Unfortunately, in recent years pollution has become such a common component
of estuaries that the term ”estuary” is almost becoming synonymous with pollution.
Algal blooms and red tides (blooms of red-pigmented algae, dinoflagellates such as
Gonyuulux and Gymnodinium) are an unfortunately common occurrence. An estuary’s
capacity to handle pollution depends greatly on its flushing time. Flushing time is
the time it takes to drain the freshwater volume in the estuary through its outlet to
the sea.
Increasingly, man is impounding estuaries for barrages and barriers (see Chapter 11,
Section 11.5, ”Dams and Barriers”). These impounded waters have a greatly reduced
natural capacity for aeration, disease control, and handling wastes and pollutants.
2.2.3 Corrosion in Estuaries
Depending on composition brackish waters can be more aggressive than seawater. In

tidal estuaries, the highest corrosion rate of carbon steel is just below the tidal zone,
while in open seawater the highest corrosion rates are in the splash zone.19
The use of brackish water cooling systems in Maracaibo, Venezuela and the sur-
rounding region is becoming increasingly imperative because fresh water is in limited
supply. Following recurring failures with different copper alloys in brackish water, elec-
trochemical studies were carried out in this medium with different materials, including
super stainless steels (duplex 2507, UNS $32750, and 6%Mo stainless steel UNS N08367),
grade 2 litanium (UNSR50400),and Cu/lONi (UNS C70600) with and without chlorine
treatment. The results indicated that the corrosion resistance in this medium decreases
in the order of 6% Mo stainless, titanium, duplex, and Cu/10Ni.20
2.3 Seawater 17
2.3 SEAWATER
Seawater is a complex solution of gases, dissolved salts, and other chemical substances
dissolved in water. It covers the majority (71%)of the surface area of our planet.
2.3.1 Physical Properties
Water is essentially opaque to all electromagnetic radiation except visible light. Light is
attenuated with depth by scattering and absorption. The color of seawater is predom-
inantly blue because blue light (short wavelength) scattering predominates. Very little
of the red end of the visible spectrum penetrates the water column because of high ab-
sorption of these long wavelengths. Even at relatively shallow depths (10 to 15 m) divers
notice the huge difference in colors of marine organisms when artificially lit, with many
apparently black organisms becoming bright red under the light beam.
Suspended silt, organic matter, and organisms tend to make the sea look more green
than blue. Large numbers of certain planktonic organisms, such as dinoflagellates and
blue-green algae, can create the so-called "red tides," which are often toxic to marine
organisms and people.
2.3.2 Chemistry
Almost every chemical known on Earth exists in the sea. The oceans have been in exis-
tence for a considerable geologic time. As a result of continuous mixing and circulation,
the proportion of the major dissolved salts is fairly constant in all seas, although in coastal
areas it is diluted by fresh water and is often also influenced by runoff and pollution.
This constancy means that the dissolved solids are in constant proportions to each other,
which is very furtunate as it permits us to measure salinity (S) by measuring only one
constituent. That constituent is chloride and the relationship is expressed as
SYm = 1.80655 Cl'h.
In the open Ocean the total dissolved salts, or salinity, is approximately3.5%,usually

expressed as g/ kg or parts per thousand ( O h ) . The main constituentsare listed in Table 2.5.
Many of the chemical and physical characteristics of seawater change with salinity,
temperature,and biological activity.The typical values for someimportantcharacteristics
for those working with seawater are given in Table 2.6.
2.3.3 Oxygen and Carbon Dioxide
Oxygen and carbon dioxide are the two most important dissolved gases in seawater.
Because they are important in engineering and corrosion it is worth making an effort to
understand their properties and behavior.
18 OceanoaraDhv and Limnolonv
Table 2.5 The Major Chemical Constituents of Seawater

of Salinity 34.48% (Chlorinity 19%)7,21
Constituent Concentration ("A)
Chloride (Cl-) 18.98
Sodium (Na+) 10.556
Sulfate (q-1 2.649
Magnesium ( M e ) 1.272
Calcium (Ca2+) 0.400
Potassium (K+) 0.380
Bicarbonate (HCO; ) 0.140
Bromide (Br-) 0.065
Boric acid (H3B03) 0.026
Strontium (SS+) 0.008
Fluoride (F-) 0.0013
Table 2.6 Typical Values of Important Physical, Chemical, and Biological Parameters of Clean,
Openacean S e a ~ a t e r ~ - ~ ~ - ~
Characteristic Value
Salinity (%) 34-36
Specific gravity at 17.5"C 1.0262
Density at 17.5"C 1.02542
Temperature of maximum density "C -3.52
Conductivity (millimhos)at 10°C 38.07
Conductivity (millimhos)at 18°C 45.86
Dissolved oxygen (ppm) range 0-12
Dissolved oxygen saturation (ppm) at 10°C 6.07
Dissolved nitrogen (ppm) 10-18
Dissolved argon (ppm) 0.4-0.7
Hydrogen sulfide (ppm) 0
Carbon dioxide as COz, H2CO3, HCO;, and CO;' (ppm) 64-107
Particulate organic carbon as plankton and detritus in deep waters (pg C/L) 10
Particulate organic carbon as plankton and detritus in surface waters (pg C/L) 100-500
Dissolved organic carbon (ppm C) 0.4-2
Alkalinity 2.3825
PH 8.1-8.3
Nitrogen as NO; (ppm) 0.001-0.6
Nitrogen as NO; (ppm) 0.0001-0.05
Nitrogen as NH;' (ppm) 0.004-0.05
Phosphorus as PG- (ppm) 0.001-0.10
Organic phosphorus (ppm) tl-0.03
Silicate (ppm) 0.01-4.6
Fe, mostly as particulates (ppm) 0.003-0.07
2.1 Seawater 19
The amount of gas that water can hold, its saturation value, varies with temperature,
pressure, and salinity. Because of the importance of oxygen concentration in ecological
and industrialprocesses, dissolvedoxygen (DO)and biochemical oxygen demand (BOD)
are becoming the most intensively measured physical factors.
Water may be undersaturated or supersaturated with these important gases and the
amount of gas in any given volume of water may vary greatly over small changes in
time and space. Water samples taken in the sea can vary in oxygen content from totally
anoxic (0 mL/L) to supersaturated (12 mL/L). Carbon dioxide in the sea is somewhat
less variable, varying around the value of 40 mL/L.
Quantities of oxygen and carbon dioxide are controlled primarily by biological activ-
ity which, in turn,is determined by light levels. Plants in the sea (primarily phytoplank-
ton), like those on land, photosynthesize during the day, consuming C02 and water to
produce simple sugars using light energy and releasing 0 2 .
photosynthesis
6CO2 + 6 H20 + energy- c C6H1206+ 602
respiration
Because photosynthesis can only occur in light, during the night plants respire and
the equation is reversed. Similarly, photosynthesis is limited by light penetration in the
sea and does not occur at depth. The amount of sunlight penetrating the water column
depends on the angle of irradiance (i.e., the time of day and season) and the clarity of
the water (i.e., the number of particulates and organisms).Although the detection limit
by man of light penetration is more than 1000m, the maximum limit for photosynthesis
is approximately 200 m, and, in practice, it is often considerably less.
Respiration, on the other hand, occurs at all depths and one might expect this to lead
to decreasing oxygen concentration with depth. In fact,there is an oxygen minimum
at intermediate depths (200 to 1,000 m), where biological demand is high and oxygen
supply is small (Figure2.2).In some seasonsthere may be two thermoclines, a temporary,
shallow one in the overturn layer and a deeper, permanent one. The depth of minimum
concentration usually coincides with the thermocline before increasing to a fairly stable
2000
2500
0 1 2 3 4 5 6
Dissolved Oxygen (pprn)
Figure 2.2 This graph shows a typical profile of
dissolved oxygen concentration vs. depth in the
ocean. (Figure courtesy of CARIAD Consultants.)
20 Oceanography and Limnology
concentration at depth. In most deep water zones biological demand is low and the
oxygen is replenished by surface water, which sinks at high latitudes and flows along
the bottom of the sea. Where oxygen replenishment is restricted by ridges or in deep
trenches, oxygen may again be decreased. The bottom of the Black Sea is an example of
near-anoxic conditions on the bottom.
Anoxic conditions may also be created locally when decomposition exceeds photo-
synthesis. Such conditions may occur after a phytoplankton or algal ”bloom.” Blooms
occur when large quantities of nutrients are introduced to a body of water, usually an
enclosed bay or estuary. Phytoplankton production increases dramatically and contin-
ues until one of the essential nutrients is used up. During this period of high primary
production the population of small floating animals (zooplankton) may also increase as
they feed on the plant material. When essential nutrients are used up all the plant and an-
imal material begins to die and decompose, using oxygen and giving off carbon dioxide.
Plankton blooms and locally anoxic conditions are becoming increasingly frequent in
coastal waters as a result of eutrophication pollution by man. Examples are the polluted
Gulf Coast of Florida and the northern Adriatic Sea.
Factors that affect the development of algal blooms are the same factors that influence
algal growth and reproduction. They include light, temperature, and nutrients. C, H, O,,
N, P, Ca, Mg, Na, K, S, Fe, Mn, Cu, Zn, Mo, B, C1, Co, and V are all essential for
A considerable amount of the carbon dioxide in the sea is bound up as carbonic acid
(H2C03), bicarbonate (HCO;), and carbonate ( C q - ) because when carbon dioxide is
added to pure water the gas combines with the hydrogen.
This equation shows that the various forms of carbon dioxide are all present in equilib-
rium with each other and with hydrogen atoms. When carbon dioxide is removed from
seawater the equilibrium is upset and the pH increases. Conversely, pH decreases when
C02 is added. Seawater has a large buffer capacity and is normally slightly basic, having
a pH of 8.0 to 8.3 in the open ocean and a somewhat larger range in isolated shallow
pools. It rarely, however, is acidic, normally being above 7.5.
If the mass of C02 in the atmosphere is considered as one unit, then the amount of C02
in the earth’s waters and rocks is 58 and 38,000 units, respectively. Thus, the atmosphere
is the smallest C02 reservoir and most easily affected by transfer from one reservoir to
another. Since the solubility of C02 in the sea is great and increases when the partial
pressure of CO2 increases, the sea acts as a regulator of C02 for the atmosphere. Carbon
dioxide can be removed from the sea by photosynthesis and by formation of calcium
carbonate skeletons by organisms. The most important calcium carbonate-producing
organisms are planktonic animals, such as the foraminiferan, Globigerina, and shallow
water bottom dwellers, such as corals, coralline algae, and mollusks (clams, oysters,
snails, etc.). Calcium carbonate deposits are more common in tropical water because,
unlike most substances, calcium carbonate solubility decreases with increasing temper-
atures, which is why coral reefs are found in tropical areas.
2.3 Seawater 21
2.3.4 Nutrients
In addition to the major elements of seawater, there are also a large number of minor,
or trace, elements. Although these are not present in large quantities (only about 0.01X
or less), many are critical for biological processes in the sea. Constituents present in
seawater that are important for and affected by biological processes are called ”non-
conservative”and can vary in unpredictable ways. These nonconservative constituents
include inorganic and organic matter and gases. They include the important and of-
ten limiting nutrient compounds of phosphorus (usually orthophosphate ions, H2POT
and HP0T2) and nitrogen (nitrate, nitrite, ammonia, urea, and other organic nitrogen
compounds). Inorganic nitrogen, a major constituent of air, is relatively unimportant
in marine processes because only a few nitrogen-fixing bacteria can convert it for bi-
ological processes. Other biologically important elements are silicate (which is used
by some plants, such as diatoms, to make skeletons), iron, manganese, cobalt, and
molybdenum.
Organic matter is composed of relatively constant amounts of carbon, oxygen, nitro-
gen, and phosphorus. The ratio of these elements is
0:C :N :P = 109 :41 :7.2 :1 by gram molecular weight, or

0:C:N:P = 212:106:16: 1 by atoms
That is, 212 atoms of oxygen, 106 atoms of carbon, and 16 atoms of nitrogen are needed
for every atom of phosphorus to make organic matter. When one of these is present in
quantities less than that needed, it becomes a limiting nutrient and further production
of organic material (primary production) stops.
Primary production in the top layers of the oceans depletes these waters of nutrients
and eventually limits productivity. Nitrates or phosphates are usually considered to be
the main limiting nutrients. In recent years, however, much attention has been given to
iron as a limiting nutrient, even though it is required in only minute quantities. Nutrients
are replenished in the sea by runoff from the land, by decomposition of organic matter,
and by upwelling of nutrient-rich water from the depths. The most spectacular example
of upwelling, resulting in nutrient-rich and highly productive waters, is the East Pacific
Ocean off the west coast of South America.
Nutrients may also be replenished during major storms, which increase the depth of
the mixed layer. For example, 4 days after Hurricane Gordon in the Atlantic Ocean in
1994 phytoplankton productivity increased by five times. The storm influence reached
as deep as 150 m and nutrients from deeper water and the sea bottom were mixed into
upper layers where they were made available for primary p r o d ~ c t i o n . ~ ~
Also present in seawater in small, but important quantities are organics. Organic
materials exist as carbohydrates, proteins, enzymes, amino acids, lipids, and vitamins.
They are introduced as excretory products of living organisms and as plants and animals
decompose. Because their presence is dependent on biological processes the quantities
of organics vary greatly.
2.3.5 Sediments
Sedimentsare insoluble particulate matter in or at the bottom of the sea. They come from
terrestrial and freshwater sources (wind action, runoff, erosion, glaciers, etc.), marine
sources (biological activityof corals, mollusks, plankton, etc.), and human activity (waste
disposal).
Most coastal processes involve movement of sediments. Particle size and shape of
sediments are important in determining their transportability. Perhaps surprisingly, it
requires more energy to move both very large (gravel)and very fine (clay)sediments than
intermediate sizes (sand). Because of these various energy requirements for transport,
sediments are often sorted on beaches. Generally, the greater the wind and wave energy,
the larger the particles you find on the beach and the steeper its gradient.
2.3.6 Circulation
The oceans are in continuous circulation. Temperature differences between the poles
and equator create strong winds that, together with the Coriolis force, drive the main
ocean currents. The Coriolis force results from the Earth’s rotation and causes currents
in the Northern Hemisphere to rotate clockwise. In the Southern Hemisphere the deflec-
tion is counterclockwise. In addition, variations in sea temperature and salinity create
circulation patterns that affect all seas (Figure 2.3).
Another feature of ocean circulation is oceanic weather patterns called “eddies.”
These are currents about 100 km across traveling at a few centimeters per second. They
are readily distinguished from surrounding water by characteristic features, such as
salinity, temperature, and planktonic species. They may survive for months or years.
The unusual fact that water reaches a maximum density at 3.98”C is of crucial impor-
tance in recycling of deep-water nutrients and, therefore, of biological activity. During
the summer heating from the surface results in a stable layer of warm, less dense wa-
ter on the surface. Although there is mixing within this warm layer because of surface
wind activity, the mixing does not penetrate the deeper waters. The result is a strati-
fied warm layer sitting over a colder, denser layer with a well-defined sharp boundary
called the ”thermocline,” where the temperature drops dramatically over a small depth
change. The thermocline varies in depth from 10 to 200 m and its effect can be dramatic.
Descending slowly and smoothly in a research submersible, it is possible to “land” on
the thermocline with a thud. Additional buoyancy must be released before the sub can
penetrate the higher density cold water layer.
Most of the activity of the oceans happens in the upper mixed layer. Since plants
need light to photosynthesize they must live in the surface waters. Over time phyto-
plankton use up all the nutrients in the stable mixed water layer. Primary productivity
is then dramatically reduced until additional nutrients are added. Generally, nutrients
are added during well-defined periods called ”turnovers.” As with freshwater systems,
these turnover periods are of critical importance for coastal engineers because they affect
2.3 Seawater 23
Figure 2.3 Map shows the major Ocean currents. The main features are a result of winds blowing
from the tropics to the poles, being deflected by the spinning of the Earth. (Figure courtesy of
the oxygen concentration, pH, algal growth, nutrient availability,bacterial content, and
other factors that affect the clarity, chemical composition, and corrosivity of the waters.
The initial freezing temperature and the temperature of maximum density both de-
creasewith increasing salinity.At salinity24.7Yi the curves of initial freezing temperature
and of maximum density intersect. In seas of salinity below 24.7"A, water behaves like
fresh water, reaching maximum density before freezing. The warm, less dense surface
waters form a stable layer during the summer. In the autumn the water cools and sinks,
resulting in thermally driven overturn, as in lakes, because with sufficient cooling the
maximum density point is passed before ice forms. In the short period between passing
the maximum density and formation of ice overturn ceases. When ice forms the salinity
of the water below the ice increases. If the salinity increases sufficiently another over-
turn will occur under the ice. When temperatures increase and the ice melts the melt
water dilutes the seawater by mixing and returns it to its original salinity. The water
temperature again approaches maximum density and overturn occurs. Thus, there are
two overturns a year.
When the salinity is above 24.7"A, the maximum density is not attained with cooling
since the maximum density occurs below the initial freezing point. At these higher
salinities overturn occurs as the water cools after the summer. When ice forms overturn
continues but is now driven by the density increase of the underlying seawater during
24 OceanoaraDhv and Lirnnoloav
freezing and by temperature. In spring the warm surface waters stabilize immediately
and overturn does not occur. Thus, there is only one long period of overturn.
2.3.7 Waves
Waves in the sea are generated mainly by wind. Once waves move out of the area of
wind generation they move as free waves, called "swell," until their energy is dissipated
and they die out at sea or against a shoreline.
As waves approach a shoreline they "feel the bottom," that is, the waves are affected
by friction with the ocean bottom. This friction causes the waves to slow down, which
is why even though waves approach a shore obliquely they usually straighten out as
the leading edge is refracted (slows down to allow the deeper parts to catch up) and
the waves turn parallel to the shoreline. As they slow, waves also steepen, becoming
unstable, until they break in the pattern very familiar to surfers.
Tsunamis are waves generated by seismic disturbances. They are long waves that
travel at speeds determined by the water depth, often at high speeds. For example, if we
take the average ocean depth as 4,000 m, a tsunami will travel at approximately200 m/s
or 640 km/h. Tsunamis are sometimes mistakenly called "tidal waves."
Another type of wave that can be up to 5 m high and occur in completely calm water
under windless conditionsis caused by the wash from high-speed ferries, which produce
a solitary wave when they reach critical speed. The wavelength of these bow waves is
twice that of normal ferries. Recently, Britain's Marine Accident Investigation Branch
investigated several fatal and near-fatal accidents caused by these waves.26
2.3.8 Tides
Tides are waves of long wavelength and period that never escape their generating forces.
Tidal waves are generated by the gravitational influence of the moon and sun and are
affected by the Coriolis force that deflects them in the same way it deflects currents. The
gravitational effect of the moon is stronger because of its proximity to Earth; its effect is
more than twice as strong as the sun.
When the moon and sun are in line with a point on the Earth's surface, tides at
that point and at 180" opposite it on the other side of the globe will experience the
combined force of these bodies resulting in higher high tides and lower low tides. These
are inappropriately called "spring" tides although they have nothing to do with seasons.
When the sun and moon are at 90" angles to each other their forces cancel out to some
extent, resulting in less extreme high and low tides, which are called "neap" tides. Spring
tides occur every new and full moon, neap tides every first and last quarter.
The tidal range and frequency at a given location are greatly affected by the shape
of the coast or bay. In some places tides are diurnal, i.e., only one high and one low tide
per day. In others they are semidiurnal, two highs and lows per day, or mixed. Tides
approximate standing waves like the waves generated in a teacup when it is disturbed.
If the node (pointof zero oscillation) of the wave is at the mouth of a bay or basin and its
length is approximatelyone quarter of the tidal wavelength, the tidal amplitude will be
great at the head (or antinode) of the bay. The Bay of Fundy in New Brunswick, Canada
is an example of this resonance and has the highest tidal range in the world, nearly 17m.
Tides are fairly regular and predictable and can be learned by consulting tide tables,
which are published annually. Tide tables give the time of day and height of highs and
lows at many positions around the world, along with estimates for places between these
measured locations. Variations in timing and height of the tides can, however, be caused
by local wind effects. For example, strong winds upriver in an estuary may delay the
flushing out of seawater that came in with the incoming tide.
Tides affect local currents, as well as the height of the water line. Maximum cur-
rents are reached midway between high and low tides and minimums occur as the tide
reverses.
No activity in coastal areas can be undertaken without consideration of tidal effects.
Tidal range affects, among other factors, the area of alternately submerged and exposed
portions of piers, oil platforms, and other structures in the sea. Alternate wetting and
drying in the tidal and splash zones results in corrosion rates higher than either per-
manently exposed or permanently submerged sections.27These areas are, therefore, at
greatest risk of failure.
2.3.9 Coasts and Beaches
The zone where the land meets the sea is the most important marine environment to
humans.Here land, sea, and air meet, nutrients are recycled, and productivity is generally
high. Brackish waters predominate in many regions.
In nearshore environments the relatively shallow water and strong vertical mixing
allow a strong influence of benthic biological, chemical, and physical processes. Unlike
in the open ocean, primary production of the benthos (sea bottom organisms) may pre-
dominate over that of the water column. Examples are the highly productive kelp beds,
seagrass meadows, and mangroves.
The intertidal zone is the border between land and sea, where the land is periodically
covered by ocean. One of the most notable features of the intertidal is strong vertical
zonation. Plants and animals live at different levels depending on their tolerance to
desiccation and their ability to withstand physical buffeting by waves.
Nearshore environments may be dissipative, reflective, or intermediate. Dissipative
shores have a flat, shoaling slope (tl") and a wide surf zone, in which there are several
waves at a given time. Sedimentsare silt to fine sand and are transported on and off shore.
Offshore bars are common. Sand dunes are a common feature of dissipative coastlines
with strong winds. They are formed by the wind-driven transport of sand. They form an
excellent buffer against waves and wind but are often highly unstable, especially when
the delicate plants whose roots stabilize them are disturbed by human activity.
Reflective shores have only one plunging/collapsing wave in the surf zone at any
one time and it approaches at a greater angle to the shore than those of dissipative
environments. The slope of the shoreline is steeper (>3").Sediments are larger (coarse
sand, gravel, or boulders) and are transported alongshore.
The processes by which beaches are formed, moved, and destroyed are poorly un-
derstood. We do know, however, that these processes are easily disturbed. For example,
when hotel owners in the center of the long beach at Negril, Jamaica noticed that the sea
was creeping ever closer to their buildings and the white sand beach in front of the hotel
was disappearing, they wanted to find the reason and stem the erosion. A year of mea-
surements, however, revealed that there was no loss of shoreline. What had happened?
A few years before, one of the hotels at the end of the beach built a new pier to enhance its
water facilities for guests. The construction changed the dynamics of the longshore cur-
rents and caused the center of the bay to be scooped out. By the time the measurements
of the coastline were taken, the bay had restabilized at the new configuration.
Somebeaches undergo large seasonalvariations. During the season of winter storms,
large waves wash away the accumulated sands brought in by gentler waves. The beach,
therefore, may fluctuate between a wide sandy beach and a narrow or nonexistent one.
Rocky shores with cliffs are reflective coastlines. Headlands capture wave energy
and when they protrude into the tide, cause tidal eddies. Erosion of cliffs occurs and the
rate depends on the material composition of the rock, the tidal range, wave energy, and
the composition and configurationof the bottom of the cliff. In some parts of the world
erosion is nothing short of spectacular.On the East Anglian coast at Dunwich, England,
the coastline is calculated to have retreated 388 m in 386 years (Figure2.4). The erosion is
extremelyirregular, varying from almost zero to severaltens of meters in a large storm. In
recent years, however, construction of a 2.5-mile (4-km)-longshingle sea wall has almost
stopped this progression.28Farther north on the east coast of England in the relatively
short distance (approx. 125 km) between the Humber River and Flamborough Head
erosion rates vary between less than 0.3 m/y in the north to 1.75m/y in the ~0~1th.'~
Cliff erosion is sometimes accelerated by the action of rock-boring bivalves. On the
Pacific coast of North America cliffs infested by the rock-boring clam, Penitella penita,
erode many times faster than uninfested cliffs, 1.2 and 0.05 cm/y, respectively? These
clams also bore concrete and plastic. Similarly, in Oman the carbonate cliffs are being
eroded by the coral boring mussel, Lithophgu, as is a local limestonejetty.31
Residential,recreational,agricultural,and industrialactivitiescreate strong pressures
on the world's coasts. There is currently a worldwide tendency toward coastal erosion as
a result of a combination of sea level rise, climatic change, and human interference.These
erosional processes have obvious consequences for marine and nearshore structures.
2.3.1 0 Marine Biology
The sea contains an astonishingly diverse assemblage of living organisms. It is not sur-
prising that there is a greater diversity of life in the sea as life itself is widely believed to
have evolved there. The earliest known fossils are marine.
Marine life has dramatic effects on the planet. Ancient marine organisms discharged
oxygen into the atmosphere, creating the world in which the rest of us live. Marine
2.3 Seawater 27
Figure 2.4 The spectacularrates of cliff erosion in East Anglia, England have been measured for
centuries. This house used to be a long walk from the cliff and sea. (Photocourtesy of D. Stubley.)
life today is responsible for a large proportion of the carbon dioxide sink, ameliorating
the effects of global warming. In global oceans, living organisms are responsible for
fluctuations of many important gases and minerals.
Marine organisms have a crucial influence on materials used in the sea. They are re-
sponsible for corroding steel and other metallic materials (see Chapter 7, Section 7.2,
"Microbiologically Influenced Corrosion"). They cause fouling of all submerged
structures(see Chapter 7, Section 7.1.4, "Macrobiofoulingand Biodeterioration"). Larger
marine organisms may cause substantial damage to many different materials used in
the sea, including nonmetallics such as concrete and plastics (see relevant materials in
Chapter 6, "Nonmetallic Materials").
Among plants there are a greater variety of algae in the sea than in fresh water. Brown
and red algae are chiefly marine, while green and yellow algae are common to both. Only
higher seed plants, which are large, bottom dwellers, are poorly represented in the sea,
except for eel grass, Zosteru, and a few other genera.
Every major animal phylum on earth contains marine representatives; many are
dominantly or exclusively marine, such as sponges, corals, starfish, sea urchins, annelid
worms, and mollusks (clams, snails, and octopods).Ocean life may be divided into two
broad categories.The first is those organismsthat live in the water column, either floating
28 OceanoeraDhv and Lirnnoloev
(planktonic)or swimming(pelagic).The second is those bottom-dwellingorganisms that

are on or attached to surfaces (epibenthos)or livingin the substrate(infauna).As a general
rule, plankton are of more economic importancein their effects on water chemistry, while
the benthos is more important as fouling organisms, affectingheat transfer efficiency and
causing drag on boats.
Coral reefs are complex structures built by plants and animals in tropical environ-
ments. Barrier reefs form highly effective protection for the coastal environment against
wave and storm action. They are also important land formers, being the origin of all
atolls and coral islands. Devastating consequencesusually result from their destruction.
In the Maldives, where the barrier reefs have been destroyed on the capital island of
Male by human activity, they have been replaced at great expense with a breakwater of
tetrapods (Figure 2.5). Inhabitants discovered several years ago during a major storm
that the artificial barrier solution was much less successful than the natural coral one in
keeping the sea at bay. Many buildings were destroyed.
Mangrove swamps are another tropical coastal phenomenon. These are intertidal
forests of trees specially adapted to living in salt water (Figure 2.6). Some mangrove
seeds sprout and develop on the tree before dropping like an arrow into the mud, where
they quickly root to avoid being washed away. Mangroves are also involved in land
Figure 2.5 Where natural sea defenses have been destroyed or where man has built too close to
fragile coastlines, artificial barriers, such as these tetrapods, are designed to dissipate the force of
the waves. (Photo courtesy of CARIAD Consultants.)
2.3 Seawater 29
Figure 2.6 Mangroves, such as these in Thailand, are fomts in the sea. The roots are covered
at high tide and special adaptations have evolved for life in the intertidal. (Photo courtesy of
reclamation; the roots of the plants stabilize the mud so it is not washed away with the
tides. Eventually deposits build up to above the water level, becoming permanent land,
and the mangrove community moves seaward toward the new shoreline.
Mangroves also form efficient barriers to wave energy for coastal ecosystemsbehind
them. They are much more effective as buffers than the engineering solutions that have
attempted to replace them. Many tropical communities that have cut down their man-
groves for fuel, building material, or to make way for fish farms have paid the price of
a seriously eroding coastline.
2.3.1 1 Corrosion in Seawater
Seawater is used for many purposes, particularly intakes and distribution systems for
the following:
Sea-going and coastal vessels of all types

Offshore oil and gas platform installations
Desalination plants producing fresh water from seawater
30 OceanoaraDhv and Lirnnoloav
Coastal petroleum and petrochemical processing plants

Coastal electricity-generating stations
The degradation behavior of various materials in seawater service may be summa-

rized as follows:
a Wood-fails by organisms, mechanical damage, swelling, etc., impregnants can pro-

long life
0 Concrete-attack of reinforcement by chlorides or carbonation, mechanical; Can use
cathodic protection, coatings
0 Plastics-generally good but damaged by UV or in highly chlorinated water
a Cu alloys-good below their critical velocity, poor in polluted water (sulfur), better
corrosion fatigue than stainless steels
a Ti-highly resistant, can crevice corrode or hydrogen embrittle
a Ni based-resistant but usually too expensive for general use
a Mild steel/cast iron-depends on oxygen and velocity
a 300 stainless steels-good in flowing seawater, tend to pit or suffer crevice corrosion
in stagnant seawater
a Superaustenitic stainless steels-better resistance to general and localized corrosion
than the 300 series
a Ferritic stainless steels-better than the austenitics but can be difficult to produce or
fabricate
a Duplex stainless steels-orrosion resistance between austenitic and ferritic; its main
advantage is strength
a General for stainless steels-avoid crevices, need oxygen, prone to corrosion fatigue,
often needs cathodic protection (CP)
The corrosionof metals in seawater depends on many factors,including the following:
a Temperature. As temperature increases corrosion rate increases if other factors are

unchanged. However, as temperature increases the oxygen solubility decreases and
the likelihood of forming protective calcareous scales increases. In this case increased
temperature can reduce corrosion rates, e.g., carbon steel in seawater.
a Dissolved oxygen. Higher oxygen content increases corrosion of carbon steels. Higher
oxygen decreases corrosion of stainless steels and aluminum by helping to maintain
the protective oxide film. If localized corrosion is occurring, for example, on stainless
steel, then the pitting penetration rate can be increased by increased oxygen supply.
a Pressure. The main effect of pressure on corrosion rate is its effect on dissolved gases
in the seawater. For example, if the seawater is vacuum degassed its corrosivity is
greatly reduced for most metals.
Salinity. As salinity increases the likelihood of localized attack increases. Biofouling
and calcareous deposits are also more likely.
a Sulfides. Sulfides, produced by sulfate-reducingbacteria (SRB), for example, increase
corrosion of steels, copper alloys, stainless steels, and aluminum.
a Heavy metals. The presence of copper ions causes pitting in aluminum.
2.4 Pollution 31
2.4 POLLUTION
Pollution is the introduction of materials or effects at a harmful level. There are two main
types of pollution and the distinction between them is important for biofouling and MIC
processes. Eutrophication pollution is the enrichment of natural nutrients in the envi-
ronment. Increased eutrophication of an aquatic environment often leads to an increase
in biofouling and corrosion problems (see below). Nitrates and phosphates are essen-
tial for the normal functioning of ecosystems but when present in excess, they become
pollutants. Eutrophication occurs primarily when sewage and agricultural fertilizers are
dumped or run off into rivers, lakes, and coastal seas (Figure 2.7). For example, the
amount of phosphate in unpolluted waters is 0.001 to 1.0 mg/L, but after primary and
secondary treatment it is 6.2 to 9.6 mg/L in sewage effluent.32The main source of phos-
phates in sewage and water treatement plants comes from residential use of detergents
(washing powders and cleaners), which contain large quantities of phosphate.
The effects of eutrophication include the following:
1. The development of a blanket of algae (macrophytes and filamentous algae), which

can cause major changes in the fauna in the ecosystem
Figure 2.7 The unmistakable, unpleasant grimy foam is a sign of pollution at the intake of a
coastal chemical plant. Pollution here contributed to a problem of microbiologically influenced
corrosion in the plant. (Photo courtesy of CARIAD Consultants.)
32 OceanoEraDhv and Limnoloav
2. Decay of the accumulated algal biomass that can increase carbon dioxide (acidity)
and decrease oxygen in the ecosystem
3. Respiration by the algae, especially at night, depleting oxygen in the environment
4. Production of toxic algal blooms that can kill off other organisms
The other main type of pollution is the introductionof poisons into aquaticenvironments,
that is, materials which are inherently harmful to living organisms.These include heavy
metals, agricultural chemicals (such as biocides and pesticides), industrial wastes, and
by-products.
Toxic pollutants, unlike eutrophication, often lead to a decrease in aquatic life and,
thus, a decrease in biofouling and MIC problems. In recent years, for example, tighter
environmentalrestrictions on effluent release and the cleanup of harbors and lakes have
sometimes led to an increase in biofouling of submerged structures.
Heavy metals include elements of atomicweight >40,excludingalkalineearth metals,
alkali metals, lanthanides, and actinides. The most important in aquatic environments
are Zn, Cu, Pb, Cd, Hg, Ni, and Cr plus A1 in acidic waters. Some, such as Cu and Zn, are
trace metals, required by organisms in minute amounts but which become poisonous in
high concentrations. Others, such as Pb and Cd, have no known biological function and
are toxic in minute quantities. In general, these metals are in the following decreasing
order of toxicity:
Hg + Cd + Cu + Zn + Ni + Pb + Cr + A1 + Co
Heavy metals are usually associated with industrial activity, especially mining and
ore processing, finishing and plating of metals, and manufacture of metal objects. They
are also found in the paint and dye industries, and in the manufacture of leather, rubber,
textiles, and paper. Domestic waste can also be contaminated by contact with copper,
zinc, and lead pipes and tanks?2
Other toxic pollutants includeammonia (a raw material, by-product, and end product
of many industrial processes, such as coke production, power generation, heating, and
combustion of fuel and water treatment plants), cyanides (which come from coking,
steelworks, gas production, power generation and metal extraction, hardening, plating,
and cleaning), and phenols (from gas and coke production, petroleum refining, power
generation, production of glass, rubber, textiles, and plastics).
Other pollutants include suspended solids and extreme pH from very acid or alkaline
industrial processes. These pollutants may have important influences on water quality
and corrosion of materials used in intakes and cooling water systems. Pollution may also
be physical, for example, in the form of heat, such as heated effluent from power stations.
Increased pollution levels do not only present problems in harbors. As water re-
sources become increasingly scarce reuse of water for industrial applications such as
cooling water and boiler feedwater is becoming a more common pra~tice.3~ Increased
microbial activity and pollutants such as ammonia, phosphate, etc. create technical chal-
lenges for the safe use of equipment in these environments.
2.4 Pollution 33
2.4.1 Pollution and Corrosion
Studies on corrosion rates of mild steel in polluted harbors in Japan indicate that in
waters with low oxygen concentration and high sulfide concentration corrosion rates
can be increased by 200 to 300%. In mildly polluted waters where oxygen is still present
and sulfide is less than several ppm, the dissolved oxygen concentration seems to have
the greatest influence on corrosion rates, as it does in clean seawater.34
Polluted seawater has been shown to increase corrosion of carbon steels and to in-
crease pitting depth. One study in the polluted harbor of San Diego determined an
average depth of pitting of 0.056 mm/y with maximum pit depth of 1.5 mm?5
The effect of pollution on corrosion rates has been demonstrated in a laboratory study
using decomposing algae and mild steel. The corrosion rate was considerably enhanced
when the microbes oxidized sulfur in algal proteins. Acidification of the seawater also
occurred.%
The amount of pollution and concentration of pollutants which seriously accelerate
corrosion processes has been little studied. In one study of polluted and unpolluted
water along Bombay Harbor, weekly samples revealed that levels of hydrogen sulfide of
less than 40 mg/L were associated with open, fairly clean water (BOD values of 10 to 20
mg/L).37The authors suggest that this might be an appropriate limit for the acceptable
level of hydrogen sulfide, although it corresponded to a number of SRB of approximately
12,000 organisms/mL.
The sulfur-oxidizing bacteria (SOB), Thiobacillus, have also been found in greater
numbers in polluted water. T.ferrooxidans, T. Thiooxidans,and T. fhioparus were obtained
from polluted seawater, microbiological slime, and corroding metal surfaces at Tuticorin
Harbor, India. Viable counts indicated that polluted harbor waters contain considerably
higher numbers of thiobacilli than those reported elsewherefrom other marine sources.38
Ammonia, a common constituent of polluted seawater, increased the susceptibility
of copper alloys to crevice corrosion under heat transfer condition^.^^ Addition of
10 ppm of ammonia to water inoculated with SRB significantly increased the corrosion
of 70/30 copper-nickel.40The authors could not concludewhether the enhancementwas
a result of biological or chemical effects.
Shewanella pufrefaciens is a facultative aerobe often associated with rotting fish and
other foods. When carbon steel electrodes were exposed to this bacterium, microbiolog-
ically influenced corrosion was demonstrated electrochemicallyand microscopically?1
Under anaerobic conditions Shewanella uses various molecules as oxygen substitutes,
including nitrate, nitrite, Mn(II1) and Mn(IV) oxides, Fe(II1) oxides, elemental sulfur,
thiosulfate, sulfite, and a variety of different organic oxidants.
2.4.2 Pollution and Fouling
It has been demonstrated that fouling rates are greater in polluted waters. In Bombay
Harbor, India metallic coupons, both inert and toxic, support thicker films in polluted
waters than in clean waters.42Similarly,in Hong Kong biomass (weight)of the biofouling
was correlated with nutrient levels, indicating that there was more fouling in more
polluted ~ a t e r s . 4 ~
The species of fouling organisms found in clean and polluted waters are different.
In Italy, for example, barnacles, serpulids, and ascidians are the climax community in
polluted water, while mussels dominate in cleaner waters.& Among plant species, green
algae are found in more polluted waters; red algae are dominant in cleaner waters,
especially at d e ~ t h . 4 ~
2.4.3 Pollution and Biodeterioration
Eutrophication of the environment from anthropogenic sources can accelerate attack

and biodeterioration of marine materials. Attack of plastics is more rapid in polluted
than unpolluted environment^.^^^^ Suspension-feedingborers of concreteand plastic are
more abundant in eutrophic environmentswhere enhanced nutrients result in increased
algal
Sites characterized by high population densities and busy harbor facilities (prime
sites for coastal development)are most likely to suffer from sewage pollution. Thus, the
locations where man-made structures are most likely to be built are also those waters
in which they are most likely to be attacked. It would appear, therefore, that there are
sound economic reasons (as well as environmental ones) for reducing the pollution that
normally accompanies coastal development.
2.5 INTRODUCED SPECIES
Introduced species, as the name implies, are species that are artificially and unnaturally
transported to new areas. Most species transported by man simply die out in the new
environment and are never heard from again. Occasionally, however, the newcomer
finds the environment suitable and often without some of the dangers and predators it
left behind. These speciesmay explode in population and become a substantial nuisance.
Eventually the natural cycle usually prevails and new predators or diseases will reduce
the population to normal levels. After this, the species becomes just one more factor in
the ecosystem to be dealt with.
Most introduced species are brought in the ballast water of cargo ships. In Australia
alone, for example, 12,000 ships discharge150million tonnes of ballast annually.Unfortu-
nately the practice of dumping ballast water is unenforced, unregulated, or only recently
regulated in many countries. Damage to local ecosystems and to marine and freshwater
structures can be substantial when the introduced species thrives, especially if it has no
natural predators in its new home. The large seaweed Unduriu has virtually eliminated
abalone from SoutheastAustralia. Similarly,in 1990in the Black Sea, the American comb
jelly Mnerniopsis ate so many zooplankton that the fish fry starved. Combined with other
problems such as pollution, this has led to a collapse of the fishery?
Mussels use their byssal threads to attach to hard surfaces, such as rocks and pipes.
With densities up to 700,000/m2 they cause serious fouling of raw water intakes and can
occlude even large-diameter pipes because successive generations of mussels attach to
and live on the dead shells of older populations. In addition, they cause underdeposit
corrosion. The zebra mussel, Dreissena polyrnorph, is an introduced species that spread
from the Caspian Sea to Europe and Great Britain in the 19th century where it blocked
pipes, channels, and aqueducts of domestic and industrial water supply systems. In
1985, it was introduced to North America where it clogged intakes and piping systems
all over the Great Lakes within a few years of its introduction. So far zebra mussels have
spread down to Louisiana and the problem has cost industry $300 million to clean up.5o
Although the species will probably never be eradicated in North America, its pop-
ulations are now beginning to decline. The population of diving ducks, which eat the
mussels, has increased dramatically in zebra mussel areas. More recently, a sponge,
Eunapiusfragilis, has been found living in increasing numbers on the shells of the mus-
sels, making them unable to open their valves to breathe or eat. In some areas in Lake
Michigan mussel populations are relatively low where the sponges are abundant?l In
spite of population decline, it is highly probable that zebra mussels will remain a per-
manent part of the fauna in North America. Scientistshave been searching for means to
control them. Ontario Hydro in Canada, North America’s largest nuclear power gener-
ation facility, has spent $15 to 20 million retrofitting its nuclear and conventional power
plants with chlorination systems designed to kill mussels.52
A case of mussels traveling in the other direction is found with Mytilopsis sallei. This
estuarine harbor species occurs naturally in Central America, where it is not a pest. In
1967, however, it was introduced to India, possibly on the hull of a ship where it has
become a plague in Visakhapatnam Harbor, Andhra Pradesh, fouling pilings, jetties,
barges, pipes, and visiting ships.53
An interesting report of species introduction by human refugees came from Hong
Kong in 1980 when shells of the bivalve M . sallei were found on a piece of driftwood
in To10 Harbor.%It is highly unlikely that a wooden-hulled boat traveling legitimately
from India via the Straits of Singapore to Hong Kong could be wrecked without any
report being made. There were, however, numerous small wooden boats arriving in
Hong Kong with refugees from Vietnam and China, where, if the refugees arrived safely
and were not detected, they beached their boats. Thus, M . sallei was probably introduced
by refugees. This species is only one of at least six marine fouling species introduced to
Hong Kong in recent ~ e a r s . 5 ~
Another freshwatermussel, Lirnnopernafortunei, which occurs naturally in Asia rivers,
has been introduced to the freshwatersupply system in Hong Kong, probably from water
transported by pipelines and canals from China?6 A new reservoir at Plover Cove was
built by damming an inlet in the sea and was opened in 1967. Within a year breeding
populations of the mussel had been established that provided a larval supply for fouling
the tunnels and pipes of the raw water supply system.57
Corbiculaflurninea, the Asian clam, normally inhabits fresh and estuarine waters and
is widely distributed in Asia. It is a highly prized food for ceremonial occasions and is
thought to be beneficial for the liver. It was probably introduced to the United States for
food, although no one can be certain. The Asian clam first appeared in the southwest in
1945 and in the eastern states in the 1950s. By 1977, it had crossed the Brazos River and
completed its spread across the United States. It now appears right across the country
in every major river system south of latitude 40°?8
Unlike mussels, which attach to hard surfaces, the Asian clam is a sand and gravel
dweller. Although it prefers flowing water in its natural habitat, it also lives in lakes and
reservoirs. Population densities can reach 3,000/m2 and in these numbers they render
useless gravel beds used in making concrete. One engineer said, “It was unnerving to
watch a recently poured concrete column come alive in a swirling mass of clams, not
to mention the structural weakness caused by the decaying shells after the concrete
hardened.”58
Corbicula also clogs smaller cooling water intakes, pipes, and vessels. It occluded
a water main adjacent to a fire hydrant, cutting off the water that was required in an
emergency to put out a fire.58
The water-hyacinth Eichhornia crassipes is a free-floating perennial herb. The plants
grow to 1 m as they float on the water’s surface, with stems intertwining to form dense
mats. In the Amazon the plant is held in check by natural enemies such as insects and
microbes. Unfortunately, since the 1800s it has been introduced to friendlierwaters where
it has no natural predators. Often, visitors, drawn by its lush leaves and blue-to-lavender
flowers, have taken it home as an ornamental, but it also has hardy, long-lived seeds and
spreads well under a wide variety of environmental conditions. It has now spread to
tropical and subtropical parts of the Americas, Asia, Australia, and Africa.
Capable of doubling within a couple of weeks, it is among the fastest growing of
plants. The mats can block boat travel. Chunks of mat can break free to clog downstream
pumping stations supplying water for drinking, irrigation, and hydropower. Because
chemical control is undesirable scientistsare currently seeking agents for biological con-
trol, including Thrypticus flies and the sap-sucking insects Taosa and Megumelus, which
can transmit plant pathogens. More positively, scientists are searching for uses for the
plant so that it may be harvested. For example, it can be used for food and in paper-
making.
2.6 REFERENCES
S. Baird, www.chemresources.com(12 November, 2000).

* T. Fujii, T. Kodama, H. Baba, “Theeffect of cwling water quality on pitting corrosion of copper
tube in hot soft water,” Corros. Sci. 24 (1984):pp. 901-912.
G.N. Flint, “Resistance of stainless steels to corrosion in naturally occurring waters,” INCO
(1980):pp. 1-19.
W.T. Young, P. Fairer, “Freshwater,”in Corrosion Tests and Standards: Application and Inter-
pretation, ed. R. Baboin (West Conshohocken, P A ASTM, 1995), pp. 316-330.
WHO Guidelines for Drinking Water Quality, 2nd ed., Vol. 1, Recommendations (Geneva,
Switzerland:World Health Organization, 1993), pp. 8-29.
2.6 References 37
M.F. Obrecht, J.R. Myers, “Potable Water Systems in Buildings: Deposit and Corrosion Prob-
lems,” Heating/Piping/Air Conditioning, 45,5 (1973):pp. 77-83.
A.C. Duxbury, The Earth and Its Oceans (Reading, MA: Addison-Wesley Publishng Co., 1977),
pp. 1-381.
P.J.B. Scott, Report on testing of portable water in Kato Asites, Crete, Greece, Unpublished report
for Kato Asites Viiage Office, Crete, Greece (1998),pp. 1-3.
M. Davies, P.J.B. Scott, Final report on cooling water to Polifin, CARIAD Consultants (1999).
lo F. Smith, Chemetics International Co. Memo to M. Davies, July 11,1980.
P.E. Doherty, M.W. Shanahan, “The corrosion performance of nickel alloy heat exchanger bun-
dles in freshwaterService,”in 3rd Int. Symp. Environmental Degradationof Materials in Nuclear
Power Systems-Water Reactors, eds. G.J. Theus, J.R. Weeks (The Metallurgical Society, 1988),
pp. 629-635.
l2 C. Harrington, D. Hopkins, F. Sykes,A. Stein, C. Merlino, K. McDowell, ”Servicewater materials
corrosion test,” in 4th Symposium on Environmental Degradationof Materials in Nuclear Power
Systems-Water Reactors, Georgia, 1988, ed. D. Cubicciotti (Houston, TX NACE, 1989).
l3 R.L. Tapping, J. Donaldson, P.A. Lavoie, P.E. Doherty, “Pitting of Fe-Ni-Cr alloys in freshwater,”
in 4th Symposium on Environmental Degradationof Materials in Nuclear Power Systems-Water
reactors, Georgia, 1988, ed. D. Cubicciotti (Houston, TX NACE, 1989), pp. 13-11 to 13-24.
l4 A.S. Krisher, ”Raw water treatment in the CPI,” Chem. Eng., August 28 (1978):pp. 79-98.
l5 B.W. Forgeson, C.R. Southwell, A.L. Alexander, “Corrosion of metals in tropical environments,”
Corrosion 14,2 (1958):pp. 33-41.
l6 A.E. Greenberg, L.S. Clesceri, A.D. Eaton, eds., Standard Methods for the Examination of Water
and Wastewater, 18th ed. (Washington, D.C.: American Public Health Assoc., American Water
Works Association and Water Environment Federation, 1992).
l7 EN. Kemmer, ed., The NALCO Water Handbook (New York: McGraw-Hill Book Co., 1979),
pp. 4-10.
Anon., “Pure white out,” New Scientist 161,2173 (1999):p. 23.
l9 S.K.Coburn, ”Corrosion in seawater,” in Selection of Materials for Service Environments, ed.
H.E. Boyer (Metals Park, O H ASM International, 1987), pp. 310-317.
M.F. De Romero, O.T. De Rincon, Z. Duque, P. Bohorquez, M. Espinoza, “Electrochemicalbehav-
ior of super stainless steel, titanium and Cu-10% Ni alloys in brackish water,” Corrosion/2OOO,
paper no. 642 (Houston, TX NACE, 2000).
R.V. Tait, Elements of Marine Ecology (London, U.K.: Butterworths, 1977), 314 pp.
22 H.H. Uhlig, The Corrosion Handbook (New York: John Wiley & Sons,1948), 1188 pp.
23 T. Parsons, M. Takahashi, B. Hargrave, Biological Oceanographic Processes (Oxford, U.K.:
Pergamon Press, 1977), 332 pp.
24 J.A. Steel, ”Factors affecting algal blooms,” in Microbial Aspects of Pollution, G. Sykes, F.A.
Skinner, eds. (London: Academic Press, 1971), pp. 291-213.
25 M.L. Fogel, C. Aguilar, R. Cuhel, D.J. Hollander, J.D. Willey, H.W. Paerl, ”Biological and iso-
topic changes in coastal waters induced by Humcane Gordon,” Limnol. Oceanogr. 44,6 (1999):
pp. 1359-1369.
N. Hamer, ”Solitary killers,” New Scientist 163,2201 (1999):pp. 18-19.
27 EL. LaQue, Marine Corrosion (New York John Wiley & Sons, 1975), 332 pp.
J. Bacon, S. Bacon, Dunwich, Suffolk (Colchester, U.K.: Segment Publ. 1988), 62 pp.
29 H. Valentin, “Present vertical movements of the British Isles,“ Geog. J. 119 (1953):pp. 299-305.
3o J.W. Evans, “The role of Penitella penitu (Conrad 1837) (Family Pholadidae) as eroders along the
Pacific coast of North America,” Ecology 49,4 (1968):pp. 156-159.
31 C. Vita-Finzi, P.F.S. Cornelius, ”Cliff sapping by mollusks in Oman,” J. Sediment. Petrol. 43,l
(1973):pp. 31-32.
32 P.D. Abel, Water Pollution Biology (Chichester, U.K.: Ellis Horwood Ltd, 1989), pp. 1-231.
33 W.T. Bresnahan, ”Water reuse in oil refineries,” M P 36,7 (1997):pp. 40-44.
T. Kakehi, H. Yoshino, ”Corrosion of steel in polluted sea waters,” in Proceedings of the 5th
International Congress on Metallic Corrosion (Houston, TX NACE, 1972), pp. 796-801.
35 J.R. Davis, ed., Corrosion, Metals Handbook, Vol. 13,9th ed. (Metals Park, OH. ASM Interna-
tional, 1987), 906 pp.
36 M. Eashwar, P. Chandrasekaran, G. Subramanian, K. Balakrishnan, ”Microbiologically influ-
enced corrosion of steel during putrefaction of seawater: evidence of a new mechanism,”
Corrosion 49,2 (1993):pp. 108-113.
37 A.A. Karande, R.B. Srivastava, “Pollution of coastal sea water and sulfate reducing bacteria,”
in 6th Int. Congress on Marine Corrosion and Fouling (1984),pp. 347-354.
38 M. Eashwar, S. Maruthamuthu, S.T. Manickam, S. Ambalavanan, K. Balakrishnan, “Characteri-
zation and testing of metal corroding thiobacilli from a sulfur polluted harbor environment.”in
4th International Symposium on Frontiers of ElectrochemistryScience & Technology, Madras,
India, 14-16 Nov. 1989, Trans. SAEST 24,3 (1989):p. 1.26.
39 R. Francis, “Effect of pollutants on corrosion of copper alloys in sea water. Part 1: Ammonia and
chlorine,” Brit. Corros. J. 20 (1985):pp. 167-182.
P.J. Weimer, M.J. Van Kavelaar, C.B. Michel, T.K. Ng, ”Effect of phosphate on the corrosion of
carbon steel and on the composition of corrosion products in two-stage continuous cultures of
Desulfovibrio desulfiricuns,” Appl. Environ. Microbiol. 54,2 (1988):pp. 386-396.
41 B. Little, P. Wagner, K. Hart, R. Ray, D. Lavoie, K. Nelson, C. Agullar, “The role of metal-reducing
bacteria in MIC,” Corrosion/97 paper no. 215 (Houston, TX NACE, 1997).
42 R.B. Srivastava, S.N. Gaonkar, A.A. Karande, ”Biofilm characteristics in coastal waters of
Bombay (India),” Proc. Indian Acad. Sci. 99,2 (1990):pp. 163-174.
43 Z. Huang, Z. Li, B. Morton, T.Y. Leung, ”Biofouling of cage mariculture zones in the southern
waters of Hong Kong,“ Asian Mar. Biol. 16 (1999):pp. 77-99.
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rosion and Fouling, Oebalia XD( Suppl. (1993), pp. 103-154.
45 E. Cecere, A. Petrocelli, G. Relini, 0. Saracino, ”PhytobenthicCommunities on Fouling Panels
at Loan0 (Savona, Ligurian %a)‘’ Obelia XIX Suppl. (1993),pp. 163-172.
46 B.S. Morton, “A note on Martesiu striatu (Pholadidae) tunnelling into plastic piping in Hong
Kong,” Malacol. Rev. 4 (1971):pp. 207-208.
47 P.J.B. Scott, ”Rapid destruction of PVC piping by boring bivalves,” Int. Biodet. 27 (1991):
pp. 87-92.
C.S. Rose, M.J. Risk, “Increase in Cliona deletrix infestation of Montustreu cuvernosu heads on an
organically polluted portion of the Grand Cayman fringing reef,” P.S.Z.N.I. Mar. Ecol. 6 (1985):
pp. 345-363.
49 P.J.B. Scott, M. Cope, ”Tolo revisited: a resurvey of the corals of Tolo Harbor and Channel six
years and one half million people later,” in Proceedings of the Second International Workshop
on the Marine Flora and Fauna of Hong Kong and Southern China, Hong Kong, 1986, B. Morton,
ed., (1990), pp. 1203-1220.
D. MacKenzie, “Alien invaders,” New Scientist 1622,2183 (24 April, 1999): pp. 18-19.
51 T. Early, T. Glonek, “Zebra mussel destruction by a Lake Michigan sponge: populations in vivo
31Pnuclear magnetic resonance and phospholipid profiling,” Environ. Sci. Technol. 33,12 (1999):
pp. 1957-1962.
52 Anon., “Copper-nickelalloy repels zebra mussels,” Nickel 12,3 (1997): pp. 6-7.
2.6 References 39
53 B. Morton, ”The biology and functional morphology of Mytilopsis sullei (Recluz) (Bivalvia:
Dreissenacea)fouling Visakhapatnam Harbor, Andhra Pradesh, India,’’ J. Moll. Stud. 47 (1981):
pp. 25-42.
54 B. Morton, ”Mytilopsis sullei (Recluz) (Bivalvia: Dreissenacea) recorded from Hong Kong: an
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55 B. Morton, “Recent marine introductions into Hong Kong,” Bull. Mar. Sci. 41, 2 (1987):
pp. 503-513.
56 B. Morton, ”Some aspects of the biology and functional morphology of the organs of feeding
and digestion of Limnopemu fortunei (Dunker) (Bivalvia: Mytilacea),” Malacologia 2 , 2 (1973):
pp. 265-281.
57 B. Morton, “The colonisation of Hong Kong ’s raw water supply system by Limnopemu fortuneu
(Dunker 1857) (Bivalvia:Mytilacea)from China,” Malacol. Rev. 8 (1975):pp. 91-105.
58 J.C. Britton, B.S. Morton, “A dissection guide, field and laboratory manual for the introduced
bivalve Corbiculnflumineu,” Malacol. Rev. Suppl. 3 (1982):82 pp.
Chapter 3
Standards and Specifications
This chapter discusses the principal standards and specifications that are applied to
materialsand their applicationsin waters. Selected standards and specificationsreferring
to particular materials or uses are listed at the end of the relevant sections.
3.1 METALS AND ALLOYS
As modem alloys began to be developed and manufactured to consistent alloy content

and/or properties, they began to acquire names indicating their use, such as admi-
ralty brass, gunmetal, cartridge brass, etc. Other alloys acquired names indicating their
method of manufacture, e.g., wrought iron, cast iron, etc., while other names indicated
composition,such as 18-8 stainlesssteel, 70/30 brass, etc. Some of the alloys that were de-
veloped by individual companies were given trade names such as Carpenter 20, Inconel,
and Hastelloy C. Many of these alloys are still referred to by these original trade names
although they are often now made by a number of alloy producers. Gradually, national
and then international trade organizations and societies starting developing standards
to define composition and properties of alloys, often using some form of numerical
or alphanumerical system of identification. For example, the American Iron and Steel
Institute (AISI) categorized stainless steels in this way. Designations such as AISI Type
304, AISI Type 316, or AISI 316 became widely used and these numbers are still readily
understood.
Later, national and international specifications(legalrequirements for analysis, prop-
erties, etc.) and standards (accepted voluntarily by industry) began to be produced in
many countries around the world by various governmental or trade bodies. Specifi-
cations include those by the American Society of Mechanical Engineers (ASME) that
control the manufacture of pressure vessels and piping. These specifications, in turn,
refer to and are consistent with the materials specifications of the American Society for
Testing and Materials (ASTM). Standards relating to the use of alloys were, and still
are, prepared by industry organizations such as the American Water Works Association
41
42 Standards and SDecifications
(AWWA),the NORSOK standards prepared by the Norwegian oil industry through the
Norwegian Technology Centre, and the National Association of Corrosion Engineers
(NACE). Bodies such as the Aluminum Association, Inc. (AA) and the Copper Devel-
opment Association (CDA) issue standards relating to the composition and properties
of these alloys. Other countries have developed independent systems, while yet oth-
ers have adopted the existing American, British, German, and other systems. Over the
years attempts have been made to rationalize and harmonize the many national and
international specifications and standards and an international body, the International
Organization for Standardization (ISO), was formed as part of this process.' The situ-
ation is still developing and evolving, but given the international nature of trade there
are strong economic and technical reasons for this harmonization process to continue.
In terms of identifymg alloys by their composition the Unified Numbering System
(UNS),developedjointly by ASTM and the Societyfor Automotive Engineers, Inc. (SAE),
is becoming widely used in many countries.2This is not a specificationsince it does not
define form, alloy condition, properties,or quality.It is an attempt at providing a uniform
identifier for specific alloys that can then be purchased to the relevant specification.The
UNS method for numbering metals and alloys is contained in the joint SAE and ASTM
recommended practice (SAE J1086Dec 85 and ASTM E527). The letter at the beginning
of the UNS designation indicates the class of metal or alloy that is being described; e.g.,
N indicates nickel and nickel alloys, S describes heat and corrosion-resistant stainless
steels,etc. Wherever possible the early industry designation numbers have been incorpo-
rated into the UNS numbers to aid recognition. For example, the nickel alloy Incoloy 800
is UNS N08800, Type 304 stainless steel is UNS S30400, and so on. The earlier trade des-
ignations for copper and aluminum alloys are similarly identifiable in the UNS system.
The development of modern metal-producingtechniqueshas permitted increasingly
complicated alloys with better corrosion properties to be made consistently. The
distinctionbetween stainless steels, nickel alloys, super stainless steels, etc. has become
somewhat indistinct, particularly for alloys containing appreciable amounts of iron and
nickel but with neither being more than 50%. Nickel alloys are sometimes defined as
alloys with substantial quantities of nickel; nickel-based alloys are those in which the
principle constituent is nickel, even if it is less than 50%. In this book we include alloys in
the section where they seem to best fit from a properties and applications point of view.
The ASTM specification system designates ferrous alloys by the letter A before the
specification number; B comes before specifications relating to nonferrous alloys. Re-
cently some of the alloys that were included as nickel alloys are now to be included
under the ferrous group of A alloys. This particularly relates to alloys that have more
iron than nickel but with neither element present at 50%or more. Previously, iron alloys
were those that contained more than 50% iron. Now stainlesssteels are defined by ASTM
as alloys with iron as the largest element by wt% containingat least 10.5%chromium and
less than 1.2% carbon. Alloys such as alloy 20, alloy 800,904L, etc. are now to be included
with the stainless steels rather than with the nickel alloys. ASTM also now permits the
use of common names to designate alloys provided that the names are in wide use, not
subject to trademark, and not linked to a particular producer. An example of this type of
alloy name is 904L.3 The main distinction between the UNS and ASTM systems is that
3.2 Nonmetallic Materials 43
the UNS number identifies an alloy composition but does not include properties, while
the ASTM system specifies required properties, treatments to be applied, test methods,
etc. relating to a particular product form and group of all0ys.4.~
In North America cast stainless steels and nickel alloys are designated using the
Alloy Casting Institute (ACI) system and this has been adopted by ASTM. A designa-
tion beginning with the letter C means that the casting is primarily intended for corrosive
service; an H signifies a high temperature alloy. The second letter indicates the approx-
imate nickel and chromium content on the FeCrNi ternary diagram (ASTM A781). For
C grades the single- or double-digit number after the letters indicates the maximum
carbon content, % x 100. Any other letters in the designation indicate the presence of
other alloying elements, e.g., M = molybdenum, N = nitrogen, Cu = copper, etc.
In Europe the situation is changing rapidly. Before the European Union was formed
most countries had their own national standards and specifications. These are to be
gradually replaced by European Standards (EN) being developed by the European
Committee for Standardization (CEN)! CEN is a network of national standards bod-
ies, associate members, and the central secretariat. The work of the national standards
bodies is at a voluntary standstill to avoid duplicationand to concentrate resources on the
Europe-wide standards. All countrieshave agreed to adopt the European standards once
they are approved and to withdraw conflicting national standards. An EN is the result
of a series of formal stages of public inquiry, voting, and modification leading to pub-
lication and adoption. Standards under development are known as prestandards and
are designated by the prefix "pr". Some standards that have been completed are given a
trial period in industrial use before being adopted and issued. These are designated as
Ems. This standardization work is organized through a series of technical committees
(TCs)with responsibility for specific areas.7
Describing materials by a recognized designation system is needed so that orders
can be placed with a clear understanding that correct materials will be supplied. Such
systems are an essential part of material standardization common to all countries. There
are three basic types of designations based either on terms, symbols, or numbers. For
European standards, a numbering system was developed that can be easily understood
by personnel with or without computers and has a common meaning across all countries
and all languages without conflicting with others in use elsewhere in the world.*
To avoid duplication of work, many IS0 standards are being taken over by CEN and
this process is governed by the Vienna Agreement, which was signed in January 1989.
This agreement defines the process of technical cooperation between the two bodies
and specifies the procedures to be followed to develop joint standards or adopt existing
ones?
3.2 NONMETALLIC MATERIALS
The situation regarding nonmetallic materials is less clear. Trade names are still
widely used to describe thermoplastics and some of these have become generic, e.g.,
44 Standards and Specifications
Teflon (DuPont trade name for PTFE and FEP) is often used for any fluorocarbon.
Thermoplastics and thermosetting resins may contain fillers, plasticizers, fire retardants,
etc., all of which have an effect on properties. Each major supplier uses different for-
mulations and processing for similar basic polymers and applies their trade name with
an identifier for the grade. Concrete is largely defined by specifications such as those
from ASTM that specify mixes for different applications and the properties required of
the components and of the final product. Woods are defined as hardwood or softwood
together with the tree species from which it came. Glasses and ceramics are usually
described by the type of compound from which they are formed.
Most nonmetallic materials and equipment are supplied to a general resin or material
type with specified properties rather than to a chemical analysis of the materials. Speci-
fications and standards also exist for the mechanical design, testing, and quality control
of piping and equipment in nonmetallic materials such as fiber-reinforced plastic (FRP).
As with metals, these specifications and standards are changing and developing with a
certain amount of rationalization and integration taking place. Apart from ASTM, other
bodies involved in standards and specifications for nonmetallic materials include the
U.S.Department of Commerce, National Bureau of Standards (NBS),ISO, CEN, etc.
3.3 REFERENCES
For lists of standards and specificationssee sections on individual metals and alloys and on specific
industries.
International Standards Organisation, ISO, www.iso.ch (July 16,2001).

Anon., Metals & Alloys in the Unified Numbering System (Warrendale,PA: Society of Automo-
tive Engineers, 1986), 371 pp.
R.M. Davison, ”ASTM update for stainless steels,” MP 38,2 (1999):p. 69.
* Annual Book of ASTM Standards (West Conshohocken, PA: ASTM, latest edition).
ASTM, http://www.astm.org (August 20,2001).
CEN Standards, http://www.cenorm.be Uune 28,2001).
Anon., Responding to Changing Needs (Brussels, Belgium:CEN, 2001), pp. 1-8.
* Anon., The Copper Page, http: //www.copper.org/standard/euronumb.htm(June 12,2001).
Anon., ”Vienna Agreement,” CEN, http://www.cenorm.be/boss/prodpro/pp018.htm(August
12,2001).
Chapter 4
Corrosion Mechanisms
This chapter provides a summary of the principal metallic corrosion mechanisms rele-
vant to aqueous corrosion. The specific application of these mechanisms is discussed in
Chapter 11, "Applications".
4.1 GENERAL CORROSION
General or uniform corrosion is metal loss or thinning occurring over the whole of
the exposed surface. If a metal is to be exposed to an environment that causes general
corrosion of that metal, then the rate of corrosion can be determined and additional metal
can be designed into the structure as a corrosion allowance. Most metals and alloys can
be subject to general corrosion in waters, but many are more prone to loss of metal
preferentially from some areas, (localized corrosion).
4.2 LOCALIZED CORROSION
Metals that rely on surface oxide films to resist attack, such as titanium, stainless steels,
and aluminum, are more likely to suffer from localized attack such as pitting or crevice
corrosion.
4.2.1 Crevice Corrosion
Crevice corrosion describes the form of corrosion that occurs at crevices or gaps between
two metal surfaces or between a metal and a nonmetal. Crevicescan be formed at gaskets,
tube to tubesheet joints, O-rings, etc. or discontinuities formed at welds, threaded joints,
etc. They can also be formed at organic or inorganic deposits on the metal surface.
45
46 Corrosion Mechanisms
Crevice corrosion results from a concentration cell between the environment within the
crevice and the bulk environment outside. Initially,corrosion occurs inside and outside
the crevice in a similar manner. In a neutral aerated solution, for example, the reactions
may be represented as follows:
at the anode: M +. M+ e +
+ +
at the cathode: 0 2 2H20 4e +. 40H-
The oxygen in the crevice will become depleted, but this on its own will not greatly
affect the corrosion rate in the crevice. Metal ions continue to go into solution in the
crevice, where they build up a positive charge, and outside of the crevice, where they
tend to become dispersed. If chlorides are present in the solution these small, mobile
negatively charged ions are attracted to the positively charged area in the crevice and
react with the metal ions to form metal chlorides. Metal chlorides readily hydrolyze in
the presence of water by the following reaction:
M+C1- + H20 +. MOH + H'C1-
The acid produced within the crevice can reduce the pH to 2, while the pH in the
bulk fluid remains neutral. This acidic environment is very corrosive to most metals
so metal dissolution increases and the whole process becomes autocatalytic. The rate
of oxygen reduction in the region immediately outside the crevice also increases and
this area becomes cathodicallyprotected and is relatively uncorroded. Crevice corrosion
continues until the metal is perforated or the electrochemical driving force becomes
insufficient.In some cases hydroxides form at the mouth of the crevice and can effectively
block the passage of ions and stop the corrosion.
Crevice corrosion can be reduced or prevented in the following ways:
Specify butt joints with full penetration welds.

Avoid lap joints or seal weld them.
Provide rounded corners, not sharp ones.
Prevent the formation of stagnant areas.
Clean regularly to remove surface deposits.
Provide filters to limit solid deposits.
Keep velocities high in heat exchangersbut not high enough to cause erosion.
Use alloys with a better resistance to localized corrosion, e.g., high molybdenum
stainless steels.
4.2.2 Underdeposit Corrosion
Underdeposit corrosion is really crevice corrosion beneath deposits. These deposits can
be water-borne inorganic compounds, such as carbonates, phosphates, silicates, etc. that
4.2 Localized Corrosion 47
precipitate on hot surfaces, or they may be sand, silt, corrosion products, microbial
colonies, biological debris, etc. carried from elsewhere and deposited where flow ve-
locity is lower. Crevice corrosion and pitting can occur under the deposits. This form
of corrosion can be controlled by the same methods used to control pitting and crevice
attack and by chemical and mechanical water treatment to remove constituentslikely to
form deposits. (See Chapter 10, Section 10.2, ”Cooling Water Treatment.”)Coatings can
also help to prevent deposition.
Poultice corrosion is a special case of deposit attack in which an absorptive material
such as cloth, wood, or paper is in contact with metal surfaces and becomes wetted
periodically. Near the edge of the wet zone differential aeration cells initiate pitting and
crevice attack.
4.2.3 Tuberculation
Tuberculation is a form of crevice corrosion that particularly affects cooling water sys-
tems. Mounds or tubercles of corrosion product are scattered over the metal surface. This
type of attack affects carbon steel and cast iron in oxygenated water and particularly in
waters with high levels of bicarbonates, sulfates, chlorides, and other aggressive anions.
Biological organisms are sometimesinvolved in tuberculation. The tubercles have a com-
plex structure consisting of distinct regions overlying the dish-shaped corroding region.
Avoidance is by the use of inhibitors, control of water flow and temperature, or coatings.
4.2.4 Filiform Corrosion
Filiform corrosion is a special form of localized corrosion that occurs under coatings and
is related to crevice attack. Fine filaments of corrosion product form under the coating
emanating from a scratch or defect. Filiform corrosion takes place in high humidity
atmospheres, typically 65 to 90% relative humidity, and particularly affects coated or
painted steel (e.g., tin-plated steel cans), aluminum, or magnesium. It can be avoided by
reduction of humidity, the use of galvanizing or zinc primers under the coating, or the
use of a less active metal substrate.
4.2.5 Pitting Corrosion
Pitting corrosion occurs when discrete areas of a metal undergo rapid attack while the
majority of the surface remains virtually unaffected. Essentially all metals and alloys
undergo pitting corrosion under some set of experimental conditions, though the relative
susceptibilityvaries widely. The basic requirement for pitting is the existence of a passive
state for the material in the environment of interest. Pitting of a given metal depends
strongly upon the presence of an aggressive species in the environment (e.g., C1- in
neutral, aerated aqueous solution for Type 304 stainlesssteel)and a sufficientlyoxidizing
potential.
Pitting occurs under similar conditions of chloride, pH, etc. as crevice corrosion.
Most alloys that suffer from crevice corrosion are likely to pit in the same environment
if the temperature is raised. However, the modern high molybdenum and high nitrogen
stainless steels can crevice corrodebut rarely pit in industrial applications.Pitting occurs
on open metal surfaces when the potential of the metal equals or is noble to its pitting
potential under the specific environmental conditions. This happens when the pitting
potential is displaced in the active direction, e.g., by an increase in temperature, or when
the corrosion potential becomes more noble, e.g., by the addition of strong oxidizers such
as chlorine or the formation of biofilms which aid the cathodic reactions.' Unlike pitting,
crevice corrosion can occur at potentials much lower than the pitting potential. Pitting
can initiate at deposits, crevices, or local defects in the surface film. Pitting normally
requires an initiation period, unlike crevice corrosion where the initiation time is shorter
or nonexistent. Propagation of both pits and crevices proceeds by similar mechanisms
and generally involves a large driving force due to the large cathodic area (uncorroding)
and the small anodic area in the pit or crevice?
There are many different forms of pit depending on the metal and the environment.
The standard classification of types of pits is detailed in ASTM G 46. Different types of
pit can be present in the same pitted sample, as shown in a section through a 904L heat
exchanger tube using seawater to cool sulfuric acid (Figure 4.1).
Halide salts, particularly chlorides, promote pits. Oxidizing metal chlorides, such as
cupric and ferric chlorides, are strong pit/crevice agents because they can provide an
alternative or additional cathodic reaction to oxygen reduction to accept electrons. For
example, note the following:
+
Cu2+ 2e + Cu.
Some of the methods used to reduce crevice attack also help prevent pitting, e.g.,
regular cleaning to remove surface deposits, providing filters to limit solid deposits, and
keeping velocities high.
4.2.6 Microbiologically Influenced Corrosion
Microbiologically influenced corrosion (MIC) is the initiation and/or enhancement of

the rate of corrosion by the metabolic activity of microorganisms, including bacteria,
algae, and fungi. Higher organisms, such as barnacles and mussels, may also contribute
to corrosion by creating crevices under which corrosion may occur. (See also Chapter 7,
"Biofouling and Biodeterioration.") h4IC has been documented in almost all waters,
including distilled, potable, fresh, brackish, seawater, and brines as well as waste water,
soils, process chemicals, and petroleum.
4.3 Environrnentallv Assisted Crackine 49
Figure 4.1 A section through a 904L seawater heat exchanger tube shows different forms of
pitting in the same tube. (Photo courtesy of D. Hodgson)
4.3 ENVIRONMENTALLY ASSISTED CRACKING
The presence of a specific environment can cause the brittle failure of some metals at
stress levels that would not cause failure in the absence of that environment. At least five
phenomena can be included in this classification as environmentally assisted cracking.
These are the following:
1. Stress corrosion cracking

2. Hydrogen embrittlement
3. Corrosion fatigue
4. Liquid metal embrittlement
5. Hot corrosion cracking
Liquid metal embrittlement and hot corrosion cracking occur at elevated temperatures
and are not generally relevant to water applications.
4.3.1 Stress Corrosion Cracking
Stress corrosion cracking (SCC)describescracking that occurs in a metal under the action
of a tensile stress in a specific environment. Three factors must be simultaneously present
for SCC to occur:
1. A distinct environment must be present. This includes chemical composition, tem-

perature, pH, etc.
2. The metal must be in a metallurgicalcondition susceptible to SCC in this environment.
Grain boundary precipitates may initiate SCC.
3. A tensile stress greater than some threshold value must be present. This stress may
be applied or residual.
Many specific environment metal combination can lead to SCC. The most relevant in
waters are chloride stress cracking of stainless steels, caustic cracking of carbon steels,
and ammonia cracking of copper-based alloys. Copper alloys are also known to have
cracked in sulfide-polluted seawater. SCC is often closely associated with hydrogen
damage. For details of SCC in specific metals see the relevant material in Chapter 5,
”Metals and Alloys.”
4.3.2 Hydrogen Effects
Hydrogen is often available in metals or at their surfaces and can have a strong influence
on their properties and service life because it generally reduces ductility and encourages
brittle fracture. It is produced during aqueous corrosion, from sour gas in oil produc-
tion, metal melting, welding, pickling, electroplating,and heat treatment. The hydrogen
produced can be molecular or atomic and may react with the metal to form hydrides.
A number of different forms of hydrogen damage have been identified, including the
following:
Hydrogen embrittlement occurs when high strength steels containing hydrogen are
stressed in tension. The steel may fail prematurely and in a brittle manner.
Cracks from melting. Hydrogen can be absorbed into molten metal and precipitate
at voids and discontinuities when the metal solidifies and cools. It can affect forgings
and castings and form fish eyes, flakes, and shatter cracks.
Decarburizationis a form of hydrogen damage that affects steels in high-temperature
atmospheres containing hydrogen, e.g., in oil refineries. Hydrogen reacts with
carbides in the steel to form methane that collects at discontinuities producing
cracks.
Hydrogen blistering is a form of attack in sulfuric acid storage tanks and in petroleum
refining equipment. Atomic hydrogen produced by corrosion of the steel diffuses to
4.3 Environmentally Assisted Crackinn 51
an internal defect where it forms molecular hydrogen. The hydrogen gas develops
pressure high enough to cause the steel to blister. Cathodic protection can eliminate
the problem in sulfuric acid tanks.
Hydride formation. Some metals, such as titanium, tantalum, etc., absorb hydrogen at
high temperature, which then forms brittle hydrides on cooling. Hydride formation
can be avoided by vacuum melting or the use of low hydrogen welding rods. The
hydrogen can be removed by vacuum annealing.
The most important of these hydrogen effects in waters is hydrogen embrittlement.

High carbon steels with a tensile strength above about 1,241 MPa (180 ksi) can become
embrittled in fresh or seawater. Lower strength steels appear to be immune to this form
of embrittlement unless hydrogen sulfide is p r e ~ e n t . ~ . ~
In sour waters, i.e., with hydrogen sulfide present, a number of cracking mecha-
nisms are possible. Many of these are specific to the oil-producing or refining industries.
The crack mechanisms (sometimes called wet H2S cracking mechanisms) include the
following:
Sulfide stress cracking (SSC). This is a form of hydrogen stress cracking. It oc-
curs mostly in high strength steels or in hard weld zones of steels and is initi-
ated by cathodic processes in the presence of tensile stress and aqueous sulfide
corrosion.
Hydrogen-inducedcracking (HIC),Blistersand crackscan occur in steelpipes carrying
sour wet gas. Cracks develop parallel to the pipe wall and can link up in characteristic
stepwise cracking.
Stress-oriented hydrogen-induced cracking (SOHIC).Arrays of cracks perpendicular
to the stress are formed by small HIC cracks that join up in the steel.
Alkaline stress corrosion cracking (ASCC) is produced in aqueous alkaline solutions
containing H2S and C02 under the action of tensile stress. This type of cracking is
known as carbonate cracking when it occurs in alkaline sour waters and as amine
cracking when occurring in alkanolamine-treatingsolutions.
Polythionic acid cracking is a form of attack that occurs in austenitic stainless steels
that have become sensitized and have a sulfide scale from high temperature refining
operations. Cracking occurs on cooling once water is present. Neutralization and/or
washout procedures have largely eliminated this form of attack.
Some of the hydrogen cracking phenomena are similar to SCC. However, SCC is
an anodic dissolution process that can be alleviated by cathodic protection (CP),where
hydrogen-assisted cracking processes are cathodic and can be initiated or accelerated
by CP.
Avoidance or control of these forms of cracking is usually effected by the selection
of suitable materials in an appropriate metallurgical condition. The process of selecting
materials for this type of service is described in specifications and other publicationsby
NACE International and others5q6
Table 4.1 Corrosion Fatigue Strengths (CFS) for Various Alloys

in Seawater7
Alloy Type (UNS No.) CFS at 100 megacycles ksi (MPa)
Alloy 625 (N06625) 50 (344.8)
UTS 149 h i (1027.3)
Alloy 625 (N06625) 40 (275.8)
UTS 129 ksi (889.5)
Alloy C (N10002) 32 (220.6)
Alloy K-500 (N05500) 26 (179.3)
Alloy 800 (N08800) 24 (165.5)
304 (S30400) 15 (103.4)
304L (S30403) 14 (96.5)
316 (S31600) 14 (96.5)
316L (S31603) 13 (98.6)
Cast bronzes (CA955,957,865) 8-12.5 (55.2-86.2)
Mild steel 1.4 (9.7)
4.3.3 Corrosion Fatigue
"Fatigue" is the term used to describe damage to a metal by the cyclic application of
stresses below yield. Corrosion fatigue describes the reduction in fatigue strength of a
metal in a corrosive environment compared with its fatigue strength in air. Corrosion
fatigue strength (CFS) is often taken to be the fatigue strength for 108 cycles at 0 mean
stress. It is not a true endurance limit because failure can occur at >lo8.CFS is important
for piping, pumps, heat exchangers, and undersea equipment. The endurance limit for
304 in air is of the order of 35,000 psi (241 MPa) and for 316 about 40,000 psi (276 MPa).
The CFS in seawater drops to 15,000for 304 and 14,000 for 316 at lo8cycles and continues
to drop as the number of cycles increases. The mechanism by which seawater (which is
not particularly corrosive to stainless steels) affects the fatigue strength is not clear, but
the effect is real. Results of 48-day tests in seawater are shown in Table 4.1. CFS tends
to increase with increasing ultimate tensile strength (UTS); see, for example, alloy 625
(UNS N06625).7
4.4 VELOCITY-INFLUENCED CORROSION
Velocity of the fluid can have a considerable effect on the rate and type of corrosion.
Increased velocity can reduce corrosion by removing stagnant areas or increasing the
supply of oxygen or inhibitors.It can also increase corrosion by the removal of protective
films, metal, or corrosion products. This phenomenon is also known as flow-assisted
corrosion (FAC).The velocity of the fluid can have a direct influence on the mass transfer
4.4 Velocity-Influenced Corrosion 53
Table 4.2Limits of Water Velocity for Various Copper Alloys in Potable Water
and SeawateP
Velocity Limit ft/s (m/s)
Alloy Seawater Potable Water
70/30 Cu/Ni 10-12 15-18
(3.0-3.7) (4.6-5.5)
90/10 Cu/Ni 8-10 12-15
(2.4-3.0) (3.74.6)
Aluminum brass 7-7.5 10-11
Aluminum bronze (2.1-2.3) (3.0-3.4)
Arsenical admiralty brass 5-5.5 7-8
(1.5-1.7) (2.1-2.4)
Red brass 2.5-3 6
Phosphorized arsenical copper Phosphorized copper (0.8-0.9) (1.8)
Everdur Cu + 2%Si, 1%Mn
of species between the metal surface and the fluid. The mass transfer rate will depend not
only on velocity, but also on geometry of the pipe or system and the properties of the fluid.
Low velocity or stagnant conditions in seawater can adversely influence the corro-
sion of all metals because these encourage deposition and fouling. Pitting and crevice
attack are probably the most common forms of attack in seawater and are most likely to
occur under low-velocity conditions. Localized corrosion can be prevented or reduced
by removing solid particles and by using fabrication and design practices that avoid
crevices, i.e., at tube to tubesheet joints, weld profiles, bolted joints, etc.
The corrosion rate may uniformly increase with increase in velocity or may suddenly
increase above a certain threshold or critical velocity. Copper alloys, for example, often
exhibit a sudden change in corrosion rate when a threshold velocity is exceeded. The
critical velocity for any copper alloy is higher for potable water than for seawater, with
the copper-nickel alloys having the best resistance to velocity in either water (Table 4.2).
Some materials are more susceptible than others to velocity-induced corrosion, such
as the fol10wing:~
Inert-alloy C, titanium
+ +
Good-90/10 Cu/Ni 1.5Fe, 70/30 Cu/Ni 0.5Fe, bronze, brass
Fair-austenitic Ni cast iron, cast iron, carbon steel
Poor-alloy 825, alloy 20, nickel-copper, copper
Deep pits in crevice-Tme 316,304, Ni/Cr alloys, 400 series stainless steels
As the velocity of moving seawater increases, corrosion of many metals, including

copper alloys and mild steel, also increases. Other metals or alloys, such as titanium and
Table 4.3 Effect of Velocity on Seawater Corrosion (Corrosion Rates in m / y )

Low Velocity Medium Velocity High Velocity
Material General Pitting 5m/s 8.2 m/s +
30 m/s Ref.*
Carbon steel 0.1 0.5 1 10 1

0.075 - 4.5 3
Cast iron 0.1 0.5 1 10 1
0.55 4.4 13.2 3
Stainlesssteels 0.01 0.5 0.01 0.01 1
316 SS 0.02 (0.02 <0.01 3
6% MOSS 0.01 0 t0.02 <0.01 3
Copper alloys 0.02 0.02 Some suffer 1 1
impingement
attack
Ni/Al bronze 0.055 0.22 0.97 3
90/10 Cu/Ni 0.015 0.5-1.3 2
+ 1.5% Fe
70/30 Cu/Ni 0.0065 0.9-1.8 2
+ 0.6% Fe t0.02 0.12 1.47 3
70/30 Cu Ni 0.001 0.22 0.5 3
+ 1.6% Cr
Alloy 400 >0.008 - 0.01 2
0.02 (0.01 0.01 3
Ni/Cu alloys 0.01 0.2 0.01 0.01 1
‘Ref. 1,’O Ref. 2,” Ref. 3.’*
stainless steels, are relatively insensitive to this factor. Velocity can affect both general
corrosion and localized attack (Table 4.3).
Copper-based alloys are more resistant to pitting in stagnantconditions, while nickel-
based alloys are generally better under velocity conditions. Increased seawater velocity
increases the corrosion rate more for some alloys than for others (Table 4.4).”
In seawater stainless steels can be used at velocities as low as 1.5 m/s at ambient
temperature as long as the normal oxygen levels of 6 to 10 ppm are present. Maximum
velocity in sea or fresh water is up to at least 20 ft/s (6.1 m/s). Titanium can withstand
seawater containing entrained sand from stagnant conditions up to velocities of 40 m/s.
Partial tube blockage, e.g., by macrofouling,can cause severeerosion attack downstream
of the deposit.15
Critical or limiting velocities are mostly based on empirical measurements and are
used as a rule of thumb to help prevent or reduce velocity-induced corrosion. More
fundamental studies have been based on wall shear stress. The initial tests were made
on copper alloys in seawater flowing at between 1.5and 15m/s. These tests determined
the critical shear stress to remove the protective surface films and these stresses were
used to predict critical velocities in any system in which the fluid dynamics are known.16
+
Tests on corrosion of carbon steels in a solution of 3% NaCl 1,000 ppm HCO; at pH
4.4 Velocitv-influenced Corrosion 55
Table 4.4 Corrosion Rates in Seawater at Different Vel~cities'~*'~
Corrosion Rates mm/y (mdd)at Various Velocities

1 ft/s 4 ft/s 27 ft/s
Alloy (0.3 m/s) (1.2 m/s) (8.2m/s)
Carbon steel 0.33 1.17
(72) (254)
Cast iron - 1.36
(270)
Silicon bronze 1.46
(343)
A1 bronze 1.10
(236)
90/10 Cu/Ni 0.40
(99)
70/30 Cu/Ni 0.16
(39)
Alloy 400 0.016
(Ni/Cu) (4)
316 SS t0.005
(<I)
Alloy c 0.012
(3)
Titanium 0
Note: Corrosion data have been converted from the original mdd.
6.0 with 20 to 30 ppb 0 2 and 1.3 bar (20 psia) C02 at 50°C compared results in pipe
flow with jet impingement and laboratory rotating cylinder tests. The rotating cylinder
results did not correlate with pipe flow based on wall shear stress, while jet impingement
tests at radial distance r/ro = 3 correlated well. The general equation for flow-induced
corrosion of carbon steel in this environment is
where KOris the corrosion rate in mm/y, t-, is the wall shear stress in N/m2 for this
environment, a = 12.5 f0.5, and b = 0.10 f0.02.
The major effects of fluid flow on corrosion depend on heat transfer, momentum
transfer, and mass transfer. Changes in the wall shear stress (momentum transfer) will
also affect the diffusion coefficient (mass transfer) as will changes in thermal gradient
(heat transfer). These factors are interrelated and all must be considered in flow-affected
corrosion.17
4.4.1 Erosion Corrosion
Erosion corrosion normally refers to a process in which mechanical wear or abrasion

is occurring simultaneously with corrosion. Most metals can suffer erosion corrosion
under specific conditions but some are more susceptible than others.
The presence of dissimilar metals in a flowing system can increase or even create
erosion corrosion. In some cases metals that are not susceptible when exposed indi-
vidually in the fluid become eroded when coupled galvanically in the same fluid at the
same velocity. An example of this is lead and 316 stainless steel in sulfuricacid. The 316 is
unaffected by high velocity sulfuric acid, 316 and lead coupled together are not corroded
in static sulfuricacid, but if coupled in high velocity sulfuric acid the 316 corrodesrapidly
since the passive film is destroyed by the combination of galvanic and velocity effects.
Impingement attack is a localized form of erosion corrosion caused when high ve-
locity fluid strikes a metal surface. This type of attack can occur in pumps or at areas of
turbulence in pipes, valves, heat exchanger tubes, etc. This effect is exacerbated if the
fluid carries abrasive particles, such as sand or metal oxides.
4.4.2 Cavitation
Cavitation is a special form of velocity-induced corrosion that affects pipes, pumps,

valves, ships propellers,etc. in flowing water. This form of attack is caused by the forma-
tion of gas bubbles as the liquid passes through areas of reduced pressure and subsequent
collapse of the bubbles in areas of higher pressure. The imploding bubbles can produce
jets of liquid with velocities from 100 to 500 m/s. When these jets impact the surface of
the metal they can dislodge the surface films and cause local metal deformation. In this
way fresh surfaces are being continuously exposed to corrosion and the films that form
are stripped off. The damage often has a characteristic gouged appearance as though
metal has been scooped out of the surface, as indeed it has.
Cavitation can be avoided by changing the dynamics of the flow to reduce pres-
sure differentials; using harder, more resistant materials; ensuring surfaces are smooth;
using resilient coatings such as rubber or plastics although cavitation can remove such
coatings.
4.4.3 Fretting Corrosion
Another special form of velocity-influenced corrosion is fretting corrosion, in which

small relative movements between metallic surfaces occur in the presence of corrosion,
usually dry oxidation. The oxide debris formed between the surfaces is removed by the
movement and exposes fresh surfaces by abrasive wear for further oxidation to take
place. This type of corrosion is normally found on machine components operating at
elevated temperatures.
4.5 GALVANIC ATTACK
A metal immersed in an electrolyte, e.g., seawater, will establish its own electrochemical
potential. If two metals are in contact or connected electrically then current will flow in
response to the potential differencebetween them. One metal will corrode preferentially
while tending to protect the other. The effect on the less noble member is known as
galvanic corrosion and is the basis of cathodic protection by consumable anodes.'*
Galvanic corrosion is a dynamic process that changes with time so that the use of
short-term galvanic seriesdata can be misleading and should only be used as an indicator
of possible behavior. The metals in a galvanic couple can change potential with time by
the process of polarization, i.e., the potential of the anode and cathode may tend toward
each other. Also, corrosion product can build up on the anodic metal reducing the rate
of corrosion. The driving force for this type of corrosion is very sensitive to relative
areas of the couple. The classic example is the use of copper rivets to hold steel plates
together in seawater. This is acceptable, but the use of steel rivets to hold copper plates
is not because the small steel anodes are corroded rapidly, driven by the large copper
~athode.~
Despite the fact that galvanic corrosion has been known for many years, since Sir
Humphry Davy's trials on copper-bottomed ships, it still causes failures. Examples in-
clude the following:
In 1962 the copper end plate fell off a seawater evaporator in a submarineit had
been attached with steel bolts.
In 1982 the nose wheels collapsed on two Harrier jets operated in marine
environments-magnesium alloy wheel hubs were fitted with stainless steel bear-
ings.
In 1991 marine biologists attached test mussel cages to lighthouses; the cages
disappeared-aluminum clips had been used to fasten steel eye to wire rope.19
A yacht with an alloy 400 (UNS N04400) hull and steel rivets became unseaworthy
when the rivets rapidly corroded?0
Aluminum tubing was badly attacked when connected with brass return bends.*l
Steel pump shafts and valve stems have failed when in contact with graphite packing
or seals. Valve seats containing graphite should be avoided for the same reasonFO
Steel domestic hot water tanks failed when copper piping was attached to them.20
Galvanized steel pipes attached to copper water tanks or cylinders corrode unless
separated using brass or gunmetal connectors.21
Lead lining was severely attacked when in contact with carbon bricks in a gas cleaning
tower.
Alloy 20 (UNS N08020) vessel top was severely attacked when connected to a lead-
lined tower in sulfuric acid service.
The developmentand use of a galvanic seriesfor predicting galvanic corrosionperfor-

mance are described in the ASTM standard G 82.22The classic chart produced in flowing
aerated seawater after short exposure times shows the relative potentials of many metals
Ms
zo
Al alloys
Carbon steel, cast iron
Aust Ni Cast Iron
Al Bronze
cil
Admiralty & A1 brass

SS 410, 416
90/10 Cu Ni
SS 430
Lead
70/30 CulNi
NAB
Alloy 600
302, 304, 321, 347
Alloy 400, K500
Ti
Graphite
I I I I I I
-2000 -1500 -1000 -500 0 500
Potential mV SCE
Figure 4.2 schematic shows a galvanic series in seawater for some metals in
flowing seawater at 2.4 to 4.0 m/s for 15 days at 30°C. Data are from ASTM
Standard G 82.
in seawater (Figure 4.2).= The possibility of galvanic corrosion occurring between two
metals in seawater can initially be assessed by reference to such a chart. Metals, such as
stainless steels, that show passivity occupy two different ranges of potential depending
on whether they are in the passive or active condition. These active/passive metals can
therefore act anodically or cathodically when coupled to some other metals in seawater.
Galvanic series charts only give an indication of the possibility of galvanic attack since
they are based on short-term tests and do not take into account effects of polarization,
biofilms, corrosion product buildup, relative areas, etc. They do, however, indicate the
possible driving force that can be developed between dissimilar metals in seawater.
In the case of stainlesssteelundergoing crevice attack the conditionswithin the crevice

of oxygen depletion and acidification are such that the less noble (active) potentials
should be used."
Other charts have been developed from longer-term testing that take the presence of
biofilms into account, and also show the considerableeffect of temperature on potentials
in seawater. These tests showed that for stainless steels, titanium, and nickel alloys in
natural seawater at 10°C microbial activity leads to an increase in the free corrosion
potential of up to 300 mV SCE (saturated calomel electrode)over a 1-to 3-week period.
Nickel showed a smaller increase because of considerable corrosion. This increase in
potential was not observed at 40°CE (Figure 4.3). Other charts also incorporate the
presence of a b i ~ f i l mor~ show
~ the effects of seawater velocity on potentials.26The
potentials for individual metals and alloys in these various charts differ from the short-
term data in Figure 4.2, but, in general, individual alloys occupy similar relative positions
in all of these series.
Galvanic seriescharts are confirmed by the long-term experience that the super stain-
less alloys can safely be coupled to titanium and Hastelloy C276 (UNS N10276). In the
case of the 300 series and 904L stainless steels which are susceptible to crevice attack,
rate of propagation of attack will be increased by galvanic coupling to more seawater-
resistant alloys and may induce crevice corrosion of the more resistant
It is possible to divide alloys into groups or classes depending on their corrosion
resistance in waters. Galvanic coupling between alloys within the same group should
not produce a significant increase in corrosion rate of either alloy. Coupling with alloys
from other groups will probably produce galvanic corrosion, the severity of which will
depend on the individualalloys and other factors such as area ratio, fouling, temperature,
etc. Grouping of alloys in ambient seawater is compared with groupings in moderately
hard fresh water at 25OC in Table 4.5.
Groups are ranked from 1 (most resistant, passive, or noble) to 4 (least resistant,
likely to corrode). The subdivision of some of the groups is necessary because there
is a substantial potential difference between the sub group alloys and they need to be
considered ~eparately.~~
Galvanic corrosion tests were conducted in clean, quiescent seawater, at a depth of
1m, at ambient temperature. These tests were run for three consecutive 1-year periods
at various anode to cathode ratios. In most cases the 6% molybdenum austenitic alloy,
UNS S31254, was the cathode with various copper alloys as anode. This extensive test
program showed the following:N
All the copper alloys tested suffered galvanic corrosion when coupled to UNS S31254.
Muntz metal was attacked by rapid dezincification at all area ratios tested.
A1 and NiAl bronze, 90/10 and 70/30 Cu/Ni, and alloy 400 were compatible with
UNS S31254 up to at least 1:1area ratio.
When alloy 400 was coupled with UNS S31254 crevice corrosion of the nickel alloy
induced secondary corrosion on the stainless steel.
UNS S31254 was compatible with titanium and alloy C-276 at all area ratios tested.
UNS S31254 and titanium had about the same galvanic effect on copper alloys.
Mg
Al
zo
4 2 . 7 Mg
Cast Iron
Carbon Steel
Sn
Aust Cast Imn

Brass
A1 Brass
Cn
90/10 Cu Ni
S i e r Solder
Al Bm,aze
NAB
Lead
Ni
316L
Alloy 400
10°C
Ti
Supers 40 O C
C276
AUoy 625
Graphite
I I I I I I
-2Ooo -1so0 -1Ooo 600 0 so0
Potential mV SCE
Figure 4.3 Schematic shows the potential of metals in seawater at 10 and 40"C.23.24
Table 4.5 Alloy Grouping by Corrosion Resistance in Water29
Group Alloy in Seawater Alloy in Fresh Water

~~~~~~~~ ~~~
1 Ni/Cr/Mo alloys, Mo>7% Austenitic SS (304,316)

6%Mo austeniticSS Ferritic SS (13%Cr, 18%Cr)
Superduplex SS
E and alloys
2 Alloy 400/K500 Copper and alloys
904 Silver solder
22% Cr Duplex Soft solder (Sn/Ag)
Alloy 825
Alloy 20
316L
3 Cu alloys Cast iron
Austenitic cast iron Carbon steel
4 Carbon steel Aluminum and zinc
Cast iron
A1 alloys
UNS 91254, titanium, and 90/10 Cu/Ni had about the same galvanic effect on mild
steel.
UNS 91254, titanium, and alloy C-276 were unattacked in these tests, apart from the
secondary corrosion of UNS 91254 mentioned above.
Accelerated crevice corrosion on 316L flange faces coupled to 6% Mo stainless steel,

UNS NO8367, has been reported in once-through water from the Delaware River. Tests
showed that there was a significantgalvanic influencebetween these two stainless steels
at temperatures between 15and 24°C. As the temperature increased to 32°C the galvanic
effect became insignifi~ant.~~
Cast iron or steel waterboxes in a seawater heat exchanger can cathodically protect
copper-based tubes. If these metal water boxes are coated or rubber lined to extend their
life, attack of the tube ends may increase. Titanium tubes have a strong galvanic effect
on most copper-based alloys and can stimulate corrosion on copper-nickel waterboxes
and tubeplates. Care is needed to avoid galvanic corrosion when titanium tubes are used
and where copper-nickelnozzles are used in titanium plate exchangers.Galvanic effects
can be controlled by cathodic protection but care is needed to ensure that overprotection
does not cause hydriding of the titanium tubes.12
Titanium should not be directly coupled to less noble metals such as magnesium,
zinc, or aluminum since the other metals will experience accelerated corrosion and the
titanium may pick up hydrogen and become embrittled. Titanium may be coupled in
neutral, slightly reducing, and oxidizing environmentsto corrosion-resistantalloys such
as 6% Mo austenitic stainless steel, 2205, alloy 625, and alloy C-276. Duplex alloy 2205
coupled to titanium in seawater will suffer from crevice corrosion unless CP is applied.
Metals and materials such as graphite and carbon fiber composites can be safely coupled
to titanium and will raise the corrosion potential of the titanium into the passive region.
This effect is the basis of increasing the resistance of titanium to reducing acids by
coupling or treating it with palladium or platinum. Impressed current CP of a base
metal coupled to titanium should operate at no more than -0.85 V SCE in seawater or
near neutral brines. Sacrificial zinc or aluminum anodes are generally satisfactory as
long as the titanium is lightly stressed and is at least 6 mrn thick. Magnesium anodes
should be avoided because the potentials produced are too negative.32Zirconium is
normally noble in seawater because of the presence of its oxide film and will not corrode
if connected to more noble metals. Carbon steel, aluminum, or zinc will corrode rapidly
if connected to zirconium and these couples should be av0ided.3~
Copper alloys are cathodic to most other metals in an electrolyte. The extent of the
galvanic effect on corrosion depends on oxygen content, the relative solubilities of the
metals, and their polarization characteristics,e.g., copper nickels in seawater readily po-
larize and cause less galvanic attack on coupled cast iron than does pure copper.Stainless
steels coupled to copper can be anodic if active or cathodic if passive. Copper alloys usu-
ally corrode preferentially when coupled with high nickel alloys, titanium and graphite.
Condensers and heat exchangers in water service are often fabricated from some
combination of copper alloys, e.g., admiralty, A1 brass, or Cu/Ni tubes in naval brass,
Muntz metal, or Al bronze tubesheets. Generally these combinations of copper alloys do
not suffer from major galvanic effects. When condensers were retubed with titanium or
6% Mo austenitic stainless steel the tube materials polarized so readily that the whole
of the tube area became cathodic to the copper alloy tubesheet, which suffered severe
galvanic attack. This problem was solved by installing impressed current CP in the water
boxes, controlling at potentials that do not cause hydrogen embrittlement problems in
titanium or ferritic stainless steel tubes (if they are used).
Nuclear submarines used exchangers with alloy 400 water boxes and UNS C71500
Cu/Ni tubing, which severely corroded even though the potential difference was only
0.1 V. This problem was solved by coating the water box with 50% Pb 50%Sn solder that
reversed the couple making the tubing cathodic. Later the water boxes were replaced
with UNS C71500 water boxes.
In a desalinationplant bare steelwater boxes facing a Cu/Ni tubesheet suffered rapid,
severe corrosion. Epoxy coating the water boxes was only a partial solution since they
then suffered deep pitting at discontinuities in the coating. The successful solution was
to epoxy coat the tubesheet and tube ends, thus reducing the cathodic area available to
support the corrosion reaction.
The use of stainless steel valves in a copper-based seawater piping system is not
generally a problem because the galvanic effect is spread over the large area of the pipe
surface. Welds on hulls and rudders of ships can be attacked by galvanic corrosion
resulting from the connection with the steel plate. It is normal to use a more highly
alloyed filler metal for these welds to avoid this corrosion.
To help prevent galvanic corrosion the following are suggested:
Select metals that are close together in the galvanic series or install a third metal or
alloy with a potential between the two.
Make the critical component of the more noble metal, e.g., use a copper-based trim in
a cast iron body valve.
Avoid large cathodes coupled to small anodes.
COMPLETELY insulate dissimilar metals.
Apply coatings. Coat the cathodic metal if only one is coated, for if only the anode is
coated any defects will rapidly corrode. The anode can be left uncoated or the coating
may be removed to spread the area of attack and increase the time before repairs are
needed.
Use inhibitors to reduce corrosion.
Apply cathodic protection but operate at potentials that do not produce hydrogen,
particularly if metals susceptible to hydrogen embrittlement (high strength steels) or
hydriding (e.g., titanium) are present.
Use metals for fasteners, welds, pumps, etc. that are cathodic to the main piping or
equipment materials.
Avoid threaded joints.
Avoid the use of graphite joints or carbon deposits that can cause severe galvanic
corrosion on copper alloys and stainless steels.
The advisability of using UNS NO8367 sleeves to solve an inlet erosion-corrosion

problem on 90/10 Cu/Ni tubes in a heat exchanger with tube side seawater as coolant
was discussed on the NACE Corrosion Network. One respondent quoted 19 years of
service experience at Con Edison (New York) in polluted seawater for steam surface
condenser service and their use of UNS NO8367 inserts for 6 in. (15 cm) on the inlets
of aluminum bronze and aluminum brass tubes. About 20 tubes were removed 10 to
12 years after the inserts were installed and no galvanic corrosion was seen on the tubes
or inserts. Isolated erosion was noted at the end of the insert on one or two tubes, so
10-in. (25-cm)UNS NO8367 inserts were installed. Inserts of 12 in. (30 cm) UNS NO8367
in arsenical admiralty brass were used for about 15 years with no galvanic problems.
Copper alloy 722 was also used as inserts for copper alloy tubes.34Cu/Ni 90/10 was
extensively used in most of the heat exchangers of multi-stage flash (MSF) desalination
plants in one location. Erosion of the tube inlets was not encountered,particularly if the
flow rate was kept below 2 m/s.35
Galvanic corrosion of copper (UNS CllOOO), 1018 carbon steel (UNS G10180), alu-
minum alloy 3003 (UNS A93003), and zinc (UNS 232121) coupled to cathodes of UNS
NO8367 was tested with and without natural marine biofilms on the cathode surface.
Weight losses were significantly higher, and corrosion currents were up to 2 decades
higher with a biofilm on the cathode for anodes of copper, steel, and aluminum. There
was no difference for zinc. An increase in the consumption of the anode should be ex-
pected where biofilms on the cathode of a galvanic couple result in a systematic and
significant increase in reduction current at the mixed potential of the couple. Cathodic
reduction currents (vs. control with no biofilm) were increased at all potentials down to
approximately -900 mV SCE, resultingin an elevated current capacitycapable of increas-
ing the weight loss of anodic materials over at least 2 months. Biofilms, however, did not
increase consumption of zinc anodes. Potentiodynamic polarization curves taken from
the corroded samples were used successfullyto predict the effect of biofilms on galvanic
corrosion rates for the materials tested. Weight-loss values calculated by Faraday’s law
using corrosion currents from the polarization curves agreed well with actual mea-
sured values for anodes of steel, Al, and Zn,although there were some discrepancies
for C U . ~
4.6 INTERGRANULAR CORROSION
“Intergranular corrosion’’is the term used to describe attack on the grain boundaries or
the material immediately adjacent to them. The specific mechanisms vary depending on
the alloy but generally involve potential differences between adjacent areas that have
different alloy contents. The variation in composition is usually caused by the precipita-
tion of alloy-rich particles at the grain boundary that deplete the adjacent matrix of these
alloying elements. The precipitation is caused by heating and cooling during casting,
heat treating, or welding. Stainless steels and aluminum alloys are most often subject to
this form of corrosion.
Exfoliation is a form of intergranular corrosion in which attack proceeds along local
subsurface paths parallel to the surface. Layers of uncorroded metals between these
paths are split apart and pushed above the original surfaceby the voluminous corrosion
product. Aluminum and alloys are particularly prone.
4.7 DEALLOYING OR SELECTIVE ATTACK
Dealloying occurs when one phase of an alloy system is preferentially attacked. This
can result in a weak network of the more resistant phase that often results in mechanical
failure.Thebest known examplesof this type of corrosionare probably the dezincification
of brass and graphitic corrosion of gray cast irons.For details, see section on relevant
alloy in Chapter 5, “Metals and Alloys.”
4.8 REFERENCES
’ R.G. Kelly, ”Pitting,”CorrosionSource,http://www.corrosionsource.com/index.htm(April 12,

2000).
* E.E. Stansbury, R.A. Buchanan, Fundamentals of Electrochemical Corrosion (Materials Park,
O H ASM Intemanional, ZOOO), 487 pp.
J.R. Davis, ed., Corrosion-Understanding the Basics (Materials Park, O H ASM Intenational,
2000), 563 pp.
M.G. Fontana, N.D. Greene, Corrosion Engineering, 2nd ed. (New York McGraw-Hill Book
Co., 1978), 465 pp.
4.8 References 65
NACE Materials Recommendation, “Sulfide Stress Cracking Resistant Metallic Materials for
Oilfield Equipment,” MRO175-99 (Houston, TX, NACE International, latest revision).
NACE Recommended Practice, “Protection of Austenitic Stainless Steels and Other Austenitic
Alloys from Polythionic Acid Stress Corrosion Cracking During Shutdown of Refinery
Equipment,” RPO170-97 (Houston, TX, NACE International, latest revision).
A.H. Tuthill, ”Corrosion Fatigue in Seawater,” in Proceedings-Materials Engineering Work-
shop,” NiDI Reference Book no. ll,OOl,2nd ed. (Toronto,Canada: NiDI, 1994), pp. 36-38.
* C.D. Tapley, ”Copper and Its Alloys,” in Process Industries Corrosion, eds. B.J. Moniz, W. I.
Pollock (Houston, TX NACE, 1986),pp. 191-200.
M.G. Fontana, N.D. Greene, Corrosion Engineering, 2nd ed. (New York McGraw-Hill Book
Co., 1978), p. 269.
lo B. Todd, P.A. Lovett, ”Selecting Materials for Sea Water Systems, Part 10,” Vol. 1, Marine
Engineering Practice (London, U.K.: The Institute of Marine Engineers), pp. 1-56.
l1 B. Todd, ”Nickel-Containing Materials in Marine and Related Environments,” 25th Annual
Conf. of Metallurgists, CIMM, NiDI Technical Series 10,011 (Toronto,Canada: NiDI, 1986), p. 8.
l2 B. Todd, “Materials Selection for High Reliability Seawater Systems,” in The Application of
Copper-Nickel Alloys in Marine Systems (New York CDA, 1991), II1-II14.
l3 InternationalNickel in Metals Handbook-Corrosion, Vol. 13,9th ed. ed. J.R. Davis (MetalsPark,
OH: ASM International, 1987), p. 333.
l4 M.G. Fontana, N.D. Greene, Corrosion Engineering, 2nd ed. (New York McGraw-Hill Book
Co., 1978), p. 76.
l5 T. Smith, ”Metals for Sea-Water Systems,” Anti-corrosion, Sept.(1981):p. 10.
l6 K.D. Efird, “Effects of Fluid Dynamics on the Corrosion of Copper-Base Alloys in Seawater,”
Corrosion 33,1(1977): p. 3.
l7 K.D. Efird, E.J. Wright, J.A. Boros, T.G. Hailey, ”Experimental Correlation of Steel Corrosion in
Pipe Flow with Jet Impingementand Rotating Cylinder Laboratory Tests,” Corrosion/93, paper
no. 81 (Houston, TX: NACE, 1993),p. 21.
l8 A.H. Tuthill, C.M. Schillmoller, ”Guidelines for Selection of Marine Materials,” The Ocean
Scienceand Ocean Engineering Conference, 1965 (TorontoCanada: International Nickel, 1971),
p. 15.
l9 K.R. Trethewey, D.A. Sargeant, “The Galvanic Effect: A Continuing Corrosion Problem,” Metals
and Mater. 7 (1992):pp. 378-382.
*O M.G. Fontana, N.D. Greene, Corrosion Engineering, 2nd ed. (New York McGraw-Hill Book
Co., 1978), p. 33.
21 R. Francis, Galvanic Corrosion: A Practical Guide for Engineers (Houston, TX NACE, 2001),
142 PP.
22 ASTM G 82, “Development and Use of a Galvanic Series for Predicting Galvanic Corrosion
Performance,” Annual Book of ASTM Standards (West Conshohocken, PA: ASTM, 1983),
pp. 357-363.
23 R.S. Treseder, ed., NACE Corrosion Engineer’s Reference Book (Houston, TX:NACE, 1980),
p. 59.
24 A.J. Sedriks, “Corrosion Resistance of Austenitic Fe-Cr-Ni-MoAlloys in Marine Environments,”
Int. Metals Rev. 27,6 (1982),pp. 321-353.
25 S. Valen, E. Bardal, T. Rope, J.M. Drugli, “New Galvanic Series Based on Long Duration Testing
in Flowing Sea Water,” 11th ScandinavianCorrosion Conference, Stavanger,Norway, paper no.
F-63 (1989), pp. 1-7.
26 R. Francis, Galvanic Corrosion: A Practical Guide for Engineers (Houston, TX: NACE, 2001)
p. 10.
27 P. Gallagher, R.E. Malpas, “The Success and Limitations of High Alloy Stainless Steels in Sea-
water Service,” Corrosion/89, paper no. 113(Houston, TX NACE, 1989), p. 13.
A.J. Sedriks, “Review: Advanced Materials in Marine Environments,” Corrosion/93, paper no.
505 (Houston, TX: NACE, 1989),p. 18.
29 R. Francis, ”Galvanic Corrosion-A Practical Guide for Engineers” (Houston, TX: NACE, 2001),
pp. 38 and 96.
3o B. Wallen, T. Anderson, ”GalvanicCorrosionof Copper Alloys in Contact with a Highly Alloyed
Stainless Steel in Seawater,” 10th Scandinavian Corrosion Congress (NKM lo), paper no. 29,
Stockholm (1986),pp. 149-154.
31 B. Krantz, ”Galvanic Effects Accelerate Crevice Corrosion of Type 316L SS Flanges Coupled to
6% MOAlloy,” MP 38‘6 (1999): pp. 72-74.
32 D.K. Peacock, “Connecting Titanium to Other Metals,” MP 37,8 (1998):p. 68.
33 Anon., ”Zircadyne Corrosion Properties,” Teledyne Wah Chang (1986):p. 16.
34 Anon., Con Edison, NACE Network (1999).
35 N. Asrar, SABIC TechnologyCenter, Al-Jubail, Saudi Arabia, NACE Network (1999).
36 S.C. Dexter, J.P. LaFontaine, “Effect of Natural Marine Biofilms on Galvanic Corrosion,”
Corrosion 54,11 (1998):p. 851.
Chapter 5
Metals and Alloys
This chapter describes the common metals and alloys that are used in waters and their
relevant properties. Corrosion resistance and behavior in aqueous environments of the
individual alloys are emphasized.
Various alloys and types of alloys have been ranked on corrosion resistance to sea-
water. Scores from l to 10 were assigned to each metal based on resistance to general
corrosion, pitting, crevice, erosion, cavitation, SCC, polluted seawater, and corrosion
fatigue. The following total scores were calculated (high values mean better overall re-
sistance):
Superduplex stainless steels-72

Superaustenitic stainless steels48
Nickel aluminum bronze (NAB)--66
Duplex stainless steels40
Ni Resist@-57
UNSS31600-53
This does not, of course, mean that superduplex stainless steels are the best choice for
all seawater applications; it merely means that they have a good all-round resistance.
Some of the alloys are more sensitive to certain types of attack than others. For example,
if polluted seawater is not encountered the NAB ranks higher. It should also be pointed
out that galvanic corrosion is not included in this ranking and that can have considerable
effect on the performance of alloys in seawater. In any given application all factors should
be considered to select the best material.'
5.1 FERROUS M E T A L S - C A R B O N , L O W ALLOY STEELS,

A N D CAST I R O N S
Pure iron is a white metal that is soft and ductile with a melting point of 1,535"C. Its
properties are stronglyinfluenced by the presence of impurities or alloying elements. Iron
67
68 Metals and Allovs
is the fourth most common element in the Earth’s crust and the second most abundant
metal. Iron ore was known long before the technology for smelting, developed by the
Hittites in Anatolia, or Asia Minor, in about 1400 B.C. By producing a harder metal than
copper or bronze, the Hittites helped change the tools of agriculture and the weapons of
war. Later, the cementation process was discovered in which iron was hammered and
heated in contact with charcoal to produce a hard iron. The Iron Age began around 1000
B.C. when widespread use of iron weapons and tools began. From about A.D. 1500 coal
began to be used in iron-making but the iron produced tended to be brittle because of
the presence of sulfur and phosphorus. In 1709, Abraham Darby of England first used
coke successfully to smelt iron and in 1784, Henry Cort of England developed puddling
in which air was stirred into the molten iron and the iron run through a rolling mill to
produce wrought iron. At this time only soft wrought iron and brittle cast iron were
being made.
The steel age began around 1860 when the Bessemer converter was developed to
convert molten iron into steel. Since then steel-making has developed in many ways so
that the composition and properties of modem steels can be engineered precisely for
their applications. An incredible range of iron-based alloys is now available, including
carbon steels, cast irons, and stainless steels.2
Carbon steels and cast irons are both groups of alloys of iron and carbon, with im-
portant alloying additions to modify structure and properties. The equilibrium struc-
ture, i.e., the structure resulting from slow cooling, can be determined from an iron-
carbon equilibrium diagram (Figure 5.1). The structures developed are controlled by
the composition and mechanical/heat treatment and will be some combination of the
following:
Ferrite-body-centered cubic (BCC) iron. Ferrite is magnetic, soft, and ductile with
low strength.
Austenite-an interstitial solid solution of carbon in face-centered cubic (FCC) iron.
Austenite is generally unstable below 723°C and transforms into other phases on
cooling.
Martensite-a tetragonal structure caused by distortion of the BCC lattice with a
supersaturated solution of carbon. It is formed when austenite is rapidly cooled to
room temperature and is a highly stressed, metastable phase that is hard and brittle.
Cementite-iron carbide, FeSC, containing 6.67% carbon by weight.
Pearlite-a eutectoid mixture of alternate layers of ferrite and cementite. It is strong
and tough, is the equilibrium product of slow cooling from austenite temperatures,
and contains 0.83% carbon.
Other structures, such as sorbite, troostite, bainite, etc., can be developed by ajustment
of composition or, more usually, by heat treatment. This range of structures means that
a wide variety of mechanical properties can be developed in these steels. Cast irons
have similar structures but, because of their higher carbon content, also have a separate
graphite/carbon phase.
5.1 Ferrous Metals-Carbon. Low Allov Steels. and Cast Irons 69
1600
1200
3
e
f 800
+€
400
0
0 1 2 3 4 5 6 7
Carbon (Wt%)
Figure 5.1 Schematic shows an iron-carbon equi-
librium diagram, indicating the principal phases
formed. (Figure courtesy of CARIAD Consultants.)
5.1.1 Carbon and l o w Alloy Steels
Carbon steels are a series of alloys of carbon and iron containing up to about 1%carbon
and up to 1.65% manganese with elements added in specific quantities for deoxida-
tion (usually silicon and/or aluminum) and residual quantities of other elements. The
total alloy content is generally less than 2%. Low carbon steels, known as mild steels,
contain up to about 0.28% carbon and are probably the most widely used construction
materials.
Low alloy steels have a total alloying element content of less than about 5%, but
more than specified for carbon steel. For many low alloy steels the main function of
the alloying addition is to increase hardenability and improve mechanical properties
after heat treatment. In some low alloy steels, such as chromium-molybdenum steels,
the corrosion resistance is improved compared with carbon steels, particularly at high
temperatures.
70 Metals and Alloys
The principal effects of individual alloying elements in carbon and alloy steels are as
follows:3
Carbon-principal hardening alloying element

Manganesedeoxidizer, desulfurizer, but also contributes to strength and hardness
Silicon-principal deoxidizer
Aluminum-added to complete deoxidation
Phosphorus-impurity that decreases ductility and toughness
Sulfur-usually an impurity except where added to improve machinability
Copper-improves atmospheric corrosion resistance
Chromium-improves depth of hardenability and corrosion resistance, prevents
graphitization
Molybdenum-prevents graphitization, increases high temperature strength
Nickel-improves toughness, response to heat treatment, and corrosion resistance
Vanadium-refines grain size, increases hardenability
Carbon and low alloy steels undergo a transition from ductile to brittle behavior at
some temperature that depends on composition and treatment. Most grades need to be
stress relieved for low temperature use.
5.1.1.1 Corrosion Behavior
Carbon steels are widely used and are common constructionmaterials, particularly in at-
mospheric applications.They are usually painted or coated, which, apart from providing
additionalprotection, also improves the aesthetic appearance that would be diminished
by rusting. Corrosion in dry atmospheres is low but the presence of moisture greatly
accelerates attack, which is the reason for the "time of wetness" concept, i.e., length of
time when samples are wet, in atmospheric corrosion studies. Halides, sulfides, sulfur
dioxide, etc. increase atmosphericcorrosion of carbon steels. The corrosion of mild steel
reinforcement in concrete is a special case that is discussed in Chapter 6, Section 6.2,
"Concrete and Ceramics." Carbon steel is used in boilers for steam production and in
this case the corrosion is largely controlled by the availability of oxygen. This is discussed
in Chapter 11, Section 11.13, "Steam Systems."
Alloy steels exhibit higher mechanical properties than carbon steels because of the
effects of alloying elements such as chromium, nickel, and molybdenum. In severe en-
vironments the corrosion resistance of this group of steels is often no better than carbon
steels. Low alloy steels exhibit superior resistance in the atmospheric and splash/ tidal
zones of marine environmentsbut are of little advantageif fully immersed.High strength
alloy steels used for submarine structural applications include HY-80, HY-100, HY-130,
HY-180, and ASTM A710."
While carbon steel can be subject to pitting or other forms of localized attack, the
majority of corrosion takes the form of general attack and weight loss because environ-
ments that cause pitting also tend to cause rapid general corrosion. In ambient seawater
5.1 Ferrous Metals-Carbon,Low Alloy Steels, and Cast irons 71
general corrosion of carbon steel is about 5 to 16 mpy (0.13to 0.41 mm/y) with a pitting
rate of 10 to 40 mpy (0.25 to 1.02 mm/y), forming pits that are broad and shal10w.~
Since most corrosion is general and carbon steel is comparatively cheap it is appro-
priate to add a corrosion allowance to the design thickness, calculated from pressure and
stress consideration. This allowance consists of the expected corrosion rate multiplied
by the desired life of the equipment. This approach cannot be used if corrosion products
entering the working environment are undesirable or unacceptable.
Factors affecting the corrosion of carbon steels i n ~ l u d e : ~
pH. Acidic solutions (<pH 5) are very aggressive to carbon steels, while alkaline
solutions tend to be less corrosive and can form protective films.
Oxygen content. At ambient temperatures and near-neutral solutions the rate of cor-
rosion of carbon steels is directly proportional to the oxygen content. In deaerated
room temperature water the corrosion rate of carbon steel is negligible, but this rises
linearly up to about 17mpy (0.43 mm/y) at oxygen saturation levels of 6 mL/L.
Temperature. Increase in temperature increases the diffusion of oxygen through the
oxide film and increases corrosion rate. From ambient temperature up to about 80°C
the corrosionrate doubles for every 15to 30°Cincrease in temperature. In open systems
the corrosion rate decreases above 80°C as oxygen solubility decreases.
Dissolved salts. Acid or neutral salts may increase corrosion while alkaline salts may
lower it. When sodium chloride is added to air-saturated water the corrosion rate of
iron will increase up to concentrationsof about 3%NaC1, then decrease linearly until
saturation at 26% NaC1.
Fluid velocity. Increase in solution velocity increases the corrosion rate especially if
chlorides are present. Carbon steel corrodes in fresh water at 10 to 30 mpy (0.25 to
0.76 mm/y) at about 8 ft/s (2.4 m/s). In 10 ft/s (3 m/s) seawater the corrosion rate
will be 30 to 50 mpy (0.76 to 1.3 mm/y).
5.1.1.1.1 Stress Corrosion Cracking
The first identified cases of SCC were in riveted carbon steel boilers that failed by caustic
cracking. The caustic soda used to treat the boiler feed water became concentrated in
crevices at the riveted joints, which were highly stressed.6Causticcracking occurs within
a defined range of temperature and caustic concentrations. For example, at about 10%
NaOH caustic SCC is possible at temperatures >80"C, while at 20% it may occur at
temperatures >60"C.
Carbon steels can be subject to SCC in a number of environments including the
following:
Acidic hydrogen sulfide Amines, aqueous
Anhydrous ammonia Carbonates/bicarbonates
Caustic soda Cyanides, aqueous
Mixed sulfuric-nitricacids Nitrates, aqueous
Sodium-lead molten metal High temperature water
5.1.1.1.2 Microbiologically Influenced Corrosion
MIC was first discovered in underground piping of carbon steel and many authors have
since reported MIC of various grade~.~-'O Galvanized steel is also attacked."*'*
Alloying elements are important in steel resistance to MIC. In low alloy steels the ma-
terial composition, particularly the chromium and molybdenum content, was demon-
strated to be more important for resistance to MIC than bacterial population, incubation
time, sulfide content, or other end products of bacterial g r 0 ~ t h . l ~
Significantcorrelationhas been found between MIC susceptibilityand inclusion size,
shape, chemical stability, and spatial distribution in low alloy steels (AISI 8630 with
varying content of the minor elements Si, S, and Ce). Grain structure and minor phase
fraction of major alloying element content, however, did not correlate with MIC.14
5.1.2 Cast Irons
Like carbon steel, cast irons are also iron-carbon alloys but they contain approximately
1.7 to 5% carbon. Cast irons are classified in a number of ways; common classifications
include the following:
Gray cast iron-cast iron that has a gray surfacewhen fractured because of the graphite
flakes in the structure
White cast iron-cast iron that has a white fracture surface because of the presence of
cementite (Fe3C)
Malleable cast iron-white cast iron that is thermally treated to convert most or all of
the cementite to graphite (temper carbon)
Ductile (nodular or spheroidal graphite, SG)cast iron-cast iron that has been treated
while molten with an element (usually magnesium or cerium) that causes the graphite
to form spheres or nodules
Austenitic cast iron-cast iron with sufficient nickel added to produce an austenitic
matrix
Alloy additions improve mechanical and corrosion properties in the following

ways:I5
Silicon. Common up to 3% in many cast irons, higher levels increase corrosion resis-
tance, especially at >14%,but at these levels the iron is brittle and difficult to produce.
Nickel. Up to 4% nickel, in combination with chromium, improves strength and cor-
rosion resistance. Nickel >12% improves resistance especially to reducing acids and
alkalis and seawater.
Chromium. Small amounts added alone or with nickel or silicon improve resistance
to seawater and weak acids. At levels of 15 to 30% chromium increases resistance in
oxidizing conditions such as in nitric acid.
5.1 Ferrous Metalearbon, Low Alloy Steels, and Cast Irons 73
Copper.Smallamountsincreaseresistance to atmosphericcorrosion, dilutehydrochlo-

ric, acetic, and sulfuric acids, and to mine waters.
Molybdenum. Increases strength and resistance to acidic chlorides.
Both ductile iron and gray cast iron pipe have approximately the same percent car-
bon by weight. In gray cast iron, the carbon is present in the form of flakes intercon-
nected throughout the metal matrix. These flakes create planes of weakness within the
metal that limit mechanical properties, and are responsible for the characteristic low
ductility of gray iron. In ductile iron pipe, carbon is present in the form of discrete nod-
ules or spheroids in a more continuous ferritic structure. Ductile iron is a form of cast
iron with much greater strength and ductility. ANSI/AWWA C151/A21.51 requires the
metal to meet minimum physical characteristics of 410 MPa (60,000 psi) ultimate ten-
sile strength, 290 MPa (42,000 psi) yield strength, and 10%elongation for water piping
applications.I6
Cast irons containing alloying elements are produced for particular applications.For
example, the addition of 11to 14% silicon produces an iron that has outstanding resis-
tance to hot sulfuric acid, although it is brittle. The addition of small amounts of nickel
plus chromium produces the martensitic irons, Ni-Hard@with improved mechanical
properties and resistance to wear. Austenitic gray cast irons with 13 to 38% nickel and
other alloying elements, especially Cr and Cu, are known as the Ni-Resist@ irons and
these have excellent resistance to corrosion as well as low thermal expansion coeffi-
cient. Magnesium, contained in Type 2 Ni-Resist@,converts flake graphite to spheroidal
graphite, improving ductility and impact resistance. Type D2 (ductile)is used in service
requiring resistance to corrosion, erosion, frictional wear, and temperatures up to 750°C.
This type has high thermal expansivity. Trpe D2-W is a modification of the D2 grade,
the W indicating improved weldability, achieved by a small addition of niobium and
reducing the phosphorus and magnesium contents. These alloys are widely used for the
bodies of seawater pumps and valves since they have good corrosion performance and
also provide some galvanic protection to stainless steel components, such as shafts.
5.1 2.1 Corrosion Behavior
Cast irons have similar corrosionbehavior to carbon steelsbut with importantdifferences

related to the form of carbon in the material.
5.1.2.1.1 Pitting and Crevice Corrosion
The presence of chlorides produces conditions favorable to pitting or crevice corrosion

in cast irons. Pitting has been reported in various chemical environments and in calm
seawater. In seawater nickel alloying additions reduce the susceptibilityto pitting. Sim-
ilarly, high silicon cast irons with chromium and/or molybdenum have increased resis-
tance to pitting and crevice corr~sion.'~
5.1 2.1.2 Stress Corrosion Cracking
X C is possible in cast irons but is not common because stresses are kept low by design.
It is too brittle for use in applications where stresses are high. Since unalloyed cast irons
have generally similar corrosion resistance to carbon steels the same environments will
cause SCC in both types of alloy. Environments that may cause SCC in unalloyed cast
irons include the f~llowing:'~
Acidic chloride Acidic hydrogen sulfide

Ammonium nitrate Calcium nitrate
Hydrogen cyanide Mercuric nitrate
Molten sodium-lead alloys Oleum
Seawater Sodium hydroxide
Sodium hydroxide-sodium silicate Sodium nitrate
Sulfuric/nitric acid mixtures
Graphite morphology can play a major role in X C ; for example, gray cast iron can
fail catastrophicallyby SCC in oleum but ductile irons are immune.
5.1.2.1.3 Erosion Corrosion
Fluid flow by itself or in combination with solid particles can cause erosion attack.
Resistance can be increased by increased hardening through solid solution or phase
transformation. Martensitic or white cast iron, being harder, is also more resistant. Cast
irons with better inherent corrosion resistance, such as nickel cast irons, are more resistant
to erosion. The structure of gray cast irons makes them more resistant than steels since the
iron is corroded from the matrix, but the corrosion products are trapped in the graphite
network, thus protecting against further corr~sion.'~
5.1.2.1.4 Graphitic Corrosion
Graphitic corrosion is caused when iron in a gray cast iron is selectively leached out
leaving a network of graphite flakes. The selective leaching or dealloying occurs because
the graphite flakes are cathodic to the iron, setting up an excellent galvanic cell in some
mildly corrosive environments. Typical environments that can cause graphitic corrosion
include soft waters, slightly acidic waters, waters with low levels of hydrogen sulfide
(aslittle as 1ppm), and brackish and other high conductivity waters. In more aggressive
environmentsboth the iron and the graphite are removed and general corrosion0 ~ c u r s . l ~
This type of attack (sometimeserroneously called "graphitization") is often observed on
gray cast iron water piping. The piping can appear to be unattacked while, in fact, the
structure has been seriously damaged. Sometimes the corroded pipe can be adequate
5.1 Ferrous Metals-Carbon, Low Alloy Steels, and Cast Irons 75
for the service since the graphite network, while weaker than the original cast iron, still
has considerable mechanical strength.
Sections of cast iron pipe were tested in soils of varying corrosivity for periods up to
11years and most of the specimens subsequently withstood pressures of up to 3.4 MPa
(500 psi). Cast iron pipe in an advanced stage of graphitic corrosion is therefore able
to withstand the minimum pressure required of Pressure Class 150 psi (1.0 MPa) pipe.
Removal of the corrosion products from the test pipes, however, revealed numerous
holes of various diameters.18It is debated whether nodular cast iron suffers to a similar
extent, but the generally accepted view is that the tightly adherent corrosion product
only remains intact on gray cast iron and that the presence of nodular graphite does not
provide a network to hold the corrosion products together.I5
5.1 2.1.5 Microbiologically Influenced Corrosion
Microorganisms can and do corrode cast iron. This material has been used in laboratory
experiments to determinevarious aspects of MIC processesin aquatic environments.’”’
In another experiment, galvanized gray cast iron electrodes and coupons were corroded
by SRB.=
In the field, buried cast iron water pipes have suffered corrosion, especiallyby SRB in
anaerobic, wet soil environment^.^^ In some cases one quarter inch (0.6-mm)-thickpipes
have perforated in less than a year, although 3 years to perforation is more C O ~ O ~ .
Nodular cast iron impellers on centrifugal pumps in a wastewater treatment plant had to
be replaced six times in 2 years. The localized areas of sulfur concentration and graphitic
corrosion led to the conclusion that MIC was the cause of the corrosion.8
5.1.3 Corrosion of Carbon Steel and Cast Irons in Fresh Waters
Under immersed conditions in natural waters, carbon steels and low alloy steels exhibit
essentially the same corrosion behavior. The concentration of carbon, manganese, sulfur,
silicon, or phosphorus at normal levels has no significant effect on the corrosion rate in
natural or salt waters. Low levels of chromium, nickel, or copper have no clear effect in
neutral waters but can reduce corrosion in seawater.= Unalloyed and low alloyed cast
irons are the primary ones used in waters. Their corrosion resistance is strongly affected
by their ability to form protective scales. In hard water corrosion rates are low, while
in softened or deionized waters corrosion can occur. In industrial waste waters chlo-
rides increase the corrosion rates but the effect is small at neutral pH. Highest corrosion
rates occur in waters at low pH because the evolution of hydrogen tends to prevent the
formation of the protective fih.15
Mild steel corrodes in neutral aqueous solutions by oxygen reduction processes. In
the absence of dissolved oxygen the water itself can act as the oxidizing species:
4H20 + 4e- = 2H2 + 40H- (cathodic)

Table 5.1 Effect of Velocity on Corrosion in Fresh Wates
Velocity ft/s (m/s) Effect on Corrosion

<1 (<0.3) May prevent pitting
-1 (-0.3) Corrosion rate may increase up to 40 mpy (1mm/y) by increasing supply
of oxygen
1-10 (0.3-3) Further increase in oxygen can passivate surface; corrosion rate about
10-30 mpy (0.25-0.76 mm/y)
>15 (>4.6) Turbulence at bends etc. may greatly increase corrosion rate
>>I5 ( M . 6 ) Erosion can occur; corrosion rates up to 200 mpy (5 mm/y) at 39 ft/s
(12 m/s)
The rate of uniform corrosion of unalloyed steel is proportional to the oxygen content of
the water. Dissolved salts such as chlorides and sulfates have no significant influence on
the measured rate of uniform corrosion.26Typical values of uniform corrosion rate are
0.05 to 0.4 mm/y. If the dissolved oxygen is removed by thermal degassing or chemical
addition, the rate is reduced to <0.02 mm/y Oxygen is routinely removed to reduce
corrosion in boilers, in water heating and in secondary water injectionsystems.
Increased velocity in natural water tends to increase the supply of oxygen and in-
creases the corrosion rate of mild steel. However, in treated water increased velocity
tends to decrease corrosion rate by improving the supply of inhibitor. At low velocities,
less than 0.5 m/s, corrosion is possible under deposits unless very effective filtration is
applied. As velocity is increased erosion damage becomes possible especially if particles
are present.%The general effects of velocity on carbon steels in fresh water is shown in
Table 5.1.
Carbon dioxide in fresh water has little effect on corrosion except that it affects the
solubility and precipitation of carbonate scales, which, in turn,can affect general corro-
sion and pitting rates. Hydrogen sulfide can cause rapid attack of carbon steel even in the
absence of oxygen. Between 4.5 and 9.5 pH has little effect on corrosion of steel in fresh
water. Corrosion in alkaline waters tends to be in the form of pitting and tuberculation,
while in acidic waters general corrosion (producing "red water") is more
Galvanized mild steel pipes can last 20 years or more in hard, fresh waters compared
with only 1 to 2 years in seawater. In fresh water zinc is anodic to mild steel and will
provide cathodic protection. Above about 60°C the polarity can reverse and the zinc
can become cathodic. This change in polarity depends on the conditions of the water
and will not happen in deaerated water. Sulfates, chlorides,carbonates, and calcium ions
reduce the likelihood of reversal, while bicarbonates and nitrates increase the probability.
Reversal can OCCLU in distilled water and hard water.
5.1.4 Corrosion of Carbon Steel and Cast Irons in Seawater
Carbon steel and cast iron corrode in seawater at a rate dependent upon the availability
of oxygen or other oxidizing agents. Corrosion of steels in aerated seawater is about
5.1 Ferrous Metals-Carbon. Low Allov Steels. and Cast Irons 77
Table 5.2 Corrosion of Mill-Scaled and Pickled Carbon Steel Specimens31
Pickled Surface Mill-Scaled Surface

Corrosion Rate Max Pit Depth Corrosion Rate Max Pit Depth
Location (rn/Y) (mm) (rn/Y) (mm)
Halifax, Nova Scotia 0.120 1.9 0.110 1.7
Auckland, New Zealand 0.075 1.1 0.085 3.7
Plymouth, England 0.060 1.65 0.060 4.0
Colombo, Sri Lanka 0.090 1.6 0.100 6.1
the same as in aerated fresh water but the higher electrical conductivity of seawater can
lead to increased pitting. Alternate immersion and exposure to air produces more pitting
than continuous immersion. While increasing temperature normally increases corrosion
in seawater, it can cause deposition of scale or reduce oxygen in solution, both of which
can reduce attack.30
Corrosion rates around the world are similar for carbon steel in seawater, but max-
imum pit depth is normally much greater for samples that are covered in mill scale.
Table 5.2 shows data comparing scaled specimens with pickled steel.
The composition of carbon or low alloy steels within normal commercial limits has
no practical effect on the corrosion rates in natural waters. In seawater corrosion rates
increase as carbon content is increased from 0.1 to 0.8%; small amounts of copper have no
effect. Up to 5% chromium in a 0.08% carbon steel was found to decrease weight losses
in seawater in the Panama Canal over a 1-year exposure period. Over longer periods the
chromium-containingsteels corroded more than the chromium-free samples. Up to 5%
nickel in a 0.1% carbon steel did not appreciably change the weight loss in the Panama
Canal trials for up to 16 years. Depth of pitting during long exposures was increased by
the presence of
Carbon steel in the splash zone corrodes at about 16 mpy (0.41 mm/y); below the
surface in quiet seawater it corrodes at 5 to 7.5 mpy (0.13 to 0.19 mm/y) but pitting
rate can be 15 to 40 mpy (0.38 to 1mm/y). The corrosion rate of low alloy steels in the
splash zone can be considerably lower. In quiet ambient seawater carbon steel rates of 4
to 15 mpy (0.1 to 0.38 mm/y) are likely, while at 50°C or higher in agitated seawater it
can be >50 mpy (1.3 m m / ~ ) . ~
Corrosion rate increases continuously with velocity; at 3 m/s the corrosion rate of
carbon steels can be 30 to 50 mpy (0.76 to 1.3 mm/y) depending on amount of turbulence.
Some measured rates for carbon steel in seawater are shown in Table 5.3.
Cast irons in seawater can suffer from graphitic corrosion and they can cause galvanic
corrosion in contact with most other seawater alloys. Carbon steel coupled to stainless
steel can lead to greatly increased corrosion of the carbon steel. A similar increase in
corrosion of the carbon steel can occur when it is coupled to high strength low alloy
steels. Cast iron is initially anodic to low alloy steels and has a potential similar to
carbon steel. As cast iron corrodes, graphite becomes exposed, especially if graphitic
Table 5.3 Corrosion of Carbon Stdeel in Seawater

of Different Velocities3
Velocity in ft/s (m/s) Corrosion Rate (mm/y)
l(0.3) 0.16
4 (1.2) 0.33
27 (8.2) 1.18
corrosion occurs, and the potential shifts in the noble direction. In seawater moving
at 4m/s the open circuit potentials of gray cast iron, ductile iron, and carbon steel are
similar at around 0.61 V SCE. Once corrosion of cast iron has produced a graphite layer
on the surface, the potential can increase by several hundred millivolts.34This can have
a large effect on galvanic corrosion between cast iron and other steels or alloys.
5.1.5 Biodeterioration of Steel and Cast Iron
Destruction of steel by macroorganisms is not usually considered but can occur. The
steel pilings of a pier belonging to the Signal Oil and Gas Company in California were
bored by the sea urchin Strongylocentrotus p u r p u ~ a t u sAbout
. ~ ~ half the 40 piles erected
in 1929 were attacked and the urchins made so many holes in the 3/8-in. (95-mm)
H beams that the lower ends of the flanges separated completely. Damageby sea urchins
of steel H beams of an offshore structurehas also been described elsewhere, but may be
the same case.%
5.1.6 Standards and Specifications-Steels and Cast Irons
5.1.6.1 ASTM
A36/A36M-OOa-Standard Specification for Carbon Structural Steel

A47/A47M-99-Standard Specification for Ferritic Malleable Iron Castings
A126-95(2001)-Standard Specification for Gray Iron Castings for Valves, Flanges,
and Pipe Fittings
A178/A178M-95(2000)-Standard Specification for Electric-Resistance-WeldedCar-
bon Steel and Carbon-ManganeseSteel Boiler and Superheater Tubes
A179/A179M-90a(1996)el-Standard Specification for Seamless Cold-Drawn Low-
Carbon Steel Heat-Exchanger and Condenser Tubes
A220/A220M-99-Standard Specification for Pearlitic Malleable Iron
A278-93-Standard Specificationfor Gray Iron Castingsfor Pressure-ContainingParts
for Temperatures Up to 650°F
A285/A285M-90(2001)-Standard Specification for Pressure Vessel Plates, Carbon

Steel, Low- and Intermediate-TensileStrength
A436-84(1997)el-Standard Specificationfor Austenitic Gray Iron Castings
A439-83(1999)-Standard Specification for Austenitic Ductile Iron Castings
Steel, for Intermediate- and Higher-Temperature Service
Steel, for Moderate- and Lower-TemperatureService
A517/A517M-93(1999)-Standard Specification for Pressure Vessel Plates, Alloy Steel,
High-Strength, Quenched, and Tempered
A536-84(1999)el-Standard Specificationfor Ductile Iron Castings
A571M-&Q(1997)-Standard Specification for Austenitic Ductile Iron Castings for
Pressure-Containing Parts Suitable for Low-TemperatureService
5.1.6.2 EN
CR 10260:1998-Designation systems for steel-additional symbols

EN 10020:200&Definition and classificationof grades of steel
EN 10021:1993-Generaltechnical delivery requirements for steel and iron products
EN 10027-1:1992-Designation systems for steel-Part 1: Steel names, principal
symbols
EN 10027-2:1992-Designation systems for steels-Part 2: Numerical system
5.2 STAINLESS STEELS
In the late 1800sRobert Hadfield experimentedwith increasing the content of manganese

in steel. Small increasesproduced brittle steel, but adding 12%manganese and heat treat-
ing gave a hard, work-hardening alloy. By 1883he had patented his alloy and was now
Sir Robert. Rails made from the manganese steel lasted 22 years instead of the 9 months
for ordinary steel. This was the first recorded development of an alloy Iron alloy
development continued; in 1912 Harry Brierley recognized the superior corrosion re-
sistance of an iron-based alloy containing chromium and this ferritic steel containing
12.8% chromium began to be used to make rustless cutlery. Later he gave this group
of steels the title of "stainless" steels.% Since these early beginnings alloy develop-
ment and steel-making technology have produced a range of stainless steels and related
alloys.
Stainless steels are usually grouped according to their metallurgical structure. The
structure and properties of steels depend on the composition and treatment of the metal.
The basic structures are the same as in carbon steels, i.e., ferrite, austenite, or martensite,
and, as with carbon steels, the addition of alloying elements has a strong influence on
structure and properties. Some elements aid the formation and stability of ferrite; others
do so for the austenite phase. Note the following:
Ferrite stabilizers are Ti, P,V, W, Mo, Al, Cr, Sn, Zr, Si, Nb.
Austenite stabilizers are C, N, Mn, Ni, Cu, Zn.
This effect can be incorporated into equations that calculate chromium or nickel
equivalent in terms of structure.
YO chromium equivalent = %Cr + 2(%Si) + 1.5(%MO) + 5(%V)+ 5.5(%A1)

+ 1.5(%Ti)+ 0.75(%w)
+1.75(%Cb)
YO nickel equivalent = %Ni + %Co + 3O(%c) + 25(%N) + 0.5(%Mn)+ 0.3(%CU)
These equations can be shown graphically in the form of Schaeffler or other diagrams
that permit the equilibrium structure to be calculated on the basis of composition. Such
diagrams are often used to predict the structure in a stainless steel weld.
All stainless steels, to a lesser or greater extent, can suffer from sigma (a)phase
embrittlement. Sigma phase is a hard, brittle intermetallic compound that forms slowly
at grain boundaries when the material is exposed to temperatures in the 560 to 980°C
range. Its presence can significantly decrease the ductility and toughness of the steel and
can also reduce corrosion resistance of some stainless steels under certain environmental
conditions, e.g., austenitic stainless steels in nitric acid. Sigma phase can be removed by
heating to form a! ferrite followed by rapid cooling.
5.2.1 Wrought Stainless Steels
The western world output of stainless steel is estimated to reach 18.5 million tonnes in
2001, exceeding the record level of 17.3 million tonnes in 1999 of which the austenitic
share was 76.4%. The importance of stainless steel in the various regional markets varies,
but with the exception of the United States, stainless steel accounts for 50 to 70% of the
primary nickel c o n s ~ m p t i o n . ~ ~
Wrought stainless steels dominate the market in tonnage terms. They are widely
available in a range of products and forms from many suppliers world-wide. They
are usually categorized by their structure (martensite, austenite, or ferritic) with the
additional categories of duplex (austenite/ferrite) and precipitation hardening.
5.2.1.1 Martensitic Stainless Steels
The simplest stainless steels contain only iron and chromium. Stainless steels with at
least 11.5% chromium plus carbon have an austenitic structure at high temperature that
transforms into the magnetic, ferritic structure when slowly cooled to room temperature.
More rapid cooling transforms the austenite into the martensitic phase. The rate of
cooling needed to form martensite depends on alloy composition. These steels can be
heat treated (tempered) to modify the hard, brittle martensitic properties to produce a
hard but tough alloy. Exemplified by UNS S41000 and UNS S42000, most contain no
nickel and have a carbon content in the range 0.15 to 1.2%. UNS S42000 was the original
cutlery grade, having the ability to keep a cutting edge and be tarnish resistant, i.e.,
stainless. The high carbon grades are used where high hardness and wear resistance are
required. Martensitic stainless steels have only moderate corrosion resistance, so they
have limited applications in corrosive environments. Since they have good abrasion re-
sistance they are used, for example, in mining equipment. They are difficult to weld and
need associated heat treatment as part of welding procedures.
5.2.1.2 Precipitation Hardening Stainless Steels
Precipitation hardening stainless steels were developed for the aerospaceindustry where
high strength-to-weight ratio and good corrosion resistance were needed. This class of
alloy requires careful control of composition and purity to achieve the optimum proper-
ties. Precipitation hardening stainless steels are classified as martensitic, semiaustenitic,
or austenitic grades. The zteel grades, such as UNS S17400 (e.g., Armco 17-4 PH) and
UNS S45500 (e.g., Custom 455), are supplied in the martensitic condition. The finished
component is then subjected to a low temperature aging process that causes precipita-
tion of intermetallic compounds and tempers the martensite structure. In this way the
required hardness and strength are developed. The semi-austenitic grades are supplied
in the austenitic condition and must be transformed to martensite by heat treatment prior
to precipitation hardening. The austenitic grades remain austenitic and are hardened by
the precipitation process.
The higher strength precipitation hardening steels can be subject to hydrogen embrit-
tlement. Corrosion resistance depends on composition and structure but precipitation
hardening steels generally are better than the martensitics and are similar to the austenitic
304 in most environments. These steels find limited applications in corrosive service, for
example, in valve stems, bearing surfaces, pump shafts, etc., where strong, tough, wear-
and corrosion-resistant properties can be exploited.The precipitation hardening stainless
steel, 17-4 PH, has been particularly effective in boat shafts for marine service.40
5.2.1.3 Ferritic Stainless Steels
Because chromium is a ferrite stabilizer the stability of the ferritic structure increases as
the chromium content increases. Stainlesssteels with a chromium content of at least 15%
have a stable ferritic structure. This group of stainless steelsis exemplified by UNS S43000
with 16% Cr. Other ferritic stainless steels have lower chromium content but contain
other ferrite-stabilizing alloy elements. The ferritic stainless steels show a transition
from ductile to brittle behavior over a narrow temperature band. If high levels of carbon,
nitrogen, or chromium are present the transition can occur above ambient temperature.
This effect, combined with a tendency to sensitize from heating, limited the usefulness
of the early ferritic stainless steels and restricted them to thin sections. The modem low
carbon, low nitrogen grades (with or without stabilizing additions) still have limited
toughness and are generally restricted to thin sections. The ferritic stainless steels are
resistant and sometimes immune to chloride stress corrosion cracking. This type of alloy
can be subject to 475°C embrittlement caused by precipitation of a’ chromium-rich phase.
The ferritics are also particularly prone to (T phase precipitation because of their high
chromium and molybdenum contents. Both types of embrittlement can be removed
by heating and rapid cooling. The ferritics have better corrosion resistance than the
martensitic grades but are also difficult to weld.
The standard ferritic grades of stainless steel such as 409430 (UNS90900-S40300),
434, and 444 (UNS 93400 and s44400) contain 11 to 17”/0Cr with C and N levels kept
low to avoid embrittlement. The early superferritic steels were based on 26% Cr, 1%Mo,
and were developed to provide better resistance to chloride SCC than the austenitic 300
series. The modem superferritic stainless steels are based on a 29% Cr, 4% Mo alloy and
+
they also need low C N levels, i.e., less than 0.025%, to avoid intergranular corrosion
caused by chromium depletion from precipitation of carbides and nitrides. Some of the
+
current ferritics contain higher levels of C N and have additions of titanium or niobium
as carbon/nitrogen stabilizers. Trpical superferritic steels include 29-4C (UNS S44735)
and Sea-Cure (UNS S44660). Ferritic stainless steels with at least 27% Cr and 3.4% Mo
are resistant to crevice attack in 25°C seawater!l The superferriticshave excellentpitting
and crevice corrosion resistance and immunity to chloride SCC and have been used for
marine heat exchanger tubing, in some cases replacing the more expensive nickel-based
alloys and superaustenitics.42
Two problems were encountered in the early use of the superferritic stainless steels:
1. Hydrogen induced cracking. It was found that if 29-4C and Sea Cure were polarized
in the range of -0.9 to 1.4 V SCE they could become charged with hydrogen and em-
brittled. The potential of cathodically protected water boxes was restricted to around
-0.8 V SCE.
2. When superfemtic tubes were fitted in 316L tubesheets, the 316L suffered from crevice
corrosion. This produced sufficiently acidic conditions in the crevice to destroy the
passivity on the ferritic tubes. The problem was solved by using more highly alloyed
tubesheets, seal welding, or cathodic pr~tection!~
5.2.1.4 Austenitic Stainless Steels
The addition of nickel or other austenite formers to iron produces an alloy in which the
austenite phase is stable at higher chromium levels. The basic austenitic stainless steel is
18% Cr, 8% Ni (type 304). Austenitics are non-magnetic, ductile, and weldable and are
not heat-treatable but are very susceptible to mechanical work hardening.
The austenitics are by far the biggest group of stainless steels in industrial use. A
wide range of stainless steels has been developed from this basic 18-8 composition by
the addition of other alloying elements. Molybdenum additions improve pitting and
crevice corrosion resistance. Because molybdenum is a ferrite stabilizer, 316 with 2 to 3%
Mo needs extra nickel to maintain the austenitic structure and properties.
The presence of carbon in austenitic stainless steels can increase strength and high
temperature properties but can also cause brittleness and reduce corrosion resistance.
Low carbon grades are commonly used in waters or other environments where corro-
sion may occur, particularly if the equipment is to be welded. Low carbon grades are
designated by the addition of L after the grade in the ASTM system (in the UNS system
low carbon steels have a different number). Another approach to the problems of high
carbon is to stabilizeit by the addition of other alloying elements that have a higher affin-
ity for carbon than does chromium. For example, Type 321 (UNS 91200) has the carbon
stabilized by the addition of titanium;Type 347 (UNS S34700) has the carbon stabilized
by niobium.
Modern steel-making control makes it possible to make low carbon stainless steels
with controlled nitrogen additions so that L grades can now be produced with the me-
chanical properties of the equivalent high carbon, non-L grade. Dual-grade stainless
steels, 304/304L and 316/316L, are also now available and permitted for use in many
applications. ASME has ruled that a dual-grade steel may use the straight non-L grade
allowable stresses for all forms up to 540°C. If this trend continues, the incidence and
likelihood of intergranular attack from carbide precipitation will diminish and demand
for 321/347 will also decrease further. Improved steel-making control also means that
316 can be made more cheaply with the molybdenum content at the low end of the per-
mitted range of 2 to 3%.This can have a serious effect on the corrosion resistance of this
grade of steel. In applications where molybdenum is a key factor in corrosion resistance
a minimum level should be specified or type 317 or 317L, with 3 to 4% Mo, should be
used.44
Localized corrosion of the 300 series stainless steels is the main factor limiting their
use in saline waters. This was also one of the main incentives that led to the develop-
ment of the super stainless steels once the necessary steel-making technology became
available.43Since the mechanisms of crevice and pitting corrosion are closely related the
same metallurgical changes that improve the resistance of stainless steel to one improves
resistance to both. Molybdenum and nitrogen are both very effective in increasing re-
sistance to localized attack in seawater and these alloying elements, together with the
appropriate amounts of chromium and nickel, are the basis of the superaustenitic stain-
less steels. The resistance of these alloys to localized corrosion by chlorides is related
to their composition, which can be indicated by the use of the PRE (pitting resistance
equivalent) number. Experience has shown that alloys with PRE number values greater
than 40 are required for adequate resistance to ambient temperature seawater.45
The superaustenitic stainless steels are typified by alloys containing around 6%
molybdenum and 0.2% nitrogen. Austenitic stainless steels with at least 25% Cr, 5%
Mo, and 0.2% N are resistant to crevice attack in 25°C seawater!l Although some of
these 6% Mo alloys are classified as nickel-based in the ASTM classification system,
they are for all intents and purposes superaustenitic stainless steels. Examples of these
steels include 254 SMO (UNS S31254), AL-6XN (UNS N08367), 1925hM0, and 25-6Mo
(UNS N08926), all of which are now being used to handle high chloride waters in many
industries.46
5.2.1.5 Duplex Stainless Steels
Duplex stainless steels, with a structure containing both austenite and ferrite, were de-
veloped in the 1930s. The early duplex alloys contained high carbon and were found
to have better intergranular corrosion resistance than the existing austenitic stainless
steels. Once low carbon austenitic steels became available in the 1960s the advantage of
intergranular corrosion resistance became less important. The standard duplex grades
generally have higher chromium content than the austenitic grades and so have a better
general corrosion resistance in some environmentsand better resistance to chloride SCC.
As steel-making improved, duplex alloys such as 2205 (UNS S31803) with low carbon
and additions of nitrogen began to be produced. Three ranges of duplex stainless steels,
+ +
based on composition and PRE (where PRE = %Cr 3.3% Mo 16% N), have been
identified:
1. Low alloy duplex, LD, with a PRE <32

2. Moderately alloyed duplex, MD, with a PRE 32-37
3. Super duplex, SD, with a PRE >37
In general, duplex stainless steels are often selected for use in waters in preference to
austenitic stainless steels where there is a concern for the possibility of chloride SCC.47
The modem duplex alloys contain 3 to 4% Mo, 22 to 26% Cr, 5 to 7% Ni, and around
0.2% N and are typified by 2205, 2304, and 2507 (UNS S31803, S32304, and S32750).
Duplex stainless steels with at least 25 Cr and 3.2% Mo are resistant to crevice attack in
25°C seawater!l Of all duplex stainless steels produced, 30% are used in the offshore
industry for platforms, floating production facilities, process equipment, pipes, etc. Of
the current annual tonnage of around 150,000 tonnes, 2205 accounts for about 80% of
the total, with 2507 a further 12%.* Tests in flowing seawater indicated that duplex
stainless steels containing at least 25% Cr, 3% Mo, and 0.15% N can be successfullyused
in seawater systems handling ambient or heated North Sea water!9
Superduplexeshave higher strength than the other super stainless steels, a big factor
in applications where equipment weight is important, e.g., in offshore oil production.
Model heat exchanger tests showed that duplex DP3 tubes allow a maximum process
fluid temperature of up to 100°C with a minimum seawater flow of 0.5 m/s. This cor-
responds to a maximum skin temperature of 80"C.50Proprietary brands of superduplex
stainless steels, such as modified Ferralium 255 (UNS S32550) and Zeron 100 (UNS
S32760), are also being extensively used in seawater systems. Many seawater-cooled
heat exchangers have been successfullymade from alloys such as SAF 2507, which have
better resistance to chloride pitting than lower alloy duplex steels such as SAF 2205
and standard 300 series stainless steels.51Other new duplex alloys with better strength
5.2 StainlessSteels 85
and corrosion resistance are still being developed, although the steel-making and heat
treatment operationsneed to be more tightly controlled than with existingduplex grades.
An example of one of these new grades is Bohler steel no. A920 with 26% Cr, 7”/0Ni, 3%
Mn, 4%Mo, 0.35%N, and a PRE number of 45.&
5.2.2 Cast Stainless Steels
Cast versions of many of the wrought stainless steels are available, although their com-
positions are modified to take account of the properties required by the manufacturing
process. The wrought alloys need to have good hot and cold workability, while the cast
grades need good fluidity. For example, the cast grade may contain extra silicon to aid
liquid flow. The cast grade will have larger grain size, while the wrought version will
have directional properties induced by working.52Cast stainless steels generally have
similar corrosion resistance to the equivalent wrought alloy but corrosion resistance may
be decreased by segregation, lack of homogeneity, or contamination in the casting. The
structure of the cast alloy of an austenitic grade, for example, is likely to contain fer-
rite that increases the strength and improves weldability but can increase susceptibility
to intergranular corrosion. Solution heat treatment may be needed to remove harmful
carbide precipitates at grain b ~ u n d a r i e s . ~ ~
Corrosion-resistant castings are produced with the same range of structures as in
the wrought alloys. Some examples of cast and wrought equivalents are shown in
Appendix B, although, as discussed above, composition and properties may vary
between the two.
5.2.3 Corrosion Behavior
Stainless steels are widely used in corrosive environments in both cast and wrought
forms. They rely on the presence of a passive surface film for their corrosion resistance.
Any factor that damages or removes this film can strongly influence the behavior of the
stainless steel in that environment. For example, chlorides, presence of surface deposits
or crevices, etc. can have a detrimental effect. The stability of the protective film relies on
the presence of chromium in the steel so that removal of chromium from the structure,
e.g., by carbide precipitation, can also decrease resistance. Similarly, because molybde-
num is important in resisting localized corrosion, precipitation of second phases rich in
molybdenum reduces resistance.
Stainless steels are normally resistant to general corrosion by waters so the use of av-
erage weight loss or corrosion allowance is not appropriate.They can, however, be sub-
ject to various forms of localized attack in waters. Factors that influence their corrosion
behavior are levels of oxygen or other oxidizers, chloride ion concentration,conductiv-
ity, contact with other metals (galvaniceffects),crevices, sediment, scales and deposits,
biological activity, chlorination practice, surface condition, pH (5, and temperature.%
86 Metals and Allow
5.2.3.1 Crevice Corrosion
The most common form of attack of stainless steels in waters where chloridesare present
is crevice corrosion. This occurs where crevices are produced, for example, at flanged
joints, welds, deposits, biofouling, etc., as the stagnant solution within the crevice be-
comes depleted in oxygen and becomes acidic from hydrolysis of metal ions.
Hydrogen sulfide stimulates the anodic reaction but at the same time it strongly
reduces the potential of stainless steels in seawater. The overall effect of contamination
of seawater by hydrogen sulfide is to reduce the likelihood of crevice attack on stainless
steels.50Sulfide-containing seawater is less corrosive than natural, but mixed aerobic-
anaerobic conditions may be more aggressive. Sulfide levels of 1 g/L in seawater at
ambient temperatures did not cause crevice corrosion on UNS S31254, S32654, or 316L
after 95 days of exposure. The only corrosion seen was in welds and in the vapor phase
on 316L ~amples.5~
Normally, stainlesssteels are used without any type of coating,but they may be coated
in specific application.For example, antifouling coatings may be applied over anticorro-
sion barrier coatings for seawater service. Testing in natural seawater has demonstrated
that coatings can protect susceptible stainless steel from barnacle-related crevice corro-
sion and localized corrosion at welds. Coating defects and other unintentional or inten-
tional interfaces with bare metal may create new areas for crevice corrosion to initiate.
The risk of serious crevice corrosion damage to the substrate increases with the amount
of bare metal exposed. Tests demonstrated that even a relatively small area of bare stain-
less steel is sufficient to support cathodic reactions able to produce crevice corrosion
penetrations in excess of 2 mm in less than 6 months. Even a 6%Mo alloy was suscepti-
ble in these tests. It was demonstrated that localized corrosion can be prevented by the
use of cathodic protection from sacrificial zinc anodes, but the degree of polarization
contributed to blistering and disbonding of the coating in some cases.%
Corrosion-resistant stainless steels were assessed for Australian naval applications,
such as periscope housings, holding tanks, and fasteners. The crevicecorrosion resistance
of selected stainless steels was compared with the commonly used 316L austeniticstain-
less steel. Two ASTM immersion test methods, G 48 (ferricchloride)and G 78 (seawater),
were used in conjunction with a modified version of ASTM G61 (cyclicpolarization) to
measure the performance of the alloys. Duplex 2507 and austenitic UNS S31254 were
rated the best alloys, marginally superior to another duplex alloy, Ferralium 255 (UNS
S32550).The lower alloyed duplex 2205 also performed well, while of the two relatively
low-alloyed test materials, duplex 2304 appeared to be marginally more resistant than
austenitic 316L.57
In order to increase the resistance of stainless steels to localized corrosion, a mechan-
ical surface treatment or pickling is often applied. The resistance to crevice corrosion in
seawater of the austeniticstainlesssteel AISI 904L and the duplex stainlesssteel 2205 was
investigated after various surface treatments. Most of the mechanical surface treatments
tested did not lead to an improvement in the resistance to crevice corrosion, compared
with the condition "c2" (cold rolled, annealed, brushed, and pickled) as supplied by the
manufacturer. Short pickling also did not improve resistance. However, a combination
of mechanical surface treatment and short pickling led to a significant improvement of
the resistance to crevice corrosion. The positive effect of this combined treatment fulfills
the two requirements for resistance to crevice corrosion. The first is that large defects
present at the surface of the steel as delivered must be removed, which short pickling
does not achieve but mechanical treatment can. The second requirement is the removal
of sulfide inclusions that can initiate localized corrosion, and these can only be removed
by pickling.58
Trials on a range of commercial and experimental stainless steels in syntheticseawater
showed that crevice corrosion is very sensitive to surface finish. A pickled rough surface
was better than either a ground or highly polished surface in resisting crevice attack in
seawater.59Gasket materials were also found to have a strong influence on the crevice
corrosion of cast CF3M and wrought 316 in natural seawater.Gaskets containing carbon
or graphite were found to promote attack, but PTFE and some fiber-filled gaskets had
an even stronger effect. The best gaskets in terms of crevice corrosion were natural and
synthetic elastomers.60
Electrochemicalpolarization measurementswere made on a graphite laminategasket
and a superduplex stainless steel (DSS) in deaerated 1M NaCl solution over a range
of pH. The open circuit potential of the graphite is significantly more noble than that of
the duplex stainless steel and the kinetics of the hydrogen ion reduction are greater at
potentials more positive than -0.0 V SCE. The data were used as input to a model of
crevice chemistry and predictions made for potentials up to +0.4 V SCE. For crevices of
parallel plates of DSSDSS and DSSPlastic, the usual acidic conditions were predicted,
but for a DSSGraphite combination the pH was predicted to be alkaline. The latter is
a consequence of the enhanced kinetics for cathodic reduction of hydrogen ions and
water on the graphite, which, when confined within the crevice, elevate the pH. The
predictions suggest that coupling to graphite, within the crevice, may act to prevent
crevicecorrosion initiation in contrast to the usual perception of behavior when coupling
to more noble materials. In practice, there have been significantcrevice corrosion failures
of superduplex stainless steels associatedwith graphite gaskets. However, in all cases, the
failures were in chlorinated systems for which the corrosion potentials are particularly
high and beyond the range for which a benefit from graphite could be anticipated.6*
5.2.3.2 Pitting Corrosion
The other common form of localized corrosion of stainless steels in chloride-containing

waters is pitting. The mechanisms and conditions under which pitting occurs are very
similar to those for crevice corrosion. Crevice corrosion usually initiates at temperatures
less than those that will cause pitting. For any given alloy the critical pitting temperature
(CPT) will always be higher than the critical crevice temperature (CCT). The alloying
elements that improve resistanceto crevice corrosion,e.g., molybdenum, chromium,etc.,
will also improve pitting resistance.
Tests to investigate the effects of variables on localized corrosion in seawater found

that resistance of the alloys increased with increasing content of nitrogen, chromium,
and molybdenum, the alloy resistance increasing in the order alloy 31 (UNS N08031) >
alloy 24 > alloy 926 (UNS N08926) > alloy 33 (UNS R20033) > 316L.6’
5.2.3.2.1 Pitting Resistance Equivalent of Stainless Steels
The corrosion resistance of stainless steels in chloride-containingmedia is often assessed

by the use of the PRE number (PREN).This is calculated using empirical formulae such
as the following:27
Austenitic stainless steels with t 3 % Mo and for ferritic stainless steels
PRE = % Cr + 3.3 x % Mo
Austenitic stainless steels with = or >3% Mo
PRE = % Cr + 3.3 x % Mo + 30% N

Duplex steels
PRE=%Cr+3.3 x % M o + l 6 % N
Most sources agree on the Cr and Mo effect but some use different multipliers for
nitrogen content.63 Austenitic stainless steels with PRE values >40 are denoted as su-
peraustenitic. PRE values in excess of 40 are sometimes quoted as being the minimum
necessary for seawater use. Other sources suggest that PRE should be equal or greater
than 42 to indicate alloys that have good corrosion resistance in chlorinated seawater.
Zeron 100 alloy (UNS S32760) is claimed to be the only alloy made to a guaranteed
minimum PRE of 40.61
The use of PREs implies that the alloyingelements are to some extent interchangeable
when it comes to resisting pitting and crevice attack. While there is certainly some syn-
ergy between the alloys other factors are involved such as structure, grain size, surface
finish, e t ~ . This
6 ~ simple formula also does not include elements, such as tungsten, which
is present in, for example, Zeron 100 and is believed to have a similar effect to molyb-
denum on the breakdown and repassivation of the protective film.Another formula has
been suggested for calculating PRE when tungsten is present as an alloying element in
the stainless steel:&
+ + +
PRE = Cr YO 3.3 (Mo YO 0.5 W YO) 16 N YO
The effect of alloying elements that are not included in the normal PRE were seen
in an analysis of the correlation between pitting potential in chloride solution and PRE
number. This relationship was linear for the standard grades of stainless steels DIN
1.4306 (Bohler grade A604, equivalent to 304L), 1.4404 (Bohler grade A200, equivalent to
316L), and 1.4539 (Bohler grade A962, equivalent to 904L). Bohler grade P555, which is a
manganese-based austenitic,had a pitting potential much lower than predicted from its
PRE number because negative effects of Mn are not included in the PRE number formula.
Conversely, Bohler P558 (another Mn-based austenitic but with a high [0.2%]C content)
showed a higher pitting potential than would be expected from its PRE number. In this
alloy the carbon has been used to replace nitrogen in the alloy but is not included in the
PRE formula.67
There has been a strong interest in the relationship between PRE number and some
measure of resistance to localized corrosion such as CPT or CCT . Part of the reason for
testing this connection has been to see if these parameters can be related to each other
and to actual service behavior in seawater. It was also important to determine whether
these parameters can be used to specify materials for actual applications,rather than just
ranking alloys in terms of localized corrosion resistance in laboratory tests. It was found
that for austenitic stainless steels this relationship is
CCTG-B = -0.81 + 2.7 (PRE)

+ +
where PRE = Cr 3.3Mo 16N and CCT was determined using ferric chloride and a
method similar to method B in ASTM G 48. Correlations were also developed between
CCT and the tendency for crevice corrosion initiation under a given set of conditions. For
stainlesssteels exposed to seawater at 30 to 32.5"Cthe CCTG-Bis about 35°C irrespective
of whether the stainless steel is austenitic, ferritic, or duplex. It was also found that the
CCT can be related to quantitative measures of crevice corrosion as percentage of sites
attacked or depth of attack. In other words, these parameters can be applied to practical
exposure conditions and give some indication of expected service behavior.68
Another investigation of the correlation of PRE number with CPT found an accept-
able linearity between CPT and PRE calculated using any of the published formulae for
solution-annealed austenitic plate or sheet. The PRE value of stainless plate is a rough
estimate of the pitting resistance and cannot be used to predict the pitting corrosion of
a practical construction. This is because other factors have a strong influence on pitting
behavior in actual applications. These factors include depletion of chromium or molyb-
denum by precipitation, metal production processes, welding, and surface finish. Also,
some alloying elements, such as sulfur, that affect pitting are not included in the PRE
f0rmula.6~The elements that are the most potent in preventing pitting are also those
that promote formation of precipitates. A comparison between CPT and PRE number
for various austenitic and duplex alloys showed a close but not perfect relationship.
Results of CPT and CCT taken from a number of published sources show quite wide
variations (Table 5.4). Some of this variability are presumably caused by factors other
than differences in alloy composition of the samples, i.e., production routes, surface
finish, etc.
The PRE technique does provide a convenient way of ranking alloys based on
chemical composition. In general, the higher the PRE, the higher will be the CPT and
CCT and the better will be the localized corrosion resistance of the stainless steel in
Table 5.4 Typical CCT, CPT, and PRE Numbers for Some Stainless
Steels and Nickel Alloys. Ferric ChlorideTests to ASTM G4848368*7"-n
Alloy Name (UNS No.) cmc cmc PRE
304L (S30403) t2.5-4 19
316L (S31603) t5 4-15 26
317L (S31783) 0 28-35 28
904L (N08904) 15-25 4045 36
254 SMO (S31254) 30-60 65-80 46
654 SMO (S32654) 60+ >100 63
AL-6XN (N08367) 43 78 47
1925hMo (N08926) 40 65-70 46
3127hMo (N08031) 65 9 5 54
2205 (S31803) 17.5-25 2042 34
2304 (S32304) 4-5 15-20 25
2507 (532750) 35-43 55-80 43
255 (S32550) 25 56 35
Zeron 100 (S32760) 67-76 41
Ferralium (S32550) 23-30 40+ 39
Sea-Cure(S44660) 3045 38
29-4C (S44735) 52-55 42
Alloy G (N06007) 25-30 72
Alloy 625 (N06625) 42->50 95
Alloy C276 (N10276) 50-59 >100
chloride-containing waters. However, many other factors are involved and the PRE
alone cannot be used to directly predict the behavior of a stainless steel component in
seawater.
5.2.3.3 Stress Corrosion Cracking
Chloride SCC is a phenomenon that affects stainless steels when exposed to tensile
stresses in the presence of chloride solutions at temperatures between room temperature
and about and 150"C, depending on the pH. At pH 0 to 1 cracking can occur at room
temperature, at pH 3 to 4 cracking only occurs above 40/50"C, and in near neutral envi-
ronments only above about 80"C?3 It is not usually a problem in waters, even seawater,
at temperatures up to boiling. SCC of 316 has not been seen in desalination processes
because the oxygen levels are too low.
SCC is sometimes encountered when cold water evaporates on a hot stainless steel
surface concentrating any chlorides present. Under these conditions external SCC can
occur. This phenomenonis all too common underneath thermal insulation of hot stainless
steel piping and vessel^.^^,^^ This type of external SCC is simulated by drop evaporation
tests using 0.1 M NaC1. This severe test ranked the alloys tested: most resistant UNS
5.2 StainlessSteels 91
926.54 > UNS 912.54 > 904L = 2507 > 2205 = 2304 > 304L = 316L least r e ~ i s t a n tThe.~~
cracks formed on these specimens were transgranular in both the austenitic and duplex
materials, although the crack tip tended to avoid the austenite phase in the duplex alloys.
The cracks are less branched than in classical SCC and the crack walls are significantly
corroded.
The effect of temperature on chloride SCC on duplex stainless steels in severe
marine environments where concentrated chloride solutions may form was studied.
A new test method was developed that simulated the conditions existing when sea-
water is evaporated and concentrated. Safe temperature limits with respect to chloride
SCC for 22% Cr duplex stainless and superduplex stainless steels, valid for all con-
ditions on an offshore platform, were determined as 100 and ll0"C, respectively.
For the austenitic 6Mo grades the safe temperature limit was 120°C. Using this
test method produced chloride SCC in AISI 316L at a temperature between 50 and
60"C.n
5.2.3.4 Intergranular Corrosion
There are two main types of intergranular corrosion that can affect stainless steels, weld
decay and knife line attack.
5.2.3.4.1 Weld Decay
At temperatures above about 1,035"C, all the chromiumin the stainlesssteelis in solution.
During rapid cooling the chromium will stay in solution but if the steel is cooled slowly
chromium carbides become precipitated at grain boundaries. A similar precipitation
process occurs if the stainless steel is held in the temperature range of 425 to 815°C. The
chromium carbide precipitates contain higher levels of chromium than does the matrix
and the area immediately around the precipitate will be chromium depleted and less
corrosion resistant. This area will be preferentially attacked when exposed to a corrosive
environment,often even a mildly corrosive one. This sensitizationto corrosion is known
as weld decay since it is commonly associated with welding. Some area in the heat
affected zone (HAZ) is held in the critical temperature range for carbide precipitation
and renders it susceptible to intergranular corrosion. This process occurs most readily
when welding thick sections where the cooling rates are slower than in thin sheet.
Carbide precipitates can be removed by heating to temperatures above 1,035"C and
cooling rapidly. The problem can also be solved by adding stabilizing elements such as
niobium or titanium (Types 347 and 321, respectively) that have a greater affinity for
carbon than does chromium , The other method of avoiding this type of sensitization
by carbide precipitation is to use low carbon stainless steels. This is the most usual
approach today since it is now relatively easy to produce this type of stainless steel, e.g.,
304L, 316L.
Next Page
5.2.3.4.2 Knife Line Attack
Knife line attack is a related sensitizationto which stabilized stainless steels (e.g., Types
347 and 321) are particularly prone. The stabilizing carbides can be dissolved during
welding and remain in solid solution if the cooling rate is sufficiently fast to pre-
vent their re-precipitation. Subsequent welding passes can cause the precipitation of
chromium carbides and stabilizing carbides in a very narrow zone immediately next to
the weld fusion zone. A narrow "knife line" attack can then occur in this chromium-
depleted zone in some corrosive environments, particularly in hot nitric acid. This
can be avoided by annealing after welding or using a low carbon stainless steel. The
niobium-stabilized Type 347 is less susceptibleto this attack than the titanium-stabilized
Type 321.
5.2.3.5 Microbiologically Influenced Corrosion
In the 1970sand early 1980sfailures of 300 series stainless steel storage tanks and service
piping systems were These were principally 304, but also one case each
of 304L and 316L. These pitting failures under deposits were all diagnosed as MIC.79
Corrosion involved much less weight loss than with carbon steels but the pipes often
failed catastrophically because of the presence of through-wall pits. Since then many
other cases of MIC of 300 series stainless steels have been reported.w82
As with carbon steel, there appears to be a correlation between the microstructure
of austenitic stainless steels and their susceptibility to MIC, with the greatest attack
in chromium-depleted zones.83Pronounced deformation lines in the microstructure of
304 and 316 increases susceptibility to MIC but sensitization does not. High annealing
temperatures to reduce deformation lines may improve MIC resistance.@
There may be a correlation between the stability of the carbides and susceptibility
to MIC by ferritic and martensitic steels. Annealed states may also be more resistant
than quench and tempered states.s3Electrochemicaland metallurgical tests indicate that
martensitic steel, type 420, is less resistant than austenitic stainless steels5
There are fewer data on field cases of MIC in stainless steels other than austenitic.
Floodgate rollers of a martensitic stainless steel, type 420 (13%chromium),in freshwater
in hydroelectric plants failed in 1year when attacked by iron bacteria and SRB.%
Tubing of type 439, a ferritic alloy, in a heat exchanger of a Lake Michigan power
station failed by pitting caused by SOB. After being left stagnant the tubes were filled
with "muck and failed only 6 weeks after in~tallation.~~
Experimental evidence exists that duplex steels are also susceptible to MIC. UNS
S31803and a 25%Cr duplex alloy experiencedboth localized and general corrosionwhen
exposed to marine environments containing SRB.88There are, however, no published
cases of MIC corrosion of duplex alloys in the field.
The case for MIC of super stainless steels is less clear. A number of studies have
demonstrated in laboratory experimentswith sterile controls that various 6% Mo steels
are corroded by microorganism^.^^^ Both superaustenitic (UNS s31254) and superdu-
plex (UNS S32760) stainless steels were found to be susceptible to SRB corrosion,
Previous Page
Figure 5.2 Scanning electron micrograph shows microbiologically induced

pitting in a high alloy stainless steel. Bacteria can be seen in large concentra-
tions in the pit but only sparsely cover the uncorroded surfaces. (Photo courtesy
of CARIAD Consultants.)
including general, localized, and crevice attack. The 6% Mo superaustenitic steel ex-
hibited electrochemical behavior not normally observed in aerated saline conditions.88
Under real operating conditions, however, few studies have demonstrated h4IC of high
alloy steels. Seawater-cooled 904L heat exchangers in North Africa were demonstrated
conclusively to have failed because of MIC94 (Figure 5.2). Another case of MIC of
904L was diagnosed in the Arabian Gulf where localized corrosion under deposits was
attributed to SRB. Energy-dispersivex-ray analysis (EDS) of pit interiors indicated high
sulfur and low silicon and calcium, unlike areas surrounding the pits?5 Sanicro 28 (UNS
N08028) failed prematurely from SRB corrosion under a uniform deposit in the Arabian
Gulf. EDS of pit interiors indicated high sulfur and low silicon and calcium, unlike areas
surrounding the pits?5
One review of case studies concluded that if MIC represents a real threat in the high
performance stainless steels, there would be more reported failures in the field and that,
therefore, super stainless steels may be considered more or less immune to MIC.96
5.2.4 Corrosion of Stainless Steels in Waters
All grades of stainless steel have found some application in waters, including seawater
service. Austenitic grades are the most commonly encountered. Since all stainless steels
rely on the presence of a surface oxide film to provide corrosion resistance, the oxygen
content of the environment and the presence of other oxidizing species are important
factors in their corrosion behavior. Normal seawater has an oxygen content of about
6 to 10 ppm at ambient temperatures and this is adequate to maintain the passive film
on stainless steels as long as the water velocity exceeds about 1.5 m / ~ In ? ~crevices or
under deposits oxygen becomes depleted and localized corrosion is likely even at high
average water flow. Pitting initiateswhen the steel’s corrosionpotential equals the pitting
potential. This condition can arise from elevation of the corrosion potential, for example,
by the presence of strong oxidizers such as chlorine, or formation of a biofilm. It can also
arise from depression of the pitting potential, for example, by increased temperature.
When exposed to alternate wet and dry conditions in the splash zone aeration is good
and passivation is better than when completely immersed and pitting is less likely.
Often when stainless steel is part of a complex system some measure of cathodic
protection is afforded by galvanic coupling to a more active metal such as carbon steel.
This factor is sometimes overlooked when trying to explain differences in corrosion
performance under nominally identical service conditions.
The successful application of stainless steels in seawater is dependent on selection
of appropriate grade, the presence of sufficient velocity or turbulence to prevent depo-
sition, absence of crevices from fabrication and, in some cases, the presence of cathodic
protection from consumable anodes, or galvanic coupling to other components.
The largest application for the superaustenitic stainless steels is in seawater. Tests in
flowing seawater showed that austenitic stainless steels containing at least 6% Mo and
0.2% N can be successfully used in seawater systems handling ambient or heated North
Sea ~ a t e r .However,
4~ there are still areas where the best nickel-based alloys are superior.
To fill this gap an austenitic grade (UNS S32654) with around 7% Mo and higher N, Cr,
and Ni was developed. This alloy has even better resistance to localized corrosion than
the 6% molybdenum superaustenitics. The 6% Mo alloy is unsuitable for use in plate
exchangersin full strength seawater (failures of UNS S31254 seawater plate coolers have
been reported)?8 A limit of 3,000 ppm chloride ions at 40°C has been recommended.
However, UNS S32654 can be used for full strength seawater with 25,000 pprn chloride
at up to at least 50°C.It can also be used at higher chlorine levels and temperatures than
UNS S31254 in flanged piping systems.w
5.2.4.1 Effect of Biofilms and Chlorination in Seawater
When stainless steels are immersed in natural seawater the free corrosion potential
quickly rises in the noble direction and can continue rising over a period of weeks.
This potential rise is not dependent on alloy composition and has also been observed in
other passive metals such as titanium and some nickel-based alloys and in other natu-
ral waters such as brackish or river water. This effect is attributed to the presence of a
microbial slime layer that starts to form immediately on an inert surface. This layer has
a catalytic effect on the cathodic reaction, i.e., oxygen reduction, and thus increases the
cathodic efficiency but has no effect on the anodic reaction. This means that in natural
seawater the risk for initiation of localized or galvanic attack is greater than in sterile or
artificial seawater. The cathodic current density is also much higher in natural seawater
because of the presence of the biofilm. Temperature will have an effect on the biofilm and
thus on the initiation and progress of crevice attack. The risk of crevice attack is likely to
be highest at temperatures just below those required to kill the biofilm, i.e., around 25 to
30°C in northern waters.lW
As chlorine is added at levels sufficient to kill the biofilm or prevent its formation
the potential initially decreases from its unchlorinated level. With further increases of
chlorine the potential then rises, increasing the risk of initiation of pitting and crevice
corrosion.At the same time, removal of the biofilm decreases the cathode current density,
thus decreasing the rate of propagation of localized corrosion. At still higher levels of
chlorine, corrosion will increase as chlorine reduction becomes the preferred cathodic
reaction and is able to support a higher anodic current.@
In the absence of a biofilm the risk of crevice corrosion always increases with in-
creasing temperature. The maximum chlorine level that can be tolerated without initi-
ating crevice corrosion under gaskets in UNS S31254 flanges was determined in tests
in natural seawater for 30 to 100 days. The chlorine levels that initiated crevice attack
were found to be 2 to 5 pprn continuous at 30°C; 2 pprn continuous or >10 ppm inter-
mittent 30 -/day at 35°C; 0.5 pprn continuous at 40°C; or 1.5 to 2 pprn continuous
at 45"C.lo1
Seawater taken from depths of 60 m in the Trondheim Fjord and continuously chlo-
rinated at 0.1 pprn residual or intermittently with 1 pprn for 30 &/day showed no
or very low bacterial activity on exposed stainless steel specimens for periods of up
to 3 months. Even at 0.1 pprn residual chlorine the open circuit potential of stainless
steel was higher than in unchlorinated seawater. While intermittent chlorination also
permitted low bacterial activity the potential remained lower than in unchlorinated
seawater. No corrosion was seen on UNS S31254 or 2507 with chlorine levels up to
0.2 ppm.lo2
Other tests on super stainless steels in flowing, continuously chlorinated seawater at
Trondheimfound that neither UNS S31254nor 2507 suffered crevice corrosion up to 35°C
and 2 ppm chlorine. Under more severe conditions UNS S31254 corroded at 35"C, while
2507 did not corrodeuntil45"C and 10ppmchlorine.These results were all obtained using
samples freshly prepared before the test. It was found that old samples of either material,
i.e., with existing oxide films, did not corrode even at 45°C and 6.5 pprn This
effect of aging has since been confirmed by laboratory tests and field experience and has
been incorporated into startup procedures by a number of companies. For example, the
normal recommendationsfor austenitic steels with at least 6%molybdenum are that their
use in seawater should be limited to 30°Cand 1ppmresidual chlorine. However, if during
startup a new piping system is exposed to unchlorinated seawater at a low temperature
for a week to build up a protective film, the maximum operating temperature can be
increased to 35"C.'04
The potentials of high alloy stainless steels, such as 6% molybdenum austenitic or
the superduplex stainless steels, will vary greatly depending on the conditions of the
seawater. In completely deaerated water their potential will be about -450 mV SCE, but
the addition of 200 ppb oxygen will increase the potential to -100 mV SCE. In the presence
of a biofilm the potential will be +250 to +350 mV SCE, but if the biofilm is destroyed by
heating natural seawater 25 to 30°C above local ambient temperature, then the potential
will be reduced to about +lo0 mV SCE. This potential is also achieved if chlorine is added
in sufficientconcentration(around 0.1 to 0.2 mg/L) to control biofouling.At higher levels
of chlorine, e.g., 0.5 to 1.0 mg/L free chlorine, the potential can reach +500 to +700 mV
SCE. The potential developed is thus very dependent on factors such as temperature,
chlorine or oxygen levels. This will, in turn, influence all aspects of corrosion behavior,
especially galvanic and localized corro~ion.'~~
Where seawater conditions are too severe for the 6% austenitic stainless steel to be
used, the 7% molybdenum austenitic stainless steel, UNS S32654, may be an acceptable
alternative. The effects of seawater on the corrosion potential of this, as on all stainless
steels, depend greatly on the presence of chlorine and oxygen. Corrosion potentials of
UNS S32654 in seawater under various conditions are the following:'06
Natural, with biofilm-around 300 mV SCE

Sterile-->100 mV SCE
Chlorinated-depends on chlorine levels but typically 500 to 600 mV SCE
Deaerated-->lOO mV SCE, depending on temperature and level of oxygen
The effects of high levels of chlorine at the chlorination point were tested with crevice
specimensand samples containing welds. The tests were performed in artificial seawater
with a constant level of 500 ppm total chlorine. Weight loss and penetration depth of
multiple crevice assemblies (MCAs)were greatly increased by chlorination for 316L and
were little affected for a superduplex stainless steel, UNS S32760 (Table 5.5).
The dominant form of attack in both stainless steels was crevice corrosion, mostly
intergranular in the austenitic steel. There was evidence to suggest that high levels of
chlorine (>200 ppm) accentuated the deposition of calcium carbonate and magnesium
hydroxide. There was no increased susceptibility to attack of the weld or HAZ in the
super duplex stainless steel at levels of chlorine up to 500 to 600 ppm.'07
Table 5.5 Weight Loss and Penetration Depth of Multiple Crevice Assemblies in Chlorinated
and UnchlorinatedSeawaterlW
Weight Loss (mg)
Penetration Depth (mm) Is in Brackets
316L UNS S32760
Time (months) Seawater Chlorinated Seawater Seawater Chlorinated Seawater
1 2.7 (0.048) 16.4 (1.50) 0.4 (0) 0.4 (0.011)
2.5 5.1 188.1 0.6 0.5
4.5 7.4 413.5 0.7 0.8
6 7.8 (1.10) 484.7 (4.10) 0.6 (0.012) 0.9 (0.032)
5.2.5 Standards and Specifications-Stainless Steels
5.2.5.1 ASTM
A167-99-Standard Specificationfor Stainless and Heat-Resisting Chromium-Nickel

Steel Plate, Sheet, and Strip
A213/A213M-Ol-Standard Specificationfor Seamless Ferritic and Austenitic Alloy-
Steel Boiler, Superheater, and Heat-Exchanger Tubes
A2401A240M-Ol-Standard Specification for Heat-Resisting Chromium and
Chromium-NickelStainless Steel Plate, Sheet, and Strip for Pressure Vessels
A 743/A 743M-98ael-Standard Specification for Castings, Iron-Chromium, Iron-
Chromium-Nickel, Corrosion-Resistant, for General Application
A 744/A 744M-00-Standard Specification for Castings, Iron-Chromium-Nickel,
Corrosion-Resistant, for Severe Service
A 747/A 747M-Standard Specification for Steel Castings, Stainless, Precipitation
Hardening
A 890/A 890M-99-Standard Specification for Castings, Iron-Chromium-
Nickel-Molybdenum Corrosion-Resistant, Duplex (Austenitic/Ferritic) for General
Application
5.2.5.2 EN
The different grades of stainless steel can be identified by a grade number and a grade des-
ignation; either may be used. The grade number consists of five numbers, e.g., l.xxx. The
1designates that it is a steel, 2 would designate a nickel-based alloy, the next two num-
bers denote that it is a stainless steel of a particular type (e.g., 44 = CrNiMo austenitic),
and the last two numbers denote a particular grade within this steel type. The grade
designation consists of a combination of letters and numbers, eg., X5CrNiMo 17-12-
2. X = a highly alloyed wrought steel (GX = a highly alloyed cast steel), and the 5 =
nominal carbon content, i.e., 0.05% (2 would = the low carbon L grade), and CrNiMo =
the principal alloying elements with the numbers following indicating their nominal YO
content. The EN designations are not exactly equivalent to other standard systems, but
approximate equivalents for some common grades are EN 1.4301 = 304,1.4436 = 316,
1.4404 = 316L.'08
EN 10028-72000-Flat products made of steels for pressure purposes-Part 7 Stain-

less steels
EN 10088-1:1995-Stainless steels-Part 1:List of stainless steels
EN 10088-2:1995-Stainless steels-Part 2: Technical delivery conditions for sheet/
plate and strip for general purposes
EN 10095:1999-Heat-resisting steels and nickel alloys
EN 10272:2000-Stainless steel bars for pressure purposes
EN 10283:1998-Corrosion-resistant steel castings

ENV 1090-6:200O-Execution of steel structure-Part 6: Supplementary rules for stain-
less steel
prEN 10296-2-Welded circular steel tubes for mechanical and general engineering
purposes-technical delivery conditions-Part 2: Stainless steel tubes
prEN 10297-2-Seamless circular steel tubes for mechanical and general engineering
purposes-technical delivery conditions-Part 2: Stainless steel tubes
prEN 10216-5-Seamless steel tubes for pressure purposes-technical delivery
conditions-Part 5: Stainless steel tubes
prEN 10217-Welded steel tubes for pressure purposes-technical delivery
conditions-Part 7 Stainless steel tubes, stainless plate
5.3 NICKEL ALLOYS
Pure nickel is ductile and tough; nickel alloys are readily formed and fabricated by con-
ventional techniques. Nickel can be used alone as a construction material, as a cladding
on a steel vessel, or as a plating on steel or other metallic substrate. It may be plated by
electrochemicalor chemical reduction technique^.^
The use of nickel in stainless steels varies but typically 50 to 70% of the primary
nickel production is used to make stainless steels. In 1999,7.4% of nickel was used as
nickel, 6.5% in Ni/Cu alloys, 33.9% as Ni/Fe alloys, 19.8% as Ni/Cr/Fe alloys, and
28.5 as superalloys.lWOnly about 13% of world production of nickel is used in making
nickel-based alloys.l1°
5.3.1 Wrought Nickel Alloys
The term "nickel alloy" usually means an alloy containing substantial amounts of nickel,
while nickel-based alloys are those in which nickel is the principle constituent, although
not always more than 50%. Some of the alloys included in this section could equally
well have been included with the superstainless steels. Nickel and nickel-based alloys
fall generally into two groups. The first group is often called superalloys and they are
used principally for their corrosion resistance. The second group is used mainly for high
temperature applications and will not be discussed here.
The basic alloy in the group of nickel-containing/super stainless alloys is alloy 800
(UNS N08800). This alloy contains less than 50% nickel and less than 50% iron and was
arbitrarily given the nickel-based UNS ' N designation. Other similar alloys, such as
alloy 825, alloy 20, etc., falling in-between the UNS 'S' and 'N' designations, have also
been given an 'N'number. Many of these nickel alloys were originally patented and/or
developed by commercial alloy suppliers. Since these alloy names are still commonly
known and used they will be included in the following description of alloys, together
with the current generic designation and UNS number.
5.3 Nickel Alloys 99
5.3.1.1 Alloy 200-Nickel
Nickel is more noble than iron but less noble than copper. Pure nickel (UNSN02200) has
good corrosion resistance to cold and hot caustic solutions and to cold-reducing acids
because of the slow discharge of hydrogen from its surface. Corrosion rate in reducing
acids increases rapidly with increasing acid strength or temperature. Nickel does not
develop a very protective passive film so the presence of oxidants in acids or in neutral
aqueous solutions increases the corrosion rate."O
5.3.1.2 Ni/Cu Alloys-Monels
Monel400 (UNS NWOO), also called alloy 400, was the first commercial alloy based on
nickel, developed in 1905. It contains about 30% Cu with up to 2.5% Fe and has high
strength and good corrosion resistance in many aqueous environments."' The addition
of copper to nickel makes it more noble compared to pure nickel so that this type of
alloy has a lower corrosion rate in reducing conditions than nickel and a lower rate of
corrosion than copper under oxidizing conditions. Alloy 400 is especially resistant to
hydrofluoric acid and fluorine-containing media with corrosion resistance, decreasing
with increased temperature or if air or oxidants are present."O
UNS NO4400 is nonheat-treatable and can only be hardened by cold working. The
addition of Al, Fe, and Ti produced alloy K-500 (UNS N05500), which is a precipita-
tion hardening alloy with improved strength, hardness, machinability, and resistance to
galling.
5.3.1.3 Ni/Mo Alloys-B Hastelloys
The first alloy of this type was Hastelloy B (UNS NlOOOl), which is nickel with around
30% molybdenum. It was developed to withstand hydrochloric acid at all temperatures
and concentrations. It has excellent resistance in reducing conditions but corrosion in-
creases rapidly in the presence of oxidizing species. Other Hastelloys of this type, viz.,
B-2 (UNSN10665),B-3 (UNSN10675),and B-4 (UNSN10269), have been developed from
the original B grade with low carbon and better resistance to intergranular corrosion.
5.3.1.4 Ni/Cr/Mo Alloys-C Hastelloys
Hastelloy C (UNS N10002) containing 15.5% Cr, 16% Mo, and 5.5% Fe was the first
Hastelloy introduced commercially in 1932 in a cast form. The high chromium con-
tent gives good resistance to highly oxidizing conditions, e.g., hot, strong H2w4,
and the molybdenum provides reasonable resistance to reducing conditions. Since
then various versions have been developed: C-276 (UNS N10276), C-4 (UNS N06455),
C-22 (UNS N06022), 686 (UNS N06686), 59 (UNS N06059), and C-2000 (UNS N06200)
from this original alloy, with better resistance to localized corrosion and to oxidizing
and reducing acids. This group of alloys also has exceptional resistance to localized
corrosion.
5.3.1.5 Ni/Cr/Fe Al loys-lncoloys and lnconels
The first of these alloys was Incoloy 800 (UNS N08800), also known as alloy BOO, con-
taining 21% Cr, 32% Ni, and the balance Fe. The addition of more Ni together with Cu
and Mo produced alloy 825 (UNSN08825), which has better general corrosion resistance
and is often specified where the 300 stainless steels would be subject to SCC. A cast alloy
containing20% Cr, 29% Ni, 2.25% Mo, and 3.25% Cu was developed in the 1930s.As steel-
making technology developed by 1947it became possible to produce a wrought version
of this alloy and Carpenter 20 began to become commercially available. In 1948,niobium
was added to the alloy to solve problems of chromium carbide precipitation in the HAZ
of welds. In 1963 the nickel content was raised to 30 to 33%. These alloys, now known
as alloy 20 and alloy 2OCb3 (UNS N08020), are similar to alloy 825 with good resistance
to acids, particularly sulfuric and phosphoric and to chloride pitting and SCC.112More
recently the chromium-based alloy 33 (UNS R20033) has been introduced as a possible
seawater alloy with good resistance to crevice corrosion.
Alloy 600, or Inconel 600 (UNSN06600)-containing 77%Ni, 15%Cr, and the balance
F e - is often used in higher temperature aqueous corrosion conditions. Its resistance to
localized corrosion is not particularly good so it can be subject to chloride pitting or
crevice attack. The addition of more Cr and about 8% Mo produced alloy 625 (UNS
N06625) with improved resistance in seawater. The addition of chromium helps reduce
the deleterious effects of sulfur species, but sulfur contamination should still be avoided,
especially if the alloy is to be heated.
Hastelloy G (UNS N06007), or the modem G-3 (UNS N06965) and G-30 (UNS
N06030), is in the same class of alloys but also contains tungsten and more Mo than
alloy 825. It has better corrosion resistance than alloys 400,600, and 825 in many appli-
cations, particularly sulfuric acid and contaminated phosphoric acid. This type of alloy
has better resistance to localized attack than alloys 600 or 825.
5.3.2 Cast Nickel Alloys
Cast nickel alloys generally have similar corrosion resistance to the equivalent wrought
alloy, although their composition may be different because of alloying additions to im-
prove castability and soundness. The corrosion-resistant castings are produced with the
same range of structures as in the wrought alloys. Some examples of cast and wrought
equivalents are shown in Appendix B, although composition and properties may vary
between the
Most of the nickel alloy castings used for corrosion applications need to be solution
heat-treated to minimize segregation and molybdenum precipitation.
5.3 Nickel Allovs 101
Most nickel alloys have excellent corrosion resistance to a wide range of environments.
Some of the alloys have been formulated to have resistance to particular environments,
e.g., strongly reducing ones, and these have limited applicability in oxidizing condi-
tions. Nickel and nickel-based alloys are not generally subject to hydrogen embrittle-
ment, particularly at temperatures below about 200°C. They can be attacked by sulfur
species so it is important to avoid contamination, e.g., with grease, prior to any heating
process.
The resistance to uniform or general corrosion of nickel alloys relies on the presence
of a surface film.This film is improved by alloying with chromium for oxidizing condi-
tions or with molybdenum for reducing conditions. The addition of both chromium and
molybdenum in the same alloy gives better resistance to both conditions.
Compared to stainless steels nickel can accommodate larger amounts of alloying ele-
ments in solid solution, particularly chromium, molybdenum, and tungsten. The effects
of alloying elements on corrosion resistance of nickel-based alloys may be summarized
as f01lows:"~
1. Copper improves resistance to nonoxidizing acids. Alloys with 30 to 40% Cu are

resistant to nonaerated sulfuric acid. Additions of 2 to 3% Cu to Ni-Cr-Mo-Fe alloys
improve resistance to hydrochloric acid.
2. Chromium improves resistance to oxidizing media such as nitric and chromic acids.
Cr also improves resistance to high temperature oxidation and sulfur attack.
3. Iron reduces costs while maintaining strength and toughness.
4. Molybdenum improves resistance to nonoxidizing acids and to pitting and crevice
corrosion.
5. Tungsten is similar to Mo.
6. Silicon is usually only present in small quantities. Larger amounts of Si improve
resistance to hot, strong sulfuric acid.
7. Cobalt has similar properties to nickel and is more expensive so is not a common
alloying element in corrosion-resistant alloys.
8. Niobium and tantalum were used to stabilize carbon but no longer needed for that
purpose.
9. Aluminum and titanium are added in small amounts to tie up residual carbon or
nitrogen.
10. Carbon and carbides-Low carbon is preferred to avoid low ductility carbide for-
mation.
5.3.3.1 Localized Corrosion
Localized corrosion in the presence of chlorides or other halides is increased by the

presence of acidic or oxidizing conditions. Alloying with chromium, molybdenum, and
tungsten improves resistance to pitting and crevice corrosion. Alloys with high levels
of these beneficial elements, such as UNS N10276, N06022, N06686, and N06059, have
good resistance to this type of attack.
Nickel alloys are very resistant to SCC but can be stress cracked in the presence of
chlorides or caustic solutions. SCC resistance is increased by increasing nickel content of
the alloy. Ni-Cr-Fe alloys with more than about 40% nickel are used to replace stainless
steels that have failed by chloride SCC. High nickel alloys, such as alloy 600, with a
minimum nickel content of 72%, have good resistance to chloride SCC. There have been
failures of alloy 600in steam generator applications in nuclear power plants. Alloy 690
(N06690)is now the material normally specified for this service. Most other nickel alloys
can be subject to chloride SCC but under more severe conditions than for the stainless
steels. In aqueous chloride solutions SCC of nickel alloys is promoted by the following
conditions:
Elevated temperatures, especially above 205°C

Chloride contents in the % range
Low pH, usually <4
Aeration or the presence of other oxidizing agents
Presence of H2S
High stress and/or high strength alloys
Caustic SCC is possible with many nickel alloys at elevated temperatures, but UNS
NO2200 is virtually immune and is resistant even in molten caustic soda. Ni/Cu and
Ni/Cr/Fe can suffer from SCC in hydrofluoric acid; Ni/Cr/Fe have also failed by
SCC in high temperature, high purity water in nuclear steam generators. SCC can also
occur in nickel alloys in high temperature hydrogen sulfide environments containing
chloride^."^
5.3.3.3 lntergranular Corrosion
Ni/Fe/Cr and Ni/Cr/Fe can be sensitized by the precipitation of chromium and then
be prone to intergranular attack in highly oxidizing environments. This sensitization
is similar to that occurring in stainless steels and can be prevented by the addition of
stabilizing alloy elements such as titanium or niobium or reduction in carbon levels.
Highly alloyed Ni/Cr/Mo alloys may become sensitized by heating in the temperature
range 649 to 1,038"C, which causes grain boundary precipitation of intermetallic phases
such as p.ll1
In laboratory and field experiments alloy 400 was highly susceptible to SRB attack in both
chlorinated and unchlorinated seawater in the presence of oxygen. Circular cavitieswere
detected below nodules composed of beige (calcareous),green (copperhydroxychloride),
and black (iron-nickel sulfide) 1a~ers.l'~
There have been a number of industrial cases of MIC in various nickel alloys. These
Alloy 400 tubes failed in 3 to 8 months in a refinery heat exchanger using Arabian
Gulf seawater as coolant. Pits formed under multicolored, layered deposits.'16
MIC of Ni/Cu heat exchanger tubes have also been reported in fresh water of pH 7
within 1110nths.l~~
In one case of attack on Ni/Cu heat exchangertubes, large numbers of discretedeposits
contained slime, iron, and manganese-oxidizing bacteria and several million SRB
per pit."*
Moderator heat exchanger tubes of alloy 800 and alloy 400 in nuclear power plants at
Ontario Hydro in Ontario, Canada failed after 2 years freshwater ~ervice''~and the
corrosion mechanism was shown to be MIC underdeposits.'20
An unexpectedly rapid failure of Nickel 201 at 60°C led to the investigation of MIC,
which was concluded to be caused by unidentified thermophilic bacteria.'"
Alloy 22, UNS N06022, a candidate alloy for nuclear waste packaging, suffered pos-
sible MIC attack in groundwater and nonsterile rock.'"
Crevice corrosion by bacteria under marine macrobiofouling organisms (barnacles
and mussels) was observed in Scotland in the high nickel alloy, UNS N06625. Attack
occurred in 18 months but was less severe than on stainless steel alloys.123
5.3.4 Corrosion of Nickel Alloys in Fresh Water
Nickel and nickel-based alloys generally have good resistance to distilled and fresh
water. Typical corrosion rates for commercially pure nickel (Nickel 200) in a distilled
water storage tank at ambient temperature and domestic hot water service are <0.0025
and ~0.005mm/y respectively.
Nickel-copper alloys such as 400 and 405 are used in freshwater service for valve
seats and other fittings. For many freshwater applications there are cheaper stainless
steels that can be used unless nickel alloys are required to prevent pitting or SCC. Alloys
600 and 690 are used to prevent SCC in high-purity water nuclear steam generators.
In steam-hot water systems, such as condensers, appreciable corrosion of alloy 200 and
alloy 400 may occur if C02 and air are present. Deaeration or venting stops this attack
or alloy 600 may be used.lZ4Ni/Cu alloys are generally resistant to waters and they are
used for water meter parts, pumps, valves, etc., and alloy 400 is used in hot-water tanks.
Soft waters can attack Ni/Cu and some fresh waters cause pitting under heat transfer
conditions, i.e., in condensers or cooler^.^
Table 5.6 Stagnant Seawater Exposure at Ambient

Temperature for 3 Years124
Alloy Type Maximum Pit Depth,
(UNS No.) mil (mm)
625 (N06625) 0
825 (N08825) 0.98 (0.025)
K-500(N05500) 34 (0.864)
400 (NO4400) 42 (1.067)
316 (91600) 62 (1.575)
5.3.5 Corrosion of Nickel Alloys in Seawater
Nickel 200, alloy 400, and nickel alloys containing chromium and iron are very resistant
to flowing seawater. In stagnant or low velocity seawater pitting or crevice corrosion can
occur, especially beneath deposits. Alloy 400 is often used for pumps, valve trim and
transfer piping, and as sheathing to protect carbon steel in splash zones of offshore oil
platforms. Alloy 400 can pit in stagnant seawater but pitting usually slows down and
rarely exceeds 1.3 mm in depth. Age-hardenable alloy K-500 is used for high strength
fasteners and pump and propeller shafting in freshwater and seawater applications.
Other nickel-base alloys can offer increased resistance to pitting in stagnant seawater
compared with stainless steels. The depth of pitting of various nickel alloys has been
tested in comparison with 316 in ambient, stagnant seawater (Table 5.6).
In hot seawater applications, such as heat exchangers, alloys 625 or C-276 are some-
times used. Alloys 625,400, and K-500 are often specified by the U. S. Navy for wetted
components in seawater.'"
The nickel alloys, particularly those with molybdenum,are more resistant than many
of the stainless steels. Some results from 30-day tests in filtered natural seawater using
MCAs are shown in Table 5.7. Results for 316 and UNS 91254 are included for com-
parison. It should be noted that these test results were generated prior to 1982 so the
Table 5.7 Crevice Corrosion Tests Using MCA in Filtered Seawater at 3O"ClB
Alloy Type Number of Sites

( U N S No.) %Mo Attacked Depth of Attack (mm)
316 (534600) 2.4 33 0.29-1.93
825 (N08825) 2.7 37 0.25-2.42
G (N06007) 5.8 6 0.02-0.87
254 SMO (S31254) 6.1 18 0.02-0.51
G-3 (N06985) 7.0 2 0.06-0.21
625 (N06625) 8.5 0 0
C276 (N10276) 15.5 0 0
composition of many of these alloys has changed. However, the results do demonstrate
the beneficial effects of molybdenum in resisting crevice corrosion.
The more highly alloyed nickel-based alloys, such as the Hastelloys and Inconels,
have good resistance to seawater and find applications in critical components such as
bellows expansion joints, fasteners, and shaft seals. These alloys are often too expensive
for general seawater applications. They are used, however, as weld overlays or cladding.
Substantial quantities of nickel are used in seawater as alloying elements in copper-
nickels and stainless steels.'26
The nonchromiumnickel-based alloys, such as alloy 400 (UNSN04400) and Hastelloy
B-2 (UNS N10665), are rarely used in seawater heat exchangers. The chromium-bearing
nickel alloys, such as alloy 625 (UNS N06625) and alloy C-276 (UNS N10276), have
outstanding resistance to seawater and can be safely used if they are compatible with
process side conditions and are cost effe~tive.'~~
The U. S. Navy tested several candidate materials for use in seawater butterfly valves
over a 4-year period in a variety of test facilities using various test techniques. C-276
showed crevice/pitting attack up to 4 mil (0.1 mm) depth in an unchlorinated trough
test; in a flow loop test deep etch pitting was observed. Alloy 59 (UNS N06059) showed
some discoloration in some of the loop tests but no significant corrosion. This alloy has
a very high PRE number of 76 so should be a suitable material for seawater service even
in the presence of crevices.'28
The austenitic chromium-based material (alloy 33 UNS R20033), with nominally 31%
Ni, 32% Fe, and 33% Cr with 1.6% Mo, 0.6% Cu, and 0.4% N, has a PRE of 50. Tests
in 10%FeC13.6H20 (pH 1)solution determined a CPT of 85°C. Low segregation in the
matching weld metal means that the CPT of a 5-mm pulsed arc weld seam is only 10°C
lower. Potentiostatic corrosion tests in artificial seawater at 0.3 V SCE with additions of
0.5 M NaCl showed no pitting corrosion at 85°C. Crevice corrosion in artificial seawater
at 0.3 V SCE was not observed at temperatures below 55°C. In saturated CaC12 solutions
at 125°C under constant load conditions the resistance to SCC of this alloy is better
than that of alloy 926 (UNS N08926). The alloy has yield strength 30% above that of
the nitrogen-alloyed 6% Mo stainless steels, so can be used to save weight offshore
structures.'29
Various nickel alloys and stainless steels were tested with and without chlorination in
the Baltic, the North Sea, and the Atlantic to assess their crevice corrosion resistance. The
results from these seawater tests were compared with those obtained in the laboratory.
Laboratory tests showed that the ranking of the alloys was similar in crevice and pitting
tests and that the average CCT is about 20°C less than the CPT. The overall conclusions
drawn from this extensive test program were the following:
316L is highly susceptible to crevice corrosion in seawater.

The 6% molybdenum austenitic stainless steel, 1925 hh40 (UNS N089250), showed
good crevice corrosionresistance in laboratory tests and sufficientresistance in natural
seawater tests.
Alloy 59 UNS NO6059 was judged to be the optimum choice under the most severe
test c~nditions.'~~
imi Metals and Allovs
In loop tests in natural seawater in the German North Sea the following were
found:
317LN, 904L, and alloy 28 (UNS N08028) were susceptible to crevice corrosion at 50
and 70°C.
+
UNS NO8926 and alloy24 (18Ni, 24.5Cr,4.3MorO.6Cu N) showed excellentresistance
to crevice corrosion up to 50°C; at 70°C slight crevice corrosion may occur.
Up to 70°C alloy 31 (UNS N08031), alloy 59 (UNS N06059), alloy 625 (N06625Gr-l),
and alloy C-276 (UNS N10276) were re~istant.'~'
Alloy 400 (UNSN04400) has excellent seawater resistance as long as the water is well
aerated. It has been used for cladding the splash and spray zones of steel jacket and risers
on offshore structures and on the steel piles at the LaQue dock structure, Wrightsville
Beach, NC, more than 35 years ago.
The resistance to corrosion of nickel alloys has been put to good use in marine
engineering for many years. Some applications, such as bolting, require high levels
of strength as well as corrosion resistance. New high strength nickel alloys and their
weldments are resistant to hydrogen embrittlement and seawater corrosion. Solid
solution nickel-based alloys, such as alloy 686 (UNS N06686), obtain their strength
through cold work. Other highly corrosion-resistant nickel alloys such as alloy 925
(UNS N09925) and alloy 725 (UNS NO7725) are precipitation hardened. Both the cold-
worked and the precipitation-hardened alloys have exceptional strength, ductility, and
toughness.132
The behavior of some nickel and other alloys in seawater applications may be sum-
marized as follows:
Alloy 825 (UNS N08825)-susceptible to crevice corrosion when submerged, similar

to 300 stainless steels, but has better SCC resistance.
Alloys 625 and C-276 (UNS NO6625 and N10276)-very good localized corrosion
and SCC resistance. Some susceptibility to crevice attack under very severe crevice
geometries.
Alloy 400 (UNS N04400)-excellent SCC resistance and corrosion resistance in atmo-
spheric and splash zones, pitting in quiescent seawater, some susceptibility to crevice
corrosion.
Alloy K-500 (UNS N05500)-as for 400 but is susceptible to hydrogen embrittlement
under some conditions.
90/ 10Cu/Ni-excellent resistance in atmospheric, splash zones and seawater, upper
velocity limit in tubing/piping applications, excellent antifouling properties, suscep-
tible to sulfide attack.
70/30 Cu/Ni-similar to 90/10 Cu/Ni but higher velocity limit.
NAB-excellent resistance to atmosphere and seawater, but upper velocity limit, fair
antifouling properties.
Ni-Resist@alloy cast iron-same as NAB but no fouling re~istance.'~~
5.4 Comer Allovs 107
5.3.6 Standards and Specifications-Nickel Alloys
5.3.6.1 ASTM
A 494/A494M-00-Standard Specification for Castings, Nickel, and Nickel Alloy

B127-9SStandard Specificationfor Nickel-Copper Alloy (UNSN04400) Plate, Sheet,
and Strip
B163-98a-Standard Specification for Seamless Nickel and Nickel Alloy Condenser
and Heat-Exchanger Tubes
B165-93-Standard Specification for Nickel-Copper Alloy (UNS N04400) Seamless
Pipe and Tube
B 626-01-Standard Specification for Welded Nickel and Nickel-Cobalt Alloy Tube
B 725-93-Standard Specificationfor Welded Nickel (UNSN02200/UNS N02201) and
Nickel-Copper Alloy (UNS N04400) Pipe
B 730-93-Standard Specificationfor Welded Nickel (UNSN02200/UNS N02201) and
Nickel-Copper Alloy (UNS N04400) Tube
B 751-99-Standard Specification for General Requirements for Nickel and Nickel
Alloy Welded Tube
Alloy Welded Pipe
Alloy Seamless Pipe and Tube
B 906-00-Standard Specificationfor General Requirementsfor Flat-Rolled Nickel and
Nickel Alloy Plate, Sheet, and Strip
5.3.6.2 EN
To date the only EN standards existing for nickel alloys are in the field of high temperature
steels and nickel alloys. These are the following:
EN 10095heat-resisting steels and nickel alloys, 1999

prEN 10302 creep-resisting steels, nickel alloys, cobalt alloys, 2001
Other nickel alloys are included in stainless steel standards; see Section 5.2.5.2, "EN."
5.4 COPPER ALLOYS
Copper was first used in its natural ore state as a substitute for stone tools, probably
as early as 8000 B.C. With the introduction of metallurgy between 5000 and 4500 B.c.,
copper was reduced from ore to metal. Egyptians, Sumerians, and American Indians
were among the early users of copper.2
Copper occurs in its native form (especiallyaround Lake Superior in North America)
or as sulfide or oxide ores. It also occurs in combination with other metals such as iron
or nickel. It is usually extracted from the sulfide ore by smelting and from oxide ores
by hydrometallurgical methods. Copper has a melting point of 1,083"C, is the most
malleable and ductile of all metals (except gold and silver), and has high electrical and
heat conductivity.Copper and its alloys are readilyjoined and fabricated and have a wide
range of mechanical properties depending on alloying element present. Most copper-
based alloys cannot be hardened by heat treatment, only by cold work. They have limited
high temperature mechanical properties with poor creep resistance.
5.4.1 Alloys of Copper
There is a wide range of copper-based alloys, many of which have been known since
antiquity. The earliest bronze was probably made by accident since some copper ore
deposits also contain small amounts of tin. When such ore is refined, the metal looks like
copper but is harder and more useful for making tools, weapons, and artwork. Early
metal workers appreciated this improved "copper" and later learned to mix copper and
tin, sometimes with other metals, in different proportions to obtain various desirable al-
loys, thus beginning the Bronze Age around 3500 B.C. Today there are many useful copper
alloys; modem, industrially important ones may be classified as shown in Table 5.8.
The general characteristics of these alloys are summarized in Table 5.9.
The corrosion of copper depends on the presence of oxygen or other oxidizers be-
cause copper is cathodic to the reversible hydrogen electrode in all solutions except
strong acids. This means that hydrogen liberation is not normally a part of the corro-
sion process. The reduction of oxygen to hydroxide ions is the usual cathodic reaction.
The normal anodic reaction produces a film of cuprous oxide which is predominately
Table 5.8 Classificationof Copper Alloys by Type and UNS Numbers"
Name Wrought Alloys Cast Alloy Composition

Coppers C101OO-Cl5815 C80100431200 >99.3%c u
High copper alloys C162OO-Cl9900 C81400432800 >96%CU
Brasses C21000448600 C8330K89940 Cu-Zn, some with Sn, Pb
Bronzes C5010O-C69710 C9020K95900 Cu-Sn, some with P, Pb, Al, Ni,
Fe, Mn, Si
Copper-nickels C9620K96950 Cu-Ni plus Fe
Nickel-silvers C97300497800 Cu-Ni-Zn, some with Pb, Sn
Leaded coppers C9820O-C98840 Cu-Pb
Special alloys C9930K99750
Table 5.9 Characteristics of Classes of Copper alloy^'^.'^

Alloy Type Characteristics
Coppers and high All have similar good resistance to corrosion in seawater and to biofouling but are
copper alloys very sensitive to velocity. The high copper alloys are used where better mechanical
properties are needed, often at slightly elevated temperature.
Brasses These are probably the most widely used group of copper alloys. The resistance to
aqueous corrosion does not change markedly as long as zinc is less than about
15%. Brasses with more than 15% zinc are prone to dezincification and to SCC.
Examples of single phase a brasses (usuallyused in cold worked condition)include
cartridge brass (UNSC26000), admiralty brass (UNSC44300), and aluminum brass
(UNSC68700). Examples of two-phase brasses (usually used hot worked or as cast)
include Muntz metal (UNS C28000) and naval brass (UNS C46420).
Bronzes These have good resistance to impingement attack and better resistance to SCC than
brasses. The tin bronzes are mainly used in the cast condition. Examples include
phosphor bronze (UNS C51100), aluminum bronze (UNS C61300), and nickel-
aluminum bronze (UNS C95800).
Copper-nickels These alloys have the best resistance to aqueous corrosion of all the copper alloys
and are highly resistant to impingement attack and SCC. The two most common
examples are 70/30 Cu/Ni (UNSC71500) and 90/10 Cu/Ni (UNS C70600).
Nickel-silvers These have good resistance to corrosion by fresh water and they are usually much
more resistant to seawater than brasses with similar copper content.
responsible for its corrosion protection. The effect of alloying elements is to reduce the
ionic and electronicconductivity of this oxide film, and to improve the metal’s mechanical
properties.
Copper and its alloys are readily dissolved by nitric acid at all concentrations and by
hot concentrated sulfuric acid, i.e., strong oxidizers. Copper is resistant to dilute sulfuric
acid, up to around 70% at ambient temperature; brasses are subject to dezincification;
aluminum bronzes show reasonable resistance. Copper and its alloys are only attacked
by hydrochloric acid or strong alkalies, such as sodium hydroxide, if oxygen is present.
If oxygen is present they are also dissolved by ammonia or potassium cyanide. They
have good resistance to urban, industrial, and marine atmospheres and waters.
Crevice corrosion of copper alloys in seawater normally occurs outside but immediately
adjacent to the crevice where metal ion concentration cells form. The classic crevice
corrosion by oxygen concentration cells, as in stainless steels, is not usually found
in copper alloys except in those with aluminum or chromium, which form passive
films.
Copper-nickel alloys have good resistance to crevice corrosion and it is rarely found
in these alloys. The 70/30 Cu/Ni (UNS C71640) or the 85/15 (UNS C72200) resists
deposit corrosion better than most other copper alloys. Corrosion can occur under
biofilms or inorganic deposits. In the presence of chlorides copper chlorides can form
beneath the copper oxide layer under the deposit. Sulfates, and to a lesser extent chlo-
rides, can promote intergranular, under deposit attack. Also, brasses are more suscep-
tible to dezincification beneath deposits, particularly in the presence of sulfates and
chlorides.
Pitting sometimes occurs in copper alloys, often spread over the whole of the exposed
surface. Pitting is more likely in seawater at low velocity. The aluminum bronzes with
less than 8%aluminum and the low zinc brasses are most resistant to pitting, while the
copper nickels and tin bronzes have intermediate resistance and the high copper alloys
and silicon bronzes are the most prone to pitting.135
Environmentsknown to cause SCC in copper alloys includeammonia, amines, water, and

water vapor. Moist air, particularly in the presence of pollutants such as nitrates, oxides
of sulfur, mercury, and ammonia, can cause SCC of many copper alloys. Aluminum
bronzes not containing tin are prone to SCC in steam. Chlorides also can cause SCC of
some copper alloys.
SCC of brasses by ammonia is known as season crackingbecause brass cartridges sent
to India for the British troops were noted to crack more often in the rainy season. There is
an apocryphaltale of World War I1 POWs urinating on shellcasesin Japan causing them to
split before or during firing. Ammonia can be caused by bacterial decomposition of moist
organic matter. SCC in copper is usually intergranular but occasionallytransgranular in
admiralty and aluminum brass.
Copper alloys with low resistance to SCC : brasses with more than 15%zinc with or
without small amounts of Pb,Sn, A1
Intermediate resistance: brasses with less than 15% Zn, aluminum bronzes, nickel
silvers, phosphor bronzes
Good resistance: silicon bronzes, phosphorized copper
Excellent resistance: commercially pure copper, copper nickels, nickel coppers
Resistance to SCC in susceptiblecopper alloys may be increased by stress relief heat

treatment.137
SCC of some copper alloys in sulfide-polluted seawater has also been reported. A
slow strain rate study showed that both90/10 and 70/30 Cu/Ni alloys can be susceptible
to SCC in seawater with sulfide levels of 200 to 3,120 ppm. The most severe cracking
was seen with 3,120 ppm sulfide at 25°C. Other studies claim practical immunity for
these alloys under normal conditions. The levels of sulfides chosen for this study were
intended to simulate conditions of the oil spills and oil fires on the marine environments
of Kuwait.'%
5.4.2.3 Selective Leaching or Dealloying
This is the preferential removal of one element from a solid solution by corrosion.
Examples of this form of attack include the following:
Dezincification, in which the brass corrodes, the zinc stays in solution, and the copper
is plated back onto the metal surface. This is the best known example of dealloying. It
can occur uniformly, which is known as layer-type, or locally, called plug-type attack.
The former usually occurs in acid environments, the latter in environments close to
neutral. High temperature and low velocity are accelerating factors. Sometimes this
process increases corrosion resistance to water but the porous, permeable structure
is mechanically weak and mechanical failure often follows dezincification. Brasses
containing less than 15% zinc are usually resistant to this type of attack. Additions
of tin to brasses to form admiralty metal and naval brass increase resistance. Arsenic
(0.02 to 0.1%) added to admiralty metal or aluminum brass also increases resistance
but does not help in two-phase alloys because it does not inhibit dezincification in
the beta phase. Dezincification in susceptible alloys is particularly likely in quiescent
seawater, brackish water, or mildly acidic solution^.'^^
Denickelification, the preferential removal of nickel from the structure, has been
reported on copper-nickel refinery condenser tubes in high heat flux, low wa-
ter velocity ~0nditions.l~ It has also been reported in 70/30 Cu/Ni (UNS C71500)
heat exchanger tubing in stagnant seawater. Dealloying occurred by the process
of dissolution followed by redeposition of copper in Cu/Ni tubing from a naval
~esse1.l~~
Dealuminization, preferential removal of aluminum from copper alloys, has been
investigated in Cu-9Al-2Mn alloy tube. It was found that this alloy can suffer dea-
luminization in a marine environment. The presence of the metastable beta phase
has a negative effect on this process, which starts at the interface of the alpha matrix
and the eutectoid structure and then develops into the eutectoid. The alpha phase
was resistant to the marine environment and there was no evidence for a dissolution
redeposition process.140
At one time it was thought that since copper ions are inherently toxic, copper alloys would
be immune to this type of attack. Although copper is commonly used for its resistance to
macrobiofoulingbecause of this toxicity, it nonetheless appears to be highly susceptibleto
MIC by bacteria. Copper-tolerant strains of bacteria have been discovered. For example,
Thiobucillus thiooxiduns has been shown to be able to withstand concentrations of copper
ions as high as 2%.l18
Several cases of MIC in copper have been reported. Marine copper-tolerant SRB at-
tached to and grew on 90/10 copper-nickel in the 1ab0ratory.l~~ MIC rates for copper were
up to 20 times higher than steel, especially in the presence of reduced sulfur compounds,
and were up to 3 times higher than for sterile controls.'42
A copper-tolerant bacterium, tentatively identified as Oceunospirillum sp., increased
corrosion rates of 99% copper by five times. Copious amounts of extracellular polymeric
substances (EPS)were produced which are believed to immobilizetoxic ions.'43 Bacterial
cells produce different exopolymers in response to increased concentrations of copper
ions in the environment and these exopolymers were capable of binding copper ions in
the solution.'44
Admiralty brass, UNS C44500, heat exchanger tubes were corroded under freshwa-
ter biofilms in experiments that included mass loss testing, polarization resistance, and
electrochemicalimpedance spectro~copy.'~~ Microbiologically produced sulfides are re-
ported to attack Fe and Ni in copper alloys preferentially, giving an effect of dealloying.
In the presence of SRB the improved corrosion resistance imparted by these alloying
elements may be reduced.'& Additional mechanisms of MIC of copper alloys include
ammonium, sulfide, and acid production and underdeposit c o r r ~ s i o n . ' ~ ~
MIC of copper and copper alloys has been found in the field. Examples include:
90110copper/nickel tubes in a heat exchanger experiencedunderdeposit attack under

iron and manganese bacteria."*
90/10 Cu/Ni tubes suffered from MIC in polluted, alkaline (pH 7.2 to 8.8) brack-
ish water. Chlorination further accelerated the rate of corrosion by increasing the
oxidation potential that generated localized attack. This alloy was found to be
very active in this water, a situation made worse by the presence of chlorine or
hypochlorite.la
Admiralty brass condenser tubes suffered ammonia-induced SCC as a result of the
activity of ammonia-producing b a ~ t e r i a . ~ ~ . ' ~ ~
MIC problems have also occurred in copper piping of hot water systems if tempera-
tures were not maintained above 55°C.'50
MIC of copper pipes carrying potable water has been reported in Europe and the
Middle East.15'
MIC of admiralty brass condenser tubes in fresh water in a nuclear power plant in
'
India. 52
5.4.3 Corrosion of Copper Alloys in Fresh Waters and Condensates
In natural waters, oxygen and carbon dioxide react with minerals in the water and
copper to form protective films that reduce corrosion rate. In this case corrosion rate can
be low, 5 to 25 pm/y in most exposures. In distilled or very soft waters these films do
not form and corrosion can be 0.1 to 5.0 mpy (3 to 130 pm/y) or more, increasing with
increasing 0 2 and COz contents. Similarly, in pure condensate the presence of oxygen
and/or carbon dioxide greatly increases the rate of attack on copper and copper alloys.
For example, condensate with 4.6 ppm 02,14 ppm C02, and pH 5.5 at 68°C caused an
average penetration of 175 to 350 pm/y in alloys UNS C12200, C14200, C23000, C44300,
C44500, and C71000. In aerated water, if pH drops below about 5, copper alloys corrode.
In deaerated water, even at low pH, corrosion resistance is g 0 0 d . I ~ ~
Factors that affect the corrosion of copper by potable water include the f ~ l l o w i n g : ' ~ ~
pH. Low pH tends to promote cuprosolvency.

Free chlorine can promote copper corrosion.
Free C02 promotes cold water pitting.
Calcium can form protective film.
Silica can form protective film.
Flow rates. High velocity or local turbulence increases corrosion.
Temperature. If there is no protective film, increased temperature increases corrosion.
Metal ions. Fe, Mn, A1 if > threshold levels cause hot water pitting.
Chlorides may facilitate cold water pitting.
Sulfates may facilitate cold water pitting.
Sulfides may promote pitting.
Copper and its alloys are generally resistant to corrosion by steam and are used
extensively for condensers. Their use in feedwater heaters is less widespread because of
creep and lack of strength at moderately elevated temperatures. Copper-nickel alloys are
preferred at elevated temperatures and pressures. If steam is contaminated by ammonia
or contains appreciable quantities of COz or oxygen, then attack by condensate can
be rapid. Amines, added as inhibitors to prevent corrosion of iron-based alloys, can
decompose to produce ammonia. Wet steam at high velocity can cause impingement
attack.'35
5.4.4 Corrosion of Copper Alloys in Seawater
Copper alloys have been widely used in seawater applications such as condensers, heat
exchangers, piping, cladding of vessels and structures, etc. in many different indus-
tries. For many years it was the primary choice in cases where it was important to
avoid corrosion in seawater. Today, there are alternatives such as the highly alloyed
stainless steels, plastics, nickel alloys, and titanium. However, many tonnes of cop-
per alloys, particularly the copper-nickel alloys, are still used in seawater applications
annually.
5.4.4.1 Effect of Temperature
The data generated by an extensive ASTM corrosion study carried out in the 1980s were
reexamined recently to take into account differences in velocity and environmental con-
ditions. This survey initially gave conflicting results for 90/10 Cu/Ni alloys at different
temperatures. It now seems that the temperature of initial exposure can have a major in-
fluence on the long-term corrosion behavior. Initial immersion in seawater at 18 to 28°C
leads to considerably higher rates of long-term corrosion than exposure at temperatures

either above or below this temperature range.'%
While 90/10 Cu/Ni has been successfully used for cladding in the splash and spray
zones of offshore platforms, it is less likely to be suitable for protecting the outside of
hot risers because of the increased corrosion rate at higher temperatures. Both 90/10 and
70/30 Cu/Ni have found extensive use in seawater heat exchangers because of their
excellent heat transfer and antifouling properties.
5.4.4.2 Effect of Oxygen
Dissolved oxygen may retard corrosion by the promotion of a protective oxide film
but could increase the rate by depolarizing cathodic sites and oxidizing Cu+ to more
aggressive Cu2+ions.Deep ocean tests showed that the corrosion rates of copper and
copper-nickel alloys do not change significantly for dissolved oxygen contents between
1 and 6 mg/L and consequently were not greatly affected by depth in the ocean. This
lack of effect of oxygen content was explained by the presence of the protective oxide
film outweighing the effects from cathodic depo1arization.l3
Much of the interest in the effects of oxygen content on corrosion in seawater comes
from the increase in desalination and secondary oil recovery. In these plants hot, deaer-
ated seawater is one of the primary environments. Deaerated seawater is generally less
corrosiveto some copper alloys than oxygenated seawater. For example, aluminum brass
corrodes at 0.04 mm/y in seawater containing 20 ppb oxygen, but at 0.24 mm/y when
the oxygen content is 200 ppb. These were 90-day tests at 105"C, TDS 35,000 ppm, and
velocity of 8 ft/s (2.44 m/s). In the same tests the change in the corrosion rate of 70/30
and 90/10 Cu/Ni alloys was negligible.126
5.4.4.3 Effect of Sulfides
Low concentrations of sulfide, as low as 10 ppb, can greatly accelerate corrosion of

copper alloys. Some benefit is gained by dosing the water with ferrous ions, usually in
the form of ferrous sulfate, or by use of cathodic protection anodes in the water boxes
if the problem is on the tube side of a heat e~changer.'~~ In the presence of sulfur or
sulfides in polluted seawater the film forming on copper alloys is a mixture of oxide
and sulfide instead of the passive cuprous oxide. Accelerated attack is most likely when
copper alloys are exposed to sulfur-bearingseawater before a protective oxide film has
been formed.
It is not yet agreed whether these sulfide films are harmful once the source of sulfur
has been removed. One source states that the sulfide film is cathodic to the copper
and that any traces remaining will continue to cause pitting even in clean water.'%
Another review found that accelerated attack does not take place unless exposure to
sulfide pollution is followed by exposure to flowing, aerated seawater, or sulfide and
oxygen are simultaneouslypresent.157Others report that sulfide films can be repaired and
Table 5.10 Effect of Pollution on the Corrosion of Copper Alloy Condenser

in Seawater'59
Corrosion Rate mpy (mm/y)
Alloy Clean Seawater Polluted Seawater
90/10 Cu/Ni (C70600) 3 (0.075) 34 (0.86)
70/30 Cu/Ni (C71500) 5 (0.13) 26 (0.66)
2% A1 brass (C68700) 3 (0.075) 22 (0.56)
6%A1 brass (C60800) 5 (0.13) 21 (0.53)
Arsenical admiralty brass (C44300) 13 (0.33) 35 (0.89)
Phosphorus deoxidized Cu (C12200) 14 (0.36) 105 (2.7)
corrosion stopped by subsequent exposure to open, aerated seawater. Sulfide exposure

is shown to increase the corrosion rate on 90/10 Cu/Ni from that in clean seawater. The
clean seawater rate is recovered if the sulfide-exposed sample is then immersed in clean,
aerated seawater for 12 to 13 days.158This effect explains why ships with copper-nickel
onboard condensers can remain in polluted ports for days or weeks without damage.
The sulfide film formed in port is replaced by the protective oxide film within a few days
of the ship returning to the open ocean.
Corrosion rates of copper alloy condenser tubes in clean and polluted seawater
(containing 3 ppm hydrogen sulfide) were measured (Table 5.10). These tests were run
at 2.3 m/s (7.5 fps) for 64 days.
There is general agreement that copper alloys should not be used for applications
which are constantly exposed to sulfur-polluted waters and that it is preferable for the
first exposure to be in clean, unpolluted seawater. Ferrous ion treatments can be used
to protect copper alloy equipment in polluted harbors immediately after fabrication.
Water containing 2 to 3 ppm ferrous sulfate is circulated during the commissioning
period or during exposure to sulfide conditions. Such control methods are ineffective in
the presence of chlorination.lm Ferrous ion treatments may produce surface films that
reduce heat transfer at heat exchange surfaces.
The effects of iron released from consumable anodes on the corrosion of copper-
nickel alloys in sulfide-polluted seawater were investigated. The results suggested that
sacrificial iron anodes should be fitted to Cu/Ni heat exchangers that operate in sea-
waters containing sulfides. Exposure of unprotected Cu/Ni to sulfide delayed or even
prevented the development of a protective film during subsequent exposure to clean sea-
water. If a passive film did not develop, the corrosion rate of 70/30 was approximately
twice as high as the 90/10. Even after initial exposure to sulfides, however, there was
a possibility that the 70/30 could eventually passivate in clean seawater and then the
corrosion rate would be much lower than that of 90/10. The formation of the films was
very dependent on the water chemistry and length of exposure and this could explain
conflicting reports of corrosion results.161
An investigation in the polluted Arabian Gulf seawater found that sulfides have
a strong influence on the galvanic protection of 70/30 Cu/Ni (UNS C71500) tubes
by carbon steel. In unpolluted, warm (45°C) seawater, coupling to carbon steel an-
odes at both ends of the copper alloy tubing provided a steady potential of about
250 mV SCE along the whole of its 6-m length. In the presence of 5 or 10 ppm sul-
fides the potentials achieved were about 100 to 150 mV SCE, also achieved throughout
the tube length. The galvanic protection current demand increased in the presence of
sulfides.162
5.4.4.4 Effect of Chlorination
Accelerated corrosion of some copper alloys, notably admiralty and aluminum brasses,
was found in low velocity seawater tests at low levels of continuous (0.1 ppm) or inter-
mittent (0.5 ppm) chlorine. Similar levels of chlorine reduced corrosion on 70/30 Cu/Ni
but results on 90/10 Cu/Ni were erratic.’@ A literature survey of the effects of chlorine
in seawater found that corrosion rates were not significantly increased by moderately
low levels of chlorine, although in high velocity chlorinated seawater problems were
reported in some alloys, notably admiralty brass.’@
5.4.4.5 Effect of Velocity
Copper-based alloys corrode at a low rate in quiet seawater, generally at less than
0.02 mm/y, with little tendency to pit. This corrosion rate remains fairly constant with
velocity until a certain critical velocity is exceeded when intense local corrosion, im-
pingement attack, occurs. The critical velocity varies with alloy type and composition,
for example, the critical velocity for 70/30 Cu/Ni is about 4 m/s and for pure copper is
about 0.5 m/s.la
Additions of iron to copper-nickel alloys and aluminum brass improves the pro-
tective nature of the film by decreasing its electronic and ionic conductivity. Additions
of iron to Cu/Ni, however, can decrease resistance to pitting. The alumina film which
forms on A1 bronzes and A1 brasses increases resistance to erosion and impingement
attack.
The need to improve resistance to impingement attack led to the development of
the copper-based alloy UNS C72200, containing approximately 16% Ni and 0.5% Cr.
Results of numerous impingement and erosion corrosion tests of copper, admiralty, and
aluminum brass, 90-10 and 70-30 copper-nickel, and the chromium-containing copper-
nickel alloy led to industry-accepted design velocity limits for condenser tubing.’@
(See Chapter 10, “Water Systems.”) Experience has shown that 90/10 Cu/Ni can be
used in condensers and heat exchangerswith velocity up to 2.5 m/s; the 70/30 alloy can
be used up to 3 m/s. Higher velocities can be used in larger-diameter pipes; maximum
recommended velocity is 3.5 m/s for 90/10 in 100-mm and larger-diameter pipes and 4
m/s for 70/30. These flow rates are conservativeand based on continuous flow. For pipes
with intermittent or occasional flow, such as fire mains, velocities up to 12 to 15 m/s are
acceptab1e.ll8
While high velocities can cause damage to copper alloys, low velocities can also cause
problems. At less than about 1m/s there is time for even light mud and sediment to settle
and lead to underdeposit corrosion. The minimum design velocity should be 1.0 m/s
with a normal design velocity of 2.0 m/s. Inlet end erosion of heat exchanger tubing can
be caused by turbulence in the inlet water box if it is too small to handle the volumes
going through an exchanger.
The effect of abrasion by sand has been investigated but is difficult to quantify. Sand
loadings of less than 200 pprn rarely damage good protective films on copper-nickel
alloys. Very fine sand (t0.05 mm) loadings are tolerable up to about 1,000 ppm. Larger-
diameter and harder sand particles tend to be increasingly abrasive to the film in the
200- to 1,000-ppmrange. UNS C71500 has somewhat greater tolerance for sand than UNS
C68700. For sand loadings above 1,000 pprn and for larger particle sands in the 200- to
1,000-ppm range, UNS C71640 has proved very resistant in shallow water estuaries and
in shallow water intakes of desalination plants along the Arabian Gulf. UNS C72200
would be expected to resist sand abrasion quite well, also. The ranking of most to least
resistance is UNS C71640 > C72200 > C71500 > C70600 > C68700.
Silt or mud has no abrasive effect on the corrosion film, but can be very damaging if
allowed to deposit in tubing and remain in place over substantial periods of time. Silt
tends to be swept through the tubing when the units are operated near normal design
velocities of 2 m/s. At lower velocities, the amount of silt deposited is a function of the
settling rate, the actual velocity, and the length of the tube. At velocities below 1 m/s,
experience has shown that corrosionfailurescan be expectedwithin 6 to 12months unless
frequent cleaning is successful in removing deposits before underdeposit corrosion is
initiated.165
A test program using a condenser tube rig in polluted seawater in the Arabian
Gulf compared erosion corrosion of 70/30 and 90/10 Cu/Ni alloys, and the nickel-
based alloys UNS S32550, N06022, and N06030. It was found that the nickel-based al-
loys performed better than the copper-based alloys and the nickel-copper alloys. The
90/10 Cu/Ni alloy had poor resistance to erosion corrosion at room temperature and
at 45°C in seawater with and without up to 3 pprn sulfide ions. Both types of Cu/Ni
alloys were less susceptible to erosion corrosion in warm seawater with 5 pprn sulfide.
70/30 Cu/Ni was prone to pitting and crevice attack and UNS NO4400 suffered from
pitting in low flow areas, agreeing with practical experience in this area. For the alloys
tested the erosion corrosion resistance was ranked as UNS NO6030 > S32550 > NO4400 >
70/30 Cu/Ni > 90/10 Cu/Ni.'"
5.4.5 Standards and Specifications-Copper Alloys
5.4.5.1 ASTM
B 75M-99-Standard Specificationfor Seamless Copper Tube

B171/B 171M-99el-Standard Specificationfor Copper Alloy Plate and Sheet for Pres-
sure Vessels, Condensers, and Heat Exchangers
B 224M-98-Standard Classification of Coppers

B 251M-97-Standard Specificationfor General Requirements for Wrought Seamless
Copper and Copper Alloy Tube
B 315M-99-Standard Specificationfor Seamless Copper Alloy Pipe and Tube
B 369M-96Standard Specification for Copper-Nickel Alloy Castings
B 395M-95-Standard Specification for U-Bend Seamless Copper and Copper Alloy
Heat Exchanger and Condenser Tubes
B 447M-00-Standard Specificationfor Welded Copper Tube
B 466/B466M-98-Standard Specificationfor Seamless Copper-Nickel Pipe and Tube
B 467M-88(1997)-Standard Specificationfor Welded Copper-Nickel Pipe
B 543M-96-Standard Specification for Welded Copper and Copper Alloy Heat Ex-
changer Tube
B 601M-99a-Standard Practice for Temper Designations for Copper and Copper
Alloys-Wrought and Cast
B 608M-9SStandard Specificationfor Welded Copper Alloy Pipe
B 706M-00-Standard Specification for Seamless Copper Alloy (UNS No. C69100)
Pipe and Tube
5.4.5.2 EN and I S 0
I S 0 designates alloys using a compositional system (IS0 1190Pt 1)based on the element
symbols and the descending order of magnitude of alloying elements; e.g., a leaded
brass containing 60% Cu and 2% Pb is designated CuZn38Pb2. This system can be un-
wieldy when used to describe complex alloys with many alloying elements, but it has
been widely adopted throughout Europe. I S 0 proposed an alternate designation system
( I s 0 Technical Report No, TR 7003, "International Numbering System for Metals") us-
ing an alpha-numerical series of numbers easily understood by computers. While this
system was not adopted by I s 0 it was used as a basis for the EN standards. A six-digit
system is used with C as the first letter, indicating a copper alloy. The second letter indi-
cates the material state (i.e., W for a wrought material, B for ingots, C for castings, and M
for master alloys). Three numbers are then used to identify the material and a final third
letter is used to identify the classification of individual copper material groups and to
enlarge the capacity. This also prevents confusion with the existing BSI designations and
the old C/three-digit CDA numbers administered by Copper Development Association,
New York.
This system will include both CEN materials and nonstandard materials, but initial
allocations have been made for the numbers to ensure a minimum of confusion within
CEN-preferred materials. This means that not every material subgroup starts at number
"1"; while coppers do start at 001, miscellaneous copper alloys start at 100, copper alu-
minum alloys start at 300, copper-nickel alloys start at 350, copper-zinc alloys at 500, and
so on. An example would be wrought 70/30 Cu/Ni, which is designated CuNi30MnlFe
in the I S 0 system and CW 354H in the CEN system.
5.5 Aluminum Allovs 119
Tempers are designated using a system similar to that for the German DIN standards.
This indicates the minimum value of specified properties. For example, tensile strength
R 250 indicates a minimum of 250 N/mm2, while a hardness of H090 indicates a value
of 90 (Vickers for wrought materials and Brinell for cast) and Y140 indicates a minimum
0.2% proof stress of 140 N/mm2. The letters designating the relevant properties are
A-elongation, B-spring bending limit, G-grain size, H-hardness (Brinell for cast-
ings, Vickers for wrought products), M-(as) manufactured, i.e., without specified me-
chanical properties, R-tensile strength, Y-0.2% proof stress.'67
CR 12776:1997--Copper and copper alloys-provisions and procedures for the allo-

cation of material numbers and registration of materials
CR 13388:199Hopper and copper alloys+ompendium of compositionsand prod-
ucts
EN 1173:1995-Copperand copper alloys-material condition or temper designation
EN 12449:1999--Copper and copper alloys-seamless, round tubes for general
purposes
EN 12452:1999<opper and copper alloys-rolled, finned, seamless tubes for heat
exchangers
EN 1412:199Mopper and copper alloys-European numbering system
EN 1981:1998-Copper and copper alloys-master alloys
5.5 ALUMINUM ALLOYS
Aluminum, also known as aluminium, is the most plentiful metal in the Earth's crust.
As a silicate or oxide compound it is found in every clay bank and in most common
rocks. Nearly all aluminum is produced from bauxite (a name derived from Les Baux-
de-Provence,France, where it was first discovered).Bauxite contains hydrated alumina,
A1203-2H20,usually combined with impurities of iron, silicon, and titanium oxides.
The ore is found in most countries, but the major deposits are in Guinea, Jamaica, and
Surinam. It has also been extensively mined in France, Italy, Greece, and Australia.
Although people have used alum, a naturally occurring aluminum compound, since
biblical times, its chemical identity was not discovered until 1746, when the German
chemist Andreas Marggraf proved that alum has as its base an unknown metal that
is now called "aluminum." Many attempts were made to isolate the metal but it was
not until 1886 that Charles Martin Hall of the United States and Paul-Louis-Toussaint
Heroult of France developed independently a method, still used today, of dissolving
alumina in molten cryolite (Na3AlF6)and reducing it electrolytically.*
Aluminum is white, soft, and nonmagneticwith a face-centered cubic structure. It has
a melting point of 658.7"C, a density of 2.7 g/cm3, and excellent electrical and thermal
conductivity.It is a highly reactive metal that oxidizes readily. The wrought alloys exhibit
a high degree of anisotropy,i.e., properties that are different in different directionsrelated
Next Page
to mechanical working. This anisotropy has a major influence on mechanical test results
and also on corrosion behavior, particularly SCC.
Commercially, pure aluminum is rarely used in corrosive environments; it is mainly
alloys that are of industrial importance. The influence of various alloying elements on
corrosion resistance is as follows:'68
Copper greatly reduces corrosion resistance leading to greater general corrosion; also
leads to a higher incidence of pitting but can reduce rate of pit penetration.
Iron has a detrimental influence on corrosion resistance; probably most common pro-
moter of pitting; iron with nickel is added to special alloys to increase their resistance
in very hot water (150 to 250°C).
Nickel tends to reduce corrosion resistance but is added with iron for hot water
applications.
Manganese has a slight beneficial effect.
Magnesium has a beneficial effect, especially in alkaline solutions.
Chromium has beneficial influence, especially on SCC for certain alloys.
Zinc has slight influence, tends to reduce resistance in acid media, and increases
resistance to alkalis.
The common groups of wrought aluminum alloys are the f~llowing:'~
lxxx-Pure A1 (99.00% or greater), good corrosion resistance, reduced by the presence

of impurities
2xxx-Al-Cu alloys, not particularly good corrosion resistance, used where high
strength needed
3xxx-Al-Mn alloys, good corrosion resistance
4xxx-Al-Si alloys, generally good resistance
5xxx-Al-Mg alloys, good in marine applications and some alkaline solutions
6xxx-Al-Mg-Si alloys, moderately high strength and corrosion resistance
7xxx-Al-Zn alloys, high strength, used for structural members; least resistant to SCC
and exfoliation
A similar range of cast alloys exists, although the designation system is different from
that for wrought alloys. See Section 5.5.4 for details.
The mechanical properties of aluminum alloys are strongly influenced by the alloying
elements present, but also by applied heat or mechanical treatments. These treatments
are known as tempers and range from fully annealed to fully hardened by strain or
heat treatment depending on the specific alloy. These tempers also influence corrosion
resistance.
In chemical plants where there is risk of explosion or fire, contact between aluminum
and rusty steel should be avoided, as this can produce sparks through a thermit reaction.
This is the strongly exothermic reaction between aluminum and metal oxides that is the
basis of thermit welding that has been used to join massive metallic structures and was
used to weld tram rails together in situ.
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5.5 Aluminum Allovs 121
Aluminum is a thermodynamically reactive metal and owes its corrosionresistance to the

presence of a barrier oxide layer that is strongly bonded to the metal. On a freshly rolled
aluminum sheet the film is extremely thin, about 25 A. The film is thermodynamically
stable over a pH range of 4.5 to 5.5 but the presence of certain anions and cations affects
stability.When aluminum is immersed in water the oxide film thickensmore rapidly than
in air. For example, commerciallypure aluminum immersed in distilled water for 20 days
developed a film thickness of 55,000 A. Water purity affects film growth and the same
alloy immersed in alumina-saturated Kingston (Ontario, Canada) tap water for 22 days
developed a f ilm of only 4,800 A. Within the passive range general corrosion is not
usually encountered; any corrosion occurring under these conditions is predominantly
pitting. Outside this range of passivity general attack can occur in environments (such
as strong alkalis or acids) that dissolve the surface oxide since the oxide can dissolve in
either, i.e., aluminum is an amphoteric metal.'@
5.5.1.1 Pitting
Because aluminum depends on a protective film for resistance it is susceptibleto localized

attack. Pitting occurs at sites of local film breakdown. Resistance depends on purity, with
pure aluminum being the most resistant with the alloy groups listed below in decreasing
order of resistance, as follow^:'^
lxxx
5xxx
3xxx
6xxx
7xxx (must be clad)
2xxx (also must be clad)
Rate of penetration of pits in aluminum falls off rapidly with time in a cube root
relationship. This time/penetration relationship has been determined in laboratory ex-
periments and confirmed in field experience, for example, in a 13-year exposure of a
2,000-ft (610-m)-long industrial water pipeline. This can be further illustrated by the
case of the thin gauge aluminum (0.020 in., 0.51 mm) activated by etching in phosphoric
acid, that perforated in Kingston tap water in 1week. Thicker sheet and plate from the
same ingot developed a maximum pit depth of only 62 mil (1.6 mm) in 10 years. This
type of relationship also applies to pitting in seawater.As temperature increases both the
density and probability of pitting increase, while the pitting rate decreases. The initiation
and rate of pitting are influenced by velocity of water. In Kinston tap water 8 fpm (0.04
m/s) was sufficient to completely suppress pitting of pure aluminum. Water movement
is thought to be beneficial because it increases the supply of oxygen to the surface and
removes the acidic or alkaline species from corrosion sites.'@
Pitting does not usually occur in fresh water with or without oxygen unless some
alternate cathodic reaction is available. Pitting is most often initiated by the presence
of halides which reduce the pitting potential. The pitting potential can be exceeded if
oxygen is present or some other cathodic reaction is available. In the absence of halides
pitting does not occur in aerated solutions because the pitting potential is higher and the
metal is not polarized to these potentials in normal service.'69
5.5.1.2 Crevice Corrosion
Crevice corrosion is not common in aluminum alloys but can occur in seawater where
the form of attack within the crevice is usually pitting and rates are low. Alloys that are
most resistant to general corrosion are also least likely to suffer crevice attack. In fresh
water, crevice corrosion of aluminum is negligible.'@
5.5.1.3 Galvanic Corrosion
Intimate contact between aluminum and more cathodic metals should be avoided in any
environment in which aluminum alone would be subject to pitting. Because aluminum
is at the active end of any galvanic series, the electrochemical driving force can be large.
Aluminum can be safely coupled to zinc, cadmium, and chromium under all normal
circumstances. Zinc tends to be protective while cadmium and chromium are almost
neutral. Titanium and stainless steel are next in terms of effect, followed by steel and
lead. Contact with copper, nickel, and their alloys should be avoided.'@
5.5.1.4 Deposition Corrosion
Ions of several metals have reduction potentials that are more cathodic than the solution
potential of aluminum, so they can be reduced to metallic form by aluminum. This can
lead to severe localized corrosion of the aluminum by the development of galvanic cells.
Copper, lead, mercury, nickel, and tin are the metals most usually involved. The effects
of these metals are particularly severe in acidic environment^.'^
5.5.1.5 Intergranular Corrosion
The extent to which intergranular corrosion is a problem will depend on the actual
aluminum alloy involved (alloys containing copper are especially susceptible),its heat
treatment, temperature, and the environment to which it is exposed. Different alloys
are attacked along different anodic paths depending on the differences in composition
between the grain boundaries and the adjacent regions.
A special case of concern is the use of aluminum alloy load-bearing equipment, such
as ladders, scaffolding, or lifting gear, in environments where exposure to corrosive
chemicals is likely. Such equipment is constructed from high strength aluminum alloys
containingsome combination of manganese, magnesium, silicon, copper, etc. Their high

strength is usually developed by heat treatment which produces a very different com-
position at the grain boundaries. This, in turn, can make the alloy susceptible to inter-
granular corrosion in which a strong electrochemical driving force exists between the
mostly aluminum grains and the alloyed material in the grain boundary. Under tensile
stress this can lead to SCC.
In this form of aluminum alloy corrosion there is often no obvious evidence of a
corrosion problem on visual inspection. There have been cases in chemical plants where
safety equipment such as ladders had been unused for years and looked in perfect
condition. Unfortunately, when they were needed, they collapsed under load!
5.5.1.6 Exfoliation
Exfoliation corrosion occurs in some wrought aluminum alloys at certain tempers. Ex-
foliation occurs predominately in products that have markedly directional structures.
It is not accelerated by stress and does not lead to SCC. Exfoliation problems with the
original 5xxx alloys led to the development of special boat hull plate tempers, H116 and
H117,for alloys 5083,5086, and 5456.169
Only aluminum alloys containing appreciable amounts of soluble alloying elements,

especially copper, magnesium, silicon, and zinc, are susceptible to SCC. For most com-
mercial alloys tempers have been developed that provide a high degree of immunity
to SCC in many environments. SCC is strongly dependent on heat treatment, compo-
sition, grain structure, and stress dire~ti0n.l~ ASTM G 64 tabulates the susceptibility of
the various alloys and environments.
Whether or not SCC develops in a susceptible alloy depends on both magnitude
and duration of tensile stress acting at the surface. SCC of susceptible alloys is greatly
affected by stress direction in relation to the worked microstructure, i.e., whether the
tensile stress is applied parallel or at right angles to the direction of working. In rolled
plate the resistance to SCC is greatest when stress is applied in the longitudinal direction
and least when it is applied across the plate thickness. Cast alloys rarely suffer from SCC
and since they are relatively isotropic, direction of applied stress has little influence on
re~istance.'~~
5.5.1.8 Corrosion Fatigue
Fatigue strength of aluminum alloys is less in corrosive environments, such as seawater,

than in air. This corrosion fatigue effect is especially pronounced when evaluated
by low stress, long duration tests. Reduction in fatigue strength is least in the more
corrosion-resistant alloys. Corrosion fatigue is not appreciably affected by test direction
or direction of stress application because fracture from this type of attack is predomi-
nantly tran~granu1ar.l~~
Aluminum has been demonstrated to be attacked by bacteria and fungi. The best known
examples are in fuel tanks. Organisms implicated include the bacteria Pseudomonus, Aer-
obucter, Clostridium, Desulfovibrio, Micrococcus, and Sphuerotilus, and the fungi Penicillium,
Aspergillus, Spicuriu, Hormodendrum, and C l ~ d o s p o r i u m . ” ~Attack
~ ’ ~ ~ of an aluminum out-
board motor in South Africa was attributed to MIC in polluted water.171
Severe corrosion of storage tanks with floating aluminum roofs was caused by a
microbial consortium, including general aerobes and anaerobes, SRB IOB, Thiobacillus
thiooxiduns, and fungi. Aluminum-magnesium alloys were found to be more susceptible
to MIC than pure aluminum.’”
5.5.2 Corrosion of Aluminum Alloys in Fresh Water
Aluminum alloys are used in fresh water as industrial water storage tanks, industrial and
urban water supply pipelines, portable irrigation water pipe systems, logging flumes,
heat exchangers, canoes, rowboats, and other pleasure craft.la
Aluminum has good resistance to high purity water that is not decreased significantly
by the presence of oxygen, carbon dioxide, or the commonly added chemicals, e.g.,
to boiler feed water, to reduce corrosion of carbon steel. Elements that improve room
temperature resistance tend to increase corrosion at higher temperature. Aluminum-
nickel alloys tend to have the best high temperature corrosion resistance in pure water.’”
Aluminum is generally good in fresh water but can be attacked under stagnant con-
ditions. It has been successfully used for boats for fresh water since around 1890. Nor-
mally, potable water is benign to aluminum alloys. Corrosion is affected by pH, copper,
bicarbonate, chloride, sulfate, oxygen, and mercury. Deviation of pH away from neutral
increases the risk of pitting attack. Hardness also increases the corrosion of aluminum; for
example, water with 300 to 500 pprn total hardness and 0.08 pprn copper destroyed alu-
minum water pipes in4 to 6 years. As temperatures increase from 24 to about 38°C the rate
of pitting increases. Further increase up to 85°C causes the pitting rate to decrease. The
absence of oxygen in the water reduces pitting in aluminum; even at 2 ppm the rate is re-
duced by90%. Where water is in motion in aluminum equipment, velocities >8 ft/s (2.44
m/s) are beneficial and may prevent pitting in aggressive waters. At velocities >20 ft/s
(6.1 m/s), turbulence at bends or fittings may result in impingement or cavitation attack.
Chlorine at normal levels, i.e., t0.5 pprn residual, is not detrimental to aluminum, but
in one case in which the water was intermittently chlorinated to 10 to 50 pprn residual,
the incidence of pitting in aluminum pipe was rapidly and considerably increased.la
Aluminum alloys are extensively used for outboard motor parts and are generally
satisfactory in fresh or marine applications.However, one such motor was left immersed
for about 4 months in a freshwater marina in the Vaal Dam, South Africa. When an at-
tempt was made to start it, the casingbelow the water line was completely destroyed and
the propeller had fallen off (Figure 5.3). It was concluded that the attack was caused by
MIC; ideal conditions for the growth of microorganismswere provided by the stagnant,
polluted water. Phytoplankton blooms caused by excessive nutrient input and warm
water temperatures were frequent, resulting in increased bacterial growth and activity
as well as cycling pH and oxygen condition^.'^^
5.5.3 Corrosion of Aluminum Alloys in Seawater
The wrought alloys used in structural marine applications are chiefly the 5xxx type,
represented by 5052,5086, and 5083. These A1-Mg alloys are strain hardenable and have
high strength and good corrosion resistance. In applicationswhere they may be contin-
uously exposed to temperatures above lOO"C,5xxx alloys with more than 3%Mg should
not be used. Under these conditions the alloy may become sensitized and susceptible
to SCC. Where high temperature exposure is likely 5454 or 5754 should be used. High
speed single hull ships, e.g., the Proserio, use 5083-H113/H321machined plates for hulls,
hull stiffeners, decking, and superstructure. The standard material for spheres, 5083, is
used for shipboard transport of liquefied natural gas.'74
+
The 3xx.x Al/Si Cu or Mg alloys are heat-treatable, high strength casting alloys used
in water applications such as in outboard motor structural parts subject to continuous
or intermittent immersion. Outboard motor parts such as motor hoods, shrouds, and
miscellaneous fittings and hardware are typically made from grades such as 360.0.'75
Cast 356.0 and 514.0 (Al/Mg) alloys show good resistance to seawater and are used in
fittings, housings, and other marine parts.169
Aluminum is commonly used for a large variety of marine applications including
main strength members such as hulls and deckhouses. Other applicationsinclude stack
enclosures, hatch covers, windows, air ports, accommodationladders, gangways, bulk-
heads, deck plate, ventilation equipment, lifesaving equipment, furniture, hardware,
fuel tanks, and bright trim.'75They are also used in boat hulls, ship superstructures,
lighthouse fixtures, buoys, and submarine pipelines.'@
The use of aluminum alloys can save up to 50% of the weight of similar designs
in steel. Substantial weight-saving in deckhouses and other topside structures means
that the supporting structures can also be reduced. This overall weight-saving by using
aluminum improves stability and allows the beam to be decreased, which improves fuel
effi~iency.'~~ Weight reduction has led to increasing use of alloys 5454,5086, and 5083
in offshore oil rig topside applications. Single or multiple hull ferries use 5083 and 5454
sheet and plate with 6xxx extruded sections in an all-welded con~truction.'~~
Tests of flowing seawater in aluminum pipes at up to 37 ft/s (11.28m/s) showed no
general thinning of the pipe for 3.5 years. An increase in velocity first reduced the rate of
pitting, then increased it. The general conclusion is that aluminum alloys, particularly
those containing magnesium, are highly resistant to seawater and, in the absence of
dissimilar metal contact, will perform well in submarine applications.la
Figure 5.3 Pollution was responsible for the demise of this aluminum
outboard motor in only a few months. Plankton blooms in the lake cre-
ated cycling oxygen concentrations and pH as well as the proliferation of
bacteria. (Photocourtesy of CARIAD Consultants.)
5.5.4 Standards and Specifications-Aluminum Alloys
5.5.4.1 AA and UNS

The Aluminum Association Alloy and Temper Designation System is recognized by
the American National Standards Institute (ANSI) as the U.S. national standard, and
as such is incorporated into ANSI Standards H35.1 and H35.2. The maintenance of the
system is managed by the Aluminum Association, Inc. under ANSI's charter.In addition,
there is an International Accord recognizing the Aluminum Association Wrought Alloy
Designation System as the de facto international standard; this Accord has been ratified
by almost all of the world's aluminum-producing countries.
The alloy designation system for wrought alloys is based on a four-digit identification
code that follows:
First digit-Principal alloying constituent(s)

Second digit-Variations of initial alloy
Third and fourth digits-Individual alloy variations (number has no significancebut
is unique)
lxxx-Pure A1 (99.00%or greater)

2xxx-Al-Cu alloys
3xxx-Al-Mn alloys
4xxx-Al-Si alloys
5xxx-Al-Mg alloys
6xxx-Al-Mg-Si alloys
7xxx-Al-Zn alloys
Bxxx-A1 +other elements
9xxx-Unused series
Cast alloys are designated by a somewhat different four-digit system as follows:
First digit-Principal alloying constituent(s)

Second and third digits-Specific alloy designation (number has no significance but
is unique)
Fourth digitxasting (0) or ingot (1,2) designation
Variations indicated by preceding letter (A, B, C)
1xx.x-Pure A1 (99.00% or greater)

2xx.x-Al-Cu alloys
3xx.x-Al-Si + Cu and/or Mg
4xx.x-Al-Si
5xx.x-Al-Mg
7xx.x-Al-Zn
8xx .x-Al-Sn
9xx.x-Al+ other elements
6xx.x-Unused series
The tempers designation system defines the mechanical condition of the alloy as
follows:
F-As-fabricated
0-Annealed
H-Strain-hardened (wrought products only)
W-%lu tion heat-treated
T-Thermally treated to produce tempers other than F, 0, H (usually solution heat-
treated, quenched, and precipitation hardened)
Numeric additions indicate specific variation, e.g., T6 = solution heat-treated and

artificially aged.
These Aluminum Association designations have also been used as the basis for UNS
numbers applied to aluminum alloys. For example, wrought pure aluminum alloys are
UNS A9lxxx, alloys containing copper are A92xxx, etc. The cast alloys start with 0, i.e.,
UNS Olxxx, O ~ X X X etc.
,
5.5.4.2 ASTM
B 209M-00-Standard Specification for Aluminum and Aluminum Alloy Sheet and

Plate
B 210M-00-Standard Specification for Aluminum and Aluminum Alloy Drawn
Seamless Tubes
B 234M-00-Standard Specification for Aluminum and Aluminum Alloy Drawn
Seamless Tubes for Condensers and Heat Exchangers
B 241/B241M-OO-Standard Specification for Aluminum and Aluminum Alloy Seam-
less Pipe and Seamless Extruded Tube
B 404/B404M-00-Standard Specification for Aluminum and Aluminum Alloy Seam-
less Condenser and Heat-Exchanger Tubes with Integral Fins
B 483/B483M-O&Standard Specification for Aluminum and Aluminum Alloy
Drawn Tubes for General Purpose Applications
B 491/B491M-O&Standard Specification for Aluminum and Aluminum Alloy Ex-
truded Round Tubes for General-Purpose Applications
B 597-92(1998)-Standard Practice for Heat Treatment of Aluminum Alloys
5.5.4.3 EN
EN 485-1:1993-Aluminum and aluminum alloys-Sheet, strip, and p l a t e p a r t 1:

Technical conditions for inspection and delivery

Mechanical properties
EN 485-3:199~Aluminumand aluminum alloys-Sheet, strip, and p l a t e p a r t 3:
Tolerances on shape and dimensions for hot-rolled products
Tolerances on shape and dimensions for cold-rolled products
EN 515:1993-Aluminum and aluminum alloys-Wrought products-Temper desig-
nations
EN 573-1:1994-Aluminum and aluminum alloys4hemical composition and form
of wrought products-Part 1:Numerical designation system
EN 573-2:1994-Aluminum and aluminum alloys-chemical composition and form
of wrought products-Part 2: Chemical symbol-based designation
EN 575:199%Aluminum and aluminum alloys-Master alloys produced by
melting-Specifications
EN 604-1:1997-Aluminum and aluminum a l l o y s x a s t forging stock-Part 1: Tech-
nical conditions for inspection and delivery status
EN 604-2:1997-Aluminum and aluminum a l l o y s x a s t forging stock-Part 2: Toler-
ances on dimensions and form
EN 1592-1:1997-Aluminum and aluminum alloys-HF seam-welded tubes-Part 1:
Technical conditions for inspection and delivery
Mechanical properties
Tolerances on dimensions and form for square, rectangular, and shaped tubes
EN 1706:1998-Aluminum and aluminum alloys-Castings-Chemical composition
and mechanical properties
EN 1780-1:1996-Aluminum and aluminum alloys-Designation of unalloyed and
alloyed aluminum ingots for remelting, master alloys, and castings-Part 1: Nu-
merical designation system
EN 1780-2:1996-Aluminum and aluminum alloys-Designation of unalloyed and al-
loyed aluminum ingots for remelting, master alloys, and castings-Part 2: Chemical
symbol-based designation system
EN 12258-1:1998-Aluminum and aluminum alloys-Terms and definitions-Part 1:
General terms
EN 12392:2000-Aluminum and aluminum alloys-Wrought products-Special re-
quirements for products intended for the production of pressure equipment
5.6 TITANIUM A N D ITS ALLOYS
Titanium and its alloys were first developed in the 1950s. The high strength-to-weight
ratio of the metal was the property that first attracted industrial interest. The density
of titanium is approximately half that of iron, nickel, and copper alloys. The thermal
conductivity of titanium is about 30% higher than the 300 series stainless steels and
more than 60% higher than the super stainless ~ t e e 1 s . l ~ ~
Titanium's excellent corrosion resistance was soon discovered and it began to be used
in the chemical process industry in the 1960s. Commercially pure titanium (grades 1,2,3
or UNS R50250, R50400,R50550) is used in a number of industries, with grade 2 being
the most widely used of all the grades. The addition of palladium improves corrosion
resistance to reducing media and high temperature chlorides.There are several grades of
titanium alloys containing palladium: grades 7 and 11the traditional grades containing
up to 0.15% Pd and the "lean" palladium grades 16 and 17 with up to 0.05% Pd. The
higher strength grades 5 and 9 contain A1 and/or V. Details of grades and properties are
given in ASTM 0 265.
The stable room temperature structure of pure titanium is hexagonal close packed
(alpha), but this can transform into a body-centered cubic structure (beta) stabilized by
the presence of alloying elements such as iron. Most of the commercial grades are alpha
or near alpha (containing small amounts of beta phase), apart from grade 5 which has
substantial amounts of beta phase and grades 19and 21 which are metastablebeta grades
that can be heat-treated to develop very high strengths.
The strength of pure titanium is greatly increased by the addition of small amounts
of alloying elements, particularly oxygen (0.1 to 0.4%), nitrogen (0.01 to 0.025%), iron,
carbon, and hydrogen. At low levels strength is increased without adversely affecting
ductility; greater amounts of these elements, particularly oxygen or nitrogen, can cause
ernbrittlement.la
Uniform corrosion is not usually a factor in the use of titanium for three reasons:
1. It is not normally cost-effective in applications where a corrosion allowance has to be

included.
2. If general corrosion is occurring other forms of corrosion, such as crevice attack, are
also occurring and will cause failure before general metal loss does.
3. Under conditions where titanium is corroding, hydrogen is probably being absorbed
into the structure causing mechanical embrittlement.
All of these factors are particularly important since titanium is normally used in the
form of thin sheets or tubes, for example, in heat exchangers.
Titanium, like aluminum, is highly reactive and owes its corrosion resistance to the
presence of a strong, adherent oxide film. It is good in oxidizing conditions, e.g., in
strong nitric acid, but poor in reducing conditions, e.g., HC1. It is particularly susceptible
to attack by fluorides. It has outstanding resistance to hypochlorite and wet chlorine but
can be rapidly attacked in dry chlorine with a risk of ignition. Its resistance to corrosion
in neutral or slightly reducing conditions depends on the alloying elements, metal ions,
and temperature.
Titanium and its alloys have much better resistance to pitting and crevice corrosion
than, for example, the stainless steels. If crevice corrosion does occur the passivated
metal outside the crevice helps to drive the corrosion within. Crevice corrosion of the
unalloyed titanium grades can be severe under some conditions and accounts for about
two thirds of all failuresof titanium equipment. Threshold temperatureand pH are much
more important than chloride concentration in causing crevice attack.176The addition
of palladium, for example, in grade 7, or rubbing titanium surfaces with platinum or
tantalum foil (leaving traces of the noble metal on the titanium) improves resistance
to crevice attack and reducing conditions. Precious metals can also be applied by elec-
troplating, brush coating, cathodic deposition, or thermal diffusion.Iron contamination
greatly decreases corrosion resistance since the less noble metal on the surface can be
corroded and initiate attack of the titanium galvanically. Titanium can become contam-
inated with iron during welding or by the use of steel wire brushes. Iron in the alloy
can cause preferentialweld attack in some environments,e.g., nitric acid solutions. Con-
versely, iron in solution can increase corrosion resistance by a process of anodic pro-
tection. In this process, the switch from Fe3+ to Fez+ can cause titanium to passivate.
Pitting attack is rare on titanium except in the presence of iron contamination of the
surface.
5.6.1.2 Hydrogen Effects
Titanium readily absorbs hydrogen and can become embrittled if nascent hydrogen
diffuses into the structureand produces brittle titanium hydride. This is a rare occurrence
because the oxide film normally provides an excellent barrier to the ingress of hydrogen,
but hydrogen can be a problem in the following cases:176
Titanium is coupled to a less resistant metal (galvanic corrosion).

It is exposed to a cathodic protection system where the negative potential is < -0.9 V
SCE.
Titanium is subjected to tensile stresses while hydrogen is being generated.
pH is less than 3 or greater than 12, and then the risk of hydrogen uptake is increased.
Temperature is elevated; diffusion of hydrogen in titanium is very slow at tempera-
tures below about 80°C.
Titanium is essentially immune to chloride stress cracking, the only exception possi-
bly being the high strength, high oxygen grade 5 alloy. Samples of this alloy contain-
ing loaded flaws can stress crack in seawater. In applications requiring a high strength
titanium alloy and where SCC might be possible, the low interstitial grade 23 is normally
used. SCC is possible with most grades of titanium only in the extremely rare environ-
ments of red fuming nitric, some methanol solutions, nitrogen tetroxide, and cadmium
5.6.1.4 Microbiologically Influenced Corrosion of Titanium and

Other Transition Metals
Titanium has repeatedly demonstrated its resistance to MIC?191n-178including corrosion

by marine and thermophilic ~rganisrns?~ although it is biofouled in preference to some
other metals.179
There have been few studies on the susceptibilityof other transition metals to h4IC. In
one study, biofilms formed on zirconium, chromium, niobium, tantalum, and molybde-
num but not on tungsten, and corrosion was slight. Corrosion was less on experimental
molybdenum and tungsten coupons than on controls. Zirconium and niobium weight
loss was nil or negligible. Weight loss for chromium and tantalum was small, but greater
than controls. A low alloy steel, UNS G43400,was also used in these laboratory experi-
ments and produced conflicting results, with corrosion rates greater than controls in one
SRB inoculum and less than controls in the other.lsO
Permeation of hydrogen produced by bacteria through palladium has been demon-
strated. There was a close relationship between growth of the fermentative bacterium
Clostridium acetobutylicum and hydrogen permeation, suggesting that it is biologically
produced.lS1
5.6.2 Corrosion of Titanium in Waters
Titanium is completely inert to distilled water at all oxygen levels and resists corrosion
in fresh, natural waters even if they contain manganese or are heavily chlorinated. It is
resistant to fresh water and steam at temperatures in excess of 600°F (316°C).
Titanium is highly resistant to attack by seawater and brackish water even under
stagnant conditions and at elevated temperatures. Titanium in its passive state is noble
to most metals and is cathodic in a galvanic couple; the potential of titanium in seawater
is -0.10 V SHE. This sometimes leads to accelerated attack of the less noble metal and
can produce a risk of hydrogen damage to the titanium. However, since the oxide on
titanium is not self-healing in reducing conditions it can become strongly anodic to many
other metals. Care must be taken to ensure that the ratio of anodic to cathodic areas does
not lead to severe corrosion of the anodic metal.
Titanium rarely pits in seawater but can be subject to crevicecorrosion at temperatures
above about 80°C. Titanium alloyed with Mo, Ni, or Ta has increased crevice corrosion
5.6 Titanium and Its Allovs 133
resistance; e.g., grade 12 (UNS R53400) resists crevice attack in seawater at temperatures
up to 500°F (260°C). Multivalent ions of metals such as copper, nickel, or molybdenum
in the crevice can reduce attack by cathodic depolarization. The presence of fluoride ions
can increase the susceptibility of titanium to crevice attack. Titanium has outstanding
resistance to seawater at velocities up to 120 ft/s (36.6 m/s). The presence of entrained
particles causes relatively little effect on the corrosion of titanium compared with, for
example, copper alloys.
Titanium does not suffer a significant reduction in fatigue strength in seawater. For
example, in unalloyed titanium the stress to cause failure in lo7 cycles is 52 ksi (359 MPa)
in air and slightly higher at 54 ksi (372 MPa) in seawater; for Timetal 6-4 (UNS R56400)
the values are 70 ksi (480 MPa) in air and 60 ksi (410 MPa) in seawater.
Titanium does not display toxicity to marine organisms; biofouling can occur in sea-
water. Biofouling, for example on heat exchanger surfaces, can be prevented by seawater
velocities in excess of 2 m/s. At lower velocities chlorination is advisable.lg2
TIMETAL 5111 (UNS R55111) is a near-alpha titanium alloy of intermediate strength
that was developed jointly by Xmet and the U.S. Navy. This alloy has been designed
for high toughness, good weldability, SCC resistance, and room temperature creep re-
sistance. It is suitable for use in marine environments where toughness and corrosion
resistance are essential and it is being used in submarine communication masts. Forging
and machining characteristics are very similar to grade 5 titanium (UNS R56400). This
alloy is designated as ASTM grade 32.lS3
Extensive crevice corrosion testing of UNS R55111 (Ti 5111) alone and coupled with
alloy 625 (UNS N06625) was carried out in seawater for 1 year at the Naval Research
Laboratory, Key West, FL.No crevice corrosion was seen on the Ti 5111 in Ti 5111:Ti 5111
or Ti 5111:alloy 625 couples. Alloy 625 did not crevice corrode in the Ti 5111:alloy 625
couple but did corrode in the alloy 625:alloy 625 assemblies. No evidence of SCC was
found in environmentally assisted cracking and sustained load cracking tests. The alloy
was also assessed as a possible candidate tubing material for water injection service
by testing at elevated temperatures with and without C02 and CO2/H2S. It did not
corrode under any of these test conditions. The combination of mechanical properties
and corrosion resistance of this alloy makes it a good candidate for high strength marine
fastener applications.lM
5.6.3 Standards and Specifications-Titanium Alloys

5.6.3.1 ASTM
B265-99-Standard Specification for Titanium and Titanium Alloy Strip, Sheet, and
Plate
B338-99-Standard Specification for Seamless and Welded Titanium and Titanium
Alloy Tubes for Condensers and Heat Exchangers
B348-0kStandard Specification for Titanium and Titanium Alloy Bars and Billets
8367-93(1998)-Standard Specificationfor Titanium and Titanium Alloy Castings

B381-00-Standard Specificationfor Titanium and Titanium Alloy Forgings
B600-91(1997)el-Standard Guide for Descaling and Cleaning Titanium and Titanium
Alloy Surfaces
B861-00-Standard Specification for Titanium and Titanium Alloy Seamless Pipe
B862-99-Standard Specification for Titanium and Titanium Alloy Welded Pipe
B891-98el-Standard Specificationfor Seamless and Welded Titanium and Titanium
Alloy Condenser and Heat Exchanger Tubes With Integral Fins
5.7 ZIRCONIUM
Zirconium was first discovered in 1789 but has only been produced commercially since
the 1950s. It was first used for nuclear power plant applications but has gradually found
specific uses in the chemical process industries and occasionally in marine applications.
Like titanium, it is a reactive metal that relies on the presence of a dense, stable oxide
film to provide corrosion resistance. In fact, it is so reactive that care must be taken in
machining operations to prevent pyrophoric reactions with air. All commercial grades
of zirconium contain up to 4.5% Hf (hafnium), typically 2%, including the "unalloyed"
grade 702 (UNS R60702). This has little effect for most applications but must be removed
for nuclear use to produce the nuclear-grade hafnium-free zirconium, UNS R60001. The
addition of niobium (grade 705, UNS R60704) greatly increases mechanical strength with
very little effect on corrosion properties.

Zirconium has excellent resistance to acids, particularly hydrochloric, weak sulfuric, and
nitric acids. Under acidic-reducing conditions it is better than titanium but the presence
of oxidizing ions in hydrochloric or sulfuric acids can greatly increase the corrosion
rate of zirconium. Zirconium has no resistance to hydrofluoric acid and the presence of
fluorides in nitric acid increases corrosion rate. It has outstanding resistance to crevice
corrosion in chloride solutions. Pitting corrosion can occur in chloride solutions in the
presence of oxidizing ions such as Fe3+or Cu2+.
Zirconium is resistant to SCC in most environments but is known to crack in the
following:
Ferric chloride solutions

Copper chloride solutions
Methanol + hydrochloric acid or iodine
Concentrated nitric acid
Liquid mercury or cesium
5.7 Zirconium 135
5.7.2 Corrosion of Zirconium in Waters
Zirconium is very resistant to corrosion in alkaline solutions and to fresh water and
seawater even when polluted. Grade 704, UNS R60704 (containing 1.5% Sn with small
additions of Cr and Fe), is particularly resistant to high temperature water and steam
and is used for this type of application in some power plants, particularly nuclear.'85
In pure high temperature water the oxide film on pure zirconium can become unstable
and permit local attack. Zirconium alloys (such as grades 702 and 704) have much better
resistance to this environment and better resistance to hydrogen pickup. Zirconium has
been used successfully in fresh waters and seawaters at temperatures up to 300°C. Two
zirconium heat exchangerswere used in a Urea plant for 20 years. They were then broken
down, inspected, and the tubes reused in another exchanger. The tubes were "like new"
with the water side of the tubes covered with a thin oxide layer.'%
The corrosion behavior of zirconium in seawater is relatively unaffected by pH, tem-
perature, velocity, presence of crevices, or bacteria. Grade 702 zirconium was exposed
in seawater in Newport, OR for up to 129 days. No corrosion was detected on plain or
crevice assembly specimens. Although fouling occurred there was no corrosion beneath
the fouling or within the crevices. Zr 702 and Zr 704 were tested in boiling seawater for
275 days and to 200°C seawater for 29 days. Both alloys were resistant to general corro-
sion, pitting, and crevice attack in these tests. SCC tests in boiling seawater showed no
cracking in 365 days for a range of zirconium alloys. All alloys remained ductile except
for a welded specimen Zr 704, containing nickel, that was coupled to iron. This specimen
showed a much higher absorption of oxygen and hydrogen and hydrides were formed in
the structure.'87 Zirconium has better resistance to seawater under reducing conditions
than titanium and much better crevice corrosion resistance. Under oxidizing conditions
in seawater titanium has superior resistance to zirconium.'88
5.7.3 Standards and Specifications-Zirconium Alloys
5.7.3.1 ASTM
B493-83(1998)-Standard Specification for Zirconium and Zirconium Alloy Forgings

B523-97-Standard Specificationfor Seamless and Welded Zirconium and Zirconium
Alloy Tubes
B550-97-Standard Specificationfor Zirconium and Zirconium Alloy Bar and Wire
B551-97-Standard Specificationfor Zirconium and Zirconium Alloy Strip, Sheet, and
Plate
B614-95(2000)-Standard Practice for Descaling and Cleaning Zirconium and Zirco-
nium Alloy Surfaces
B658-97-Standard Specificationfor Seamless and Welded Zirconium and Zirconium
Alloy Pipe
B752-97-Standard Specification for Castings, Zirconium Base, Corrosion-Resistant,
for General Application
5.8 LEAD
Lead is one of the metals that has been used by man for millennia. For example, in the
search for effective and economical means to protect ship hulls and marine structures
from the ravages of seawater and marine life, lead sheathing was fitted to the wooden
hulled ships used by tramp coastal traders in the time of Alexander the Great. Like
copper alloys, lead effectively resists biofo~ling.'~~
Lead has a low melting point (327"C),low mechanical strength, virtually no elasticity,
and extreme softness. Most of its mechanical properties are very sensitive to test condi-
tions and chemical composition so that laboratory data cannot be readily reproduced.
For example, tensile tests, identical except for variations in speed of testing, may give
UTS figures varying from as much as 14 to 7 MN/m2. Similarly, composition variations
between 99.99 and 99.9999% purity can result in UTS variations from 14 to 9 MN/m2.
Lead is equally sensitive to small changes in many other parameters such as grain size,
temperature of testing, and previous metallurgical history of the sample.
Lead has generally good corrosion resistance and is often used industrially as a loose or
bonded liner on steel for vessels handling sulfuric acid or for gas cleaning where acidic
vapors are condensed. Lead tanks, reinforced with steel, are occasionally used to handle
aggressive chemicals (Figure 5.4).Lead is being replaced by other materials for many of
Figure 5.4 Lead is still occasionally used to manufacture tanks for reactions
involving aggressive chemicals. (Photo courtesy of CARIAD Consultants.)
5.8 Lead 137
these applications because of perceived environmental concerns. By far the biggest use
of lead is in the lead acid battery where it is alloyed with antimony or with calcium and
tin. For corrosive applications in chemical plants it is often alloyed with other elements,
e.g., with about 0.06% Cu to produce chemical lead. Lead is an amphoteric metal, i.e.,
attacked by both acids and alkalis. It is also a reactive metal and its corrosion resistance
largely results from protective corrosion products. In air, lead first reacts with oxygen
to form lead oxide, followed by a second reaction between the lead oxide and carbon
dioxide in the air, to form a protective film of lead carbonate. Lead has good resistance
to most oxidizing acids because of the protective film. It is attacked by hydrochloric acid
and by strong alkalis.”
The use of white lead (basic lead carbonate) in decorative paints has been phased out
but still has the reputation of making paint with good external weathering characteristics.
Red lead is the traditional pigment for rust-inhibiting priming paints applied directly to
iron and steel. Calcium plumbate-based paints are particularly effective on galvanized
steel, avoiding the need for etch primers. Lead chromate (yellow) and lead molybdate
(red-orange) are still used in plastics and, to a lesser extent, paints. Lead chromate is
used extensively as the yellow pigment in road marking^."^
Lead appears to have good resistance to MIC. A case of fungal attack of lead sheathing
of underground cables has been reported, however. The lead coating was sheathed with
bituminized paper and jute. After 5 years of operation, humidity and COz production
by fungus in the jute resulted in holes in the lead coating.’”
5.8.2 Corrosion of lead in Waters
In aqueous electrolytes lead enters the solution at anodic sites as metallic cations or is
converted anodically to solid compounds. In most environments lead is cathodic to steel,
aluminum, zinc, cadmium, and magnesium and will accelerate the corrosion of these
metals. Lead is anodic to titanium and passive stainless steels. Accelerated corrosion
can occur when lead in contact with a corrosive environment is subjected to a load
exceeding its creep strength. The process of creep continually exposes fresh surfaces
to the environment. Lead creeps at room temperature under its own weight and has
virtually no work-hardening capabilities. Lead, particularly in the cast form, can also
suffer intergranular c o r r ~ s i o n . ’ ~ ~
Lead is not attacked by distilled water free of oxygen with or without carbon diox-
ide. If oxygen and carbon dioxide are present the corrosion rate will increase with in-
crease in the COz content. The corrosion rate in natural and potable waters will de-
crease with increasing hardness because hard waters tend to deposit protective scales.
If magnesium and calcium salts are present at >125 ppm then a protective film is
likely to form. In soft aerated natural and potable waters (<125 ppm) corrosion rate
increases with increasing oxygen and carbon dioxide ~ 0 n t e n t . Corrosion
l~~ rate of lead
Table 5.11 Corrosion Rate of Lead in Various Waters

Type of Water Temperature ("C) Agitation Corrosion Rate (mm/y)
Condensate, traces of acid 21-38 Slow 0.0216
Oxygenated lake water 16-29 None 0.1346
Treated aqueduct water, Los Angeles Ambient Flowing, 150 mm/s 0.0097
Chromate-treatedwater 16 Spray cooling 0.0094
Gatun Lake, CZlg3 Tropical None 0.0020
Bristol Channel, U.K.Ig4 Temperate Immersed 93% of time 0.0127
Southampton Docks,U.K.lg5 Temperate Mean tide 0.0028
San Francisco Harbor Temperate Mean tide 0.0107
Port Hueneme Harbor, CAI% Temperate Immersed 0.0056
Kure Beach, NC Temperate Immersed 0.0152
Fort Amador, CZ Tropical Mean tide 0.0051
Fort Amador, CZ Tropical Immersed 0.0091
All other data in this table.I9*
is very dependent on the type of water, the temperature, and degree of agitation
(Table 5.11).
Lead has been used to transport water since Roman times and has only been banned
during the last 30 years for this duty because of health concerns. The passive oxide on
lead makes it highly resistant to attack by most waters but it is attacked by soft waters.
The calcium carbonate deposits that form on lead are usually protective and reduce
corrosion of lead. Lead corrosion in waters increases with increasing oxygen levels.
Theoretical calculations based on lead solubility show that in waters having a pH 7.5 to
8.5, carbonate alkalinity of at least 100 mg/L as CaC03 can dissolve sufficient lead to
exceed the maximum contaminant level set by the U.S.EPA. Lead solubility decreases
rapidly with increasing pH in potable waters with t 5 0 mg/L CaC03 but is largely
unaffected by pH in waters with >lo0 mg/L. Lead is also susceptible to galvanic attack
when coupled to copper alloys. This is particularly so in the case of lead solders such as
soft solder, 50 :50 t h ~ / l e a d . ' ~ ~
5.8.3 Standards and Specifications-lead Alloys
5.8.3.1 ASTM
A 308-99-Standard Specification for Steel Sheet, Terne (Lead-Tin Alloy) Coated by

the Hot-Dip Process
B 29-92(1997)-Standard Specification for Refined Lead
B121/BlZlM-95-Standard Specification for Leaded Brass Plate, Sheet, Strip, and
Rolled Bar
5.9 References 139
B 749-97-Standard Specification for Lead and Lead Alloy Strip, Sheet, and Plate
Products
E 1605-00-Standard Terminology Relating to Lead in Buildings
5.9 REFERENCES
J.W. Oldfield, G.L. Masters, “AluminiumBronze with Cast StainlessSteelsand Ni-Resist,”CDA

Publication No. 115,1996, CDA, http://www.cda.org.uk (June 17,2001).
* Compton’s Interactive Encyclopedia,CD, TLC Properties, Inc. (1999).
C.P. Dillon, Corrosion Control in the Chemical Process Industries, 2nd ed. (New York: McGraw
Hill, 1986), 424 pp.
T.G. Oakwood, ”Corrosion of alloy steels,” in Metals Handbook-Corrosion,Vol. 13,9th ed., ed.
J.R. Davis, (Metals Park, OH: ASM International, 1987), p. 545.
G.N. Kirby, “Corrosion performance of carbon steel,” Chem. Eng. Mar. 10 (1979):p. 72.
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145 J.R. Ibars, D.A. Moreno, C. Ranninger, F. Montero, J. Izquierdo, ”Biofouling and microbio-
logically influenced corrosion in admiralty brass heat exchanger tubes,” EFC #29 4th EFC
workshop, ed. C.A.C. Sequira (London, UK: IOM CommunicationsLtd., 2000), pp. 53-60.
8.J. Little, P. Wagner, R. Ray, J.M.Jones, “Microbiologicallyinfluenced corrosionof copper alloys
in saline waters containing sulfate-reducing bacteria,” Corrosion/91, paper no. 101 (Houston,
TX: NACE, 1991), pp. 1-20.
147 F. Mansfeld, B.J. Little, “Microbiologically influenced corrosion of copper-based materials ex-
posed to natural seawater,” Electrochem. Acta 37,12 (1992):p. 2291-2297.
M. de Romero, Z. Duque, 0.de Rincon, 0.Perez, I. Araujo, A. Martinez, ’’Online monitoring
systems of microbiologically influenced corrosion of Cu-10% Ni alloy in chlorinated, brackish
water,” Corrosion 56,8 (2000):pp. 867-876.
149 T.S. Rao, K.V.K. Nair, ”Microbiologicallyinfluenced stress corrosion cracking failure of admi-
ralty brass condenser tubes in a nuclear power plant cooled by freshwater,” Corros. Sci. 40,11
(1998):pp. 1821-1836.
J.T. Walker, A.B. Dowsett, P.J.L. Dennis, C.W. Keevil, ”Continuous culture studies of biofilm
associated with copper corrosion,” Int. Biodet. 27 (1991),pp. 121-134.
W.R. Fischer, D. Wagner, H. Siedlarek,“Microbiologicallyinfluenced corrosion in potable water
installations,” M P 3 4 , l O (1995):pp. 50-54.
Is2 K.K. Satpathy, T.S. Rao, R. Rajmohan, K.V.K. Nair, ”Some investigations of condenser slime
and biocorrosion at Rajasthan Atomic Power Station,” Trans. Indian Inst. Metals 54,3 (2001):
pp. 125130.
153 A. Cohen, J. Myers,”Water treatment to mitigate corrosion of copper plumbing systems,” MP
32,8 (1993):pp. 4345.
R.E. Melchers, ”Temperature effect on seawater immersion corrosion of 90-10 copper-nickel
alloy,” Corrosion 57,5 (2001):pp. 440451.
Is5 B.C. Syrett, Corrosion of Condensers, Metals Handbook-Corrosion, Vol. 13, 9th ed., ed. J.R.
Davis, (Metals Park, O H ASM International, 1987), pp. 986-989.
S.C. Dexter, ”Seawater,” in ed. J.R. Davis, Metals Handbook-Corrosion, Vol. 13,9th ed. (Metals
Park, O H ASM International, 1987), p. 898.
Is7 P.T. Gilbert, “A review of recent work on corrosion behavior of copper alloys in sea water,” MP
21,2 (1982):pp. 47-53.
R.W. Ross, ”Applications in Seawater Systems, Pumps and Valves,” in Materials Workshops
for the Power Industry, NiDI Reference book no. 11, 011 (Toronto, Canada: NiDI, 1993),
pp. 12-14.
Is9 A.J. Sedriks, “Review: advanced materials in marine environments,” Corrosion/93, paper no.
505 (Houston, TX:NACE, 1993), pp. 1-12.
Anon, ”Copper-NickelFabrication,” NiDI Publication no. 12014 (Toronto,Canada: NiDI, 1999),
p. 27.
D.R. Lenard, J.G. Moores, G.E. Morin, “Effects of ferrous ions released from sacrificial steel
anodes on corrosion of copper-nickelalloys in sulphide polluted sea water,” Brit. Corros. J., 24,
1, (1989) pp. 19-24.
162 J.A. Carew, A. Al-Hashem, A. Al-Sayegh, ”Cathodic protection of UNS C71500 heat exchanger
tubes in sulfide polluted arabian gulf sea water,” Brit. Corros. J. 35,2 (2000):pp. 115-119.
D.B. Anderson, B.R. Richards, ”Chlorination of sea water-effects on fouling and corrosion,”
J. Engi. for Power 88 Series A No. 3 (1966), pp. 203-208.
B. Todd, P.A. Lovett, Selecting materials for sea water systems, Part 10, Vol. 1, Marine Engi-
neering Practice, (London: The Institute of Marine Engineers, undated), pp. 1-56.
5.9 References 147
165 W.W. Kirk, A.H. Tuthill, ”Copper-nickelcondenser and heat exchanger systems,”in The Appli-
cation of Copper-NickelAlloys in Marine Systems, CDA Technical Report 7044-1919 (undated)
pp. III 1-111 14.
J.A. Carew, M. Islam, “Erosion corrosion of copper- and nickel-based alloys in polluted seawa-
ter,” MP, 34,4 (1995), pp. 54-57.
Anon., The Copper Page, http:/ /www.copper.org/standard/euronumb.htm.(2001).
H.P. Godard, W.B. Jepson, M.R. Bothwell, R.L. Kane, The Corrosion of Light Metals, (New York
John Wiley & Sons, 1967), p. 360.
169 E.H. Hollingsworth, H.Y. Hunsicker, “Corrosion of aluminum and aluminum alloys,” in Metals
Handbook-Corrosion, Vol. 13, 9th ed., ed. J.R. Davis (Metals Park, OH ASM International,
1987), pp. 583-609.
170 H.A. Videla, The Action of Cludosporiurn resinue Growth on the Electrochemical Behavior of
Aluminum in Biologically Induced Corrosion NACE-8, ed. S.C. Dexter (Houston, TX: NACE,
1986), pp. 215-222.
P.J.B. Scott,M. Davies, “Outboard motor corrosion in polluted water,” Aluminium Today 12,4
(2000):pp. 49-50.
I n J. Starosvetsky, R. Armon, A. Groysman, D. Starosvetsky, ”MIC of storage tank aluminum
floating roofs during hydrotest,” MP 41,4 (2002):pp. 50-54.
173 J.R. Davis, ed., Aluminum and Aluminum Alloys, ASM SpecialtyHandbook (MetalsPark, OH:
ASM International, 1993).
174 Anon., Selection and Applications (Washington, D.C.: The Aluminum Association Inc., 1998),
p. 20.
175 J.R. Davis, ed., “Properties and selection: nonferrous alloys and special-purpose materials,”
Metals Handbook, 10th ed., Vol. 2 (Metals Park, OH: ASM International, 1991) 1328 pp.
176 J.S. Grauman, “Titanium-properties and applications for the chemical process industries,” in
Encyclopedia of Chemical Processing and Design, Vol. 58, ed. J.J. McKetta, (New York: Marcel
Dekker Inc., 1998),pp. 123-147.
In D.K. Peacock, ”Titanium-a natural solution to microbiologically influenced corrosion,‘’ UK
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178 R.W. Schutz, “A case for titanium’s resistance to microbiologically influenced corrosion,’’ MP
30,l (1991), pp. 58-61.
179 T.E. Ford, M. Walch, R. Mitchell, ”Corrosion of metals by thermophilic microorganisms,” MP
26,2 (1987):pp. 35-39.
R.M. Natishan, J. Jones-Meehan,G.I. Loeb, B.J. Little, R. Ray, M. Beard, ”Corrosion behavior of
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181 T.E. Ford, P.C. Searson, T. Harris, R. Mitchell, ”Investigation of microbiologically pro-
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182 Anon., Corrosion Resistance of Titanium (Titanium Metals Corporation, 1999), 39 pp.
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http://www.timet.com/5lllmain.html(March 3,2001).
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paper 641, Corrosion/2000 (Houston, TX: NACE International, 2000), p. 41.
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no. 01331 (Houston, TX NACE, 2001), pp. 14-16.
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p. 207.
T.-L. Yau, The Corrosion Properties of Zirconium in Chloride Salt Solutions (Albany, OR Tele-
dyne Wah Chang Albany, 1982), p. 15.
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Int. Biodeterior. Biodegrad. 2 9 , s (1992), pp. 357-365.
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ed. J.R. Davis, (MetalsPark, OH: ASM International, 1987), pp. 784-792.
193 B. W. Forgeson, C.R. Southwell, A.L. Alexander, H.W. Mundt, L.J. Thompson, ”Corrosion of
metals in a tropical environnment,” Corrosion 14 (1958), pp. 3341.
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The results of four years’ exposure in the bristol channel,”J. Inst. Metals 39 (1928):pp. 111-143.
195 J.N. Friend, ”The relative corrodibilities of ferrous and non-ferrous metals and alloys-Part 111.
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197 B.P. Boffardi, “Minimization of lead corrosion in drinking water,” MP 29,8 (1990): pp. 4549.
Chapter 6
Nonmetallic Materials
Many differenttypes of nonmetallicmaterials are used in water applications.This chapter

describes those materials, their properties, and their behavior in waters. For complete-
ness, the chapter also includes brief descriptions of other nonmetallics not commonly
used in waters.
6.1 PLASTICS
Plastics are solid materials that contain one or more polymeric substances that can be
shaped by flow. Polymers, the basic ingredient of plastics, are a broad class of natural
and synthetic materials. Plastics are readily divided into two classes, thermoplastics and
thermosets. There are applications in which the advantages of both classes of plastic are
used, e.g., in dual-laminate tanks or pipes a fiber-reinforced thermosetting resin is lined
with a thermoplastic.
6.1.1 Thermoplastics
Thermoplastics soften with increasing temperature and return to their original form
when cooled. Thermoplastics can be shaped while the resin is in a molten state and so
can be extruded or molded into a variety of shapes, such as valves, pump bodies, pipe
flanges, etc. Only similar thermoplastics can be welded together and for plastics that
have different grades, i.e., different melt viscosities, only similar grades can be welded
together. Thermoplasticsoften contain fillers such as colorants, stabilizers, antioxidants,
or other ingredients that protect and enhance properties during fabrication and service.
6.1.1.1 Polyvinyl Chloride
Polyvinyl chloride (PVC) is easily worked, can be solvent welded or machined, and has
good resistance to inorganic media and oxidizing agents but limited resistance to organic
149
150 Nonmetallic Materials
solvents. The addition of plasticizers makes unplasticized PVC (uPVC or PVC-U) less
brittle but also reduces its chemical resistance. Rigid or uPVC piping has found wide
application in water supply and distribution systems, chemical processing, wastewater
handling, etc.l
PVC can be chlorinated to produce chlorinated PVC (CPVC), which has improved
corrosion resistance and the ability to withstand operating temperatures that are 50 to
60°F (10 to 15.6"C)higher than PVC. Its chemical resistance is similar to that of rigid PVC.
CPVC is chiefly used in pipe, fittings, ducts, tanks, and pumps for handling corrosive
liquids.
Polyvinyl dichloride (PVDC)or polyvinylidene chloride has improved chemical re-
sistanceand mechanicalproperties,includingheat stability(100"C/212"F).PVDC valves,
pumps, pipes, and liners are used in corrosive applications.It is also used in the form of
rigid or flexible sheet liner in metal and fiber-reinforced plastic (FRP) vessels.
6.1.1.2 PoIyolef ines-Pol yethy lene, Polypropylene, and Poly buty Iene
High and low density polyethylene (PE),polypropylene (PP),and polybutylene (PB)are

widely used in water applications. They are the lowest cost polymers for piping, small
structural shapes, containers, etc. Selected properties of the polyolefines are shown in
Table 6.1 together with those with some for some other thermoplastics for comparison.
PE was first produced in the laboratoriesof the Imperial Chemical Industries (ICI)in
England in 1933, but it was not commercialized until 1939 when it was used to insulate
telephone cables and coaxial cables that were important in the wartime development
of radar. The early polymerization processes used high pressure (14,000 to 44,000 psi
Table 6.1 Properties of Polyolefines and Other Common Plastics*
Plastic
Property HDPE LDPE UHMWPE PP UPVC PVDC
Resistance to conc. acid good fair good good
Resistance to alkalis good go* good
Resistance to aromatic fair-poor poor fair fair
hydrocarbons
Resistance to halogens poor Poor fair-poor Poor fair good
Elongation at break, YO - 400 500 - - -
Tensile modulus, GPa 0.5-1.2 0.5-1.2 0.1-0.3 0.9-1.5 for 2 5 4 .0 0.3-0.55
biaxial film
Tensile strength, MPa 15-40 5-25 2040 25-40 for 25-110
biaxial film
Density g cmW3 0.95 0.92 0.94 0.9 1.4 1.63
Lower working temperature, "C - -60 - -10 to -60 -30 -
Thermal expansivity x K-l 100-200 100-200 130-200 100-180 75100 190
6.1 Plastics 151
[97 to 303 MPa]) autoclavereactors and temperatures of 200 to 600°F(93to 316°C).It was
produced in a free radical chain reaction by combining ethylene gas under high pressure
with peroxide or a trace amount of oxygen. Today it is produced by one of several low
pressure catalyzed processes that polymerize ethylene or co-polymerize it with small
amounts of other monomers such as butene, propylene, hexene, and octene?
LDPE (low density polyethylene) is used extensively for piping because of its ease
of handling and fabrication. It can be readily fusion-welded and installations of welded
piping are the least expensive and most durable of any material available for waste
and water lines, and other services not subjected to high pressures or temperatures.
Chemical resistance is excellent up to the temperature limit of around 60°C. It is also
available in a fiber-reinforcedversion that has better mechanical properties. It can suffer
environmental stress cracking in some environments but resistant grades are available.
HDPE (high density polyethylene) has better chemical resistance and mechanical
properties than LDPE. Only strong oxidants will attack HDPE appreciably within their
temperature ranges. It can be subject to stress cracking if an appropriate grade of resin
is not used. HDPE is also available in high molecular weight, HMWHDPE, and ultra-
high molecular weight versions, UHMWHDPE. These polymers with higher molecular
weight have better resistance to environmental cracking than does HDPE, have better
mechanical properties, and have excellent abrasion and wear resistance.
PP is light weight and has good impact properties. It has similar chemical resistance
to HDPE. It can be used to around lOO"C, is weldable, and is widely used in piping
and tanks. The coefficient of thermal expansion of PP is less than for HDPE, while its
modulus is somewhat higher than HDPE, which can help resist environmental cracking.
PB is flexible, yet stronger, than even HDPE. Its defining characteristic, however, is
that its strength increases at higher temperatures. Its temperature limits are 200°F (93°C)
for pressure applicationsand slightly higher for nonpressure applications.Polybutylene
is mostly used for hot effluent lines and slurry transportationbecause it has good abrasion
re~istance.~ PBT (polybutyleneterephthalate) is a rigid plastic with high tensile strength
and good impact and scratch resistance.
6.1.1.3 Fluorocarbons
There are a number of different fluorinated copolymers in industrial use including the
following:5
PTFE (polytetrafluoroethylene) was the original, totally fluorinated plastic. It is the

most difficult fluorocarbon to work or produce but has the best chemical resistance
and highest temperature stability. The material has adequate heat resistance to 290°C
and has been used in severe chemical service as high as this temperature.
PFA (perfluoroalkoxy)has similar chemical resistance to PTFE and can be used at up
to 260°C. It is often used as a liner for pipes, pumps, valves, and tanks.
FEP (fluorinatedethylene propylene) has a lower heat resistance of 200°Cbut is more
workable than PTFE.
ECTFE (ethylene-chlorotrifluoroethylene) has a working temperature of up to 190°C.

It is used as a liner for equipment where avoiding contamination of the product is
important, e.g., pharmaceuticals and electronics.
CTFE (chlorotrifluorethylene)has heat stability of 180°C and a slightly lower chem-
ical resistance than do the totally fluorinated materials. Its working properties are
relatively good so it is used in coatings, prefabricated liners, and O-rings.
PVDF (polyvinylidenefluoride)has lower heat resistance, 150"C, and chemical stabil-
ity than other fluorocarbons, but is more workable. Complete pumps, valves, piping,
smaller vessels, and other fittings have been made from this plastic. It can also be
applied as a coating or liner.
The fluorocarbonsare not widely used in water service because their chemical inert-
ness and high temperature properties are not normally needed and their high cost can
rarely be justified.
6.1.1.4 Other Thermoplastics
POM (polyacetal)has excellent dimensional stability and toughness and is used for
gears, pump impellers, other types of threaded connections, such as plugs, and me-
chanical uses. It can be used up to -105°C.
ABS (acrylonitrile-butadiene-styrene)can be used over a wide temperature range,
-40 to +80"C. The material properties can be varied considerably by changing the
ratio of acrylonitrileto the other two components of the tripolymer. Often used in low
temperature piping because of its comparatively high impact resistance.
PMMA (polymethylmethacrylate)is transparent with good resistance to UV. It is one
of the family of acrylics that are used in high impact window panes and protective face
shields. Upper temperature limit is approximately 90°C. The loss in light transmission
was only 1%after 5 years exposure in Florida and Arizona.
Nylons are a family of polyamides that are used in coatings and machined parts because
of their excellent mechanical properties and ease of fabrication. The heat resistance
varies, but is typically up to 100°C.
PET (polyethylene terephthalate) is a rigid transparent material with high tensile
strength and good resistance to abrasion.
PC (polycarbonate)is also transparent with exceptional impact resistance. It can be
used up to about 120°C.It has poor resistance to stress cracking.
Polyirnides can be used over a very wide range of temperatures, -190 to +370"C. Some
combinationsof the resins can be taken to 510°C for short periods. It has excellentcreep
and abrasion resistance, good chemical resistance, good modulus, and strength that
does not decrease rapidly with temperature.
PPO (polyphenylene oxide) and PPE (polyphenylene ether) are similar plastics with
high strength, excellent heat resistance, dimensional stability, and resistance to chem-
icals and impact. Low water absorption and dimensional stability mean that these
materials are often found in pump and valve parts. Their temperature limit is around
120°C.
6.1 Plastics 153
PPS (polyphenylene sulfide) has outstanding chemical resistance and can be used
from -170°C to +190"C. Higher strength with high modulus can be obtained by
adding glass or other fillers to the material.
Sulfones such as polyphenylene sulfone are flame resistant and can be used at high
temperature (up to 260°C) with good dimensional stability and solvent resistance.
They can be attacked by some solvents and may be prone to stress cracking.
PEEK (polyetherketone)is a high temperature corrosion-resistant thermoplastic suit-
able for wire coating, injection molding, film, and advance structural composite
fabrications.
PS (polystyrene)is widely used but rarely in industrialapplications.Other forms such
as foamed PS and high impact PS have been developed for particular applications.
The heat resistance of the material is only 65°C and chemical resistance is poor.
CeZluZosic derivatives include those of acetate, butyrate, and propionate thermoplas-
tics; typified by CAB (cellulose acetate-butyrate).They are not widely used industri-
ally because, although they have good resistance to water and salt solutions, they are
attacked by acids, alkalies, or solvents. They can be used up to about 60°C.
lonomers are occasionally used in industry, usually in coatings. The toughness and
atmospheric stability of ionomers is excellent but it can be attacked by a wide range
of chemicals, particularly organic chemicals. They can be used up to about 70°C.
6.1.2 Thermosets
Thermoset plastics are produced from liquid polymers by a process of chain extension
and cross-linking.This is a chemicalreaction by which polymer chains are bonded to each
other by the formation of new cross-links,the process usually taking place during or right
after shapingthe final product. Cross-linkingis the random bonding of molecules to each
other to form a giant three-dimensional network. Thermoset resins form a permanent
and infusible shape after the application of heat or a curing agent. As heat is applied
to a thermoset part, degradation occurs at a temperature lower than the melting point.3
Thermosetting resins cannot usually be recycled or reworked once they have set.
6.1.2.1 Polyester Resins
An ester is produced by the reaction between an alcohol, usually glycol, and organic
acids. Different proportions of saturated and unsaturated acids provide polyesters with
varying properties. The polyesters are generally named after the predominant acid or
alcohol in their production. For example, isophthalic polyester is prepared by reacting
isophthalic and maleic anhydrides with propylene glycol.
Orthophthalic polyesters are the cheapest, have limited chemical resistance, and are
often used in the reinforcement structure in dual laminate cons,mction.
Isophthalic and terephthalic polyesters have better chemicapJistance and molding
properties than orthophthalic resins.
Bisphenol and HET acid (chlorendic acid) have improved chemical resistance com-
pared to the phthalic r e ~ i n s . ~
6.1.2.2 Vinyl Ester Resins
These are produced by reacting methacrylic acid with an epoxy resin and styrene. They
are similar to the polyesters and are often grouped with them. Their properties depend
on the particular formulation but they generally have higher mechanical properties
and better thermal and impact shock resistance than the polyesters. They have become
widely used for applications requiring better chemical resistance or for use at higher
temperatures than the polyesters.
6.1.2.3 Epoxy Resins
Liquid epoxy resins are used for the manufacture of high performance water piping
systems and composite pressure vessels. Epoxy-based composites with an anhydride
curing system are available but have a lower temperature resistance than the amine-
cured epoxies. Polyamine-cured epoxies account for more than 80% of all the epoxy pipe
systems manufactured in the world, although the improved anhydride-cured epoxies
are cheaper and becoming more available?
Epoxies reinforced with fiberglass have very high strengths and resistance to heat,
up to about 95°C. Chemical resistance is excellent in nonoxidizing and weak acids but
not in strong acids. Alkali resistance is excellent in weak solutions. Chemical resistance
of epoxy-glass laminates may be reduced by any exposed glass in the laminate. Epoxies
are available as castings, extrusions, sheet, adhesives, and coatings. They are used as
pipe, valves, pumps, small tanks, coatings, and linings.
6.1.2.4 Other Thermosetting Resins
Phenolics. Phenolic resins are often filled with asbestos, carbon or graphite, and silica;
with relatively low cost, good mechanical properties, and chemical resistance except
to strong alkalis.
Furanes. Furane plastics, filled with asbestos, have much better alkali resistance than
phenolic asbestos. They are more expensivethan the phenolicsbut also offer somewhat
higher strengths!
6.1.3 Fiber-Reinforced Plastics
Thermosets are normally used in either coatings or in composites in which the ther-
mosetting plastic is fiber reinforced, usually with glass fiber (Figure 6.1). This type of
6.1 Plastics 155
Figure 6.1 Photo shows a typical FRP spirally wound stirred tank. (Photo courtesy of CARIAD
Consultants.)
composite is variously known as GRP (glass-reinforced plastic), FRP (fiber-reinforced

plastic), or RTP (reinforced thermoset plastic). Glass fiber provides strength and stiff-
ness to the resin. Composites are built up of layers of fibers impregnated or coated with
thermosetting resin into the desired shape of pipe or vessel. The layers may be applied
by hand lay-up or by machine as in filament winding, or by some combination of the
two. In the filament winding process glass fiber rovings are impregnated with resin and
wound onto a rotating mandrel. The angle of the head feeding the fibers can be altered
depending on the type of structure being fabricated.
Irrespective of the method used, the layers of resin and fiber are applied to a mold
starting with the a barrier layer known as the gel coat. This resin-rich layer is usually
reinforced with glass tissue and provides the main resistance to penetration of fluids into
the structure. After the gel coat the next layers are reinforced with chopped strand mat
(CSM) glass, then the structural reinforcement with CSM, woven rovings, or filament
winding depending on design and application. The outer layers use CSM, then surface
tissue with fire retardants, W stabilizers, etc. as required. Depending on the application
the resin used may be the same throughout the structure or different resins may be used
in different layers. Once the structure is complete it must be cured before removal from
the mold or mandrel. Postcuringmight also be required before the equipment is put into
service. Other techniques such as casting, spraying, pultrusion, or molding are also used
to produce FRP components.
Different types of glass fiber are used in the reinforcement.These include the follow-
ing:
Surface veils, E, C, or ECR glass is normally used to reinforce the inner resin layer
and provide the chemical-resistant barrier. Materials other than glass can be used as
surfacing veils for specific applications. Surface veils used on the outside of pipes,
e.g., help resist the UV attack of the resin.
CSM or chopped fibers are used either to reinforce and increase the anticorrosionlayer
or as part of the structural laminate.
Continuous rovings form the structural component of all filament-wound structures.
Woven rovings are used to build up the structural laminatein contact-moldedor band,
wound structures, increasing the glass-to-resin ratio and the strength of the laminate.
Fabrics are used in a similar way to woven rovings but may offer superior handling
properties or strength.
Glass flakes or spheres are used to reinforce resin-based coatings and lining^.^
When glass is drawn into fibers its strength increases considerably compared to that
of the bulk glass. The main type of glass fiber used in FRP reinforcement is E glass, which
is a low-alkali, borosilicate glass fiber. C glass has a composition that gives it improved
chemical resistance so it is used as surface veils in FRP. S and R glasses are special high
strength glasses used in high performance composites?
Resin selection has the single biggest influence on long-term performance of FRP
equipment and can have an equally significant effect on cost. Resin suppliers publish
detailed chemical-resistance guides that indicate the suitability of their products for
a broad range of applications over a range of temperatures. However, some of these
recommendations may be based on tests carried out on laminate coupons that have
been postcured, i.e., heating the FRP component at an elevated temperature for a period
of time to enhance cross-linking of the resin molecules. Even in applications where the
chemicalenvironment is relativelybenign, operating temperature may cause mechanical
deterioration of the resin. In general, the properties of a resin will start to decrease as
its heat distortion temperature is approached and, therefore, for higher temperature
applications, in most cases, a postcure is advisable!
There are three basic approaches that can be used to design FRP equipment?
1. Design to performance criteria is somewhat limited because of the impracticabilityof

verifymg performance through testing of large-diameter (>18 in.) components.
2. Design by rules is appropriate for the majority of applications. For piping, use ASTM
D1599. For vessels, three possible methods are available:
ASME BPV Sec. X provides design rules for FRP pressure vessels. This should be
used when designing FRP tanks operating above 15 psi (0.103MPa).
ASTM D 3299 is intended for tanks operating at atmospheric pressure. Generally,
it is not applicable to pressure piping.
6.1 Plastics 157
ASME RTP-1 is for tanks operatingat or below 15psi (0.103MPa). This specification
has some design rules and general practices that can be used for pressure piping.
For other types of equipment (e.g., ducts and stacks), design criteria need to be
specified or borrowed from a standard such as ASME RTP-1. The fabricator is then
required to provide design calculations prepared and signed by a professional en-
gineer, demonstratingthat the design satisfies requirements similar to those stated
in ASME RV-1.
3. Design by stress analysis is another approach.
6.1.3.1 Dual Laminate Construction
"Dual laminate construction" describes piping or vessels which are constructed from a
combination of thermoplastic and thermosetting plastics. These are made by first con-
structing the liner on a support by welding together thermoplastic sheet, typically 3 to
5 mm thick. Dual laminate tanks and pipes have been made using most thermoplastics,
most commonly PVC, CPVC, PP, PE, PVDF, ECTFE, FEP, PFA, and PTFE. Some thermo-
plastics, such as PVC, bond well with the reinforcing FRP so only need to be covered
with a bonding resin. Others, such as PP and PVDF, need to be produced with a layer of
glass cloth mechanically keyed into the plastic. This glass cloth must be removed local
to the welds. The side of the welds that will be covered with FRP must first be coated
with electricallyconducting tape or paste to permit spark testing. Once the thermoplas-
tic liner has been fabricated the reinforcing FRP is applied in the same way as for a
nonlined FRP item except that often cheaper isophthalic resins are used instead of more
chemical-resistantones.
Dual laminate equipment can often be used at higher temperatures than the thermo-
plastic that is used for the lining. For example, PVC and PE would not normally be used
at temperatures above about 60°C, and PP up to about 80°C,but dual laminates with
any of these thermoplastics could be used up to at least 100°Cwith appropriate resins.
As with unlined FRP hand lay-up, the final quality is very dependent on the skill of the
fabricators and the degree of quality control applied (Figure 6.2).
6.1.4 Elastomers
Elastomers are a class of polymers that have some degree of cross-linking and are rub-
bery. They possess memory, that is, they return to their original shape after a stress is
applied. Natural rubber is a well-known example of an elastomer. The first evidence
of the use of rubber comes from excavations of the 11th century Mayan remains in
Honduras. The use of rubber in Central and South America is mentioned in the 16th
century writings of Spanish explorers. It was used to manufacture waterproof garments,
shoes, and small vessels. In 1761 it was found that rubber could be dissolved in ether
so could be shaped to form tubes, for example, which held their shape once the ether
evaporated. Later it was found that the application of heat and pressure, vulcanization,
Figure 6.2 Photo shows dual laminate piping

with a defective flange, containing major pores
due to faulty workmanship. (Photo courtesy of
could be used to form rubber items. The addition of sulfur enabled items to be formed
that kept their shape better and were not sticky when warm and stiff when cold, as
was the case with pure rubber. The addition of sulfur also increases the strength and
improves chemical resistance. With 7% sulfur rubber can be stretched some eight to
ten times its original length without breaking. With higher levels of sulfur, rubber be-
comes hard and brittle up to the maximum amount of 32%sulfur that can combine with
rubber.’
Elastomers, such as natural rubber, are used in industry for lining vessels, pipes,
pumps, valves, etc. and in joints and gaskets. Elastomers have similar structure and
composition to thermosetting resins, and are in a “rubbery” state at room temperature.
At lower temperatures they can become hard, brittle solids. Elastomers are often used
where abrasion is a problem. Natural rubber is obtained from the latex that exudes from
some 500 different species of plants, especially the tree Hmea brasiliensis. There are many
different types of natural and synthetic elastomers with a wide range of properties and
uses.lvloThese include the following:
6.1 Plastics 159
Natural rubber (NR)is a high molecular weight polymer of isoprene, resistant to most
inorganic chemicals apart from strong oxidizers. It is used in hard or soft linings.
Synthetic polyisoprene is also used industrially,
Polybutadiene (BR) and styrene-butadiene (SBR) have similar properties to natural
rubbers and are often used blended with natural rubber.
Polychloroprene (CR),better known as neoprene. Compounds made from this poly-
mer have better resistance to sunlight, ozone, and hydrocarbons than does NR.
Butyl (IIR), copolymer of isobutylene and isoprene, has better resistance to oxidiz-
ing acids and ozone than NR or CR but is not suitable for exposure to chlorine, or
halogenated or aromatic hydrocarbons.
Polyisobutylene sheet is used as a lining, usually beneath acid bricks, for acid towers,
floors, etc.
Nitrile (NBR),e.g., Buna N@,is a copolymer of acrylonitrile and butadiene, particularly
resistant to mineral oils and fuels. It is difficult to use as a lining material.
Chlorosulfonatedpolyethylene(CSM),e.g., Hypalon@,is formed by treating polyethy-
lene in solid or liquid form with sulfur dioxide and chlorine. This has excellent resis-
tance to ozone, acids, and abrasion.
Polysulfide (PTR), e.g., Thiokol@,has low mechanical properties and heat resistance
but good resistance to water.
Polyalkylene oxide polymers (CO ECO) or epichloro-hydrin has good water, hydro-
carbon, and weathering resistance. It is used for gaskets, seals, hoses, etc.
Ethylene propylene (EP) and ethylene propylene diene monomer (EPDM) e.g.,
Nordel@,have similar properties to IIR; selected compounds have excellent resistance
to water and steam up to 100°C.
Fluoroelastomershave excellent chemical resistance. They are expensivebut find spe-
cialist uses in linings and jointing applications. Examples are Kalrez@,Viton@,and
Kel-F@.
Silicone rubbers, based on silicon rather than carbon, are used in seals and joints.
Their chemical resistance is not particularly good but they are resistant to water, ozone,
and oils. They have a wider range of temperature of use than many elastomers. Fluoro-
vinyl silane (FVMO)or fluorosiliconehas excellentresistance to water and most common
chemicals, but generally poor mechanical properties.
Rubbersbegin to degrade to a lesser or greater extent as the temperature increases.The
resistance to temperature is very sensitive to formulation, additives used, contaminants
on the surface, etc. (Table 6.2).
6.1.5 Degradation of Plastics
6.1.5.1 Environmental
Polymers can degrade by a number of different mechanisms and most are unusable
without additivesthat inhibit degradation. The failure of a polymer will take one of two
forms. Either it will start to lose its surface appearance by discoloration, loss of gloss,
Table 6.2 Upper Temperature Limits for Continuous Service for

Some Elastomers
Temperature
Elastomer Limit, "C
Soft natural rubber 60
Hard natural rubber 80
Nitrile rubber 100
Butyl rubber 125
Ethylene propylene rubber 150
CSM (Hypalon@) 150
Copolymer of vinylidene fluoride 210
and hexafluoropropylene (Won@)
Silicone rubber 250
Perfluroelastomer (Kalrez@) 290
or chalking (appearance of white deposits), or it cracks or breaks. These failures can

be caused by physical or chemical mechanisms. Plastics tend to age, i.e., they tend to
become brittle with time until they crack under applied or residual stresses. They can be
damaged by external impact (Figure 6.3).
The ability of a polymer to respond to stress depends greatly on temperature and most
embrittle upon cooling below their glass transition temperature. Most useful plastics
Figure 6.3 Star cracking on the inside of this dual laminate piping was caused by an
external impact. (Photo courtesy of CARIAD Consultants.)
6.1 Plastics 161
have glass transition temperatures well above room temperature. As a function of pro-
duction, plastics will have internal stresses that can gradually cause distortion, or ag-
ing, with time. The balance between ductile and brittle behavior can be influenced by
anything that changes the molecular motions of the polymer, e.g., time. It can also be
influenced by things that change the energy of the fracture surface. Normally tough
plastics can become brittle in contact with organic liquids and craze, or fail at stresses
well below those that would cause brittle failure in air. This phenomenon is known as
"environmental stress cracking." Detergents or alcohols are known to cause this type of
failure in a number of plastics.
Ultraviolet light can also weaken many plastics and most must contain stabilizing
additions to reduce this effect. Most polymers are largely inert to water and absorb very
little; however, they can be degraded by extremes of pH. Fiber-reinforced thermosetting
polymers can absorb water and be damaged by hydrolysis at the fiber/resin interface."
The engineering use of plastics is often limited by their resistance to heat. Most
plastics soften, expand, and distort as temperatureincreases.The maximum temperature
at which any type of plastics can be used depends on the formulation and treatment it
has received, the load to be applied, the consequences of distortion, etc., so it is difficult
to specify a maximum service temperature. The temperature limits suggested here are a
compilation from many sources and assume no applied loads. Actual applications may
permit higher temperature use or require lower limits (Table 6.3).
Table 6.3 Upper Temperature Limits for Some Nonmetallics ("C)
Source of Data
Nonmetal Authors Ref. 12 Ref. 13 Ref.4 Ref. 14 Other
Porcelain 815
Cement lining 540
PTFE 260 290 260 232
FEP 205 208 204 149
PFA 260 232
PVDF 120-135 150 150 135
ECTFE 150 150
CTFE 180-200 218
ETFE 150 177 149
PVC 60 65-80 60 54-66
CPVC 80 110 80-100
PE 60 54-71
PP 80 105-150 100 93 107
FRP polyester 150-180
FRP epoxy 150-260
PVC/FRP, PP/FRP -100
LDPE 80-100 122
HDPE 80-120 7015
855
UHMWE 129
Table 6.4 Temperature Limits for Plastics in Seawater

Plastic Temperature limit, "C
PVDF (Kynar@)-linedpipe16 135
PP-lined pipe 107
PVDC (Saran@)-lined pipe 79
Epoxy vinyl ester (Hetron@922)17 99
Chlorendic polyester (Hetron@197) 82
54 in conc. desalination water
Vinyl ester (Derakane@470/411)18 99/82
82/82 in conc. desalination water
Bisphenol A Polyester (Atlac@382)19 99
Vinyl ester (Atlac@580) 93
The maximum temperature of use will be modified by loads applied and by the
environment to which it is exposed. For handling seawater typical temperature lim-
its for common thermosetting plastics are slightly reduced from the maximum for
the material, while limits for thermoplastic-lined steel pipe are generally unaffected
(Table 6.4).
6.1.5.2 Biodeterioration of Plastics and Rubber
6.1.5.2.1 Organisms That Attack Plastics
Three types of macroborers predominate in plastics destruction: Limnoridae (gribbles),

Teredinidae (shipworms), and Pholadinae (piddocks).20
Murtesiu striutu is a mechanical borer and one of the most destructive members
of the Pholadidae. It bores by rasping with the thickened anterior margins of the
shell.21+"Unlike other boring bivalves, such as Lithophguln penetration is not assisted
by chemical dissolution of the substrate and, hence, attack is not limited to calcium
carbonate substrates. Any soft rock, wood, plastic, or other material is subject to attack.
The failure of PVC piping in Java from pholad attack occurred in approximately
1 year. It appears to be the most rapid yet reported. All bamboo posts and supports
in the vicinity were also heavily infested with M . striutu but the concrete pier was not
attacked" (Figure 6.4).
Microbial biodeterioration of plastics has also been documented. Among FRP com-
posites, experiments showed that SRB degraded the organic surfactant on glass fibers.
Hydrogen-producing bacteria appeared to disrupt bonding between fibers and vinyl
ester resin and to penetrate the resin at the interface.25
Fungi, including Aspergilus uersiculur and Chetumium sp., can also degrade FRP com-
posites. The matrix resin, additives, and fibers are degraded. There is evidence that the
fungi may be able to use carbon fibers and chemicals in the resins as nutrientsF6
6.1 Plastics 163
Figure 6.4 Boreholes in PVC pipe delivering seawater to a marine laboratory were caused by the
bivalve Murtesia striutu. These mechanicalborers can bore a variety of materials, including wood,
plastic, and soft stone. (Photo courtesy of CARIAD Consultants.)
6.1.5.2.2 Materials Attacked
Polyethylene, polypropylene, polystyrene, polyesters, acrylics, and nylon can be at-

tacked and bored by large marine organisms.27In some cases they are merely etched; in
others they may be penetrated completely.
A number of molding, casting, and extrusion grades of plastic, rubber, laminates,
and cable coverings were tested for periods of up to 15 years in Florida and North
Carolina. All samples were subject to occasional deep penetration by borers.27The
authors concluded that “none of these materials could be expected to be completely
immune.”
The shipworms Teredo apparently cannot bore polyethylene coatings of piping when
immature (before the boring apparatus had calcified), but if they settle on tar or wood
on the coating they can mature and penetrate the coating in days.28
Superficially,there appears to be some confusion about whether PVC is attacked. This
is because, although PVC itself does not appear to be attacked by bacteria, plasticizers in
it are. ”It is a well-known fact that due to its content of plasticizers flexible PVC is highly
susceptible to microbial attack.”29More importantly, PVC is also highly susceptible to
164 NonmetalIic Materials
attack by higher organisms, such as pholads. The most susceptible of several materials
tested in marine exposure was PVC?7 In Brazil, pholads penetrated a PVC pipe in Rio
de Janeiroharbor in 3 years.30It took a similar period for the same species to penetrate
a PVC pipe in Hong Kong3' and less time in Ind~nesia.~'
Polyester-basedpolyurethane is susceptibleto attack. Experimentswith extracellular
esterasesextracted from fungi confirmed that microorganismshydrolyzedboth urethane
and ester/urethane links of polymers but the mechanism may not be the same for all
microorganisms.33Polyurethane may, however, be less susceptible to bacterial attack.
In a study of 16 bacteria on polyester polyurethane, attack was limited and confined
to cultures enriched with nutrients.%Therefore, bacterial attack may be more severe in
polluted environments, as has been found in other studies (see Chapter 2, Section 2.4,
"Pollution").
Susceptibility of polyurethane to bacterial attack may be about to change. In contra-
vention of international treaties on chemical and biological weapons and U.S.law, the
U.S.governmenthas patented a geneticallymodified microorganismthat would decom-
pose polyurethane, in addition to developing other microorganisms that would cause
deterioration of roads, runways, metals, and f ~ e l s . 3 ~
The organic surfactant on glass fibers of FRP composites is degraded by SRB.
Hydrogen-producingbacteria disrupt bonding between fibers and vinyl ester resin and
penetrated the resin at the interface. Acoustic emission testing demonstrated reduction
of tensile strength in a stressed carbon fiber-reinforced epoxy composite after exposure
to SRB.25An FRP composite containing fluorinated polyimide resin and glass fibers
was the most susceptible to fungal attack and showed a rapid deterioration in physical
properties.%
Barnacles are capable of penetrating coatings of coal tar enamel, exposing the under-
lying metal to attack.37
Natural rubbers are degraded by enzymes produced by bacteria, such as Xantho-
rnonas.38
6.1.5.2.3 Remedial Measures
The most common method of prevention of fungal attack of PVC is incorporation of

fungistatsand fungicides into the material. Effectivenessof the fungicideis influencedby
the addition of stabilizersand production procedure^.^^ Addition of fungicides to plastics
appears to be of limited usefulness, however, in preventing some attack. Polyurethane
containing the biocide Actifresh PD1116@was degraded by fungi.33
Plastics used in hospitals frequently contain the biocide hexachlorophene. Biocide
additives in PVC have included quaternary ammonium compounds, pentachlorophe-
nols, halogenated dinitrobenzene compounds, copper 8-quinolinolate, organotin, and
0thers.3~
To our knowledge no one has come up with a solution to the problem of macroborers,
such as pholads, in plastics.
6.1 Plastics 165
6.1.6 The Use of Plastics in Waters
The first plastic pipes were made for sanitary drainage in Germany in the mid-1930s.
Plastic pipe is now used in almost every industry throughout the world. From the cor-
rosion point of view plastic piping can be used for waters, nearly all acids, alkalis, salt
solutions, and other corrosive liquids, and gases. Chemical attack usually increases with
increasing concentration of chemical and with increasing temperature. The smooth in-
ner surfaces of plastic pipes permit high flow rates and discourage the formation of
deposits. Unlike metal pipes, most plastics do not corrode to produce a rough inner sur-
face that increases friction loss. Plastics have considerably lower thermal conductivity
than most other piping materials, resulting in low heat losses or gains. For drain-waste-
vent (DWV) applications, the lower thermal conductivity is an advantage since fatty
substances either do not deposit within the drain line or do so at a reduced rate. The
high thermal expansion of plastic pipes compared with metals must be allowed for in
the design of supports for hot piping systems. For example, the coefficient of thermal
expansion of PVC Type I (50 to 63 x 10-6/oC) is about 4 to 5 times greater than that
of steel (12 x 10-6/oC), and that of polyethylene (PE) Type I is approximately 15 times
greater than for steel.
Plastics are not subject to galvanic or electrolytic corrosion and cannot be used
to ground electrical circuits. Plastic pipe is considerably lighter than metal, concrete,
and asbestos-cement pipe; it ranges in density from 0.90 to 2.0 g/cm3. It can of-
ten be installed by hand instead of using lifting equipment, thus reducing erection
costs.
With the exception of sewer and drainage pipe, all plastic pipe is pressure rated.
There are three different methods of determining pressure ratings:40
1. Schedule number, obtained from the expression 1000 x P/S, where P is the service
pressure and S is the allowable stress, both being expressed in the same units.
2. Standard dimension ratio (SDR), calculated by dividing the outside diameter of the
pipe by its wall thickness.
3. Pressure-level rating, which gives the pressure rating of the pipe at a given tempera-
ture. Plastic pipes are available commercially at many pressure ratings, and the most
popular of these are 50,100, and 125 psi (340,690, and 860 kPa); 160,200,250, and
315 psi (1.1, 1.4, 1.7, and 2.2 MPa).
The designation of thermoplasticpipe uses four digits and an alphabetic prefix show-
ing the kind of resin it contains. The first and second digits show the type and grade
of resin, respectively; the third and fourth indicate hydrostatic pressure divided by 100.
For example, PVC 1120 indicates a pipe made of PVC, Type I, Grade I, with a 2,000 psi
(13.8 MPa) hydrostatic test pressure. The deterioration that occurs in most plastics when
exposed to UV light can be largely counteractedby incorporating W stabilizersinto the
formulation.
1hh Nonmetallic Materials
The most important uses of plastic piping in waters are the following:4o
Home and commercial DWV applications, where permitted by local building codes
Irrigation and water distribution systems because of resistance to soil environments,
ease of installation as a result of their light weight, and low cost
Handling of acidic mine drainage waters
Sewage treatment applications
Water treatment plants for high purity and deionized water since contamination is
minimized
Plastic-lined and all plastic pumps are becoming increasingly used in waters, waste
waters, and in chemicalplant applications.Part of the reason for this trend is the demands
from regulatory agencies for sealless pumps to avoid environmental contamination. An
ASME specification now covers plastic pumps for the first time. ASME specification
B73.5M deals with horizontal centrifugal pumps that use solid plastic for the wet end
parts; it does not include lined pumps. Some plastic pumps use metallic materials for
the shaft or other components. If all materials in contact with the fluid must be non-
metallic then the shaft should be sheathed or encapsulated in a thermoplastic material.
Plastics that are used in rigid plastic pumps include PVC, CPVC, PE, PJ?, PVDF, ECTFE,
PTFE, FRP/GFW!l Plastic and plastic-lined pumps can be damaged, for example, by
extremes of temperature and pressure or mechanical impact. They can also be damaged
by abrasion, e.g., a PTFE-lined pump was damaged when handling a fluid containing
abrasive particles (Figure 6.5).
Most of the compositesused in the water industry are thermosetting resins reinforced
with glass fiber. There is little demand for the high-performance reinforcements such as
carbon or aramid. The resins mainly used in the water industry are polyesters, epox-
ies, and polyurethanes. The vinyl esters and bisphenol resins are not commonly used
in handling clean water but have applications in handling waste waters and aqueous
effluent^.^
Plastics are becoming increasingly common materials of construction for marine ap-
plications, with the possibility of lighter structures being an important consideration
for the offshore industry. Most thermoplastics such as PVC, PP, PE, and the fluorocar-
bons are resistant to seawater and can be applied within their mechanical and thermal
limits. Similarly, FRP based on thermosetting resins, such as polyesters, epoxies, and
phenolics, have good potential for seawater use. All of these polymeric materials suffer
from degradation by ultraviolet light to some extent and so must be correctly formulated
for prolonged external exposure. Poor resistance to fire damage and flame spread is a
negative factor in the use of plastics in some offshore d ~ t i e s . ~
FRP (GRP) piping is used extensively in desalination and power plants for water
transportation and distribution, sanitary/storm/combined sewers, industrial effluents,
power-plant cooling, oilfield applications, slurry, ocean outfalls/intakes, irrigation,
geothermal, well casings, ducts and vents, chemical process lines, and fire fighting.
FRP pipes have been used in Saudi Arabia for seawater temperatures exceeding 60°C.
6.1 Plastics 167
Figure 6.5 This PTFE lined pump was damagedby abrasive particles in the pumped fluid. (Photo
courtesy of CARLAD Consultants.)
This piping is made by various methods: centrifugally cast (CEN),continuous filament

winding (CFW), discontinuous helical filament winding (DHFW), and hand lay-up.
An extensive research and industrial test program looking at the use of FRP pipe for
desalination and power plant applications concluded the following:
Fiberglass pipes are equal to or better than steel, ductile iron, PVC, HDPE, MDPE,
LDPE, asbestos cement, and concrete, where corrosion resistance is required in these
applications. CEN and CFW pipes have used mostly fittings and special parts made of
other pipe materials for higher operating pressures. DHFW pipes have the broadest
applications in the fiberglass pipe industry. Pipe for desalination and power plant
projects should be designed and specified to AWWA C-950,ASTM D-3839, and other
ASTM standards referenced in these two standards.
Quality control and assurance programs should follow ASTM standards require-
ments. Geotechnical and corrosion data for the pipeline alignments should guide
the choice of appropriate designs and specifications. Where there are no adequate
geotechnical data, if the actual soil conditions at site are worse than those specified,
adjustmentsin trench width, quality of bedding material, method of placing and com-
pacting, and the pipe stiffness should be made in accordance with the German ATV
A-127 and finite element analyses of the pipe-soil system.
All FRP pipe lengths should be hydrotested at the fabrication plant for zero leakage
at 200% of the nominal pressure and each joint shall be individually tested for zero
leakage at 150% of the nominal pressure in the trench before any backfilling.42
Fibercast@FRP piping is used in brine and seawater handling in various industries.

For example, 3,000 ft (914 m) of Fh4 grade was used for 225 psi (1.55 m a ) under-
ground firewater piping at a refinery in Cardon, Venezuela. RB-2530 grade of 14-in.-
diameter piping was chosen by the refinery on the basis of a better external corrosion
resistance than the alternatives, stainless steel and carbon steel, and it was more cost-
effe~tive.4~
The possibility of catastrophic failures of GRE/GRP piping in seawater service was
discussed on the NACE Corrosion Network.44Overpressurizing and exceeding design
conditionswere the only circumstances in which such failurewas thought to be likely. The
sealing of flanged joints could be difficult because the flange faces tend to be wavy and
uneven and a soft gasket is needed (typically 1/8 in. thick, Shore A durometer hardness
of 50-70). A torque of around 35 ft-lb (47.5 N-m) is needed to make a seal but the flange
can be overtorqued and cracked (B. DuFresne, Dow Corning Corp.). Another potential
problem is failure from external loading of buried pipe. A seawater line failed under a
road crossing in less than a year. UV degradation, blooming, is generally cosmetic and
not normally a cause of GRP pipe failures (G. Ruschau, CC Technologies).GRP pipe can
also fail catastrophicallyby external impact and should be protected from traffic, moving
objects, etc. (see Figure 6.3).
6.1.7 Standards and Specifications-Plastics
6.1.7.1 ASTM
D 1785-99-Standard Specification for PVC Plastic Pipe, Schedule 40,80, and 120
D 2104-99el-Standard Specification for PE Plastic Pipe, Schedule 40
D2310-97-Standard Classification for Machine-Made "Fiberglass" (Glass-Fiber-
Reinforced Thermosetting-Resin) Pipe
D 2447-99-Standard Specification for PE Plastic Pipe, Schedules 40 and 80 Based on
Outside Diameter
D 2996-99-Standard Specification for Filament-Wound "Fiberglass" (Glass-Fiber-
D2997-99-Standard Specification for Centrifugally Cast "Fiberglass" (Glass-Fiber-
D 3000-95ael-Standard Specification for PB Plastic Pipe (SDR-PR) Based on Con-
trolled Outside Diameter
D 3035-95-Standard Specification for PE Plastic Pipe (SDR-PR) Based on Controlled
Outside Diameter
D3299-00-Standard Specification for Filament-Wound Glass-Fiber-Reinforced Ther-
moset Resin Corrosion-Resistant Tanks
6.2 Concrete and Ceramics 169
D3517-96-Standard Specification for “Fiberglass” (Glass-Fiber-Reinforced Thermo-

setting-Resin) Pressure Pipe
D4097-95ae3-Standard Specification for Contact-Molded Glass-Fiber-Reinforced
Thermoset Resin Corrosion-Resistant Tanks
F 412-00-Standard Terminology Relating to Plastic Piping Systems
F 423-95-Standard Specificationfor PTFE Plastic-Lined Ferrous Metal Pipe, Fittings,
and Flanges
F 441/F441M-99-Standard Specificationfor CPVC Plastic Pipe, Schedules 40 and 80
F 442/F442M-99-Standard Specificationfor CPVC Plastic Pipe (SDR-PR)
F 1545-97-Standard Specificationfor Plastic-Lined Ferrous Metal Pipe, Fittings, and
Flanges
Standards related to biodeterioration of plastics include:
D 5210-92(2000)-Standard Test Method for Determining the Anaerobic Biodegrada-

tion of Plastic Materials in the Presence of Municipal Sewage Sludge
D 5271-93-Standard Test Method for Determining the Aerobic Biodegradation of
Plastic Materials in an Activated-Sludge-Wastewater-TreatmentSystem
G 22-76(1996)-Standard Practice for Determining Resistance of Plastics to Bacteria
G 29-96-Standard Practice for Determining Algal Resistance of Plastic Films
6.2 CONCRETE AND CERAMICS
6.2.1 Concrete
Concrete is a construction material composed of portland cement and water combined

with sand, gravel, crushed stone, or other inert material such as expanded slag or vermi-
culite. The aggregate (stones and sand) used in concrete is graded according to particle
size to minimize the spaces filled with the cement/water matrix. Portland cement is
produced by firing a mixture of limestone and clay and then grinding to a powder (10 to
30 pm). It consists of complex aluminates and silicates of calcium with some free lime.
ASTM C 150 defines it as a hydraulic cement produced by pulverized clinker, consisting
essentially of hydraulic calcium silicates, usually containing one or more of the forms of
calcium sulfate as an interground addition.
In order to describe the composition of a cement a shorthand notation using the
following letters to depict the oxides present can be used:
C-lime, CaO
%-silica, SiO2
A-alumina, A1203
F-ferric oxide, Fen03
M-magnesia, MgO
K-potassium alkalis, K 2 0
N-sodium alkalis, Na2O
5-sulfur trioxide, SO3
-
C-carbon dioxide, CO2
H-water, H20
A typical general-purpose portland cement could be described using this notation as

having the following weight YOof the oxides: C 63, S 22, A 6, F 2.5, M 2.6, K 0.6, N 0.3,
and 5 2.0.
Alternatively, a notation defining the chemical compounds can be used:
C3!%tricalcium silicate, 3CaO.SiOz

CZS-dicalcium silicate, 2CaO.SiO2
C3A-tricalcium aluminate, 3CaO.Al203
C4AF-tetracalcium aluminoferrite, 4CaO.Al203.Fez03
CsH2-calcium sulfate dihydrate (gypsum), CaS04.2H20
Using this notation and weight % of these compounds a normal portland cement can
be defined as C3S 50, C2S 25, C3A 12, C4AF 8, CsH2 3.5.4’
The types of portland cements are specified in ASTM C-150 according to their appli-
cation as follows:
* I General, no special requirements

IA As for I but where air entrainment is needed
I1 Where moderate sulfate resistance or heat of hydration needed
IIA As for Type I1 but where air entrainment is needed
I11 Where high early strength is needed
IIIA As for Type I11 but where air entrainment is needed
*Iv Where low heat of hydration is needed
* v Where high sulfate resistance is needed
The standard chemical requirements for these types of cement are given in Table 1
in ASTM C 150. Optional chemical requirements and standard and optional physical
requirements are also included in this specification.
Type I is the most commonly used general construction cement where no special
properties are required and this is the type supplied if no other is specified. If a more
rapid rate of hardening is required, for example, in precast work where forms are reused
or when concreting at low temperatures, then a Type I11 cement could be used. The same
effect can be achieved by grinding a Type I cement more finely. The increased surface
area produces faster hydration and more rapid development of strength. Type I11cement
should not be used when placing thick sections (>0.5 m) such as piers and abutments,
as the rapid increase in temperature can cause cracking from thermal stress generation
during setting. Thermal cracking can be a problem even with Type I cement and was
frequent with early concrete dams. Type IV cement was developed to counteract thermal
cracking as it produces only a small amount of heat during setting. It also has a slow rate
of hardening but this is not a problem for many applications.
Early concrete constructions were damaged by sulfates in the soil or water in contact
with the structure. This was a problem particularly in the intertidal zone of seawater
where the concrete was exposed to alternate wetting and drying. Type V cement was
formulated to resist this type of attack. In the United Kingdom four types of portland
cement are available: ordinary (BS 12),rapid hardening (BS 12),low heat (BS 1370), and
sulfate resisting (BS 4027). These grades correspond with ASTM Types I, 111, IV, and V,
re~pectively.~~
When hydrated the cement particle surface dissolves and the material recrystallizes
into needle-shaped crystals that bond with the aggregate, rendering the mass rigid. The
concrete mix, i.e., the materials in the mix and their relative proportions, is designed to
produce a final product possessing a certain compressivestrength.Typically this strength
will be 2,500 to 5,000 psi (17 to 34 MPa). Concrete mixes can also be designed to make
the product dense and impermeable, porous and light, water-resistant, etc. depending
on the end use.
There has been a recent trend to produce higher strength concretes. This has been
largely driven by the need for large oil platforms, known as Condeep platforms, for use
in the North Sea. These platforms can contain more than 100,000 m3 of concrete with a
specified minimum strength of at least 80 MNmP2.The principal way that this higher
strength has been achieved is by reducing the amount of excess water in the mix. This
is obtained by the use of superplasticizersand water-reducing agents which work for a
short time while the concrete is being placed and compacted. Another improvement in
strength is achieved by the addition of fine silica, known as silica fume or microsilica,
particles to the cement. The final change has been the partial replacement of some of
the cement with pulverized flue ash or granulated blast furnace slag. These react more
slowly and reduce the potentially damaging high temperatures during setting while
achieving the same final strength as high cement mixes.&
6.2.2 Reinforced Concrete
The disadvantage of concrete (togetherwith brickwork and masonry) is that while it has
excellent compressivestrength it has a low tensile strength and is brittle. This brittleness
and lack of tensile strength limited the constructional use of concrete since only short
self-supportingspans could be built. Reinforcing with stronger, more ductile materials
began with cement-bonded steel. In this, steel members were incorporated in three di-
mensions into concrete thus providing resistance to delamination and buckling. In 1848,
Lambot in Francebuilt a series of rowing boats, some of which have survived, out of steel-
bonded bars and wires. This concept was developed into reinforced concrete in which
the concrete bears the compressive stresses while the steel carries the tensile loads.47
In 1900, Thomas Edison had a house in Florida where he made and tested many of
his prototype inventions. He also built a concrete swimming pool that was reinforced
Figure 6.6 An elevated reinforced concrete tank that is used for water storage. (Photo courtesy
with a special strain of locally grown bamboo. This pool has apparently never needed
repairs.48The use of bamboo reinforcement has not become widely adopted although
other natural and synthetic fibers are used in the reinforcement of concrete and cement
mortars. Reinforced concrete is extensively used for water piping, troughs, and tanks
(Figure 6.6).
6.2.3 Prestressed Concrete

Prestressing of concrete structures was developed as early as 1886, but the French engi-
neer Eugene Freyssinet first implemented modern prestressed concrete construction in
1940. He proposed the use of high strength steels with high elongation to provide far su-
perior structural performance than was previously possible with concrete construction.
Prestressed concrete is widely used in all forms of building and civil engineering struc-
tures. The use of high performance steels has led to significant advances in prestressed
concrete design but susceptibility of these steels to corrosion has become a major con-
cern. The discovery of corrosion and tendon failure in post-tensioned buildings and
parking structures has had a major influence on the value of these buildings. Prestressed
concrete nuclear containment structures require inspection of the prestressing elements

every few years to ensure continuing structural integrity. In the United Kingdom, fol-
lowing the collapse of two prestressed bridges, the Highways Agency banned the use
of grouted posttensioned bridge construction for a period of 4 ~ e a r s . 4 ~
Prestressed concrete provides a permanent state of stress that opposes that induced
by an external load. Prestressing is usually achieved by high strength steel wires that
are held in tension while the concrete sets. Because the wires in prestressed concrete are
subject to stresses equal to 70 to 75% of their ultimate tensile strength, they can reach
a failure condition after only limited metal corrosion. A 20 to 30% reduction in wire
diameter by corrosion can cause them to
Prestressed concrete cylinder pipe (PCCP)is widely used to carry all types of waters,
including potable and waste. It is also used in supplying fresh, brackish, or seawater to
industrial plants including coal fired and nuclear power plants. For example, Figure 6.7
shows a typical installation for a cooling seawater intake to a power plant. PCCP pipe
Figure 6.7 Photo shows a PCCP seawater intake system for cooling water for a power plant. The
pipe is 108 in. (2.7 m) diameter and the manifold 168 in. (4.3 m). (Photocourtesy of Price Brothers
Company.)
1 74 Nonmetallic Materials
16 to 48 in. (0.4 to 1.2 m) diameter is a lined cylinder pipe (LCP) in which a steel cylinder
is lined with concrete by centrifugal casting. Embedded cylinder pipe (ECP) in which a
vertical steel cylinder is embedded within concrete is used for larger diameters. In both
cases prestressing wire is wrapped helically under tension around the outside of the
cylinder to maintain the concrete in compression. Cement slurry is applied between the
wire and the cylinder on LCP and between the wire and the concrete surface on ECP,
followed by a layer of dense concrete. Concrete is cured under controlled conditions of
temperature and humidity. All normal fittings such as tees, elbows, reducers, etc. can be
made using the same technique^.^^^^
PCCP has been in use for more than 60 years with more than 28,000 km in service in
fresh and waste water. Corrosion failures have mainly been caused by chlorides, sulfates,
or low pH conditions. The early pipes were not provided with corrosion protection but
now CP is sometimes used in high chloride environments. Requiring the potential to
be moved -850 mV (CSE) is unnecessary and uneconomic because only local elements
are likely to be corroding and need protection. A minimum shift of 100 mV (CSE) is
suggested and no more than -1000 mV (CSE) should be applied because of the dangers
of hydrogen embrittlement. CP increases the pH around prestressing wire in carbonated
mortar or around corroding wire to initial uncarbonated or noncorroding levels. The
ductility of prestressing wire under excessiveCP recovered after CP was removed. Most
of the ductility was recovered in the first 4 weeks after removal, but 8 weeks was required
for complete recovery?
6.2.4 Deterioration of Concrete in Waters
Concrete can be damaged or destroyed by physical, mechanical, chemical, or biological

attack. The deterioration of the concrete can be the first step in the corrosion of the steel
reinforcement that leads to loss of structural integrity. Examples of the processes that
can damage concrete include:
Freeze/thaw cycles. Water in the pores of the concrete freeze and expand causing
spalling. This can be avoided by intentionally including pores in the concrete. De-
icing salts increase the problem.
Chemicalattack. Acids, soft water, or seawater can dissolve alkalinecomponents of the
cement or aggregate. Cold seawater does not attack concrete with low permeability,
i.e., high cement content, low water/cement ratio.
Sulfates and magnesium salts can form corrosion products with large volume.
The aggressiveness of waters has been classified according to composition in DIN

4030 (Table 6.5). This classification cannot be applied to seawater, which would be clas-
sified as aggressive on the basis of its magnesium and sulfate contents.
Concrete has been used extensively for marine construction for many years. It is an
extremely variable material whose properties depend mainly on constituents used and
Table 6.5 Classification of Aggressiveness of Waters from DIN 403053
Degree of Attack
Component Fair Strong Very Strong
PH 6.5-5.5 <5.54.5 t4.5

Free COZ(mg/L) 15-40 40-100 >100
Ammonium ion (mg/L) 15-30 30-60 >60
Magnesium ion (mg/L) 300-1000 1000-3000 >3000
Sulfate ion (mg/L) 200-600 600-300 >3000
method of manufacture The concrete itself is normally reasonably resistant to seawater

although magnesium salts in seawater can cause deterioration and concrete structures
can suffer mechanical damage from, for example, wave action. Generally the problems
with concrete are caused by inferior materials, bad formulation or technique, or, most
commonly, to attack on the reinforcement. Examples of poor materials and formula-
tion include unsound or reactive aggregates, cement with high alkali or tricalcium alu-
minate, cement, water or aggregate with high sulfide content, and insufficient cement
content.
Techniquesthat increase the life of marine concrete structures include the following:54
Use cements with low tricalcium aluminate levels; less than 5 to 6% portland Type 3
is recommended for marine applications.
Cements must have a low alkali content, less than 0.65%.
Water used for mixing should be potable and chloride free, as should the aggregate.
All sand should be washed thoroughly with potable water to remove chlorides from
seawater contamination.
A cement content of at least 300 kg/m3 is required with a water-to-cement ratio no
greater than 0.4.
Concrete cover should be adequate to protect the steel. Thickness needed will depend
on the application but should never be less than 5.0 cm.
The reinforcement can be protected by using stainless steel, coating the carbon steel,
using inhibitors in the concrete, sealing the concrete surface, or applying cathodic
protection (sacrificialanodes or impressed current).
A review of many case histories found that the permeability of concrete is the key
to overall durability. The harmful reactions between seawater and the hydrated cement
paste, such as carbonation, sulfate attack, and magnesium ion attack, can be limited
to the surface if measures to restrict permeability are implemented. Unreinforced con-
crete structures made with low water/cement ratio and high cement contents (e.g., more
than 350 kg/m3) have usually given good marine service except when exposed to high
thermal gradients, frost action, or alkali aggregate attack. High permeability in newly
Next Page
176 Nonmetal Iic Materials
built concrete structures is not limited to poorly proportioned mixes, i.e., low cement,
high water/cement ratio, and improper aggregate grading. Well-proportioned mixes
can still be permeable from poor concreting practices, e.g., incomplete mixing, inade-
quate consolidation and curing after placement, insufficient cover over reinforcement,
and badly constructed joints. Even a well-constructed structure with good mixes can
become permeable from cracking caused by settlement, premature loading, overloads,
and repeated impacts. Control of cracking in service is at least as important as the initial
concrete quality.
To produce a marine structure with low permeability and long life a very high strength
concrete mixture (60 MPa or higher compressive strength) is needed. Such mixtures
invariably contain a high cement content, a low water/cement ratio (max 0.40), a high
quality coarse aggregate of relatively small size (max 20 mm), a water-reducing agent
(usually a superplactisizer),and a mineral admixture, condensed silica fume, or a good
fly ash or granulated blast furnace slag. An air-entraining mixture must be used when
protection against frost is needed. In concrete mixtures with little or no permeability
the chemistry of the cement seems to have little effect on the long-term durability in
seawater. The concrete must be placed so that the final concrete is as uniform as possible
with a smooth surfacefinish. Temperatureand humidity conditions that facilitatecement
hydration must be maintained for a sufficient period of time. Avoidance of shrinkage,
overloads, and the provision of adequate concrete cover over reinforcement are the final
requirements to produce a durable marine structure.55
A discussion on the NACE Corrosion Network debated the effect on durability of
using a concrete of a lower strength than specified. This was for an application near a
river that could become brackish but where water immersion or regular spray was not
expected.% The general opinion was that while compressive strength was not a good
guide to durability the denser the concrete the less likely it was that chloride ingress
and rebar corrosion would occur. Concrete deck units for a major U.K. road tunnel
required a design life of 120 years. They were built with 65% ground-granulated blast
furnace slag 0.36 w/c ratio and worst-case minimum cover 30 mm (typical 40 nun) with
a waterproofing system on the deck. That was felt to be the level of protection needed in
a high chloride environment for durability beyond a decade or two at most. In order to
prove the durability, the chloride levels on the old deck units were computer-modeled
using the mix design to predict the diffusioncoefficientand calculatethe time to corrosion
initiation and cracking. The computer model showed well over the required 120years of
life. Cores taken out of the concrete were used to measure the actual diffusion coefficient,
which was better than the predicted one. When the compressive strength dropped from
around 60 MPa to under 55 MPa the diffusion test was repeated and the decrease in
diffusion coefficient was negligible. In this case changes in the grinding and reactivity of
the cementitiousproducts gave a slower strength development. This is likely to improve
the long-term durability (and compressive strength) of the concrete as cement matrix
develops more slowly and more fully. If the lower 28-day strength were caused by
a higher than specified water/cement ratio or a lower cement content, however, then
durability would be decreased as well as concrete strength (J.P. Broomfield, BGB Projects
Ltd.).
Previous Page
Figure 6.8 Bridge span over a tropical estuary showing area of exposed, corroded rebar. (Photo
courtesy of CARIAD Consultants.)
6.2.4.1 Corrosion of Reinforcement
The main problem with reinforced concrete is corrosion of the reinforcing metal (rebar)
that is usually mild steel (Figures 6.8 and 6.9). Initially, the alkalinity in the concrete pro-
vides some protection from corrosion. As water, often containing chlorides and carbon
dioxide, seeps through the cracks and porosity in the concrete this alkalinity becomes
neutralized, and the steel becomes depassivated and begins to corrode. Carbonation
describes the reaction by which the alkalinity of the concrete is gradually reduced by
reaction with carbon dioxide from the environment. A similar reduction in alkalinity oc-
curs by reaction with sulfur dioxide from acid rain. Chloride depassivation occurs when
free chloride ions (acid-soluble chlorides) reach the iron surface. Much of the chloride in
the concrete is bound physically and chemically and is not involved in this reaction. The
resulting corrosion product has a volume many times larger than the steel from which
it is formed. This expansion induces tensile stresses that cause disruption and cracking
of the relatively brittle concrete surrounding the steel, thus permitting more ingress of
water and allowing the process to continue.
A survey of more than 100concrete structures in the Arabian Gulf found that a typical
life was 10 to 20 years, well short of the design life of 50 years. Some of the methods used
Figure 6.9 Close-up photo of corroded rebar in bridge shows flaking of concrete and steel cor-
rosion products. (Photocourtesy of CARIAD Consultants.)
to prevent corrosion have been the following:57
Increase concrete cover.

Use low permeability concrete.
Apply penetrating sealers.
Install waterproof membranes.
Coat the rebar with epoxy.
Use galvanized or alloy rebar.
Add corrosion inhibitors to the concrete mix.
Some of these methods must be included at the design stage and rely heavily on
quality control during construction. Some of them, such as sealers, need to be reapplied
periodi~ally.5~
Fusion-bonded epoxy-coated reinforcement (FBECR) has often been used success-
fully but has also had major failures, often attributed to coating damage during or prior
to installation. Galvanized rebar is said to be an inferior option to FBECR but is more
resistant to mechanical damage. Many different chemicals have been used as inhibitor
additives, including chromates, phosphates, hypophosphates, alkalies, nitrites, and flu-
orides. Calcium nitrate is being used since it is also a set accelerator, but it is consumed
by reactions with chlorides so long-term durability is questionable. Cathodic protection
Table 6.6 Concrete Requirements Related to Service Exposure from European Pre-Standard ENV”
Max Water/ Min Cement Min Concrete

Cement Ratio Content (kg/m3) Cover (mm)
Exposure Class Reinforced Prestressed Reinforced Prestressed Reinforced Prestressed
Dry 0.65 0.60 260 300 15 25

Humid/no frost 0.60 0.60 280 300 20 30
Humid / frost 0.55 0.55 280 300 25 35
Humid/frost/ 0.50 0.50 300 300 40 50
deicing salts
Seawater/no frost 0.55 0.55 300 300 40 50
Seawater/frost 0.50 0.50 300 300 40 50
(CP)can be readily included in construction by using catalyzed titanium ribbon attached

directly to the rebar cage before the concrete is poured. This method is being increasingly
used in new structures as a long-term solution to rebar corrosion.
The recommended requirements for durable concrete according to the European Pre-
Standard ENV 206 are shown in Table 6.6. This relates water-to-cement ratio, minimum
cement content, and minimum concrete cover to the type of exposure expected of the
concrete.
Attack of the steel reinforcement occurs in a number of phases. During the initiation
phase aggressive substances, usually chlorides or carbon dioxide, penetrate from the
surface into the bulk of the concrete. This phase ends when these substances reach the
steel in sufficient concentration to cause depassivation by chloride ions or carbonation.
The time taken for initiation depends on depth and quality of the concrete cover and the
extent of wetting/drying at the surface. Once the steel has been depassivated the prop-
agation phase, corrosion in the presence of oxygen and moisture, can proceed. The rate
at which corrosion occurs will depend on temperature, humidity, concrete composition,
e t ~ . ~ ~
The corrosion of reinforcement in concrete when exposed to seawater depends on the
supply of oxygen to the metal surface. The rate of supply of oxygen depends on the
thickness of the concrete cover and on the cement/water ratio. Increase in either of
these factors decreases the rate of oxygen diffusion through the concrete to the rebar. If
the concrete is cracked or porous oxygen and corrodents can reach the steel without the
slow process of diffusion.
Damage to concrete exposed to seawater is most severe in the intertidal area where
the concrete is subjected to frost action, wetting and drying that concentrates chlorides,
capillary rise of seawater in pores of the concrete, and to attrition by wave action.60
The level of chlorides that can be accepted in concrete structures has been hotly
debated. Chlorides are often present in constituents of concrete mixes and are sometimes
deliberately added in the mix if, for example, calcium chloride is used as an accelerator.
A recent report has suggested acceptable limits to be used in new construction. The first
three rows in Table 6.7 are the recommended limits with data from current national codes
included for comparison.
Table 6.7 Chloride Limit % by Weight of Portland Cement?
Prestressed Reinforced Concrete Reinforced Concrete

Test Method Concrete in Wet Conditions in Dry Conditions
Acid-soluble 0.08 0.10 0.20
ASTM C 1152
Wa ter-soluble 0.06 0.08 0.15
ASTM C 1218
Wa ter-soluble 0.06 0.08 0.15
Soxhlet*
ACI 318 0.06 0.15 if exposed to 1.00
chlorides, 0.30 for all
other reinforced
concrete
Norwegian Code 0.002 0.60, acid-soluble chloride
NS 3474
British Code 0.35 for 95% of the results with no result >0.50,
CP 110 acid-soluble chloride
T h e Soxhlet method is said to determine only those water-soluble chlorides that are involved in
the corrosion process. The method is described in this report and in ASTM PS118-99.
Avoiding or minimizing corrosion of the reinforcement in new concrete can be tackled

in a number of ways:
1. Specify other reinforcement-stainless steel, galvanized or coated reinforcement.

2. Use special cements, e.g., those containing inhibitors.
3. Apply cathodic protection or cathodic prevention.
4. Coat the concrete surface with, e.g., organic coatings or hydrophobic surface
treatments-silanes or siloxanes. The surface cannot be protected in permanently
wet applications.
All of these methods are being used and are discussed below.
6.2.4.2 Reinforcement Materials Other Than Carbon Steel
One of the most popular remedies to improve durability of new concrete structures
in high chloride environments is to use reinforcement that is either a more corrosion-
resistant material than carbon steel or is coated.
6.2.4.2.1 Stainless and Low Alloy Steels
The use of stainless steel reinforcement of concrete in marine structures dates back at
least 60 years. One of the best-known examples is the 2,100-m pier at Progreso, Mexico.
This pier was constructed between 1937 and 1941 using 220 tonnes of 304 stainless
rebar 30 mm in diameter. Stainless steel was used because of the hot, humid marine
environment and because the concrete was made of local limestone aggregate that has
a relatively high porosity. A later pier was constructed next to the first one using carbon
steel rebar and virtually disappeared within 30 years. The pier with the stainless steel
rebar was inspected in 1998 and judged to have at least 20 to 30 years of remaining life
even without significant routine maintenance.62
In practice, for the vast majority of applications of stainless steel reinforcement, the
choice will be between EN grades 1 . 4 3 and ~ ~ 1.44xx (usually 1.4301 [304]or 1.4436[316]).
The choice of grade is a major cost factor since the 1 . 4 3 grades
~ ~ are some 15 to 20% less
expensive than the 1.44xx grades. The primary reason for the lack of use of stainless
steel rebar is initial cost, but this is only part of the costs involved, particularly if costs
of maintaining, refurbishing, or rebuilding structures can be reduced. The cost premium
associated with using stainless steel can be minimized by the following:
Using the material only where there is both a significant risk of corrosion and where
remedial work would be difficult and disruptive, e.g., in intertidal and splash zones.
By selecting the most appropriate grade of stainless steel for a given situation; in most
cases this will be EN 1 . 4 3 steel
~ ~ but it depends on the use of coatings, membranes,
and life expected.
By recognizing the inherent corrosion resistance of stainless steel and altering design
for durability requirements to take account of this, e.g., cover can be reduced to 30 mm
or allowable design crack width i n ~ r e a s e d . ~ ~
A recent U.K. Highways document advises that stainless steel reinforcement should
be used in the following cases:
On parapet edge beams

On substructures in splash zones adjacent to carriageways
On substructures in marine environments (and superstructures subject to spray)
Below movement joints and on associated bearing shelves (continuous decks and
integral bridges are still the preferred solutions as opposed to bridges with movement
joints)
For most structures 1.4301 (304) grade 500 N/mm2 ribbed is recommended with
1.4436 (316), 1.4462 (318), or 1.4429 used in specific circumstances, eg., where there is
direct exposure to chlorides or where higher strength is needed. Where stainless steel
reinforcement is used some of the requirements of design for durability can be relaxed,
namely, the cover thickness can be relaxed to 30 mm, the design crack width can be
increased to 0.3 mm, and silane treatment is not required.@While most stainless steel
rebar used has been 304,316, or 316LN, some duplex 2205 has also been used.@
Stainless steel reinforcement was tested in stagnant and flowing seawater for expo-
sure times up to 12 years.66These tests on 316 found the following:
316 partly embedded in concrete showed excellent corrosion resistance to seawater.

The alkalinity of the concrete was thought to exert a beneficial effect even to areas
remote from the embedded section.
When the area of stainless steel outside the concretewas small, attack was nonexistent
or superficial even after 12 years of exposure.
When the area was larger, i.e., 250-mm-long specimens with 72 mm in flowing sea-
water, some localized corrosion occurred but it did not affect strength or ductility.
Crevice corrosion was observed on only one specimen and that after >12 years of
exposure.
The slight tendency to crevice corrosion by 316 can be reduced by using concrete
with low aggregate/cement and water/cement ratios to provide a dense concretewith a
substantial reserve of alkalinity and the maximum permissible content of C3A to reduce
the effects of chlorides. The beneficial effects of high C3A in resisting chloride attack,
however, conflict with the benefits of having low C3A to resist attack by sulfates. The
area of stainless steel outside the concrete should be minimized; copper alloys should
not be allowed to contact the steel. This contact can be prevented by painting, and the
electrochemical effects removed by contacting the stainless steel with mild steel, zinc, or
Various stainless steels were tested electrochemically in solutions simulating the so-
lutions in the pores of both alkaline and carbonated concrete in the presence of chlorides.
The pH was 7.5 to 13.9. The use of stainless steel rebar was able to delay or stop the ini-
tiation of corrosion. In saturated calcium hydroxide the chloride level for initiation of
corrosion in the low chromium AISI 410 was 2%,while in the austeniticand duplex steels
it was 5%.A temperature increase from 20 to 40°Cdecreased resistance to localized corro-
sion. In solutions simulating carbonated concrete the critical chloride content decreased,
especially for steels with low chromium. Nickel in the steel was beneficial in alkaline,
noncarbonated solutions. Similar pitting resistance in alkaline solutions was shown by
304 and 316 stainless steels, while no localized attack was seen on superaustenitic UNS
S31254 under any test ~onditions.6~
Other trials on the use of stainless steel rebar involved exposing concrete prisms
containing different rebar materialsto marine environmentsin SouthAfrica. The concrete
cover used was thin (12.5 and 25 mm) to ensure rapid results. In one of these trials the
prisms were exposed to alternate wet and dry conditions, using a salt fog of 3.5%NaCl
for the wet phase. All of the prisms with carbon steel or galvanized steel rebar showed
evidence of corrosion and cracking within the first year and were extensively corroded
and cracked long before the end of the 5-year test period. The epoxy-coated rebar was
generally in good conditionwith only isolated areas of corrosion. The prisms with 3CR12
(a low chromiumferritic stainless, grade 1.4003to EN 10088)and those with 304 stainless
steel rebar were generally uncracked with only negligible corrosion of the rebar. This
type of alloy steel rebar was demonstrated to be cost-effective for applications such as
road or bridge decks in marine environments.68
In some cases, the need for cost reduction has led to the use of stainless steel re-
placement only in critical areas with carbon steel for the rest of the structure. This has
raised concerns about possible galvanic corrosion between the two types of steel rebar.
This effect was studied in chloride-contaminated reinforced concrete specimens. The
cathodic behavior of stainless steel and carbon steel was also studied by means of PO-
tentiostatic and potentiodynamic tests in alkaline solutions. These tests showed that the
galvanic coupling with stainless steel can enhance the corrosion rate of active carbon
steel reinforcement in carbonated or chloride-contaminated concrete, but this increase is
appreciable only under particular situations. In any case it was no worse than coupling
with passive carbon ~teel.6~
A comparative investigation of corrosion characteristics of conventional, corrosion-
resistant, and low nickel grade stainless steels in environment similar to those faced
by concrete rebar was carried out to assess the use of stainless steel as reinforcement
bar in marine applications. Dissolution kinetics and polarization investigations were
carried out on these steels in artificial seawater, calcium chloride (3M),sodium hydrox-
ide (3M), and saturated calcium hydroxide solutions. The dissolution kinetics for all
the steels in these media follows a linear rate law. Dissolution rate of low nickel con-
taining stainless steel was found to be the highest in artificial seawater and lowest in
saturated calcium hydroxide solution. The low nickel-grade stainless steel has a cor-
rosion resistance about five times higher than that of conventional concrete reinforc-
ing steel and corrosion-resistant steel in various corroding media. Low nickel-grade
stainless steel was also found to have better resistance to pitting for rebar applica-
tion~.~~
A new high strength low alloy (HSLA) steel reinforcing bar was compared with
carbon steel in saline and sulfurous electrolytes in potentiodynamic tests as well as in
natural marine and industrial environments. The HSLA and mild steel rebar embedded
in concrete were also tested in saline water by alternate immersion test and by im-
pressed anodic current methods. The bare HSLA rebar showed 2 to 3 and 1.5 to 9 times
better corrosion resistance than mild steel rebar in laboratory and field exposure tests,
respectively. The HSLA rebar embedded in concrete and exposed to saline water with
impressed anodic current of 200 pcm’ showed 2.5 times better corrosion resistance than
mild steel rebar. X-ray diffraction analysis of the rust formed on the samples of field
exposure tests clearly showed the formation of compounds that reduce the corrosion
rate of steel.71
6.2.4.2.2 Coated Rebar
Metallic coatings, either passive film formers, silicon or chromium based, or sacrificial
galvanized steel, have been evaluated and occasionally used. The film former coatings
can lead to severe pitting if they are broken or damaged since the steel is anodic to
the coating. On the other hand, the zinc in galvanized steel is cathodic, i.e., protective,
to the steel. Galvanized coating is passive in concrete and can remain passivated at
lower pH levels (perhaps down to 9.5) than can black mild steel. It can also withstand
exposure to chloride ion concentrations several times higher than that which corrodes
mild steels.Other coatings such as inhibited cement slurry,bitumen paints, etc. have also
received a certain amount of attention as possible methods to limit chloride corrosion of

reinforcement.72
Electrogalvanized reinforced concrete was exposed in the atmosphere or immersed
in seawater and potable water over a 2- to 3-year period. The potential was monitored.
Two grades of concrete were used: lean with 1 part cement, 3 sand, 6 aggregate, and
0.68 water; and rich with 1 part cement, 1.71 sand, 2.09 aggregate, and 0.5 water. To
induce corrosion of the rebar, chlorides were deliberately added to the concrete mix at
levels from 0 to 3.5 wt% sodium chloride. Damage was more severe in lean mix concrete,
but if chlorides were high (>0.5%) attack would occur even in the rich mix concrete.
The galvanized coating was substantially corroded and the underlying steel attacked
in all immersion tests. Corrosion increased with increasing levels of chloride but was
significant even without added chlorides.”
A novel method for corrosion protection of rebar in concrete is to attach a zinc wire
along the length of the carbon steel rebar. The results from accelerated corrosion tests
indicated that the zinc wire effectively protected the rebar and it could last longer than
the zinc coating of equivalent weight on galvanized rebar. The self-corrosion loss and
galvanic corrosion loss of the zinc wire depended on the water/cement ratio and the
concrete cover thickness. The galvanic corrosion loss is also a function of the size of the
protected steel, and for a steel pipe larger than several centimeters most of the loss is
by galvanic corrosion. More effective protection can be obtained when the surface of the
steel is also coated with an insulating coating.74
FBECR has been used for more than 20 years in high chloride applications such as
bridges, parking garages, etc. It has been estimated that this product has been used
in more than 100,000 structures in the United States and Canada and this equates to
more than 2 million tonnes of epoxy-coated rebar. A review in 1982 concluded that
the use of galvanized rebar was unlikely to give the desired life of 40 years plus and
FBECR became the North American rebar of choice for these duties. In Europe, this
product is comparatively little used and membranes seem to have been selected more
often.75Marine bridge supports using FBECR in Florida were found to be extensively
corroded after less than 10 years of service. Investigation revealed severe metal loss with
additional local pitting. Accumulation of low pH water was found at the metal coating
crevices where the coating had become disbonded. The coating disbonding extended
beyond the areas of high metal loss. The deterioration could not be attributed to any
deviation from construction design or materials specification. It was concluded that the
coating was damaged by a combination of factors, including mechanical, weathering
prior to construction, and macrocell action during service in the severely corrosive,
marine e n ~ i r o n m e n t . ~ ~
Concerns over adhesion of the epoxy to the steel have been addressed over the years
and the product available today is much better in this respect. The requirements for
the steel, coating process, testing, and number and size of allowable defects for epoxy-
coated reinforcing bars is detailed in ASTM A 775. There have also been developments
in the use of reinforcement cages that are prewelded, then dipped in epoxy, before being
installed in the structure and the concrete poured. This technique should reduce the
risk of damage and the exposure of cut ends. The high electrical resistance of FBECR,
however, largely precludes the application of electrochemical techniques for corrosion

control or m o n i t ~ r i n g . ~ ~
Black, galvanized, and epoxy-coated reinforcing steels were compared in chloride-
contaminated concrete in laboratory tests. Epoxy-coated rebar provided excellent pro-
tection as long as the coating was intact. At points of damage, such as cut ends, corrosion
was similar to that of black bar and progressed along the bar under the coating. The large
negative half-cell potentials measured were generated at minor holidays and points of
damage in the coating. This finding suggested that the use of half-cell potentials is not a
reliable way of assessing the corrosion occurring in epoxy-coated rebar. Half-cell poten-
tial measurements were effective in assessing the performance of galvanized rebar and
estimating the remaining life of the zinc coating. Galvanized reinforcing was shown to
be able to tolerate chloride levels at least 2.5 times higher than that causing corrosion in
black steel. Zinc provided sacrificialprotection of exposed steel at cut ends for a distance
of about 8 mm. The total period over which galvanizing delayed the onset of corrosion
was of the order of 4 to 5 times that for black steel rebar under the same conditions.n
Similar results were obtained from tests in natural exposures in seawater tidal zone
and an accelerated wetting and drying regime. Precracked and loaded specimens were
included in the program. Uncoated bars were badly corroded under natural exposure
and a concrete cover of up to 70 mm was inadequate to protect the steel under natural and
accelerated conditions.The zone below mean tide was more aggressive than above mean
tide for these bars. The galvanized bars showed much improved performance but pitting
and damage of the zinc coating was observed even under natural exposure. The upper
tidal zone was more aggressivefor these bars. Epoxy-coatedbars with a coating thickness
of 200 to 300 pm were practically unaffected under natural and accelerated conditions,
under concrete cover as little as 20 mm, and even in the case of artificially damaged
coatings. In cracked concrete containing chloride-contaminated aggregate undamaged
epoxy coatings were excellent. Damaged coatings in similar conditions showed signs
of rusting but the rate of corrosion was far less than that of uncoated or galvanized
bars.78
Experience in the field with metallic and nonmetallic-coated reinforcement has been
mixed with effects varying from the none to strong pitting or general attack to strongly
positive. Many of the problems reported in the literature can be traced to poor work-
manship or installation, e.g., bad coatings, damage during construction, poor concrete
formulation, inadequate cover, etc.
Two of the most widely used corrosion protection systems for steel in reinforced con-
crete are epoxy-coated steel and calcium nitrite. In severe exposures to de-icing or marine
environments engineers often specify more than one protection system, referred to as a
”Beltsand Suspenders” approach. The performances of calcium nitrite and epoxy-coated
reinforcing bars in combination were assessed during several years of accelerated testing
in good quality concrete. The presence of calcium nitrite improved the performance of
epoxy-coated reinforcing bars, even when they were severely damaged such as might
occur in poor handling or concrete placement. Undamaged epoxy-coated reinforcing
bars had similar performance to calcium nitrite alone and the combination system was
an i m ~ r o v e m e n t . ~ ~
6.2.4.2.3 Nonmetallic Rebar
Fiber-reinforced plastics have also been used as concrete reinforcement. These materials
have high tensile strength, low density, and are nonmagnetic, but the choice of fiber
and resin is important since some fibers and resins can be attacked in highly alkaline
environments. Glass fiber-reinforced and prestressing reinforcements have been used in
some applications.Carbon fiber and aramid fiber compositeshave been used to repair or
strengthen existing structures and are increasingly being used in prestressing tendons.
Alkali-resistant glass or the use of carbon or aramid fibers are needed to avoid attack by
the alkaline concrete but the resins have received relatively little attention to date.53
FRP specimens were made of carbon and glass fibers using a procedure similar to
that used in actual manufacture of an FFW grid. These samples were exposed to water,
saline and alkaline solutions, and air under a tensile load of 50 or 30% of their ultimate
strengths. A total of 120 specimens were tested, 96 made of carbon fibers and the rest of
glass fibers. The specimens were examined at 45,122, and 370 days from beginning the
exposure by scanning electron microscopy and Fourier transform infrared spectroscopy.
The glass-fiber specimensexposed to an alkalinesolution failed even before the first series
of examinations (45 days) could be carried out. The carbon-fiber specimens exposed to
the alkaline solution showed signs of physical damage in the form of etching, cracking,
and even spalling of the resin?O
6.2.4.3 Modifying the Concrete Mix
The effects of adding hydraulic or pozzolanic minerals to the cement on resistingchloride

penetration in marine exposure were investigated in a laboratory study simulating splash
zone environment. This study found that blended (composite)cements containing blast
furnace slag or fly ash and silica fume have service lives that are several times longer
than concrete with ordinary portland cement ( O K )concrete. Adding only 5%silica fume
did not significantly improve durability. The calculated service life in the splash zone
ranged from about 10 to 80 years with increasing service life in the order of lightweight
aggregate/OPC < gravel/OPC < gravel/silica fume/OPC < gravel/silica fume/fly
ash/OPC< gravel/blast furnace slag. This ranking is in general agreement with expec-
tations from concrete exposure research and experience.81
Another study was conducted to evaluate durability of 15 plain and blended cement
concretes exposed to a typical salty sabkha environment (15.7%C1- 0.55% + q-).
(Sabkha refers to the broad, salt-encrusted supratidal coastal flats bordering lagoonal
or inner shelf regions. An essential feature is that it is only flooded occasionally and
comprises carbonate sediments with gypsum depositsa2) The concrete mixtures were
designed to assess the influence of C3A content, water-cementitiousmaterials ratio, and
type of supplementary material, such as fly ash, silica fume, and blast furnace slag, on
sulfate attack and reinforcement corrosion. The sulfate attack was evaluated by visual
inspection and weight change. Reinforcement corrosion was monitored by measuring
corrosion potentials and polarization resistance at periodic intervals. Despite the high
sulfate concentration in the test solution, classified as "aggressive," results of this inves-
tigation indicated that sulfate attack was totally hindered in a sabkha environment. Data
on time to initiation of reinforcementcorrosion and polarization resistance indicated that
the main contributing factors for mitigating chloride-induced corrosion in sabkha envi-
ronments, in increasing order of importance, were C3A content, water/cement ratio of
plain cements, and incorporation of mineral admixtures. The most significant improve-
ment was achieved when the water-to-cementitious materials ratio was reduced at the
same time as silica fume was added.m
The effect of admixtures,namely, silica fume, latex, methylcellulose,and short carbon
fibers (invarious combinations)in concreteon the corrosion resistance of steel-reinforced
concrete, was assessed by measuring the corrosion potential and corrosion current den-
sity during immersion in Ca(OH)*and NaCl solutions. Silica fume (15%by weight of
cement) was most effective in improving corrosion resistance by decreasing water ab-
sorptivity and, to a lesser extent, by increasing electrical resistivity.Latex (20% by weight
of cement) improved the corrosion resistance because it decreased the water absorptiv-
ity and increased the electrical resistivity. Methylcellulose (0.4% by weight of cement)
improved corrosion resistance only slightly. Carbon fibers (0.5% by weight of cement)
decreased the corrosion resistance by decreasing electrical resistivity but this negative
effect could be compensated for by adding either silica fume or latex, which reduced the
water absorptivity.84
Cement can also be reinforced with randomly oriented, discontinuous,discrete fibers.
The first use of this type of fiber reinforcement was the addition of asbestos fibers to
produce asbestos cement (A/C), which is widely used in water piping. Many other types
of fiber have been used, including steel, glass, Kevlar@,carbon, polypropylene, nylon,
cellulose,jute, and sisal. The use of fiber-reinforcedconcrete is diverse, for example, steel
fiber-reinforced concrete is used in linings, asbestos or wood-reinforced composites are
used in roofing, etc. Fiber reinforcement is being investigated for use in marine concrete
as an aid to protecting imbedded carbon steel reinforcement. Cement reinforced with
fibers such as sisal, fique (a Colombian native fiber), coconut, glass, polypropylene,
and steel together with mineral additions was tested in a marine environment. These
tests showed that compressive strength was reduced by the presence of fibers; sisal was
the most deleterious, steel was least, but the addition of silica fume could restore the
compressive strength and decrease permeability and chloride penetrati0n.8~
6.2.4.3.1 Inhibitors
Corrosion inhibitors have been incorporated into concrete mixes to reduce rebar cor-
rosion and thus improve durability. The best known inhibitor is calcium nitrite which
is effective in improving corrosion resistance, especially when used in good quality
concrete. Sodium nitrite may be added at up to 4% of the concrete to prevent pitting
of the rebar. The common practice is to add both of these inhibitors together with the
concrete mixing water. Inhibitor treatments of existing concrete have also been investi-
gated.In this techniquesolutions of inhibitors,such as sodium nitrite, sodium phosphate
derivatives, or some combination of them are poured over the hardened concrete. There
is some evidence that this procedure can produce an improvement in the corrosion resis-
tance. Organic migrating corrosion inhibitors (MCI) have also been developed for this
purpose. Tests have shown that this type of treatment can improve corrosion resistance
without adverse effects on the concrete structure.72
MCIs are based on amino carboxylate chemistry that are mixed inhibitors, cathodic
and anodic. Under pressure they can migrate through the concrete pore structure and
become absorbed onto the carbon steel reinforcement. These inhibitors can be used to
treat existing concrete or can be incorporated into the original concrete mix to prolong the
life of the reinforcement. Tests by a manufacturer of these products showed that either
of these approaches does significantly retard corrosion of the reinforcement. The MCIs
used were shown to be compatiblewith the concrete mix.%The effectivenessand the rate
of diffusion of these proprietary inhibitors were investigated and it was concluded that:
Laboratory tests proved that these corrosion inhibitors migrate through the concrete.
This opens the possibility of using MCI as a topical treatment or by injection into
concrete. This could slow the corrosion activity substantially, thus increasing the life
span of the structures.
Field studies of salt-contaminated structures overlaid with new concrete containing
a migrating corrosion inhibitor vs. control samples showed a strong trend toward
reduction of corrosion potential on the inhibited portion. Incorporation of this type
of inhibitor could substantially extend the life span of renovated structures.
Tests showed that physical and mechanical properties of concrete containing these ad-
mixtures were not affected. This is critical as certain conventional inhibitors do affect
pr0perties.8~An MCI based on hydroxyalkylamineswas found to inhibit steel corrosion
in chloride solutions if present in high concentrations. When the inhibitor was present
at lower concentrations pitting was initiated but the corrosion rate was lower than in
the absence of inhibitor. No repassivation was observed even with 10% inhibitor con-
centration. In parallel tests in mortars it was found that the inhibitor did not reduce the
corrosion rate nor completely prevent pitting initiation. It did, however, delay initia-
tion of corrosion. This MCI was found to have no effect on the rate of corrosion caused
by carbonation of the concrete. The high rate of diffusion of the inhibitor through the
mortar measured in these tests was explained by the high porosity and, especially, the
incomplete water-saturated pore system. In tests in which the mortar samples were im-
mersed in the inhibitor solution no inhibiting effect on the chloride-induced corrosion of
the rebar in mortar was observed. The explanation for this unexpected finding was that
to be effective both the volatile and nonvolatile fraction of the inhibitor have to reach
the steel surface. The fast migration rate was only determined for the volatile fraction
and the implication was that the nonvolatile fraction did not diffuse through the mortar,
probably because of precipitation with calcium ions in the pores. Until it can be proved
that all of the ingredients of the inhibitor migrate through the concrete and are effective
in inhibiting chloride corrosion of the rebar, then this approach to remediation has to be
questioned.88
Calcium and sodium nitrites are both good passivating inhibitors for steel when
present at levels above their critical concentration. If present at too low a level they can
increase corrosion rate. Calcium nitrite acts as a concrete set accelerator so normally
requires the addition of a water reducer and retarding agent in the concrete mix. Sodium
nitrite can cause strength loss in concrete and enhances the risk of alkali-silica reaction.
Alkanolamines and amines can be added to the wet concrete mix or formulations exist
that are vapor phase inhibitors that can be inserted into set concrete through drilled
holes. Trials and field applications are continuing but some proprietary blends of these
chemicals do seem to be effective and able to penetrate through set concrete.
MFP (sodium monofluoro phosphate) cannot be used as an admixture with fresh
concrete because of a chemical reaction but is used as a treatment of set concrete, pene-
trating from the concrete surface to the steel. This patented inhibitor seems to be effective
if present at the steel surface in sufficient concentration,but whether it is feasible to treat
the concrete so that the inhibitor reliably reaches the rebar is still being debated.
Organic-based inhibitors added as an emulsion to the mix are also being investigated
and used on a trial basis. The oil phase of the emulsion consists of unsaturated fatty acid
esters of an aliphatic carboxylic acid with a mono-, di-, or trihydric alcohol and the
water phase is a saturated fatty acid, an amphoteric compound, a glycol, and a soap.
Upon contact with the high pH of the concrete the emulsion collapses and allows contact
between the active ingredients and the steel surfaces. Other inhibitors, such as stannous
chloride and sodium benzoate, have been investigated but for various reasons have not
been generally accepted for use in reinforced concrete.89
Research has shown that if sufficient calcium nitrite is added to the concrete mix to en-
sure a chloride-to-nitriteratio of less than one at rebar depth, then the nitrite will prevent
corrosion. Inhibitor is likely to be used to replace FBECR in some of the Florida appli-
cations with the added advantage that, unlike with epoxy-coated rebar, electrochemical
techniques can then be used to monitor performance. The use of nitrite inhibitor in the
initial concrete does not restrict the use of cathodic protection or chloride extraction in
later life should they be necessary. Treatment of existing concrete with inhibitors is still at
the development stage and the major question is whether it is possible to get the inhibitor
to the reinforcement without concrete removal and subsequent patching.75
In a series of long-term experiments (which are still ongoing) to compare the inhibit-
ing effects of calcium nitrate and nitrite, the following results were found:
Calcium nitrate works as a retardant with respect to chloride-initiated corrosion of

steel embedded in concrete.
The corrosion-retardingmechanism for nitrate is analogous to the mechanism for the
well-known corrosion retardant, nitrite.
Nitrite cannot work as an oxygen scavenger in sound concrete (i.e., high pH).
Nitrates are prohibited in injection grout for cable ducts and prestressed concrete
elements because of the risk of stress corrosion. The rate of stress corrosion is strongly
pH dependent, and the corrosion rate is reduced to 25% when pH 2 9.5. SCC can only
occur where there is extreme constructional conditions (scant cover) and high wear from
chemical exposure. Stress corrosion is not believed to take place in sound concrete with
pH 12.5 to 13.5.90The sales of calcium nitrate as concrete admixture increased from a
few 100 tons of another quality in 1991 (the main technical application at that time was
as latex coagulant in rubber gloves production) to 40,000 tonnes annually todayg1
SCC of low carbon reinforcing steel is usually caused by nitrates. In carbonated
concrete the resistance to SCC is lower than in alkaline concrete. The sensitivity of the
steel increases with decreasing carbon content. In dynamically stressed cracked concrete
constructions under seawater exposure (e.g., offshore constructions) corrosion fatigue
may take place. Permanently immersed parts are more resistant than those occasionally
sprayed. Epoxy coating cannot protect the steel sufficiently because the coating may be
damaged by fretting?2
6.2.4.4 Cathodic Protection of Reinforced Concrete
Cathodic protection is becoming increasingly used in new and existing structures. In

new structures one approach is to apply low levels of cathodic current to the rebar in
order to ensure initial passivation, known as cathodic prevention. The other is to take
the opportunity of installing a cathodic protection system that can be activated at some
time in the future if corrosion begins and chloride penetration takes place.
Cathodic prevention applies <2 mA/m2 of cathodiccurrent to the steel reinforcement
in new concrete. The aim is to make the concrete more resistant to chloride environments
by decreasing the cathode potential, producing alkalinity from the cathodic reaction,
and moving chloride ions away from the steel by electrophoretictransport. Repair work
on existing concrete usually benefits from only one of these three mechanisms when
cathodic protection, electrochemical realkalization, or electrochemical chloride removal
are applied. Cathodic prevention applies all three mechanisms to new concrete before
chloride contamination has occurred. The application of cathodic current densities in the
range of 0.4 to 1.7 mA/m2 to reinforcement in chloride-free concrete quickly depressed
the potential by about 150 to 200 mV from the free corrosion potential. This potential
was stable over the 15months test period and although chloride penetration of the cover
did occur, corrosion was not initiated even in the control slab. This technique should be
safe from hydrogen embrittlement even with high strength steel. This investigation did
not give any clear evidence of control of chloride ingress; chloride levels were slightly
less in the cathodic region after 14 months of testing. The indications are that cathodic
prevention should allow the steel reinforcement to remain passive even in concrete with
a significant chloride c~ncentration?~
There are several criteria that may be selected to ensure an adequate cathodic pro-
tection potential for steel in concrete. In tests, steel was polarized with three different
overpotentials (-100, -250, and -500 mV) taken with respect to the corrosion potential
of bare steel in two different electrolytes (tap water and 3% sodium chloride solution).
Mortar specimens were polarized for 1 year and then subjected to a pullout test to
determine bond strength variations at the steel-mortar interface. The steel-mortar adhe-
sion was reduced by lo%, compared with nonpolarized specimens, when a -500 mV
overpotential was applied. These changes may be related to hydrogen evolution but
changes in the crystalline microstructure of the mortar paste were also ~ b s e r v e d ? ~
Safe CP limits for prestressing steel in concrete pilings and the adequacy of CP using
established criteria were evaluated in terms of hydrogen embrittlement (HE) and the
effectiveness of protection in the tidal/splash zone. Impressed-current CP was applied
to laboratory scale pilings at current densities from 0.1 mA/cm to 3.0 mA/cm2 from a
skirt anode located at the waterline. The pH of the local steel/concrete interfaceincreased
with position above the waterline, reaching local values of 5.5. At typical levels of CP
(e.g., 0.33 pA/cm2) it was found that the cathodic reactions at the steel surface were
faster than the rate at which oxygen diffused through the 5 cm of concrete cover. The
result was a steadily decreasing applied current-on potential until a cathodic reaction
other than 0 2 reduction (in this case, hydrogen evolution) became thermodynamically
favorable, particularly in the submerged and splash zones where the water-saturated
pore structure within the concrete hindered oxygen diffusion. This current density was
sufficient to achieve 100 mV of depolarization from 25 cm above to 25 cm below the
waterline in one piling, but hydrogen absorption was detected 25 and 50 cm above the
waterline at this current density. Hydrogen concentrations measured were insufficient
to cause embrittlement.
To achieve 200 mV of depolarization above the waterline a cathodic current density
of greater than 1pA/cm2 was required. This current density produced hydrogen in the
region but it was still insufficient to cause embrittlement. To achieve the commonly used
780-mV SCE protection criterion from 30 cm above the waterline to 30 cm below needed
a current density of 2.5 pA/cm2. This produced hydrogen concentrations 30 cm below
the waterline at levels in excess of the critical levels for crack initiation (2 x mol/cm3
for bluntly notched prestressing steel). Since the pH of the steel/concrete interface en-
vironment within a pile changes with vertical position, there may not be a universally
applicable reversible potential for hydrogen production that would ensure adequate CP,
as defined by the -80 mV SCE criterion, while preventing hydrogen production and
ab~orption?~
An example of a protection system incorporated into a new structure is one to be
fitted to the concrete piles of the U.S. Navy pier in Diego Garcia in the Indian Ocean. The
existing concrete piers were badly corroded, particularly the concrete jackets over the
steel piles from above the low tide line to the top of the piles. The chloride had reached
the steel piles in less than 10 years despite the use of high quality concrete, adequate
cover, etc. Once the replacement piles have been reinforced, titanium anode mesh will
be attached with plastic cable straps over plastic mesh spacers to the outer layers of the
reinforcing steel. The concrete cover will be about 75 mm with a 0.4 water/cement ratio.
The intention is to energize the system some time in the future, estimated to be about
10years after installation?6
Cathodic protection of concrete reinforced with mild steel does not induce damage
by hydrogen evolution. An impressed current-controlled system allows the voltage to
respond to changes in resistance. There have been concerns about using such systems
with high strength steel reinforcement, however, because of the possibility of hydrogen
embrittlement of these steels. Operating on voltage and controllingat above the hydrogen
evolution potential is attractive, but there are practical difficulties, such as determining
the location for reference electrodes and providing reference cells that can work reliably
over the life of the structure.
An approach, used in Florida, is to run E vs. Log I tests at startup to determine
current. Limits are set on current and voltage and subsequently the system is run on
voltage control, typically at very low voltages. Using catalyzed titanium with a voltage
of less than 1.2 V is inherently safe, i.e., hydrogen evolution is effectively impossible. The
catalyzed titanium mesh is installed using fiberglass foam that prevents current leakage
to the seawater and excessive current discharge to the steel below the waterline. In 1992,
44 pilings on a bridge over the Ribault River in Florida were cathodically protected using
this system with the anode/foam installed to straddle the high tide level. The initial trial
provided data on current/voltage demand that enabled a battery to be designed that
can run the system at 100 mA and 1.2 V for 3 to 5 ~ e a r s . 9 ~
Tests to determine long-term effects of CP on prestressed concrete structures found
that the local environment in a bridge pile varies greatly with position relative to the
water line and is very different from the highly alkalinebulk concrete,pH >12.5. The local
pore pH may be t6.5 within the atmospheric zone, 4.8 within the splash zone, and 11.8
within the submerged zone. At modest levels of CP it is possible to produce conditions
at which hydrogen evolution becomes thermodynamically favorable. It is possible to
calculate the mobile hydrogen concentration in the steel for a given set of chemical and
electrochemical conditions at the steel-concrete interface. It is also possible to predict
whether the local applied stress exceeds the fracture initiation stress as a function of
position during the application of CP.98
CP can also be retrofitted to existing structures that have become damaged during
service. For example, the Western System of the Madrid water supply distribution sys-
tem consists of prestressed concrete pipe with a maximum design velocity of 3.8 m3/s.
Two sections of 1,600-mm ID pipe fractured when the prestressed wires corroded. The
application of a 30-mA current to the wires and measuring potentials enabled other dam-
aged wires to be identified and the pipes replaced. To avoid further damage a CP system
was installed using consumable magnesium anodes. The average protection potential is
-0.85 to -1.08 V vs. CSE. It was also shown that the application of consumable anode
CP to prestressed concrete pipe or concrete-lined steel or cast iron pipe can help seal
cracks in the concrete and prevent corrosion of the metallic components. The mecha-
nism is one of alkalization by cathodic reaction. Magnesium anodes were applied to a
24-km-long, 2-m-diameter prestressed, plate-lined concrete pipe. Inspection after 2 years
of operation showed that all of the fissures in the concrete lining had become sealed. The
magnesium anodes were estimated to have a life'span of around 20 years in this potable
water service.%
Another method being used to rehabilitate concrete structures is the use of thermal-
sprayed zinc on the surface of the concrete to cathodically protect the reinforcement. The
zinc acts as an anode and can protect either galvanically (GCP)or as part of an impressed
current system (ICCP).The GCP system is normally adequate for environments that are
wet such as in bridge supports just above the water line. It has been suggested that if
the anode surfaces are treated with humectants the moisture content in the zinc coating
increases and the electricalresistance is reduced. Tests on the humectants LiBr and LiN03
found that they both improved the effectivenessof new or aged anodes. In GCP tests the
LiBr was more effective than the LiN03; in ICCP the reverse was true. These humectants
are undergoing comparative field trials.lm
6.2.4.5 Coating Concrete
The use of an airtight protective coating on the surface of a concrete structure would
inhibit carbonation and limit the ingress of moisture, chloride, sulfates, etc. Various
coating formulations have been suggested for this method of improving concrete dura-
bility. These have included polyurethane, methyl-silicone polymer, acrylic rubber, and
silane monomer. Of these the silane monomer was found to have the best combination
of water barrier and corrosion suppressant properties.”
The requirements of a waterproof membrane are that it should be easy to install,
bond well to the substrate, be compatible with the components of the system, and
be impermeable to chlorides and moisture. The currently available products are either
preformed sheets or applied liquids. Field performance has been found to depend on
quality of workmanship, weather conditions, design details, and service conditions.
Performance has ranged from satisfactory to major failures requiring removal of the
membrane. Blistering is the single greatest problem and it affects both sheet and liq-
uid products. It is caused by expansion of trapped gases, solvents, and moisture in the
concrete. Blistering is controlled by careful preparation of the concrete surface and ap-
plying the membrane under suitable weather conditions. Damage during installation,
such as tears, cuts, bad joints, etc., has also led to premature failures. In service, failures
can be difficult to detect since membranes are usually overlaid with an asphalt wearing
course.
Polymer impregnation (PIC) is a form of coating in which some of the voids in
the hardened concrete are filled with a monomer which is polymerized in situ. The
best results are obtained when the concrete is dried, subjected to a vacuum treatment,
impregnated with the monomer under pressure, and polymerized while preventing
monomer evaporation.Polymerization in the field is accomplishedby the use of chemical
initiators that decompose under the action of heat or a chemicalpromoter. This technique
has not yet been extensively used, partly because the monomers are expensive and the
process is lengthy and also expensive. There has also been some tendency for the concrete
to crack during heat treatment.
Polymer concrete overlays of aggregate in a polymer binder have been placed ex-
perimentally. Concrete and aggregate must be dry and placed over a bond coat of neat
polymer. Early attempts at this process were largely unsuccessful with blistering being
the main problem. Portland cement concreteoverlayscan be placed as part of a two-stage
process with the overlay being placed before the first concrete has set or soon after using
a bonding layer. One of the advantages of this method is that additives can be incor-
porated into the second layer to resist chloride ingress, provide antiskid properties, etc.
Low slump and latex-modified concrete have been the overlays most often used to deter
chloride ingress. Low slump concrete uses conventional materials but reduces the water
content to the minimum practical by using a high cement content. Latex-modified con-
crete is conventional portland cement with the addition of a polymeric latex emulsion.
Both types of overlay are very dependent on workmanship and on the use of appropriate
mixing, placing, and curing techniques.'0'
6.2.4.6 Repair and Remediation of Existing Concrete
Damage to reinforced concrete is not always obvious until it becomes severe. There are
various procedures and equipment that can be used for identifjmg corrosion environ-
ments and active corrosion in concrete. These include the following:1o1
Visual examination-looking for cracks, crumbling, staining, etc.

Pachometer-a tool that can determine the cover over reinforcement
Delamination detectors-range from drag tools, chains, hammers, etc. to sophisticated
devices
Electrical potential measuring equipment-measures steel potential with a copper-
copper sulfate half cell to determine whether steel is active or passive (see Chapter 8,
"Monitoring," for details of monitoring techniques)
Chloride analysis-determines acid and water-soluble chloride on sample cores
Rate of corrosion probes-linear polarization or electrical resistance probes (see
Chapter 8, "Monitoring," for details of monitoring techniques)
Electrical resistance-used mainly to assess the condition of membranes
Other techniques-ultrasonic, infrared, radar have all been attempted
Irrespective of how the reinforcement corrosion is identified, there are a number of

actions that can be taken to solve the problem following one or more of the principles
below:lO'
Insulating the concrete from the corrosion environment-coatings, membranes, poly-

mer impregnation, etc.
Modifymg the environment to make it less corrosive-inhibitors, chloride ion re-
moval, etc.
Actively controlling the electron flow-cathodic protection.
Patching and coating are used to repair concrete that has been damaged by carbon-
ation or chlorides. This approach is more likely to be successful with carbonation since
once chlorides have penetrated corrosion is likely to continue largely irrespective of
changes in conditions at the surface of the concrete. Patch repair of concrete contami-
nated with chlorides is only likely to succeed if damage is local and all the contaminated
concrete can be removed and replaced after inhibitor treatment of the rebar. If the con-
taminated concrete is removed and replaced with fresh concrete, without inhibitor treat-
ment, corrosion is likely to continue. Of the treatments examined calcium nitrite-based
inhibitor, ponded or placed in a mortar, proved to be the most effective. Experimental

borate inhibitors were also found to be effectivewhen ponded or added to mortar but re-
tarded the cement setting. Proprietary inhibitors also worked well when ponded or used
in a mortar admixture. In general, ponding was found to be a more effective technique
than backfilling with a treated mortar.lo2
The repair of chloride-damaged existing structures often begins by locating the cor-
roding areas using potential mapping techniques (see Chapter 8, Section 8.2, ”Corrosion
Monitoring of Reinforced Concrete Structures”) and removing and replacing chloride-
contaminated concrete in these areas. Where there is chloride contamination but the
reinforcement is not corroding, electrochemical removal of the chlorides can permit the
reinforcement to repassivate. An anode and an electrolyte are applied to the concrete and
a current is passed between the anode and the reinforcement (the cathode). The chloride
ions migrate away from the cathode and the process is continued until the carbon steel
reinforcement is able to passivate.”
In the case of carbonation,removing concrete and restoring alkalinity should stop cor-
rosion. Patching and treating with an anticarbonation coating will slow carbon dioxide
ingress. The alternative is to apply a realkalization treatment. Electrochemicalrealkaliza-
tion applies 20 to 50 V DC between an anode and the steel. It is possible that this treat-
ment can induce hydrogen embrittlement in prestressing steel and careful monitoring is
needed to ensure the steel is not subject to hydrogen conditions that could embrittle?5
Electrochemical repair techniques include chloride removal (ECR)and realkalization
(ER).They differ from CP in that CP is a permanent installation and uses currents below
about 10 mAm-2, while electrochemical remediation processes are temporary and use
currents up to 2 Am-*. For ECR all studies show a reduction in total chloride content
of between 50 and 60%. ER only reestablishes an alkaline pore solution; the alkalinity
reservoir present in uncarbonated concrete cannot be restored. Electrochemical repair
techniques are only feasible when the rebar is comparatively undamaged so that struc-
tural properties are not reduced and where only small parts of the concrete surface are
visually damaged. In one case where ECR was applied to a lightly damaged structure,
the treatment removed the negative potentials, indicative of corroding areas and the po-
tential field became more homogeneous. The average value of the half-cell potential was
shifted by about 80 mV more positive. The increase in alkalinity at the rebar surface by
electrolysis and chloride migration are both related to current density and charge flow.
The ECR process becomes inefficient at a total charge flow >1,500 Ahm-2 and the treat-
ment can then be stopped. In ER an empirical value of 450 Ahm-2 is being used. After
completionof ECR treatment a thinpolymer-modified cementitious coating was applied
to avoid further chloride penetration. No surface treatment was applied after the ER treat-
ment. Six years after the ECR treatment and 2 years after the ER treatment the treated
surfaces were still in the passive state. In the ER-treated concrete the carbonate solution
in the concrete pores maintained a pH value of >10.5 and the rebar remained passive.59
Physical realkalization, in which carbonated concrete is coated with a layer of alkaline
cement, is also being assessed. The principle is that the hydroxyl ion is driven toward
the steel by the concentration gradient between the carbonated and the noncarbonated
concrete. Electrochemical realkalization (ERA) was introduced commercially in Norway
in the late 1980s. The external electrolyte is normally 1.0 M sodium carbonate with
cathodic current densities in the order of 1A/m2 applied for several days. This forms a
zone of high alkali concentration around the steel together with some penetration of the
alkali electrolyte into the concrete.
Ponding and treating carbonated concrete with solutions of nitrites is also being used.
Exposure of the rebar, treatment with nitrite solution, and then repair with mortar con-
taining nitrites were said to significantly reduce the corrosion rate. Other investigations
suggested that calcium nitrite was only effective in treating steel that had been exposed
to low levels of chlorides or were only lightly corroded. This type of treatment is more
likely to be successful with carbonation rather than chloride attack. This review of the
use of inhibitors concluded that their use in repair of reinforced concrete is far less well
established than their use as concrete admixture^.'^^
Fiberglassjackets, incorporating zinc anodes, have been developed to retrofit corrod-
ing reinforced concrete columns. These jackets are being used to protect the tidal and
splash zones of bridge or road supports that are partly immersed in water.104
6.2.5 Ceramics, Bricks, Stone, and Related Materials
Ceramics are mostly based on oxides, such as silica, magnesia, and alumina. These
oxides are highly resistant to waters and to most common chemicals, although fluorides
or strong alkalis can attack some ceramics. Ceramics tend to be strong in compression
but brittle and weak in tension. Once they have been fired into their final form, joining
requires special techniquessuch as bonding with cements or resins or mechanicaljointing
methods. Ceramics are most widely used for their resistance to high temperatures as
insulators, chimney or vessel linings, etc.
Glass is based on silica which in its pure form has a melting point approaching
1,700"C.This high melting point can be lowered by the addition of potash, soda, or lime.
Glass and glass-lined piping are used for specialist applications in chemical plants and
laboratory handling of waters and aggressive fluids. The addition of borax or boric acid
produces borosilicate glass, which has a lower coefficient of thermal expansion than
other glasses. This means that it is more resistant to thermal shock and this type of glass
can be used to line mild steel equipment. This equipment is known as "glass-lined"
or as "enamel-lined'' steel. It is also resistant to most chemicals but can be attacked by
fluorides, phosphoric acid, and condensing pure water at high temperatures. The well-
known thermal shock-resistant Pyrex@glass contains about 81% silica, 11% boric acid,
and 4% soda.9 Fused silica is also used in selected corrosive applications, particularly
in acidic environments and where thermal shock is likely. Other ceramic materials, such
as silicon carbide and silicon nitride, are normally used in high temperature application
but find occasional use in linings or heat exchangers for strong acids.
Clays are formed by the natural decay and disintegration of igneous rocks. They
are finely divided with the characteristic property of becoming plastic when moist so
that they can be readily shaped or molded. When dried and baked they become hard
and dense but often brittle. Their composition can vary but typical clays are based on
hydrated silicates of alumina, invariably containing a range of other compounds that
affect properties and appearance.
“Earthenware” is the term used to describe equipment made from fired clays. Chem-
ical stoneware describes equipment, made from selected clays, which is stronger and
more chemically resistant than earthenware. Porcelain is a dense product with compar-
atively poor mechanical properties and thermal shock resistance. It is made from silica
and alumina and has good resistance to all acids, except hydrofluoric, but generally
little resistance to alkalies. These ceramics are typically glazed for chemical application
to assist in cleaning and sealing any surface porosity.’o5 Earthenware, stoneware, and
porcelain have all been used for sanitary and industrial waste and water piping but have
become less common as plastics take over many of these traditional applications.
Some naturally existing clays are especially corrosion resistant and are used to make
acid-resistantbrick. Once these silica alumina shales have been fired they are particularly
resistant to most chemicals, to abrasion, and to high temperatures. Bricks and tiles made
from these materials are used to line chemical tanks and towers, sewers, wastewater
treatment equipment, floors, etc. They are normally made from red shale or fireclay,
both alumino-silicate mixtures.
Glazed, vitrified clay piping is used for water and wastewater applications. It has
excellent resistance to sulfuric acid and hydrogen sulfide so is particularly good in do-
mestic sewage applications where sulfides are present and in low-flow situations where
deposits are formed (see Chapter 11, Section 11.7, “Wastewater Handling”).
Stonework has been used for centuries for the construction of buildings, aqueducts,
dams, jetties, ports, etc. (Figure 6.10). The principal types of stone used for building and
structures are granite, limestone, sandstone, marble, and slate. In the United States, in
1952, the amounts of these materials produced were 519,000, 787,000, 352,000, 89,000,
and 146,000 tons (471,714,319,81, and 132 M kg), respectively?
Granite is a coarse-grained igneous rock consisting largely of quartz (silica) and
feldspar (mixed oxides used in glassmaking).There are many different forms and colors
of granite depending on their source and the trace elements present. Granite is one of the
most important building stones being hard, durable, and resistant to moisture absorption
and weathering. Typical crushing strength is 23,000 to 32,000 psi (158 to 221 MPa).
Limestone is a general term for a range of calcium carbonate rocks. It is much softer
than granite and tends to absorb moisture, which leads to spalling and weathering.
Limestone is a very common building stone as well as being used as aggregate in making
concrete.lM The mechanical properties of stone vary considerably depending on the
source, porosity, moisture content, and type of stone. Typicallybuilding stone is stronger,
particularly in compression, than other man-made building materials (Table 6.8). The
strengths quoted are for the materials; the strength of structures constructed of any of
them will be considerably less since the mortar joints have a weakening effect.
Asbestos cement (A/C) is mainly used in the form of piping, made by the
Hatchek/Mazza process from an intimately mixed aqueous slurry of portland cement
(80 to 85%) and a mixture of relatively long and medium-grade chrysotile asbestos fibers
(15 to 20%). The slurry is dewatered using a rotary sieve cylinder and a continuous
felt to produce a very thin layer of asbestos cement that is wrapped around a mandrel
Figure 6.1 0 Photo shows typical masonry walls submerged in seawater in the port of Heraklion,
Crete. (Photo courtesy of CARIAD Consultants.)
under pressure until a pipe with the desired wall thickness is produced. The mandrel is
then extracted and the pipe is cured by passing through a low temperature tunnel oven
followed by immersion in or spraying with water, or by autoclaving. After curing, the
ends of the pipe lengths are cut and finished to receive couplings that are produced by
cutting larger diameter pipe into sections. A/C pressure pipe is used primarily for the
distribution of potable water, as well as for sewer force mains and industrial effluent and
process piping. A/C nonpressure pipe is used for sanitary and storm drainage systems,
casings for electric cables, and for duct work.108
6.2.6 Biodeterioration of Concrete and Stone
Concrete, brick, and stone are attacked by both micro- and macroborers. Many of the
macroborers are the same organisms that occur naturally in submarine rocks and reefs
and they are more prevalent in the tropics (Figures 6.11 and 6.12).
The problem of destruction of man-made structures in tropical marine environ-
ments can be expected to increase with increasing construction in developing countries;
there has been increased interest in the extent and possible causes and solutions to this
problem.lW
Table 6.8 Properties of Clay Products, Brick, and Dry Building Stone107
Compressive Modulus of Shear Thermal

Strength, Rupture, Strength, Expansion
Material psi W a ) psi (MPa) psi (MPa) Coefficient106/"F Porosity, YO
Brick 1,m,000 300-1200 1,000-1,500
(741) (2.1-8.3) (6.9-10.3)
Paving brick 8,000-10,000 1,500-2,500 1,200-1,800
(5549) (10.3-17.2) (2.1-12.4)
Firebrick 3,000-6,OOO 300-1,600 500-1,000
(2141) (2.1-11) (3.4-6.9)
Terra cotta 3,000-4,OOO 500-1,000
(21-28) (3.4-6.9)
Hollow blocks 2,000 (14) 500 (3.4)
Stoneware - 3,OOO-10,000
(21-69)
Limestone 3,000-28,000 5004,700 1,000-2,800 0.64.7 0.3-20
(21-193) (3.4-32.4) (6.9-19.3)
Granite 15,OOO-30,000 1,2004,000 1,800-3,800 3.14.2 0-1
(103-207) (8.3-27.6) (12.4-26.2)
Sandstone 7,000-20,OOO 500-2,500 1,000-2,500 3.2-6.9 5-28
(48-138) (3.4-17.2) (6.9-17.2)
Marble lO,OOO-26,000 1,000-3,000 1,000-5,600 2.0-5.6 0.2-0.6
(69-179) (6.9-21) (6.9-38.6)
Slate 7,000-30,OOO 7,000-l0,OOO 2,000-3,500 5.1 0.1-0.7
(48-207) (-9) (13.8-24.1)
6.2.6.1.1 Organisms That Attack Concrete and Stone
The sulfuric acid-producing bacteria of the genus Thiobacillus are well known for their
ability to destroy concrete.11oThese sulfur-oxidizingbacteria can reduce pH to 1by pro-
duction of inorganic acids, particularly sulfuric acid. Nitrifying bacteria, which produce
nitric acid, also degrade concrete. In addition to inorganic acids, microorganisms also
produce harmful organic acids."' Carbon dioxide and hydration caused by salt stress
also contribute to the deterioration."*
In a recent study of the organisms found in a corroded sewer pipe in Houston,
TX were the bacterial species Thiobacillus thiooxiduns, Bacillus sp., Ochrobactrum
anthropi, and Microbacterium sp., four unidentified additional bacteria, and four fungal
specie^."^ Studies suggest that although sulfate-reducing bacteria may not destroy
concrete dire~tly,"~they are certainly implicated in corrosion of the steel reinforce-
ment. The fungi, Fusarium, may cause even more rapid destruction than bacteria.
Organic acids produced by the fungi react with concrete to form soluble calcium
cornplexe~."~
Boring by macroorganismsis termed "bioerosion." Among macroorganismsthe most
important borers are bivalves. These are divided into mechanical and chemical borers.
Figure 6.1 1 This statue of a Greek youth was found at the bottom of the
sea. His head and right side were embedded in mud and are pristine. The
exposed left half has been severely attacked by marine organisms. (Photo
Figure 6.12 Concrete blocks submerged for 13 years in Jamaica were bored by sponges, poly-
chaetes, and bivalves. This massive mussel, Lithophap antillarum, was almost 6 cm long. Smaller,
but more numerous sponge holes in the coarse aggregate are apparent around the edges (arrow).
(Photo courtesy of CARIAD Consultants.)
Pholads, which also bore into wood and plastic, mainly bore mechanically although they
also possess chemical boring glands.l16They inhabit both temperate and tropical seas.
Any substance that is calcareous or cemented together with a calcareous paste is
susceptible to attack by most chemical bioeroders. For example, in addition to coral
and calcium carbonate rocks, Lithophap can bore into carbonate-cemented ~andstone."~
Boring in this group is a mechanically assisted chemical process in which boring glands in
the middle mantle fold secrete acidic and basic granules"* that combine to form a neutral
mucoprotein capable of chelating calcium ions.23The secretion is not particularly acidic;
it has a pH of approximately 6.5. Attack can be severe, particularly when the structure
is exposed above the sea bottom in aerated waters accessible to bivalves, polychaete
worms, and other .marine borers. Borings by the bivalve mussel Lithophuga in ancient
Roman marble have been measured to a depth of 10 cm.l19
Boring sponges also excavate calcium carbonate and concrete by chemical and me-
chanical means. Chemical dissolution is accomplishedby an unknown secretion by etch-
ing cell processes at the cell-substrate interface.120Fine CaCO3 chips are excavated and
ejected through the ex-current canals. The mineralogy of the substrate seems to have
little effect on the burrowing rate of sponges.121
Susceptibility to bioerosion varies with locality on both geographic and local scales.
For example, in a study of bivalve boreholes in museum coral specimens the percentage
of massive corals containing bivalves varied with geographical area. There is a global
pattern of correlation between planktonic primary productivity and number of boring
bivalves. Areas (oceans) are rated from most to least bored as follows: eastern Pacific >
western Atlantic > Indian > western Pacific.12 Corals on continental shelves were also
more bored than corals on islands and the same trends can be expected in man-made
calcareous substrates. Similarly, boring bivalves were more common at upwelling sites
in the Galapagos,'23 and Panama124where productivity is high.
Artificial nutrient enrichment of the environment (see Chapter 2, Section 2.4, "Pollu-
tion") also has the unequivocal effect of increasingthe number of bioeroders. In Kanoehe
Bay, Hawaii, where sewage enrichment in the south bay increased food supplies (plank-
ton and detritus), there were substantially more coral borers than in the unaffected north
bay.125Moreover, diversion of the sewage did not immediately have any effect on the
boring community, indicating that the enhancement effect may occur in larval settlement
stages and, once established, borers can tolerate conditions of reduced nutrient inputs.
Borers are greater in number and species in the tropics than in temperate climates and
boring rates are faster in warmer water^.'^^.'^^ Maximum bioerosion rates generally occur
in the summer.128Bioerosion of submarine structures is affected by season of placement.
Since susceptibilityto bioerosion is at least partially influenced by competitors for space
on the substrate, settlement space may go to borer or epifaunal competitors depending on
the season during which the substrate becomes available. The larval settlement season
varies with location and must be known locally to be useful. In Australia there were
distinct spring and summer peaks of polychaeterecruitment.129Subsequent research also
revealed strong seasonality as well as inter-year and spatial variations in recruitment."
Most researchers have found similar findings for other borers.
The evidence is fairly conclusive that there is no relationship between depth and
bioerosion in the depth range of interest to most engineers. Several authors have tested
for depth effects in various parts of the world and found none.131-135Boring sponges
have been found from the shallows to depths of 100 m.13 Lithophga has been collected
at depths from 0 to 79 fathoms (145 m).l19
6.2.6.2 Structures Attacked
In the 1980s, new concrete sewer systems in Germany and United States were attacked
by bacteria, particularly the acid-producing species ThiobaciZlu~.'~~~'~ It has been esti-
mated that a substantial portion of the costs (several hundred million dollars annually
in the United States) from corrosion of concrete and its reinforcement in the wastewater
collection and treatment industry can be attributed to micr~organisms.'~~
The first recorded instances of attacks on concrete in seawater by macroinfaunal
organisms occurred in California. Concrete jackets were placed around wooden piles to
protect them from wood borers. After about 14 years, 16 of the 18piles were attacked by
pholads, 5 of which had more than 6 borers/fP.lM
In the Arabian Gulf, a 10-km-longtrestle made of very high strength, extremely dense,
centrifugally cast concrete was severely attacked by mussels, Lithophga, and sponges,
Cliona. The bivalves had penetrated to a depth of several centimeters, approaching the
central steel reinforcement in only 4 years, and were recorded at densities of up to 2,000
individuals per square meter.141
A similar attack was observed in Jamaica in concrete cinder blocks and Pleistocene
coral rubble in 5 m of water.lQ Both the aggregate and cement phases of the concrete
were attacked by bivalves, sponges, and polychaetes, removing 3%of the total material.
Lithophap penetrated to the center-most portion of the blocks, creating large, amphora-
shaped borings.
6.2.6.3 Remedial Measures
The degree of attack of concrete by Thiobucillus has been directly correlated with bacterial
numbers:10,143 suggesting that eliminating bacteria through biocide treatment or similar
measures is an important factor in preventing attack. The use of biocides to prevent
growth on stone and concrete has been attempted.l4 Biocides can be added to piped
water but treatment is not practical for structures in open waters.
Thin film coatings and surface treatmentsof concrete pipes have not prevented attack,
but thicker, resin-based coatings such as urethanes, epoxies, and vinyl esters are more
successful. Acid-resistant concrete based on potassium silicates was also found to be
protective.139
In the case of the attack of a concrete trestle in Saudi Arabia, there was no precedent
for remedial measures, which had to be developed.Piles were first mechanically cleaned,
then pressureblasted to remove all growth. The piles were then surrounded by fiberglass
jackets from below the seabed to above the splash zone. A 10- to 13-mmannulus between
the jackets and piles was created by polymer spacers. Finally, a two-part epoxy grout
was pumped into the annulus in sif~4.l~~
Other remedial and prevention measures may have to rely on knowledge of those
factors affecting the susceptibility of concrete and stone to bioer~sion.'~~ Larval dispersal
stages of most bioeroders are less than 500 pm. It is, therefore, almost impossible to filter
them out of the water. Only a few bioeroders can survive very high wave energy, while
most others (including all important bioeroding species) can tolerate a wide spectrum
from low to high energy.133
Results on the effect of material density on boring rates are ambiguous.There is some
evidence that there are bivalves and sponges that may prefer coral skeletons of greater
The opposite trend has been reported for p01ychaetes.l~~ In Hawaii, there
were larger populations of all borers in less dense coral skeleton^.'^^ Other studies have
found quicker and deeper penetration but no more material removed per unit time by
sponges in less dense coral ske1et0ns.l~~
It is fairly obvious that the longer the substrate is available, the more it will be bored,
and in some cases the relationship between the amount of material removed and time
is directly linear.132*133Proximity to carbonate substrates or living corals could also po-
tentially affect bioerosion rates of man-made structures by providing a local source for
recruitment, at least in the Caribbean.lM
Experiments with two concrete types in Discovery Bay and Port Royal, Jamaica re-
vealed that concrete with a high percentage of calcareous coarse aggregates was more
Next Page
susceptible to attack, and that boring sponges avoided a portland cement matrix and
bored only calcium carbonate. Bivalves initially penetrated the experimental core with
higher calcareous content but were also able to penetrate its cement matrix.149
6.2.7 Standards and Specifications-Concrete and Reinforcement
6.2.7.1 ASTM
A775/A775M-Ol-Standard Specificationfor Epoxy-Coated Reinforcing Steel Bars

A615/A615M-Ola-Standard Specification for Deformed and Plain Billet-Steel Bars
for Concrete Reinforcement
A9961A996M-Ol-Standard Specificationfor Rail-Steel and Axle-Steel Deformed Bars
for Concrete Reinforcement
C 33-01-Standard Specification for Concrete Aggregates
C 94/C 94M-00el-Standard Specificationfor Ready-Mixed Concrete
C 150-97-Standard Specification for Portland Cement
C 361M-99-Standard Specificationfor Reinforced Concrete Low-Head Pressure Pipe
C 494/C 494M-99a-Standard Specificationfor Chemical Admixtures for Concrete
C 822-98el-Standard Terminology Relating to Concrete Pipe and Related Products
C 1116-00-Standard Specificationfor Fiber-Reinforced Concrete and Shotcrete
C 1240-00el-Standard Specificationfor Silica Fume for Use as a Mineral Admixture
in Hydraulic-Cement Concrete, Mortar, and Grout
D 4258-83 (1999)-Standard Practice for Surface Cleaning Concrete for Coating
D 4259-88 (1999)-Standard Practice for Abrading Concrete
D 4260-88 (1999)-Standard Practice for Acid Etching Concrete
D 4261-83 (1999)-Standard Practice for Surface Cleaning Concrete Unit Masonry for
Coating
D 4262-83 (1999)-Standard Test Method for pH of Chemically Cleaned or Etched
Concrete Surfaces
D 4263-83 (1999)-Standard Test Method for Indicating Moisture in Concrete by the
Plastic Sheet Method
G109-99ael-Standard Test Method for Determining the Effects of Chemical Admix-
tures on the Corrosion of Embedded Steel Reinforcement in Concrete Exposed to
Chloride Environments
PS118-99-Provisional Standard Test Method for Water-Extractable Chloride in Ag-
gregate (Soxhlet Method)
6.2.7.2 NACE
RP0100-200Mathodic Protection of Prestressed Concrete Cylinder Pipelines

RPO187-96-Design Considerations for Corrosion Control of Reinforcing Steel in
Concrete
Previous Page
6.3 Coatinns and Linings 205
RP0288-94-Inspection of Linings on Steel and Concrete

RP0290-2000-Impressed Current Cathodic Protection of Reinforcing Steel in Atmo-
spherically Exposed Concrete Structures
RP0390-98-Maintenance and Rehabilitation Considerations for Corrosion Control of
Existing Steel-Reinforced Concrete Structures
RP0395-99-Fusion-Bonded Epoxy Coating of Steel Reinforcing Bars
RP0591-96-Coatings for Concrete Surfaces in Nonimmersion and Atmospheric
Services
RPO892-92-Linings over Concrete for Immersion Service
TMO294-94-Testing of Embeddable Anodes for Use in Cathodic Protection of Atmo-
spherically Exposed Steel-Reinforced Concrete
6G191-Surface Preparation of Contaminated Concrete for Corrosion Control
6G197/SSPC-TU 2-Design, Installation, and Maintenance of Coating Systems for
Concrete Used in Secondary Containment
6.2.7.3 EN
CR 13901:2000-The use of the concept of concrete families for the production and
conformity control of concrete
CR 13902:2000-Test methods for determining the water/cement ratio of fresh con-
crete
EN 206-1:200O-Concrete-Part 1: Specification, performance, production, and con-
formity
EN 450:1994-Fly ash for concrete-definitions, requirements, and quality control
EN 934-2:1997-Admixtures for concrete, mortar, and grout-Part 2: Concrete
admixturedefinitions and requirements
EN 1766:2000-Products and systems for the protection and repair of concrete
structures-test methods-reference concretes for testing
EN 12504-1:200O-Testing concrete in structures-Part 1: Cored specimens-testing,
examining, and testing in compression
EN 12636:1999-Products and systems for the protection and repair of concrete
structures-test methods-determination of adhesion concrete to concrete
EN 12696:200O-Cathodicprotection of steel in concrete
6.3 COATINGS AND LININGS
There is no clear distinction between a coating and a lining-the terms overlap to some
extent. In general, coatings are thinner but thick coatings and thin linings exist in some
materials and for some applications. Coating and paint layers are usually nonmetallic,
are generally t0.5 mm thick, and are applied by spray, roller, brush, immersion, etc.
Vapor deposition processes, physical and chemical, are used for coating punches, dies,
and tools with hard surfacing materials, mainly ceramics.lWCoatings are bonded to
the substrate; linings may be bonded or loose depending on material and application.
Linings are generally >0.5 mm thick, can be metallic or nonmetallic, and are applied by
thermal spray, weld deposition, sheet cladding, adhesive bonding, etc.
Coatings and linings work by providing one or more of the following:
An inert or resistant barrier, e.g., chrome plating, enamel, resistant alloy cladding
A sacrificial layer that corrodes preferentially to the substrate, e.g., Zn, Cd, A1
A high resistance path, e.g., most polymers, rubbers
A reservoir of inhibitor, e.g., primer paints
Cathodic protection, e.g., Zn-rich paints, galvanizing
6.3.1 Coatings
Coatings may be any of the following:
Nonmetallics, including:
Paints, phenolics, epoxies, acrylics, etc.
Thermoplastics, PVC, PE, fluorocarbon (PFA, FEP)
Ceramics, carbides, nitrides, etc.
Metals-zinc galvanizing, chromium or cadmium plating, alloy thermal spray,
etc.
Plastic paints and coatings are based on many different synthetic and natural poly-
mers. Only a small number of these are suitable for long-term service in water, but more
of them are appropriate for atmospheric exposure above water, for example, offshore
marine. Some of the solvent-based coatings can no longer be used in various parts of
the world because of restrictions on the release of volatile organic compounds (VOCs)
as the coatings dry. Some of the formulations have been changed to cater for this and
water-based versions of some coatings are now available. The main types of industrial
paints include the following:1o
Acrylics-not suitable for immersion; used as topcoat over other types

Alkyds-not suitable for immersion; used as topcoat over other types
Asphalt and coal tar-good to excellent water resistance; coal tar usually cross-linked
with other polymers such as epoxies
Chlorinated rubber and hydrocarbons-excellent water resistance; used to coat steel
or concrete for water immersion service
Epoxies-range of formulations with excellent chemical resistance; widely used in
maintenance painting and in combination with coal tar for water service
Fluoropolymer-good chemical resistance but often poor adhesion; used little in
waters
Phenolics-best solvent resistance; used as antifouling coating in heat exchangers and

in hot water immersion
Polyesters-mainly used in FRP and in thick linings
Polyurethanes-xist in many formulations varying from soft to hard, good corrosion
resistance; soft grades good for concrete
Silicones-mainly used in high temperature applications but have been tested and
used for antifouling applications
Vinyls-poor resistance to solvents but good resistance to marine and other waters;
used as topcoat in these environments
Zinc-rich organic and inorganic-good resistance to neutral fresh or salt waters; usu-
ally used with top coat of vinyl, epoxy, coal tar, etc.
A major survey of coatings use in industrial applications summarized industrial

coatings and their estimated service life. Two numbers are provided for the service life:
one is Ideal/Optimum the other is Practical. Most users follow the Practical approach
but long-term analysis normally shows the Ideal/Optimum approach to be most cost-
effective. Many of the coating systems surveyed are not recommended for immersion
use in waters, but for those that are, the estimated service life is shown in Table 6.9.
Table 6.9 Estimated Service Life in Years before First Maintenance Painting151
Number or Years
Immersion Service*
Application No. of Min. D R , Potable
Coating System Method Coats mil (mm) Water Fresh Water Salt Water/ Brine
Epoxy primer/HB CS, AS, Br, Ro 2 6.0 (0.15) 7.5 (10) 5 (7.5) 4 (6)
epoxy
Epoxy primer/HB CS, AS, Br, Ro 2 8.0 (0.20) 8 (12) 6 (9) 5 (7.5)
epoxy
Epoxy primer/HB CS, AS, Br, Ro 3 10.0 (0.25) 10 (15) 8 (12) 7 (10.5)
epoxy
Zinc metallizing/ Other 2 9.0 (0.23) 17 (20) 10.5 (16.5) 9.5 (14.5)
HB epoxy
Zinc metallizing/ Other 3 13.0 (0.33) 19 (24) 13 (19.5) 17 (18)
HB epoxy/
HB epoxy
Coal tar epoxy CS, AS 2 16.0 (0.41) N 11 (16.5) 9 (13.5)
Organic zinc rich CS, AS 1 3.0 (0.08) N (6) (5)
Zinc metallizing Other 1 5.0 (0.13) (15) (9);; (@**
*Numberof years = Ideal/Optimum life and is the time until touch-up is required, 3 to 5%breakdown of topcoat
occursbut before active rusting begins. Number of years in brackets = Practical life and is the time until touch-up
is required, 5 to 10% breakdown of topcoat, active rusting of the substrate present. N-not recommended.
**AssumespH between 6.0 and 10.5.
DFT = dry film thickness, CS = conventionalspray, AS = airless spray, Br = brush, Ro = roller.
A system for ranking coating is a~ai1able.l~~ This system, still being developed, takes
each component of a paint specificationand ranks it in comparison to other specifications.
It is not intended to give an answer to a specific question or determine the suitability
of a particular specification for a particular application. The tables follow a logical pro-
gression dealing with each coat in a specification (primer, barrier(s), and finishes). For
each coat an assessment is made on the key parameters of resin type, pigment type, and
thickness. Each variable within each coat is assigned a value and the sum of these values
for individual coats and the whole specification gives an overall ranking of the coat or
specification. The tables have been compiled so that the higher the final total value, the
"better" that specificationis for a given service condition. In its present form the ranking
system is only really appropriate for conventional multicoat systems and does not deal
with high film thickness elastomeric urethanes or polysiloxane coatings. It also does not
include water-borne coatings at this stage.
For applications of coatings in waters see chapter 11, Applications, for relevant in-
dustrial application.
6.3.1.1 Thermal Spray
Thermal spray coatings are applied by feeding wires or powders of metal, ceramic,
or carbide into a high velocity, high temperature gas stream that propels the molten
material at the surface to be coated. In some cases the resulting coating is heat treated,
fused, and/or sealed after spraying. Techniques used include the following:
High velocity oxygen fuel (HVOF) systems produce hard coatings with low porosity
and oxide levels. Materials sprayed include tungsten carbide, chromium carbide, etc.
Plasma spray produces coatings with materials which include molybdenum, iron,
copper-based powders, etc. as well as ceramics.
Arc spray is widely used for anticorrosion applications and reclamation of worn com-
ponents. Materials sprayed include steels, bronze, zinc, aluminum, etc.
Flame spray is also widely used for anticorrosion applications as well as reclamation
work and original equipment manufacture, particularly automotive.
Thermal spraying processes and materials can be selected to give short-, medium-,
or long-term protection against seawater and wave erosion to offshore structures. These
systems have been used to protect drilling equipment, submarines, and ship superstruc-
tures.
Group I-Life to first maintenance 5 years, finite life 10 years

Group 11-Life to first maintenance 10 to 15 years, finite life 20 to 30 years
Group 111-Life to first maintenance 20 to 25 years, finite life 40 to 50 years
The metals used are either zinc or aluminum with coating thickness varying from 100
to 250 pm. The more durable coatings need sealing with sealers such as polyurethanes
or micaceous iron oxide e p 0 ~ i e s . l ~ ~
The thermal spray committee of the Japan Association of Corrosion Control con-
ducted corrosion tests of thermal-sprayed Zn, Al, and Zn-A1coatings beginning in 1985.
Twelve kinds of Zn, Al, and Zn-13Al coatings were deposited on steel pipes by DC
arc-spraying and flame-spraying in various thicknesses, and seven kinds of them were
subjected to various sealing and heavy painting posttreatments. The samples were set
vertically into the seawater at a port 80 km south of Tokyo. The corrosion performance
of the coated steel pipes was inspected annually by recording the appearance and coat-
ing thickness in sea air, splash, and tidal zones. After 5 years of exposure, no significant
changes were observed on any of the coatings. After 7 years of exposureZn coatings with
or without sealing suffered rust corrosion in the tidal zone. Arc-sprayed A1 with sealing,
flame-sprayed Zn-A1 with sealing, and flame-sprayed A1 with heavy painting showed
excellent rust resistance, while flame-sprayed Zn or A1 without sealing permitted heavy
rusting of the steel pipes.lM
6.3.1.2 Plating
Metals can be plated onto a substrate by either electroplating or electroless processes.

These plated coatings are usually thin and often porous, thus do not make good bar-
rier coatings. Metals commonly plated to give corrosion resistance, usually onto carbon
steel, include tin, zinc, cadmium, and nickel. Decorativeplating of chromium,brass, and
copper is also common. Zinc and cadmium-plated items such as bolts, wire, fasteners,
etc. find some use in water service.
6.3.1.3 Hot Dipping
Hot dipping refers to the process in which the item to be coated passes through a bath of
the molten coatingmetal or alloy. Zinc, aluminum, and zinc-aluminumare hot dip coated
onto steel using batch and continuous processes. The hot dip zinc coating (galvanized)
is commonly used in wet, corrosive atmospheres but rarely in water immersion service.
The life of galvanized steel can be further extended by the use of sealers and specially
formulated paints.
6.3.2 Linings
Linings can be loose or bonded and commonly consist of thermoplastics, rubber, lead,
nickel alloys, ceramics, and glass. The linings are fitted to metallic, plastic, or concrete
structures or vessels.
6.3.2.1 Thermoplastics
Many thermoplastics are resistant to corrosion by chemicals and waters but do not have
the mechanical strength to be used in the form of large tanks, vessels, or pipes, in high
pressure valves or pumps, or in applications where impact resistance is needed. The

good corrosion resistance of plastics can still be used in these applications by inter-
nally lining a metal, concrete, or FRP form. Linings can be bonded or loose depend-
ing on the plastic and substrate used and the conditions of use. The most common
substrate for thermoplastic lining is carbon steel, but stainless steel and cast iron are
also lined. FRP lined with thermoplastics (dual laminate) is dealt with in Section 6.1,
"Plastics."
Many of the common thermoplastics are used as liners. The most common plastics
used in lining carbon steel or FRP, with their normal temperature limit of use, are PVC
60"C, PP lOO"C, PVDF 150"C, FEP 2OO"C, PVDF 150°C, ECTFE 160"C,and PFA 260°C.
These temperatures refer to the largely unloaded polymer and are too high for general
use of lined e q ~ i p m e n t .A
' ~temperature
~ limit of 100°Cis typical for PP, PVDF, and PTFE-
lined mild steel pipe in waters including acid mine, deionized, demineralized, distilled,
fresh, salt, and sewage.'% Plastic liners that are to be bonded are usually supplied with
a glass or synthetic fabric imbedded into one surface. This enables nonstick polymers to
be adhesively bonded to steel using, for example, a high grade epoxy. The bond has to be
strong enough to survive the thermal stresses that derive from the differences in thermal
expansion between the lining and the substrate. The sheet linings are first bonded to
the prepared steel or concrete substrate and then the joints between sheets are fusion
welded, sometimes using a cover strap over the joint. Spark testing is used to prove the
integrity of the finished joint.'55
Concrete troughs, manholes, and sumps can be thermoplastically lined by making
a former of the plastic sheet that comes supplied with dovetail-shaped protuberances
on one side. The liner is welded and formed to the required shape and the concrete cast
around it. The protuberancesbecome embedded in the concrete and firmly hold the liner
in place. The joints between the lining sections are then seal welded and spark tested.
Standard liner sections are commonly available in PE, PP, or PVC and UHMWPE for
abrasive liquids and slurries. This type of lined concreteis used in water and wastewater
treatment, chemical process plants, and offshore facilities.
When carbon steel pipe is lined with a thermoplasticthe liner is not normally bonded
to the steel. The steel pipe is normally vented to release trapped air or vapor diffusing
through the liner in service.A number of different techniquesare used in the manufacture
of lined pipe to ensure that the liner stays in place. One method is to insert a stretched
plastic tube into a steel pipe and then release it. The liner length reduces and the diameter
increasesso that the liner fits firmly against the steel. Both ends of the liner are then flared
over the radius at the flanged ends of the pipe. The other common method of manufacture
is to insert the plastic liner into an oversized steel pipe that has a series of barbs on the
inside. The steel and liner are then fed through a swaging machine that compresses the
pipe onto the liner. The barbs help to lock the liner in place and the liner ends are then
flared over the flanges.Some manufacturersfit steel reinforcementcollars under the liner
at the flange to further anchor the liner in place.
The reason for the interest in locking or holding the liner in place is that very high
thermal stresses can develop because of large differences in thermal expansion between
the steel and the thermoplastic (see Table 6.10 for typical liner properties). The thermal
Table 6.1 0 Properties of Thermoplastic Liners in Carbon Steel
Liner PVDF PVDF

Characteristics PTFE PFA PP (homopolymer) (copolymer) ETFE FEP PVDC
Service -20 to -20 to 0 to 0 to 275 (-18 -20 to 275 -20 to -20 to 0 to
temperature 500 500 225 to 135) (-29 to 135) 300 300 275
range, OF(,,)* (-29 (-29 (-18 (-29 (-29 (-18
to to to to to to
232) 232) 107) 149) 149) 135)
Coefficient 5.5 x 7.8 x 4.8 x 6.6 x 7.8 10-5 7.4 x - -
of thermal 10-5 10-5 10-5 10-5
expansion,
in. /in./"F
Thermal 1.7 1.3 0.8 0.9 1.18 1.65
conductivity,
BTU -h./h-
ft?/OF
Tensile 3000- 3800- 4000- 5000-6000 4500-5500 6700
strength at 4000 4500 4500
yield, PSI
% Elongation 250- 300- 10-13 8-10 10-20 150-
at yield 350 350 300
SG 2.14- 2.12- 0.90- 1.75-1.78 1.76-1.78 1.70-
2.19 2.17 0.92 1.72
*Max.allowable temperature depends on the specific contact chemicals.
expansion coefficient of mild steel is typically 0.67 x in./in./"F. In the early days
of using lined pipe there were many occurrences of liners cracking at the flange radius
and/or contracting back into the pipe. During operation at temperature the stresses
induced in the liner during manufacture relax and the liner thickness increases. When
the pipe is then cooled the liner tries to contract more than the steel and will either
end up with high tensile stresses or the stresses will relax by breaking the liner, usually
at the flange radius. There are also cases of liners failing by blistering or collapsing by
permeation of gases through the liner. Many of these early problems have been overcome
by improved design and manufacture of lined pipe and their use at more realistic upper
temperatures and service environments.
Environmental stress cracking ( E X ) is well known in plastic materials. E X occurs
in plastic-lined parts when the plastic liner is exposed to specific chemicals while under
mechanical or thermal stress. ESC can lead to failuresat stressesbelow the tensile strength
of the material. In some instances, the presence of a contaminant may act as an accelerator.
For example, iron or copper contamination in concentrated sulfuric or hydrochloric acid
can result in stress cracking of polypropylene liners. All plastics, including PTFE, are
known to be susceptible to E X . The occurrence of ESC is hard to predict and depends on
the process chemistry, operating conditions, physical piping system layout, and quality
of field fabrication of the piping system.'58
Lining of pumps and valves with melt processible polymers is usually by some form
of molding process that ensures a thick, seamless lining. The metallic shell of the pump
or valve is usually cast iron or fabricated carbon steel. Pipe with bonded liners made by
molding is also available (Fusibond@).
A PVDF-lined carbon steel pipe, used for handling chlorinated water with 5,000 to
20,000 ppm chlorides, suffered a through wall pit after 9 years of service. The liner was
seen to be severely cracked with the main crack starting from the liner flange. Tests
showed that the liner was not chemically attacked but was more brittle than unexposed
liner. The conclusion was that the PVDF liner had become embrittled by an aging process
in the presence of chlorinatedbrackish water. This chlorination solution line was replaced
with FRI'.'59
6.3.2.2 Thermosets
The thermosets used for linings are similar to those used in the thinner coatings. They
are usually reinforced with fibers, flakes, or powders and can be laid on steel or concrete
surfaces. The methods of applying these linings are hand lay-up, flake reinforced, or
troweled resin mortars. Hand lay-up linings are usually glass fiber mat reinforced, with
a lining thickness of 2.2 to 3.8 mm. Thermoset linings may also be reinforced with mica or
glass flakes and these vary from 1to 2 mm thick. Another lining system uses thermoset
resins mixed with silica fillers and these are troweled onto the surface to be lined. These
linings are also often reinforced with glass fiber rovings. Polyesters, vinyls, and epoxies
are the resins most often used for any of these linings. The most important factor in
producing a durable lining is to ensure that the surface is properly prepared and the
resin and hardener are well mixed in the correct proportions.lm
There are resin-based spray and trowel-applied linings and coatings formulated for
application to either metallic or concrete surfaces. These range from barrier coatings
based on flake glass-reinforced polymers in which the flakes overlap to reduce perme-
ation and increase durability. These flake-reinforced coatings are also formulated for
application as linings up to 1mm thick and have been used for seawater service in the
oil and gas industry. Other linings are fiberglass-reinforcedpolyester or vinyl resins that
are hand applied up to 3 mm thick. Topcoats can be polyester, vinyl ester, or epoxy
depending on the app1ication.l6l
6.3.2.3 Rubber
Rubber linings have been used for many years in process industry and marine applica-
tions and where wear is a factor. Natural or synthetic rubbers are used depending on
application. Natural rubber linings can be soft or hard. Hard natural rubber linings are
more susceptible to mechanical damage and thermal shock than soft linings but have
better adhesion, chemical resistance, and resistance to permeation by water and water
vapor. Rubber linings are bonded to the steel surface by curing unvulcanized (uncured)
rubber in contact with a pretreated steel surface. The chemical bond strength can be
higher than the tensile strength of the rubber in the case of natural rubber linings. The
steel surface is grit blasted and a bonding agent is applied and allowed to dry. The
bonding agent used depends on the rubber formulation. The rubber sheets are laid on
the prepared steel equipment and the lining is rolled out to remove air bubbles. Joints
between sheets are sealed, often with a cover strap. Upon completion the lining is given
a partial cure and is then spark tested. Defects found on spark testing can be cut out and
repaired. The cure is then completed and a final spark test is carried out. The temperature
limit for most soft rubber compounds is 60°C for continuous service and about 80°C for
hard rubbers. For higher temperature applications synthetic rubbers, such as nitrile or
chlorosulfonated polyethylene, can be used.
6.3.2.4 Cement and Concrete
Cement and concrete are used extensively to line steel or existing concrete structures.
They are also used directly on prepared floors, ditches, trenches, etc. to provide a durable
surface layer. The concrete is often laid over an impermeable membrane of rubber or
plastic if fluid leakage is to be avoided. Normal concrete is used for water service and
silicate-based cements are used in acid service. These linings are cast in place or gunned
onto prepared surfaces and can be reinforced with steel or fibers. Prestressed concrete-
lined steel pipe is widely used for water and wastewater applications.
6.3.2.5 Metals
Corrosion-resistant metals can be used to coat or line cheaper metal structures, usually
carbon steel, to permit their economic use in applications requiring large or high pressure
equipment. These metal linings can be applied in a number of ways depending on the
application and the metal used for the lining; the following are examples:
Homogeneous lead lining-produced by the process of lead burning, in which lead is

melted and fused to a carbon steel shell; often protected from the process conditions
by brick lining over the lead
Stainless steels, titanium, nickel, copper alloys, etc.; thermal sprayed
Metals and alloys welded using rod or strip electrodes deposited by hand or machine
Sheet lining or "wallpapering" weld attached and sealed; used for lead, nickel alloys,
etc.
Cladding by roll or explosion bonding onto carbon steel; the clad carbon steel is then
fabricated into the desired form
6.3.3 Biodeterioration of Coatings and Linings
Biodeterioration of coatings and linings has the same susceptibilityto biodeterioration as

other products made from these materials. Their biodeterioration, therefore, is discussed
under the relevant material. See, for example, Section6.2.6, ”Biodeterioration of Concrete
and Stone.”
6.3.4 Standards and Specifications-Coatings and linings
6.3.4.1 NACE
MR0274-95-Material Requirements for Polyolefin Cold-Applied Tapes for Under-

ground Submerged Pipeline Coatings
NACE No. l/SSPC-SP %White Metal Blast Cleaning (RP0494-2000)
NACE No. 2/SSPC-SP 10-Near-White Metal Blast Cleaning (RP0594-2000)
NACE No. 3/SSPC-SP 6-Commercial Blast Cleaning (RPO694-2000)
NACE No. 4/SSPC-SP 7-Brush-off Blast Cleaning (RPO794-2000)
NACE No. 5/SSPC-SP 12-Surface Preparation and Cleaning of Steel and Other
Hard Materials by High- and Ultrahigh-pressure Water Jetting Prior to Recoating
(RPO595-2000)
NACE No. 6/SSPC-SP 13-Surface Preparation of Concrete (RPO397-97)
NACE No. 7/SSPC VIS 4(1)-Interim Guide and Visual Reference Photographs for
Steel Cleaned by Water Jetting
NACE No. 8/SSPC-SP 14-Industrial Blast Cleaning (RPO299-99)
RPO178-95-Fabrication Details, Surface Finish Requirements, and Proper Design
Considerations for Tanks and Vessels to Be Lined for Immersion Service
RPO184-91-Repair of Lining Systems
RP0185-9f~ExtrudedPolyolefin Resin Coating Systems with Soft Adhesives for Un-
derground or Submerged Pipe
RPO188-99-Discontinuity (Holiday) Testing of Protective Coatings on Conductive
Substrates
RP0190-95-External Protective Coatings for Joints, Fittings, and Valves on Metallic
Underground or Submerged Pipelines and Piping Systems
RP0199-99-Installation of Stainless Chromium-Nickel Steel and Nickel Alloy Roll-
Bonded and Explosion-Bonded Clad Plate in Air Pollution Control Equipment
RP0274-98-High-Voltage Electrical Inspection of Pipeline Coatings Prior to Installa-
tion
RP0292-98-Installation of Thin Metallic Wallpaper Lining in Air Pollution Control
and Other Process Equipment
RP0298-98-Sheet Rubber Linings for Abrasion and Corrosion Service
RPO375-99-Wax Coating Systems for Underground Piping Systems
RP0394-94-Application, Performance, and Quality Control of Plant-Applied,Fusion-
Bonded Epoxy External Pipe Coating
h .4 Wood 215
RP0399-99-Plant-Applied External Coal Tar Enamel Pipe Coating Systems: Appli-

cations, Performance, and Quality
RP0487-200O-Considerations in the Selection and Evaluation of Rust Preventatives
and Vapor Corrosion Inhibitors for Interim (Temporary)Corrosion Protection
RP0490-95-Holiday Detection of Fusion-Bonded Epoxy External Pipeline Coatings
of 250 to 760 pm (10 to 30 mils).
lOD199-Coatingsfor the Repair and Rehabilitationof the ExternalCoatingsof Buried
Steel Pipelines
6AlOO-Coatings Used in Conjunction with Cathodic Protection
6A194-Surface Preparation Overview for Electroless Nickel Coatings
6A195-Introduction to Thick-Film Polyurethanes
6A198-Introduction to Thick-Film Polyurethanes, Polyureas, and Blends
6A287-Electroless Nickel Coatings (1997 Edition)
6A294-Quality Evaluation of Electroless Nickel Coatings
6G186-Surface Preparation of Contaminated Steel Surfaces
66194/SSPC-SP-TR-l-ThermalRecleaning
6G198/SSPC-TR 2-Wet Abrasive Blast Cleaning
6H188-Coatings over Nonabrasive-Cleaned Steel Surfaces (1996 Edition)
6H192-Conversion Coatings: A State-of-the-ArtReport
6.3.4.2 EN
Aspects of thermal spraying are covered by the following EN standards:
EN 582-Determination of tensile adhesive strength

EN 657-Terminology and classification
EN 1274-Powders, composition, and technical supply conditions
EN 1395-Acceptance inspection of thermal spraying equipment
EN 14918-Approval testing of thermal sprayers
EN 22063-Zinc, aluminum, and their alloys
6.4 WOOD
Wood is probably the material with the longesthistory of use in structural applicationson
land and in water. It has been used for the constructionof boats, piers, breakwaters, dams,
etc. for millennia. It is also occasionallyused to manufacture tanks for storing water and
other aqueous solutions (Figure6.13). Wood consists of three main organic constituents,
each having different properties. Cellulose is a complex carbohydrate taking the form of
long chains oriented along the grains of the timber. It generally accounts for some 40 to
50%of the dry weight and is responsible for wood’s high tensile strength. Lignin is hard,
brittle, and elastic and accounts for 20 to 35% of the dry weight and is responsible for
Figure 6.1 3 Wooden tanks are used for storing aqueous solutions in a chemical
plant. (Photocourtesy of CARIAD Consultants.)
the hardness, resilience, and compressive strength of wood. The third constituent is the
family of organics known as hemicelluloses or pentosans. These are similar to cellulose
but have shorter chain length and are more readily hydrolyzed. They may be between
7 and 30% of the dry weight. Wood may also contain varying levels of tannins, waxes,
oils, starch, resins, gums, and pigments.
There are about 180different kinds of wood grown commercially in the United States
and many others grown throughout the world. Some of these trees, such as pines and
oaks, have a variety of uses; others, such as ebony or balsa, are grown for specific ap-
plications? The classification into hard woods and soft woods does not relate to the
strength of the wood but to the structural and growth characteristics, e.g., hard woods
are deciduous while soft woods are evergreens. Within the tree there are two distinct
areas of wood with different properties, the sapwood and heartwood. The sapwood on
the outside of the tree is gradually converted to the heartwood, which is more resistant
to decay. Round timber posts and pilings are made from many types of wood, including
Douglas fir and southern pine, and properties are specified in ASTM D 25. Class B in this
specificationis used for wharves, docks, etc. and Class C is required for fully submerged
foundations, coffer dams, etc.162
The tensile strength and modulus of elasticity of wood are not impressive but if
we make allowance for its low density by calculating its specific properties (i.e., UTS
or modulus divided by density), the mechanical properties are competitive with other
common structural materials (Table 6.11). Since wood is by nature fibrous the mechanical
h .4 Wood 21 7
Table 6.1 1 The Mechanical and Physical Properties of Wood Compared to Other Common
Structural Materia@
Specific Tensile Strength, Specific Tensile Modulus of Specific Modulus,
Material Gravity MN/m2 Strength, MN/m2 Elasticity, GN/m2 GN/m2
Spruce wood 0.46 104 226 10 22
Pine wood 0.5 110 220 10 22
Mild steel 7.9 459 58 203 26
Aluminum 2.8 247 88 69 25
Concrete 2.5 4 2 48 19
RigidPVC 1.5 59 39 2.4 1.7
properties are anisotropic and its behavior under load will vary greatly depending on
whether the load is applied across or with the grain.la
The strength of timber is very dependent on moisture content. As moisture increases
the ultimate strength decreases and the deformation increases up to the fiber saturation
point. Additional moisture above this point has no significant effect on strength. The
strength is also sensitive to the rate of loading and on the duration of the load. The
modulus of rupture of a beam loaded very slowly or one which has been under load
for a matter of years is considerably (about 40%) less than one that is tested in a normal
short-term test?
Wood, particularly Ekki, Kauri, pitch pine, Douglas fir, teak, and oak, is used for
vessels that are stirred or pressed, piping, and cooling towers. It has good resistance to
~25% nonoxidizing acids and ~ 6 0 % organic acids, is poor in alkalies, and can be attacked
by fungus and rot or termites in the tropics. Wooden cooling towers can be attacked by
alkaline water or chlorine and must be pre-treated to prevent soft rot by fungi.'@
Wood is being used for helipads on offshore oil and gas platforms. These Douglas
fir decks are supported by steel frames and some of them have been in service for
around 30 years. The original timber thickness was 100 mm supplied in standard sizes of
6 m x 350 mm width. After 20 years of service some of the timber has suffered mechanical
damage and perhaps deterioration from the occasional exposure to oil and water.'65This
is a good application for wood because of its energy-absorbing capacity, in which it is
at least nine times better than mild steel.'% This is also an important aspect of its use in
docks or wharves where ships are likely to impact the piling.
6.4.1 Degradation of Wood
6.4.1.1 Environmental
Woods are attackedby strong acidsbut more readily by even weak alkaline solutions that
dissolve the hemicellulose and the lignin leaving a soft, pulpy residue. (Separation of
celluloseand lignin is the basis for paper production; see Chapter 11, Section 11.11, "Pulp
and Paper Mills.") Wood often has a very short lifetime in seawater because of general
degradation by marine organisms, mechanical damage by wave action, swelling and
delaminationby water absorption, or some combination of these mechanisms. The type
of wood used will greatly influence the life achieved, with hardwoods generally lasting
many times longer than softwoods or bamboo, for example. However, in many parts of
the world, softwoods are readily available and comparatively cheap, thus still finding
many applications.To achieve a longer and more predictable life, recommended actions
include painting, use of impregnants such as creosote or biocides, periodic removal from
the seawater for freshwater washing, cladding with other materials such as thin metal
sheet or concrete, or simply regular in situ cleaning as long as strongly alkaline soaps
and detergents are
6.4.1.2 Biodeterioration
While wood has served well as a construction material, it has always needed constant
maintenance and frequent replacement, primarily as a result of biodeterioration. For
example, Columbus lost four ships from wood-borer attack on a voyage to the new
world in 1503 (see Chapter 11, Section 11.1, "Ships and Boats"). Decay or rot is often
caused by bacteria, molds, fungi, and insects that can digest cellulose and obtain food
from the wood. Since this process requires both oxygen and moisture to proceed, wood
that is either completely dry or totally submerged in anaerobic water will tend not to rot.
6.4.1 2.1 Organisms That Degrade Wood
B a ~ t e r i a ' ~and ~ 'O can and do degrade cellulose materials. In aquatic environ-
* ' ~fungi'
ments microbial degradation of wood by soft-rot fungi (in aerated environments) and
bacteria (in aerated or low-oxygen environments) are most common, unlike terrestrial
environments, where white- and brown-rot fungi pred~minate.'~'Soft-rot fungi belong
to the subdivisionsAscomycota and Deuteromycota.
In marine habitats bacteria can cause extensive decay of the superficial layers of the
wood but are unable to penetrate deeply. Fungi, however, can penetrate cell walls, feed-
ing on both lignin and cellulose and decay wood to a depth of more than 40 mm.17*
Wood degradation by fungi involves two sequential or concurrent mechanisms, oxida-
tion and hydrolysis, the former probably being nonenzymatic and the latter catalyzed
by a complex of enzymes.'"
Catastrophic failures of wooden marine structures such as ships and piers are more
likely to occur from attack by macroorganisms (Table 6.12; Figure 6.14). There are two
families of wood-boring bivalves: Teredinidae (shipworms)and Pholadidae (piddocks).
The distribution of shipworms is worldwide and they can occur in deep water. Ship-
worms use the wood they bore for food and can bore at a rate of about 0.3 m/month?O
Pholads are more generally found in warm, shallow water where they can be very
6.4 Wood 219
Table 6.1 2 The Most Common Wood-BoringAnimalsi76

Mollusca (clams, mussels, snails)
Teredinidae (shipworms)
Bactronophorus
Bankia
Licyathifer
Lyrodus
Nausitoria
Neoteredo
Nototeredo
Psiloteredo
Teredo
Teredora
Teredothyra
Sphathoteredo
Uperotus
Pholadidae (pholads)
Lignopholas
Martesia
Xylophaga
Crustacea (shellfish)
Isopoda (isopods)
Limnoria
Paralimnoria
Phycolimnoria
Cymodoce
Exosphaeroma
Sphaeroma
Amphipoda (amphipods)
Chelura
Insecta (insects)
Coleoptera (beetles and weevils)
Pselactus
Nacerdes
Euophy u m
Pentarthrum
Mesites
destructive of shoreline structures. One genus of wood-eating pholad, Xylophgu, can

occur in deep water, however, and caused the failure of submarine telegraph cables in
the Mediterranean and Black Seas in the 19th century when they penetrated the jute and
g~ttapercha.'~~ Texture may be an important cue for settlement. The wood-boring tere-
dinid Xylotryu gouldi will seek a depression as a likely point of attack on the ~ubstrate.'~~
Crustaceans that attack wood include the Limnoridae (gribbles),which eat it, Sphaer-
imatidae (pill bugs), which simply use the wood for shelter, and Cheluridae, which are
rarer.
Figure 6.14 Shipworms and pholads have caused the sinking of many boats
throughout history. These numerous holes, each a few millimeters in diameter,
are from a wrecked boat in Suva, Fiji. (Photocourtesy of CARIAD Consultants.)
Sphueromu species tolerate a wide range of salinities and are most active in the inter-
tidal zone. Since they do not ingest wood, preservatives may not reach the digestive tract.
Timbers resistant to other borers, such as turpentine (Syncurpiuglornuliferu), greenheart
(Ocofeu rodiuei), and kasi kasi (Xunfhosfemonsp.), have been found to be vulnerable to
Sphueromu. Preservatives such as creosote, copper/chrome/arsenic (CCA), or combined
CCA/creosote do not provide sufficient protection.ln
Wooden structural timbers of ports, harbors, and beaches of England and Wales were
examined for attack by invertebrates. The most common borer was the beetle, Pselucfus
spadix, present in 64% of the timbers examined from the midintertidal to the splash zone.
Another beetle found in the samples was Nucerdes melunuru, which colonized 13%of the
samples in the high intertidal and splash zones. Unidentified anobiids were also found
from midtidal levels and above. The presence of so many beetles is surprising because
they are little recorded as borers in marine timber and may be a more important pest than
realized. In addition, they were found in timbers not attacked by soft rot fungus, suggest-
ing they can tunnel in undecayed wood as well as in timbers attacked by fungus. From
midintertidal levels and lower, the gribble, Limnoriu, was present in 7% of the timbers.178
Conifers, such as pine and fir, are particularly susceptible to borer attack.179In Mon-
terey Bay, untreated fir and pine are commonly attacked, with degree of attack greatest
at 15 to 70 m depth, where untreated wood is destroyed in less than a year."
Some woods, however, particularly some tropical hardwoods, are naturally more
resistant to attack. Unfortunately, the basis for this resistance is not fully understood, and
6.4 Wood 221
considerable interspeciesand intersite variation has been found in experiments involv-

ing four Central American heartwoods: cocobolo (Dulbergiu retusu), guayacan (T'bebuiu
guuyucun), laurel negro (Cordiu ulliodoru), and cedro espino (Bombucopsis p i n a t a ) . In Mon-
terey Bay, for example, fir and oak controls were destroyed by shipworms while the
heartwoods were not attacked at all in 3 years. In the Panama Canal, however, all the
hardwoodswere attacked and only cocoboloremained after 90 months. Although the rea-
son for the differencesin attack are unknown, the authors speculated that unspecified
extractives in the heartwood provided the greatest resistance. Resistance decreased ra-
dially toward the pith and also varied depending on the height of the bole from which
the wood was taken. Intersite differences in the marine borer populations and possibly
chemical alteration of the leachable extracts by local waters could also have influenced
the rate of attack."
The degree of attack of unprotected natural woods may be of only academic interest
since under some circumstances almost all will be destroyed. In an extensive study of
60 species of wood, including those used in boat building, exposed in Goa, India, all
were destroyed within a year in this aggressive environment.lgl
Factors other than material used affect the degree of boring by macroorganisms.
Unlike the case of stone and concreteborers, depth appears to be an important influence,
perhaps because wood borers often use their substrate as food. In a 2-year investigation
of wood borers in India from 2 to 62 m the greatest attack occurred at 42 m depth.182
Competition with other organisms settling on the wood may also be important. The
lowest attack in the study occurred at 22 m where the panels were heavily settled by
oysters. In a harbor area the greatest attack occurred near the sea bottom.
6.4.1 2.2 Structures Attacked
Virtually all wooden structures, including boats, docks, piers, and cooling towers, placed
in seawater are at risk from micro- and macroorganisms. (For wooden vessels see also
Chapter 11, Section 11.1, "Ships and Boats.") Intermittent wetting provides the most
favorable conditions for rapid destruction by decay. Bridge or pier piles made from
untreated timber will be rapidly attacked near the water line (Figure 6.15).
On December 12,1995a 70-ft (21-m)section of a 50-year-old wharf at the Consolidated
Edison power plant in New York collapsed. When divers investigated they found that a
dozen pilings supportinga major road were also missing or severely deteriorated, forcing
the temporary closure of the road. All the pilings had been attacked by shipworms,
Teredo, and gribbles, Limnoriu. Attack was accelerated by pollution of the harbor with
warm water effluent from the power ~ t a t i 0 n . l ~ ~
Limnoriu species have also been found in wooden piles in Queensland, Australia.
They were most frequently encountered on the outer heartwood of untreated turpentine
wood (Syncurpiuglomuliferu) and on CCA-treated turpentine sapwood.lMWooden dykes
attacked by shipworms have threatened the very existence of the Netherlands.lg5
Wooden cooling towers are also susceptible to attack, even if impregnated with
biocide.'% Especially in the tropics cooling tower water systems provide a suitable
Figure 6.15 Photo shows attack by marine borers in wooden piling. The buried end was not
attacked. (Photocourtesy of CARIAD Consultants.)
environment for the growth and development of a variety of fungi. Differences

in the physical and chemical factors (e.g., temperature, effluent concentration, etc.)
in cooling tower water systems have a profound effect on the composition of the
mycoflora.lB7
6.4.1.2.3 Remedial Measures
The common treatment of wood for marine service is to coat periodically with antifoul-
ing paint or to impregnate with creosote or a creosote/coal tar mix, where permitted.
Antifouling paints release toxic compounds, such as tributyl tin or copper, and depend
for their reliability on a constant rate of release at concentrations high enough to inhibit
settlement,but not so high as to reduce excessively the useful life of the paint. (SeeChap-
ter 10, Section 10.2.4, ”Biofouling Control,” and Section 10.2.5, “MIC Control,” for more
on antifouling compounds.)
Some of the traditional, very effective treatment chemicals, such as copper sul-
fate, arsenic, mercuric chloride, etc., are no longer permitted because of environmental
6.4 Wood 223
concerns.' The use of others, such as creosote, are restricted where people, animals, and
drinking water may come in direct contact with them.
Creosote contains known carcinogens and is not effective at preventing attack by
Limnoria species. It is more effective against shipworms and pholads. In a 5-year study
in Madras Harbor, India, seven species of timber were tested for the effectiveness of
treatment by CCA or creosote-fuel oil. The creosote mixture protected all species from
attack for the whole 5-year study, although untreated controls were attacked and mostly
destroyed.la8These preservatives were not effective, however, at eliminating all fungal
gr0~th.l~~
Other wood preservatives, chromated copper arsenate, and ammoniacal copper
arsenite are more effective at preventing attack but weaken the wood and embrit-
tle it.'90 Various boron formulations have also been tried as preservatives on woods
used in historic ships. When impregnated for 1 to 4 months, the boron penetrated
the heartwood of oak (Quercus) and pine (Pinus) and did not substantially alter the
Na-N-methyldithiocarbamate(Vapam@),methylisothiocyanate (Vorlex@),and
trichloronitromethane (chloropicrin) have been placed in piles to diffuse gas through
the wood as a treatment against marine borer attack. PTFE and Saran@can be ap-
plied to the surface and after some months they are stripped off with the fouling.
Nontoxic repellents such as tannic acid, benzoic acid, and acrylamide prevent the set-
tlement of micro- and ma~rofouling.'~~ More recently, the calcium-precipitating agent
N,N-naphthaloylhydroxylamine (NHA) was found to inhibit decay by brown-rot and
white-rot fungi.192
Coating wood with polyurethane has been suggested as a protective measure. As
expected from the discussion on plastics (Section 6.1, "Plastics"), however, species like
the pholad Murtesiu striutu, which can penetrate both wood and plastic, renders this
protection mechanism less than perfect.193
6.4.2 Standards and Specifications-Wood
6.4.2.1 ASTM
D 9-87(1999)-Standard Terminology Relating to Wood

D 25-99-Standard Specification for Round Timber Piles
D1860-95(2000)-Standard Test Method for Moisture and Creosote-TypePreservative
in Wood
D 2017-81(1994)el-Standard Test Method for Accelerated Laboratory Test of Natural
Decay Resistance of Woods
D2481-81(1994)el-Standard Test Method for Accelerated Evaluationof Wood Preser-
vatives for Marine Services by Means of Small Sue Specimens
D 2555-98-Standard Test Methods for Establishing Clear Wood Strength Values
D 2899-95-Standard Practice for Establishing Design Stresses for Round limber Piles
D 3507-97(2000)-Standard Test Methods for Penetration of Preservatives in Wood

and for Differentiating Between Heartwood and Sapwood
D 4446-84(1995)el-Standard Test Method for Antiswelling Effectiveness of Water-
Repellent Formulations and Differential Swelling of Untreated Wood When Ex-
posed to Liquid Water Environments
D 5583-00-Standard Test Method for Detection and Estimation of Retention of Wood
Preservativesby Aspergillus Bioassaying
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6.5 References 229
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124
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126
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127
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133 R.G. Bromley, “Bioerosion of Bermuda reefs,” Palaeogeogr. Palaeoclimatol. Palaeoecol. 23
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135 R.C. Highsmith, R.L. Lueptow, S.C. Schonberg, ”Growth and bioerosion of threemassive corals
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137 W. Sand, E. Bock, “Concrete corrosion in the Hamburg sewer system,” Environ. Tech. Letters
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139 G.R. Hall, “Control of microbiologicallyinduced corrosion of concrete in wastewater collection
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140 C.A. Kofoid, R.C. Miller, ”Rock boring mollusks attack concrete pile jackets,” Eng. News Rec.
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142 P.J.B. Scott, D. Moser, M.J. Risk, “Bioerosion of concrete and limestone by marine organisms: a
13-year experiment from Jamaica,” Mar. Poll. Bull. 19 (1988):pp. 219-222.
143 W. Sand, E. Bock, D.C. White, ”Biotest system for rapid evaluation of concrete resistance to
sulfur-oxidizing bacteria,” MP 26 (1987): pp. 14-17.
144 B.A. Richardson, ”Control of microbial growths on stone and concrete,” in Biodeteriora-
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145 P.J.B. Scott, “Factors influencing the susceptibility of submarine calcareous substrates to attack
by bioeroders,” in Marine Biodeterioration: Advanced Techniques Applicable to the Indian
Ocean, Goa, India, 1986, eds. M.-F. Thompson, R. Sarojini, R. Nagabhushanam (New Delhi,
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pp. 193-198.
147 K. Rutzler, ”The role of burrowing sponges in bioerosion,” Oecologia 19 (1975):pp. 208-216.
P.J.B. Scott, ”Associationsbetween corals and macrofaunal invertebrates in Jamaica, with a list
of Caribbean and Atlantic coral associates,” B d . Mar. Sci. 40 (1987):pp. 271-286.
149 P.J.B. Scott, Report on Experimental Analysis of Susceptibility of Two Types of Concrete to
Chemical Bioerosion, for Raymond International Builders, Inc. (1985),pp. 1-16.
150 H.O. Pierson, ”CVD/PVD coatings,” in Metals Handbook-Corrosion, Vol. 13,9th ed. ed. J.R.
Davis (Metals Park, O H ASM International, 1987), pp. 456-458.
151 G.H. Brevoort, M.F. MeLampy, K.R. Shields, “Updated protective coating costs, products, and
service life,” M P 36,2 (1997):pp. 39-51.
152 G. Gedge, Comparison of Paint Specifications-Ranking System, http://corrosion-doctors.
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vironment for 10 years,” Corros. Sci. Prot. Technol. 12,3 (2000):pp. 125-129.
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162 E.R. Parker, ”Materials Data Book-For Engineers and Scientists, (New York McGraw-Hill,
1967), pp. 229-233.
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165 K. Matthews, Zadco, NACE Network (2001).
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167 J.R. Aaron, Notes on Timber and Chemical Activity (High Wycombe, U.K.: Timber Research
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169 C.A. Clausen, “Bacterialassociation with decayingwood: a review,” Int. Biodeterior.Biodegrad.
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170 J. Kohlmeyer, E. Kohlmeyer, eds., Marine Mycology. The Higher Fungi (New York: Academic
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Delhi, India: Oxford and IBH Publ. Co. Ltd., 1988),pp. 345-356.
173 T.L. Highley, B.L. Illman, “Progress in understanding how brown-rot fungi degrade cellulose,”
Biodeterior. Abstr. 5,3 (1991): pp. 231-244.
174 R.D. Turner, ”Deep water wood-boring molluscs,” in Proceedings of the 3rd International
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176 G. Relini, “The state of the art in the protection of marine structures from biodeterioration,” in
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17* P. Oevering, B.J. Mathews, S.M. Cragg, A.J. Pitman, ”Invertebrate biodeterioration of marine
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186 K. Udaiyan, S. Manian, ”Fungal deteriogens from preservative treated service timber packing
in water cooling towers,” Int. Biodeterior. 27,3 (1990): pp. 275-279.
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6.5 References 233
timber panels treated with preservatives," in Biodeterioration and Biodegradation 9 (Rugby,

'90 P. Boyle, "Marine wood biodeterioration and wood-boring crustaceans," in Marine Biodete-
rioration: Advanced Techniques Applicable to the Indian Ocean, Goa, India, 1986, eds. M.-F.
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1988), pp. 167-188.
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vation of oak and pitch pine heartwoods," in Biodeterioration and Biodegradation 9 (Rugby,
19* R. Green, T.A, Kuster, L. Ferge, T.L. Highley, "Protection of Southern Pine from fungal decay
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and Biodegradation 9 (Rugby, U.K.: Institution of Chemical Engineers, 1995), pp. 663-671.
Chapter 7
Biofouling and Biodeterioration
Organisms have a profound effect on materials submerged in waters and on those used
to contain it. This chapter looks at the wide variety of organisms and how they foul,
corrode, bore, and degrade materials.
7.1 BlOFlLMS AND BlOFOULlNG
Biofouling is the undesirable growth of organisms on structures placed in aquatic en-

vironments (Figure 7.1). Almost all materials placed in natural waters will quickly be
colonized by and covered with living organisms, creating a biofilm. The effects of biofilms
are detrimental in many industrial systems.'
Biofouling can be either microbiological fouling, caused by algae, bacteria, etc., or
macrobiological fouling by macroalgae (seaweed) and animals, such as barnacles, mus-
sels, clams, worms, etc., which are easily visible to the naked eye. All living organisms
are classified according to a hierarchical system (Table 7.1).
Classic early work on marine biofouling was conducted by the LaQue Center for
Corrosion Technology under the auspices of the Ocean Thermal Energy Conversion
(OTEC) project of the U.S. Department of Recent advances in techniques,
including nuclear magnetic resonance imaging and microprobes, have greatly enhanced
our understanding of biofilms and their constituents."
Wet biofilms are composed of many species of bacteria, fungi, algae, other microor-
ganisms, metabolic by-products of the bacteria, water, and miscellaneous inorganic mat-
ter, including debris, iron, and corrosion products. We now know that biofilms are not
a homogenous matrix of extracellular polymeric substances (EPS) interspersed with
bacterial cells. Individual cells occur in discrete microcolonies separated by water chan-
nels within which there is convective flow in a chaotic system. The advantages and
disadvantages of recent techniques for studying biofilms and MIC, including electro-
chemical noise, concentric electrodes, scanning vibrating electrode mapping, electro-
chemical impedance spectroscopy, atomic force microscopy, confocal laser microscopy,
235
236 B iofoul ing and B iodeterioration
Figure 7.1 A heavy growth of marine fouling organisms, mostly barnacles, was found in the
water box of a heat exchanger.(Photocourtesy of CARIAD Consultants.)
Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy, Auger elec-

tron spectroscopy, extended x-ray absorption fine structure, and utilization of piezo-
electric materials, were recently reviewed. The authors concluded that many of these
techniques were more effective when used in combination and that, while several are
useful for studying various aspects of the mechanisms of MIC, more work will be needed
before they are useful as field-monitoring
An important aspect of biofouling is that populations of sessile bacteria in biofilms
achieve population densities orders of magnitude higher than in the planktonic state.
Solid surfaces have a stimulating effect on the growth of bacteria in dilute solutions,
such as natural waters. This is because in open water organic matter is not sufficiently
concentrated to permit bacteria to take up the nutrients within cells. Both organic matter
and bacteria (even dead bacteria) are adsorbed onto surfaces, however, effectively con-
centrating nutrients and permitting enhanced bacterial growth. Thus, populations may
increase by over a thousand times.8 This population explosion often leads to problems
resulting from the metabolic activity and by-products of the organisms.
In addition to a greater abundance of microorganisms, biofilms differ from bulk
water in species composition. Unfortunately, these biofilms are difficult to identify using
conventional techniques. Preparation procedures for fixing, dehydrating, and staining
7.1 Biofilms and Biofoulina 237
Table 7.1 The ClassificationSystem

of Living Organisms
Classification Example
Kingdom Animalia
Phylum' Mollusca
Class Bivalvia
Order Mytiloida
Family Mytilidae
Genus Mytilus
Species edulis
* Plural phyla. Plant phyla are often

called Divisions.The genus and species
should always be written in italics.
for scanning electron microscopy can remove much of the biofilm, especially diatoms
and metal species trapped in the EPS, leaving a thin monolayer of bacteria connected by
stringy remnants of EPS (Figures 7.2 and 7.3).9
Biofilms are inherently more resistant to biocides than planktonic bacteria. In some
cases they have been shown to be 10 to 1,000 times more resistant." Some of the possible
Figure 7.2 An environmental scanning electron micrograph (ESEM) shows a

biofilm on steel. Bacteria and debris are imbedded in a watery, gelatinous matrix.
238 Biofouling and Biodeterioration
Figure 7.3 A scanning electron micrograph (SEM)gives a different image of a

biofilm on steel. The bacteria are now visible because preparation of the speci-
men requires dehydration. The EPS matrix is reduced to a few stringy filaments
entangling the cells. Rods,cocci, and vibrios are all present on the sample. (Photo
reasons for this resistance are listed below:"
Biofilms contain large quantities of EPS, which may protect bacteria from biocides.
Sessile bacteria have a higher ratio of unsaturated to saturated fatty acids.
Organisms can produce an enzyme that destroys the biocide.
Permeability of the cytoplasmic membrane may be altered to prevent the entry of
biocide.
Changes may take place in the composition of the cell wall.
A spontaneous mutation may occur on the chromosome or in a plasmid.
Unfortunately, natural biofilms are almost impossible to replicate in the laboratory.

In laboratory cultures species composition of the biofilm depends on culture conditions
such as temperature1*-14and culture medium comp~sition.'~ The medium composition
has been shown to affect growth kinetics and EPS production and compositionin several
strains of Desulfovibrio.l6
Biofilms alter the concentration of ions, pH, oxygen concentration, flow velocity,
and other factors at the material/water interfa~e.'~ Biofilms also modify the surface of
7.1 Biofilms and Biofouline 239
structures and condition them for settlement of subsequent communities. Thus, they
lead to further fouling and/or attack by macroorganisms.
7.1.1 Problems Caused by Biofilms and Biofouling
The most seriousproblemsare loss of heat transfer efficiencyin heat exchangers,blockage

of tubes and pipes, energy losses from drag on ships' hulls, contamination of waters,
biodeterioration of nonmetallic materials, and corrosion of metals.
Biofouling organisms have long been a concern for those involved in maritime ship-
ping. Fouling of ships has been a problem since at least the time of the ancient Greeks and
was mentioned by Aristotle. Early attempts to control fouling include the use on ships'
bottoms of tar, wax, and lead sheathing by the ancient Greeks and pitch and possibly
copper sheathing by the Phoenicians and Carthaginians.ls
For a slow ship, like a tanker, the part of the resistance caused by friction between
hull and water is about 95% of the total resistance and even in fast ships it is generally
much greater than 50%.Since the power required to drive the ship is proportional to the
resistance, friction is responsible for a major part of fuel consumption. Roughness and
fouling may increase the friction by more than 100%.19
The large variety and abundanceof marine fouling organismscost the maritime ship-
ping industry millions of dollars annually in energy, maintenance, and repair costs. One
estimate, published in 1987, gave a figure of $420 million for losses of availability and per-
formance at fossil fuel plants caused by condenser macrofouling.20Another claimed the
cost to the shipping and other marine industries worldwide is more than $6.5 billion per
year.21Untreated ships' hulls can increase fuel costs by more than 15%(or approximately
U.S. $75 to 100million annually in the U.S. Navy) because of increased drag. In addition,
increased turbulence from fouling can degrade the self-noisecharacteristics of ships and
submarines, compromising their sonar operations. The U.S. Navy spends an additional
estimated U.S. $100 million a year on hull cleaning, antifouling paint removal and re-
painting, toxic water and grit disposal, Occupational Safety and Health Administration
(OSHA)health requirements, and labor associated with corrective measures.22
The nature of fouling communitieshas changed in modem times. Short turn-around
periods of ships in port, a consequence of the introduction of containerized shipping in
the 1960s, resulted in the replacement of fouling animals by macroalgae. More recently,
with highly effective antifouling coatings and paints, slime-fonning organisms such as
bacteria, diatoms, choanoflagellates,small filamentousalgae, and blue green algae have
become the most troublesome f ~ u l e r s . ~ ~
It had been calculated that a primary fouling film of between 25 and 250 pm would
cause 10 and 50%reduction in heat transfer coefficients of OTEC heat exchanger tubes.
Thus, biofouling and deterioration of heat transfer in the heat exchanger tubes became a
limiting factor in OTEC plant operation. Because of the inability to control the develop-
ment of a primary fouling film of only 55 pm thick, OTEC power plants were never able
to become operationally feasible. The inability to control biofouling in its earliest stage
doomed the initial U.S. Department of Energy OTEC project to commercial failure."
240 Biofoulina and Biodeterioration
Biofilms can be a serious problems in pulp and paper plants. When they form slime
layers they can trap fibers, fillers, and other debris, cause slime breaks and slime spots
during sheet formation,hinder efficient operation of the paper machine, causebrightness
loss of the fibrous finish, and cause unwanted odors in the paper.=
Microbiofilms have now been demonstrated conclusively to initiate and acceler-
ate corrosion of various steels (see Section 7.2, "Microbiologically Influenced Corro-
sion"). Experiments have confirmed that the presence of marine aerobic microorganisms
(bacteria and algae) on stainless steel caused ennoblement of the free corrosion poten-
tials. Specimens in sterile seawater were not attacked?6 Biofilms usually shift the open
circuit potentials of stainless steels, super stainless steels, and other metals in a positive
direction by several hundred millivolt^?^-^^
In addition to initiating pitting, biofilms accelerate crevice corrosion. Biofilms in
coastal seawater decreased initiation time, maximum penetration, and weight loss for
crevice corrosion of alloys 304,317,2205, and 904L.31
It is now well established that macrobiofouling, as well as microfouling organisms,
presents an increased risk for corrosion of metals. Intergranular corrosion occurred under
barnacles on aluminum brass condenser tubes. The corrosionoccurred after the barnacles
died and was attributed to bacterial reduction of sulfate to sulfide, which created anodic
sites near the outer edge of the barnacle Corrosion is more severe (deeper) under
larger barnacles.33Localized corrosion has also been observed under live barnacle bases
on 316L.34
Some species of barnacles can physically remove protective coatings on materials. As
it grows, the base of the barnacle Balanus eburneus exerts a strong downward pressure,
pushing the paint film up onto the sides of the organism.In some thick, bituminous enam-
els and asphalt coatings the organisms may penetrate through a quarter inch (0.5 cm) of
coating to the base metal, exposing it to corrosion.35
Other problems include increased condenser back pressure when cooling water flow
is reduced, malfunctioning of online tube cleaning equipment, and accelerated erosion
of tubingzo
7.1.2 Biofilm Development
The sequence of events in the biofouling of a clean, sterile material immersed in water
results from a combination of physical, chemical, and biological processes that have been
well d ~ c u m e n t e d .Within
~ . ~ ~ minutes of immersion organic molecules are transported
to and adsorbed onto the surface. These molecules condition the surface, permitting
the adhesion of pioneering microbial cells, which are attracted and transported to the
surface. Adhesion is first reversible, then permanent, when polymeric fibrils exuded by
the bacteria attach to the surface. Metabolic processes and the production of extracellu-
lar polymers by permanently attached cells permit the attachment of more cells, other
bacterial species, algae, fungi, and inorganic material, including metals and corrosion
products. The result is the development of a complex, multispecies biofilm in a matrix
that includes water, live and dead cells, EPS, and detritus. Viable cells may constitute
only 1 to 10% of the volume of wet biofilms, the major constituent is water. The total
organic content of dry biofilms and scale, when analyzed, is often in the order of only
about 10 to 20% of the material, even though the deposit is biologically induced and
mediated.
After adhesion by microorganisms, surfaces are further colonized by larger foulers,
such as mussels and barnacles, when these are present in the water. Although the mi-
crobial film is not an absolute requirement for settlement of macrofoulers, it is usually a
precursor to it, since sheer weight of numbers leads to a high probability that the usual
sequence of events is organic film, microorganisms, then macrofoulers.
Upon maturity, the biofilm reaches a maximum thickness, after which it becomes less
stable and will periodically slough off in parts, exposing the surface to new colonization.
The rate of detachment increases with increased fluid shear stress.37
7.1.3 Microbiofouling
The microbial constituents of biofilms include bacteria, algae, and fungi. Microbiofouling
is an important concern in heat transfer equipment. A cooling tower containing warm,
aerated, nutrient-rich water is an ideal environment for many organisms. Heat transfer
resistance and consequent energy losses can be dramatic even in thin biofilms. The
thermal conductivity of biofilms is similar to water (0.61 to 0.62 W/m K) with a range of
0.57 to 0.71 W/m K. This compares with 51.9 W/m K for carbon
Occasionally, if the heat exchange system goes totally out of control deposits by
microbialbiofilms can become massive enough to block tubes and tubesheets completely.
In one case, "serious" blockage of a carbon steel heat exchanger after 1.5 years was
attributed primarily to iron bacteria, especially Sphaerotilus.38
7.1.3.1 Bacteria
Bacteria are ubiquitous, prokaryotic (the genetic material is not contained in a nucleus),
primitive, and ancient organisms, some of the oldest life forms on Earth. They are invis-
ible to the naked eye (approximately 0.25 to 1 pm in. diameter). They have an asexual
doubling time that may be as short as 20 min under ideal conditions. Their spores are
highly resistant to boiling, freezing, drying, and disinfectants. They are adaptable and
motile. Species may be autotrophic (make their own food from inorganic constituents,
like plants), heterotrophic (like animals), or both.
Bacteria and another group that used to be classified as bacteria, the Archaea, can
thrive under a wide range of temperatures (freezing to at least lOOOC), pressure (down
oil wells and to deepest ocean floors), pH (approximately 1 to 13), oxygen concentration
(anoxic to supersaturated water), salinity (distilled water to brines), and velocities
(stagnant to pumped v e l o c i t i e ~ ) . ~ ~ ~ ~
242 Biofouline and Biodeterioration
Nutrients required for cell protoplasm are carbon (as carbon dioxide, inorganic, or
organic carbon), nitrogen (as gas, ammonia, nitrate, or nitrite), phosphorus (usually or-
thophosphates), and micronutrients (iron, manganese, etc.). Electron donors for energy
reactions come from water (photosynthesis),ammonia (nitrifyingbacteria), glucose (lac-
tic acid bacteria), or hydrogen sulfide (sulfur bacteria). Electron acceptors for energy
reactions come from oxygen (aerobic bacteria), nitrate (denitrifying bacteria), or sulfate
(SRB).
Bacterial identificationis usually achieved by biochemical analysis. It is not possible
to identify a species of bacteria by looking at it. For the most part this is not a serious
limitation because the name does not matter in industrial situations. Functional groups
are more important and can be identified by using media that select for them.
Bacteria are conveniently divided into two groups, depending on whether they take
up and retain a purple stain in a differential staining process developed in the 19th
century called the "Gram stain" after the Danish bacteriologist, Christian Gram. The stain
is so important because it reveals fundamental differences important in treating bacteria.
Gram-positive bacteria have thicker, more impermeable cell walls than Gram-negative
bacteria and are more resistant to drying.*Gram-negativebacteria have more chemically
complex cell walls and are more resistant to biocides?l The walls are firmly attached to an
outer membrane and both act as protective barriers to substances, including biocides!2
Gram-negative bacteria appear pink after staining. Most bacteria important in indus-
trial biofilms are Gram-negativerods or vibrios, e.g., Pseudornonas, Desulfovibrio,Thiobacil-
Zus, and Gallionella. Gram-positive bacteria are dark violet after staining. They are more
commonly cocci (spheres) such as Staphylococcus and Streptococcus. Therefore, although
by no means fool-proof, finding large numbers of Gram-negative rods in corrosion areas
is an indicator of potential MIC problems, while large numbers of Gram-positive cocci
can give reason for optimism (Figure 7.4).
Some bacteria, notably Bacillus and Clostridiurn, form spores, that are much more
resistant to heat, desiccation, and biocides. Among the SRB, DesulfotornacuZurn forms
spores, but not Desulfovibrio.
An important characteristic of bacteria is that they secrete a slime of exopolymers
and live in biofilms of many different types of organisms. Biofilms sequester individual
bacteria and provide a more hospitable environment for them. The EPS of biofilms
traps organic and inorganic material and accelerates scale formation and underdeposit
corrosion. Multiple species in biofilms allow bacteria of different groups and dietary
habits to feed off each others' by-products, making the entire community more robust.
7.1.3.2 Algae
Algae are eukaryotic (theDNA is contained in a nucleus), autotrophic organisms (plants),

which reproduce mostly by asexual cell division. Among the microorganisms they are
relatively large. They are usually motile and are colored. They are divided into red,
brown, yellow, and green but only the latter two groups are important in corrosion. They
live at <O to >4OoC,pH 5.5 to 9, freshwater to brine conditions. They need light, COz,
7.1 Biofilrns and Biofoulina 243
Figure 7.4 Photo shows planktonic bacteria as seen in a normal light microscope at 1,000~
magnification after being stained with a Gram stain. Dark purple cells are Gram positive, light
pink ones Gram negative. (See color plate.) (Photocourtesy of CARIAD Consultants.)
and inorganic nutrients, and produce Ozduring photosynthesis. They cause corrosion
directly as well as indirectly and cause problems when they do the following:
Foul heat exchangers

Supply food to bacteria
Produce aggressive metabolites
Create differential aeration cells
A number of photosynthetic bacteria and algae have been identified in fouling and
corrosion problems (Table 7.2). Plant operators have recently been surprised to discover
that algae have an unexpected ability to survive and occasionally metabolize under
conditions of little or no light, such as inside heat exchangers.
7.1.3.3 Fungi
Fungi (yeastsand molds) are eukaryotic,heterotrophic organisms.Contrary to manypeo-

ple’s ideas, they are not plants but belong to an independent Kingdom. They reproduce
244 Biofoulingand Biodeterioration
Table 7.2 Some of the Important Microfouling

Photosynthetic Organisms
Division Cyanophyta (Blue-green algae, now usually
classified as bacteria =Cyanobacteria)
Mycrocoleus
Trichodesmium
Division Bacillariophyta (Diatoms)
Coscinodisceae
Melosira
Thalassiosera
Coscinodiscus
Skeletonema
Cocconeis
Soleniae
Leptocylindrus
Biddulphiae
Biddulphia
Fragilarioideae
Striatella
Grammatophora
Licmophora
Climacosphaenia
Fragilaria
Synedra
Thalassiothrix
Naviculoideae
Navicula
Pleurosigma
Trachyneis
A mphiprora
Nitschia
Surirella
Gyrosigma
both sexually and asexually. They can live from 0 to >60°C and pH 2 to 8. They have a
resting stage of spores, which are resistant to desiccation and can live for years. They are
important in fouling and biodeterioration (Table 7.3).
7.1.4 Macrobiofoulingand Biodeterioration
There is almost no material, natural or man-made, that is immune to fouling and/or

degradation by macroorganisms when placed in marine environments. The costs
7.1 Biofilms and Biofouline 245
Table 7.3 Important Fungi Involved

in Fouling
Division Mycota
Penicillium
Aspergillus
Spicaria
Hormodendrum
Fusarium
Hormoconis
incurred from damage, maintenance, replacement, and lost use of materials total bil-
lions of dollars per annum worldwide.
The terms ”biodeterioration”and “biodegradation” are often used interchangeably.
A precise definitionof these terms, however, distinguishes them on the usefulness of the
materials attacked and produced. Biodeterioration is the biological breakdown of useful
materials, which yields undesirable products, while biodegradation is the breakdown
of pollutants and toxins to harmless pr0ducts.4~
Bioeroding organisms comprise a diverse assemblage of at least four Kingdoms and
most Phyla of flora and fauna, and include bacteria, fungi, algae, sponges, coelenterates,
polychaetes, bivalves, gastropods, sipunculans, barnacles, thalassinids, shrimp, crabs,
bryozoans, echinoderms, ascidians, and fish.
For only a few of these groups, however, do we have more than the most rudimentary
knowledge of their boring mechanisms and significanceas bioerosion agents. Moreover,
although most are sedentary invertebrates for which substrate selection occurs during
larval stages, larval settlement behavior and strategies are known for only one or two
species.Since, as noted by Crisp,44it is ”unusual for a sessileorganism to fix permanently
immediately it touches a surface,” larvae generally “taste”and test a variety of substrates
and environmental conditions before permanent settlement and metamorphosis. Con-
ditions influencing their settlement success will significantly alter the susceptibility of
the substrate to subsequent biodeterioration.
Mechanism of attack depends on the type of material, location, and the organisms
involved. Knowledge of these mechanisms is an important step in specifying the appro-
priate material for a given application and in minimizing the risk of premature failure.
Rates of fouling and destruction are generally higher in polluted and tropical waters. In
many instances, severe problems can be avoided by accurate assessment of the condi-
tions of service, appropriate selection and treatment of materials, and/or suitable water
treatment.
Common materials of marine construction and their principal attackers are reviewed
in the relevant materials in Chapter 5, ”Metals and Alloys,” and Chapter 6, ”Nonmetallic
Materials.”
246 Biofoulinn and Biodeterioration
Table 7.4 The Main Groups of Marine MacrofoulingPlants with Examples of All the Common
Genera (ExamplesAre Worldwide and Will Not Be Found in All Locations)
Division Rhodophyta (Red algae). (These are mainly feathery plants growing on rocky coasts
in warm oceans but do occur in fresh water as well. Red algae usually settle on surfaces after
brown and green algae.)
e.g., Gloiopeltis,Ceraminum, Ptilota,Antithamnion, Apoglossum, Audouinella, Callithamnion,Chon-
dria, Dasya, Erithroglossum, Fosliella, Grifithsia, Lophosiphonia, Polysiphonia, Pterothamnium,
Ptilothamnium, Seirospora, Spyridia, Stylonema, Pneophyllum, Bangia, Eythrotrichia, Fucus
Division Phaeophyta (Brown algae, seaweed, including kelp). (Theseare most abundant as large
seaweeds along rocky temperate coasts.)
e.g., Acinetospora, Cladostephus, Cutleria, Cysfoseira, Dictyopteris, Dictyofa, Discosporangium,
Ectocarpus, Giraudia, Halopteris, Hincksia, Lobophora, Myriactula, Sphacelaria, Stictyosiphon,
Stilophora, Zanardinia
Division Chlorophyta(Greenalgae).(Commonfreshwateralgae, but also includesmarine species,
especially in tropical waters. May be single cells, filaments, or delicate blades.)
e.g., Enteromorpha, Rhizoclonium, Ulva, Cladophora, Byopsis, Chaetomorpha, Palmophyllum,
Ulvella, Ulothrix, Entocladia, Ochlochaetae
7.1.4.1 Macrofouling Organisms
Major macrofouling organisms include both plants (encrusting algae and seaweed)
(Table 7.4) and animals (Table 7.5). Macrofouling organisms can be found in all oceans,
from the Arctic to the Antarctic, and more than 1,000 species have been reported world-
wide (Figure 7.5). A total of 59 major fouling species were identified in the Mediterranean
from Italy" and 106 species from mariculture rafts in Hong K0ng.4~
Most macrofouling organisms are attached or sedentary as adults. There is a short
larval stage during which the tiny, free-swimming, planktonic juvenile seeks a suitable
substrate for settlement where it will metamorphose into an adult and spend the rest
of its life. These larval stages are more vulnerable than adults and it is generally at this
stage that we would like to control their behavior and prevent attachment.
The mode of attachment of fouling organisms varies. Many important foulers secrete
permanent proteinaceous adhesives as liquids and these harden within minutes when
exposed to the water. Oysters and barnacles are cemented to the substrate. Oysters always
attach by their left valve, closely following the contours of the substratum. Attachment
area is usually a few square millimeters.46Mussels attach by means of tough byssal
threads secreted from glands in the foot. The force of attachment on slate is approxi-
mately 0.56 MPa (or approximately 0.1% of the tensile strength of steel).Attachment area
is generally a couple of square millimeters and is larger on smooth surfaces than
Barnacle larvae secrete a cement through ducts in the antennules. After metamorpho-
sis to an adult, an additional protein-based cement binds the barnacle to the surface.&
As the barnacle grows, attachment area increases as new rings are cemented under the
enlarged shell.
Figure 7.5 A concretemarinepier in Indonesiais fouled.The light circlesare the shellsof intertidal
oysters. (Photocourtesy of CARIAD Consultants.)
7.1.4.2 Factor Affecting Macroiouling and Bioerosion
The degree of macrofouling depends on a number of factors, including temperature,

length of immersion, time of immersion, material, location, and water quality. Settlement
on artificial fouling panels and other surfaces by marine larvae and spores is highly
complicated.
Most spores, eggs, and larvae are released by sessile adults into the water where they
spend the first part of their lives drifting fairly helplessly on Ocean currents. This stage
may last for minutes or months and they may drift meters or thousands of kilometers
from the parent. During this time they are often attracted to light and so rise toward the
surface, where they may or may not feed (depending on species). When they have devel-
oped to the settling stage they are “competent” and often become repelled by light. They
sink to the bottom where they begin to search actively for a suitable substrate. On this
smaller spatial scale organisms have more control over their movement and direction.
Timing of immersion has an important influence on the species composition of the
fouled surface. In colder waters most organisms only breed in the summer and there
will be little or no settlement of fouling organisms in the winter. In tropical waters
Table 7.5 The Main Groups of Marine Macrofouling Animals with Examples of All the Common Genera
(Example Are Worldwide and Will Not Be Found in All Locations)
Phylum Porifera (Sponges).(Sessileorganisms that gave us the bath sponge. Most with siliceousspiculesand/or
spongin fibers.)
Class Demospongiae.Usually upright, firmly attached, but may be encrusting. This group also includes the
boring sponges.
e.g., Sycon, Haliclona, Mycale, Halichondria, Leucosolenia, Scypha
Phylum Cnidaria (= Coelenterata)
Class Hydrozoa (Hydroids). (As fouling organisms usually branching, tree-like polyps, but also includes
jellyfish.)
e.g., Tubularia,Bougainvillea (=Bougainvillia),Eudendriurn, Companularia,Bimeria, Laomedia, Electra, Obelia,
Clytia, Sertularella, Gonothyraea
Class Anthozoa (Solitaryor colonial polyps)
Actiniaria (Anemones). (Soft-bodied tubes with tentacles.)
e.g., Sagartia, Coynactis, Anthopleura, Metridium
Scleractinia (Reef-buildingcorals). (Anemone-likebut with a hard calcium carbonate skeleton.)
e.g., Astrangia
Phylum Nemertinea (= Rhynchocoela) (Proboscis worms)
e.g., Lineus
Phylum Annelida (Segmentedworms)
Class Polychaeta (Maybe free-swimming,crawling, or burrowing worms. The most important fouling species
build tubes.)
e.g., Nereis, Perinereis, Typosyllis, Typanosyllis, Marphysa, Halosydna, Eulalia, Demonax, Placostegus,
Laonome, @to, Cirratulus, Branchiomma, Pomatoleios, Terebellides
Serpulidae (Construct calcareous tubes)
e.g., Serpula, Hydroides, Spirobranchus, Spirorbus, Mercierella, Pomatoceros, Salmacina, Vermiliopsis,
Pileolaria, lanua, Ficopomatus
Sabellariidae,Sabellidae, and other families (Constructtubes by cementing sand grains and other
available material.)
e.g., Phragmatopoma, Sabellaria, Gunnerea
Phylum Sipuncula (Peanut worms)
e.g., Phascolosoma
Phylum Bryozoa (= Polyzoa, = Ectoprocta) (Bryozoans)
Class Gymnolaemata (May be stalked and branching or encrusting colonies. Both types contain important
fouling organisms.)
e.g., Celleporaria, Calypotheca,Eudendrium, Cryptosula, Microporella, Savignyella, Zoobotyon, Benedenipora,
Arachnidium, Schizoporella, Watersipora,Electra, Membranipora,Flustra, Callopora,Alderina, Scrupocellaria,
Conopeum, Bugula, Bowerbankia, Victoriella
Phylum Entoprocta (Entoprocts).(A small group similar to Bryozoans.)
e.g., Pedicellina, Barentsia, Loxosomatoides
Phylum Mollusca. (Molluscs). (A large, diverse group important in fouling. Most with a hard, calcareous shell.)
Class Amphineura (Chitons).(Calcareousshell on top with eight plates. Cling to rocks with their foot, moving
slowly to feed.)
e.g., Acanthochiton
Table 7.5 (Continued)

Class Bivalvia (Clams, mussels, oysters). (Mussels and oysters are among the most important and common
fouling organisms.)
Mytilicea (Mussels).(Attached by strong byssal threads.)
e.g., Mytilus, Mytilopsis, Modiolus, Perna, Musculista, Brachidontes, Septqer, Geukensia
Ostreacea (Oysters). (Cemented to the substrate.)
e.g., Ostrea, Crassostrea,Saccostrea
Other fouling bivalves of various Orders and Families (Most of these also attach by byssal threads.)
e.g., Arca, Scapharca, Beguina Pteria, Pinna, Pycnodonta, Hyatella, Chlamys, Lima, Plagiocardium,
Paruicardium, Benerupis, Hiatella, Electroma, Pinctada, lsognomon, Anomia, Pododesmus
Class Gastropoda (Snails, limpets, slipper shells, etc.)
e g , Siphonaria, Cellana, Patelloida, Crepidula, Thais, Mitrella, Zafra, Littorina, Euchelus, Siphonaria
Phylum Arthropoda (Includesinsects on land and tasty crustaceans in the sea. Mostly hard shelled.)
Class Crustacea
Cirripedia (Barnacles).(Cemented or stalked, among the most important fouling organisms.)
e.g., Balanus, Megabalanus, Chthamalus, Chirona, Conchoderma, Lepas
Decapoda (Crabs).(Hard-shelled,usually mobile.)
e.g., Nanosesarma
Isopoda (Isopods)
e.g., Sphaeroma, Cirolana,Dynoides
Amphipoda (Amphipods). (May be surface dwelling or tube building. The most important foulers
[Ericthonius,Jassa,Corophium]build muddy tubes.)
e.g., Caprella, Podoceros, Elasmopus, Maera, Microdeutopus, Grandidierella,Photis, Ampelisca,
Gammaropsis,Hyale, Stenothoe, Ericthonius, Jassa,Corophium
Phylum Echinodermata
Class Crinoidea (Feather stars). (Except for deep sea stalked crinoids these spend long periods attached by
grasping cirri, alternating with swimming and crawling.)
e.g., Capillaster, Comanthina, Comaster, Comatella, Heterometra, Lamprometra, Stephanometra, Tropiometra,
Leptometra
Class Asteroidea (Starfish).(Mobile carnivores, moving along on tube feet with suckers.)
e.g., Astropecten, Asterina, Pentaceraster, Linckia
Class Ophiuroidea (Brittlestars). (Highly mobile, moving along substratum with rowing movements.)
e.g., Astroboa, Amphipholis, Ophiocomella,Ophiactis, Ophiarachnella,Amphiura
Class Echinoidea (Sea urchins), (Mobile, moving along the bottom by means of tube feet and spines.)
e.g., Salmacis, Psammechinus
Class Holothuroidea (Sea cucumbers).(Sluggish animals moving on tube feet.)
e.g., Synaptula, Holothuria
Phylum Chordata
Class Ascidiacea (Sea squirts or tunicates). (These contain solitary and colonial, attached species and both
are important fouling organisms.)
e.g., Ciona, Styela, Ascidia, S y m p l e p , Polyclinum, Molgula, Clavelina, Botyllus, Didenmum, Diplosoma,
Botylloides, Polycarpa, Lissoclinum, Polyandrocarpa, Amaroucium, Botylloides, Ascidiella
250 Biofoulicr ind Biodeterioration
Figure 7.6 Stalked barnacles thrive on this Mediterranean driftwood. The

larvae settle preferentially on the rough end grain and other irregularities.
(Photocourtesy of CARIAD Consultants.)
there may be settlement all year round, although not by the same organisms. In a 1-year
experiment,mild steel and other panels were immersed monthly in Hong Kong's Victoria
Harbor and the mass and composition of macrofouling strongly correlated with season
of immersion, being variously dominated by algae, serpulids, hydroids, bryozoans, tube-
building amphipods, and barnacles."
Hard surfaces are more heavily fouled than soft ones. In general, marine invertebrate
larvae settle more readily on rough rather than smooth surfaces.44Larvae of Lithophga
bisulcata rapidly moved across smooth surfaces of dead coral and concrete but paused
to explore all holes and crevices encountered?0 All bivalves observed eventually settled
in a crevice deep enough for them to retract fully. Although the mechanism of this
response is unknown, it has obvious survival value, giving protection from grazers and
predators.
Larvae select concavities and avoid convexities (Figure 7.6). Effects of light and grav-
ity seem to be important as dispersal and settlement cues for larvae, and simple re-
sponses to light have been noticed by a multitude of researchers in a wide variety of
taxa. Undersides, shaded, and dark-colored surfaces attract more marine larvae than
do well-illuminated and light-colored surface^.^' This affect can sometimes be seen in
moored boats, where the sunny side is always least fouled. In laboratory experiments,
for example, larvae of the boring sponge Cliom celata initially swam to the surface, then
sank to creep on the bottom after 20 to 30 h?*
There is evidence of avoidance of algal mats and other fibrous surfaces by many
invertebrate l a r ~ a e .In~one
. ~ study,
~ however, there were more boring polychaeteswhere
7.2 Microbiolonicallv Influenced Corrosion 251
there was a high percentage of epiphytes and algae.% In substrate-choice experiments

with concrete in Jamaica, concrete cores with substantial cover of filamentous algae and
epifauna were not bored, while unprotected surfaces of the same concrete were attacked
by clionid sponges.55
Capillary forces may be involved in an inhibitory effect of algal mats by impeding
dislodgment of the water film at the larva-substrate interface. Larvae of the bryozoan
Bowerbunkiu cannot establish contactwith hydrophobic surfaces exhibitingcontact angles
less than 17". Only at larger angles is it possible to overcome the electrostatic repulsion
barrier built up by electrical double-layer energies between the larva and the solid.56
Encrusting organisms also impede borers by preventing establishment of larvae and by
blocking openings and previously formed b0reholes.5~
Most materials are susceptible to fouling, including wood, plastics, stone, ceramic,
concrete, and metals. After 18 months of exposure in the North Atlantic off Scotland,
heavy fouling occurred, primarily by barnacles and mussels, on two duplex stainless
steels (UNSS31803and UNS S32760),an austenitic stainless steel (UNS S31254),a nickel-
base alloy (UNS N06625), and a cobalt-base alloy (UNS R30006).34
Copper-nickelalloys have long been recognized for their inherent resistance to marine
macrofouling with excellentservice experience in seawater intake systems including pip-
ing, screens, waterboxes, tubesheets, and tubing. Many researchers have demonstrated
that little or no fouling occurs on alloys containing 80% copper or more, even after long
exposure times.58 In Arabian Gulf seawater after 3 and 9 months of exposure 70/30
Cu/Ni (UNS C71500) had no macrofouling organisms but was covered by a yellowish-
green substance that was interpreted as bacterial EPS and corrosion products. Stainless
steel and nickel alloys (UNS S31600, N08028, N08825, and N06030) were f0uled.5~
7.2 MICROBIOLOGICALLY INFLUENCED CORROSION

Microorganisms were first implicated in corrosion of steel pipes almost 100 years ago
(see reviews of the history of MIC, especially SRB60+61). Today the problem is recognized
as a common and expensive one. MIC is such a common problem because water is a
prevalent fluid in industrial systems. It has been estimated that 15 to 30% of all corrosion
failure^^^,^^ and 50% of all failures of buried pipelines are caused by MIC.@
The literature contains abundant case histories of MIC failures in almost all industries
and applications (Table 7.6).
Several reviews of MIC by industry and application are also available, as well as
compilations of case histories from many industries.'" Process industries have had con-
siderable MIC problems" especially in cooling water ~ y s t e m s . " ~ ~One
" ~ of the most
common problems with MIC has occurred in chemical process industries because of
the practice of leaving stagnant water in vessels during shutdown or after hydrostatic
t e ~ t i n g . " ~ "Corrosion
~ and souring by microorganisms have also been an important
problem in the oil and gas ind~stry."~*"~
The classic mechanism for MIC of steel and iron was proposed by von Wolzgen Kuhr
in 1934.It is thought that SRB consume hydrogen through the action of their hydrogenase
Table 7.6 Some Industries and Applications Which

Have Reported MIC-Related Corrosion Problems
Industry or Application References
Fossil fuel power generation 65-67
Geothermal power generation 68-70
Nuclear power generation 71-75
Nuclear waste facilities 76
Oil and gas production 77-79
Petroleum pipelines 80-83
Gas pipelines 84
Potable water installations 85,86
Water piping systems 87-89
Water wells 90
Hot water systems 91
Desalination 38,92
Fire protection systems 93-95
Construction 96
Ships' hulls 97
Piers and wharves 98
Wastewater treatment 99-103
Chemical process industries 104-106
Alcohol distillation 107
Pulp and paper 25,108,109
Steel-making 110
Mining 111
enzymes, and thus "depolarize" the cathode, accelerating corrosion. Kuhr believed that
the rate-limiting step in corrosion is the dissociation of hydrogen from the cathodic site.
It has been pointed out, however, that since SRB in pure cultures result in lower corrosion
rates than mixed, real-world biofilms, this mechanism cannot be the only one.lZo
The oxygen reduction effect was found in natural seawater only at temperatures
below 40°C.'21 A catalyst, probably linked to bacterial exopolymers, was considered
the most likely explanation for the cathodic depolarization.lZ Others suggested that
an unknown phosphorus-containing corrosive metabolite produced by SRB must be
implicated.l' SRB produce a highly corrosive phosphorus-containingcompound from
an organic compound, inositol hexaphosphate,the major source of phosphorusin plants.
It reacts with iron to form a black precipitate, iron phosphide (Fe3P).lZ4
Hydrogenase production may influence corrosion rates but, if so, the relationship is
not simple. Similar corrosion rates were found in hydrogenase-positive and -negative
species of bacteria.lE Corrosion rates do not always correlate directly with hydrogenase
production (or, for that matter, with number of SRB).lZ6
It has also been suggested that corrosionby SRB can be attributed mostly to their pro-
duction of highly corrosive ferrous sulfide. Iron sulfide particles may be more important
than bacteria in the anaerobic corrosion process and the role of the mixed SRB biofilm is
7.2 Microbiologically Influenced Corrosion 253
to supply hydrogen sulfide continuously to keep loose iron sulfidecathodically active.127

Its corrosive effect depends on bacterial activity as it is not lasting in sterile solutions.'28
In aerobidanaerobic biofilm systems SRB corrosion mechanisms may be different from
totally anaerobic ones. In the former, it is thought to be caused by the establishmentof an
FeS/Fe galvanic cell when oxygen is present.129After total oxygen depletion localized
sulfide attack occurred."
Others have also found that in the absence of an efficient oxygen cathode, SRB corro-
sion of stainless steels involves cathodic depolarization induced by FeS corrosion prod-
ucts. In longer-term exposure tests, in addition to pitting and crevice corrosion, SRB
caused general corrosion, grain boundary attack in austenitic stainless steels, and selec-
tive corrosion of austenite grains in duplex stainless ~tee1s.I~~
Recent support for the importance of iron compounds comes from experiments on
the growth of the SRB Desulfovibrio gabonensis in an iron-free medium but in the presence
of a mild steel coupon. The organism could not grow at pH 7.4 but could grow at pH 6.0,
only in the presence of the coupon. The authors suggested a mechanism whereby at
lower pH, metabolic products, such as acetic acid, increase the level of corrosive sulfides
which in turn promote attack of the coupon, releasing Fe2+ for bacterial growth and
further corr~sion.'~~
Hydrogen sulfidecan inducefailuresby intergranular corrosion cracking and enhanc-
ing growth of corrosion fatigue cracks.'33 The complexities of biofilms make it difficult
to unravel the precise nature of the role of SRB and other sulfide-generatingbacteria al-
though it appears they increase hydrogen entry and growth of cracking from hydrogen
embrittlement of steel.lM
Hydrogen gas generated by the fermentativebacteria Clostridiurn acetobutylicurn and
others has also been implicated in hydrogen embrittlement of metals.'35g'36The presence
of SRB deposits has been proposed to cause stress corrosion cracking outside the normal
conditions for this type of corrosion, i.e., at 40°C in a reducing en~ironment.'~~ Other
bacterial by-products, such as thiosulfate and sulfite, promote hydrogen evolution and
permeation within iron, especially in acidic solutions.138
The complex and poorly understood role of biogenic sulfur compounds in corrosion
has recently been discussed and reviewed by various author^.'^^^'^ It is now clear that
metabolic sulfur compounds are extremely corrosive and that bacterial consortia create
synergistic effects that enhance the corrosiveness of these compounds. Sulfur adsorbed
onto metal surfaces weakens the metal-metal bonds, permittingdissolution of the metal
and, in addition, can block or delay formation of the passive film.14'
Anodic depolarization during sulfide production by SRB was suggested in the 1950s
as a mechanism to stimulate corrosion,'42 although this effect has been disputed.'43
The arguments for anodic depolarization have been revived.14 For more details on
mechanisms of SRB corrosion see reviews by several a ~ t h o r s . ' ~ ~ Future
- ' ~ ~ research in
the area will undoubtedly find more mechanisms by which microorganisms corrode
materials. Recent research has concentrated on the role of biomineralizationin MIC.14
One thing on which most workers agree is that, paradoxically, corrosion by anaer-
obic bacteria is many times greater in aerated or alternately aerated and deaerated
environments.lMAmong aerobic bacteria, a mechanism of cathodic depolarization of
stainless steels has also been r e ~ 0 r t e d .In
l ~manganese-oxidizing
~ bacteria accumulation
of manganese oxide deposits by bacterial processes alone leads to breakdown of the

passive film and there is no requirement for preexisting sulfide corrosion products.'50
Metabolic end-products of bacterial metabolism include short-chain fatty acids (such
as acetic, malic, gluconic, oxalic, succinic, and citric acids). These organic products are
often aggressive to steel when concentrated under a colony or other d e p ~ s i t . ' ~ ~ * ' ~ ' - ' ~
Metabolically produced acetic acid has been blamed because it dissolves the protective
calcareous film.'% Other enzymatic activity by microorganisms can also increase the
corrosion potential of stainless steels. Glucose oxidase, combined with the action of
hydrogen peroxide and gluconic acid produced by the enzymatic activity, increases
the p0tentia1s.l~~ Some bacteria also produce highly aggressive inorganic end-products
(for example, sulfuric acid in the sulfur-oxidizing bacteria, as well as the previously
mentioned hydrogen sulfide produced by SRB).
An additional mechanism in MIC is the creation of anodic sites and establishment
of differential aeration and other corrosion cells. The distribution of microorganisms on
surfaces is always patchy. Sites may be chosen for colonization because of roughness,
preexisting corrosion sites, inclusions, or surface charge. As the biofilm forms it attracts
other biological and nonbiological (metals, chloride) species. Oxygen and metals may
be concentrated or depleted within biofilms, leading to the formation of oxygen and ion
concentration cells, encouraging corrosion. These aggregations fix the anodic sites which
develop, and consequently pits are and ~ r 0 p a g a t e d . lBacteria
~~ may be
attracted to established anodic sites or initiate them by their metabolic activity. In any
case, once the bacteria are established at the site, repassivation of the pit is unlikely and
corrosion will occur.158
EPS exuded by bacteria in biofilms have been implicated directly in corrosion of
Corrosion current density increased with the deposition of EPS on 304 stainless
steel and decreased when it was removed. Similarly, removing the slime layer was an
efficient anticorrosion measure as it decreased corrosion potential values of stainless
l ~ ~ work also provides corroborating evidence of the corrosiveness of EPS
~ t e e 1 . Recent
component^,'^^ which may include enzymes,'60 pyrovuate or pyruvate-like group^,'^'
or a high-molecular-weight, iron-chelating protein-carbonate complex.'62 Research on
the corrosiveness of EPS will be hampered by the fact that EPS secreted by planktonic
phases of bacteria are not the same as those when sessile.la Furthermore, EPS produced
may be different in the same bacterium under different circumstances.'64
In nature microorganisms always live in biofilms of multispecies communities.
Multispecies consortia are more corrosive to steel than monocultures.'65~'66Waste
products of some species may be used by others, as in the well-known example of
sulfate-reducing and the sulfur-oxidizing bacteria. Similarly, metabolic uptake of oxy-
gen by aerobic heterotrophicbacteria creates anaerobic sites at the base of biofilms, which
allows anaerobic bacteria to thrive.
It is not surprising that corrosion rates are greater in cultures with growing cells
than those with resting stages since active growth is associated with more metabolic
by-product^.'^^*'^ Researchers also report that there are discrepancies in corrosion rates
between "natural" seawater and synthetic seawater. Natural seawater causes greater
corrosion in most rnaterial~.'~~
7.2 Microbioloaicallv Influenced Corrosion 255
Welds, HAZ, and areas adjacent to welds have frequently been demonstrated to be
more susceptibleto MIC than parent metal.170In austenitic stainless steelboth the austen-
ite and ferrite phases may be attacked, although ferrite phase attack is more common.
There was no correlationfound, however, between degree of attack and ferrite ~ 0 n t e n t . l ~ ~
In a comparative study of welds of several materials, weld corrosion rates were higher
in natural seawater containing microorganisms than in controls in the stainless steels
304L and 316L, the low alloy steels HY-80 and HSLA-80, alloy 400 and 90/10, Cu/Ni but
not UNS N08367, aluminum 5086, or titanium. In creviced welds, corrosion by MIC was
enhanced in all alloys except aluminum 5086 and titanium.’”
The thermo-mechanical cycle associated with welding produces extensive micro-
structural change in the vicinity of the weld, including changes in the microstructure of
the weld fusion zone, the partially melted zone, and the base material, all of which affect
susceptibility of low alloy steels to MIC. The creation of extensive subgrain boundary
coupled with solute redistribution in the fusion zone and extensive continuous grain
boundary films in the partially melted zone foster MIC in these locations.’”
7.2.1 Organisms Implicated in MIC
7.2.1.1 Bacteria
“Slime bacteria” is a name which refers to a diverse assemblage of aerobic, heterotrophic

rods or cocci. These are the bacteria generally cultured in a total heterotrophic plate count
or dip slide. They deplete oxygen, create differentialaeration cells, and create habitatsfor
SRB and other anaerobic bacteria. Pseudomonas, Bacillus, Aerobacter, and Flavobacteriurn
are some examples.
In some cases, Pseudomonas and Serratia may be protective, inhibiting corrosion of
~ t e e 1 . Microorganisms
l~~ on a metal surface can induce corrosion inhibition in several
ways: (1)by neutralizing the action of a corrosive substance already present in the
medium; (2) by stabilizing a protective film on a metal surface; or (3) by inducing a
decrease in the medium aggressi~eness.’~~ The effect, however, may not be long last-
ing. When mild steel was exposed to Pseudornonas sp. S9 or s. marcescens in synthetic
seawater corrosion inhibition was observed. When specimens coated with bacteria were
transferred to a natural seawater flow system, however, the inhibition effect disappeared
during the first 2 weeks.’76
An experimental study showed that the bacterial species and their by-products may
be a factor in determining whether a biofilm inhibits or enhances corrosion. A significant
reduction in corrosion rate was observed in a corrosive medium when mild steel was
incubated with growing, biofilm-forming bacteria that had direct access to the steel
surface, but not with non-biofilm-forming bacteria. Iron(I1)-phosphate, vivianite, was
found to be the cause of the corrosion inhibition.ln
The category of corrosion-causing bacteria known as acid-producing bacteria (APB)
produces organic acids that can cause corrosion of steels. Examples of APB in-
clude species of the anaerobic bacteria C2ostridium,C. acetobutylicum, C. bifermentans,
C. butyricurn, C.felsinium, and C. sporogenes. In experiments with acetic and sulfuric acids
at pH 6, the acetic acid was more aggressive to ~ t e e 1 .The
l ~ ~term "APB" can be mislead-
ing, however, because all bacteria produce organic acids and the distinction is, therefore,
a fine one. Furthermore, the bacteria that produce the strongest acids, such as Thiobacillus,
produce inorganic acids.
Iron and manganese bacteria are aerobic, heterotrophic sheathed chains, more com-
mon in fresh water than salt. They inhabit iron-bearingwaters, where they oxidize ferrous
to ferric and manganous to manganic compounds which are commonly chlorides. Some
species of the genera Gallionella, Sphaerotilus, Shewanella, and Pseudornonas can also selec-
tively reduce iron. Voluminous deposits may be brown or reddish. Corrosion cells under
the tubercles may proceed independently after all the bacteria die. They attack most met-
als, including copper. Examples include the stalked bacteria of the genus Gallionella and
filamentous genera Sphaerotilus, Crenothrix, and Leptothrix.
Iron-oxidizing bacteria have been isolated from rust deposits of carbon steel heat
exchangers where they can cause considerable damage from plugging and c o r r ~ s i o n . ' ~ ~
They were shown to increase both the cathodic and anodic reaction rates.lmManganese-
oxidizingbacteria may be responsiblefor the production of biomineralized MnOz, which
causes depolarization of stainless steel.lsOIn association with SRB, they are widely im-
plicated in MIC. Iron and manganese bacteria were implicated in the attack of 304L and
316L storage tanks. Reddish-brown deposits were common. Pits in the weld seams were
ink bottle-shaped and rust-colored streaks were found normal to the weld seams in the
sidewall below the pits. No other corrosion-causing bacteria were found."5
Metal-reducing bacteria have also been implicated in steel corrosion. Shaoanella
putrefaciens reduces solid ferric oxides to soluble ferrous ions. When carbon steel elec-
trodes were exposed to S. pu trefaciens, MIC was demonstrated electrochemically and
microscopically.
Nitrogen-reducing bacteria reduce nitrate to ammonia, which is highly corrosive
to some copper alloys. Examples include Alcaligens, Bacillus, Micrococcus denitrificans,
Pseudornonas aeruginosa, and P.jluioescens. These bacteria were implicated in SCC of
admiralty brass condenser tubes in a nuclear power plant.'82
Sulfur-oxidizing bacteria (SOB) are aerobic, autotrophic rods, divided into two
groups-the colored SOB which are photosynthetic and the colorless SOB, which are
chemolithoautotrophs and include species important in corrosion processes, as well
as microbial leaching of ores and contaminants. SOB oxidize sulfide, sulfite, thiosul-
fate, and sulfur-producing sulfur or sulfuric acid, depending on species. They grow at
pH c 1 and can tolerate high temperatures up to 90°C. Examples are Thiobacillus and the
high-temperature bacterium, Sulfolobus. Thiobacillus caused much more severe corrosion
of electroless nickel-plated mild steel than the SRB Desulfovibrio in laboratory experi-
m e n t ~SOB. ~ ~have
~ been found to cause corrosion of concrete and steel in contact with
concrete, sometimes forming consortia with SRB.96,'s4*185
SRB are anaerobic, heterotrophic vibrios (corkscrews or curved rods). They reduce
sulfate, sulfite, and several other chemical species of sulfur, producing hydrogen sulfide
or iron sulfide and removing cathodichydrogen. They are especially common in polluted
7.2 Microbiolonicallv influenced Corrosion 257
fresh or salt water. Most, but not all, produce hydrogenase. The most common examples
are Desulfovibrio and Desulfotomaculum.
Recently it has been pointed out that "sulfate-reducing bacteria" is a misnomer for
those organisms that produce hydrogen sulfide and blacken diagnostic media. Some or-
ganisms reduce intermediatelyoxidized sulfur compounds, such as sulfite, and therefore
"sulfide-producing bacteria" would be a more accurate name. One of these, Shewanella
putrefaciens, not only dominated SRB in cultures isolated from cooling water, it was
also capable of promoting M C in biofilms that were not completely anaerobic at the
base.'%
Other anaerobic bacteria have also been implicated in steel corrosion. Escherichia coli
corroded mild steels with 0.10 to 0.94%carbon c ~ n t e n t . ' ~ 'Two
- ' ~ ~species of salt-loving,
nonsulfate reducing, aerobic to anaerobic Vibrio, V; natriegens, and V; anguillarum, in-
creased corrosion current density of 304 stainless steel in laboratory experiments. Corro-
sion corresponded with production of EPS and rates were greater with V; natriegens.'%
Thermophilic bacteria belong to several different groups. Thermophiles reproduce
most rapidly at temperatures around 60°C. Examples include the SOB, Sulfolobus and
Thermothrix, and species of the SRB, Desulfotomaculum. Thermophiles are found in some
of the most extreme conditions supporting life and include some of the most ancient
bacteria known,the Archaebacteria.Archaebacteria promoted corrosion of 316 stainless
steel vapor ducts, steam lines, and condenser components at an electric power plant
in Mexico, even at temperatures of about 100"C.69Thermophilic SRB have also caused
corrosion of 304 stainless steel in the condenser of a geothermal electric power unit. The
condenser works with steam temperatures in the range of 40 to 150"C.@
Thermophilic sulfate-reducing and other bacteria have been recovered from a variety
of locations on oil production platforms, at temperatures higher than 80"C.'88 After
exposure to temperatures of 100°C and pressures of 1,000 psi for more than 1 h, a few
thermophilic SRB (less than 10%) demonstrated activity in a recovery medium.'89 In
experiments with thermophilic SOB and SRB the 6% Mo UNS S31254was severelypitted
by thermophilic SRB, but commercially pure titanium was not attacked.Ig0
7.2.1.2 Algae
Marine algae cause oscillations in pH at the algal/substrate interface, although these

rarely drop below seawater values in healthy c~mmunities.'~' Under decomposingalgae
the pH may drop to as low as 1.8.Algae corrode directly by setting up local concentration
cells, through cathodic depolarizationenhancinghydrogen removal and through anodic
depolarization influencing protective oxide films. Indirect corrosion occurs when algae
create an appropriate environment for anaerobic SRB.'92
Diatoms are among the first algae to settle on North Sea oil and gas platforms and are
numerically second to bacteria, reaching 270,000 diatoms/cm* in 28 days.'93 Although
microalgae may be beneficial when mucilage consolidates scale and corrosion products,
preventing ingress of oxygen, macroalgae can disrupt calcareousscale when the rhizoids
(holdfasts) break away or are pulled off, exposing more bare metal to corrosion. Algal
rhizoids may also disrupt coatings and antifouling paints.
In lab experiments, the open circuit potential of 304 stainless steel increased under
biofilms exposed to light and dominated by algae, but not with biofilms in the dark,
dominated by bacteria. The passive current density increased (measured in cyclic polar-
ization studies) with thickness and age of the algae-dominated bi0fi1m.l~~
7.2.1.3 Fungi
Fungi produce aggressive metabolites and organic acids. They consume 0 2 , create dif-
ferential aeration cells, and cause corrosion directly. They are often implicated in corro-
sion of aluminum alloy fuel tanks, esp. Cladosporium. Attachment points of the fungal
mycelium to the metal act as nucleation centers for pitting and acidic metabolites fa-
cilitate the breakdown of passivity by ~ h l 0 r i d e s . Other
l ~ ~ fungi implicated in corrosion
of fuel tanks are Penicillium luteum, Aspergillus jlavus, Spicariu sp., Hormodendrum hordei,
and Cladosporium S P . ' ~Hormoconis
~ resinae is also considered to be very aggressive to
aluminum alloys in contaminated jet fuels.63
Recently the fungi Fusarium, Penicillium, and Hormoconis were found to produce or-
ganic acids that caused localized corrosion of carbon steel cables in PVC sheaths.'97
7.2.2 Metals Susceptible to M I C

Metals that have been demonstrated to date to be susceptible to MIC are mild steel,
austenitic SS, superaustenitic SS, martensitic SS, ferritic SS, duplex SS, copper, bronze,
brass, and nickel/copper and nickel alloys. A study group established in the late 1970s
found evidence in the literature of MIC of many industrial alloys,'" and since that time
more alloys have been found to be susceptible. For details of MIC in particular alloys,
see the relevant materials section in Chapter 5, "Metals and Alloys."
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174 A. Pedersen, M. Hermansson, “Inhibition of metal corrosion by bacteria,” Biofouling 3 (1991):
pp. 1-11.
175 H.A. Videla, ”Corrosion inhibition in the presence of microbial corrosion,” Corrosion/96 paper
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176 G. Hernandez, V. Kucera, D. Thierry, A. Pedersen, M. Hermansson, “Corrosion inhibition of
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178 R.S. Rao, R.N. Sairam, B. Viswanathan, K.V.K. Nair, “Carbon steel corrosion by iron oxidising
and sulphate reducing bacteria in a freshwater cooling system,” Corros. Sci. 42 (2000):pp.
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181 B. Little, P. Wagner, K. Hart, R. Ray, “The role of metal-reducing bacteria in microbiologically
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sulphide-producingbacteria isolated from extreme environments and their role in corrosion,”
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191 R.G.J. Edyvean, L.A. Terry, “The influence of microalgae on the corrosion of structural steel
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& Sons, 1982),pp. 336-347.
192 L.A. Terry, R.G.J. Edyvean, “Algae and corrosion: a review,” in Annual Meeting of the Phyco-
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Ellis Horwood Ltd. 1984), pp. 38-44.
194 R.P. George, A.P. Muraleedharan, N. Parvathavarthini, H.S. Khatak, R.C. Newman, “Electro-
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1986),pp. 215-222.
196 D.H. Pope, D.J. Duquette, A.H. Johannes,P.C. Wayner, “Microbiologicallyinfluenced corrosion
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Biodeterior. Biodegrad. 47,2 (2001): pp. 71-77.
Chapter 8
Monitoring
Monitoring describes the process of taking regular measurements to look for changes
that might indicate problems with equipment or processes. This chapter describes the
techniques used to monitor corrosion, process changes, and biological activity in water
applications.
The aim of monitoring corrosioncan be to predict remaining safe life of the equipment,
to evaluate the effects of operating changes on corrosion, or to evaluate the corrosivity
of the process stream. Many different methods are used to monitor corrosion,
ranging from thickness measurements, immersion specimens, to very sophisticated
electrochemical techniques.
Some corrosion measurement techniques can be used online, with a probe constantly
exposed to the process stream, while others provide off-line measurement, such as that
determined in a laboratory analysis. Some techniques give a direct measure of metal
loss or corrosion rate, while others are used to infer that a corrosive environment may
exist.
Where you monitor is as important as how and what you monitor. The test loca-
tion must be as representative of the environment of interest as possible. For example,
if you are interested in corrosion in a pipeline, testing at some convenient branch con-
taining static liquid will not be appropriate. If you are monitoring corrosion of heat
exchanger tubing, samples placed in the water box will be of limited value. A particu-
larly difficult case is that of two-phase flow where there is a liquid phase with a vapor
phase above, or two immiscible liquids. Multiple specimens or a survey done by moving
the samples or probes to different locations is often necessary. The main point is that the
results you get and the value that they have will depend greatly on where and how you
monitor.
269
8.1 TECHNIQUES USED TO MONITOR CORROSION
8.1.1 Operating Conditions
As well as monitoring corrosion within the pipes, heat exchangers, towers, and vessels,
factors that affect corrosion, such as chemistry and physical conditions of the environ-
ment, should be monitored.
8.1.1.1 Chemical Composition
The chemical composition of the environment has a major influence on the corrosivitiy
of a fluid. The constituents of interest include the following:
Metal ions in the environment. In some cases these ions are beneficial, e.g., where
oxidizing species assist Ti to resist corrosion. In other cases oxidizing ions can be
detrimental, e g , for alloy B in acids. A buildup of metal ions in the environment
can be used to monitor and assess corrosion if it is known that they originate from
corroding equipment.
Other ions. Other ions can also indicate corrosion or the development of corrosive
conditions. Different ions will be important for different metal/environment combi-
nations. For example, in stainless steel equipment a buildup of chloride ions would
be an indicator that pitting or crevice corrosion is likely.
Gases, e.g., 0 2 , COZ,HzS. The presence of these or other gases in the atmosphere or
fluid can initiate, accelerate, or reduce corrosion in some metal/environment combi-
nations.
Levels of inhibitor. If inhibitors are being used to control corrosion their concentration
in the fluid should be monitored. This may be direct, by analysis, or indirect,by testing
for effectiveness of inhibition.
Biological species. The presence and concentration of macro- and microorganisms
can greatly influence fouling and corrosion. Again they may be monitored directly or
indirectly.
8.1.1.2 Physical Conditions
Corrosion and corrosivity of any given fluid/environment combination are strongly

influenced by the physical conditions. The following should be monitored:
Temperature. In general, reactions, including corrosion, happen faster as temperature

increases. Increased temperature, however, can release gases or dissolved solids from
solution which can reduce corrosion and/or form protective scales.
pH. Monitoring the pH of the environment can, for example, enable the balance to be
made between scale formationand corrosion in coolingwater systems (seeChapter 10,
Section 10.2, "Cooling Water Treatment"). Changes in pH can also affect the efficacy
of water treatment chemicals.
Pressure. Changes in pressure can affect corrosion rate; for example, operation under
a vacuum can reduce the boiling point of a liquid and permit the operation to
be carried out at lower temperatures, e.g., concentration of sulfuric acid. Changes
in pressure on produced or injection water in oil production can release corrosive
gases.
Flow rate. Too low a fluid velocity can lead to deposition and fouling; too high
can produce erosion corrosion. The optimum flow rate will be different for differ-
ent metal/environment combinations.
8.1.1.3 Operating Equipment
Pipes, valves, and heat exchangers should be regularly checked for changes that might
indicate corrosion is occurring or the presence of conditions favoring corrosion. These
Blockages. Equipment should be inspected to ensure the absence of blockages caused

by debris, sand, corrosion product, scale, etc. Such blockages can cause underdeposit
corrosion, crevice attack, MIC, pitting, or local boiling in heat exchangers. If blockages
are found their sources should be identified, because if they are corrosion products,
they are a clear indicator of a problem.
Fouling. Fouling can cause similar problems to blockages. Monitoringfor fouling may
use a visual unit consisting of a metal tube in a larger glass sheath. Water flows be-
tween the glass and the heated metal thus simulating heat exchanger conditions. This
type of unit provides qualitative information about the probable fouling or deposition
occurringwithin the system. Indirect techniquesfor measuring fouling include differ-
ential pressure measurements to determine changes in fluid frictional resistance and
heat transfer resistance measurements. Fouling monitoring devices work by tracking
changes in metal skin temperatures that increase as the metal becomes fouled. None
of these techniques distinguish between biological and nonbiological fouling or give
any information as to which biological organisms are present.*
Leaks. Liquids or vapors escaping from equipment are often an indicator that corro-
sion monitoringor control has not been effective.Leaks that are dealt with immediately
can often prevent further corrosion to the outside of the leaking equipment and to
adjacent items.
Noise. Mechanicalnoise or vibration can be a good indicator of corrosion. For example,
a cavitating pump makes an identifiable sound before major damage has occurred.
Vibration that might lead to corrosion fatigue can be detected by noise. Sound is also
the basis of corrosion monitoring by acoustic emission, discussed below.
272 Monitorine
Smells. Leaking fluids can often be found and identified by characteristic smells.
Sulfide smells can be a good indicator of the presence of anaerobic bacteria; water
drain valves should be opened occasionally and the stagnant water examined and
smelled.
8.1.1.4 Inspection
Regular inspections of plant equipment, with properly recorded results, can provide
valuable corrosion monitoring data. Inspection techniques include the following:
Visual, with or without magnifiers or boroscope, can indicate corrosion, scaling, or

fouling (Figure 8.1).
Dye penetrant examination can identify pitting, porosity, and cracks.
Magnetic flux can detect corrosion or cracking in ferromagnetic metals.
Radiography, ultrasonics, or eddy current examination can detect subsurface defects
or cracking.
Thermography can be used to look for hot or cold spots that could indicate the presence
and location of corrosive conditions, defective thermal insulation, etc.
Figure 8.1 Internal inspectionof a seawater heat exchanger tube showed fouling.
(Photocourtesy of Kvaerner Chemetics Equipment Division.)
Intelligent pigs, equipped with non-destructive test (NDT) equipment or cameras,

can be used to examine the inside of pipelines for corrosion, blockages, fouling,
etc.
8.1.1.4.1 Inspection Protocol
Whether inspection is carried out during service or only at shutdowns will depend on the
type of plant and the method of operation. Whenever items of equipment are inspected
the following general principles should be followed:
Use quantitative measurements whenever possible, such as calipers, micrometers,

ultrasonics, etc.
Keep records, such as replicates of surfaces or dye penetrant examinations, video or
still photographs, etc.
Look for fouling, pitting, cracking, and corrosion, using microscopes, boroscopes and
dye penetrant tests as appropriate.
In particular, watch for changes over a period of time. Slow general corrosion can be
tolerated in some equipment, but if the rate of metal loss suddenly increases the cause
should be identified and corrected.
Make inspections cost-effective by identifying critical items of equipment to include
in a regular schedule.
8.1.1.5 Failure Analysis
A corroded or cracked piece of equipment can provide the most direct evidence of a prob-
lem and careful failure analysis may be considered to be part of the overall monitoring
process. To obtain the maximum benefit one should do the following:
Carry out a thorough investigation using appropriate techniques, e.g., ultrasonics,

dye penetrant tests, or eddy current.
Use proper and complete recording of results and data.
Analyze the results to indicate whether changes of material, inspection, testing, or
fabrication are indicated for repair or replacement.
In general, failures should be investigated using a logical sequence of procedures.

These include the following:
Assess the history of the failed part; look for changes in operation or exposure.
Record relevant evidence by on-site photography and measurements together with
the results of detailed visual examination.
Obtain samples of the failed part, corrosion products, etc. together with samples of
unexposed items if available.
274 Monitoring
Laboratory investigation should include visual and microscopic examination, chem-

ical analysis, and mechanical property testing.
Corrosion testing, as part of the material assessment or to simulate operating condi-
tions, can provide additional information about the cause of the failure.
8.1.2 Corrosion Monitors
Corrosion monitors that can be installed in appropriate locations and provide informa-
tion about corrosive conditions either directly or indirectly are readily available com-
mercially. Many of them consist of interchangeableelements that can be inserted into the
fluid through various access systems, such as valves or glands. The operating tempera-
ture of this type of monitor is largely controlled by the seals used in the probe element.
Typically the stated limitsare 150°Cfor normal epoxy seals,260°Cfor high-temp ceramic,
PTFE, or glass seals, but practical limits may be less than this if long service is expected.
Some monitoring techniques and equipment are very specific to particular applica-
tions; others can be applied generally. Some are very low-tech and direct, while others
are based on complex electrochemical principles. Techniques in general use include the
following:
Corrosion coupons
Probes such as electrical resistance (ER) or inductive resistance (IR)
Hydrogen probes
Acoustic emission
Sand/erosion monitors
Sentinel holes-predrilled to indicate when corrosion allowance has been reached
Electrochemicalprobes, such as polarization resistance, galvanic, impedance, noise
8.1.2.1 Corrosion Coupons
The use of corrosion coupons is probably the most widely used technique in industry
(Figure 8.2; see also test rack assembly, Chapter 9, Figure 9.6). In this method a weighed
sample (coupon)of the metal or alloy under considerationis introduced into the process,
and later removed after an appropriatetime period. The exposuretime will depend on the
process, materialsbeing tested, and ease of access (a plant shutdown may be needed),but
is typically 30 to 90 days duration.The coupon is then cleaned of all corrosionproduct and
is re-weighed and visually examined. The weight loss is converted to a total thickness
loss, or average corrosion rate, using standard equations. The technique is extremely
versatile, since weight loss coupons can be fabricated from any commercially available
alloy. Nonmetallic materials can be included in the test “rack,” but their assessment is
usually based on factors other than weight loss, e.g., strength,hardness, and appearance.
Using appropriate types of coupon, a wide variety of corrosion phenomena may be
studied such as weld effects, SCC, and galvanic corrosion.
8.1 Techniaues Used to Monitor Corrosion 275
Figure 8.2 Typical stainless steel corrosion specimen after exposure in a pitting
environment. (Photo courtesy of CARIAD Consultants.)
Advantages of the weight loss coupon method include the following:
It is simple and direct with no complicated calculations or scientific assumptions to

be made.
The technique is applicable to all environments-gases, liquids, solids/particulate
flow.
The samples can be inspected visually and retained for comparison.
Corrosion deposits can be observed and analyzed.
Weight loss can be readily determined and corrosion rate easily calculated.
Localized corrosion can be identified and measured.
Inhibitor performance can be easily assessed.
The use of coupons will provide an average corrosion rate over the exposure pe-
riod, but if all of this corrosion occurs in one short upset period this method will not
show this. The techniques used to prepare the specimens before and after exposure
will greatly influence the results obtained. Surface finish often makes a big difference
to corrosion rate; the presence of passive films can reduce corrosion significantly so
it may be necessary to activate specimens at the beginning of the exposure. Cleaning
afterward is equally important-too vigorous and the measured corrosion rate will be
increased. Corrosion deposits left on the specimen will falsely indicate less corrosion.
Standard methods are available in relevant specifications (e.g., NACE RP0497, ASTM
G 1and G 4),but one of the most important aspects is to always use consistent methods.
276 Monitoring
See also Chapter 9, "Corrosion Control," and Chapter 10, Section 10.2, "Cooling Water
Treatment."
8.1 2 . 2 Electrical Resistance Method
ER is the basis for one of the most common commercially available corrosion monitoring
probes. It is based on a Wheatstone Bridge circuit-as metal is dissolved the electrical
resistance of the element increases (see ASTM G 96 for details of the principle). During
exposure the resistance of the corroding electrode is compared with a similar element
sealed inside the probe. Since temperature affects resistance the use of two elements, one
exposed and the other sealed, at virtually identical temperature provides compensation
for any fluctuations in bulk temperature. These simple, robust probes work well in high
resistance fluids but do not give good results under conditions that produce localized
corrosion or SCC. The ER probe can be permanently installed with direct readings of
corrosion rate provided to a data collection facility or can be read regularly using a
portable instrument. The active element should be made from an electrically conducting
metal with a composition as similar as possible to that of the equipment being moni-
tored.
Different configurations of elements are available to satisfy different requirements
(Figure 8.3, a to h):
(a) Wire loop elements are the most common. These have high sensitivity and low sus-
ceptibility to system noise, making it a good choice for most monitoring installations.
Wire loops are generally glass or epoxy sealed into an end cap, which is then welded
to the probe body.
Figure 8.3a-h Schematic shows

ER probe elements for different
applications. (Figure courtesy of
(b) Tube loop elements are recommended where high sensitivity is required to detect low
corrosion rates rapidly. Tube loop elements are manufactured from a small bore, hol-
low tube formed into a loop configuration. Carbon steel is the alloy most commonly
used.
(c) Strip loop elements consist of flat strip formed into a loop that may be sealed with
glass or epoxy into the end cap depending on the application. It is a very sensitive,
fragile element so should only be considered for very low flow applications.
(d) Cylindrical elements are made by welding one tube inside another tube. They are
all-welded, so exotic alloy elements can be produced relatively easily. This probe is
ideally suited to harsh environments including high velocity and high temperature
systems, or anywhere a glass-sealed element is not an option.
(e) Spiral loop elements consist of a thin strip of metal formed on an inert base. The
element is particularly rugged and ideal for high-flow regimens. Its comparatively
high resistance produces a high signal-to-noise ratio, which makes the element very
sensitive.
(0Flush mount elements are designed to be mounted in the vessel or pipe wall. This
element is very effective at simulating the true corrosion condition along the interior
surfaces of the vessel wall. It is not prone to damage in high velocity systems
and in pipelines that are pigged regularly. More sensitive flush elements are also
available (h).
(g) Surface strip elements are thin rectangular elements with a comparatively large sur-
face area to allow more representative results in nonhomogeneous corrosiveenviron-
ments. Strip elements are used in underground probes that monitor the effectiveness
of CP applied to the external surfaces of buried structure^.^-^
8.1.2.3 Inductive Resistance Method
IR probes have many similaritiesto ER probes but offer significantlyimproved sensitivity.

Mass changes in the sensor element are detected by measuring changes in the inductive
resistance of a coil, located inside the element. As with ER probes, IR probes require
temperature compensation and can be used in a broad range of environments, including
low conductivity and nonaqueous environments, where electrochemical techniques are
often unsuitable. For a given excitation current these probes will give 100 to 2,500 times
the signal from an ER probe. For a given sensor element life, they will tend to show
a change in corrosion rate much sooner than the equivalent ER version. IR sensors
are generally thought to be at least two orders of magnitude more sensitive than the
corresponding ER type.5
8.1.2.4 Hydrogen Probes
If the cathodic corrosion process is one in which hydrogen is produced, then the concen-
tration of hydrogen can be correlated with the corrosion that produced it. If the cathodic
278 Monitoring
reaction is, for example, oxygen reduction, then this type of probe is not appropriate.
The hydrogen probe consists of a narrow, double-walled steel tube that is exposed to
the process fluid. Nascent hydrogen produced by corrosion diffuses through the outer
wall of the probe and forms molecular hydrogen in the annular space. The pressure of
the gaseous hydrogen is measured on a gauge and gives a qualitative indication of the
corrosion.6 The hydrogen produced during the cathodic reaction can be absorbed by
steel particularly when traces of sulfide or cyanide are present. If hydrogen is trapped
within the structure, e.g., in forming blisters or cracks, then this type of probe will not
provide an accurate indication of corrosion rate.
Modern probes detect the amount of hydrogen permeating the steel by mechanical
or electrochemical measurement and use this as an indication of corrosion rate. One
method directly measures the rate of hydrogen migration through a vessel or pipe wall by
determining the penetration current set up by the hydrogen as it moves through the steel.
The hydrogen patch probe consists of a thinpalladium foil that can be mounted directly
on the pipe wall. The foil is polarized and acts as a working electrode quantitatively
oxidizing the hydrogen as it emerges from the pipe wall. After an initial pumpdown
period, the current indicated by the instrument is directly equivalent to the real-time
hydrogen penetration rate.7
8.1.2.5 Acoustic Emission
Sounds generated during cracking, mechanical stress, and some corrosion processes
can be detected and recorded by sensitive listening devices. The sounds are emitted in
a series of pulses, indicative of the process. This technique is being used in specialized
applications,for example,to screen inhibitors, to detect filiform corrosionunder coatings,
and to monitor wire breaks in prestressed concrete.6
8.1.2.6 Sand/Erosion Monitors
These are devices that are designed to measure erosion in a flowing system. They find
wide application in oil/gas production where particulate matter is present. One end
of the probe is attached to a tee-type, high pressure access fitting with a solid plug
by means of a sand probe nut. The other end is a sealed, thin-walled tube placed
within the process stream to be exposed to particulate flowing through the system.
(To minimize the effects of corrosion and thus more accurately detect erosion within
the stream, the exposed element is made of stainless steel.) As particulates impinge on
the surface of the sensing element, a hole is eventually eroded through the element.
Once penetration has occurred, the system pressure is then transmitted to a pressure
gauge assembly that detects the perforation of the tube. If required, electronic pres-
sure sensors can be connected to alarm systems to signal the exact moment when failure
occurs.
8.1.2.7 Sentinel Holes
These are small holes drilled into the outside of a vessel or pipe in an area where corrosion
is considered to be likely. The holes are drilled so that remaining wall thickness equals
the pressure design thickness. If the wall corrodes fluid will leak out of the sentinel hole
and indicate that action is required. The hole is sometimes fitted with a screw thread and
a plug so that the leak can be readily sealed.
8.1.3 Electrochemical Corrosion Monitoring Techniques
Because corrosion is normally an electrochemicalphenomenon, many of the techniques

used to investigate or monitor it are based on electrochemistry. Many of the commer-
cial units being used for corrosion monitoring use the same electrochemicaltechniques
that are used for corrosion research in the laboratory. To be useful as a monitoring tool
the equipment must be robust and the operation should be simple, preferably requir-
ing little or no understanding of the electrochemical principles. Ideally, the instru-
ment will give a direct reading of the corrosion rate experienced by the probe, which,
in turn, should be the same as that taking place in the equipment being monitored.
(For the electrochemical theory behind these techniques see Chapter 9, ”Corrosion
Control”).
8.1.3.1 Linear Polarization Resistance
This type of probe consists of two or three similar metal elements exposed to the fluid.
The potential between them is varied over 610 mV around the corrosion potential. The
change in current is measured and related to change in potential using Ohms law to
give polarization resistance per unit area. The data collected can give a direct reading of
the instantaneous corrosion rate from the corrosion current, Polarization resistance
(R,) is inversely proportional to the corrosion current, which is directly proportional to
the corrosion rate (see ASTM G 59 and G 96). This is the basis of the commercial LPR
probes.
The advantage of the linear polarization resistance (LPR)technique is that the corro-
sion rate is measured instantaneously. The disadvantageis that it can only be successfully
performed in relatively clean aqueous electrolytic environments. LPR will not work in
gases, low conductivity fluids, or water/oil emulsions where fouling of the electrodes
will impede measurement. The probes normally have either two or three cylindrical
elements that may be flush or protruding. If two electrode probes are used in high con-
ductivity solutions, e.g., seawater, results will be similar to those with three electrode
probes. Three element probes are generally better where corrosion rates are high or
in lower conductivity fluids, e.g., oils have resistivity of 100 Megohm cm, seawater is
10 ohm cm. In these cases, three electrode probes provide an approximately tenfold
280 Monitoring
decrease in error. LPR can be used under localized corrosion conditions, with caution,
since a lot of assumptions need to be made in the interpretation of the results.
8.1.3.2 Zero Resistance Ammeter or Galvanic
With zero resistance ammeter (ZRA) probes, two electrodes of dissimilar metals are
exposed to the process fluid. When immersed in solution, a natural voltage (potential)
differenceexits between the electrodes. The current generated by this potential difference
is related to the rate of corrosion on the more active electrode. Alternatively, current can
be measured between two identical electrodes where localized corrosion is occurring
on one of them. Galvanic/potential monitoring is applicable to the following corrosion
processes:
Bimetallic corrosion
Crevice and pitting attack
Corrosion-assisted cracking
Corrosion by highly oxidizing species
Weld decay
Galvanic current measurement has found its widest applications in water injection
systems where dissolved oxygen concentrationsare a primary concern. Oxygen leaking
into such systems greatly increases galvanic currents and thus the corrosion rate of steel
process components. Galvanic monitoring systems are used to provide an indication
that oxygen may be invading injection waters through leaking gaskets or deaeration
system^.^
8.1 3 . 3 Alternating Current Impedance
Electrochemical impedance spectrocscopy (EIS), also known as AC impedance, applies

alternating current (AC) and measures the phase shift. This technique has been used
for monitoring corrosion on structures in soil and on reinforcement in concrete. There
are distinct changes in the impedance spectra as conditions change from corroding to
cathodically protected.8 It is also widely used in coating research and testing.
8.1.3.4 Other Techniques
Other electrochemical techniques that are occasionally used in corrosion monitoring

include electrochemical noise (particularly good for pitting), harmonic analysis, poten-
tiodynamicpolarization, thinlayer activation (TLA), gamma radiography, electrical field
signature method (EFSM),and corrosion potential.
Some commercial monitoring equipment incorporates the capability of monitoring

using multiple techniques simultaneously; for example, equipment is available that
uses LPR, EIS, electrochemical potential noise (El”), and ZRA to monitor general and
localized corrosion.
8.2 CORROSION MONITORING OF REINFORCED

CONCRETE STRUCTURES
Monitoring the condition of a reinforced concrete structure can rely on visual inspection
and impact sounding. At its simplest, this means striking the concrete and listening for
a hollow sound that indicates delamination. More sophisticated corrosion monitoring
systems consisting of linear polarization, concrete resistivity, and other probes have been
installed in existing structures to evaluate rehabilitation strategies such as corrosion
inhibitor application and patch repairs. Similar equipment installed in new structures
monitors durability. Corrosion monitoring, when used in association with “snapshot”
surveys, can give a more complete picture of the changing condition of a structure in
time as well as in the three physical dimensions of the structure. In order to monitor the
rate of deterioration it is important to follow the change in condition with time. This is
now being done on new structures with long lifetime requirements and older structures
when corrosion damage is present and repair is being deferred for cost, logistical, or
other reasons?
8.2.1 Half-Cell Potentials
It is not economic to install half cells all over a structure to monitor its changing corrosion
condition. However, either during construction or after a condition survey, vulnerable
and representative locations can be determined and corrosion monitors installed. On
very long-life structures it may not be possible to use normal embeddable half cells be-
cause their life is only 10 or 20 years, whereas structures may be expected to last much
longer. In this case a pseudo reference half cell, such as graphite, stainless steel, lead,
or mixed metal oxide, may be installed. These alternatives are less stable than a true
half cell such as Cu/CuSO4 (CSE), because the interface that produces the electrochem-
ical reaction against which the steel/concrete interface potential is being measured is
also experiencing environmental changes. Such pseudo half cells will therefore be more
affected by changes in moisture, oxygen, chloride level, and pH than would a “true”
reference half cell. Empirical comparisons can use the half-cell potential measurements
to predict the probability of corrosion.’o
The technique for taking half-cell measurements using CSE are detailed in ASTM
C 876. The accuracy of the method is very high when proper concrete prewetting is
used. The significance of the measurements can be summarized as f01lows:~
282 Monitoring
Potentials more negative than -0.35 V CSE indicate a very high probability of active
corrosion.
Potentials more positive than -0.20 V CSE indicate a very high probability of no
corrosion.
Potentials in the range of -0.20 V to -0.35 V CSE indicate possible corrosion.
In existing structures corrosion monitoring cells can be retrofitted by drilling, coring,

or excavating the concrete and installing half cells and auxiliary electrodes. Isolating
a piece of rebar permits access to a controlled measurement area without resorting to
guard rings or separately embedded working electrodes. In this way the corrosion mea-
surement is made on a representative piece of bar in an undisturbed environment."
8.2.1.1 Macrocell Current Measurements
In new construction a macrocell current device can be set up using a configurationwith a

series of mild steel working electrodes and a stainless steel cathode instead of a half cell.
This is fixed in the formwork with the first working electrode resting on the form with
minimal cover, and the last at rebar depth. As each working electrode depassivates with
incoming chlorides (or carbonation),there is a step-up in the current flow between the de-
passivated working electrode (which becomes an anode) and the stainless steel cathode.
8.2.2 Linear Polarization Measurements
Linear polarization (LP) is usually conducted in aqueous solutions on small, uniformly

corroding specimens, but a number of LP devices are now available to monitor steel in
concrete . The system consists of a half cell to measure the potential and its change, an
auxiliary electrodeto pass the current, and, in this case, a guard ring around the auxiliary
electrode to constrain the electric field from the auxiliary electrode because of the size of
the corroding rebar. This ensures that the measurement is taken from a defined area of
steel and prevents gross errors in the area of measurement.
If LP is used for corrosion monitoring in new construction the measurement can be
made with an embedded half cell against a mild steel "working electrode" with one or
more stainless steel auxiliary electrodes. The system has been designed to fit into the
rebar cage. A cable runs from the unit to a multipin socket fixed to the formwork. After
casting and curing the concrete, the formwork is removed, leaving the socket exposed
for connection to a hand-held or permanently wired monitoring system.
8.2.2.1 Surface Surveys of Concrete
It is possible to scan the surface of concrete and develop a map of the corrosion potential
and corrosion rate determined by the LPR technique. Commercial instruments are now
available that comprise a centrally mounted Ag/AgCl potential mapping reference elec-
trode surrounded by a conductive rubber pad. Corrosion rate measurements are made
using the three-electrode potentiostatic LPR technique, the main reinforcement forming
the test electrode. Corrosion potential and corrosion rate readings are taken on a grid
over the test area. This technique can be used to evaluate the effectivenessof an inhibitor
treatment, for example.
All cabling is routed through a flexible conduit along the concrete surface to a con-
veniently located junction box. The distance between the probe and the junction box
can be 10 m or more. Any exposed steel is coated with epoxy compound prior to filling
in the excavations. Measurements of corrosion potential and corrosion rate of both the
isolated section and of the main reinforcement together with readings of concrete tem-
perature and electrical resistivity are taken at 1-to 3-month intervals using a hand-held
instrument.'2
8.2.3 Concrete Resistance and Resistivity Measurements
Two or four pin probes can be embedded in the concrete at different depths to mon-
itor moisture movement and permanent changes associated with chloride ingress.
These can be sets of pins or a series of "washers" separated by insulating cylin-
ders.l0 Resistivity is measured at the surface using AC current and since it is strongly
influenced by temperature, values measured must be corrected to some normalized
temperature.
8.2.4 Acoustic Emission Monitoring of Prestressing Steel
The general inaccessibility of prestressing steel makes evaluation difficult, costly, and
often inconclusive. Random examination of prestressing tendons by excavating inspec-
tion recesses in the concretegives only a very localized knowledgeof the strand condition
and can be misleading, often resulting in an underestimate of the extent of corrosion or
strand failure. An acoustic monitoring system has been developed to determine the
time and location of tendon failures. Continuous monitoring of entire structures is pos-
sible with this system, which uses sensors to detect acoustic energy released when a
prestressed wire breaks. The data generated from these sensors are analyzed to assess
the condition of the structure and to predict future tendon breakage.13 This system has
mainly been used in buildings, parking garages, and bridges but has also been applied
to prestressed concrete cylinder pipe (PCCP).
PCCP is reinforced by spirally wrapping high strength wire around a concrete cylin-
der. If the pipe is in a state of distress, the prestressing wire can break in a relatively
brittle fashion, with an instant release of the tensile force of up to 5,000 kg. Much of
this energy is in the form of sound energy which propagates through the pipe core and
into the column of water within the pipe. If the deterioration continues, the protective
mortar will be further compromised and the stored energy within the prestressing wire
284 Monitorinp.
will be released in a series of discrete events. The process of deterioration that leads to
a corrosion-related failure takes several years and is a noisy process. Acoustic emission
testing of PCCP uses hydrophones to monitor sound and screen them for particular
patterns known to indicate wire failures. The arrival time of the signals can be used to
indicate the location of the event.14
8.2.5 Eddy Current
The patented Remote Field Eddy Current/Transformer Coupling (RFEC/TC) technique

for the nondestructive evaluation of PCCP has been commercially available since 1997.
It has now been used to inspect more than 300,000 pipes, totaling more than 1,600 km.
It is a rapid technique that currently requires pipe dewatering to enable the radio trans-
mitter and receiver to be progressed through the pipeline. The prestressing wires act as
a secondary antenna and wire breaks anywhere along the pipe length can be detected.
It is also possible to resolve multiple regions of wire breaks. Periodic reinspection us-
ing this technique is an excellent way to monitor the rate of deterioration of individual
sections and may also lead to future applications in monitoring CP systems and rates
of corrosion. The technique has proved effective on different configurations of PCCP
pipe including lined and embedded cylinder pipe (LCP and ECP) and noncylinder pipe
(NCP),in single-, double-, and triple-wrapped pipes, in pipes with and without shorting
straps, and in pipes from 16 in. (0.41 m) to 275 in. (7.0 m) diameter. RFEC/TC can be
compared with other techniques used to inspect and monitor the condition of PCCP.
These include the following:
Acoustic emission detects a characteristic sound when a wire breaks but is only effec-
tive if a wire break occurs while the testing is underway.
Internal visual inspection and pipe sounding can be used to find areas of pipe where
delamination is beginning. However, hollow areas can form without wire breaks and
wires can break without forming hollow, delaminated areas.
Impact echo is similar in principle to manual pipe sounding with similar difficulties.
Potential mapping requires full excavation to access the outside of the pipe. Correla-
tion with RFEC/TC can be good but if wire breaks are caused by embrittlement the
potential will not change. Potentialscan also change in pipes without breaks occurring.
The drawbacks of the system are that only one system is commercially available,
dewatering is currently required, and the equipment and data analyses are complex,
requiring skill and experience. A large body of data is required to interpret indications
from the wide range of pipe sizes, designs, and configurations.These data were amassed
from testing a range of lines and are increasing with every inspection undertaken.l5.l6
RFEC/TC can detect five or more prestressing wire failures on a single pipe. It cur-
rently can only detect wire breaks, not wire thinning. Hydrophone deployment to detect
wire breaks in a water-filled pipeline is real time and while it gives useful informa-
tion, it does not give the total number of wire breaks unless deployed from the start
8.4 Monitorine of MIC 285
of the pipeline life. Potential measurement does not give accurate data because mixed
potentials are being measured on large diameter PCCP.17
8.3 MONITORING OF BIOFOULING
Although closely linked to MIC monitoring, biofilm monitoring is sometimes a separate

activity using slightly different techniques, for example, biofilm monitoring to measure
decreases in heat exchanger efficiency in cooling water systems or fuel efficiency in ships.
The early 1990s was a period of intense research into this field and many techniques
were examined. Free corrosion potential was found to be an ambiguous index of the
presence of biofilms but galvanic currents between stainless steel (254SMO UNS S31254)
and an iron anode and potential measurements at a prefixed distance from the pipe inlet
proved more reliable.'s*'9
Sidestreamand online coupons, such as Renaprobes and Bioprobes, respectively, have
been used to measure the biofilm Adenosine triphosphate (ATP)assays were
considered successful during field tests during its initial use but require skilled opera-
tors.= More recent studies have found, however, that environmental influences on the
ATP measurements render it impractical.Although ATP measurement in the laboratory
correlated well with culture methods, in the field it was found to be sensitive to salt con-
centration, temperature, UV light, purity of reagents, inorganic ions, and microorganism
concentration, rendering it next to useless as a practical monitoring
Several indirect biofouling monitors have been attempted. Heat transfer resistance
is increased by organic (and inorganic) fouling and resistance is proportional to biofilm
thickness. Frictional resistance increases with biofilm development and can be measured
as a pressure drop or a decrease in liquid flow rate in the system. This drop depends
primarily on the roughness of the biofilm layer?4
The quartz crystal microbalance, attenuated total reflectance-Fourier transform in-
frared spectrometer (FT-IR) bioluminescent bacterial markers, open circuit potential
(OCP),and online monitoring using electrochemicalimpedance spectroscopy (EIS)have
also been developed.= Candidates for monitoring that have yet to be thoroughly field
tested use fiber optical sensors, a differentialturbidity measurement device, or FTIR flow
cells.26A radiorespirometric assay for determining sulfate reduction activity of biofilms
was developed with modifications for field use in 1986 but has severe limitations in
high-sulfide environment^.^^
8.4 MONITORING OF MIC
In recent years, with the now proven connection between bacteria and corrosion, it
has become commonplace to monitor for MIC. Such monitoring programs may include
monitoring of water quality, monitoring for the presence of bacteria, and corrosion mon-
itoring. Biological corrosion monitoring can be divided into two main types according
286 Monitoring
to their goal, viz., early detection and biocide efficacy monitoring. There is overlap in
the techniques used for these two types.
The aim of early detection monitoring is to catch incipient MIC and change the pro-
cess conditions, environment, or materials before the problem becomes acute. This type
of monitoring usually includes monitoring of water quality parameters, such as pH, nu-
trients, etc.; bacterial monitoring, both planktonic and sessile; and corrosion monitoring,
such as electrochemical measurements and corrosion coupons.
The second category of MIC monitoringis biocide efficacy monitoring. The main goal
of this program is to determine the minimum quantity of biocide required to maintain
acceptable levels of bacterial numbers and corrosion rates in the system. This type of
monitoring usually comprises some form of microbial counts and/or corrosion rates to
be compared with biocide levels. It is impractical and probably impossible to maintain
bacterial numbers at zero, but it is often difficult to know how many is too many. "Ac-
ceptable" numbers are usually determined empirically, unfortunately often using the
system as a test case.
There are a number of general rules to keep in mind for monitoring programs. Know
your goals. Be clear about what you would like your monitoring program to achieve and
determine the best program to implement those goals. For example, if you are checking
to see if your biocide works, check microbial numbers, fouling,and corrosionboth before
and after the biocide addition.
There is no single monitoring method that is foolproof?' Employ a multi-facetted
approach using as many techniques as affordable. Corrosion prevention is considerably
cheaper than corrosion cure. Do not assume that what worked next door or last year
will work here and now. The nature of biological ecosystems is that they are living,
unpredictable, and subject to many forces not yet understood.
Follow the instructions! In measuring water quality parameters (using pool kits,
portable spectrophotometers,etc.) and bacterial numbers (using quick kits) follow in-
structions carefully and consistently.Monitoring should be carried out during the entire
life of the equipment. Large seasonal and annual changes can occur in bacterial counts
and in bactericide demand.29*30
The most important rule in MIC monitoring is be consistent. Trends cannot be
determined when the monitoring program and techniques are themselves constantly in
a state of flux.
There are a number of published standards and recommended practices for moni-
toring various aspects of MIC. Although these standards refer to specific systems the
techniques are general and are appropriate for most applications.Techniques discussed
include the collection and culture of bacteria, water sampling, monitoring biocides, etc.
8.4.1 Early MIC Detection
The thrust of this early warning system is to detect and correct incipientproblems before
they become severe. One of the main weapons in this arsenal is bacterial counts. Changes
in trends in planktonic and sessile numbers are an important indicator of changing
system conditions and can occur for a number of reasons. Perhaps the quality of the
8.4 Monitorine of MIC 2a7
intake water has deteriorated as a result of changing environmental or weather condi-

tions. This could occur, for example, if water is drawn from a diminishing supply such
as a lake or pond, concentratingnutrients. Wind or storms can introduce more airborne
and waterborne nutrients and microorganisms in the system. This can be a significant
problem in open recirculating cooling water systems. In freshwater and estuarine sys-
tems heavy rains introduce more runoff from the land, which contains large amounts of
nutrients. In open seawater systems storms can introduce nutrients and particulates by
upwelling and resuspension.
Problems may also be internal. Biocide habituation can result in gradually increasing
bacterial counts even if no other conditions in the regime have changed. When monitor-
ing programs show changes in counts or corrosion rates, it is important to act early to
determine the cause of the changes and counteract them.
8.4.2 Water Monitoring
The aim of water monitoring is to identify factors in the bulk water which may promote
bacterial growth and increase corrosion rates, to identify potential problem bacteria and
other microorganisms, and to detect trends in their quantity/abundance as they enter
the system.
All water quality parameters important to MIC should be monitored. Temperature,
pH, nitrate, phosphate, sulfate, total suspended (TSS) and dissolved solids (TDS), total
(TOC) and dissolved organic carbon (DOC), turbidity, as well as number of micro-
organisms (bacteria, algae, and fungi) are all useful in obtaining clues to the health
of the system. Paradoxically, dissolved oxygen is often not very helpful because it gives
misleading data about microenvironments where corrosion may be occurring. Biofilms
can sequester anaerobic bacteria in deoxygenated environments even in waters super-
saturated with oxygen. Additional parameters may be measured in specific systems,for
example, sulfide, nitrite, ammonia, and contamination by product in the chemical pro-
cess and oil and gas industries. Changes in these numbers, especially long-term trends
in one direction or large anomalies, should be cause for concern.
Measure all important water parameters on a frequent basis (approximatelyweekly).
Correlate water quality measurements with microbial numbers. Bacteria may increase,
for example, during influxes of particulates into the cooling water system in the windy
season. They are also usually strongly correlated with temperature.
Equipment required for water monitoring is readily available from commercial
sources and standard practices are available. Online monitoring of these parameters
is ideal but the equipment is more expensive. Many operators reduce costs by measur-
ing some, such as temperature, pH, conductivity, and TDS, with online monitors and
use portable or laboratory spectrophotometersand kits for the rest.
8.4.3 Bacterial Monitoring
The most important thing to remember about bacterial counts is that the actual numbers
are virtually meaningless. Culture media provide optimum growth conditions for only
288 Mon itorine
a small percentage of known bacteria. Under the best conditions media usually only
count about 10% of the viable bacteria present. Some other, direct count techniques
determine numbers of bacteria but do not distinguish between live and dead cells. Far
more important is the trend of increasing or decreasing numbers, which can only be
established by consistent and conscientious monitoring.
There are several published guides on the detection and enumeration of MIC mi-
croorganism~?'-~~ Do not change the method of collection, culture, or measurement of
the system unless necessary. There is a very poor correlation between bacterial numbers
counted using commonly used culture media and the resulting differencesare not consis-
tent or p r e d i ~ t a b l e . If~ necessary,
-~~ check the effect of the new conditionsby overlapping
the two methods until the relationship between the two results is clear for your system.
Biological counts are generally divided into two main techniques, bulk water mon-
itoring of planktonic organisms and sessile counts of biofilm bacteria on equipment
surfaces or coupons. Although sessile bacteria are recruited initially from bulk water
there is usually little correlation between the two.29.37 Where there is a correlation, it has
been found, at least in some cases, to be negative, i.e., increasing planktonic numbers
correlating logarithmically with decreasing sessile numbers.38
8.4.3.1 Planktonic Bacteria
Planktonic bacterial counts have been much maligned in recent reviews of bacterial
monitoring. At least some of the bad experiences with planktonic counts, however, are
a result of poor techniques and practices. As a measure of changing system conditions,
planktonic counts can provide useful data but only if measured rigorously. Samples
should be collected in the same way from the same place, incubated for the same time,
at the same temperature in the same medium, and counted by the same operator. Errors
introduced by changing any of these variables are so large they can swamp any changes
in the system, rendering the monitoring program useless.39This point is important but
in our experience is rarely recognized by technicians in the field.
The effect of changing incubation time, temperature, and interpreting technician
on resulting bacterial counts, including anaerobic bacteria, is well understood among
microbiologists and has been illustrated frequently in the medical In a
recent study it was shown that reading culture plates (recommended to be read after
48 f 2 h) at 24,48,72, and 96 h resulted in an order of magnitude increase in counts at
each successive time peri0d.3~
One of the most common counting methods is measurement of the number of colony-
forming units (CFU) per millimeter of bulk water on standard culture plates or dip
slides (Figure 8.4). These generally count the number of heterotrophic, aerobic bacteria
culturable on standard media (such as blood agar or nutrient broth). Dip slides are more
convenient because they eliminate the need to measure accurately a known quantity of
water, but are more expensive. Results are usually obtained in 1 to 3 days. Anaerobic
bacteria are usually cultured in liquid media, in which it is easier to exclude oxygen, at
least at the bottom of the culture tube. Results are obtained in a few days, longer for SRB
(up to 28 days).
Figure 8.4 One of the most common methods of culturing bacteria is the culture
plate. Bacteria grow and multiply into colonies visible to the naked eye. (Photo
Since microorganisms grow selectively on various media, it is necessary to culture

a wide variety of potentially corrosion-causing microbes, at least initially. Monitoring
programs should include media for general aerobic bacteria, sulfur-oxidizing bacteria,
sulfide-producingbacteria, fungi, algae, and any other groups that have been suspected
to be a problem in the system. A good general source for media formulae for a variety of
microbial types is the AWWA book on standard methods, which is updated reg~larly.4~
If some of the media routinely produce negative results they can be dropped from the
regular monitoring program but should still be checked occasionally. General aerobic
counts and SRB should always be continued, however.
ATP (adenosine triphosphate) photometry, respirometry, fluorescent antibody tests,
and redox indicator tests are faster techniques, measuring biomass in about 10 min,
but are more expensive, require sophisticated equipment and/or techniques, and have
detection limits that are quite high.33The turbidity method for bacterial counts uses
light transmission. It counts silt, floccules, and other particles as well and therefore
requires calibration. Recently, fluorescent bioreporters have also been used to measure
total biological activity online.44
8.4.3.2 SuIfate-Reducing Bacteria
Media for SRB cultures were developed by Postgate and most depend on the generation
of hydrogen sulfide gas, which combines with ferrous iron in the medium to form FeS
290 Monitoring
and cause blackening.& Postgate's media are still in common use today. A large number
of other media have been developed using similar principles, such as the American
Petroleum Institute's API 38,& variations on iron sulfite medium,%and many 0thers.4~
In addition to culture media, other techniques for more rapid detection and enumer-
ation of SRB have been developed. The enzyme-linked immunosorbant assay (ELISA)
method for field applications involves the use of antibodies and results are obtained in
about 2 h, but specialist knowledge and equipment are needed.4,49Another method is
based on the detection of the enzyme bisulfite reductase and has a detection limit of
104 cell/mL.w
In one study of six techniques for SRB, culture methods were found to be more
sensitive, detecting lower numbers of SRB, but may be strain specific. API 38 takes
28 days for best results, agar deeps were faster but less reliable, and agar melt tubes
tended to be insensitive and gave false positives. ATP assay did not correlate with SRB
numbers. Epifluorescence/cell surface antibody (ECSA)had a detection limit of lo4bac-
teria and was accurate but required trained personnel. APS reductase antibody method
was fast, field friendly, and compared well with API 38 bottles. Its lower detection limit
was lo3 bacteria.M
In comparison tests of various commercially available test kits for SRB there was
little correlation between results of the techniques or with in-house media used by each
0perator.3~A literature review of all available techniques concluded that, in spite of
advancesin detectionof specificcellular constituentsof SRB, the most reliable techniques
remain those involving sensitive liquid culture media.51
8.4.3.3 Sessile Bacteria
Sessile bacterial numbers should be sampled in the areas that are most susceptible to
corrosion problems. Many monitoring programs include removable, in-process coupons
or probes, such as tubular flow Robbins or RenaprobesF0VMwhich
provide real-time data on the system conditions and can be used to gain information
on biofilm development and corrosion rates. The probes may also be located in a side-
stream device. Side-streamdevices have the additionaladvantage that biocide levels and
process conditions can be altered experimentally under controlled conditions, giving
reasonably fast and reliable information on their effects on the ~ystem.5~Coupons have
been found to be a useful and an effective field monitoring technique for MIC as in other
corrosion problems, especially when included in a larger monitoring program using
several technique^.^^^^
The problem with all of these coupon and probe devices is that they are destructive
and time consuming to analyze. To obtain information on long-term buildup of biofilms
couponsmust be removed sequentially,requiring placement of numerous coupons in the
same location. These shortcomingshave led to many recent attempts to develop faster,
more user-friendly methods of monitoring biofilm development. Some of these have in-
cluded electrochemical techniques.58*' While these techniques have proved themselves
for laboratory research opinions vary as to the usefulness of some of them in the field.
Other monitoring techniques are helpful in laboratory studies of MIC but more limited
in usefulness in the field.24*62
Some techniques have been developed for specific applications. An online monitor-
ing system for corrosion and bacteria in oil and gas pipelines removes fluid from the
pipe and separates the water for corrosion rate and bacterial analysis. Many techniques
can be coupled to the system, including coupons, electrical resistance probes, galvanic
probes, hydrogen probes, linear polarization resistance, alternating current impedance
spectroscopy, electrochemical noise, pH, and conductivity. These techniques have met
with success in field appli~ations.~~
Another new online technique uses fluorogenic dye bioreporters, which react with
planktonic and sessile microorganisms. Separate signatures identify the products before
and after interaction with microbes and are expressed as a
8.4.3.4 Microbial Sampling of Equipment Surfaces
Examinationof metal surfacesduring planned (or unplanned) shutdowns is an extremely

important component of biological corrosion monitoring. Direct examination of equip-
ment surfaces is the best method to determine the success or failure of biocide programs.
As soon as vessels, equipment,pipes, etc. are opened samples should be collected before
the system has a chance to change in condition. MIC monitoring technicians should be
the first people into the equipment before it dries out and/or has been contaminated
by exposure to air and technicians. Samples should be collected for culturing, scanning
electron microscopy (SEM) (see Section 8.4.5, "MIC Diagnosis and Failure Analysis,"
for details), energy dispersive x-ray spectrocscopy ( E M ) examination, x-ray diffraction
(XRD) analysis, and, where possible, metallography.
Biologically mediated fouling does not necessarily result in large quantitiesof organic
material in deposits. Deposits which are 90% mineral have been shown to be organically
driven.&
8.4.4 Biocide Monitoring
Two aspects of biocide need to be monitored, quantity delivered to the system and
efficacy of the biocide.
8.4.4.1 Biocide Quantity
Oxidizing biocides can be measured using simple, easy to use, and inexpensive
techniques, which may be online or taken with hand-held instruments. Frequent mea-
surement of these biocides is necessary. They are highly susceptible to unexpected fluc-
tuations in effective dose because they react with light and organic matter. Dosage
informationfrom dosing pumps gives little useful informationon the amount of effective
292 Monitoring
biocide received by the system. Large variations in the residual free chlorine, for exam-
ple, can occur for the same dosing concentrations. Practical experience has shown that
residual free chlorine can vary according to time of day, season, and other factors.&
Changes in weather, sunshine, temperature, organic content, pH, etc. all affect the ratio
of residual free chlorine/bromine to total chlorine/bromine. This is particularly impor-
tant for chlorination since chloramines have poor biocidal properties compared to free
chlorine (although they have been found recently to be more effective in biofilms than
previously b e l i e ~ e d ~Biocides
~). should always be measured as closely as possible to the
equipment at risk.
Oxidizingbiocides should be measured immediately after the sample is taken because
the half-life of free halogens is extremely short, sometimesjust a few minutes.66Portable
chlorine/bromine N,N-diethyl-p-phenylenediamine(DPD) check kits are essential for
monitoring oxidizing biocides at the collection site if online equipment is not used.
Three types of monitoring devices are 1)DPD (individual samples or online),2) online
measurement of redox (oxidation reduction) potential (OW), and 3) an amperometric
electrode. Strong oxidizers, such as chromate, will interfere with DPD or redox moni-
toring, resulting in high readings. Redox responds sluggishly at pH higher than 8.2 and
becomes increasingly unreliable at increasing pH. In addition, oC1-, formed at higher
pH levels, cannot be detected by OW..'
Nonoxidizing biocides are more difficult to monitor than oxidizing biocides and are
often calculated on dosing rate alone, i.e., quantity of chemical added to the system.
Fortunately they also tend to be less volatile, although they may interact unexpectedly
with other chemicals in the system. Correct feed doses are usually best determined by
correlation with bacterial results. Other techniques may be complicated or inapplica-
ble at low doses. For example, the laboratory techniques of iodometric titration and
high performance liquid chromatography are used to detect the biocide 2,2-dibromo-
3-nitrilopropionamide (DBNPA) but have detection limits of 1 mg/L and 100 pg/L,
respectively. An antibody-based immunoassay technique usable in the field detects this
biocide at lower detection limits.68Another nonoxidizing biocide, gluteraldehyde, may
be monitored by a techniquebased on a solution of 3-methyl-2-benzothiazolinone hydra-
zone (MBTH)hydrochloride. Results can be obtained within a few minutes in the field.69
Biodispersant concentration is also usually difficult to measure in the field. Some
may be measured with a colorimetric determination of the active ingredients, others
require laboratory equipment such as high pressure liquid chromatography (HPLC).
Some products may be measured with addition of an inert tracer which is easier to
measure.
8.4.4.2 Biocide Efficacy
Biocide efficacy monitoring requires the coupling of biocide dosage to microbial numbers
or corrosion rate. Microbial numbers and corrosion rates must be checked before, during,
and for frequent periods after biocide addition.
Bacterial numbers are somewhat easier to measure than corrosion rates. They are of
direct relevance to fouling rates but are only indirect measures of corrosion. Biocides
should be screened on sessile bacteria in biofilms since they are known to be many times
more resistant than planktonic forms. Coupons or probes are often used for screening.70
If possible, use real life conditions such as in-line or side stream devices.
The major difficulty with monitoring biocide efficacy is that there are no quick, re-
liable methods to measure corrosion by microorganisms. Most corrosion monitoring
techniques do not distinguish between corrosion by bacteria and other causes. In some
cases this is hardly significant, since the goal is a reduction in corrosion in the system
and many plant operators are not interested in the causes, only the results. Reduction
in corrosion rates after biocide addition may be taken as a reasonable indicator that the
corrosion was caused by microorganisms.
The most reliable techniques for biocide efficacy monitoring seem to be corrosion and
fouling coupons, which can provide information on both biofilm buildup and corrosion
rates. These must be carefully placed in the process stream or in representative side-
stream conditions.Side-stream devices should be maintained at flow rates, temperatures,
or other conditions that are representative of process conditions, preferably those which
represent the worst-case scenario of the plant operation. Careful analysis of coupons is
necessary to determine whether the corrosion is MIC.
Measuring microbial respiration, an indirect approach to monitoring bacterial
numbers and activity after biocide addition, was attempted for the biocide
methylchloro/methylisothiazolone (MCMI). Although inhibition of respiration was
rapid (less than 10 min) longer periods (4to 6 h) were required to achieve significant
reductions in viable count^.^' This method, of course, must be conducted in the dark
if algae are present in the system because algal photosynthesis would confound the
dissolved oxygen measurements.
Attempts to use electrochemical methods to measure MIC corrosion rates in the field
have met with limited success and do not generally repay the expense, effort, and time
required for effective p r e d i ~ t a b i l i t y . Electrical
~ ~ . ~ ~ ~ resistance
~~ and linear polarization
techniques are not particularly efficient at detecting localized corrosion, such as MIC,
and are not highly recommended even by the manufacturers. Electrochemical noise and
impedance methods have been found to be better for monitoring corrosion by MIC but
are difficult to interpret.73
There has been a concentrated effort in recent years to develop reliable online mon-
itoring techniques for biocide efficacy using various techniques, such as fluorescent
bioreportersT4 localized corrosion monit0rs,7~and others.768’
Biocide efficacy should be monitored continuously. Variationsin diurnal and seasonal
changes as well as periodic changes in process or operating conditions, which may affect
temperature, nutrients, etc., must be included. Biocide efficacy does change with time.
Bacteria may adapt, mutating to strains that are more resistant. Long-term monitoring
will indicate that increasing amounts of biocide are required to maintain an acceptable
kill rate. When that happens it is necessary to change the biocide, at least for a short
period.
294 Monitoring
8.4.5 MIC Diagnosis and Failure Analysis
It is becoming apparent that it is extremely difficult to prove MIC conclusively and MIC
failuresare often ascribed by default because no other cause is obvious. There are several
reasons why MIC is so difficult to diagnose. These include the following:
The topography of MIC can be identical in appearance to chemical corrosion.*’

MIC organisms may be present without causing corrosion.83
Bacteria, even dead bacteria, can be attracted to anodic sites which may cast doubt on
their causality in all cases.84
There are few, if any, guaranteed ”fingerprints” of MIC to distinguish it from other
types of corrosion. In particular, the much vaunted MIC fingerprint comprising tun-
neling and ”ink-bottle pits” has now been largely discredited as it is found in other
types of corrosion as well.
The difficulty in diagnosing MIC is not improved by the casual way in which MIC
diagnoses and failure analyses are often conducted. Bacterial samples from water and
corrosion products are often handled in a fashion that nullifies any possible results
obtained from those samples.&
Notwithstanding the difficulties, it is possible, using careful techniques and analysis,
to ascertain whether there is a microbiological corrosion problem.
Corrosion product mineralogy may provide clues for MIC diagnosis in some cases.
Djurleite, spionkopite, and the high temperature polymorph of chalcocite appear to be
mineralogical evidence of SRB corrosion of copper nickel alloy^.^^,^ Similarly, machi-
nawite, and possibly greigite and smythite, formation may be an indicator of SRB
corrosion of iron and steel since these compounds are not normally found in abiotic
corr~sion.~~
Some workers found no difference in corrosion products resulting from biotic and
abiotic corrosion.88In contrast, however, other studies did find that the composition
and structure of the films formed in the presence of SRB and in an abiotic sulfide
medium are different. In biogenic sulfide films FeS is the major species, whereas in
abiotic sulfide films, F e s is predominant. SRB are responsible for alterations in the
local chemical conditions and in the buildup of corrosion layers, resulting in a more
adherent film.Formation of the biofilm and bacterial metabolism can enhance corrosion
through changes in diffusional processes, in the ion concentrations(Fez+, e-, S2-, C1-,
H+), and in the structural characteristics of the corrosion products in which EPS is also
inv0lved.8~
One technique that shows promise as an indicator of SRB activity is analysis of stable
isotope fractionation of corrosionproducts. Natural sulfur containsfour stableisotopes-
32S,33S,%, and % ! + o fwhich 32Sis the major component (approximately 95%) and
%S the next most abundant (approximately4.2%). The different isotopes vary in mass
and therefore react slightly differently in most biological reactions. During bacterial
reduction of sulfate, lighter isotopes of sulfur are preferentially converted to sulfide,
Table 8.1 Sulfur Isotope FractionationAnalysis horn Two Wells in Irian Jaya, Indonesia
Well Sulfur Source Sample 8%
Matoa-1 Generated gas HS- Distilled water +15.9

plus gas +9.9
Hs- Produced water +11.5
Residual sulfur q- Produced water +36.8
+36.4
Matoa-3 Generated gas HS- Distilled water +4.1
plus gas
HS- Produced water Insufficient sample
Residual sulfur !30- Produced water +34.2
+34.4
Miocene marine +21
sediments
Note: Where two numbers are given in column "8% S," the results represent two samples. Note
that this table was omitted in error from the original article?'
resulting in a product that is enriched in 32Scompared to geochemical sulfur, while the

residual sulfate is enriched in %.
These differences are detected by mass spectrographic analysis and are usually ex-
pressed on a 8% scale, according to the following equation:
34S/32Sin sample
8% in % =
34S/32Sin standard
where MS/32Sis the ratio of the number of 34S to the number of 32Satoms in the sample or
the standard. If bacteria were responsible, the H2S sulfur should be lighter (i.e., depleted
in %) relative to the sd4-sulfur. If the H2S were generated thermochemically, this
fractionation would not be apparent and the values for sulfate and sulfide would be
approximately the same.
This technique requires specialist knowledge and equipment. It has been known, at
least theoretically, for some time45and has been tested in the laboratory.g0
The technique has also proved itself in the field?' To determine whether souring
in new oil wells in Indonesia was generated by bacterial activity or geochemically, the
isotopes of the hydrogen sulfide gas were compared with residual sulfate in the water.
The results showed a large fractionation, with H2S sulfur considerably depleted in %
(a smaller number) relative to the SO- sulfur (Table 8.1). Miocene marine sediment,
the formation rock, is normally about +21, intermediate between the gas and residual
sulfur. Although conditions were marginal for the survival of bacteria (bottom temper-
atures around 100°C and pressures of 11.20 to 30.24 MPa), it was demonstrated conclu-
sively that the gas was generated biologically. Therefore, accumulation of 32Sin corrosion
products could also be a reliable indicator of MIC in other systems.
296 Monitorine
In diagnosing MIC as many techniques and tests as possible should be used. The
following are steps to follow and questions to ask in the diagnosis:
Is there water in the system? At what temperature? Without water living organisms
cannot survive so MIC can be eliminated. Furthermore, few bacteria thrive above
approximately 8PC, except under special and unusual circumstances, so MIC will be
unlikely, although not impossible.
What is the material corroded? What is the water source? Find out about the con-
ditions, water temperature, pH, and chemistry-hlorides, nutrients, dissolved and
suspended solids. In recirculating cooling water what are cycles and blowdowns? If
answers are not satisfactory check these yourself.
Ask about operating history. Find out what chemical treatments have been carried
out, including all additives and their doses. Has anything changed recently, such as a
change in the water source or treatment chemicals?
Examine the corroded area for general appearance. Take careful notes on the type,
color, smell, and location of corrosion.
Biological samples should be collected immediately from water, surfaces, and cor-
roded and uncorroded areas for culturing in a variety of media. Culture media should
include those for general aerobic bacteria, SOB, SRB, acid-producing bacteria (APB),iron
and manganese bacteria, fungi, and algae.
Sterile pipettes, swabs, forceps, and scrapers should be used to collect samples and
sterile, labeled glass bottles (both empty and filled with sterile media) should be ready
to receive samples. In all cases, the pipette and scraper ends, swabs, inside of the lid,
and neck and rim of the bottle should not be touched. After swabbing wet surfaces,
the swab can be placed part way in the bottle of medium and the end should be
snapped off well below the area touched so the clean end of the stick with its swab
can drop into the medium before the lid is replaced. The lid of culture bottles should
be removed for the minimum time necessary. Vials of buffered gluteraldehyde in glass
bottles should be ready for placing samples immediately upon collection for SEM/EDS
preparation.
Bacteria should be collected for culturing in a wide variety of media but we do not
recommend bacterial counts for MIC diagnosis. Plate counts count viable CFUs, but
underestimate by 90% or more. Membrane filtration underestimates numbers because
many slip through the filter. The most probable number (MPN) technique, a statistical
technique for counting bacteria, generally, overestimates numbers and would require a
large amount of media and be time-consuming when culturing with several different
media. ATP counting techniques assume equal ATP content of all organisms and must
be calibrated. Total bacterial counts generally count dead and live bacteria. Direct mi-
croscopic counts in a counting chamber require a microscope and staining. The bacteria
are killed and identification of bacteria is difficult unless fluorescent antibody methods
are used to stain for targeted bacteria.
In general, we have found that qualitative plate counts and reaction time in liquid
media (e.g., time to clouding, blackening [in SRB media], etc.) give a reasonable estimate
of quantity, if needed. Comparison can be made in reaction time (if it occurs) between
corroded and uncorroded areas.
Where counts are not required liquid culture media are easier to use in the field as
liquid or solid samples can simply be dropped into the culture tube and sealed. Two
to three replicates of each sample should be taken for each medium and all the culture
tubes labeled carefully as the samples are taken. Samples should be incubated as soon
as possible at temperatures similar to the conditions from which they were taken.
After the biological collectionsare finished, collect samples of the deposits, corrosion
products, and, if possible, corroded area for metallurgical analysis, microscopy, and
SEM/EDS. Is there blistering or tuberculation? What is the color and appearance of
corrosion products-black, yellow, red, or brown? What is the appearance of the metal
under the corrosion products, e.g., bright or dull? Bright, shiny metal usually indicates
active corrosion is still occurring.Is there an H2S smell like rotten eggs? If not, add a little
HC1 to the corroded area and try smelling again. Lead acetate paper can also be used to
detect the presence of sulfide.
Examination of corrosion products and corroded areas by SEM requires fixation in
gluteraldehyde and 2% buffered osmium tetroxide. The osmium will be taken up by
living tissue and show up as an EDS spike, helping to identify bacteria and distinguish
them from similarly shaped artifacts. Samples are then dehydrated through alcohols of
5 to 100% and critical point dried by placing them in a transitional fluid, such as C02,
N20, or freon and taken to a critical point temperature and pressure where there are no
phase boundaries or forces between transitional states. Finally, they are gold or carbon
coated. Carbon coating is used to detect light elements by EDS and when samples are
postfixed with osmium tetroxide to detect microorganisms.66
This technique is routine for laboratories that have scanning electron microscopes
(althoughyou may have to specify the additionalstep of post-fixingwith OsOa). Samples
should be scanned and then examined at magnifications that permit easy identification
of objects 1to 3 pm long. EDS will show up differences in the elements in corroded and
noncorroded areas. Presence of an osmium spike indicates biological material.
Presence of large numbers of bacteria in corrosion products and corroded areas is
a good indicator of MIC. Although bacteria may be present without causing MIC, if
present in large numbers their metabolic activity will likely lead to corrosion. Although
identification of bacteria is not possible in stains for general microscopy or SEM, check
the morphology of the organisms. Rods, especially Gram-negative curved rods (such as
many slimebacteria, SOB, and SRB) and filamentous, stalked bacteria or sheathed chains
(such as iron bacteria) found in large numbers, lead to a more likely diagnosis of MIC
than large numbers of Gram-positive cocci.
When doing chemicalanalysisof corrosion products or samples from corroded equip-
ment by XRF,EDS, or atomic absorption spectroscopy (AAS),total or organic carbon of
greater than 20% leads to a suspicion of MIC. Sulfur of approximately 1%or more sig-
nals involvement of sulfide-producingbacteria (if black and smelly)or sulfur oxidizing
bacteria (if yellow or highly acidic). Iron oxide deposits could indicate the activity of
iron-oxidizing bacteria. High chlorides in fresh water also indicate possible iron and
manganese bacteria (Gallionella or Siderocupsu) especially if high in manganese or iron
298 Monitoring
(in non-iron materials). Very low nickel concentration (below material ratio) indicates
possible MIC. High phosphorus may also indicate sulfide-producing ba~teria.9~9~~
If several of the above indicators of MIC are positive a presumption of MIC should be
concluded and operating conditions or biocide programs changed in order to eliminate
the problem. Vigilant monitoring is required during this period to detect system re-
sponses to these changes.
8.5 STANDARDS AND SPEC1FICATIONS-MON ITORl NG
8.5.1 ASTM
These are some of the ASTM specifications related only to corrosion monitoring. Corro-
sion tests that are used in monitoring are included in Chapter 9, Section 9.1.2.1, “ASTM.”
C 876-91(1999bStandard Test Method for Half-Cell Potentials of Uncoated Reinforc-

ing Steel in Concrete
D 932-85(1997)-Standard Test Method for Iron Bacteria in Water and Water-Formed
Deposits
D 4412-84(1997)-Standard Test Methods for Sulfate-Reducing Bacteria in Water and
Water-Formed Deposits
D Wi4-85(1997)-Standard Test Method for Simultaneous Enumeration of Total and
Respiring Bacteria in Aquatic Systems by Microscopy
D 4455-85(1997)-Standard Test Method for Enumeration of Aquatic Bacteria by Epi-
fluorescence Microscopy Counting Procedure
E 1326-98-Standard Guide for Evaluating Nonconventional Microbiological Tests
Used for Enumerating Bacteria
F 488-95-Standard Test Method for On-site Screening of Heterotrophic Bacteria in
Water
G 4-95-Standard Guide for Conducting Corrosion Coupon Tests in Field Applica-
tions
G 96-90(1996)el-Standard Guide for Online Monitoring of Corrosion in Plant Equip-
ment (Electrical and Electrochemical Methods)
8.5.2 NACE
RP0189-95---online Monitoring of Cooling Waters

RP0497-97-Field Corrosion Evaluation Using Metallic Test Specimens
TM01949AField Monitoring of Bacterial Growth in Oilfield Systems
TMO299-99-CorrosionControl and Monitoring in Seawater Injection Systems
3T199-Techniques for Monitoring Corrosion and Related Parameters in Field
Applications
8.6 References 299
8.5.3 E N
CR 12793:1997-Measurement of the carbonation depth of hardened concrete
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S.A. Borchardt, R.L. Wetegrove,J.D. Martens, ”New approachesto biocide effectivenessmonitor-

ing using on-site biocide active analysis, ATP analysis and on-line dosage/monitoring control,”
Corrosion/97 paper no. 466 (Houston, TX NACE, 1997).
81 R.L. Wetegrove, R.H. Banks, M.R. Hermiller, ”Optical monitor for improved fouling control in
cooling systems,” CTI J. 18,l (1997): pp. 52-56.
J.G. Stoecker, ”Microbiological and electrochemical types of corrosion,” MP 34, 5 (1995):
pp. 49-52.
83 D.H. Pope, “A study of microbiologically influenced corrosion in nuclear power plants and a
practical guide for countermeasures,”EPRI Research project 1166-6, Report “-4582 (Palo Alto,
CA: EPRI, 1986).
B.J. Little, R.I. Ray, R.K.Pope, J. Jones-Meehan, C.C. Lee, F. Mansfeld, “Spatial relationships
between marine bacteria and localized corrosion on steels,” in 14th Int. Corrosion Congress,
Capetown, South Africa, paper no. 193 (1999)pp. 1-10.
85 M.B. McNeil, J.M. Jones, B.J. Little, ”Production of sulfide minerals by sulfate-reducing bacteria
during microbiologically influenced corrosion of copper,” Corrosion 9 (1991):pp. 674-677.
86 M.B. McNeil, J.M. Jones, B.J. Little, ”Mineralogicalfingerprints for corrosion processes induced
by sulfate reducing bacteria,” Corrosion/91 paper no. 580 (Houston,TX: NACE, 1991),pp. 1-16.
87 M.B. McNeil, B.J. Little, “Mackinawite formation during microbial corrosion,” Corrosion 46,7
(1990): pp. 599-600.
@ B.J. Little, R. Ray, R. Pope, M. Franklin, D.C. White, ”Spatial and temporal relationshipsbetween
localised corrosion and bacterial activity on iron-containingsubstrata,” in Microbial Corrosion,
EFC #29 Proc. 4th EFC Workshop, ed. C.A.C. Sequira (London: IOM Communications Ltd.,
2000), pp. 21-35.
89 C.L. Swords, R.G.J. Edyvean, P. Watkins, I.B. Beech, M.F.L. de Mele, H.A.Videla, “The role of
corrosion products protective layers in SRB influenced corrosion of steel in biotic and abiotic
sulfide media,” in 14th Int. Corrosion Congress, Capetown, South Africa, paper no. 166.2 (1999)
pp. 1-9.
9o B.J. Little, P. Wagner, J. Jones-Meehan, ”Sulfur isotope fractionationby sulfate-reducingbacteria
in corrosion products,” Biofouling 6,3 (1993):pp. 279-288.
91 P.J.B.Scott, M. Davies, “Souring of new Irian Jaya wells traced to indigenous bacteria,” Oil Gas
J. 91,24 (1993):pp. 47-50.
92 G. Licina, Detection and Control of Microbiologically Influenced Corrosion, Report no. NP-
6815-D (Palo Alto, CA: EPRI, 1990).
93 C.C. Gaylarde, A.R. Lino, “How to identify biocorrosion,” in Practical Manual of Biocorrosion
and Biofouling for the Industry, M.D. Ferrari, M.F.L. de Mele, H.A. Videla, eds. (Argentina:
CYTED Research Network, 1998), pp. 27-32.
Chapter 9
Corrosion Control
There are a number of ways in which corrosion can be controlled or prevented. While
not all of the techniques mentioned in this chapter are particularly relevant to materials
in waters they have been included for completeness. Emphasis is placed on those that
are the most applicable to water applications. The methods used to control corrosion
Materials selection
Design features
Modification of process conditions
Anodic protection
Cathodic protection
Inhibitors
Coatings and linings (see Chapter 6, Section 6.3, ”Coatings and Linings”)
Water treatment as a corrosioncontrolmethod is covered in Chapter 10, ”Water Systems.”
9.1 MATERIALS SELECTION
Faced with the great number of possible materials that could be used in an industrial
or marine application, one often finds it difficult to decide which materials are the most
appropriate, or even which candidates to test. The factors that must be considered include
the following:
True cost, including capital cost and costs of fabrication, maintenance, corrosion
control, etc.
305
306 Corrosion Control
Life required from the equipment, e.g., standby heat exchanger, or nuclear power
plant
Physical and mechanicalproperties, e.g., thermal conductivity, expansion, toughness,
UTS
Applicable codes and regulations, ASME, ANSI, national and international standards,
and specifications
Fabrication and forming characteristics-do you need a pump or a heat
exchanger?
The preliminary materials selection requires information on the operating environ-

ment, major/minor constituent of every stream-pH, aeration, trace elements; operat-
ing conditions-temperature, pressure, including upset, start-up, shut-down; possible
contaminants+.g., from condenser leaks, recycle buildup; the type of equipment-.g.,
pumps, valves can be cast, vessels only wrought and welded; quality assurance during
fabrication, erection.
The differences in production methods of cast and wrought metallic equipment with
nominally the same composition can result in very different corrosion behavior. For
example, the cast version may contain second-phaseprecipitates,segregationof alloying
elements, porosity, etc. In general, the choice between cast and wrought is made on the
basis of the shape and size of the item and on the ease and cost of making that item by
either method.
The presence of welds can have a big influence on corrosion resistance in either case.
For example, welds can introduce discontinuities that can cause turbulence and lead to
erosion. Welds can also introduce inhomogeneousalloying content by precipitation that
can lead to intergranular corrosion and can leave residual stresses, which cause SCC in
some cases. The weld metal can be anodic or cathodicto the bulk metal inducing galvanic
corrosion. This is particularly dangerous if the small area weld is anodic to the bulk of
Figure 9.1 Photo shows both sides of a

PTFE crevice corrosion test washer. It is
used to produce multiple crevices on the
surfaces of metallic specimens in, for ex-
ample, ASTM G 48 Method B tests. (Photo
cathodic metal. This is not to suggest that welding should be avoided. Welds should be
designed and executed properly taking into account their effect on corrosion resistance
and using appropriate filler metal to suit the service conditions. Heat treatment should
be included in the fabrication process if appropriate.
9.1.1 Corrosion Testing
Once an application has been defined in terms of operating conditions, the next stage
is to review all published data and experience. Many case studies describing good
and bad experiences have been published. Corrosion testing may be necessary in the
field or laboratory or both. Laboratory immersion testing may include artificial crevices
(Figure 9.1), surface treatment or coating (Figure 9.2), welds (Figure 9.3), or special-
ized tests for specificapplicationsor environments. Standard ASTM methods for testing
various forms of corrosion and NACE Test Methods (TMxxxx)and Recommended Prac-
tices (RPxxxx)are available.Someof the standards and specificationsrelating to corrosion
and corrosion testing are listed below:
General corrosion G 31, G 102, TM0169,TM0171

Stress corrosion cracking C 692, G 30, G 36, G 38, G 39, G 44, G 47, G 58
Pitting corrosion G 5, G 46, G 48, G 61, G 78
Crevice corrosion G 48, G 61, G 78
Intergranular corrosion A 262, A 763, G 28
Dealloying G 31
Exfoliation (A1 alloys) G 34, G 66, G 67
Galvanic corrosion G 31, G 71, G 82
Cavitation/erosion G 32
Figure 9.2 Photo shows a specimen used to test coat-

ing durability by exposure in a test environment. (Photo
Figure 9.3 Photo shows metallic rod specimens in which the welds have been
preferentially corroded. (Photocourtesy of CARIAD Consultants.)
Figure 9.4 Photo shows laboratory apparatus and specimen used to test for pitting corrosion in
FeC13 according to Method A in ASTh4 G 48. (Photocourtesy of CARIAD Consultants.)
Other specifications contain general information about how to conduct corrosion

tests, prepare and assess specimens, and interpret results. These include the following:
Preparing and cleaning specimens G1
Electrochemical testing G 3, G 5, G 59, G 61, G 106
Conducting plant corrosion tests G 4, RP0497, RP0775
Conducting lab immersion tests G 31, TM0169, TM0171
Terminology G 15
Statistics and calculation of rates G 16, G 31, G 102, G 107
Seawater and substitute ocean water D 1141, G 52
Corrosion monitoring C 876, G 96
The most appropriate test method to use for any particular application will depend
on the materials being evaluated and on the environment in which the equipment is
to serve. For example, the corrosion resistance of different stainless steels in seawaters
can be compared with each other and with other materials in a number of different
ways. There are a number of standard tests to assess localized corrosion resistance in
chloride solutions. Methods in ASTM G 48 are routinely used to assess pitting and
crevice resistance; method A is a ferric chloride pitting test (Figure 9.4). Method B is a
ferric chloride crevice corrosion test (Figure 9.5) and methods C and D are critical pitting
temperature (CPT) and critical crevice temperature (CCT) tests, respectively.
Figure 9.5 Photo shows laboratory apparatus and specimen used to test for crevice corrosion
in FeC& according to Method B in ASTM G 48. (Photo courtesy of CARIAD Consultants.)
Figure 9.6 An assembled corrosion test rack used to test corrosion of different materials under
the same exposureconditions. Specimensare separated by PTFE spacers to avoid galvaniceffects.
9.1.1.1 Immersion Testing
Immersion of test specimens of the appropriate material in the environment of interest

can be an integral component in the selection of materials of construction. This may either
be carried out in the laboratory or, in some cases, under field conditions. Controlling
exposure conditions is often easier in the laboratory but the field provides the actual
operating environment.
Test racks of corrosion coupons and nonmetallic specimens can be exposed to oper-
ating conditions using a method such as described in ASTM G 4 (Figures9.6 and 9.7). It
is important to follow standard, or at least consistent, procedures in terms of specimen
preparation, method of attachment, exposure times, and conditions and assessment of
specimens after exposure. The use of corrosion weight loss coupons are only appropriate
for general corrosion and are not accurate at low corrosion rates.
A more direct but slower way of testing the suitability of alloys for seawater service
than the use of laboratory testing is to expose samples in seawater. ASTM G 52 is a
standard practice for exposing and evaluating materials in surface seawater. Artificial
and natural seawater have been used in the laboratory but are criticized as being not as
good as fresh flowing seawater because of the absence of biofilms. Many long-term tests
in flowing seawater have been conducted at the LaQue Center for Corrosion Technol-
ogy, Wrightsville Beach, NC,'-4 Shell Research, Holyhead, Anglesey?V6 and Norwegian
seawater laboratories in Trondheim and Sandefjord?-9
Crevice corrosion measured in the Shell flowing seawater tests was substantially
greater than in artificial seawater.'O However, other test work found that 60-day artificial
Figure 9.7 PTFE spacers and metallic corrosion test coupons after rack ex-
posures show pitting corrosion of the coupons. (Photo courtesy of CARIAD
Consultants.)
crevice tests in filtered seawater at 25°C were more severe than a 2-year artificial crevice
test in ambient seawater. This research also concluded that the crevice tests in filtered
seawater correlated well with the crevice corrosion tests in acidified ferric chloride solu-
tion? These same authors later found that the crevice results in acidified ferric chloride
agreed well with crevice testing in filtered seawater at 25°C for the ferritic and duplex
alloys but were not consistent for the austenitic alloys."
9.1.1.2 Electrochemical Techniques
Electrochemical techniques explore corrosion processes from a more fundamental basis

than is possible with immersion specimens. They can give information about the pro-
cesses occurring and assess the effects of changes in environment in a direct, short-term
test. 0
9.1.1.2.1 Potentiostatic and Potentiodynamic Polarization
9.1.1.2.1.1 General Corrosion. In the potentiostatic test a suitable test specimen

is exposed to the test solution and held at a specific potential and the current is mon-
itored. The current supplied is related to the weight loss and corrosion rate. Another
form of potentiostatic test is one in which the potential is increased in stepped incre-
ments to develop a polarization curve. Potential is plotted against the log of the current
to produce a curve that provides information about the corrosion behavior of that metal
or alloy under the test conditions. For example, if it is an alloy that shows passivity the
polarization curve will indicate this and show the range of potentials over which it is
passive. These polarization curves are now normally generated using cyclic potentiody-
namic polarization. The potentiostatic test measures the corrosion current in the passive
state, which can be used to calculate the corrosion rate (CR):
CR = K I & ~ * /x~EW
where CR is the corrosion rate in mm/y

komis the corrosion current density in vA/cm2
p is the density in of the metal or alloy in g/cm3
EW is the equivalent weight (refer to Table 1in ASTM G 102)
K1 is a constant (refer to Table 2 in ASTM G 102)
Another electrochemical technique used to obtain a measure of corrosion rate is

linear polarization resistance (LPR; ASTM G 59). Polarization resistance is measured by
scanning through a potential range that is very close to the corrosion potential. The LPR
may be approximated either from potentiodynamic measurements near the corrosion
potential or from stepwise potentiostatic polarization using small potential steps, e.g.,
10 mV. The corrosion current &om can be calculated from the slope of the voltage/current
curve and used to calculate the corrosion rate. In order to make these calculations one
needs to know Tafel constants which must be derived from a Tafel plot.
A Tafel plot is produced by polarizing a metal specimen about 300 mV in both the
anodic and cathodic directions and plotting the voltage against the log of the current.
Near the corrosion potential portions of both the anodic and cathodic curves are usually
linear. The slope of these linear portions can be used to calculate the Tafel constants that
are then used to calculate corrosion rate from the polarization resistance. By extrapo-
lating these linear portions back to where they intersect, the corrosion current can be
determined. From the corrosion current the corrosion rate can be calculated:
where R, is the polaization resistance and B is the Steam-Geary constant that is calcu-
lated or estimated from Tafel information.
B= BA x Bc
2.303(B~+ Bc)
BA and Bc are the Tafel constants for the anodic and cathodic partial reactions.
This equation is only valid if overvoltage, i.e., the difference between the voltage
applied to the specimen and the corrosion potential, is small compared to values of the
Tafel constants. Typically B is 100 mV/decade of current and overvoltage must be less
than 10 mV. The polarization resistance method can only be used if the metal dissolution
is solely activation controlled without passivation at the open circuit potential.
9.1.1 .2.1.2 Localized Corrosion. The potentiostatic or constant potential test

measures the current density of a specimen vs. time under a constant applied potential.
Figure 9.8 Photo shows laboratory apparatus for cyclic potentiody-

namic polarization testing according to ASTM G 61. (Photo courtesy of
This method is usually employed to verify the pitting incubation time and critical pitting
potential. The cyclic potentiodynamic polarization technique (ASTM G 61) is also used
to determine the susceptibility of certain alloys to localized corrosion, both pitting and
crevice corrosion (Figure 9.8). The potential is increased from the corrosion potential in
the anodic direction until localized corrosion initiates, as indicated by a large increase
in the anodic current. At this point, the direction of the scan is reversed, and the cur-
rent decreases until it changes polarity. The pitting or crevice potential (depending on
specimen type) is the potential at which the current increases sharply in the forward
scan. The higher the pitting potential the more resistant is the alloy. The shape of the
curve in the reverse direction is usually different from the forward curve, producing a
hysterisis loop. The potential at which the current density crosses the passive range on
the reverse scan is the protection potential, E, which is a measure of the ease with
which the passive film can reform if damaged. The degree of hysteresis on the reverse
scan indicates the ability of the alloy to repassivate and overcome the local environment
causing the pitting or crevice attack.12This short-term test can generate many data in
a reasonable time frame but the fact that it is short-term is criticized since pitting is a
long-term process. Examples of results of measuring pitting potential vs. SCE in 1 M
NaCl at 90°C are: 316 is 40mV, 904L is 235mV, and UNS S31254 is 685 f 135 mV. These
latter results are typical for the 6% Mo austenitic al10ys.l~
Most standard tests for localized corrosion are not severe enough for modem sea-
water stainless steels. One would expect all the super stainless steels to pass ASTM
G 61, for example, unless the samples came from defective batches. On the other hand,
tests, that are able to distinguish between these super alloys may need such aggressive
environments that they cannot be considered to be representative of normal operating
conditions. A severe test that has been used successfully to distinguish between sim-
ilarly resistant alloys determines pitting potentials by polarizing samples at 80°C in a
1M NaCl solution, acidified to pH 2.2 with HC1, continuously oxygenated and stirred.
Samples are first equilibrated for 1h with potential monitoring and then scanned from
-50 mV below the free corrosion potential at a scan rate of 0.17 mV/s. The scan rate
is reversed once a current density of 1,OOO pA/cm2 is reached. Using this method the
pitting potentials measured on duplicate samples of two 6% Mo stainless steels that had
both passed G61 were the f~llowing:'~
UNS S31254 680 mV SCE

Transpassive without pitting
UNS NO8926 500 mV SCE
493 mV SCE
Using this test on 904L tubing measured average pitting potentials of 900 mV SCE at
30°C and 230 mV SCE at temperatures between 50 and 80°C.
9.1.1 2 . 2 Electrochemical Impedance Spectroscopy
The electrochemical impedance spectroscopy (EIS) technique is a development of LPR

that employs an AC signal to perturb a corroding specimen. The electrical response
of the metal/environment interface is monitored over a frequency spectrum in the range
of 10 kHz to 50 pHz and the resulting current is correlated with the voltage input to
measure impedance, Z, as a function of frequency:
Impedance Z = V/i
A corroding interface can be considered as comprising the following:
Solution resistance, analogous to the resistive polarization

The film contribution resulting from the dielectric properties of the film material and
associated bound water
The charge transfer resistance resulting from the electron transfer processes (activation
overpotential)
The electrochemicaldouble layer (producingcapacitance) resulting from adsorption
of water dipoles, molecules, and ionic species
A diffusion (Warburg)impedance analogous to concentration polarization
These various components will react differently to different frequencies.

At higher frequencies >10 kHz only the electrolyte resistance is observed; lower
frequencies allow the film properties to be studied. At midrange frequency (100 to 1Hz)
the charge transfer and double-layer response are measured. At even lower frequency
adsorption and diffusion of electroactive species and/or electrocrystallization may be
studied. Data can be plotted in a number of different ways, i.e., in Nyquist, Bode, or
Randles plots. The plots used will depend on the metal/environment system and on the
corrosion aspects of interest.
For basic corrosion testing or monitoring it is not always necessary to obtain all the
impedancedata since often the important informationis the change in corrosion rate. The
area of most interest is therefore at the high frequency area, which is mainly resistive and
can give polarizationresistance, which includes r solution, r charge transfer, r adsorption,
etc.
Two approaches are used:
1. Two frequency method. Takes a measurement at high f equivalent to r solution and

at a low f equivalent to r charge transfer plus r solution. This gives r charge transfer
which can be used to calculate corrosion current:
2. Tangential impedance method. Here the frequency is swept to determine the specific
f at which the phase angle is maximum.
Kt = 2/Z/tan max phase angle

This method uses more complex circuitry but gives a complete impedance diagram
and is very useful for testing coatings. The validity of the impedance data obtained
can be tested using Kramers-Kronig transforms. These transforms test the condition
of the system on the basis of causality, linearity, stability, and finiteness. Using these
transforms has cast doubt on the validity of some EI data, e.g., in well-inhibited systems.
EI used in high resistance solutions can lead to errors. If the technique is used on an
unstable or rapidly changing system it can give incorrect values of R, and corrosion
rate. Impedance techniques have been successfully used to study localized corrosion
proce~ses.'~
9.1.1.2.3 Electrochemical Noise
Electrochemical noise derives from random events such as rupture of the protective
film and dissolution of metal at local sites. These fluctuations are particularly obvious
with localized corrosion. Monitoring current noise and mean current flow between two
identical electrodes and correlating these with corrosion potential noise via a third iden-
tical electrode can indicate stage of pitting (initiation, propagation)1618 and distinguish
passivity in a low noise system.
9.1.1.2.4 Zero Resistance Ammeter (ZRA)
A zero resistance ammeter (ZRA) is normally used to measure the galvanic current
between two dissimilar metals but is also used to measure the current flow between two
identical electrodes where localized corrosion is occurring on one of them.
9.1.1.2.5 Scanning Electrode Techniques
Various scanning electrode techniques have been used to study localized corrosion by
measuring currents and potentials directly at anodic and cathodic sites on the speci-
men. Modern scanning electrode techniques include the scanning reference electrode
technique (SRET) that has been used to study pitting and SCC on stainless steels and a
scanning vibrating electrode technique (SVET) originally developed for biological ap-
plications but adapted for corrosion research. As well as mapping potential and current
these techniques can also measure local impedance. SVET has been used to study the
breakdown of passivity, galvanic corrosion, inhibition, MIC, and protective polymeric
~0atings.l~
9.1.2 Standards and Specifications-Corrosion Testing
9.1.2.1 ASTM
A 262-98-Standard Practices for Detecting Susceptibility to Intergranular Attack in

Austenitic Stainless Steels
A763-Standard Practices for Detecting Susceptibility to Intergranular Attack in

Ferritic Stainless Steels
C 692-00-Standard Test Method for Evaluating the Influence of Thermal Insulation
on External Stress Corrosion Cracking Tendency of Austenitic Stainless Steel
D 1141-98e1-Standard Practice for Substitute Ocean Water
G 1-90(1999)el-Standard Practice for Preparing, Cleaning, and Evaluating Corrosion
Test Specimens
G 3-89(1999)-Standard Practice for Conventions Applicable to Electrochemical
Measurements in Corrosion Testing
G 4-95-Standard Guide for Conducting Corrosion Coupon Tests in Field Applica-
tions
G 5-94(1999)-Standard Reference Test Method for Making Potentiostatic and Poten-
tiodynamic Anodic Polarization Measurements
G 15-99b-Standard Terminology Relating to Corrosion and Corrosion Testing
G 16-95(1999)el-Standard Guide for Applying Statistics to Analysis of Corrosion
Data
G 28-97-Standard Test Methods of Detecting Susceptibility to Intergranular Corro-
sion in Wrought, Nickel-Rich, Chromium-Bearing Alloys
G 30-97-Standard Practice for Making and Using U-Bend Stress-Corrosion Test
Specimens
G 31-72(1999)-Standard Practice for Laboratory Immersion Corrosion Testing of
Metals
G 32-98-Standard Test Method for Cavitation Erosion Using Vibratory Apparatus
G 34-99-Standard Test Method for Exfoliation Corrosion Susceptibility in 2xxx and
7xxx Series Aluminum Alloys (EXCO Test)
G 36-94(2000)-Standard Practice for Evaluating Stress-Corrosion-Cracking Resis-
tance of Metals and Alloys in a Boiling Magnesium Chloride Solution
G 38-01-Standard Practice for Making and Using C-Ring Stress-Corrosion Test
Specimens
G 39-99-Standard Practice for Preparation and Use of Bent-Beam Stress-Corrosion
Test Specimens
G 44-99-Standard Practice for Exposure of Metals and Alloys by Alternate Immersion
in Neutral 3.5% Sodium Chloride Solution
G 46-94(1999)-Standard Guide for Examination and Evaluation of Pitting Corrosion
G 47-98-Standard Test Method for Determining Susceptibility to Stress-Corrosion
Cracking of 2xxx and 7xxx Aluminum Alloy Products
G 48-00-Standard Test Methods for Pitting and Crevice Corrosion Resistance of
Stainless Steels and Related Alloys by Use of Ferric Chloride Solution
G 49-85(2000)-Standard Practice for Preparation and Use of Direct Tension Stress-
Corrosion Test Specimens
G 51-95(2000)-Standard Test Method for Measuring pH of Soil for Use in Corrosion
Testing
G 52-00-Standard Practice for Exposing and Evaluating Metals and Alloys in Surface
Seawater
G 58-85(1999)-Standard Practice for Preparation of Stress-CorrosionTest Specimens

for Weldments
G 59-97-Standard Test Method for Conducting Potentiodynamic Polarization Resis-
tance Measurements
G 61-86(1998)-Standard Test Method for Conducting Cyclic Potentiodynamic Polar-
ization Measurements for Localized Corrosion Susceptibility of Iron-, Nickel-, or
Cobalt-Based Alloys
G 64-99-Standard Classification of Resistance to Stress-Corrosion Cracking of Heat-
Treatable Aluminum Alloys
G 66-99-Standard Test Method for Visual Assessment of Exfoliation Corrosion
Susceptibility of 5xxx Series Aluminum Alloys (ASSET Test)
G 67-99-Standard Test Method for Determining the Susceptibility to Intergranular
Corrosion of 5xxx Series Aluminum Alloys by Mass Loss After Exposure to Nitric
Acid (NAMLT Test)
G 69-97-Standard Test Method for Measurement of Corrosion Potentials of Alu-
minum Alloys
G 71-81(1998)el-Standard Guide for Conducting and EvaluatingGalvanic Corrosion
Tests in Electrolytes
G 78-01-Standard Guide for Crevice Corrosion Testing of Iron-Base and Nickel-Base
Stainless Alloys in Seawater and Other Chloride-Containing Aqueous Environ-
ments
G 82-98-Standard Guide for Developmentand Use of a Galvanic Seriesfor Predicting
Galvanic Corrosion Performance
G 102-89(1999)-Standard Practice for Calculation of Corrosion Rates and Related
Information from Electrochemical Measurements
G106-Standard Practice for Verification of Algorithm and Equipment for Electro-
chemical Impedance Measurements
G 107-95-Standard Guide for Formats for Collection and Compilation of Corrosion
Data for Metals for Computerized Database Input
G 112-92(1997)-Standard Guide for Conducting Exfoliation Corrosion Tests in Alu-
minum Alloys
G 139-96-Standard Test Method for Determining Stress-Corrosion Cracking Resis-
tance of Heat-Treatable Aluminum Alloy Products Using Breaking Load Method
G 148-97-Standard Practice for Evaluation of Hydrogen Uptake, Permeation, and
Transport in Metals by an Electrochemical Technique
G 157-98-Standard Guide for Evaluating the Corrosion Properties of Wrought Iron-
and Nickel-Based Corrosion Resistant Alloys for the Chemical Process Industries
9.1.2.2 NACE
TM0169-2000-Laboratory Corrosion Testing of Metals

TM0171-95-Autoclave Corrosion Testing of Metals in High-Temperature Water
TM0174-9GLaboratory Methods for the Evaluation of Protective Coatings and Lin-
ing Materials in Immersion Service
TM0177-96Laboratory Testing of Metals for Resistance to Sulfide Stress Cracking

and Stress Corrosion Cracking in H2S Environments
TM0183-2000-Evaluation of Internal Plastic Coatings for Corrosion Control of Tubu-
lar Goods in an Aqueous Flowing Environment
TM0193-2000-Laboratory Corrosion Testing of Metals in Static Chemical Cleaning
Solutions at Temperatures below 93°C (200°F)
TM0196-9Hhemical Resistance of Polymeric Materials by Periodic Evaluation
TM0274-95-Dynamic Corrosion Testing of Metals in High-Temperature Water
TM0284-96Evaluation of Pipeline and Pressure Vessel Steels for Resistance to
Hydrogen-Induced Cracking
TM0398-98-Laboratory Corrosion Testing of Metals in Static Chemical Cleaning
Solutions at Temperatures Above 100°C (212°F)
RP0197-97-Standard Format for Computerized ElectrochemicalPolarization Curve
Data Files
RP0497-97-Field Corrosion Evaluation Using Metallic Test Specimens
RP0690-98-Standard Format for Collection and Compilation of Data for Computer-
ized Material Corrosion Resistance Database Input
RP0775-99-Preparation and Installation of Corrosion Coupons and Interpretation of
Test Data in Oilfield Operations
3D170-Technical Committee report (latest revision), ” Electrical and Electrochemical
Methods for Determining Corrosion Rates”
5A195-Controlled-Flow Laboratory Corrosion Tests
9.1.2.3 EN
EN IS0 3651-1:1998-Determination of resistance to intergranular corrosion of stain-

less steels
Part 1:Austenitic and ferritic-austenitic (duplex) stainless steels-corrosion test
in nitric acid medium by measurement of loss in mass (Huey test) ( I s 0 3651-
1:1998)
Part 2: Ferritic, austenitic, and ferritic-austenitic (duplex) stainless steels-
corrosion test in media containing sulfuric acid (IS0 3651-2:1998)
EN I S 0 6509:1995-Corrosion of metals and alloys4etermination of dezincification
resistance of brass (IS0 6509:1981)
EN IS0 7539-1:1995-Corrosionof metals and alloys-stress corrosion testing:
Part 1:General guidance on testing procedures (IS0 7539-1:1987)
Part 2: Preparation and use of bent-beam specimen (IS0 7539-2:1989)
Part 3: Preparation and use of U-bend specimens (IS0 7539-3:1989)
Part 4 Preparation and use of uniaxially loaded tension specimens (IS0 7539-
4:1989)
Part 5: Preparation and use of C-ring specimens (IS0 7539-5:1989)
Part 6: Preparation and use of precracked specimens (IS0 7539-6:1989)
Part 7 Slow strain rate testing (IS0 7539-71989)
EN IS0 8044:1999--Corrosion of metals and alloys-basic terms and definitions (IS0

804:1999)
EN IS0 9400:1995-Nickel-based alloys-determination of resistance to intergranular
corrosion (IS0 94001990)
EN 10229:1998-Evaluation of resistance of steel products to hydrogen-induced crack-
ing (HIC)
EN I S 0 11130:1999-Corrosionof metals and alloys-alternate immersion test in salt
solution (IS0 11130:1999)
EN I S 0 11306:1998-Corrosion of metals and alloys-guidelines for exposing and
evaluating metals and alloys in surface seawater ( I S 0 11306:1998)
9.2 DESIGN FEATURES
Design and construction of vessels and equipment can have a strong influence on corro-
sion. Many corrosion problems can be avoided by consideration of the factors affecting
corrosion at an early design stage. Some of the factors that should be considered during
plant design include:
Avoid anything that can encourage deposits to form, produces crevices or stagnant
areas, or makes cleaning and inspection difficult. It should be convenientto completely
drain and flush tanks and piping.
Gaskets should fit properly, and not protrude into the fluid causing turbulence or be
recessed, providing a crevice.
Welds should have a smooth profile and, like gaskets, should have a form that does
not encourage turbulence or produce crevices.
All metal surfaces should be clean and free from deposits, pits, cracks, etc. In some
applications it may be necessary to specify a postweld cleaning and/or passivation
procedure.
Coatings, if used, should adhere properly and be of adequate, uniform thickness and
be fully resistant to the process fluid.
If corrosion is expected to be uniform then the corrosion allowance must be adequate
to provide the desired life. This approach is not suitable if localized corrosion is pre-
sent or if metallic ion contamination is not acceptable in the process stream. In this
case a more resistant material must be specified.
Velocities must be high enough so that pipe and vessel diameter may be minimized,
but low enough to avoid erosion/corrosion. The limiting velocity will depend on
the materials of construction, type of equipment, and process fluid. Velocities in
piping are typically 1.2 to 1.8 m/s and in heat exchanger tubing can range from
1to 8 m/s.
Vessels must be supported so that they do not suffer from external corrosion of their
base. This might require elevated supports, domed base supports, or skirts to prevent
water ingress.
9.4 Anodic Protection of Metals 321
Heat exchangers pose particular design challenges and an appropriate type of tube
to tubesheet joint must be selected depending on the operating conditions (see
Chapter 10, Section 10.1.1, “Heat Exchangers,” for design details).
Galvanic corrosion should be avoided by selecting compatible materials or applying
coatings, electrical insulation, or CP.
Thermal insulation must be correctly designed and applied to avoid ingress of water
and possible concentration of salts, such as chlorides, at the hot metal surface.
9.3 MODIFICATION OF OPERATING CONDITIONS
All of the operating parameters, including upset conditions, should be assessed for their
effect on corrosion behavior. This is especially important whenever even minor changes
in operating conditions or procedures are contemplated. A careful review of conditions
and their effect on corrosion can identify small operating changes that can permit the
use of cheaper or more durable materials. Examples of the parameters and their effects
pH decrease generally increases corrosion rate except in aluminum, zinc, and lead.
Also strong caustic can cause SCC in iron alloys. pH can be controlled if necessary by
acid or alkaline additions to avoid corrosive or cracking conditions.
Oxidizing agents can increase corrosion for metals that are designed for reducing
conditions, e.g., alloy B, or reduce it for metals that passivate or form protective
oxides, e.g., stainless steels.
Temperature increase generally increases rate of reaction, can start localized attack,
e.g., SCC, pitting. Alternatively, increased temperature can vaporize corrosive liquids
and render them noncorrosive. Increased temperature can also reduce corrosion by
reducing oxygen solubility or by causing protective deposits or scales to form.
Velocity can increase corrosion rate, as with copper alloys in seawater, or decrease rate
by supplying inhibitors or oxidants to stainless steels.
Surface films are usually protective, so they reduce corrosion but can induce crevice
or underdeposit corrosion; incomplete coating or surface f ilm can accelerate attack.
Biological organisms usually accelerate rate.
9.4 ANODIC PROTECTION OF METALS
This method of protection drives the potential of a metal into a region where it is passive.
It is only applicable to certain metal/environment combinations. The most common
example is in the use of stainless steel for cooling strong sulfuric acid. Virtually all
sulfuric acid produced is cooled in anodically protected stainless steel heat exchangers.
This method is also used for most mild steel sulfuric acid storage tanks and stainless steel
acid piping. Anodic protection is also used on both mild steel and stainless steels in pulp
and paper digesters, clarifiers, liquor tanks and washers, and on titanium equipment,
e.g., for Rayon production. It is not applicable to water use since the metals and alloys
cannot be readily passivated in water.
9.5 CATHODIC PROTECTION
Cathodic protection (CP) was first defined by Sir Humphry Davy in 1824 when he re-
ported the successful use of zinc anodes to protect copper sheathing attached by iron
nails to the wooden framework of warship’s hulls. The corrosion of the copper was
reduced but fouling of the hulls increased.’O
It is an electrochemicalmeans of corrosion control in which the oxidation reaction in a
galvanic cell is concentrated at the anode and suppresses corrosion of the cathode in the
same cell. For example, if zinc and iron are separately immersed in an acid solution
both will corrode and develop anodic (oxidation reactions) and cathodic sites (reduction
reactions) on their surfaces. The usual reactions in an acidic environment would be metal
dissolution at the anode and hydrogen reduction at the cathode. The rate of reactions
would be balanced to maintain electrical neutrality. If these same two metals were now
connected electrically almost all of the anodic reaction would take place on the zinc and
the hydrogen reduction on the iron. At the same time the overall rate is increased so that
dissolution of the zinc increases while the dissolution of the iron virtually stops. This
example demonstrates the principle of cathodic protection.
The CP of bare steel immersed in wet soil or seawater would require very large
currents, but if only small areas of the steel need to be protected currents required are
greatly reduced. This is achieved by applying a coating to the steel so that the only steel
exposed is at “holidays” or defects in the coating. CP is then applied to protect these
areas. This combination of protective coating and CP is used on virtually all immersed
or buried carbon steel structures and pipelines. There are two common ways to achieve
cathodic protection, sacrificial anodes or applied current.
9.5.1 Sacrificial Anode Protection
CP can be obtained by connecting a noble metal to a less noble one (or a passive to
an active one) as described above. A common example is in the protection of steel by
coupling it to a less noble metal anode such as zinc, aluminum, and magnesium alloys.
The consumable anode becomes corroded and provides a supply of electrons to protect
the steel structure.
There are three common consumable anodes:
1. Zinc has been proven to be an excellent anode material for marine CP. A uniform
corrosion pattern with nonadherent corrosion products is assured by the inclusion of
different elements, e.g., cadmium. This type of zinc anode has a driving voltage of
approx. 220 mV against protected steel and delivers 780 Ah/kg. It is very suitable for
use in conjunction with coating systems where low operating current densities will
be experienced in the first years of the system’s life.
2. Aluminum has a very high capacity as an anode material. Different aluminum
alloys were developed by different companies to replace zinc as a sacrificial anode
material. Aluminum alloys with zinc and indium have proved to be reliable and
efficient seawater anodes since their introduction in 1960. These aluminum anodes
have a driving voltage of 300 mV against protected steel and deliver approximately
2,700 Ah/kg.
3. Magnesium is used as an anode material to suit specialist requirements in water
applications, e.g., for hulls in fresh water and ballast tanks carrying fresh water.**
Magnesium anodes can supply around 1,100 Ah/kg.
Other new sacrificial anodes are being developed to suit particular needs. For ex-
ample, a dual anode consisting of aluminum alloy on the inside and magnesium on the
surfacelayershas been produced largely for use in steeljackets on offshoreplatforms.The
principle of this type of dual anode is that the magnesium provides the initial currents
needed and produces a protective calcareous deposit. The aluminum provides the CP
for the life of the structure, which the magnesium polarized and covered with deposits.
In trials, a lower average current density was needed than for samples polarized initially
with aluminum. Deposits on samples that were overprotected were largely magnesium
hydroxide and were only slightly protective.22
The growth of calcareous deposits and their interaction with sacrificial anode CP
were investigated off the Ligurian Coast in the Mediterranean’ partly to determine to
what degree the deposits remained protective after CP was removed. The results of
galvanic coupling of stainless steels with various anode materials for 1 month were the
following:
Iron anodes did not produce calcareous deposits and protection failed soon after the
galvanic coupling was removed.
Zinc anodes produced a light deposit of aragonite and the protection persisted for
>3 weeks after the galvanic coupling was removed.
Magnesium anodes produced thick calcareous deposits and protection persisted for
>1 year after the galvanic coupling was removed.
The protective effect of the deposits was attributed to their buffering properties that
hindered the occluded cell mechanism leading to localized corrosion. Deposit forma-
tion was said to be independent of the composition or surface finish of the stainless
steels.=
The metal loss from consumable anodes used to protect steel structures off the coast
of Singapore was measured. The average current consumption was calculated to predict
more accurately the mass of anodes needed to protect structures in this environment for
their design lifetime. The average corrosion rate for steel in this location is high, 0.53
and 0.3 mm/y for 2 and 12 months, respectively, but is much lower in inland marine
exposure and higher in open sea exposure. Current density demand was strongly in-
fluenced by seawater current, anode type, steel type, and depth of exposure in the sea.
The average current density for protection of steel by zinc anodes was 114 mA/m2 for
2 months exposure, dropping to 58 mA/m2 for 9 months of exposure. The average cur-
rent density determined from a 13-year-old jetty protected by aluminum anodes was
19.1 mA/m2. The following current density relationships were developed for different
depths of seawater exposure:
At 2 m depth: Current density (mA/m2) = 55.6 x (exposure time, y)-0.421

At 12 m depth: Current density (mA/m2) = 50.0 x (exposure time, y)-0.393
These equations can be used to estimate the anode weights for use in this location and
other similar tropical marine application^.'^
9.5.2 Impressed Current Systems
A metal can also be cathodically protected if it is coupled to the negative pole of a direct
current source, while the positive pole is coupled to an auxiliary anode. Unlike in the
sacrificial anode system,in an impressed-currentsystem the anodes need not be naturally
anodic to steel, and in fact they seldom are. Most impressed-current anodes are made
from nonconsumable electrode materials that are naturally cathodic to steel. If these
electrodes were wired directly to a structure, they would act as cathodes and would
cause accelerated corrosion of the structure they are intended to protect. The direct
current source reverses the natural polarity and forces the materials to act as anodes.
Instead of corrosion of the anodes, some other oxidation reaction, that is, oxygen or
chlorine evolution, occurs at the anodes and the anodes are not consumed or are only
slowly consumed.25
Impressed-current systems are more complex than sacrificial anode systems. The
capital expense necessary to supply direct current to the system is higher than for a simple
connection between an anode and a cathode. The voltage differencesbetween anode and
cathode are limited in sacrificial anode systems to approximately 1V or less, depending
on the anode material and the specific environment. Impressed-current systems can
use larger voltage differences. The larger voltages available with impressed currents
allow remote anode locations, which produce more efficient current distribution patterns
along the protected cathode. These larger voltages are also useful in low conductivity
environments, such as fresh water and concrete, in which sacrificialanodes would have
insufficient throwing power.
9.5.3 Requirements for Cathodic Protection
The original NACE specification for buried or submerged metallic pipelines included
a number of possible criteria to determine whether a steel or cast iron structure is
adequately cathodically protected. The criteria in NACE RPO169-96 are as follows:
A potential of -0.85 V relative to a CSE electrode with CP applied. Voltage drops,

other than those across the structure to electrolyte boundary, must be considered for
valid interpretation of this voltage measurement.
A negative polarized potential of at least 850 mV relative to a saturated copper/copper
sulfate reference electrode.
A minimum negative (cathodic)voltage of 100 mV between the structure surface and
a stable reference electrode contacting the electrolyte.
There are limitations and conditions placed upon these criteria based on the type of
exposure. For example, pipes encased in concrete may need less negative potentials for
protection but in the presence of bacteria, sulfides, elevated temperatures, or dissimilar
metals these criteria may be inadequate. On bare, long pipelines the measurement of
protective current at various points may be acceptable. The 100-mV criterion is also
recommended for buried aluminum or copper pipe.
There is a danger that the use of -0.85 V will produce enough hydrogen to cause
hydrogen embrittlement in some steels. Whatever the control limit set, overprotection
should be avoided to prevent hydrogen damage, blistering of coatings, etc. The most
common and most widely applicable criterion is the -0.85 V vs. a copper/copper sul-
fate reference cell. Most structures can be tested to determine if they are protected relative
to this standard. The only equipment necessary is a reference cell and a wire lead con-
nected to the structure. The use of potential measurements to monitor and control CP
suffers from IR drop that makes the measured potential more negative than the polar-
ized potential. Also, potential measurements do not give a direct measure of corrosion.
For these reasons there has been extensive research to find other criteria and methods of
measurement that do not suffer from IR problems and give a more direct indication of
corrosion under CPF6
The two most common techniques used to allow for the IR drop use reference cells
located as close as possible to the interface or current interrupt to measure an instant-off
potential. Both of these methods can be used with test coupons. The use of coupons to
determine the effectiveness of CP and interference from AC sources is in general use in
many ~ountries.’~
Since potential criteria do not directly measure the corrosion of the protected struc-
ture research is ongoing to explore so-called kinetic criteria. The basis of these kinetic
criteria are electrochemical measurements of corrosion current. Various concepts and
techniques are being evaluated such as EIS, electrochemicalnoise, Faradaic rectification,
and Harmonic analysis, but none of them is yet ready for field operations on protected
equipment. If such electrochemical methods can be developed into working systems
they will greatly improve the effectiveness of CP monitoring.”
For offshore steel structures, such as oil and gas platforms, the criterion (NACE
RPO176-94) to determine whether cathodic protection is achieved is a cathodic voltage
of at least -0.80 V measured between the platform surface and a silver-silver chloride
reference electrode. An alternative criterion is the production of a minimum negative
voltage shift of 300 mV when the protection voltage is applied. These criteria are said to
be adequate for waters exposed to the air and at typical ambient temperatures. For other
conditions it is recommended that potential requirements to control corrosion should
be estimated from the Nernst equation. As well as using these potential criteria current
surveys can provide useful information about the distribution of protection current and
predicting anode life. Additionally, the effectivenessof CP to reduce or prevent corrosion
can be assessed by visual examination and by the use of corrosion coupons.
9.5.4 Practice of Cathodic Protection
Seawater applications of 300 series stainless steels are often corrosion free when used
in key components of a multialloy assembly. For example, in a power plant seawater
pump a cast CE 30 steel impeller that was coupled to an austenitic cast iron suction bell
and diffuser worked successfully for many years. Other successful applications rely on
consumable anodes, e.g., a cast CF-4propeller works well on a seagoing tugboat that has
consumable zinc anodes attached to the carbon steel rudder.29Carbon steel anodes have
been used to prevent crevice corrosion of 316 stainless steel in an immersed seawater
application in Brazil.30The extensive test work by Shell concluded that, ”It is impossible
to imagine that steels of the AISI 316L type could be used in seawater for extended
periods unless they were receiving some form of cathodic protection.”6
Cathodic protection can prevent crevice and pitting attack of 304 and 316 but 410 and
430 can develop hydrogen blisters at current densitiesbelow those required for complete
protection?1 A trial on the effects of cathodic protection on fatigue resistance of materials
in artificial seawater concluded that UNS S31254 and Cu/Ni alloys tested showed no
or very little liability to hydrogen embrittlement; Ni/Cr, Ni/Fe/Cr, and 2507 showed
some effect; and Ni/Cu and low alloy steel showed great effect.32Slow strain rate tests
in artificial seawater at 11°C on three bolt materials investigated the effects of CP. CP
produced hydrogen embrittlement in alloy K-500(UNS N05500), to a lesser extent in
2507, and UNS S31254 was ~ n a f f e c t e d . ~ ~
The cathodic current density of the austenitic stainless steels containing 6% Mo is
very low at potentials around -100 to -200 mV SCE. Thus a single sacrificial anode can
protect a long pipe length in this type of alloy and permit its use at temperatures above
the normal limit of 30°C and 1ppm chlorine without crevice attack.34
This finding has led to the development of a new technique to prevent localized
corrosion of stainless steels in seawater systems. In this resistor-controlled cathodic pro-
tection (RCP) technique a resistor in series with the anode is used to control both the
potential on the stainless steel and the anode output. The technique is aimed at keep-
ing the stainless steel pipe protected without developing excessive negative potential.
This method is particularly appropriatefor chlorinated seawater systems where a single
anode can protect long lengths of pipe with very low current requirements. This tech-
nique has been used on 6% molybdenum stainless steel seawater systems in oilfield
applications where the temperature of operation is above the initiation temperature for
crevice corrosion. It is also being used to provide local protection of stainless steel pumps
and valves instead of using titanium for these key component^.^^ Analysis of a Norsk
Hydro seawater piping system for a gas platform showed that the most cost-effective
solution was to use GRP piping with 316 valves protected with RCP. This selection was
found to be less than half of the cost for a complete system made from titanium, or a
system with GRP piping and titanium valves.%
Lake Maracaibo, Venezuela is a tropical basin with an area of some 16,000 km2.On
the north side the lake opens into the Maracaibo Strait which connects with the Gulf
of Venezuela. On the southern side, the lake is fed by several rivers. As part of oil
production, hundreds of pipelines have been installed in the lake, many of which are
not properly isolated or are in direct contact with each other. Extensive dredging of the
channel to permit large tankers to enter the lake has caused it to become increasingly
saline, from an average salinity of 1.20X in 1952 to 4.25"L in 1996. This change in
salinity has increased the water conductivity and caused stratificationof the lake water
and variations in oxygen content.
The combination of these factors produced a situation in which galvanic and dif-
ferential aeration corrosion have increased, necessitating the development of a control
strategy. Pipeline coatings have also deteriorated from damage during installation and
increase in marine borer activity. Corrosion tests on mild steel determined general cor-
rosion rates of up to 1.0 mm/y with pitting rates as high as 3.7 mm/y. A review of the
conditions in this unique environment concluded that the most appropriate approach
was to use remote, cylindrical, high purity, consumable zinc anodes to protect the sub-
merged steel structures. Magnesium anodes are not suitable for long-term use because
of their high consumption rate and low efficiency but can be used in conjunction with
the zinc to encourage the formation of protective calcareous deposits. Aluminum is not
suitable since it passivates in this environment. Coating selection needs to take account
of marine borers and crustaceansso soft organic coatings must be avoided. Polyethylene,
fusion-bonded epoxy, mortar, and polypropylene coatings have proved to be more ap-
propriate than asphalt pipeline c0atings.3~
The main effect of biofilms on the cathodic reaction is to increase the current density
necessary to polarize the metal to the protection p ~ t e n t i a l . Biofilms
~ . ~ ~ and CP also
interact to change the nature and structure of calcareous deposits on metals. A biofilm
may either enhance or decrease the effectiveness of CP depending on the magnitude of
the applied current density? The interaction among biofilms, deposits, and CP are site
specific and local testing must precede an effective CP program>*
Cathodic protection of mild and stainless steel appears to reduce bacterial settlement
in the short term (on a scale of This effect may not be lasting, however,
as during an experiment of more than 7 months, SRB population increased on several
alloys tested, which could decrease CP effectiveness" Similarly, cathodically produced
hydrogen may serve as an energy source for hydrogenase containing SRB, increasing
their population.&
There is some evidence that macrofoulers prefer mild steel protected by zinc sacri-
ficial anodes to unprotected steel and will settle on the protected steel refer en ti ally.^^
In Florida, fouling communities dominated by barnacles developed on sacrificial alu-
minum anodes, achieving total cover when operatingat low current densities and patchy
cover when operating at high current densities. The biofilm significantly increased the
resistance between the anode and electrolyte (seawater) and reduced the effectiveness
of CP.48
See Chapter 6, Section 6.2.4.4, ”Cathodic Protection of Reinforced Concrete.”
9.5.5 Standards and Specifications-Cathodic Protection
9.5.5.1 NACE
RP0169-9Montrol of External Corrosion on Underground or Submerged Metallic

Piping Systems
RPO176-94-Corrosion Control of Steel-Fixed Offshore Platforms Associated with
Petroleum Production
RP0193-93-External Cathodic Protection of On-Grade Metallic Storage Tank Bottoms
RP0285-95-Corrosion Control of Underground Storage Tank Systems by Cathodic
Protection
RP0286-97-Electrical Isolation of Cathodically Protected Pipelines
RP0572-95-Design, Installation, Operation, and Maintenance of Impressed Current
Deep Groundbeds
TM0190-98-Impressed Current Test Method for Laboratory Testing of Aluminum
Anodes
TM0497-97-Measurement Techniques Related to Criteria for Cathodic Protection on
Underground or Submerged Metallic Piping Systems
10A190-Measurement Techniques Related to Criteria for Cathodic Protection of
Underground or Submerged Steel Piping Systems (as Defined in NACE Standard
RPO169-83)
10A196-Impressed Current Anodes for Underground Cathodic Protection Systems
10A292--Corrosion Control of Ductile and Cast Iron Pipe
10A392-Effectiveness of Cathodic Protection on Thermally Insulated Underground
Metallic Surfaces
1E100-Engineering Symbols Related to Cathodic Protection
54276-Cathodic Protection Monitoring for Buried Pipelines (1988)
7G181-Investigation of the Effects of Corrosion-InhibitingTreatments on Mechanical
Seals in Recirculating Hot Water Systems (1997 Edition)
7H19O-Waterside Inspection Methods and Tools for Industrial Boilers
7H290-Information Required for Boiler Tube Failure Investigation
9.5.5.2 EN
EN 12473:2000--Generalprinciples of cathodic protection in seawater

EN 12474:2001--Cathodic protection of submarine pipelines
EN 12495:200Hathodic protection for fixed steel offshore structures
9.6 References 329
EN 12954:2001--Cathodic protection of buried or immersed metallic structures-

general principles and application for pipelines
EN 13173:2001--Cathodicprotection for steel offshore floating structures
EN 13174:2001--Cathodicprotection for harbour installations
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caibo,” MP 39,12 (2000):pp. 34-38.
38 B.J. Little, PA. Wagner, “The interrelationshipbetween marine biofouling and cathodic protec-
tion,” Corrosion/93 paper no. 525 (Houston, TX:NACE, 1993), pp. 1-7.
39 G. Hernandez, W.H. Hartt, H.A. Videla, “Marine biofilms and their influence on cathodic pro-
tection: a literature survey,” Corros. Rev. 12,l-2 (1994):pp. 2940.
S.C. Dexter, S.H. Lin, “Effect of marine biofilms on cathodic protection,” Int. Biodeterior. Biode-
grad. 29 (1992):pp. 231-249.
9.6 References 331
41 S.T. Paakkonen, S.F. Lockwood, D.H. Pope, V.G. Homer, E.A. Morris, D.P. Werner, “The role
of coatings and cathodic protection in microbiologically influenced corrosion,” Corrosion/93
paper no. 293 (Houston, TX NACE, 1993), pp. 1-21.
42 R.G.J. Edyvean, A.D. Maines, C.J. Hutchinson, N.J. Silk, L.V. Evans, “Interactions between
cathodic protection and bacterial settlement on steel in seawater,” Int Biodeterior. Biodegrad.
29 (1992):pp. 251-271.
43 M.F.L. de Mele, “Influence of cathodic protection on the initial stages of bacterial fouling,” in
Biocorrosion and Biofouling NSF-CONICET Workshop (Memphis, TN: Buckman Laboratories
International Inc., 1993), pp. 181-190.
44 A.D. Maines, R.G.J. Edybean, L.V. Evans, ”The influence of cathodic protection on aerobic
bacterial settlement on stainless and structural steel,” in Proc. 8th International Congress on
Marine Corrosion and Fouling, Oebalia XIX Suppl. (1993), pp. 303-311.
45 G. Nekoksa, B. Gutherman, ”Test results from electrochemical exposure racks at the Crystal
River Nuclear Power Plant,” Corrosion/91 paper no. 275 (Houston,TX: NACE, 1991), pp. 1-16.
46 J. Guezennec, M. Therene, “A study of the influence of cathodic protection on the growth of
SRB and corrosion in marine sediments by electrochemicaltechniques,” in Microbial Corrosion
1 (London: Elsevier Applied Science, 1988), pp. 256-265.
47 D. Tay, H.K. Hoe, K.I. Johannessen,W. Wai, K.O. Vilpponen, “A study of tropical marine growth
and its effect(s) on corrosion and corrosion control of steel in seawater,” Asia Corrosion ‘88,
Singapore (1988),pp. 1-24.
48 G.W. Swain, J. Patrick-Maxwell, “The effect of biofouling on the performance of Al-Zn-Hg
sacrificial anodes,” Corrosion 46,3 (1990):pp. 256-260.
Chapter I0
Water Systems
This chapter describes water systems from the point of view of factors that are common
to many industrial uses of water. Water systems applicable to specific industries are
described in the relevant application in Chapter 11, Applications. Vast quantities of
water are used by industry for cooling, production processes, and steam raising. In the
United States in 1990the total quantities of water used industrially approached 28 billion
gallons per day (Bgal/d; 106 BL/d; Table lO.l).'
In 1995, a similar amount of water, about 27.1 Bgal/d (103 BL/d), was being used
industrially in the United States. This is about 6.7% of the total daily water use of about
402 Bgal/d (1,520 BL/d). In 1995, about 78% of industrial water used was surface water,
about 22% was ground water, and about 6% was saline.' This industrial water use figure
does not include the water used by thermoelectric plants. In 1995, this was about 132
Bgal/d (500 BL/d) of fresh water.3
10.1 COOLING WATER SYSTEMS
Much of the water used industrially removes heat from production processes. It is one
of the major applications for water and is a major factor in siting plants and processes.
In Britain, for example, 28% of all the rainfall and 50% of the total river flow are used for
cooling water.* Cooling water systems can be classified as follows:
Once through. The cooling water passes through heat exchange equipment once and
then is returned back to source. The water for this type of cooling can come from lake,
river, well, or ocean. This is the simplest form of process heat removal but requires
the availability of large, reliable quantities of good quality water.
Closed recirculating. The water is contained within the heat exchangers and piping of
the plant and the process heat removed by the circulating water is usually dissipated
by air cooling. Any corrosion product remains within the system and can lead to major
fouling and/or further corrosion.
333
334 Water Systems
Table 10.1 Industrial Water Use in the United States in 1990,

in Millions of Gallons per Day'
Source of Water Fresh Saline

Self-suppliedwithdrawals Ground water 3,950 9.7
Surfacewater 15,400 3,260
Total water received from 5,190 -
public water works
Totals 24,500 3,270
Open recirculating systems. The cooling water also remains within the plant but the
system is open to the air through a cooling tower so that makeup water is being contin-
uously added to replace water lost by evaporation at the cooling tower (Figure 10.1).
This type of system has the greatest potential for fouling and corrosion problems
because of the following:
Generally it has higher water temperatures leading to more scaling and corrosion.
The cooling tower acts as a scrubber, collecting microorganisms, dust, and dirt.
Makeup water brings a fresh supply of scale and corrosion-forming constituents.
Oxygen, which can cause or enhance corrosion, is present in all parts of the system.
10.1.1 Heat Exchangers
Heat is removed from exothermic processes, hot gases, and liquids, and to control oper-
ating temperatures through heat exchangers cooled with water. Some heat exchangers
remove heat with air, heat transfer fluids, or interchange with other process streams.
These types of exchangers will not be considered here, only those that use water for heat
removal. In some cases the extracted heat is wanted and is used elsewher; in other cases
it is simply removed and lost to the system. Heat exchangers can be extremely simple,
such as cold water pouring over a pipe containing the hot fluid, or cold water flowing
through a coil immersed in a tank of the fluid to be cooled. Both of these types of heat
exchangersstill find occasional applicationstoday. Cast iron pipes connected with bolted
return bends to form a "serpentine" cooler over which cold water is sprayed are also in
occasional use (Figure 10.2).They suffer external corrosion in the often polluted cooling
water (Figure 10.3).
Shell and tube heat exchangers consist of a bundle of tubes connected to tube sheets
which are then installed into a shell (Figure 10.4). Tube bundles can be parallel with
once-through flow from one end to the other, or with U-tube in which the hot and cooled
fluid enter and exit from the same end of the exchanger. The tube to tubesheet joint can
be mechanical, such as rolled or expanded, or welded using various joint configurations.
The cooling water can be either in the shell or in the tubes, although the latter is preferred
wherever possible. The tube materials must be selected to provide good heat transfer
and be resistant to corrosion by the water on one side and the process fluid on the other.
10.1 Coolina Water Svstems 335
Figure 10.1 This typical cooling tower is used to cool water for chemical
plant heat exchangers. (Photo courtesy of CARIAD Consultants.)
336 Water Svsterns
Figure 10.2 In a serpentine cast iron cooler the solutionto be cooled flows
through the pipes and cooling water cascades over the outside. (Photo
courtesy of Kvaerner Chemetics Equipment Division.)
Figure 10.3 Close-up photo shows a cast iron bolted joint in a serpentine cooler
with major externalcorrosion from the coolingwater. (Photocourtesyof Kvaemer
Chemetics Equipment Division.)
Plate exchangersare made from formed, thin sheets of metal that are stacked together
in a frame to form a series of channels separating different fluid streams (Figure 10.5).
The hot liquid flows on one side of the plates while the cooling liquid flows in a counter-
direction on the other. The individual plates are separated from each other by gaskets.
Units can be expanded by installing additional plates. Potential problems with this type
of exchanger are leaking gaskets and crevice corrosion under gaskets or at points of
metal-to-metal contact where plate corrugations meet. Fouling is usually prevented by
incorporating high local fluid velocities to deter deposition and settling. Design is very
compact and heat transfer efficient. The bolted structure can be dismantled for cleaning
and maintenance and individual plates can be replaced if necessary.
Spiral exchangers are formed by two thin sheets of metal rolled around a central core
to form two concentric, spiral channels (Figure 10.6). For liquid-to-liquid duties the hot
and cold liquids flow countercurrent in each of the channels. In most designs, alternate
channels are seal-welded so that intermixing of the liquids is avoided. Gasketted flat
covers are fitted to the open sides of each channel. Spiral exchangers are able to utilize
smaller temperature differences than other types of exchangers. Fouling is minimized
since if deposition begins local velocities increase and tend to remove the fouling. The
covers are removed for inspection and maintenance. Spiral exchangers are very compact
and require less heat transfer surface than shell and tube units.
Because of the differences in heat transfer coefficients, optimal flow velocities, and
fouling factors the heat transfer surface and required space vary depending on the type
338 Water Systems
Figure 10.4 During assembly of a heat exchanger the tube bundles and
baffles can be seen. (Photo courtesy of Kvaemer Chemetics Equipment
Division.)
10.1 Cooline Water Svsterns 339
Figure 10.5 A plate heat exchanger is opened for cleaning and plate in-
spection. (Photocourtesy of CARIAD Consultants.)
of exchanger used. A shell and tube exchanger with 125 m2 heat transfer surface could
be replaced for the same duty by a spiral with 90 m2 or a plate exchanger with 60 m2.
The spiral exchanger would take up the least space and both the spiral and plate would
require considerably less space than the equivalent shell and tube unit, especially if
the open space required for tube removal is ~onsidered.~Despite the compact, efficient
340 Water Systems
Figure 10.6 A spiral heat exchanger in 6% Mo stainless steel has its cover opened to show the
spirals, spacer pins, and PTFE gasket. (Photocourtesy of CARIAD Consultants.)
design of plate and spiral exchangersit is still true that the vast majority of heat exchang-
ers are shell and tube.
The various metals commonly used in heat exchangers have quite different thermal
conductivities (Table 10.2).6*7
However, the thermal conductivity of the metal wall is only one component of the
resistance to heat transfer in a heat exchanger tube. In a condenser (i.e., where steam is
condensing on cold tubes), for example, the resistance to heat transfer through a tube
wall is made up of a number of components:
Steam side water film 18%

Steam side fouling 8%
Tube wall 2%
Water side fouling 33%
Water side film 39%
The tube wall resistance is comparatively small so that changes in thermal conduc-
tivity from the use of different metals in not necessarily very ~ignificant.~ The overall
heat transfer factor, U, includes factors for water velocity, inlet water temperature, metal
Table 10.2 Thermal Conductivity of Various Alloys
Thermal Conductivity,
Alloy Btu/hr.f? "F/in. (W/m-K)
Admiralty metal 770 (111)
Aluminum brass 696 (100)
Aluminum bronze 552 (79.5)
90/10 Cu/Ni 312 (44.9)
70/30 Cu/Ni 204 (29.4)
304 stainless 104 (15.0)
U N S NO8367 77 (11)
UNSw735 118 (17.0)
U N S 94660 118 (17.0)
Commercially pure titanium 150 (21.6)
correction, and cleanliness. Using this type of calculation, which includes resistance to
fouling, velocity constraints imposed by the tube material, and strength that affects the
normal wall thickness, values for U are much more similar than would be expected
purely from a consideration of thermal conductivity.6
Heat exchanger tubing is sometimeslined to limit fouling, for example, with phenolic.
Baked phenolic coatingshave been used in copper alloy condenser tubing for many years,
particularly in Europe. The coating limits deposition that can cause pitting on uncoated
tubes. Although the coating reduces the heat transfer compared with the bare metal tube,
the heat transfer remains constant throughout the life of the exchanger and is still greater
than that of a fouled, uncoated tube. Design and fabrication must take into account the
fact that the exchanger is to be coated, e.g., sharp corners must be avoided, weld profiles
must be smooth, surfaces must be prepared, and there must be no crevices.
There are a number of potential problems to be avoided in the design of shell and
tube exchangers. These include the following:
1. The integrity of the tube to tubesheet joint must prevent contamination of one fluid
by the other. This can be achieved by close tolerance preparation, tight rolled-in joints,
and seal welding.
2. Prevention of deposition. Clean, pure water is ideal but this is not always possible to
obtain. In the case of normal industrial waters some combinationof filtration, settling,
chemical treatment, etc. is required. Water on the tube side with an adequate velocity
will also help avoid deposition.
3. Tubes must be of adequate quality and integrity. It is possible to get defective welded or
seamless tubes and quality assurance should be set at a level to suit the application and
the consequences of fluids mixing, e.g., strong sulfuric acid and water is hazardous,
but the same water at different temperatures is not.
4. Galvanic interaction should be avoided. It is not uncommon to use a different alloy for
the tubes and the tubesheet. These should be selected so that galvanic corrosion and
342 Water Systems
possible hydrogen cracking are not encouraged. Sometimes the tubesheet material is
selected to provide some cathodic protection to the tube ends, e.g., steel tubesheet
with copper alloy tubes. In other cases CP is applied to prevent this type of attack.
Most metals used in heat exchangersperform well in clean water, i.e., free of sediment,
debris, fouling organisms, and pollutants. Sediment or debris can cause underdeposit
corrosion or can cause turbulence that can damage or remove the protective film, par-
ticularly on the less resistant copper-based alloys. Effective screening or filtering can
limit this problem. Copper alloys are, in general, better at resisting the attachment of
organisms than stainless steels or nickel alloys.
Chlorides in the water can cause corrosion, particularly in the case of stainless steels.
Typically 304 is satisfactory up to about 200 pprn chlorides, while 316 can withstand
around 1,000 pprn and 4.5%molybdenum austenitic stainlesssteels and duplex stainless
steels are known to have suffered from crevice attack at 2,000 to 3,000 pprn beneath
fouling. Titanium and the 6% molybdenum stainless steels have been shown to resist
crevice attack in seawater (1,900 pprn chlorides) under deposits. Copper alloys and
stainless steels perform best in water that has enough oxygen, around 3 to 4 pprn to
keep fish alive. Copper alloy tubes do not work well in polluted water where the oxygen
has been consumed and sulfides are present. Tubes of titanium or high alloy stainless
steels are better in this type of water. Copper alloy and stainless tubes work well in
water chlorinated at up to 2 ppm free chlorine, although higher chlorine levels can cause
damage. In aerated water of pH less than 5, copper alloys can corrode but resist attack
in deaerated acidic water. Manganese in the water can cause corrosion of stainless steels
but not of copper alloys. Both stainless steels and copper alloys perform well in hard
and soft waters that could cause scale-related problems in carbon steels?
Operational problems can cause corrosion of stainless steel and copper alloy heat
exchangers. Stagnant water left from hydrotesting or from inadequate draining at shut
down can cause fouling and/or MIC. Heat exchangers should be drained and mechan-
ically cleaned frequently; the water should also be treated with chemicals to minimize
scaling, fouling, and corrosion if this is appropriate for the application. Fluid velocities
should be kept high enough (>3 ft/s [0.9m/s]) to avoid fouling/sediment problems, but
not high enough to cause erosion corrosion; upper velocity limits depend on the alloy.
In general, larger tube diameters are better because any debris passing through screens
or filters will also pass through the exchanger. It is also easier to clean larger diameter
tubes adequately. Similarly,once-through exchangers are generally preferred to U-bend
bundles since they are less likely to become plugged. The preferred orientation for ex-
changers, particularly condensers, is horizontal with water in the tubes. Shell-sidewater
exchangers are much more likely to foul and scale. Vertical condensers with shell-side
water in both copper alloy and stainless steel are likely to suffer from stress corrosion
cracking of the tubes just below the top tubesheet. Venting or the use of more resistant
alloys in this region is sometimes necessary?
The design and production of the tube to tubesheet joint are critical factors in the
successfuluse of shell and tube heat exchangers. Roll-leakscan be caused by tubes being
pulled out of the tubesheet under the action of thermal stresses. This is particularly so
where different metals with different expansion coefficients are used for the tubes and
the tubesheet. This effect can be prevented by using an expansion joint in the shell.
Properly designed and executed seal or strength welds may prevent leakage at this
joint. Seamless,as-welded,bead-worked (locallycold-worked)or cold-drawn are equally
likely to perform well in most services.In criticalapplication or where localized corrosion
may be initiated by surface defects adequate inspection and testing are recommended
regardless of method of tube manufacture.
Heat exchangers for reliable freshwater service are less critical than for salt waters.
The primary considerations are the limitations imposed by the relatively thin-walled
tubes. Heat exchangers handling soft corrosive water can use 304 or 316 tubes, tube-side
water is strongly recommended. Other componentsof the exchanger can be carbon steel,
with or without coating, depending on the water composition and temperatures? For
more aggressive fresh waters, e.g., low pH, high chlorides,etc., copper, admiralty brass,
alloy 625, or C-276 tubes may be needed. Tubesheets may be bronze or stainless steel
depending on the tube materials. Heads can be lined carbon steel, FRP, or bronze. With
water in the tubes the shell materials will depend on the process chemistry.1°
Heat exchangers with fresh, brackish, or seawater in the tubes can suffer from
erosion by impingement attack on the inlet end of tubes. The ingestion of air trapped in
the water box can increase the attack even if CP is applied or if the carbon steel water
box is expected to protect the alloy tubes. The degree of attack also depends on the
material of the tubes and on the water velocity. Copper alloys in order of increasing
resistance to impingement attack are as follows:
Arsenical copper UNS C14200

Admiralty brass UNS C44300
Aluminum brass UNS C68700
90/10 Cu/Ni UNS C70600
70/30 Cu/Ni UNS C71500
If inlet erosion is encountered and a material upgrade is not possible, coating the
tubesheet and the first 6 to 8 in. of the tubes will usually prevent the attack. A high
quality epoxy coating is preferred and the preparation and spray techniques used must
ensure that the coating does not flow or sag after application.Areas of thin coating must
also be avoided."
10.1.I .I Startup/Lay-Up Procedures
The extended startup periods of modem power plants as well as the extended outfitting
periods of shipshave led to failuresof copper alloys where water is left in, or incompletely
drained from, the seawater cooling system.Leaving the systemsfull, partially drained, or
simply wet begins putrefaction of seawater which can occur within 3 to 4 days. Oxygen
is consumed by corrosion and biological oxygen demand, i.e., decay of organic matter
found innearly all natural waters. Bacteria thrive and create local environmentsthat favor
MIC. Most failures reported during these startup periods may well be MIC, although
often the failures are described as sulfide-type pitting corrosion in copper alloy units. If
344 Water Systems
Figure 10.7 Water gushes out of a shell and tube heat exchangerbundle when the insides of the
tubes are hydroblast-cleaned.(Photo courtesy of Kvaemer Chemetics Equipment Division.)
exchangers are to be left full for more than 2 or 3 days, pumps should be started once
each day to displace the stagnant water with a fresh supply of the natural cooling water.
If units are to be down for more than a week, they should be fully drained and blown
dry to remove all water in low areas between tubing supports.”
Chemicalcleaning may be required in some cases and the chemicals used will depend
on the materials and the nature of the fouling. The best and safest way to remove a
buildup of hardened fouling material is probably by hydroblasting, in which a high
pressure water jet assembly progresses through each of the tubes (Figure 10.7). If this
is not successful manual cleaning with brushes or rods may be needed. Some attempts
have been made to use online automatic mechanical cleaning, e.g., sponge balls forced
through the bundle, but these methods have not been generally adopted.*O
10.1.2 Once-Through Freshwater Cooling Systems
Water taken directly from a lake or river removes process heat from chemical or other
industrial plants using heat exchangers of various types. The selection of materials in
these applications is often a compromise between the requirements of the process fluid
and the water. Associated with such heat exchangers are pumps, pipes, valves, etc. used
to distribute the water and return it to source.
10.1 Cooling Water Svstems 34s
10.1.2.1 Tanks, Screens, and Filters
Tanks for handling fresh once-through water can be 304 or 316 if the pH is 25.5 at
temperatures of 25 to 40°C. Typical acceptable chloride levels are 250 ppm for 304 and
1,000 ppm for 316. At 40 to 80°C duplex or super stainless may be required; for pH ~ 5 . 5
nickel-based alloys may be needed. Stainless tanks should only be used where the water
is permanently sterile as well as free from insoluble matter, and the tanks should be
pickled and passivated before use? Screens to remove large objects and debris should
be made from coated mild steel or UNS N04400. Filters to remove the smaller particles
can be made from FRP or coated mild steel. Copper filters with UNS NO4400 elements
may be required for more aggressive waters."
10.1.2.2 Piping
Cement or rubber-lined steel, cast iron, or concrete is often used for underground supply.
Aboveground, FRP, copper, or galvanized steel may be satisfactory.Martensitic (12%Cr)
and femtic (17% Cr) grade piping are suitable for freshwater systems but are susceptible
to pitting in waters with higher chloride levels. On the grounds of availability and ease
of fabrication, 304L and 316L are often preferred for freshwater piping. A minimum
flow velocity of 3 ft/s (0.9 m/s) is recommended and the water should be free of solid
particles. Duplex steels such as 2205 and austenitic 6% Mo stainless steels are sometimes
used in fresh waters with higher chloride levels?
10.1.2.3 Pumps
Pumps are exposed to higher velocities than any other component and must resist
erosion corrosion, abrasion, cavitation, etc. Bronzes are traditionally used in once-
through waters, with the nickel aluminum bronzes being preferred in more saline waters
(although subject to attack when sulfides are present). Both straight chromium (e.g.,
CA6NM, J91540) and cast austenitic stainless steels (e.g., CF3M, J92800)are used where
water chemistry permits, and the modern duplex stainless steels of the 25 Cr-5 Ni-3
Mo + N type have better pitting and crevice corrosion resistance in saline waters?
Vertical turbine pumps are commonly used for pumping waters. The materials for
these pumps for fresh and mildly brackish water service are as follows:13
Column pipe--epoxy-coated mild steel

Diffuser-furnace stress-relievedANI-D2W/D2 or welded 316L
Bowl-2%0 nickel cast iron with 316 shroud, or CF8M
Inlet bell-2% nickel cast iron
Impeller-CF3M, CFSM, CD4MCu, CF3, CF8, or austenitic or duplex stainless steels
Shaft-316 or N50,2205,304
Shaft sleeve316 CrOz coated or uncoated.
346 Water Svstems
Other successful fresh water pump materials include stainless, bronze, or Ni-Resist@
bodies with duplex or austenitic stainless steel impellers."
10.1.2.4 Valves
Materials for metal valves range from cast iron to stainless steels and nonferrous metals,
including bronzes and the nickel-based alloys. Gray or ductile iron bodies may be used
with a corrosion-resistant trim,but the more aggressive waters require other alloys (e.g.,
bronze, nickel-bearing stainless steels, nickel cast irons, and even nickel-based alloys
such as alloy 400)?
10.1.3 Once-Through Seawater Cooling Systems
Seawater systems are used in shipping, oil and gas, power plants, and coastal industrial
plants. The seawater is mainly used for cooling but also for fire-fighting, oilfield water
injection, and as supply to desalination plants. All stainless steels have good resistance
to flowing seawater but are not good at resisting corrosion under static conditions, par-
ticularly in crevices. Standard grades of stainless, such as 316, have been found to be
generally unsuitable for seawater systems. Pitting, particularly at or near welds and in
crevices, has often resulted in perforation within a few months. It is necessary, there-
fore, to choose an alloy with better resistance to localized attack, i.e., an alloy with a
high PRE number. Modern grades of stainless steel are available with high resistance
to pitting and crevice corrosion and these are now being used for seawater systems.
These stainlesssteels are typically either austenitic with about 20% chromium, 7% nickel,
and 6% molybdenum, plus nitrogen, or duplex with about 25% chromium, 7% nickel,
4% molybdenum, and nitrogen.
Copper-based alloys and carbon steels are velocity limited and must be used at
velocities below which impingement attack occurs.
Nickel-based alloys such as alloys 625, C-276, and C-22 and titanium are not subject
to pitting or crevice corrosion in low velocity seawater, nor do they suffer impingement
attack at high velocity. However, price often limits their use to special applications in
seawater systems.
Local velocities may vary considerably from design velocity. This is particularly im-
portant where features of the system such as small radius bends, orifices, partly throttled
valves, misaligned flanges, etc. can generate turbulence and give rise to local high veloc-
ities that accelerate corrosion. It follows that design and fabrication of the system should
aim at minimizing turbulence raisers.14
See also seawater systems in Chapter 11,Section 11.10, "Chemical Process Plants."
10.1.3.1 Seawater Exchangers
Coastal plants are sometimes designed to have one large heat exchanger with seawater
on the tube side and multiple, closed-loop cooling systems on the shell side. More often,
10.1 Coolina Water Systems 347
Figure 10.8 Shell and tube heat exchangers are commonly used to cool sulfuric acid. The acid
is in the anodically protected shell and the water flows through the tubes. (Photo courtesy of
Kvaemer Chemetics Equipment Division.)
seawater passes through the heat exchanger tubes while the process fluid to be cooled
passes through the shell (Figure 10.8). Materials must be selected to handle steam or
other working fluids on the shell side as well as the seawater in the tubes. Any leakage
from the tube side will readily contaminate whatever working fluid is on the shell side.
If the process fluids are at high pressure it may be necessary to put the seawater in the
shell. This is not the preferred option and needs special care in design and operation to
prevent deposition, fouling, low velocity/stagnant regions.
10.1.3.1.1 Tubing
Arsenical admiralty brass predominated the field of condensers until the development
of aluminum brass with better impingement corrosion resistance. Much research and
development in the copper industry during the 1920-1960 period was devoted to de-
velopment and enhancement of the stable, protective corrosion film on copper-nickel
alloys. This resulted in the series of alloys that became the industry standard for these
duties, UNS C70600, C71500, C71640, and C72200. These last three alloys became the
standard alloys for seawater use at higher velocities or in the presence of turbulence and
entrained solids.
348 Water Svstems
Table 10.3 Suggested Maximum Design Velocity in Condenser Tubing in Seawater
Max Design Velocity, m/s (ft/s)

Material Ref. 15 Ref. 12 Ref. 16 Ref. 17
Copper 0.91 (3)' - - -
Phosphorus copper (C12200) - 0.6 - 0.76-0.91 (2.5-3)
Silicon bronze 0.91 (3)* - - -
Admiralty brass (C44300) 1.52 (5)' 1.2 - 1.52-1.68 (5-5.5)
Aluminum brass (C68700) 2.43 (8)* 2.4 - 2.13-2.29 (7-7.5)
Aluminum bronze - - - 2.13-2.29 (7-7.5)
90-10 Cu/Ni (C70600) 3.05 (10)' 3.6 - 2.43-3.05 (8-10)
70-30 Cu/Ni (C71500) 3.66 (12)' 4.6 - 3.05-3.66 (10-12)
Copper nickels - - 3.05 (10) -
Cu/Ni (C72200) - >9 - -
Alloy 400, SS316, alloy 825, alloy 20 No max velocity, min 1.52 (5) - - -
Alloy 625, alloy C No velocity limit - - -
Titanium, zirconium, nickel alloys No velocity limit - 6.10 (20) -
* In deaerated brines, e.g., in desalination units, the critical velocity can be increased by 1 to 2 ft/s.
UNS C70600 tubes were also regularly used in the process industry where they were
compatible with process side conditions. When not compatible, duplex or bimetallic
tubes, of either steel or a suitable grade of stainless steel over an internal copper-nickel
tube, were sometimes used." The stated critical design velocity for seawater condensers
varies considerably, particularly in the case of copper-nickel alloys (Table 10.3).A mini-
mum velocity should also be specified; 3 to 4 ft/s (0.91 to 1.22 m/s) is typical.
A rule of thumb for safe maximum velocities for copper-based alloys in small-
diameter (25-mm)heat exchanger tubing is about 3 m/s for 90/10 and about 3.7 m/s for
70/30 Cu/Ni. These velocities can be safely increased by about 0.5 m/s if the seawater
is deaerated. Based on shear stress considerations safe velocities can also be increased
as pipe diameter increases.'*
Tube materials for primary cooling duties include aluminum brass, 90110 and 70/30
Cu/Ni, titanium, 6% Mo stainless steel, and superduplex stainless steels. For secondary
or auxiliary duties admiralty brass, 316L, and 22% Cr duplex tubes could also be con-
sidered."
Titanium tubes are also being used for seawater heat exchangers, e.g., in power plant
condensers, shipboard heaters and coolers, etc. Because titanium has a relatively low
modulus of elasticity baffle spacing must be reduced compared with other alloys. The
low modulus, however, increases the resistance to shock?O
In brackish water carbon steel heat exchanger tubing normally lasts between 1 and
6 years, which can be prolonged by the application of a suitable lacquer. When deposits
are present and the temperature is below 60"C, 316 lasts less than 4 years; 316 is not
used above about 60°C because of the dangers of SCC. More durable choices for this
service have been superduplex stainless steels, such as 2205, which has been used for
more than 20 years even at temperatures above 60°C as long as the velocity is higher
than 1.5 m/s. The duplex stainless steels 2205,2507, and the 6% Mo austenitics are rec-
ommended for brackish or seawater applications for temperatures up to 100°Cprovided
stagnant conditions are avoided. Duplex 2304 and 2205 have also been used in situations
where cleanliness as well as resistance to seawater corrosion is required. Examples are
lubrication and seal oil lines on oil and gas platforms.21
Superduplex and superaustenitic stainless steel tubing are increasingly used in sea-
water heat exchangers. See Chapter 11, Section 11.10, "Chemical Process Plants," and
Chapter 11, Section 11.8, "Oil and Gas," for examples.
10.1.3.1.2 Tu besheets
Tubesheets should be made from the same material as the tubes, or at least a compatible
material to avoid galvaniceffects and make welded joints easier. In seawater,UNS C70600
for tubesheets and tubes is a good selection. If the same alloy cannot be used for both tubes
and tubesheets the alloy used for the tubesheet should not be more noble than the tubing.
If UNS C71500 or C71640 tubes are used, the best tubesheet would be UNS C71500.
Bronze tubesheets are still being used, including UNS C28000 or the leaded alloy UNS
C63500. Aluminum bronze UNS C61400 is also used, but the more corrosion-resistant
nickel-containing alloy, UNS C63000, is often preferred. These tubesheet materials are
anodic to UNS C70600 and C71500 tubing and provide a small measure of protection to
the tube ends.
Solid alloy tubesheets are desirable, although there are some instances in process
industry heat exchangers where clad tubesheets may be used, depending on shell-
side requirements. In the case of clad tubesheets, the tube-to-tubesheet joint should be
welded.12 With titanium or super stainless steel the tubesheet should be a matching
composition, either solid or clad. Tube plate materials for primary cooling duties in-
clude naval brass, NAB, 90/10 Cu/Ni, titanium clad steel, 6% Mo stainless steel, and
superduplex stainless steels. For secondary or auxiliary duties 60/40 or naval brass or
NAB could also be considered."
10.1.3.1.3 Waterboxes
Waterboxes should be generously sized and designed to minimize turbulence at the tube
entry. Waterboxes and return ends should be vented at their highest points. Thin linings
of UNS C70600 have been used in steel waterboxes. The process of attaching the lining to
the steel by metal inert gas (MIG) spot welding was developed in the United Kingdom
by the British Royal Navy.
The nickel-containing cast irons, Ni-Resist@,have been used for small waterboxes
because they have better corrosion resistance than carbon steel and unalloyed cast iron.
If uncoated they will galvanically protect the tubesheets and tube ends but may interfere
with the antifouling characteristics ifl for example, copper-nickel is being used. Solid
350 Water Systems
UNS C70600 or C71500 waterboxes have been widely used in ships and desalination
plants. Sometimes carbon steel clad with Cu/Ni sheet can provide the most economical
design. Cast aluminum-bronze or cast NAB waterboxes are used and, in most cases, are
acceptable with copper-nickel tubes and tubesheets.12 NAB waterboxes are also used
with titanium tubes to avoid galvanic corrosion. These are usually cast since fabricated
boxes need cathodic protection to avoid selective corrosion on welds. For stainless steel
systems, waterboxes can either be rubber-lined carbon steel or made from the same
materials as the piping.14
Unlined carbon steel or cast iron waterboxes used to be used with copper alloy tubing
and as they corroded they tended to protect the rest of the exchanger. If coated carbon
steel waterboxes are used they are normally fitted with CP. Coatings should be an epoxy
(100%solids, coal tar, or heavy duty catalyzed) and should cover the tubesheet and the
first 4 to 6 in. of the tube if copper-nickel or chromium-free nickel alloy tubing is used.
Coating the tube ends is ineffective in the case of titanium, zirconium, or super stainless
steels since 50 to 75% of the tube length may function as the cathode in these alloys. Alloy
heads such as copper-nickel, aluminum-bronze, or super stainless steels can be used for
seawater boxes. Nickel alloys or titanium boxes are suitable but are used rarely because
of cost.16
As well as coated steel waterboxes for primary cooling duties, waterbox materials
include gunmetal, 90/10 Cu/Ni, solid or clad titanium, 6% Mo stainless steel, and su-
perduplex stainlesssteels. For secondary or auxiliary duties cast iron, coated iron or steel,
and gunmetal are also used.” In some cases CP is applied to the waterbox. For exam-
ple, consumable anodes were fitted in a 904L waterbox that was experiencing corrosion
caused by lack of control of the chlorination system (Figure 10.9).
10.1.3.2 Intakes and Strainers
Design, operation, and maintenance of the seawater intake system have a strong effect
on heat exchanger tubing performance. Shipboard systems are relatively simple, since
ships operate in large bodies of water with very low debris and biological loadings and
quite clean seawater, except in port. These intake systems include a grate, flush with or
slightly recessed in the hull, to keep out large logs, fish, or floating garbage. Stationary
screens or strainers are normally provided between the pumps and the waterbox to
screen out smaller debris. Additional screens with small openings are essential ahead of
small-diameter tubes in auxiliary exchangers such as oil coolers and keel co01ers.l~
The design of the intake system for coastal plants is much more elaborate and more
critical. It is preferable to take clean water well offshore and from a depth of at least
30 m but also not within 5 m of the bottom. This deep, mid-column water is less likely
to contain sediments, marine plants, and animal life that will cause fouling or corrosion
problems in the system. It will also have lower chlorine or other biocide demand than
surface waters. However, taking surface, near-shore water is cheaper and needs less
maintenance so is often the approach taken by coastal plants. Typically, the seawater is
directed to the screens, filters, chlorination units, and pumps via a channel constructed
Figure 10.9 Water box of a seawaterheat exchanger showsiron anodesthat were

fitted to control corrosion caused by lack of control of the seawaterchlorination.
(Photocourtesy of CARIAD Consultants.)
from the shore some distance out to sea. This channel helps solids and marine life to settle
prior to reaching the handling equipment. Small plants have channels with galvanized
steel pilings (Figure 10.10), stone, etc., while larger ones tend to have more elaborate
reinforced concrete structures (Figure 10.11).
Large floating debris is kept out of the inlet by the bar grates. These are usually
made of steel or cast iron protected by paint and/or CP,with cathodically protected 316
becoming common. Water velocity through the bar grates must be low enough so that
fish and trash are not held against the screens, reducing the flow area and increasing
velocity through the screens.
Traveling screens downstream of the bar grates remove fish, seashells, twigs, plastic
bags, and similar trash. These screens discharge accumulated debris as they slowly ro-
tate. The hole size in the traveling screens is of the order of 1 / 2 in. (1 cm) or less, and
the heat exchanger tube size is usually set at a minimum of twice the screen opening.
The stationary screens, which may be basket or automatic strainers or filters, provide the
final screening before the cooling water enters the waterbox and tubing. Sometimestwo
strainers are installed; the plant operates until one is plugged and then switches to the
other. The strainer is removed from service, thoroughly cleaned, and the screens repaired
or replaced so that the strainers, not the tube bundle, will remove debris from the system.
The condenser or heat exchanger should never function as a main filter or screen.'*
Other types of screens and filters are made from FRP or coated cast iron body with
UNS NO4400 used for the internal elements.'O
352 Water Svstems
Figure 10.10 This seawater intake channel is made from galvanized

steel sections.It is used to supply seawater to cooling water filters and
pumps for a chemical plant. (Photo courtesy of CARIAD Consultants.)
10.1 Cooline. Water Svsterns 353
Figure 10.1 1 Reinforced concrete channel feeds seawater to the filters

and pumps of a large fertilizer plant in North Africa. The chlorination fa-
cility is seen in the foreground. (Photocourtesy of CARLADConsultants.)
354 Water Svstems
10.1.3.3 Seawater Piping
Many different piping materials are, or have been, used to transport seawater for cooling
or other purposes. Some actual cases are included in Chapter 11, "Applications." The
intention of this section is to provide an overview of the main materials being used for
seawater systems and to present some of the pros and cons of each.
As most alloys are sensitive to seawater velocity many guidelines and standards
exist that provide maximum and minimum velocity limits for seawater piping systems.
For example, the NORSOK standard for process design2 contains recommendations
relating to the velocities for various piping applications (Table 10.4).This states that the
velocities shall, in general, be kept low enough to prevent problems with erosion, water
hammer, pressure surges, noise, vibration, and reaction forces. A compromise has to be
made between line size and pump power.
Other values for critical velocity in seawater related to pipe diameter are given in
British Standard MA 18. It is possible to calculate the critical velocity in m/s for im-
pingement in different pipe diameters. For example, if pipe diameter is 72.15 mm, then
critical velocity is 4.70 m/s. If the pipe diameter is 447.20 mm, the critical velocity for
impingement increases to 5.52 m/s. Therefore, the permitted velocity increases with
pipe diameter irrespective of piping material. These values are based on parallel flow
Table 10.4 NORSOK Recommended Maximum Velocities

for Pipe Sizing
Material Untreated Seawater Deoxygenated Seawater
cs 3 6
SS/Ti 7 No limit
Cu/Ni 3 3
GRP 6 6
Notes:
1. For pipe less than DN200 (8 in.), use velocity limits in
British Standard BS MA-18.
2. For stainless steels and titanium the maximum ve-
locity is limited by system design (available pressure
drop/reaction forces); 7 m/s may be used as a typical
starting value for sizing.
3. Minimum velocity for all materials is 0.8 m/s, with 1.0
m/s for Cu/Ni.
4. If substantial quantities of sand, mud, or silt are present
maximum velocity must be reduced for all pipe materials.
5. When the service is intermittent, the velocity can be in-
creased to 10m/s. For CuNi the maximum velocity is 6 to
10 m/s depending on duration and frequency of opera-
tion.22
Figure 10.12 Cast iron pipes are used to supply coolingseawaterto sulfuricacid heat exchangers.
(Photocourtesy of CAIUAD Consultants.)
tests and do not include any consideration of turbulence, bends, etc. They are only a
guide and are not intended to be used to size pipe or specify maximum flow velocity.23
See also Chapter 4,Section 4.4,"Velocity-Influenced Corrosion," for more data on effect
of velocity on corrosion rates.
10.1.3.3.1 Carbon Steel and Cast Iron
Mild steel, cast iron, and steel with cement or organic coatings are used for low initial
cost piping (Figure 10.12). The corrosion rate of steels in flowing seawater increases
from about 0.1 mm/y under static conditions to almost 1mm/y at 3 m/s. Even when
the design velocity is less than 3 m/s increased corrosion can occur in areas of turbulence.
Also, as pipe thicknesstends to increasewith diameter,experiencehas shown that failures
start in the smaller-diameter pipes. As service life increases, failures occur on larger
diameters so that repair costs accelerate with time. Small-diameter steel or cast iron
pipes are also easily clogged by corrosion products if not in continuous service.14 The
velocity effects on carbon steel are influenced by the oxygen present in the seawater
(Table 10.5).
Next Page
356 Water Svstems
Table 10.5 Corrosion Rates of Carbon Steel in Various

Oxygen and Velocity regime^'^.^
Velocity (m/s) Oxygen (ppb) Corrosion Rate (mm/y)
1 10 0.1
1 100 1.0
2 10 0.25
2 100 2.5
<3 <20 0.025
10.1.3.3.2 Cement-Lined Pipe
Cement-lined pipes are often used to handle seawater. The main considerations here are
listed as follows:
1. Need for care in handling and fitting.If pieces of the lining break off, the area of bare
steel exposed is anodic to the steel embedded in the cement. Potential differences up
to 400 mV have been measured between embedded and exposed steel. The corrosion
rate in such a cell will be determined by the flow of oxygen through the cement and,
as the area relationship of embedded to exposed steel is high, the corrosion rate can
also be high.
2. Joints at valves and fittings. Similar considerations apply as in (1) above. All joints
must be covered with a cement lining if corrosion is to be avoided.
3. Spalling off of linings. If corrosion occurs, corrosion product will tend to cause the
lining to spall off and pieces of lining can partially block heat exchangertubing causing
local impingement attack. Physical damage can also cause the lining to spall with
similar results.
Cement linings are most effective in long, straight runs of large (>1 m) diameter. The
ability to maintain lining integrity decreases rapidly with diameter, number of fittings,
and ~a1ves.l~
Some concrete pipes, popular in North Africa and Europe, are concrete lined inside
and out over a carbon steel pipe core (known as Bonna pipe). When carefully installed
these can and have given long service in seawater and are often preferred for under-
ground supply with, for example, FRP aboveground.
10.1.3.3.3 Copper Alloys
When using copper-based piping the system must be designed on the basis of water
velocity in order to avoid impingement attack.Typical velocity limits for aluminum brass,
70/30 Cu/Ni, and 90/10 Cu/Ni are 2.5,3.0, and 3.5 m/s, respectively.Two copper-based
alloys have been widely used for seawater handling, namely, aluminum brass and 90/10
copper-nickel. In recent years, particularly for large-diameter piping, there has been a
Previous Page
10.1 Cooline Water Svsterns 357
strong trend toward 90/10 copper-nickel because of its better weldability, its high stress
corrosion resistance, and its good experience.
Some use has been made of aluminum bronzes for piping in components such as
pump columns. NAB is preferred for seawater usually in the cast form (UNS C95800).
Care is needed with components fabricated from plate as the heat-affected zones are
sensitive to selective attack (dealuminification)which can lead to cracking. Risk of this
can be reduced by heat treatment (at 650 to 675°C for 6 h) after welding.
The design water velocities given above worked well over many years and, as expe-
rience has been good, there has been a tendency to raise limits to achieve economies in
pipe costs.14
10.1.3.3.4 Stainless Steels and Nickel Alloys
For details on the use of these alloys in seawater piping for offshore applications see
Chapter 11,Section 11.8, ”Oil and Gas.”
Duplex steels such as 2205 or 6% Mo austenitics are the preferred grades in high
chloride fresh waters or seawater. Nickel-based alloys (e.g., alloy 625) are used for sea-
water piping that is intermittently stagnant or polluted? Ferritic stainless steels have
not found much application in this service, partly because of the difficulties in welding
thick-walled pipe. Duplex alloys have found many applications in seawater, particularly
where their higher strength and lower thermal expansion compared with the austenitics
are beneficial. There have been reports of failures of 2205 from SCC in the presence of hy-
drogen sulfide contamination. The 6% molybdenum austenitic stainless steels are being
used extensively in seawater systems with few problems.26
10.1.3.3.5 Titanium
After testing a titanium pipe loop in Key West, FL the U.S. Navy decided to specify an all-
titanium firemain water piping system for the new generation craft, the LPD 17. The life
cycle cost calculation by the navy showed this titanium option to be more cost-effective
than the copper-nickel alloy normally used for this a p p l i c a t i ~ n . ~ ~
Titanium seawater piping does not require repair or replacement for erosion corrosion
over the ship’s life (contrasted with the seven to eight times customary for Cu/Ni).
As it has improved design features, greater life expectancy, and reduced maintenance
requirements it is slated for installation as part of the midlife maintenance upgrade for
five LHA Tarawa-class amphibious assault ships. It will provide the same improved
performance for ship upgrades and new construction.28
10.1.3.3.6 Plastics
A range of FRP piping is used in seawater, including various polyesters and epoxies,
usually reinforced with glass fibers. For example, GRE (glass-reinforced epoxy) piping
has been used for seawater in offshore oil and gas operations since 1974. This piping is
358 Water Systems
routinely used to transport such waters as fire, potable, drain, sea, produced, ballast, and
waterflood injection as well as for seawater cooling to heat exchangers. Some potential
problems in the use of FRP have not been borne out by experience. These include the
following:
Susceptibility to impact. Where a substantial impact incident occurs with GRE, the
damage at point of impact is usually restricted to a break in the pipe liner. Water will
migrate through the liner and cause a wet spot on the outer surface. Very rarely will
impact cause catastrophic failure of the GRE line. In an incident in which a crane
dropped a 200-L container full of set concrete from about 6 m onto an empty pipe, the
pipe showed little evidence of the impact. This line was hydrotested at 28 bar for 1 h
and during that test the impact point leaked at a rate of less than 500 mL/h.
Joint making. Standard GRE pipe joints, such as Bondstrand@ Quick-Lock or
Taper/Taper joints, are simpler to make than welded joints in alloy systems used
in seawater piping. The training required to make GRE joints is less than the training
required for Code welding of metals.
Lack of non-destructive test (NDT) methods. Apart from a hydrotest for 60 min at
1.5 times the design pressure, no NDT is normally applied or needed.
Aging does occur with some plastic pipes but not with good quality GRE materials.
Osmosis can also occur on some plastic pipes but not on properly made GRE piping.
UV damage does occur with GRE pipes but the damageis limited to the resin-richouter
surface of the pipe, producing a ”bloom.” This bloom prevents further penetration of
UV. Pipe spools that have been exposed to full UV in the desert in the Middle East for
some 14 years have been tested for loss of mechanicalpropertiesand have been found
to have suffered less than 10% loss of the original design properties when installed.
If the pipe is painted, no bloom will
FRP pipe is also used for handling seawater in industries other than offshore oil
and gas. For example, coastal chemical and power plants routinely use FRP piping to
deliver seawater for cooling duties. In some cases similar piping is used as for offshore
oil platforms, e.g., GRE, but in other cases specifications based on polyesters are used
successfully (see Chapter 11, Section 11.10, ”Chemical Process Plants”).
Deep water air conditioningsystems consist of seawater supply, a freshwater circula-
tion system, and heat exchangers to transfer heat between them. High molecular weight
polyethylene piping is used for this seawater duty in Hawaii with intake depths of 650
to 700 m.
10.1.3.3.7 Rubber or Other Polymeric-Lined Pipe
Other types of linings have been considered and sometimes used for seawater piping. A
study by the British Ship Research Association on a wide range of pipe linings showed
that only two, namely, chloroprene and soft natural rubber, withstood laboratory tests
simulating shipboard conditions. They were cheaper than nonferrous piping only in
sizes above about 150 mm diameter. When installed costs were included on an offshore
platform, lined pipe had only a marginal cost advantage over 90/10 Cu/Ni piping. The
advantage in materials cost was offset by the extra care needed for installati~n.'~
The interior of all the seawater intake lines and deaerator vessels at a Dubai desalina-
tion plant were lined with a glass flake polyester coating. The evaporator channel head
boxes were ebonite (hard rubber)lined. An inspectionafter 5 years of continual operation
showed that the linings were in good condition and required no remedial work.30
10.1.3.4 Pumps
Conventional stainless steels such as 316L and the cast CF 3M are widely used for sea-
water pumps and give good service as long as the pump is never left under stagnant
conditions. The combination of 316L impeller and Ni-Resist@or NAB casing works well
since the casing provides cathodic protection. Applied CP is often used to improve the
life of stainless pumps. Stainless steel pumps are also particularly well suited to pump-
ing seawater that has lower oxygen levels (10 ppb instead of the normal 8 ppm), e.g., in
desalination plants and for seawater injection pumps.
To be able to pump seawater at various temperatures, oxygen content, pH, etc., it is
becoming more common to use one of the super stainless steels such as cast UNS S31254,
Inco alloy 862 (Cu, 31 Ni, 1.8 Cr), or the duplex alloys Ferralium 255 (UNS S32550)
or Zeron 100 (UNS S32760). The high strength of these duplex alloys has the added
advantage in weight saving that is important in many offshore applications. Wrought
nickel-basedalloys such as alloys K500 and 625 are commonly used for shafts in seawater
pumps because of their high strengths under fatigue conditions and excellent corrosion
resistance in flowing or stagnant seawater. Titanium is an excellent choice for seawater
pumps where weight and freedom from maintenance are the overriding factors; for
example, they are being used by the U.S.Navy for fire-fighting pumps?l
The impeller of a pump is in contact with fast flowing, highly turbulent seawater, and
for circulating pumps in continuous use they should be made from a material with high
resistance to these conditions.The use of cast iron or mild steel can only be contemplated
in pumps operated occasionally.Ni/Cu, alloys400 and K-500, and 316 stainlesssteelhave
good resistance to flowing seawater, and cast versions of these alloys are preferred for
pump impellers.
These alloys do not suffer from impingement attack but may pit when the pump is
stationary and full of seawater. It should be noted, however, that pitting is often less
severe than the general impingement corrosion that may occur at the tip of a copper-
based alloy impeller, and hence stainless steel or cast alloy 400 are preferred for this
application. Alloy 20 and some higher alloy duplex stainless steel with higher resis-
tance to pitting than 316 stainless steel are sometimes used for impellers in seawater
service.
For Ni-Resist@Type D-2 pump casings, cast stainless steel impellers are preferred.
The cast iron being somewhat anodic to stainless steel gives a beneficial galvanic effect
which lessens the risk of pitting on the impeller when the pump is ~tationary.'~ The
360 Water Svstems
Table 10.6 Some Successful Materials Combinations Used in Seawater

Pumps for Various Duties32
Impeller Case Shaft
Firewater and 316 Austenitic cast iron Alloy K-500
seawater lift 25%Cr duplex 25%Cr duplex
NAB NAB 25%Cr duplex
Gunmetal Alloy K-500
Superduplex
25%Cr duplex 25%Cr duplex Superduplex
Superduplex Superduplex Superduplex
Auxiliary NAB NAB 316L
Gunmetal 25%Cr duplex
Alloy K-500
Gunmetal Gunmetal NAB
316L
25%Cr duplex
316 Austenitic cast iron Alloy K-500
Cast iron 25%Cr duplex
Injection 25%Cr duplex 25%Cr duplex Superduplex
Superduplex Superduplex Superduplex
combination of materials used in pumps is important if galvanic corrosion of some of

the components is to be avoided (Table 10.6).
The grouping of metals within each use category are based on galvanic compatibil-
ity and these combinations should not be subject to major galvanic corrosion effects.
For more information on these compatible alloy groupings see Chapter 4, Section 4.5,
“Galvanic Attack.” Another successful specification for seawater pumps is NiResist@
with an alloy 400 impeller.1°
Casting alloys recommended for seawater valve and pump applications in power
plants include the duplex alloys CD-~MCU, alloy 255, alloy 2205, FMN,UNS S32760,
and S39276; the austenitics 904L, alloy 411, 6% Mo super stainless, and the alloys C-4,
C-22, and C-276.The austeniticswith less than 6%Mo should be cathodicallyprotected.33
Ferrous materials recommended for use in vertical turbine pumps for saline water are
given in Table 10.7, and copper alloys for brackish and recirculated water in Table 10.8.
For stainless steel piping systems, the pumps should be of similar materials. During
operation, the risk of pitting and crevice corrosion is reduced as the metal surfaces are
either exposed to fast-flowing seawater or are subject to slight relative movement, which
appears to discourage crevice corrosion. However, if seawater is left standing in the pump
during shutdown, pitting and crevice corrosion are likely. This problem can be solved
by either flushing the pump with fresh water or operating it every few days.
The speed of rotation of centrifugal pumps is normallytoo high for copper alloys to
be used for impellers. There is, however, normally sufficient clearance left between the
impeller and the casing so that the water flowing from the impeller does not impinge
Table 10.7 Ferrous Materials for Vertical Turbine Pumps-Saline

Water Service13
Part Preferred Alternatives
Transition CFSM, 316L(W) ANI-D2W /D2(FSR)
Section Epoxy-coated steel
Column pipe ANI-D2W, D2,316L(W) Epoxy-coated steel
Diffuser ANI-D2W / D2-(FSR) 316L(W)
Bowl ANI-D2W/D2 (FSR) CF8M
with 316 shroud
Inlet bell ANI-D2W /D2(FSR) ANI-D2W/ D2-(FSR)
Impeller CF3M, CFSM, CD4MCu Austenitic and duplex
stainless steels with Mo
Shaft N04400,316 N50 (UNS S32910), 2205
Shaft sleeve N04400,316L CrO2 coated N04400,316
(FSR) = Furnace stress relieved.
(W) = Welded.
directly on the casing but is absorbed into the slower moving stream of water flowing
over the metal surface toward the pump delivery pipe. Provided direct impingement is
avoided, materials such as gunmetals, aluminum bronze, and cast 70/30 Cu/Ni perform
satisfactorily,although cases of premature pump casing failures have shown that direct
impingement can occur. Increase in pump speed or output above standard pump limits
may have been the cause. Where such failures have been experienced, the life of the
casing has been very short, e.g., around 18 months. To avoid failures of this type, the
design must be amended to reduce seawater velocity at the metal surface, or materials of
higher resistance must be used. Experience shows that cast 70/30 Cu/Ni and 5% NAB
are more resistant than gunmetal or tinbronzes. The chromium-containing70/30 Cu/Ni
has even higher resistance than other copper-based alloys to fast-flowing seawater.
Table 10.8 Copper Alloys for Vertical Turbine

Pumps-Brackish and Recirculated Waters (up to
12,000 ppm chloride^)'^
Part Preferred
Column pipe C61300(W), C164OO(W)
Diffuser Modified C95500,
C61300(W), C63000(W)
Bowl C95400, C61400(W)
Inlet bell C95400, ANI-DW2/D2
Impeller Modified C95500
Shaft C63000
(W) = Welded.
362 Water Svstems
Suggested maximum peripheral velocities for some copper-based alloys for pumps
or propellers are shown below:
Leaded red brass and silicon brass (UNS C83600 and C87600) t 9 . 1 m/s ( t 3 0 ft/s)
Tim bronze and leaded tin bronze (UNS C90300 and C92200) t13.7 m/s ( t 4 5 ft/s)
Manganese bronze (UNS C86500) and aluminum bronzes (UNS C95200, C95500,
C95700, and C95800) >22.8 m/s (>7 ft/s)34
To date, several hundred vertical heavy duty seawater supply and brine pumps with
silicon carbide bearings have given years of excellent service. As an example, they have
proved to be the ideal bearing design for offshore heavy duty high speed seawater
injection pumps (capacity 625 m3/h, head 2,200 m, shaft speed 3,600 rpm, power 5 MW).
The cooling water, seawater supply, and brine pumps of the large-scale, MSF plant at
A1 Taweelah B in Abu Dhabi are also equipped with silicon carbide bearings.35
10.1.3.5 Valves
Many corrosion problems in seawater systems occur in valves. These problems can be
caused by the use of steel or cast iron valves with non-ferrous piping. Although the life
of such valves in a steel or cast iron pipe system is short (i.e., 2 to 3 years), galvanic effects
may reduce it to less than a year in a copper-based system. Even in a system with a low
nominal seawater velocity turbulence and much higher local velocities may develop in
the valve, particularly if it is used for control.
The basic low cost valve used in ferrous pipe systems has a cast iron body with 60/40
brass internals. Depending on design, corrosion rates of several mm/y can occur on
the body which cathodically protects the intemals. Once a layer of graphitic corrosion
product forms this protection stops. Generally such a valve will function for 2 to 3 years.
Coatings on valve bodies are often used but their success depends mainly on the valve
design. Any break or defect in the coating can result in intense corrosion and perforation
of the valve body.
Upgrading of valve body materials to give higher reliability requires the use of more
resistant alloys such as Ni-Resist@austenitic cast irons and copper-based alloys such as
NAB, admiralty and leaded gunmetals, and cast copper-nickels. All of these alloys are
characterizedby good resistance to static seawater (necessaryfor shutdown conditions)
and to flowing seawater. Where impingement is a possibility, alloys such as NAB or cast
copper-nickel (plus chromium) should be used.
Ni-Resist@iron valves are often used in ferrous systems to improve valve reliability.
NAB has high strength and this makes it attractive, particularly for large valves. Also, it
has high resistance to impingement attack and this may be of importance in globe valves
used under throttling conditions.
Stainless steels have high resistance to flow, so no problems should arise from erosion
corrosion when used for valve bodies, but cavitation can occur if flow is turbulent.
The 7-m/s valve used in the offshore industry takes cavitation into account. As pitting
and crevice corrosion are important in valves, alloys with similar resistance to that of the
piping are needed for valve bodies. Cast valve bodies are available in many of the high
alloy stainless steels, or they can be fabricated from wrought material.
Valve seats, particularly those in throttling service, experience high water velocities.
Stainless steels, nickel-based alloys, and alloy 400 should be used. Type 316 seats give
good life in a nonferrous valve but are liable to pit (particularly in crevices) and on a
life cycle cost basis, the nickel-copper alloys may be a better choice. Stainless steels with
lower alloy content than 316 can pit very rapidly in seawater. Such materials are 12%Cr
(Type 410 UNS 41000) and 18%Cr (Type 430 UNS 43000) stainless steels. These alloys
usually fail rapidly in seawater systems.
In ball and butterfly valves, one of the seats may be nonmetallic, e.g., an elastomer.
Alloy 625, which has high resistance to both static and flowing seawater, has been used
as a weld overlay to produce highly resistant surfacesin critical areas of valves and shafts
and also on pump castings. This alloy has excellent weld deposition characteristics and
can be used as a general purpose overlay for avoidanceof, or repair to, areas of corrosion
damage in carbon and low alloy and stainless steel components.
Valve seats can be machined areas on the valve body, disc, gate, or ball, depending
on the valve design. In some cases separate seats are used so that they can be readily
replaced in case of mechanical damage. In such cases the seat material can be different
from the body or disc material. For example, the greater hardness of a high alloy duplex
stainless steel seat may be of benefit in a high alloy austenitic alloy component.
Stems in stainless steel valves are made of materials with similar corrosion resistance
to the body. The higher strength of duplex stainless steel makes them attractive for stems.
All copper-based alloys have similar potential and can be used together without
serious galvanic effects. Where carbon steel or cast iron bodies have brass trim, the
brass will have received considerable galvanic protection from the large area of ferrous
material and may give a useful life. Upgrading the body material to copper-basedalloys
can, by removing the CP effect, cause corrosion of the trim. It is good practice for the
trim material to be cathodic to the body, hence the use of alloys such as alloys 400 and
K-500 and stainless steels. The use of copper alloy valves is desirable in copper alloy
pipe systems to retain galvanic compatibility. The use of unprotected ferrous valves in
nonferrous systems should be avoided.
Nonferrous valves are sometimes used in steel piping systems and while this will
lengthen the life of the valve, galvanic corrosion of the piping adjacent to the valve may
occur. A better choice of valve material in steel systems would be Ni-Resist' cast iron,
as this is galvanically more compatible with steel.
For stainless steel systems, galvanic compatibility is not a problem in the system
itself, even though different alloys may be used for different components.Care is needed,
however, if the system is used to supply copper alloy heat exchangers, as there can be
a pronounced galvanic effect between stainless steels and copper-based alloys. This can
be prevented by fitting iron, zinc, or aluminum anodes in the waterb~xes.'~
High performance materials are being evaluated by the U.S.Navy for seawater valve
applications. Of particular interest are the galvanic interactions between commercially
pure titanium and 90/10 Cu/Ni (UNS C70600) piping alloys and the prospective valve
materials as well as the galvanic relationships between valve body and valve trim ma-
terials. Galvanic couples with area ratios representative of piping material/valve body
364 Water Svqtems
and valve body/valve trim were immersed in quiescent, natural seawater for 180 days.
Uncoupled control specimens of the valve and piping materials were also exposed. Tita-
nium piping was compatiblewith Ti-45Nb, titanium, and Ni-Cr-Mo alloys for valve body
and trim; 90/10 Cu/Ni piping material was galvanically compatible with 70/30 Cu/Ni,
CW6MC, or stainless alloys such as CN7M, CN3MN, or CK3MCuN for valve body ap-
plication (piping body area ratios of 1O:l or greater). For the valve trim components in
the 90110 piping system, alloy 400, CN7M, alloy 2507, UNS N08367, commercially pure
titanium, and Ni-Cr-Mo alloys are recommended. Coupling anodized titanium with
untreated titanium did not result in adverse galvanic effects. Poor performance of cast
alloys in the galvanic couple tests emphasized the need for optimum quality castings or
utilization of similar wrought compositions to ensure good seawater performance.%
10.1.4 Recirculating Water
When cooling water is recirculated within the plant it is usually cooled by a cooling tower
and chemicallytreated to avoid scaling, fouling, and corrosion.Pumps, valves, filters, and
heat exchangers are often 300 series stainless steels, but they are rarely used for piping.
There are many examples of failures of 300 series heat exchangers using recirculating
water. Some of these failures have been positively identified as MIC, often caused by
incorrect water treatment or interruption of water The normal materials used for
piping is carbon steel because the water is always treated. If carbon steel is compatible
with the process it is also used for heat exchangers.
10.1.4.1 Cooling Tower Types
Cooling towers are categorized by the way they make air and water interact. In the
counterflow tower water falls down as the air passes up. In the crossflow tower, water
flow is down while the air flow is horizontal. When a crossflow tower is constructed with
two opposing air streams joining in a common plenum, the design is called a "double
flow," crossflow tower.
Counterflow towers tend to be the most compact. This is because the coldest air is in
intimate contact with the entire cross section of water just before it falls into the basin.
Space is saved by this increased efficiency and the fact that unlike crossflow towers
they do not need a plenum. Because the air flows in direct opposition to the water flow
increased fan horsepower is needed. Operational cost savings make crossflow towers
popular. They often have the lowest initial cost and a simple, easy-to-maintain design.
Blow-through designs generally have easier mechanical component access because the
moving parts are located at the base. They are less prone to corrosionbecause they handle
dry, ambient air instead of the saturated air of the draw-through arrangement.
Another distinction involves the location of the fan as in "blow-through or "draw-
through and is determined by whether air is pushed into or pulled through the tower.
Yet another distinction is made between factory- and field-assembled towers.
Factory-assembled towers are limited by the practicality of transporting large loads
Figure 10.1 3 Photo showsa power station and four concrete,hyperboliccooling

towers to the right. (Photo courtesy of CARIAD Consultants.)
by trucks with typical limits of 14 ft W x 12 ft H x 48 ft L (4.3 x 3.7 x 14.6 m). Large

factory-assembled cooling towers are shipped in multiple sections for assembly at the
job site. The biggest single-cell crossflow tower manufactured in the United States is
about 1,050 nominal tons. For counterflow, it is about 1,350 nominal tons. Both must be
broken into several pieces for transport. Multiple factory-assembled cooling towers are
used but there comes a point where field-erected towers become more practical.
Towers built on site are wood, steel, fiberglass, or concrete, typically on a concrete
basin, although fiberglass or steel basins are used on smaller models. Very large projects
such as power plants can employ hyperbolic cooling towers, characterized by their dis-
tinct shape (Figure 10.13). These towers have the advantage of not requiring any fans,
motors, gear boxes, etc. The design consists of a ring of wet deck surface arranged in a
crossflow fashion encircling the base of the tower. The center contains a large, hyperbol-
ically shaped chimney. Any warm air at the base of the chimney rises and accelerates
as the cross section diminishes, creating a negative pressure that draws additional air
through the wet deck fill. Such towers need little control, with capacity increasing as the
cooling requirements increase. Pumping costs would be high for conventional cooling
towers built to an appropriate scale for such projects. The low elevation of the hot water
distribution basins offers substantial pump horsepower savings.38
10.1.4.2 Cooling Tower Materials
Redwood was an early favorite as a construction material for cooling towers because of
its natural tendency to inhibit decay. As supplies of good quality redwood diminished,
366 Water Svstems
Douglas fir began to be used. Its superior strength allowed the use of fewer structural
members but it deteriorated more easily so treatments were developed to reduce this
decay.The wood is either incised, then exposed to the treating chemicals, or exposed to a
vacuum followedby a pressure treatment to ensure entry of the chemicals into the wood.
At about the same time that fir began to replace redwood, ever larger factory-
assembled steel units began to be more widely used. Galvanized steel performed well
with the water treatment chemicals of the day, chromates and acid. Acid was used to
lower the pH allowing higher cycles of concentration of the dissolved solids, while chro-
mates controlled the corrosionthat would otherwiseoccur.Asbestoscementboard casing
side panels were common on field-erected cooling towers. Asbestos was also found in
the wet deck and sealing compounds of many towers.
Increasing environmentalconcerns in the 1970ssaw the end of chromates except for
a few very large facilities, where they were removed from the discharge water at site
treatment facilities. Without chromates, the low pH water was very corrosive and many
cooling towers and piping systems corroded very quickly. Substitutes have never lived
up to chromates for effectiveness and cost. The potential hazards of wood treatment
chemicals became more apparent, causing revised formulations and tighter controls,
both leading to increased costs. Asbestos came into disfavor and was quickly replaced
in cooling towers as the manufacturers became more aware of the potential health and
financial hazards.
Type 304 stainlesssteelbecamemore popular as the probabilityof corrosionincreased.
Manufacturers simply substituted stainless steel for galvanized steel components. To
save costs, typically only the cold water basin was upgraded to stainless steel. There
were cases where galvanized and stainless steels were fastened together below the wa-
ter line causing rapid galvanic corrosion of the galvanized steel. Type 316 stainless steel
is sometimes used for nuts, bolts, and some small subassembliesbut it is largely incom-
patible with the tooling used by the manufacturers.
The galvanized steel cooling tower has remained the factory-assembled standard.
The thickness of the steel has steadily declined with more economical designs, while the
thickness of the zinc layer has steadily increased to a current standard of G235 (2.35oz. of
zinc per fl?) from a 1970s standard of G90 (0.90 oz/fl?). This thickening of the sacrificial
zinc layer has had a beneficial effect on cooling tower life. Various enhancements to the
galvanized steel in the form of barriers have been used by some manufacturers. Their
suitability largely depends on the local water quality.
Concrete can be an excellent construction material for basins and even for side walls,
fan decks, discharge stacks, and mechanical support beams. Its use beyond basins, how-
ever, is not justified for typical commercial applications.Extensive concrete construction
is used for architectural reasons, eg., where the tower is disguised to look like or blend
in with a building or the cooling tower is designed as a structure with a life expectancy
equal to the facility it serves, such as a hospital or university.
Pultruded fiberglass is increasingly replacing steel in structural applications. These
are composites with precisely located glass fibers that make the parts very strong. This
allows the additionof surfacetreatmentsthat limit ultra-violetdegradation, an important
requirement for cooling tower duty.
10.2 Cooline Water Treatment 367
Fill, also called ”wet deck” or “surface,”is the heart of most cooling towers. Generally,
it takes the form of a PVC film-type surface. Water is made to spread out on this surface,
maximizing its contact area with air to encourage evaporation. It consists of individual
vacuum-formed sheets with proprietary patterns of ridges, bumps, and wrinkles. When
arranged vertically (side-by-side),the individual sheets space themselves apart leaving
passagewaysfor water and air. The sheets can simply press against each other or be glued
together. Edges can be folded for increased strength. Expanded metal is also sometimes
used for mesh grids.%Mesh grids made from the ferritic stainless steel 3CR12 has been
used in cooling towers exposed to circulatingpurified sewage effl~ent.3~
Sinceits first introduction to the market in the 1970s,cooling tower film fill technology
has significantly increased thermal performance and reduced the size of cooling towers.
However, the narrow spaces between film fill sheets make them more susceptible to
fouling. Without proper chemical treatment, deposits can accumulate within the film
fill resulting in reduced tower efficiency, increased fouling, and plugging of the fill.
These phenomena can eventually lead to collapse of the tower structure.4oA coal-fired
electrical generating station experienced a gradual loss of cooling tower efficiency after
they changed part of their fiber sheet fill with a high efficiency fill. This loss of efficiency
was caused by fouling that consisted mainly of silt with appreciable levels of bacteria.
The problem was solved when the existing intermittent treatment with nonoxidizing
biocide and cationic dispersant polymer was replaced by a continuous, low level feed of
silt and iron dispersantstogether with surfactant-basedbromine biocide. The dispersant
dosage was continuously controlled with fluorescence-basedtechnology?
All plastic cooling towers are available in smaller size units. Seamless HDPE shells
enclose PVC fill and other plastic components for forced draft towers up to 400 ton
capacity and induced draft units up to 4,000 ton capacity. These all-plastic cooling towers
have been in reliable operation for many years.42
10.2 COOLING WATER TREATMENT
Coolingwater, particularly in recirculating systems, is typically treated to control fouling,

scaling, and corrosion. Sometimes the requirements of these three aspects of treatment
are in conflict and the challenge is to provide a treatment that will control all aspects at
minimum cost and environmental impact.
10.2.1 Inorganic Fouling and Deposit Control
Deposit problems can be divided into two parts: fouling and scale. Fouling is the ac-
cumulation of suspended solids in the water on heat exchanger surfaces. It may be
biological, inorganic, or mixed. Biological fouling, or biofouling, is caused by microbial
slimes and/or large organisms, such as mussels or barnacles. Scale is predominantly
inorganic materials that are supersaturated in the water and become deposited on the
368 Water Systems
heat exchange surface. Although the distinction is somewhat arbitrary, scale is typically
more adherent and homogeneous than fouling. All deposits can lead to reduced heat
transfer and the possibility of underdeposit corrosion.
Fouling not only reduces heat transfer but also prevents treatment chemicals, such
as corrosion inhibitors, from reaching the metal surfaces. Insoluble substances sus-
pended in the cooling water are the usual cause of fouling. These substances can be
natural, such as mud, silt, dust, micro- and macro-organisms or vegetation, or artifi-
cial, such as coagulants, flocculants, detergents, sewage, corrosion products, or inhibitor
reactants.
10.2.1.1 Design and Operation
Control of fouling starts with design-avoid low velocity areas that encourage settling
out of particles, particularly in heat exchangers. Avoid water on the shell side of ex-
changers wherever possible. Low velocity regions are unavoidable on the shell side,
making deposition more likely (Figure 10.14). In general, fouling will increase with in-
creased temperature so avoid rapid temperature changes, for example, at shut down and
startup. Fouling deposits can be removed regularly from critical equipment by passing
balls through heat exchanger tubes or regularly water jetting, but it is better to prevent
deposits forming rather than to have to remove them.
Figure 10.14 The outsideof the tubes are heavily fouled in a heat exchangerwith
the cooling water on the shell side. (Photocourtesy of CARIAD Consultants.)
10.2 Coolina Water Treatment 369
10.2.1.2 Filtration
Filters are used to help control fouling. A 100-ton cooling tower processes about 40 tons
of air in an 8-h period retaining all the airborne debris in the tower water. Ideally, this
debris would stay in suspension and be removed by the bleed, but a good portion
typically manages to settle in the tower basin and on heat exchange surfaces.
Full flow filtration can use pairs of strainers, one in operation while the other is
being backwashed. Alternative full flow filtration needs devices that operate with low
pressure drop, for example, centrifugal separators.The centrifugal separator directs the
water flow tangentially into a cylinder causing the water to rotate. Debris particles that
are heavier than water migrate to the outer wall area and slide down into a collection
bowl that is periodically blown down. Very little water is lost. Typical performance is the
removal of 97.8% of solids with specific gravity exceeding 1.2 down to 45 pm diameter.
Side stream filtration is more common in cooling tower applications. This uses a
small dedicated pump to draw dirty water from the sump, direct it through a filtration
device, and send it back to the basin. In addition to being smaller and less expensive, side
stream filtration has the advantage of allowing the return water to be routed through
a perforated PVC distribution pipework or, better yet, nozzle jets that agitate the water
at the basin floor, placing the debris in suspension and increasing its chances of being
drawn into the filter suction piping.43
The actual side stream filtration device can be a centrifugalseparator, strainer device,
or sand bed filter. The sand bed filter is especially effective in removing particulate
matter, including the lightweight biological material killed by biocides. Filtration to 10
pm is commonplace.When the sand begins to get clogged, a pressure differential switch
signals a backwash cycle that lasts about 3 min. The valves reposition to reverse the
flow through the sand bed lifting it and carrying off debris to the drain. Side stream
filtration devices applied to open cooling towers are typically sized to pass the entire
system volume at least once each hour for good water clarity.
When the system volume is not known, and for all evaporative condensers and fluid
coolers, the filter can be sized from the air flow by the formula%:
Filter GPM = Cooling Tower CFM x 0.0004
10.2.1.3 Dispersants and Coagulants
Chemicals are available to help treat fouling problems. Dispersants, such as polyacry-
lates, help reduce fouling as well as scaling. Flocculants,such as polyacrylamides, cause
the fine particles to agglomerateand form a removable sludge.43Particulatesin the water
can be treated by mechanical means, e.g., side stream filtration with coagulation or by
chemical additives such as surfactants or polymeric dispersants to prevent settling and
allow removal through blow down.@
Biodispersants are nontoxic, surface-active agents which are added to break up mi-
crobial aggregates suspended in the bulk water, disperse biofilms, and improve the
370 Water Svstems
penetration and activity of biocides. They are frequently used in conjunction with bio-
cides to improve their effectiveness and assist biofilm removal. Biodispersants may be
cationic, anionic, nonionic, or amphoteric and are described as biopenetrants or biode-
tergents. Biodispersants are fed as either intermittent slug or continuously, depending
on the severity of the fouling and biodispersant chemistry.
Low foaming, non-ionic surfactants are also used to mobilize oily foulants. They
damage the cell by reducing permeability, disrupting nutrient flow into the cell and
waste removal out of the cell.45
Biofilms in a coke oven coolingsystemwere removed by the additionof an antifoulant
dispersant, biodispersant, oxidizing biocide, and nonoxidizingbiocide. A total of 930 kg
of material was dispersed as suspended solids into the bulk water and removed by
bleed-off in 20 days.&
10.2.2 Scaling Control
Water is said to be saturated with calcium carbonate when it will neither dissolve nor
precipitate calcium carbonate scale. This equilibriumcondition is based on water, at con-
stant temperature, which is allowed to remain undisturbed for an infinite period of time.
Water is said to be undersaturated if it can still dissolve calcium carbonate and super-
saturated if it will precipitate calcium carbonate when allowed to rest. The rate of scale
formation depends mainly on the temperature, alkalinity or acidity, and the amount of
scale-formingmaterial in the water. The most frequent scale-formingcompounds in wa-
ter are calcium carbonate, calcium sulfate, calcium phosphate, magnesium silicate, and
silica. Scaling is caused less frequently by iron oxide, zinc phosphate, calcium fluoride,
and iron carb0nate.4~
Silica deposition results from polymerization, coprecipitation with other minerals,
precipitation with multivalent ions, and biological activity. These processes may be con-
current.Silicaproduces a hard scalewhen calcium carbonateor other mineral precipitates
form a crystalline matrix to hold the silica. Control of silica deposition is best achieved
by overall water treatment that controls scale, deposition, biofouling, and corrosion,
although the use of silica polymerization inhibitors and dispersants may help!7
Scale buildup can be minimized by controlling the cycles of concentration, i.e., the
number of times the ions in the water have been concentratedin the cooling tower basin.
This is normally monitored by measurement of conductivity and using this value to
control addition of fresh makeup water.
Scale formation is also controlled in a number of ways:
1. Removal or reduction of the scale-formingminerals, by lime softening,ion exchange,

or reverse osmosis.
2. Increasingthe water solubilityof the scale-formingmineralsby adding chemicals such
as acids (sulfuric, hydrochloric, citric, sulfamic) or complexing chemicals, e.g., phos-
phates, polyacrylates, or phosphonates. This method does not work on silica scaling.
3. Modifymg the scale-forming mineral so that it precipitates as a removable sludge
rather than as a hard deposit. The sludge can then be removed in the cooling tower or
flushed out. Crystal modifiers include polymaleic acid and sulfonated polystyrenes
that have largely replaced the lignins, tannins, and starches used previ~usly.~~
Chemicals used to prevent scaling usually work by forming chelates with the metal
ions that would otherwise form scaleson surfaces.The most common group of chemicals
for this use are phosphate and phosphonates, many of which are toxic. In recent years
new groups of chemicals,based on polyacrylic acid (PAC)and on polyacrylamide (PAM),
have been developed to replace some of the phosphorus-based antiscaling chemicals.
Although PAC and PAM are nontoxic they are also nonbiodegradableso have an adverse
environmental effect. A "greener" scale inhibitor appears to be thermal polyaspartate
(TPA), which can be used to inhibit calcium carbonate, calcium sulfate, and barium
sulfate scale. TPA is nontoxic and biodegradable and can also act as a corrosion inhibitor
in oilfield applications in the presence of carbon dioxide.48
10.2.2.1 Scaling Indices
Calcium carbonate is the most common form of scaling chemical and it is possible to
predict whether scaling will occur at a given pH and temperature using one of many
scaling indices. These indices indicate the tendency of any particular water to deposit or
dissolve carbonate scale. If scaling is predicted this does not mean that corrosion will not
occur; the scales formed can be continuous and protective, porous and nonprotective, or
discontinuous leading to localized corrosion. Scaling indices cannot be used to predict
the corrosivity of waters since that depends on other factors such as the metals involved,
chlorides, sulfates, oxygen, velocity, etc. For example, if a natural water containscolloidal
silica or other colloidal matter, calcium carbonate may precipitate on the suspended
particle instead of on the metal surface and corrosion rate may be high even with a
scaling index that would indicate the formation of scale.
In waters with high levels of dissolved salts, such as sodium chloride, or waters
at high temperature, the carbonate film may lose its protective ability and pitting may
occur. Scaling indices can give a qualitative guide to the corrosivity of natural waters
in contact with metals in which the corrosion rate depends on diffusion of oxygen to
the surface, such as iron, copper, brass, and lead. These indices do not give any useful
indication of the corrosion of passive metals such as stainless steels or aluminum that
often corrode less at higher oxygen concentration^.^^
10.2.2.1 .I Langelier Saturation Index
The Langelier saturation index (LSI)is an equilibriummodel derived from the theoretical
concept of saturation and provides an indication of the degree of saturation of water
with respect to calcium carbonate. It can be shown that the LSI approximates to the
base 10 logarithm of the calcite saturation level. The LSI level approaches the concept of
saturation using pH as a main variable and can be interpreted as the pH change required
to bring water to equilibrium. Water with an LSI of 1.0 is 1 pH unit above saturation,
i.e., reducing the pH by 1will bring the water into equilibrium. This occurs because the
portion of total alkalinity present as C G - decreases as the pH decreases.
The LSI is probably the most widely used indicator of cooling water scale potential. It
provides no indication of how much scale or calcium carbonate will actuallyprecipitate.It
simply indicates the thermodynamic driving force for calcium carbonate scale formation
and growth in terms of pH as a master variable. In order to calculatethe LSI, it is necessary
to know the alkalinity (mg/L as CaCO3), the calcium hardness (mg/L Ca2+as CaCO3),
the total dissolved solids (mg/L TDS), the actual pH, and the temperature of the water
-
("C). TDS can be estimated from conductivity using tables that use an approximate
conversion factor of 1mho/cm 0.41 mg/L as CaC03.50
Using these data the LSI can be determined:
LSI = pH - pH,
where pH is the measured water pH

pH, is the pH at saturation in calcite or calcium carbonate and is defined as
pH, = (9.3 A+ + 8) - (C + D)
where A = (Log,, [TDS] - 1)/10
+
B = -13.12 x Log,, ("C 273) 34.55 +
C = Log,, [Ca2+as CaC031 - 0.4
D = Log,, [Alkalinity as CaC031
Published tables give values of A from total solids, B from temperature, C from
calciumcarbonate content, and D frommethyl orange alkalinity?352 These charts can also
indicatethe temperature at which the water may become scaling.Charts are also available
to determine Langelier Index and pH, from hardness, alkalinity and temperat~re.5~9~~
If the LSI = 0 the water is in chemical balance; if index is >O then there is a tendency
for calcium carbonate to deposit; if LSI <O then carbonate scale will tend to dissolve and
there may be a tendency to corrode some metals if oxygen is present.
10.2.2.1.2 Ryznar Stability Index
The Ryznar stability index (RSI) attempts to correlate an empirical data base of scale
thickness observed in municipal water systems to water chemistry. Like the LSI, the
RSI has its basis in the concept of saturation level. Ryznar attempted to quantify the
relationship between calcium carbonate saturation state and scale formation.
where pH is the measured water pH

pH, is the pH at saturation in calcite or calcium carbonate
The actual values of these indices are also tabulated in many sources. Thus by
knowing the basic composition it is possible to predict whether cooling water is likely
to deposit scale based on the following ranking:43
LSI RSI Tendency to Scale

3.0 3.0 Extremely severe
2.0 4.0 Very severe
1.0 5.0 Severe
0.5 5.5 Moderate
0.2 5.8 Slight
0.0 6.0 Stable water, no tendency to form or dissolve scale
-0.2 6.5 No scaling, very slight tendency to dissolve scale
-0.5 7.0 No scaling, slight tendency to dissolve scale
-1.0 8.0 No scaling, moderate tendency to dissolve scale
-2.0 9.0 No scaling, strong tendency to dissolve scale
-3.0 10.0 No scaling, very strong tendency to dissolve scale
I 0.2.2.1.3 Puckorius Scaling Index
The LSI and RSI do not take into account two other critical parameters: the buffering
capacity of the water and the maximum quantity of precipitate that can form in bringing
water to equilibrium. The Puckorius scaling index (PSI) attempts to quantify the rela-
tionship between saturation state and scale formation by incorporating an estimate of
buffering capacity of the water into the index. Water high in calcium but low in alka-
linity and buffering capacity can have a high calcite saturation level. The high calcium
level increases the ion activity product. A plot of ion activity product vs. precipitate for
the water would show a rapid decrease in pH as calcium is precipitated because of low
buffering capacity. Even miniscule decreases in carbonate concentration in the water
would drasticallydecrease the ion activity product since only a small quantity is present
before precipitation begins.
Such water might have a strong tendency to form scale but the quantity formed might
be unobservably small. The water has the driving force but not the capacity and ability
to maintain pH as precipitate forms. The PSI is calculated in a manner similar to the
RSI. The PSI uses an equilibrium pH rather than the actual system pH to account for the
buffering effects:
where pH, is the pH at saturation in calcite or calcium carbonate

+
pH, = 1.465 x loglo [Alkalinity] 4.54
[Alkalinity] = [HCOJ 2 + [Cq-]+ [OH-]
374 Water Svstems
10.2.2.1.4 Stiff-Davis Index
The Stiff-Davis index attempts to overcome the shortcomings of the LSI with respect
to high total dissolved solids' waters and the influence of "common ion" effects on the
driving force for scale formation. Like the LSI, the Stiff-Davis index has its basis in the
concept of saturation level. The solubility product used to predict the pH of saturation
(pH,) for a water is empirically modified in the Stiff-Davis index.
Stiff-Davisindices will predict that water is less scale forming than the LSI calculated
for the same water chemistry and conditions. The deviationbetween the indicesincreases
with ionic strength. The index is interpreted using the same scale as for the LSI.
10.2.2.1.5 Oddo-Tomson Index
The Oddo-Tomson index accounts for the influence of pressure and partial pressure of
carbon dioxide on the pH of water, and on the solubility of calcium carbonate. This
empirical model also incorporates corrections for the presence of two or three phases
(water, gas, and oil). The index is interpreted using the same scale as for the LSI and
Stiff-Davisindices.
10.2.2.1.6 Larson-Skold Index
The Larson-Skold index differs from the other indices in that it attempts to relate water
chemistry to corrosion of mild steel. The index is based upon evaluation of in situ corro-
sion of mild steel lines transporting Great Lakes waters. The index is the ratio of equiv-
alents per million (epm) of sulfate (G-) and chloride (Cl-) to the epm of alkalinity in
the form of bicarbonate plus carbonate:
Larson-Skold index = (epm C1- + epm G - ) / ( e p m HCO; + epm CG-)

The Larson-Skold index correlated closely with observed corrosion rates and the
type of attack in the Great Lakes water study. Extrapolation to other waters, such as
those of low alkalinity or extreme alkalinity, goes beyond the range of the original data.
The index has proved a useful tool in predicting the aggressiveness of once-through
cooling waters. It is particularly interesting because of the preponderance of waters of
composition similar to the Great Lakes waters and to its usefulness as an indicator of
aggressivenessin reviewing the applicability of corrosion inhibition treatment programs
that rely on the natural alkalinity and film-forming capabilities of a cooling water.
The Larson-Skold index can be interpreted by the following guidelines:
Index << 0.8. Chlorides and sulfate probably will not interfere with natural film for-
mation.
0.8 << index << 1.2. Chlorides and sulfates may interfere with natural film formation.
Higher than desired coi-rosion rates might be anticipated.
10.2 Coolinn Water Treatment 375
Index >> 1.2. The tendency toward high localized corrosion rates should be expected
as the index increases.50
10.2.3 Corrosion Control by Inhibitors
Small amounts of chemicals added to a fluid that reduce the corrosion of specific metals
in that fluid are inhibitors. There are many different chemicals that act as inhibitors
depending on the environment, the metals exposed, temperature, etc. The biggest use
of inhibitors is in cooling waters where chemicals are also needed to control scaling and
fouling. The most important factor in the selection of inhibitors for cooling water is pH.
The selection of an inhibitor for an application begins with an assessment based on
physical properties. Questions include the following:
Must the inhibitor be a solid or liquid?

Are melting and freezing points of importance?
Is degradation with time and temperature critical?
Must it be compatible with other system additives?
Are specific solubility characteristics required?
The effectiveness of inhibitors to control corrosion can be laboratory tested using im-
mersion and/or electrochemical techniques. The techniques used to study inhibitorsand
synergisticeffects between them include electrochemicalscanningtunneling microscopy
(EC-STM),atomic force microscopy (AFM), and impedance EIS.%
Inhibitors can be classified in a number of ways, including the following:54
Anodic, cathodic, or mixed depending on the part of the corrosive reaction that they
affect
Organic or inorganic depending on the chemical composition
Oxidizing or nonoxidizing depending on the effect on the metal potential
Interface (2D) or interphase (3D) according to the thickness of the formed layer
Cooling water, oil field, acid cleaning, etc. depending on the field of application
They can also be classified as the following:
Neutralizing inhibitors, e.g., ammonia, sodium carbonate, amines

Barrier layer formers, can be cathodic, anodic, or mixed
Absorbed layer formers in nonacidic systems, e.g., benzotriazole for Cu alloys and
imidazoline or fatty amines for steel
Absorbed layer formers in strong acid, e.g., quinoline or rosin amine for steel
Oxidizing inhibitors (passivators),e.g., molybdates
Conversion layer formers, e.g., sodium phosphate, silicate, or chromate
Anodic inhibitors interfere with the anodic reaction and so can encourage pitting or
other localized attack. Chromateswere the most often used anodic inhibitorsand they can
376 Water Svstems
protect mild steel, copper alloys, and aluminum alloys. Other anodic inhibitors include
orthophosphates, nitrites, and orthosilicates.
Cathodic inhibitors are generally considered safer than the anodic ones because they
do not carry the risk of pitting. Polyphosphatesare common cathodic inhibitorsbut they
can cause fouling and provide nutrients for algae in cooling towers. Polysilicatescan be
effective in controlling corrosion of mild steel, copper alloys, and aluminum alloys but
they do not work well in low pH waters or in the presence of high levels of silica. Zinc or
molybdates are also commonly used as inhibitors for mild steel. Multiple inhibitors are
often used at the same time since it has been found that many of them act in a synergistic
way. For example, steel in acidic media is inhibited better by a mixture of iodide ions
and amines and imines. Similarly, there is a clear synergistic effect between benzotriazole
and bemylamine, ethanolamine,or potassium ethylxanthate on copper alloys. Zinc ions
present with chromates,phosphonates,or polyphosphates give protection under various
operating conditions.%
The inhibition by various commercial phosphonates on mild steel and cast iron
was studied using thermal stability tests, weight loss, and dynamic polarization
testing. The stability of the phosphonates decreased with temperature in the order
PBTA(2-phosphonobutane 1,2,4tricarboxylic acid) > HEDP(1-hydorxyethylene 1,l-
diphosphonate) > A M P (aminotrimethylenephosphonate). Phosphonates inhibit mild
steel and cast iron by adsorption at a concentration of 12.5 to 50 mg/L. Adsorption is
weaker on the cast iron than on mild steel thus giving a lower degree of protection on
the cast iron. Cast iron corrosion increases with time because of phosphonate decompo-
sition caused by iron ions accumulating in solution.The corrosion potential of mild steel
is shifted in the noble direction in the presence of phosphonates; that of cast iron is vir-
tually unchanged. If both metals are present the cast iron becomes anodic and galvanic
corrosion can occur. On the basis of this study a new inhibitor, BC-80, was developed
that is claimed to protect mild steel, cast iron, and also prevent scaling in hard waters.
This new inhibitor contains two phosphates and two phosphonates, one of which is
phospho-carboxylic ~opolymer?~
Corrosion control in open recirculating cooling systems can be achieved by adding
acid and inhibitor or allowing the pH to elevate by alkalinity concentration and then
adding a scale inhibitor and a corrosion inhibitor. In the first approach the acid is added
to reduce scaling and to keep the corrosion inhibitor in solution. As the pH drops, of
course, the water becomes more corrosive and less scaling so water treatment is a balance
between these competing tendencies.
Once-through systems rarely use corrosion control treatments and rely on the use
of resistant materials and, in some cases, cathodic protection. The use of inhibitors is
normally only practical in closed systems. In closed systems the pH is usually kept
at 8.5 to 9.5, which helps reduce corrosion, but few corrosion inhibitors exist that are
effective at these levels of pH. Chromates used to be the preferred inhibitor but envi-
ronmental concerns mean that they can no longer be used in many parts of the world.
In nonchromate systems pH and conductivity need to be controlled within fairly tight
operating ranges. Alternatives include molybdates, ”boron nitrite” (borax with mixed
inhibitorssuch as sodiumnitrite, sodium nitrate, copper-based inhibitor),phosphonates,
and lignins. Hydrazine is sometimes used as an oxygen scavenger/corrosion inhibitor

in this type of closed system.43
Commercial sodium nitrite/sodium tolytriazole (TTA) inhibitor in deionized water
at 50°C is an anodic passivating inhibitor that forms protective films on metals and de-
creases corrosion current. This inhibitor greatly reduced the corrosion rate of commer-
cially pure copper and 90/10,70/30, and 85/15 Cu/Ni. It was also an effective pitting
inhibitor for mild steel in water containing 5 to 20 pprn chlorides at inhibitor levels of
at least 750 ppm nitrite and 7.5 ppm TTA, and for 304L stainless steel in the same water
250 pprn nitrite with 7.5 pprn TTA protected against pitting.56
The selection of inhibitors can be particularly difficult if mixed metals are present
in the system. Inhibitors are unlikely to be effective if the system is already fouled or
scaled. If the fluid is multiphase, such as oil and water, it is important not only to select
suitable inhibitors but to ensure that they are distributed to all surfaces or corrosion can
increase.In some cases the inhibitor needs to be distributed mechanicallyrather than just
being added to the bulk fluid. For example, in long pipelines it may be necessary to send
a mechanical pig through the line regularly. Some inhibitor chemicals are an excellent
source of nutrients for bacteria and can lead to fouling and MIC if biocides are not being
used or are ineffe~tive.4~
Disposal of the treated water may be a major factor in selecting inhibitors or other
water treatment chemicals. Typical regulations and environmental rules restrict use of
chromates, nitrates, heavy metals, and phosphates, and encourage the use of biodegrad-
able treating chemicals. Research is aimed at producing inhibitors that are environmen-
tally acceptable, effective at low concentrations (often achieved by synergy with other
inhibitors),and consist of specific inhibitor molecules and multifunctional compounds.
An example of an environmentally friendly group of inhibitors is the acylated deriva-
tives of amino acids that are converted by microbes to amino and other acids in rivers
and lakes.57The development of more environmentally friendly inorganic inhibitors to
replace chromates has been slow but the tungstates and molybdates come into this cat-
egory. More usually, toxic inorganic inibitors are being replaced with organic inhibitors
such as hydrazine and carbohydrazide.Both of these are used in closed sytems and work
mainly as oxygen scavengers"
The effectivenessof inhibitors can be monitored in the field using copper ion displace-
ment (CID)coupons. These are a special form of test coupon used to check the inhibitor
filming action in a treated water system. Steel coupons are exposed in the system for 7 to
10days. Upon removal they are washed in solvent, then immersed in 10%copper sulfate
solution. Any part of the coupon not covered with inhibitor film will plate out with a
distinctive reddish-copper film. This method is not quantitative and is mainly used as a
check when changes are being made to the water treatment?8
10.2.3.1 Inhibitors and Biofilms
The effect of inhibitors on microorganisms varies from acting as a biocide to enhancing

growth by providing nutrients, depending on the product used. In general, it appears
378 Water Svsterns
that corrosion inhibitorsare not effectivebiocides and can occasionally enhancebacterial

growth and/or increase MIC.
Diethylamine/alkylamines, polyamine/aromatic naptha, a thioalkyl-substituted
heterocycle in aromatic hydrocarbon and methanol, and a proprietary corrosion in-
hibitor /biocide blend did not significantly reduce bacterial populations, especially ses-
sile ba~teria.5~One study suggests, however, that although the biocidal activity of a
quaternary amine inhibitor may be minimal, colonization and corrosion rates are re-
duced. Thus, MIC may be prevented by mechanisms other than killing bacteria and that
treatments preventing surface colonization may persist longer than most biocidesa
A corrosion inhibitor containingtallow trimethylene diamine was tested for its bioci-
dal activity with contradictoryresults. In most cases bacterial numbers were similar with
and without the corrosion inhibitor,but in some cases SRB populations were larger in the
presence of the inhibitor while planktonic anaerobic bacterial populations decreased.6l
In tests with biocides (gluteraldehyde and cocadiamine) and a corrosion inhibitor
(a tallow diamine) the inhibitor had no effect on planktonic SRB and acid-producing
bacteria (APB) or on sessile bacteria on coupons. The biocides were more effective than
the corrosion inhibitor but neither completely controlled bacterial growth.62
Pseudomonas j7uorescms grew moderately using an organic film-forming inhibitor
blend (a mixture of amides, amines, imidazolines, morpholines, cyclohexylamines, and
quaternary ammonium compounds) as sole carbon source, but the efficacy of the in-
hibitor was not adverselyaffected.63The polyphosphate corrosion inhibitor, sodium hex-
ameta phosphate (SHMP),apparently provided nutrient phosphatefor a mixed microbial
community from a coolingwater reservoir. Bacterialpopulations were higher during the
8 weeks of the study in the presence of the inhibitor but corrosion rates did not increase.bp
Inhibitors could have the effect of exacerbating corrosion problems indirectly.In the
hot water system of a large office block in London a nitrite inhibitor was converted to
ammonia by nitrite-reducing bacteria. The system contained large amounts of copper
and brass, which were attacked by the ammonia.@Bacteria have also been reported
elsewhere to break down nitrite and nitrate-based inhibitors.&
10.2.4 Biofouling Control
A number of mechanicaland chemical controls of fouling have been attempted.Probably

the oldest practical method is scrubbing and it is still widely used today on both external
and internal surfaces.
10.2.4.1 Nonchemical Methods
High water velocity has been used to prevent fouling in some piping systems. At Vado
Ligure Power Station four 2.2-m-diameter culverts remained free of fouling for 14 years
with seawater velocities of 2.9 m/s. Air bubbles, sonic cleaning, electric currents, mag-
netic fields, and surface modification (texture, chemical composition, and electrical
Next Page
charge) have been used with varying degree of success.67Other control measures in-
cluded gas diffusion, strippable films, and repellents.
A thermal shock in the water intake can eliminate adult mussels and barnacles. Heat-
ing seawater to 110 to 120°F(43 to 49°C) 30 min per week was successful in preventing
fouling.@Thermal control treatment is only practical where volumes of water to be
heated are relatively small. Thermal shock is impractical in cooling systems,
because the cooling water would need to be isolated and circulated through heaters. This
would require major modification of the intake and the cooling system.
Thermal backflushing did not successfully control zebra mussels in fresh water in
Canada. With a heating time of 6 to 10 h at Bruce Heavy Water Plant mussels acclimated
to 5 to 14°Cchanges in t e m ~ e r a t u r eRapid
. ~ ~ temperature changes and extended periods
at peak temperature were required to kill the mussels.
Copper alloys have good resistance to biofouling which used to be attributed to the
release of toxic copper ions close to the metallic surface. It is now more generally thought
to be caused by conversion of the oxide film metal into cupric hydroxy chloride which
allows some fouling, but the biofilms produced are loosely adherent and are periodically
sloughed off.71A copper-nickel alloy with 10%nickel has been designed for screens that
cover water intakes at municipal and industrial facilities. The high copper repels zebra
mussels.”
Osmotic control, adding fresh water to dilute the salinity, can be effective against
some marine species. UV radiation was tested on fouling organisms in a seawater intake
for a power station in Japan. Although no details were provided the authors claim that
they would be able to achieve total biofouling prevention with this ~ystem.7~
10.2.4.2 Chemical Methods

Chlorinationcan be an effective control method for macrofouling organisms. It has been
found to be more effective in preventing foulingby blue mussels than copper or iodine.74
Doses that are required to control bacteria will generally also control larger, more
complex organisms. One study, for example, found that a continuous dose with a free
chlorine residual of 0.25 ppm was sufficientto provide 100%effectivenessagainst fouling
organisms in intake water for a power plant.@Other authors have found that adult
mussels can only be controlled by continuous ~hlorination.~~
Another oxidizing biocide, chlorine dioxide, has also proved to be effective against
fouling development in a once-through cooling system in Italy. Even at the lowest con-
centration tested (0.07 ppm) there was no settlement of fouling organisms, although
polychaetes and bryozoans settled upstream from the biocide addition.”
The nonoxidizing biocide with the active ingredients dodecylguanidine hydrochlo-
ride (DGH) and n-alkyl-dimethylbenzylammoniumchloride(QUAT) has been used to
control biofouling by the freshwater bivalves CorbicuZufZurnineu (Asian clam) and Dreis-
senu polyrnorph (zebra mussel). It was more effective than chlorine in controling fouling
of seawater intakes by Crussostreu virginicu (oysters), Bulunus sp. (barnacles), Geuken-
siu dernissu (ribbed mussels), and unspecified hydro id^.^^ Other experience suggests
Previous Page
380 Water Svsterns
that a quaternary ammonia-based molluscicide may also be successful against zebra

mussels.n
Chlorinationof intake waters during the breeding season is the most popular method
of control for the introduced nuisance species, D.polymorph, in the Great Lakes but a
number of other techniques have also been tested. Ontario Hydro, Canada experimented
with several other methods to clean surfaces of mussels.78Mechanical methods using
air lift with vacuum, high pressure power wash, hydraulic pump, tandem water pump
with jetting nozzle, and fire hose were unsuccessful or only partially successful. A hy-
draulic pump with scraper and a low pressure abrasive slurry system worked well.
Thermal shock blasting using liquid carbon dioxide to feed dry ice pellets onto the sur-
face was considered a useful technique in applications where substrate damage, worker
safety, and disposal costs are key issues. Chemical cleaning using phosphoric acid was
considered safe, fast, and effective for piping and heat exchangers.
Additional biocides, such as the reducing biocides sodium sulfite and metabisul-
fite, were also investigated and compared with non-biocidal control methods, including
acoustical control (with limited initial success), mechanical filtration (veliger larvae can
pass through 80 pm screens),pressurized flow (hydrostaticpressures of 200 psi [1.4MPa]
resulted in 0 mortality, flows of greater than 2 m/s inhibited settlement),and antifouling
coatings.79
10.2.4.3 Antifouling Coatings
The first really effective antifoulingcoating systemsbecame available in the 1970s. Orig-
inal antifouling paints were based on toxicants that are slowly soluble in seawater and
could reliably prevent biofouling for up to 5 years. In some cases only the toxic sub-
stance is leached out; in other systems the binder and active agent leach out together,
i.e., the coating layer becomes thinner. Organotin and copper compounds are typical
active ingredients.
The major types of toxic antifouling paints today are soluble matrix paints and self-
polishing copolymers. In soluble matrix coatings, active biocide is incorporated into
a rosin-containing, film-forming matrix. The rosin dissolves slowly in seawater while
the film-formers are usually insoluble vinyl or acrylic polymers. Modem paints of this
type have extended the effective coating life to about 4 years by adding more rosin and
plasticizer and less insolublepolymer, allowing them to erode more readily. Antifouling
activity depends on water movement; under static conditions the toxic substances do
not leach out. Self-polishing copolymer paints have an acrylic polymer as the binder.
This copolymer hydrolyzes in seawater releasing biocide and at the same time making
the surface smoother. Active life is up to 5 years and depends on the thickness of the
coatingm
Various antifouling coatings were tested by the Electric Power Research Institute
(EPRI)in 19 U.S. power generating stations. The most successfulwere the toxic coatings
acrylictributyltinpolymer and rosinated vinyl. The nontoxic coating silicone elastomer
also showed potential as an antifouling agent.81
Tributyltin (TBT) has been found to be highly effective as an antifouling agent, giving
up to 5 years protection of naval vessels. It can be incorporated into self-polishing
coatings, designed to wear away gradually as water flows by, releasing the barnacle-
inhibiting compound at a constant rate. Unfortunately tributyltin use has serious en-
vironmental consequences. It is considered the most toxic material ever deliberately
introduced into the marine environment. It affects sex and reproduction in dog whelks
and causes oysters to have thickened shells, among other Environmental
regulations differ from country to country but typically prohibit the use of TBT antifoul-
ing coatings on vessels t 2 5 m in length and they must have a maximum release rate
of 4 pg TBT per cm2/day. Its use is now banned completely in some countries and it is
expected that an agreement will shortly be reached through the International Maritime
Organization to a world-wide ban on the use of TBT on all ships by January 2003.
Other common biocides for use in antifouling paints include the following:8o
Zineb (zinc ethylenebisdithiocarbamate),a fungicide

Maneb (manganeseethylenebisdithiocarbamate)
Ziram (zinc bis(dimethy1dithiocarbamate)).
Diuron@(3-(3,4-dichlorophenyl)l-l-dimethylurea), a herbicide
Irgarol 1051@ (2-methylthio-4-tert-butylamino-6-cyclopropyla~o-s-triazine), a
herbicide
Sea-Nine 211@ (4,5-dichloro-2-n-octyl-4-isothiazolone-3-one), a broad-spectrum
antifoulant
Zinc pyrithione (zinc-2-pyridinethiol-N-oxice/2-mercapto-pyridine-N-oxide),a
broad-spectrum microbiocide
Copper is also toxic and has also been found to have deleterious environmental
effects. Copper-based products in some countries must have a maximum release rate of
40 pg Cu per m2/day.
Three classes of new antifouling coatings have been identified. They are as follows:
1. Tin-free conventional, such as chlorinated rubber or vinyl using cuprous oxide as

biocide.
2. Tin-free erodablepaints, based on rosin and erosion of the binder, gives desired release
rate.
3. Ti-free self-polishing, in which a hydrophilic film controls the release of the biocide,
usually copper or zinc organic compounds.
Other alternatives include the use of acrylic polymers with an ester linkage that is
hydrolyzed in seawater; copper acrylate coatings; quaternary ammonium compounds
bonded to a polymeric chain; nonstick coatings without biocides and based on silicones
or fluorinated polymers.83
In recent years scientistshave been searchingmarine organismsfor potential antifoul-
ing compounds that are more environmentallyfriendly. Observations that some marine
species are not naturally fouled led to testing of these organisms for natural antifouling
382 Water Systems
compounds. Species may, however, have other means of deterring fouling than pro-
duction of secondary metabolites. For example, coralline algae of the Rhodophyta shed
surface tissues in sheets, sloughing off attached epiphytes mechanically.
Most studies to date have been laboratory studies of crude extracts. For example, ex-
tracts from 31of 44spongesfrom Curacao sigruficantlyinhibitedbarnacle cyprid (larvae)
settlement at 0.1 mg mL/L and of these, 22 sigruficantlyinhibited settlement at 0.01 mg
mL/L.@ Other candidate compounds identified include the lipids pukalide and epoy-
pukalide from soft corals, Leptogorgiu virgulata;the diterpene, renillafoulin from Renilla
renijomzis, a sea whip; tribromogramine from the bryozoan Zoobotyon pellucidum; vari-
ous antifoulingcompoundsfrom the bacterium,Alteromoms sp.; and bromine-containing
furanones from the red alga Delisea p u l c h r ~ ? ~
Organisms tested for antifouling properties now include terrestrial plants, mi-
croalgae (Cyanophyceae, Chrysophyceae, Dinophyceae, and Chlorophyceae),macroal-
gae (Phaeophyceae, Rhodophyceae, and Chlorophyceae), sponges (Porifera), soft
corals (Cnidaria: Octocorallia), bryozoans (Bryozoa), echinoderms (Asteroidea and
Holothruia), ascidians (Ascidea), and dogfish (Scyliorhinus c ~ n i c u l a )No
. ~ ~natural com-
ponents have yet been tested, however, in long-term commercial operations.%
One researcher concluded that nontoxic antifouling using natural products or their
analogues is a theoretical impossibility for the following reasons:
Fouling is a result of a large number of different mechanisms. A surface can only be

protected if the entire spectrum of mechanisms is inhibited.
An effective approach would require a delivery at the correct concentrations to an im-
practical number of molecules that interfered with specific kinds of fouling. Delivery
of large numbers of molecules in a single effective coating with correct physical and
mechanical properties is unlikely.
Organic molecules contain energy and those energy-containing molecules serve as
food for some kinds of fouling organisms. Organisms that colonize the surface and
consume this available food source would neutralize the antifouling activity.
Many fouling mechanisms are physical-chemical interactions that cannot be chemi-
cally i~hibited.8~
To these arguments may be added an economic one, the enormous cost of registering
and licensing a new biocide today.
A nontoxic approach that is gaining favor is to use a coating that allows easy me-
chanical removal of fouling, ideally by water movement as a vessel moves through the
water. Known as "fouling release" coatings, they depend on having a smooth surface
with low wettability to which fouling organisms cannot form a strong bond. A class
of water-based nonstick coatings contains pendant perfluoroalkyl groups that become
orientated to provide a low energy surface.This type of coating should prevent adhesion
of biological foulants.88
Two fouling release coatings were evaluated in static and dynamic tests, fluorinated
urethane and a silicone elastomer, and found to result in cost savings over organotin
and ablative copper. The silicone elastomer coating, in particular, was found to be both
flexible and durable on the elastomeric surfaces and to retain effective fouling release
properties through long-term immer~ion.8~ A recent review of antifouling paints sug-
gests that new silicone paints being developed are the most promising coatings effective
for long enough to extend dry-docking intervals to 36 months.%Silicone elastomer coat-
ings have more widespread use in specialized applications such as oil and gas pipelines,
underwater markers, and fish farmingg1Silicone coatings were found to be more effec-
tive at inhibiting attachment of zebra mussels than copper polyester, wax, polyurethane,
epoxy polyamine, and PTFE.92
The resistance to marine fouling of some room temperaturevulcanizing siliconeelas-
tomers, some of which were modified by the addition of siliconeoil, has been assessed in
exposure trials, and their surface energies have been compared by measurement of con-
tact angles with water. Of the unmodified elastomers, a poly(dimethyldipheny1siloxane)
was found to have the most hydrophobic surface (contact angle 123"),and also showed
by far the best resistance to fouling. All other poly(dimethy1siloxane)elastomers were
slightly less hydrophobic (112 to 120"),but their antifoulingperformancewas little better
than that of neoprene (82").Addition of a low-viscositypoly(dimethy1siloxane)oil to the
poly(dimethyldipheny1siloxane)elastomer reduced the contact angle but improved the
antifouling performance, apparently by formation of a surface film. Good antifouling
performance was also shown by an elastomer of a poly(dimethylsi1oxane)modified with
a low-viscositypoly(methylphenylsiloxane)0il.9~
Investigations on the adhesion of a diverse range of biological systems including
proteins, tissues, microbes, algae, and invertebrates all indicate that minimal long-term
adhesion is associated with surfaces having initial surface tensions between 2 and 3
Pa, i.e., low energy surfaces. However, all surfaces rapidly become modified on im-
mersion in natural waters through the adsorption of "conditioning films," which may
influence subsequent adhesive events associated with the permanent attachment of
0rganisms.9~
Microorganisms have been shown to be able to adapt to lowered surface tension
within a few days. Bacteria and diatoms possess compensationmechanisms to overcome
weaker attachment strength on materials with surface tensions between 1.9 and 6.5 Pa.
Therefore, some researchers believe that surfacetension cannot be considered a powerful
long-term device to prevent micr~fouling?~
10.2.5 MIC Control
MIC is insidious and difficult to control because biological systems are much less pre-
dictable than chemical ones. Althoughconditionsare apparentlythe same in two adjacent
environments the microecosystem could differ in some essential component, leading to
acceptable operating conditions in one case and catastrophic failure in another. To con-
trol MIC it is necessary to detect MIC, but in industrial systems biofouled surfaces are
often inaccessible, making it difficult to determine the extent of the problem. In practice,
384 Water Svstems
problem-causing microorganisms are often not measured. The result of this is that the
most common method of detecting MIC is failure analysis of a corrosion problem.
MIC control has been the subject of many investigations in recent years leading to
significant advances in our knowledge of control methods, including biocides and how
they work?6-98Control strategiesconsist of two main types. The first is to upgrade mate-
rials to those that are inherently more resistant to MIC. This strategy initially backfired,
however, when steels were upgraded from carbon to stainless steel. The result was that
there was, indeed, less overall corrosion, but it took the form of a few throughwall pits,
rather than wall thinning. Later, upgrades went from 300 series stainless steels to super
stainless steels or other materials.
A serious concern in MIC control by materials selection is the difficulty of correlat-
ing laboratory results with field operating conditions. Laboratory MIC test results are
unreliable as a method for ranking alloys in the real worldw and there is no correlation
between lab tests for MIC and results of standard ferric chloride tests.lmWherever pos-
sible, tests should be conducted in the field, using organisms from the system studied.
Under identical conditions, for example, SRB from different environments vary in their
aggressiveness to steel.lo1
The second strategy is control of microorganisms MIC control includes not only
preventing the metabolic activity of microorganisms,but also removing the biofilm that
can cause underdeposit corrosion, heat transfer, and flow problems. Biofilms are more
difficult to remove as they age. Biocides that are fixatives, such as formaldehyde, can
make biofilm removal more difficult by cross-linking proteins.lo2
The best control method, without doubt, is prevention. Prevention primarily means
good housekeeping, which is as relentless, interminable, necessary, and as boring as it
is in the home. Good housekeeping prevents the initial introduction of microorganisms
into the system and discourages those that do get in from establishing residence. The
best way to achieve this is by using clean water, as free as possible from microorganisms
and the nutrients they need to thrive. Equipment should be monitored for cleanliness
and cleaned promptly if it does get fouled. Preventing debris and suspended solids
from entering the system, and removing them when they occur are important tools in
preventing MIC.97Debris may be sand, soil, corrosion products, sludge, and biomass
from accumulated microorganisms.
Most control methods are chemical but physical and mechanical controls are occa-
sionally used alone or in conjunction with chemical biocides. Pigging, plastic balls, wire
brushing, backwashing, steam-cleaning,and ultrasonic cleaning are used in various sys-
tems. Thermal shock is more effective against macrofouling organisms than bacterial
biofilms and is often impractical in heat exchangers. Increasing flow velocity can re-
duce attachment of foulers but is only marginally effective against microorganisms and
can increase erosion corrosion and, again, is often impractical in heat exchangers. Design
changes in equipment are also used as control methods for MIC as they are for other types
of corrosion. For example, dead end, stagnant, and low velocity areas can be avoided,
oxygen can be removed from the system, and water handling time can be minimized.
An electrochemicalapproachto biociding uses ionization.Ionization, already in use in
some residential, commercial, and public swimmingpools, reduces the need for chlorine
and other chemicals.A low voltage DC current (milliamps)disperses positively charged

copper and silver ions into the water. Copper is toxic to many organisms and is known
to be an effective algaecide. Silver is used as the drinking water purification for half the
world's airlines and in more than 1,000 passenger ships. The positively charged copper
and silver ions form electrostatic bonds with negatively charged areas on the microor-
ganism cell walls. These bonds create stressesthat lead to distorted cell wall permeability,
minimizing the nutrient intake and resulting in death of bacteria. Copper and silver at-
tack sulfur-containing amino acid residues in the proteins used for photosynthesis by
algae. As a result, photosynthesis is blocked. Even if the algal cell survives, reproduction
is hampered by the presence of the copper ions.lo3
The destroyed microorganisms flocculate and are removed by the pool filter. Small
amounts of chlorine are still needed with ionization,but at levels typically 80% less than
conventional pool systems. Commercialionization units typically consist of a micropro-
cessor control box and a set of electrodes composed of copper and silver that are set
slightly apart from one another in a cartridge near the pool filter.'04
10.2.5.1 Biocides
A biocide is a chemical agent that inactivates organisms by killing them or preventing

their multiplication. Disinfectants are biocides that are used on inanimate objects. An
ideal biocide would be cheap, safe (nonflammable, nonexplosive), nontoxic to other
organisms, nonvolatile, and heat and light stable. It would control a broad spectrum of
microorganismsbut not react with organic matter or injure the materials of construction.
Since the ideal biocide does not exist we must compromise by selecting the criteria that
best fit our needs. Biocides may be organic or inorganic compounds.
The choice of biocide depends on several factors. These are the following:
The type of system-closed loop or once-through cooling water, swimming pool,

injection water, etc.
Water composition-potable, condensate, fresh, brackish, seawater, brine, sweet, or
sour
Materials in the system-e.g., stainless or carbon steel, copper alloys, plastics
Other constituents of the system-other added chemicals, process fluids
Government regulations
Effective biocides may act as bacteristats (inhibiting metabolic activity of the mi-
crobes)or bactericides (killingthe microbes).They are sometimesclassifiedby the target
region of the cell, which may be the cell wall, membrane, or cyt~plasm.'~~ The are more
than 250 commercialbiocides available, which have various modes of action: membrane-
active, electrophilicallyactive, and chelating.lMNew products and combinations of prod-
ucts are being developed all the time.
Biocide programs in a system may include oxidizingbiocides, nonoxidizingbiocides,
or both in combination or in sequence. Combining oxidizing and nonoxidizingbiocides
386 Water Svstems
can produce a synergistic biocidal efficacy. For example, the oxidizing biocide halohy-
dantoin and nonoxidizingbiocide isothiazolone were more effective together than either
one alone in killing the sheathed, filamentousiron bacterium, Spherotilus n u f ~ n s . ' ~ ~
10.2.5.1.1 Oxidizing Biocides
Oxidizing biocides include chlorine, sodium, and calcium hypochlorite, chloroisocya-

nurates, halohydantoin, chlorine dioxide, bromine, ozone, hydrogen peroxide, and per-
acetic acid. They are generally cheap and effective at low concentrationsbut are volatile
and reactive. The most popular biocide worldwide is chlorine, in the form of sodium
hypochlorite, or electrolyticallyproduced chlorine from seawater.
Dosing amounts and regimes of oxidizing biocides vary considerably throughout
industry. The long debate about whether continuous or intermittent chlorine dosing
is best continues with both regimes still in practice. These days continuous dosing is
probably more common than intermittent, or slug, dosing. Oxidizingbiocides are often
dosed at a low continuous level, with slug dosing of nonoxidizing biocide at regular
intervals (such as once a week) or as needed.
Oxidizing biocides disrupt the cell wall. They do not penetrate biofilms very effec-
tively although they weaken the biofilm matrix when they are consumed by reactions
with E l 3 and proteins.
Chlorine hydrolyzes when dissolved in water,
C12 + H20 + H+ + C1- + HOCl

and dissociates to hypochlorous acid (HOC1)and hypochlorite (OC1-) (Figure 10.15).
HOCl t,H+ + OC1-

At pH greater than 3 there is virtually no molecular chlorine and dissociation is more
or less complete. The hypochlorous and hypochlorite species of chlorine together form
the free available chlorine.
When chlorine is added in the form of sodium hypochlorite, the following reactions
take place, depending on pH:
+
NaOCl H20 t,HOCl NaOH +
HOCl ++ OC1- OH- +
2OC1- + H20 ++ HOCl + OC1- + OH-
Between pH 5 and 9 both HOCl and OC1-are present. Hypochloriteions predominate

above pH 7.5 and are almost the only species present above pH 9.0.
PH
Figure 10.15 The curve of pH vs. species for chlorine (solid lines)
and bromine (dashed lines).At pH 9 and above there is little remain-
ing hypochlorous acid, the most biocidally active form of chlorine.
The curve for bromine, however, is shifted to the right and it re-
mains a useful biocide at higher pH. (Figure courtesy of CARIAD
Consultants.)
NaCl + H20 -
Chlorine can be generated electrolytically from seawater. The main reaction is:
NaOCl + HZ
Free chlorine readily reacts irreversibly with contaminants present in cooling water
such as organics, and organic and inorganic nitrogen, including ammonia and amines.
In the presence of amines, chloramines are formed. The effective concentration required
to maintain a given free chlorine residual is the “chlorine demand.” It varies with the
method of application, pH, temperature, and water quality.
Free chlorine killing power decreases with increasing pH and increases with increas-
ing temperature. To kill planktonic bacteria 25 times as much chloramine is required
than free chlorine. If the quantities are the same it takes 100 times as long to achieve the
same kill with chloramine.los Monochloramine, however, has been found to me more
effective than hypochlorite against sessile biofilm bacteria.lW
Fresh water (potable, waste water, and swimming pools) is routinely chlorinated to
control biological activity. In long-term corrosion trials the following were found:
The corrosion rate of carbon steel and cast iron increases significantly with as little as
0.5 mg/L chlorine and continues to increase as the residual chlorine level increases.
Austenitic nickel cast iron and copper-based alloys are not significantly affected by
up to 2 mg/L chlorine in fresh water.
388 Water Systems
Aluminum alloys suffer measurable general and localized corrosion in raw and chlo-
rinated fresh water but not enough to preclude their use where some corrosion and
maintenance can be tolerated.
Types 304 and 316 were resistant to localized attack in fresh unchlorinated water or
water chlorinated with up to 2 pprn chlorine. At 3 and 5 mg/L there was incipient
pitting of both grades with substantial crevice corrosion.
There was no localized or general corrosion of 304 or 316 in 31- to 32-day exposure at
20 to 25 mg/L chlorine.
Stainless steels, 317,17-4PH (UNS S17480), and 2OCb-3 (UNS N08020), were not cor-
roded in fresh water with up to 2 mg/L chlorine, but 2OCb-3 suffered 5 mil (0.13 mm)
depth of local corrosion in the 3- to 5-mg/L tests.
More highly alloyed stainless steels and chromium-containing nickel-based alloys
(alloys 700, C, and 625) were not corroded in fresh water with up to 5 mg/L chlorine.
Alloy 400 can suffer severe crevice corrosion in mildly chlorinated fresh water.
The results from this work support the widespread use of stainless steels in chlo-
rinated fresh water in municipal wastewater and potable water treatment plants, heat
exchangers, and swimming pools."o
The effects of chlorination on polyethylene potable water pipe were tested using
the methods outlined in AWWA standard C651. The tests were based on the normal
industry methods of chlorinating, tablet, continuous flow, and slug. Mechanical and
physical properties were not found to have been changed significantly by exposure to
chlorination."'
The effect of chlorine level in seawater on the open circuit potential of various metals
was tested in the laboratory. The potential of aluminum bronze and carbon steel was
unaffected by residual free chlorine levels from 0 to 10 pprn in aerated seawater at 23°C
(Figure 10.16). The potential of 904L (UNS N08904) increased by 270 mV SCE by the
addition of 1 ppm free chlorine. Further increases in chlorine level raised the potential
to a lesser extent. The potential of platinum reacted in a similar way to that of the 904L.
Copper alloys and stainless steel heat exchanger tubes have performed well in sea-
water containing up to 2 pprn residual chlorine. Both types of alloys have failed in more
heavily chlorinated water."'
Tests on the effect of chlorination on various materials in seawater showed that the
uniform corrosion rate on most of the metals tested (titanium, Cu/Ni alloys, alloy 625,
alloy 405, steels, and phosphor bronze) was either unchanged or reduced by the presence
of chlorine (at 1or 4 mg/L). In the case of beryllium copper and zinc, the corrosion rate
increased at 1ppm chlorine but was unaffected at 4 ppm. The rate of localized corrosion
was reduced for most alloys by the presence of 1 mg/L chlorine with no significant
effect from the 4-mg/L chlorine. Nitrile rubber and ethylene propylene O-rings were
seriously degraded by chlorination in 1year exposure and only the fluorocarbon Viton@
was sati~factory."~
Laboratory test results in natural seawater clearly show that galvanic corrosion of
Cu-based alloys coupled to stainless steels is significantly "inhibited" in the presence
>
E
Y
Residual Free Chlorine (ppm)

Figure 10.16 Graph shows the effect of chlorine on the potential of
various metals in seawater. (Figure courtesy of CARIAD Consultants.)
of low levels (e.g., -1 ppm) of chlorine. The present hypothesis for this observation is
that biofilms that enhance the oxygen-reduction reaction (in this case on the cathodic
stainless steel insert surface) are removed by low-level chlorination. Bacteria and sulfide
production are a concern at the interfacebetween the tube and tube insert. Unfortunately,
these areas are not very accessible to ~hlorination."~
See Chapter 5, Section 5.2.4.1, "Effect of Biofilms and Chlorination in Seawater," for
details of effects of chlorination on stainless steels.
Bromine hydrolyzes in a similar fashion to chlorine:
Br2 + H20 + H+ + Br- + HOBr

and dissociates to hypobromous acid (HOBr) and hypobromite (OBr-) (Figure 10.15):
HOBr t, H+ + OBr-
Bromine is more effective than chlorine at high pH. More of the effective biocidal
species are present at high pH. In addition, bromamines have a greater biocidal activ-
ity than chloramines but do not persist as long because of their greater reactivity with
reducing agents and therefore are considered more environmentally friendly. As a re-
sult, bromination is becoming increasingly popular in cooling water systems with high
a1kalir~ity.l'~
Bromination has also become increasingly popular in other freshwater sys-
tems, such as swimming pool treatments, sometimes in combination with chlorination.
Swimming pool treatment is notorious for its difficulty, for reasons that have more to
do with familiarity by the general public than because it presents a unique problem
(Figure 10.17).
390 Water Svstems
Figure 10.1 7 If algae are not tightly controlledby careful water chemistrya pool can change from
sparkling clear to opaque green in a remarkably short time. We once literally watched as a pool
turned bright green in a few hours. (See color plate.) (Photoscourtesy of CARIAD Consultants.)
In seawater systems bromination comes automatically with electrolytic generation

of chlorine because seawater (35%0salinity) contains 65 ppm of bromide ion. Therefore,
where the source of chlorine is electrolytic generation from seawater, the added biocide
has always been a combination of chlorination and bromination, even though operators
may not realize it.
Experiments at two coal-fired power generating plants demonstrated that bromine
was a safer, more effective biocide than chlorine gas in their cooling water systems
although it was slightly more expensive.l16
Chlorine dioxide is popular in the pulp and paper industry. It is explosive and cannot
be stored. It is generated on demand from chlorine and sodium chlorite.
2NaC102 + C12 -+2C102H++ 2NaCl

Chlorine dioxide is readily soluble in water but is expelled by minimal aeration and
subject to photodecompositionso it is not suitable for open vessels and systems.It is more
toxic than chlorine, especially at high pH, does not hydrolyze or dissociate, and does
not react with ammonia and nitrogenous compound^."^ In comparative tests, chlorine
dioxide has been found to be greatly superior to chlorine as a microbiocide. Chlorine
dioxide could achieve 90 to 99% kill at 1to 2 ppm chlorine dioxide, whereas 5 to 6 pprn
chlorine was required to achieve the same efficiency. In addition, chlorine dioxide was
not sensitive to pH in the range of 6 to 11,unlike chlorine.l18
Ozone ( 0 3 ) is a powerful oxidizingbiocide that produces fewer toxic by-products and
is, therefore, more environmentallydesirable,but has low solubility in water and is about
four times as expensive as chlorine. Another disadvantage is that it cannot be stored, so
must be made on demand. Ozone is usually generated by the corona discharge method.
An ozone system generally consists of an air compressor, air-drying system, filters and
pressure regulator, an ozone generator with power pack and ozone generating electrodes,
injections system, and control system^."^
Nitrogen oxides formed during ozone generation react with water to produce nitric
acid. At pH of 8 and higher, which is common in cooling water systems, ozone decom-
poses to form hydroxyl freeradicals that are poor biocides because of their short half-life.
For effective disinfection ozone residuals must be present in the system or by-products
may increase bacterial and algal growth.
Ozone lyses (breaks open) microbial cells. It also breaks down and removes biofilms
at concentrations of 0.2 to 1.0 mg/L.lZoBiofilm removal by ozone apparently, however,
depends on the substrate. Although ozone decreased sessilebiofilm bacteria by a similar
amount on carbon and stainlesssteel under similar experimental conditions, the bacteria
were detached only from the stainless steel.l*l
Experience with ozone as a biocide in cooling water systems has been mixed. Al-
though it is an effective biocide it is highly reactive with organic matter in the system,
including wood, rubber, and PVC. Residual biocide is rapidly reduced to zero, perrnit-
ting biofilm buildup in the system. It is also corrosive to some copper-based metals at
concentrations of greater than 0.2 ppm, although if ozone is generated from air, rather
than pure oxygen, nitrates and nitrites that act as inhibitors are also generated. Ozone
appears to influence scale formation, increasing it at low levels and in cooling towers
and decreasing it on heat exchange surfaces at concentrations above 0.3 ppm.'"
Since the 1980s,ozone has become increasinglypopular as a disinfectant in swimming
pools. Ozone and ionization are sometimes used in combination in swimming pool
purification to avoid the use of chlorine entirely.
10.2.5.1.2 Nonoxidizing Biocides
Nonoxidizing biocides may be broad-spectrum, like oxidizing biocides, or effective

against only a narrow range of physiological types of microorganisms. They vary in
contact time requirement and some may be more suitable for recirculating than for once-
through systems.
Phenols dissolve the cell membrane and precipitate proteins in the cytoplasm. Halo-
genated phenols, cresols, diphenols,and bisphenols have excellent antimicrobialactivity.
Examples include dichlorophene and hexachlorophene. Halogenation and addition of
aliphatic and aromatic groups increase the antimicrobial activity of phenols?6
Biguanides are polymer derivatives of guanidine. Polyhexamethylene biguanide
(PHMB) and 1,6-di(4-chlorophenyldiguanido)-hexane(chlorhexadine) are two that are
used in industrial cooling water. They are noncorrosive, bacteristatic in low concentra-
tions, and bactericidal in high doses. They are membrane-active agents effective against
a broad spectrum of bacteria, especially Gram negative?6
Isothiazolones are primarily bacteristatic. Isothiazolones react oxidatively with ac-
cessible thiols such as cysteine and glutathione?6 Thiocarbamates similarly react with
accessible thiols and amines. Their effectiveness decreases with increasing ferrous iron
concentration.123
Quaternary ammonium compounds are cationic surface-active agents that adsorb
onto the cell membrane and react with the negatively charged cell wall, leading to cell
392 Water Svstems
lysis and death.They also denaturecell proteins.Their action is attributedto their positive
charge and they are generally more effective in alkaline pH ranges. They are less effective
in heavily fouled systems and at higher temperatures?6
Gluteraldehyde (1,5-pentanedial) is generally preferred over formaldehyde (which
is a potent carcinogen) and has been a popular biocide choice in the oil industry. At lev-
els above 20 ppm it has been shown to penetrate biofilms and destroy biofilm bacteria,
as well as increase rate of biofilm removal. The important factors for determining effi-
cacy of the biocide are pH, contact time, temperature, and biocide c o n ~ e n t r a t i o n . ' ~ ~ ~ ' ~
Gluteraldehyde performed poorly, however, in another oil and gas system, where isoth-
ioazoline gave the highest kill rates.lZ6Similar results were found from other produced
waters.lZ7
A comparative study of four nonoxidizing biocides in waters of high pH and
alkalinity suggests that gluteraldehyde may not be an effective biocide in cooling
water systems. Gluteraldehyde inhibited algal growth but did not control bacteria
or fungi. Methylchloro/methylisothiazolone was the most effective treatment. Trib-
utyltin oxide/quaternary ammonium salt was an effective fungicide but less effec-
tive against algal cells and ineffective against biofilms. Methylene (bis)thiocyanate,
an organ0 sulfur compound, was also-ineffective at controlling biofilms at high
pH.lZ8
Peracetic acid may become a more common biocide in industry since it appears
to be effective and its breakdown products (acetic acid, water, and oxygen) are more
environmentallyacceptable than many other possible choices.'z9
10.2.5.1.3 Biocide Resistance
When exposed for long periods or to gradually increasing doses of non-oxidizing bio-
cides, microorganismscan become resistant.Loss of porin proteins through gene deletion
can cause a reduction in cell surfacepermeability.Biocides may also be excreted by efflux
pumps or they may be inactivated enzymatically or chemically." Biofilm ecosystems
respond to stress (i.e.,biocides) in ways similar to macroecosystems.Generally, there is a
decline in species diversity and a selectionof more tolerant isolates. These developments
have placed the spotlight on alternative technologies, like biodispersants, which have
shown potential as biofouling control agents.13'
Examples of resistant species include the highly quaternary ammonium compound
(QAC)-resistant Serrutiu murcescens and the chlorhexidine diacetate (CHA)-resistant
microorganisms Escherichiu coli, Pseudomonus aeruginosa, Proteus mirabilis, and Serrutiu
rn~rcescens.'~~The iron bacterium Sphaerotilus natans in an established biofilm was re-
ported to develop resistance to isothiazolon in laboratory experiment^.'^^
In China, SRB became resistant to dodecyldimethyl-benzylammonium chloride (also
called 1227) to the extent that the minimum lethal concentrations increased from 20
to 30 mg/L initially to at least 100 mg/L for resistant strains. The resistant bacteria
were killed by a combination of 9:l bisquaternary ammonium compound (BQA) and
metronidazol flagyl (ME) at concentrationsof 10 mg/L.133
10.2.5.1.4 Biocide Application
Biocide application is as important as biocide type and appears to be site specific. The
three steps to effective biocide application are biocide selection; determine minimum
effective concentration and dosage rate; and monitor application and effectiveness.
10.2.5.1.4.1 Biocide Selection. In addition to the obvious point of effectiveness

in killing microbes in a particular system, it is necessary to check compatibility with exist-
ing system chemicals and materials. Practical experience has demonstrated that biocides
may interact with other treatment chemicals and system components, decreasing the
effectivenessof one or both. For example, oxygen scavengerswhich are commonly used
in the oil and gas industry react with oxidizingbiocides such as hypochlorite and hypo-
bromite, resulting in the deactivation of the biocide and the need for addition of more
oxygen scavenger. The scavenger, ammonium bisulfite, also reacts with chlorine and
aldehydes.Quaternary ammonium chloride reduces the oxygen scavengingrate by half.
Hypobromite,however, acceleratesthe reaction rate between oxygen scavengers and low
concentrationsof oxygen and increases the filtration efficiency of media filters.”
Sulfides, present in many systems, inhibit the activity of many biocides, in-
cluding 2,2-dibromo-3-nitrilopropionamide(DBNPA), isothiazolone, and methylene
(bis)thiocyanate(MBT).They had no effect on alkyl dimethyl benzyl ammonium chlo-
ride (ADBAC),gluteraldehyde, gluteraldehyde/quatemaryammonium chloride blend,
and poly (oxyethylene-(dimethyliminio)ethylene-(dimethy1iminio)ethylene)dichloride
(polyquat).135
10.2.5.1.4.2 Determine Minimum Effective Concentration and Dosage

Rate. Establishing the minimum effective concentration and dosing rate of a biocide
is an important step. The relationship between biocide concentration and death rate
is rarely proportional and if so, usually exponential.13 The wrong dose can result in
bacterial resistance or in higher corrosion rates.
Dosage must be determined by tests on biofilms, not planktonic bacteria. Bacteria
in biofilms are 10 to 1,000 times more resistant to biocides.lo2Even more intriguing is
that biofilms differ in susceptibility to biocide type. Although hypochlorous acid was
effective against planktonic bacteria, the by-product monochloramine was more potent
against sessilebiofilm bacteria. Substrate may also be important since biofilms on carbon
were more resistant than those on steel.lW
Testing of biocide effectiveness in injection water in Kuwait indicated that biocides
effective against planktonic bacteria are not always effective against sessile forms. In
addition, sour systems responded differently from sweet. For example, the most effective
biocide against planktonic and sessilebacteria in tests without sulfide was a combination
of mixed aldehydes, QAC, and surfactant. When 75 mg/L of sulfide was added the most
effective biocide for planktonic was aldehydes, QAC, and surfactant and for sessile
bacteria it was gluteraldehyde. For all biocides higher doses were required for effective
kill of sessile bacteria.137
394 Water Svstems
In Texas waterflood injection water severely contaminated by bacteria, the effective-

ness of an organic amine-type biocide was tested using a modified Robbins device. In
most wells a 3-h treatment once a week did not give effective kill rates but a 6-h treatment
did.138In Kuwait one biocide treatment per week was insufficient to achieve good kill
of biofilm bacteria; two per week were necessary to prevent biofilm buildup in water
injection systems.137
10.2.5.1.4.3 Monitor Application and Effectiveness. Adding chemicals to a

system without checking them is a basic, often disastrous error committed by many
operators. These checks should include the following:
How much is getting to the equipment (particularlyin the case of oxidizing biocides)
If they are effective
That they continue to be effective over time
Continuous,consistent monitoringis an integral part of any biocide program and should

be conducted, if possible, independently of the chemical supply company. Basic moni-
toring principles and techniques are discussed in Chapter 8, Section 8.4, "Monitoring of
MIC."
10.2.6 Combined Treatment Programs
Water treatment chemicals must be selected based on the temperatures, pH, and other
chemicals present in the water system. Some chemicals added for one purpose react with
other chemicals added for another, e.g., lignins and tannins create a chlorinedemand and
react with iron salts that can contribute to fouling. Dispersantscan provide nutrients for
microorganisms, which increase biofouling and MIC4 In a closed-loop cooling water
system the addition of a organosulfur biocide reduced the chromate corrosion inhibitor
from the hexavalent to a trivalent form, which was ineffective as a corrosion inhibitor.139
Chlorination reduces the effectiveness of ferrous sulfate corrosion inhibitors, possibly
because it encourages flocculation, preventing the formation of the protective colloidal
form.140,141
The approach to water treatment must be an integrated one. An effective cooling
water treatment program must control scale, particulate matter, corrosion, and biological
growth. Over the years a number of such programs have been developed. These include
the following:
Acid/chromate
Zinc/chromate
Stabilized phosphate-may exclude heavy metals but typically require acid feed to
maintain neutral pH
Phosphonate/zinc/polymer
All organic-beneficial where heavy metals must be excluded and where inorganic
phosphates are unsuitable
A major advantage of the all-organic approach is that one product can be effec-
tive in controlling both scale and corrosion. These formulations contain one or more
phosphonates (i.e., amino-tris[methylenephosphonic acid], AMP; 1-hydroxyethylidine
1,l-diphosphonic acid HEDP; and 2 phosphonobutane 1,2,4-tricarboxylic acid, PBTC)
for calcium carbonate inhibition and mild steel corrosion control. A copper corrosion
inhibitor such as tolytriazole and a polymeric dispersant for deposit control are often
added. The efficacy of phosphates and phosphonates in stabilized and all-organic treat-
ment programs hinges on the polymeric inhibitor that controls the thickness of the film
and prevents precipitation of calcium phosphates or phosphonates. The dosage of poly-
mer is critical to calcium phosphate inhibition performance. A terpolymer of acrylic
acid, sulfonic acid, and sulfonated styrene was found to perform better than copoly-
mers containing sulfonic acid. pH, temperature, iron, and cationic polymers all affect
the inhibiting performance.'42
There is increasing concern about the adverse environmental effect of chemicals
added to cooling water. There is also a constant search for more environmentally friendly
chemicals and for ones that are biodegradable.For example,polyacrylate scale inhibitors
and dispersants are generally of low toxicity but are nonbiodegradable and are unac-
ceptable for use in the North Sea. A biodegradable alternative that has been shown to be
effective in laboratory testing is polyaspartates, based on aspartic acid. Polyaspartates
are now being field tested in North Sea oil production rigs and in coal mining operations
in Europe.143
Most of the corrosion and scale inhibitors used in modem cooling water systems
function best within prescribed dosage ranges. Continued operation above or below
these ranges can lead to a range of operating problems. Underdosing and overdosing of
chemicals can have detrimental effects and should be avoided.
The protective films formed by common corrosioninhibitorsfor steel, includingphos-
phates, phosphonates, molybdate, and zinc, are stable only in the presence of a sufficient
concentration of the active inhibitor. At lower levels the film tends to dissolve. Occa-
sional excursions are acceptable but continuous low inhibitor levels reduce corrosion
protection and some corrosion is likely. The resulting corrosion products hinder the film
reforming and can lead to pitting or underdeposit attack even when correct inhibitor
levels are reestablished. When scale inhibitors, such as phosphonates and polymers, are
underdosed scales form on heat transfer surfaces. Once formed they are not removed by
higher doses of scale inhibitors and can also provide sites for underdeposit corrosion.
Occasional overdoses are not particularly harmful but increase costs and can cause
undesirable reactions to take place. For example, at high concentrations zinc can precip-
itate as zinc hydroxide to form a nonprotective deposit; some phosphonates react with
calcium to form a nonprotective calcium phosphonate precipitate; higher-than-normal
levels of inorganic phosphates increase the danger of forming calcium phosphate scale;
at high dosages, anionic polymeric dispersants can react with cationic biocides to form
precipitates that remove both the biocide and the dispersant from solution.
396 Water Svstems
There are a number of ways in which chemical addition can be controlled, based on
blowdown, i.e., chemical dosing whenever the blowdown valves operate; makeup, in
which all makeup water is dosed; or online control, in which chemical analysis of the
water is used to increase or decrease rate of additions. A new method of control uses a
tracer chemical added to the treatment chemical. The tracer fluoresces when exposed to
filtered light and the fluorescence is proportional to the amount of treatment chemical
present. The fluorescence measurement is used to control the chemical addition.14
10.2.7 Standards and Specifications-CoolingWater
10.2.7.1 ASTM
D4778-94(1999)el-Standard Test Method for Determination of Corrosion and Foul-

ing Tendency of Cooling Water Under Heat Transfer Conditions
D5851-95(2000)-Standard Guide for Planning and Implementing a Water Monitoring
Program
10.2.7.2 NACE
RP0182-95-Initial Conditioning of Cooling Water Equipment

RP0196-96--Galvanic Anode Cathodic Protection of Internal Submerged Surfaces of
Steel Water Storage Tanks
RP0300-2000-Pilot-Scale Evaluation of Corrosion and Scale Control Additives for
Open Recirculating Cooling Water Systems
RP0388-9%Impressed Current Cathodic Protection of Internal Submerged Surfaces
of Steel Water Storage Tanks
RP0392-9%Recovery and Repassivation After Low pH Excursions in Open Recircu-
lating Cooling Water Systems
TMO286-94-Cooling Water Test Unit Incorporating Heat Transfer Surfaces
7K1894ontrol Factors in Performance Testing of Nonchemical Water Treatment
Devices (1997 Edition)
7Kl98-Predictably Effective Equipment and In Situ Processes Applied to Water
Systems
7N197-Considerations for Water Reuse in Industrial Plants
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Anon., Industrial Water Use, USGS Water Resources, http://ga.water.usgs.gov/edu/
wuin.html (Aug. 15,2001).
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Anon., A discussion of Stainless Steels for Surface Condenser and Feedwater Heater Tubing
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124.
Anon., “Once through waters,” Chem. Corros. 8, MTI/NACE/NiDI/NIST (1994).
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Process Industries, MTI Publication No. 26 (St. Louis, M O MTI, 1987), 123 pp.
l7 C.D. Tapley, “Copper and its alloys,” in Process Industries Corrosion, eds. B.J. Moniz, W.I.
Pollock (Houston, TX NACE, 1986), p. 196.
l8 B.S. Phull, R.M. Kain, ”Corrosion resistance of nickel-containing engineering materials in ma-
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l9 R. Francis, Galvanic Corrosion: A Practical Guide for Engineers (Houston, TX: NACE, 2001),
142 PP-
2o D.M. McCue, D.K. Peacock, ”Titanium-first choice for desalination plant heat exchangers,”
in Proc Titanium ’92, San Diego (1992), pp. 2795-2802.
21 J.M.A. Quik, M. Geudeke, “Specifying materials for heat exchanger tubing,” MP 34,8 (1995):
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NORSOK Standard for Process Design, P-001, Rev. 4, Oct. 1999, NORSOK, http://www.
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23 British Standard BS MA 18, Salt water piping systems in ships. British Standards Institute
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24 G.L. Swales, B. Todd, “Nickel-containingalloy piping for offshore oil and gas production,” in
28th Annual Conference of Metallurgists CIMM Halifax, Canada (1989),p. 21.
25 C.C. Patton, ”Corrosion control in water injection systems,” MP 32,8 (1993):pp. 4649.
26 W.R. Herda, M.R. Jasner, Materials for Seawater Piping Systems, (Duisburg, Germany: VDM
Technologies,1989):p. 11.
27 J.S. Grauman, Titanium-The Enduring Choice for Sea Water Service, Titanium Metals Corpo-
ration, Internal document, (2000):2 pp.
398 Water Svstems
28 R. Bloomquist, Improved Ship Seawater Piping, Industrial Outreach Div., http://www.

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29 A. Hyde, Wenco Onshore\Offshore Services Division, Adelaide, Australia, e-mail to authors,
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3o Anon., ”Ceilcote Linings from KCH Ensuring the Provision of Fresh Water in
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31 T.J. Glover, ”Recent developments in corrosion resistant metallic alloys for the construction of
sea water pumps,” Corrosion/88, paper no. 323 (Houston, TX: NACE), pp. 1-13.
32 R. Francis, Galvanic Corrosion: A Practical Guide for Engineers (Houston, Tx:NACE, 2001),
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33 R.W. Ross, ”Applicationsin Seawater Systems, Pumps and Valves,” in Materials Workshops for
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34 D.T. Peters, K.J.A. Kundig, ”Selecting coppers and copper alloys. Part I1 Cast products,” Adv.
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35 H. Hofmann, “Advanced innovative and environmental friendly technology of pumps for
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36 D.M. Aylor, R.A. Hays, L.S. Marshall, “Galvanic corrosion evaluation of high performance
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37 G. Kobrin, S. Lamb, A.H. Tuthill, R.E. Avery, K.A. Selby, “Microbiologically influenced cor-
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38 D. Davis, ”Cooling towers,” Cooling Tower Doctor, www.ctdoc.com, 1999 (March 7,2000).
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41 R.E. McCarthy, J.G. Ritter, ”Case histories of cooling tower fill fouling in the electric utility
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42 Anon., Delta Cooling Towers, www.deltacooling.com(2001).
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rosion,” Power, June (1984):pp. S3-S24.
44 G.J. McGiffney, ”Particulate interference and treatment within a recirculating cooling water
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45 T.E. Cloete, V.S. Brozel, A. Von Holy, ”Practical aspects of biofouling control in industrial water
systems,“ Int. Biodeterior. Biodegrad. 29 (1992): pp. 299-341.
46 A. Marshall, G.N. Walker, “Increased awareness of biological control and its implications,”
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47 G.S. Gill, “Silica scale control,” MP 37,11 (1998):pp. 4145.
48 D. Darling, R. Raksphul, “Green chemistry applied to corrosion and scale inhibitors,” MP 37,
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49 H.H. W i g , The Corrosion Handbook (New York John Wiley & Sons, 1948), 1188 pp.
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52 C.P. Dillon, Corrosion Control in the Chemical Process Industries, 2nd ed. (St. Louis, M O MTI,
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57 E. Kalman, I. Felhosi, F.H. Karman, I. Lukovits, J. Telegdi, G. Palinkas, “Environmentally
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76 L.A. Lyons, R. Holliday, S. Zullo, S. Cumnti, “A review: macrofouling control to industrial
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78 C. Gauthier, D. Lowther, ”Remedialcleaning methods for zebra mussel removal,” Corrosion/93
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79 F.S. Spencer, “Zebra mussel research program-1992,’’ Report no. G92-32-K (Toronto,Canada:
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84 P.R. Willemsen, “The screening of sponge extracts for antifoulingactivity using a bioassay with
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85 S. Abarzua, S. Kacan, P. Fuchs, ”Status and potential of natural product antifoulants in recent
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1999), pp. 173-201.
87 D. Rittschof, ”Fouling and natural products as antifoulants,” in Recent Advances in Marine
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88 Y. Imanishi, ”Marine antifouling coating materials,” in Concise Polymeric Materials Encyclo-
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89 J.A. Lewis, ”Prevention of marine growth on naval vessels. A TTCP case study report on the
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91 L.V. Evans (1988) in N. Clarkson, ”The antifouling potential of silicone elastomer polymers,”
in Recent Advances in Marine Biotechnology, Vol. 3, Biofilms, Bioadhesion, Corrosion and
Biofouling, eds. M. Fingerman, R. Nagabhushanam, M.F. Thompson (Enfield, NH: Science
Publishers Inc., 1999), pp. 87-108.
92 E.G. Leitch, “Evaluation of coatings to control zebra mussel colonization: year two interim
report, 1990-1991,” Report no. 02-129-K (Toronto, Canada: Ontario Hydro Research Division,
1992), pp. 1-16.
93 D.P. Edwards, T.G. Nevell, ”Resistance to marine fouling of elastomeric coatings of some
poly(dimethylsi1oxanes)and poly(dimethyldiphenylsiloxanes),”Int. Biodeterior. Biodegrad.
34,3/4 (1994):pp. 349-359.
94 M.E. Callow, ”The influence of low surface energy materials on bioadhesion-a review,” Int.
Biodeterior. Biodegrad. 34,3/4 (1994):pp. 333-348.
95 K. Becker, “Detachment studies on microfouling in natural biofilms on substrata with different
surface tensions,” Int. Biodeterior. Biodegrad. 41,l (1998):pp. 93-100.
96 T.E. Cloete, L. Jacobs, V.S. Brozel, “The chemical control of biofouling in industrial water sys-
tems,” in Int. Workshop on Biofouling & Biocorrosion (Pretoria, RSA: University of Pretoria,
1998), pp. 1-24.
97 R. Prasad, ”Control of MIC in oil production industry: a review,” in 8th Middle East Corrosion
Conference, Bahrain (1998), pp. 95-105.
98 C. Boscan de Gonzalez, H.A. Videla, ”Preventionand control,” in Practical Manual of Biocorro-
sion and Biofouling for the Industry, eds. M.D. Ferrari, M.F.L. de Mele, H.A. Videla (Argentina:
CYTED Research Network, 1998),pp. 54-64.
99 P.J.B. Scott,J. Goldie, M. Davies, “Ranking alloys for susceptibility to MIC,” MP, 30,l (1991):
pp. 55-57.
loo N.J.E. Dowling, D.C. White, R.A. Buchanan, J.C. Danko, A. Vass, S. Brooks, G.L. Ward, ”Micro-
biologically influenced corrosion of 6%molybdenum stainless steels and AISI 316: comparison
with ferric chloride testing,” Corrosion/90, paper no. 532 (Houston,TX: NACE, 1990), pp. 1-11.
lol I.B. Beech, C.W. Cheung, C.S. Chan, M.A. Hill, R. Franco, A.-R. Lino, ”Study of parameters
implicated in the biodeterioration of mild steel in the presence of different species of sulphate-
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Io2 H.C. Flemrning, G. Schaule, ”Measures against biofouling,” in Microbially Influenced Corro-
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1996), pp. 121-139.
lo3 Anon., Ionization, Nature’s Secret Way to Purify Water, (May 5, 2001). http://members.
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E. Heitz, H.C. Flemming, W. Sand (Berlin, Germany: Springer-Verlag, 1996), pp. 105-120.
lo7 M.L. Ludensky, F.J. Himpler, P.G. Sweeny, ”Control of biofilms with cooling water biocides,”
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(London: Wallace & Tieman, 1953), pp. 1-11.
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Microbiol. 54,lO (1988):pp. 2492-2499.
402 Water Svstems
’lo A.H. Tuthill, R.E. Avery, S. Lamb, G. Kobrin, ”Effect of chlorine on common materials in fresh
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E.O. Thomas, K.E. Lucas, E.A. Hogan, S.L. Burton, P.J. Kollmer, ”The effect of electrolytic
chlorination on the degradation of marine materials,” Corrosion/90, paper no. 154 (Houston,
TX:NACE, 1990), pp. 1-7.
‘14 B.S. Phull, LaQue Center for Corrosion Technology, Inc., Wrightsville Beach, NC, NACE
Network (1999).
‘15 S.T. Ginn, J.C.Conley, R.H. Sergent,B.D. Fellers, ”Brominebiocides in alkaline and high demand
cooling waters,” Corrosion/89 paper no. 157 (Houston, TX: NACE, 1989), pp. 1-13.
A. Smith, R. Breckenridge,V. Clay, D. Swindle, “Brominevs. gaseouschlorineA comprehensive
review of case histories,” Corrosion/93 paper no. 637 (Houston, TX NACE, 1993),pp. 1-12.
‘17 M.A. Benarde, B.M. Israel, V.P. Olivieri, M.L. Granstrom, ”Efficiency of chlorine dioxide as a
bactericide,” Appl. Microbiol. 13,5 (1965): pp. 776-780.
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water systems of heat and power station,” in International Congress on Metallic Corrosion 4
(1984), pp. 213-220.
‘19 H.B. Edwards, ”Ozone systems and equipment,” Corrosion/91 paper no. 210 (Houston, TX:
NACE, 1991),pp. 1-29.
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lzz J.M. Brooke, P.R. Puckorius, ”Ozone for cooling tower systems. Is it a panacea?”Corrosion/91
paper no. 212 (Houston, TX NACE, 1991),pp. 143.
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lZ8 W.R. McCoy, J.E. Ridge, E.S. Lashen, “Efficacy of biocides in a laboratory model cooling tower,”
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10.3 References 403
132 A.D. Russell, ”Mechanismof bacterial resistanceto biocides,” Int. Biodeterior.26 (1990):pp. 101-
110.
133 H. Liu, L. Xu, J. Zheng, J. Liu, ”New bactericide for biocide-resistant sulfate-reducingbacteria,”
MP 39,4 (2000):pp. 52-55.
134 C.C. Patton, ”Corrosion control of water injection systems,” MP 32,8 (1993): pp. 4649.
135 L.A. Grab, A.B. Theis, ”Comparative biocidal efficacy vs sulfate-reducing bacteria,” Corro-
136 R.N. Smith, ”Kinetics of biocide kill,” Int. Biodeterior. 26 (1990):pp. 111-125.
137 A. Al-Hashem, M. Salman,J. Carew, ”Screeningand evaluation of microbiologically influenced
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138 R.A. Agostini, R.D. Young, “Investigationof MIC in a West Texas waterflood,” MP 30,3 (1991):
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139 D.G. Honneysett, W.D. van den k r g h , P.F. OBrien, “Microbiological corrosion control in a
cooling water system,” MP 24,lO (1985):pp. 34-39.
140 P.T. Gilbert, “A review of recent work on corrosion behavior of copper alloys in sea water,” MP
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chemical reactions,” Brit. Corros. J. 22,1(1987): pp. 56-62.
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process variables,” MP 36,1(1997): pp. 32-38.
143 J.R. Ross, K.C. Low, J.E. Shannon, ”Polyaspartate scale inhibitors-biodegradable alternatives
to polyacrylates,” M p 36,4 (1997):pp. 53-57.
144 Anon., ”How TRASAR works,” ONDEO NALCO Co., http://www.nalco.com/
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Chapter I
Applications
Material and water interactionsand their subsequent problems apply in many industries.
This chapter describes the principal materials issues and presents typical cases. It also
describes problems and failures where these have occurred. Appropriate materials are
suggested for specific applications based on reported experience.
11.1 SHIPS AND BOATS
Two centuries ago all ships and boats were made of wood. Now, ships are made of
steel, small pleasure boats are made of FRP, and small commercial vessels, including
fast ferries, patrol boats, pilot boats, and work boats, are made of a variety of materials
for a variety of reasons. The material that is considered first for small, slow commercial
vessels is steel because it still is the cheapest. However, if a number of identical vessels
are to be made FRP can become cost competitive because the initial high cost of a mold
can be spread over a number of units. The use of molds to make multiple identical boats
is generally restricted to small pleasure or work boats.'
In the United States there are 737 vessels in the Great Lakes, 33,668 inland, 7,014 Ocean
vessels, 12.3 million recreational boats, and 122 cruise ships. Corrosion is a significant
cost factor in ships and boats totaling, $2.7 billion annually, with new ships costing $1.1
billion, maintenance and repairs 0.8 billion, and corrosion-related downtime 0.8 billion.2
11.1.1 Wood
Wood has been used for marine construction since prehistoric times. Archaeological
investigation has shown that trade existed as early as 4000 B.C. between the Maltese
archipelago and Sicily some 100 km away. No evidence remains about the type of craft
used then; they may have been as simple as rafts or hollowed-out logs. The earliest
representations of recognizable vessels date from 3000 B.C. and show Egyptian craft
405
406 Applications
designed for the Nile and others intended to venture out into the Red Sea. The ship
found in the pyramid of Cheops dates back to about 2600 B.c., is about 40 m long, has
no keel, and is built entirely of short planks of acacia joined together like brick^.^ Marine
engineers have sought effective and economical means to protect ship hulls and marine
structures from the ravages of seawater and marine life for centuries. Wooden hulled
ships were sheathed with lead by tramp coastal traders in the time of Alexander the
Great. Lead, like copper, resists biofouling growth!
The Minoans of Crete were also expert sailors at about this time but little is known
about the type of craft they used. We have some idea of their shape from frescoes and
painted pottery. It is supposed that they were constructed from cypress trees that were
common on the island at that time and used by the Minoans in building construction
(as, for example, at the Minoan Palace of Knossos). The years 480 to 490 B.C. witnessed a
period of feverish shipbuilding throughout the whole of Greece and the Levant that was
responsible for major deforestation of much of the eastern Mediterranean. Ships were
not only lost in battle, but were also attacked by shipworms and had to be frequently
repaired or repla~ed.~
The Vikings have also been mariners since early times. The first known Stone Age
vessels were dugout canoes, which have been found at many coastal sites in Denmark,
the earliest dating to about 5000 B.C. Using flint tools, boatwrights sculpted logs of
soft, durable linden wood to an even thickness of 2 cm. As in all dugouts, the shell
itself provided structural integrity-a true exoskeleton. The canoes reached lengths of
10 m and seem to have been paddled out to sea for cod fishing, whaling, and raiding
expeditions. Some canoes later served as coffins. The creators of dugouts bequeathed
to their successors the ideal of light, open vessels with shallow drafts and long, narrow
hulls.
About 3000 B.c., boat builders along the amose River in Denmark began to bore a
row of holes along the upper edges of their dugout canoes. They could then secure the
lower edge of a plank, with matching holes, to the top of the dugout with cords of sinew
or fiber. The resulting overlap marked the birth of the distinctive northern European
construction technique known as “lapstrake,” a strake being a line of planking. The
added plank improved seaworthinessby increasing the extended dugout’s “freeboard,”
the distance between the waterline and the hull’s top. Axes of Danish flint found in the
far north of Norway and Sweden confirm these Stone Age voyages.
During the Bronze Age (2000 to 500 B.c.), the watercraft of Scandinavia took on some
of the appearance of the future Viking ship, including high posts at each end crowned
with spirals or animal heads. In 1997, one of these longships in which the Vikings made
incredible journeys came to light near Copenhagen. This longship must have been s u n k
by a storm centuries ago, then hidden by silt. Tree-ring dating of its oak planks showed
that the ship had been built about 1025 A.D. during the reign of King Canute the Great
who united Denmark, Norway, southern Sweden, and England in a Viking empire. With
its immense length of 35 m, the Roskilde longship surpasses all previous longship finds.
Other longshipshave been found. One measuring 29 m was made from Irish oak, cut
about 1060 A.D. near the Viking stronghold of Dublin. Another perished as a fire ship,
11.1 Shim and Boats 407
a vessel intentionally set ablaze as an offensive weapon, during an attack on the town
in about 1000 A.D. Here, too, the wood was remarkable, local oak cut from 300-year-old
trees in lengths exceeding 10 m without a knot or blemish.6
While it has served well, wood has alwaysneeded constantmaintenance and frequent
replacement, mainly because of biodeterioration. It became a major problem for the early
explorers who were undertaking longer and longer voyages, often in tropical waters. It
appears certain that many of the earlier explorers who set out on voyages of discovery
and were never heard of again were probably wrecked, not because of poor navigation,
but because their vessels were so weakened by shipworms that they could not withstand
the buffeting in heavy storms.Columbus, on his fourth voyage, lost all of his vessels from
shipworm attack and had to be rescued from Jamaica where the Capitana and Santiago
had been beached at what is now called St. Ann’s Bay on the North Coast. The caravels
in common use in those days were made from pine boards on oak frames and keels.7
The Victory, the fifth British naval vessel to bear this name, was launched in 1756.
This vessel represented the state of the art of shipbuilding at that time and went on to
earn fame at the Battle of Trafalgar. It was built entirely of English oak and elm, with an
oak hull more than 2 ft (0.6 m) thick. The stern post was made from one huge oak tree
and most of the oak used in construction was at least 100 years old. The keel was made
of teak, one of the hardest and most worm-resistant woods in the world, and this was
protected by a false keel of elm. Fastenings consisted of oak pins and copper bolts 6 ft
(1.8 m) long and 2 in. (5 cm) diameter. The Victory was designed to be 2,000 tons but it
has been estimated that it probably displaced closer to 3,500 tons?
The problem of shipworm damage is not merely a problem relegated to history
because wooden boats are still being built today (Figure 11.1).Fisherman in the Jepara
area of Java, Indonesia traditionally locate their villages in the upper reaches of estuaries
so that their boats are docked in fresh water to kill shipworms and fouling organisms.
As in many other traditional societies the boats are also beached about twice a month
and scraped and washed to clean them of marine foulers and borers. Unfortunately, the
Jepara Marine Laboratory of Universitas Diponegoro did not learn from local experience
and moored its wooden research vessel in the sea for long periods. When it began to leak
it was taken in for a refit and the hull was so badly attacked below the water line that
the top half separated when it was dragged up the slip.8
11.1.1.1 Copper Bottoms
In the late 1700s, all ships were made from wood. This was generally satisfactory in
temperate climates but wooden ships could be wrecked in the tropics in 2 months by
shipworms and/or seriously slowed by biofouling. This was a time when the British
Empire was expanding and trying to control large parts of the globe by its naval power.
The British Admiralty tried many methods to try to overcome the attack and fouling
on the wooden bottoms, including lead plate, false bottoms, and cladding with copper
sheets. Captain Cook feared shipworms but did not trust the new procedure of copper
408 Aoolications
Figure 11.1 A wooden boat is under construction in Guyana. (Photo courtesy of CARIAD
Consultants.)
sheathing for ships that he used for his voyages of exploration. He preferred the older
double-hull method of protection, with the space between the outer wood sheathing and
the true hull filled with animal hair and tar. The choice proved fortunate when he struck
a reef in Queensland, Australia in 1770.9
The first recorded scientific trial with copper bottoms was on HMS Alarm in 1763.
After 2 years in service the ship was dry-docked and inspected. The hull was clean
and its timbers sound; the poisonous copper had kept both weed and worms at bay.
Unfortunately, it was found that the copper cladding was virtually completely detached
when iron bolts fixing it to the wooden hull corroded. The only bolts that were not
corroded were ones that were separated from the copper by the brown paper used to
protect the copper sheets in transit.l0
In 1782, four ships sank off Newfoundland when the bottoms fell out in storm. In
this tragedy 3,500 men drowned. Despite these setbacks most naval captains wanted
copper-bottom ships because they were faster and handled better. Under pressure from
the ships' captains in 1799, the whole of the British fleet was fitted with copper bottoms.
Although they did not understand the galvanic effect that was causing the iron bolts to
corrode, they tried to reproduce the beneficial effects of the brown paper on HMS Alarm
by fitting an insulating interlayer of paper coated with tar, linseed oil, rosin, beeswax,
and tallow between the copper and the hull.
Copper bolts were tried but these were found to be too soft. One enterprising
Welshman, Thomas Williams, who had derived much of his wealth by selling copper
sheets, finally developed acceptable copper bolts. These bolts were hardened by drawing
through grooved rollers and their use solved the galvanic corrosion problem. Copper
bottoms were again fitted to naval ships. The naval example was soon followed by own-
ers of commercial ships who found that fitting copper bottoms cut 2 months off the
voyage to India for tea, making a vital improvement in their profitability. Another com-
mercial advantage was obtained by the shippers bringing slaves from Africa to Europe.
They found that with copper bottoms a larger proportion of their "cargo" was still alive
when they arrived at market."
Copper bottoms were still subject to corrosion and erosion so they had to be replaced
frequently. One approach to solving the corrosion problem was the use of cathodic pro-
tection, developed by Sir Humphry Davy. At the instigation of the Commissioners of
the Navy he undertook laboratory tests. After his initial laboratory trials he concluded
that seawater corrosion was not caused by impurities in the copper and that copper
only corroded when oxygen was present. He tested the relative protection afforded by
coupling copper to tin,iron, or zinc and found that, "A piece of zinc as large as a pea, or
the point of a small iron nail, were fully adequate to preserve forty or fifty square inches
of copper. . . "12 After immersion trials in Portsmouth Harbour and extensive field trials
on seagoing ships, he reported that when the copper was completely protected by sac-
rificial zinc or iron anodes, deposition of calcium and magnesium carbonate occurred,
which could lead to biological fouling. If the copper were slightly underprotected foul-
ing would not occur and the copper would corrode only slowly. The seagoing trials
using Davy's recommended amounts of anodes were completely successful in control-
ling corrosion without biofouling. However, some traders from Liverpool, using greater
amounts of sacrificial metal on their copper bottom ships, reported serious f0u1ing.l~The
British Navy was so concerned about the effect of fouling on ship speed that cathodic
protection was not used in practice and copper bottoms were largely abandoned by the
1830s.'* Around this time wooden ships were beginning to be replaced by iron ones.
However, copper cladding was still being used for wooden ships and pleasure craft up
until the mid-l950s, when modem antifouling paints became a~ai1able.l~
11.1.2 Iron and Steel
By the late 1700s, stocks of suitable wood for shipbuilding within Britain were just about
depleted and a European war meant that supplies of suitable timber were becoming
increasingly difficult to obtain. As a short-term solution in countries that were friendly
to Britain, the British Admiralty started to build ships from softwoods or to use tropical
hardwoods such as teak. In 1784, Henry Cort invented the process of iron puddling,
which made iron available in a form and in quantities that made it a candidate for
shipbuilding. The first recorded use of iron to construct a vessel was the 70-ft (21-m)long
barge Trialbuilt in 1787,but the first breakthrough in iron boats came with the launching
of the fast passenger barge Vulcun in 1819. This was used on the Forth and Clyde canal
410 Applications
service between Glasgow and Edinburgh and incorporated designs and methods that
were to initiate the famous Clyde shipbuilding yards that came to dominate the world.
The age of iron shipbuilding in Britain is generally taken to be between 1830 and 1885,
during which time iron began to dominate the output of British shipyards. The change to
iron began some 10 to 15 years later in America and was not so dramatic. An important
year for metal boats in Britain was 1834, when the 125-ft (38-m) all-metal boat, Gary
Owen,was the only boat to survive being driven ashore in severe storms when many
similarly sized wooden boats were de~troyed.’~
The use of iron to replace wood meant that bigger ships could be built, but because
iron could not easily be reshaped once formed, new techniques had to be developed to
produce precision fabrication. Methods of joining using rivets were important because
plates from the puddling process were always small; those used in the Vulcan were only
as wide as 24 in. (61 cm). As iron-making processes improved plates as large as 16 x 3 ft
(5 x 1 m) became available. There was still a lot of skilled, heavy labor required to build
iron ships although this was made easier by the advent of steam-driven tools which
aided boring, shaping, riveting, and caulking of the s e a m (sealing of the riveted seam
by a percussion tool).16
One of the most famous iron ships was the SS Great Britain. This ship was completed
in Bristol in 1843 to a design by Brunel. At that time it was the largest iron ship ever built.
It made its maiden voyage to New York and back in 1845, the first transatlantic voyage
by a steam ship driven by a rear propeller rather than by side paddle wheels. In 1970,
after 33 years beached in Sparrow Cove in the Falklands, the ship was returned to the
Bristol dock where it was originally built and it is now on public
The use of iron only lasted for some 50 years; the first ship of high tensile steel was
launched in 1858 and mild steel was first used in 1879. Within a decade mild steel was
the standard material used for ships and steel prices dramatically fell. Steel ships could
be made larger and lighter than iron ones. Iron and steel ships compared with wood had
two major problems that had to be faced. The first one was that they were much more
prone to underwater corrosion and fouling by various marine organisms. This problem
has only really been solved by the advent of modern paints and coating system. The
other problem was the effect of the ferrous material on the ship’s compass. This magnetic
deviation was tackled by neutralizing the ship’s magnetic field by fitting soft iron bars
and spheres in the vicinity of the compass.16
In 1858, the largest ship in the world at the time, the Great Eastem, was launched. This
vessel was 700 ft (213 m) long and compares with the largest wooden ship ever built, the
Dunderberg, which was a mere 377 ft (115 m) long. Today, we are building steel ships up
to the size of the “Seawise Giant” at 1,504 ft (459 m) weighmg 564,763 tons.15
During World War I1 there was a constant demand for many more ships than were
initially available, and for replacements for those that were sunk. The solution to the
problem was that the United States started producing the welded, so-called “Liberty”
ships in large numbers and much more quickly than was possible by riveting. These
Liberty ships undoubtedly had a positive effect on the war in the Atlantic but, unfor-
tunately, they suffered a high number of dramatic failures. The most famous example
was the SS Shenectudy which broke in two while still in dock, being fitted out for service.
Another Liberty ship was travelingup the River Mersey to Liverpool at a speed of 3 knots.
It grazed a sand bank, broke in two,and immediately sank. A survey of 4,694 ships found
that 970 had sustained some fractures of which at least 12 (one source says 19)broke in
two with the loss of 26 lives. A common factor in these failures was found to be cold
water. It was concluded that they failed because of the following:
The steels used were notch sensitive at low temperature.

The design contained sharp corners and notches, e.g., at hatch covers.
The welds were often poorly made and contained defects.
Residual welding stresses were a factor.
Inspection and quality assurance procedures were inadequate.
Changes in design, material, and procedures were made based on this investigation
and the next generation of welded transport ships, the Victory ships, encountered fewer
and less serious fractures. The unexpected failures in these first mass-produced welded
ships led to the study and understanding of the phenomenon of brittle fra~ture.'~
Steel is now the predominant material for commercial freighters, tankers, and most
passenger ships. This representsvast amounts of steel; e.g., in 1997,the world's merchant
fleet consisted of 85,494 ships with a total gross registered tonnage of 522,197,000.20Un-
fortunately, steel ships do not have an indefinitelife, particularly if they are not regularly
maintained by coating repair and replacement of CP anodes. Eventually they can be-
come completely uneconomic to keep in service (Figure 11.2). More usually, operating
steel ships are kept in much better condition (Figure 11.3).
Steel ship hulls can also be corroded from the inside. It is common practice for the
hull to form part of the internal ballast tanks. These tanks are normally empty but when
they are filled the water used is whatever is available, usually in port. Sometimes these
tanks are subject to very severe pitting, up to 8 mm deep in 12months. This pitting attack
has been determined to be microbiologicallyinduced corrosion (MIC)under mud/slime
deposits containing aerobic and anaerobic bacteria. It was postulated that the bacterial
contamination comes from polluted water used as ballast which would also provide
nutrients. Because the use of biocides or coatings with CP was judged to be impractical,
it was recommended that clean, fresh ballast water be used whenever possible, but that
a program of regular cleaning and monitoring for bacteria should be instituted?l
Modern minesweepers require nonmagnetic equipment, such as winches, and these
are being made from austenitic stainlesssteels such as UNS S20910 (nominallyZCr, 13Ni,
5Mn). Other nonstructural items, such as instrument housings, are made from 316L."
Some military submarines and minesweepers are being built from nonmagnetic steels
to avoid detection by airborne surveillance systems and undersea mines that work on
magnetic principles. The austenitic stainlesssteel being used for these hulls is EN 1.3964
(nominal 21Cr, 5Mn, 3Mo, 16Ni).This alloy was chosen because it is nonmagnetic and
maintains its high ductility and toughness even at high load rate, low temperatures, and
triaxial stresses.=
As ships become bigger and the desire for fuel efficiency increases there is increasing
demand for the use of high strength structural steels with improved toughness, brittle
412 Applications
Figure 11.2 An abandoned ship gently rusts away in the harbor at

Heraklion, Crete. Lack of maintenance is obvious. (Photo courtesy of
CARLAD Consultants.)
1 1 . 1 Ships and Boats 41 3
Figure 11.3 A modern ferry in daily use transports vehicles and people across
the Aegean Sea. (Photo courtesy of CARIAD Consultants.)
fracture behavior, and crack arrest properties. Such steels reduce weight but can be
subject to corrosion fatigue, for example, in ballast tanks. This same desire for weight
reduction is also leading to increased use of aluminum alloys and fiber-reinforcedplastics
in selected applications.”
11.1.2.1 CP of Steel Ships
As steel hulls of ships have become thinner it has become common practice to use a
combination of coating and cathodic protection. A cathodically protected ship with a
good organic coating can remain in service for up to 2 1/2 years without needing to
be dry docked for maintenance. Trials on a mixed system of consumable anodes and
applied current CP were carried out on four Corvettes of the Spanish Navy. They found
that the sacrificialanodes provided almost all of the current required and current demand
was very low. The organic coating used and its frequent inspection and touch-up were
important, as was replacement of the anodes. The level of polarization achieved by the
mixed system was -0.10 to -0.15 V, which was considered to be excellent. In ships of this
type where CP was fitted during construction and maintenance of the hull was rigorous,
the supply of 100 A at 12 V may be unnecessarily high. A lower current of around 1.5
to 2 A and the appropriate number of sacrificial anodes spaced along the hull could be
economically more attractive.=
414 Applications
The current required to protect a ship’s hull depends on the materials, size, and
complexity of the structure, coatings, fouling, and operating environment. A typical CP
system on a modern ship needs to be able to protect coated steel, bare steel where the
coating has become damaged, and the propeller, typically some bronze alloy. It must also
be able to protect under the widely different conditionsthat exist when a ship is steaming
in the open Ocean or static in dock. Seawater flow has been found to greatly increase the
power required to protect bare steel and bronze up to at least 3 m/s. Chalking deposits
have relatively little effect in static seawater, but markedly reduce the effects of flow.
Propeller rotation increasesprotection requirementsmore stronglyon bright bronze than
on aged surfaces. The majority of the effect is at low rpm with relatively little increase
thereafter. It is not sufficient to merely s u m the current requirements of the individual
components;account must be taken of the configurationof the specificprotection system.
Design must also include consideration of the requirements depending on whether the
hull and propeller are clean or fouled, moving or static.26
It is normal to fit two electrodes to a ship’s hull as part of an impressed current CP
system. A zinc electrode is usually used to provide the set point for the potential control.
Because zinc is not a stable electrode, a Ag/AgCl electrode is also installed that is used
to periodically calibrate the zinc electr0de.2~
A particular challenge in the use of CP to protect a steel hull was the case of the
Admiral. In 1907 this ship was a car ferry, in 1940 it was converted into an excursion
boat, and in 1986 it was extensively renovated, fitted with a CP system, and became a
permanently moored entertainment center on the Mississippi River at St. Louis. In 1993,
it was decided to convert the ship into a casino and inspection showed that the 1986 CP
system needed extensive improvement.This early CP used five high silicon iron anodes
in perforated PVC jackets and these had been badly damaged by the debris carried by the
river in the 19-km/h current. The new design in 1993used flush-mounted, high silicon,
button anodes mounted through the hull using watertight stuffing boxes. This meant
that all the wiring and connections could be made inside the hull and does not have to
withstand the river or the passing debris. Permanent copper/copper sulfate reference
electrodes were fitted to the hull and the whole system is now powered by separate
circuits, one on each side of the boat.%
Two French-built ferries for a Greek ferry company will have what is probably the
largest impressed current cathodic protection (ICCP)systems ever installed in this type
of vessel. Nine ICCP systems will be installed on the two ferries, one on each of the hulls
and one on each of the seven propulsion units (four on the 140-m-longferry, three on the
103-m-longone).Mixed metal anodes will be used in this application with reference elec-
trodes installed next to the anodes for monitoring and control. The anodes and reference
electrodes are to be attached with a weld-in-place gland assembly with PTFE seals.29
11.1 2.2 Coatings
Coatings are used to protect steel ships below and above the waterline. The purpose
in both cases is mainly corrosion prevention but the immersed coatings also need to
11.1 Shins and Boats 415
prevent fouling. Immersed sectionsare usually cathodically protected. A typical coating

system for a British Navy anti-submarine ship is as follows:3o
Below the water line-coal tar epoxy covered with antifouling coating.
Above the water l i n e l e a d chromate primer with vinyl topcoat. Restrictions on the
use of lead, hexavalent chromium, organo-tin, and volatile organics mean that new
coating systems will need to be developed for protecting hulls.
Examples of successful applications of coating system include the following:
The FpsoBleo Holm. The topsides were modified and the hookups of the accommoda-
tion module and the helideck were installed on this 100,000-tonvessel to be used in the
North Sea. The exterior areas (80,000 m2)of the accommodationmodule, helideck, and
other facilities were coated with zinc epoxy primer and engineered siloxane topcoat
in 1998.
Tanker Nikator. This tanker, built in 1994 and owned by United Shipping and Trading
Co. of Greece, dry-docked at Hellenic Shipyards for maintenance work for the first
time in 1999. The underwater area showed no fouling or deterioration of the siloxane
coating.
Various coating systems are used for topside equipment.They include the following:
C-1-Two 6-mil (0.15-mm)coats of abrasion-resistant epoxy with 2 mil (0.05 mm) of

either acrylic epoxy gloss or polyurethane gloss
C-2-Two 4-mil (0.10-mm)coats of multipurpose epoxy with 2 mil (0.05 mm) of either
acrylic epoxy or polyurethane gloss
C->Two 4-mil (0.10-mm) coats of multipurpose polyamide epoxy with 2 mil
(0.05 mm) of either acrylic epoxy or polyurethane gloss
C-4-e 3-mil (0.08-mm) coat of zinc epoxy primer with one 3-mil (0.08-mm) coat
of an engineered siloxane
C-%Two 3-mil (0.08-mm) coats of alkyd primer with one 2-mil (0.05-mm) alkyd
finish coat
C-6-e 10-mil (0.25-mm) coat of abrasion-resistant epoxy with one 10-mil
(0.25-mm)coat of an Arctic ice breaker coating
C-7-e 20-mil (0.51-mm) coat of high-solids glassflake epoxy coating
C-8-One 3-mil (0.08-mm)coat of zinc epoxy primer and one 5-mil (0.13-mm)coat of
aliphatic polyurethane
Notes on the systems follow:
1. For C-2, C-3, and C-5a holding primer may be required.

11. For low-temperature application use scheme C-2.
111. For surface tolerance use scheme C-2.
41 6 ADDlications
IV. For long-term protection with minimal maintenance use schemes C-4, C-6, C-7, or
c-8.
V. For long-term protection against mechanical damage use schemes C-1, C-6, C-7, or
c-8.
VI. SpecificationC-4 conforms to NORSOK standard M-CR-501 test requirements as an
anticorrosive two-coat-high performance system.
For ballast tanks one of the following coating systems is recommended:
J-1-Two 6-mil (0.15-mm)coats of polyamide epoxy

J-2-Two 6-mil (0.15-mm) coats of surface-tolerant epoxy; use for low temperature
application
J-&Two 6-mil (0.15-mm)coats of multipurpose epoxy1
Operating vessels still need regular maintenance painting and touch-up (Figure 11.4).
For details of antifouling coatings see Chapter 10,Section 10.2.4, “BiofoulingControl.”
11.1.3 Aluminum
Aluminum has been used to make boats for use in fresh water since at least 1890. For
example, the Swiss firm of Escher-Wyss built the power launches Zephir in 1890, Mignon
in 1892, Wilhelrninu in 1893, and Alurniniu in 1894. Aluminum was first used for marine
Figure 11.4 Maintenance painting is an ongoing process, needed for most ships
in service. (Photo courtesy of CAIUAD Consultants.)
11.1 Shim and Boats 41 7
craft for the Arctic expeditions of Wellman and Jackson in 1894. In the same year a 60-ft
(18-m)torpedo boat, Le Lansqueret, was built in Britain for the French Navy using A1-6Cu
alloy. Over the next decade other marine vessels, mainly racing yachts and naval ves-
sels, were constructed in various aluminum alloys. Many of these early vessels suffered
from severe corrosion because of galvanic corrosion or the use of unsuitable alloys. This
deterred others from using aluminum in marine construction for some time.
By the 1930s, aluminum alloys again found favor and an English boat builder,
Birmabright Ltd., built a whole range of vessels from an A1-Mg alloy. The best known
is the 55-ft (17-m) cruiser, Diana, which was still afloat in 1967 after heavy service that
included a fire and a sinking.Since 1945,aluminum canoes, dinghies, rowboats, and plea-
sure craft have been produced in tens of thousands annually. Whether used in marine
or freshwater service they are either left bare or painted depending on the appearance
desired. The binary wrought A1-Mg has excellent resistance to seawater without any
additional p r ~ t e c t i o n . ~ ~
Welded aluminum is becoming increasingly popular for boats and fast ferries (up to
120m long) because it is lightweight. The alloys being used are 5083 for plate, 6082 for ex-
trusions, and 6061 in the United States. Paint on aluminum lasts longer than on wood or
steel and aluminum is often left unpainted above the water line and on internal surfaces.
Aluminum does suffer from two problems: a low fatigue strength and galvanic corrosion
if in contact with most other metals. Both of these problems are well understood; cor-
rosion fatigue is controlled by limiting stress in critical areas, and galvanic corrosion is
controlledby avoiding dissimilar metal contact and by using insulation when necessary.'
Aluminum and its alloys are not attacked by marine borers or worms or the acids
produced by them, but aluminum boats operating in salt water need antifouling paints
because they have no natural resistance to biofouling. The preferred antifouling paints
for aluminum hulls are those containing tin. Aluminum boats that operate in fresh and
salt water, i.e., in estuaries, do not need coating since exposure to fresh water alleviates
seawater fouling problems.33
11.1.4 Copper-Nickel Alloy
To some extent the story of copper bottoms has come full circle because copper-nickel
alloys have been used for ships' hulls since the 1960s.These alloys are resistant to marine
corrosion and fouling, reducing the need for maintenance. A well-known example is the
Copper Mariner, which was launched in 1971. This vessel has a hull constructed from
6-mm-thick welded copper-nickel plates (UNSC70600) and operates as a shrimp trawler
off the coast of Nicaragua. The hull has shown negligible corrosion and has never had to
be beached for maintenance. In the same operating period her sister ship, of conventional
steel construction, was beached six times for cleaning and repainting.34
Copper-nickel cladding has been shown to be more effectivein preventing biofouling
than 316, aluminum bronze, or tar epoxy coating in a series of 1-year trials.35Solid welded
copper-nickel hulls are becoming popular and can be cost-effective for some vessels.
There is a fuel saving because the hulls stay unfouled, unlike coated steel vessels in
which fuel consumption increases as the hulls become fouled.34
418 Applications
An old 48-tonne ferry, the MV Koru, had its FRP hull sheathed with adhesive-backed
copper-nickel foil in 1993. Koru is a slow ferry that travels at about 10 knots in Auck-
land harbor and is held mostly in reserve for emergencies. The fouling and corrosion
performance of the sheathed hull was monitored by inspection at dry-docking intervals
over the following years. Problems were encountered from galvanic corrosion between
the new hull material and existing hull fittings. A 70/30 Cu/Ni shoe had been installed
along the keel which, unexpectedly, promoted galvanic corrosion of the adjacent 90/10
panels. The keel shoe was replaced with FRP. Silicon-bronze fasteners holding the shoe
were also corroding and these were replaced with 316 stainless steel. The manganese-
bronze rudder shoe and bearing attachmentsshowed signs of dezincification, as did the
propeller. The original CP system had been removed to achieve the optimum biofouling
of the copper-nickel and these other components were no longer protected. Zinc anodes,
electrically insulated from the hull, were installed on the rudder shoe.
Slight to medium fouling, mainly slime formation, had occurred. This tended to
be heavier on sides exposed to sunlight when moored. Patches of small barnacles had
formed, preferentially on the adhesive at the overlap of the panels. Barnacles on the
copper-nickel were easily removed by finger pressure. More recent inspections of the
Koru’s hull during dry-docking (1995-1999) have revealed that the early teething prob-
lems encountered with hull sheathing have been overcome.
A 21-m catamaran, MV Osprey, built as a fast passenger ferry, was launched in
December 1994. The ferry has since been in service for about 30,000 nautical miles
(56,000 km) on the Waitemata Harbour in Auckland. Both FRP hull pontoons were
sheathed from the waterline down with 90/10 Cu/Ni foil panels during construction.
During slipway inspections of the Osprey hull over the next 2 years, galvanic corrosion
of the keep strip similar to that on the Koru was found, and again, FRP was used to
solve the problem. The adhesive performed very well on the FRP hull. The other parts
of the hull appeared in good condition, apart from the leading edges of the two rudder
skegs which showed evidence of erosion corrosion after 6-months’ service. The erosion-
corrosion problem on the foil at the stem can be tolerated and periodically the affected
panels are replaced during a maintenance haulout.
Fouling again consisted of moderate algal growth. The growth was heavier on the
exterior sides of the catamaran pontoons exposed to more sunlight. On the sheathed
hull surfaces between the pontoons, where seawater velocity/turbulence is higher and
sunlight exposure is less, the development of surface slime was minimal. Another factor
that was found to be consistent on both the Koru and the Osprey, was that mechanical
damage to the copper-nickel panels (sustained through collisions with floating debris)
was also minimal. The foil panels were not only durable, but they exhibited excellent
mechanical properties, such as toughness and impact resistance. Additionally, any sig-
nificant mechanical sheathing damage sustained on both vessels was quickly and easily
repaired during normal maintenance time on the slipway?
The initial doubts about the use of copper nickel were based on cost, possible erosion
damage, and galvaniceffects between the copper-nickelalloy and steel or other materials
in contact with it. Although the initial installed cost is high, a number of studies have
shown that copper-nickel hulls, solid, clad, or sheathed, can be cost-effective. Cleaning
11.1 Ships and Boats 419
and fuel costs can be reduced since hull fouling is largely eliminated. The early copper-
nickel boats did not operate at high speed so that erosion resistance was not really tested
in these vessels. Experiments with larger ships were started by cladding the complete
rudder of the roll-on, roll-off ferry Great Land, which operates at up to 24 knots in the
Cook Inlet off the coast of Alaska. Alloys UNS C70600 and C72200 proved to be durable
in this turbulent and abrasive duty. Copper-nickel has also been used in a patrol boat
that has operated up to its maximum velocity of 38 knot for 200 h with no measurable
corrosion.
There is a potential problem with galvanic corrosion of a steel hull covered in copper-
nickel. If there is any contact between these materials in the presence of seawater the
driving force will be large and the steel will corrode rapidly. Techniques have been
developed to insulate the copper alloy effectively from the steel. If there is a leak at a
weld in the cladding and seawater enters the space between the cladding and the steel
supports the steel will initially corrode rapidly. This corrosion will slow and then stop
as the available oxygen is consumed. Tests in the sea and operating experience have so
far shown that galvanic effects have not been a major pr0blem.4.~~
11.1.5 Titanium and Its Alloys
The U.S. Navy’s deep diving research vessel Alvin, originally designed with a steel per-
sonnel sphere, was certified to operate at depths of up to 1,800 m. Subsequent installa-
tion of a personnel sphere made from titanium alloy UNS R56210 and buoyancy spheres
made from the low oxygen titanium alloy UNS R56400 increased Alvin’s certified depth
capability to 4,000 m. There is some danger of stress corrosion cracking or corrosion
fatigue when using high strength titanium alloys in seawater, although the alloys used
in Alvin have relatively good resistance to these forms of attack. The Russian Navy has
built ALFA class submarines with titanium alloy hulls reportedly capable of diving to
depths in excess of 700 m.30The pressure hulls of other deep diving submersibles,e.g.,
the French Nautille, are also high strength titanium alloy.%
Forged titanium parts and components are being used in the Dolphin 3K, an un-
manned cable-laying submersible, the Shinhi 6500 deep-sea research vessel, and a
10,000-m, deep-diving unmanned exploration vessel, the Kaiko. The Shinhi 6500 car-
ries a crew of three, which required a forged sphere with an inner diameter of 2 m and a
wall thickness of 7.35 cm, weighing 4.8 metric tonnes. This sphere needed a number of
new technologies:melting a %ton ingot, the largest at that time; hot forging and rolling
to a thickness of 13 cm with uniform grain and no defects; shaping the hemispheres by
hot pressing the plate while maintaining an even thickness; heat treating for uniform
internal structure; and applying ultrasonic flaw detection.39
There is also at least one all-titanium fishing boat now in service. This was built
by Nippon Steel Corp., Toho Technical Service Co., and Eto Shipbuilding Co. The 4.6-
gross ton titanium boat measures 12.5 m long and 2.8 m wide. It was built at Eto’s
shipyard in Karatsu, Saga Prefecture, on the southern island of Kyushu, using about
3 metric tonnes of titanium. Eto Shipbuilding Co. built FRP ships until 1982, when
420 A d ications
it switched to aluminum. The company has built nearly 70 aluminum fishing boats
and police boats. The titanium fishing boat is lightweight, corrosion-resistant, easily
recyclable, and virtually maintenance-freecompared with FRP and aluminum alloy boats
that need painting to prevent biofouling. Any marine growths that adhere to the titanium
hull can be removed very easily. This Japanese group plans to build pleasure boats,
yachts, and high-speed police boats in addition to more fishing boats.40
11.1.6 Plastics
The U.S.market for small boat hulls (5 to 25 m) is dominated (92%) by fiber glass-
reinforced plastic (FGRP). This material is also extensively used by the U.S.Navy and
coastguard for the hulls of their small boats. These materials are subject to an initial rapid
reduction in strength upon immersion in seawater. With time the rate of loss of strength
declines and finally becomes zero. This strength reduction is included in the design of
hulls by using the final wet strength rather than the initial dry strength. Blistering also
can occur in FGRP hulls. A 1987 survey of readers of Practical Sailor magazine found
that 27% of FGRP boat hulls had developed blisters. Blister formation may be formed by
osmosis of water through the gel coat. A water-resistant barrier layer applied to the gel
coat should reduce the blistering tendency. While blisters have been found in polyester-
based FGRP composites, they have not been reported in those based on epoxy resins.
Carbon fiber construction and mixed carbon and glass fiber composites are also being
considered for use in this type of small boat
Carbon fiber-reinforced plastic (CFRP) is already popular for use in large racing
yachts. For example, the Muri C h ZZZ, which broke the transatlantic speed record in
1998, used structural carbon and aramid epoxy resins extensively in the 200-mm-thick
hull. One attraction in using this type of material is that the structural properties can
be tailored to suit the needs of particular areas of the construction. It can also reduce
the weight of struts that need good specific stiffness in bending and compression. The
efficiency in bending requires high specific stiffness, E/p (where E is Young's Modulus
and p is density), while the higher the ratio of & / p the more efficient the structure
will be in compression. In both of these areas CFRP is more efficient than metals that
might be used for these boat applications. For example, specific stiffness of steel is 26.9,
titanium is 26.7, and aluminum is 26.0, while for high strength CFRP it is 86. Similarly,
the r a t i o a l p for aluminum is 5.1, for steel and titanium it is 5.2, and for high strength
CFRP it is 9.3.41
The Goss Challenger, a catamaran built for long-distance Ocean racing, was largely
made from CFRP.'l This is the yacht (then known as Team Philips) on which a 25-ft (7.6-m)
section of the port bow broke off during sea trials near the Scilly Isles during preparation
for an around-the-world race. The starboard hull was also damaged.42The breaking of
the bow section was identified as a failure of the unidirectional carbon strakes (strips) that
run the length of each side of each hull. These strakes, which are about 500 mm wide and
6 mm thick, are manufactured as part of the inside skin of the sandwich structure of the
hull. The strakes are subject to compressive end loads and tensile loads. The successful
loading of this area is wholly reliant on a satisfactory adhesion of the strake to the
Nomex@core used in the sandwich structure.
Successfulbonding of thick carbon laminates to a Nomex@core has not been problem-
free in the past because it is difficult to remove air, which expands during the high
temperature cure cycle. To overcome this, production methods were devised to enhance
the bleed of air from the cells within the core, thereby enabling a complete bond between
the carbon skins and the core material. Core samples revealed that the expanding air
prevented the carbon strakes from bonding to the core and were therefore unable to
accept the end load applied without buckling. This was diagnosed as an isolated problem
that could be 0vercome.4~
FGRP is also being used to construct the nonmagnetic and shock-absorbing hulls of
minehunters. The first warship with a FGRP hull was the HMS Willow,which was 46.3
m long and displaced 450 tonnes. This was the prototype of the Hunt class of British
naval minehunting ships. Testing during development showed that contact with some
chemicals must be avoided; for example, chlorinated hydrocarbons often found in clean-
ing fluids can severely attack polyester composites. The Osprey class minehunters of the
U.S.Navy are 57.25 m long, displace 800 tonnes, and comprise 300 tonnes of polyester-
glass composite. This type of material has also being used for superstructure compo-
nents for United States naval submarines and is being assessed for other submarine
components.41
The Royal Australian Navy is currently commissioning the Huon Class coastal mine-
hunter which has a structure entirely of glass-reinforcedpolymer (GRP)composites. With
a potential service life of up to 30 years the application of GRP in such large ship struc-
tures requires an understanding of its long-term durability in a marine environment. A
test program is underway to determine the suitability of accelerated test methods for
predictive modeling of mechanical property degradation. Several important issues have
been identified, including reliability of mass measurements for water uptake, the use of
elevated temperature for acceleration, and the dependence of durability on composite
resin c0ntent.4~
Fire regulations are restricting the types of plastics used on passenger boats. In a
number of cases some combination of different materials is being used, such as structural
members made from aluminum sheathed in FRP.'
The thermosetting resins used for boats include isophthalic and orthophthalic
polyesters and epoxy vinyl esters. For seawater an isophthalic resin, such as AROPOL
IS 4633@,is recommended. To mitigate the osmosis effect it is recommended that the first
layer be a chemical barrier layer made with an iso-neo resin type, e.g., AROPOL 7130@,
or with a vinyl ester resin, type Hetron 922@.&
Typical of FRP vessels is the 105-ft (32-m)motor yacht built by Yonca Teknik shipyard,
Istanbul, Turkey. This yacht has a maximum speed of 35 knots with two 1600 HP MTU
engines and a hull designed for 80 knots. It was built using a sandwich construction
consisting of PVC Foam, Kevlar (1)44@ aramid fibers, and Derakane 8084@resin. This
elastomer-modified vinyl ester resin was selected for its superior mechanical strength,
toughness, and good bonding capabilities, which are essential in sandwich structures. It
also protects against osmosis which can be a major problem for GRP marine ~ r a f t . 4 ~
422 Applications
11.1.7 Concrete or Ferrocement Boats
”Ferrocement” is the name given to a boat-building method using steel wires covered
with a sand and cement plaster, patented in 1855by the French, who called it ”Ferciment.”
The earliest recorded examples are the two dinghies built by Joseph Louis Lambot in
1848, in Miraval, France. The Italians call the method of construction ”Ferro-cemento”.
The British, New Zealanders, and Canadians who pioneered the method for amateur
construction called it ”Ferro-cement,” often referred to as “concrete,” which is a mis-
nomer. It is the cheapest and easiest form of construction for boats more than 25 ft
(7.6 m) and apart from strip-plank composite construction, it is the only viable material
for large round-bilge boats within the amateur capability, without the requirements of
special tools or a weatherproof building.
There are three basic methods of construction:
1. Hand lay-up of netting/mesh on a rod matrix is the preferred method for amateur
ferrocement boat construction. The other two methods are quicker but intended for
commercial production.
2. Hand lay-up of ferrocement directly over a mold is also used.
3. The ferrocementslurry can also be sprayed on to the steel reinforcement.This is known
as the shot blast method.
The sheathingof old wooden constructed boats with ferrocementis a tried and proven
process that has been in use for at least 35 years.48
It is estimated that at least 10,000 ferrocement hulls are produced worldwide. In
China, there are some 650 boat yards producing junks in ferrocement.About 20 years ago
more than 700 hulls were manufactured in China and 700 in Cuba. In England one com-
pany has produced more than 1,000hulls and a companyin the United Stateshas built big
fishing boats in ferrocement 30% cheaper than in wood. In Sweden 30 fishing boats and
ice-going fishing vessels were produced in ferrocement.In France the building of the first
ferrocement supertanker started in 1998and a second will follow. In Sweden a company
is producing 35-ft (lo-m) sailboats in steel fiber-reinforcedshotcrete using high strength
steel wire and very high strength concrete, sprayed with heavy duty eq~ipment.4~
The Russians are considering building concrete submarines, called “C-subs.” These
six-man vessels will differ from today’s submarines in several important ways. While
conventional submarines float until they take on water, C-subs will stay afloat using four
electric turbine pumps. The swivelingnozzles that direct this flow also enable the C-sub
to move. The concrete is strong in compression; C-subs could submerge well below the
1,800-ft (550-m) “crush depth” for steel, according to the British Ministry of Defense;
and on sonar displays, the concrete will be hard to distinguish from a sandy sea bottom.
C-subs will also fight differently. Conventionalsubmarines prowl the seas. On a typical
patrol, a C-sub will sink offshore, waiting for enemy ships to pass overhead. Then it will
fire vertical-launch, rocket-powered torpedoes. These torpedoes, code-named “Shkval”
(Russian for squall), can travel through the water at 230 mph (370 km/h), about four
times as fast as conventional torpedoes.50
11.2 ProDellers. Shafts, and Fittings 423
11.1.7.1 Ferrocement and Epoxy/GRP Combinations
Either cement on its own or sand and cement mixed with epoxy to create an “epoxy
mortar” is marketed by many manufacturers around the world under various brand
names. There are also manufacturers who market it with added shredded glass, carbon
fiber, and various other stranded materials, used mainly for bridge and building re-
pairs. Experimentsto improve steel-reinforcedplaster (ferrocement)and glass-reinforced
plastic (GRP) by mixing the two in various combinations have been made, mainly in
the 1950s and 60s. The intention has been to combine the long-life and high-impact
resistance of ferrocement, with the weight advantage but rapid deterioration of fiber-
glass. The experimentslooked for reduction in weight, increased flexibility,or increased
strength/impact resistance. In most cases there have been problems caused by osmosis
and expansion?1
11.2 PROPELLERS, SHAFTS, A N D FITTINGS
The design and materials used for propellers are very dependent on the size and type of
ship involved. In larger ships they are often based on some type of bronze (Figure 11.5),
while smaller props can be made from iron-based alloys. CF3 (cast 304L) is a standard
Figure 11.5 This bronze propeller from a naval vessel dates from World War 11.
424 ADDlications
material for propellers on work boats, controllable pitch propellers, and bow thrusters.
Despite its low corrosion fatigue strength (CFS)this stainlesssteel is satisfactory, probably
because when in motion the seawater is not corrosive. When the ship is at rest in dock
the sacrificialanode system protecting the hull and rudder also protects the propeller.52
It has been shown that the CFS of CF4 (cast 304 with 0.04% C maximum) can be increased
from 62 to 138 MPa by cathodically protecting to -0.85V.53
Propellers, shafts, and rudders made from Ferralium 255 (UNS S32550) have been in
service in patrol boats and hovercraft, in some cases since the 1970s. This alloy has also
been used in aircraft carrier catapult trough covers, submarine mechanical shaft seals,
and many components in submersibles, such as the research vessel Duplex
2507 is also being used for propellers.
Despite its short service life as a result of crevice corrosion 304 is widely used for
marine wire ropes. Diverse marine applications use 316,316L, CF3M, and CFBM and
their success depends largely on factors such as cleanliness, weld quality, and avoiding
stagnant conditions. Where higher strengths are needed 17-4PH (UNS S17400) is used;
for example, it has been used for shafts on trawlers where stagnant conditions and pitting
would not be expected.%When seagoing vessels are expected to lie idle more resistant
shaft material, such as 22 Cr, 13 Ni, and 5 Mn, are preferred. Shafts with intermediate
corrosion resistance are provided by 18 Cr, 2 Ni, 12 Mn, and the high nitrogen 304 stainless
steel (304 HN).52
Carbon fiber composites are also being used for shafts. While they are of a larger
diameter than the steel equivalent they are also much lighter.'
Propellers for very large ships are usually made from cast aluminum-bronze. For
example, Cu 77-82, A1 7-11, Mn 0.5-4, Zn <1, Fe 2-6, Ni 3-6, Sn <1, and Pb t0.03.
For vessels with very wide hulls the propeller is sometimes set off-center to increase
efficiency and save energy?7 Cast NAB is also used for propellers and bow thrusters;
and 316L is regularly used on deck fittings, pulley blocks, hinges, etc.
Canadian Forces ships adopted the practice of grounding shafts and propellers, which
was found to lead to increased fouling of the aluminum-bronze propellers and increased
CP current requirements. Grounding was instituted to avoid problems of intermittent
protection of the shafts and propellers. Trials on some ships using the Canadian naval
standard antifouling paint, 0.5 pm vinyl wash primer, 125 pm aluminum vinyl anticor-
rosive, and 125 pm cuprous oxide antifouling, found that fouling was reduced and CP
current demand on the hull decreased by 20 to 30%. The coating was undamaged except
where cavitation had occurred?*
The cast copper-based alloys that are used for propellers can be damaged by high
velocity water (Table 11.1).
Concerns have been expressed about possible galvanic/crevice effects between
graphite/ITFE composite-type packing and stainless steels. Natural seawater testing
of simulated boat shaft/stuffing box assemblies revealed little difference in the overall
crevice corrosion behavior of 316L when in contact with a graphite/PTFE composite
or flax fiber-type packing. While periodic rotation of the shaft showed some beneficial
effect, the use of sacrificial zinc anodes was almost fully effective in preventing attack in
60-day tests.60
11.3 Shipboard Equipment 425
Table 11.1 Water Velocity Guidelines for Copper

Alloy Propellers and Pumps59
Peripheral
Alloy Velocity, m/s
Leaded red brass (C83600) t9.1
Silicon brass (C87600)
Tin-bronze(C90300) t13.7
Leaded tin-bronze (C92200)
Aluminum-bronze(C95200) t22.8
High-strength brass (C86500)
Aluminum-bronzes(C95500, >22.8
C95700, C95800)
It is possible to reclaim worn shafts by thermal spraying the bearing areas with a
coating of 316 stainless steel. Arcspray or flamespray techniques are suitable to bring the
shaft up to its original diameter at much less than the replacement cost. On manganese-
bronze propeller shafts, bearing areas reclaimed in this way with 316 gave up to twice
the life of the original materials and reduced total maintenance costs. The same thermal
spray processes using 316 stainless steel can be used to repair worn rudder posts and
put them back into service cheaply and quickly?
11.3 SHIPBOARD EQUIPMENT
11.3.1 Marine Tankers
Marine chemical tankers are generally used to transport wet process phosphoric and
sulfuric acids but they may also be used for other chemicals. They have typically been
made from 316L, 317L, 317LN, and 317LMN. The 317 grade is a lot better at handling
the impurities present in wet process phosphoric acid but even this stainless steel can be
attacked by some grades of acid.62Marine chemical tanks are not designed to be filled
with seawater as ballast but should be able to withstand occasional washing out with
chloride containing water in an acidic environment.
In order to withstand this occasional washing better and to be able to carry a wider
range of chemicals duplex 2205 is now being used for this application. This duplex alloy
has a higher strength than the standard austenitics so can also offer a substantial weight
saving. Since the duplex alloys are more corrosion resistant they are also more difficult to
clean and pickle than the 300 series austenitics. It is important to use the correct solution,
HF and HNO3, and to leave the cleaning solution in place for longer periods, around
50% longer than for the austenitics.63
426 A d ications
11.3.2 Marine Fasteners
Fasteners to be used in seawater need to be resistant to corrosion, particularly to crevice

attack, and have sufficient strength for the duty. Marine fasteners are used on metals,
wood, plastics, or other nonmetallic materials. Fasteners exposed below the water line,
such as bolts in the keel and bilge area, are an integral part of the safety of all boats
and ships. Very few fasteners can be used with aluminum when immersed in seawater
since the bolt or fastener hole tends to enlarge rapidly by galvanic corrosion. The only
possibility is to use a stainless steel or aluminum alloy that is noble to the aluminum
structure. Insulation by the use of sealants may help avoid galvanic attack but cannot be
relied upon in critical applications.Similarly,galvanic corrosion is often a major factor in
the use of copper-based alloys and stainless steels as fasteners for copper, stainless steel,
or Ni-Cr-Mo alloys. Pitting or crevice corrosion may be a problem in this type of joint.
The higher alloyed Ni-Cr-Mo can be used as fasteners for these materials. Graphite or
carbon packing, gaskets, etc. or rubber with carbon filler should be avoided in contact
with any metals immersed in the sea because the driving force between carbon and
most metals is very large. All of the high strength alloys may be subject to hydrogen
embrittlementfrom hydrogen produced by galvanic action or applied CP. Typical alloys
used as marine fasteners are as follows:6q
Precipitation hardening Cu/Ni alloys with Mn, Al, and Fe

Nickel-based alloys such as 625, C-276, and 59
Precipitation hardening nickel-based alloys such as 925 (UNS N09925), 725 (UNS
N07725), and MP35N (mUS R30035)
Duplex stainless steels 2507 and 255
6%Mo austenitic stainless steels
Titanium has excellent resistance to all forms of seawater corrosion and high strength
titanium alloys are being used in marine fasteners, such as in navy submarine hatch
covers.65Ti-5Al-lSn-lZr-lV-O.8Mo(Ti-5111)is a near-alpha titanium alloy of interme-
diate strength, excellent toughness, and room-temperaturecreep resistance designed in
a U.S. Navy-sponsored titanium alloy development program for structural submarine
applications. This alloy is now being used in a new submarine communication mast.
Ti5lll’s desirable mechanical properties and excellent corrosion resistance make this
alloy an ideal fastener material from both a technical and economic perspective.66Its
dynamic initiation toughness is more than three times that of TIMETAL 6-4 ELI (UNS
R56402) and about half that of alloy K-500 for 1-in.-thick samples. Weld toughness is
generally within -30% of the parent material toughness. TIMETAL 5111 is classified as
ASTM Grade 32 and UNS R5111.67
A new high strength copper-nickel alloy (nominally Cu with 14.5% Ni, 3% Al,
1.5%Fe, and 0.3% Mn) has been introduced into marine applications.The alloy, Nibron
Special@,is said to have better strength, ductility, and corrosion resistance than the
copper alloys and stainless steels currently used in marine environments. Testing in
sulfide-contaminated artificial seawater showed that this alloy had a lower corrosion
11.3 Shinhoard Eauioment 427
rate than 90/10 or 70/30 Cu/Ni. It is also immune to hydrogen embrittlement and resis-
tant to a variety of marine environments, including ammonia and amine-contaminated
solutions. Initial applications have been for manifold bolting in offshore subsea struc-
tures and riser clamps. It has also been used in diving set components and hose
connectors
Achieving reliable long-term performance of high strength bolts for flange connec-
tions in subsea service is a critical issue for the offshore industry. Viable bolting materials
with high strength that are not susceptible to embrittlement or galvanic corrosion with
stainless steel flanges are limited. The viability of using 87 carbon steel stud bolts and 316
stainless steel (SS) seal rings in a duplex SS flange for subsea service was investigated.
The laboratory test system used full-size commercial flanges, bolts, and seal rings to
simulate electrochemical conditions that occur in crevices associated with carbon steel
bolts in a duplex SS flange and with the use of a 316 stainless steel seal ring in a duplex
SS flange. Current densities and potentials at precise locations within the crevices were
monitored throughout the tests as parameters were changed. Test parameters included
cathodic protection level, temperature, and sealing the outer flange gap. CP was pro-
vided by remote aluminum sacrificial anodes to achieve potentials typical for a subsea
manifold. Both electrochemical data and examination of the components at the end of
the 164-day exposure showed that sufficient CP reached the crevices to give long-term
corrosion control of all of the components. The possibility of using B7 bolts instead of
high alloy bolts offers significant cost savings.70
Bolting for marine service can also be protected using inhibited grease under pressure
in a thermoplastic cover. This system has been shown to be effective in actual applications
and in salt spray and hydrogen sulfide tests.71
11.3.3 Condensers and Heat Exchangers
The 90/10 Cu/Ni alloy (UNS C70600) has been the standard material used by the U.S.
Navy for seawater piping, heat exchangers, and condensers. It has sufficient biofouling
resistance to avoid the need for chlorination or sponge-ball cleaning needed by other
materials. Problems have been experienced with this material, however, with sulfide-
accelerated corrosion and erosion corrosion.Titanium and stainless steels can withstand
higher velocities than the Cu/Ni alloys and have also been used for ship condensers. A
trial titanium ship service turbine generator condenser was installed in the USS Elmer
Montgomery in 1983. This condenser consisted of seamless grade 2 titanium tubes rolled
into a grade 2 outer tubesheet. The inner tubesheet is steel, the waterbox is alloy 625
(UNS N06625), and the cooling water is chlorinated.44
11.3.4 Multieffect Desalination Evaporators
Multieffect evaporative desalination units have been designed specifically for use on
ships and oil and gas platforms to produce a supply of fresh water. On ships such as
428 Aoolications
cruise liners, merchant fishing, and fish factory ships, waste heat is available to power
such units. The compact units comprise 316 heat exchangers and condensers with the
rest of the plant made from 90/10 Cu/Ni (UNS C70600). A six-effect unit can produce
800 m3 of fresh water per day with very efficient energy recovery and use.72
11.3.5 Naval Centrifugal Pumps
Centrifugal pumps are used on naval vessels for many different applications. They are
required to withstand arduous conditions and be very reliable. The pump case is often
made from a metal that is anodic to the impeller to provide it with some galvanic protec-
tion, particularly during standby periods. Stainless steel centrifugal pumps use CN7M
for the case and impeller with alloy 20Cb3 or K500 shafts. Various combinations of non-
ferrous materials are also successfully used for these pumps, for example, cast Cu/Ni
(UNSC96400)case with an alloy 400 impeller and alloy 400 or K500 shaft. An alternative
that is used by the British Navy is IN768@case, heat-treated cast aluminum-bronze (UNS
C95800) impeller, and alloy 400 or K500 shaft.73
11.3.6 Marine Valves
High integrity valves are fitted into naval ships of many countries for a variety of appli-
cations, including:
Surface ship valves-low pressure systems and hull valves

Submarine inline valves-low and medium pressure
Submarine hull valves-shockproof hull penetration
Weapon discharge system valves-for vent and blow, flood, and drain applications
These valves are mostly made from copper alloys, particularly nickel-copper, copper-
nickel, and nickel-al~minum-brone.~~
11.3.7 Ferry Decks
The profitability of roll-on/roll-off ferries can be increased if the payload they carry can
be increased. The use of a stainless steel sandwich construction reduces the thickness
of decks, which gives more headroom between decks, higher payload, and reduces the
center of gravity of the ferry. The modular deck panels are made from 304 stainless steel
that is durable and needs no painting or other maintenance. These panels are also lighter
than conventional steel deck panels so ferries fitted with these car decks should be able
to increase speed and fuel effi~iency.~~
11.4 DOCKS, PIERS, AND OTHER AQUATIC STRUCTURES
Breakwaters and simple docks have been built since man first began to venture out
on lakes, rivers, and oceans in wooden boats, rafts, and canoes. The early structures
were made from stones and rocks or wood. Today there are many elaborate structures
such as trestles, piers, harbors, breakwaters, etc. built for a variety of purposes in many
different aquatic environments.The most common materials for these modern structures
are concrete or steel, with wood still being used occasionally.
Probably the most ambitiousmarine structurecurrently under discussionis the Mega
Float project in Japan.Japan has limited land resources and already uses about 50%of its
shallow sea area; therefore it has looked at reclaiming more deep sea areas for expansion
projects. The Mega Float concept is to build a very large floating marine structure to
provide additional space for development. In April 1995, the Technological Research
Association of Mega Float consisting of shipbuilders and steel-makers was established
to implement a research and development project of structures with spans of several
kilometers and a lifetime of more than 100 years. These very large floating structures
could have a wide variety of possible activities, including airports, harbor terminals,
energy-related facilities, and leisure fa~ilities.~~
11.4.1 Wood
Some wooden marine structuresfrom antiquityhave been preserved by freak conditions.

A good example is Seahenge near Holme-next-the-Sea in Norfolk, England. This Bronze
Age monument was submerged in the sea until the shifting sands finally revealed the
remains some 4,000 years later, in 1998. The circle consists of a large central oak stump
surrounded by 56 oak posts and is thought to have formed some kind of ceremonial
site, perhaps with special astronomical or other significance. Alternatively, it has been
suggested that it was a place of "excarnation," where bodies were laid out after death
to hasten the process of decomposition and speed the spirit on its way to the afterlife.
In the summer of 1999, the find was recorded and removed to the Flag Fen Bronze
Age Centre, near Peterborough. There the ancient timbers, as well as being preserved,
were subjected to detailed dendochronology(tree-ringdating) and carbon dating. It was
from these that such a precise date could be arrived at for the felling of the trees that
make up the Seahenge circle. The tree-ring data was statistically analyzed to give the
date of felling as 2050 B.C. The time of year was found by examining the final growth
ring of the main stump, which showed that the tree had been felled between April and
June.n
Unfortunately, not all wooden structures last so long in marine exposures. For exam-
ple, a 70-ft (21-m) section of a wooden wharf at a power plant on the East River, New
York collapsed suddenly after some 50 years in service. The cause was wood boring
organisms that have apparently become more prevalent as pollution has decreased and
water quality has improved. Increased damage to wooden structures has been reported
Next Page
430 Aoolications
all along the city's 1,000 km of shoreline. To control damage to the remaining pilings
the intention is to wrap them in plastic sheets that are sealed at the top and bottom.
Hopefully, this will restrict the oxygen supply to the wood-boring organisms around the
piles.78
Wood has usually performed well in dock and harbor applications, limited mainly
by borer attack in the immersion zone and termite and fungus attack in the atmospheric
zone. Chemical treatments traditionally used to protect timber have, however, become
less available because of environmental concerns. As coastal waters have become less
polluted with toxic substances there has been an increase in marine borer activity in
many harbors. This has meant the timber is often no longer the first choice for new
construction or repair
In cases where wood is readily available locally it is still being used in traditional
ways even if durability is limited. Rapid destruction of wood and bamboo is a well-
known problem on the north coast of Java, Indonesia. Bamboo poles are used primarily
for fishing structures and are notorious for collapsing within about 6 months, with un-
fortunate results if they happen to be inhabited. All the bamboo examined at Jepara, Java
which had been in the water for a year or more was extensively bored.'
Sometimes attempts to improve durability of existing wooden structures introduces
new problems. Dunoon Pier, on the north side of the Clyde estuary in Scotland, is made
of wood and has operated as a ferry terminal since the early 1800s. Changes have been
made over the years as the traffic at the pier altered, until in 1972 it was decided to start
operating side and stem loading, roll-on/roll-off ferries from the pier. This required the
construction of a concrete ramp with a steel link span. By 1986, a survey found that
the concrete work was in a bad condition from chloride attack, largely resulting from
poor design and workmanship when the new reinforced concrete had been attached
to the existing wooden structure. The concrete was repaired with sprayed-on concrete
and a cathodic protection system was installed using conductive polymer and expanded
titanium mesh anodes. Silver/Silver chloride referenceelectrodeswere incorporated into
the construction. Because both bare steel and reinforcing steel were connected through
the CP system, the bare steel tends to act as an anode for the concrete-encased steel and
reduces the current demand from the CP system.80
11.4.2 Stone
Piles of rocks can often be seen acting as a main sea barrier and also support jetties,
breakwaters, harbor walls, etc. (Figure 11.6). Sometimes the stones are shaped into large
blocks (also known as ashlar masonry) and massive structures have been built in this
way since antiquity. An early example is the port facilitybuilt in the 3rd and 4th centuries
B.C. at Phalasarna in Western Crete. Since the island of Crete is tilting up at the west and
down at the east this ancient port is now high and dry, some 100 m inland. The stone
walls used to construct the port facility, protective fort, and inner basin can still be seen
(Figure 11.7).
Previous Page
11.4 Docks, Piers, and Other Aquatic Structures 43 1
Figure 11.6 Piled rocks are often used to provide a protected entry for small ves-
sels to a sheltered harbor. This breakwater is in Heraklion,Crete. (Photo courtesy
11.4.3 Concrete
Today reinforced concrete is often used for marine structures. In the case of breakwaters
concrete tetrapods are commonly used and are reasonably effective at dissipating the
power of the waves, thus protecting the coastal areas (Figure 11.8).
The use of concrete in these applications has not been entirely trouble-free. For exam-
ple, reinforced concrete docks in Venezuela were seen to be corroding after only 6 years
of service. One is a ship dock located 1 km from the shore, the other is a boat dock at
the shore. The compressive strength of the concrete used was found to be less than the
specified 210 g/cm2 and was thus inadequate for this marine application. The worst
damage was seen in the tidal and splash zones and on the footbridge giving access to the
boat dock. Cracks were seen to penetrate right through the platform and severe crack-
ing was also found in the prestressed concrete support beam. The stressing cables and
reinforcing were badly corroded by chloride ingress. It was recommended that chloride-
contaminated concrete should be removed, the docks repaired, and impressed current
cathodic protection should be applied to the quay of the boat dock and to the beams of
both docks after repair.61
Similar problems with concrete were identified in a survey of five major commercial
harbors in Taiwan. They found that chloride penetration into the reinforcement had
occurred and the reinforced concrete structures were deteriorating. Half-cell potentials
432 Aooiications
Figure 11.7 This is part of the port facilitybuilt in the 3rd and 4th centuries
B.C.at Phalasama in western Crete. Large stone blocks were used in this
early construction. (Photocourtesy of CARIAD Consultants.)
Figure 11.8 Concrete tetrapods protect Male, the capital of the Maldives. The entire country
consists of low-lyingatolls with a maximum altitude of a few meters. (Photo courtesy of CARIAD
Consultants.)
measured at a wharf in the Taichung harbor indicated with a 90 to 95% probability

that corrosion had initiated in the area measured. The main factors causing corrosion of
reinforced concrete in these marine applications were the following:
Insufficient concrete cover on the reinforcement

Design and construction not applicable for marine exposure
No periodic maintenance
Severe ingress of aggressive agents, C1- and SO;* 82
The first phase of a port in the Arabian Gulf was completed in the late 1960s using
reinforced concrete. When the second phase was started in the late 1970s indications of
reinforcement corrosion were noted on the earlier phase. The highest chloride levels were
seen in areas that become wet at extremelyhigh tides and then dry out completelybefore
being wet again. This allows chloride levels to build up and cause reinforcement cor-
rosion. Conventional repairs were undertaken on the damaged areas and an impressed
current CP system was in~talled.8~
In the Arabian Gulf, a 10-km-longtrestle made of very high strength,extremely dense,
centrifugally cast concrete was severely attacked by mussels, Lithophap, and sponges,
434 ADDlications
Clionu. In only 4 years the bivalves had penetrated to a depth of several centimeters,
approaching the central steel reinforcement.84This case was particularly interesting be-
cause of a lawsuit over who was responsible for the damage. The courts found that the
problem was to be considered an "act of God" as it was completely unprecedented and
no blame could be attached to the construction company. That company had engaged
experts in the field to determine the cause of the problem. Cores from two concrete types
that were used in Saudi Arabia and another from a tropical location that had not ex-
perienced problems of borer attack were exposed to Lithophgu and Cliona in Jamaican
~ a t e r s . 8The
~ primary factor in the biodeterioration was found to be the high calcium
carbonate content in the Saudi Arabian concrete, as the fine and coarse aggregates were
both carbonates. Because Lithophgu and Cliona are both chemical borers, they perceived
the concrete as merely a rather hard carbonate rock, such as coral.
When the repair contract went out to tender the original construction company
won the job, as by that time they were the only world experts on the problem. The
piles were mechanically cleaned and coated in epoxy resin in situ to prevent further
attack.@
The Living Seas is a 21.6-ML seawater aquarium constructed of reinforced concrete.
Despite the use of good quality concrete and a design cover of 7.5 cm concrete over
the reinforcement, rust stains and corrosion were observed on the saltwater side of
the main tank walls only 2 years after construction. A CP system was designed and
installed to prevent further deterioration. The factors considered to be important in
the design were compatibility with the marine life, the seawater chemistry, the poten-
tial for stray current corrosion with structures in the aquarium, ease of installation,
aesthetic appearance, and cost. The system selected uses sacrificial magnesium anodes
because:
1. The magnesium ions liberated from the anodes replenish magnesium in the seawater
which benefits the water chemistry.
2. The potential gradients generated by the anodes have no detectable effect on fish
behavior.
3. The anode current output can be controlled enabling the system to be fine tuned.
4. The system was simple and easy to install.
5. The system is economical to run,currently consuming some 365 kg of magnesium
annually.s6
Most properly made concrete structures, however, perform well. The 2,100-m-long
pier at Progreso, Mexico is said to be the most durable concrete structure in marine
service in North America. It was constructed between 1937and 1941using stainless steel
rebar because of the hot, humid marine environment and because of high porosity in
the limestone aggregate. A later pier was constructed next to the first one using carbon
steel rebar and virtually disappeared within 30 years. The pier with the stainless steel
rebar was inspected in 1998and judged to have at least 20 to 30 years remaining life even
without significant routine m a i n t e n a n ~ e . ~ ~
11.4 Docks, Piers, and Other Aauatic Structures 435
11.4.4 Steel
Steel, often protected by coatings and/or CP, is a common material of construction for
piles, piers, jetties, etc. It used to be accepted that mild steel immersed in seawater
corroded at around 5 mpy (0.13 mm/y) and that this rate was linear with time. Long-
term corrosion tests showed that this was incorrect and that the corrosion rate decreased
with time. This effect was shown clearly when a steel pier near Santa Barbara was
dismantled after being immersed for 23.6 years. The piles from the pier were measured
and compared with some of the original pile material that had been encased in concrete
during this period. Corrosion rates were determined at around 1.5 mpy (0.038 mm/y)
ranging from 1.34 to 1.72 mpy (0.034 to 0.044 mm/y). It was concluded from these data
that a conservative estimate of corrosion rate of steel immersed in seawater was an
average of 2 mpy (0.05 mm/y) for the first 20 years, reducing to an average of 1 mpy
(0.025 mm/y) thereafter.88Other tests at Wrightsville Beach found average corrosion
rates of about 3 mpy (0.08 mm/y) for mild steel over an 8.5-year period.89
The corrosion rate of carbon steel piles varies considerablywith depth of immersion.
A number of corrosion zones have been identified. They include the following:
Marine atmosphere. Rate of corrosion is highly sensitive to alloy content that affects
durability of protective surface film.
Splash/spray zone. This is an aerated seawater environment that acceleratescorrosion
for some metals, e.g., mild steel; others, such as stainless steels and titanium, are
generally resistant here. The extent of the splash zone varies depending on location,
e.g., in the Gulf of Mexico it covers about 2 m (6 ft), in Cook Inlet, AK it is around 9 m
(30 ft), and in the North Sea it can approach 10 m (33 ft) during winter
Intertidal. With metals alternately wet and dry, biofouling occurs, which can cause
localized corrosion of other metals including stainless steels.
Shallow ocean. Biofouling also occurs in this zone. Titanium performs well here; the
rate of corrosion of steel largely depends on the availability of oxygen.
Deep ocean. Biofouling is reduced, and temperature and oxygen content are more
stable. Steel corrosion is less than at the higher levels.
Mud zone. Here anaerobic sediments contain bacteria that produce sulfides corrosive
to steels and copper alloys. The rate of corrosion of steel is normally lower than in the
water column because of the reduced oxygen?l
The subtidal zone extends for about 0.3 to 1.0 m immediately below mean low tide.
In this region steel corrodes at a higher rate than anywhere else in the immersed zone.
This and the low corrosion rate in the adjacent tidal zone have been attributed to a
galvanicoxygen-corrosionmechanism.This effect was illustrated by exposing individual
steel samples under the same conditions as a continuous steel strip. The metal lost by
corrosion for individual specimens in the tidal zone ranged from 0.37 to 0.52 mm over a
5-month period. The corrosion loss was only 0.05 mm in the sameregion of the continuous
strip in the same period, while the anodic corrosion sites below mean low tide were
436 Aoolications
penetrated to around 0.13 mm. The galvanic process operating on a continuous steel
item immersed in seawater can be explained in terms of differential aeration and can be
completely suppressed by the use of CP. In the splash zone the maximum penetration in
the continuous strip was 0.34 mm, while the discrete specimen lost 0.61 mm in the same
time?9
Recent experience in the United Kingdom and Northern European waters has indi-
cated that the worst area of corrosion for mild steel is not necessarily in the splash zone
but may be in the subtidal, i.e., that part of the pile that is never dry. This subtidal corro-
sion is very localized, typically being a large pit 50 to 100 mm in diameter; the outward
appearance is of a very red-orange deposit that hides a black mass, beneath which is
bright, shiny steel. This phenomenon, which is referred to as accelerated low water cor-
rosion (ALWC),has been recorded in the United Kingdom, France, Germany, Belgium,
and the Netherlands. There is also evidence that it has been found in the Caribbean,
Japan, Hong Kong, and Singapore.92Consortia of bacteria have been implicated in this
type of corrosion and rates of at least 2 mm/y have been observed. Both sacrificial and
impressed-current CP systems can protect a sheet piling wall or similar steel item from
this type of atta~k.9~
The MIC mechanism was confirmed by a multinational European research project
that also looked at methods of prevention or remediation. Sulfur-oxidizingbacteria were
present in greater numbers at sites where accelerated attack of piles was occurring. Other
parameters that varied between accelerated and normal low-water corrosion harbors
were the mean tidal range, the thickness, homogeneity and organic content of corrosion
products, the pH beneath corrosion products, the redox potential of seawater, the pres-
ence of algae and invertebrates, and the total organic carbon content of the water. Steel
coupons coated with epoxide or polyurethane proved to be resistant to these simulated
~onditions?~.~~
The highest corrosion rate is often in the splash zone where the steel is intermittently
wet and dry, while the highest rate in the immersed section is just below the mean low
tide. Some grades of high strength, low alloy steels (HSLA), particularly those with
Ni-Cu-P, are more resistant to the atmospheric and splash zones than carbon steel, but in
the immersion zones there is very little difference between any of the HSLA steels and
carbon ~tee1.8~ The combination of HSLA with CP or coating to protect the immersed
sections might be the optimum solution for piling where the splash zone is particularly
aggressive.
11.4.5 Alloy Sheathing
Trials on the use of copper-nickel sheathing of piles to protect against fouling and corro-
sion were carried out at the LaQue Center for Corrosion Technology. More than 50 steel
piles were sheathed with 4.6-mm-thick plate. Some of the sheathing was welded directly
to the steel, while some was insulated from the steel with concrete or butyl rubber. The
biofouling mass that accumulated on the bare steel control was more than 50 times as
great as that on the insulated sheathing. Only a few isolated barnacles were seen on
the insulated sheathing after 5 years of exposure. Similar trials have been done on oil
platform legs with similar positive results on reducing fouling and protecting the steel
Alloy 400 has been used as protective sheathing for 35+ years to protect the steel
piles on the LaQue Center dock structure at Wrightsville Beach, NC. Alloy 400 has also
been used on offshore oil and gas platforms to provide protection in splash and spray
zones on the carbon steel legs."
Following extensive research into potential applications for titanium in civil engi-
neering, titanium-clad steel has been used as a protective lining in the splash and tidal
zones of steel piers for the Trans-Tokyo Bay Highway (TTB) Bridge.97
11.4.6 Plastics
Concern over wood-preserving chemicals used in jetties and locks has led to the use
of plastics for some of these applications, often in combination with composites, steel,
or concrete for heavy-duty installations. Various systems of retaining walls are avail-
able using different materials and manufacturing processes such as pultrusion, casting,
or filament winding. For example, a filament-wound epoxy FRP shell is filled with ex-
panded cementitious foam to produce a strong, durable structure. Another manufac-
turer uses PE extrusions reinforced with composite bars to produce pilings. A French
company has produced canal lock gates to replace wood and steel by contact molding
an isophthalic resin system. The lighter weight facilitates installation and use and the
buoyancy of the new gates reduces mechanical stress on the operating assembly during
operation.
More than 21,000 ft (6,400m) of 12.7-in. (323-mm) diameter composite piling has
been used by the U.S. Army Corp of Engineers Waterways ExperimentStation to replace
deteriorated timber piling on the Lake Pontchartrain Causeway near New Orleans?*
Eighty-four FRP marine terminal fenders measuring 7 ft wide x 16 ft high x 1ft thick
(2.1 x 4.9 x 0.3 m) and weighing approximately 2,700 lb (1,225 kg) each were installed for
the Delaware River and Bay Authority in New Castle, DE over a 3-year period beginning
in early 1994.The timber and steel pile clusters traditionally used for pier fendering and
vessel positioning are subject to breakage and abrasion from vessel impacts, as well as
rot and marine-borer attack. The demanding marine conditions also include constant
exposure to salt water and W, plus ambient temperatures ranging from below 0 to
above 100°F(-17.8 to >38"C).
The FRP fenders were fabricated using epoxy vinyl ester resin and quadraxial E-glass
reinforcement via the Seemann Composite Resin Infusion Molding Process (SCRIMP).
The SCRIMP technology produces strong, lightweight composite parts that are resistant
to corrosion and seismic shock. These composites also help eliminate water contamina-
tion caused by chemical leaching from creosote-soaked timbers and corroding steel face
plates.
This resin was selected for its excellent mix of corrosion resistance and mechanical
properties, including good elongation and flexural, compressive, and tensile strength.
438 ADD^ ications
The fenders absorb 300,000 to 400,000 lb (136,000 to 181,000 kg) of energy on a 6-in.
(15-cm) load line approximately 15 times a day. The timber piles in this ferry service
typically last up to 7 years, but some have needed to be replaced in 6 months. The
composite fenders are expected to last at least 50 years.%
Some floating piers are now produced commercially using FW because of its corro-
sion resistance. Their fabrication is labor intensive because automated production sys-
tems such as resin transfer molding (RTM)and hot press forming are only used on some
blow-molded floats. A modular system using PP-based GMT (glass fiber mat-reinforced
stampable sheets) as a primary structural material for main components such as floats,
frames, and decks has been developed. Tests showed that damage to PP-GMT in seawa-
ter was similar to that caused by potable water, the static and fatigue strengths decreased
by water absorption. PP-GMT is applicable to floating piers as a primary structural ma-
terial as long as this strength reduction is included in the design. A prototype system
of floating piers has been designed and fabricated based on the fatigue test data for
PP-GMT laminate in a water environment.lm
11.4.7 Coatings
A 100% solids polyurethane coating dramatically outperformed a coal tar epoxy sys-
tem in protecting steel pilings at the Trident submarine base in King's Bay, GA over a
5-year period. During the spring of 1986, the U.S.Navy started construction of its new
submarine base. The program involved 200,000 !tf (18,580 m2)of steel pilings and a sim-
ilar quantity of pipe pilings. The pilings were coated with a 100% solids polyurethane
and the pipe pilings were protected with coal tar epoxy. CP was not fitted when the piles
were installed in 1986.
Forty percent of the pilings supported a permanent infrastructure of docks and piers.
The remaining pilings were used to construct a temporary dry-dock facility for use over
a 5-year period for the rehabilitation of submarines. As part of a navy plan, these pilings
were removed during the summer of 1990and scheduled for disposal. The pilings coated
with the polyurethane were in such pristine condition that they could be reused or sold
for future projects. Further inspection of the permanent pilings protected with the 100%
solids polyurethane showed that they, too, were in excellent condition. They showed no
flaking, brittleness, cracking, or delamination after 5 years of abrasion, salt spray, and
tidal activity. Large sections of the pilings had little barnacle growth and they were easily
removed. Where the coating had been gouged as a result of severe abrasion there was
some spot corrosion, which did not extend beyond the damaged areas.
The epoxy pilings coated at approximately the same time with the same surface
preparation and exposed to the same service conditions did not fare nearly as well. The
epoxy blistered and delaminated in many spots. There were also large areas where the
steel had rusted through the coating. The barnacle growth was extensive and difficult to
remove.lol
The use of a dual-powder fusion bond epoxy coating (FBE) for protecting steel piles
on a new dock subject to ice and ship impact was questioned.lo2This dock was to have
CP and piles and would be shop-coated. Illustrating that there is no one correct answer,
a great variety of suggestions were made:
Use a paste-and-tape system (from Denso@or Trenton@)perhaps with a thick outer PE

shield for wave (and ice) action. (T. Laundrie, Corrosion and Machinery Engineering)
Use a coal tar epoxy or coal tar urethane. (J. Lichtensein)
In Europe a glass flake epoxy (GFE) system for sheet, tubular, and H bearing piles
would be used. Abrasion resistance of GFE-type materials is good and it is used to
protect things like ice breakers, ship’s hull, and legs of offshore platforms’ wearing
surfaces. The traditional coating of pitch epoxy is out of favor, not because it cannot do
the job, but because there are concerns about health and safety in use. An alternative
to GFE that is preferred in some parts of the world (Australia and parts of the Far
East) is a glass flake vinyl ester. (Graham Gedge Ove Arup & Partners)
Alloy 400 cladding was suggested. (Victor Nicolas Nouel)
Use shop-applied aluminum metallizing ( e g , at 200 pm) and a sealer and topcoat
applied on site. (G. Ackx, SGS Axa-Med)
If sufficient CP is applied no coating should be needed. (C.F. Speed, Tuboscope Inc.)
While in theory it might be possible to provide adequate protection by CP in a tidal
situation, there could be a large change in surface area to be protected resulting in large
fluctuations in current demand with the state of the tide. Also, the current would need
to be adequate to polarize the steel throughout the cycle of each tide (as opposed to
maintaining a constant value). If CP is used in combination with a coating the current
demand can be greatly reduced because the CP only has to deal with the areas of
damage. (G. Gedge, Ove Arup & Partners)
In the worst area of attack at the splash zone epoxy-impregnated fiberglass wraps
and fiberglass shells filled with concrete and reinforcing steel have been used. At the
ground line under the water most of the coatings applied prior to driving are either
partially or completely stripped from the pile as it enters the soil. As it is always wet
CP would work here. (T. Gibbons, Sr.)
In a 19-year test in Florida the best performer was a two-coat system of zinc
primer/aluminum topcoat, followed only slightly behind by a two-coat inorganic
zinc system, followed by the third performer, the NASA system. From experience the
best performance comes from an organic zinc-rich (having at least 0.50 lb [227 g] of
zinc per square foot [930 cm2]in the dry film), moisture-cure urethane (MCU)primer
over the entire pile, with two coats of a coal-tar moisture-cure urethane up to just
above the splash zone, followed by a micaceous iron oxide (MI0)-rich high build
intermediate MCU, and finally, an Aliphatic, MIO-rich MCU topcoat. (R. Olmstead,
Diversified Corrosion Technologies)
In the United Kingdom and in many other parts of Northern Europe coal tar epoxy
coating would traditionally have been used on piles to deal with the splash and
immersed parts. Some sacrificialallowance might also be used. As people are moving
away from coal tar, glass flake epoxy is being favored. Below the mud line the corrosion
rate would be expected to be much lower and a corrosion allowance alone is sufficient.
(G. Gedge, Ove Amp & Partners)
440 A d ications
In order to permit navigation along the Ohio River as far as Pittsburgh the U.S.
Army Corps of Engineers installed 53 lock and dam facilities prior to World War 11. In
the 1950s, work began on the construction of 18 locks and dams, replacing most of the
original structures. The new dams have maintenance problems because water flowing
under gates reaches 35 ft/s (11 m/s) in some cases and the river carries large quantities of
debris and sand. The originalvinyl coatings, used successfullyon similar applicationsin
the MississippiRiver, failed by erosion in as little as 1to 2 years. It was decided to evaluate
various metallized coating and sealer systems for use in this difficult application.These
trials showed that coatings that were anodic to mild steel, such as 85-15 zinc-aluminum
and pure zinc, are a likely alternative to the present coatings. Trials to assess durability
are continuing. Coatings that were cathodic to mild steel, such as stainless steel and
aluminum-bronze, should not be used in fresh water unless access to the substrate is
prevented. Penetration of water through the coating to the steel was not adequately
prevented by any of the sealing systems tested.lo3
Petrolatum tape has also been used to protect the splash zone of marine structures
that are cathodically protected below the water line. In this case, the splash zone can
suffer very severe corrosion. In locations where wave action or mechanical damage is
likely, it is usual to apply a protective jacket of PP or FRP.lMThere are commercially
available pile-shielding products that are based on petrolatum tape. One such system
starts with the application of a corrosion-inhibitingwax-based compound that displaces
moisture. This is then wrapped with a polyfiber felt saturated with wax and corrosion
inhibitors and finally the pile is wrapped with an outer wrap or with a high density PE
shield.This pile-shieldingsystem protects against corrosion and also against mechanical
damage from ice, debris, or impact.lo5
Exposure tests of coated steel piles in the splash and tidal zones were carried out for
15 years in seawater in the Philippines. Coating defects and some rusting were seen on
piles coated with inorganic zinc-rich paint topcoated with either coal-tar epoxy or epoxy
paints. Some cracking was observed in piles coated with organic zinc-rich paint plus
glass-filled epoxy or glass-filled polyester. Some undercoating corrosion also occurred
on steel top coated with glass-filled epoxy. Coatings of PE or petrolatum-saturated tape
with FRP cover were unaffected after 15 years of exposure.lM
11.5 DAMS AND BARRIERS
11.5.1 Dams
People have always constructed barriers across rivers and other water courses to store
or divert water. The first known irrigation works were some 200 km from Ur in
Mesopotamia (the plain between the Tigris and Euphrates Rivers). This irrigation by
the Sumerians some 7,500 years ago transformed the area into the granary of the Middle
East. Gradually the water from these irrigation channels became loaded with salt, dis-
solved from the rocks over which it passed, and turned the fertile fields into barren land.
This salination and the deposition of silt are the two factors that cause most irrigation
systems to fail eventually.
Dams were first known to have been used some 4,900 years ago, with the dam at
Wadi el Garawi in Egypt being a spectacular example from this time. The greatest ancient
dam was the Marib Dam on the Wadi Dhana in Yemen that was 700 m long built around
800 B.C. This dam collected floodwaters from a huge area and operated for 1,300 years
until it became washed away in a flood. The Dujiang irrigation project, which supplied
800,000 ha in China, is 2,200 years old. Dams and aqueducts built by the Romans to
supply drinking water and sewer systems for towns still exist today.Io7
Dykes and canals have often been used to drain low-lying land in Europe with the
Netherlands being the obvious example. The invention of the windmill greatly helped
in pumping water from the waterlogged land over the dykes into the sea. There have
been many occasions in history where the dykes have been breached often leading to
great loss of life. In the 1800s, the British began to build dams in the moors to store the
water from the headwaters of rivers in order to provide drinking water to the towns and
cities in the valleys below.
Using wheels to lift water from rivers or ditches to irrigate fields is almost as old as ir-
rigation itself. The use of water wheels to drive mills is more recent, probably datingback
to Roman times. At the end of the 11thcentury the Doomsday Book recorded 5,624 water
mills in Britain. Initially these wheels were used to grind grain but as their power began
to increase through the use of better designs they were often used to provide driving
power to lathes, pumps, and crushers. They are the forerunners of modem hydroelectric
power production but their use declined when steam power became common.
Today the trend is to build super dams, defined as being more than 150 m high, and
there are now more than 100 of these large dams, more than three quarters of them built
in the last 35 years. These controversial projects have a large effect on the environment
and the flow of rivers over large areas. Their total capacity is 6,000 km3,equivalent to
15%of the annual runoff of the world's rivers. They have already lowered the tides on
the world's beaches by a few millimeters. The main justification for these dams is the
production of cheap hydroelectric power."'
Dams were first used for hydropower generation around 1890. By 1900, several hun-
dred dams had been built in different parts of the world, mostly for water supply and
irrigation.The last century saw a rapid increase in dam building and by 1949about 5,000
dams had been constructed worldwide, three quarters of them in industrialized coun-
tries. The InternationalCommission on Large Dams (ICOLD),established in 1928,defines
a large dam as one with a height of 15m or more from the foundation or dams 5 to 15m
high with a reservoir volume of more than 3 million m3. Using this definition, there are
now more than45,OOO large dams in more than 140countries around the world, most con-
structed from stone and/or reinforced concrete. The two main categories of large dams
are reservoir-type storage projects and run-of-river dams, which often have no storage
reservoir and may have limited daily pondage. Within these general classifications there
is considerable diversity in scale, design, operation, and potential for adverse effects.
Reservoir projects impound water behind the dam for seasonal, annual, and, in some
cases, multiannual storage and regulation of the river. Run-of-river dams (weirs and
442 Annlications
barrages, and run-of-river diversion dams) create a hydraulic head in the river to divert
some portion of the flow to a canal or power station.lo7
Types of dams include the following:
Cofferdams are temporary dams built to hold water back so that work can be done
on the main dam.
Dykes keep the sea off land that is below sea level.
Levees are artificial riverbanks high enough to prevent flooding.
A barrage is a dam across a river intended to permit flow, once a certain depth of
water has been reached.
A weir is a small dam that forms a millpond or fishpond.
Dams are also classified into types depending upon their materials, design, and
method of construction. The usual types are concrete or masonry, earth, rock, steel, tim-
ber, and movable dams. Plain or reinforced concrete is more often used than masonry.
Concrete dams include the following:
Solid gravity dams withstand the pressure of water by their weight. In cross section,
they are like a triangle, broad at the base and narrow at the crest. They are built in
this shape because water pressure becomes greater with the depth of water. Pressure
depends not on how far water is backed upstream but on its depth at the dam.
Hollow gravity dams are made of less concrete than solid gravity dams. They rely
more on their structure than their weight to resist the force of water. They have a thin
facing supported at an incline by a series of triangular buttresses, or piers. Hollow
gravity dams may be of three types. The multiple arch dam consists of a number
of arches supported on buttresses, while the flat slab dam is a straight wall resting
against buttresses. Similar to the multiple arch dam is the multiple dome dam, which
has domes instead of arches.
Arched dams consist of a horizontal curve using the principle of the arch for strength
against water pressure. They are curved upstream. The force of the water is transmitted
to the canyon walls.
Earth dams are made by building an embankment of gravel, sand, and clay across
a river. To prevent leakage, often a core, or inner wall, of concrete or other watertight
materials is used. In a rolled fill dam, earth is hauled by vehicles onto the dam and
compacted with heavy machinery. In the hydraulic fill dam, earth is carried to the dam
by water in pipes or flumes and deposited from the water. The placing of the earth is
controlled so that the finer, watertight materials form the core. In the semihydraulic fill
dam, earth is brought to the dam and distributed by jets of water. Rock dams are made
by dumping rocks across the river. A wall of rocks is then laid on the upstream side and
over this is built a waterproof facing of reinforced concrete, timber, or steel.’Og
The first Aswan Dam on the Nile was proposed and designed by the British engi-
neer William Willcocks, who was brought from India where he was heavily involved
11.5 Darns and Barriers 443
in Victorian water control projects. The first Aswan Dam was 3 km long, 27 m high,
constructed from 40,000 m3 of granite blocks. This early dam was designed to act as a
weir to allow the passage of silt during the summer months. The later High Aswan Dam
effectively stopped the flow of silt to the Nile Delta and made Egypt one of the heaviest
users of chemical fertilizers in the world. The delta ceased to grow more than a century
ago when the first dams were built. Since 1964 it has been in full retreat and the fishing
industry in that part of the Mediterranean collapsed when deprived of the nutrients and
algae on completion of the dam.
The Old Aswan Dam at the First Cataract of the Nile in Egypt was first built in
1898-1902. It was raised in 1910-1912 and again in 1930-1933. In 1904, severe erosion of
the rock downstream of the dam necessitated the removal of the rock and replacement
with a 20-m masonry apron. Various surveys have shown considerable cracking and
porosity developing within the dam leading to water seepage and weakening of the
structure.The originalcracking was caused by the lack of expansionjoints in the original
dam. The structure of the dam and subsequent heightening all consist of granite blocks
set in a portland cement mortar; the bond between the blocks and the mortar was often
not tight. In 1959-1960 a vertical curtain of grout was installed over the whole of the face
of the dam using slag and diatomite portland cement.
The Nile water has a negative Langelier index varying from -0.8 to -0.43 so is
undersaturated with calcium carbonate and contains aggressive carbon dioxide. The
damage to the original dam, and particularly to the first heightening, was caused by
excessive porosity and construction defects permitting penetration of the river water
into the structure of the dam. This, in turn,has enlarged the original defects by chemical
and, to some extent, mechanical action. The grout curtain on the face of the dam was
found in 1990 to be strong, dense, and sound.110
Modem dams not only provide a constant source of water for towns and cities and
irrigate large areas of farmland, they also provide huge quantitiesof hydroelectric power.
For example, the Itapui power station on the Rio Parana in Brazil is the largest retaining
barrage in the world and is able to produce 75,000 million kW annually."'
Today's dams are often immense, complex,and controversialfeatsof civil engineering
having a huge effect on the environment and the lives of people. For example, the Three-
GorgesProject to dam the Yangste River is estimated to need 11million tons of cement and
18 million tons of steel and will submerge 140 towns and 1,600 factories. This structure
will be more than 2 km wide and tower 575 ft (175 m) over the landscape. There will
be a reservoir that will stretch some 400 miles (640 km) behind the dam. Many people
(1.2 million) will be displaced and 200,000 acres (81,000 ha) of fertile farmland will be
flooded in the process. The amount of power that will ultimately be produced from
the 26,700-MW turbines has been estimated at 18,000 MW or 84 billion kW-h. This is
planned to supply 1/9 of China's power. The dam will, it is hoped, control Yangtze's
killer floods that have already displaced 38 million people, destroyed 5.6 million homes,
and submerged 12,000 acres (4,900 ha) of crops. Also, it will allow vessels up to 10,000
tonnes to travel 1,500 km inland to Chongquing, opening up markets where 380 million
people live. Perhaps not surprisingly, many technical, social,and environmentalconcerns
444 Applications
have been expressed regarding this immense project started in 1994 and scheduled for
completion in 2009.112-114
11.5.1.1 Dam Failures
Dams can and do fail, often with catastrophicconsequences.The failure of a large dam has
the potential to cause more death and destruction than the failure of any other man-made
structure. Tailing dams, which sometimes store toxic materials, may pose additional
environmental danger, e.g., the Omai Tailings dam, Guyana, failed in 1995 releasing
cyanide slurries and the Stava Tailingsdam, Italy, failed in 1985 killing 268 people. Dams,
both large and small, have failed, but only a few have significantlyinfluenced dam design
and engineering. The most common causes of dam failures are the f~llowing:"~
1. Overtopping of embankment dams resulting from inadequate spillway discharge

capacity to pass flood waters. This is one of the most common causes of dam failures.
Any embankment dam will fail if the spillway is too small and flood waters rise high
enough to flow over the top of the dam wall.
2. Faults in construction methods (e.g.,inadequate compaction of fill)or use of the wrong
type of constructionmaterials (e.g., silt) may lead to internal erosion or piping failures
of embankment dams. An example is the failure of the Teton Dam in Idaho (United
States) in 1976.
3. Geological problems with the dam foundation. The failure of the St. Francis Dam
falls into this category. In 1928 500 people lost their lives along the Santa Francisquito
Canyon and the Santa Clara Valley in California. Some of the foundation rock, a
conglomerate, disintegrated when it was immersed in water so that the rock lost
all its strength when saturated. Another example of a dam collapse from foundation
failureis the Malpasset Dam in France, which failed in 1959. This was the first collapse
of a concrete arch dam.
4. Landslides, falling into the storage reservoir, send a wave of water over the top of the
dam and may cause a dam to fail. If the dam is made of concrete it may survive, but
a destructive flood may still devastate the river valley downstream, as happened at
the Variont Dam in Italy in 1963 when more than 1,900 people were killed.
5. Earthquakes can certainly cause damage to dams but complete failure of a large dam
from earthquake damage is very rare. The Lower San Fernando Dam in California
(United States)did fail during an earthquakein 1971, which caused the fill in the dam
wall to liquefy resulting in the collapse of the upstream part of the dam. A disastrous
flood was only prevented because the reservoir level happened to be low at the time
of the earthquake and no water escaped downstream. (The weight of water in dams
frequently causes earthquakes by destabilizing faults in the area.)
6. Dams are likely to exist, perhaps for hundreds of years, even after they are no longer
required for their original purpose. During these years, dangerous alterations to the
operation of the dam and/or its structure may lead to failure, e.g., South Fork Dam
(Johnstown)which failed in 1889.
7. Incorrect operation of a dam at any time can result in overtopping and failure, e.g.,
Euclides da Cunha Dam, Brazil which failed in 1977.
11.5.2 Barrages and Barriers
Barrages and barriers are now being built in or near river estuaries to control floods and
provide waterside amenities. These are major engineering undertakings that push the
limits of materials used in waters and many of them are as heavily debated as some of
the big dam projects.
A recent exampleis the Cardiff Barrage, completed in 1998.This barrage is 1.1km long
and was designed as part of the massive drive to create a new waterfront environmentfor
Cardiff, the capital city of Wales. The impounded waters of the Taff and Ely Rivers now
form a 500-acre (200-ha)freshwater lake, keeping out the seawater of the Severn Estuary.
Cardiff has a tidal range of 14 m, one of the greatest tidal ranges in the world. Low tide
conditions made the bay inaccessible by water for up to 14 h/day when only exposed
mudflats were visible. The barrage and the resulting freshwater lake are designed to
encourage public use of the area but result in the loss of the rich intertidal ecosystem. It
will be possible to walk along the whole length of the barrage (which will be landscaped
along its inner face). The permanent waterfront is some 12.8 km long.
The major justification for the project was an economic one. It was estimated that
some 30,000 new jobs could be created together with 4 million f$ (370,000 m2)of office
space, plus numerous artistic, leisure, and recreational projects. A minor reason for the
project was that the flows of the rivers Ely and Taff could be better controlled, and
therefore prevent flooding of the city center which had occurred in the past. Although
not its intended purpose, the barrage will also act as a sea defense for the city. The
barrage project also includesdiversionsto the existing sewageoutfallsand new treatment
facilities, improving the water quality over the entire area.l16J17
The Thames Barrier in England is the world's largest movable flood barrier. It was
designed to protect London from flooding until at least the year 2030, according to
current estimates of rising sea levels. After that, if necessary, the gates can be raised
an extra meter by turning them approximately 20". The downriver flood walls would
also have to be raised. A flood control barrage at Gravesend was proposed in 1907 and
in 1928. It was after the 1953 floods, however, in which more than 300 people were
drowned and 65,000 ha of farmland were flooded with salt water, that the government
appointed a committee to consider the problem. Several schemes were proposed and
rejected and it was only after the formation of the Greater London Council (GLC) in
1965 that government consent was given to build a barrier. The design chosen from
41 proposals minimizes interference with the natural flow of the river, does not pose a
headroom restriction for shipping, is attractive, and is practical. Charles Draper was the
engineer whose idea for radial gates (normally parked flat below the bed of the river)
evolved from the working principle of a domestic gas tap.
The high water level at London Bridge has risen by about 75 cm each century, caused
by a combination of melting polar ice caps and the tilting of the British Isles toward
446 ADDlications
Europe (the south of England is sinking at a rate of 30 cm/century). As a result of global

warming, some authorities now suggest that sea levels may start rising globally at about
1m/century. The major flood threat to central London, where the Barrier was designed
to protect, is from surge tides. These derive from zones of low pressure originating
off the Canadian coast, beneath which the sea rises approximately 30 cm over an area
approx. 1,600 km in diameter. These humps of water, crossing the Atlantic at 80 to 100
km/h, usually pass north of Britain but, if driven by northerly winds (usually in winter),
may descend to the North Sea. Here they can be funneled toward the Straits of Dover
and can cause flooding on the surrounding coasts and along the banks of the tidal
Thames.
The Thames Barrier, valued at over €1,000 million, took 8 years to build. It spans
520 m across the Thames at Woolwich Reach (where the river is comparatively straight
and the chalk-with-flints strata is suitable for its construction).A half million tonnes of
concrete was used to build the piers and sills on which the gates rest when being used.
When raised, each of the four main gates is as high as a five-story building and as wide
as the opening of Tower Bridge (61 m). The two gate arms weigh 8,700 tonnes. The gates
are moved by electricallypowered "hydraulic power packs," housed immediately below
the stainless steel rods. Since electrical power is crucial for Barrier operation, there are
three on-site power generators as well as three alternative supplies. Since its completion
in 1982, the Thames Barrier has been raised more than 25 times, largely as a precaution,
to protect London from flooding. The gates are raised monthly for a 2.5-h test period at
low tide and annually for a full day to test the effects of a full tide.118
The roofs that cover the shells over the control gates are clad in 316 stainless sheet.
Stainlesssteel was also used in the bearings and supports for the gates and nickel-copper
alloys (UNS N05500, N04400) were used for bolts that connect the gate leaves to the gate
arms.119
There is a proposal under consideration to install 79 hinged flaps at the entrance to
the lagoon of Venice (Figure 11.9). During the half dozen times a year when Venice is
threatened with flooding the flaps would be filled with air and float up to block the
entrance of the lagoon. Each of the metal flaps would be anchored to the seabed by
300 tonnes of concrete.12o
11.5.3 Man-Made Rivers
The Great Man-Made River project in Libya is not strictly a dam or barrage but uses
large holding tanks as part of the distribution system. It exploits the vast reserves of fresh
water from natural reservoirs beneath the desert. The project started in 1984 and is now
largely complete. Water is transferred from the Kufra and Sareer Basins through pipes to
the concentrated coastal populations in Benghazi, Sirte, and Tripoli. Upon completion,
there will be some 3,380 km of pipelines. Two special pipe factories were constructed to
provide the concretepipes, varying in weight between 73 and 78 tons. In total this project
requires the drilling of 960 wells with depths varying from 450 to 650 m. The network of
wells covers on area of 8,000 km*.'*'
Figure 11.9 This is the famous Venice lagoon in which it is proposed to install protective barrier
gates to prevent flooding. The bow of a wooden sailing ship is seen in the foreground. (Photo
The production wells are about 1.3 km apart and are connected through collector
pipelines to off-line steel header tanks, each with a capacity of 170,000 m3. The header
tanks balance the hydraulic pressures, allow the system to adjust to variations in water
flow, and prevent water loss through the overflow facility. A chlorination station is in-
stalled to inhibit biological growth in the pipes. At the end of this system, pressure control
valves reduce the excess water pressure arising from the difference in level between the
wellfields (an additional head of about 80m after allowing for friction losses in the 256-km
pipe length). The pipeline to Sirte is designed to carry 820,000 m3/d by gravity which can
be increased to 2.3 million m3/d in the future by the use of three pumping stations. The
pipeline to Benghazi delivers a maximum gravity flow of 1.18 million m3/d which can
increase to 2.5 million m3/d using two pumping stations. Turnouts have been located
along both pipelines to deliver water to agricultural, municipal, and industrial users.
Each pipeline discharges into a circular earth embankment end reservoir designed to
balance fluctuations in supply and demand, with a storage capacity of 6.8 million m3 at
Sirte and 4.7 million m3 at Benghazi.lZ
There is a similar U.S. project known as Central Arizona Project (CAP) that supplies
water from the Colorado River Basin to Arizona through a series of pipes and aqueducts.
Construction began in 1973with excavation for the Havasu Pumping Plant (now Mark
448 Annliratinnq
Wilmer Pumping Plant)on the shores of Lake Havasu. The main aqueduct system, which
runs from Lake Havasu to a terminus southwest of Tucson, was completed in 1993.Most
of the concrete and masonry dams needed for the project were completed by 1994 and
the distribution system supplying water for agricultural and domestic use is now also
complete.
The project provides large quantitiesof hydroelectricpower to the region and includes
15 pumping stations, 6 major inverted siphons totaling 6.5 miles (10.5 km),15 miles
(24 km) of tunnels, and 336 miles (541 km) of concrete aqueducts. For example, the
Hayden-RhodesAqueduct consistsof about 173.9miles (279.8km)of concrete-lined open
channels, seven major inverted siphons with a total length of about 7.4 miles (11.9 km),
three tunnels totaling 8.2 miles (13.2 km),and 0.6 miles (1km)through three pumping
plants. The aqueduct has a maximum capacity of 3,000 @ / s (85 L/s). Relift pumping
stations contribute to the total pump lift from the Colorado River to the Phoenix service
area of about 1,200 ft (366 m). The concrete lining for the aqueduct sections is about
3.5 in. (9 cm) thick with 20 in. (0.51 m) of concrete lining in the tunnels; the siphons are
21 ft (6.4 m) internal diameter prestressed concrete pipe.'= The pipe sections include
a 19 5/8-in. (50-cm)-thick concrete core spirally wrapped with Class 3 steel wire. This
wire is in turn coated with mortar at a minimum thickness of 3/4 in. (1.9 cm). In January
1990, corroded wire and damaged PCP were discovered on some of these CAP siphons.
These corrosion problems led to the development of techniques for monitoring and de-
tecting damaged pipes, preferably without the need for excavationor emptying/drying.
Prestressed strands emit characteristic sounds when they break and it was found that
acoustic emission using hydrophoneswas the most reliable method for monitoring these
critical siphons and pipe^.'^^,'^
11.6 POTABLE WATER HANDLING
11.6.1 Treatment of Potable Water
The specification in most countries for potable water, e.g., chlorides 250 to 300 ppm, pH 6
tog, and temperature20to 25"C, means that it is not corrosiveto most materials. However,
during the processing of water to make it fit for consumption there are stages where
chemicals, e.g., strong oxidizers such as potassium permanganate, ozone, or chlorine
can be added. In these areas there is some danger of localized attack and a superduplex
or superausteniticstainless steel may be needed in the area of the injection point.'26
There have also been cases of failures of 304 and 316 stainless steels in chlorinated
freshwater that would not have been expected from the stated chloride and temperature
conditions. These have been identified as being caused by manganese in the water. It
is suggested that manganous dioxide deposits are formed which, in the presence of
chlorine, are converted to manganic and permanganate ions that initiate pitting. The
presence of biological activity is thought to facilitate this phenomenon but not to be
essential for it to A potable water treatment plant designed to remove iron and
manganese from well water experienced leaks in a 304 raw water header after 9 months.
The leaks had all occurred under deposits in the HAZ of welds where the heat tint from
welding had not been removed. It was not possible to determinewhether metal oxidizing
bacteria (Gullionella spp.) played a role in this underdeposit crevice corrosion.’28
UNS S45000 (Custom 450 precipitation hardening grade) has been used as shafts for
large butterfly valves in potable water. Type 201 has been used in revetment mats to
reduce shoreline erosion in freshwater lakes.%Stainless steel was introduced for use in
the large central control gravity filters in water treatment plants in 1965 and has since
been used in more than 75 plants. Good performance is reported for all the more than 75
stainlesssteel central control columns installed to date with no replacement or significant
repairs needed.
Stainlesssteel piping has been used instead of ductile iron in potable water treatment
plants, largelybecause of the cost savingspossible with the thinner, lighter, stronger stain-
less steel. Savings attributed to the use of stainless steel over ductile iron were estimated
at $50,000 for the Taunton, MA potable water treatment plant. Stainless steel piping is
now in use in more than 100 North American domestic potable water treatment plants
and is also being used in the Middle East to transport potable water from desalination
plants.129Cast iron and ductile iron valves have been used in stainless steel piping in
water treatment plants, with no adverse effects rep01ted.l~~
There have been reports of multiple pitting-type corrosion of stainlesssteel piping in
two plants, attributed to moist chlorine collecting in the pipe. In one instance a backwash
line not in use was left open in an area where chlorine vapors could enter and collect in
the line. In the second instance, flow was so low that the pipe was only half full,allowing
chlorine dissolved in the water to collect in the vapor space in the upper half of the pipe.
Closed atmospheres containing moist chlorine can be aggressive to both 304L and 316L
stainless steel piping.131
Potable waters have been categorized by composition in terms of corrosivity and
tendency to scale (Table ll.2).13’
Pitting/underdeposit corrosion was reported on a large water treatment 6061 T6
(UNSA96061-T6)aluminum filter housing after about 1year in service.The groundwater
feed contained Fe and Mn. Sodium hypochlorite (NaOC1) was being added upstream
of the filter to accelerate the oxidation of the Fe and Mn and provide some residual
disinfectant for the potable water. The aluminum contained randomly distributed white
tubercule deposits with significant underdeposit pitting. The deposit was analyzed as
amorphous aluminum hydroxide that did not contain bacteria.” Tubercular pitting
is not unusual in aluminum in fresh waters; it was reported in ”trash screens” im-
mersed in dam waters in South Africa. Tubercules from one of the fresh-water dam
screens were found to contain aluminum, silicon, and sulfur, presumably as oxides, in-
side the tubercule. On the brown outer surface there were oxides of iron and manganese
present in relatively large quantities. It was suggested that they were caused by iron-
and manganese-concentratingbacteria. Similar tubercles over pits were also reported in
Banbury, England supply water after 2 years of exposure. The region of “nodular pit’’
formation was said to not only exist at above about 100 ppm carbonate hardness, but
also to be influenced by chloride ~ 0 n t e n t . l ~ ~
450 Applications
Table 11.2 Potable Water Categorization13

Calcium, Sulfate, Silica, Dissolved 0 2 ,
Category pprn PPm PPm PPm Character
1A 0-18 As found 0-15 1-10 Extreme corrosion hot and
cold
1B 0-18 0-25 0-15 0-1 Moderate corrosion hot
and cold; extreme
corrosion if CO2 >8 pprn
1c 0-18 0-60 >15 1-5 Slight corrosion cold,
considerable hot;
aggressiveness reduced
by high natural silica
2A 18-35 >Ca, not t 2 5 0-15 1-10 Considerable corrosion hot,
moderate cold; may be
slightly scaling very hot
2B 18-35 0-25 0-15 1-10 Moderate to slight
corrosion hot and cold;
may be scaling hot
2c 18-35 <Ca >15 1-8 Corrosion unlikely, may be
scaling hot
2D 18-35 tCa As found 0-1 Corrosion unlikely, may be
scaling hot
3A 35-75 <1-1/2 Ca 0-15 1-10 Moderate corrosion hot,
slight cold; considerable
scaling hot
3B 35-75 >1-1/2 Ca 0-15 1-10 Considerable corrosion hot,
slight cold; considerable
scaling hot
3c 35-75 tl-1/2 Ca >15 1-10 Considerable scaling, slight
corrosion hot
3D 35-75 As found As found 0-1 Considerable scaling,
corrosion unlikely
3E 35-75 >1.5 Ca, >30 1-10 Corrosion unlikely hot and
t 3 Ca cold, excessive scaling
4A >75 t 2 Ca 0-30 1-10 Excessive scaling, corrosion
unlikely to slight cold,
slight to moderate hot
4B >75 >2 0-30 1-10 Excessive scaling,
considerable galvanic
corrosion hot and cold
4c >75 <3 Ca >30 1-10 Excessive scaling, corrosion
unlikely
Notes: This table is applicable to all metals for scaling but only to iron, steel, and galvanized steel,
but not stainless steel, for corrosivity. The presence of >lo0 pprn chlorides with high sulfates
makes water more corrosive than indicated by this table. The presence of >5 pprn carbon dioxide
accelerates corrosion in categories indicated to be corrosive; >20 pprn may cause noncorrosive
categories to become corr~sive.'~~
11.h Potable Water Handline 45 1
11.6.2 Potable Water Distribution
In prehistoric times, small villages were probably supplied with water carried from
streams. As the populations of early cities grew, these water supplies became inadequate
and in Egypt, Assyria, and Babylonia, open canals were dug to bring river water to the
cities. When cities were attacked, they often fell because they ran out of stored water. In
the 7th century B.C. a ruler of the Greek island of Samos ordered a tunnel dug through a
mountain to bring water into his fortified city. At that time it was an enormous engineer-
ing achievement. Deep, lined wells were dug in Mohenjo-daro, located in present day
Pakistan, in about 3000 B.C. A forerunner of pumps, the human-powered shadoof was
first used in Egypt in about 1600B.C. This water-raising device is still used in Egypt, India,
and the Near East. In about 250 B.c., a water-raising device, the Archimedes Screw, was
invented by the Greek scientist, Archimedes. This was followed by the Persian wheel,
usually animal powered, developed in the Near East in about 200 B.C. and it is still used.
Pumps were invented by the Greeks in about 100 B.C. but were first put to practical use
by Roman engineers.
Many early cities built aqueducts to carry water into the city from distant as well
as nearby sources (Figure 11.10).The Romans constructed their first aqueduct in about
312 B.C. At one time Rome had 11 major brick or stone aqueducts to supply the city’s
fountains, public baths, and public buildings. During the Middle Ages many of Europe’s
water-supply systems, originally built by the Romans, fell into ruin. City water supplies
Figure 11.1 0 This stone aqueduct was used to supply water to the district around
Knossos, Crete in Roman times. (Photo courtesy of CARIAD Consultants.)
452 ADDlications
were limited and often contaminated, often responsible for typhoid, dysentery, and
cholera. In 1550, a resident of Paris, France could expect only 1 qt (0.9 L) of water a
day. By 1700, the supply had increased but only to 2.5 qt (2.4 L) per person per day.
In 1582, waterwheels first pumped water from the Thames River into mains in
London, England. In 1613, the New River water company brought water into London
from various sources located outside the city. America's first waterworks, privately
owned, were built in Boston, MA in 1652. By the late 1700s, steam engines pumped
water in many Europeancities. In 1908,chlorine was used in the United States for the first
time to sterilize city water. Many modem cities get water from distant sources through
long aqueducts. The 242-mile (389-km)Colorado River Aqueduct furnishes water to the
San Diego-Los Angeles area. In the 1940s, a desalting plant was first built in Kuwait to
convert seawater into fresh water.
Early distribution systems used hollow logs as mains. The tapered end of one log fit
into the hollow end of the next. These early waterworks pumped water for only a part
of each day. Pressure was so low that water could not be raised above the ground floors
of houses. Stagnant water could seep into the mains and contaminate the supply. By
1800, iron pipes were replacing wooden mains. The invention of the steam engine and
its application to water pumps brought great improvements.lW
Pressure in a water distribution system is affected by numerous factors including
water consumption during day and night, seasonal changes, age of the piping network,
and topography. Control of pressure in a water distribution system is important for a
number of reasons, including the following:
Pressure fluctuations. Maintaining sufficient pressure in the water distribution net-

work is vital for a drinking water supply.
Water leakage. Also called nonrevenue water (NRW),water leakage has a significant
effect on water management. Leakage can account for anywhere from 10% to more
than 50% of the total volume treated for supply. Excessive pressures and/or pressure
fluctuations in the distribution system can be a major contributor to leaks.
Waterhammer. This is transient internal pressure caused by stoppage of flow when a
valve is closed abruptly or a pump is stopped. This has a sigruficanteffect on pumps,
check valves, and the piping network.
Pressure control is normally achieved by the use of water towers or ground/

underground reservoirs equipped with pumps and control valves. Variable frequency
drives (VFD) on pumps is an alternative way to provide a constant pressure throughout
the system. This works by obtaining a feedback pressure signal that controls the output
of the pump motor.136
11.6.2.1 Potable Water Tanks
The first major use of CP by municipalities began in the 1950s with the protection of the
internal, immersed surfacesof steel storage tanks.These tanks were bare or poorly coated
so needed large impressed currents using graphite anodes. Modem tanks, well coated
with vinyl, high build epoxies, or urethane, are effectively protected with consumable
magnesium anodes.137
11.6.2.2 Potable Water Piping
Many different materials are being used to transport potable water with varying degrees
of success. Data were collected on water main breaks in 21 Canadian cities during 1992
and 1993. The total numbers of water main breaks during these 2 years were 3,601 and
3,773, respectively. The most common material in use for this service was cast iron, rep-
resenting 50% of the total water distributionnetwork. The average rate of breaks in cast
iron pipe was 35.9 breaks/100 km/y. Ductile iron pipe represented 24% of the network
and had an average break rate of 9.5 breaks/100 km/y Asbestos-cement pipe consti-
tuted 12%of the networks with an average break rate of 5.8 breaks/100 km/y. PVC pipe
represented 10%of the inventory and had an average 0.7 breaks/100 km/y. Other factors
that influence the rate of water main break, such as age of pipe, soil bedding, backfill
materials, ground water conditions, climate or installation, and operational factors were
not considered in this survey.138
The source of the fresh water can have a large effect on its corrosivity. For example,
fresh water on the east coast of Saudi Arabia is said to be very aggressive, with pitting
being the predominant form of attack (Table 11.3).
11.6.2.2.1 Cast Iron
The earliest recorded installation of cast iron pipe was in 1455 at the Dillenburg Castle
in Germany. In 1664, French King Louis XIV ordered the construction of a 24-km cast
iron pipeline from a pumping station at Marly-on-Seine to Versailles to supply water
for the fountains and town. Sections of this cast iron pipeline are still functioning after
350 years. Cast iron pipe was installed in Philadelphia, PA as early as 1804.Today, more
than 275 utilities in the United States have cast iron pipes that have provided service for
100years or longer.At least 14of them have cast iron mains that have served continuously
for 150 years or more.
Table 11.3 Static Corrosion Rates in 3,500-h Lab Tests in Various Waters,
Sa~diArabia'~~
Maximum Corrosion Rate, mm/y
Material Untreated Water Drinking Water Distilled Water
Mild steel 13.40 19.48 13.73
Galvanized steel 5.67 15.25 2.4
Stainless steel 0.011 0.625 0.035
Copper 0.532 0.57 0.165
454 ADDlications
The first ductile iron (DI) pipe was cast experimentally in 1948 and this type of
pipe entered the marketplace in 1955. Since 1965, DI pipe has been manufactured in
accordance with ANSI / A W A C151/A21.51 by centrifugal casting methods. By 1979,
DI pipe had replaced cast iron pipe as the predominant waterworks piping material.
These pipes are made in standard sizes ranging from 3 to 54 in. (0.08 to 1.4 m) diameter
with nominal lengths of 18 to 20 ft (5.5 to 6 m) and use rubber gasket jointing systems.
Although several types of joints are available, the push-on joint and the mechanical
joint are the most prevalent. For water applications, DI pipe is typically furnished with
cement-mortar lining to prevent internal corrosion.
External corrosioncan be a problem with buried ductile and gray iron piping. The out-
side is normally coated with 1-mil (25-pm)-thickasphaltic coating that offers some pro-
tection but is not intended to provide long-term corrosion protection. A number of meth-
ods are used to control this corrosion in aggressive locations, including the following:
Polyethylene encasement--effective and relatively cheap

Cathodic protection-not widely used because of cost and the fact that cast iron pipe
is discontinuous electrically because joints are insulated
Bonded coating-because of the difficulty of effectively coating the joint area this
method only used in conjunction with CP
The most widely used method of corrosion protection is probably PE encasement.

Methods of application are specified in ANSI/AWA C105/A21.5 and ASTM A 674
details the requirements of polyethylene film to be used for cast iron in aggressive soils.
This standard also describesprocedures to determine whether encasement is required in
any given location. I S 0 8180 was accepted as an international standard for polyethylene
encasement in 1985.140
In the 1970s, DI piping less than 10 years old began to fail in many Canadian cities.
The ductile iron had been used to replace the older, more brittle gray cast iron. These
failures were caused by a combination of thinner iron pipe, cosmetic external coating
leading to local attack at coating defects, and an increased corrosivity of urban soils
from chloride salts. The problem was largely solved by retrofitting magnesium anodes,
inserted in augured holes along the pipe length.137
Cast iron water mains usually fail by fractures, in which the pipe separates into two
or more parts. These fractures can be caused by mechanical overloads, impacts, blasting,
metallurgical defects, or corrosion. External corrosion can be either general over large
areas or localized pitting, and can be accelerated by galvanic effects or stray currents.
Internal corrosion will depend on water hardness, alkalinity, chlorides, sulfates, silica,
dissolved gases, pH, temperature, and velocity. Graphitic corrosion and bacterial attack
are common causes of fracture of cast iron water piping.141
11.6.2.2.2 Steel and Galvanized Steel
The use of steel and galvanized steel can be highly successful for potable water distri-
bution and can last for hundreds of years in some cases or can fail rapidly. Locations
where these materials work well are usually where the water is hard and a thick protec-
tive scale is formed. Galvanized steel systems often need to be replaced in hard water
service because the pipes become blocked by scale formation. The galvanized coating
can become cathodic to steel in some waters in temperatures >6OoC.Since pitting can
be facilitated by the deposition of copper on the zinc, galvanized steel should never be
installed downstream of copper tubes and fittings. Oxygen differential cells can be set
up under deposits or at crevices and can lead to rapid c o r r ~ s i o n . ' ~ ~
In some areas domestic water can best be described as brackish and corrosion of
distribution piping is more severe than with truly potable water. For example, galvanized
water piping in Dhahran on the east coast of Saudi Arabia is said to last between 5 and
10 years compared with North American pipe-handling river water, which lasts 17 to
20 years. Cast iron pipe in Dhahran lasts 12 to 15years while in North America it is 26 to
30 years. Failures are usually by pitting.'39
A small municipality in India obtains its water from a river 60 km away. Midway
between the river and the city a treatment plant was built for water purification. The
raw water line to the treatment plant was 71.1 cm (28.7 in.) in diameter; the potable
line to the city was 66.60 cm (26.2 in.) in diameter. Both carbon steel pipelines had a
wall thickness of 7.14 mm (0.28 in.). No internal lining was used as it was believed the
wall thickness would be adequate to tolerate any possible uniform corrosion. When
the pipelines started leaking approximately 7 years after startup it was not possible to
undertake a full examination. Water treatment to reduce deposition was started and
unaffected parts of the lines were cement lined. When the damaged lines were replaced
it was found that the damage had been caused by MIC with SRB and iron bacteria
involved. The lines were pigged and chlorinated and will be monitored and chlorinated
regularly.'42
11.6.2.2.3 Concrete
Concrete pressure pipe, prestressed concrete cylinder pipe (AWWA C301), and con-
crete cylinder pipe (AWWA C303) are used in agricultural, industrial, and residential
water distribution systems. Since about 1972 they have been externally coated with a
100% solids coal tar epoxy over a mortar cover whenever corrosive conditions are an-
ticipated. This coating is also applied to concrete pipes where cathodic protection is to
be used. There have been concerns that the coating might shield the reinforcing steel
from complete CP in regions of localized coating defects. A series of experiments on
the interrelationship between coating, mortar with and without chlorides, and cathodic
protection found the following:143
1. With high ambient chloride concentrations chloride ions did not diffuse more than
3.8 cm from a coating pinhole in highly permeable mortar. This means that CP current
only needs to be distributed 3.8 cm away from pinholes.
2. CP current is distributed at least 15.2 cm from a pinhole or crack in the epoxy coating
on a chloride-free and contaminated mortar layer.
456 ADD^ ications
3. Corrosion did not occur 15.2cm away from a defect when a polarization shift of 20 mV
or greater was applied. Current density is highest immediatelyunder the pinhole and
decreases within 2.5 to 5 cm to a relatively constant level.
4. Coal tar epoxy can be used as a supplemental coating on concrete pipe to reduce
concern for chloride penetration at levels that can cause depassivation.
5. CP can effectively be used to protect coal tar epoxy-coated concrete pipe.
PCCP is used in water and wastewater systems that serve virtually every major city in
North America. It is available in diameters ranging from 0.4 to >6 m. For details see
Chapter 6, Section 6.2.3, ”Prestressed Concrete.”
The Great Man-Made River project in Libya selected prestressed concrete for the vast
quantity of piping to be used. Eventually the system will carry 3.68 million m3 of water
using a total of about 1,900 km of prestressed concrete cylinder pipe, ranging between
1.6 m diameter for wellfield networks and 4.0 m diameter for the main conveyance
pipeline, laid and buried in a 6- to 7-m-deep trench. Prestressed concrete pipes 4 m in
diameter were found to be the most cost-effective by a significant margin because most
of the raw materials required for their production are availablein the country. It was also
established that pipe buried in trenches 6 to 7 m deep was the best method of protect-
ing the pipe from hazards, including temperature variations and other environmental
factors.lZ See Section 11.5, ”Dams and Barriers,” for more details of this project.
11.6.2.2.4 Asbestos Cement
Chrysotile asbestos-cement (A/C) pipe has been used in water distribution systems
around the world for more than 70 years with more than 2.5 million km of A/C pipe
now in use. A/C pressure pipe is used primarily for the distribution of potable water,
as well as for sewer force mains and industrial effluent and process piping.14
The use and deterioration of A/C water mains in the United Kingdom were studied
to assess whether asbestos-containingmaterial was suitable for supplyingpotable water.
A/C pipes account for approximately 11%(37,000 km)of the total length of mains in the
U.K.water supply system and approximately22% of the population (12million people)
receive water that has passed through A/C pipes. Most of it was laid during the 1950s
and 1960s. With the introduction of plastic pipes, use of A/C for the small diameters
has declined. An increasing proportion of the A/C pipe laid over recent years has been
for large-diameter mains where its materials and laying costs compare favorably with
alternative pipe materials. The general failure rate of this type of pipework is similar to
that of both cast iron and uPVC. The overall failure rate for the four areas in this study
was 0.10 failures/kilometer year (fails/km y), which broadly compares with previously
reported rates of 0.14 fails/km y for cast iron and 0.139 fails/km y for uPVC pipes laid
in L0nd0n.l~~
A later stage of this study found that low pH, low alkalinity waters are aggressive to
asbestos cement pipes and approximatelyhalf the laid A/C pipe is in locations where the
water may be considered aggressive. The most reliable method of assessing the depth of
degradation of A/C pipe was elemental analysis through sections of the pipe, although
phenolphthalein staining showed a very good correlation with elemental analysis. In
areas where the conveyed or ground water is aggressive, corrosion-relatedfailures have
been reported in pipes less than 20 years old. Most of the A/C pipes in the United
Kingdom are bitumen coated and pipe degradation is very localized around defects
in the coating. The maximum internal degradation observed was 8 mm in a period of
40 years. Coatingnew or existingA/C pipes with epoxy resin or cement mortar improved
resistance to degradation. Rates of deterioration can be reduced by chemically treating
the conveyed water to increase its buffering capacity but it cannot prevent release of
fibers from pipes that are already degraded.'&
The requirements for A/C pipe used for water transmission are detailed in
ANSI/AWWA standard C403.00.This standard also indicates ways to assess the aggres-
siveness of the internal and external environment and the suitability of various grades
of this type of pipe. A/C pipe for water distribution, manufactured to AWWA Standards
C400 and C402, is constructed of a mixture of asbestos, cement, and silica formed over
a mandrel at high pressures and steam cured. This pipe has a much smoother interior
surface than concrete but has similar chemical re~istance.'~~
A/C pipe can be damaged by the leaching of the cement binder out of the pipe wall
by the water flowing inside or by external groundwater. Forty-five samples of A/C water
distributionpipe from geographically diverse areas and of varying ages were examined
for signs of corrosive water attack and loss of structural integrity. All but three of the
samples tested for crush strength exceeded the requirements for new pipe; corrosion
penetration was minimal or absent in most cases, particularly for pipe conveying low
to moderately aggressive water. The long-term performance of factory-appliedcoatings
was found to be excellent. Iron-based inorganic deposits, apparently from the corrosion
of metallic system components, were deposited in situ on some of the pipe samples but
the protection thereby provided against aggressive attack was indeterminate. Data from
other industry and EPA studies show that metal salt-based corrosion inhibitors added
to the water can, under certain conditions, retard aggressive water attack on asbestos
cement pipe provided the inhibitor is added properly and continuously to the water
stream.14
11.6.2.2.5 Stainless Steel
Early experience with the use of stainless steels in the U.S. domestic water supply was
unsuccessful. Ferritic 409 welded tubing failed, probably from chlorides from the solder-
ing fluxes used. The austenitic stainless steels should be more successful and soldering
can be avoided by using mechanical joints.13*
Rapid economic growth in Japan in the period 1955-1960 led to greatly increased
demand for water, particularly in Tokyo. Contaminants such as nitrogen oxides, organic
acids, etc. increased in the raw water requiring more aluminum sulfate and chlorineaddi-
tions at the treatment plants, thereby decreasing the pH and accelerating corrosion of the
city supply pipes. The chlorine injection also caused corrosion of iron pipes, producing
458 Aoolications
"red water," resulting in a rapid decline in the use of galvanized piping for city building.
Some of the city pipes were replaced with unplasticized PVC which reduced the red
water problem but was unsuitable for hot water supply piping. Copper pipe has long
been used for hot water supply but pitting was initiated by the increased concentration
of chloride ions and sulfuric acid in the water.
The Japanese Stainless Steel Association initiated an extensive corrosion testing pro-
gram into the use of stainless steel piping for providing water to and within buildings.
The trial was based on the use of 304 stainless steel and included soldered, compression,
and press-type fittings. The test piping carried hot and chilled, nonpotable, and cooling
water to four buildings over a 10-year period. This study found the following:
1. "Migration rust" coated the inside of some pipes but no corrosion was found beneath
the coating.
2. No corrosion was found on welds of test pipes and lap joints even where oxide re-
mained.
3. Local corrosion at soldered and brazed joints was rarely seen.
4. No significant local corrosion was seen on compression joints of bronze castings,
despite the potential difference.
5. No stress corrosion cracking or other localized corrosion was found on pressed joints.
6. Galvanized steel pipes were severely corroded.
7. The corrosion of copper pipes was more variable than that of the stainless steel and
depended more on water characteristics.
8. Crevice corrosion occurred frequently under the gaskets in joint surfaces. This was
thought to be caused by the use of water-absorbingmaterial, such as asbestos packing,
and to uneven bolt tightening.149
After more than a decade of testing, the Tokyo Metropolitan Bureau of Waterworks
pioneered the use of stainless steel for the connecting piping (connectors)from the sub-
main in the street to the meter at the dwelling, primarily to reduce leakage rates. The
stainless steel pipe connectorswere insulated from the ductile iron submain in the street
and from the meter at the dwelling to avoid galvanic corr~sion.'~~ More recently they
have also started to use corrugated stainless pipe to reduce the costs of installation.lm
Coiled stainless steel tubing is being used increasingly in Japan to supply hot and cold
water to multiunit residential properties. Trpe 316 is used in preference to 304 because
its lower work hardening characteristics make bending easier and it can be installed as
one continuous run without joints. This coiled material was originally developed for
injecting chemicals in the enhanced oil recovery process. Standard dimensions available
are 9.52 mm OD with 0.7 mm wall, and 12.7 and 15.88 mm OD with 0.8-mm-thick
wa11.151
Piping (316L) can be buried in Tokyo soils without external protection. No failures
have been reported after many years of operation. Other tests and experience indicate that
stainless steels perform well in well-drained soils with clean backfill. In poorly drained
soils,however, such as under river crossings and in poor backfill, underdeposit corrosion
Next Page
and MIC may occur. In this case, buried stainless steel piping should be wrapped and
cathodically ~ r 0 t e c t e d . l ~ ~
The use of 304 stainless steel piping on road bridges to replace troublesome under-
river lines was also pioneered in Tokyo. The water pipes form the beam of the bridge,
can be supported from a girder or truss of a bridge, or can be suspended from a surface
transportation bridge. The stainless steel river crossings are insulated at either end to
avoid galvanic effects with the cast iron pipes."
On the basis of a 15-year evaluation of candidate materials, New York City initiated
substantial use of 304L stainless steel in municipal water distribution systems for the
large-diameter risers in a water tunnel, stage 1, that went into service in 1993. Stainless
steel piping is being used selectively for sections that are difficult to replace and where
maximum durability is desired.131
In Italy, 304 piping is being used to refurbish existing cast iron or asbestos cement
pipe in situ. Lengths of the new stainless pipe are slid into the old main from a single pit,
thus avoiding the necessity of digging trenches. Subsequent lengths of pipe are joined
by tungsten inert gas (TIG) welding.152
The result of all of this testing and service experience with stainless steel water piping
is that it is now becoming more accepted by many authorities as an alternative to tradi-
tional materials. The use of stainless steel can give cost and weight savings in selected
potable water and wastewater treatment app1i~ations.l~~
Some of the reasons for using stainless steel for potable water distribution are the
following:'54
Stainless steel has good corrosion resistance to all potable waters including soft ones.
It is strong and ductile.
It is unaffected by high velocities.
It requires low maintenance.
It does not need water treatment chemicals apart from those for bacterial control.
It is nontoxic.
It is manufactured from a high proportion of recycled material and is recyclable.
Stainless steel looks good.
A new 316 hot water system started to leak at welded joints after only 6 weeks
in operation. Corrosion tubercles were found at leaks in the welds and parent metal.
Scallop shell patterns were reported beneath the tubercles, suggesting MIC attack. High
manganese levels were determined in one location, surprising because the water was
softened, chlorinated, and contained essentially no manganese. Then the tanks began
to leak. The investigation initially focused on MIC, but no bacteria were found at any
corrosion site. The corrosion was finally explained by the formation of carbon dioxide
bubbles at discontinuities on the surface. Ions, including chlorides, could then concen-
trate to many times their bulk concentrationby electrophoresis and start pitting of the
stainless steel. The use of a mineral acid to provide a stable pH throughout the system
reduced the tendency for COz bubbles to form.lS5
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T
11.6.2.2.6 Copper
Copper is the most common piping material for domestic supply of potable water. Each
year about 1billion ft (0.3 billion m) of copper water tubing is installed in the United
States. Since statistics began to be collected in 1946 about 40 billion ft (12 billion m)
of copper tubing has been installed in water service and distribution systems in the
United States. In general, the use of copper in this application is successful, with very
few reported instances of corrosion or failures.
The Copper DevelopmentAssociationinvestigatesincidents of problemswith copper
water tubes. Over the years from 1988to 1994the number of incidents relating to specific
causes varies, but totals for this 7-year period are as follows:
Cold water pitting 49

Concentration cell corrosion 35
Flux corrosion 79
Underground corrosion 25
Green water 12
Erosion corrosion 51
Sulfate attack 11
Stress corrosion cracking 7
Hot water pitting 17
Workmanship 11
Galvanic corrosion 1
Cold water pitting is strongly correlated with water chemistry and is particularly
prevalent in well waters in arid areas. Raising the pH of an aggressive water to 8 and
reducing the carbon dioxide content to less than 5 mg/L will successfully mitigate cold
water pitting of copper.156
Erosion corrosion can occur in hot water copper piping if the velocity exceeds 4 to
5 ft/s (1.2 to 1.5 m/s). This phenomenon rarely occurs in cold water unless excessive
pressures (approximately>80 psig [550Wa]) are developed. Also, cold water is normally
continuously circulated, unlike hot water. To avoid hot water erosion-corrosion velocities
and pressures should be kept below these limits, temperature should not exceed 49 to
54"C, workmanship should be good to avoid turbulence, and abrasive particles should
be e ~ c 1 u d e d . l ~ ~
Some of the corrosion problems in copper potable water piping can be avoided by
modification of the water supplied by the utility company. For example, the pH can
be elevated by the addition of lime, caustic soda, or soda ash. This helps avoid cold
water pitting by reducing the free CO2 but would not avoid pitting in hot water. The
free C02 that is mainly responsible for cold water pitting can also be removed by aerat-
ing the water. Air stripping oxidizes some of the metallic species that cause hot water
pitting and allows them to be removed by filtering. Liquid silicate/phosphate additions,
normally used to avoid corrosion of galvanized piping, can form a protective film on
copper.'58
If the potable water comes from a local well, galvanized steel pipe is often used to
bring it to the storage tank. From the tank the water is distributed throughout the house
in copper piping. If these two materials are joined together directly galvanic corrosion
is inevitable at the interface. The best solution to joining such dissimilar metals is to use
a dielectric union, i.e., a screwed coupling in which one half is copper and the other is
galvanized and the two halves are electrically separated by a nonmetallic, nonconducting
se~ti0n.I~~
In some waters and in some systems lead contamination is still a potential health prob-
lem. The lead comes from corrosion of lead tin solder, lead piping, and lead-containing
brasses in plumbing fixtures. Inhibitors can be added to the water to slow the corro-
sion but their effectiveness depends on specific water chemistry so they need to be
evaluated for individual cases. The normal method for monitoring lead in water is the
EPA standard, but recently a quicker, cheaper, gravimetric technique was developed
and evaluated on a water supply. In this Canadian study it was found that the new
method could distinguish between inhibited and uninhibited water in as short a period
as 1month and assess the relative effectiveness of candidate inhibitors. Sodium hydrox-
ide and polyphosphates gave the greatest decrease in corrosion while sodium silicate
gave mixed results. The better inhibitors reduced the corrosion rate by about 50%but
seasonalor other changes gave an even greater variation over the 2 years of the project.lW
11.6.2.2.7 Plastics
Various plastics are being used to carry potable water, although health and durability
issues have been raised in some areas. Polybutylene piping has been used for distributing
cold and hot potable water in some parts of the United States as it was perceived to be
a cheaper alternative to copper.'32 Recently, homeowners have been complaining about
leaking polybutylene potable water piping. This type of plumbing system was installed
from 1979 through 1995in more than 6 million homes in the United States. Hundreds of
thousands of alleged leaks led to several class action lawsuits against the manufacturers
of the material as well as against the pipe manufacturers.
This particular piping material is commonly found in two forms in residential prop-
erties: (1)bright blue piping used underground from the street water meter to the house
and (2) a medium-gray-coloredpiping used inside the house. Where the two pipes join,
a male-male fitting is used to connect the ends, which are then clamped at the joints
with either brass or aluminum bands. There are different theories as to why the material
appears to be defective. One theory is that when the piping is stored outdoors for a
period of time or exposed to sunlight after installation, UV radiation adversely alters
the chemistry of the plastic causing deterioration. The second theory is that chlorine
in the water attacks the plastic. Problems have also been reported at pipe joints where
improper installation of clamps caused leaks.'61
Polyethylene retains its strength and flexibility even at subfreezing temperatures.
Since coiling is possible with small-diameter PE pipe it is used for gas distribution and
water services. PE can be cross-linked to raise the maximum operating temperature up
462 Applications
to 200°F (93”C),at which it can be used for underfloor heating systems, melting ice and
snow, and hot-cold water systems.162Polyethylene is also used to rehabilitate old water
pipes by the process of sliplining. See Section 11.7.2, “Sewers and Wastewater Piping,”
for details.
A deteriorating cast iron water main in Henryetta, OK was leaking 300,000 gal
(1,100,000 L) of water per day and threatening to shut off the city’s water supply. Com-
plicating factors included water temperature that changed 30” in short time periods and
steep slopes in the area of the leak. HDPE pipe was selected to reduce the number of
joints along the slope and cope with the temperature differential. Fourteen-inch (35.6cm)
iron DR-11 water pipe was installed along the 1,400-ft (430-m) section of line extending
over the steep slope to the flatland below. The HDPE pipe solved the elevation and water
temperature problems and allowed for rapid installation that avoided shutting off the
city’s main water supply for a n extended period of time.la
Composite piping, made of an aluminum tube that is laminated to interior and ex-
terior layers of plastic, can be used for hot and cold water supply and is approved by
nationalcodes. Brass fittings, tees, elbows, and couplingsare availablein both mechanical
compression and crimping styles. It is lightweight at 41 lb/600 ft of 112 in. (18.6 kg/183 m
of 1.2 cm)coil, can operate at pressures ranging from 90 to 300 psi (0.6 to 2 m a ) , and
withstands operating temperatures of up to 210°F (99°C).It can be easily bent or formed
by hand. The material eliminatesthe need for pastes, solder, and torches and resists cor-
rosion and scale buildup. Fewer leaks are possible because fewer connectionsare used.’@
11.6.3 Electrochemical Protection of Domestic Water Systems
To protect hot and cold domestic water systems it is common in many areas to incorporate
some form of CP. Magnesium alloy anodes have been used in many types of installations
in fresh water, including heaters, boilers, heat exchangers, etc., but hydrogen evolution
is sometimesa problem. Zinc alloy anodes are rarely used in domesticsupply equipment
because of the effect on water quality but zinc dip coatings are used in heaters, pipes,
tanks, etc. Aluminum alloy anodes are also occasionally used in potable water systems.
Applied current CP is used for tanks and water heaters with platinized titanium being
the most widely used anode material. In some applications the use of CP with epoxy
or polyurethane coatings has been effective. The Guldager system was developed in
Denmark and consists of consumable aluminum anodes connected to an external DC
power supply. The effect is to produce a thin layer of aluminum hydroxide that coats
and protects all metallic surfaces.16
11.7 WASTEWATER HANDLING
“Waste water” is a term used to cover many fluids ranging from household sewage to
highly toxic industrial solutions. As environmental standards improve, more and more
treatment of waste water is required. The treatment applied will depend both on the
constituents of the water and the use to which the product will be put. The water can be
treated to potable standards, e.g., the river Thames in its 338-km length is treated and
drunk many times. In some cases the material taken out of the water is the prize, e.g., in
the case of removal of trace metals in mine waste waters. For waste water from mines
see Section 11.15, ”Mining.”
Domestic waste water may be transported and treated alone or may contain surface
runoff and storm water as well. In this type of sewer system flow volume and velocity
will vary considerably depending on the season. This, in turn,can affect the corrosion
caused by the interaction between sulfides and bacteria.
11.7.1 Treatment Plants
The first wastewater treatments for drinking water simply reduced the amount of sus-
pended matter in rivers. Biological treatment for further reduction of suspended matter
and reduction in phosphorus was added as a cleaning process in the 1970s, followed
later by methods for nitrogen removal. During the 1990s, the use of an activated sludge
process in the biological treatment of waste water has increased. In Sweden, biological
purification is used in 95% of the country’s sewage treatment plants. This process in-
volves using microorganismsto enhance the rate of natural biological processes to clean
the water.
The main purification processes are mechanical, chemical, and biological treatment.
Some plants use only mechanical and chemical treatments, while others use all three
stages.
In mechanical treatment, the sewage enters the plant through screens that remove
large particles. It then continues to a grit chamber, where grit, gravel, oil, and fat are
removed, and then on to the primary settling stage.
In chemical treatment, orthophosphates are removed by precipitation using one of a
number of chemicals, such as ferrous sulfate, aluminum sulfate, or iron(II1) chloride. In
Sweden, the use of poly-aluminum chlorides and poly-aluminum sulfatesin wastewater
treatment is a relatively recent development. The dosage point may be prior to the
primary settlingstage and/or, in someplants, before the final settlingtank to ensure a low
phosphorus content in the effluent. The positive ion in the precipitation chemical, e.g.,
aluminum ion, combines with orthophosphate to form aluminum phosphate that does
not dissolve easily. Aluminum phosphate can then be removed by flocculation. At the
flocculation stage chemicals, e.g., polymers, are added to combine with the precipitated
phosphate to produce particles large enough to settle.
Biological treatment removes nitrogen and organic carbon and in some plants may
also reduce phosphorus. This purification process can be divided into several stages.
The biological treatment alternates between anaerobic and aerobic conditions where air
is blown into the water. Biological nitrogen is removed by nitrification in the aerobic
environment and denitrification under anaerobic conditions. During nitrification, am-
monia is converted to nitrate. In denitrification, nitrate is converted to free nitrogen that
464 ADOIications
is released into the atmosphere. Organic carbon is converted to carbon dioxide and water
during the aerobic stage.
After the biological treatment the waste water passes on to the final settling tanks
where the remaining active sludge settles. The sludge may then be recycled to the bio-
logical treatment stage or transferred to the digestion process. The temperature of the
flowing water in the final settling tanks varies between 10 and 15°C. After the final
settling stage, the liquid effluent can be released into the sea, lakes, or rivers.
Sludge is removed during biological treatment and later transferred to large digesters.
The active digestion of the sludge is oxygen-consumingand the process is considered to
be anaerobic.The temperature during the digestion process remains relatively constant at
38°C and the pH level of the sludge can vary between 6 and 8. During biological digestion,
biogas containing hydrogen sulfide gas is produced. The sludge may be dewatered after
digestion by centrifuging and may be used as fertilizer if no heavy metals are present.'%
The final stage, before the cleaned water is used for drinking, is disinfection to destroy
pathogens using chlorine, ozone, or UV light.
If industrial and domestic waste water are being treated in the same plant biological
treatment is usually the primary method used. If it is only industrial waste water it
is more usually treated by physical/chemical methods because the industrial waste
often contains pollutants that cannot be removed efficiently by microorganisms. Some
industries, such as food, dairy, and brewing, deal with their biodegradable materials by
biological treatment. Biological plants also use some physical and chemical processes.
A physical process usually treats suspended, rather than dissolved, pollutants. The
process may be any of the following:
Passive, such as simply allowing suspended pollutants to settle out or float to the top
depending on their density
Stirred to mechanically aid separation
Chemical flocculation to produce larger particles
Pressure air bubbling to aid flotation
Filtration through a medium such as sand as a final treatment stage which can result
in very clear water
Ultrafiltration, nanofiltration, and reverse osmosis to remove colloidal matter and
some dissolved material
Adsorption on activated charcoal to remove dissolved matter; technique used in mu-
nicipal plants for odor control
Air or steam stripping to remove pollutants that are gasses or low-boiling liquids;
produced vapors often pass through beds of activated charcoal to reduce air pollution
Chemical treatment processes used for industrial waste water include the following:
Precipitation of a dissolved metal with an alkaline material like sodium or calcium

hydroxide. Dissolved iron, aluminum salts, or organic coagulants can aid flocculation.
Using chlorine to oxidize highly toxic cyanides in mining and metal finishing indus-
tries into carbon dioxide and nitrogen.
using ozone or hydrogen peroxide to destroy organic chemicals, either alone or with
catalysts and/or UV light.'67
The environment in wastewater treatment plants can be very corrosive as a result

of the presence of acids, sulfides, chlorides, bacteria, etc. It can also contain solids that
can be abrasive or deposit on surfaces. Sources of sulfide in waste water include unreg-
ulated and/or uncontrolled industrial discharges, degradation of sulfur-containing or-
ganic matter, or the microbiologicalreduction of sulfate or other oxidized forms of sulfur.
The construction of regional collection and treatment systems has increased wastewater
travel time, culminating in anaerobic waste water and, consequently, increased sulfide
generation. Odors from manholes or waste water treatment facilities create significant
nuisance problems. A major cause of odors is hydrogen sulfide, a toxic gas detectable
at extremely low concentrations. The gas is somewhat corrosive to concrete and other
materials in sewers and treatment plants but the main cause of concrete corrosion is
the aerobic microbial oxidation of hydrogen sulfide to sulfuric acid and the subsequent
attack of the concrete by the acid.'68
Different materials are used in wastewater plants, with selection often made on the
basis of cost and availability. Apart from the primary items of equipment used in treat-
ment, i.e., filters, settlers, clarifiers, biological and chemical treating vessels, etc., vast
lengths of piping are required to transport the waste water to and from the treatment
facility.
11.7.1.1 Stainless Steels
Stainless steel 316 has been used as wire for microstrainers in tertiary sewage treatment
and for water containing minor amounts of chloride. Stainless steel 304 has provided ex-
cellent service as valve parts, weirs, fasteners, and pump shafts in water and wastewater
treatment plants.% Ferritic 3CR12 has been used in sewage treatment plants for weir
plates, flood and sluice gates, etc. It has also been used successfully in the form of ex-
panded metal mesh exposed to circulatingpurified sewage effluentsince 1986. This water
is high in chlorides (90 to 160 pprn), nitrates (40 to 70 pprn), and sulfates (100 to 150 ppm)
with a pH of 7.3 to 9.3. The high pH and nitrates may be helping to reduce corrosion.
One Swedish company designing filters has evolved a rule of using 304 for air-
saturated water containing <lo0 pprn chlorides and 316 for up to 400 pprn chlorides.
When these design criteria have been applied no corrosionproblems have been observed.
In one application designed for 80 pprn chlorides, 304 equipment was severely pitted
when an overdose of ferric chloride produced >500 pprn chlorides. A Dutch engineering
company specifies the use of 316 even in waters with less than 200 pprn chlorides and
their experience in 14 plants has been excellent. They have used 2205 in an industrial
effluent treatment plant in areas where higher chlorides are en~0untered.l~~
Stages in treatment plants where oxygen consumption is high are generally harmless
to stainless steels. In aerated areas biological activity can increase the corrosion potential
and promote localized attack of 304 in the presence of a few hundred pprn of chlorides.
466 Applications
This ennoblement effect in the presence of a biofilm is similar to that on stainless steels in
seawater. Field trials in Scandinaviaconcluded that in plants where the chloride content
exceeds 500 ppm and ennoblementreached 300 to 350 mV an alloy such as 2205 should be
used.’66The use of stainless steel can give cost and weight savingsin selected wastewater
treatment and potable water application^.'^^
SevereMIC has been reported on the internal mechanismsof primary clarifiers, made
of 403 stainless steel. Extensive damage to the epoxy coating on the inside surfaces of
the clarifier walls, as well as to the concrete, also occurred in this municipal wastewater
treatment plant. 170
11.7.1.2 Galvanized Steel
A major corrosion test program involving 35 sites over a 5-year period in three North
American wastewater treatment plants assessed the corrosion behavior of galvanized
steel in this application. This survey concluded that while hot dip-coated galvanized
steel is excellent for atmospheric exposure in wastewater treatment plants it is only
of limited value for immersion service. All the immersion test panels in this program
suffered extensive corrosion, mostly localized, most severe in the primary treatment
section. The joint action of bacterial attack and crevice corrosion was mainly responsible
for the observed corr~sion.’~~
11.7.1.3 Concrete
MIC is a prime source of deterioration of concrete infrastructures in the wastewater

collection and treatment industry. The current annual cost of rehabilitation and replace-
ment is several hundred million dollars.The needed repairs are estimated to be well over
$1billion. While not all of the deterioration can be blamed on MIC, a substantial portion
can. Coatings can help reduce these corrosion problems. Two systems that are particu-
larly effective are a resin-rich, high solids epoxy coating and a potassium silicate-based,
acid-resistant concrete c0ating.l”
Concrete in waste water can be attacked by hydrogen sulfide, sulfates, and chlorides
of sodium, magnesium and ammonium, ammonium nitrate, etc. A coating system must
protect the concrete against these chemicals, attack by microorganisms,and damage by
moisture penetration. Coatings are applied to concrete surfaces for immersion service
in tanks, troughs, aerators, filter beds, and clarifiers; moist atmospheric exposure on
tank exteriors and wet walls; moderate industrial exposure on exterior concrete; and
dry exposure on concrete walls, floors, and masonry. Each of these types of application
requires different coating systems and application. Surface preparation for coating on
concrete must overcome problems such as the following:
Laitance-A weak surface layer caused by a water-rich surface mixture. Will cause
poor bonding and must be removed by light abrasive blasting or acid etching.
Efflorescence-Salts deposited by evaporation as moisture moves out of the concrete.

Removed by acid etching.
Form oils and waxes-Used to ease removal of forms. These deposits can prevent
coating adhesion and should be removed by emulsifymg, then water washing.
Air pockets-Voids at or just beneath the surface of the concrete. If left, they can form
holes or bubbles in the coating. Avoid by good working practice.
Concrete hardenereused to improve surface hardness, resistance to chemical attack,
and permeability to liquids. Should not be used if concrete is to be coated as they can
make adhesion difficult.
Concrete to be coated should be clean, dry, and well cured with a tightly adherent
surface. Coatings used in water and wastewater applicationsinclude the following:
Two-component epoxy-Hard, durable surface; many are suitable for immersion.

May "chalk" in sunlight.
Coal tar epoxy-Economical, easy to apply in thick coats, good chemical and abrasion
resistance.
Vinyl-Fast drying, often need more coats to achieve required film thickness. Does
not comply with volatile organic compound (VOC) standards in some ~ 1 a c e s . l ~ ~
On rehabilitation projects coatings that can be applied quickly are sometimes spec-
ified. Among the coatings used in this case are 100% solids urethanes and epoxies,
polyesters, vinyl esters, polymer mortars, acid-resistant cements, sheet-applied linings,
and spray-applied rubber e1a~tomers.l~~
11.7.1.4 Vitrified Clay
Vitrified clay paviors with interlocking joints are used for lining metallic or concrete
structures to improve wear and corrosion resistance. They can be fitted as part of new
construction but are also often used as part of a restoration or rehabilitation program.
Reinforced concrete pipe lined completely or in part with vitrified clay paviors is factory
p r 0 d ~ c e d . Vitrified
l~~ clay brick and tiles are also used to line vessels, ditches, floors,
etc. in wastewater treatment plants, either in new construction or restoration work. The
bricks or tiles are laid using resistant mortars, often over an impervious membrane.'76
11.7.1.5 Corrosion Protection
Coatings and CP are used in selected applications in wastewater treatment plants and
collection systems. Corrosion on submerged metal treatment mechanism, agitator, filter,
etc. within a concrete-reinforcedbasin will be under the control of a galvanic couple. This
exists between the anodic mechanism and cathodic rebar in the concrete. The anode-
cathode relationship will determine the corrosion rate of the steel structure exposed
468 Annlications
to the electrolyte. On poorly coated structures, corrosion activity may be spread over
the entire mechanism. On a well-coated structure, all corrosion activity will occur at
the flaws in the coating system where metal penetration can develop relatively rapidly
unless cathodic protection is also applied.ln
11.7.2 Sewers and Wastewater Piping
Piping is a major component of wastewater handling with many kilometers of sewers

and connecting piping to and from the treatment plant. Whenever possible, waste
water is made to flow under gravity because of the difficulties involved in pumping
this type of fluid. A number of different materials are used in this service. For example,
a study conducted in 1990 in Germany surveyed 72 towns and local authority districts
with a total of 14.3 million residents and a total sewer length of 45,951 km. They found
that the materials used for these sewers comprised 45% vitrified clay, 44% concrete,
7% masonry, 2% fiber cement, 1%plastic, and 1% Some sewers in the United
Kingdom date back to Roman times when clay pipes and masonry were already being
used to construct sewers.179
Sulfide production in sewers is one of the main causes of corrosion. All sanitary
sewage contains water, bacteria, sulfates, and organic matter so that the production of
hydrogen sulfide is likely. This gas can be convertedby bacterial action into sulfuric acid
which can then attack concreteand any metals present. Sulfideis not usually a problem in
short sewers if temperatures are low and there is plenty of rainfall and water infiltration
into the sewer. Similarly, if the sewer is only partly filled and there is plenty of oxygen
present the hydrogen sulfide is likely to be oxidized to thiosulfite. If flow is rapid the
sulfidebuildup in the slime layer on the pipe is reduced and the escape of sulfur species
into the stream and atmosphere is more likely. In small sewer pipes with less than about
10 to 20 mm liquid, sulfidebuildup is not likely even at low flow rates. Where hydrogen
sulfide is oxidized by bacteria on the wet walls of sewers corrosion can be rapid and
concrete pipes have collapsed in less than 3 years.
Corrosion occurs in the vapor space of the pipe and is usually more severe in the
area of the liquid surface where flow removes the damaged concrete layer or corrosion
products in metallic pipes. If sulfides are expected where resistant materials are not
used, corrosion can be minimized by ensuring fast flow, adding air or oxygen into the
sewer, or adding chemicals, such as hydrogen peroxide, sodium hydroxide, potassium
permanganate, or chlorine/hypochlorite.lm
11.7.2.1 Concrete
Concretedrain tiles were made in the Netherlands during the 1830s and were introduced
into the United States during the following decade. This was followed by the production
of concrete sewer pipe with the first one being laid in St. Louis in 1868 where it remained
in service for more than 100 years. The United Kingdom concrete pipe industry started
soon afterward and one of the early concrete sewers was laid in the center of Norwich in
1887 and is still in service. The sulfide/sulfuric acid problem is exacerbated if velocities
are low and if deposits are allowed to build up on the surface. If slopes are sufficiently
steep and the concrete is made with high cement content and limestone aggregate then
degree of attack can be acceptable even if sulfides are present.’79 PCCP has been widely
used in sewers and other wastewater handling for many years in diameters ranging from
0.4 to >6 m. For details see Chapter 6, Section 6.2.3, Trestressed Concrete.”
Sulfide generation and attack in the vapor space of concrete sewers, crown corrosion,
increased dramatically in Los Angeles in the years following a requirement for industry
to undertake wastewater pretreatment. The relationship between sulfide generation and
composition of the wastewater was investigated. The wastewater concentrations of dis-
solved and/or total sulfide correlated with concentrations of several transition metals,
including Ni, Fe, Pb, Cd, and Cr. Experiments were made to determine the effects of
these metals alone or in combination on the activity of SRB. None of the metals alone at
levels prior to the requirement for industrial pretreatment inhibited sulfide generation
but when tested together at these earlier levels Cr, Cu, Ni, Zn, and Cd inhibited SRB
activity in the various types of reactors tested. These results showed that cleaning up the
waste water flowing in the sewers increased the corrosion of the concrete pipes.ls’
Within 4 to 6 years after the Hamburg sewer system was put into service severe
corrosion of the concrete piping occurred. The concrete pipes had been given a thin coat
of epoxy before installation. The concrete matrix had been damaged to a depth of 6 cm
or more and the surface pH was 1 to 2. The corrosion was caused by bacterial action
and the corrosion process was simulated in laboratory tests using a bacteria breeding
chamber.18*This chamber was also used to compare corrosion by biogenic sulfuric acid
in the laboratory with actual experience in the sewer system. It was found that the
chamber could reproduce this type of attack but that it happened more quickly than in
actual operation-9 months for the first corrosion to appear in the chamber compared
with 6 years in the sewer. The cell counts of Thiobucillus thiooxiduns gave a good indication
of the extent of the corrosion. Hydrogen sulfide proved to be the most important source
of sulfide for sulfuric acid corrosion and severe corrosion was produced when sufficient
substrate was a~ai1able.l~~
Concrete piping used for waste water is often coated to form a continuous protective
barrier over the often rough concrete surface. Such coatings are defined in, for example,
the American Concrete Institute’s Standard ACI 515,1R-79. After surface preparation of
the concrete, which is an essential step, the screed coating is applied. Typically a 100%
solids, thixotropic putty is used, often based on epoxy although other resins are used.
The alternative is to apply a cementitious screed either by spray or trowel. Once the
screed is dry, the barrier coating is applied. This coating should be thick enough to fill
any discontinuities and minimize the likelihood of holidays. Minimum thickness should
be 1.5 mm.lM
Various types of lining systems are presently available in North America for the inter-
nal coating of municipal water and wastewater pipelines. These systems included 100%
solids polyurethanes, ceramic epoxies, and polyethylenes. The behavior of the two 100%
solids polyurethanes was excellent not only in all tests, but in their handling and safety
470 Applications
characteristics as well. Polyethylenes were good in many tests, such as impact resistance
and abrasion resistance, but performed poorly in the cathodic disbondment test. Even
though the ceramic epoxy showed relatively good chemical resistance and undercutting
resistance, its poor adhesion,low impact resistance, and brittleness raised concernsabout
its ability to provide long-term corrosion protection in aggressive sewer application^.'^^
Another protective system that has been successful is a combined elastomer/acid-
resistant concrete coating. The concrete is first coated with a resin-rich, high-build epoxy
followed by a potassium silicate-based acid-resistantconcrete layer. Tests show that this
type of protection is effective and does not support the growth of bacteria as is the case
with some organic coatings.17*
In order to improve concrete's resistance to sulfide/sulfuric acid attack inhibitors
are being added to concrete pipes. Organic corrosion inhibitor ( X I ) additives contain
amines to protect steel reinforcement and esters to reduce permeability. A study of
the effectiveness of some of these additives in solutions at different pH concluded the
following:
Metakaolin additive performed similarly to normal concrete at pH 1.

Silica fume and OCI additives performed 30%better than normal concrete at pH 1.
OCI additive (higher concentration of amines and esters) concrete had only 20% the
degradation of normal concrete at pH 1.'%
11.7.2.2 Asbestos Cement
Although chrysotile asbestos cement (A/C) pressure pipe is used primarily for the dis-
tribution of potable water, it is also used in sewer force mains and industrial effluent
and process piping. A/C nonpressure pipe is used for sanitary and storm drainage
system^."^ A/C pipe is also attacked by sulfides/sulfuric acid in sewers, although the
high cement content makes it more resistant than concrete. This advantageis offsetby the
thinness of the pipe wall and this material should not be used in sewers where sulfides
are present." A/C pipes are made to ASTM C 428 or C 663 for sewage applications.
This type of pipe can be damaged by the leaching of the cement binder out of the pipe
wall by sewage or external ground water.
11.7.2.3 Vitrified Clay
Clay pipes are formed from wet clay and grog (recovered clay dust) with a glaze added
before drying at 80°C and firing at about 1,250"C. The glaze is made from the same basic
materials plus metallic oxides to provide color. Ends of the pipes are spigot and socket
and various types of jointing systems are available. Jacking pipes permit trenchless in-
stallationby the process of microtunneling from a shaft. A double-pipe system consisting
of a vitrified clay inner and steel outer pipe is used for applications that require double
pipe to protect the water table.lMVitrified clay pipes are immune to the sulfide/sulfuric
acid attack that can damage concrete or metal sewer pipes.lW
11.7 Wastewater Handline 471
11.7.2.4 Plastics
Plastic pipes for sewage are made from PVC, ABS, PE, and FRP and these materials are
resistant to the sulfide/sulfuric acid attack that can damage concrete and metals." They
can, however, deform under load and the permissible deformationmust be specified,e.g.,
5%of the vertical diameter is typical. Concerns have been raised about possible damage
to plastic sewers during cleaning with conventional rods and power cleaning tools.179
Over 7,500 ft (2,300 m) of concrete sewer pipe, varying in diameter from 12 to 18 in.
(30 to 46 cm), was rehabilitated in 1992 with a patented cured in-place pipe (CIPP)
process for the City of Victoria, TX. The 20- to 40-year-old sewer lines are designed to
handle either residential or light industrial to heavy commercial waste. Deterioration
ranged from slight corrosion to near decay, with repairs needed on several pipe systems
located beneath state highways and railroad tracks. The CIPP process allowed pipelines
to be restored without the disruption caused by traditional dig-and-replacemethods and
saved countless man-hours. Using a specially designed polyester felt tube impregnated
with epoxy vinyl ester resin (Derakane411-700TB),a seamless new "pipe within a pipe"
was formed. This resin was specified because the acidic and alkaline conditions in most
sewer lines often exceed the capabilities of polyester resins.la9
In 1997,the first polypropylene (PP)sewer pipe system (ultra rib 2 9 came on the mar-
ket. PP had already been extensively used in building services and has the advantagesof
high impact strength, abrasion resistance, and temperature resistance. Wall thickness has
been increased from earlier versions and a white liner has been fitted to aid inspection."
Polyethylene (PE) sewer pipes were first used in direct burial in Scandinavia and
Germany in the mid-1960s. Before then PE had only been used as a liner for ductile iron
sewer pipe. No significant changes in the PE liner's chemical or physical properties were
seen after more than 25 years in sewer service. PE is unaffected by the biogenic sulfuric
acid that attacks concrete and metallic sewers and is also resistant to microbial attack
in sewage. More than 30 years of utilizing PE piping in sewage applications has shown
that it can provide reliable long-term perf~rmance.'~'
The San Rafael, California Sanitation District was faced with preventing tons of raw
sewage from overflowing a canal and being dumped into San Francisco Bay. A sewage
and groundwater transfer pipeline constructed in the 1940swas corroding and its capac-
ity was severely restricted by internal deposits. Two new parallel PE pipelines were laid
15 ft (4.6 m) below the bottom of the canal, involving complicated directional drilling,
without disturbing the nearby wetlands. SDR-ll(l6in. [0.4m]) and SDR-11HDPE (26in.
[0.7 ml) pipe were used. Excavation and environmental impact were kept to a minimum
and the project was completed in 4 weeks, one third the time required for the average
trench-digging 0perati0n.l~~
PE is also used to rehabilitate old sewer pipes by the process of sliplining. When
complete, the liner pipe should extend from one access point (e.g., a manhole) to the
next access point in a continuous, watertight length. This technique has been used to
rehabilitate gravity sewers, sanitary force mains, water mains, outfall lines, gas pipes,
highway, and drainage culverts on pipe as small as 1 in. (2.5 cm) diameter with no
apparent limit to the maximum diameter. The process of sliplining is detailed in ASTM
472 Amlirations
F585 and consists of a number of ~ t e p s : ' ~ * ~ ' ~ ~
Inspection and cleaning. All debris must be removed, tree roots or other obstacles
may make lining impossible or uneconomical.
Temporary bypass lines may need to be installed.
Excavation may be required to provide access for lining.
Pipe lengths are assembled by thermal butt fusion or thermal extrusion welding
methods.
Insertion of the fused and welded liner into the existing pipe. The length of the
liner to be inserted at any one time is governed by the winch capacity and size and
condition of the existing pipe.
In some cases the annular space between the liner and the existing pipe needs to be
filled with grout to avoid buckling of the liner.
Manholes are then replaced and the liner sealed in place.
Service connections can then be made downstream of the first manhole, using heat
fusion or strap-on saddles.
The rehabilitated line is then backfilled and put into service.
Unsaturated polyesters based on isophthalic acid have been the workhorse matrix
resin for GRP pipe, tanks, and structures used in the transmissionand treatment of water
and sewage for more than three decades. The largest use of GRP is in sewer pipe, but it
is also used in reservoir pipe, power plant outfalls, municipal sewer pipe relining, weirs,
filters, and tanks for the storage of water treatment ~hemica1s.l~~
Polymer concrete does not contain cement and is made from 90% quartzitic, oven-
dried fillers, i.e., mineral sands and grit, bonded with polyester, either epoxy or vinyl
ester. This type of material has been used in various applications for decades and more
recently has been used as piping to collect waste water in chemical plants. Polymer
concrete sewer pipes, with and without reinforcement, are manufactured by centrifugal,
centrifugal rolling, and vibrating processes in 3,000-mm construction lengths and in
diameters of 300 to 2,500 mm as standard. Pipes are joined and fittings and manholes
are attached using couplings of glass fiber-reinforced polyester resin with a permanently
integrated elastomer double-lipseal. The pipes and couplingsare watertight when tested
at up to 2.4 bar. Where water flow is variable there are advantages to be gained by using
oval section pipes, which are also available in polymer ~ 0 n c r e t e . l ~ ~
11.7.2.5 Steel and Cast Iron
Steel pipes are particularly susceptible to attack in the presence of sulfides, being cor-
roded by both hydrogen sulfide and sulfuric acid formed on the steel surface in the
vapor phase. If the pipe is completely full corrosion is slow on carbon steel and slower
on cast iron even if sulfides are present, as long as chlorides are low and the pH is >6.5.
Corrosion can be severe in cast iron pipes if sulfides are present and the pipes are only
partly filled."
The Abu Dhabi National Oil Company’s (ADNOC)refinery at Ruwais treats waste
waters from process plants together with sanitary and ballast waters. The waters from
the refinery, discharge from desalters, crude tank drainage, polluted condensate, ef-
fluent from the process units and laboratory, and oily storm and sanitary waters are
separated from the ballast and clean waters, i.e., return cooling waters and brine. Oil is
separated from the water using an American Petroleum Institute (API)separator.A num-
ber of failures of carbon steel piping have been reported from this plant, including the
following:196
An 8-in. (20-cm) carbon steel effluent line taking water from the separator failed by
pitting corrosion after being contaminated by chlorides and sulfates from the crude
oil tank farm and desalters. MIC was the primary cause of this failure and because it
was impossible to eliminate SRBs from the waste water it was recommended that the
line be replaced with titanium or FRP.
A 4-in. (lo-cm)slop line also failed from MIC following contamination with chlorides
from the slop oil and the presence of SRB in deposits and slime.
Cast iron impellers on two centrifugal lift pumps transferring effluent water from the
separators to the ballast tanks failed by pitting after 4 months service, also caused by
SRB. The cast iron impeller was replaced with a Ni-Cr 20-2 Nb stress-relieved alloy.
Ballast water tanks pitted through from MIC in less than 15 months. The wetted sur-
faces of the tank were coated with epoxy amine adduct and aluminum anodes were
fitted to the roof support columns and tank base.
Pitting failures of carbon steel piping systems have been investigated in other plants
treating either domestic/storm and domestic/industrial waste waters. MIC was the
cause of these failuresin return-activated sludge piping systems, one of which containing
0.75 to 1.3 mg/L dissolved oxygen and the other 0.0 to 0.2 mg/L. It was postulated that
anaerobic bacteria could be active beneath the biofilm although in the first case SRB
were below the limits of detection. The piping was carbon steel with a coal tar epoxy
lining. The water was judged to be corrosive in the first case and moderately corrosive
to corrosive in the second case on the basis of conductance. FRP or HDPE was suggested
as a rep1a~ement.l~~
Some cast iron pipe needed to be replaced as part of a modification of a 6-year-old
underground sewer line. The materials to be used for the replacement pipe were dis-
cussed on the NACE Corrosion Network.’98Cast iron or carbon steel were judged to be
appropriate (J. Lichtenstein), as was HDPE (T. Laundrie). If cast iron were to be used
in a force main, i.e., operating full at all times, a cement-mortar lining would provide
adequate internal corrosion protection. If it were a gravity line, the cast iron should be
lined with, for example, an amine-cured novalac epoxy containing at least 20% by vol-
ume of a ceramic quartz pigment. The outside of the pipe should also be protected by
cathodic protection and coating with, e.g., polyurethane. It is common practice in the
United States to encase such pipes in loose film polyethylene to AWWA standard C105
or IS0 8180 (G. Craft).
474 Annlications
11.7.2.6 Coatings
Ductile iron, concrete, and other municipal pipe suppliers have been faced with the
challenge of supplying a product to the wastewater industry that will last 50 to 100years
at the lowest cost possible. Competition,mainly from the plastic pipe industry, has forced
them to find materials that will perform adequately at minimum cost. The result has been
the development of polyurethane coatings containing more tar filler (reducingthe cost)
while maintaining the corrosion resistance. The material used to coat the interior of a
sewer pipe is slightly softer and more susceptible to damage than the system for the
exterior of the pipe. However, because the coating's primary function is to protect the
inside of the pipe from chemical attack, its reduced impact strength is still acceptable.
The cost is 40% lower than the less extended system for the pipe externals.
An example of the use of this type of coating is the &mile (10-km), 12-in. (0.3-m)
ductile iron pipeline known as Fiesta Island Replacement Project (Phase 1)in San Diego,
CA. The system used 25 mils (625 pm) of a 100%solids polyurethane coating and sac-
rificial magnesium anodes. After 2 years in-service inspection showed that the coating
system had an installed efficiency of 99.66% and the pipe had an actual CP current re-
quirement three times less than the design value. Another similarly coated line carries
digested sludge at high pressure from the Point Loma Wastewater Treatment to a new
biosolids processing plant 19 miles (31 km) away. The polyurethane is applied in one
coat (no primer) directly to the blasted metal using an automatic spray gun and pipe
conveyor at a rate of 20 ft of pipe per minute (6 m/min), much faster than is possible
with coal tar epoxy.1o1
The 100%solids (i.e., containing no solvents to dilute the resin) polyurethane coating
technology is often used for internal and external corrosion protection of water and
wastewater pipelines. These coatings are available in a wide variety of setting times
ranging from very fast systems that allow rapid factory application to conventional
brush and roller application to simple field castings.lo1
11.7.3 Standards and Specifications-Water and Waste Water
11.7.3.1 AWWA/ANSI
11.7.3.1.1 Ductile-Iron Pipe and Fittings
C104/A21.4-95-ANSI Standard for Cement-MortarLining for Ductile-Iron Pipe and

Fittings for Water
C105/A21.5-99-ANSI Standard for Polyethylene Encasement for Ductile-Iron Pipe
Systems
CllO/A21.10-98-ANSI Standard for Ductile-Iron and Gray-Iron Fittings
Clll/A21.11-OO-ANSI Standard for Rubber-Gasket Joints for Ductile-Iron Pressure
Pipe and Fittings
11.7 Wastewater Handline 475
C115/A21.15-99-ANSI Standard for Flanged Ductile-Iron Pipe with Ductile-Iron or

Gray-Iron Threaded Flanges
C116/A21.16-98-ANSI Standard for Protective Fusion-Bonded Epoxy Coatings for
the Interior and Exterior Surfaces of Ductile-Iron and Gray-Iron Fittings for Water
Supply Service
C15O/A21.50-96-ANSI Standard for Thickness Design of Ductile-Iron Pipe
C151/A21.51-96-ANSI Standard for Ductile-Iron Pipe, Centrifugally Cast, for
Water
C153/A21.53-00-ANSI Standard for Ductile-Iron Compact Fittings, 3 in. through
24 in. (76 mm through 610 mm) and 54 in. through 64 in. (1,400 mm through
1,600 mm), for Water Service
11.7.3.1.2 Steel Pipe and Tanks
C200-97-Steel Water Pipe6 in. (150 mm) and Larger

C203-974oal-Tar Protective Coatings and Linings for Steel Water Pipelines-
Enamel and Tape-Hot-Applied (Includes Addendum C203a-99)
C205-95-Cement-Mortar Protective Lining and Coating for Steel Water Pipe-4 in.
(100 mm) and Larger-Shop Applied
C206-97-Field Welding of Steel Water Pipe
C207-94-Steel Pipe Flanges for Waterworks Service-Sizes 4 in. through 144 in.
(100 mm through 3,600 mm)
C208-96-Dimensions for Fabricated Steel Water Pipe Fittings
C209-004old-Applied Tape Coatings for the Exterior of Special Sections, Connec-
tions, and Fittings for Steel Water Pipelines
C210-97-Liquid-Epoxy Coating Systems for the Interior and Exterior of Steel Water
Pipelines
C213-96-Fusion-Bonded Epoxy Coating for the Interior and Exterior of Steel Water
Pipelines
C214-00-Tape Coating Systems for the Exterior of Steel Water Pipelines
C215-99-Extruded Polyolefin Coatings for the Exterior of Steel Water Pipelines
C216-00-Heat-Shrinkable Cross-Linked Polyolefin Coatings for the Exterior of
Special Sections, Connections, and Fittings for Steel Water Pipelines
C217-994old-Applied Petrolatum Tape and Petroleum Wax Tape Coatings for the
Exterior of Special Sections, Connections, and Fittings for Buried or Submerged
Steel Water Pipelines
C218-994oating the Exterior of Aboveground Steel Water Pipelines and Fittings
C220-98-Stainless-Steel Pipe, 4 in. (100 mm) and Larger (Includes Addendum
C220a-99)
C222-99-Polyurethane Coatings for the Interior and Exterior of Steel Water Pipelines
and Fittings
D100-96Welded Steel Tanks for Water Storage
476 Aooiications
D102-97-Coating Steel Water-Storage Tanks

D103-97-Factory-Coated Bolted Steel Tanks for Water Storage
D104-97-Automatically Controlled, Impressed-Current Cathodic Protection for the
Interior of Steel Water Tanks
11.7.3.1.3 Concrete and A/C Pipe and Tanks
C300-97-Reinforced Concrete Pressure Pipe, Steel-Cylinder Type

C301-99-Prestressed Concrete Pressure Pipe, Steel-Cylinder Type
C302-95-Reinforced Concrete Pressure Pipe, Noncylinder Type
C303-95-Concrete Pressure Pipe, Bar-Wrapped, Steel-Cylinder Type
C304-99-Design of Prestressed Concrete Cylinder Pipe
C400-93 (R98)-Asbesto~-Cement Pressure Pipe, 4 in. through 16 in. (100 mm through
400 mm), for Water Distribution Systems
C401-98 (R98)-The Selection of Asbestos-Cement Pressure Pipe, 4 in. through 16 in.
(100 mm through 400 mm), for Water Distribution Systems
C402-00-Asbestos-Cement TransmissionPipe, 18in. through 42 in. (450 mm through
1,050 mm), for Water Supply Service
C403-98-The Selection of Asbestos-Cement Transmission Pipe, Sizes 18 in. through
42 in. (450 mm through 1,050 mm), for Water Supply Service
D110-95-Wire- and Strand-Wound, Circular, Prestressed Concrete Water Tanks
(Includes Addendum D110a-96)
D115-95-Circular Prestressed Concrete Water Tanks with Circumferential Tendons
F585-94(2000)-Standard Practice for Insertion of Flexible Polyethylene Pipe into
Existing Sewers
11.7.3.1.4 Plastic Pipe
C900-97-Polyvinyl Chloride (PVC) Pressure Pipe, and Fabricated Fittings, 4 in.

through 12 in. (100 mm through 300 mm), for Water Distribution
C901-96-Polyethylene (PE) Pressure Pipe and Tubing, 1/2 in. (13 mm) through 3 in.
(76 mm), for Water Service
C905-97-Polyvinyl Chloride (PVC) Pressure Pipe and Fabricated Fittings, 14 in.
through 48 in. (350 mm through 1,200 mm), for Water Transmission and Distri-
bution
C906-99-Polyethylene (PE) Pressure Pipe and Fittings, 4 in. (100mm) through 63 in.
(1,575 mm), for Water Distribution
C907-91-Polyvinyl Chloride (PVC) Pressure Fittings for W a t e r 4 in. through 8 in.
(100 mm through 200 mm)
D120-84 (R89)-Thermosetting Fiberglass-Reinforced Plastic Tanks
D130-96-Flexible-Membrane-Lining and Floating-CoverMaterials for Potable Water
Storage Plant Equipment
F101-96-Contact-Molded, Fiberglass-Reinforced Plastic Wash Water Troughs and

Launders (Includes Addendum F101a-97)
F102-96-Matched-Die-Molded, Fiberglass-Reinforced Plastic Weir Plates, Scum
Baffles, and Mounting Brackets (Includes Addendum F102a-97)
11.7.3.2 ASTM
A7498-Standard Specification for Cast Iron Soil Pipe and Fittings

A746-99-Standard Specification for Ductile Iron Gravity Sewer Pipe
B88M-99-Standard Specification for Seamless Copper Water Tube
B306-99-Standard Specificationfor Copper Drainage Tube (DWV)
B698-97-Standard Classification for Seamless Copper and Copper Alloy Plumbing
Pipe and Tube
C14M-99-Standard Specificationfor Concrete Sewer, Storm Drain, and Culvert Pipe
C76M-00-Standard Specificationfor Reinforced Concrete Culvert, Storm Drain, and
Sewer Pipe
C118M-99-Standard Specificationfor Concrete Pipe for Irrigation or Drainage
C506M-00-Standard Specification for Reinforced Concrete Arch Culvert, Storm
Drain, and Sewer Pipe
C507M-00-Standard Specification for Reinforced Concrete Elliptical Culvert, Storm
Drain, and Sewer Pipe
C913-98-Standard Specification for Precast Concrete Water and Wastewater Struc-
tures
C985M-00-Standard Specification for Nonreinforced Concrete-Specified Strength
Culvert, Storm Drain, and Sewer Pipe
C1417M-00-Standard Specification for Manufacture of Reinforced Concrete Sewer,
Storm Drain, and Culvert Pipe for Direct Design
C1433M-00a-Standard Specification for Precast Reinforced Concrete Box Sections
for Culverts, Storm Drains, and Sewers
C1479-00el-Standard Practice for Installation of Precast Concrete Sewer, Storm
Drain, and Culvert Pipe Using Standard Installations
D2661-00-Standard Specification for Acrylonitrile-Butadiene-Styrene(ABS) Sched-
ule 40 Plastic Drain, Waste, and Vent Pipe and Fittings
D2665-00-Standard Specification for Poly(Viny1 Chloride) (PVC) Plastic Drain,
Waste, and Vent Pipe and Fittings
D2680-95a-Standard Specification for Acrylonitrile-Butadiene-Styrene (ABS) and
Poly(Viny1Chloride) (PVC) Composite Sewer Piping
D2729-96a-Standard Specification for Poly(Viny1 Chloride) (PVC) Sewer Pipe and
Fittings
D2751-96a-Standard Specificationfor Acrylonitrile-Butadiene-Styrene(ABS)Sewer
Pipe and Fittings
D2846/D2846M-99-Standard Specification for Chlorinated Poly(Viny1 Chloride)
(CPVC) Plastic Hot- and Cold-Water Distribution Systems
478 Aooliratinns
D2852-95-Standard Specification for Styrene-Rubber (SR) Plastic Drain Pipe and

Fittings
D2949-00-Standard Specificationfor 3.25-in. Outside Diameter Poly(Viny1Chloride)
(PVC) Plastic Drain, Waste, and Vent Pipe and Fittings
D3034-00-Standard Specification for Type PSM Poly(Viny1Chloride) (PVC) Sewer
Pipe and Fittings
D3262-96-Standard Specification for "Fiberglass" (Glass-Fiber-ReinforcedThermo-
setting-Resin)Sewer Pipe
D3309-96a-Standard Specificationfor Polybutylene (PB)Plastic Hot- and Cold-Water
Distribution Systems
D3754-96-Standard Specification for "Fiberglass" (Glass-Fiber-ReinforcedThermo-
setting-Resin)Sewer and Industrial Pressure Pipe
F645-95-Standard Guide for Selection, Design, and Installation of Thermoplastic
Water Pressure Piping Systems
F679-01-Standard Specification for Poly(Viny1 Chloride) (PVC) Large-Diameter
Plastic Gravity Sewer Pipe and Fittings
F789-95a-Standard Specification for Type PS-46 and Type PS-115 Poly(Viny1
Chloride) (PVC)Plastic Gravity Flow Sewer Pipe and Fittings
F794-99-Standard Specificationfor Poly(Viny1Chloride)(PVC)Profile Gravity Sewer
Pipe and Fittings Based on Controlled Inside Diameter
F810-01-Standard Specification for Smoothwall Polyethylene (PE) Pipe for Use in
Drainage and Waste Disposal Absorption Fields
F877-01Standard Specification for Cross-Linked Polyethylene (PEX) Plastic Hot-
and Cold-Water Distribution Systems
F892-95-Standard Specification for Polyethylene (PE) Corrugated Pipe with a
Smooth Interior and Fittings
F894-98a-Standard Specification for Polyethylene (PE) Large Diameter Profile Wall
Sewer and Drain Pipe
F949-01-Standard Specification for Poly(Viny1 Chloride) (PVC) Corrugated Sewer
Pipe with a Smooth Interior and Fittings
F1499-00-Standard Specification for Coextruded Composite Drain, Waste, and Vent
Pipe (DWV)
F1866-98-Standard Specification for Poly (Vinyl Chloride ) (PVC) Plastic Schedule
40 Drainage and DWV Fabricated Fittings
F2019-00-Standard Practice for Rehabilitation of Existing Pipelines and Conduits by
the Pulled-in-Place Installation of Glass-Reinforced Plastic (GRP) Cured-in-Place
Thermosetting Resin Pipe (CIPP)
11.7.3.3 EN
EN 295-Vitrified Clay Pipes and Fittings and Pipe Joints for Drains and Sewers,
Issued in Several Parts
EN 12889-Twnchless Construction and Testing of Drains and Sewers
11.8 OIL AND GAS
Waters associated with oil production come from a variety of sources and have a wide
range of compositions and corrosive properties. Examples of such waters include the
following:
Formation waters. Present in the hydrocarbon-producing formation or related rock

layers. Usually contain significant amounts of dissolved solids.
Injection waters. Supplied from surface sources and used to maintain formation pres-
sure. Can contain significant amounts of dissolved solids and often contain treatment
chemicals.
Produced waters from gas wells. These waters are usually produced by condensation
and do not normally contain quantities of dissolved solids.
The corrosion behavior of these waters is largely dependent on the amount of carbon
dioxide, sulfides, and chlorides present.
Much of the modern development of stainless steels and other alloys has been a
reaction to the special needs of the oil industry. These needs have included materials
suitable for use in the hostile environment of offshore production in various parts of the
world (Figure 11.11).These offshore rigs use seawater for cooling, secondary recovery,
and other services such as fire fighting, ballast, etc. The original offshore structures were
Figure 11.11 An oil rig in the JavaSea shows the construction of the painted steel
supportsand the production platform. (Photocourtesy of CAFUAD Consultants.)
480 Applications
in the comparatively shallow waters of the Gulf of Mexico and were constructed from
wood or steel and needed to be maintained or replaced regularly. When required, ex-
isting CP systems were used. As oil exploration has been extended into deeper water,
material selection had to be concerned with reducing weight of equipment and increas-
ing reliability in severe corrosive and operating environments. Coatings, CP systems,
and other ways of preventing corrosion had to be developed to cope with the harsh
environment of, for example, the North Sea or the Middle East.
11.8.1 Oil Rigs and Other Offshore Structures
In the North Sea in 1992there were more than 200 of the world's largest marine structures.
More than 90%of them were unpainted steel, each cathodicallyprotected with thousands
of tons of zinc or aluminum alloys bolted or welded at strategic locations. Virtually all
of the 5,000 km of underwater piping in the North Sea is protected by massive anodes
around the circumference, each weighing 300 to 400 kg and placed at approximately
150-m intervals.'O
The modem platforms in the North Sea are complex engineered structures usually
made from welded carbon steel tubes. The nodes between these tubular sections are
designed to withstand the fatigue loadings from wave, storm, and tidal effects. These
highly stressed joints need to be regularly inspected underwater and inspection has
generally been visual, coupled with techniques such as magnetic particle, ultrasonics,
and radiography. Inspection by divers is now being supplemented or replaced by the
use of remote operated vehicles (ROVs) using various inspection techniques.'* One
technique is the alternating current field measurement (ACFM) that is a non-contacting
electromagnetic method able to detect and size surface breaking defects in different
materials through coatings of varying thicknesses. This technique is now being used on
offshore structures in the North Sea, the Middle East, the Gulf of Mexico, and the west
coast of the United States and on many materials including ferritic, austenitic and duplex
stainless steels, aluminum, and nickel alloys. It is used topside of platforms as well as
subsea.200Magnetic particle inspection of a 24-in. (61-cm)-diameterweld can take up to
200 min, or up to 4.5 h if time for cleaning is included. ACFM inspection of the same
weld can be done in an hour. More than 30 operators worldwide are now using this
inspection technique.2Ol
Weight reduction for deep water oil and gas production can be achieved by us-
ing stronger or lighter materials. The use of higher strength structural steels (such as
thermo-mechanical controlled processed [TMCP] and microalloyed [MA] steels) is now
becoming more common. Steel tendons for tension-leg platforms can now routinely be
made with yield strengths in excess of 770 MPa, although concerns have been expressed
over accelerated fatigue crack growth rates and hydrogen embrittlement in these ma-
terials. Duplex stainless steels are also being used in seawater piping, for example, to
save weight. Lighter materials, such as titanium alloys and special grades of FRF, are
increasingly being used in seawater systems and injection applications.202
The need for weight reduction has led to the development of concrete with much
higher strength than previously. This has been largely driven by the need for large oil
platforms, known as Condeep platforms, in the North Sea. These platforms can contain
more than 100,000 m3 of concrete with a specified minimum strength of at least 80
mm-2
203
In the offshore oil industry microalloyed high strength steels are being used as a
low cost, lightweight structural material for legs on jack-up oil drilling rigs. Lack of
information about corrosion fatigue behavior of these materials limited the extent of
their offshore application. These data are now being generated by research projects at
Imperial College, London and elsewhere.’@
The selection of materials for these applications is covered by oil industry standards.
One of these is issued by the NORSOK organization and states that any components
permanently exposed to seawater and for which efficient CP cannot be ensured need
to be fabricated in materials immune to corrosion in seawater, unless corrosion can
be tolerated in specific components. Material selection should take into account prob-
ability for, and consequence of, component failure. This standard lists the following
materials as being immune to corrosion when submerged in ambient temperature sea-
water:
Alloy 625 and other nickel alloys with equal or higher PRE value
Titanium alloys (not to be used for submerged applications involving exposure to
seawater with CP unless suitable performance in this service is documented for the
relevant operating temperature range)
GRF
Other materials, provided adequately documented
Ambient seawater temperature is related to normal North Sea water temperatures.

Mo stainless steels (6%) and Cr duplex (25%) are borderline cases and should not be
used for creviced components, particularly threaded connections, without CP when
their material temperature exceeds ambient seawater tem~erature.2~~
11.8.1.1 Cathodic Protection
Most offshore platforms are now cathodically protected carbon steel. The design of the
systems used to control corrosion is described in various industry standards, such as
NACE RP0176, that provide details of the design and operation of CP on platforms and
recommend coatings.
Another industry standard is that produced by the Norwegian petroleum industry as
a part of the NORSOK initiative. This CP standard includes the following requirements
and recommendations:
Stand-off, flush-mounted, and bracelet sacrificial anodes can be used. The location
and distribution of the different types of anodes are part of the detailed corrosion
protection design that needs to be verified once installation is complete.
The CP system needs to be capable of polarizing all submerged steel to a poten-
tial between -800 and -1050 mV vs. Ag/AgCl seawater reference electrode, and
482 Aool ications
Table 11.4 Current Densities for CP Design206
Current Densities, d / m 2
Initial Mean Final
Southern North Sea (up to 57"N) 160 80 105
Northern North Sea (57-62"N) 180 90 120
Norwegian Sea (62-68"N) 200 100 130
Internally in flooded compartments 160 80 95
Pipelines if burial is specified 50 40 40
Sediments (mud) 25 20 20
to maintain the potential within this range throughout the design life of the struc-
ture. Impressed current cathodic protection systems can be considered for floating
production units.
Steel that is exposed to seabed mud (and rock-dumped pipelines)needs to be cathod-
ically protected with sacrificial anodes, preferably installed in the submerged zone.
Concrete-embedded steel that is in contact with steel exposed to seawater should be
polarized using sacrificial anodes mounted on permanent steel items or embedment
plates. These plates are exposed to seawater and are in electrical contact (that should
be verified) with the rebar system through welded connections.
The current densities to be used in CP design for steel (valid for bare steel surface
temperatures up to 25"C),stainlesssteel, aluminum, and other metallic materialsdepend
on location (Table 11.4).
These current densities need to be increased by 10%for the first 20 m below mean
water level and increased by 1mA/m2 for each 1°C above 25°C.
For embedded steel in concrete structuresthe initial, final, and mean current densities
are as follows:
Concrete, exposed to seawater on one side below -10 m requires 2 d / m 2 embedded

steel.
Concrete, exposed to seawater on both sides below -10 m requires 1mA/m2 embed-
ded steel.
For surfaces -10 to +5 m these values must be increased by 50%.
For light weight aggregate concrete or other concrete grades with equivalent pore
structure, values can be reduced by 30%.
When the actual embedded steel surfacearea (m2)to reinforced concrete volume (m3)
ratio, B, exceeds 6, an adjustment factor 6/B can be applied to the design current
densities.
This standard also includes requirements for the protection of pipelines, mud mats,
coated steel, etc. and for required properties of consumable anodes.207
Another NORSOK standard details required design and installation of monitoring

systems for external and internal corrosion on offshore structures and production sys-
tems in carbon steel material. The effectiveness of CP of submerged carbon steel struc-
tures is monitored by measuring the potential of the steel surface at strategic locations.
The reference electrodes used are either high purity zinc or Ag/AgCl. To supplement
these data current output from selected anodes and current density may also be mea-
sured. To monitor the internal corrosion of piping, e.g., in produced, injection, or cooling
water lines, a combination of two of the following methods should be used:
Weight loss measurements

Linear polarization resistance measurements (LPR)
Electrical resistance measurements (ER)
Galvanic measurements (injectionwater)
Additional monitoring methods which may also be included are bacterial probes,
water, and chemical analysis.20s
In shallow water, CP system designs are relatively simple, easy to maintain, and
come with substantial experience in many locations around the world. However, with
the advent of deep water operations, a greater emphasis has developed on design for
long-term service and reliability. Retrofitting anodes on depleted or poorly designed
CP systems in deep water is expensive. Likewise, with the weight constraints on new
deep water platforms, costly overdesign of sacrificial anode systems must be avoided.
In deep water structures, the range of ambient conditions is subject to greater variation
with water depth. Water temperature, oxygen content, pH, and resistivity may be very
different on the sea floor from that at the surface. The CP system usually has to be
designed for shallow, medium, and deep portions separately. The CP criteria in NACE
RP0176 that are widely used in shallow waters still apply for deep water applications.
The difference comes in the greater current requirements to achieve these criteria in
deep water as a result of the decrease in protection obtained from calcareous deposition
and changes in seawater resistivity at low temperature. Questions remain about the
effects of various A1 anode systems with different Zn contents on initial polarization and
maintenance currents and on anode output performance in low temperature sea bottom
conditions.202
The performance of the CP system on the Cognac Platform in the Gulf of Mexico was
monitored regularly since it was commissioned in 1977. After some 5 years in operation
it was found that in deep water areas, >76 m down to 320 m, there was some evidence of
underprotection. It was decided to upgrade the system and install additional aluminum
anodes. Using conventional anode installation would have been prohibitive in terms of
time and cost so an anode-carrying member (ACM)was designed. The ACM is a 46-cm
OD pipe to which the individual anodes were mounted, and then the ACMs were in-
stalled in the correct location through guides along the side of the platform. In this way
an additional 3,100 A of protection current distributed in 10 zones was installed. The
system is monitored regularly and continues to perform satisfactorily some 20 years
after initial installation and more than 15 years after the upgrade of this platform?@)
484 Annlirations
As oil was extracted from deeper waters it became clear that any reduction in weight
of the rigs had a major influence on costs. Rapid polarization has been used to reduce
the total weight of the structures and to reduce the weight and rate of consumption of
the consumable anodes. Rapid polarization reduces the maintenance current for CP by
producing a denser, more protective calcareous scale. In the Rijn Field in the North Sea
high capacity magnesium anodes were used to achieve rapid polarization (500 mA/m2)
during the first month and aluminum anodes supplied the maintenance current. This
dual anode systemhas proved to be successfuland anticipated problems of depassivation
during storms have not materialized.210
On the Norwegian Continental Shelf exploration has started in the area of the shelf
between 63 and 67” N at water depths down to 1,500 m. A field testing program has been
performed at depths from 100m down to 1,300m, which covered exposures at the blocks
Helland Hansen, More West, h e n Lange, Vema/Nyk, and Gjallar. Testing has been
done to establish the CP current demand for carbon steel, thermally sprayed aluminum,
stainless steel (6 Mo), and titanium (grade 5). The initial current demand in the zone
from 100 to 200 m was found to be especially high (>0.22 A/m2). While at depths from
600 to 1,300 m an initial design current density of 0.22 A/m2 resulted in a polarization
to the protective potential on carbon steel within a 2-month period.211
A common approach to corrosion prevention of deep water platforms has been the
combined use of coatingswith CP. A number of platforms in the Gulf of Mexicohave been
protected in this way with good results. The coating used was an epoxy polyamide and
the CP was applied using aluminum alloy anodes, with magnesium anodes for the mud
mats. This combined approach has proved to be successful and cost-effective for this
type of deep water platform.212
In some cases straight members of a platform have been coated while leaving some
20% uncoated. This reduces the CP current demand while avoiding the difficulties of
coating in the field. The system used was 100% coating with solventless epoxy in the at-
mospheric and splash zones, 80% coating with solventlessepoxy combined with bracelet
aluminum sacrificial anodes in the submerged zone (-2.8 to -39.8 m), and an 80% sol-
ventless epoxy coating combined with stand-off aluminum anodes for the submerged
zone (-39.8 to -109 m).213
11.8.1.2 Cladding
Copper-nickel cladding has proved to be successful in the splash zone of offshore oil
platforms. Corrosion of steel in the splash zone can vary from 0.5 to 1.5 mm/y. In the
case of hot riser pipes that carry hot fluids from subsea to the platform, temperatures
can reach 90°C and corrosion rate of steel can reach 8 mm/y. Splash zone sheathing
is normally 3 to 5 mm thick and extends from below mean tide level up to well into
the atmospheric zone. Attachment is usually by welding directly to the steel. Galvanic
corrosion of adjacent steel is avoided by painting the top atmospheric junction while
the lower submerged junction is protected by the CP applied to the steeL214Alloy 400
sheathing has also been used for many years on offshore oil and gas platforms to provide
protection in splash and spray zones on the carbon steel legs.”
11.8.1.3 Coatings and Linings
The NORSOK standard for materials selection gives guidance on coatings to be used for
offshore applications. Carbon steel in the splash zone must have corrosion allowances
added to the design thickness of the following:
Structures with thin film coating: min. 5 mm. For design lives >17.5 years: corrosion
allowance = (design life -5 years) x 0.4 mm/y.
Risers: min. 2 mm in combination with min. 12 mm vulcanized chloroprene rubber.
At elevated temperature the corrosion allowance needs to be increased by 1 mm for
every 10°C that the operating temperature exceeds 20°C.
The coating systems selection and requirements are covered by NORSOK Standard
M-501 for structures and topside equipment; however, the following areas/conditions
need special evaluation:
Coatings for areas in the splash zone

Use of thermally sprayed aluminum coating for elimination of maintenance coating
Coatings for passive fire protection
Coatings for bolts and nuts, flanges, machined surfaces of valves, etc.; wax coating
can be considered for these applications
Coating and/or insulation when connecting aluminum, stainless steel, carbon steel,
and other materials where galvanic corrosion may occur
The extent and type of coating applied can be determined by the following factors:
Cost savings by reduced anode weight

Coating needed to obtain rapid polarization, including use of shop primers only
Required coating quality to obtain low coating breakdown
Accessibility for coating application
Cost saving by not coating weld areaszo5
Four projects used a field-applied, all polymer encapsulation (jacketing) process for
splash zone corrosion protection and repairs to offshore structures. This technique is suc-
cessful because certain polymer grouts can bond to prepared surfaces underwater. FRP
outer jackets form all polymer corrosion barriers with steel forming the structural con-
nections. Composite barriers installed in the splash zone offshore were still performing
well after 5 years in service. It appears that corrosion of a steel member can be arrested
when a composite barrier remains tightly bonded to the member.215
Coating maintenance of existing aging offshore structures is a major ongoing chal-
lenge. For areas that are exclusively above the water surface, corrosion prevention has
been achieved by many generic renewable paints and coating systems. For steel sur-
faces that are totally below the water line, cathodic protection (both with and without
organic coatings) has been effective. Areas near the water’s surface, in the splash and
Next Page
486 ADDlications
tidal zone, pose the most difficulties. Field repairs to any structure at the splash zone
can be very difficult and dangerous to maintenance personnel, especially in rough seas.
While splash zone protection of the structure is of importance, of greater concern are the
riser pipes which serve as transporters of crude oil, natural gas, waterflood, or utilities
such as gas used for gas lifts. Corrosion-induced rupture and other accidents involving
these risers have led to substantial environmentaland economic losses, personnel injury,
and loss of life. Various methods are used for corrosion protection in the splash zone,
including metal sheeting, cladding and flame spraying (Ni/Cu, Cu/Ni, stainless steel,
titanium), polymeric bamers, concrete, and waxes and organic coating.216
In the splash zone of platforms the surfaces are wet/dry so CP is not really applica-
ble here. A combination of corrosion allowance and coating is the usual approach. The
NORSOK Standard M-001 gives a corrosion rate of 0.4 mm/y in this region and rec-
ommends a corrosion allowance of 5 mm. This corrosion allowance can mean a thicker
section in the splash zone or the use of wear plates. This standard also recommends
a thick coating, such as rubber, glass flake/fiber-reinforced paint system, or thermal-
sprayed aluminum in this area. With a thick, durable coating the corrosion allowance
can be reduced to 2 mm. Concrete structures use thicker rebar cover in the splash zone.
If stainless steel is used for risers corrosion allowance is not appropriate and measures
must be taken to resist localized corrosion?17
Many of the coating systems used on offshore structuresare based on inorganic zinc,
which gives good adhesion and some degree of cathodic protection to the underlying
steel. It can be used as a single coat but is more usually overcoated with other layers. In
the subsea zone the inorganic zinc may be covered with one coat of epoxy polyamide
primer and two coats of coal tar epoxy to give a total thickness of 500 to 600 pm (20 to
25 mil).In the aggressivetidal zone speciallyformulated heavy epoxy coatings reinforced
with siliceous aggregate have been used. This is spray applied at up to 250 mil or 1/4in.
(6 mm) thickness over a heavily blasted surface. The above water/atmospheric zone steel
is often coated with postcured inorganic zinc. A typical system is one coat of inorganic
zinc (eitherwater or solvent based), one coat of high-build epoxy, and one or more coats
of an aliphatic polyurethane. An alternative system that has also worked well is one coat
inorganic zinc, one coat of vinyl primer and one or more high-build intermediate coats,
and one or more vinyl top coats?18
Examples of the successful use of coatings in offshore applications include the
following:
The “ H e r r n o d ” 4 e of the world’s largest semisubmersible crane vessels was in-

spected in 2000 after recoating some 7 years previously. The coating system, an epoxy
top coated with a siloxane, was found to be in good condition and only minor repairs
of the epoxy were required and a new fullcoat of the siloxane was applied.
Shell USA-The floaters of this tension leg platform were constructed and coated
with multipurpose epoxy, high solids epoxy, and polyurethane top coat in 1998prior
to entering service in the Gulf of Mexico.
Shelf5-The refurbishment of this semisubmersible drilling rig in Baku, Azerbaijan
started in March 1997and was completed in 1998. More than 100,000m2 of columns,
Previous Page
bracings, and underside deck were coated with multipurposeepoxy and polyurethane
top coat; the sponsons were internally coated with two coats of multipurposeepoxy.31
Caissons are used on production platforms to raise natural gas under high pressure,
to take in seawater, and to carry fire water. It was decided to apply a 12-mm-thickrubber
line to the outside of caissons of one gas production platform. The linings are manually
applied, vulcanized in an autoclave, and high voltage spark-tested.Once lined, the seven
caissons, up to 13 m long, 1,200 mm diameter, and 25 mm wall thickness, will be welded
together before being lowered into the sea at the platf0rm.2~~
11.8.2 Seawater Handling Systems
Seawater has many applications in offshore production in heat exchangers for cooling,
desalination, firefighting systems, ballast water, injection for secondary production, etc.
(Figure 11.12). Seawater handling systems are, thus, a common feature of oil and gas
production and a number of different materials are commonly used for piping carrying
seawater. Their selection depends on many factors, including cost, corrosivity of the
seawater, weight, and availability.For general information on seawater systems see also
Chapter 10, Section 10.1.3, “Once through Seawater Cooling Systems.”
A survey of operating problems in the North Sea found the following:22o
Corrosion is the most common cause of materials failures on offshore structures with
severe corrosion failures of cement-lined carbon steel and Cu/Ni seawater piping be-
ingexperienced.Statoildoes not recommend cement-linedpipe or Cu/Ni for seawater
piping systems.
Most of the UNS S31254 piping was reported to be in good condition after 4 to 5
years of service on the Gulflaks A platform. Some failures were caused by the use of
incorrect weld materials and some by crevice corrosion.
Submerged parts of duplex stainless steel pumps need to be cathodically protected as
do all parts of the subsea production system. High strength materials can suffer from
hydrogen cracking.
Pumps made from NAB corrode in polluted seawater.
Corrosion has been reported in carbon steel tubing in injection systems from galvanic
attack at welds or high levels of dissolved oxygen.
On the Statfjord A platform failures occurred in field joints in cement-lined pipes.
These failures occurred at sections with turbulence or high velocity, sections with
cracks or defects, and in areas where metallic couples initiated galvanic corrosion.This
piping was replaced with grade 2 titanium and UNS S31254valves. The titanium parts
were polyurethane coated internally to reduce available cathode area for galvanic
corrosion.
Failures were reported in 90/10 and 70/30 Cu/Ni seawater piping by erosion, pres-
ence of pollution, low iron content in the alloy ( t 1 . 3 wt%), galvanic corrosion by
coupling with stainless steel valves, and carbon residues in the pipe.
4aa Applications
Figure 11.1 2 A close-up of the oil rig in the Java Sea shows the
topside treatment facilities that are part of modem, offshore oil pro-
duction and that add to the weight of platforms. (Photo courtesy of
The NORSOK Standard on Materials Selection for offshore applications contains

requirements for seawater handling. Hot dip galvanized carbon steel can be used in
seawater systems if it is documented to be cost-effective,and design includes replacement
if necessary. If this material is used in firewater systems there is a risk of plugging of
sprinkler/deluge nozzles that must be considered. Based on an evaluation in each case,
internal CP of stainless steel and other passive materials may be needed for piping
and components. Graphite gaskets must not be used in seawater piping systems. Piping
downstream of heat exchangers must take into account the possibility that relatively high
operating temperatures may occur when marine fouling is not present inside the heat
exchanger, i.e., initiallyand after cleaning operations.NORSOK-recommendedmaterials
for use in seawater and injection systems for topside facilities are given in Table 11.5 and
for subsea equipment in Table 11.6.
It is recommended to limit pressure rating of seawater systems to 10 bar in order to
be able to use qualified valves in GRP and carbon steel with polymeric lining. If carbon
steel valves with polymeric lining are considered for CRA-based piping systems, the
valve design needs to be critically assessed with respect to possible accelerated galvanic
corr0sion.2~~
The American Petroleum Institute (API)has analyzed the advantages and disadvan-
tages of different piping materials used for firewater systems. These systems usually
have to withstand long periods of stagnant, no-flow water but be available and fully
functioning on demand. In some ways the service is easier than a flowing line because
the supply of oxygen in a static line will become depleted, while in a flowing line it is
replenished. Corrosion can still continue in the absence of oxygen if, for example, bacte-
ria are present. The alternative dry or deluge system is less prone to corrosion problems
but has operating drawbacks. Firewater piping materials and their relative merits are as
follows:~
Carbon steel is the most common material used for this service offshore. It has good
fire resistance and can withstand mechanical abuse; carbon steel is available and
cheap and welding techniques are widely known. Disadvantages are that service life
is short, it corrodes, and the corrosion products can plug up spray jets making the
system unsafe. It needs to be tested and inspected regularly.
Lined carbon steel reduces corrosion, increases complexity,and cost and makes tie-ins
or modifications difficult.
Galvanized carbon steel is more durable than unlined carbon steel and has similar
drawbacks to lined carbon steel.
Stainless steel has similar advantages to carbon steel but the cost is higher. Its biggest
disadvantage is that the 300 series stainless steels are prone to pitting or crevice cor-
rosion and the highly alloyed stainless steels are more expensive.
Copper-nickel has long life (>20 years), light weight, low corrosion rates, low friction
losses, and minimal marine fouling. Disadvantages are high initial cost, low heat
tolerance (dry system), low mechanical strength, limited flow velocities, susceptible
to mechanical abuse, requires extra supports, and more difficult to install.
Fiberglass pipe is light, corrosion resistant, lower cost, and easy to install. Disad-
vantages are that it has low heat tolerance (dry systems), low mechanical strength,
susceptibleto UV.W stabilizerscan be incorporated into the surface and a high tem-
perature resin can be specified. To increase fire resistance the pipe can be insulated or
mechanically shielded.
490 Applications
Table 11.5 Materials for Topside Facilities for Seawater and Injection Systemsz1
Application Materials Note
Piping, vessels for produced 316,22Cr duplex, 25Cr duplex, 6M0, titanium, or GRP
water
Seawater svstems and raw seawater iniection 3
Wellhead e&ipment/Xmas Carbon steel with weld overlay
trees
Vessels Titanium, GRP, carbon steel with internal rubber lining, or organic
coating in combination with cathodic protection
Piping materials 6Mo,25Cr duplex, titanium, GRP
Piping components 6Mo,25Cr duplex, titanium, alloy 625, alloy C276, alloy C22 1,2
Valves in GRP systems GRP, carbon steel with polymeric lining, NiAl bronze
Normally drained systems Copper-base alloys, 6M0, titanium; carbon steel for short lifetimes, 3
e.g., 5-10 years
Pumps 25Cr duplex, 6M0, titanium 4’5
Deaerated seawater injection
Wellhead equipment/Xmas Low alloy steel with alloy 625 weld overlay in sealing surfaces; design .
trees must allow for corrosion on nonoverlaid parts; API 6A
Piping Carbon steel, GRP
Deaerated tower Carbon steel with internal organic coating, plus cathodic protection in
bottom section
Pump and valve internals Provided carbon steel housing: 13Cr4Ni,316,22Cr duplex, 25Cr 5
duplex
Produced water and aquifer Carbon steel, 316,22Cr duplex, 6M0, titanium, GRP; wellhead and
water injection Xmas trees as for deaerated seawater injection
Fresh and potable water Hot dip galvanized carbon steel, GRP, polypropylene, 316, 6
copper-base alloys
Drains and sewage
Open drain GRP, carbon steel
Closed drain without oxygen 316, carbon steel
Closed drain with oxygen 22Cr duplex, 25Cr duplex, 6M0, titanium, GRP
Sewage GRP, polyethylene
Notes:
1.Also to be used for process-wetted parts of instrument systems.
2. Some design limitations apply. Weld overlay can be applied to prevent crevice corrosion.
3. Copper alloys shall not be used in combination with CRAs and titanium. Exception can be components
in firewater systems, provided galvanic corrosion can be avoided by proper isolation. If electrical isolation
(15,000 ohm in dry system) is ensured and verified after installation, mechanical connections between
bronze/brass and alloys such as 6Mo austenitics and titanium alloys are acceptable.
4. Some design limitations apply.
5. Ceramic-filled epoxy coatings can be used for shorter lifetimes, eg., 5 to 10 years.
6.Large-diameter piping and tanks can be made in internally coated carbon steel. Tanks not intended for potable
water shall, in addition, be cathodically protected. GRP, polypropylene, and coating used for potable water
shall be accepted by the national health authorities.
Table 11.6 Material Selection for Subsea Seawater and Injection Systemsm
Application Materials Notes

Wellheads and Xmas trees
Wellhead equipment/Xmas trees 13Cr4Ni,low alloy steel with alloy 625 1
for production overlay; relevant API/ISO standards
Wellhead equipment/Xmas trees Low alloy steel with alloy 625 weld overlay 1
for deaerated seawater in sealing surfaces; design must allow for
corrosion on not-overlaid parts; relevant
API/ISO standards
Wellhead equipment/Xmas trees carbon steel with weld overlay according to
for aerated seawater Section 4.3 in this standard
Wellhead equipment/Xmas trees As for production
for produced water and aquifer
water
Subsea manifold piping
Piping for deaerated seawater 6Mo,25Cr duplex; carbon steel can be used
for shorter design life, i.e., less than 15
years
Piping for produced water and 22Cr duplex, 25Cr duplex, 6Mo; carbon steel
aquifer water can be used for shorter design life (i.e., less
than 6-8 years) and if low corrosivity
Piping for raw seawater Titanium
Subsea rigid flowlines 2
Deaerated seawater injection Carbon steel 3
Produced water and aquifer water Carbon steel, 22Cr and 25Cr duplex, 6Mo 4
injection
Raw seawater injection Titanium, 6Mo,25Cr duplex, internally
polyethylene-lined carbon steel
Notes:
1.Sealing surfaces of components Type 13Cr4Ni shall be overlay welded with alloy 625. For weld
overlay, ref. Section 4.3 in this NORSOK standard.
2. Flexible pipe should be considered as alternative to rigid pipe. Carbon steel clad with CRA can
be used as alternative to solid CRA.
3. Carbon steel and weld metal can be alloyed with approx. 0.5% chromium for oil production
and deaerated seawater injection flowlines to improve corrosion resistance.
4. Types 25Cr and 1 X r to be documented with respect to fea~ibility/weldability?~~
11.8.2.1 Carbon Steels
In the early offshore developmentsin shallowwater and mild climates galvanized carbon
steel and cast iron were commonly used. Corrosion rates in flowing seawater of up to
1mm/y were experienced so that replacement was frequently required and velocities
were kept low, usually 2 to 2.5 m/s. Carbon steel piping still finds some applications
492 ADDiications
offshorebut only in deaerated (to less than 10ppb oxygen) seawater that has been filtered
and biocide-treated. Velocity must also be kept low to avoid erosion if carbon steel is
used; at higher velocities alloy piping is needed.224
11.8.2.2 Stainless Steels
Stainless steel first began to be used in North Sea offshore oil production for Norwegian
platforms that were experiencing problems with cement-lined steel piping. The cement
linings were being damaged by alternate exposure to crude oil containing sulfides and
seawater. Standard 300 stainless steels could withstand the sulfides but would have been
subject to pitting and crevice attack, so 6% molybdenum austenitic stainless was spec-
ified. Small amounts of UNS S31254 have been used offshore since 1979 but the first
major use of this alloy began in 1986 at the Norwegian Gulflaks field where approxi-
mately 5,000 tomes of piping was installed. The higher design stress and the ability of
this alloy to handle higher velocities allowed a substantial weight savings over the alter-
native copper-nickel piping. No serious corrosion has been reported from the Gulflaks
A platform with UNS S31254 after 4 to 5 years of service. Seawater systems handling
cooling water, ballast, fire mains, etc. have been made from 6% Mo austenitic and 25% Cr
duplex. Duplex alloys, such as Zeron 100 (UNS S32760), are also being used in offshore
seawater piping, for example, in the U.K. Amerada Hess, Ivanhoe, and Rob Roy fields.224
The UNS S32760piping system at the Rob Roy/Ivanhoe field has been in operation since
1990 with no reported problems; castings in this alloy have been used for seawater lift
pumps and firewater pumps since 1986.These have also performed well with no reports
of any corrosion problems.225
Historically the offshore oil and gas industry has used 90/10 Cu/Ni piping with NAB
valves and NAB is being considered as a cheaper alternative for valves in superduplex
piping systems. NAB tubeplates have also been used in heat exchangers with titanium
or stainless steel tubes. Concerns over galvanic effects between NAB and stainless steels
prompted a test program to investigate couples between NAB and Zeron 100 (Z100-UNS
S32760).In natural seawater the NAB corroded rapidly in localized areas when coupled to
an equal area of ZlOO piping. When the NAB/Z100 area ratio was changed from 1:lto 1 : l O
the corrosion of the NAB became more widespread but not much deeper. In chlorinated
seawater NAB did not suffer any significant corrosion when coupled to an equal area of
Zeron 100, but at 1:lO coupled area the NAB pitted in crevices. Recommendations based
on this study and on service experience are that NAB should not be coupled to ZlOO in
natural seawater unless the area of NAB greatly exceeds that of the 2100, e.g., a stainless
steel pump shaft or valve stem in a NAB body. NAB can be coupled to ZlOO piping in
chlorinated seawater provided the crevice areas are protected, e.g., coated flanges, and
the temperature does not exceed 2 5 C Z 6
In the early 1990s1,000 tons of 1925hMopiping, forgings, bends, and fittingswere in-
stalled to handle seawater and hydrocarbon seawater mixtures in the Norwegian Snorre
Field of Saga Petroleum after an exhaustive test program.2271925hMois used in seawater
piping operating at flow rates up to 25 m/s and for handling seawater containing hydro-
gen sulfide.228UNS NO8367 is alsobeing used on North Sea oil platforms, for example, 430
tonnes were used on Statoil's Gulflaks platform and more than 545 tonnes on Conoco's
Heidrun platform.229
Seawater piping in 6% Mo austenitic and superduplex steels has generally been satis-
factory in seawater up to 30°C but threaded joints must be avoided?30At higher temper-
atures with chlorination and crevices present severe crevice corrosion has occurred and
the 6% Mo steel has been replaced with the higher molybdenum UNS S32654 in some
of these cases, at least for flanges and other crevice areas. This combination of materials
has handled chlorinated seawater at temperatures up to 50"C.231
Continuously chlorinated seawater from the North Sea at 45°C was used to test UNS
S31254piping with UNS S32654 flanges. The results obtained with this high temperature
seawater showed the following:
1. UNS S31254 flanges suffered severe crevice corrosion; UNS S32654 flanges were re-
sistant.
2. Longitudinally welded UNS S31254 and S32654 pipes were resistant.
3. Welds joining UNS S31254 or S32654 flanges with UNS S31254 or S32654 pipe were
resistant except on two occasions where weld defects initiated pitting.
4. UNS S32654 threaded couplings were resistant.
5. Socket welds must be avoided because of crevice corrosion.
6. Copper cracks are initiation sites. Use of copper tools for joint preparation should be
prohibited.
7. Weld metal >50% Ni <15% iron may suffer mild transpassive uniform corrosion.232
Provided that the pump is always drained and flushed when not in use 316L or
cast version CF3M is routinely used for seawater. CP using consumable iron anodes
improves the corrosion resistance of the stainless impeller. 233 Vertical turbine seawater
intake pumps typically use a Ni-Resist@casing with CF8M impeller and 316 shaft. This
combination of materials has been in use for many years and works well because the
casing effectively provides cathodic protection for the other components and the stainless
steels are unaffected by the high velocities in these pumps.73
316L is also used for injection pumps in secondary oil recovery. Deaerated seawater is
successfully pumped with 316L in desalination plants. For more demanding conditions
of temperature, pH. etc. the super stainless alloys are becoming more widely used. For
example, 59 eight-stage sour water injection pumps for the Middle East were supplied
in IN 862 (21Cr, 24Ni, 5Mo) to handle water with 150,000 ppm of chloride, 500 ppm
hydrogen sulfide at 77°C with a pH of 4.2. Similarly, the superduplex alloys are also
being used for these more severe seawater duties and their better mechanical properties
permit a bigger weight savingm
Firewater pumps at Statpipe riser platform were made from 2205 with the cofferdam
pipe and wear rings made from 904L. Inspection of the pumps after 4.5 years of service
showed that 2205 and 904L needed CP to be used in seawater. A similar 2205 pump was
494 Applications
installed in a UNS S31254 piping system at Veselfrikk B, but this pump is not normally
operating and is constantly filled with seawater. After less than 2 years severe pitting
was discovered in the pump housing and impeller. The pump material was changed
to UNS S31254.= In other cases it was necessary to apply sacrificial CP to submerged
parts of duplex seawater pumps to avoid localized corrosion.220Of all duplex stainless
steels produced, 30%are used in the offshoreindustry for platforms, floating production
facilities, process equipment, pipes, etc. Of the current annual tonnage of around 150,000
tonnes, 2205 duplex accounts for about 80% of the total with the higher alloy 2507 duplex
a further 12%.235
Superduplex stainless steel (XDSS) UNS S32760 was selected in 1990 for seawater
piping and valves for Northwestern Australia offshoredrilling platforms. It soon became
evident that reported leaks and other corrosion problems were occurringat unacceptably
high, but roughly constantrates. Localized corrosionin the low temperatureheat-affected
zone of welds was apparent and correlated to the excessive sigma intermetallic iron-
chrome carbide (5 to 20%) phase. This microstructure resulted in Cr depletion of alpha
ferrite and consequent selective chloride attack upon the ferrite. It requires considerable
care to weld or heat treat XDSS without producing carbide growth. There was also severe
galvanic corrosion between gaskets (graphite-loaded Ni/Cu) and XDSS and between
valves (NAB) and XDSS. Repairs have been tedious and costly because the corroded
weld segments were cut out, replaced, and clamped using FRP and ceramic-loaded
epoxy to reduce electrolytic current flow.%
11.8.2.3 Titanium
The resistance of titanium to seawater has been well known for many years but it has
often been considered too expensive for industrial use. As demand for titanium has in-
creased the availability and price have remained stable while the number of experienced
fabricators and suppliers has increased. Its low density makes it an attractive option as
weight savings become more important in the modem, larger, and more complex rigs.
In the early days of offshore exploration and production only a few hundred kilograms
of titanium were used in special applications for heat exchangers and in chlorination
systems. Its use has increased dramatically as offshore production has developed and
in 1996 total consumption of titanium and alloys in North Sea production was reported
to be several thousand tonnes. Typically some 50 to 100 tonnes of topside piping are
made from titanium. It is being used for low pressure ballast, fire, and service water
piping where stainless steel has sometimes failed from crevice corrosion. Titanium is
being suggested as a prime candidate material for the flexible risers from deep subsea
to floating production storage and off-loading platforms.
Insulating joints are installed to avoid galvanic corrosion when coupled to other
metals. However, titanium equipment is sometimes connected directly to alloys such as
the 6% molybdenum stainless steels that are nearly compatible galvanically. The other
potential problem is hydrogen absorption, to which titanium is particularly sensitive.
Hydrogen pickup can be caused or aggravated by the following:237
Coupling to a less corrosion-resistantmetal

CP systems operating at potentials >-0.8V SCE
Tensile load or residual stress if absorption is occurring
pH <3 or >12
Higher temperatures that cause increase corrosion at the anode and higher hydrogen
activity at the titanium cathode
Hydrogen sulfide which accelerates uptake in the presence of a cathodic potential
The first major application for titanium piping for ballast water was on the Statfjord
A platform in 1986. litanium was used to replace concrete-lined mild steel piping that
had failed in this duty. Titanium firewater systems are now installed on a number of oil
rigs in the North Sea, including Froy/TCP, Steipner West, Troll B, Brage, and Njord.238
11.8.2.4 FRP Piping
There is a range of FRP products for use in seawater. They include various polyesters
and epoxies, usually reinforced with glass fibers. For example, GRE (glass-reinforced
epoxy) piping has been used for seawater on offshore oil and gas operations since 1974.
This piping is routinely used to transport such waters as fire, potable, drain, sea, pro-
duced, ballast, and waterflood injection as well as for seawater cooling waters to heat
e~changers.2~~
The use of FRP pipe in offshore oil and gas applications is covered by a NORSOK
standard which contains amendments to a U.K. recommended practice document.240
Typical acceptable applications of FRP (called GRP for Glass Fiber Reinforced through-
out this standard) piping include service water, process water, cooling medium, potable
water, sewage/gray water (nonhazardouswaste), nonhazardous drains, nonhazardous
vents, chemicals, firewater ringmain, firewater dry deluge, firewater wet deluge, pro-
duced water, and ballast water. The use of GRP for piping systems on platforms is limited
as follows:
No use in hydrocarbon and methanol systems

Maximum internal design pressure 40 bar g
Design temperature range from -40 up to 95°C for epoxy and up to 80°C for vinyl
ester
The possible hazard of static electricity buildup to be accounted for
The use of GRP for tanks and vessels has the following limitations:
Design pressure in bar times internal volume in liters shall not exceed 75,000 and a
design temperature of maximum 75°C.
A96 Annlicatinns
The potential hazard of static electricity buildup shall be accounted for.

The use for systems containing hydrocarbons shall be based on risk assessment.
For systems where GRP can be applied, epoxy and vinyl ester resins are candidates
for piping components and tanks. Polyester resin can be used in tanks for seawater and
open drain ~ervices.2~~
For systems handling hypochlorite, GRP with vinyl ester resin and PVC lining or tita-
nium are appropriate. If GRP is considered for use as rigid pipe for downhole-produced
water and seawater injection tubing, material properties shall be documented in accor-
dance with relevant API standards and ASTM D 2992?05
As the U.S.oil industry has extended its exploration into deeper water, weight-
sensitive floating platforms have tended to replace stationary, bottom-founded struc-
tures. On the Shell MARS TLP, it is estimated that the use of composite pipe for the
firewater ring main and drain systems alone reduced the topside weight by 160,000 lb
(72,576 kg). With a design life of more than 20 years and an installed cost of approxi-
mately one third that of 90/10 copper-nickel pipe, the economic attractions of composite
piping are clear. Corrosion data on epoxy and isopolyester composite pipe in seawater
service applications date back to the 1950~."~
11.8.2.5 Copper Alloy Piping
Copper alloys, mainly Cu/Ni, has been used for aerated seawater piping for many
years. The experience has generally been good as long as critical velocities have not
been exceeded. The flow rates used in North Sea applications are usually based on
British Standard, BS MA-18, which limits 90/10 Cu/Ni piping above 100 mm diameter
to 3 m/s. In a 20-year period there were only nine recorded failures of 90/10 Cu/Ni
piping, mostly caused by excessive turbulence or exposure to polluted seawater during
service or commi~sioning.~~
One of these rare failures of Cu/Ni pipe occurred on a firewater system that had
been exposed to a seawater and sodium hypochlorite solution over an extended period.
Sodium hypochlorite was injected into an offshore firewater system to reduce internal
corrosion and inhibit marine growth. A flange leak released the protected seawater
solution onto the exterior surface on the firewater pipe, which weakened the pipe by
corrosion. An annual fire pump flow test ruptured the firewater pipe.243
11.8.3 Injection Systems for Secondary Recovery
The NACE Standard RP0475 provides detailed guidance on the selection of metallic
materials for all aspects of water handling for injection into formations. In particular,
this standard provides information to aid in the selection of pumps and valve for this
service.
For secondary oil recovery it is common to pump seawater back down into the well.
The raw seawater is treated at the intake with chlorine or hypochlorite and is pumped
up with lift pumps. The early pumps were made from austenitic cast iron with duplex
stainless shafts. Some of the cast iron impellers suffered corrosion but the shafts were not
attacked. The impellers as well as the shaft are now typically made from duplex stainless
The treated seawater is then filtered. At Statfjord A, 8, and C, 316 was used in the
back-flushing filter. On A the temperature is 16 to 18°C with 0.7 to 1.0 ppm hypochlorite,
and no corrosion has been seen. On B and C severe crevice corrosion was found on the
flange faces and corrosion in the drain. Operating temperatures in these two fields are
22 to 25°C. Sacrificial anodes were fitted and the flange faces were painted.245
The seawater is filtered and treated before injection to avoid souring the field.
It is also deaerated to prevent corrosion. Stainless steels are resistant to pitting and
crevice corrosion in deaerated seawater, even if hot. After treatment and deaeration
carbon steel pipe can be used but stainless steels are required where velocities are
high, e.g., in pumps, valves, and reducers. Because of the high pressures involved
duplex stainless steels are often used for larger components because their higher
strength can reduce weight. Seawater injection pumps have typically been made from
410, 316, and 318 stainless steels and these have generally been satisfactory. Gradu-
ally, however, there has been a trend toward using proprietary duplex alloys, such
as UNS S32550, S32760, and S39276, for injection duty to avoid corrosion and reduce
If sweet seawater (i.e., not containing hydrogen sulfide) is deaerated to less than
20 ppb oxygen, velocities are low, and SRB are controlled, it has been found that carbon
steel can be used for injection. If these conditions cannot be met then it is safer to use
more corrosion-resistant materials, such as those used in sour seawater.246
Desulfated seawater as the secondary recovery medium may retard reservoir souring.
Decreased sulfate concentration in seawater significantly restricted activity of SRB in a
high pressure bioreactor. The mass of produced hydrogen sulfide decreased as a direct
function of the mass of available sulfate.247
Injection water can be deaerated seawater, raw untreated seawater, or produced
water. NORSOK evaluation of corrosivity for deaerated injection seawater is, for the
conventional deaeration process, based on a maximum operating temperature of 30°C
+
and the following oxygen equivalent (oxygen equivalent = ppb oxygen 0.3 x ppb free
chlorine) levels:
50 ppb for 90% of operation time

200 ppb for 10% of operation time, noncontinuous
These criteria should be the basis for materials selection even if the specification for
the deaeration equipment gives stricter requirements. If the specified oxygen equivalent
is above 50 ppb or temperature is above 30°C for normal operation, material selection
needs to be subject to special evaluation.
For carbon steel submarine injection flowlines, the recommended minimum corro-
sion allowance is 3 mm. In injection water systems where alternating deaerated sea-
water, produced water, aquifer water, and/or gas could flow through the systems,
498 Aoolications
the material selection needs to allow for this. All components that may contact injec-
tion water or back-flowing fluids, must be resistant against well-treating chemicals
or well-stimulating chemicals. For carbon steel piping the maximum flow velocity is
6 m/s.205
The most common injection water for onshore oil and gas production is produced
water. This often contains high concentrations of ions and dissolved gases, e.g., chlo-
rides, bicarbonates, sulfates, carbon dioxide, and hydrogen sulfide. Many materials
have been used for injection piping handling produced water, with differing degrees
of success. Exxon has used FRP piping with threaded connections successfully and
has had more than 261,000 m in use for more than 15 years and 220,000 m in use for
6 years.
FRP is Exxon’s preferred material for all small bore injection piping with an expected
life of more than 20 years. Internally coated steel, 316, or 2205 stainless steels are used
for wellhead tie-ins, headers, meter runs, waterway crossings, or other high traffic areas.
Steel with an internal cement lining (denseASTM C 150Type I11pozzolana cement lining
specified to API RP 10E) has an expected life of 20 years, with some repair work likely
at joints. Steel with an internal HDPE lining is expected to last 25 years. Steel with shop-
applied coating, for example, modified baked phenolic, is used together with chemical
treatment and can be expected to last about 7years.Bare steel,even with inhibitor and/or
biocide-treated water, has a life expectancyof approximately5 years, typically 2 to 7 years
before repairs are needed?&
11.8.4 Standards and Specifications-Oil and Gas
11.8.4.1 NACE
RP0176-94-Corrosion Control of Steel-Fixed Off shore Platforms Associated with

Petroleum Production
RP0387-99-Metallurgical and Inspection Requirements for Cast Sacrificial Anodes
for Offshore Applications
RPO475-98-Selection of Metallic Materials To Be Used in All Phases of Water Han-
dling for Injection into Oil-Bearing Formations
RP0492-99-Metallurgical and Inspection Requirementsfor Offshore Pipeline Bracelet
Anodes
TM0173-99-Methods for Determining Quality of Subsurface Injection Water Using
Membrane Filters
TMO184-94-Accelerated Test Procedures for ScreeningAtmospheric Surface Coating
Systems for Offshore Platforms and Equipment
TMO299-99-Corrosion Control and Monitoring in Seawater Injection Systems
1D199-Internal Corrosion Monitoring of Subsea Production and Injection Systems
1G191-Metallic and Thermal Spray Coatings for Oilfield Production Equipment
1G194-Splash Zone Maintenance Systems for Marine Steel Structures
1G290-Plated and Galvanized Coatings for Oilfield Applications

3A1944Ixygen Scavengers in Steam Generating Systems and in Oil Production
7Ll924athodic Protection Design Considerations for Deep Water Structures
7Ll98-Design of Galvanic Anode Cathodic Protection Systems for Offshore
structures
11.8.4.2 NORSOK
NORSOK (the competitive standing of the Norwegian offshore sector) was the industry
initiative to add value, reduce cost and lead time, and remove unnecessary activities
in offshore field developments and operations. NORSOK standards are developed by
the Norwegian petroleum industry as a part of this initiative and are jointly issued
by OLF (The Norwegian Oil Industry Association) and TBL (Federation of Norwegian
Engineering Industries). They are administered by NTS (Norwegian Technology Stan-
dards Institution). These standards are intended to replace individual oil company
specifications for use in existing and future petroleum industry developments, sub-
ject to the individual company’s review and application. NORSOK standards make
extensive references to international standards. Where relevant, the contents of these
standards will be used to provide input to the international standardization process.
Upon incorporation into international standards, the relevant NORSOK standard will be
withdrawn.
The original NORSOK initiative ended in June 2000 and was replaced by the KON-
project. This project is intended to complete remaining NORSOK tasks within a
2-year period. Relevant NORSOK standards include the following:
J-003-Marine operations Rev. 2, Aug. 1997

L-001-Piping and valves (Internet version only) Rev. 3, Sept. 1999
M-001-Materials selection Rev. 2, Nov. 1997
M-101-Structural steel fabrication Rev. 3, Sept. 1997
M-102-Structural aluminum fabrication Rev. 1,Sept. 1997
M-120-Material data sheets for structural steel Rev. 2, Sept. 1997
M-121-Material data sheets for structural aluminum Rev. 1,Sept. 1997
M-501-Surface preparation and protective coating Rev. 3, Sept. 1997
M-503-Cathodic protection Rev. 2, Sept. 1997
M-CR-505-Corrosion monitoring design Rev. 1, Dec. 1994
M-506-COz corrosion rate calculation model Rev. 1,June 1998
M-601-Welding and inspection of piping Rev. 2, Nov. 1997
M-CR-621-GRP piping materials Rev. 1, Dec. 1994
M-630-Material data sheets for piping Rev. 2, Nov. 1997
M-65O-Qualification of manufacturers of special materials Rev. 2, July 1998
M-CR-701-Materials for well completion equipment Rev. 1, Dec. 1994
M-702-Ml string components Rev. 2, June 1999
500 Amlications
M-CR-703-Casing and tubing materials Rev. 1,Jan. 1996

M-CR-7104)ualification of nonmetallic sealing materials and manufacture Rev. 1,
Dec. 1994
P-001-Process design Rev. 4, Oct. 1999
P-100-Process systems Rev. 1,Aug. 1997
11.9 PETROLEUM REFINING
Oil was originally refined to produce kerosene as a better, cheaper source of light than
whale oil. Since then, the demand for more complex hydrocarbon products has meant
that the refining industry has evolved and now operates processes that can lead to corro-
sion and cracking of the equipment. While many of the processes are high temperature
and/or do not involve water, others generate or use large quantities of water that are
often contaminated.
The annual costs of corrosion in the U.S. refining industry were estimated to be $3.7
billion of which maintenance costs were $1.8 billion, vessel costs $1.4 billion, and fouling
costs $0.5 billion.2
Refining processes and operations can be separated into several areas as follows:
1. Fractionation (distillation)is the separation of crude oil in atmospheric and vacuum

distillation towers into groups of hydrocarbon compounds of differing boiling-point
ranges called "fractions" or "cuts."
2. Conversion processes change the size and/or structure of hydrocarbon molecules
including:
Decomposition (dividing) by thermal and catalytic cracking
Unification (combining)through alkylation and polymerization
Alteration (rearranging) with isomerization and catalytic reforming
3. Treatment processes prepare hydrocarbon streams for additional processing and pre-
pare finished products. Treatment includes the removal or separation of aromatics
and naphthenes as well as impurities and undesirable contaminants. Treatment may
be chemical or physical separation, such as dissolving, absorption, or precipitation.
Treatment may also be by a variety or combination of processes including desalt-
ing, drying, hydrodesulfurizing, solvent refining, sweetening, solvent extraction, and
solvent dewaxing.
4. Formulating and blending are the process of combining hydrocarbon fractions, addi-
tives, and other components to produce finished products with specific performance
properties.
5. Other operations include light-ends recovery, sour-water stripping, solid waste and
wastewater treatment, process-water treatment and cooling, storage and handling,
product movement, hydrogen production, acid and tail-gas treatment, and sulfur
recovery.249
11.9.1 Refinery Waste Water
Process, runoff, and sewerage water are treated prior to discharge or recycling. Waste
water typically contains hydrocarbons, dissolved materials, suspended solids, phe-
nols, ammonia, sulfides, and other compounds. Waste water includes condensed
steam, stripping water, spent caustic solutions, cooling tower and boiler blowdown,
wash water, alkaline and acid waste neutralization water, and other process-associated
water.
These waste waters are pretreated by separating hydrocarbons and solids from waste
water. API separators, interceptor plates, and settling ponds remove suspended hydro-
carbons, oily sludge, and solids by gravity separation, skimming, and filtration. Some
oil-in-water emulsions must be heated to assist in separating the oil and water. Grav-
ity separation depends on the specific gravity differences between water and immisci-
ble oil globules and allows free oil to be skimmed off the surface of the waste water.
Acidic waste water is neutralized using ammonia, lime, or soda ash. Alkaline waste
water is treated with sulfuric acid, hydrochloric acid, carbon dioxide-rich flue gas, or
sulfur.
After pretreatment, suspended solids are removed by sedimentation or air flotation.
Waste water with low levels of solids may be screened or filtered. Flocculation agents
are sometimes added to help separation. Secondary treatment processes biologically
degrade and oxidize soluble organic matter by the use of activated sludge, unaerated or
aerated lagoons, trickling filter methods, or anaerobic treatments. Materials with high
adsorption characteristics are used in fixed-bed filters or added to the waste water to
form a slurry which is removed by sedimentation or filtration. Additional treatment
methods are used to remove oils and chemicals from waste water. Stripping is used
on waste water containing sulfides and/or ammonia, and solvent extraction is used to
remove phenols.
Tertiary treatments remove specific pollutants to meet regulatory discharge require-
ments. These treatments include chlorination, ozonation, ion exchange, reverse osmo-
sis, activated carbon adsorption, etc. Compressed oxygen is diffused into wastewater
streams to oxidize certain chemicals or to satisfy regulatory oxygen-content require-
ments. Waste water that is to be recycled may require cooling and/or oxidation by
spraying. It may also require air stripping to remove any remaining phenols, nitrates,
and ammonia.250
The quantity and characteristics of waste waters depend on the process configura-
tion. As a general guide, approximately 3.5 to 5 m3 of waste water per ton of crude is
generated when cooling water is recycled. Refinery waste waters contain biochemical
oxygen demand (BOD) and chemical oxygen demand (COD) levels of approximately
150 to 250 and 300 to 600 mg/L, respectively. Phenol levels of 20 to 200 mg/L; oil levels
of 100 to 300 mg/L in desalter water and up to 5,000 mg/L in tank bottoms; benzene
levels of 1 to 100 mg/L; benzo(a)pyrene levels of less than 1 to 100 mg/L; heavy metal
levels of 0.1 to 100 mg/L for chrome and 0.2 to 10 mg/L for lead; and other pollutants
are also typically present.251
502 Aodications
Usually the desalter is the major source of contaminated process waste water and
typically also has the highest content of BTEX (benzene, toluene, ethyl benzene, and
xylenes). At some refineries the desalter effluent flow can be as high as 50% of the total
wastewater flow and over 70% of total BTEX discharge. Benzene is classed as a HAP
(hazardous air pollutant) as well as a VOC (volatile organic compound) and discharge
of these types of chemicals is restricted.
The main effluent treatment facility often includes an activated sludge unit where
biodegradation converts the final traces of aromatics and other HAPs in the waste water
to carbon dioxide and water. Open process drains are not permitted because HAPs could
evaporate before reaching the treatment facility. Because closed drainage systems are
expensive, it is common to place the treatment plant close to the source of contaminated
waste water. Flows of this type of contaminated water range from 100 gal/min (GPM)
(380 L/min) to more than 3,000 GPM (11,000 L/min) in a large refinery. Several methods
exist to limit the levels of HAPs and VOCs in wastewater discharge. These include the
following:
Desalter Emulsion Breaker: The desalter water wash produces an emulsion that holds
more benzene and other aromatics than water, and if the emulsion is discharged with
the wash water it increases the aromatics discharge. Emulsion is minimized by using
heat, electrical fields, and demulsifiers. Dependent upon feedstock chemistry it can
be advantageous to increase demulsifier usage or change demulsifiers to reduce the
amount of emulsion discharge. One trial found that changing demulsifier reduced
benzene discharge by 50%.
Activated Carbon: Direct treatment of the waste water with activated carbon reduces
aromatics content to below acceptablelimits. The carbon also captures oil, grease, and
other organics. Although effective, the operating costs are high.
Steam Stripping: Volatiles can be steam stripped from waste water down to less than
0.5 wt ppm aromatics in the discharge. Steam stripping has several concerns: fouling
of equipment with oil/grease; fouling of packing with salts, particularly those that
precipitate at stripper operating temperatures; and energy consumption.
Air Stripping:Stripping waste water with air is very effective and reduces total BTEX
to less than the required 0.5 wt ppm. Air stripping is best at around 100°F (38°C).
At lower temperatures the packing height must be increased. Typical stripping air
discharges contain 500 to 3,000 vol ppm aromatics and these need to be reduced
by passing through vapor phase carbon before discharge. Areas of concern for air
strippingare safety (upsetconditionscan lead to explosion risk) and fouling of packing
and carbon.=’
An improved benzene recovery unit has been developed that strips with nitrogen,
thus making the process inert and gaining the advantages of air stripping without the
problems. The cleaned gas is recycled to the stripper to save nitrogen costs. If HzS is
present the process can be modified by the addition of a caustic scrub section to remove
the sulfide from the organic-rich gas in the strippetE2
11.9.2 Sour Water Corrosion
Sour water may be characterized as water at pH 8 to 9.5 containing ammonia and H2S
with small amounts of chloride and no oxygen. When the crude oil being processed
contains large amounts of nitrogen compounds, 20 to 100 ppm of free cyanide can be
present. Sulfur remains as undissociated H2S when pH is lower than 5. In the range of
pH 5 to 9 H2S and HS- coexist, while at pH 9 to 10 the HS- species predominates and
constitutes almost the total fraction of sulfur. At higher pH, S2- is predominantly stable,
and when pH reaches 14 all the sulfur is in this form. In alkaline-sour environments
containing H2S, NH3, cyanide, and water at pH 8 to 9.5 the predominant cathodic reaction
will be HS- reduction promoting atomic hydrogen, while iron dissolution is the anodic
reaction. A protective iron sulfide f ilm is formed on the surface of the material, but
cyanide ions can remove this film by reacting with it to form an iron cyanide complex
and hydrogen ions, which can enter the metal. In this sour water environment corrosion
and hydrogen embrittlement can
Sour water corrosion occurs in hydroprocessing units and particularly in reactor
effluent air coolers (REAC) and stripper overheads. Organic sulfur and nitrogen com-
pounds are converted to hydrogen sulfide and ammonia in hydrotreater reactors. When
the effluent is cooled below 250°F (121"C), the gases combine to form ammonium bisul-
fide (ABS) salt. To prevent accumulation of the salt, water is injected before the reactor
effluent cools to the ammonium bisulfide deposition temperature. Downstream from
the point of injection, the equipment is then subjected to a sour alkaline solution with
high concentration of hydrogen sulfide, ammonium bisulfide, and contaminantssuch as
chloride, cyanide, and dissolved oxygen. Change in feedstock, upset conditions, and/or
wash water injection problems result in plugging of some exchanger tubes causing un-
derdeposit corrosion. The non-plugged tubes are then subjected to high effluent flow
and experience severe erosion-corrosion. Sour water corrosion is characterized by se-
vere corrosion of carbon steel at high velocity and turbulent areas, such as the inlet end
of tubes and in U-bends. To prevent erosion-corrosioncarbon steel tubes in one case were
replaced by 403 (UNS S43000)stainless steel. This alloy pitted under the ABS deposits
and was replaced by alloy 800 (UNS N08800).254
Sour water corrosion can occur in vapor recovery in catalytic cracking units and in
reactor effluent and light ends sections of hydrotreating and hydrocracking units. Most
of the equipment in these parts of the plant are normally made from carbon steel. Ex-
ceptions to this are the use of UNS S405500 and UNS S41000 as tower internals and
the use of admiralty metal (UNS C44300), alloy 400 (UNS N04400), or grade 2 titanium
(UNS R50400) as tubing in overhead condensers and compressor aftercoolers. Admi-
ralty metal tubes may fail in less than 5 years in overhead condensers by ammonia stress
cracking. Sour water corrosion of carbon steels is often associated with hydrogen blister-
ing. This has been a particular problem in coolers, separator drums, absorber/stripper
towers, and, occasionally, in overhead condensers. In some cases austenitic stainless
steels are severely attacked and only titanium grade 2 (UNS R50400) has sufficient
resi~tance.~~
504 Applications
A survey of published information on sour water corrosion concluded the fol-

lowing:
1. Ammonium bisulfide (alkaline sour water) corrosion is a significant problem in hy-

droprocessing unit REAC systems and other refinery systems. It has a particularly
high risk related to failure, including lost production time and safety/environmental
problems associated with refinery incidents.
2. Most of the available information is qualitative and experimental and does not ade-
quately define limits of operation for typical materials of construction.
3. Sour water corrosion involves a velocity-sensitive mechanism that needs to be quan-
tified in terms of both mechanical and chemical factors.
4. Operational limits for various alloys can be developed based on laboratory flow loop
tests conducted under closely controlled environmental simulation and hydrody-
namic conditions.%
A survey was conducted by the NACE T-8 committee covering corrosion in the
FEACs and associated piping in 42 hydrocrackers and hydro treater^.^^ This survey
showed that sour water corrosion was mild to negligible when the concentration of
ammonium bisulfide was 2% or less and velocity was 20 ft/s (6.1 m/s) or less. This
rule of thumb has been used for operating this type of unit and has generally controlled
sour water corrosion. Although an actual corrosion threshold was not identified by the
survey results, it was noted that corrosion rates for steel may be severe, above 3 to 4%
ammonium bisulfide concentration in the sour water. The survey also showed that the
K, factor (mol% NH3 times the mol% H2S in the reactor effluent) could be useful in
assessing the potential system corrosivity, with K, values above 0.7 being particularly
aggressive.
The effect of ammonium bisulfideconcentrationwas assessed in laboratory studies.258
These tests were conducted in a stirred autoclave at low velocity (around 1 to 2 ft/s
(0.3 to 0.6 m/s). Carbon steel and 316 stainless steels had low corrosion rates up to
about 35% ammonium bisulfide, with high rates of attack above that concentration.
The reason for this transition was suggested to be the formation of a metal ammonium
complex that could remove the protective sulfide film from the surface. Velocity has
long been considered to be a major factor in this type of corrosion. This aspect was
investigated in laboratory studies of carbon The corrosion rate increased by 40
to 64%, respectively, when the velocity was increased from 3.5 to 6.5 m/s. These tests
showed that the most corrosive conditions were those where the ammonium bisulfide
levels and velocity were both high.
The factors important in sour water corrosion in hydroprocessing units (particularly
REAC systems) have been summarized as follows:
Corrosion results from the presence of ammonium bisulfide and corrosion rate gen-
erally increases with its concentration.
The K, factor may be used to monitor the potential corrosive severity of process
environments and potentially in materials selection.
Sour water corrosion involves flow velocity as a primary parameter, with excessive
corrosion generally experienced at flow rates greater than 6 m/s. Stainless steels may
provide acceptable corrosion resistance up to 9 m/s, based on service experience.
Maintaining water injection rate to result in at least 25% unvaporized (liquid)water
in the effluent stream also appears important.
The injected water must be free of dissolved oxygen (<50 ppb) to prevent rapid
corrosion.
Good flow distribution (in terms of vapor, liquid hydrocarbon, and water phase) is
important. Tube velocities of less than 3 m/s in the air cooler can result in problems
due to separation (stratification)of phases and the formation of corrosion deposits on
tubes.
Deposition of solid ammonium bisulfide salt may occur as a result of flow maldis-
tribution, which starves some tubes of wash water and exacerbates both fouling and
corrosion problems.
U-bend tube designs may cause problems in the REAC system due to the possibility
of velocity-acceleratedcorrosion in tubing bends.260
A survey of hydroprocessingunits found that many hydrocrackingand high severity

hydrotreating units have experienced severe local corrosion attack of the REAC and
associated piping. In all cases, the common factors were the processing of high sulfur and
high nitrogen feedstocks. This study supported the view that a limit of 2% ammonium
bisulfide is necessary to control sour water corrosion and found a threshold K, of 0.2
for the onset of this type of attack. Flow conditions in the header (e.g., balanced and
nonbalanced) were shown to be an important factor affecting the severity of corrosion.
For example, a limiting value of 2% ammonium bisulfide was shown for the onset of
corrosive conditions in REAC systems; for systems with balanced inlet conditions, this
concentration increased to 8%. Additionally, a velocity limit for balanced systems was
6.7 m/s, while for unbalanced systems the velocity limit could be as low as 3 m/s. The
limiting operating conditionsof 6 m/s and 8%ammoniumbisulfidewere only applicable
for REAC systems that had a completely balanced header.261
Some examples of problems caused by sour water corrosion that have been solved
by using modem duplex stainless steels include the following:
Hydrotreating. REAC and piping-2205 (UNS S31803) and 2304 (UNS S32304) per-
formed well where carbon steel failed by ammonium bisulfide attack.
Hydrodesulfurization. Feed/effluent exchanger 18%duplex replaced 321 that failed
from chloride SCC.
Sulfurous sour water stripper feed/bottoms exchanger in duplex materials (UNS
S32205/S31803) and associated condenser (UNS S32750) have worked well in the
presence of C1-, H2S, and ammonia at temperatures up to 115°C.262
Duplex stainlesssteels also have been used successfullyin a wastewater feed/effluent

exchanger where AISI 430 (UNS S43000) had failed by pitting after 6 months of service
and 316L had failed by SCC in less than 6 months.263
506 Applications
Aluminum sour water stripper piping, including the tower overhead, piping to the
distillatedrum and the reflux piping were all lined with UNS N10276 to eliminateerosion
problems. Later, solid UNS N10276 elbows were fitted. This alloy piping has also been
used to replace corroding carbon steel piping in similar duties in other refineries.’@
Titanium is being used under the most aggressive conditions in sour water stripper
overheads where the column-condensed water can contain as much as 30 to 40 wt%
ammonium bisulfide, together with chlorides, cyanides, and other corrosive species. A
sour water stripper air cooler condenser was tubed with grade 2 titanium in 1995 and has
been in continuousoperation since then. The condensate leaving this condenser contains
about 15%ammonium bisulfide, 30 to 35 ppm chlorides, and 30 to 50 ppm cyanides?65
Another corrosion problem that can occur in hydrotreater reactor effluent coolers is
the formation of ammonium chloride. If this deposits on the tubes it can cause severe un-
derdeposit corrosion. Mitigation methods include minimizing the sources of chlorides,
using better materials, and/or optimizing critical design details. When high chloride
levels are present it is essential to ensure good contact between the water wash and the
inlet stream vapor phase.266
The cost of sour water corrosion in some U.S.refineries has been estimated to be
$50 million per incident in terms of lost production and damages?67
11.9.3 Wet H2SCracking
Somerefinery equipmentcan be subjected to various formsof stress crackingor hydrogen

damage that are specificto this and related industries. See Chapter 4, Section 4.3.1.Stress
Corrosion Cracking and 4.3.2, “Hydrogen Effects,” for mechanisms.
Crack mechanisms that can operate in wet HzS environmentsinclude the following:
Sulfide stress cracking (SSC)

Hydrogen blistering
Hydrogen-induced cracking (HIC)
Stress-orientedhydrogen-induced cracking (SOHIC)
Alkaline stress corrosion cracking (ASCC)
Severalof these crack mechanisms (SSC,hydrogenblistering, HIC, SOHIC)are related

to hydrogen permeation and absorption by steel. The principal variables affecting these
hydrogen effects are pH and composition of the environment. Hydrogen permeation
flux in steel is minimal at pH 7 and increases at lower or higher pH. At low pH corrosion
is caused by H2S, while at high pH the primary cause is ammonium bisulfide. Hydrogen
permeation increases with H2S partial pressure and with the presence of cyanide at
alkaline pH. The likelihood of ASCC occurring increases with temperature and is most
likely in the pH range 8 to 11. ASCC is promoted by carbonates in the presence of weak
sulfiding agents such as thiosulfate and thiocyanate.
SSC is not generally a problem in refinery equipment because high strength steels
have not normally been used to construct it. Most of these types of crackingoccur in steels
with a tensile strength >620 MPa. The incidence of cracking can be reduced by reducing
11.1 0 Chemical Process Plants 507
the levels of inclusions and sulfur in the steel and heat treatments, such as normalizing
or quench and tempering. SOHIC is encouraged by the presence of notches and tensile
stress and its likelihood can be reduced but not prevented by postweld heat treatment
(PWHT). ASCC is also strongly affected by tensile stress levels and susceptibility can be
reduced by PWHT or heat treatment after cold forming. The incidence of this type of
cracking was assessed by a NACE survey of nearly 5,000 pressure vessels, of which some
26% were found to contain cracks. Of 132 sour water strippers, 28% were found to be
cracked. Of all the cracking detected, the highest incidence occurred in the temperature
range 65 to 93°C. Carbonate cracking (a form of ASCC) was common in alkaline sour
waters and cracking was also prevalent in caustic and amine service.’&
Cracking in wet H2S service is often detected by the wet fluorescentmagnetic particle
test (WFMT) that has found cracks not detected by other inspection techniques. This
technique is sometimes used in conjunctionwith ultrasonic testing to detect surface and
subsurface cracks.269
Cracking in carbon steel refinery vessels is often associated with welds. Control of
cracking is by control of tensile strength of the steel, hardness of the weld metal, and
cleanliness of the steel in terms of inclusion and sulfur content. The hardness of welds
should be ~ 2 0 HB0 (Brinellhardness)F70While the bulk hardness of welds as determined
by Brinell or other test equipment may by acceptable,crackinghas been shown to initiate
from small hard zones associated with welds.271
11.9.4 Standards and Specifications-Petroleum Refining
11.9.4.1 NACE
RPO170-97-Protection of Austenitic StainlessSteels and Other AusteniticAlloys from

Polythionic Acid Stress Corrosion Cracking during Shutdown of Refinery Equip-
ment
RP0296-964uidelines for Detection, Repair, and Mitigation of Cracking of Existing
Petroleum Refinery Pressure Vessels in Wet H2S Environments
RP0472-95-Methods and Controls to Prevent In-Service Environmental Cracking of
Carbon Steel Weldments in Corrosive Petroleum Refining Environments
8x194-Materials Fabrication Practices for New Pressure Vessels To Be Used in West
H2S Refinery Environments
TM0177-96-Laboratory Testing of Metals for Resistance to Sulfide Stress Cracking
and Stress Corrosion Cracking in H2S Environments
11.10 CHEMICAL PROCESS PLANTS
Chemical process plants exist around the world and most of them use large quantities
of water for cooling, raising steam, and in production processes. A survey in the United
Statesin 1972found that there were 1,345plants that took in a total of 2,927 billion gallons
(11,079 BL) of fresh water, of which 929 billion gallons (3,520 BL) were used for process
508 Applications
cooling, 348 billion gallons (1,320 BL) for condenser cooling, 227 billion gallons (859 BL)
for process use, and 44 billion gallons (167 BL) for boiler feed.2n
Waters used for cooling equipment in chemical, petrochemical, and other industrial
applications may be classified according to their use as follows:273
Category I waters
Distilled, should contain no mineral salts or chlorides
Demineralized, should also contain little or no mineral salts
Potable, has minerals and chloride contents prescribed, e.g., WHO says 350 ppm
chlorides max.; U.S. Standards, 250 ppm chlorides max.
Raw, untreated water except perhaps for chlorination, usually with mineral con-
tent higher than potable
Seawater, contains high levels of chloride plus calcium and magnesium sulfates
Category I1 waters
Softened, in which all the total hardness salts have been removed to prevent
scaling; softened and naturally soft waters are very corrosive unless completely
deaerated
Boiler feed, may be partially softened or demineralized or be largely returned
steam condensate
Condensate, is condensed steam but differs from distilled water in that it may
contain dissolved gases, entrained minerals, and salts
Desalinated, produced from saline water, not necessarily high quality or potable
Utility, describes a water that is more salty than potable but is sanitized for use
in eye baths, safety showers, etc.
Category I11 waters
Process, any kind of water used in chemical or other process plants, may contain
contaminants or return process chemicals
Chilled or tempered, held at specific temperature for reaction control
Produced, the water associated with oil or gas production
Fire, used for firefighting, can vary from potable to seawater
Cooling, the term used for water used to remove sensible heat from processes,
machinery, vessels, etc.
Waste, either municipal or industrial; see Section 11.7, “Wastewater Handling”
and Section 11.15, “Mining.”
Category I describes the nature or chemistry of the water, in category I1 the nature of the
water is implied, and category I11 is wholly descriptive of the use of water and does not
provide information about its nature.
11.1 0.1 Cooling Water Systems
Much of the general discussion and information on cooling water systems is contained
in Chapter 10, “Water Systems.” Requirements and examples of cooling water systems
specific to the chemical process industry are presented in this chapter.
11.1 0.1.1 Once-Through Seawater
A typical example of the use of once-through seawater to remove process heat is in

coastal sulfuric acid plants. Sulfuric acid plants exist around the world as this acid
is important in many industries, such as fertilizer and explosives production, metal
pickling and plating, and in electrical batteries. Sulfuric acid is made from sulfur or
some other source of sulfur, such as the gases produced during extraction of copper
and other sulfide ores. The sulfuric acid plant converts sulfur dioxide gas into sulfur
trioxide by catalytic processes that are exothermic reactions and only operate effectively
at elevated temperatures. The trioxide is then dissolved to form the acid. The acid that
is produced is hot, up to 100°Cor more, and needs to be cooled during circulation and
before being transferred to storage. The acid is on the shell side of the exchanger which
is anodically protected. The cooling water, in some cases seawater or brackish water, is
in the tubes with a design velocity of 3 m/s. This design of sulfuric acid cooler with
anodically protected acid in the shell was developed by a Canadian company and it
is estimated that approximately 60% of all the world’s sulfuric acid is now cooled in
exchangers fabricated by this company (Figure 11.13).
About 1,100 of these coolers have been supplied, of which 179 or about 17% are cur-
rently used on seawater or brackish service. This amounts to some 3,500 miles (5,600 km)
Figure 11.13 Sulfuric acid heat exchangers are used to recover thermal energy from the acid
production process. (Photocourtesy of Kvaemer Chemetics Equipment Division.)
Figure 11.1 4 Seawater used for cooling water in heat exchangers is often
returned to the sea by gravity flow along reinforced concrete channels.
of tubing, about 600 miles (1,000 km) of it for chloride water service using the trade name
Ciramet@.This tubing was originally based on 904L but now one of the 6% molybde-
num superausteniticstainlesssteels is used. The alloy is bought as sheet to specifications
that include a minimum PRE number, and is then converted into welded tubing using
a company-based quality assurance and testing specification. The shell is 316L with
Ciramet@tubesheets, channels, and lined end covers. The tubing is usually 3/4 in. (2 cm)
18 BWG but some exchangers have been built using 5/8 in. (1.6 cm) 16 BWG to reduce
water consumption. Designs that use two pass water or water in series through exchang-
ers are avoided. For the equivalent duty where fresh water is available these coolers are
made with 304L or occasionally 316L tubesheets and carbon steel channels. Tubes for
fresh water are316L, 3/4 in. 16 BWG, or 5/8 in. 16 BWG where water volume is limited.274
Seawater is taken from a clean, preferably offshore source, filtered, chlorinated, and
pumped through the heat exchanging system to return to the sea at some other location.
Various materials are used for piping the seawater and some systems use open concrete
ditches, particularly for the return (Figure 11.14). Most plants use reinforced concrete
or carbon steel lined with concrete (Bonna pipe) for buried sections of the supply and
return. Within the plant aboveground piping to and from the heat exchangers is made
from the following:
Carbon steel
Rubber-lined carbon steel
Stainless steel
PVC
CPVC
FRP
The choice depends on pipe size, pumping pressure, materials availability, price, and
client preference. Filters, strainers, etc. are usually stainless steel with CP.
FRP is commonly used for aboveground piping (Figure 11.15) and it is made to a
Canadian Standard?75 The pipes have a corrosion liner consisting of one layer of C
glass veil and two layers of chopped strand mat, with a minimum total thickness of
0.01 in. (0.25 mm). The structural reinforced section is made to the same standard and
depends on size and operating conditions.The resins used are epoxy vinyl esters (either
Derakane 411@or Hetron 922@)and the outside of the pipes have a 1/8 in. fire retardant
layer together with UV pr~tection?~~
The control of chlorine levels is of great importance: too low and biofouling and
MIC are likely, too high and pitting or crevice corrosion is probable. Both of these prob-
lems with chlorine control were experienced some years ago on the same 904L heat
exchangers (Figures 11.16,11.17,and 11.18).In this plant seawater is taken directly from
an open basin, passed through a screen and a rotating stainless steel filter, and chlori-
nated by direct electrolysisof the seawater (Figure 11.19).From here the filtered, treated
seawater is pumped through concrete pipes to an open concrete ditch some 1.5 km
away (Figure 11.20). This concrete ditch is several hundred meters long. It permitted
photosynthesis by marine organisms and evaporation of chlorine, contributing to the
512 ADDlications
Figure 11.15 Large-diameter FRP piping supplies seawater to the heat exchangers in this North
African chemical plant. (Photocourtesy of CARIAD Consultants.)
difficulty in chlorine control and MIC. Water is pumped from the ditch, through rubber-
lined carbon steel pipes and a cathodically protected stainless steel filter to the heat
exchangers. After the heat exchangers the water is returned to the sea via rubber-lined
pipes and a cascading series of concrete canals.276
Saudi Arabia has the largest deposits of petroleum in the world. The gas associated
with it has been flared for decades but in the early 1970s the government decided to
embark on a massive industrialization program using this gas both as fuel and feedstock
for petrochemical production. This program resulted in the building of two new cities,
Jubail on the Arabian Gulf and Yanbu on the Red Sea.
At Jubail an extensive canal system was constructed to serve as a sink for the waste
heat from the petrochemical production. As the possibility of corrosion was anticipated
because of high salinity and temperature, relatively porous local aggregates, and fast
construction, the concrete was specified as the following:
28-day strength: 25 N / m 2
Minimum cement content: 400 kg/m3
Maximum chlorides: 0.06%
w/c ratio: 0.50 by weight
Maximum placement temperature: 28°C
7-day wet cure, then curing compound added
Figure 11.16 Severe crevice corrosion occurred on the water

outlet flange of a seawater-cooled heat exchanger that had
been operated with poorly controlled chlorination. This lack
of control had produced high potentials and corrosion from
high levels of chlorine and MIC when chlorine levels were
too low. (Photo courtesy of D. Hodgson.)
Figure 11.17 Corrosion at the edge of a nozzle attachment

weld is caused by lack of control of the seawater chlorination.
(Photo courtesy of D. Hodgson.)
514 Aoolications
Figure 11.18 Lack of effective biocide led to fouling and MIC at this North
African chemical plant. These barnacles (inside the chalk circles) were growing
in the water box of a heat exchanger. (Photo courtesy of CARLAD Consultants.)
Rust stains were noted on the wall of Canal 2 in 1982, only 1 week after wetting for
hydraulic testing. More extensive staining was seen 3 months later when this canal was
put into operation. Substantial areas with less than minimum cover were found so repairs
were undertaken. Fifty percent of Canal 2 walls were overlaid to some extent with new
concrete. A program was initiated to investigate contributing factors and assess options
to arrest corrosion. This extensive investigation concluded the following:2n
High quality concrete alone is insufficient to preclude chloride contamination and

corrosion of the reinforcement in this environment.
High quality concrete paste may not be justified with porous aggregates.
Chloride ion contamination can be experienced substantiallyabove externally wetted
areas.
Chloride ion contamination can be experienced on the outer face of wetted structures
by permeation of water through concrete and evaporation.
Sacrificial anode CP is able to control corrosion in submerged areas.
Impressed current anode systems can be satisfactorily installed and performed effec-
tively on dry walls.
Impressedcurrent anode system overlayscan be installed abovewaterline and operate
compatibly with immersed SACP or ICCP even when the system normally above
water is immersed.
Automatic and portable monitoring equipment is available to monitor or survey the
condition of reinforced concrete structures.
11.10 Chemical Process Plants 51 5
Figure 11.19 Concrete channel supplies cooling seawater to pumps through rotating filters,
seen on the left. After the pumps the water is chlorinated at the electrolytic chlorination facility,
seen in the center, before being delivered to the fertilizer plant. (Photo courtesy of CARIAD
Consultants.)
CP systemsare financially competitivewith alternatemeans to control corrosion, such

as fusion-bonded epoxy coatings.
The participation of a corrosion engineer in civil design is essential to assure the most
economic corrosion-resistant structure.
Saudi Basic Industries Corporation (SABIC) is one of Saudi Arabia’s leading indus-
trial companies, producing more than 20 million tonnes of petrochemicals, chemicals,
fertilizers, metals, plastics, and industrial gases. It is located at the new industrial city
of Jubail, together with the Saudi Iron & Steel Co. (HADEED).A series of open canals
supplies cooling seawater to 15 industrial complexes. Concrete reservoirs and intake
structureswere built in each of the complexes.Several of these structures were showing
signs of damage, cracking, and spalling above the water level. The submerged sections
were in good conditionbecause they had been cathodically protected from the beginning.
The intake structures were surveyed physically and electrochemicallyand damaged ar-
eas were repaired. An inert sealing slurry coatingwas applied over old and new material
designed to reduce chloride ingress by at least 90%.
A CP system was installed above the water line using titanium mesh-type anodes
with mixed metal oxide coating. The anodes were arranged in panels connected together
516 Aoolications
Figure 11.20 An open concrete ditch receives cooling seawater from the
main pumps some 1.5 km away. This ditch permits settling of sand and
provides steady flow to the heat exchangers in the fertilizer plant. (Photo
Next Page
11 .I 0 Chemical Process Plants 517
in zones. All the anodes were overlaid with cement, sand, 15% silica fume, and water.
The design criteria required the provision of a current density of 20 mA/m2 of steel to
be protected. Ag/AgCl reference electrodes were installed within the concrete structure.
Within 28 days of applying the concrete overlay the CP system was commissioned using
a 100-mV polarization development/decay criterion to determine adequacy of current.
Detailed surveys of the system and response to polarization showed that the structures
were well protected and current demand was well within design.278Recent surveys
showed that the concrete is still well protected and also showed the following:279
The passive condition of the reinforcement has been restored.

CP is judged to be a more effective and durable approach to chloride-damaged con-
crete than patch repairs.
A steel current density of 15 mA/m2 is sufficient to provide protection.
In sacrificial anode systems the -800 mV Ag/AgCl current on potential requirement
was not met at most of the monitoring points, but this has not resulted in damage in
submerged areas.
New seawater structures should incorporate impressed current CP systems.
A new 2,400-Mw power plant to provide 80% of the power to an expansion of SABIC
facilities at Jubail will incorporate CP for all new immersed concrete. Titanium ribbon
mesh will be installed on the rebar during construction?m
Seawater is used for cooling at another industrial plant in the Arabian Gulf. The
intake is on a jetty and seawater runs through reinforced concrete culverts under the
jetty and then aboveground to a pump house. Deterioration and corrosion were seen
within 10 years of construction when chlorides built up on the exposed surfaces of
the culverts. Repairs were made and the problem was greatly reduced by building an
insulated block roof over the culvert, thus reducing temperatures and e v a p ~ r a t i o n . ~ ~
Ruwais Fertilizer Industries (FERTIL)was established in 1980 as a joint venture be-
tween Abu Dhabi National Oil Company (ADNOC)and Total Fina Elf. Its objective is to
utilize lean gas from ADNOC to produce fertilizers for local and international markets.
Located in Abu Dhabi City, the FERTIL ammonia and urea plants have design capac-
ities of 1,050 and 1,500 tonnes per day, respectively. The complex also includes fully
integrated utility plants, storage, and loading and shipping facilities. Construction of
the plant began in November 1980 and the complex was commissioned at the end of
1983.
From 1986 to 1994, the ammonia plant on stream time averaged around 88%. The
major contributing cause for the downtime was frequent failure of the waste heat boiler
(downstream of the secondary reformer) and the main seawater supply line. This line
was reinforced concrete and was failing because of corrosion attack, which penetrated
to the steel structure from outside. This line (2.1 m diameter, 500 m long) was replaced
in 1994 with GRP pipe of the same diameter.281
The reinforced concrete seawater system at a liquefied gas/sulfur plant in Kuwait
suffered rapid corrosion. Structures most badly affected by spalling, cracking, and de-
lamination of the concrete cover and corrosion of rebar were the cooling water intake
Previous Page
518 Amlications
and outfall, the loading jetty, and the flume bridge. The main cause of the damage was
chloridecorrosion of the rebar coming from the Gulf water used to mix the concrete, sea-
water spray and splash from salt-bearing soil and ground water, and marine salts carried
by the wind. The contribution of aggregates to the chloride levels was insignificant. In
some areas the damage was intensified by inadequate concrete cover.282
A fertilizer plant in India has a steam condenser with admiralty bronze tubes using
once-through seawater at a temperature of 31 to 41°C. Seawater is taken from a 4-km-
long open channelusing 316L stainlesssteel pumps and concrete-lined carbon steel pipe.
Initially, no biocides were used and problems of tube fouling were experienced. These
were solved by installing a continuous cleaning filter and feeding sodium hypochlorite
at the inlet. The exchanger has now been in operation for more than 25 years.283
11.1 0.1.2 Once-Through Fresh Water
Fresh water from wells, lakes, and rivers is also used for cooling chemical plants. The
quality of the water can vary seasonally and annually, particularly if the water source is
a river that discharges into an estuary or the sea. One plant had 64identical 304 shell and
tube heat exchangers with shell side river water in which the chlorides varied from (50
up to 2,000 ppm. These exchangers failed by pitting at the baffles with an almost perfect
correlation between the number of tube failures in a month and the average chloride
content.284
A plant that had been using treated, recirculated coolingwater for 10 years was forced
to use untreated river water as a temporary measure. This temporary use lasted about
48 h and led to massive SCC failures of five of the stainless steel heat exchangers some
weeks later. This corrosion was caused by a buildup of mud in the exchangers that led
to higher tube wall temperatures and drying out of surfaces.285
11.10.1.3 Recirculating Water Systems
When cooling water is recirculated within the plant it is usually cooled by a cooling
tower and chemically treated to avoid scaling and corrosion. Pumps, valves, filters, heat
exchangers, etc. are commonly made of 316 SS, but this stainless steel is rarely used
for piping. There are many examples of failures of 300 series heat exchangers using
recirculating water, some of which have been positively identified as MIC, often caused
by incorrect water treatment or interrupted water flow.%
A chemical plant using a recirculating treated water system was having corrosion
problems with some of its carbon steel exchangers. The corrosion was diagnosed as
being caused by a combination of heat exchanger design, with low velocity water on the
shell side and inappropriate, poorly controlled water treatment. The water treatment
program was changed and its control was improved, but as a further safeguard ten of
the carbon steel exchangers were replaced with 2205 duplex and the one that was most
at risk with 2507.
11.10 Chemical Process Plants 519
A new synthetic fuel plant in South Africa suffered major problems with cooling
water systems during the first years of operation. These problems included major foul-
ing of heat exchangers with silica sediment and uncontrolled microbiological growth.
High levels of suspended solids were attributed to dusty site conditions and the use of
forced draft cooling towers. The microbiological contamination was traced back to the
hydrotest water used. These initial problems were solved by installing side stream filter
units, cleaning heat exchangers, coating water boxes, and fitting CP anodes. The wa-
ter treatment control philosophy was changed from a reactive one based on laboratory
measurements to one based on performance relative to targets for corrosion, fouling,
pH, TDS/conductivity, and microbiology. Additional instrumentation enabled better
monitoring and control of the system to be implemented. This total systems manage-
ment approach to cooling water treatment produced a substantial decrease in corrosion,
major improvement in water cleanliness, and significant water savings.287
11.10.2 Hydro Testing and Storage
A hydrostatic pressure test, carried out at the completion of fabrication, is required

by pressure vessel codes. Moisture often remains in the vessel following this test and
additional moisture can enter during transit through nozzles and openings that have not
been properly covered.Chlorides are present in most hydro test waters, includingpotable
waters, many common cleaning chemicals, and all marine atmospheres. Although the
levels of chlorides in the water may initially be very low, they can rapidly increase by a
process of diurnal evaporationand condensation.If inorganic particles are present attack
can initiate under the resulting deposits.
Although 304 and 316 stainless steels are most susceptible to preservice corrosion,286
there are also known cases of problems caused by preservice corrosion in the superstain-
less steels.28sThe techniques that can minimize preservice damage include the following:
1. Cleaning the equipment thoroughly after fabrication

2. Using hydro test water that is
a. Low in chlorides, less than 1ppm
b. Low in bacteria; use potable water (not well water) or treat with biocide
c. Free from particles and bacterial nutrients
3. For critical vessels, drying with warm air and padding the vessel with dry gas under
pressure
4. Closing all openings in the equipment and sealing against ingress of moisture
5. Adding desiccants to the vessel prior to sealing
6. Avoiding shipping and storing in exposed marine conditions
Carbon steel equipment can be protected in transit by the use of vapor phase or
contact inhibitors or by the applicationof temporary coatings of greases or waxes. These
methods are not usually applicable to stainless steels, however, as such techniques can
increase the likelihood of localized c o r r o ~ i o n . ~ ~
520 Applications
A 304 stainless steel heat exchanger shell failed during hydrotest at a fertilizer plant
although it had passed the test 3 months before at the fabricator's shop. The failure
occurred near a weld in the shell. The shell had been cleaned with nitric/hydrofluoric
acid solution immediately after welding and before hydrotest at the fabricators. Inter-
granular SCC was caused by the action of the acid solution on a sensitized weld H A Z in
the presence of residual tensile fabrication/welding stresses. The cracks initiated after
fabricationand propagated through the shell thickness during the 3 months of storage.'%
Examples of corrosion failures during storage of equipment prior to startup are com-
mon. A 304 sample tube header for a pressurized heavy water reactor failed by trans-
granular chlorideSCC. This header had passed a hydrostatic test at 2,400 psig (17.2MPa)
at the time of purchase. After about 2 years storage it leaked when rehydro-tested. The
failure was diagnosed as external contamination by chlorides from the local marine
atmosphere coupled with residual stresses from the tube-straightening operation.290
Crackswere detected in the 304 stainlesssteelplates used to line the spent fuel storage
tank at a nuclear power station. The plates had been stored for about 2 years in a marine
atmospherebefore being used for the lining. This failure was also diagnosed as chloride
SCC with the tensile stressescoming from the shearing operation which had been carried
out with blunt tools?9o
11.1 1 PULP A N D PAPER MILLS
Paper gets its name from the Egyptian papyrus plant, used to make paperlike sheets as
early as 2300 B.C. The process is still being demonstrated to tourists in Cairo today. The
first paper was made in China from natural fibers, such as hemp or bamboo, or from
cotton or linen rags. The Arabs learned papermaking from the Chinese and brought
paper to Europe in the 12th century. The first European paper mill was built in 1270 in
Fabriano, Italy and the first North American one was built by William Rittenhouse in
Germantown, PA in 1690.
In the past, the vast majority of paper and paper products were made from wood
fibers taken from logs of conifers (such as spruce, fir, pine, and hemlock) and deciduous
trees (including birch, oak, and aspen). Today, much of our paper comes from chips
and timber waste from saw mills, recycled paper, and board and from specially grown
forests of renewable timber. Most writing and magazine papers have between 1 and 30%
of mineral filler, usually calcium carbonate and clay. These fillers improve the optical
and printing qualities and make the paper smoother, less absorbent, and more opaque.
Americans use nearly 71 million tons (64 M tonnes) of paper and board per year. The
annual output of paper mills in the United States alone totals more than 64 million tons
(58M tonnes) of paper and board and 51 million tons (46 M tonnes) of pulp.'Og
The primary raw material in paper manufacture is cellulose fiber. Wood consists of
approximately 50% cellulose, 30% lignin (a resinous adhesive which holds the fibers
together), and 20% aromatic hydrocarbons and hemicellulose carbohydrates. To obtain
cellulose for papermaking the wood or plant material must be pulped to separate the
11.1 1 PUID and PaDer Mills 521
Figure 11.21 A pulp mill dominates the landscape in rural Swaziland. (Photo courtesy of
fibers and remove impurities (Figure 11.21).The higher the cellulose content of the pulp
and the longer the fibers, the better the paper quality. Hardwoods generally contain a
higher proportion of cellulose but of shorter fiber length than softwoods, which are more
resin0us.2~~
Vast quantities of water are used at all stages of pulp and paper production. In
the early days of pulping, mills were located near sources of water that were used in
the process and to drive the grinders and mill machinery. Most of these mills were made
from carbon steel and cast iron, repairing and replacing as necessary. As environmental
concerns have increased, mills have had to "close up" their water and the majority is
now recycled, often after treatment. This has introduced more corrosion problems as
the contaminants, such as chlorides and oxidized sulfur species, have increased. The
closing up of mills has also caused the temperatures of circulating liquors to increase,
also increasing corrosion. New, more efficient processes have been introduced, many
of which require more corrosion-resistant materials than previously. Closing up and
chemical recovery programs have also meant that the atmospheric and water pollution
traditionally associated with mills is becoming a thing of the past in many countries.
In the United States in 1990 there were around 555 facilities manufacturing pulp and
paper. Overall, the pulp and papermaking process is water-intensive and is the largest
522 ADDlications
industrial process water user in the United States. In 1988, a typical pulp and paper mill
used 16,000 to 17,000 gal (60 to 64 m3)of water per ton of pulp produced. This translated
into a total industry discharge of 16 million m3/day of water. Pulp and paper mills
usually operate wastewater treatment plants to remove BOD, total suspended solids
(TSS), and other pollutants before discharging waste waters to a receiving waterway.292
According to a recent corrosion cost survey (September 2001), the pulp and paper
industry’s heavy reliance on corrosive chemicals makes it the most expensive industry
sector in terms of direct corrosion costs.293Another recent survey estimated the total
annualcost of corrosionto be $6 billion, calculated as a fraction of the overallmaintenance
costs? Earlier surveys in Sweden and Canada found that at a time when the pulp price
was very low the costs of corrosion amounted to 4 to 5% of the market value of the pulp
produced.294
11.11.1 Pulp Mills
Water is used to wash wood pulp at every stage of the process and to convey the pulp
through the mill. In coastal mills where logs are transported by sea the chloride levels
in the pulp mill may be ten times higher than in inland mills. The first use of water is
in the debarking drum where the bark is removed. This water, high in BOD and often
coliform bacteria, is recycled. Wood from the debarker is then chipped and fed into
pulping equipment. Wood chips are converted into pulp using a number of processes
that are mechanical or chemical or some combinati~n?~ On a tonnage basis, chemical
pulping methods produced approximately85%of the pulp manufactured in the United
States in 1991, mechanical pulp lo%,and semichemical5%.292
11.1 1.2 Mechanical Pulping
The original mechanical pulping process forced logs against a grindstone, which turned
90% of a log into pulp. This groundwood pulp is weak and has poor aging properties.
Newsprint used to be made from a mixture of groundwood pulp and rag fibers. Grad-
ually, chemical pulping was introduced and chemically pulped and groundwood fibers
were often blended. In the 1960s, attrition mills began to be used. In this type of mill
wood chips are pulped using a disk refiner.295Disk refining has now largely replaced
groundwood because it produces higher strength pulp and can use chips and sawmill
residue as feedstock. The disks are usually cast, often of some proprietary white cast
iron or stainless steel with good wear and corrosion resistance;2%the associated shower
nozzles are usually made from 316L stainless steel.
Fiber quality in the pulp-makingprocess can be varied by controllingtemperature and
pressure and by using chemical additives. In mechanical pulping, wastepaper pulping,
and de-inking, 300 series stainless steels have largely replaced carbon steels. The grade
most commonly used is 316 although 304 has been successful in a number of mills.
Duplex 2304 has also been used as an alternative to 316 in some cases. SCC failures of
11.11 PUID and PaDer Mills 523
316 have been reported in screw conveyors and SCC and underdeposit corrosion has
occurred in 316 disc filters. In both cases 316 was replaced by 2205, which has also been
used in applications where the metal loss mechanism of carbon steel has been corrosion
and e r o s i ~ n / w e a r . ~ ~
In thermomechanical pulping, chips are washed with recycled water and then fed
through a screw press that produces a homogeneousslush that passes continuously into
a steam heated digester. This softens the fibers and permits them to be separated at
boundaries that are relatively free of l i g n i n ~ ? ~ ~
11.11.3 Chemical Pulping
In the 1800s, chemical processes were developed that are able to dissolve most of the
lignins remaining in groundwood pulps and produce stronger fibers able to make finer-
grade papers. Wood chips for the chemical processes are fed into digester tanks and
cooked with steam in chemical solutions called "cooking liquors." Cooking times vary
from 2 to about 6 h, depending on the kind of chemicals used and degree of refinement
needed. The process may be continuous or batch. Pulp from the digesters is washed by
countercurrentflow with water that picks up the chemicals in the pulp to become a weak
black liquor with 3 to 5%solids. Since many of the pulping processes are based on sulfur,
much of the recycled water is high in sulfur compounds.
About 80% of the world's chemical pulp production is made by the kraft ("kraft" is the
German word for strength) process that uses sodium hydroxide and sodium sulfide in
the cooking l i q u ~ r .Digesters
~ ~ , ~ may~ ~ be direct steam heated or indirect steam heated
using shell and tube heat exchangers. These exchangers used to be carbon steel but
have been gradually upgraded through 400 series stainless steels, which suffered from
corrosion and fatigue, to 300 series stainless steels, which suffered from SCC; now mills
are using duplex stainless steels or nickel-based alloys such as alloy 600or alloy
Piping in a kraft mill is still often carbon steel, with 304L gradually being introduced.
Pumps and valves are cast CF8M which is usually resistant to krafi liquors. Liquor reheat
heat exchanger tubing in 304L has failed by corrosion, caustic cracking, and chloride
SCC. Differential thermal expansion between the stainless tubes and the carbon steel
shell has apparently provided the stresses. Duplex 3RE60 (UNS 531500) has eliminated
the problem in many mills.298
The majority of chemicals leaving the digesters must be recovered using a com-
plicated series of processes and recycled within the mill. This recovery often involves
burning evaporated spent liquors in high temperature recovery boilers. The gases leav-
ing the boilers pass through wet scrubbing systems. In a flue gas scrubber of a kraft
recovery boiler, gases enter the scrubber at around 165"C, entering the washing water
that is circulating at 70°C, pH 7, and 4,000 ppm chlorides. The 316L scrubber had failed
by pitting on a number of occasions and had been relined. The lower part of the scrubber
was replaced by UNS S31254 which was unattacked?%
Other methods of chemical pulping include the alkaline-soda process, used mainly
to pulp some hardwoods, and the neutral-sulfiteprocess used for some hardwoods and
524 ADDlications
softwoods. The cooking liquor in the sulfite process is sulfur dioxide (made by burning
sulfur) dissolved in calcium, sodium, magnesium or ammonium hydroxide. The liquor
can be neutral, alkaline, or acid. The equipment in a sulfite mill is mainly stainless steel,
with 904L, 6% Mo austenitic, or 2205 duplex being used for some equipment items in
some mills.
11.11.4 Hybrid Pulping Processes
In-between the mechanical process and fully cooked chemical pulps are pulps produced
by varying the amount of chemical and mechanical treatment. Usually the same chem-
icals are used as those found in chemical pulping liquors but under more dilute con-
ditions. Sodium hydroxide, sodium sulfite, or sodium sulfide are the most commonly
used chemicals. The particular chemical included in the liquor depends on the wood
species and the paper product required. Because these combined processes do not com-
pletely dissolve undesired substancesin the pulp, chemimechanicalpulps require more
mechanical treatment before they can be used.
11.11.5 Bleaching
If white paper products are required from the mill, the washed, treated pulp goes through
a bleaching stage. Bleaching processes, primarily used to whiten and brighten pulps for
paper manufacture, can produce waste waters containing chlorinated compounds such
as dioxins. Bleaching may be considered an extension of the pulping process in that
lignins and their reaction products are part of the color that is removed by bleaching.
Prior to bleaching, the pulp is often subject to oxygen delignification, in which the pulp
cooking is continued by the addition of alkali and oxygen. This stage can drastically
reduce chlorine use and remove much of the lignin remaining after cooking. As long
as the consistency (content of pulp in the water) is not too high 316 stainless steel is
generally satisfactory, although external SCC has caused it to be replaced by 2205 UNS
S31803 in at least one mill. The high strength of the duplex stainless steels, principally
2205, is useful in the fabrication of these high pressure rea~tors.2~~ High temperature
oxygen reactors are sometimes made from alloy 2OCb3 (UNS NO8321) to avoid SCCm
Bleaching is carried out in several stages. The sequence and operating conditions
vary from plant to plant and depend on the pulp source and required properties. The
bleaching processes are designated as C = chlorine, E = extraction by alkaline solution,
D = chlorine dioxide, H = hypochlorite, and P = peroxide.
The alkaline extraction stage has high pH with sodium hydroxide and often oxi-
dizers such as oxygen, sodium hypochlorite, and hydrogen peroxide are added. This
environment is not particularly aggressive even in the presence of the high levels of
chlorides released when the chlorinated lignins are liberated. The bleaching tower and
the associated washers are satisfactory in 316 stainless steel.
Temperatures and chloride levels in the C and D stages have risen as a response
to pollution control and economics. The conditions in these stages have become more
11.1 1 PUID and PaDer Mills 525
corrosive and the traditional 316L and 3152 materials in C and D stage washers have
become marginal in a lot of mills. Extensive trials at a Canadian mill found that 316L
and 317L were no longer suitable for this application. Although 904L was considerably
better the 6% Mo austenitic stainless (UNS S31254) was the only stainless steel able to
withstand the C stage washer gas phase. Titanium, alloy G, and alloy C 276 were also
uncorroded in this environment.
Autogenous welds in stainless steel washers have been preferentiallyattacked in this
environment.Welds in stainlesssteels should be made using higher alloys such as Inconel
112, alloy C 276, or P12 filler metals. The residual chlorine levels in C stage stainless
steel washers should be less than 0.025 g/L to avoid corrosion. In the D stage the critical
pH range of 3.5 to 5.5 should be avoided in the presence of residual chlorine dioxide. A
pH range of 6 to 8 is more desirable.”
In mills where C and D washers made from 904L, 17-14-4L, 2366 (similar to 317L),
and FFW have been attacked, UNS S31254 has been successfully used. However, in the
presence of several thousand pprn chloride and 50 pprn or more residual chlorine 6%
Mo steel is not adequate, particularly in the gas phase. The residual chlorine levels in the
piping between mixer and tower can also be too high for this stainlesssteel. In these cases
the 7% Mo alloy (UNS S32654), titanium, or alloy C 276 should be considered.294The
7% molybdenum austenitic stainless steel, UNS S32654, has been used to replace other
troublesome components in D stage bleaching. This alloy replaced a 316L nozzle in a
bleach tower that had failed in 4 weeks in an environment of 3,000 pprn chlorine dioxide,
pH 3 to 3.5 at 70°C. It has also been used in filter washer vats and filter washersN2
For D stage filtrate piping 317L can be marginal and titanium, alloy G, or carbon steel
piping lined with PTFE or PVDF is r e c ~ r n m e n d e dRecycle
. ~ ~ of filtrates between stages
can exacerbate corrosion problems. For example, recycling of D stage filtrates to C stage
should be avoided because the more acidic conditions (pH 2) in the C stage regenerates
chlorine dioxide making the water highly aggressive to stainless steelsm
Hypochlorite bleaching is carried out in high pH solutions of calcium or sodium
hypochlorite and washers are usually satisfactory in 316L.m Temperatures are of the
order of 85 to 115°F (29.4 to 46°C) with pH 11.0 to 11.5, dropping to 8 or more. Type 316L
and 317L are the principal materials used for H stage piping, mixing equipment, and
pulp washer drums.297
Hydrogen peroxide and ozone are sometimes used in pulp bleaching and peroxide
is regularly used to brighten mechanical pulp. These oxidants can cause severe localized
attack of stainless steels in the presence of chlorides. The alkaline conditions in peroxide
bleaching are less aggressive than the acidic ozone solutions, even if chlorides are high.
In ozone bleach towers or pressurized peroxide bleach towers, 316L is unlikely to be
adequate and a duplex steel such as 2205 is preferred because of higher strength and
corrosion resistance.294
Stainlesssteelbleach washers can be protected electrochemicallyfrom corrosion. The
high potentials from the presence of oxidizing agents in the washer can initiate pitting
and crevice attack of stainless steels. If this potential is decreased, i.e., polarized in a
negative direction, corrosion can be controlled.This principle has been successfullyused
in a number of washers. Protection can be retrofitted to existing washers by installing a
526 Aoolications
platinized anode and monitoring coupons, one of which is insulated and the other is in
contact with the drum. A comparison of protected 3152 and unprotected UNS 91254
showed the benefits to be similar.300C stage washers made from 316L, 3152, and 904L
have now been electrochemically protected in many mills.
Additional refining of the pulp includes many washings and screening out bits of
knots, sand, and other foreign matter. The pulp is then conditioned (a process also known
as beating or refining). The pulp, in liquid form or in thick, almost dry sheets called
"laps," is mixed and refined. The fibers are frayed, sheared, and cut so they will cling
together when matted. Chemicals such as sizes (resins, starch, or gypsum) to strengthen
the paper and make it water-repellent, loading materials (clay, pigments, and chalk) to
form a surface coating and make the paper opaque, and fillers and dyes for coloring may
also be added to the mixture at this point.
In the last step, the pulp passes through a Jordan, a cone-shaped machine that cuts the
fibers to the proper length. Other mills use refiners, such as disk, wide angle, or conical
refiners. The final pulp product, called furnish, stuff, or stock, is stored until needed in
the head boxes of papermaking machines.
11.1 1.6 Paper Machines
The pulp is carried to the paper mill in large quantities of water, e.g., 1%pulp in water,
which is known as 1%consistency.The bulk of this water is removed by drainingthrough
a screen or wire. The rest of the water is graduallyremoved by vacuum, pressing, blotting,
and evaporation. The water from the wire pit of a typical fourdrinier paper machine,
known as white water, is continuously recycled with the incoming pulp. The dissolved
solids and fibers gradually build up in the white water and some is continuously bled
through a device to remove fibers and then sent back to the upstream processes, even
as far as the pulp mill. Cast iron, carbon steel, plastics, and 304 and 316 stainless steels
have been the traditional materials of construction of paper machines. Copper-based,
titanium, and aluminum alloys are used to a much lesser extent. Corrosion rates in a
fourdrinier section are typically 0.012 to 0.014 in./y (0.30 to 0.36 mm/y) for cast iron
and 0.040 to 0.12 in./y (1.0 to 3.0 mm/y) for carbon steeLm Gradually, various grades of
stainless steels are taking over most of the duties in paper mills, particularly at the wet
end of the process.
With the increase in system closure and the use of new practices in brightening have
come new corrosion problems in paper machines. Bronze fourdrinier wires, cast stainless
steel suction press rolls, cast iron vacuum pump impellers, and 304 process piping have
all suffered greatly increased corrosion.3o4
Materials used for white water have evolved from carbon steel through 304 stainless
to the current standard of 316L. Pitting of 304L piping has been shown to be due to
thiosulfates even in water where chloride levels are low. Thiosulfate pitting can also
occur in the absence of chloride if another anion, such as sulfate, is present. A limit
of 5 ppm thiosulfates is suggested in paper machines to avoid pitting of 304L. Higher
levels of thiosulfates and chloridescan be handled in 316L piping. In some mills operated
11 .ll PUID and Pawr Mills 527
under a high degree of closure, 316L has proved to be inadequate and duplex 2205 is
being used.294Most mills still use thin gage 304L or 316L for stock piping, and these
are satisfactory with most white waters as long as surfaces are smooth and are kept
clean. White water provides hospitable conditions for growth of microorganisms and
MIC has frequently been a problem. Protruding welds or roughened or fouled surfaces
soon become attacked by MIC or under deposit pitting.
Cleaning and surface finish is also important in the head boxes that convert flow
from a circular pipe into flow through a rectangular orifice onto the paper machine.
Headboxes are made from 3152 or 316L, often with critical components, such as aprons
and slice lips, made from some more resistant alloy such as a 6%Mo austenitic stainless
steel. In some cases, head boxes have been made from nickel alloys to avoid corrosion
and roughening and to try to eliminate maintenance of this critical piece of equipment.
Paper machine wire is now often made from plastics or from bronze coated with nickel,
tin, or plastic. Inhibitors are also often added.305
The suction rolls are said to be the largest corrosion-related expense in paper ma-
chine operations. Failures in these rolls are usually caused by corrosion fatigue from
the corrosive white water environment in the presence of high cyclic stresses from the
rotation of the drum. Duplex stainless steels have better corrosion fatigue resistance in
this application and 3RE60 (UNSS31500) has been used for fabricated suction rolls since
1973; duplex 2205 is now also being used for this Bronze, martensitic, and pre-
cipitation hardening stainless steels are also being used for suction rolls. Most suction
roll shells are made from continuouscast bronze, rolled and welded stainlesssteels (UNS
S31500), and forged stainless steels.3o6
Cylinder machines are also used for making paper in smaller mills and for making
heavier grades of paper board. A rotating cylinder board mold in a paper and board
manufacturing plant failed in 3 years in the crevice regions between the axial rods and
the outer face of the external spirally wound stainless steel mesh. The cause was deter-
mined to be MIC. All corrosion products and deposits were heavily contaminated with
pseudomonads, flavobacteria, bacilli, SRB, and fungi.307
The latest innovation in papermaking has been the introduction of two-wire ma-
chines. The pulp slurry is forced between two meshes of wire, and water is removed
from both sides of the paper. This innovation not only speeds up the papermaking pro-
cess, but it also improves the quality of paper produced.
11.11.7 Water Treatment
Because such large volumes of water are circulating around pulp and paper operations
and are collecting organic and inorganic chemicals, water treatment within the mill is of
vital importance. This is also so because the environmentalrestrictions are being contin-
ually tightened on water discharged from mills. The type and quantities of contaminants
within any mill will depend on the processes being operated, the condition of the plant,
and the products being produced. Treatment plants required in a pulp and paper mill
are similar to those used in municipal wastewater treatment plants.295
528 Aodications
11.1 2 POWER PLANTS
The vast majority of electrical power is generated from stations burning fossil fuels, a
significantportion of the rest being produced by nuclear fuel. A much smaller proportion
is generated using renewable sources such as wind, water, tide, etc. Power generation
plants use large volumes of water for cooling and steam raising so are usually located
near lakes, rivers, or seas. Steam electric generating plants are the largest industrial user
of water in the United States, using about 80%of all such water in 1970. About 70%of the
water used by utilities is fresh, the remainder being saline water for coastal stations.295In
1995, the total volume of fresh water being used by thermoelectric plants in the United
States was 132 Bgal/d (500 BL) out of a total freshwater use of 264 Bgal/d (999 BL).308
11.1 2.1 Fossil Fuel and Nuclear Plants
Fossil fuel and nuclear plants suffer from similar corrosion problems but each have some
that are specific to the differences in the way they generate electricity. Water-related
corrosion is important to both industries and the total cost of corrosion to U.S. utilities
has been estimated to be about $3.5 billion per year.- A study in 2001 based on data
for the calendar year 1999, however, found that the corrosion-related costs of producing
electric power in the United States was about U.S. $17.3 billion, equivalent to about 7.9%
of the total cost of electricity. This study estimated that about 22% of these costs could
have been avoided by better materials selection, design, fabrication, and water chemistry.
The cost of corrosion, excluding depreciation costs, for the nuclear industry was U.S.
$7,801,362,000 (20.2%of total costs to consumers) while for power produced from fossil
fuels it was U.S. $5,368,504,000 (4.6% of total costs to consumers).Other corrosion losses
occurred in the hydro and other electric generating operations and in transmission and
distribution of power.310Another study found that the total direct cost associated with
corrosion in the electrical supply industry was $6.9 billion, of which $4.2 billion was in
the nuclear industry, $1.9 billion in fossil fuel stations, $0.15 billion was due to hydraulic
and other power raising, and transmission and distribution accounted for $0.6 billion.*
11.12.1.1 Cooling with Fresh Water
In Canada, Ontario Power Generation Company (formerly Ontario Hydro) has had fail-
ures using copper-based, nickel-based, and stainless steels for heat exchangers and has
done extensive research on tubing materials. They found that the copper-based alloys
do not generally perform well in the waters of the Great Lakes and fail by pitting under-
deposits of biofilms, sand, silt, and minerals. Their best experience was with austenitic
alloys having a pitting index (wt Cr + 3.3 wt Mo) >36, such as 904L. When alloys with
indices <22, such as alloy 800, were used failures were rapid. Prediction of performance
based on ratings of pitting resistance was not, however, reliable. For example, 304L ir-
radiated fuel bay exchangersworked well at one site, Pickering, for more than 12 years,
11.1 2 Power Plants 529
while moderator exchangers in alloy 800 at the same site suffered extensive failures after
2 to 3 years.311
In long-term isothermal corrosion tests at 45°C in Lake Ontario water, 304, alloy 400,
alloy 800, alloy 600, alloy 690, 90/10, and 70/30 Cu/Ni were not attacked; admiralty
brass showed slight crevice attack. In the presence of silt crevices and deposits, however,
most of these alloys were corroded. In heat transfer tests only titanium and alloy 625
were not pitted; the high molybdenum stainless steels tended to show isolated deep
pitting312
11.1 2.1.1.1 Feedwater Heaters
Copper alloys used for closed feedwater heaters (using steam from the turbines to heat
the feedwater) are liable to SCC from ammonia in the steam coming from water treatment
chemicals. This tendency can be reduced by stress relief but other forms of corrosion can
also occur. There have been some failures of alloy 400 tubes, principally the U-bends,
that can be prevented by stress relief. General corrosion in feedwater heaters decreases
from carbon steel, brasses, copper nickels, and alloy 400 to stainless steel (immune).
Pitting is prevalent only in stainless steels, mainly on the water side. Erosion-corrosion
has only caused extensive failures with carbon steel tubes. Exfoliation has been seen on
Cu/Ni alloys, with the degree of susceptibility increasing with increasing Ni content.
"Snake skin"effects, in which copper from the water is redeposited on the tubing surface,
are sometimes seen on high pressure feedwater heaters. The tubing for these heaters is
usually alloy 400 or 70/30 Cu/Ni. The source of the copper is usually the admiralty
brass tubes in the low pressure feedwater heaters and the effect is to reduce heat transfer
effi~iency.3~~
Type 439 ferritic stainless steel has been in freshwater use in utility heat exchangers
since 1983, with more than 7 Mm now in operation, mainly in feedwater heaters, con-
densers, and heat recovery steam generator exchangers. The only major failure of type
439 was a MIC failure that occurred in a utility station on Lake Michigan. An exchanger
was in intermittent service with the water left stagnant between uses. Only 6 weeks after
installation tubes failed by pitting and were found to be full of silt and mud.314
11 .I 2.1 .I.2 Condensers
Steam surface condensers are an integral part of power plant equipment. They are made
from a variety of materials, including 304, 316, admiralty metal, alloy 400, 90/10, and
70/30 Cu/Ni alloys. The use of copper alloys can lead to copper ions getting into the
system and help prevent MIC on the water side, but on the condensate side they can
cause galvanic corrosion in the boiler. Stainless steel is poor from the heat transfer point
of view, but thinner tubes can be used because they have better mechanical properties
than copper alloys. On the steam side stainless steels are generally good because of
their high tolerance of oxygen, but they can be subject to MIC and fouling corrosion on
530 Applications
the water side. Condenser tube failure can lead to major boiler water contamination.
Common causes of condenser tube failures include the following:
1. Steam side corrosion, including steam impingement erosion-corrosion

2. Water side corrosion
3. Leaks where the tubes are rolled into the tubesheet
4. Failure of tubes at tube supports caused by vibration from flowing steam
Steam side corrosion of copper alloy tubes is often caused by ammonia carryover
from the boiler. This type of corrosion can be reduced by minimizing air and by using
more resistant materials such as the Cu/Ni alloys instead of admiralty metal. Carryover
of S O 2 from boilers treated with sodium sulfite can cause SCC of copper alloy tubes.
Water side corrosion is usually associated with surface deposits, often involving MIC
attack beneath the fouling. Adequate water treatment, avoiding stagnantconditions, and
regular cleaning are needed to control this form of corrosion. To avoid erosion-corrosion
use more resistant alloys, remove solids from the water, and maintain water velocity to
below the safe limit for the particular material, e g , in freshwater <2 m/s for admiralty,
( 3 m/s for 90/10 Cu/Ni, and up to at least 3.7 m/s for stainless ~ t e e l s . The
3 ~ ~corrosion
mechanisms causing tube failures in power plant condensers depend on the material
(Table 11.7).
11.12.1.1.3 Moderator Heat Exchangers
These exchangers are normally alloy 800 U tube bundles that reject heat from the mod-
erator and reactor structures in nuclear power plants during normal operation. During
emergencies these exchangers can act as a heat sink for the reactor fuel. Water is on the
shell side and there have been through-tube wall underdeposit pits from the water side
Table 11.7 Causes of Tube Failures in Condensers316
90/10 70/30 Admiraltyand

Cause AlBronze Cu/Ni Cu/Ni AlBrasses 304 CPTi
Erosion W W W W N N
Sulfide W W W W N N
Dealloying (W) (w) - (w) N N
Crevice/pit (W)sulf (w)sulf (W)sulf wsulf (w) N
Galvanic (W) (w)sim (W)sim (w) N galv Ngalv
SCC or Hzcracking (S) - - w/s N (N)
Condensate (S) (S) (S) S N N
W =water side, S = steam side, ( ) = minor attack, N = not a problem; galv = can induce galvanic
corrosion of adjacent copper alloys, sulf = perhaps only a problem when sulfide is present, sim =
problems have occurred in similar alloys.
in less than 2 years using Lake Ontario water.311Replacement exchangers were retubed
with alloy 825 and UNS N08028?17
Other moderator heat exchangers are tubed with 70/30 Cu/Ni and this has been suc-
cessful?l* Other alloys such as alloy 625,6% Mo austenitic stainless steels, and titanium
are also being assessed for this duty. Biofouling is a factor in stabilizing the deposits so
that water treatment to limit biofouling also reduces pitting/underdeposit corrosion?19
11.1 2.1.1.4 Shutdown, Bleed, and Recirculation Coolers
Copper-nickels and admiralty brass did not perform well in lake water, particularly
under stagnant or low flow conditions and underdeposits.Alloy 400 was the alloy chosen
for the most critical dutie-hutdown coolers, steam generators, and bleed coolers. In
the latter two applications it has apparently performed well but many pitting failures
have occurred in shutdown coolers on Lake Ontario. The probable cause was biomass
binding inorganic silt giving underdeposit/MIC attack.
Sixteen shutdown coolers with alloy 400 tubes and Lake Ontario water on the shell
side with a flow of <1 m/s failed. The minimum time to failure was 36 months and they
were replaced with alloy 825. The bleed coolers have alloy 400 tubes with demineral-
ized water on the shell side with a flow of <1 m/s. Two of these coolers failed with a
minimum time to failure of 48 months. These failures were caused by contamination of
the demineralized water with lake water. These coolers were replaced with alloy 400
exchangers.
Recirculation coolers with 90/10 Cu/Ni tubes have demineralizedwater on the shell
side and Lake Ontario water on the tube side with a flow of t 2 m/s. Sixteen of these
failed with a minimum time to failure of 24 months. These were replaced by 316L.317
11.1 2.1.2 Cooling with Brackish and Seawater
Super stainless steels have been used for nuclear service water piping. A test program
at the Oskarshamn Nuclear Plant at Figeholm, Sweden evaluated titanium, 2507, UNS
S31254, and UNS S32654 for use in the polluted brackish water of the Baltic. Titanium
was found to be adequate from the corrosion point of view but was not selected because
of perceived difficulties in welding. Crevice corrosion problems were reported with
the "lean" duplex 2205 and this steel was not selected. The material chosen to replace
any failures of existing piping was UNS S31254 on the basis of its corrosion resistance,
strength, and availability. This alloy has been in use since 1984 for piping and since 1991
as condenser tubes at this plant.320
In the Salem Nuclear Generating Plant in New Jersey a similar test program coupled
with in-service experience led to the conclusion that 6% Mo austenitic stainless steels
are the most suitable materials for service piping. The once-through water used in this
plant is taken from the Delaware River. It is brackish, with a high silt content. This
plant has used 6%Mo austenitics since 1986 and UNS S31254, or 25-6Mo, is used for all
532 Amlic-ations
replacement piping here and at the Hope Creek plant. They did not find any difference in
performance between the various 6%Mo alloys available and use them interchangeably
depending on price and availability?21
UNS S31254 has also been used for tubesheets, condenser tubing, and auxiliary heat
exchangers for both nuclear and conventional fuel power plants. In 1991,611,960 m of
UNS S31254 tubing was installed in utility steam condenser^.^^ Some nuclear contain-
ment coolers were made from AL-6X (UNSN08366) in the early 1980s and the improved
alloy AL-6XN (UNS N08367) containing nitrogen has also been used for nuclear ser-
vice piping and service water air-cooled exchangers.323Titanium and UNS S31254 tubes
were used to replace copper-based alloy tubes in power plant condensers in Sweden
and Finland. Results have been generally good apart from some erosion problems on
the outer titanium tubes. UNS S32654 stainless steel (94,000 m) was used to replace tita-
nium tubes at Forsmark 1 in 1995,56,000 m at Ringhals in 1995/1996, and 58,000 m at
TVO, Finland in 1996/1997.=O
In the early days of using ferritic stainless steels industrially two general problems
were encountered. The first was hydrogen cracking under the action of CP in the range
(-0.9 to -1.4 V SCE) used to protect the water boxes of condensers. The second problem
was caused by roller expanding these ferritic tubes into 316L tube sheets. The tight
crevice and the poor resistance of 316L to crevice corrosion in the high chloride service
environments produced a strongly acidic solution in the crevice which destroyed the
passive film on the tubes. These problems were solved by using a more highly alloyed
tube sheet, seal welding the crevice or cathodically protecting at potentials no more
active than -0.8 V SCE, and by alloy improvements. A review reported that by 1990
there was a total of more than 8 Mm of superferritic condenser tubes installed in U.S.
power plants. This condenser tubing was made up of the alloys, UNS S44660 and 29-4C,
and some had been in service for 10 years by then.3o
UNS S44660 is still regularly used in utility stations, mainly for condensers and
feedwater heaters. Of some 60 exchangers installed, 41 were on seawater or brackish
duties; UNS S44660 had been specified for most of the others for resistance to MIC. By
2000, there were more than 10 Mm of UNS S44660 tubing in utility operations with other
exchangers in nonutility duties. The only failures were one feedwater heater that failed
by being operated above the 475°C embrittlement temperature, and one exchanger that
failed when water froze in the tubes in a refrigeration system.314
The corrosion of surface condensers can be increased by the presence of impurities,
particularly sulfides, and by sand particles. Tests to investigate these aspects of con-
denser corrosion were carried out as part of a &year project sponsored by EPRI. The
alloys investigated were titanium (UNS R50250), 90/10 and 70/30 Cu/Ni (UNSC70690,
C71590),aluminum brass (UNSC68700)tubes, and Muntz metal (UNSC28000) and alu-
minum bronze alloy D (UNS C61400) tubesheets. Increasing the sand content from 0.03
to 0.2 g/L increased corrosion rates in some cases and decreased them or had no effect in
others. For example, sand injection increased the general corrosion and pitting of copper
alloy tubes in unpolluted water but in sulfide-polluted water sand decreased the pitting
rate and had no consistent effect on the general corrosion rate. When the tubesheet ma-
terials were coupled to copper alloy tubes, sand injection had no effect on corrosion in
polluted or unpolluted seawater. When the tubesheet samples were coupled to titanium
tubes, however, corrosion rates were decreased by sand injection in both types of water.
It was concluded that detrimental effects of sand, when present, were small compared
with the effects of sulfide^.^"
Titanium tubing, usually unalloyed grade 2 (R50400),has been used in power plant
condensers in Japan. These exchangers use solid titanium or titanium clad tubesheets
without CP. If a tubesheet material requiring CP is used there is a risk of hydrogen
embrittlement of the titani~m.~’ Titanium-welded tubing is being used for seawater
condensers at temperatures up to 80°C.More than 100Mm is in service with no reported
corrosion problems.325
Corrosion problems in condensers can also originate from the steam side. Aluminum
brass (UNS C68799) condenser tubes failed after chemical cleaning of the water side of
the exchanger in a 32-MW coastal unit in Spain.Tubes were suffering from dezincification
on the steam side with many through-wall cracks. SCC of the brass was caused by the
presence of ammonia in the steam from decompositionof hydrazine and oxygen that had
leaked in through faulty seals. Cleaning on the water side was not a factor; it had merely
uncovered the cracks. Another condenser suffered from erosion-corrosion on the steam
side caused by turbulence from calcium carbonate/sulfate deposits. Direct impingement
of high pressure/high temperature steam should be avoided.326
Pumps or valves for use in brackish or seawater include the cast duplex alloys,
255,2205, or Zeron 100 (UNS S32760), or the cast austenitic alloys such as CM3M or
CK3MCuN. If alloys with less than 6% Mo are used, CP should be applied. In all cases
if the pumps or valves are out of service they should be drained and flushed with fresh
water.327
11.1 2.2 Power Generated from Alternative Energy Sources
Many different methods of generating electrical power from renewable energy sources
are being used or investigated. Water plays a key role in many of these technologies.
11.1 2.2.1 Hydroelectric
Hydroelectric plants, large and small, are increasingly being used to generate energy
from rivers. Large hydro-generating plants can have a capacity of more than 10,000 M W
(10 GW).Each of these large-scale systems requires a very large dam, or series of dams, to
store the enormous quantities of water required by the system. For example, the Kariba
dam in Zambia holds 160 billion m3 of water. In 1994, hydroelectric power represented
only 2% of the world’s primary energy consumption. In 1998, there was about 700 GW
of installed hydro capacity worldwide, generating about 2,600 TWh (2.6 x 1012 kWh) of
electricity per year, and producing 19% of the world’s electricity. Hydro power supplies
at least 50% of electricity in 66 countries, and at least 90% in 24 countries. It is estimated
that only 32% of the economically feasible hydro power potential worldwide has been
s34 Andications
developed so far. Small hydroelectric plants produce only a tiny fraction of the total
hydroelectricitygenerated,e.g., in 1990the installed capacity worldwide of hydro power
plants of less than 10 MW each was only 19.5 GW.328
In Europe, small plants in six countries have a capacity of 5,632 MW with an average
expected annual production of 23,105 GWh. Most of these small plants were built up
to 120 years ago to serve local needs because electricity transmission was not possible
then. Some of these old plants have been tumed into museums, others have been closed,
and some have been modernized and fitted with new turbines. One such plant is at
Laufenberg, Switzerland, near the German border. It started production in 1914 using
10 turbines to produce 40 MW and has since been gradually upgraded until it was
capable of generating 110M W by 1992.The critical part of the turbines is the runner. It is
exposed to abrasionfrom entrained sand and gravel, cavitation, high stress from pressure
distribution, and radial pull from the magnetic field of the generator. The runners in the
present turbines are made from a soft martensitic stainless steel (UNSJ91540)nominally
containing 0.05% C, 13%Cr, 4% Ni, and 0.5% M O . ~ ~
An early hydroelectric system that still provides large quantities of hydroelectricity
harnesses some of the power of Niagara Falls on the border between Canada and the
United States. In 1759, Daniel Joncairsdug a ditch above the falls on the American side
and diverted water to a waterwheel to power a small sawmill. Over the years other
projects were undertaken to use the power of the Niagara River but it was not until 1881
that a small generating station was built, which provided electricity to light the village
of Niagara Falls, Canada and to provide power to several mills. Today, the Niagara
generating stations supply one quarter of all power used in New York State and Ontario
and are the biggest producers of hydro power in North America.
The normal flow of water over Horseshoe Falls is approximately 100,000 f$/s
(2,800 m3/s) with a measured peak flow of 225,000 fi?/s (6,370 m3/s). A concrete and
steel dam extends 2,200 ft (670m) to the international boundary and 18 gates control the
flow over the falls. Flow can be increased or held back for diversion into the canals and
tunnels that feed the turbines. When water is being diverted to generate electricity, flow
over the falls drops to a mere 50,000 fi?/s (1,400 m3/s).330
11.1 2.2.2 Tides
The generation of electricity from tides is similar to hydroelectric generation, i.e., water
flowing through a turbine. The simplest system for tidal plants, an ebb-generating sys-
tem, involves a barrage across an estuary. Sluice gates on the barrage allow the tidal
basin to fill on the incoming tides and to exit through the turbine system on the ebb tide.
Systems that generate power from the flood tide are possible, but are less favored than
ebb-generatingsystems.There are two commercialscalebarrages in operation:a 240-MW
bulb turbine at La Rance, France and a 16-MW plant at Annapolis Royal, Canada?31
The Annapolis Royal is an ebb-generating system taking advantage of the 17m tides
in the Bay of Fundy. Unlike the bulb turbine (that drives a separategenerator) used at the
La Rance plant, the Annapolis Royal plant has the world’s largest axial rim, straight flow
turbine generator. The turbine blades, each weighing 7,750 kg, were cast from a 16%Cr,
5%nickel martensitic stainlesssteel (AvestaSheffield 248 SV). Each blade is welded to the
carbon steel runner and the joint is then covered with a thick weld overlay of 316L. The
248 SV alloy was also used to fabricate the 18,730-kg runner ring. The bearing surface at
the edge of the runner ring was overlaid with 904L before machining. Localized corrosion
of the hub in the area of the blade roots has been overlaid with stainless steel. Hubs on
future units are likely to be made from cast stainless steel or from carbon steel completely
weld overlaid with stainless steel. This installation produces 30 GWh of electricity each
year.332
Tidal turbines that are fixed to the sea bed in a tidal current have been under devel-
opment for years. They became closer to reality with the installation of a 15-kW proof of
concept turbine on Loch Linnhe, Scotland. Devices to harness the energy in waves are
also being actively developed and evaluated.331
11.1 2.2.3 Offshore Wind
Another major development involving offshore structures is the siting of power-

generating windmills in coastal waters, for example, in the North Sea. Although they are
more expensive to build offshore they are an economic proposition because the strong
winds make the turbines more efficient. In addition, offshore windmills do not encounter
the opposition that land-based ones sometimes do on the grounds of noise and unsight-
liness. As with the early oil rigs, most offshore windmills are currently being sited in
shallow coastal waters.
Denmark is a world leader in wind power and plans to develop 750 MW of offshore
wind power by 2008 in addition to the 1,755 MW already installed on land. Denmark's
shallow coasts are very suitable for wind power since the water is less than 10 to 20 m
deep as far out as 30 km from land. Offshore wind turbines are built on large concrete
platforms or drilled down into the seabed. Costs are estimated at 50 to 90% more than
the investment needed for land developments. Germany is the world's biggest wind
power producer with a capacity of 4,447 MW installed by the end of 1999. Germany
is also planning offshore wind power installations, with the first one being a 1,OOO-
MW windpark near Heligoland, due for erection in 2006. While the use of wind power
is accelerating in Germany most projects are land-based because of Germany's limited
c ~ a s t l i n eThe
. ~ ~United Kingdom is also committed to the use of windpower, with much
of it coming from offshore installations. Five hundred and forty units are planned that
will supply 1%of Britain's energy needs by 2004 to 2005. Eighteen companies have leases
for 13 sites that will produce between 1,000 and 1,500 MW of power. The windmills, each
more than 100 m high, will be erected in groups of 30 located between 1.5 and 10 km
offshore?34
11.1 2.2.4 Ocean Thermal Energy Conversion
The conceptof ocean thermal energy conversion (OTEC)datesback to 1881, when Jacques
DArsonval envisioned the idea. He did not live to see his idea come to fruition, a task
536 Applications
completed in 1930 by his student Georges Claude. Although the theoretical efficiency
of OTEC is small (approximately2%), there are vast quantities of seawater available for
use in power generation. It has been estimated that there could be as much as 107 M W
of power available worldwide.335
OTEC converts solar radiation stored in the ocean to electric power using the Ocean's
natural thermal gradient. As long as the temperature between the warm surface water
and the cold deep water differs by about 20°C (36"F),an OTEC system can produce a sig-
nificant amount of power. The economics of energy production today have delayed the
financing of a permanent, continuously operating OTEC plant. OTEC is a promising alter-
native energy source for tropical island communities that rely heavily on imported fuel.
OTEC systems can generate electricity using a closed-, open-, or hybrid system. In the
closed-cycle system, warm seawater vaporizes a working fluid, such as ammonia, flow-
ing through an evaporator.The expanding vapor drives a turbine coupled to an electrical
generator. The vapor is then condensed with cold seawater. The working fluid stays in
the system and circulates continuously. Titanium is suitable for the large heat exchangers
needed but is expensive, Cu/Ni alloys are not compatible with ammonia. Aluminum
alloys are preferred. Intermittent chlorination is proposed to control biofouling. The
closed-cycle system was the original concept envisioned by D'Arsonval.
In the open-cycle system warm seawater is "flash evaporated in a vacuum chamber
to produce steam at a pressure of about 2.4 kPa absolute. The steam produces electricity
via a turbine and generator and is then condensed by cold seawater. In the hybrid system
warm seawater is flash evaporated into steam which then vaporizes the working fluid of
a closed-cycle loop of an ammonia vaporizer. The vaporized fluid then drives a turbine
that produces electricity.
OTEC systems can also be used to do the following:
Desalinate.This is done by using surface condensers to recover fresh water from open-
or hybrid-cycle plants.
Support mariculture. Deep drawn seawater from an OTEC plant is cold, rich in nu-
trients, relatively free of pathogens, and available in large quantity so is an excellent
medium for growing phytoplankton and microalgae. These, in turn, support a variety
of commercially valuable fish and shellfish including some, such as salmon, lobster,
abalone, trout, oysters, and clams, that are not indigenous to tropical waters.
Extract minerals. In the past it has been uneconomic to pump the vast quantities of
seawater to extract some of the many minerals dissolved in seawater. With OTEC
this pumped seawater is already available and extraction processes are the subject of
research.
Provide refrigeration and air conditioning.The cold (5°C [41"F])seawater in an OTEC
system can be used to cool buildings close to the OTEC facilities and cool fish farms.336
The Natural Energy Laboratory of Hawaii has installed three different deep water
pipelines and conducted years of testing on heat exchangers. Pipelines are operating at
Keahole Point on the island of Hawaii, bringing in deep, cold seawater for OTEC and
aquaculture research and development. These pipelines range in diameter from 300 mm
to 1 m and have intake depths ranging from 650 to 700 m. The 1-m-diameter pipeline
11.1 3 Steam Svstems 537
has been in continuous operation for nearly 5 years, and the 300-mm pipeline of the
same design has been servicing Keahole for more than 10 years. All of these pipelines
are made of HMWPE. Some of early concerns were with fouling on heat exchangers but
it has been shown that biofouling in the heat exchangers and the pipeline on the cold
water side is nonexistent. Aluminum or titanium heat exchangers have been found to
be excellent for this appli~ation.3~~
11.1 3 STEAM SYSTEMS
Steam is an integral part of many industries including power generation,petrochemical,

chemical, and oil and gas production. The water used for steam generation has to be
selected, deaerated, and treated to avoid major corrosion problems within the boilers and
associated equipment, such as condensers.Saltsor ions that can form deposits on the high
temperature surfaces in steam systems must be controlled to avoid underdeposit attack.
Of the total annual cost of corrosion to U.S.utilities of some $3.5 billion, around
$600 million has been estimated to be caused by turbine corrosion alone. Major corrosion
problems also occur in refineriesin feedwaterpiping, boiler tubes, superheaters,turbines,
and steam and condenser systems.
Preboiler corrosion is usually caused by oxygen pitting, flow-assisted corrosion and
deposition. Most of the oxygen present in feedwater is removed mechanically in the
deaerator, which typically reduces the oxygen content to t20 ppb. Even at this level
corrosion can occur in the feedwater system, so chemical oxygen scavengers such as
hydrazine or sulfites and organic scavengers such as hydroxylamines, ascorbic acid,
hydroquinone, or oximes, with or without catalysts, are added to the feedwater. Most
attack occurs off line or during startup or shutdown so suitable operating procedures
must be used. It is usually also necessary to adjust the pH of feedwater to 8 to 9 to avoid
pitting. Various industry guidelines exist that recommend maximum contaminant levels
in feedwater systems (Table 11.8).
The levels of oxygen and metal oxides permitted by ASME vary with pressure
(Table 11.9).
Boilers can suffer from caustic attack when the small amounts of sodium hydroxide
usually present are allowed to concentrate. In the worst case this can lead to caustic
embrittlement or caustic SCC. Flow-assisted corrosion occurs in boiler feedwater lines
and in heat recovery steam generators when design velocities are high. This type of
attack is exacerbated by high heat input, pH, or oxygen. High levels of oxygen or carbon
dioxide are the usual cause of corrosion in condensate systems.-
The use of sodium sulfite as an oxygen scavenger has been common in low and
medium pressure boilers since the 1930s. It is still used today in boilers operating at
t900 psi (6.3 MPa). In medium pressure boilers, 900 to 1,500 psi (6.3 to 10.4 MPa)
sodium sulfite can decompose and cause severe boiler corrosion. For high pressure boil-
ers, >1,800 psi (12.5 MPa) volatile scavengers such as hydrazine are more usual. Some
admiralty brass (UNS C44300) condensers have failed from carryover of sodium sulfite
decomposition products. These failures were diagnosed as SCC, caused by moist sulfur
Table 11.8 Typical Industry Recommended Guidelines for
Oxygen and Metal Oxides in Boiler Feedwater Systemsm
Contaminant, pg/L (ppb)
Guideline Oxygen Iron Copper
ASME a t7 (10-100 <lo-50
TAPPI t7 t 10 t10
EPRI t5 t10 <2
"ASME guidelines are for units with superheaters, turbine
drives, or process restrictions on steam purity.
bTAPPI guidelines are for systems operating at >900 psig
(6,300 kPa). Maximum oxygen excursions are permitted at
25 pg/L (ppb) for 2 h.
CEPRl guidelines are for systems on coordinated pH-
phosphate control for systemswith reheat. Levels are doubled
for cycling duty and are permitted for a period of 2 weeks/y.
dioxide from thermal decomposition of the sulfite. This decomposition is increased by

increasing temperature and sulfite concentration and decreased by increased pH.=
Scale buildup and corrosion are major cost factors in industrial steam systems. These
problems are caused partly by lack of training of the people controlling water treatment.
Water purification equipment is now available that can produce high purity makeup
water. Water treatments that are now being used for utility units worldwide include the
following:
1. Congruent phosphate (Na/P04 molar ratios 2.2 to 2.8)

2. Coordinated phosphate using trisodium phosphate
3. Phosphate plus hydroxide/equilibrium phosphate
4. Sodium hydroxide
5. All volatile treatment
6. Oxygenated treatments (combined water treatment, neutral water treatment)
Table 11.9 ASME Requirements for Oxygen and Metal Oxides in Boiler Feedwater Systems at
Various Pressuresm
Pressure, psig (MPa)
0-300 301-450 451-600 601-750 751-900 901-2000
(0-2.07) (2.08-3.10) (3.114.14) (4.15-5.11) (5.10-6.89) (6.90-13.79)
Oxygen t7 t7 t7 t7 t7 <7
Iron tl00 t50 t30 t25 t20 t 10
Copper t50 t25 <20 <20 <15 t10
11.1 3 Steam Systems 539
The first four are boiler water treatments and the last two are feedwater treatments
that only affect the boiler water by keeping the feedwater corrosion products under
control.In addition, there are many combinationsof polymeric dispersants and chelating
agents with other chemicals. The most common is to use phosphate (plus hydroxide)
boiler water treatments, combined with chelants and polymeric dispersants in lower
pressure industrial boilers. Control of feedwater, steam, and condensate pH is achieved
by injecting ammonia or volatile amines and an oxygen scavenger into the f e e d ~ a t e r . ~ ~ ~
Hydrogen failures have occurred on water-cooled boilers using conventional water
treatment. These high pressure boilers were working at about 1,500 psig (10 MPa) and
were treated with phosphates added to the mud drum. No dispersants were used and
makeup water was deoxygenated in a deaerator followed by hydrazine additions. Cyclo-
hexylamine was added to control corrosion in the condensate system. The hydrogen
damage that led to tube rupture was initiated by poor control of the treatment,producing
low pH in the boiler. Condenser leaks had also contributed to the problem by introducing
chlorides into the system. Lack of cleaning and flow restrictions from the presence of
"window" repair coupons in some of the tubes contributed to the failures.34o
Coordinated phosphate treatments have been used for decades in high pressure boil-
ers. There are few constraints with this program in terms of materials of construction
or operational procedures. All volatile or oxygenated treatments impose rigid require-
ments on system integrity and on the alloys used in the feedwater heaters. As long as
deoxygenated water is held in a certain pH range, steel will naturally form a protective
magnetite film. The phosphate system buffers the water to keep it in this pH range even
if small amounts of impurities or corrosion products enter the boiler.
One problem with this program has been hideout, in which the soluble phosphate
concentration decreases as the boiler load or steam flow increases. It is thought to be
caused by precipitation of phosphate salts, which can be acidic, resulting in an increase
of the bulk water pH. Local hot spots can develop as part of this phenomenon. The other
problem has been caustic gouging caused by improper treatment control or sodium
leakage from the demineralizers. Caustic gouging and acid phosphate attack have been
confusedbecause they are morphologicallysimilar and the elevation of pH during phos-
phate hideout seems to preclude acid attack. Salts can become concentrated underde-
posits formed in the boiler. If there is a small excess of caustic or if acid is present in the
boiler, the pH under the deposit can become high enough to cause caustic gouging or
low enough to produce hydrogen that, in turn, reacts with carbon in the steel and causes
decarburization. The phosphoric acid/caustic system is intended as a buffer in boilers
to avoid these swings in
In some cases phosphates can combine with iron corrosion products and produce
characteristic corrosion morphologies and corrosion products, such as NaFeP04. Phos-
phate corrosion can have the following causes and characteristics:342
Congruent control, the feeding of monosodium phosphate, disodium phosphate, or

both
Chemical treatment outside of control limits
Significant water side deposits
540 ADDlications
The presence of corrosion products containing NaFeP04

The absence of a dense magnetite layer
Hydrogen produced during corrosion
Occurrence of overheating
The presence of a concentrationmechanism, such as boiling within porous particulate
matter
Overlaying deposits containing porous magnetite and elemental copper
Metal wastage in the form of gouges, pits, and grooves
Corrosion rates up to 90 mpy (2.3 mm/y)
Steam can also become contaminated with chlorides, which cause corrosion of stain-
less steel equipment. For example, a 316 plate heat exchanger was being used to inter-
change heat between two streams of steam condensate. Fluid temperatures ranged from
140 to 90°C. Contamination by chlorides in the condensate caused SCC failures after
about 7 years of service.M3The main contaminants causing corrosion in steam equip-
ment, however, are oxygen and carbonates. High oxygen causes general and pitting
attack on carbon steels, low alloy steels, and copper alloys and, in conjunction with high
chlorides, can cause SCC, pitting, and corrosion fatigue on stainless steels. Carbonates
contribute to corrosion and can assist erosion corrosion by increasing pH.
Aerated water is often used to refill equipment after draining or to make up service
losses. Dosing the tanks with ammonia and hydrazine can reduce the oxygen but any
ammonium carbonate produced breaks down at higher temperatures, causing carbonate
corrosion. The use of nitrogen to sparge and blanket water storage can reduce corrosion
and scaling in steam equipment and reduce the use of oxygen-scavenging chemicals,
with low nitrogen consumption if nitrogen is used for online deaeration.M
11.14 DESALINATION
The possibility of transforming saline water into potable water by the removal of salt has
been postulated for many years. Sir Humphry Davy experimented with copper and iron
immersed in seawater in separate containers, connected electrically through a cotton or
asbestos membrane in a n intermediate vessel. He concluded that ” . . . the water in this
intermediate vessel continuallybecomes less saline; and undoubtedly, by a continuance
of the process, might be rendered fresh.”M5These tests were part of his investigations
that led to the development of CP for copper bottoms on wooden warships.
Desalination or desalting, is the process that separates saline water into two streams,
the freshwater stream and the concentrate or brine stream. Energy is needed for this
process and a number of different technologies are used. Desalination has now become
common as a consequence of oil production in areas of the world where water is scarce
and often heat and/or electrical power are cheap and plentiful, such as in the Middle
East.
The majority of people living along the shores of Florida and California get their
drinking water by desalination. Many island nations lack sufficient ground water and
also utilize desalination.Desalination must reduce typical seawater at about 35% salinity
to an acceptable drinking water standard of below 500 ppm TDS.=
The conventional technologies for desalination are based on evaporation and con-
densation or on membranes. An alternate technique has recently been developed in
New Mexico. The Rapid Spray Distillation@process ejects saline water at high velocities
through special nozzles. Evaporation takes place in a single-stage process, fresh water
is condensed, and salts are removed as crystalline solids. Water recovery efficiencies of
95% are claimed and construction costs are estimated to be half of present desalination
systems. Operating and maintenance costs should also be greatly reduced.3q7A number
of other processes, such as freezing, membrane distillation, solar dehumidification,and
other solar and wind-driven desalters, have also been used to desalinate.=
11.14.1 Thermal Desalination Processes
About half of the world’s desalted water is produced by distillation. The modern trend
is toward more efficient energy use by combining desalination with cogeneration of
electricity. To do this economically in a desalination plant, the operating temperature
is reduced by applying a vacuum to the system. This reduction of the boiling point is
important in the desalinationprocess to reduce the energy needed (by allowing multiple
boiling in successive vessels) and to reduce scaling. Chemicals may still be needed to
control scaling or be added to permit the use of higher temperatures. There has also been
interest in using nuclear power for desalination,but to date the only operating units are
in Kazakhstan and JapanM9
11.14.1.1 Multistage Flash
Water can be made to boil just as effectively by reducing the pressure as by raising
the temperature. Water and steam together in a closed vessel are at a temperature and
pressure that are so close that any reduction in pressure causes immediate boiling of
some water, with a “flashing”effect. A multi-stage flash (MSF)distillation plant consists
of a series of chambers, usually 20 or more, each operating at a lower pressure than the
last. As heated brine flows from one chamber to the next, some of it flashes off into water
vapor. This passes through moisture separatorswhich remove any entrained droplets of
brine. The water condenses on colder condenser tubes and drops as distillate into trays
from which it is led away to storage.
In passing from chamber to chamber the brine becomes progressively cooler. Some
of this brine is mixed with seawater from the heat rejection stages and is then pumped
back through the condenser tubes to act as the coolant in the condenser section of each
chamber, becoming progressively hotter as it picks up the latent heat of condensation.
Consequently, when it reaches the heat input section, and before reentering the first flash
chamber, it needs to be raised in temperature only by the few degrees necessary to allow
the vapor released in the flash chamber to condense on the condenser tubes. This extra
heat is normally supplied by low pressure steam.35o
The MSF process is the most widely used technology for seawater desalination.The
total capacity of all seawater desalination plants worldwide grew from about 32 million
imperial gallons per day (MIGD) (145 ML/d) in 1966, to 3 billion imperial gallons per
day (BIGD) (14 BL/d) in 1997. The MSF process alone grew from a total capacity of
30 MIGD (140 ML/d) in 1966, to 2 BIGD (9 BL/d) in 1996. The MSF process produced
about 95% of the world’s seawater desalination in 1966, about 91% in 1976, and about
75% in 1997. In 1997,the total installed capacities of MSF plants in the Gulf Cooperation
Council (GCC)countries reached almost 81%of the world’s total installed capacity, with
Kuwait alone having about 15%.The actual available production capacity of MSF plants
in Kuwait reached 283.2 MIGD (1,287 ML/d) in 1999.
Kuwait, like other GCC countries, has adopted the MSF technology as part of dual-
purpose systems providing power and water cogeneration. The MSF process has proved
to be the most reliable and safest source of the highest purity and best quality fresh water
from the sea, regardless of the feedwater quality which, in Kuwait, is characterized by
a high silt content. The distilled water produced from MSF plants usually has a TDS
content of less than 30 ppm. This water must then be stabilized by blending it with
brackish water, pH adjustment, and disinfection. The final product water is suitable for
all types of fresh and domestic uses.
Some of the circumstances that have resulted in the present extensive utilization of
MSF plants in Kuwait are the following:
The sudden, vast increase in the industrial, social, and economic growth in Kuwait
since the 1960s could not be sustained without sufficient power and freshwater re-
sources. The MSF and steam boiler turbine generator combinations were the only
suitable candidates for the large power and water cogenerationplants needed then.
The MSF process is thermally driven, which requires relatively high thermal energy
inputs. The abundance of oil as the primary source of thermal energy made such
extensive application of the MSF process affordable and held in check any concern
over its high energy consumption.
MSF units with very large capacities, e.g., the 6 MIGD (27 ML/d), which became
the standard capacity in Kuwait, favored the MSF process over other commercially
available processes. Such a capacity proved to be very suitable for maximum plant
utilization under the prevailing conditions in Kuwait.
The use of MSF technology in Kuwait has some major advantages as follows:
Very high reliability and safety record

Very high product water quality
High independence regarding feedwater quality
Availability of highly experienced manpower for operation and maintenance
Capability to provide huge amounts of high quality fresh water to meet the ever-
increasing demand with minimal impact on the environment
MSF technology also has some disadvantages as follows:
Very low water recovery ratio. Typically about 10%of the total feedwater to the MSF
is recovered as distilled water.
High thermal energy input. Typically 290 kJ/kg of product water puts the MSF process
in the highest energy consumption category in comparison to other commercially
available desalination processes.
There is inflexibility in power and water cogeneration systems because the MSF relies
on the steam imported from the SBTG as the main source of energy.
It has relatively high capital
The current materials of construction for MSF plants in Kuwait may be summarized
as follows:351
Evaporators. A minimum corrosion allowance in chamber walls of 12.7 mm for the

first and last flash chambers, and 9.3 mm in other chambers, a thickness of >38.1 mm is
required to prevent structural failure. Some evaporators are lined with stainless steel
in high temperature stages and in areas below the demisters to avoid stage corrosion
and accumulation of iron oxide corrosion products in the recirculation stream. Brine
splash plates and brine orifices (high turbulence)are normally made of stainless steel.
Condensers. Tubes for the brine heater, heat rejection section, and the first and second
stages of the heat recovery section are made of Cu/Ni (66%copper, 30% nickel, 2%
iron, and 2%manganese). Aluminum brass tubing is used for all remaining stages.
Water boxes. These are usually made of carbon steel clad with Cu/Ni or other
corrosion-resistant metals.
Demisters. Ni/Cu wire mesh or 316 stainless steel demisters are usually used in all
stages. The knitted wire mesh demisters consist of a bed, usually 10 to 15 cm deep, of
fine diameter wire interlocked by a knitting operation to form a wire mesh pad with
a high, free volume usually 97 to 99%.
Product water troughs. These are difficult to repair and to replace and suffer corrosive
attack from distillate water and from flashing brine (on the lower surface). If the
vent cooling section is near the trough, noncondensable gases may also contribute to
corrosion.Materials used for product water troughs are solid 316 stainlesssteel, 90/10
Cu/Ni, or carbon steel with liberal corrosion allowance.
Pumps. 316 stainless steel impellers, casing, and shafts are recommended to obtain
maximum service life in large feed water and brine recirculating pumps in any type
of desalination plants. For smaller pumps and for product water service bronze,
Ni-Resist@and cast iron impellers or casing are acceptable.
The first-generation MSF plants were designed for 20 years of life with copper-nickel
tubing, and various combinations of carbon steel, coated carbon steel, copper-nickel,
544 ADD^ ications
and 316L stainless steel for the water boxes, piping, flash chambers, and distillate trays.
Carbon steel and coated carbon steel required more maintenance than expected and were
gradually replaced with lined or solid copper-nickel and 316L, which have performed
better. Titanium tubing has been used in a number of heat reject sections and in portions
of a few heat recovery sections as an alternative to copper-nickel tubing, but has not been
used for water boxes, piping, or flash chambers.
Titanium tubing was first used in all the exchangers of the 1.5-MGD capacity MSF
plant in St Croix, Virgin Isles in the mid-1960s. Thin-wall welded titanium tubing is rou-
tinely specified for brine heaters with temperatures up to 140”C,evaporators, condensers,
air ejector condensers, and other heat exchangers. More than 14 Mm (4,250 tonnes) of
tubing are currently installed in plants worldwide. The heat recovery sections operate at
higher temperatures than in heat rejection but titanium is also being used successfully in
this service. For example, the A1 Taweelah plant uses 2,233,000 m (556 tonnes) of 34-mm
OD, 5-mm wall titanium tubes in heat reje~tion.3~~
In two locations, Al-Jubail and Al-Khobar, in Saudi Arabia, two desalination plants
with a combined capacity of almost 350 MGPD (1,300 ML/d) of water per day used
6,854,440 lb. (3,109,174 kg) of titanium tubing. Based on 1.25 in. (3 cm) OD x 0.020 in.
gauge (0.51 mm) tubing, this represents 45,363,600 ft (13,827km)of titanium tubing. De-
salination service is an excellent environment for thin-wall tubing because the corrosion
rate on both the steam side and the water side is essentially nil. Tube wall thickness as
low as 0.016 in. (0.4 mm) has been successfully used with a heat transfer rate higher
than 90/10 copper-nickel tube of 0.049 in. gauge (1mm). In addition to improved heat
transfer, the thin-wall tubing is an economical choice. In a properly designed MSF plant,
vibration is not a serious condition because steam velocities are extremely low compared
to a power plant surface ~ondenser.3~~
The complex at Al-Jubail consists of 40 plants, each rated at 23,000 m3and using about
23,000 tonnes of stainless steels and 40,000 tonnes of copper-nickel tubing. Another
installation at Jebel Ali in the UAE Emirate of Dubai linked eight units together. The
total design capacity of these plants is 275,000 m3/day and each of the evaporator shells
weighs 1,000 tonnes. Copper-nickel alloys are normally used at the hot and cold ends of
the plant where corrosive conditions are most ~evere.~”
Cu/Ni (90/10) is often used for piping, water boxes, evaporator shells, tube plates,
etc. and 70/30 Cu/Ni is used for tubing in large heat exchangers that produce up to
57,000 m3 of water per day. About 40 water boxes are used in a typical unit and these
are usually 2 to 3 mm clad plate. Cu/Ni (90/10) piping is used for both natural seawater
and hot deaerated brine. Pipes are seamless up to about 400 mm, with pipes made from
plate used for larger sizes, up to 1.37 m OD.214
Failures of 3,550 90/10 Cu/Ni heat exchanger tubes have been reported from a de-
salination plant on the east coast of Saudi Arabia, despite the excellent performance of
the alloy in seawater systems elsewhere. Studies have shown good performance of the
alloy in Arabian Gulf water at velocities up to 4.97 m/s and with ammonia concentra-
tions up to lo-’ mol/L. Attempts have been made to replace copper-nickel materials with
cheaper modified aluminumalloys. The alloy2778(A1with2.78% Mg, 0.71%Si, 0.19% Cu,
0.01% Cu, 0.02% Mn, and 0.29%Cr) in both the cold rolled and annealed conditions has
shown excellent resistance to pitting in Arabian Gulf water.'39
In Abu Dhabi virtually all of the potable water is produced by MSF desalination.
More than 220 million gallons of drinking water is produced daily. There has been vapor
side corrosion on some of the 70/30 Cu/Ni condensers in the first three high temperature
cells of the units. This problem has been investigated using electrochemical techniques
in aqueous solution that simulates corrosion on the outside of the condensers. This
investigation supports the view that the corrosion is started by oxygen leaking into the
cells. The oxygen produces copper oxide on the tube surfaces, which is then dissolved
in the carbon dioxide-rich condensate. Although the nickel in the alloy dissolves with
the copper it does not seem to play a role in the corrosion mechanism.355
Southern Peru Copper Company's (SPCC) facility located in 110, Peru uses MSF de-
salination plants to produce high purity water for boiler makeup at the smelter power
plant, process water for various smelter and mining operations, and potable water for
the town and Port of 110. The first plant, producing 720,000 USGPD (2.7 ML/d), was
commissioned in 1966, followed by a second in 1976, with a capacity of 960,000 USGPD
(3.6 ML/d).
The ocean off the southern coast of Peru is noted for being some of the world's richest
fishing waters. Predesign concerns focused on feed water highly polluted by offshore
guano deposits. In addition, frequent occurrences of "red tides" cause severe anaerobic
conditions that increase the risk of corrosion. The design included deaeration and vent
systems able to remove the significant amounts of carbon dioxide released from the
seawater. The evaporator, operating at a top brine temperature of 230°F (llO"C), used
90/10 Cu/Ni tubes and tubesheets, with mild steel shells. Both of these systems are
still functioning with the original tubes and carbon steel shells. Plant reliability and
performance have been outstanding, with online times exceeding90% at design capacity
and product purity. The shell material selection is testimony to the fact that carbon steel,
when in a properly controlled environment, does have a long life expectancy and can do
an excellent job in high temperature seawater MSF plants.356
Low carbon steels are often used for piping, heat exchanger heads, and tanks, even
though the corrosion rate is high compared with other metals. Carbon steels usually fail
from pitting, which is more intense when mill scale is present. Necessary conditions for
satisfactory service of carbon steel are the following:
1. Dissolved oxygen is <50 ppb.

2. pH >7; severe corrosion is likely at pH <6.
3. Velocity should be 1.5 to 2 m/s.
4. Temperature should be as low as possible. Carbon steel corrodes about twice as fast
in seawater at 120°Cthan at 80°C.
5. Galvanic couples should be avoided, e.g., copper tubes with carbon steel tubesheet.
6. Biofouling should be controlled.
7. There should be removal of noncondensable gases, e.g., oxygen, carbon dioxide, hy-
drogen sulfide, etc. by effective deaeration and venting.
546 ADDlications
External corrosion of carbon steel is often severe in desalination plant environments.

High performance coatings, e.g., silicon alkyd or silicon acrylic, should be used under
thermal insulation to avoid corrosion. Noninsulated components should be hot dip gal-
vanized at 2 oz/fi? (0.06 g/cm2) or coated with catalyzed epoxy on inorganiczinc primer.
Low alloy steels, with the possible exception of Cor-Ten A, seldom justify the additional
cost compared with carbon ~ t e e l s . 3 ~ ~
Modem desalination plants use stainless steels, often 316 but sometimes 317, in vent
piping, distillate trays, transfer troughs, evaporator vessel linings, and demisters. The
entire distillate system is often 316 following experience of corrosion of carbon steels by
this high purity water. The low oxygen levels in these plants permit the use of 316 to
handle boiling brine and seawater without sufferinginternal stress corrosion cracking.358
There have been reports of pitting failures of 316L distillate piping from a combination
of low velocity, poor welding, and the chemical treatment used.359
In MSF units the normal standard material is 316L and this is generally satisfactory.
If brine recycling is provided, 316L or 3152 can withstand the internal environment but
there is a risk of external stress corrosion cracking. Duplex stainless steels, such as 2205
or 2304, reduce this risk. The concept of once-through brine means that the evaporator
vessel must handle aerated chlorinated seawater at >lOo"C in the first chamber. It must
also resist the external environment, which might include boiling seawater on a hot wall.
There has been successful experience with the use of 254 SMO for the hottest first six
chambers, with UNS S32654for the sealing surfaces of flanges to avoid crevice attack. For
the remaining six chambers 3152MN was used. If temperatures are below 80"C, duplex
stainless steel such as 2205 can be used.m,msxl
Test racks with multiple crevice specimenswere placed in a seawater stream entering
the 1st flash chamber of an MSF plant in South America. This stream had 20,200 ppm
chloride, was at 99"C, air saturated, and contained 0.2 pprn residual chlorine. Some
deaeration and dechlorination occurred in the water before the test rack. Results from
these 5-month tests showed that 1.4435 (316L) and 1.4439 (317L)suffered crevice cor-
rosion up to 0.05 mm deep. Alloys 2205, UNS $31254, and UNS S32654 were resistant
and were not attacked. UNS S32654 has been used for critical components flanges with
sealing surfaces in the first stage of a 2,000 m3/d seawater MSF plant since late 1986.The
rest of these first-stage evaporators are UNS S31254. Conditions in this plant are 105°C
at the inlet, 8 pprn oxygen, and 0.2 pprn residual chlorine. No corrosion was observed
after 6 months in operation.m
Seawater MSF or vertical tube evaporation (VTE) heat exchanger tubes in 90/10
Cu/Ni, 70/30 Cu/Ni, and titanium have given excellent service. Alloy 400 and these
copper-nickel alloys have proved to be suitable alloys for tubesheets, support plates, and
water boxes.x2
Studies at the Al-Khafji Power and Desalination Plant in Saudi Arabia examined
vapor-side corrosion in the MSF units. In acid-dosed plants almost all of the CO2 is
removed in the decarbonator; in additive treatment plants CO2 and 0 2 are present in the
noncondensable (NC) gases. Other gases such as hydrogen sulfide, ammonia, bromine,
and chlorine may also be present in significant amounts. It was found that the corrosion
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rates of copper-nickel in the vent lines were much higher than when exposed in the
evaporators. Sulfur was invariably present in corrosion products on copper-nickel in
the vents. Carbon steel in the early stage vents corroded more than carbon steel in the
evaporators. In the later stages, corrosion in evaporators was much higher. In either
evaporators or vent lines 316L showed very little corrosion. The highest corrosion rate
was found in the middle stage units for all the alloys.This was explainedby the combined
effect of temperature, air leakage into vent lines, and cascading of NC gases, together
providing the most favorable conditions for corrosion in these particular stages.363
The Royal Commission power, desalination, and seawater cooling complex at
Madinat Yanbu Al-Sinaiyah (MYAS),Saudi Arabia includes six 380 m3/h MSF seawater
desalination units. Each unit is designed for a top brine temperature of 121"C,employs
decarbonationusing sulfuric acid for scale control, and has a performance ratio of 19 kg
of distillate per 1,000 Kcal heat input. Fifteen years of experience with the existing de-
salination units and the current desalination technology has been used as the basis for
selectingmaterials for the recently installed Desalination Units 7 and 8 (570m3/h each)in
order to avoid corrosion and improve plant reliability. Notable changes from the existing
plant materials are as follows:
Solid NAB waterboxes and crossover pipes instead of carbon steel lined with alu-
minum bronze
Evaporator stages (1to 28) lined with stainless steel instead of only the high temper-
ature stages (1to 6) and stage 28
Stainlesssteel tube support plates for all stages instead of stainlesssteel support plates
only in the high temperature stages (1to 6) and stage 28
Alloy 825 steam jet ejectors instead of 316L
Bolted arrangement of evaporator waterbox tube plate and shell instead of welded
construction
Specifications for the new units, aimed at avoiding problems found on the existing
units, are summarized as follows:
Brine recycle pump discharge and the brine heater bypass valves: metal-seated valves
instead of rubber seats
Lubricating water system: stainless steel piping instead of PVC
Evaporators vent and drain pipe: all stainless steel piping instead of stainless steel for
stages 1to 10 and then FRP
Major pumps motors: totally enclosed fan-cooled type for all major pumps including
brine recycle pump motors instead of Class 2 outdoor type
Product water tray: weld passivation and proper preservation
Waterbox liner: solid NAB waterboxes and two-pass evaporatorsinstead of four-pass,
avoiding elaborate liner arrangement
Crossover pipe and tube plate: solid NAB crossover pipes instead of carbon steel clad
with aluminum bronze; tube plates bolted instead of welded
Previous Page
548 ADolications
Evaporator roof and tube support plate: all evaporator roofs clad with stainless steel
and all stainless steel tube support plates
Ejector: alloy 825 instead of stainless steel
Acid supply piping: carbon steel without polypropylene lining.=
11.14.1.2 Other Distillation Processes
Other distillationprocesses in industrialuse are separated according to their heat source.

These are multiple effect distillation (MED) in which the latent heat comes from a solid
surface, and vapor compression distillation (VC) in which the latent heat is obtained
regeneratively.Low temperature multi-effect desalination plants operate at much lower
brine temperatures than MSF. This means that 316 is normally adequate for the evapo-
rator although UNS 91254 and 2205 have also been used in this application.361
The Ruwais refinery in Abu Dhabi was fitted with ten desalination units: six were
temporary to provide fresh water during construction, and four were for permanent
use. All are low temperature package units based on MED supplemented with ejector
VC. Maximum distillation temperature is 59°C. Severe crevice corrosion occurred at
the joints between titanium tubes and alloy 904L tubesheets during the early stages of
operation. Anodes, initially aluminum alloy but later replaced with iron, were installed
and provided effective CP. Erosion-corrosion attack on 90/10 Cu/Ni ejector condensers
was mitigated by replacement of tubes with alloy UNS 91254. It was concluded that
low temperature desalination plants could be successfullymade from stainless steels as
long as CP was provided and that hot external surfaces could be protected from pitting
and SCC from the marine atmosphere.365
11.14.2 Membrane Desalination Processes
Membranes are used in two commercially important desalting processes: electrodial-

ysis (ED) and reverse osmosis (RO). In each of these processes membranes selectively
remove salts from water. ED was introduced commercially in the early 1960s and is a
voltage-driven process that uses an electrical potential to move salts selectively through
a membrane. RO is a newer, pressure-driven process.
11.14.2.1 Electrodialysis
Electrodialysis(ED)desalinateswater by using membranes that will allow either cations

or anions to pass between a pair of electrodes.These membranes are arranged alternately,
with an anion-selectivemembrane followed by a cation-selectivemembrane and a spacer
sheet between each pair of membranes. This spacer permits water to flow along the
face of the membrane, thus providing a channel that carries feed (and product) water,
while the next channel carries brine. As the electrodes are charged and saline feedwater
flows along the product water spacer at right angles to the electrodes, the anions (such
as sodium and calcium) in the water are attracted through the membrane toward the
positive electrode. This dilutes the salt content of the water in the product water channel.
The anions pass through the anion-selectivemembrane, but cannot pass any farther than
the cation-selectivemembrane, which blocks their path and traps the anions in the brine
stream.
Similarly, cations move in the opposite direction through the cation-selective mem-
brane to the channel on the other side. By this arrangement, concentrated and diluted
solutions are created in the spaces between the alternating membranes. This pair of
membranes separated by a space are called “cells.” Several hundred cells with elec-
trodes makes up a membrane stack. Feedwater passes simultaneously in parallel paths
through all the cells to provide a continuous flow of desalted water and brine from the
stack. Chemicals may be needed to reduce scaling in the stacks.
In the early 1970s, the electrodialysisreversal (EDR)process was introduced that uses
the same general principle as a standard ED plant except that the product and the brine
channels are identical. At intervals of several times an hour, the polarity of the electrodes
is reversed, and the flows are simultaneouslyswitched so that the brine channelbecomes
the product water channel and vise versa. The reversal process is useful in breaking up
and flushing out scales, slimes, and other deposits in the cells before they can build up
and create problems.
11.1 4.2.2 Reverse Osmosis
In reverse osmosis (RO), saline feedwater is pumped into a closed vessel where it is pres-
surized against a membrane. Different membrane configurations are used for RO, the
most popular being spiral wound and hollow fiber. Some of the water passes through the
membrane with the remaining feedwaterbecoming increasinglysaline. Someof this feed-
water is discharged without passing through the membrane in order to prevent the salt
content increasing too greatly. If this is not done precipitationof supersaturated salts and
increased osmotic pressure across the membranes can develop. Pretreatment to remove
suspended solids is important to prevent salt precipitation or microbial growth forming
on the membrane surfaces. The water is then prepared for distributionby adjusting the
pH and posttreatment to stabilizethe water by removing gases such as hydrogen sulfide.
Another development in the RO area has been the use of membranes called “nanofil-
tration” (NF), which are more porous to the passage of dissolved solids. This process is
used to soften water by removing mostly divalent ions, calcium, and magnesium. The
rejection by NF membranes of monovalent ions, like chlorides, is much lower than with
RO membranes and they are being used even where the feedwater is essentially fresh,
although still containingdissolved solids that cause hardness. NF membraneshave been
used effectively to soften seawater. The NF softened seawater as a feed to distillation and
RO processes offers the potential of significant improvement in seawater desalination
costs. There is also an increased interest in the use of membranes for municipal potable
water treatment.318
550 ADDlications
RO plants operate in pressurized water up to 90 bar (9,000 Wa), temperatures up to

40"C, with industrial and biological contaminants and chlorine additions up to 30 ppm.
Under these conditions316L, 317L, duplex stainlesssteels, and 904L all have experienced
localized corrosion. The optimum material for this duty is one of the 6% Mo austenitics,
such as 1925hM0.~~ These materials are also used for high-pressure seawater intake and
release systems and tubes for RO desalination.m UNS S32760 has been used for high
pressure feed and brine reject pumps in RO plants. The pressure in these lines is typically
around 70 bar (7,000 P a ) and for many pipe sizes this can be accommodated with
schedule 10s pipe in this alloy, while schedule 40s is required for 6% Mo austenitic.=
There has been sporadic use of 317L, 904L, and 2205 as alternatives to 316L, and some
use of 6% Mo austenitic stainless steels in vent condensers and in seawater piping.
While each of these materials has its particular usefulness and advocates, the current
interest in larger and longer-lived plants requires materials that are likely to perform
well for up to 40 years. The 6% Mo stainless steels are particularly well suited for 40
plus years of life as tubing and fabricated components in a wide range of desalination
environments.366
Metals and alloys have been studied for their corrosion behavior in seawater de-
salination over a 15-year R&D program at the Kuwait Institute for Scientific Research
(KISR). Techniques included electrochemical, such as linear polarization, cyclic polar-
ization, open-circuit potential, impedance spectroscopy, together with crevice corrosion
and erosion-corrosioninvestigations. The main findings have been the following:
1. Metallic componentsused in the construction of an RO plant can greatly affect plant's

performance.
2. Electrochemical studies give an indication of the relative resistance to pit initiation,
propagation, and repassivationbehavior. Good correlation was obtained between the
electrochemical results and weight loss results.
3. Increased Cr, Mo, Ni, and N greatly improve the corrosion resistance of alloys in high
salinity seawater and concentrated brine.
4. The poor performance of 316L and 317L in electrochemical tests is attributed to the
nucleation and repassivation of pits on the surfaces of the alloys.
5. The incidence and intensity of crevice attack on 316L and 3152 were the most severe.
6. UNS S31726, S31254,S32550, N05500, N08904, N06625, N08367, and N10276 are good
alternatives for the construction of RO units, however, the initial cost is higher.367
Fouling control is a major challenge in RO. Biofouling causes decrease of water

productivity by half and increase of differential pressures across the RO membrane. In
addition, the membrane becomes susceptible to biological deterioration. Chlorination
has been the most used disinfection process to control biological activity in open sea-
water RO plants. Because commonly used types of membranes in seawater RO, cellulose
acetate and polyamide, are sensitive to chlorine, dechlorination is required to prevent
membrane degradation, usually by activated carbon filtration or excessive dosing of
sodium bisulfite. Most open seawater RO plants using the chlorinationdechlorination
technology, however, have exhibited extreme biofouling and aftergrowth, especially
when the seawater temperature rises above 25°C; so alternative disinfectants, such as
11.1 4 Desalination 551
chloramines and copper sulfate, have recently been proposed to control biofouling in
open seawater RO plants.=
The island of Gibraltar is entirely supplied by a combination of desalination pro-
cesses, RO, MSF, and an MED plant attached to a refuse incinerator. The RO plants have
had problems with membranes, chemical treatment, contamination with sewage, and
problems relating to the growth of algae. The chemical costs are reasonably stable and
can be apportioned as follows:
Potable water conditioning 62%

Chlorination 13%
Flocculant 1%
Antiscalant 14%
Bisulfite
RO is also being used to clean up waste water being returned to river systems. Poland
is using a large-scale RO and thermal desalination plant to punfy waste mine water that
is being carried by its two main rivers to the Baltic Sea. The plant is designed to treat
about 17,300 m3/day of highly brackish waste water from two coal mines. Each day
it recovers about 11,800 m3 of drinking and process water, 5,500 m3 of distilled water,
almost 300 tomes of pure sodium chloride for use in the chemical industry and 30 tomes
of calcium sulfate. The evaporator and crystallizer vapor bodies are made from UNS
S31254 and N08367. Low temperature piping is made from fiberglass-reinforcedepoxy
or polyester. Permeate and reject sections of the RO plant use PVC or polyethylene.
Pretreatment filters are reinforced concrete, epoxy ~ a i n t e d . 3 ~ ~
11.14.3 Waste Water from Desalination
In general, wastewater effluent from desalination plants may have the following types
of potentially adverse constituents and qualities:371
High salt concentrations(seawateris about 35,000 ppm; desalination plants discharge

brine with 46,000 to 80,000 ppm). Salt concentrations may be reduced by mixing
desalination plant discharges with other discharges, such as waste water.
Temperatures above those of intake water (about 5°F [2"C] increase at the point of
discharge)for discharges from distillation plants.
Turbidity levels above those of intake waters.
Oxygen levels below those of intake waters from deaeration to reduce corrosion
(distillationplants only).
Chemicals from pretreatment of the feedwater. These may include biocides, sulfur
dioxide, coagulants(e.g., ferric chloride),carbon dioxide,polyelectrolytes,antiscalants
(e.g., polyacrylic acid), sodium bisulfite, antifoam agents, and polymers.
Chemicals used in flushing the pipelines and cleaning the membranes in RO plants.
These may include sodium compounds, hydrochloric acid, citric acid, alkalines,
polyphosphate, biocides, copper sulfate, and acrolein.
552 A~~lications
Chemicals used to preserve the RO membranes (e.g., propylene glycol, glycerine, or

sodium bisulfite).
Organics and metals that are contained in the feedwater and concentrated in the
desalination process.
Metals that are picked up by the brine in contact with plant components and pipelines.
Waste disposal is particularly difficult in desalination plants that are located away
from the sea. In these cases the brine solution is usually disposed of by land spreading,
sewer systems, deep well injection, piping to the ocean, or solar evaporation ponds. The
disposal method chosen is dependent on geographical location, brine concentration, and
waste disposal costs.%
11.1 4.4 Standards and Specifications-Desalination
11.1 4.4.1 ASTM
B 552-98e1-Standard Specification for Seamless and Welded Copper-Nickel Tubes

for Water Desalting Plants
11.15 MINING
Acid mine drainage from abandoned mine lands is a major problem in many parts of
the world. This water can have very low pH and be contaminated with metallic ions.
One approach is to fill parts of the mines with limestone in an attempt to neutralize
the acidity.3n However, it is often still necessary to deal with this corrosive water. For
example, corrosion rates of lead in aerated, slowly agitated mine water (hardness 110 to
160 ppm) were 0.00635 to 0.00711 mm/y3”
Mine waters with pH down to at least 2 are encountered. At this low pH CF8M
becomes increasingly susceptible to localized corrosion and more highly alloyed steels
are preferred.73The pH of mine waters can range from 2.8 to 12.3, with the high values
usually caused by lime in the cement added to backfill. Chloride content varies from
5 to 25,000 ppm, with sulfates from 57 to 5,100 ppm. Most mine waters also contain
abrasive solids so materials used must be able to withstand corrosion and abrasion.
High manganese steels are often used for abrasive, noncorrosive waters.
Pumps for mine waters of 0 to 13 pH with abrasives are made from low-carbon
high-manganese steels, low alloy cast iron, ACI CD4MCu, CF3M, CN7M, ASTM A
743,304/316 stainless steels, or 27% Cr white cast irons. Piping is 316 stainless, CN7M,
Ni-Hard@cast irons or rubber-covered FRP. Corrosion mechanisms include pitting and
crevice corrosion with failures from abrasion, erosion, and cavitation in pumps. Tanks
used for mine waters are usually carbon steel lined with cement, epoxy, epoxy-phenolic,
neoprene, latex, sprayed polyresin coating, polyesters and vinyl esters, or baked phe-
nolic. CP may also be applied with the coating. Mine water tanks have been lined with
11 . l h Fish Farmine 553
natural or synthetic rubber, rubber-backed polypropylene, and glass. In specific appli-

cations, titanium and stainless steel tanks have been
Deep gold mines rely on refrigeration to provide acceptable working conditions.
Chilled water is passed through large bulk air coolers before being used for dust sup-
pression and rock drills. The water leaving these activities must be settled and possibly
treated before being returned to the refrigeration plants. Hydropower requires equip-
ment that can operate with fresh water. Pressures of between 14 and 18 MPa are devel-
oped by the hydrostatic head between the surface and the underground workings. The
water supplied for hydropower must be noncorrosive, after treatment if necessary, but
the main corrosion problem is in the lines handling the return water to the refrigeration
and treatment units. Alloys for handling this return water, contaminated with chlorides
and sulfates, have been ranked on a cost-life basis as 304L > 316L > 2205 > hot-dip
galvanized > mild
A horizontal centrifugal pump was specified to handle acidic (pH 1 to 2) mine
runoff water that was severely corroding the existing stainless steel and carbon steel
pumps. These pumps remove drain seepage water from open-pit coal excavation sites.
A polypropylene pump was fitted with a PVDF impeller to resist the abrasive coal fines.
Instead of the single-seal product flush, a PTFE-packed gland and product flush ar-
rangement was supplied. This pump has operated for more than 2 years moving 16 to 18
million gallons of acidic fluid per week at 1,800 gal/- and a head of 165ft (50 m) with
only minor maintenance. Another five polypropylene pumps have been successfully
used to meet lower flow and head applications in the open mine. Because of the rough
terrain and the pumps’ proximity to the edge of the water, all of these vertical units are
installed on pontoons made of foam-filled HDPE, high density polyethylene.376
Mine dewatering is often needed to maintain safe working conditions because the
presence of water can cause the open pit or excavation to become unstable and introduce
other hazards. Wherever possible, water is pumped from collection sumps. In other
cases wells are used to intercept and lower groundwater levels around open-pit and
underground excavations.A well field can consist of 30 or more wells, up to 2,000 or more
feet (>600 m) deep, and with production casing diameters up to 24 in. (0.6 m). Vertical
turbine line shaft pumps, 400 to 2,340 hp depending on depth, are used to remove well
water. Individualwell production capacities can decrease dramatically depending upon
aquifer system characteristics, which means that pumps must be selected that can cope
with both initial and subsequent conditions.This is especially true if the mine is expected
to be lowered substantially below the static water level. The wells must be of large-
enough diameter and deep enough to cater for these changes in pumping requirements.
A conservative approach is to specify various types of bronze for the main component^.^^
11.16 FISH FARMING
With the steady depletion of natural resources of finned and shellfish, it is becoming
more economic to rear many commercial species of fish in cages suspended in seawater
554 Applications
Figure 11.22 A raft of fish cages in Hong Kong is an untidy sight, as well as a source of pollution.
(Figure 11.22). These cages have open mesh sides to allow free flow of water through
them, bringing nutrients and oxygen and assisting the removal of feces and other de-
tritus. Most cages are made of net and nylon mesh, which despite antifouling coatings
become restricted by growths of molluscs and seaweed and require frequent cleaning
and maintenance.
Barnacles were found to be most damaging to fish cages in Hong Kong because of
their rapid growth and large accumulated weight. Removing them by smashing and
beating further shortens the useful life of the net cages?78
Following extensive trials, it has been shown that the use of mesh made from 90/10
copper-nickel diminishes the fouling problem, reducing the need for frequent mainte-
nance. It is also more resistant to storm and predator damage, which can result in the
disastrous loss of fish from the cage. Other advantages of copper-nickel mesh for the
fish farmer are improved growth rates and higher stocking densities as well as a cage
suitable for use at more exposed sites. While woven wire mesh can be used, the mesh
can also be made from expanded sheet metal. The mesh opening is chosen to suit the
fish size and water conditions. As an example, for salmon a 9-mm mesh is needed with
a 76% open area to allow easy water flow?%
While the biocidal properties of the 90/10 Cu/Ni alloy surface help reduce fouling,
there is no extra uptake or accumulation of copper by fish. They are as palatable as
those grown naturally and they appear to grow more rapidly than fish reared in cages of
11.I 7 Swimming Pools 555
other material. The excellent biofouling and corrosion resistance of 90/10 Cu/Ni mesh,
coupled with its mechanical strength and low resistance to water flow, make it a good
material for the large-scale development of underwater pens and enclosures?5o
A question was asked in the NACE discussion group about the most suitablematerial
for a centrifugal, low-pressure/high-volume, salt/brackish water pump for a shrimp
farm?79It was stated that shrimps would not tolerate copper-containing compounds, so
brass, bronze, and Ni/Cu were said to be unacceptable. Suggested materials included
FRP, cast iron or a nickel cast iron case with a nickel cast iron impeller, CF3M (316L;
as long as the temperature is below 140°F [6O"C]), NiResist@,Type 1,2, or D-2 (PWHT)
should be better than CF3M, with a maximum velocity of 45 ft/s (14 m/s), and if expense
is not a factor a 5 to 6%Mo stainlesssteel (PWHT)should out-performthe other materials
(Geoff).If solidssuch as sand or silt are present duplex stainless steel was said to be better
(T. Spence, Flowserve Corp). Ductile iron lined with vulcanized rubber (E.A. Martinez)
was also suggested and Simsite@(a resin-based material) impellers were reported to
have been very successful in seawater (A.A.).
11.1 7 SWIMMING POOLS
Swimming pools are traditionally built by casting concrete around steel reinforcement
in an excavated hole (Figure 11.23). The completed basin is then lined with plastic or
Figure 11.23 Many swimming pools are made from reinforced concrete. They
can be in ground, above ground, or some combination, as shown here. Once
construction is complete the pool will be lined with ceramic tiles. (Photocourtesy
556 A~~lications
tile. The gunite pool is a modification of this, in which the steel reinforcement, drains,
etc. are fixed in the excavated hole and then sprayed with high strength concrete from
a high pressure pump through a gun.In this method the walls and base are formed in
one operation, eliminating the potential problem at the wall to base joint produced in
cast concrete pools. Gunite pools can also be made in a wider range of shapes than can
conventional cast pools.38oConcrete or gunite pools are usually finished with ceramic
tiles or special cement rendering. Vinyl or other sheet plastic linings are also available,
as are pools constructed completely from FRP.
Many swimmingpools were built in the 1960sand 1970sas part of leisure facilitiesor
schools. These typically comprised a cast in situ reinforced concrete base and walls with
cast in situ promenade decks around the pool. These structures are now often in severe
distress from corrosion of the reinforcement in the walls and decks. The use of cathodic
protection to stop this degradationof the reinforcementis the standard repair method in
Denmark. Anodes are installed in boxes, recessed into the side walls of the swimming
pool. The economic benefits of this form of repair are so impressive that it is now also
being used in Great Britain where the first installation of this type was at Tenby Leisure
Centre in South Wales. In this installation, the swimming pool walls and base were
protected using anodes in the pool water. The support columns and other concrete parts
which also suffer from reinforcement corrosion are protected by internal anodes placed
in holes drilled in the concrete. The cathodic protection system is computer-controlled,
giving accurate, continuous control of the output current to each part of the structure
based on real-time readings from reference electrodes. Better, more even protection from
corrosion is achieved, increasing the life of the anodes. It also switches off the anodes in
the water when bathers are in the
Stainless steel fittings, supports, etc. are often used in swimming pool environ-
ments. Concrete ceiling supports (304 stainless steel) failed by SCC causing fatalities
in Switzerland and other countries.The cracking was caused by wet, low pH, high chlo-
ride atmospheresnear the ceiling. Alternative materials such as 904L, alloy 400, or alloy
825 should be considered for these applications;304,316, and 2205 stainless steel were
found to crack in laboratory tests simulating these conditions.382Stainless steel bolts
supporting air conditioning units and air channels failed by SCC in the Netherlands.
The units fell onto the ceiling which then collapsed into the pool. These SCC failures can
occur at temperatures below the normally accepted threshold temperature due to the
presence of aerosols with sodium hypochlorite and high internal stresses in fasteners
and threaded bars.383For structural members of a suspended acoustic ceiling 904L was
used at an alpine resort in Switzerland.
Outdoor swimming pools using 304 and 904L seem to work well, providing pools
that are hygienic, durable, and easy to cleanw An indoor hockey arena in Sweden was
converted into a temporary championship swimming pool using stainless steel sheets.
The base was constructed from sand covered with cellular plastic and coated fabric. The
pool manufacturer has installed more than 250 stainless steel pools which are popular
at health care and rehabilitation centers because of their hygienic proper tie^.^^
In fact, stainless steel swimming pools are becoming more popular world-wide.
They are much quicker to build than conventional concrete and tile pools, some 9 days
11.1 8 References 557
compared with 10 to 12 weeks. The first unit to be built in Canada was a 15 x 25 m pool
in Cold Lake, Alberta. These stainless steel pools use 304 or 316 panels bolted together.
The panels are laminated on the water side with 1.5-mm-thick PVC that makes the seal
between panels and is attractive. The oldest known stainless steel pool of this type is a
35-year-old pool in Munich, Germany.%
Solar panels for water heating are becoming increasingly popular as auxiliary equip-
ment for swimming pools. The most common solar collectors are flat plate collectors, in
which water or a heat exchange fluid is passed through pipes to an insulated absorber
plate. Heat is transferred from the absorber to the liquid as it passes through the collec-
tor. Potable water is the most common liquid, except where there is significant risk of
freezing. Aluminum or copper piping is used. Copper is preferred because it is a better
conductor and less susceptible to corrosion.
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desalination plants,” MP 38,4 (1999):pp. 66-71.

364 A.D. Khawaji, J.-M. Wie, ”Performance of MSF desalination plant components over fifteen
years at Madinat Yanbu Al-Sinaiyah,” Desalination 134 (2001):pp. 231-239.

365 S. Narain, S.H. Asad, ”Corrosion problems in low-temperature desalination units,” MP 31,4
(1992):pp. 64-67.
366 A.H. Tuthill, G.E. Moller, B. Todd, D. Homburg, ”The suitability of 6%molybdenum austenitic
stainless steels for desalination plant service,” in IDA World Congress on Desalination and
Water Sciences, Abu Dhabi (1995), pp. 1-20.
367 A. Al-Odwani, J. Carew, M. Al-Tabtabaei, A. Al-Hijji, “Materials performance in SWRO
desalination plant at KISR research and development program,” Desalination 135 (2001):
pp. 99-110.
368 H. Winters, ”Biofouling-its history and how it affects today‘s desalination industry,” in IDA
World Congress on Desalination and Water Sciences, Abu Dhabi (1995), pp. 1-11.
369 E.G. Darton, E. Buckley, “Thirteen years’ experiences treating a seawater RO plant,” Desalina-
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370 C. McDermott, ”Salt water solution,” Nickel 11,4 (1996):pp. 13-14.
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374 G.A. Minick, D.L. Olson, “Corrosion in the mineral industry,” in Metals Handbook, Vol. 13,9th
ed., ed. J.R. Davis (Metals Park, O H ASM International, 1987),pp. 1293-1298.
375 J. McEwan, “The corrosion performance of potential hydropower piping alloys in chilled
mine water circuits,” in 14th International Corrosion Congress, Cape Town, Paper 258.1
(1999): pp. 1-10.
376 ”Pumps and systems staff, floating pumps for corrosive mine water in South Africa,” Pumps
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377 M. List, “Well pump applications for mine dewatering,” Pumps & Systems Magazine,
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378 Z. Huang, Z. Li, B. Morton, T.Y. hung, “Biofouling of cage mariculture zones in the southern
waters of Hong Kong,” Asian Mar. Biol. 16 (1999):pp. 77-99.

379
A.P. Reynolds, University of South Carolina, Columbia, SC NACE Corrosion Network (1999).
380 Anon., “Swimming Pools in Gunite with a 10 year guarantee on the Costa del Sol,”
Waterworks, http://www.property-spain.com/wateMrorks/swimming-pool~ons~ction.
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swimming pools,” Insight 42,1(2000): pp. 29-33.
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3&2 Anon., ”Stainless steel swimming pools,” Nickel 9 , 3 (1994):p. 11.
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About the Authors
Michael Davies is a qualified metallurgist with an M . 9 . from Aston University and a

Ph.D. from Cranfield University. He is a professional engineer in a number of countries,
a corporate member of the Institution of Materials, Minerals, and Mining, and has been
a member of NACE since 1990.
Dr. Davies has many years of experience in all aspects of metallurgy, materials engi-
neering, corrosion, and electrochemistry, and has worked in steel production, closed die
forging, the chemical process industry, and in chemical plant engineering and corrosion
control.
P.J.B.Scott received a B . 9 . in Marine Biology and a Ph.D. in Oceanography from McGill

University in Montreal, Canada, with special emphasis on the impact of marine and
freshwater organisms on the biodeterioration of natural and synthetic materials.
Using an interdisciplinary approach to problems and working under a variety of field

conditions, Dr.Scott has extensive experiencein the oil, nuclear, and chemical industries.
He works on biological corrosion problems in marine and fresh water as an industrial
consultant and by directing research programs.
For the last 13years Drs. Davies and Scott have successfully operated an independent,
international corrosion consulting company, CARIAD Consultants. Initially based in
Canada, they are currently located in Kato Asites, Heraklion 70013, Crete, Greece,
cariad@her.forthrtet.gr.
xxi
Color Plate 1
Figure 1.1 The effect of lack of maintenance of steel in water is illus-

trated by these sunken and sinking ships. (Photo courtesy of CARIAD
Consultants.)
2 Color Plate
Figure 7.4 Photo shows planktonic bacteria as seen in a normal light microscope at 1 , 0 0 0 ~mag-
nification after being stained with a Gram stain. Dark purple cells are Gram positive, light pink
ones Gram negative. (Photo courtesy of CARIAD Consultants.)
Figure 10.17 If algae are not tightly controlled by careful water chemistry a pool can change
from sparkling clear to opaque green in a remarkably short time. We once literally watched as a
pool turned bright green in a few hours. (Photos courtesy of CARIAD Consultants.)
List of Tables
Table 2.1 WHO Limits for Inorganic Constituents of Health Significancein DrinkingWater 9
Table 2.2 WHO Limits for Disinfectants and Disinfectant By-Products in Drinking Water 9
Table 2.3 The Average Composition of Soluble Materials in Rivers 10
Table 2.4 Some Chemical Analyses of Various Fresh Waters 11
Table 2.5 The Major Chemical Constituents of Seawater of Salinity 34.48"A
(Chlorinity 19%) 18
Table 2.6 Typical Values of Important Physical, Chemical, and Biological Parameters of
Clean, Open-Ocean Seawater 18
Table 4.1 Corrosion Fatigue Strengths (CFS) for Various Alloys in Seawater 52
Table 4.2 Limits of Water Velocity for Various Copper Alloys in Potable Water
and Seawater 53
Table 4.3 Effect of Velocity on Seawater Corrosion (Corrosion Rates in mm/y) 54
Table 4.4 Corrosion Rates in Seawater at Different Velocities 55
Table 4.5 Alloy Grouping by Corrosion Resistance in Water 61
Table 5.1 Effect of Velocity on Corrosion in Fresh Water 76
Table 5.2 Corrosion of Mill-Scaled and Pickled Carbon Steel Specimens 77
Table 5.3 Corrosion of Carbon Steel in Seawater of Different Velocities 78
Table 5.4 TypicalCCT, CPT, and PRE Numbers for Some StainlessSteels and Nickel Alloys
Ferric Chloride Tests to ASTM G48 90
Table 5.5 Weight Loss and Penetration Depth of Multiple Crevice Assemblies in
Chlorinated and Unchlorinated Seawater 96
Table 5.6 Stagnant Seawater Exposure at Ambient Temperature for 3 Years 104
Table 5.7 Crevice Corrosion Tests Using MCA in Filtered Seawater at 30°C 104
Table 5.8 Classification of Copper Alloys by Type and UNS Numbers 108
xvii
Table 5.9 Characteristicsof Classes of Copper Alloys 109
Table 5.10 Effect of Pollution on the Corrosion of Copper Alloy Condenser in Seawater 115
Table 5.11 Corrosion Rate of Lead in Various Waters 138
Table 6.1 Properties of Polyolefines and Other Common Plastics 150
Table 6.2 Upper Temperature Limits for Continuous Service for Some Elastomers 160
Table 6.3 Upper Temperature Limits for Some Nonmetallics ("C) 161
Table 6.4 Temperature Limits for Plastics in Seawater 162
Table 6.5 Classification of Aggressiveness of Waters from DIN 4030 175
Table 6.6 Concrete Requirements Related to Service Exposure from European
Pre-Standard ENV 179
Table 6.7 Chloride Limit %by Weight of Portland Cement 180
Table 6.8 Properties of Clay Products, Brick, and Dry Building Stone 199
Table 6.9 Estimated Service Life in Years before First Maintenance Painting 207
Table 6.10 Properties of Thermoplastic Liners in Carbon Steel Pipe 211
Table 6.11 The Mechanical and Physical Properties of Wood Compared to Other Common
Structural Materials 217
Table 6.12 The Most Common Wood-Boring Animals 219
Table 7.1 The Classification System of Living Organisms 237
Table 7.2 Some of the Important Microfouling Photosynthetic Organisms 244
Table 7.3 Important Fungi Involved in Fouling 245
Table 7.4 The Main Groups of Marine Macrofouling Plants with Examples of All the
Common Genera 246
Table 7.5 The Main Groups of Marine Macrofouling Animals with Examples of All the
Common Genera 248
Table 7.6 Some Industries and Applications Which Have Reported MIC-Related
Corrosion Problems 252
Table 8.1 Sulfur Isotope Fractionation Analysis from Two Wells in Irian Jaya, Indonesia 295
Table 10.1 Industrial Water Use in the United States in 1990, in Millions of Gallons per Day 334
Table 10.2 Thermal Conductivity of Various Alloys 341
Table 10.3 Suggested Maximum Design Velocity in Condenser Tubing in Seawater 348
Table 10.4 NORSOK Recommended Maximum Velocities for Pipe Sizing 354
Table 10.5 Corrosion Rates of Carbon Steel in Various Oxygen and Velocity Regimes 356
Table 10.6 Some SuccessfulMaterials CombinationsUsed in Seawater Pumps
for Various Duties 360
Table 10.7 Ferrous Materials for Vertical Turbine Pumps-Saline Water Service 361
List of Tables xix
Table 10.8 Copper Alloys for Vertical Turbine Pumps-Brackish and Recirculated Waters
(up to 12,000 ppm Chlorides) 361
Table 11.1 Water Velocity Guidelines for Copper Alloy Propellers and Pumps 425
Table 11.2 Potable Water Categorization 450
Table 11.3 Static Corrosion Rates in 3,500-h Lab Tests in Various Waters, Saudi Arabia 453
Table 11.4 Current Densities for CP Design 482
Table 11.5 Materials for Topside Facilities for Seawater and Injection Systems 490
Table 11.6 Material Selection for Subsea Seawater and Injection Systems 491
Table 11.7 Causes of Tube Failures in Condensers 530
Table 11.8 Typical Industry Recommended Guidelines for Oxygen and Metal Oxides
in Boiler Feedwater Systems 538
Table 11.9 ASME Requirements for Oxygen and Metal Oxides in Boiler Feedwater Systems
at Various Pressures 538
Appendix A
Nominal Composition of Alloys
Common Name UNS No. Nominal Composition, %

Austenitic Stainless Steels
304L s30403 19 Cr, 10 Ni, t0.03 C
316L S31603 17 Cr, 12 Ni, 2.7 Mo, (0.03 C
317L S31703 19 Cr, 13.5 Ni, 3.5 Mo, t0.03 C
317LM S31725 19 Cr, 15Ni, 4.5 Mo, 0.5 Cu, 0.05 N, (0.03 C
317LN S31753 19 Cr, 13Ni, 3.5 Mo, 0.15 N, (0.03 C
317LMN S31726 17.5 Cr, 13.5 Ni, 4.5 Mo, 0.17 N, (0.03
904L NO8904 21 Cr, 25.5 Ni, 4.5 Mo, 1.5 Cu, t0.02 C
2FX65 NO8904 20 Cr, 25 Ni, 4.5 Mo,1.5 Cu, t0.025 C
254SMO s31254 20 Cr, 18Ni, 6.2 Mo, 0.7 Cu, 0.2 N, t0.02C
1925hMo NO8926 20 Cr, 25 Ni, 6.2 Mo, 0.8 Cu, 0.2 N, t0.02 C
3127hMo NO8031 27 Cr, 31 Ni, 6.5 Mo, 1.2 Cu, 0.2 N, t0.015 C
AL6X NO8366 21 Cr, 24.5 Ni, 6.5 Mo, (0.035 C
AL6XN NO8367 20.5 Cr, 24 Ni, 6.3 Mo, 0.2 Cu, 0.2 N, tO.02 C
654 SMO S32654 24 Cr, 22 Ni, 7.3 Mo, 0.5 Cu, 0.5 N, (0.01 C,3 Mn
alloy 28 NO8028 27 Cr, 32 Ni, 3.5 Mo, 1.0 Cu, (0.03 C
alloy 31 NO8031 27 Cr, 31 Ni, 6.5 Mo, 1.2 Cu, 0.2 N, tO.02 C
2ocb3 NO8020 20 Cr, 35 Ni, 2.5 Mo, 3.5 Cu, 0.07 Cb,t 2 M n , t l Si
Duplex Stainless Steels
2205 S31803 22 Cr, 5.5 Ni, 3.0 Mo, 0.14 N, (0.03 C
2304 S32304 23 Cr, 4 Ni, 0.1 N, (0.03
2507 S32750 25 Cr, 7 Ni, 4.0 Mo, 0.3 N, (0.03
3RE60 S31500 18.5Cr,5Ni,2.7Mo,O.lN,tO.O3C
Ferralium 255 S32550 25.5 Cr, 5.5 Ni, 3.4 Mo, 2.0 Cu, t0.04 C, t1.5 Mn
Zeron 100 S32760 25Cr,7Ni,3.5Mo,0.25N, t0.03C,0.75Cu,
0.75 W
Femtic Stainless Steels
Sea-Cure s44660 27.5 Cr, 1.2 Ni, 3.5 Mo, 0.5 Ti, 0.3 Si
Monit 94635 25 Cr, 4.0 Ni, 4.0 Mo, 0.5 Ti, 0.35 Si
575
5 76 Nominal ComDosition of Allovs
Common Name UNS NO. Nominal Composition, %

29-4C 94735 29 Cr, 0.3 Ni, 4.0 Mo, 0.5 Ti, 0.35 Si
29-4-2 woo 29 Cr, 2.1 Ni, 4.0 Mo, 0.1 Si
3CR12 - 11.7 Cr, 0.35 Ni, 0.02 N, (1 Si, (1.5 Mn
Precipitation Hardening Stainless Steels
17-4 PH S17400 16.5 Cr, 4 Ni, 4 Cu, t0.07, Cb
Nickel-Based Alloys
Incoloy 800 NO8800 20 Cr, 31 Ni, (0.08 C, 0.4 Si, 0.3 Al, 0.4 Ti
Incoloy 825 NO8825 21.5 Cr, 42 Ni, 3 Mo, 2.3 Cu, (0.05 C, 0.9 Ti, (0.2 A1
Monel400 NO4400 66.5 Ni, bal Cu, (0.3 C, t2.5 Fe, t 2 Mn, t0.5 Si
Monel K500 NO5500 66.5 Ni, bal Cu, 2.5 Al, t0.25, t 2 Fe, t1.5 Mn
Inconel 600 NO6600 16 Cr, >72 Ni, t0.5 Cu, (0.15 C, 8 Fe
Inconel 625 NO6625 22 Cr, 61 Ni, 9 Mo, (0.10 C, t 5 Fe, 3.6 Nb
Hastelloy B-2 N10665 (1.0 Cr, 68 Ni, 28 Mo, t0.02 C, t l Co, 1.8 Fe
Hastelloy NO6455 16 Cr, 54 Ni, 15.5 Mo, (0.015 C, (3 Fe, 0.7 Ti,
c-4 (2 c o
Hastelloy N10276 15.5 Cr, 54 Ni, 16 Mo, t0.02 C, (2.5 Co, 5.5 Fe, 4 W
C-276
Hastelloy NO6030 30 Cr, Bal Ni, 5 Mo, 1.7 Cu, (0.03 C, 15 Fe, 2.7 W,
G-30 t 5 Co, 0.9Cb + Ta
Hastelloy NO6200 23 Cr, Bal Ni, 16 Mo, 1.6 Cu, t O . O 1 C, t0.08 Si
c-2000
alloy 59 NO9059 59 Ni, 23 Cr, 16 Mo, 5 Fe, 4 W
Copper-Based Alloys
Cartkdge brass C26000 70 Cu, Bal Zn
Admiralty brass C44300 71.5 Cu, Bal Zn, (0.6 Fe, t0.07 Pb, 1Sn, As
Aluminum brass C68700 76 Cu, 22 Zn, 2 Al, As
Muntz metal C28000 61 Cu, Bal Zn
Naval brass c46420 62.5 Cu, Bal Zn, (0.2 Fe, (0.2 Pb, 1.2 Sn,
Phosphor bronze C50200 >99.5 Cu, (0.04 P, (0.1 Fe, t0.05 Pb, 1.2 Sn
Aluminum bronze C61400 90 Cu, 0.2 Zn, 7 Al, 2.5 Fe, 1Mn
Nickel-aluminum
Bronze NAB C95800 81 Cu, 9 Al, 4 Fe, 5 Ni, 1 h4n
70/30 Cu/Ni C71590 31 Cu, >67 Ni, t0.03, (0.05 Co, (0.005 Fe
90/10 Cu/Ni C70600 10 Cu, 4 6 . 5 Ni, t l Mn, 1.4 Fe, t l Zn
IN 768 BalCu,30Ni,1.7Cr,0.6Fe,0.7Mn
Cast Cu/Ni C96400 Bal Cu, 30 Ni, 1Mn, 1 Fe
Cast A1 bronze C95800 Bal Cu, 4.5 Ni, 9 Al, 4 Fe
Titanium Alloys
Grade 2 R50400 (0.3 Fe, Bal Ti
Grade 7 R52400 t0.3 Fe, Bal Ti, 0.15 Pd
Zirconium Alloys
Zirconium 702 R60702 +
t0.2 Fe + Cr, 99.2 Zr Hf, < 4.5 Hf
Zirconium 704 R60704 +
0.3 Fe Cr, 97.5 Zr + Hf, t 4.5 Hf, 1.5Sn
Nominal ComDosition of Allovs 577
Common Name UNS No. Nominal Composition %

Aluminum Alloys
5052 A95052 2.5 Mg, 0.25 Cr, t0.40 Fe, t O . l Mn, (0.1 Zn, (0.1 Cu
5083 A95083 4.5 Mg, 0.15 Cr, t0.40 Fe, 0.7 Mn, t0.25 Zn, (0.4 Si,
t0.15 Ti, t O . l Cu
5086 A95086 4.0 Mg, 0.15 Cr, (0.50 Fe, 0.45 Mn, t0.25 Zn, t0.4 Si,
t0.15 Ti, < 0.1 Cu
5456 A95456 5.1 Mg, 0.12 Cr, (0.40 Fe, 0.75 Mn, (0.25 Zn, t0.2 Ti,
(0.1 c u
356.0 A03560 7.0 Si, 0.32 Mg,0.12 Cr, (0.60 Fe, (0.35 Mn, t0.35 Zn,
(0.25 Ti, t0.25 Cu
360.0 A03600 9.5 Si, 0.50 Mg,(2.0 Fe, t0.35 Mn, t0.50 Zn, (0.60 Cu,
t0.50 Ni, t0.15 Sn
514.0 A05140 4.0 Mg,0.12 Cr, t0.50 Fe, t0.35 Mn, t0.15 Zn, t0.25 Ti,
(0.15 Cu, t0.35 Si
Appendix B
Approximate Equivalent
Grade of Some Cast and
Wrought Alloys
structure Alloy Name Cast (ACI) Cast (UNS) Wrought ( U N S )

Austenitic SS 304L CF3, CF3A J92500 S30403
304 CF8 J92600 S3O400
316L CF3M, CF3MA J92800 91603
AL-6XN CN3MN J94651 NO8367
254 SMO CK3MCuN J93254 S31254
Alloy 20 CN7h4 NO8007 NO8020
Duplex SS Alloy 2205 CD3MN J92205 $31803, S32205
Zeron 100 CD3MWCuN J93380 S32760
Martensitic or Alloy 410 CA15 J9ll50 SQlOOO
Ferritic SS Alloy 420 CA40 J91153 s42000
Precipitation 17-4 PH CB7Cu-1 J92180 S17400
Hardening SS
Nickel alloys Pure nickel CZlOO NO2100 NO2200
Alloy 825 Cu5MCuC NO8826 NO8825
Alloy 600 CY40 NO6040 NO6600
Alloy 625 CW6MC N26625 NO6625
Alloy 400 M35-2 NO4020 NO4400
Alloy C-4 cw2M N26455 NO6455
Alloy C-22 CX2MW N26022 NO6022
579
INDEX
Index Terms Links
(F) indicates a Figure.
A/C. See asbestos cement

Abu Dhabi 545 548
accelerated low water corrosion (ALWC) 436
acid-producing bacteria 255
acoustic emission 278
prestressed concrete 283 284 448
adenosine triphosphate (ATP) 285 289 290 296
adhesion
by bacteria 240
by macrofoulers 246
Admiral 414
Adriatic Sea 20
Alexander the Great 136 406
algae 12 48 235 239
246 250 251 257
287 289 293 296
376 382 383 385
436 551
blooms 13 16 20 125
brown 246
green 246
in seawater 27
This page has been reformatted by Knovel to provide easier navigation.

Index Terms Links
algae (Cont.)
nutrients for 20
red 246
alkaline stress corrosion cracking (ASCC) 51 506
Al-Khafji Power and Desalination Plant 546
Alloy Casting Institute (ACI) 43
Aluminia 416
aluminum alloys 129 321
anodes 322 327 363 427
462 473 480 483
484 548
boats 417 420 421
chlorination 388
coatings 208 485
CP 325
exfoliation 64
galvanic 61 63 426
inhibit 376
MIC 255 258
motor (F) 126
oil and gas 480 482
OTEC 536
potable 449 462
pulp and paper 526
Aluminum Association, Inc. (AA) 42
Alvin 419 424
Amazon River 15
Amerada Hess 492
American Indians 107
American Iron and Steel Institute (AISI) 41

Index Terms Links
American Petroleum Institute (API) 489

American Society for Testing and Materials
(ASTM) 41
American Society of Mechanical Engineers
(ASME) 41
American Water Works Association (AWWA) 42
ammonium bisulfide 503
âmose River 406
anaerobic bacteria 257
anemones 248
Annapolis Royal 534
anodic inhibitors 375
anodic protection 321
antifouling coatings 381
aqueducts 451
Roman (F) 451
Arabian Gulf 93 103 115 117
177 202 251 433
512 517 544
Archimedes Screw 451
Aristotle 239
asbestos cement 187 197 366
potable water 457
wastewater 470
ascidians 249
Asian clam 379
ASTM G 48
crevice apparatus (F) 309
pitting apparatus (F) 308
ASTM G 61
polarization apparatus (F) 313

Index Terms Links
Aswan Dam 442

Atlantic Ocean 21 105 202
atomic force microscopy (AFM) 375
Australia 34 202 494
bacteria 8 12 21 48
242 257 286 327
387 435 465 468
519
and anodic sites 294
and corrosion inhibitor 378
culture plate (F) 289
Gram stain (F) 243
monitoring 296
Baku 486
Baltic Sea 105
bamboo 172 218 430
Banbury 449
Barnacles 34 48 103 164
235 240 241 245
246 249 327 367
379 418 436
on wood (F) 250
stainless steel biofouling (F) 514
Battle of Trafalgar 407
bauxite 119
Bay of Fundy 15 25 534
beaches 25
erosion 26

Index Terms Links
Belgium 436
Bessemer converter 68
biguanides 391
biochemical oxygen demand (BOD) 19 33 522
biocides 164 218 237 286
381 385
519 551
and biodispersants 370
and corrosion inhibitor 378
biofouling 379
cooling tower 367
in antifouling paints 381
in concrete 203
monitoring 293
nonoxidizing 391
resistance to 392
selection 385 393
biodeterioration 27 34 48 214
235 244 245
of concrete and stone 204
of plastics 164
of steel and cast iron 78
of wood 218
biodispersants 369
bioerosion 201 245
factors affecting 247
biofilm 235
and biocide resistance 392
and biofouling 235
and chlorination 94
and CP 327

Index Terms Links
biofilm (Cont.)
and galvanic corrossion 59
and inhibitors 377
and oxidizing biocide 386
corrosion inhibition 255
development 240
effect on cathodic currents 63
EPS 242 254
ESEM (F) 237
formation of anodic sites 254
gluteraldehyde 392
monitoring 285 290
ozone 391
SEM (F) 238
biofouling 13 31 33 133
235 251 367 379
394 406 407 417
435 436 531 537
550 555
control 378
control by antifouling paints 380
in heat exchanger (F) 236
of ships 239
bivalves 249
boring 26
Black Sea 20 34
Bleo Holm 415
boats
bioerosion (F) 220
carbon steel (F) 412
coatings (F) 416

Index Terms Links
boats (Cont.)
steel (F) 2
wood, under construction (F) 408
boilers 10 12 71 76
124 462 508 517
523 529 530 537
540 542
Bombay Harbor 33
Boston 452
Brazil 164 326 443 445
bridges 173 182 184 192
196 221 283 423
437 445 459
rebar corrosion (F) 177 178
Brierley, H. 79
Bristol 410
bromine 386 389
Bronze Age 108 406 429
Bruce Heavy Water Plant 379
Brunel, I.K. 410
bryozoans 248
calcium carbonate
in seawater 20
California 202 541
Canada 15 25 35 103
121 379 380 522
528 534 557
Capitana 407

Index Terms Links
Captain Cook 407

carbon dioxide
equilibrium in water 20
carbon steel 75 79 374 540
acid tanks 321
biofouling 250
boats 410
boats (F) 2
bolts 427
chlorination 388
coated 440
CP 322
desalination 546
estuary 16
firewater 489
galvanic 62 63
galvanized 76
heat exchangers 343 348 350 511
518 543 545
hydrogen 51
inhibit 376 377
lined 196 210 213
MIC 33 92 253 255
256
monitors 277 282
offshore platform 480 484
oil and gas 491
piers 435
piles 435 437
polluted seawater 33

Index Terms Links
carbon steel (Cont.)

potable water 455
pulp and paper 521 523 525 529
pumps 359
rebar 175 177 180 191
195
seawater 436
seawater piping 355 511
tuberculation 47
velocity 346
wastewater 473
carbonation 30 175 177 179
188 193 282
Cardiff Barrage 445
Caribbean 203
Carthaginians 239
Caspian Sea 35
cast iron 72 79
chlorination 387
CP 324
filters 351
heat exchangers 61 334 350
inhibit 376
intakes 351
lined 212
piping (F) 355
potable water 454
pulp and paper 521 526
pumps 326 345 359 497
543
seawater piping 355

Index Terms Links
cast iron (Cont.)

valves 362 363
velocity 53
wastewater 473
cast iron pumps
mine water 552
cathodic inhibitors 376
cathodic protection 61 174 322 328
350 351 359 427
430 434 439 452
455 462 474 480
493 514 515 517
532 533 540 548
concrete 193
oil and gas 484
ships 414 424
caustic cracking 71 523
cavitation
propellers 56
pumps 56
valves 56
cellulose 215
Central Arizona Project (CAP) 447
ceramic 196
chalcocite 294
Cheops 406
Chesapeake Bay 15
China 35 392 422 441
443 520
chitons 248

Index Terms Links
chloride SCC 82 90 505 520

chlorination 94 116 292 379
386
effect on corrosion 389
chlorine 386
effect on potentials (F) 389
chlorine and bromine vs. pH (F) 387
chlorine dioxide 390
chlorinity
of seawater 17
chromate inhibitors 376
Claude, G. 536
clay 196
cliff erosion (F) 27
Clyde River 430
Clyde shipbuilding yards 410
coastal development (F) 6
coastal erosion 26
coating test speciment (F) 307
coatings 215 223 239 258
307 315 320 322
323 327 341 350
355 359 362 410
411 413 414 417
454 455 457 462
466 467 469 474
484 490 515 546
552 554
antifouling 383
concrete 194
docks, piers 440

Index Terms Links
coatings (Cont.)
rebar 185
coconut 187
Cold Lake 557
colloids 15
colony-forming units (CFU) 288
Colorado River 448
Colorado River Aqueduct 452
Columbus, C. 407
concrete 30 205
barriers 446
biodeterioration 36
bioerosion 26 34
bioerosion (F) 201
boats 423
coatings on 206 207
cooling towers 365 366
corrosion monitoring 285
CP 324 325 482
dams 171 441 442
docks 429
docks, piers 434
intake 351
intake channel (F) 353
linings 210 213
linings on 209 212
MIC 256
PCCP 173
piers 430
piping 345 356
potable water 456

Index Terms Links
concrete (Cont.)
seawater 174 511 514
seawater channel (F) 516
seawater return (F) 510
swimming pools 171 555
wastewater 465 467 470
concrete pier
biofouling (F) 247
concrete reinforcement. See rebar
concrete tank (F) 172
Condeep platforms 171 481
cooling tower (F) 335
Copenhagen 406
copper alloys 119 133 540
biofouling 379
brackish 16
chlorination 388
coatings 213
CP 325
galvanic 57 59 62
heat exchangers 341 350 529
inhibit 377
MIC 30 256 294
piping 345 357
pollution 33 50 532
potable 455 461
propellers 425
pumps 360
seawater 343
sheathing 322 409 437
valves 363

Index Terms Links
copper alloys (Cont.)

velocity 53 346 348
Copper Development Association
(CDA) 1 42
Copper Mariner 417
copper nickel 106 426 427
biofouling 251
CP 326
fish farming 554
fresh water 529
galvanic 59
530
piping 357
pollution 115 117
pumps 361
seawater 251
sheathing 114 419 484
velocity 53
copper/chrome/arsenic (CCA) 220
corals 20 22 27 28
202 203 382
Corbicula 35 379
Coriolis force 22 24
corrosion
chlorination control (F) 513
corrosion coupon
pitting (F) 275
corrosion coupons 274 310
corrosion inhibitors. See inhibitors

Index Terms Links
corrosion mechanisms 45
corrosion fatigue 52
crevice 45
dealloying 64
environmentally assisted
cracking 49
filiform 47
fretting 56
galvanic 57
general 45
hydride formation 51
hydrogen embrittlement 50
intergranular 64
localized 45
MIC 48
pitting 47
SCC 50
tuberculation 47
underdeposit 46
corrosion test rack (F) 310
coupons and spacers (F) 311
corrosion testing 307
Cort, H. 68 409
Corvettes 413
counterflow towers 364
CP. See cathodic protecton
creosote 218 220 222 223
437
Crete 406 430
crevice corrosion
aluminum alloys 122

Index Terms Links
crevice corrosion (Cont.)

ASTM G48 309
biofouling 240
cast iron 73
chlorination 95 96 511
copper alloys 109
CP 326
heat exchanger (F) 513
mechanism 46
MSF 546
seawater 104 497
stainless steel 86 87
titanium 131
valves 362
wire ropes 424
zirconium 135
crevice corrosion test washer (F'), 306
crinoids 249
critical crevice temperature (CCT) 89
critical pitting temperature (CPT) 87
crustaceans 249
Cuba 422
Cyanobacteria 244
dams 445
D'Arsonval, J. 535
Davy, Sir H. 57 409 540
delamination detectors 194
Delaware River 61 437

Index Terms Links
Denmark 406 462 535

desalination 540
MIC 252
Desulfovibrio 238 242 253 257
dezincification 111
Dhahran 455
diatoms 21 244 257
Diego Garcia 191
Dillenburg Castle 453
dioxins 524
dip slides 288
Discovery Bay 203
dispersants 369
djurleite 294
Dolphin 3K 419
Draper, C. 445
Dreissena 35
dual laminate 153 157
dual laminate piping
star cracking (F) 160
Dubai 359
Dujiang irrigation project 441
Dunoon Pier 430
Dunwich 26
earthenware 197
eddy current technique 284
Edison, T. 171
Egypt 441 443 451 520

Index Terms Links
Egyptians 107 405

Eichhornia 36
Electric Power Research Institute (EPRI) 380
electrical resistance method 276
electrochemical impedance
spectroscopy (EIS) 280 314
electrochemical noise 316
electrochemical scanning
tunneling microscopy (EC-STM) 375
electrodialysis (ED)
desalination 548
elstomers 157
England 15 26 77 150
220 406 422 429
445 446 449 452
entoprods 248
Environmental Protection
Agency 8 138 457 461
enzyme-linked immunosorbant
assay (ELISA) 290
EPA. See Environmental
Protection Agency
Epifluorescence/cell surface
antibody (ECSA) 290
ER probe elements 276
ER probe elements (F) 276
erosion corrosion 56
erosion monitors 278
estuaries 14 445
inverse 15
salt wedge 15

Index Terms Links
Euclides da Cunha Dam 445

European Committee for
Standardization (CEN) 43
European Standards (EN) 43
eutrophication 13 31 34
exfoliation 64
aluminum alloys 123
extracellular polymeric
substances (EPS) 235 254
fasteners 86 104 105 209

418 427
ferrocement 422 423
fertilizer 31 464 509 517
518 520
Fiesta Island 474
filters 342 345 351 364
369 465 472 511
523
cooling water 518
seawater 350
stainless steel 449
filtration 369
Finland 532
fique 187
fire protection systems 168 357 359 485
487 489 490 492
493 495 496
MIC 252

Index Terms Links
fish cages 553

fish cages (F) 554
fish farms 553
Flag Fen 429
Flamborough Head 26
flocculants 369
Florida 20 152 163 171
184 189 192 327
357 439 541
flow-assisted corrosion (FAC) 52 537
fluorogenic dye bioreporters
for monitoring 291
formaldehyde 384
fouling organisms 34 35
fouling release coatings 382
Fourier Transform Infrared
Spectrometer (FT-IR) 285
France 119 171 422 436
444 452 534
fresh water
corrosion of carbon steel and
cast iron 75
Freyssinet, E. 172
FRP 157 485
biodeterioration 162
boats 405 418 421
carbon fiber 420
chlorination 212
dual laminate 150 157
epoxy 357

Index Terms Links
FRP (Cont.)
filters 351
oil and gas 480
piers 438
piles 437
piping 345
polyesters 207
pulp and paper 525
rebar 186
seawater 166
seawater piping 496
FRP (GRP). See also plastics
FRP piping
seawater (F) 512
FRP tank (F) 155
full flow filtration 369
fungi 12 48 124 162
164 199 217 218
222 223 240 241
243 258 287 289
296 392 527
in wood 218
fungicide
in plastics 164
Galapagos 202
galvanic corrosion
examples 57

Index Terms Links
galvanic series charts 58

garages 283
Guy Owen 410
gaskets 45 95 280 320
337 458 494
graphite 87 426 489
gastropods 249
Germany 165 202 436 453
468 471 535 557
Gibraltar 551
glass 196
glass fiber 156
gluteraldehyde 392
Goa 221
Goss Challenger 420
Gram, C. 242
granite 197
graphitic corrosion
cast iron 74
Great Eastern 410
Great Lakes 35 380 528
Great Land 419
Great Man-Made River 446 456
Greece 406
greigite 294
Guinea 119
Gulf of Mexico 435 480 483 484
486
Gulflaks A 487 492

Index Terms Links
Hadfield, R. 79
Hall, C.M. 119
Hamburg 469
harbor
rocks (F) 431
harbors 34
hardness 10
heartwood 216
heat exchanger
internal (F) 272
364 388 519 532
aluminum 124
biofouling 239
biofouling (F) 368
cast iron (F) 336
cast iron joint (F) 337
coatings 207
condensate 540
cooling water 333 344 518
copper nickel 111
corrosion fatigue 52
energy recovery (F) 509
erosion 63
fouling 368
fresh water 92 518 528
glass 196
impingement 56

Index Terms Links
heat exchangers (Cont.)

MIC 112 115 256
MSF 544 546
OTEC 536
plate (F) 339
pulp and paper 523
seawater 61 82 84 93
104 350 388 511
shell and tube (F) 338 347
ships 427
spiral (F) 340
titanium 130 133
velocity 116
water box cathodic protection (F) 351
zirconium 135
heat transfer resistance 285
heavy metals 30
Heidrun 493
helipads 217
hemicellulose 216
Henryetta 462
Hermod 486
Heroult, P. 119
high pressure liquid
chromatography (HPLC) 292
Hittites 68
HMS Alarm 408
HMS Willow 421
Honduras 157
Hong Kong 33 35 164 246
250 436 554

Index Terms Links
Horseshoe Falls 534

hot dipping 209
Houston 199
Hurricane Gordon 21
hydroblast cleaning (F) 344
hydrogen
titanium 131
hydrogen blistering 50 506
hydrogen effects
decarburization 50
hydrogen-induced cracking (HIC) 51 506
hydrogen probe 278
hydroids 248
Ilo 545
immersion testing 310
Imperial Chemical Industries (ICI) 150
India 33 35 451 455
518
Indian Ocean 191 202
Indonesia 164
inductive resistance method 277
inhibitors 113 178 190 194
196 270 368 370
371 376 457 461
470
cooling water 396
in concrete 187
intakes 12 32 35 36
166 351 379

Index Terms Links
International Commission on Large Dams 441

International Organization for
Standardization (ISO) 42
intertidal zone 25 28 171 179
181 220 435 445
486
introduced species 34
ionization 384
iron bacteria 256
iron-carbon equilibrium diagram (F) 69
iron-oxidizing bacteria 256
isothiazolones 391
Italy 246 379 520
Ivanhoe 492
Jamaica 26 119 203 251

434
Japan 33 110 209 379
429 436 457 458
533 541
Java 162 407 430
Joncairs, D. 534
Jubail 512 515 544
Kaiko 419
Kanoehe Bay 202
Kariba dam 533
Kazakhstan 541

Index Terms Links
Keahole Point 536

Key West 357
King Canute 406
Kingston 121
knife line attack
stainless steel 92
Knossos 406
Kuwait 110 452 517 542
Lake Maracaibo 327

Lake Michigan 92
Lake Ontario 529 531
Lake Pontchartrain Causeway 437
Lake Superior 108
lakes 13
turnover 14
Lambot, L. 422
Langelier saturation index 371
LaQue Center for Corrosion
Technology 235 310 436
Larson-Skold index 374
Laufenberg 534
Le Lansqueret 417
lead 139 321 406 552
in water 461
lining 213
lead tank (F) 136
Levant 406
Liberty ships 410

Index Terms Links
Libya 446
lignin 215
limestone 197
linear polarization resistance 279 282
Lithophaga 26 162 201 250
433
Living Seas 434
Los Angeles 469
Lower San Fernando Dam 444
machinawite 294
Madinat Yanbu Al-Sinaiyah 547
Madras Harbor 223
Madrid 192
Maldives 28
Malpasset Dam 444
Malta 405
manganese bacteria 256
mangroves 28
in Thailand (F) 29
Maracaibo 16
marble statue
bioerosion (F) 200
Marggraf, A. 119
Mari Cha III 420
Marib Dam 441
marine tankers 425
Marly-on-Seine 453
Mayans 157

Index Terms Links
media
liquid culture 297
Mediterranean 246 406 443
Mega Float project 429
Mersey River 15 411
Mesopotamia 440
metal-reducing bacteria 256
MIC 48 242 258 411
466 473 529 531
“fingerprints” 294
ALWC 436
anodic depolarization 253
by industry 252
cathodic depolarization 251 253
control 383 385
diagnosis 298
diagnosis and failure analysis 294
diagnosis, general rules 296
during layup 343
heat exchangers 342
in white water 527
mechanisms 251
monitoring 291
of aluminum 124
of carbon steel 72
of cast iron 75
of copper alloys 111
of nickel alloys 103
of stainless steel 92
of transition metals 132

Index Terms Links
MIC (Cont.)
recirculating water 364
stainless steel (F) 93
sulfur isotope fractionation 294
waste water 466
microbiologically influenced corrosion
see MIC 48
Middle East 480
Mignon 416
migrating corrosion inhibitors (MCI)
concrete 188
mining 32 464 553
martensitic SS 81
MIC 252
Minoans 406
Mississippi River 15 414 440
mollusks 248
molybdate inhibitors 376
monitoring
bacteria 287 293
biocide efficacy 286 292
biocides 291
early MIC detection 286
equipment surfaces 291
microbial respiration 293
nonoxidizing biocides 292
oxidizing biocides 291
planktonic bacteria 288
sessile bacteria 290
SRB 289
water quality 287

Index Terms Links
monitoring equipment for MIC 296

Monterey Bay 220
most probable number (MPN) 296
multistage flash (MSD)
aluminum alloys 544
copper-nickel 543 544 546
desalination 541
stainless steel 543 544 546 547
titanium 544
multiple effect distillation 548
mussels 13 35
MV Koru 418
MV Osprey 418
Mycota. See fungi
National Association of Corrosion Engineers

(NACE) 42
National Bureau of Standards (NBS) 44
Netherlands 221 436 441 468
556
New York 221 429
New Zealand 77
Niagara Falls 534
Niagara River 534
nickel alloys 42 43 54 59
62 94 107 345
349 388 523 527
fasteners 426
galvanic 59

Index Terms Links
nickel alloys (Cont.)

heat exchangers 350 528
lining 213
MIC 103
NiDI 1
pitting, crevice 90
pollution 117
seawater 106 481
seawater piping 357
seawater velocity 346
shafts 359
UNS 42
valves 363
velocity 53
Nikator 415
Nile River 406 442
nitrogen-reducing bacteria 256
Norsk Hydro 327
NORSOK 42 481 485 488
495 497 499
North Carolina 163
NorthSea 105 106 171 257
480 487 492 493
535
Norway 195 406 484 492
Norwich 469
nuclear power 35 102 103 134
135 173 256 520
533
MIC 252

Index Terms Links
nutrients
limiting, in water 21
trace elements 21
Ocean Thermal Energy Conversion (OTEC) 235 239 537

Oddo-Tomson index 374
Ohio River 440
oil and gas 287 349 427 537
algae 257
biocides 392
helipads 217
linings 212
MIC 251 252
MIC monitoring 291
offshore platforms 325 437
oxygen scavengers 393
seawater cooling 346
seawater piping 357
oil platform (F) 479 488
Omai Tailings dam 444
Oman 26
Ontario Hydro 35 103 380 528
organic matter
composition 21
Oskarshamn 531
osmium tetroxide 297
osmotic control
of biofilms 379
oxygen vs. depth (F) 19

Index Terms Links
ozone 390
Pacific Ocean 21 26 202

Pakistan 451
Panama 202
Panama Canal 77 221
papyrus 520
PB. See plastics
PCCP
seawater intake (F) 173
PE. See plastics
peracetic acid 392
Persian Gulf. See Arabian Gulf
Peru 545
Phalasama 430
phenols 391
Philippines 440
Phoenicians 239
pholads, boring bivalves 162 164 202 218
219 223
photosynthesis 19
phytoplankton 20
pickling 86
piers 25 26 78 162
170 180 191 215
218 221 440
MIC 252
pigging 384
piping
carbon steel 364 455 498

Index Terms Links
piping (Cont.)
piping 497
cast iron 74 455 459
concrete 446 471
copper 460
copper alloys 356 496
copper-nickel 487 489 492 496
duplex 494
FRP 156 166 168 357
471 495 498 511
547 552
MIC 252
plastic 166
polyethylene 151
PVC 150 165 456 471
seawater 354
531
titanium 487
velocity 320
pitting 326
aluminum alloys 121
ASTM G48 309
boilers 537
carbon steel 71 77 473
cast iron 455
chlorination 95 511
coated rebar 183
copper alloys 110 113
forms of (F) 49

Index Terms Links
pitting (Cont.)
and inhibitors 375
inhibited rebar 187
mechanism 48
MSF 546
nickel alloys 104
potable 449 460
potentials 314
pumps 359
seawater 77 104 497
stainless steels 87 94
thiosulfate 526
titanium 131
pitting resistance equivalent (PRE) 83 84 88
plastics 169
boats 421
docks, piers 438
seawater piping 359
wastewater 472
plate counts 296
plate exchangers 337
pollution 16 31 114 115
125
and corrosion 33
and fouling 33
eutrophication 31
heavy metals 32
on sea surface (F) 31
toxins 32
polybutylene 151
potable 461

Index Terms Links
polyethylene
biodeterioration 163
coatings 327
encasement 454 473
potable piping 388
seawater piping 358
sliplining 462
waste water 469 471
polythionic acid cracking
in refineries 51
port
ancient ashlar construction (F) 432
construction in ashlar (F) 198
Port Royal 203
Postgate, J. 289
potential of metals
in seawater (F) 60
potentiodynamic polarization 313
potentiostatic polarizaton 311
power generation 35 92 103 135
166 173 239 343
378 517 542
antifouling 380
biocides 379 390
condensers 348
cooling towers 365
dams 441
FRP piping 358
MIC 252 257
power generaton 537
pumps 360

Index Terms Links
power station
cooling towers (F) 365
PP. See plastics
prestressed concrete cylinder piping (PCCP) 173 283
fresh water 456
waste water 469
Progreso 180 434
propellers 104 125 326 362
414 418 424 425
bronze (F) 423
Proserio 125
PTFE 151 223 383 424
553
See also plastics
gaskets 87
lined pipe 210 211 525
pumps 166
seals 274 414
PTFE-lined pump
erosion (F) 167
Puckorius scaling index 373
pulp and paper 240 321 390 527
MIC 252
pulp mill (F) 521
pumps 212 345 362 364
425 428 451 473
490 493 496 523
543
carbon steel 553
cast iron 73 555
cooling water 518

Index Terms Links
pumps (Cont.)
desalination 547 550
duplex 494
impingement 56
mine water 552 553
NAB 487
plastic 150 166 210
stainless steel 326 345 428
wastewater 75
PVC 149 414 421
See also plastics
biodeterioration 162 163
coatings 206
cooling tower fill 367
dual laminate 157
lined pipe 210
ozone 391
PVC pipe
bioerosion (F) 163
quaternary ammonium compounds 391

Queensland 221 408
reactor effluent air coolers (REAC) 505

rebar 171 186 187 189
196 434 486 517

Index Terms Links
Red Sea 406 512

refineries 50 51 506
denickelification 111
desalination 548
FRP piping 168
MIC in 103
waste water 473 501
remote-operated vehicles 480
Renaprobe 285 290
reverse osmosis (RO)
desalination 549
polyethylene 551
PVC 551
stainless steel 550
rhizoids 257
Ribault River 192
Rijn Oil Field 484
Rio de Janeiro 164
Rio Parana 443
Rittenhouse, W. 520
Rob Roy 492
Robbins device 290
Roskilde longship 406
rubber 157
rubber tree 158
Ruwais 473 517 548
Ryznar stability index 372
sabkha 186
sacrificial anodes 322

Index Terms Links
Salem 531
Samos 451
San Rafael 471
sand dunes 25
Santa Barbara 435
Santiago 407
sapwood 216
Saudi Arabia 203 434 453 512
515 544 546 547
scale inhibitors 376
scanning electrode techniques 316
scanning electron microscopy (SEM) 291 296 297
scanning reference electrode technique
(SRET) 316
scanning vibrating electrode technique
(SVET) 316
SCC 50
aluminum alloy 123
carbon steels 70
cast iron 73
copper alloys 110
nickel alloys 102
stainless steel 90
titanium 132
Schaeffler diagrams 80
Scotland 251
sea cucumbers 249
sea urchins 78 249
Seahenge 429
seawater 29

Index Terms Links
seawater (Cont.)
alloy ranking in 67
corrosion in 106
immersion zones 435
intake (F) 515
velocity effects in 53
seawater intake channel (F) 352
Seawise Giant 410
sediments 22 25
sentinel holes 279
Severn Estuary 445
shadoof 451
shafts 73 359 425 428
449 465 497
Shelf 5 486
shell and tube heat exchangers 334
Shell URSA 486
Shewanella 33
Shinkai 419
shipworms 162 163 218 219
221 223 406 407
Sicily 405
side stream filtration 369
Singapore 35 323 436
sisal 187
slime bacteria 255
smythite 294
Snorre 492
Society for Automotive Engineers, Inc.
(SAE) 42

Index Terms Links
sour water 493

cracking mechanisms 51
sour water corrosion 506
South Africa 124 125 182 449
519
South Fork Dam 444
Soxhlet method 180
Spain 533
Sparrow Cove 410
Spencer Gulf 15
spionkopite 294
spiral exchangers 337
splash zone 16 25 70 77
94 104 106 114
181 186 191 192
196 203 220 431
435 439 440 484
518 543
sponges 248
boring 201 250 251 433
Sri Lanka 77
SS Great Britain 410
SS Shenectady 410
St. Croix 544
St. Francis Dam 444
St. Louis 468
stable isotope fractionation 294
103 104 240 253
257 258 326 341

Index Terms Links
stainless steel (Cont.)

345 348 377 391
411 424 427 428
446 453 519 520
523
brackish 16 348
chlorination 105
cooling towers 366
CP 326 327 482 489
crevice 59 105
fasteners 426
for potable water 459
fouling 251
fresh water 448
galvanic 61 323 494
528 529 532
hydroelectric 535
injection water 498
oil and gas 494
piping 357
pitting 314
pitting, crevice 90
pulp and paper 524
pumps 359 360 487
rebar 183 434
valves 362 363
velocity 53 54 354 530
waste water 466

Index Terms Links
stainless steel pumps

mine water 552
starfish 249
Statfjord A 487 495 497
Stiff-Davis index 374
storms 21
stress-oriented hydrogen-induced cracking
(SOHIC) 51 506
submarines 57 62 70 208
239 411 419 421
422 424 426
sulfate-reducing bacteria (SRB) 30 33 75 92
93 103 111 112
132 162 164 242
251 255 288 294
296 327 378 392
455 469 473 497
527
sulfide stress cracking (SSC) 51 506
sulfide-producing bacteria 257
sulhr-oxidizing bacteria (SOB) 33 92 256 257
296
Sumerians 107 440
surfactants 370
Surinam 119
Sweden 406 422 463 522
531 532 556
swimming pools 171 384 385 388
389 391 557
concrete construction (F) 555

Index Terms Links
swimming pools (Cont.)

control of algae (F) 390
FFV 556
PVC 557
stainless steel 556
Tafel Plot 312

Taiwan 431
tanks 124 256 258 345
462
aluminum 125
ballast 411
brick-lined 197
dual-laminate 149 157
FRP 156 472 495
lead 136
mine water 552
plastic 209
potable water 452
wood 215
Tenby 556
Teton Dam 444
tetrapods 431
sea defenses (F) 28 433
Texas 394
Thames Bamer 445
Thames River 446 452
thermal shock 384
for biofilm control 379

Index Terms Links
thermocline 22
thermophilic bacteria 257
Thiobacillus 33 199 202 203
242 256
thiocarbamates 391
Three-Gorges Dam 443
tides 24
titanium 94 134 341
boats 420
coatings 213
condensers 427 532 533
fasteners 426
galvanic 59 61 364
546
nuclear 531
oil and gas 495
piping 357
pulp and paper 525
pumps 359
seawater 348 481
seawater cooling 346
seawater injection 490 491
splash zone 435
tubing 492
valves 364
velocity 53 348 354
titanium tanks
mine water 553
Tokyo 209 457

Index Terms Links
Trial 409
tributyltin (TBT) 381
Trident submarine base 438
Trondheim Fjord 95
tsunamis 24
turnover 14 23
Tuticorin Harbor 33
Unified Numbering System (UNS) 42

USS Elmer Montgomery 427
Vaal Dam 125

Vado Ligure Power Station 378
valves 212 346 364 449
490 496 523
carbon steel 489
cast iron 73 449
coating 485
cooling water 518
duplex 494
impingement 56
marine 428
NAB 492
plastic 149 150 210
seawater 105 533
stainless steel 62 327
Variont Dam 444

Index Terms Links
velocity
copper alloys 116
wall shear stress 54
Venezuela 168 327 431
Venice 446
Venice lagoon (F) 447
Versailles 453
Victoria Harbor 250
Victory 407
Victory ships 411
Vietnam 35
Vikings 406
Visakhapatnam Harbor 35
von Wolzgen Kuhr 251
Vulcan 409 410
Wadi el Garawi 441

Wales 220
waste treatment
biological 463
chemical 463
mechanical 463
waste water 75 150 166 197
202 210 388 456
478 522 527 551
MIC 252
water
anoxic 20
brackish 6 16

Index Terms Links
water (Cont.)
carbon dioxide in 17
classification 6
concrete deterioration in 176
corrosion of lead in 138
corrosion of SS in 94
corrosion of titanium in 133
corrosion of zirconium 135
fresh 14
fresh, corrosion of aluminum in 125
fresh, corrosion of carbon steel and cast iron in 76
fresh, corrosion of copper in 113
fresh, corrosion of nickel 103
oxygen in 17
plastics in 165 168
potable 9
properties 5 17 18
salt. See also seawater
salt, corrosion of aluminum 125
salt, corrosion of copper alloys 113
salt, corrosion of nickel alloys 104
sea, corrosion of aluminum in 125
sea, corrosion of carbon steel and
cast iron in 78
sea, corrosion of copper in 117
sea, effect of chlorination on SS 96
water main breaks 453
water mills 441
water-hyacinth 36
waves 24
solitary 24

Index Terms Links
weld decay 91
weld specimen for corrosion tests (F) 308
welds 46 62 86 96
100 306 307 320
343 346 350 449
458 459 487 493
494 525 527
MIC 255
plastics 157
wet H2S cracking 506
Wheatstone Bridge 276
Wilhelmina 416
Willcocks, W. 442
Williams, T. 409
wood 35 224
aluminum paint 417
boats 407 409
docks 429
marine structures 430
piles 202
pulp and paper 520
towers 365
wood borers 219
wooden piles
bioerosion (F) 222
wooden tanks (F) 216
World Health Organization 8 9 508
worms
polychaetes 248
proboscis 248
sipunculans 248

Index Terms Links
Wrightsville Beach 106 435
Yangste River 443

Yemen 441
zebra mussels 379

Zephir 416
zero resistance ammeter (ZRA) 280 316
zirconium 62 135 348
MIC 132
zooplankton 20

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GUIDE TO THE USE

02003 by NACE International

Manager, NACE Press: Neil Vaughan

About the Cover

List of Tables xvii

Chapter 2 Oceanography and Limnology 5

Chapter 3 Standards and Specifications 41

Chapter 4 Corrosion Mechanisms 45

Chapter 5 Metals and Alloys 67

5.1.2.1.3 Erosion Corrosion 74

5.6.1.2 Hydrogen Effects 131

Chapter 6 Nonmetallic Materials 149

6.1.7 Standards and Specifications-Plastics 168

6.4.1.2 Biodeterioration 218

Chapter 7 Biofouling and Biodeterioration 235

Chapter 8 Monitoring 269

8.1.3 Electrochemical Corrosion Monitoring Techniques 279

Chapter 9 Corrosion Control 305

Chapter 10 Water Systems 333

10.1.4 Recirculating Water 364

Chapter 11 Applications 405

11.1.2 Iron and Steel 409

11.7 Wastewater Handling 462

11.10 Chemical Process Plants 507

Appendix A Nominal Composition of Alloys 575

2.1 FRESH WATER

2.1.1 Potable Water

2.1.2 Lakes and Rivers

Table 2.1 WHO Limits for Inorganic Constituents of

(P): Provisional guideline value.

Table 2.3 The Average Composition of Soluble

2.1.4 Freshwater Biology

2.2 ESTUARIES AND BRACKISH WATER

2.2.1 Types of Estuaries

2.2.2 Biology and Chemistry of Estuaries

2.2.3 Corrosion in Estuaries

Depending on composition brackish waters can be more aggressive than seawater. In

2.3.1 Physical Properties

SYm = 1.80655 Cl'h.

In the open Ocean the total dissolved salts, or salinity, is approximately3.5%,usually

2.3.3 Oxygen and Carbon Dioxide

Table 2.5 The Major Chemical Constituents of Seawater

0:C :N :P = 109 :41 :7.2 :1 by gram molecular weight, or

2.3.9 Coasts and Beaches

2.3.1 0 Marine Biology

(planktonic)or swimming(pelagic).The second is those bottom-dwellingorganisms that

2.3.1 1 Corrosion in Seawater

Sea-going and coastal vessels of all types

Coastal petroleum and petrochemical processing plants

The degradation behavior of various materials in seawater service may be summa-

a Wood-fails by organisms, mechanical damage, swelling, etc., impregnants can pro-

The corrosionof metals in seawater depends on many factors,including the following:

a Temperature. As temperature increases corrosion rate increases if other factors are

1. The development of a blanket of algae (macrophytes and filamentous algae), which

2.4.1 Pollution and Corrosion

2.4.2 Pollution and Fouling

2.4.3 Pollution and Biodeterioration

Eutrophication of the environment from anthropogenic sources can accelerate attack

2.5 INTRODUCED SPECIES

S. Baird, www.chemresources.com(12 November, 2000).

3.1 METALS AND ALLOYS

As modem alloys began to be developed and manufactured to consistent alloy content

3.2 NONMETALLIC MATERIALS