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Michael Pfeifer, PhD., P.E. Industrial Metallurgists, LLC Northbrook, IL 60062 847.528.3467 www.imetllc.com www.materialscoursesonline.com
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
Interstitial atom
Chromium carbide precipitates form on grain boundaries Required conditions High chromium content > 0.02% carbon
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 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
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
INCORRECT
There will be more diffusion for longer time at elevated temperatures
OK
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
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
Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012
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
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
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
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
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
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
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
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
Cooling rate sufficiently high to avoid carbide precipitation Heated to carbide formation temperatures
Side view
Top view
Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012
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
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
INCORRECT
As welding time increases, heat put into areas away from weld increases.
OK
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
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
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
INCORRECT
As welding time increases, heat put into areas away from weld increases.
OK
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
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
INCORRECT
Increasing carbon content results in more carbon available to form chromium carbide precipitates
OK
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
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
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
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
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
INCORRECT
Slow cool from annealing temperature gives more time for chromium carbide precipitates to form.
OK
Approaches especially important if control of thermal treatment is difficult Some components or structures require stress relief heat treatment at temperatures ideal for sensitization
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
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
(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
INCORRECT
Temperature ( C) Temperature ( F) Time to Sensitization
(Reprinted with permission of ASM International. All rights reserved.)
OK
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
INCORRECT
Temperature ( C) Temperature ( F) Time to Sensitization
(Reprinted with permission of ASM International. All rights reserved.)
OK
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
INCORRECT
Temperature ( C) Temperature ( F) Time to Sensitization
(Reprinted with permission of ASM International. All rights reserved.)
OK
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
CORRECT
Temperature ( C) Temperature ( F) Time to Sensitization
(Reprinted with permission of ASM International. All rights reserved.)
OK
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
Precipitation hardening
Aluminum
Copper
1) Solution heat treat
Microstructure
2) Fast cool
25 C
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
Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012
Grain
Grain
Grain boundary
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
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
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
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
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
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
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
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
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
Grain boundary Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012
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
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
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
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
Copyright 2012 Industrial Metallurgists, LLC and ASM International, 2012
End of Module 7