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FLUOROPOLYMER APPLICATIONS
IN THE CHEMICAL PROCESSING
INDUSTRIES
PLASTICS DESIGN LIBRARY (PDL)
PDL HANDBOOK SERIES
Series Editor: Sina Ebnesajjad, PhD (sina@FluoroConsultants.com)
President, FluoroConsultants Group, LLC
Chadds Ford, PA, USA
www.FluoroConsultants.com
The PDL Handbook Series is aimed at a wide range of engineers and other professionals working in the plastics industry,
and related sectors using plastics and adhesives.
PDL is a series of data books, reference works and practical guides covering plastics engineering, applications, processing,
and manufacturing, and applied aspects of polymer science, elastomers and adhesives.
Recent titles in the series
Biopolymers: Processing and Products, Michael Niaounakis (ISBN: 9780323266987)
Biopolymers: Reuse, Recycling, and Disposal, Michael Niaounakis (ISBN: 9781455731459)
Carbon Nanotube Reinforced Composites, Marcio Loos (ISBN: 9781455731954)
Extrusion, 2e, John Wagner & Eldridge Mount (ISBN: 9781437734812)
Fluoroplastics, Volume 1, 2e, Sina Ebnesajjad (ISBN: 9781455731992)
Handbook of Biopolymers and Biodegradable Plastics, Sina Ebnesajjad (ISBN: 9781455728343)
Handbook of Molded Part Shrinkage and Warpage, Jerry Fischer (ISBN: 9781455725977)
Handbook of Polymer Applications in Medicine and Medical Devices, Kayvon Modjarrad & Sina Ebnesajjad (ISBN:
9780323228053)
Handbook of Thermoplastic Elastomers, Jiri G Drobny (ISBN: 9780323221368)
Handbook of Thermoset Plastics, 2e, Hanna Dodiuk & Sidney Goodman (ISBN: 9781455731077)
High Performance Polymers, 2e, Johannes Karl Fink (ISBN: 9780323312226)
Introduction to Fluoropolymers, Sina Ebnesajjad (ISBN: 9781455774425)
Ionizing Radiation and Polymers, Jiri G Drobny (ISBN: 9781455778812)
Manufacturing Flexible Packaging, Thomas Dunn (ISBN: 9780323264365)
Plastic Films in Food Packaging, Sina Ebnesajjad (ISBN: 9781455731121)
Plastics in Medical Devices, 2e, Vinny Sastri (ISBN: 9781455732012)
Polylactic Acid, Rahmat et. al. (ISBN: 9781437744590)
Polyvinyl Fluoride, Sina Ebnesajjad (ISBN: 9781455778850)
Reactive Polymers, 2e, Johannes Karl Fink (ISBN: 9781455731497)
The Effect of Creep and Other Time Related Factors on Plastics and Elastomers, 3e, Laurence McKeen (ISBN:
9780323353137)
The Effect of Long Term Thermal Exposure on Plastics and Elastomers, Laurence McKeen (ISBN: 9780323221085)
The Effect of Sterilization on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9781455725984)
The Effect of Temperature and Other Factors on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9780323310161)
The Effect of UV Light and Weather on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9781455728510)
Thermoforming of Single and Multilayer Laminates, Ali Ashter (ISBN: 9781455731725)
Thermoplastics and Thermoplastic Composites, 2e, Michel Biron (ISBN: 9781455778980)
Thermosets and Composites, 2e, Michel Biron (ISBN: 9781455731244)
To submit a new book proposal for the series, or place an order, please contact
Matthew Deans, Senior Publisher
m.deans@elsevier.com
FLUOROPOLYMER APPLICATIONS
IN THE CHEMICAL PROCESSING
INDUSTRIES
THE DEFINITIVE USER’S GUIDE AND
HANDBOOK

Second Edition

Sina Ebnesajjad
Pradip R. Khaladkar
William Andrew is an imprint of Elsevier
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States
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herein).

Notices
Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in
research methods, professional practices, or medical treatment may become necessary.
Practitioners and researchers may always rely on their own experience and knowledge in evaluating and using any information, methods,
compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the
safety of others, including parties for whom they have a professional responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or
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A catalog record for this book is available from the Library of Congress

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A catalogue record for this book is available from the British Library
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Typeset by TNQ Books and Journals
Dedicated to Ghazale and Shaila
This page intentionally left blank
 Contents

Preface ................................................................................................................................................................. xiii

Acknowledgments................................................................................................................................................. xv

1 Introduction to Fluoropolymers ................................................................................................................... 1

1.1 Introduction...............................................................................................................................................1
1.2 What Are Fluoropolymers? ......................................................................................................................1
1.3 Fundamental Properties of Fluoropolymers .............................................................................................3
1.4 Developmental History of Fluoropolymers..............................................................................................3
1.5 Applications of Fluoropolymers...............................................................................................................5
References .................................................................................................................................................6

2 Materials of Construction ............................................................................................................................. 7

2.1 Introduction...............................................................................................................................................7
2.2 Historical Background ..............................................................................................................................7
2.3 Definition of Polymer-Based Materials....................................................................................................8
2.4 Comparison Between Polymer-Based Materials and Metals...................................................................8
2.4.1 Position of Fluoropolymers in the Materials Spectrum................................................................8
2.5 Applications of Polymer-Based Materials for Corrosion Control .........................................................15
2.5.1 Applications of Fluoropolymers for Corrosion Control .............................................................15
References ...............................................................................................................................................15

3 Properties of Neat (Unfilled) and Filled Fluoropolymers........................................................................ 17

3.1 Introduction.............................................................................................................................................17
3.2 Influence of Processing on Fluoroplastics..............................................................................................18
3.3 Chemical Compatibility of Fluoropolymers ..........................................................................................18
3.3.1 Chemical Compatibility of Perfluoropolymers ........................................................................... 18
3.3.2 Chemical Compatibility of Partially Fluorinated Fluoropolymers ............................................. 24
3.3.3 Chemical Compatibility of Polychlorotrifluoroethylene.............................................................24
3.4 Permeation Fundamentals.......................................................................................................................24
3.4.1 Permeation Measurement ............................................................................................................ 28
3.5 Environmental Stress Cracking ..............................................................................................................29
3.5.1 Environmental Stress Cracking of Fluoropolymers ....................................................................31
3.6 Polytetrafluoroethylene-Filled Compounds............................................................................................31
3.6.1 Granular-Based Compounds........................................................................................................ 32
3.6.2 Fine Powder-Based Compounds.................................................................................................. 34
3.6.3 Compounding With Engineering Polymers................................................................................. 35
3.6.4 Reinforced Gasketing Material.................................................................................................... 35
3.6.5 Co-coagulated Compounds.......................................................................................................... 37
3.6.6 Typical Properties of Filled Fluoropolymers .............................................................................. 37
3.6.7 Properties of Neat (Unfilled) Polytetrafluoroethylene ................................................................ 43

vii
viii C ONTENTS

3.6.8 Standard Measurement Methods for Polytetrafluoroethylene..................................................... 63

3.7 Properties and Characteristics of Melt-Processible Fluoroplastics........................................................63
3.7.1 Mechanical and Dynamic Properties........................................................................................... 63
3.7.2 Thermal Properties of Melt-Processible Fluoropolymers ...........................................................96
3.7.3 Weatherability of Melt-Processible Fluoroplastics ..................................................................... 98
3.7.4 Electrical Properties of Melt-Processible Fluoroplastics .......................................................... 110
3.7.5 Optical and Spectral Properties of Melt-Processible Fluoroplastics ........................................ 113
3.7.6 Radiation Effect on Melt-Processible Fluoroplastics................................................................ 116
3.7.7 Flammability of Melt-Processible Fluoroplastics ..................................................................... 122
3.7.8 Biofilm Formation of Melt-Processible Fluoroplastics............................................................. 122
References .............................................................................................................................................125
Further Reading ....................................................................................................................................128

4 Selecting Fluoropolymers for Corrosion Control................................................................................... 129

4.1 Introduction...........................................................................................................................................129
4.1.1 Corrosion of Metals ...................................................................................................................129
4.1.2 Corrosion of Polymer Materials ................................................................................................ 129
4.1.3 Approaches to Selection ............................................................................................................ 129
4.2 Economics of Selecting Fluoropolymers .............................................................................................130
4.3 Preparing to Determine Compatibility .................................................................................................130
4.4 Current Technology for Determining Compatibility ...........................................................................130
4.4.1 Experience.................................................................................................................................. 130
4.4.2 Manufacturers’ Literature .......................................................................................................... 130
4.4.3 Testing ........................................................................................................................................ 138
4.4.4 Fabrication Considerations in Materials Selection ................................................................... 177
4.4.5 Inspection and Maintenance Aspects of Materials Selection ................................................... 177
References .............................................................................................................................................183

5 Manufacturing of Parts From Tetrafluoroethylene Homopolymers.................................................... 185

5.1 Granular Resin Processing....................................................................................................................185
5.1.1 Resin Selection ..........................................................................................................................185
5.1.2 Compression Molding................................................................................................................ 185
5.1.3 Automatic Molding.................................................................................................................... 192
5.1.4 Isostatic Molding ....................................................................................................................... 193
5.1.5 Ram Extrusion ...........................................................................................................................198
5.2 Fine Powder Resin Processing .............................................................................................................200
5.2.1 Resin Handling and Storage ...................................................................................................... 200
5.2.2 Paste Extrusion Fundamentals................................................................................................... 201
5.2.3 Extrusion Aid or Lubricant........................................................................................................ 202
5.2.4 Wire Coating.............................................................................................................................. 203
5.2.5 Extrusion of Tubing ...................................................................................................................205
5.2.6 Pressure Hoses ...........................................................................................................................205
5.2.7 Unsintered Tape .........................................................................................................................211
5.3 Fluoropolymer Dispersion Processing..................................................................................................212
5.3.1 Dispersion Applications............................................................................................................. 212
5.3.2 Storage and Handling of Dispersions........................................................................................213
5.3.3 Dispersion Formulation and Characteristics .............................................................................213
5.3.4 Glass Cloth Coating by Dispersion ...........................................................................................215
C ONTENTS ix

5.3.5 Dispersion Impregnation of Flax and Polyaramide ..................................................................217

5.3.6 Coating Metal and Hard Surfaces With Dispersion..................................................................217
References .............................................................................................................................................217
Further Reading ....................................................................................................................................218

6 Manufacturing Parts From Melt-Processible Fluoropolymers ............................................................ 219

6.1 Introduction.........................................................................................................................................219
6.2 Materials of Construction ...................................................................................................................219
6.3 Rheology of Fluoropolymer Melts .....................................................................................................219
6.3.1 Characterization of Rheology of Fluoropolymers...................................................................220
6.4 Thermal Stability of Fluoropolymers .................................................................................................225
6.5 Melt Extrusion ....................................................................................................................................226
6.5.1 The Extruder ............................................................................................................................227
6.5.2 Film Extrusion .........................................................................................................................229
6.5.3 Sheet Extrusion ........................................................................................................................229
6.5.4 Pipe and Tube Extrusion..........................................................................................................230
6.5.5 Coextrusion .............................................................................................................................. 231
6.5.6 Drawdown Ratio ......................................................................................................................232
6.6 Fluoropolymer Tube Extrusion...........................................................................................................233
6.6.1 Sizing of Tubes ........................................................................................................................233
6.6.2 Heat Shrink Tubes ...................................................................................................................235
6.7 Fluoropolymer Film Extrusion ...........................................................................................................236
6.7.1 Polyvinylidene Fluoride Films ................................................................................................ 237
6.7.2 Ethylene Tetrafluoroethylene and Ethylene Chlorotrifluoroethylene Films ........................... 241
6.7.3 Perfluoropolymer Films ........................................................................................................... 242
6.8 Injection Molding ...............................................................................................................................246
6.8.1 Injection Molding of Fluoropolymers ..................................................................................... 246
6.9 Rotational Molding .............................................................................................................................253
6.9.1 Basic Process Technology ....................................................................................................... 254
6.9.2 Rotomolding and Rotolining Processing Conditions.............................................................. 256
6.9.3 Conclusion ...............................................................................................................................259
6.10 Other Part Manufacturing Techniques................................................................................................260
6.10.1 Compression Molding of Fluoropolymers ............................................................................ 261
6.10.2 Transfer Molding of Fluoropolymers ....................................................................................263
6.10.3 Examples of Transfer Molded Parts......................................................................................269
6.10.4 Blow-Molding Fluoropolymers .............................................................................................270
6.11 Vacuum Bagging.................................................................................................................................274
References ...........................................................................................................................................275

7 Fabrication Techniques of Fluoropolymers ............................................................................................ 279

7.1 Introduction...........................................................................................................................................279
7.2 Machining .............................................................................................................................................279
7.2.1 Sawing and Shearing ................................................................................................................. 280
7.2.2 Drilling, Tapping, and Threading ..............................................................................................280
7.2.3 Turning and Milling...................................................................................................................280
7.2.4 Centerless Grinding ...................................................................................................................280
7.2.5 Skiving ....................................................................................................................................... 280
7.2.6 Machining Filled Polytetrafluoroethylene Parts........................................................................ 281
x C ONTENTS

7.3 Adhesive Bonding Methods..................................................................................................................281

7.3.1 Contact Adhesives .....................................................................................................................281
7.3.2 Bonding Adhesives .................................................................................................................... 282
7.4 Welding Techniques..............................................................................................................................282
7.4.1 Heated Tool (Hot Plate) Welding ............................................................................................ 282
7.4.2 Hot Gas Welding......................................................................................................................285
7.4.3 Induction Welding.................................................................................................................... 286
7.4.4 Spin Welding............................................................................................................................289
7.4.5 Ultrasonic Welding ..................................................................................................................290
7.4.6 Infrared Welding ......................................................................................................................294
7.4.7 High-Frequency (Radio Frequency) Welding ......................................................................... 295
7.4.8 Solvent Welding....................................................................................................................... 296
7.4.9 Vibration Welding.................................................................................................................... 297
7.4.10 Microwave Welding................................................................................................................. 300
7.4.11 Resistant Welding .................................................................................................................... 301
7.4.12 Extrusion Welding ...................................................................................................................302
7.4.13 Laser Welding ..........................................................................................................................303
7.4.14 Welding Polytetrafluoroethylene .............................................................................................304
7.4.15 Welding Fluorinated Ethylene Propylene................................................................................308
7.4.16 Welding Perfluoroalkoxy ......................................................................................................... 308
7.4.17 Welding Polyvinylidene Fluoride ............................................................................................ 310
7.4.18 Welding Ethylene Tetrafluoroethylene ....................................................................................312
7.4.19 Welding Ethylene Chlorotrifluoroethylene.............................................................................. 314
7.5 Thermoforming .....................................................................................................................................314
7.6 Other Processes.....................................................................................................................................315
References.............................................................................................................................................315
Further Reading ....................................................................................................................................318

8 Design and Construction of Linings and Vessels.................................................................................... 321

8.1 Introduction.........................................................................................................................................321
8.2 Lining of Vessels ................................................................................................................................321
8.2.1 Adhesively Bonded Linings for Vessels.................................................................................. 321
8.2.2 Rotolining................................................................................................................................. 324
8.2.3 Spray and Baked Coatings.......................................................................................................325
8.2.4 Loose Lining ............................................................................................................................332
8.2.5 Dual Laminate..........................................................................................................................337
8.3 Welding ...............................................................................................................................................339
8.4 Lining of Pipes and Fittings ...............................................................................................................342
8.5 Lined Valves .......................................................................................................................................343
8.5.1 Plug Valves............................................................................................................................... 344
8.5.2 Ball Valves ...............................................................................................................................344
8.5.3 Butterfly Valves........................................................................................................................344
8.5.4 Diaphragm Valves.................................................................................................................... 344
8.5.5 Clamp Valves ...........................................................................................................................345
8.6 Lined Hoses ........................................................................................................................................345
8.7 Lined Expansion Joints.......................................................................................................................345
8.8 Lining or Coating of Internals............................................................................................................346
C ONTENTS xi

8.9 Design and Fabrication of Vessels for Lining....................................................................................347

8.10 Shop Versus Field Fabrication............................................................................................................347
References...........................................................................................................................................347
Further Reading ..................................................................................................................................348

9 Operation, Inspections, Maintenance, and Repairs ............................................................................... 349

9.1 Operations .............................................................................................................................................349
9.2 Inspections and Maintenance................................................................................................................349
9.2.1 Visual Examination.................................................................................................................... 349
9.2.2 Nondestructive and Destructive Examination ........................................................................... 354
9.2.3 Nonintrusive Examination ......................................................................................................... 355
9.2.4 Risk-Based Inspection Strategy.................................................................................................356
9.3 Repairs ..................................................................................................................................................356

10 Failure Analysis of Fluoropolymer Parts................................................................................................ 357

10.1 Introduction.........................................................................................................................................357
10.2 Part Failure..........................................................................................................................................357
10.3 Defect Analysis...................................................................................................................................358
10.4 Application of Failure Analysis Methodology...................................................................................362
10.4.1 Infrared Spectroscopy ............................................................................................................ 365
10.4.2 Electron Microscopy Techniques ..........................................................................................367
10.4.3 Mass Spectroscopy................................................................................................................. 369
10.4.4 Gas Chromatography ............................................................................................................. 369
10.4.5 Nuclear Magnetic Resonance ................................................................................................ 370
10.4.6 Differential Scanning Calorimetry ........................................................................................370
10.4.7 Differential Thermal Analysis ............................................................................................... 372
10.4.8 Dynamic Mechanical Analysis..............................................................................................373
10.4.9 Thermogravimetric Analysis .................................................................................................378
10.5 Surface Analysis .................................................................................................................................379
10.5.1 Electron Spectroscopy for Chemical Analysis...................................................................... 379
10.5.2 Secondary Ion Mass Spectroscopy........................................................................................380
10.6 Examples of Failure Analysis.............................................................................................................381
10.6.1 Case 1: Failed Lined Pipe......................................................................................................381
10.6.2 Case 2: Failed Check Valves .................................................................................................382
10.6.3 Case 3: Black Spots on Fluorinated Ethylene Propylene Coating ....................................... 382
10.6.4 Case 4: Braided Hose Failure................................................................................................ 382
10.7 Physical Defects Due to Part Fabrication ..........................................................................................390
10.7.1 Polytetrafluoroethylene .......................................................................................................... 391
10.7.2 Melt-Processible Fluoropolymers..........................................................................................392
10.7.3 Measurement of Flaws........................................................................................................... 393
References ..........................................................................................................................................399

11 Cost Analysis .............................................................................................................................................. 401

11.1 Introduction.........................................................................................................................................401
11.2 Cost Analysis ......................................................................................................................................401
References ..........................................................................................................................................404
xii C ONTENTS

12 Safety, Health, Environmental, Disposal, and Recycling....................................................................... 405

12.1 Introduction.........................................................................................................................................405
12.2 Toxicology of Fluoropolymers ...........................................................................................................405
12.2.1 Ammonium Perfluorooctanoate.............................................................................................405
12.3 Thermal Properties of Fluoropolymers ..............................................................................................406
12.4 Emission During Processing...............................................................................................................406
12.5 Safety Measures ..................................................................................................................................409
12.5.1 Ventilation of Degradation Products ..................................................................................... 411
12.5.2 Processing and Fabrication ....................................................................................................411
12.5.3 Spillage Cleanup .................................................................................................................... 412
12.5.4 Equipment Cleaning and Maintenance .................................................................................413
12.5.5 Protective Clothing ................................................................................................................ 413
12.5.6 Personal Hygiene ...................................................................................................................413
12.5.7 Fire Hazard ............................................................................................................................413
12.5.8 Material Incompatibility ........................................................................................................ 413
12.6 Food Contact.......................................................................................................................................413
12.7 Fluoropolymer Scrap and Recycling ..................................................................................................414
12.7.1 Introduction............................................................................................................................414
12.7.2 Polytetrafluoroethylene .......................................................................................................... 415
12.7.3 Melt Processible Fluoropolymers (PFA and FEP) ................................................................ 415
12.8 Environmental Protection and Disposal Methods..............................................................................416
12.8.1 Packaging Disposal and Recycling .......................................................................................416
References ..........................................................................................................................................416

13 Future Trends ............................................................................................................................................. 419

13.1 Introduction.........................................................................................................................................419
13.2 Fluoropolymer Applications ...............................................................................................................419
13.3 Fluoropolymer Resin Manufacturing .................................................................................................419
13.4 Growth of Fluoropolymer Industries..................................................................................................419
13.5 Technological Needs of Chemical Processing Industry.....................................................................420
13.5.1 Nondestructive and Nonintrusive Condition Assessment Leading to Fitness
for Service Decisions............................................................................................................. 420
13.5.2 Accelerated Testing for Compatibility .................................................................................. 420
References ..........................................................................................................................................420

Index .................................................................................................................................................................. 421


The aim of the present book is to address the use of
fluoropolymers in the chemical processing industry
(CPI) and other allied industries including food,
beverage, pharmaceutical, semiconductor, and pulp
and paper industries. This book is both a reference
and a source for learning the basics for those involved
in the entire product value chain related to the chem-
ical industries, from fluoropolymer producers all the
way to the end users. The reader will be able to learn
about how the unique characteristics of fluoroplastics
are utilized in the design and construction of equip-
ment exposed to harsh chemical environments. The
book offers information helpful to engineers, mainte-
nance personnel, students, material managers, and all
others involved in the CPIs.
In this book practical matters have been empha-
sized over the theoretical subjects. There are
numerous sources for in-depth study of topics,
including polymerization and the polymer science
of fluoropolymers. Those references have been listed
at the end of the chapters, as both bibliography and
additional reading sources. Review papers are partic-
ularly helpful as a starting point for finding additional
sources for concentrated reading in selected areas.
The chapters of this book have been written
to allow sequential or singular reading of them.
Chapters 1 and 2 introduce the reader to fluoropoly-
mers, fluoroelastomers, and the other materials of
construction used to manufacture parts that come in
contact with chemicals in factories. Chapters 3 and
4 concentrate on the properties and selection of fluo-
ropolymers for the construction of parts. Chapters 5
Preface
and 6 describe processes used to convert fluoropoly-
mers into shapes and parts. Chapter 7 covers the
fabrication techniques used to finish or alter the fluo-
ropolymer shapes/parts. Chapter 8 reviews the design
and construction of the basic equipment components
of a chemical processing plant.
Chapter 9 discusses the operation and mainte-
nance of vessels and tanks. Chapter 10 provides
methodology and analytical techniques for the failure
analysis of fluoropolymer parts. Chapters 11e13 are
devoted to the cost analysis, safety considerations,
and future trends of fluoropolymers. The Glossary
offers a short description of technical words and
terms of art.
We have tried to present the data in SI units
throughout the book as much as possible. A large
number of parts are, however, still specified in
English units. In such cases, conversion factors
have been listed in footnotes to allow the reader to
convert to metric units.
None of the views or information presented in this
book reflects the opinions of any of the companies or
individuals that have contributed to the book. If there
are errors, they are oversights on the part of the
authors. A note to the publisher indicating the
specific error, to correct the future editions, would
be much appreciated.
Sina Ebnesajjad
Pradip R. Khaladkar
April 2017
xiii
This page intentionally left blank

We owe the majority of our learning and experi-
ence in the field of fluoropolymers to our employ-
ment at the DuPont Fluoroproducts (now Chemours
Corp) and FluoroConsultants Group (Sina) and
DuPont Engineering Technology (Pradip). Special
thanks go to DuPont Fluoroproducts (now Chemours
Corp) for the contribution of information, figures,
photographs, illustrations, and tables. Attribution has
been made to the companies wherever the contrib-
uted material appears.
We thank all the companies that have supplied
the authors with information, figures, photographs,
and tables. They have been acknowledged in the
Acknowledgments
references section at the end of each chapter. We
sincerely thank the contributions that the data
supplied by each company have made to this book.
Special thanks go to our friend Dr. Lawrence
McKeen for contributing the powder coating tech-
nology section included in Chapter 8.
Our sincere thanks go to Nicky Carter for
managing the production of our book with care
and patience. Support by David Jackson facilitated
the completion of the second edition of our book.
We sincerely appreciate the support offered for this
book and others by Matthew Deans.
xv
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 1 Introduction to Fluoropolymers
1.1 Introduction
Carbon and fluorine are the major elements that
form polytetrafluoroethylene (PTFE) homopolymers.
The CeF bond is the main reason these plastics have
many special properties surpassing those of most
other polymers. These properties span mechanical,
electrical, and thermal characteristics of the fluo-
ropolymers in addition to their chemical resistance.
This book describes fluoropolymers in chemical
processing industries. These industries often
handle chemicals, usually corrosive, during the
manufacturing of diverse products. Examples of
important industries include chemical manufacturing,
plastics manufacturing and processing, semiconductor
manufacturing, pharmaceutical and biopharmaceutical
industries, and food processing.
Fluoropolymers replace stainless steel and exotic
alloys such as Hastelloy in processes involving
highly reactive chemicals. This plastic family has
successfully met the requirement of purity, which is
essential in semiconductor, food, and biopharma-
ceutical production. The nonstick surface and
extreme temperature characteristics of fluoropol-
ymers have reserved a special place for them in
the world of equipment construction materials. This
chapter offers a brief history of the discovery and the
evolution of fluoropolymers, their applications, and
the introduction of various types of this plastic
family.
Inception of fluoropolymers began with a small
incident that did not go undetected by the careful and
observant Dr. Roy Plunkett of DuPont Company [1].
In 1938, he had been at DuPont for 2 years,
concentrating mostly on the development of fluori-
nated refrigerants. He was experimenting with tet-
rafluoroethylene (TFE) for synthesis of a useful
refrigerant tetrafluorohydrochloro ethane
(CClF2eCHF2) [2]. The objective was to create safe,
nonflammable, nontoxic, colorless, and odorless re-
frigerants. On the morning of April 6, 1938, when
Plunkett checked the pressure gauge on a full cylin-
der of TFE, he found no pressure. The cylinder,
however, had not lost weight. Removal of the valve
Fluoropolymer Applications in the Chemical Processing Industries. http://dx.doi.org/10.1016/B978-0-323-44716-4.00001-4
Copyright © 2018 Elsevier Inc. All rights reserved.
and opening the cylinder yielded a few grams of a
waxy white powderdthe first polymer of TFE [2].
Plunkett analyzed the white powder, which was
conclusively proven to be PTFE. He could not
dissolve the slippery PTFE in any solvent, acid, or
base. After melting, it formed a stiff clear gel with no
tendency to flow [3,4]. Later, researchers were able to
fabricate parts from PTFE by processing techniques
similar to those used to make parts from metal
powders. At the time, the Manhattan Project was
seeking new corrosion-resistant materials for gaskets,
packings, and liners for uranium hexafluoride (UF6)
handling. PTFE provided the answer because of its
extreme resistance to chemicals. The US Govern-
ment maintained a veil of secrecy over the PTFE
project until the end of World War II.
Large-scale monomer synthesis and controlled
polymerization were technical impediments to be
overcome. Intense research resolved these problems,
and small-scale production of Teflon (trademark,
1944) began in 1947. In 1950, DuPont scaled up the
commercial production of Teflon in the United States
with the construction of a new plant in Parkersburg,
West Virginia. Since then, many more plants have
been built around the globe. Since the 1940s many
forms of PTFE and copolymers of TFE and other
monomers have been developed and commercialized.
Roy Plunkett recounted the story of Teflon in a
speech to the American Chemical Society at its April
1986 meeting in New York. “The discovery of pol-
ytetrafluoroethylene (PTFE) has been variously
described as (i) an example of serendipity, (ii) a lucky
accident, and (iii) a flash of genius. Perhaps all three
were involved. There is complete agreement, how-
ever, on the results of that discovery. It revolutionized
the plastics industry and led to vigorous applications
not otherwise possible.” [2].
1.2 What Are Fluoropolymers?
Traditionally, a fluoropolymer or fluoroplastic is
defined as a polymer consisting of carbon (C) and
fluorine (F). Sometimes they are referred to as
1
2 F LUOROPOLYMER A PPLICATIONS
perfluoropolymers to distinguish them from partially
fluorinated polymers, fluoroelastomers, and other
polymers that contain fluorine in their chemical
structure. For example, fluorosilicones, fluorinated
polyimides, and fluoroacrylates are not referred to as
fluoropolymers in the commercial world. An
example of a linear fluoropolymer is tetrafluoro-
ethylene polymer:
There are branched fluoropolymers such as fluo-
rinated ethylene propylene (FEP) polymer:
A simple analog would be a polyethylene
[(eCH2eCH2e)n] where all the hydrogen atoms
have been replaced by fluorine atoms. In reality,
entirely different processes prepare PTFE and
polyethylene.
Oxygen (O) and chlorine (Cl) are present in the
chemical structure of some commercial fluoropol-
ymers. Examples include perfluoroalkoxy polymer
(PFA) and polychlorotrifluoroethylene (PCTFE):
PFA
PCTFE
IN THE C HEMICAL P ROCESSING I NDUSTRIES
Rf is usually a perfluorinated group consisting of
carbon and fluorine. Introduction of nonlinearity,
oxygen and side chains, or chlorine invokes a variety
of polymer properties such as lower crystallinity,
clarity, and resistance to water vapor.
There is a second class of fluoropolymers called
“partially fluorinated” in contrast to “perfluorinated”
polymers. These molecules include hydrogen (H) in
addition to fluorine and carbon. Examples include
polyvinylfluoride (PVF), polyvinylidene fluoride
(PVDF), ethylene tetrafluoroethylene (ETFE)
copolymer, and ethylene chlorotrifluoroethylene
(ECTFE) copolymer.
PVF
PVDF
ETFE
Cl Cl
ECTFE
Partially fluorinated fluoropolymers have different
properties and processing characteristics than the
perfluoropolymers. For example, perfluoropolymers
are more thermally stable but physically softer than
partially fluorinated polymers.
1: I NTRODUCTION TO F LUOROPOLYMERS
1.3 Fundamental Properties of
Fluoropolymers
The basic properties of fluoropolymers arise
from the atomic structure of fluorine, carbon, and
covalent CeF bond in specific chemical structures.
Those properties are weakened as the fluorine
content of the chemical structure decreases as
in PVDF. Because PTFE has a linear structure, it
is a good subject for discussion of extreme
properties. The backbone is formed of carbone
carbon bonds attached to carbonefluorine bonds.
Both are extremely strong bonds, especially
carbonefluorine bond (CeC ¼ 348e368 kJ/mol
and CeF ¼ 488e544 kJ/mol) [5,6]. The basic
properties of PTFE stem from those two very strong
chemical bonds. The PTFE molecule resembles a
carbon rod completely blanketed with a sheath of
fluorine atoms [7].
The size of the fluorine atom allows the formation
of a uniform and continuous sheath around the
carbonecarbon bonds and protects them from
attack, thus imparting chemical resistance and
stability to the molecule. The fluorine sheath is also
responsible for the low surface energy (18 dyn/cm)
[8] and low coefficient of friction (0.05e0.08, static)
[7] of PTFE [9]. Another attribute of the uniform
fluorine sheath is the electrical inertness (or non-
polarity) of the PTFE molecule. Electrical fields
impart only slight polarization to this molecule, so
volume and surface resistivity are high. Table 1.1
Table 1.1 Fundamental Properties of
Polytetrafluoroethylene
 High melting point (342 C)
 High thermal stability
 Useful mechanical properties at extremely low
and high temperatures
 Insolubility
 Chemical inertness
 Low coefficient of friction
 Low dielectric constant/dissipation factor
 Low water absorptivity/adsorptivity
 Excellent weatherability
 Flame resistance
 Purity
3
Table 1.2 Useful Attributes of Perfluoropolymers
 Stability
 High continuous use temperature
 Excellent weatherability
 Excellent chemical resistance
 Excellent fire properties
 Low surface energy
 Good release properties
 Biological inertness
 Low friction
 Cryogenic properties
 Retains flexibility
 Electrical properties
 Low dielectric constant
 Low dissipation factor
summarizes the fundamental properties of PTFE,
which represents the ultimate polymer among all
fluoroplastics.
The basic properties of perfluoropolymers provide
beneficial attributes with high commercial value
(Table 1.2).
1.4 Developmental History of
Fluoropolymers
The development of fluoropolymers began with
the invention of PTFE in 1938, continued to 1992
when a soluble perfluoropolymer (Teflon AF) was
introduced, and to 2002 when fluoroplastics poly-
merized in supercritical carbon dioxide were intro-
duced. Table 1.3 summarizes the timeline for the
development of fluoropolymers that have brought
about major changes in properties and/or fabrication
processes.
The discovery of PTFE was a major leap forward
in material science. Yet the new polymer could not be
fabricated by melt-processing. The next two forms of
PTFE, fine powder and dispersion, were also not
melt-processible. The pursuit of a more easily pro-
cessible polymer led to FEP, which could be melted
in an extruder. Compared with PTFE, the major
disadvantage of FEP is its reduced thermal stability
and lower maximum continuous use temperature
4 F LUOROPOLYMER A PPLICATIONS IN THE C HEMICAL P ROCESSING I NDUSTRIES

Table 1.3 Commercialization Timeline of Major Fluoropolymers Versus Key Processing/Application Trade-Offs [10]

Year
Fluoropolymer Commercialized Monomers Trade-off D Trade-off L
PTFE 1947 TFE Continuous use Nonemelt-
temperature 260 C processible
PCTFE 1953 CTFE Melt-processible/nonemelt- Maximum
processible continuous use
temperature 180 C
FEP 1960 TFE, HFPc Melt-processible Maximum
continuous use
temperature 200 C
PVF 1961 VFa Thin film/weatherable Maximum
continuous use
temperature 107 C
PVDF 1961 VDFb Melt-processible Maximum
continuous use
temperature 150 C
ECTFE 1970 CTFE, Ed Hardness/toughness Maximum
continuous use
temperature 150 C
PFA 1972 TFE, PAVEe Melt-processible, Low molecular
continuous use temperature weight
260 C
ETFE 1973 TFE, E Hardness/toughness Maximum
continuous use
temperature 150 C
Teflon AF 1985 TFE, PDDf Soluble in special High cost
halogenated solvents
CTFE, chlorotrifluoroethylene; E, ethylene; ECTFE, ethylene chlorotrifluoroethylene; ETFE, ethylene tetrafluoroethylene; FEP, fluorinated
ethylene propylene; HFP, hexafluoropropylene; PAVE, perfluoroalkylvinylether; PCTFE, polychlorotrifluoroethylene; PDD, 2,2-
bistrifluoromethyl-4,5 difluoro-1,3-dioxole; PFA, perfluoroalkoxy; PTFE, polytetrafluoroethylene; PVDF, polyvinylidene fluoride; PVF, poly-
vinylfluoride; TFE, tetrafluoroethylene; VDF, vinylidene fluoride; VF, vinyl fluoride.
a
Vinyl fluoride (CH2 ] CHF).
b
Vinylidene fluoride (CH2 ] CF2).
c
Hexafluoropropylene (CF2 ] CF e CF3).
d
Ethylene (CH2 ] CH2).
e
Perfluoroalkylvinylether (CF2 ] CF e O e Rf).
f
Perfluoro-2,2-dimethyl-1,3-dioxole.

(200 C) (Table 1.3). PFA, which was introduced in
1973, offers both melt-processing and the same upper
continuous use temperature as PTFE (260 C).
ETFE addresses the need for a mechanically
stronger polymer, albeit at some loss of properties
compared to perfluoropolymers because of the pres-
ence of hydrogen in its molecule:
ETFE has a lower continuous use temperature
(150 C) than PTFE (260 C), less chemical resistance,
and a higher coefficient of friction. Mechanical
properties including tensile strength, elongation at
break, and tensile modulus are enhanced. Examples of
beneficial performance include increased cut-through
resistance as wire insulation when compared to PTFE.
Teflon AF is an amorphous fluoropolymer that is
soluble in select halogenated solvents. It is applied by
solution coating processes followed by removal of
the solvent. The amorphous fluoropolymer coating is
as resistant to nearly as many chemicals as PTFE.
1: I NTRODUCTION TO F LUOROPOLYMERS 5

The coating can be very thin ranging from less than a
micrometer and upwards. Other amorphous fluo-
ropolymer brands include Lumiflon and Cytop by
Asahi Glass Corp.
There are a number of other polymers in this family
including PCTFE, PVF, PVDF, ECTFE, TFE/hexa-
fluoropropylene/vinylidene fluoride terpolymers, and
chlorotrifluoroethylene/vinyl ether copolymers.
1.5 Applications of
Fluoropolymers
Consumption of fluoropolymers has increased
over time, as technological advances have required
Table 1.4 Major Applications and Some Uses of Fluoropolymers [10]
the properties of these plastics. Fluoropolymers use
spans across all facets of human life from household
appliances and cookware to aerospace and electronic
industries. Useful properties (Table 1.2) of fluo-
ropolymers in various applications include chemical
resistance, thermal stability, cryogenic properties,
low coefficient of friction, low surface energy, low
dielectric constant, high volume and surface re-
sistivity, and flame resistance. Applications of fluo-
ropolymers, typically, exploit one or a combination
of fluoropolymer properties (Table 1.4) that differ-
entiate them from other plastics.
In the chemical processing industry fluoropol-
ymers are selected mainly for their resistance to
chemical attack usually at above or below room

Industry/Application Area Key Properties Typical Uses

Chemical processing
Electrical and communications
dielectric breakdown voltage, flame cable, automotive wiring harness
Automotive and office equipment
Housewares
energy, chemical resistance, purity
Medical
Architectural fabric
Chemical resistance, good
mechanical properties, thermal
stability, cryogenic properties
Low dielectric constant, high
volume/surface resistivity, high
resistance, thermal stability
Low coefficient of friction, good
mechanical properties, cryogenic
properties, chemical resistance
Thermal stability, low surface
Low surface energy, purity,
excellent mechanical properties,
chemical resistance
Excellent weatherability, flame
resistance, low surface energy
Gaskets, vessel liners; valve, pipe,
and fitting liners; T’s, bellows,
spacer, high-pressure hoses
tubing; coatings and fluid handling
systems
Connectors, insulation of signal and
electric wire and cable, coaxial
and electronic wiring harness,
thermocouple wire, multicore
instrumentation cable, jacketing,
high-temperature automotive and
aerospace wire
Seals and rings in automotive
power steering, transmission, and
air-conditioning; copier roller and
food processing equipment
covering
Domestic and commercial
cookware and bakeware coatings
Cardiovascular grafts, heart
patches, mesh grafts for hernia
repair, ligament replacement, vent
and intravenous infusion
membranes, microporous
polytetrafluoroethylene tubing for
drug dispersion
Coated fiberglass fabric for tension
and air structures, tents, stadium
and airport roofs, exhibition halls,
super shopping malls,
entertainment complexes
6 F LUOROPOLYMER A PPLICATIONS
temperature. These plastics are used to fabricate
linings for carbon steel vessels and for piping and
other fluid handling components. They provide du-
rable, low maintenance, and economical alternatives
to exotic metal alloys. In these applications, fluo-
ropolymers also offer thermal stability for use at high
temperatures. As they do not react with process
streams, fluoropolymers help prevent contamination
of products of chemical processes.
Electrical properties of fluoropolymers are highly
valuable in electronic and electrical applications. In
data communications, for example, FEP is used to
insulate cables installed in air-handling spaces (ple-
nums) in office buildings. FEP supplies the excellent
dielectric properties these cables required to perform
well at high data transmission rates as well as long-
term stability. The performance of FEP insulated
cables remains unchanged over the life of the cabling
system. Most importantly, FEP aids these cables meet
the strict building code requirements for low flame
spread and low smoke generation.
Fluoropolymers are used to insulate wire in critical
aerospace and industrial applications where chemical
and thermal resistance in addition to cut-through
resistance and flex fatigue durability are essential.
Fluoropolymers are also materials of construction for
high-frequency cable connectors and for thermo-
couple wiring required to resist high temperatures.
In the automotive, office equipment, and other
industries, the mechanical properties of fluoropol-
ymers are beneficial in low-friction bearings and
seals that resist attack by hydrocarbons and other
fluids. In food processing, the Food and Drug
Administration (FDA) has approved fluoropolymer
grades as fabrication material for equipment due to
their resistance to oil and cleaning materials, and
their antistick and low friction properties.
Fluoropolymers are applied as nonstick coatings
for cookware and appliance surfaces. These appli-
cations depend on thermal and chemical resistance as
well as antistick performance. PTFE and ETFE are
selected to insulate appliance wiring because both
materials withstand high temperatures.
Medical articles such as surgical patches and
cardiovascular grafts rely on the long-term stability
of fluoropolymers as well as their biocompatibility,
purity, inert surface, and flex fatigue resistance.
IN THE C HEMICAL P ROCESSING I NDUSTRIES
For airports, stadiums, and other structures,
fiberglass fabrics coated with fluoropolymers are
fabricated into roofing and enclosures. Cables or air
pressure are applied to from a range of innovative
structures from these architectural fabrics. Fluo-
ropolymers provide excellent resistance to weath-
ering, including exposure to the ultraviolet rays in
sunlight, flame resistance for safety, and low surface
energy for soil resistance and easy cleaning.
References
[1] R.J. Plunkett, US Patent 2,230,654, assigned to
DuPont Co. (Feb. 4, 1941).
[2] R.J. Plunkett, The history of polytetrafluoro-
ethylene: discovery and development, in:
R.B. Seymour, G.S. Kirshenbaum (Eds.), High
Performance Polymers: Their Origin and
Development, Proc. Symp. Hist. High Perf.
Polymers: At the ACS Meeting in New York,
April 1986, Elsevier, New York, 1987.
[3] S.V. Gangal, Polytetrafluoroethylene, homopol-
ymers of tetrafluoroethylene, in: second ed.En-
cyclopedia of Polymer Science and Engineering,
16, John Wiley & Sons, New York, 1989, pp.
577e600.
[4] V. Gangal, P.D. Brothers, Perfluorinated poly-
mers, polytetrafluoroethylene, Pub. Online Ency.
Polym. Sci. Eng. (June 2010).
[5] Big Chemical Encyclopedia, http://chempedia.
info/info/99237/, April 18, 2016.
[6] University of Waterloo, Canada, www.science.
uwaterloo.ca, April 18, 2016.
[7] S.V. Gangal, Polytetrafluoroethylene, in: fourth
ed.Kirk-Othmer Encyclopedia of Chemical
Technology, 11, John Wiley & Sons, New York,
2000, pp. 621e644.
[8] W.A. Zisman, Surface properties of plastics,
Record of Chemical Progress 26 (1965) 1.
[9] Properties Handbook No. H-37051-3, Teflon
PTFE Fluoropolymers Resin, DuPont, July 1996.
[10] S. Ebnesajjad, Fluoroplastics, in: Non-Melt
Processible Fluoroplastics, second ed., vol. 1,
Plastics Design Library, Elsevier, Oxford, UK,
2014.

2.1 Introduction
An engineer has a wide choice of materials of
construction for corrosion control. There are three
broad categories of materials, used either individually
or in combination with each other: metals, polymers,
and ceramics. This chapter describes the differences
between them and explains the phenomenology of
applications of polymer-based materials. It also places
fluoropolymer materials in their appropriate contexts.
Polymer-based materials are also known as poly-
merics, polymeric materials, or simply plastics, which
is often not accurate and can lead to confusion.
2.2 Historical Background
Lead, wood, and rubber are probably the earliest
known materials of construction for the chemical
processing industry (CPI). Interestingly, it took a
little more than a century for rubber to be established
as a lining material after Charles Goodyear acci-
dentally discovered vulcanized rubber in 1839. Wood
is the first composite material to be used in the CPI.
Until the onset of World War II, these naturally
occurring materials continued to play a major role in
chemical-handling applications.
Although stainless steel was discovered at the turn
of the century and copper silicon alloys started to
emerge at about the same time, the real explosion of
materials research and development began at around
the beginning of World War II. Polymer science and
technology were no exception. Nylon was already
developed at the DuPont Company. Alloy 20 was
developed by DuPont in the late 1930s. At about the
same time, polytetrafluoroethylene (PTFE) (Teflon)
was discovered, which led to further development
of fluoropolymers and ushered in an era of high-
performance polymer materials for corrosion control.
The 1950s were known for the explosive develop-
ment and growth in elastomers. DuPont Company
developed a whole range of synthetic elastomers
such as neoprene (polychloroprene), Hypalon (chlor-
osulfonated polyethylene), and Nordel (terpolymer
Fluoropolymer Applications in the Chemical Processing Industries. http://dx.doi.org/10.1016/B978-0-323-44716-4.00002-6
Copyright © 2018 Elsevier Inc. All rights reserved.
2 Materials of Construction
of ethylene propylene diene monomer). These were
followed later by fluoroelastomers such as Viton
and Kalrez. The 1960s and 1970s saw further
refinement of these fluorine-containing elastomers
with several new grades developed for specific needs
in the CPI.
Rigid thermosetting materials have always
attracted the interest of engineers in the CPI since
Bakelite (phenol formaldehyde) was put to use for
commercial applications. Various fibers and particu-
late additives were developed to make useful struc-
tures out of these materials. The 1940s saw major
initiatives in the development of polyester resins.
Bisphenol A fumarate resins with unsaturation sites
for cross-linking were developed for processing
vessels and piping. These resins, in their reinforced
forms, were the early artificial composites for the
CPI. Development of vinyl esters, chlorendic anhy-
dride, and furans added greatly to the versatility of
fiberglass-reinforced polyester (FRP). These became
the workhorses in the chloralkali industry for
handling chlorine and chlorine-containing chemicals.
While the United States was pursuing the FRP
route, Europeans were busy taking the lead in
developing technologies using thermoplastic mate-
rials such as polyethylene (PE), polyvinyl chlorides,
and polypropylenes (PPs). The result was an increased
use of these materials as self-supporting structures as
well as linings. They achieved this through an effec-
tive partnership of governments, industries, and
academia, which ultimately produced several auton-
omous testing and training centers. A major outcome
was the use of low-end thermoplastics [PE, polyvinyl
chloride (PVC), and PP] for “dual laminate” structures
where the structural component is FRP and the lining
is a thermoplastic material. This technology was
subsequently exported to Canada and then to the
United States.
Manufacturing technologies (injection molding,
transfer molding, contact molding, compression
molding, isostatic molding, ram extrusion) and design
procedures were concurrently developed to promote
the use of these materials. The resin converters played
a bigger role in these activities than the resin
7
8 F LUOROPOLYMER A PPLICATIONS
manufacturers. The creation of a multitude of mate-
rials in a relatively short time led to high expectations
and less-than-careful application of some of these
materials. Failures, some catastrophic, inevitably
occurred. Notable among these were ruptures of FRP
storage tanks and vessels resulting in total discharge
of corrosive and hazardous contents. Less notable but
equally damaging failures also occurred in linings of
various types. The underlying causes were improper
material selection, design, quality of fabrication,
exceeding operating parameters, inability to inspect
adequately, or some combination of these.
2.3 Definition of Polymer-Based
Materials
Polymers are long chain molecules made from
organic chemicals. These materials are defined by
three distinct characteristics.

Organic chemistry basis

Mechanical strength basis

Thermal processing basis
Polymers can be distinguished from each other by
their generic organic chemistry description such as
polyolefins, fluorocarbons, styrenics, epoxies, etc.
They can also be classified by their mechanical
strength: rigid (elastic modulus >690 MPa), semi-
rigid (modulus between 69 and 690 MPa), and
nonrigid (modulus <69 MPa). Additionally, poly-
meric materials are classified by the way they are
thermally processed: thermoplastics and thermosets.
Thermoplastics are those which can be remelted and
reprocessed repeatedly. Thermosets cannot be
remelted for reprocessing since they are cross-linked
(also known as vulcanized in the world of elasto-
mers). Any attempt to remelt thermosets will result in
degradation and, ultimately, charring.
Fluoropolymers are thermoplastic and nonrigid
materials while fluoroelastomers have elastomeric
properties. See Tables 2.1 and 2.2 for a comparison of
physical and mechanical properties of select plastics
and elastomers including fluorinated materials.
Elastomers are a special class of nonrigid materials
distinguished by high elongation and high recovery.
A complete description of a polymer system must
necessarily include references to all three categories.
Some following examples illustrate the point.
IN THE C HEMICAL P ROCESSING I NDUSTRIES
1. A fiberglass tank is made of vinyl ester resin,
which is a thermoset and is semirigid in its
composite form.
2. A rubber (elastomeric) gasket can be made of
polychloroprene, which is a thermoset and is
nonrigid.
3. A fluoropolymer lining for a vessel is thermo-
plastic and nonrigid.
2.4 Comparison Between Polymer-
Based Materials and Metals
There are some obvious and subtle differences
between polymer-based materials and metals. The
obvious differences are in strength (high for metals),
elongation (high for polymers), and maximum-use
temperature (much higher for metals). Not so
obvious are anisotropy (polymers), homogeneity
(metals), changing properties in service (plastics),
responsiveness to nondestructive testing (high for
metals), ability to predict remaining life (low for
polymers), ability to carry out accelerated testing
for corrosion rates (high for metals), and sensitivity
to workmanship (high for polymers). All these fac-
tors make using plastics as effective as metals and
with the same degree of confidence and a challenge
for the end user.
Phenomenology of corrosion for metals and
polymer materials is not the same. For example, the
terms such as corrosion rate, pitting, end grain
attack, and intergranular attack used to describe
metals’ behaviors are not applicable to plastics. Not
only are the terms for plastics different (blistering,
discoloration, cracking, etc.) but they are based on a
naked-eye observation and not at a microscopic level
as for metals.
2.4.1 Position of Fluoropolymers
in the Materials Spectrum
Fluoropolymers are fluorine-containing polymers.
They are thermoplastic in nature and are semirigid
and are classified in two ways:

Homopolymers or copolymers (preferred by
chemists)

Fully fluorinated or partially fluorinated
(preferred by engineers)
 2: M ATERIALS
Table 2.1 Physical and Mechanical Properties of Plastics [1,2]

OF
Mold Tensile Break Tensile Flexural Flexural Impact

C ONSTRUCTION
Specific Shrinkage, Strength, Elongation, Modulus, Strength, Modulus, Notched Izod Compressive
Gravity % MPa % MPa MPa MPa 238C J/m (238C) Strength, MPa
Test method D792 D955 D638 D638 D638 D790 D790 D256 D695
ASTM
Polystyrene 1.06 0.5 46 2.2 3172 96 3103 10.8 96.6
ABS 1.05 0.6 48 8.0 2069 72 2621 242 69
SAN 1.08 0.4 72 3.0 3862 103 3793 27 103
Polypropylene 0.90 1.5 32 15.0 1310 41 2069 27 34.5
Polyethylene 0.96 2.0 30 9.0 1034 38 1517 70 27.6
Polyacetal 1.41 1.8 61 60.0 2827 90 2552 70 36
Polyester 1.30 2.0 55 200.0 2758 88 2345 10.8 90
Polyamide, 1.13 1.3 81 200.0 2758 103 2759 53.8 90
nylon 6
Polyamide, 1.14 1.8 79 300.0 1310 103 1310 53.8 34
nylon 6,6
Polycarbonate 1.20 0.6 62 110.0 2379 93 2345 161 86
Polysulfone 1.24 0.7 70 75.0 2482 106 2690 32 96.6
Test method D792 Measured on D4894-5 D4894-5 D638 D790 D790 D256
ASTM parts D1708 D638 D1708 D638
PTFE 2.14e2.22 2e0 20e35 300e550 550 No break 340e620 188 34.5
PFA 2.15 3.5e6.0 20e26 300 276 551 No break
FEP 2.15 3.5e6.0 20e28 300 345 No break 655 No break 15.2
ETFE 1.71 1e7 45 150e300 827 38 1034e1171 No break 17.2
PVDF 1.78 0.2e3 31e52 50e250 1040e2070 45e74 1140e2240 107e427 55e110

ETFE, ethylene tetrafluoroethylene; FEP, fluorinated ethylene propylene; PFA, perfluoroalkoxy; PTFE, polytetrafluoroethylene; PVDF, polyvinylidene fluoride.

9
 10
Table 2.2 Physical and Mechanical Properties of Elastomers [3]

Trade Name

F LUOROPOLYMER A PPLICATIONS
Viton Aflas Fluorosilicone Kalrez Adiprene Neoprene Hypalon Nordel

Chemical Name

Tetrafluoroethylene/ Chloros Ethylene/

Fluorinated Propylene Perfluoro- Polychl ulfonated Propylene
Property Hydrocarbon Copolymer Fluorosilicone elastomer Polyurethane oroprene Polyethylene Copolymer

Continuous-use Min 29 to 7 29 80 to 68 38 54 62 54 59
temperature,  C Max 227 204 to 230 232 290 to 315 121 149 135 163

Tensile strength, MPa a 3.4e20.7 13.8e22.1 3.4e9.6 3.4e10.3 2.1e24.1 3.4e27.6 e 2.1e24.1

Tensile modulus at 1.4e14 6.2e17.2 6.2 6.2e13.1 0.7e20.7 0.7e20.7 3.1e3.4 0.7e20.7
100% elongation, MPaa

IN THE
Hardness (durometer) 50e95 A 60e100 A 35e80 A 65e95 A 30e90 A 15e95 A 40e100 A 30e90 A

Compression set 9e16, 70 h at 25, 70 h at 93 17e25, 22 h at 149 20e40, 20e60, 70 h at 20e60 h at 100 38e80, 22 h at 100 20e60, 70 h at
at temperature,  C 24 70 h at 21 100 100

C HEMICAL P ROCESSING I NDUSTRIES

Elongation, % 100e500 50e400 100e480 60e170 100e700 100e800 100e700 100e700
a
To convert from MPa to psi, multiply by 145.
 2: M ATERIALS
OF
C ONSTRUCTION
Table 2.3 Water Absorption and the Effecta of Inorganic Chemicals on Polymers [1,2]

24-h Water
Weak Bases and Salts Strong Bases Strong Acids Strong Oxidants Absorption

Weight
Material 258C 938C 258C 938C 258C 938C 258C 938C Change, %
Polyacetal 1e3 2e5 1e5 2e5 5 5 5 5 0.23
ABS 1 2e4 1 2e4 1e4 5 1e5 5 0.1e0.4
Nylons 1 2 2 3 5 5 5 5 0.2e1.9
Polyester 1 3e4 2 5 3 4e5 2 3e5 0.06e0.09
Polyethylene 1 1 1 1 1 1 1 1 <0.01
Polystyrene 1 5 1 5 4 5 4 5 0.03e0.60
Polysulfone 1 1 1 1 1 1 1 1 0.2e0.3
Polyvinyl chloride 1 5 1 5 1 5 2 5 0.04e1.0
PTFE 1 1 1 1 1 1 1 1 0
PFA 1 1 1 1 1 1 1 1 <0.03
FEP 1 1 1 1 1 1 1 1 <0.01
ETFE 1 1 1 1 1 1 1 1 <0.03
PVDF 1 1 1 2 1 2 1 2 0.04
Polychlorotrifluoroethylene 1 1 1 1 1 1 1 1 0.01e0.10

ETFE, ethylene tetrafluoroethylene; FEP, fluorinated ethylene propylene; PFA, perfluoroalkoxy polymer; PTFE, polytetrafluoroethylene; PVDF, polyvinylidene fluoride.
a
Effect is defined by ASTM D543 and D2299: 1, no effect or inert; 2, slight effect; 3, mild effect; 4, softening or swelling; 5, severe degradation.

11
 12
Table 2.4 Effecta of Organic Chemicals on Polymers [1,2]

Aromatic Solvents Aliphatic Solvents Chlorinated Solvents Esters and Ketones

Material 258C 938C 258C 938C 258C 938C 258C 938C

Polyacetal 1e4 2e4 1 2 1e2 4 1 2e3

F LUOROPOLYMER A PPLICATIONS
ABS 4 5 2 3e5 3e5 5 3e5 5
Nylons 1 1 1 1 1 2 1 1
Polyester 2 5 1 3e5 3 5 2 3e4
Polyethylene 3 4 3 4 3 4 3 4
Polystyrene 4 5 4 5 5 5 4 5
Polysulfone 4 4 1 1 5 5 3 4
PVC 4 5 1 5 5 5 4 5
PTFE 1 1 1 1 1 1 1 1
PFA 1 1 1 1 1 1 1 1

IN THE
FEP 1 1 1 1 1 1 1 1
ETFE 1 1 1 1 1 1 1 1

C HEMICAL P ROCESSING I NDUSTRIES

PVDF 1 1 1 1 1 1 3 5
PCTFE 1 1 1 1 3 4 1 1
ETFE, ethylene tetrafluoroethylene; FEP, fluorinated ethylene propylene; PCTFE, polychlorotrifluoroethylene; PFA, perfluoroalkoxy polymer; PTFE, polytetrafluoroethylene; PVC, Polyvinyl
chloride; PVDF, polyvinylidene fluoride.
a
Effect is defined by ASTM D543 and D2299: 1, no effect or inert; 2, slight effect; 3, mild effect; 4, softening or swelling; 5 ¼ severe degradation.
 2: M ATERIALS
Table 2.5 Summary of StructureeRheologyeFabrication Process for Commercial Fluoropolymers [4]

Polymer Monomer Unit Melt Pointa Melt Viscosity, Pa$sb Melt Flow Rate, dg/min Fabrication Technique

OF
10 12c
Granular PTFE eCF2eCF2e 327 10 e10 Compression molding

C ONSTRUCTION
Fine powder PTFE eCF2eCF2e 327 1010e1012c Paste extrusion
10 12c
Dispersion PTFE eCF2eCF2e 317e337 10 e10 Coating methods
4 5d
FEP eCF2eCF2eC(CF3)F 260e282 10 e10 0.8e18e Melt processing
eCF2e
PFA eCF2eCF2$C(OeRf) 302e310 4  103e3  104d 1e18f Melt processing
FeCF2e
ETFE eCF2eCF2eCH2eCH2 254e279 0.7e10  103g 3.7e16h Melt processing
i
PCTFE eCClFeCF2e 210e215 1e10 Compression molding/
melt processing
ECTFE eCClFeCF2eCH2eCH2e 240 e 1e50 Melt processing
3 j
PVDF eCF2eCH2e 155e192 0.2e17  10 5e180 Melt processing
Polyvinyl fluoride eCHFeCH2e 190 e e Melt extrusion of
dispersion in latent
solvent
Soluble fluoropolymers e[CF2eCF2]n-me[Cf]mk 305 e e Latex application
methods

ECTFE, ethylene chlorotrifluoroethylene; ETFE, ethylene tetrafluoroethylene; FEP, fluorinated ethylene propylene; PCTFE, polychlorotrifluoroethylene; PFA, perfluoroalkoxy polymer; PTFE,
polytetrafluoroethylene; PVDF, polyvinylidene fluoride.
a
Second melt point for PTFE.
b
From Ref. [5].
c
Melt creep viscosity by according to procedure MVS Patent.
d
By capillary rheometer ASTM D 2116.
e
Melt flow rate by ASTM D 2116.
f
By capillary rheometer ASTM D 3307.
g
By capillary rheometer ASTM D 3159.
h
Melt flow rate by ASTM D 3159.
i
By capillary rheometer at 230 C.
j
Melt flow rate at 265 C.
k
Cf is the comonomer m > 0.2 weight fraction.

13
14 F LUOROPOLYMER A PPLICATIONS IN THE C HEMICAL P ROCESSING I NDUSTRIES

Table 2.6 Overview of Polymer Materials for Corrosion Control

2: M ATERIALS OF C ONSTRUCTION
These materials have the highest chemical resis-
tance (Tables 2.3 and 2.4) among the polymer ma-
terials as well as maximum-use temperature.
Corrosion resistance is a function of the level of
fluorine, hence the fully fluorinated ones are usually
preferred for tough applications.
1. Fully fluorinated
a. PTFE (polytetrafluoroethylene)
b. FEP (fluorinated ethylene propylene)
copolymer
c. PFA (perfluoroalkoxy) (perfluoropropyl
vinyl ether)
d. MFA (perfluoroalkoxy) (perfluoromethyl
vinyl ether)
2. Partially fluorinated
a. ETFE (ethylene tetrafluoroethylene
polymer)
b. ECTFE (ethylene chlorotrifluoroethylene
polymer)
c. PVDF (polyvinylidene fluoride)
Table 2.5 presents a summary of structuree
rheologyefabrication process relationship for com-
mercial fluoropolymers.
2.5 Applications of Polymer-Based
Materials for Corrosion Control
Applications for corrosion control are classified as
follows:

Barrier (linings)

Self-supporting structures

Others (seals, gaskets, column internals, etc.)
Table 2.6 shows the applications and the materials
typically used. It is clear from the table that fluo-
ropolymers are used principally for barriers (linings)
and other applications such as column internals,
seals, and gaskets. In rare situations they are used to
construct self-supporting structures.
15
2.5.1 Applications of
Fluoropolymers for Corrosion
Control
Fluoropolymers are principally used as barriers,
i.e., linings for storage vessels, reactors, columns,
pipes, valves, pumps, expansion joints, and hoses. In
a few cases, they are also used as self-supporting
structures such as piping and tubing. Linings are
achieved by various manufacturing techniques such
as thermoforming, welding, isostatic molding, ram
extrusion, and injection molding. Sizes range from
large field-erected storage tanks to packings for col-
umn internals in complex shapes. Various techniques
are used to manufacture parts; these are covered in
Chapters 6 and 7. Issues related to the successful use
of fluoropolymers are covered in Chapter 9. Supply
chains are typically long and complex; these are
covered in Chapter 8. Choosing fluoropolymers im-
plies evaluation of all candidate materials including
metals and other polymers. The selection methodol-
ogy is covered in Chapter 4.
This book covers the use of fluoropolymers for
corrosion control in CPIs.
References
[1] Properties Handbook, No. H-37051e3, Teflon®
PTFE Fluoropolymers Resin, DuPont, July, 1996.
[2] V. Shah, Handbook of Plastics Testing Technol-
ogy, first ed., Wiley-Interscience Pub., John Wiley
& Sons, NY, 1984.
[3] P.K. Khaladkar, Using plastics, elastomers and
composites for corrosion control (Chapter 54), in:
R. Winston Revie (Ed.), Uhlig’s Corrosion
Handbook, John Wiley & Sons, NY, 2000.
[4] S. Ebnesajjad, Fluoroplastics, in: Melt Process-
ible Fluoropolymers: The Definitive User’s Guide
and Data Book, Plastics Design Library, vol. 2,
William Andrew Publishing, Norwich, NY, 2002.
[5] S. Ebnesajjad, Fluoroplastics, in: Non-melt Pro-
cessible Fluoroplastics: The Definitive User’s
Guide and Data Book, Plastics Design Library,
vol. 1, William Andrew Publishing, Norwich, NY,
2000.
This page intentionally left blank
3 Properties of Neat (Unfilled) and Filled Fluoropolymers

3.1 Introduction Additional information for fluoropolymers can be

An essential and fundamental property of fluo-
ropolymers is resistance to organic and inorganic
chemicals (Table 3.1). A majority of the applications
of fluoropolymers rely on the inertness of fluoropol-
ymers to chemicals. Chemical properties of fluo-
ropolymers are not affected by fabrication conditions.
Other properties useful to industrial applications
include broad continuous use temperature, low coef-
ficient of friction, low dielectric constant, dielectric
breakdown strength, insulation properties, and purity.
A weakness of fluoropolymers in neat form is
lower mechanical properties than typical engineering
plastics. Addition of fillers and design strategies
overcome those shortcomings for most applications.
found in published Refs. [2e4].
Another aspect of the interaction of these plastics
with chemicals is permeation. Even though a re-
agent may not react with a fluoropolymer, it may be
able to permeate through the polymer structure. The
extent and rate of permeation depend on the struc-
ture and properties of the plastic article as well as
the type and concentration of permeant. Tempera-
ture and pressure usually influence the permeation
process.
This chapter reviews chemical compatibility of
fluoropolymers and their permeation behavior toward
different chemicals. This chapter has been divided
based on the fluorine content of fluoropolymers, that
is, perfluorinated and partially fluorinated. In general,

Table 3.1 A Comparison of the Chemical Resistance of Fluoropolymers [1]

Types of Medias PTFE PFA FEP ECTFE PVDF

Acids Inorganic þ þ þ þ þ
Organic þ þ þ þ þ
Bases Organic þ þ þ þ 
Salts þ þ þ þ þ
Halogens þ þ þ 0 0
Solvents Aliphatic þ þ þ þ þ
hydrocarbons
Aromatic þ þ þ þ þ
hydrocarbons
Chlorinated þ þ þ 0 0
hydrocarbons
Ketones þ þ þ 0 
Amines þ þ þ 0 
Alcohols þ þ þ þ þ
Furanes þ þ þ  
Esters þ þ þ 0 0
Aldehydes þ þ þ 0 þ
Phenols þ þ þ þ þ
þ, recommended; 0, may be used; , not recommended; ECTFE, ethylene chlorotrifluoroethylene; FEP, fluorinated ethylene propylene; PFA,
perfluoroalkoxy; PTFE, polytetrafluoroethylene; PVDF, polyvinylidene fluoride.

Fluoropolymer Applications in the Chemical Processing Industries. http://dx.doi.org/10.1016/B978-0-323-44716-4.00003-8

Copyright © 2018 Elsevier Inc. All rights reserved. 17
18 F LUOROPOLYMER A PPLICATIONS IN THE C HEMICAL P ROCESSING I NDUSTRIES

resistance of polymers to chemicals of all types in-
creases with an increase in their fluorine content.
Therefore, the chemical resistance of ethylene
tetrafluoroethylene (ETFE), ethylene chlorotri-
fluoroethylene (ECTFE), and polyvinylidene fluoride
(PVDF) is generally inferior to that of perfluorinated
polymers such as perfluoroalkoxy (PFA) and fluori-
nated ethylene propylene (FEP).
3.2 Influence of Processing
on Fluoroplastics
Crystallinity affects a number of important prop-
erties of semicrystalline thermoplastics including
fluoropolymers. The degree of crystallinity in a
fabricated part depends on the processing conditions
such as the length of exposure to temperatures above
the melting point and the cooling rate. Elimination of
bubbles, trapped air, and voids during processing
have a major impact on a number of properties of a
part including mechanical, electrical, and resistance
to permeation of chemicals. A group of per-
fluoropolymer properties that remain relatively in-
dependent of the fabrication conditions are listed in
Table 3.2. Partially fluorinated fluoroplastics contain
hydrogen or chlorine and can undergo significant
thermal degradation if they are overexposed ther-
mally during processing. Thermal degradation alters
many of the properties listed in Table 3.2 for partially
fluorinated fluoroplastics.
3.3 Chemical Compatibility of
Fluoropolymers
3.3.1 Chemical Compatibility of
Perfluoropolymers
Perfluoropolymers such as polytetrafluoroethylene
(PTFE), PFA, and FEP are by far the most chemically
resistant among all thermoplastics (Tables 3.3e3.7).
Few substances chemically interact with these plas-
tics. Exceptions among commercially encountered
materials include alkali metals, especially in a molten
state, and gaseous fluorine at high temperatures and
pressures. Perfluoropolymers are attacked by certain
halogenated compounds containing fluorine such as
chlorine trifluoride (ClF3), bromine trifluoride
(BrF3), iodine pentafluoride (IF5), and oxygen
difluoride (OF2). The inertness of these polymers
arises from their molecular structure [7]. Extensive
information about chemical resistance of fluoropol-
ymers has been published in References [2,3,8].
A few chemicals have been reported to attack
perfluoropolymers at or near their upper service
temperature (260 C) [5]. Those compounds include
80% sodium, potassium hydroxide, and strong Lewis
bases such as metal hydrides like boranes (B2H6),
aluminum chloride, ammonia, and some amines
(ReNH2) and imines (R ¼ NH). Slow oxidative
attacks may occur in the presence of 70% nitric acid
at 250 C under pressure. It is important to test the
effect of these reagents on perfluoropolymers under
the specific application temperature to determine the
material limitations.
Perfluoropolymers derive their chemical resis-
tance from a strong carbonefluorine bond and an
impermeable sheath of fluorine atoms surrounding
the carbonecarbon chain. Relatively high crystal-
line content renders these polymers insoluble in
solvents.
A commercially significant perfluoropolymer is the
copolymer of tetrafluoroethylene-perfluoromethyl
vinyl ether (MFA). It has chemical resistance char-
acteristics similar to the other perfluoropolymers such
as PTFE, PFA, and FEP.
Some halogenated solvents are absorbed by per-
fluoropolymers without any chemical interaction or
degradation. The action is strictly physical and the
removal of the absorbed species restores the

Table 3.2 Properties of Perfluoropolymers Unaffected by Fabrication Conditions

Mechanical Electrical Chemical

Flexibility at low temperatures Dielectric constant Insolubility
Coefficient of friction Dissipation factor Chemical resistance
Stability at high temperatures Arc resistance Weatherability
Volume resistivity Surface energy
Surface resistivity Flame resistance
3: P ROPERTIES OF N EAT (U NFILLED ) AND F ILLED F LUOROPOLYMERS 19

Table 3.3 Chemical Resistance of Polytetrafluoroethylene to Common Solvents [5]

Solvent Exposure Temperature, 8C Exposure Time Weight Gain, %

20 12 months 0.3
Acetone 50 12 months 0.4
70 2 weeks 0
78 96 h 0.5
Benzene 100 8h 0.6
200 8h 1.0
Carbon tetrachloride 25 12 months 0.6
50 12 months 1.6
70 2 weeks 1.9
100 8h 2.5
200 8h 3.7
Ethanol (95%) 25 12 months 0
50 12 months 0
70 2 weeks 0
100 8h 0.1
200 8h 0.3
Ethyl acetate 25 12 months 0.5
50 12 months 0.7
70 2 weeks 0.7
25 12 months 0.3
Toluene 50 12 months 0.6
70 2 weeks 0.6

Table 3.4 Chemical Resistance of Polytetrafluoroethylene to Common Acids and Bases [5]

Reagent Exposure Temperature, 8C Exposure Time Weight Gain, %

Hydrochloric acid
10% 25 12 months 0
10% 50 12 months 0
10% 70 12 months 0
20% 100 8h 0
20% 200 8h 0
Nitric acid
10% 25 12 months 0
10% 70 12 months 0.1
Sulfuric acid
30% 25 12 months 0
30% 70 12 months 0
(Continued )
20 F LUOROPOLYMER A PPLICATIONS IN THE C HEMICAL P ROCESSING I NDUSTRIES

Table 3.4 Chemical Resistance of Polytetrafluoroethylene to Common Acids and Bases [5] (Continued )

Reagent Exposure Temperature, 8C Exposure Time Weight Gain, %

30% 100 8h 0
30% 200 8h 0.1
Sodium hydroxide
10% 25 12 months 0
10% 70 12 months 0.1
50% 100 8h 0
50% 200 8h 0
Ammonium hydroxide
10% 25 12 months 0
10% 70 12 months 0.1

Table 3.5 Chemical Compatibility of Polytetrafluoroethylene (PTFE) With Halogenated Chemicals [5]

Chemical Effect on PTFE Sample

Chloroform Wets, insoluble at boiling point
Ethylene bromide 0.3% weight gain after 24 h at 100 C
Fluorinated hydrocarbons Wets, swelling occurs in boiling solvent
Fluoronaphthalene Insoluble at boiling point, some swelling
Fluoronitrobenzene Insoluble at boiling point, some swelling
Pentachlorobenzamide Insoluble
Perfluoroxylene Insoluble at boiling point, slight swelling
Tetrabromoethane Insoluble at boiling point
Tetrachloroethylene Wets, some swelling after 2 h at 120 C
Trichloroacetic acid Insoluble at boiling point
Trichloroethylene Insoluble at boiling point after 1 h

Table 3.6 Effect of Immersion in Inorganic Chemicals for 168 h on Perfluoroalkoxy [6]

Exposure Tensile Strength Elongation

Reagent Temperature, 8C Retained, % Retained, % Weight Gain, %
Acids
Hydrochloric (conc.) 120 98 100 0
Sulfuric (conc.) 120 95 98 0
Hydrofluoric (60%) 23 99 99 0
Fuming sulfuric 23 95 96 0
Oxidizing acids
Aqua regia 120 99 100 0
3: P ROPERTIES OF N EAT (U NFILLED ) AND F ILLED F LUOROPOLYMERS 21

Chromic (50%) 120 93 97 0

Nitric (conc.) 120 95 98 0
Fuming nitric 23 99 99 0
Bases
Ammonium hydroxide 66 98 100 0
(conc.)
Sodium hydroxide (conc.) 120 93 99 0.4
Peroxide
Hydrogen peroxide (30%) 23 93 95 0
Halogens
Bromine 23 99 100 0.5
Bromine 59 95 95 e
Chlorine 120 92 100 0.5
Metal salt solutions
Ferric chloride 100 93 98 0
Zinc chloride (25%) 100 96 100 0
Miscellaneous
Sulfuryl chloride 69 83 100 2.7
Chlorosulfonic acid 151 91 100 0.7
Phosphoric acid (conc.) 100 93 100 0

Table 3.7 Effect of Immersion in Organic Chemicals for 168 h on Perfluoroalkoxy [6]

Exposure Tensile Strength Elongation

Reagent Temperature, 8C Retained, % Retained, % Weight Gain, %
Acids/anhydrides
Glacial acetic acid 118 95 100 0.4
Acetic anhydride 139 91 99 0.3
Trichloroacetic acid 196 90 100 2.2
Hydrocarbons
Isooctane 99 94 100 0.7
Naphtha 100 91 100 0.5
Mineral oil 180 87 95 0
Toluene 110 88 100 0.7
Aromatic
o-Cresol 191 92 96 0.2
Nitrobenzene 210 90 100 0.7
Alcohol
Benzyl alcohol 205 93 99 0.3
(Continued )
22 F LUOROPOLYMER A PPLICATIONS IN THE C HEMICAL P ROCESSING I NDUSTRIES

Table 3.7 Effect of Immersion in Organic Chemicals for 168 h on Perfluoroalkoxy [6] (Continued )

Exposure Tensile Strength Elongation

Reagent Temperature, 8C Retained, % Retained, % Weight Gain, %
Ether
Tetrahydrofuran 66 88 100 0.7
Amine
Aniline 185 94 100 0.3
n-Butylamine 78 86 97 0.4
Ethylenediamine 117 96 100 0.1
Aldehyde
Benzaldehyde 179 90 99 0.5
Ketone
Cyclohexanone 156 92 100 0.4
Methyl ethyl ketone 80 90 100 0.4
Acetophenone 202 90 100 0.6
Esters
Dimethyl phthalate 220 98 100 0.3
n-Butyl acetate 125 93 100 0.5
Tri-n-butyl
Phosphate 200 91 100 2.0
Chlorinated solvents
Methylene chloride
Perchloroethylene 40 94 100 0.8
Carbon 121 86 100 2.0
Tetrachloride 77 87 100 2.3
Polar solvents
Dimethylformamide 154 96 100 0.2
Dimethyl sulfoxide 189 95 100 0.1
Dioxane 101 92 100 0.6

fluoropolymer back to its original state. Too much
absorption by a perfluoropolymer sample is likely to
be an indication of excessive porosity. A highly
porous sample may appear blistered because of the
expansion of vapors in the surface pores. A properly
fabricated part does not exhibit blistering.
3.3.1.1 Effect of Ozone on
Fluoropolymers
Ozone is considered a corrosive substance against
plastics due to its ability to readily degrade into an
atom and a molecule of oxygen. The atomic oxygen
is highly reactive allowing it to attack and etch most
polymers. PTFE has been reported to be very resis-
tant to etching by ozone in low earth orbit environ-
ment testing, where atomic oxygen is the most
abundant species [9,10].
O3 / O2 þ O
Resistance of polymers to ozone attack was stud-
ied in space environments in “actual” applications. In
the laboratory, glow discharge or plasma etching is
the common method for laboratory study of ozone
3: P ROPERTIES OF N EAT (U NFILLED ) AND F ILLED F LUOROPOLYMERS
effect. Plasma and low earth orbit environments are
not equivalent. For instance, oxygen plasma contains
a variety of other particles including electrons and
free radicals in addition to atomic oxygen. In
contrast, atomic oxygen is the dominant constituent
of low earth orbit.
The results indicated oxygen uptake was least for
PTFE and most for polyethylene in experiments in
which a series of fluorinated polyolefins were
exposed to ozone “out of glow.” This means that
plasma or glow discharge was used to produce atomic
oxygen that etched the sample placed outside the
discharge zone. The results of “out of glow” plasma
etching and low earth orbit, by and large, were in
agreement [11].
Maximum oxygen uptake decreased with an in-
crease in the fluorine content of the polymers. For
example, PVDF took up less oxygen as a result of O3
exposure than polyethylene, although more than
PTFE, in the same experiment [11]. The exception to
this trend was polyvinyl fluoride (PVF); it had a higher
etch rate than polyethylene (Table 3.8). Why was PVF
more susceptible to ozone attack than polyethylene?
Golub [12] has proposed an explanation attrib-
uting the high etch rate of PVF to the ease of fluorine
formation from the decomposition of this polymer.
Fluorine promotes degradation of molecular oxygen
to its active atomic form (O2 / 2O), further reacting
with PVF, thus enhancing the etch rate. PVDF and
FEP molecules have lower etch rates due to the
higher stability of the CF2 group to oxygen attack
than CFH in PVF or CH2 in polyethylene. Both
PVDF and ETFE have low etch rates due to the
protection provided to the CH2 groups by CF2 groups
Table 3.8 Relative Mass Loss Rates for Polymer Films Exposed to Low Earth Orbit [11]
Polymer
Polyimide
Polyether terephthalate
Polyethylene (low density)
Polyethylene (high density)
Polyvinyl fluoride
Polyvinylidene fluoride
PTFE
Tetrafluoroethylene hexafluoropropylene
copolymer (FEP)
FEP, fluorinated ethylene propylene; PTFE, polytetrafluoroethylene.
23
bonded to them. The ultimate stability was reached in
the linear PTFE chain, which consists of all CF2
groups with the exception of the few end groups.
3.3.1.2 Oxygen Compatibility of
Polytetrafluoroethylene
Oxygen is singled out due to its propensity to
facilitate autoignition of organic material including
plastics. Fluoropolymers are extensively used for
oxygen services because of their low flammability.
Oxygen does not interact with PTFE under most
circumstances.
Limiting oxygen index (LOI) of PTFE is greater
than 95% under ambient conditions. This means that
PTFE does not burn without an ignition source in an
atmosphere containing less than 95% oxygen. LOI is
not a complete predictor of all practical conditions in
which oxygen and PTFE may interact. A number of
considerations apply.
Increased pressure and temperature can accelerate
autoignition of PTFE, that is, ignition can occur
without initiation by an external source. Combina-
tions of high temperatures and high flow rates
through small orifices can initiate reaction with
PTFE. Organic impurities such as grease, oil, and dirt
react violently with oxygen and generate heat, which
can be sufficient for igniting PTFE. Surfaces are the
most common locations of contamination. Before
use, all surfaces that come in contact with oxygen
must be meticulously cleaned to assure that they are
free of any organic contaminants.
Surface condition can affect the safety of liquid
oxygen (LOX) contact with PTFE. Despite its
Mass Loss Rate Fluorine-to-Carbon Ratio
1 0
1.06 0
0.43 0
0.80 0
1.16 0.5
0.25 1
<0.03 2
<0.03 2
24 F LUOROPOLYMER A PPLICATIONS
extremely low temperature, LOX can react with
organic contaminants and ignite PTFE. Thorough
cleaning of the surfaces of all parts that come in
contact with oxygen is required. ASTM D2512 pre-
scribes procedures to determine the compatibility of
materials with LOX. This standard determines the
relative sensitivity of materials under impact condi-
tions by using an impact tester developed at the Army
Ballistic Missile Agency. Materials that are sensitive
to impact energy are usually likely to react with ox-
ygen when subjected to other forms of energy such as
heat. PTFE is commonly used in oxygen systems
because of its resistance to ignition by mechanical
impact, high autoignition temperature, high LOI, and
low heat of combustion [13].
3.3.2 Chemical Compatibility of
Partially Fluorinated
Fluoropolymers
Partially fluorinated fluoropolymers with com-
mercial significance include PVDF, ETFE, ECTFE,
and polyvinyl fluoride (PVF). The presence of
hydrogen in these plastics lowers the fluorine content
compared to perfluoropolymers and renders them
susceptible to some chemicals. This means that care
must be taken in the selection of these polymers to
ensure compatibility of process fluids.
PVDF, in general, resists inorganic acids, bases,
salt solutions, oxidizing agents, and halogens. It is,
however, attacked by concentrated sulfuric acid and
medium concentration alkaline solutions. PVDF is
unaffected by alcohols, chlorinated solvents,
aliphatic and aromatic hydrocarbons, and crude oil. It
swells in some polar solvents such as ketones and
esters. PVDF dissolves in some polar solvents
such as dimethylformamide, dimethylacetamide, and
N-methylpyrrolidone. Hot amines attack PVDF.
ETFE has excellent resistance to a great many
chemicals. It is somewhat affected by oxidizers,
chlorinated solvents, ketones, and esters but resists
acids, alkalis, and organic solvents. Tests should be
conducted in each specific application to verify the
validity of the values (data) provided. This is usually
done either by testing in laboratory or by placing
coupons of materials in the process stream for
exposure. The coupons are taken out periodically for
inspection and measurement of properties. For
example, hydrolytic stability of ETFE is measured by
the retention of its physical properties after extensive
exposure to boiling water. Tensile strength and
IN THE C HEMICAL P ROCESSING I NDUSTRIES
elongation were found to change little after 3000-h
exposure of unfilled ETFE to boiling water.
ECTFE is resistant to strong mineral and oxidizing
acids, alkalis, metal etchants, LOX, and virtually all
organic solvents with the exception of hot amines
such as aniline and dimethyl amine. ECTFE is sus-
ceptible to attack by metallic sodium and potassium;
the rate of attack is dependent on the time and tem-
perature of exposure. Some halogenated solvents can
plasticize ECTFE without impairing its usefulness.
After discontinuing contact between the part and the
solvent, it dries up and mechanical properties recover
to the original values. Clearly, the interaction be-
tween ECTFE and the solvents in these cases is
strictly physical and not chemical. ECTFE is
compatible with LOX as determined by National
Aeronautics and Space Administration (NASA) test
method MSFC-SPEC-106B [14]. It is also resistant
to nitrogen tetroxide and monomethylhydrazine.
3.3.3 Chemical Compatibility of
Polychlorotrifluoroethylene
Polychlorotrifluoroethylene (PCTFE) resists attack
by most industrial chemicals. The exceptions include
alkali metal complexes and organic amines. Chlorine
gas, nitrogen tetraoxide, and a number of halogenated
solvents are absorbed by PCTFE. Most silicones
induce stress cracking. Tables 3.9 and 3.10 summa-
rize weight gain of low-and high-molecular weight
grades after exposure to each chemical for a period of
2 weeks at room temperature. Low-molecular weight
PCTFE absorbs slightly more of some compounds
than the high-molecular weight polymer.
3.4 Permeation Fundamentals
Permeation can be defined as the passage of gases
and liquids through a second material such as a solid.
It is a significant consideration in the selection of
plastic material for the construction of chemical
processing equipment because process fluids may
travel across the thickness of the polymer by
permeation. Permeated species in sufficient quanti-
ties could cause one or more of corrosion, contami-
nation, and unacceptable environmental emission.
In its simplest form, permeation can be expressed,
using Fick’s first law, as a product of the solubility
and diffusion coefficient of the permeant in the
polymer. Permeation of a gas can be calculated from
Eq. (3.1). This equation is derived from Fick’s first
3: P ROPERTIES OF N EAT (U NFILLED ) AND F ILLED F LUOROPOLYMERS 25

Table 3.9 Weight Gain of PCTFE After 2 Weeks’ Exposure to Inorganic Reagents at Ambient Temperature [15]

Low-Molecular Weight PCTFE, High-Molecular Weight PCTFE,

Reagent SG [ 2.08 SG [ 2.12
Ammonium hydroxide None None
Aqua regia 0.10 0.04
Bromine 0.15 0.1
Carbon disulfide 0.4 0.2
Hydrochloric acid (10%) None None
Hydrochloric acid (36%) None None
Hydrofluoric acid (60%) None None
Hydrogen peroxide (30%) 0.23 None
Nitric acid (10%) None None
Nitric acid (70%) None None
Nitric acid (red fuming) 0.07 0.04
Nitric acid/hydrofluoric acid (50:50) None None
(60%)
Sodium hydroxide (50%) None None
Sodium hypochlorite None None
Sulfuric acid (30%) None None
Sulfuric acid 0.03 0.02
PCTFE, polychlorotrifluoroethylene; SG, specific gravity.

Table 3.10 Weight Gain of PCTFE After 2 Weeks’ Exposure to Organic Chemicals at Ambient
Temperature [15]

Low-Molecular Weight PCTFE, High-Molecular Weight PCTFE,

Reagent SG [ 2.08 SG [ 2.12
Acetic acid (3%) None None
Acetic acid (glacial) 0.09 0.03
Acetone 5.17 0.5
Acetophenone None None
Aniline 0.01 None
Benzaldehyde 0.02 None
Benzene 2.4 0.6
Benzoyl chloride 0.14 None
Butyl alcohol e None
Carbon tetrachloride 4.1 1.6
Citric acid (3%) None None
Cyclohexanone 0.35 None
1,2-Dichloroethane 0.11 0.03
2,4-Dichlorotoluene 0.15 0.06
(Continued )
26 F LUOROPOLYMER A PPLICATIONS IN THE C HEMICAL P ROCESSING I NDUSTRIES

Table 3.10 Weight Gain of PCTFE After 2 Weeks’ Exposure to Organic Chemicals at Ambient
Temperature [15] (Continued )

Low-Molecular Weight PCTFE, High-Molecular Weight PCTFE,

Reagent SG [ 2.08 SG [ 2.12
Diethyl phthalate None None
Dimethylhydrazine (anhydrous) 3.9 1.8
Ethyl acetate 7.65 6.0
Ethyl alcohol (anhydrous) None None
Ethyl ether 5.6 5.2
Ethylene oxide 5.8 4.0
Formic acid None None

Furan (B.P. 31e32 C) 5.4 3.7
Premium gasoline 0.83 0.2
Heptane None None
Hexachloroacetone None None
Hydraulic fluid None None
Lactic acid None None
Methanol 0.10 None
Methyl ethyl ketone 5.9 1.2
Motor oil 0.01 0.01
2,4-Pentanedione 0.17 0.20
Pyridine 0.55 0.10
Toluene diisocyanate 0.44 e
1,1,2-Trichloroethane 0.04 0.02
Trichloroethylene 10.9 7.8
Triethylaluminum 0.13 0.01
PCTFE, polychlorotrifluoroethylene; SG, specific gravity.

law of mass transfer. Permeation concerns the
movement of a species through the molecules of
another species, e.g., a gas through a polymer. It does
not take into account transport of material through
cracks, voids, and in general physical flaws in the
structure of the second species such as the polymer.
Both phenomena result in the migration of chemicals
through the structure of the solid. This means that
after an appropriate plastic material has been selected
to meet the permeation requirements of a process, the
equipment must be fabricated carefully to avoid flaws
in the polymer structure.
P ¼ D$S
P (cm3/s$cm$atm) is the permeability of the gas, D
is the diffusion coefficient (cm3/s) and S (cm3/cm3-
atm) is the solubility coefficient.
Several factors affect the permeation rate of the
polymer (Table 3.11). Temperature increase raises
the permeation rate for two reasons. First, the sol-
ubility of the permeating agent in the polymer in-
creases at higher temperatures. Second, the
polymer chain movements increase, which allow
easier diffusion of the permeating agent. Perme-
ation rate of gases increases at higher partial
pressures. For liquids, permeation rates rise with an
increase in the concentration of the permeating
(3.1) agent. Unless the permeating agent species are
3: P ROPERTIES OF N EAT (U NFILLED ) AND F ILLED F LUOROPOLYMERS 27

Table 3.11 Permeation Variables [16]

Factor Change Effect on Permeation

Permeant concentration þ þ
Temperature þ þ
Pressure þ þ
Permeant/polymer chemical þ þ
similarity
Voids in polymer þ þ
Permeant size/shape þ 
Polymer thickness þ 
Polymer crystallinity þ 
Polymer chain stiffness þ 
Polymer interchain forces þ 

highly soluble in the polymer, permeation rate in-
creases linearly with pressure, concentration, and
the area of permeation.
Permeation rate decreases at higher thickness, as
illustrated in Table 3.12 and Fig. 3.1, for two types of
PTFE and a perfluorinated ethylene propylene
copolymer (FEP). The effect of thickness is usually
nonlinear. Permeation rate is very high at a low
thickness and rapidly decreases with an increase in
the thickness. After a critical thickness is reached, the
effect of thickness is diminished and permeation rate
reaches a plateau. At lower thicknesses, the effect of
surface structure begins to play a significant role in
the permeation. A more oriented (ordered) surface
will serve to inhibit permeation.
Chemical and physical characteristics of the
polymer have powerful effects of the rate of perme-
ation, as much as four orders of magnitude [18].
Chemical affinity for the permeating agent, inter-
molecular forces such as van der Waals and hydrogen
bonding forces, degree of crystallinity, and degree of
cross-linking are the influential variables.

Table 3.12 Comparative Permeation Rates for Modified (Teflon NXT) and Standard Polytetrafluoroethylene
(PTFE) [17]

Specimen Vapor Liquid Gas

Thickness,
Permeant mm PTFE Teflon NXT PTFE Teflon NXT PTFE Teflon NXT
Perchloroethylene 1 5.5 2 13 4 e e
2 1.4 0.1 0.019 0.005 e e
4 0.08 0.05 0.006 0 e e
5 0.055 0.05 e e e e
Hexane 2 3.4 0.2 23.4 0 e e
5 0.045 0.015 e e e e
Methyl ethyl ketone 2 36.3 23.3 49.4 34.2 e e
5 22.6 20.8 35.5 25.2 e e
HCl, 20% 1 0.4 0.1 e e e e
Helium 2 e e e e 93 1
5 e e e e 0.18 0.12
28 F LUOROPOLYMER A PPLICATIONS
0.40
0.35
(grams/sq.in./24 hrs)
Transmission Rate 0.30
0.25
0.20
0.15
0.10
0.05
0.00
0 50 100 150 200 250 300
Thickness (µm)
Figure 3.1 Water vapor transmission rate of Teflon
fluorinated ethylene propylene resins at 40 C. Note:
values are averages only and not for specification
purposes.
Courtesy: Chemours Co., www.Teflon.com.
Generally, similarity of chemical structure of the
PTFE and the permeant will promote its solubility
and increase the permeation rate. Higher intermo-
lecular forces of the polymer result in less perme-
ation because of the resistance that they present to the
development of space between adjacent molecules
required for the passage of the permeating agent.
PTFE crystallinity is an important factor, which can
be controlled during the processing of the polymer.
Crystalline phase can be considered impermeable by
most species because of its orderly structure (pack-
ing) that usually minimizes its specific volume. This
means that there is little or no free space among the
polymer chains for the passage of permeant.
Amorphous phase has the opposite construction
and is disorderly with interchain space available for
permeation. The specific volumes of the crystalline
(0.43 cm3/g) and amorphous (0.5 cm3/g) phases
provide evidence for the argument. Amorphous
phase has a 13% higher specific volume, which
translates in additional space for permeation. Finally,
Figure 3.2 Schematic of the Test Cup for
measuring liquid and vapor permeation.
Courtesy: Element Materials Technology
(formerly MERL), www.MERL-Ltd.co.uk.
IN THE C HEMICAL P ROCESSING I NDUSTRIES
cross-linking acts somewhat similarly to crystallinity,
though less effectively, to limit space for permeation.
Cross-linking is size dependent and smaller species
may permeate.
The molecular size of the permeant, its chemical
structure, and condensation characteristics affect
permeation. Diffusion of the permeant increases as its
molecular size decreases, thus contributing to an in-
crease in permeation. Molecular structure is impor-
tant. A polar chemical will normally have a lower
permeation rate in a nonpolar polymer than a nonpolar
species and vice versa. This is due to the ability of
chemicals with similar structures to the polymer to
swell the polymer, that is, to create space between the
chains for permeation. A more easily condensed
chemical will also be more effective in swelling of the
polymer, resulting in higher rates of permeation.
3.4.1 Permeation Measurement
A number of methods can be used to measure
permeation rate through polymers including fluo-
ropolymers. An example of a standard permeation
technique includes ASTM Method F-739. This
method is helpful for the comparison of different
materials. The extent of the information obtained is
limited due to the inability of these techniques to
account for real-world conditions. Typically, a film of
fluoropolymer acts as a barrier to keep a gas or liquid
in a reservoir.
Fig. 3.2 shows the schematic of a transmission cup
for measuring liquid and vapor permeation. In this
test the material specimen serves as a membrane that
seals the cup interior from the outside ambient by the
use of a flange and bolt arrangement. Permeation rate
is calculated from the measured pressure or weight
loss in the reservoir. For liquid permeation, the
transmission cup mass loss test provides a direct and
simple measurement of its rate. However, the disad-
vantages of this technique are that problems in
Vapor
Another random document with
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Aurora and stars, shed their wonder-light over the scenery, the boys were
once more happy and gay.
On the days—strange to say days when all was night—when the
temperature fell to 20° and 30° below zero, cold was not complained of, but
zero itself, with the wind-fiend raging, was misery that cannot be described.
Dr. Wright did everything a brave doctor could do to keep his people in
health and fit. Curtis was no longer commander save in name. He had to
cave in to the doctor, and do all he was bidden.
MacDonald told his queerest stories after dinner, and sang his love lilts
as heartsomely as do the blackbirds in early spring.
Everybody had come to look upon Mac as a brick, and his cheerful
Doric voice even in the dark was delightful to listen to. He used to “bag the
boys” at night, as he termed it, Charlie with Nick, and Walter with Nora.
“Bag them” snugly, too. He was like a mother to them. Of course all hands
turned in very early, and as Curtis’s bag (and Collie’s) and also Dr. Wright’s
were close to Mac’s and the boys’, the Yak-dogs filling up the intervals or
lying round the sides, Mac could lie and yarn, or even sing, to all hands for
two hours at a stretch. The British sailors were not far away in their bags,
and they could listen too.
There is no seaman in the world like our handy man the British, and
through all that long and trying Antarctic night these good fellows, though I
have said little about them, behaved like heroes.
All kinds of games could still be carried on in the light, but sleighing
was discontinued.
In these regions it is just after turning in that one feels most cold, but any
such course as warm drinks or nightcaps (drinkable, I mean) would make
matters worse.
Slap-dash and his people used often to worship the moon, just as they
had the sun. The sun may be the god of these poor souls, but the moon is his
high priest, and the Aurora are his angels.
Well, a religion of any sort is better than none.
Once when the moon was about three days old she took on a strange but
most lovely appearance. The stars, except the highest, which were
exceedingly brilliant, burned somewhat less brightly at the time. But it was
towards the moon all eyes turned.
 It was, if I may so describe it, a kind of rainbow moon. The outer arc
was of the deepest orange colour, the next and largest arc was pale yellow,
but brilliant, then an arc of radiant sea-green, while inside all was an arc of
pale but indescribably beautiful mauve.
Hitherto the boys and Ingomar himself had believed, or been taught to
believe, that the Aurora Borealis, or Northern Lights, with their fringe-like
bands of opal, pink, or green, were far more lovely than the Southern
magnetic lights, the Aurora Australis.
During their sojourn in the Antarctic they had time to alter their opinion.
I feel it is presumption on my part to attempt to describe a display of this
Aurora, because I shall hardly succeed in making myself understood.
Just imagine, if you can, a wide and wondrous arch, stretching from east
to west, and nearly halfway up the sky, more rounded than a rainbow, its
ends apparently within a few feet of the snow-field.
At first the arch resembled a vast chain, every link of which was a ring
of brightest gold, each link overlapping its neighbour to about one-half its
extent, but all turbulent, all a-quiver! But lo! as one gazed on it, strangely
fascinated, the rings, though still linked together, turned half-edge-on
towards the right. Then from each ring, as a spherical base, was suddenly
thrown out a triangle of glittering, darting, quivering, golden light.
But speedily is the apex of each triangle extended zenithwards, and
broadened out, till it resembles a brush. The rings get smaller and smaller
beneath, until they are but bright points of light like heads of comets; in
very truth, there is now a broad archway of comets, heads downward
towards the snow.
But listen. While the heads of these comets retain the brightness of stars
of gold, the extended brushes, or tails, are now bunches of rainbow-
coloured, flickering, dancing, darting light.
It is a bewildering sight, and it is hard to believe it real.
Gradually the tails get shorter, become once more the apexes of spherical
triangles, and dance, and disappear, the chain of golden rings becoming
once more visible as before.
All beneath this archway is a dark-blue sky, in which stars shine, and the
rest of the firmament is quite unaffected, though the mountains and snow-
clad valley borrow the colour and add to the bewildering grandeur of the
most marvellous transformation scene the world can ever witness.
I fear I have failed to give my youthful readers an adequate conception
of the Aurora. I feared I should fail before I commenced. But Britons—and
I am one—should never funk, and I have done my best.
* * * * *
It is strange, and sadly strange, that, although Dr. Wright and his men
had borne bravely up, throughout the livelong night of the dreary Antarctic
continent, as soon as day returned, revealing blue and ghastly faces,
sickness came.
This is no place in which to inquire into the cause of this sickness;
suffice it to say that it came, and the men, hitherto brave and hearty, began
to droop and shiver.
An optimist at most times, and ever ready to look upon the bright side of
circumstances, the doctor himself began now to fear the worst.
Long before my own experiences of Arctic life, there used to be in Polar
regions a disease called the black death.
Whether or not the illness that now attacked this little camp of heroes
was a species of that ailment, I am not prepared to say.
I hate to have too much gloom in my stories, or I could describe the
symptoms so graphically that you would shudder.
Suffice it to know that, though there were no unsightly swellings, and
though the faces of the sufferers retained even their complacency when fits
of shivering and cramp abated, they were melancholy and sad sights until
they either recovered or died.
Let me say at once that though both Charlie and Walter were ill a few
days, owing to the resiliency of youth they were not stricken down, and
speedily recovered so far as to be able to assist the truly sick.
It need not be said that Dr. Wright did all that any medical man could
have done. Just one or two of the Eskimos collapsed utterly, and died on the
third day. They were buried not far off in the snow. Two days after a sailor
followed them to the snow-field. He did not say much, even at the worst,
and finally he simply fell asleep. Only one out of the four other men
attacked recovered, and this was far more from good management and the
kindly nursing of Sheelah and Taffy than from medicine. In fact, though
wine did good when the patient was at the lowest ebb, and helped him to
fight his way round the corner to restoration, medicine was for the most part
useless.
Curtis was early down, and, strangely enough, considering how truly
brave he was, his spirits drooped to zero, and he gave up hope of himself
from the first.
Ingomar nursed his dear friend indefatigably, and when, overcome with
fatigue, he dropped off to sleep, either Sheelah or Taffy was always sitting
by his brother when he awoke.
I cannot really testify in strong enough language to the marvellous
qualities of those gentle little Yak women as sick nurses.
We may laugh at such people, ah! curious though their customs be, and
droll their manners, they are our sisters before God.
Slap-dash remained his old self.
Let me cut this all short by saying that of all the crew of brave men, only
twelve remained to take the road back to the seashore.
Perhaps as sad a case as any was that of poor MacDonald, who had been
so long the life and soul of all the camp.
When Dr. Wright told the boys that he could only last a few hours, and
that they must go and see him now, they summoned courage enough to have
the interview.
They behaved splendidly in his presence, but as soon as they went into
the open air again they both utterly broke down and wept, until their hearts
appeared almost bursting.
“It does seem hard, does it not, Walter?” Charlie managed to say.
“Always so kind and good,” said Walter.
“Ay, ay, and I never knew I loved him half so much till now.”
* * * * *
Mac, once the hardy, resolute Scot, passed away that same day.
In the semi-darkness of the cave Ingomar was kneeling by his side and
holding his hand.
He had lived a Scot; he died a Scot.
Ingomar thought he had fallen into a slumber, so quiet did he lie. But he
spoke at last, though with feeble, faltering voice.
 “It’s you, isn’t it, Ingomar?”
“I’m here, dear Mac.”
“Well, I—I know I’m dying. I wouldn’t care—but mother——”
“What can I do to ease your mind?”
“She kens I love her—I’ve been single for her sake. Promise to get all
I’ve saved, Ingomar. Her dear auld-farrent[G] letters and my bank-book are
a’ in my box. Ingomar—you—promise?”
“Most sacredly.”
“God love you! She’ll no be lang ahint (behind) her laddie.”
He lay still a little while, and he spoke but once again—repeating a verse
of the 23rd Psalm.

“ ‘Yea, though I walk thro’ death’s dark veil,

Yet will I fear none ill;
For Thou art with me;
And Thy rod and staff me comfort still.’

“Is that the Aurora? Ingomar, tell me. Oh, how bright and how—joyful
—Father——”
He was gone!
He had seen the Aurora; but it was the morning dawn of a happier life.

CHAPTER XI

“ENGLAND, HOME, AND BEAUTY”

Six weeks after this, and when the captain of the Walrus had given the
explorers up for lost, after searching the snows in vain, for winter storms
had obliterated every track, ten men with two dog-sledges suddenly
appeared above Glen Bell on the ridge of the great tableland.
They rested there.
They knew they were seen.
In the stillness of the early summer’s morning they could hear the wild
shouts of greeting that arose from their shipmates.
 And you may easily guess that assistance was speedily on its way to the
top of the valley.
I leave you to guess also the kind of welcome accorded to men and dogs.
Why, Slap-dash himself came in for hugging, and Wallace hugged every
one indiscriminately all round. Dr. Wright, Ingomar, Curtis, and the boys
were all sadly worn and sallow. They had but little life in them. Even their
courage appeared to have left them. They smiled, it is true, but it was the
smile of sickly old men.
When they were helped on board at last, and had a little food and wine,
they begged for a bath and to be shaved. After this, and dressed in fresh
clothing, they were in some measure restored.
Captain Bell and the other officers of the Sea Elephant had come on
board, and to them Ingomar, who was stronger than the rest, told the sad
story of their terrible hardships, and their struggle to reach the ships. When
he spoke of poor MacDonald, there was not an eye in the room that was not
dimmed with tears.
But there! I myself must pull up. I would not have my very last chapter
dimmed with sorrow.
Suffice it to say that not only these five real heroes, but the Yak-Yaks,
including Slap-dash and Sheelah and Taffy, were in a month’s time their old
selves again.
Of the animals, strange to say the Shetland ponies, Jack and Gill, had
been least affected, while Wallace had returned hungry, Nick and Nora
standing by delightedly as he ate the food prepared for him. The
Newfoundland, as soon as he had finished, proposed a romp round the
decks. Wallace tried, but soon lay down to rest and pant.
“Another day, I hope,” the honest Collie appealed, “but somehow I feel a
little tired.”
When the good old Walrus was sawn out of her quarters and got into
blue water again, with all and everything on board, and when the Sea
Elephant lay quiet and still on the calm blue sea, a dinner was given on
board the flagship.
The blessing asked by good Captain Walt was a prayer of thanks to the
Almighty Power that had guided them through their trials, through sickness,
danger, and difficulty.
 I think all hands, fore and aft, who partook in the festivities, were just a
little great-hearted at first, but all sadness was soon dispelled.
They had all done their duties bravely and well, as British and American
sailors and soldiers always do.
So upon the whole a very happy evening was spent, the thought that next
day they would bear up once more for the shores of Merrie England—
England, home, and beauty—put life and spirit in them, and they retired at
last, happy and hopeful.
I don’t think that any one on board the Walrus or Sea Elephant is ever
likely to forget the sweetness of that Antarctic summer morning—the
morning of the start. The sea with its beauty-tints of opal and blue, a sea
studded with the snow-white of tiny bergs, the great mountains towering
skywards, and the world, the marvellous world, of bird-life.
Do you know that, great though their sufferings and hardships had been,
every one looked back to the scene of their adventures with just a little
feeling akin to sorrow!
Up steam!
Round go the screws, churning up a frothy white wake, slowly move the
ships away, slowly, and apparently reluctantly.
But, in a few hours’ time, those sturdy ships are merrily bobbing and
curtseying to each advancing wave, as if they really know that, at long, long
last, they are homeward bound.
And now nothing reigns aboard, fore or aft, except happiness and
general jollity, in which even the dogs themselves take part.
Homeward bound! Hurrah!
* * * * *
When, in about two months’ time, the Walrus and Sea Elephant came
quietly to anchor inside the breakwater of Plymouth, people gazed and
wondered what these two strange ships could be.
But when the truth was rumoured abroad that they were the Antarctic
voyagers, the wild welcome they received was enough to have turned the
heads of any sailors on this earth.
* * * * *
Parting!
 Yes, parting, yet parting—every one assured his shipmates—to meet
again and talk over old times.
The boys, Charlie and Walter, going off to their “uncle’s” home.
Dr. Wright to duties elsewhere.
The scientists to London.
Slap-dash and his dogs and Yak-Yaks, including faithful Sheelah and
Taffy, to London, with the scientists.
The boys got all the three dogs, and happy enough the dear fellows
seemed to get on shore again.
Parting! Ah, yes, it is a sad word, and so I leave it.
* * * * *
Ingomar, the prodigal son, returned to his home.
“Can you forgive me now, father?” he said, after he had embraced his
mother and sister.
“Bosh, boy!” cried the old man. “Go and sit down.” But there were tears
in his eyes nevertheless.
Curtis was here, too.
Curtis came home to find he had succeeded to a baronetcy and another
large estate. But this would not have stirred his spirits in the least had not
Marie greeted him so joyously.
He used to call her his Marie. In six weeks’ time she was his Marie in
reality.
They were married.
Ingomar says he will never marry. I simply smile.
He is owner, anyhow, of one of the most splendid yachts ever built in
America or England.
No ’long-shore yacht. Not built for racing or speed, but comfort,
pleasure, and beauty. Curtis has left the service. The yacht takes very long,
delightful cruises, but wherever she goes with Ingomar, her master, both
Arnold Curtis and his sweet wife go along as well.
My story is ended, my tale is told. I have only to say “Good-bye, my boy
reader, and God be with us all.”
I trust and hope we’ll meet again another day.
 FOOTNOTES:
[A] Skis, pronounced shees.
[B] “Making a voyage” (Greenlandish) = secure a good cargo.
[C] Young bears are now regularly trained by the Eskimos for heavy sleigh work.
[D] The sea always looks black among or near the ice.—G. S.
[E] Raxed = stretched.
[F] Bield = shelter.
[G] Old-fashioned.

Typographical errors corrected by

the etext transcriber:
first disovered=> first discovered {pg
162}
shout of the b’s’n’s=> shout of the
bo’s’n’s {pg 139}
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