Topics

Atmospheric Corrosion
Aqueous Corrosion
Soli Corrosion

Page # 1
M. A. Islam
 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Atmospheric Corrosion: The corrosion that takes place due to reaction with surrounding
environment [15]. Atmospheres vary considerably with respect to moisture, temperature
and contaminants [7].

Major classification of Atmospheric Corrosions are as follows:

 Marine Corrosion- Due to high moisture and air borne chlorides

 Industrial Corrosion- Due to contaminants from industries

 Urban Corrosion- Due to pollutants from vehicle exhausts, household fuel consumption
and sewerage contaminations

 Rural Corrosion- Due to burning of wood and Coal

 Tropical Corrosion (Wet and Dry tropical) - Due to tropical environment

 Arctic Corrosion- Due to deicing salts

ME 6351 Atmospheric Corrosion Page # 2

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Table: Atmospheric Corrosive Gases in Outdoor Urban Environments [7]

(C. Leygraf and T. Graedel, Atmospheric Corrosion, Wiley, New York, 2000, p. 41)

ME 6351 Atmospheric Corrosion Page # 3

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure: Atmospheric corrosion of steels as a function of time in an industrial

environment
( C. Larrabee, in Corrosion Handbook , H. H. Uhlig, editor, Wiley, New York, 1948, p. 124 )

ME 6351 Atmospheric Corrosion Page # 4

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Table: Average Atmospheric Corrosion Rates of Various Metals for 10 - and 20 – Year Exposure
Times, mils/year a (American Society for Testing and Materials) [4]

ME 6351 Atmospheric Corrosion Page # 5

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

The relationship for atmospheric corrosion for steels can be expressed as

p = k t n………. (1)
where p can be expressed as specimen weight loss (g/m2), or as specimen penetration (μm), during
time t (years), and k and n are constants that depend on the metal and the atmospheric
conditions at the test site.

In addition to carbon steels, this relation is also found to apply to atmospheric test data for
galvanized, aluminized, and 55% Al – Zn coatings on steel [M. Tullmin and P. R. Roberge ,
Atmospheric corrosion, Uhlig’s Corrosion Handbook , 2nd edition, R. W. Revie , editor, Wiley , New
York , 2000 , pp. 315 – 317; R. Legault and V. Pearson, Corrosion 34, 433(1978)and H. Townsend
and J. Zoccola, Mater. Perf. 18 ( 10 ), 13 ( 1979 )]

Values of n typically range from about 0.5 to 1.

n = 1 applies for a linear rate law; that is, the corrosion product film is not protective.
n = 0.5 corresponds to a parabolic rate law
Weathering steels have very low values of n < 1/2 [L. Veleva and R. D. Kane , in ASM Handbook,
Vol. 13A , Corrosion: Fundamentals, Testing, and Protection , ASM International, Materials Park, OH,
2003, pp.203–204]

ME 6351 Atmospheric Corrosion Page # 6

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

 The linear bi-logarthimic curve can be expressed as

log p = A + B log t ………. (2)
where A = log k and B = n .

The mean corrosion rate (p/t) can be calculated

log ………. (3)

The instantaneous corrosion rate (dp/dt) can be expressed as

log ………. (4)

Metallic materials surfaces that are wet and retain moisture corrode faster if the metal surfaces are
not washed completely by rain or water.
The reason for this is that sulfuric acid, for example, absorbed by rust will continue to accelerate
corrosion, perhaps by means of the cycle [7]

ME 6351 Atmospheric Corrosion Page # 7

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Factors Influencing Corrosivity of the Atmosphere

I. Particulate Matter
II. Atmospheric Gases
III. Moisture (Critical Humidity)

Comparison of Atmospheric Corrosion Rates with Average Rates in Seawater and in Soils

ME 6351 Atmospheric Corrosion Page # 8

M. A. Islam
9
Atmospheric Corrosion
 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

I. Particulate matter (PM) or Suspended Particulate matter (SPM) : Particulate matter is a

mixture of solid particles and liquid droplets in air. PM consists of several components - acids,
organic chemicals, metals and soil or dust particles.
PM can be classified as follows
a) Course Particulate (2.5 to 10 μm in diameter)
b) Course Particulate (≤ 2.5 μm in diameter)

Sources of PM
c) Near roads and some industries as smoke and haze
d) From gases emitted from power plants, automobiles and forest fires

PM prevail on an average in city air about 2 mg/m3 and in an industrial atmosphere may contain 1000
mg/m3 or more.

Dust-free air is less favorable for corrosion, whereas dusts that contain water-soluble particles or
particles that adsorb H2SO4 can cause corrosion.

ME 6351 Atmospheric Corrosion Page # 10

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

II. Atmospheric Gases: Atmospheric gases are pollutants in small a mounts of CO2, H2S, SO2 and
NH3.

Important atmospheric pollutants are sulfur dioxide (SO2 ), nitrogen oxides (NOx ), Ozone (O3)
and chloride ions (Cl−).

The carbon dioxide normally present in air neither initiates nor accelerates corrosion. Sulfur dioxide
and nitrogen oxides form corrosive acids, and ozone is a powerful oxidizing agent. SO 2 originates
predominantly from the burning of coal, oil, and Gasoline; and the reaction involved are as follows
S + O2 SO2

2SO2 + O2 + 2H2O H2SO4

ME 6351 Atmospheric Corrosion Page # 11

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Table: Variation of SO2 Content of Air with Distance from Center of City (H. Meller, J. Alley, and J. Sherrick)

ME 6351 Atmospheric Corrosion Page # 12

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

III. Moisture (Critical Humidity)

Moisture always prevail in atmosphere which varies from places to place and one of the major
contributors to Atmospheric corrosion of metals and alloys.

Vernon discovered that a critical relative humidity exists below which corrosion is negligible.
Experimental values for the critical relative humidity are found to fall, in general, between 50% and 70%
for steel, copper, nickel, and zinc. Typical corrosion behavior of iron as a function of relative humidity of
the atmosphere is shown in figure.
Relative humidity increases with the decrease of temperature

ME 6351 Atmospheric Corrosion Page # 13

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure: Corrosion of iron in air containing 0.01% SO2, 55 days ’ exposure, showing critical humidity
[W. Vernon, Trans. Faraday Soc. 23, 113 (1927)]

ME 6351 Atmospheric Corrosion Page # 14

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Remedial Measures for Atmospheric Corrosion:

 Reducing Particulate materials

 Using Organic, Inorganic, or Metallic Coatings
 Reduction of Relative Humidity.- Heating air or reducing the moisture content can reduce
relative humidity
 Using Vapor-Phase Inhibitors and Slushing Compounds
 Using Alloys - When alloyed with steel in small concentrations, copper, phosphorus,
nickel, and chromium are particularly effective in reducing atmospheric corrosion

ME 6351 Atmospheric Corrosion Page # 15

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Table: Effect of Low - Alloy Components on Atmospheric Corrosion of Commercial Steel Sheet (Eight - Year Exposure) [7]

ME 6351 Atmospheric Corrosion Page # 16

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Problems[7]:
1. A carbon steel is exposed to a highly polluted, industrial - marine environment. After one year of
exposure, the penetration is 130 μm, and after 4 years, the penetration is 190 μm. Assuming the bi-
logarithmic law applies, calculate the following:
a) The constants A and B in the equation
b) The average corrosion rate, in terms of penetration per year, over a 40 year period, assuming that
environmental conditions do not change significantly during this time period
c) The instantaneous corrosion rate, in terms of penetration per year, at 5, 25 and 40 years of exposure

2. A weathering steel is exposed to the same environment as the carbon steel in Problem 1. After one year
of exposure the penetration is 25 μ m, and after 4 years the penetration is 28 μ m. Assuming the bi-
logarithmic law applies, calculate the following:
a) The constants A and B in the equation
b) The average corrosion rate, in terms of penetration per year, over a 40 year period, assuming that
environmental conditions do not change significantly during this time period
c) The instantaneous corrosion rate, in terms of penetration per year, at 5, 25 and 40 years of exposure.

ME 6351 Atmospheric Corrosion Page # 17

 Topics

 Atmospheric Corrosion
 Aqueous Corrosion
 Soil Corrosion

Page # 18
M. A. Islam
 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Factors affecting soil Corrosion

Factors that impact Corrosivity of a given soil are as follows:
1) Porosity (Aeration)
2) Electrical conductivity or resistivity
3) Dissolved salts( Some salts can act as depolarizers or inhibitors)
4) Moisture
5) pH
Each of these variables may affect the anodic and cathodic polarization characteristics of a metal
in a soil.

ME 6351 Soil Corrosion Page # 19

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Pitting due to Soil Corrosion: Soil corrosion of metallic materials in many instances take the form
of pitting corrosion. Actual depth of pits in a given time is found to increase with size of test
specimen, probably because cathodic area per pit increases (i.e., anode/cathode area ratio decreases)

The rate at which pits grow in the soil under a given set of conditions tends to decrease with time
and follows a power - law equation P = ktn
where P is the depth of the deepest pit in time t; and k and n are constants.
The values of n for steels range from 0.1 to 0.9.
a) n = 0.1 for a well - aerated soil
b) n = 0.9 for a poorly aerated soil
The smaller the value of n, the greater the tendency for the pitting rate to fall off with time. As n
approaches unity, the pitting rate approaches a constant value, or penetration is proportional to time.

Pits tend to develop more on the bottom side of a pipeline than on the top side.

ME 6351 Soil Corrosion Page # 20

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Stress Corrosion Cracking (SCC) due to Soil Corrosion: Stress - corrosion cracking (S.C.C.) is a
well - known cause of underground oil and gas transmission pipeline failures [11]

 Stress - corrosion cracking of cathodically protected pipelines originates on the outer pipe
surface
 In most engineering structures where cathodic protection is used to protect steel from general
corrosion, the steel is polarized to a potential of −0.85V versus Cu/CuSO4 , corresponding to
−0.53V (S.H.E.).

ME 6351 Soil Corrosion Page # 21

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Remedial Measures for Soil Corrosion:

 Using Organic, Inorganic or Metallic Coatings

 Alteration of Soil
 Cathodic protection
 Combination of methods –Normally buried pipelines and tanks are protected
by a combination of cathodic protection and an organic coating

ME 6351 Soil Corrosion Page # 22

 Topics

 Atmospheric Corrosion
 Aqueous Corrosion
 Soil Corrosion

Page # 23
M. A. Islam
 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Classification of waters
Water is commonly described either in terms of its nature, usage, composition or origin.
I. Natural Water
a) Fresh Water (Surface and Underground water)- containing less than 1000 ppm
chlorides
b) Brackish - 1000 to 25,000 ppm chlorides
c) Seawater - Sodium chloride between 2.5 and 3.5 percent
d) Brines -Higher chloride concentrations
II. Treated Water
a) Potable Water
b) Distilled or Demineralized Water

 Pure water without dissolved gases (e.g., oxygen, carbon dioxide, and sulfur dioxide)
does not cause undue corrosion attack on most metals and alloys at temperatures up
to the boiling point of water.

ME 6351 Aqueous Corrosion Page # 24

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Important Constituents for Water Analysis

 Dissolved gases (oxygen, nitrogen, carbon dioxide, ammonia, sulfurous gases)
 Mineral constituents, including hardness salts, sodium salts (chloride, sulfate, nitrate,
bicarbonate, and so forth), salts of heavy metals, and silica
 Organic matter, including that of both animal and vegetable origin, oil, trade waste (including
agricultural) constituents and synthetic detergents
 Microbiological forms, including various types of algae and slime-forming bacteria

Table: Average Concentration of the 11 Most Abundant Ions and Molecules in Clean
Seawater (35.00‰ Salinity, Density of 1.023 g mL−1 at 25°C) [5]
ME 6351 Aqueous Corrosion Page # 25
 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure: Difficulties and Means of Treatment for Common Impurities Found in Fresh Water [5]

ME 6351 Aqueous Corrosion Page # 26

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

The Salt drop experiment:

A drop of 3% NaCl solution placed in abraded iron surface
 Small amount KFeCN which turns blue with Fe ions
 Phenolphthalein which turns pink in alkali

Anodic Area

Rust O2 OH- Fe2+ OH- O2

{Fe(OH)2 to FeO. OH}
Fe
Cathodic Area

a b c

Figure: a) Random distribution of anodic and cathodic areas

b) Final distribution
c) Reaction occurring due to salt drop [11]

ME 6351 Aqueous Corrosion Page # 27

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure: Effect of oxygen concentration on the corrosion of low-carbon steel in tap

water at different temperatures. [5]

ME 6351 Aqueous Corrosion Page # 28

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure : Effect of oxygen on corrosion of steel [5]

ME 6351 Aqueous Corrosion Page # 29

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure: Corrosion of steel in water containing 5 ppm of dissolved oxygen at two different
temperatures as a function of the water pH [5]

ME 6351 Aqueous Corrosion Page # 30

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure: Corrosion of steel and aluminum as a function of pH at the same temperature (22°C) [5]

ME 6351 Aqueous Corrosion Page # 31

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Comparison of diagnostic Techniques for Metallic supply [5]

Technique- Zone water audits

Advantages
 Cheap
 Covers large areas of a city quickly
 Allows for a comparison of water losses between individual districts
 Useful as a screening process for other techniques
 Can be used to evaluate the effectiveness of repair programs

Disadvantages
 Does not give the precise location of leaks
 Requires isolation of zones
 Work must be performed at night
 Only gives an overview of current problems

ME 6351 Aqueous Corrosion Page # 32

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Comparison of diagnostic Techniques for Metallic supply [5]

Technique- Sonic/acoustic leak detection

Advantages
 Widely practiced
 Known to find leaks accurately
 Known to find leaks of different sizes
 Operates from outside the water line
Disadvantages
 Percentage of leaks missed by the technique is unknown
 Currently works best in metal water lines
 Only gives information on the current condition of the line (the tool has little
predictive value)
 Background noise problems

ME 6351 Aqueous Corrosion Page # 33

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Comparison of diagnostic Techniques for Metallic supply [5]

Technique- Ultrasound
Advantages
 Most versatile NDE technique
 Established technology in oil industry

Disadvantages
 Technique will not work through tuberculation
 Not yet commercially available for water lines
 Requires access to and complete cleaning of the inside of the pipe

ME 6351 Aqueous Corrosion Page # 34

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Comparison of diagnostic Techniques for Metallic supply [5]

Technique- Half-cell potential measurements

Advantages
 Simple to conduct
 May act as a screening mechanism for more expensive methods
 Well established as method to detect corrosion activity in buried objects
Disadvantages
 Factors such as stray currents and soil conditions may affect readings
 Accuracy of results depends on distance between readings
 Small areas of localized corrosion can not be detected

ME 6351 Aqueous Corrosion Page # 35

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Comparison of diagnostic Techniques for Metallic supply [5]

Technique- Magnetic flux leakage

Advantages
 Established technology in oil and gas industry
 Known to be capable of detecting small defects and through holes in steel pipe

Disadvantages
 Not yet commercially available for water lines
 Requires access to and complete cleaning of the inside of the pipe

ME 6351 Aqueous Corrosion Page # 36

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure: Corrosion control Program by

AWWA [5]

ME 6351 Aqueous Corrosion Page # 37

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Scaling: The deposition of mineral solids on the interior surfaces of water lines and container.
(Mostly occurs due to heating of water containing the carbonates or bicarbonates of calcium and
magnesium)
Prevention of Scale deposition
 pH control
 Scale inhibitors addition
 Removal of scaling species

Type of Water Inhibitor Metals Concentration

Ca(HCO3)2 Steel, cast iron 10 ppm
Potable
Polyphosphate Fe, Zn, Cu, Al 5–10 ppm
Ca(OH)2 Fe, Zn, Cu 10 ppm

Na2SiO3 Zn 10 ppm
Seawater NaNO2 Fe 0.5%
Ca(HCO3)2 All pH dependent
NaH2PO4 + NaNO2 Fe 10 ppm + 0.5%

Table: Typical Water Systems and the Inhibitors Used to Protect [6]

ME 6351 Aqueous Corrosion Page # 38