Intergranular Corrosion

Intergranular corrosion (IGC) is the preferential corrosion of the

grain boundaries with negligible corrosion of the grain matrix [11–
15].
From: Functional Materials, 2012

Related terms:

Corrosion, Exfoliation Corrosion, Pitting Corrosion, Stress Corrosion Cracking,

Aluminum Alloys, Austenitic Stainless Steel, Grain Boundary, Impurity,
Intermetallics, Microstructure

Corrosion in Liquids, Corrosion Evaluation

D.L. Engelberg, in Shreir's Corrosion, 2010

2.06.2.1 Aluminum Alloys

The occurrence of IGC in aluminum alloys is a function of the material
composition, and certain alloying elements are responsible for the prevailing
corrosion mechanism. The IGC susceptibility of heat treatable aluminum alloys is
mainly related to the quenching and ageing treatment after solution annealing and
small changes in these routines can cause significant changes in material
resistance.14 Another important factor for the IGC behavior is also the
thermomechanical process history. Alloy groups that have been generally
associated with IGC include, precipitation hardenable 2XXX series Al–Cu alloys,
work hardenable 5XXX series Al–Mg alloys, and precipitation hardenable 7XXX Al–
Zn–Mg alloys. The 6XXX precipitation hardenable Al–Mg–Si series has also shown
IGC, but to a far smaller extent than the other alloy groups. The above-mentioned
aluminum alloys are also associated with exfoliation corrosion, which is a type of
intergranular corrosion which proceeds parallel to the specimen surface.
Exfoliation corrosion is related to the development of excessive corrosion products
at grain boundaries, indicating a layer-wise spallation of plate-like grain segments.
This type of attack occurs in highly orientated microstructures of wrought
aluminum alloys. IGC and exfoliation corrosion proceed in a similar manner, but
exfoliation has also been found in materials which were not susceptible to IGC.
In 2XXX series Al–Cu alloys, including Al–Cu–Mg and Al–Cu–Li alloys, IGC
behavior is primarily influenced by the copper concentration.5,14,15 Copper in solid
solution increases the corrosion potential of the matrix phase, and copper
segregation or depletion can cause local variations in the electrochemical potential.
Copper-depleted regions are less noble and susceptible to anodic dissolution in
particular, if adjacent to copper-rich intermetallic phases such as Al2Cu, Al2CuMg,
or Al2CuLi. Dissolution takes place in narrow regions close to precipitated phases
at the grain boundary. Dealloying of copper-containing intermetallic phases, and
copper re-precipitation has also been reported to support local dissolution
reactions.5 To reduce IGC susceptibilities, specifically designed heat and quenching
treatments can be employed, which produce a uniform distribution of
precipitates.15 In the 5XXX series Al–Mg alloys with more than 3% Mg, the
susceptibility to IGC is typically based on the dissolution of the intergranularly
precipitated β-Al3Mg2 phase.5,15 This phase predominantly precipitates in the
temperature range between 50 and 200 °C, due to a rejection of magnesium out of
solid solution. Mg-depleted regions have also been found in the vicinity of the β-
phase. Electrochemical measurements on bulk β-Al3Mg2 in NaCl solution
indicated more electro-negative corrosion and passivity breakdown potentials than
the aluminum matrix phase. These potential differences are responsible for the
anodic dissolution of the β-Al3Mg2 phase.5 Microalloying with zinc produces a
stable Al–Mg–Zn phase (τ-phase) and precludes the precipitation of β-Al3Mg2 in
the 5XXX series alloys. In the 7XXX series Al–Zn–Mg alloys, IGC has frequently
been attributed to the presence of Mg-rich grain boundary precipitates, as well as
intergranular enrichments of Mg and Zn. Copper bearing 7XXX series Al–Zn–Mg–
Cu alloys have been reported to contain copper depleted regions at grain
boundaries, with an IGC mechanism similar to the 2XXX series Al–Cu alloys.15 The
application of over-aging heat treatments, and the resultant uniform distribution
of precipitates can prevent IGC.15 In the 6XXX series, Al–Mg–Si alloys IGC has
been attributed to the anodic dissolution of the hardening phase Mg2Si.15

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Corrosion
In Smithells Metals Reference Book (Eighth Edition), 2004

31.4.5 Intergranular corrosion

Intergranular corrosion (IGC) is strongly associated with the properties and
microstructure of a metal. A well-known example of IGC is the sensitisation of
austenitic 18Cr—8Ni stainless steels. In the temperature range of 538–927°C,
insoluble chromium carbides, Cr23C6, precipitate at the grain boundaries. This
precipitate is a product of the reaction between chromium and the carbon diffusing
along the grain boundaries. Below 538°C, the carbon remains relatively immobile,
and above 927°C the chromium carbides are soluble. Formation of chromium-rich
precipitates quickly depletes chromium from a region immediately adjacent to the
grain boundary. This reduces the alloy’s ability to generate chromium oxide
protective films and leads to an increased susceptibility for localised attack in the
grain boundary region.
Welding is a common source of localised heating that can sensitise a material. IGC
is often observed within the heat affected zone after welding a material susceptible
to heat sensitisation. Figure 31.3 illustrates IGC coincident to a weld bead. Note
that the sensitisation band occurs on each side of the weld, parallel to its axis of
propagation. The displacement and width of the IGC regions is dependent upon
the thermal conductivity of the material and the duration that it resides in the
critical sensitisation temperature range.
Figure 31.3. Illustration of IGC region and heat affected zone coincident with a
weld

Knifeline attack is a highly localised form of IGC that has been observed in titanium
and niobium doped austenitic stainless steels, Types 321 and 327, respectively. The
region of attack is typically only a couple of grain diameters from the weld bead.
Knifeline attack results from dissolution of titanium or niobium carbides at high
temperatures, >1230°C, followed by rapid cooling.
IGC usually requires a strongly oxidising condition. Limiting the use of sensitised
materials to weakly corrosive environments will help insure their stability. Likewise
it is possible to control oxidation by injecting reducing gases such as H2, or by
operating at lower acidity. Metallurgical techniques are more common for
preventing IGC. Typically, those employed are: a) decreasing the level of carbon
loading; b) solution annealing; and c) stabilisation using titanium or niobium.
IGC testing is accomplished by determining the susceptibility of a material to heat
sensitisation, then exposing the material to a strongly oxidising environment. Most
involvean exposure to sulphuric acid, nitric acid, oxalic acid, or a solution of
sulphuric acid and copper sulphate. ASTM standards relating to IGC include the
following:
• A 262–02 Standard Practices for Detecting Susceptibility to Intergranular Attack
in Austenitic Stainless Steels
• A 763–93 Standard Practices for Detecting Susceptibility to Intergranular Attack
in Ferritic Stainless Steels
• G 28–02 Standard Test Methods of Detecting Susceptibility to Intergranular
Corrosion in Wrought, Nickel-Rich, Chromium-Bearing Alloys
• G 108–94 Standard Test Methods of Detecting Susceptibility to Intergranular
Corrosion in Wrought, Nickel-Rich, Chromium-Bearing Alloys
• G 110–92 Standard Practice for Evaluating Intergranular Corrosion Resistance
of Heat Treatable Aluminium Alloys by Immersion in Sodium Chloride +
Hydrogen Peroxide Solution

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Corrosion and corrosion protection of aluminium

N. Birbilis, B. Hinton, in Fundamentals of Aluminium Metallurgy, 2011

19.3 Localised corrosion: intergranular and exfoliation

Intergranular corrosion (IGC) is a phenomenon of which the precise mechanisms
have been under debate for almost half a century (Hunter et al., 1963).
Intergranular corrosion is a special form of microstructurally influenced corrosion,
whereby the grain boundary ‘region’ of the alloy is electrochemically different to
the bulk or adjacent alloy microstructure.
Corrosion activity may develop because of some heterogeneity in the grain
boundary structure. In aluminium-copper alloys, precipitation of Al2Cu particles at
the grain boundaries leaves the adjacent solid solution anodic and more prone to
corrosion. With aluminium-magnesium alloys the opposite situation occurs, since
the precipitated phase Mg2Al3 is less noble than the solid solution. Serious
intergranular attack in these two alloys may however be avoided, provided that
correct manufacturing and heat treatment conditions are observed.
In the case of the aluminium-magnesium system, almost all commercial alloys are
supersaturated as the magnesium solubility at ambient temperatures is less than
1 wt%. This effectively means that for alloys with more than 3 wt% magnesium
elevated service temperatures can lead to grain boundary precipitation and
sensitisation of grain boundaries to an intergranular corrosion susceptibility. The
extent of this sensitisation may be approximately deduced from the continuity of
Mg2Al3 precipitation at the boundaries. Apparently continuous boundaries
correspond to high levels of sensitisation to intergranular corrosion.
The level of sensitisation to intergranular corrosion of 5xxx series alloys fabricated
sheet, plate or extrusion can be easily determined by measurement of the Mass
Loss after exposure to Nitric Acid (NAMLT Test) in accordance with ASTM G67–04.
This is a 24 hours exposure to nitric acid and a measurement of weight loss due to
intergranular corrosion and loss of grains. An NAMLT value of more than 30 g/cm2
of surface is necessary before an alloy has become sensitised to intergranular
corrosion or cracking. The test method used to evaluate susceptibility to
intergranular corrosion depends on alloy type. For 2xxx and 7xxx series alloys ASTM
G110–92 (2009) is most commonly used for assessing susceptibility to
intergranular corrosion.
In the case of aluminium-zinc-copper alloys, where the precipitated phase is the
very anodic MgZn2(η), intergranular corrosion occurs rather readily.Again,however,
susceptibility to intergranular corrosion is strongly dependent on the heat
treatment condition and its effect on grain boundary solute segregation, the
morphology and composition of the grain boundary precipitate and the
surrounding alloy matrix (Knight, 2003). The most resistant heat treatments are
based on the use of overageing to the T7 temper or more complex heat treatments
which involve retrogression and reageing to minimise the trade-off between alloy
strength and intergranular corrosion resistance (Polmear, 1995; Davies, 1999).
Grain boundary density also plays a role in the amount of IGC that occurs, with the
short transverse direction more susceptible than the rolling or transverse direction
in rolled/wrought products.
The images in Fig. 19.4 help rationalise the metallurgical origins of intergranular
corrosion.
19.4. (a) Schematic of hypothetical grain boundary in an Al-X-Y alloy. This
schematic indicates the different chemistry that exists in the grain interior, solute
depleted zone (precipitate free zone) and grain boundary precipitates – giving rise
to electrochemical heterogeneity localised at the grain boundary region. (b) Dark
field STEM image of high angle grain boundary in AA7075-T651, revealing grain
boundary precipitates (MgZn2) and a distinguishable precipitate free zone.

Intergranular corrosion differs from pitting corrosion and while intergranular

corrosion may initiate from a pit, it propagates more rapidly than pitting corrosion
along susceptible intergranular pathways. Both may have a deleterious effect on
fatigue crack initiation, and act as severe stress concentrators which may reduce
the number of cycles to failure under cyclic loading. At this stage, a timely
comment needs to be made regarding the role of micro-environments. While
pitting corrosion can initiate in bulk neutral conditions, once pitting is stable and
indeed once corrosion propagation proceeds by mechanisms such as intergranular
corrosion (or other forms described below in this chapter), the local environment at
the corroding metal is likely to significantly differ to the bulk electrolytic
environment. Typically, electrolytes at pit bases or occluded regions (viz. in aircraft
lap joints, etc.) can be either acidic or alkaline (under certain conditions), further
promoting enhanced rates of localised attack.
Exfoliation corrosion (Davies, 1999; Zhao and Frankel, 2007) of aluminium alloys is
the result of intergranular corrosion. It generally occurs where the alloy
microstructure has been heavily deformed (i.e. by rolling) and the grain structure
has been flattened and extended in the direction of working. Intergranular
corrosion attack from transverse edges and pits then runs along grain boundaries
parallel to the alloy.
Exfoliation is characterised by the lifting of layers of relatively uncorroded
intragranular metal caused by the swelling of corrosion product in the layers of
IGC. Exfoliation is observed on aircraft components around rivet or bolt holes
where the end grain of the microstructure is exposed. Testing for exfoliation
corrosion is carried out in accordance with any of several ASTM tests, including the
acidified salt spray test ASTM G85-09, ASTM G66-99 (2005) (ASSET Test) and most
commonly the EXCO immersion test ASTM G34-01 (2007). A typical example of
exfoliation corrosion is seen in Fig. 19.5.
19.5. (a) and (b) Exfoliation corrosion on an AA2024-T4 aluminium alloy aircraft
component. The exfoliation corrosion is a result of corrosion initiating at fastener
holes.
(image courtesy of DSTO)

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Corrosion fundamentals and characterization

techniques
Gustavo A. Cragnolino, in Techniques for Corrosion Monitoring, 2008

2.3.5 Intergranular corrosion

Intergranular corrosion (IGC) is a form of localized corrosion characterized by
preferential corrosion at grain boundaries or areas adjacent to them, with little or
negligible attack on the grains. Similarly to other forms of localized corrosion, it
mainly occurs on passive alloys exposed to specific corrodents. IGC of commercial
alloys is generally caused by enrichment or depletion of alloying elements in the
area adjacent to the grain boundaries, by intergranular precipitation of second-
phase particles or by the presence of alloy impurities segregated at the grain
boundaries.
Most alloys, after being submitted to specific heat treatments or as a result of
fabrication processes, experience IGC when exposed to an appropriate
environment. A large number of cases involve Fe-Ni-Cr alloys, either Fe-based or
Ni-based, particularly austenitic stainless steels (SS) due to their widespread use in
many industrial applications. Austenitic SSs, such as AISI 304 (UNS S30400), after
being slowly cooled through the temperature range of 850 to 550 °C, might
become susceptible to IGC in relatively benign environments. The phenomenon is
called ‘sensitization’ to indicate that the alloy is sensitive to grain boundary attack.
Sensitization may occur as a result of various situations: (a) slow cooling from the
annealing temperature, which could be the case in heavy section components; (b)
stress relieving in the sensitization range, which is possible when ferritic steels that
require such treatment are welded to austenitic steel parts that become sensitized;
(c) welding operations, which is by far the most common cause of sensitization.
The failure of AISI 304 and 316 (UNS S31600) SS components due to IGC in the
heat-affected zone (HAZ) of the weld, the so-called weld decay, has been a problem
in many industrial applications.
Sensitization of austenitic Fe-Cr-Ni alloys is caused by precipitation of Cr-rich
carbides at grain boundaries, accompanied by Cr depletion of the regions adjacent
to the carbides to levels below those required for passivation. Within the
temperature range of sensitization, C diffuses toward the grain boundaries quite
readily whereas the bulk diffusion of Cr from the austenitic matrix to the depleted
region is too slow to allow replenishment. Since at least 12 wt % Cr is necessary to
preserve passivity in an acidic medium, depletion of Cr below such level leads to
IGC. However, if a sensitized austenitic SS is held long enough at the sensitization
temperature it becomes desensitized because Cr diffusion from the bulk
replenishes the Cr-depleted region, even though the carbides are still precipitated.
Austenitic SSs become less susceptible to sensitization, and hence intergranular
corrosion, by decreasing the C content or by adding alloying elements such as Ti or
Nb which are stronger carbide formers than Cr.
Ferritic and duplex SSs are also subject to sensitization but their susceptibility is
quite different. Ferritic SSs are sensitized at temperatures above 925 °C by Cr
depletion of the matrix in the vicinity of precipitated carbides and nitrides at grain
boundaries. Even though the rate of sensitization is faster than that of the
austenitic SSs, ferritic SSs are easily desensitized at about 650 °C because the
diffusion of Cr and C are faster than that in the austenitic phase. Duplex SSs, which
contain austenite and ferrite as constituent phases, are far less susceptible to
sensitization because typically the C content is lower than 0.03 wt %. These alloys
are more prone to exhibit precipitation of intermetallic phases, such as σ and χ, by
slow cooling through the 900 to 700 °C range due to their relatively high Cr and
Mo content. However, the effect of these intermetallic precipitates is more
pronounced in terms of impact properties than on corrosion. If the C content is
higher, preferential precipitation of carbides at ferrite/austenite boundaries make
the duplex SS less prone to IGC because the depleted zone in the austenite phase
can be easily replenished.
In terms of IGC, Ni-based alloys can be divided into two groups: Ni-Cr-Fe alloys
such as Alloys 600 (UNS N06600) and 800 (UNS N08800) and Ni-Cr-Mo alloys
such as C-276 (UNS N10276) and C-22 (UNS N06022). The first group is also
prone to IGC as a result of sensitization. Even though the C content is usually
lower (0.02 to 0.05 wt %) than in the AISI 304 or 316 SS, the solubility of C is also
lower in the Ni-base alloys and shorter heat treatments induce sensitization and
therefore IGC in acidic environments. In the case of Ni-Cr-Mo alloys such as C-22
preferential precipitation of intermetallic phases (μ and P) occurs upon heat
treatment at temperatures around 600 °C. These intermetallics, rich in Cr and Mo,
promote the depletion of both alloying elements in the region around them and
facilitate IGC in acidic environments. An example of IGC of Alloy 22 is shown in
Fig. 2.7. IGC occurred in this case inside a crevice in which strongly acidic
conditions prevailed.

2.7. Micrographs showing an example of intergranular corrosion. Attack on alloy C-

22 observed inside a crevice where acidified and concentrated chloride solutions
exist.

Segregation of impurities such as S or P to grain boundaries is also the cause of

IGC. The IGC of austenitic SS in hot concentrated HNO3 has been attributed to the
segregation of P to grain boundaries whereas the segregation of S to the grain
boundaries of Ni is the cause of IGC in H2SO4 solutions, in both cases at high
oxidizing potentials. Among others, models of sensitization and segregation for Fe-
Ni-Cr alloys and steels that account for the most important experimental
observations have been developed by Bruemmer (1990) and Gutman and McLean
(1979) respectively.
Aluminum alloys are also susceptible to IGC in Cl− solutions as a result of certain
thermal aging treatments that promote precipitation of intermetallic phases along
grain boundaries. The associated depletion of noble alloying elements (e.g., Cu) or
the enrichment of the active ones (e.g., Zn) facilitates the preferential dissolution of
the depleted area or the intermetallic phases respectively at potentials above the
Epit of each specific phase.
There are many standard chemical and electrochemical tests for evaluating the
susceptibility of alloys to IGC. A good review of the standards and test methods for
Fe-Cr-Ni alloys is presented by Streicher (2005). Standards also exist for heat-
treatable Al alloys (ASTM, 2006f; 2006g).

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Corrosion and Degradation of Engineering Materials

G.M. Scamans, ... R.G. Buchheit, in Shreir's Corrosion, 2010

3.08.5.3 Intergranular Forms of Corrosion

IGC is a phenomenon of which the precise mechanisms have been under debate
for almost half a century.70–76 While in a global sense we can consider IGC as a
special form of microstructurally influenced corrosion, in a generic sense, IGC can
be summarized as a process whereby the grain boundary region of the alloy is
anodic to the bulk or adjacent alloy microstructure.
Corrosion is often microgalvanic (or even nanogalvanic), with activity developing as
a result of some heterogeneity in the grain boundary structure. In aluminum–
copper alloys, precipitation of Al2Cu particles at the grain boundaries leaves the
adjacent solid solution anodic and more prone to corrosion.76 With aluminum–
magnesium alloys, the opposite situation occurs, since the precipitated Mg2Al3
phase is less noble than the solid solution. However, serious intergranular attack in
these two alloys may be avoided, provided correct manufacturing and heat
treatment conditions are observed.
In the case of the aluminum–magnesium system, almost all commercial alloys are
supersaturated as the magnesium solubility at ambient temperatures is less than
1 wt%. This effectively means that for alloys with more than 3 wt% magnesium
elevated service temperatures can lead to grain boundary precipitation and
sensitization of grain boundaries to corrosion as intercrystalline attack. The extent
of this sensitization may be approximately deduced from the continuity of Mg2Al3
precipitation at the boundaries as determined by optical metallography of polished
and etched cross sections. Apparently, continuous or nearly continuous etched
boundaries correspond to high levels of sensitization to IGC.
Although the precipitation of Mg2Al3 may appear continuous from examination of
polished and etched sections in an optical microscope, examination of
microstructures at higher resolution in a scanning or transmission electron
microscope invariably reveals the precipitation to be discontinuous. Susceptibility
of AA5xxx alloys is controlled in practice either by limiting the level of magnesium
in the alloy to below 3 wt%, as such alloys can be sensitized to IGC only under
extreme conditions or by the use of a deliberate stabilization treatment for a more
magnesium-rich alloy. Stabilization of AA5xxx alloys with more than 3%
magnesium is achieved by a deliberate heat treatment to promote intragranular
precipitation of Mg2Al3. The temperature and time of this treatment depend on
the precise magnesium level in the alloy. In production sometimes, this process is
carried out by a specific formal heat treatment, and sometimes the rolling practice
is modified so that the required level of intragranular precipitation is achieved
during warm rolling. The level of sensitization to IGC of a fabricated sheet, plate or
extrusion can be easily determined by measurement of the NAMLT value. This is a
24 h exposure to nitric acid and a measurement of weight loss due to IGC and loss
of grains. A NAMLT value of more than 30 g cm−2 of surface is necessary before an
alloy has become sensitized to IGC or cracking.
In the case of Al–Zn–Mg alloys, where the precipitated phase is the highly anodic
MgZn2 phase, IGC can occur rather readily. However, susceptibility to IGC is
strongly dependent on the heat-treated condition and its effect on grain boundary
solute segregation and the morphology and composition of the grain boundary
precipitate and the surrounding alloy matrix.77 The most resistant heat treatments
are based on the use of overaging to the T7 condition. More complex heat
treatments that involve retrogression and reaging are also used to provide a high
level of IGC resistance with a lower loss of strength.1,2
The images in Figure 6 help rationalize the origins of IGC.

Figure 6. (a) Schematic of hypothetical grain boundary in an Al–Cu alloy. This

schematic indicates the different chemistry that exists in the grain interior, solute
depleted zone (precipitate-free zone) and grain boundary precipitates – giving rise
to electrochemical heterogeneity localized at the grain boundary region. (b)
Conventional bright field TEM image of high-angle grain boundary in AA7022-
T651, revealing grain boundary precipitates (MgZn2) and a distinguishable
precipitate-free zone. Courtesy of Steven P. Knight.

IGC differs from pitting corrosion. While IGC may initiate from a pit, propagation
of IGC proceeds more rapidly than pitting corrosion, and while both may have a
deleterious effect on corrosion fatigue, IGC is more detrimental as the sharper
corrosion front compared to a more rounded pit front is a higher stress
concentrator that reduces the number of cycles to failure.
The test method used to evaluate susceptibility to IGC depends on the alloy type.
For 5xxx series alloys, the NAMLT method (ASTM G 67) is adopted, whereas for
2xxx and 7xxx series alloys, ASTM G 110 is most common, employing testing in
sodium chloride solutions containing hydrogen peroxide.
Exfoliation corrosion78 of aluminum alloys is also frequently due to IGC. It
generally occurs in cases where the alloy microstructure has been heavily deformed
by rolling, extrusion or forging where the grain structure has been flattened and
significantly extended in the direction of working. IGC attack from transverse edges
and pits then runs along grain boundaries parallel to the alloy surface, and the
resulting layers of corrosion attack are sometimes referred to as ‘layer corrosion.’
Exfoliation corrosion is characterized by leafing off of layers of relatively
uncorroded intragranular metal caused by the swelling of the corrosion product in
the layers of IGC. Exfoliation corrosion is observed on aircraft components, for
example, around riveted or bolted components or wing brackets. Testing for
exfoliation corrosion is carried out by a number of ASTM tests, including the
acidified salt spray test (ASTM G 85), the ASSET immersion test (ASTM G 66) and
the EXCO immersion test (ASTM G 34).

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Aluminum Alloys: Corrosion

E.L. Colvin, in Encyclopedia of Materials: Science and Technology, 2001

1.2 Intergranular Corrosion

Intergranular corrosion (Fig. 2) occurs when metal on or adjacent to grain
boundaries dissolves, or corrodes preferentially to grain interiors. The grain
boundary region acts as an anode with the grain interior being a cathode, forming
a galvanic cell (see schematic in Fig. 3) with a large cathode and a small anode in
which rapid corrosion occurs at the anode (see Corrosion, Intergranular).

Figure 2. Intergranular corrosion in a 6XXX alloy.

Figure 3. Exfoliation corrosion in a 7XXX alloy.

The grain boundary region can become anodic either because of the presence of an
anodic phase that coats the boundary, which is believed to be the case in sensitized
5XXX alloys, or because of solute segregation to or from grain boundary regions.
Solute depletion can make grain boundary regions anodic when cathodic elements,
such as copper and manganese, are incorporated into particles that nucleate and
grow preferentially at grain boundaries relative to grain interiors. This results in
lower solute content at the grain boundary than in the grain interior and a
difference in electrochemical potential which is the basis for an electrochemical cell
and rapid corrosion.
Intergranular corrosion can occur in a variety of alloys, but is especially prevalent in
the heat treatable 2XXX, 6XXX, and 7XXX systems. Alloys of the 5XXX system with
more than 3.5 wt.% magnesium can be sensitized to intergranular corrosion by
thermal exposure. 3XXX alloys containing manganese will occasionally exhibit
intergranular sensitivity.

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Corrosion, Intergranular
M.A. Streicher, S. Begum, in Reference Module in Materials Science and Materials
Engineering, 2016

1 Introduction
Intergranular corrosion (IGC) can seriously weaken the bonding force between
crystal grains and the mechanical strength of metals and alloys would be markedly
damaged due to IGC. The combination of stress and IGC, for some
alloys/environment systems will cause intergranular stress corrosion cracking
(IGSCC) (Zhou and Zuo, 2015).
At the boundaries between the grains of metals, lattices of different orientations
meet and zones of less perfect structure than that of the interior of the grains are
formed. Small amounts of impurities may segregate at the grain boundaries while
remaining in solid solution during certain heat treatments. During exposure to a
corrosive environment these impurities promote galvanic action by serving as
cathodic sites. This increases the rate of anodic dissolution of the alloy matrix in
the grain boundary zone.
So far, studies concerning IGC have been mainly focused on stainless steels (Yu et
al., 2010), nickel base alloys (Stein-Brzozowska et al., 2013), and
aluminum/magnesium alloys (Luo et al., 2012). Of greater practical importance is
the fact that precipitates which may form during exposure of metals to elevated
temperatures, for example, during production, fabrication, and welding, frequently
nucleate and grow preferentially at grain boundaries. When such precipitates are
rich in alloying elements essential for corrosion resistance, the matrix adjacent to
the precipitates will be depleted in this alloying element. The metal is thus
‘sensitized’ to intergranular attack. Such is the case with the formation of the
Cr23C6 precipitate in austenitic stainless steels, for example, Fe–18 wt% Cr–8 wt%
Ni (AISI Type 304). The Cr23C6 precipitate forms because carbon is a residual
impurity in these alloys. Figure 1 shows schematic representation of chromium
carbide precipitation at grain boundaries (Smith and Hashemi, 2006).
Figure 1. (a) Schematic representation of chromium carbide precipitation at grain
boundaries in a sensitized type of 304 stainless steel and (b) Cross-section at grain
boundary showing intergranular corrosion attack adjacent to grain boundaries.

Kupper et al. (1981) studied IGC of iron–phosphorus alloys containing 0.003–

2.5 wt% phosphorus in hot nitrate solutions. Phosphorus content increased the
degree of IGC and this could be correlated to the phosphorous concentration at
grain boundaries, which had been established by the equilibrium segregation at
the temperature range of 400–800 °C. The passive film formation on iron was
prevented due to segregation of phosphorus at the grain boundaries. Krautschick
et al. (1988) studied IGSCC of iron–phosphorus alloys with 0.003–2 wt%
phosphorus in nitrate and sulfate solutions. Polarization tests indicated that
phosphorus prevented the formation of protective oxide films on the steel surface
in nitrate solutions, which was also attributed to the segregation of phosphorus at
the grain boundaries.

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Case Study of Aluminum 5083-H116 Alloy

Christopher B. Smith, Rajiv S. Mishra, in Friction Stir Processing for Enhanced Low
Temperature Formability, 2014

4.15.1.4.1 Intergranular
IGC requires a precipitate phase at the grain boundaries and/or a depletion of the
solute adjacent to the grain boundaries. FSP exposes the AA 5083 to a short time at
high temperature in the FSP zone resulting in a fine grain, fully recrystallized,
equiaxed microstructure. There is insufficient time at temperature for a second
phase to precipitate at grain boundaries in the FSP zone. In regions adjacent to the
FSP zone, there is a gradient in temperature decreasing from ~500°C in the FSP
zone to room temperature in the far HAZ. Times at temperature are short (<1 min.)
and are insufficient to influence the grain boundary precipitate morphology. Thus,
based on the FSP microstructure, there is no reason to believe that FSP would
reduce the IGC resistance of 5083-H116.

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Fuel Performance of Fast Spectrum Oxide Fuel☆
Michel Pelletier, Yannick Guérin, in Reference Module in Materials Science and
Materials Engineering, 2019

5.3.2 Intergranular corrosion

Intergranular corrosion has been also observed in a lot of oxide pins at moderate
burnups, and again associated with high fuel temperatures related to high LHR,
low fuel density, or vibropacked oxide fuels. Such a corrosion mode is probably
linked to high-temperature gradients across the fuel-to-cladding gap, enabling the
cesium pressure in equilibrium with cesium uranate formation on the fuel surface
to become higher than the cesium partial pressure required for cesium chromate
formation on the cladding inner surface.51 In order to prevent this corrosion
mode, very high fuel surface temperatures should be avoided. Another way is to
reduce the oxygen potential by using low O/M ratio, but with adverse effects on
fuel temperatures.
Vibropacked oxide fuel pins exhibited such an intergranular corrosion when
irradiated at a high LHR. This occurred especially in vibropacked fuel pins
irradiated in the experimental reactor DFR.52 To avoid this corrosion in
vibropacked mixed oxide fuel pins irradiated in Russia, several percentages of
uranium metal powder are added to the fissile mixed oxide in order to decrease the
oxygen potential.8

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Localized Corrosion
Luciano Lazzari, in Engineering Tools for Corrosion, 2017

3.8.5.2 Sensitized alloy

Intergranular corrosion rate of sensitized alloys in Huey test is given by Eq. (3.20),
in which cathodic current density is hydrogen evolution in accordance with Eq.
(3.18). Inputs are as follows: ΔV=0.1 V, pH=0, ρ=1 Ωm, i0,H=10 mA/m2. It results
that sensitized alloy exhibits in Huey test a corrosion rate of about 30 mm/y, easily
measured by weight loss.
When exposed to the process fluid, which shows different corrosion conditions,
intergranular corrosion rate of sensitized alloy is lower although not negligible,
given by the same Eq. (3.20). For instance, pH=3.5, T=85°C, electrolyte resistivity,
ρ=1 Ωm; other input data are as follows:
driving voltage, ΔV, given by:

where inside intergranular attack;

cathodic current density, iH, by Tafel Law is conservatively calculated at anode
potential, therefore:

Rounding the driving voltage to 50 mV, cathodic current density is 26 mA/m2,

giving an intergranular corrosion rate of about 0.7 mm/y, sufficient to initiate
pitting or trigger SCC when conditions for occurrence exist.

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