Intergrannular corrosion

Intergranular corrosion is localized attack on or at grain boundaries with insignificant

corrosion on other parts of the surface. The attacks propagate into the material. This is a
dangerous form of corrosion because the cohesive forces between the grains may be too
small to withstand tensile stresses; the toughness of the material is seriously reduced at a
relatively early stage, and fracture can occur without warning. Grains may fall out, leaving pits
or grooves, but this may not be particularly important.
The general cause of intergranular corrosion is the presence of galvanic elements due to
differences in concentration of impurities or alloying elements between the material in or at
the grain boundaries and the interior of the grains:

a) Impurities segregated to the grain boundaries (causing, e.g. the AlFe secondary
phase in aluminium).

b) Larger amount of a dissolved alloying element at the grain boundaries (e.g. Zn

in brass).

c) Smaller amount of a dissolved alloying element at the grain boundaries (e.g. Cr

in stainless steel).
 Austenitic Stainless Steels
( sensitization of type 304 SS)

The most familiar example of intergranular corrosion is connected with certain austenitic
stainless steels, particularly 18–8 CrNi steels with 0.06–0.08% C. After cooling the steel from
high temperature, Cr and C are in solid solution in the austenite. At room temperature the
austenitic phase is supersaturated with these elements, and when the material is heated
again to 500–800oC, a chromium carbide, Cr23C6 is precipitated at the grain boundaries. Cr
diffuses relatively slowly, and therefore the amount of Cr forming carbide is taken from the
very nearest region. Here, the Cr concentration gradient becomes large, as shown in Figure
7.34a. The carbon content in the steel is more than two orders of magnitude less than the
chromium content, but the carbide precipitation is possible because C diffuses much
more easily than Cr and is therefore taken from larger parts of the grains.

The corrosion properties depend in principle on the Cr content, as illustrated in Figure

7.34b. The curves can be understood in two ways: 1) As pure overvoltage curves, with the
simplification that the passive current density on regions other than the grain boundaries is
disregarded. 2) The cathodic curve is understood as the sum of the cathodic polarization
curve of the cathodic areas on the surface and the overvoltage curve of a possible cathodic
reaction (hydrogen evolution reaction)within the grooves or cracks between the grains.
The important relationship is that the critical current density (maximum current density on
the anodic curve) increases with decreasing Cr content. When this content decreases to a
critical value, Ccr, corrosion is initiated. At the grain boundaries a region with active material
is produced on both sides of the carbide precipitate film,
as illustrated in Figure 7.34a.
As shown in Figure 7.34b, the critical concentration CCr depends on the cathodic curve, i.e.
on the surface state of the alloy, the concentration of oxygen and other oxidizers as well as
the pH of the environment, the temperature and possibly the flow conditions (compare with
Section 6.1). Serious material failure may occur after different times of exposure, depending
on the environment. In seawater this may happen after a few weeks or months
Weld Decay

Many failures of 18-8 occurred in the early history of this material until the mechanism of
intergranular corrosion was .understood. Failures still occur when this effect is not
considered. These are associated with welded structures, and the material attacked
intergranularly is called weld decay. The weld decay zone is usually a band in the parent
plate somewhat removed from the weld. The reason for this problem is that welding takes
the temperature up to the range where
carbide precipitation occurs. The area that is most liable to intergranular corrosion is
usually located some millimetres from the fusion zone of the weld, where the
temperature is kept within the critical range for the longest time intervals.
For thin plates (thickness < 3 mm) electrically welded with a single pass, the
problem is avoided because of the short time at critical temperatures. This makes
electric arc welding favourable compared with gas welding [7.1].
Intergranular corrosion of stainless steel does not occur in all environments. Thus
inferior corrosion resistance at the grain boundaries does not necessarily lead to
practical problems. However, a reasonable aim is to obtain corrosion properties at the
welds equal to those elsewhere on the steel surface, in order to utilize the material as
much as possible.
The risk of intergranular corrosion of austenitic stainless steel can usually be
eliminated by:
a) Annealing at about 1100oC (at which the carbide is dissolved) with subsequent
rapid cooling.

b) Alloying with Nb or Ti, which have a stronger affinity than Cr to C.

c) Reduction of carbon content (%C < 0.03)

Commercial solution-quenching treatments consist of heating to 1950 to 2050°F

followed by water quenching. Chromium carbide is dissolved at these temperatures,
and a more homogeneous alloy is obtained. Most of the austenitic stainless steels are
supplied in this condition. If welding is used during fabrication, the equipment must be
quench-annealed to eliminate susceptibility to weld decay. This poses an expensive
problem for large equipment and, in fact, furnaces are not available for heat-treating
very large vessels. In addition, welding is sometimes necessary in the customer's
plant to make repairs or, for example, to attach a nozzle to a vessel.

Quenching, or rapid cooling from the solution temperature, is very important. If cooling
is slow, the entire structure will be susceptible to intergranular corrosion.
The strong carbide formers or stabilizing elements, columbium (or columbium plus tantalum)
and titanium, are used to produce types 347 and 321 stainless steels, respectively. These
elements have a much greater affinity for carbon than does chromium and are added in
sufficient ql1antity to combine with all of the carbon in the steel. The stabilized steels
eliminate the economic and other objections of solution-quenching the unstabilized steels
after fabrication or weld repair.
Lowering the carbon to below 0.03% (type 304L) does not permit sufficient carbide to form to
cause intergranular attack in most applications. One producer calls these the extra-low-
carbon (ELC) steels.
The original 18-8 steels contained around 0.20% carbon, but this was quickly reduced to
0.08% because of rapid and serious weld decay failures. Lowering the carbon content much
below 0.08% was not possible until it was discovered that it was possible to blow oxygen
through the melt to burn out carbon and until low-carbon ferrochrome was developed. These
stainless steels have a high solubility for carbon when in the molten state and therefore have
a tremendous propensity for picking up carbon. For example, the intent of the low-carbon
grades is obviated when the welder carefully cleans the beveled plate with an oily or greasy
rag before welding!
A few isolated carbides that may appear in type 304L are not destructive for many applications
in which a continuous network of carbides would be catastrophic. In fact, the susceptibility to
intergranular corrosion of the austenitic stainless steels can be reduced by severely cold-
working the alloy. Cold-working produces smaller grains and many slip lines, which provide a
much larger surface for carbide precipitation. This is not, however, a recommended or
practical procedure.
Carbon pickup (surface carburization) during production of austenitic stainless steels has
caused premature failures. It occurs when these steels are cast into molds containing
carbonaceous materials such as organic binders and washes or baked oil sand. The hot metal
absorbs carbon from the carbon-containing environment. Increased carbon content of the
stainless steel can degrade corrosion resistance particularly to environments that are
aggressive from the stand- point of intergranular attack. Resistance to pitting is also
decreased.
Figure shows carbon profiles for CF-3 (18-8, 0.03% C max) cast in a resin shell mold. The
carbon content near the surface is 0.16 as compared to 0.03% in the metal as poured. Higher
carbon is in excess of the specification limit. Metal cast in a ceramic mold shows practically no
carbon pickup. Similar situations occur in other austenitic stainless steels.
Corrosion could continue into the metal beyond the carburized metal because intergranular
corrosion, pitting, and stress corrosion could be initiated and propagated by crevice and/or
notch effects. A number of case histories substantiate failure or reduced serviCe life. Carbon
pickup can be recognized if

(I) castings are attacked more than wrought components,

(2) intergranular attack occurs on a low-carbon (0.03 %) material,
(3) two castings of the same alloy show a substantial difference in attack,
(4) machined surfaces show less attack than adjacent as-cast surfaces
(5) carbon content near the surface is higher than in the main body of the casting.
Knife-Line Attack

The stabilized austenitic stainless steels are attacked intergranularly, under certain
conditions, because of chromium carbide precipitation. Columbium or titanium fails to
combine with the carbon. Figure 3-33 shows a section of a type 347 (18-8 + Cb) drum that
contained fuming nitric acid. Severe intergranular attack occurred in a narrow band, a few
grains wide, on both sides of the weld and immediately adjacent to it. Practically no
corrosion is observable on the remainder of the container. This phenomenon was
studied at Ohio State University and the basic mechanism for failure established. It was
christened knife-line attack because of its distinctive appearance.
Knife-line attack (KLA) is similar to weld decay in that they both result from intergranular
corrosion and both are associated with welding. The two major differences are:
(I) KLA occurs in a narrow band in the parent metal immediately adjacent to the weld,
whereas weld decay develops at an appreciable distance from the weld;
(2) KLA occurs in the stabilized steels;
(3) the thermal history of the metal is different.
The mechanism for the failure of this drum is based on the solubility of columbium in the
stainless steel. Columbium and columbium carbides dissolve in the metal when it is heated
to a very high temperature and they remain in solution when cooled rapidly from this
temperature. The columbium stays in solution when the metal is then heated in the
chromium carbide precipitation range; columbium carbide does not form, and the
metal behaves (sensitizes) as though it were 18-8 without columbium.
 The obvious remedy for avoiding
knife-line attack is to heat the
completed structure (after
welding) to around 1950"F.
According to the chart. chromium
carbide dissolves and columbium
carbide forms, which is the desired
situation. The rate of cooling after
the 1950 c F treatment is not
important.

Schematic chart showing solution and precipitation reactions in types 304 and 347.

Titanium-stabilized stainless steel (type 321) is also subject to knife- line attack under
conditions similar to type 347. Type 304L steels have given superior performance in
cases where the stabilized steels exhibited knife-line attack.
Nickel alloys may be attacked by intergranular corrosion in certain very aggressive
environments after incorrect heat treatment. In NiCr alloys, chromium carbide is precipitated in
the same temperature range as for the austenitic stainless steels. The NiCr alloys are primarily
attacked by strong oxidizers such as hot nitric acid. The prevention measures are mainly the
same as for the austenitic stainless steels.

In some aluminium alloys, anodic phases may be precipitated at the grain boundaries, which
may lead to intergranular corrosion. The actual phases are Mg5Al8 in AlMg alloys containing
more than 3% Mg and MgZn2 in AlZnMg alloys. A wellknown alloy is AlMg4.5Mn (with about
4.5% Mg and 0.7% Mn). Provided that there is appropriate production and forming and
application at ambient temperature, this and similar alloys are resistant in natural
environments, and they are very suitable under marine conditions. An AlZnMgCu alloy like AA-
7075 is liable to intergranular corrosion under such conditions.

AlMgSi alloys, where the Mg and Si contents are balanced to a ratio giving Mg2Si (e.g.
approximately 1% Mg and 0.5% Si) are less susceptible to intergranular corrosion. Their normal
corrosion form may be called pitting with an intergranular tendency. Excessive Si content gives
increased liability to intergranular attack.
High-strength aluminum alloys depend on precipitated phases for strengthening and are
susceptible to intergranular corrosion. For example, the Duraluminum-type aHoys (AI-Cu) are
strong because of precipitation of the compound CUAlz.
Selective Corrosion
(Selective Leaching)
This form of corrosion is observed in alloys in which one element is clearly less noble than
the other(s). The corrosion mechanism implies that the less noble element is removed from
the material. A porous material with very low strength and ductility is the result. Regions
that are selectively corroded are sometimes covered with corrosion products or other
deposits, and since the component keeps exactly the original shape, the attacks may be
difficult to discover. Serious material failure may therefore occur without warning.

The most common example is the selective removal of zinc in brass alloys (dezincification).
Similar processes occur in other alloy systems in which aluminum, iron, cobalt, chromium,
and other elements are removed. Selective leaching is the general term that describes
these processes, and its use precludes the creation of terms such as dealuminumification,
decobaltification, etc. Parting is a metallurgical term that is sometimes applied, but selective
leaching is preferred.
The most common example of selective corrosion is dezincification of brass, in which zinc is
removed from the alloy and copper remains. After cleaning the surface, dezincification is
easy to demonstrate because the Zn–depleted regions have a characteristically red copper
colour in contrast to the original yellow brass.
Dezincification occurs in two forms

a) Uniform (layer) dezincification, where the front of the selective attack moves more or
less uniformly through the material. This form is favoured by high Zn content and acidic
solutions.

b) Localized (plug-type) dezincification, where the localization and form of attack are
determined more or less arbitrarily. This type occurs more often in alloys with somewhat
lower Zn content and in neutral, alkaline and slightly acidic solutions.

The commonly accepted mechanism consists of three steps, as follows:

(I) the brass dissolves,
(II) the zinc ions stay in solution,
(III) the copper plates back on.
Zinc is quite reactive, whereas copper is more noble. Zinc can corrode slowly in pure water
by the cathodic ion reduction of H 2 0 into hydrogen gas and hydroxide ions. For this
reason dezincification can proceed in the absence of oxygen. Oxygen also enters into
the cathodic reaction and hence increases the rate of attack when it is present. Analyses
of dezincified
Dezincification can be reduced or prevented by:
a) Removing oxygen from the solution.
b) Cathodic protection.
(For economical reasons the use of a) and b) has been limited.)
c) Appropriate selection of alloy.
Brass with 15% Zn is almost immune in many environments. In addition, alloys that are
stabilized with about 1% Sn or of the order of 0.01% of As, Sb, or Pb exist. Cu–alloys with
better resistance to selective corrosion can also be chosen (copper–nickel, (nickel)
aluminium bronze, or other bronzes).
Regarding aluminium bronzes, it should be noticed that these as well may suffer from
selective corrosion. Dealuminization may occur in acids and strongly polluted seawater. In
seawater, rapid selective corrosion can occur in aluminium bronzes and nickel–aluminium
bronzes, particularly under conditions where hydrogen sulphide is formed. One example of
this is found in a water jet engine made of nickel– aluminium bronze (10% Al, 5% Ni, 4% Fe,
1% Mn, balance Cu), which was used in a high-speed vessel.

Selective corrosion occurs also in silicon bronze, by which silicon is removed from the
material.
Gray cast iron sometime shows the effects of selective leaching particularly in relatively mild
environments. The cast iron appears to become "graphitized" in that the surface layer has
the appearance of graphite and can be easily cut with a penknife. Based on this appearance
and behavior, this phenomenon was christened "graphitization." This is a misnomer because
the graphite is present in the gray iron before corrosion occurs. It is also called graphitic
corrosion.
What actually happens is, selective leaching of the iron or steel matrix leaving the graphite
network. The graphite is cathodic to iron, and an excellent galvanic cell exists. The iron is
dissolved, leaving a porous mass consisting of graphite, voids, and rust. The cast iron loses
strength and its metallic properties. Dimensional changes do not occur, and dangerous
situations may develop without detection. The surface usually shows rusting that appears
superficial, but the metal has lost its strength. The degree of loss depends on the depth of
the attack. Graphitization is usually a slow process. If the cast iron is in an environment that
corrodes this metal rapidly, all of the surface is usually removed and more-or-less uniform
corrosion occurs.
Graphitization does not occur in nodular or malleable cast irons because the graphite
network is not present to hold together the residue. White cast iron has essentially no free
carbon and is not subject to graphitization.
GraphitizatIOn of gray cast iron has reached the public eye because of failures of
underground pipelines, particularly those handling hazardous materials. Graphitized pipe
has cracked because of soil settlement or impact by excavating or earth-moving equipment.
In several cases explosions, fires, and fatalities have occurred. Ductile (nodular) cast iron
instead of gray cast iron (brittle). Ductile iron pipe with a cement mortar lining has been
giving excellent performance.