Corrosion of Metals Intergranular Corrosion

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 7: Intergranular Corrosion
Module learning objectives

1. Explain the mechanisms for intergranular corrosion 2. List three sets of alloys that are susceptible to intergranular corrosion 3. Explain the microstructure features and processing that leads to intergranular corrosion. 4. Describe different approaches for controlling intergranular corrosion in different alloys.
Intergranular corrosion
Localized attack at grain boundaries with relatively little corrosion of grains Two forms of intergranular corrosion Corrosion products push out grains Metal appears to be flaking Called exfoliation Grains fall out Metal disintegrates Metal loses strength
Reprinted with permission of ASM International. All rights reserved.
Two metallurgical causes behind intergranular corrosion

1. Segregation of impurities to grain boundaries Difference in composition can lead to galvanic corrosion If grain boundary is anode, then it will be attacked If region next to the grain boundary is anode, then it will be attacked 2. Formation of precipitates on the grain boundaries Precipitates are different metallurgical phase than grains Decrease corrosion resistance of areas adjacent to grain boundaries or develop microscopic galvanic cells.
Segregation of elements to grain boundaries

Occurs when metal heated during heat treatment or cooling after being cast Increase concentration on grain boundaries
Decrease concentration within grains

May promote galvanic corrosion Interstitials often impurities such as sulfur or phosphorous Best controlled by minimizing amount of interstitial impurities in an alloy
Interstitial atom
Precipitates at grain boundaries

In many alloys second phase particles form along grain boundaries Precipitates a different metallurgical phase than grains Two possible consequences 1. Decrease corrosion resistance of adjacent area due to depletion
2. Develop microscopic galvanic cells in area of grain boundary

Discrete particles Continuous film
Sensitization of Austenitic (3xx series) stainless steel

Depletion of one or more elements from areas adjacent to grain boundaries Due to formation of precipitates on grain boundaries Increases susceptibility to corrosion In austenitic stainless steels sensitization involves depletion of chromium 304 stainless steel
Corroded grain boundaries
Chromium carbide precipitates form on grain boundaries Required conditions High chromium content > 0.02% carbon
Exposure between 425 and 870 C

Sensitization best known in steels with 18% chromium and 8% nickel 304 stainless steel contains up to 0.08% C Plenty of carbon available to form chromium carbide precipitates
Chromium carbide precipitates in 304 stainless steel
0.0025 inch 0.064 mm

Courtesy of Aston Metallurgical Services
0.0007 inch 0.018 mm

Courtesy of Aston Metallurgical Services
Sensitization process
Occurs when steel heated between 425 and 870 C (797 and 1598 F) 1. Carbon and chromium diffuse to grain boundaries 2. React to form chromium carbide (Cr4C or Cr23C6) precipiates Chromium diffusion rate between 425 and 870 C is low
Chromium atom Carbon atom

Depleted region
Chromium gives stainless steel its corrosion-resistant properties Need more than 12% chromium to make stainless steel corrosion resistant Depleted regions have less than 12% chromium Areas near grain boundaries susceptible to attack
Grain
Grain Carbide
%Chromium 18 12
Problem 1
What is expected to occur as the time to cool a 304 stainless steel from 800 C to 400 C increases?
Depleted region decreases in width Depleted region increases in width No change in width of depleted region
Problem 1
INCORRECT
There will be more diffusion for longer time at elevated temperatures
OK
Problem 1
CORRECT
Exposure to longer time allows for more carbon and chromium atoms to diffuse to grain boundaries. Results in larger chromium carbides and wider depleted region
OK
Problem 1
INCORRECT
There will be more diffusion for longer time at elevated temperatures.
OK
Problem 2
What is expected to occur as the carbon content decreases in a 304 stainless steel that is cooled from 1050 C to room temperature?
Degree of sensitization decreases Degree of sensitization increases Degree of sensitization the same as at higher carbon content
Problem 2
CORRECT
As carbon content decreases there is less carbon to form precipitates
Precipitates will be smaller and fewer in number compared to a steel with higher carbon content
OK
Problem 2
INCORRECT
With less carbon available, will it be as easy for chromium carbide precipitates to form compared to an alloy with higher carbon content?
OK
Problem 2
INCORRECT
With less carbon available, will it be as easy for chromium carbide precipitates to form compared to an alloy with higher carbon content?
OK
Welding is a common cause of sensitization
Cooling rate sufficiently high to avoid carbide precipitation Heated to carbide formation temperatures
Side view
Top view
Problem 3
What is expected to occur as the welding time to join two pieces of 304 stainless steel component increases?
Decrease width of steel that is sensitized
Increase width of steel that is sensitized

No change in width of steel that is sensitized
Problem 3

INCORRECT
As welding time increases, heat put into areas away from weld increases.
OK
Problem 3

CORRECT
As welding time increases, heat put into areas away from weld increases. Increased portion heated into temperature range for carbide formation.
OK
Problem 3

INCORRECT
As welding time increases, heat put into areas away from weld increases.
OK
Sensitization during annealing

Sometimes necessary to anneal stainless steel to soften for cold working For example, deep drawing may require more than one forming step Steel work hardens to the point that it cannot be shaped in one step Steel annealed above 1000 C to restore ductility Carbides will form if steel not cooled quickly enough between 870 and 425 C
Step 1
Step 2
Problem 4
What are possible methods for reducing susceptibility to sensitization of 304 stainless steel that must be annealed?
Increase carbon content or fast cool from annealing temperature Increase carbon content or slow cool from annealing temperature Decrease carbon content or fast cool from annealing temperature Decrease carbon content or slow cool from annealing temperature
Problem 4
INCORRECT
Increasing carbon content results in more carbon available to form chromium carbide precipitates
OK
Problem 4
INCORRECT
Increasing carbon content results in more carbon available to form chromium carbide precipitates. Slow cool from annealing temperature gives more time for chromium carbide precipitates to form.
OK
Problem 4
CORRECT
Decreasing carbon content in less carbon available to form chromium carbide precipitates. Fast cool from annealing temperature reduces time for chromium carbide precipitates to form.
OK
Problem 4
INCORRECT
Slow cool from annealing temperature gives more time for chromium carbide precipitates to form.
OK
Preventing sensitization of Austenitic stainless steel

1. High-temperature solution anneal heat treatment 2. Addition of elements that are strong carbide formers (called stabilizers)
3. Reduce carbon content
Approaches especially important if control of thermal treatment is difficult Some components or structures require stress relief heat treatment at temperatures ideal for sensitization
Solution anneal heat treatment to dissolve precipitates

1. Heat the alloy above 1035 C (1900 F) Dissolve the chromium carbides Puts chromium back into solid solution
Restores the chromium-depleted zone

2. Cool rapidly (quench) below 425 C (797 F) Prevent formation of chromium carbide precipitates Chromium atom Carbon atom
Addition of strong carbide formers

Stabilizers Niobium (type 347 stainless steel) Titanium (type 321 stainless steel) These elements combine with carbon Form niobium carbide or titanium carbide particles Leaves no carbon left for chromium to react
Chromium carbides cannot form

Chromium depletion does not occur Permits fabrication of large vessels, repair welding, and other operations without subsequent heat treatment
Stabilized stainless steel as received from a steel mill Contains titanium or niobium carbides Essentially no chromium carbides Must follow certain procedures if heat treatment is required If steel is solution annealed and cooled too fast Titanium or niobium remain in solid solution and titanium or niobium carbide particles do not form When heated into sensitization temperature range, steel behaves like a steel without titanium or niobium, and sensitization results
Decrease carbon content

As carbon content decreases Number and size of chromium carbide particles decreases Elevated temperature exposure time to form particles increases Graph general guidelines. Should be verified before applied.
Temperature ( C)
Time to Sensitization
(Reprinted with permission of ASM International. All rights reserved.)
Temperature ( F)
Problem 5
How quickly should a 304 stainless steel alloy with 0.030% carbon be cooled below 600 C to avoid sensitization?
Within 100 hours Within 30 hours Less than 1 hour Within 8 hours
Temperature ( C)
Time to Sensitization
Temperature ( F)
Problem 5
INCORRECT
Temperature ( C) Temperature ( F) Time to Sensitization
OK
Problem 5
INCORRECT
OK
Problem 5
INCORRECT
OK
Problem 5
CORRECT
OK
Testing for sensitization

ASTM A262 Standard Practices for Detecting Susceptibility to Intergranular Attack in Austenitic Stainless Steels 6 different tests Tests involve exposing samples to acid solutions followed by different methods of evaluation Tests bears little relationship to intended service environment Detect metallurgical conditions that can lead to intergranular corrosion
Use for process development, supplier evaluation, and problem solving
Final remarks for sensitization

A sensitized stainless steel will not necessarily exhibit intergranular corrosion in all environments In environments where IG corrosion does not occur, the sensitized boundary and grains exhibit passive behavior
Ferritic stainless steels can be sensitized

Information available in references in Module 1
Intergranular corrosion of aluminum alloys

2 mechanisms
Galvanic corrosion Due to formation of precipitates on grain boundaries
Exfoliation
Galvanic corrosion
Galvanic cells form due to differences in composition at grain boundaries Different forms of galvanic cells Likelihood and severity of corrosion depends on Alloy composition Degree of grain boundary precipitation Corrosiveness of environment
Discrete particles
Continuous film
Al2Cu precipitates in Al-5Cu alloy
0.010 mm (0.0004 inches)

Aluminum alloys of concern

Precipitation hardenable alloys 2xxx alloys (Cu is major alloying element) 7xxx alloys (Zn and Mg are alloying elements; many with 3% Cu) Certain 2xx, 3xx, and 7xx cast alloys with Zn, Mg, and/or Cu 5xxx alloys Contain magnesium as the major alloying element Strengthened by work hardening, such as by cold-rolling Alloys with >3% magnesium can form Mg2Al3 precipitates along grain boundaries when exposed to moderately elevated temperatures or after long time periods (many years) at room temperature. Although, 6xxx alloys are precipitation hardenable, they are less of a concern
Galvanic cell 1: Copper depletion at grain boundaries

Occurs in alloys that contain copper and form Al2Cu precipitates 2xxx alloys Some 7xxx alloys Some cast alloys Depletion occurs when alloy cooled too slow after solution anneal treatment
Precipitation hardening
Aluminum
Copper
1) Solution heat treat
Microstructure
2) Fast cool
25 C
Aluminum alloy used in solution annealed condition or aged
Form precipitates at aging temperature
Microstructure after aging
1) Solution heat treat
2) Slow cool
25 C Precipitates present
If cooling rate not fast enough Form Al2Cu or Al2Cu(Zn) precipitates on grain boundaries
Easier for precipitates to form on grain boundaries than within grains Unless cooling rate is extremely slow, precipitates do not form in grains
Depleted of copper atoms Copper atom Aluminum atom
Grain boundary
Galvanic cell forms when exposed to a corrosive environment
Copper in solid solution (Cathodes)
Grain
Grain
Copper depleted regions (anodes)
% Copper in grain phase
Grain boundary
% Copper in grain phase
For underaged alloys some copper will still remain in solution within the grain phase. Possibility for galvanic cells between depleted layers and rest of grain Important that intentionally underaged components not be exposed to corrosive environments
Grain boundary
Problem 6
What are two approaches for preventing intergranular corrosion in aluminumcopper alloys that can be precipitation strengthened?
Fast cool alloy after solution anneal or underage Slow cool after solution anneal or age to maximum strength Fast cool alloy after solution anneal or age to maximum strength Slow cool alloy after solution anneal or underage
Problem 6
INCORRECT
Fast cooling after solution anneal will prevent intergranular corrosion Underaging will result in a difference of copper in solid solution between depleted areas and areas away from grain boundaries
OK
Problem 6
INCORRECT
Slow cooling after solution anneal will result in a difference of copper in solid solution between depleted areas and areas away from grain boundaries However, aging to maximum strength, or even overaging, will result in an equalization of the copper concentration in solid solution
OK
Problem 6
CORRECT
Fast cooling after solution anneal will prevent formation of grain boundary precipitates
Aging to maximum strength, or even overaging, will result in an equalization of the copper concentration in solid solution
OK
Problem 6
INCORRECT
Slow cooling after solution anneal and underaging will result in a difference of copper in solid solution between depleted areas and areas away from grain boundaries
OK
Preventing intergranular corrosion in alloys that form Al-Cu precipitates % Copper in grain phase Fast cooling after solution anneal
Aging to maximum strength or overaging
Grain boundary Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012
Yield strength (MPa)
Duration of precipitation heat treatment (hours)

Yield strength (ksi)
Galvanic cell 2: Precipitates more active than grain interior

Cold rolled 5xxx alloys with > 3% magnesium Precipitation hardenable copper-free 7xxx alloys
Precipitates preferentially attacked
Anode
Grain
Grain
Cathode
In general, 5xxx alloys have excellent resistance to corrosion In 5xxx alloys with >3% magnesium Mg2Al3 precipitates can form along grain boundaries Form when alloy exposed to moderately elevated temperatures or after long periods of time (many years) at room temperature Mg2Al3 highly anodic with respect to aluminum grain phase Precipitates corrode, weakening the grain boundaries Time required for precipitates to form depends on magnesium content, alloy temper, exposure temperature, and initial processing
7xxx alloys without copper
Anodic MgZn2 precipitates form on grain boundaries

Improper heat treatment
Exfoliation
Occurs predominantly in aluminum alloy components Highly elongated grains that are parallel to metal surface Present in extruded and heavily cold-worked components Corrosion initiates on surface and proceeds along grain boundaries Corrosion products take up greater volume than parent metal
Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012 Reprinted with permission of ASM International. All rights reserved.
Susceptibility to exfoliation depends on Alloy composition Heat treatment Severity of corrosive environment Not accelerated by stress and does not lead to stress corrosion cracking
Susceptible alloys
Certain extruded products in both marine and industrial environments 2xxx copper-magnesium alloys 7xxx zinc-copper-magnesium alloys Certain cold worked 5xxx alloys Attack generally associated with Alloy fabrication method and extent of aging Impurities in alloy matrix Metallic compounds at surface and in grain boundaries Alloys resistant to exfoliation
1100 (UNS A91100)

3003 (UNS A93003) 5052 (UNS A95052)
7xxx alloys Exfoliation susceptibility typically high in alloys aged to maximum strength For alloys with copper, overaging improves exfoliation resistance, but with significant decrease in strength from maximum strength 5xxx aluminum alloys Special processing for some alloys to control where Mg2Al3 precipitates form within grains
Intergranular corrosion of other metals and alloys

Other metals susceptible to intergranular corrosion Zinc alloys that contain aluminum Some nickel alloys Possible, but uncommon in some copper alloys
Module review
1. Mechanisms by which an alloy made susceptible to intergranular corrosion
a. Galvanic cells due to segregation of impurities to grain boundaries b. Depletion of an element that provides corrosion resistance Sensitization Austenitic stainless steels c. Galvanic cells due to depletion of element near grain boundaries Precipitation hardenable Al alloys that form Al-Cu precipitates d. Galvanic cells between grain boundary precipitates and regions adjacent to grain boundaries Precipitation hardenable Al alloys that form Mg-Zn precipitates 5xxx alloys with more than 3% magnesium
2. Various microstructure features enable intergranular corrosion Specific processing conditions lead to development of these features 3. There are different approaches for controlling intergranular corrosion Specific approaches that can be used depend on specific alloy and mechanical requirements for component in which alloy will be used
End of Module 7

Corrosion of Metals Intergranular Corrosion

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Corrosion of Metals

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Module 7: Intergranular Corrosion

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Module learning objectives

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Reprinted with permission of ASM International. All rights reserved.

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Two metallurgical causes behind intergranular corrosion

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Segregation of elements to grain boundaries

Decrease concentration within grains

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Precipitates at grain boundaries

2. Develop microscopic galvanic cells in area of grain boundary

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Sensitization of Austenitic (3xx series) stainless steel

Corroded grain boundaries

Reprinted with permission of ASM International. All rights reserved.

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Exposure between 425 and 870 C

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Chromium carbide precipitates in 304 stainless steel

0.0025 inch 0.064 mm

0.0007 inch 0.018 mm

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Chromium atom Carbon atom

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Welding is a common cause of sensitization

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Increase width of steel that is sensitized

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Increase width of steel that is sensitized

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Increase width of steel that is sensitized

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Increase width of steel that is sensitized

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Sensitization during annealing

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Preventing sensitization of Austenitic stainless steel

3. Reduce carbon content

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Solution anneal heat treatment to dissolve precipitates

Restores the chromium-depleted zone

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Addition of strong carbide formers

Chromium carbides cannot form

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012

Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012