Corrosion of Metals

Michael Pfeifer, PhD., P.E. Industrial Metallurgists, LLC Northbrook, IL 60062 847.528.3467 www.imetllc.com www.materialscoursesonline.com

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Module 6: Pitting Corrosion

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Module learning objectives

1. Explain the mechanism for pitting corrosion 2. List three alloy systems that are susceptible to pitting corrosion 3. Explain the effects of chloride concentration and exposure time on pit density and corrosion rate. 4. List four approaches for controlling pitting corrosion

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Pitting
Localized form of corrosion Small pits form on exposed surface and penetrate into metal Most common on passivated metals Can be destructive if it causes perforation of equipment and structures Minor pitting often tolerated as long as there is no perforation and change in appearance is acceptable

304 stainless steel exposed to aerated salt water

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Under certain environmental conditions some active metals lose their activity Become passive Form extremely thin tightly adhering oxide film on metal surface Passive metal can revert to active state at localized areas of the surface

Large increase in corrosion rate at these localized areas

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Reversion to active state can occur for various reasons

Changes in environment Change of concentration of corrosive species

Electrolyte chemistry may vary because of a surface deposit

Surface defects Discontinuity such as a scratch or a gouge

Metallurgical features Inclusions or second phase particles, or the regions surrounding these features, may be preferentially attacked. Constituents within a grain boundary, either second-phase particles or segregation of detrimental species, can lead to pit initiation.

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Chloride ions (Cl-) in electrolyte a common cause of pit initiation Pitting incubation time Decreases as concentration of corrosive species increases Exposed metal in pit reverts to active Exposed active metal has lower potential than passivated metal Electrolyte within pit more corrosive than bulk electrolyte

Passive oxide

Cl-

Cl-

ClClClClClCl-

ClCl-

Cathode Anode

Cathode

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Anode: M Mn+ + neCathode: O2 + 2H2O + 4e- 4OHCl-

Cl-

OHOHCl- Mn+ Mn+

OHOH-

Cl-

e-

Mn+ ClMn+ Cl

e-

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Problem 1
Which graph represents the number of pits formed per unit area as the chloride ion concentration (Cl-) in water increases? Cl-(3) > Cl-(2) > Cl-(1)

# pits/area

Cl-(1)

# pits/area

Cl-(2)

Cl-(3)

Cl-(2) Cl-(1)

Cl-(3)
Time

Time # pits/area

# pits/area

Cl-(3)

Cl-(1) Cl-(2) Cl-(3) Time

Cl-(2)
Cl-(1) Time

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Problem 1
Which graph represents the number of pits formed per unit area as the chloride ion concentration (Cl-) in water increases? Cl-(3) > Cl-(2) > Cl-(1)

# pits/area

# pits/area

INCORRECT
Increased number of chloride ions means more active species to cause corrosion

Cl-(1)

Cl-(2) Cl-(3)

Cl-(3)

Cl-(2)
Cl-(1)

Time

Time # pits/area

# pits/area

Cl-(3)
Cl-(2)

Cl-(1) Cl-(2) Cl-(3) Time

OK

Cl-(1)
Time

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Problem 1
Which graph represents the number of pits formed per unit area as the chloride ion concentration (Cl-) in water increases? Cl-(3) > Cl-(2) > Cl-(1)

# pits/area

CORRECT
Expect that the number of pits increases with time.
Increased number of chloride ions means more active species to cause corrosion.

Cl-(1)

# pits/area

Cl-(2)
Cl-(3)

Cl-(3)

Cl-(2) Cl-(1)

Time # pits/area # pits/area

Time

Cl-(3)
Cl-(2) Cl-(1) Time

Cl-(1) Cl-(2) Cl-(3) Time

OK

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Problem 1
Which graph represents the number of pits formed per unit area as the chloride ion concentration (Cl-) in water increases? Cl-(3) > Cl-(2) > Cl-(1)

# pits/area

INCORRECT
This graph shows that a large number of pits quickly forms and then the number of pits decreases with time.

Cl-(1)

# pits/area

Cl-(2)
Cl-(3)

Cl-(3)

Cl-(2) Cl-(1)

Time # pits/area # pits/area

Time

Cl-(3) Cl-(2) Cl-(1)

Cl-(1)

Cl-(2)
Cl-(3) Time

OK

Time
Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Problem 1
Which graph represents the number of pits formed per unit area as the chloride ion concentration (Cl-) in water increases? Cl-(3) > Cl-(2) > Cl-(1)

# pits/area

INCORRECT
This graph shows that a large number of pits quickly forms and then the number of pits decreases with time.

Cl-(1)

# pits/area

Cl-(2) Cl-(3)

Cl-(3)

Cl-(2) Cl-(1)

Time # pits/area # pits/area

Time

Cl-(3) Cl-(2) Cl-(1)

Time

Cl-(1) Cl-(2) Cl-(3) Time

OK

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Effect of chloride concentration on pitting rate

Increase chloride concentration Decreased incubation time Increased # pits formed at any given time Cl-(3) > Cl-(2) > Cl-(1) Cl-(2) Cl-(1)

Cl-(3)

# pits/area

Time

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Problem 2
Increasing the temperature (T) of a solution generally increases the tendency towards pitting. Which graph best represents this? T(3) > T(2) > T(1)
Tendency to pit
T(1) T(2) T(3) Tendency to pit T(3) T(2) T(1)

Chloride concentration Tendency to pit

Tendency to pit

Chloride concentration

T(1)

T(3) T(2)

Chloride concentration

T(3) Chloride concentration

T(1) T(2)

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Problem 2
Increasing the temperature (T) of a solution generally increases the tendency towards pitting. Which graph best represents this? T(3) > T(2) > T(1)
T(1)
T(2) T(3)

Tendency to pit

Tendency to pit

T(3)
T(2) T(1)

INCORRECT
Shows that tendency to pit increases as the temperature decreases

Chloride concentration

Chloride concentration

Tendency to pit

Tendency to pit

OK

T(1)

T(3) T(2)

T(3)
Chloride concentration

T(1) T(2)

Chloride concentration

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Problem 2
Increasing the temperature (T) of a solution generally increases the tendency towards pitting. Which graph best represents this? T(3) > T(2) > T(1)

Tendency to pit

T(1) T(2) T(3)

Tendency to pit

T(3) T(2) T(1)

CORRECT

Chloride concentration Tendency to pit

Chloride concentration

T(1)

T(3) T(2)

Tendency to pit

T(3)

T(1) T(2)

OK

Chloride concentration

Chloride concentration

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Problem 2
Increasing the temperature (T) of a solution generally increases the tendency towards pitting. Which graph best represents this? T(3) > T(2) > T(1)
Tendency to pit Tendency to pit T(1) T(2) T(3)

T(3)
T(2) T(1)

INCORRECT

Chloride concentration Tendency to pit This graph shows the tendency to pit decreases as the chloride concentration increases.

Chloride concentration Tendency to pit

OK

T(1) Chloride concentration

T(3) T(2)

T(3) Chloride concentration

T(1) T(2)

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Problem 2
Increasing the temperature (T) of a solution generally increases the tendency towards pitting. Which graph best represents this? T(3) > T(2) > T(1)
Tendency to pit

T(1)
T(2) T(3)

Tendency to pit

T(3)
T(2) T(1)

INCORRECT
This graph shows the tendency to pit decreases as the chloride concentration increases.

Chloride concentration

Chloride concentration Tendency to pit

Tendency to pit

T(1)

T(3) T(2)

OK

Chloride concentration

T(3) Chloride concentration

T(1) T(2)

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Influence of metal composition

Metals that form adherent, passive oxides most susceptible to pitting Chromium and its alloys Aluminum and its alloys Titanium and its alloys Metals that contain these elements in sufficient quantities Stainless steels containing > 12% chromium Within each set of alloys some have better pitting resistance than others Specific elements present in the alloys Microstructural features

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Aluminum alloys
Pitting resistance depends on purity Purest metal most resistant

1xxx alloys (best pitting resistance) 5xxx alloys 3xxx alloys Decreasing pitting resistance 6xxx alloys 7xxx alloys 2xxx alloys (lowest pitting resistance)

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Controlling pitting corrosion

Often unexpected Affects alloys selected based on their corrosion resistance Susceptibility of an alloy to localized corrosion is often overlooked 1. Select a more corrosion-resistant metal for the application Selecting different alloy from a family of alloys 316 stainless steel instead of 304 stainless steel Select different family of alloys based on same major element 3xxx series of aluminum alloys instead of 5xxx series

Select alloy based on a different major element Titianium alloy instead of stainless steel

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Controlling pitting corrosion

2. Surface treatment to modify oxide layer Passivate stainless steels Expose steel to nitric acid solution, followed by alkaline rinse Removes surface iron particles Dissolves detrimental inclusions at the surface Forms a clean, slightly thicker passive oxide Anodize aluminum and titanium alloys Grow thick oxide by anodizing Normal oxide layer much less than 1 micrometer thick Thicker than 25 micrometers after anodization 3. Apply coating Usefulness of metal may be eliminated

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Controlling pitting corrosion

4. Adjust environment Reduce concentration of aggressive species Enhance passivity and avoid passive film breakdown Difficult to implement in practice

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Module review
1. Metals that form a passive oxide are most susceptible to pitting. 2. Pitting mechanism involves a local breakdown of passive layer and formation of a corrosion cell in the area of the breakdown. 3. Chloride a major cause of pitting As chloride concentration increases, number of pits formed in a particular period of time increases. 4. Four approaches to controlling pitting corrosion. Select a different alloy Surface treatment to modify the oxide layer Apply surface coating Modify environment

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

End of Module 6

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012