Corrosion

CORROSION
CorrosionRate
CORROSION RATE
CORROSION RATE MEASUREMENT
WEIGHT LOSS METHOD
The rate of uniform corrosion can be
measured using corrosion coupon testing by
weight loss measurement.
Coupon
corrosion testing is predominantly designed
to investigate uniform corrosion. ASTM
Designation: G31 gives a definite guideline
for carrying out such an experiment. This
practice describes accepted procedures,
which includes specimen preparation,
apparatus, test conditions, method of
cleaning specimens, evaluation of results,
calculation and reporting of corrosion rates.
A good corrosion rate expression should
involve (i) familiar units, (ii) easy calculation
with minimum opportunity for error, (iii)
ready conversion to life in years, (iv)
penetration and (v) whole numbers without
cumbersome decimals.
Corrosion rates have been expressed in a
variety of ways in the literature; such as
percent weight loss, milligram per square
centimeter per day, and grams per square
inch per hour.
These do not express
corrosion resistance in terms of penetration.
The expression mils per year is the most
desirable way of expressing corrosion rate.
This expression is readily calculated from
weight loss of the metal or the alloy
specimen during the corrosion test. The
conversion from other units to obtain mils
per year is given in Table 2. As per ASTM
G31 calculating corrosion rates requires

several pieces of information and several
assumptions; (i) the use of corrosion rates
implies that all mass loss has been due to
uniform corrosion and not due to localized
corrosion, (ii) the use of corrosion rates also
implies that the material has not been
internally attacked as by dezincification or
intergranular corrosion and, (iii) internal
attack can be expressed as corrosion rates
if desired. However, in such a case the
calculation must not be based on weight
loss (except in qualification test such as
practice A 262), which is usually small but
on microsections, which show depth of
attack.
Assuming that localized or internal corrosion
is not present, the average corrosion rate
can be calculated by the following
equations:
Corrosion rate = (K x W) / (A x T x D)
Where K is a constant; T the time of
exposure in hours to the nearest 0.01 h; A
the area in cm2 to nearest 0.01 cm2; W the
mass loss in g to nearest 1 mg (corrected
for any loss during cleaning) and D the
density in g/cm3.
Many different units are used to express
corrosion rates. Using the units for T, A, W
and D from Table 3, the corrosion rate can
be calculated in variety of units with
appropriate value of K given in Table 3.
Table 2: Conversion from other corrosion rate units to obtain mills per year
Unit to be Converted
Inches per year
Multiplier
1000
Inches per month
12.1000
Pressure Vessel Engineering
CORROSION
CorrosionRate
Millimeters per year
39.4
Micrometers per year
0.039
Milligrams per square Decimeters per day (mdd)
1.44/density
Grams per square meter per day
14.4/density
Table 3: Corrosion rate units with appropriate value of K

Corrosion Rate Units Desired
Constant (K) in
corrosion Rate
Equation
Mils per year (mpy)
3.45 x 106
Inches per year (ipy)
3.45 x 103
Inches per months (imp)
2.87 x 102
Millimeters per year (mm/y
8.76 x 104
Micrometers per year (m/y)
8.76 x 107
Picometers per second (pm/s)
2.78 x 106
Grams per square per hour (g/m2h)
1.00 x 104 x D4
Milligrams per square Decimeter per day (mdd)
2.40 x 106 x D4
Micrograms per square meter
2.78 x 106 x D4
Per second (g/m2 s)
Density is not needed to calculate the corrosion rate in these units. The
Density in the constant K cancels out the density in the corrosion rate equation.
CORROSION
CorrosionRate
Monograph for mpy, ipy, ipm and mdd

A rapid and ready conversion for several
corrosion rates can be made by means of a
monograph shown above. Mathematical
computations are not necessary, and the
accuracy is good.
The monograph is
particularly helpful when data in milligrams
per square decimeter per day are
encountered.
This permits conversion of mills per year,
inches per year, inches per month and
milligrams per square decimeter per day
(mdd) from one to another. The first three
names are directly converted on the scale
A. These are then converted to mdd by
means of C scale and the B scale for
density. The mdd does not consider or
include the density or type of material
involved. Density is given as grams per

cubic centimeter.
CORROSION RATE MEASUREMENT
ELECTRICAL RESISTANCE METHOD
Weight-loss measurements indicate the
average corrosion rate over a period of
time. Electrical resistance measurement is
comparatively a better technique that the
weight loss method. In this method, a
coupon of material, identical to the alloy
whose corrosion rate to be measured is
exposed to the corrodent and periodically
withdrawn to measure its loss of weight,
which directly relates to corrosion rate [17].
Its operation is based on the increase in
electrical resistance of an exposed
CORROSION
corrosion coupon material.

A metallic
conductor sensing probe, generally a thick
wire, strip, or tube of the same material as
the equipment under test, is exposed to the
process stream. The electrical resistance of
this probe is compared with that of an
identical reference probe that is shielded
from the corrodent. As the exposed probe
corrodes, its electrical resistance increase,
and this change is related to the extent of
corrosion.
This method is fast and
sensitive. It is quite similar to the weight-
CorrosionRate
loss coupon method, but enjoys the great

advantage
of
permitting
continuous
monitoring without removing the coupon. It
is also superior to weight-loss method
because errors caused by removal of the
corrosion products is eliminated and
continuous monitoring can indicate the
effect of process variable on corrosion rate.
Electrical resistance probes can serve as an
accurate measure of the corrosion rate only
when the corrosion is uniform.
*********
Source:
Scraped from Corrosion of Austenitic Stainless Steels: Mechanisms, Mitigation

and Monitoring edited by H.S.Khatak, Baldev Rai. Chapter Uniform Corrosion of
Austenitic Stainless Steel by Nisgshen and Mudali.
CORROSION
IGSCC&TGSCC
INTERGRANULAR AND TRANSGRANULAR SCC

Stress corrosion cracking can proceed in one of
two ways:
1. Intergranular Stress Corrosion Cracking
(IGSCC) - Cracks propagate along the grain
boundaries.
2. Transgranular Stress Corrosion Cracking
(TGSCC) - Cracks run through the individual
grains.
Transgranular corrosion is also known as
intragranular corrosion and transcrystalline
corrosion.
INTERGRANULAR CORROSION
Intergranular corrosion (IGC), also known as
Intergranular Attack (IGA), is a form of
corrosion where the boundaries of crystallites of
the material are more susceptible to corrosion
than their insides.
This situation can happen in otherwise
corrosion-resistant alloys, when the grain
boundaries are depleted, known as grain
boundary depletion, of the corrosion-inhibiting
elements such as Chromium by some
mechanism. In nickel alloys and austenitic
stainless steels, where chromium is added for
corrosion resistance, the mechanism involved is
precipitation of chromium carbide at the grain
boundaries; resulting in the formation of
chromium-depleted zones adjacent to the grain
boundaries (this process is called sensitization).
Around 12% chromium is minimally required to
ensure passivation, a mechanism by which an
ultra thin invisible film, known as passive film,
forms on the surface of stainless steels. This
passive film protects the metal from corrosive
environments. The self-healing property of the
passive film make the steel stainless. Selective
leaching often involves grain boundary depletion
mechanisms.
These zones also act as local galvanic couples,

causing local galvanic corrosion. This condition
happens when the material is heated to
temperature around 700 C for too long time,
and often happens during welding or an
improper heat treatment. When zones of such
material form due to welding, the resulting
corrosion is termed weld decay. Stainless steels
can be stabilized against this behavior by
addition of titanium, niobium, or tantalum,
which form titanium carbide, niobium carbide
and tantalum carbide preferentially to chromium
carbide, by lowering the content of carbon in the
steel and in case of welding also in the filler
metal under 0.02%, or by heating the entire part
above 1000C and quenching it in water, leading
to dissolution of the chromium carbide in the
grains and then preventing its precipitation.
Another possibility is to keep the welded parts
thin enough so that, upon cooling, the metal
dissipates heat too quickly for chromium carbide
to precipitate.
The ASTM A923, ASTM A262, and other

similar tests are often used to determine when
stainless steels are susceptible to intergranular
corrosion. The tests require etching with
chemicals that reveal the presence of
intermetallic particles, sometimes combined
with Charpy V-Notch and other mechanical
testing.
CORROSION
KNIFELINE ATTACK (KLA)

Another related kind of intergranular corrosion
is termed knifeline attack (KLA). Knifeline
attack impacts steels stabilized by niobium, such
as 347 stainless steel. Titanium, niobium, and
their carbides dissolve in steel at very high
temperatures. At some cooling regimes
(depending on the rate of cooling), niobium
carbide does not precipitate and the steel then
behaves like unstabilized steel, forming
chromium carbide instead. This affects only a
thin zone several millimetres wide in the very
vicinity of the weld, making it difficult to spot
and increasing the corrosion speed. Structures
made of such steels have to be heated in a whole
to about 1950F, when the chromium carbide
dissolves and niobium carbide forms. The
cooling rate after this treatment is not important,
as the carbon that would otherwise pose risk of
formation of chromium carbide is already
sequestered as niobium carbide.
IGSCC&TGSCC
EXFOLIATION
CORROSION
LAMELLAR CORROSION
Aluminium-based alloys may be sensitive to

intergranular corrosion if there are layers of
materials acting as anodes between the
aluminium-rich
crystals.
High
strength
aluminium alloys, especially when extruded or
otherwise subjected to high degree of working,
can undergo exfoliation corrosion, where the
corrosion products build up between the flat,
elongated grains and separate them, resulting in
lifting or leafing effect and often propagating
from edges of the material through its entire
structure. Intergranular corrosion is a concern
especially for alloys with high content of copper.
Other kinds of alloys can undergo exfoliation as
well; the sensitivity of cupronickel increases
together with its nickel content. A broader term
for this class of corrosion is lamellar corrosion.
Alloys of iron are susceptible to lamellar
corrosion, as the volume of iron oxides is about
seven times higher than the volume of original
metal, leading to formation of internal tensile
stresses tearing the material apart. Similar effect
leads to formation of lamellae in stainless steels,
due to the difference of thermal expansion of the
oxides and the metal.
Copper-based alloys become sensitive when
depletion of copper content in the grain
boundaries occurs.
Anisotropic alloys, where extrusion or heavy
working leads to formation of long, flat grains,
are especially prone to intergranular corrosion.
CORROSION
IGSCC&TGSCC
orientation of atoms in each grain. In other

words, when the fracture or crack reaches a new
grain, it may have to find a new path or plane of
atoms to travel on because it is easier to change
direction for the crack than it is to rip through.
Corrosion chooses the path of least resistance.
Since the corrosion proceeds preferentially
within the grain, the grain boundary material is
retained.
Intergranular
corrosion
induced
by
environmental stresses is termed stress
corrosion cracking. Inter granular corrosion can
be detected by ultrasonic and eddy current
methods.
TRANSGRANULAR CORROSION
Transgranular corrosion is a type of localized
corrosion which occurs along cracks or faults
across the crystals in metals and alloys. It
follows the pattern of grains in the individual
lattices of the material. Stress corrosion of
austenitic steels is usually transgranular.
Transgranular corrosion occurs through or
across a crystal or grain. In transgranular
corrosion, the fracture travels through the grain
of the material. The fracture changes direction
from grain to grain due to the different lattice
In this type of corrosion, a small volume of

metal is removed in preferential paths that
proceed across or through the grains. It
sometimes accelerated by tensile stress. In
extreme cases, the cracks proceed through the
entire metal, causing rupture or perforation.
Chloride is the leading cause of transgranular
cracking.
Transgranular attack has a very characteristic
branching habit which is easily recognizable in
scanning
electron
microscopy
(SEM),
fractographic and metallographic section
examination. Transgranular stress corrosion
cracking occurs mainly in chloride cracking of
austenitic steels.
*********
Source:
ScrapedfromWikipedia(Mar.2015)
CORROSION
CommonStressCorrosionCrackingMechanisms
COMMON STRESS CORROSION CRACKING SYSTEMS

Environment
Environment
Concentration
Temp.
Mode
Hydroxides
High
High
Intergranular
Nitrates
Moderate
Moderate
Intergranular
Carbonates / Bicarbonates
Low
Moderate
Intergranular
Liquid Ammonia
Low
Transgranular
CO/CO2/H2O
Low
Transgranular
Aerated water
Very
High
Transgranular
Water
Moderate
Transgranular
Water (Y.S > 1200 MPa)
Low
Mixed
Chloride (Y.S > 800 MPa )
Low
Mixed
Sulphide (Y.S > 600 MPa )
Low
Mixed
Chloride
High
High
Transgranular
Hydroxide
High
Very
High
Mixed
SENSITISED
AUSTENITIC SS
Areated Water
Very
High
Intergranular
STAINLESS
STEELS
Thiosulphate or
Polythionate
Low
Low
Intergranular
Material
CARBON STEEL
LOW ALLOY
STEELS
(e.g. Cr-Mo, CrMo-V)
STRONG
STEELS
AUSTENITIC
STAINLESS
STEEL
(INCLUDING
SENSITISED)
CORROSION
DUPLEX
STAINLESS
STEEL
MARTENSITIC
STAINLESS
STEEL
HIGH
STRENGTH
STEELS
ALUMINIUM
ALLOYS
TITANIUM
ALLOYS
COPPER
ALLOYS
(excluding Cu-Ni)
Chloride
Very High
High
Transgranular
Chloride + H2S
High
Moderate
Transgranular
Chloride (usually + H2S)
Moderate
Low
Transgranular
Water Vapour
Low
Transgranular
Chlorides
Low
Low
Intergranular
Chlorides
High
Low
Transgranular
Methonol
Low
Transgranular
N2O4
High
Ammoniacal Solutions
and other Nitrogenous
Low
Transgranular
Low
Intergranular
This Table presents the systems for which SCC problems are well established and of practical
importance. The absence of a metal-environment combination from this Table does not mean that
SCC has not been observed.
There are rarely well-defined temperatures or concentration limits for SCC, and the ratings given
here are indicative only. As an approximate guide the terms used equate to the following ranges of
values:
Environment
Concentration
Temperature
LOW
Up to 10-2 M
Ambient
MODERATE
Up to 1 M
Below 100 0C
HIGH
Around 1 M
Around Boiling
VERY HIGH
Near Saturation
Above Boiling
CORROSION
Note that significantly increased local concentrations may be obtained under the influence of local
boiling or evaporation, or by accumulation in pits and crevices, and cracking is often obtained for
nominal concentrations that are much lower than is indicated here.
The fracture mode is classified as intergranular (I) where cracks go along the grain boundaries,
transgranular (T) where cracks go across the grains, or mixed (M) where there is a combination of
the two modes, or where the mode can vary depending on the conditions. There are often
circumstances that can cause the fracture mode to change (e.g. chloride SCC of sensitised austenitic
stainless steel may give intergranular cracking).
*******
Source:
1.
Scraped from Stress Corrosion Cracking National Physical Laboratory
CORROSION
IntergranularCorrosionEffectofSensitization
INTERGRANULAR CORROSION
(Effect of Sensitization)
Intergranular corrosion (IGC), also

known as Intergranular attack (IGA), is a
form of corrosion where the boundaries of
crystallites of the material are more
susceptible to corrosion than their insides.
Like other common materials, metals have a
visible grain structure when they are viewed
under magnification. Rapid corrosive attack
of immediately adjacent grain boundaries
with little or no attack of the grains is called
Intergranular Corrosion.
This situation can happen in otherwise
corrosion-resistant alloys, when the grain
boundaries are depleted, known as grain
boundary depletion, of the corrosioninhibiting elements such as chromium by
some mechanism. In nickel alloys and
austenitic stainless steels, where chromium
is added for corrosion resistance, the
mechanism involved is precipitation of
chromium carbide at the grain boundaries,
resulting in the formation of chromiumdepleted zones adjacent to the grain
boundaries (this process is called
sensitization). Around 12% chromium is
minimally required to ensure passivation, a
mechanism by which an ultra thin invisible
film, known as passive film, forms on the
surface of stainless steels. This passive film
protects the metal from corrosive
environments. The self-healing property of
the passive film makes the steel stainless.
Selective leaching often involves grain
boundary depletion mechanisms.
These zones also act as local galvanic
couples, causing local galvanic corrosion.
This condition happens when the material is
heated to temperature around 700C for too
long time, and often happens during welding
or an improper heat treatment. When zones

of such material form due to welding, the
resulting corrosion is termed weld decay.
Stainless steels can be stabilized against this
behaviour by addition of titanium, niobium,
or tantalum, which form titanium carbide,
niobium carbide and tantalum carbide
preferentially to chromium carbide, by
lowering the content of carbon in the steel
and in case of welding also in the filler
metal under 0.02%, or by heating the entire
part above 1000C and quenching it in
water, leading to dissolution of the
chromium carbide in the grains and then
preventing its precipitation. Another
possibility is to keep the welded parts thin
enough so that, upon cooling, the metal
dissipates heat too quickly for chromium
carbide to precipitate. The ASTM A923,
ASTM A262, and other similar tests are
often used to determine when stainless steels
are susceptible to intergranular corrosion.
The tests require etching with chemicals that
reveal the presence of intermetallic particles,
sometimes combined with Charpy V-Notch
and other mechanical testing.
Another related kind of intergranular
corrosion is termed Knifeline attack
(KLA). Knifeline attack impacts steels
stabilized by niobium, such as 347 stainless
steel. Titanium, niobium, and their carbides
dissolve in steel at very high temperatures.
At some cooling regimes (depending on the
rate of cooling), niobium carbide does not
precipitate and the steel then behaves like
unstabilized steel, forming chromium
carbide instead. This affects only a thin zone
several millimeters wide in the very vicinity
of the weld, making it difficult to spot and
increasing the corrosion speed. Structures
CORROSION
made of such steels have to be heated in a

whole to about 1950F, when the chromium
carbide dissolves and niobium carbide
forms. The cooling rate after this treatment
is not important, as the carbon that would
otherwise pose risk of formation of
chromium carbide is already sequestered as
niobium carbide.
grains, are especially prone to intergranular

corrosion.
Aluminium-based alloys may be sensitive to

intergranular corrosion if there are layers of
materials acting as anodes between the
aluminium-rich crystals. High strength
aluminium alloys, especially when extruded
or otherwise subjected to high degree of
working,
can
undergo
Exfoliation
corrosion, where the corrosion products
build up between the flat, elongated grains
and separate them, resulting in lifting or
leafing effect and often propagating from
edges of the material through its entire
structure. Intergranular corrosion is a
concern especially for alloys with high
content of copper.
Rapid attack at the grain boundaries can

result in grains dropping or falling out of
the metal surface resulting in the
disintegration of the steel. Figure 1 shows
the appearance of a surface where this is
occurring. In practical application, the loss
of cross section thickness and the
introduction of cracks can have severe
consequences for applications like pressure
containment.
Other kinds of alloys can undergo

exfoliation as well; the sensitivity of
cupronickel increases together with its
nickel content. A broader term for this class
of corrosion is lamellar corrosion. Alloys
of iron are susceptible to lamellar corrosion,
as the volume of iron oxides is about seven
times higher than the volume of original
metal, leading to formation of internal
tensile stresses tearing the material apart.
Similar effect leads to formation of lamellae
in stainless steels, due to the difference of
thermal expansion of the oxides and the
metal.
Copper-based alloys become sensitive when
depletion of copper content in the grain
boundaries occurs.
Intergranular
corrosion
induced
by
environmental stresses is termed stress
corrosion cracking. Inter granular corrosion
can be detected by ultrasonic and eddy
current methods.
Figure 1: Intergranular corrosion grain

boundary attack and dropped grains
Photo Courtesy TMR Consulting
Sensitization
Sensitization refers to the precipitation of
carbides at grain boundaries in a stainless
steel or alloy, causing the steel or alloy to be
susceptible to intergranular corrosion or
intergranular stress corrosion cracking.
Anisotropic alloys, where extrusion or heavy

working leads to formation of long, flat
CORROSION
lines consist of carbides and corrosion

products.
Unsensitized microstructure
Heavily sensitized microstructure

Certain alloys when exposed to a
temperature characterized as a sensitizing
temperature become particularly susceptible
to intergranular corrosion. In a corrosive
atmosphere, the grain interfaces of these
sensitized alloys become very reactive and
intergranular corrosion results. This is
characterized by a localized attack at and
adjacent to grain boundaries with relatively
little corrosion of the grains themselves. The
alloy disintegrates (grains fall out) and/or
loses its strength.
The photos show the typical microstructure
of a normalized (unsensitized) type 304
stainless steel and heavily sensitized steel.
The samples have been polished and etched
before taking the photos, and the sensitized
areas show as wide, dark lines where the
etching fluid has caused corrosion. The dark
Intergranular corrosion is generally

considered to be caused by the segregation
of impurities at the grain boundaries or by
enrichment or depletion of one of the
alloying elements in the grain boundary
areas. Thus in certain aluminium alloys,
small amounts of iron have been shown to
segregate in the grain boundaries and cause
intergranular corrosion. Also, it has been
shown that the zinc content of a brass is
higher at the grain boundaries and subject to
such corrosion. High-strength aluminium
alloys such as the Duralumin-type alloys
(Al-Cu) which depend upon precipitated
phases for strengthening are susceptible to
intergranular
corrosion
following
sensitization at temperatures of about
120C. Nickel-rich alloys such as Inconel
600 and Incoloy 800 show similar
susceptibility.
Die-cast
zinc
alloys
containing aluminum exhibit intergranular
corrosion by steam in a marine atmosphere.
Cr-Mn and Cr-Mn-Ni steels are also
susceptible to intergranular corrosion
following sensitization in the temperature
range of 420C - 850C. In the case of the
austenitic stainless steels, when these steels
are sensitized by being heated in the
temperature range of about 520C to 800 C,
depletion of chromium in the grain boundary
region occurs, resulting in susceptibility to
intergranular corrosion. Such sensitization
of austenitic stainless steels can readily
occur because of temperature service
requirements, as in steam generators, or as a
result of subsequent welding of the formed
structure.
Several methods have been used to control
or minimize the intergranular corrosion of
susceptible alloys, particularly of the
austenitic stainless steels. For example, a
high-temperature solution heat treatment,
CORROSION
commonly
termed
solution-annealing,
quench-annealing or solution-quenching, has
been used. The alloy is heated to a
temperature of about 1,060C to 1,120C
and then water quenched. This method is
generally unsuitable for treating large
assemblies and also ineffective where
welding is subsequently used for making
repairs or for attaching other structures.
Another control technique for preventing
intergranular
corrosion
involves
incorporating strong carbide formers or
stabilizing elements such as niobium or
titanium in the stainless steels. Such
elements have a much greater affinity for
carbon than does chromium; carbide
formation with these elements reduces the
carbon available in the alloy for formation
of chromium carbides. Or the stainless steel
may initially be reduced in carbon content
below 0.03 percent so that insufficient
carbon is provided for carbide formation.
These techniques are expensive and only
partially effective since sensitization may
occur with time. The low-carbon steels also
frequently exhibit lower strengths at high
temperatures.
Intergranular Attack
Stainless Steels:
of
Because the chromium is the primary

alloying element that makes stainless steel
corrosion resistant, the chromium-depleted
regions are susceptible to preferential
corrosion attack. It is believed that this
occurs because the chromium content
immediately adjacent to the carbide may be
below that required for the stainless steel
alloy. If the carbides form a continuous
network on the grain boundary, then
corrosion can produce a separation or gap at
the boundary and possible grain dropping or
loss.
Austenitic
Chromium Carbide Precipitation
With austenitic stainless steels, intergranular

attack is usually the result of chromium
carbide precipitation (Cr23C6) at grain
boundaries, which produces a narrow zone
of chromium depletion at the grain
boundary. This condition is termed
sensitization and it is shown schematically
Figure 2. Sensitization involves the
precipitation of chromium carbides at grain
boundaries, which results in a narrow zone
of chromium depletion at the grain
boundary.
Figure 2: Chromium depletion at the grain

boundaries or sensitization
The chromium carbides tend to precipitate at

the grain boundaries of austenitic stainless
steels in the 5100C to 787.80C (9500F to
1450F) temperature range. Any exposure
or thermal excursion into this temperature
range during metal manufacture, fabrication,
or service could potentially sensitize the
steel.
Common practices such as welding, stress
relief, and hot forming can expose the steel
to the sensitizing temperature range. The
formation of chromium carbides is readily
reversed by a solution anneal heat treatment.
CORROSION
The test methods outlined in ASTM A262

have been developed to detect susceptibility
to intergranular attack in austenitic stainless
steels.
The time and temperature required to
produce susceptibility to intergranular attack
(IGA) is dependent on alloy composition,
particularly the carbon content. Figure 3
shows the time-temperature-sensitization
curves for Type 304 alloys with varying
amounts of carbon content.
Figure 3: Time-temperature-sensitization
curves for Type 304 alloys as a function of
carbon content
Image courtesy of the Nickel Institute

Three approaches have been used with the
austenitic stainless steels to minimize to the
effects of IGA. Material that has been
sensitized can be solution annealed by
heating to a temperature where the carbides
dissolved and the chromium-depleted
regions are eliminated. The carbon is then
kept in solution by rapid cooling through the
sensitizing
temperature
range.
The
recommended solution anneal temperature
depends on the alloy and is typically done in
the range of 1037.8 to 1176.70C (19000F to
2150F) followed by rapid cooling.
Resistance to IGA can also be achieved by

reducing the carbon content to below
0.030% level. As shown in Figure 3, lower
carbon contents move the nose of the timetemperature-sensitization curve to longer
times. The low carbon grades such as Types
304L, 316L, and 317L have been designed
to resist sensitization during typical welding
operations, but they do not resist
sensitization by long term exposure in the
critical temperature range in service. The
higher alloyed, more corrosion resistant
stainless steels such as the 904L and 6Mo
alloys have very low carbon contents and
susceptibility to IGA is typically not a
concern.
The addition of stabilizing elements such as
Ti, Nb (Cb), and Ta can also provide
increased resistance to sensitization,
especially for long-term exposures in the
critical range in service. These stabilizing
elements tend to form carbides that are more
stable than chromium carbide in the
temperature range of 1232.20C to 787.80C
(22500F to 1450F). So as the alloy cools
from high temperatures, the carbon
combines with the stabilizing elements and
is unavailable for chromium carbide
precipitation at the lower sensitizing
temperature range of 5100C to 787.80C
(9500F to 1450 F). Common stabilized
austenitic grades include Type 321, 347, 20Cb3, and 316Ti. Figure 4 summarizes the
carbide precipitation reactions that occur in
type 304 and 347 stainless steels.
CORROSION
Temperature
Range
Melting point
1232.20C
(2250F)
Intergranular Attack of Ferritic Stainless

Steels:
Precipitation
Reactions
Niobium (Columbium)
carbide dissolves
Chromium carbides
dissolves
Columbium carbide
1232.20C to 787.80C precipitates
(2250 to 1450 F) Chromium carbides
dissolves
5100C to 787.80C
(14500F to 950F)
Chromium carbides
precipitates
5100C to 21.10C
(9500F to 70F)
No reaction
Figure 4: Precipitation Reactions in Type

304 and 347 Stainless Steel
With the stabilized grades, standard solution
annealing treatments generally do not tie up
all the available carbon. So when the
stabilized grades in the solution-annealed
condition have long time exposures to the
sensitizing temperature range (14500F to
950F), chromium carbide precipitation and
sensitization can occur. Stabilizing heat
treatments can be used to more effectively
tie up carbon by completing the precipitation
reactions. These treatments consist of
holding the alloy for several hours in the
815.60C 871.10C (15000F to 1600F)
temperature range. [See ASTM A403,
supplemental S10, p 301 volume 1.01.]
Although intergranular attack of ferritic

stainless steels is similar to that found in
austenitic stainless steels, there are some
important
differences.
Because
the
solubility of nitrogen is low in the ferritic
crystal structure, the precipitates that cause
sensitization in ferritic grades include both
chromium carbides (Cr23C6) and chromium
nitrides (Cr2N).
With the ferritic grades, sensitization occurs
during cooling from higher temperatures >
926.70C (>1700F).
At these high
temperatures the carbides and nitrides are
put into solution and during cooling they can
precipitate at grain boundaries resulting in
chromium depletion. The very high
diffusion rates in the ferrite structure make it
impossible to cool the steel fast enough to
avoid precipitation of carbides and nitrides
at grain boundaries. For this reason, most
commercial
ferritic
grades
avoid
sensitization by restricting the level of C and
N and requiring the addition of stabilizing
elements such as Ti, Ta, or Nb.
If sensitization has occurred in a ferritic
stainless steel, the condition can be healed
by back diffusing chromium into the
depleted regions. Healing can be
achieved by holding the material at 593.30C
648.80C (11000F 1200F) for several
hours.
The test methods outlined in ASTM A763
have been developed to detect susceptibility
to intergranular attack in ferritic stainless
steels.
*******
Source:
Main content scraped from Wikipedia.
CORROSION
TestingforIntergranularCorrosion
SENSITIZATION EVALUATION TESTS FOR STAINLESS STEELS

(Testing for Intergranular Corrosion as per ASTM A262)
Austenitic stainless steels work. unless incorrectly heat treated
In general, intergranular corrosion occurs as

a result of precipitation of nitrides, carbides,
and other intermetallic phases, such as
sigma phase, that occurs along the grain
boundaries. If materials with incorrect heat
treatment enter service, they are liable to
crack or fail by intergranular corrosion much
more rapidly than properly treated materials.
In everyday applications, corrosion varies by
materials and solutions. For example, in
highly oxidizing solutions, intergranular
attack can occur due to intermetallic phases,
while attack of carbides may occur in
somewhat less oxidizing solutions. Due to
the variance of attack in different materials,
numerous methods (Practices B-F) have
been developed to assess intergranular
corrosion.
For most of the applications of austenitic
stainless steels it is required to assess
whether a fabricated component is sensitized
and has become susceptible to IGC. ASTM
has standardized the test procedure and the
specifications are detailed in ASTM A262
(practice A-F) and G108 (45).
Muraleedharan has reviewed these tests and
has compared the various test procedures for
both conventional and electrochemical tests
(46). These standard tests are commonly
used as qualification / acceptance tests
during purchase / fabrication stages.
However non-inclusion of acceptance limits
in these standards leaves the interpretation
of the results open to the users. The salient
features of these procedures are discussed

briefly.
ASTM A 262 Practice A test Oxalic

Acid Test Oxalic Acid Etch
ASTM A262 is a screening test to help find
batches that are incorrectly processed.
Classification of the structure after A262
Practice A analysis will determine if the
material is acceptable or if additional testing
is required. Practice A, the oxalic acid etch
test is used as a rapid technique to screen
samples of certain stainless steel grades to
ensure they are free of susceptibility to
intergranular attack. The test is generally
performed for acceptance of materials, but
not sufficient for rejection of materials.
This test consists of electrolytically etching
a polished specimen in 10 wt % oxalic acid
solution at room temperature at a current
density of 1 A/cm2 for 1.5 minutes. The
etched structure is then examined at 200 X.
In this test, chromium carbide is dissolved
preferentially and the microstructure gives
an idea of chromium depletion which is
responsible for IGC.
The different
microstructures which can be obtained are
presented in Fig. 7 (a-f). If there is no
carbide precipitation step structure (a) is
obtained, because of the differences in the
rate of etching of variously oriented grains.
Dual structure (b) is obtained, if chromium
carbide precipitation is discontinuous. Ditch
structure (c) is obtained if grain boundaries
CORROSION
are completely surrounded by chromium

carbide. Even if one grain is completely
surrounded by ditch, it is characterized as
ditch structure. Step and dual structure are
acceptable but if the structure is ditch the
material may or may not be sensitized and
hence it has to be further tested by any one
of the ASTM tests (B to F). This test is only
a qualitative test but is very useful as
screening test. This cannot detect sigma
phase in molybdenum bearing alloys. Since
titanium and niobium carbides do not
dissolve appreciably in this test, this can be
used to detect chromium carbide
precipitation even in stabilized stainless
steels. ASTM further recommends a heat
treatment at 950 K for 1 h and water
quenching for low carbon SS, for weld
simulation before varying out this test. This
test also characterizes the microstructure
with inclusions as end grains. End grain
pitting (II) (transverse section) (Fig. 7g) is
not considered to be acceptable because
although these steels do not contain
chromium carbide precipitates at grain
boundaries, active inclusions in the form of
stringers undergo IGC in oxidizing
environments such as nitric acid. For
instance, (Fe, Mn) sulphide and oxide
inclusions stringers lead to catastrophic IGC
in HNO3 medium but not in other
environment.
In metallography, intergranular corrosion

shows up under the optical microscope as black
lines around the grain boundaries (with the
proper etchant).
In SEM analysis, intergranular corrosion is

clear by the dark lines where the grain
boundaries are eaten away.
CORROSION
Fig. A: Step Structure
Fig. E: Inter-dendretic ditches
Fig. B: Dual Structure
Fig. F: End Grain Pitting I
Fig. C: Ditch Structure
Fig. G: End Grain Pitting II
Fig. D: Isolated Ferrite Pools
Classification of etch structure after Oxalic acid etching

(ASTM A262 practice A)
CORROSION
ASTM A 262 Practice B test - The

Streicher Test - Ferric Sulfate-Sulfuric
Acid
Practice B, also known as the Streicher test,
uses weight loss analysis to provide a
quantitative measure of the materials
performance. This practice includes boiling
the sample for 24 to 120 hours in Ferric
Sulfate Sulfuric Acid solution, and
measures the materials performance
quantitatively. It is typically used for
stainless alloys such as 321 and 347, Cr-NiMo stainless alloys, and nickel alloys to
evaluate the intergranular attack associated
with the precipitation of chromium carbides
at grain boundaries.
In this test a sample of surface area 5 - 20
cm2 is exposed for a period of 120 h to
boiling solution of 50% H2SO4 + 2.5 % Fe2
(SO4)3. Corrosion rate is calculated from
weight loss measurements. ASTM practice
does not specify the criterion to judge the
susceptibility of the material to IGC.
Normally accepted limit for 304 SS is 48
mpy. Streicher has reported (47) that if the
ratio of the weight losses of sensitized to
annealed material is greater than 1.5 to 2.0,
the material is considered as susceptible.
This test is applicable to austenitic stainless
steels and it detects the IGC associated with
chromium carbide precipitation and
chromium depletion. Sigma phase in 321
and 347 SS are attacked whereas that in Mo
bearing 316 SS is not attacked.
ASTM A 262 Practice C test - The Huey

Test Nitric Acid
In this test, a sample of 20-30 cm2 area is
exposed to 65 wt% HNO3 for five 48 h
period. After every 48 h, the solution is
changed and the sample is weighed. The
corrosion rate for each period and the
average for the five periods are determined.
ASTM does not state the acceptance criteria.

Experience has shown that corrosion rate <
18 mpy for 304 SS and < 24 mpy for 304 L
does not lead to IGC. The material is not
acceptable, if the corrosion rate is increasing
rapidly for the successive periods. Besides
chromium depleted zone, carbides and
sigma phase in molybdenum bearing alloys
are attacked in this test. These alloys can
give high corrosion rates even when they are
immune to IGC in other tests, which reveal
sensitization caused by chromium depleted
zones. Submicroscopic sigma may also
form in stabilized grades of 321 and 347 and
show susceptibility to IGA in HNO3 test.
This test has to be followed only when the
alloy is intended to be used for nitric acid
service.
The maximum allowable corrosion rate and
any available data on the sensitizing heat
treatment performed needs to be specified
by the end user.
ASTM A 262 Practice D test

In this test samples are tested in 10% HNO3
- 3% HF solution at 343K for two, two h
periods (fresh solution is used for each
period). If the ratio of the weight loss of the
sensitized to annealed material is greater
than 1.5, the sample is considered to be
susceptible to IGC. This detects only
chromium
depletion
from
carbide
precipitation and not submicroscopic sigma.
ASTM A 262 Practice E test - The

Strauss Test Copper-Copper Sulphate16% Sulphuric Acid
In this test, austenitic stainless steel
specimen is embedded in metallic copper
chips and then exposed to boiling 16%
H2SO4 + 10% CuSO4 for 24 h. After the
CORROSION
test, the specimen is bent through 1800 over

a mandrel of diameter equal to the thickness
of the specimen. The bent specimen is
examined under low magnification.
If
cracks are seen, the material is considered to
be sensitized.
Although this is not a
quantitative test, ASTM gives acceptance
criterion for this test. Electrical resistivity
and tensile properties are changed
considerably by the IGC. These can be used
for quantifying the degree of sensitization
(DOS). Muraleedharan et al have suggested
a modified version to determine the DOS
quantitatively (48). Flat tensile specimens
can be exposed to the test solution and can
be pulled to fracture at a strain rate of 6.6 x
10-4S-1 and DOS can be correlated to % loss
in strength as follows:
materials performance, and is commonly

used to analyzed as-received stainless steels.
DOS
From the above details, it is clear that the

ASTM standard practices have three draw
backs: (i) they are only qualitative, (ii)
destructive and (iii) time-consuming (except
practice A). Hence several electrochemical
techniques were developed to determine the
susceptibility of a material to IGC which are
fast, non-destructive and quantitative.
% loss in strength
[1 UTSexp/ UTSsterp] x 100.
ASTM A 262 Practice F test - CopperCopper Sulphate-50% Sulphuric Acid
This test is useful for Mo bearing SS for

which practice B and D have been used so
far. Since practice B shown corrosion rates
due to the presence of molybdenum
associated phase in SS, IGC arising
exclusively due to chromium can be
obtained from this test. This test may also
be used to evaluate resistance of extra low
carbon grades to sensitization and IGC
caused by welding or heat treatment. It
involves exposing the specimen to boiling
Cu - CuSO4 - 50% H2SO4 for 120h and
measuring the weight loss. Similar to the
other tests it does not indicate the rejection
criteria.
Practice F, is a weight-loss based analysis

that provides a quantitative measure of the
*******
Source:
Scraped from:1.
2.
Corrosion of Austenitic Stainless Steels: Mechanisms, Mitigation and

Monitoring edited by H. S. Khatak, Baldev Raj.
www.g2mtlabs.com.
----- -
"
Behavior of Austenitic Stainless Steels in

Evaluation Tests for the Detection of
Susceptibility to Intergranular Corrosion*
MARSHALL H. BROWN
Abstract
The c:Nrac:1erlnia, advInUlIJIH. loci IImitellons of \/Irioul metl'lOch lor theOelKlion oi susceptibility
to innrllranulef corrosion In .usumldc mlnlllSS SUM!II dUI to carbld, prw:ipiQltion .re dru:ussed .
InforlTllltlon on corrosion ,.-eft and aecapUineilimlu in nlttic: Kid Ind lenic lulfale-sullurlc Kid lestl
it: pre18nted end lIIu51rl1ld by n.1lnleal tt.UI from the evauiUlon of Ipproxinwtely 10.000 amplel
represen1ing (ommettRiI A/SI 300 Jl!rill$ ttllol"" neels.
ASTM A-262 1 describes recommended practices for several

reliable methods fOf detecting susceptibility to intergranular atlack In stlUllless steels. There have been repealed
requests for the inclusion in A262 of tahles of accepTable
limits or fJ'Pico/ roltS (or guidance of those not familiar in
detail wilh Ihe application of these proct'dures. ASTM

Subcommittee AIO.04 (now A0I.14) decided that the
inclusion of such tables was not appropriate for a methods
spjfiCOlton and thai the desired information could be best
supplied by paper in which an adequate background on
the objectives of the lest and interpretalion of test results
could be included . Thls paper WitS prepared to meet that
objtctive. The author has been intimately associated since
1936 with evalualion lests on specimen.s representing
stainless steels purchased by E. I. du Pont de Nemours and
Co . Wilmington , Delaware (hereafter referred to as Du
Pont). and with the developmen.t and comparison of test
methods and conelalion of test results with service experi.
ence.
Purpose of Evaluation Test.s

It should first be emphasized that the purpose of these
evaluation tests is solely to detect susuptibility to Intergranular corrosion a:s influenced by variations in processing
and/or composition. Material shown to be susceptible mDY
or ItJJlY 1101 be intetgranularly attacked in another environment ; this must be established independently by specific
tests or by service experience. The rt'sulu of long time
service exposures which provide useful guidelines as to the
types of environmenls which are capable of intergranularly
attacking 300 series stainless steels of varying degrees of
susceptibility have been presented by Auld] and by the
High Alloys Commitlee of the Welding Research Council.'
The mosl damaging environmenu are hot solutions
containing certlin inorganic and organic acids, including
nitric, sulfuric. phosphoric. formic. acetic, and lactic acids.
Severe.ly sensitized material as determined by evaluation
tesu will be intergnnularly au acked at a more rapid rate
SuhmiUed for publiution Feb ruary. 1973.
0E. I. dll Ponl de Nemoun and CO . Int . Wilmmaton. DE
Vol. JO, No.1, January, 1974
and over a wider range of temperatures and concenuations

than mildly sensitized material.
It should also be understood thai evaluation lests for
detection of suscepu'bility to int.t'lgnlllular attack arc of no
value for !.he prediction of resistance to general conosion ,
pitting, or slress COtTogon cracking (SCC) in othel environ
ments. Such information can only be obtained by appropriate tests or service experience under the applicable
exposure conditions.
8y rar the major proportion of !.he stainless steels
manufactured are used under conditions which are nOI
rufficiently corrosive to intergranularly attack even susceptible material. Large tonnages which go into such end
uses as automotive, general and indusltial construction
equipment, aircraft, electrical equipment. appliances.
utensils. sanitary and office equipment, and architectural
applications. art seldom, If ever, used in environments
where intergranutar corrosion is a ractor. Even in chemical
processing. the bulk of the sl1'ljn]ess s1eei equipment is
specified to mini.mize product contamination under such
mildly corrosive conditions thllt inlergranullJ corrogon is
not a problem. For such purposes, Type 304 is' satisfactory
in the aswelded condition and there is no need for
evaluation teSts. h is estimated that in Do Pont current
practice evaluation tests are spedfied for only abou l 15%of
the stainless steel purchased. For services where intts'
granular corrosion of susceplibl~ material would be
expected, evaluation tests are required and, if welding is
involved, the extra low carbon (usually) or stabiUzed grades
are specified.
For uns1abiliud alloys containing more than O.OJI,l.
carbon, evaluation tests. when specified. are made on
as-receivcd material to check the erfectiveness of final heal
treatment. For the stabillud or extra low carbon grades.
evaluation tests are performed after a sensitizing treatment
(ie., one hour al 671 C (1250 F) to determine whether
susceptibility to intergranular attack might be developed in
a welding operation. Results from long time seqic:e tesu1 3
indicate that such sensitizing treat.menu inIJoduct' a considerably h igher degree of susceptibility than wou ld result

rrom good welding practice; however, it can be "sued that
safety ractor iJ need~ an order to aHow ror abuses such as
excessive heat input or extensive puddJing, which rrequentIy occur tn welding opera lions.
In seneral, but With certlin exceptions as noted tater,
susceptibility to inlergranular corrosion in austenitic stain
leu steel is believed to be due 10 the precipitation or
Mlle, type carbides al the grain boundaries. ThJs results in
localized impoverishmmt in chromium In the immediately
adjacent areas to proVide. path ror interzranulllr penetration by those corroSives which are clpable or DllDcklng
susceptible material. The primary purpose or aU evaluation
tellS discussed here u to detect susceptibility to inter
granular corrosion due 10 harmrul carbide preeipitation.
Types or Eva lu3 lion Tests

CcppoCappe SuIIQt~Sullu'ic Acid T~l
(ASTM A262, Practice EJ
The first widely used lest ror detecting susceptibility to
inlergranular corrosion wu an early version or Ihe boiling
acidified copper sulfate test commonly known as the
Strauss Test and descnbed in ASTM A393 ," Originally
JOme uwestigators rollowed Intergranular penetration by
electricaJ resistance measure men IS berore and after exposure to the testing solution, but assessment of damage IS
usually made by bendmg the exposed specimen throug.h
0
180 and examtnlng the outside surface ror crtck$. The
usual exposure time IS 72 hours. With the high carbon
contents of the early days, differentiation bttwn solulion
Qnn~laJ-'l4ia{e, qumchtd moten"Ql and ~nlitlud ma(e,iJll
was quite satisfactory. However, with the much lower
carbon contenlS or the stainless steels as now produced, a
more senSItive method IS needed to follow less extreme
changes in susceptibility , which would require much longer
boiling time5 than 72 hours in the Stnus.s solution to
delec,-! It was shown by Scharfstein and Ei5tnbrown' that
a Type 304 heat conlaining 0.068% cubon would pus the
72 how Strauss test even after a sensiliz.ing treatment of up
to 4 hOUri at 617 C.
An Improved modification or the Strauss test, employ
InB the same solution composition, but with !.he test sample
In contact with metallic copper has been developed.' ,1 This
ttst , known as the copper-copper sulrate,sulfunc acid test,
was thoroughly investipted by ASTM Subcommittee
AIO.04 and was incorporated into A-262 as Prtclict E in
1968, It is or comparable senSItivity to the other methods
In A-262 and requires only 24 hours boiling. like the
StrlUSS test, interpretation i5 ba~d on visual examination
or bend test specimens .so that the specimens Ire classified
only as acctptable or nonacceptable. Since sufficient lime
has been allowed for all to become familiar with the
Improved methOd, the ASTM balloted In 1912 to discontmue A-J93 in rOlvor of Practice E of A262. The
copper-copper sulrate-sulruric acid lest is also being
incorpomed into the new intemational ISOrrC-17/sc-7
Standards for Intergranular Corrosion Tests fot Austenitic
Stainless St. els instead or the older acidified copper sulrate
test described in A-J93.
2
NI"ic Acid Tell
(ASTM A-262,
Ptaclic~
C)
The boiling 65% nitric acid ttsl, of len rererred to as the

Huey test, was first described by W_ R. Huey in 1930.a "
Over the yean, it has had the most widtspread use in
American practice or any or the evaluation testl, Interpretation is based on corr05ion rate calculated from weight
loss, supplemented in some instances by visual or microscopic examination ror grain dropping. A quantitative
measure of the degree or sensitization iJ Ihereby providtd
for comparative purposes However, the nitric test requires
240 hours boiling. It abo hi! certain other limitations. as
described below, which must be recogmzed and guarded
against for proper interpretation or resullS,
The test solution volume to specimen surface area rat io
should be at least 125 mJllnl . If the corrosion products in
the testing solution are allowed to build up to an excessive
level, severe intergranular corrosion can occur on even
solution annealed sUIflIess rree of prtcipitated carbides,
Ttus il due to the presence or hexavalent chromIUm ions
formed through the oxidation or Crl to Cr" by the
boiUng 65% nitric acid. It was shown by Delong lO that
acceleration in con0510n tate in the nitnc acid test begms
when the chromium content of the tesung solution exceeds
about 0.004% and IOcreues rapidly with higher chromium
concentrations, Assuming a specimen surface area or 3 sq
10, a test solution volume of 600 ml and a chromium
content of 18 , 5~ 10 the alloy wllh an equal proportiOn lfl
the corrosion products, the test solution .... ould reach the
0_004~ chromium level after 48 hours bolllni With 1
corrosion rate of about 0.0071 m/ mo, or after 96 hours
boiling with a corroSion rate of about 0.OOJ61O /mo. For a
specimen of maximum surrace area to meel the 125 mllin'
ratio in 600 ml of teS! solution (4 8 sq in), the cOltespond
Ing corrosion rate for 48 hours bOlhng would be 0.0044
in/mo. These rates are well beyond either typical rutes or
specified maximum permISSible rates liS will be shown later.
Thus, with normal testing pTl'lctice, the chromium content
or the solution never reaches the level where acceleration lR
rate begins unless the sample IS In the stflSlUled cond.lion .
In rOUline evaluatton (estmg, the- selr ilcl:eleralJon or
severely senSitized materia! may even be considered an
advantage Since it increases the spread between good Hnd
bad samples.
The nUQ)lQlenl chromIum iol'/ effect in nuric acid
testing can be avoided by the use of mullisample testing
equipment such as thlll originally descnbed by DeLpng. ' o
This Involves exposu.e or tesl samples "in the lOner ~r two
concentric vessels, tach contaming boiling acid, with a
common condenser so atTlnged thai all of the condensate is
retumed to the inner \'essel or sptcimen ttSt cup, By
overflow rrom me test cup, corrosion products are continuously removed so thai the chrom ium conlent of the
test solution never reaches the critical level. This arrange
ment permits teStinB many specimens simultaneously in the
SlIme container. As would be expected, corrosion rates in
the multisample tester are essentially the same as in nask
tests ror annealed material bUI are substantially Itlwer ror
CORROSION-NACE
sev~,ely
sensitized specimens. The major portion of Du

Pont nitric ICld evaJultion tests in retent years has been in
mullisamplt lesler, usuaDy with three lest periods of12,
96, and 72 hours (not necessarily in that sequence) in order
to avoid weekend shutdowns without loss of testing Time.
In
tests, three periods lIt also used. with 600 ml of
terting solulion, specimens exposed in individual flasks, and
specimen surface ireD seldom exceeding 2.5 sq in
Cross jeetiena' &rell in bat. wire, and tubuJar products
arc somct'mes subject to end grain mack (also ca1led
pin-hOling). The probable mechanism is localized attack On
the exposed ends of inclUSion stringen to produce crevices
where CT' can accumulate. When Ihls is the else, the
proportion of the lOll] arca represented by the expo$ed
CTOSS secllon may innutnce the results It is stipulated in
A262 that specimens for Mdc (em should be proportioned so that the area of the expostd cross secuon shall
not exceed half the total exposed area of Ihe specimen.
Microscopic examination of the exposed specimen at low
power magnification lS a requirement for the InterpretaTion
of results when end p-ain Ittaa is suspected of bemg an
appreciable factor.
The nmic aCId test was successfully used for many
yellS 10 detect harmful carbide precipitation in existing
lades of austemtic stainless steels. However. when the
utra low carbon (0.03% max) grades became commercially
available, it was soon found lhat for Types JI6land 3171,.
the mlric lest IS also sensitive to lOme other phase or
condition frequently resu111ng from the reqUired sens.ltizing
heat Ireatment, whiCh experience has shown dot$ not cause
intergranulu attack In other environments. This phost has
bn generally assumed to be submicroscopic sigma, II - I]
allhough pOSJlive proof for such a mechanism has never
been demonstrated III p~senee is postulated from the flet
that longer exposure time m the senSitizing temperature
Bnge does produce readily identifIable sigma phase particles, but in that form, they have relallvely Jinle erfect on
corroSion Iale. Since the other available methods described
In A-262 are not sensitive to the presence of submicroscopIC sigma in Types 316land 3171., the nitric teSI
should not be used for evaluation of these grlde! unless the
mllenal represented Is actually iOlended for nitric ,tid
service. There IS 1150 some poSSibllilY of encountering
submicroscopic sigma 10 Type! 316 and 317, bUI these
grldes are tuted In the commerciaUy annealed condition
and with the higher carbon content. the effect of carbide
precipitation is almost Ilways predominant.
n.sk
,
I
FDTIC Sulfott-Sulfuric Acid

(ASTM A-262, Practice B)
T~st
The ferric sulfatesulfuric acid lest. often referred 10 IS

the Streicher test or the ferric sulfate test, was originally
described by M A Slreicher in 1958. 1 It is of comparlble
stnsitivity to the nitric test but requires only half the
boiling time. while retaining the advantage of a numerical
corrosion rate for comparison of the relative performance
of the specimens evaluated. It is not sensitive to the
presence of submicroscopic sigma in Types 316l and 317L
as produced by the usual sensitizing treatment (J hour al
Vol. 30, No. I, January , 1974
677 C). and in Du Pont practic:r:. the ferne sulfate lest has
long been used for the evaluation of these grades. Also it is
not sensitive to end grain aUacle. Accumulation of corro..
lion products does nOI accderale the corrosion rale as It
does in the mtric lest, so that several specimens may be
tested in tht same nask. However, there are a few
preC1lulions referred to in A-262 which must be rigidly
observed. The solution must be brought to I boillnd all of
Ihe ferric sulfale dissolved before the test specimen is
Immersed. Additional ferric sulfate inhibitor may have to
be Idded (or the solution chang~) if there I! e.xcessive
common of a very severely Ktlsilized specimen as evidenced by I color change f,om amber to dark green_ The
inhibitor ongmally added would be enlmly consumed If
the totll weight loss of the speCimen, or specimens, exceedt
Ibout 2 grams, In which case, the solulion would act like
boiling SIR sulfuric .cid and the specimen would be
dissolved_ Also. care must be liken that all scale formtd
during heat lIeatrnent is completely removed before starting the test. If. for instance, small patch of scale Is not
removed from a stamped number durinS polishing, IClIVldon due 10 galvanic action may occur. as evidenced by gas
evolution and IOCIJ color change immediately after immerlion of the specimen. In this case. Ihe specimen should be
immediately removed .nd repolished, or the scale removed
by immersion in concentrated nitne acid 8t about 93 C
(200 Fl, and the Itsl restlfted.
Nitric-Hydrofluoric Acid Test
(ASTM A-162. Pttzcli DJ

The omit.hydrofluorlc acid lest IS adopted fOT eVlluatlOn purposes was first deSCribed by O. Warren in 1958.1S
It consists of IWO 2 hour periods in 1($ IINO,-3* !iF
solution al 70 C (ISS F) and thus reqwru leu testing lime
thin any of the other methods. It was devtloped specifically to differentiate between precipitated carbides and
submicroscopic ligml In the molybdenum belring grldes.
As described In A-262 . it applies only to the evaluation of
Types 316. 316L. 317, and 317l, although il probably
could be readiJy adapted to other gradrs. if desired The
bue corrosion nit of stlinless sleels in HNO,HF solulJons
is quite high and varies substanllally with relatively slight
differences in composition Within the same grade. It IS..
therefore. neceuary 10 run IWO tesu and compare the
corrosion nle of the specimen to be evaluated (JH~iltd
for Types 3161nd 317 and 5eIlSiliztd fOf Types 116lloo
317l) Wilh another specimen of the same material which is
free from precipitated carbides as. shown by I step structure
in the oxalic ac.id etch test. If the al-feceivtd material docs
not show a step structure, a portion of it must be
laboratory annealed 10 provide Ihe required good sample
for comparison_ A ratio of less than 1.5 between Ihese IWO
rates indicatts the malerial represented to be S3lisfICtOry.
This test SI\'es consistent and reliable results but hIS nOI
had widespread we for routine evaluations. presumably
because of the ncassity of using a ratio of two ttst raTes
for interprelation. the rnconvenirnce of handling solutions
conllinins hydrofluoric acid, and the :availability of the
fenic sulfate test whkh was dt\'eloped a' :tbolll the same
lime.
]
OXl1lic Acid Etch T~t

(ASTM A-262, hactlce A)
The oxalic acid etch ttst is not actually an evaluation
test bUI a formalized classification of etch structures which
is used to sc~en OUI those specimens which would
unquestionably pass the applicable evaluation test as listed
in A-262. It was firsl described by M. A. Slrckher in
1953 16 and the results of an ASTM CoopenliYc tesllng
program were published in 19S4.1'J Details of procedure
and classification arl! given in A-262. Seep structures
(essentially free of carbides) and ditch structures (many
completely encircled grains) are easily clauified. DUDl
structures. which may ha... e many partially encircled grains,
require more extensive microscopic examination to determane if any arc completely encircled. StriCt imcrprcllI.tion
as specified in A26] stipulates thai a sample In which any
completely encircled grams arl! found cannot be accepted
without an evaluation test. Experience hI! shown that most
samples wowing only an occasional random encircled grain
will also pass any of the evaluation tem but appreciable
compromise in interpretation cannot be safely made without some risk of accepting specimens which might fail In an
evaluation test.
As indicated above, no male rial is rejected on the basis
of the oxalic etch test alone; those specimens which cannot
be aa:epted are rubjected to the appropriate cnluation
te.$1. Most of the .speCimens which are not scrtened OUI by
the oxalic elch test will still meet evaluation lest require.
ments. However, since the etch test can be performed
quickly, il is quite advantageous to use it for incoming
spctlmcm so long u a considerable proportiOn can be
screened OUi.
Early Du Pont experience with the routme use of the
oxalic ereh tesl soon disclosed thaI for Type 304l. only a
dis.3ppoiOtingly low percentage could be screened after a
sensHizing Ireatment of I hour al 677 C. The screening
percemage was fanly good for plate, sheet, and strip Ilnd
forgmgs, but much lower for rod, bar, and hex and
miscellaneous (mostly fittings such as elbows, tees, concentric R!ducers. and Hanges). For tube and pipe, especially
small diameter tublOg where both interior carburizalion anc!
end grain attack Ire frequently found, the proportion
screened was so small as to make the procedure hardly
wonhwhile. Since more evaluat Ions are made on Type
304L than any other grade, further studies were conducted. 11 It was found thai the ~reenjng ptn:enlage could
be substantially Improved , while slill retaimng assurance
th31 the specimens would meet evaluation test require.
ments. if a sensitizing lime of 20 minutes (instead of I
bour) were used. The 20 minute sensil izlng trealments are
carned oul In a neutral salt bath since varillion in time 10
reach 677 C In an au furnace Is 100 greal for consistent
results. The use of 20 minute sensitizing treatmentS
substantially increased the screening percentage for all
forms except rod, bar, and hex, which showed only a slight
difference, possibly due to the greater mtidence of end
gram allack.
DtJ POnft data on oxalic etch test screening percentages
comparing I 'hour and 20 minute senSitIzing (Jeatments on
Type 304L are Vlewn in Table I; abo included are data for
Types 304 and 316 (as commercially annealed) and Type
316l (after 20 minutes at 677 C). It is probable that the
oxalic etch leS! could also be applied to other grades such
31 Types 3095 and 341, but no studies to supply the
necessary background have been reported so far.
A limited amount of dllta on oxalic etch test screening
is also available from other sources. For bar and strip
material, one source reponed 251 of 276 samples of Type:
304 and 223 of 230 samples of Type 316 were screened in
the commerCially annealed condition, but only 2 of 49
samples of Type 304L after I hour at 617 C_ Another
source reported S3 of70 sampJes(aU forms) of Type 304L
were screened and of the 17 samples subjected to nitric
tesl,8 failed_
Experience with Evalu.ation Tests
The nitric acid lest WitS the first test to be applied on a
major scale for Ihe routine evaluation of specimem. repre
senting purchased maierial. Du POnt specifications calling
for a maximum ptrmiSSJble nitric lest lale of 0.0015 in/mo
(18 mils per year) for /8.[J-S and /8-8SMo (0.07% carbon
max) appeared III me early 193O's_ This limiting rale was
selected on the basis of available data as low enough 10
guard against mlergranular failures In services for which the
alloys were otherwise suitable, and high enough to be a
practical requirement for producers and fabricalOrs to
meet. Subsequent correlation with service ex.pcrience
proved to be so good that the originally selected value of
0.0015 In/mo has never been ch3nged. At that lime, water
quenching of fubricated equipmenl after a solution anneal
was required for austenitic stainless sleels, lltld welded
specimens representing these /illuf lIeollTe1rmellls wen: also
evaluated. When the stabilized grades appeared. the practice
of exposing incoming specimens at a temperature which
would sensllile unslabilized mlilerial$ was adppted in order
10 establish that the material represented could .be safely
used in the as-weld~d condition (ie.. without hell.l tre:ument after fabrication). A maximum permissible rate or
0.0020 in/rna after exposure for ] hour al 617 C was
specified for Type 341. and the same rate was speCIfied for
Type 304L when It became available. However, as pre
viously discussed, the behavior of Sl!l/SlIIzed Type 316L in
nitnc tests was found to be complicated by tht- presence of
rubmicroscoplc sigmD. consequently the nllnc 1,,1 is not
recommended for Type 316L unless the matenal is actually
to be used fOI nitric aCid service, which lS seldom. The
ferric test is the one most generally used with a fIlIximum
permissible rate of 0.0040 tn/ m o . '
~
It should also be ~cognized that enluation tests are
a<:ce!erated tests and that attack on susceptible material is
much more rapid and .severe than in most service environments_ Service failures have been reported whidl took as
long 31 eight years to develop.s For example, in nitric tesiJ
on- "TYpe 304. grain dropping as observed at low power
magnification begins at a corrosion rate of about 0.0010
in/mo. However. experience has shown that a limiting rate
orO.0015 in/rna provides a sufficient safety faclor to assure
that intergranular attack will not occur in any of the usual
CORROSION_ NACE

service environments. Likewise, tht sensitizing Ire&lmenIJ
used for the extra low carbon and stabilized grades are
more severe than would be experienced with good welding
practice and the reby provide a margin of safety for abusei
in welding. On the other hand. there are I few environmenlS which Irt capable of mtergranularl)' attacking even
solutiOn , annealed st!inless su:els without precipitated
cubides land which will pass all of the evaluation tests
discussed. These include hot nilric acid iueJf unde r con-
ditions where the concentration OrCr 46 can build up above

the critical level, rulric acid solutions to which mong
oxidizing Igconls such IS chromates, vlnadales, and cerales
have betn added. and hot chromjc acid solutions. Recent

work. by Armijo, AU51. and others l t-] I has resulted in the
proposal of a schae segr~ation mechanism to explain the
mtergranular attack on solution annealed materia] in these
highly OXidIZing media. Their results indicate that concentration of certain mmor elements (particularly silicon and
phosphorus) is the primary controlling factor for this type
of attack.
In current Du POOl practice, eviJUltion tests are
speCified on(y whVl il is known or su1pud IhDt nlllttriDl
shown to be susptibte 10 mterrranuJtu CQrrorion would be
1II1ugranularly attacked irz the intended Jervi~ enlJironnu:nt. SlOtt the L gudes Ire usually specified for such
ItTYlctS (except when no welding is im'oived). the numbe,
of Type 304 .nd 316 specimens evaluated has decreased to
smaJl propanaon of the whole. Incoming specimens of
Types 304 Ind 316 (also cast CF8 .nd CF8M) in the
as-received condition. and of Types 304L and 316l aOer I
sensitizing treatment, are first screened by the oxalic etch
lest Those which cannot be accepted by the etch test "e
subjected to the appropriate evaluation test. This m.y be
enher the fernc sulfate or nitric add test fot Types 304,
3041., 316, CFg, .nd CF8M (depending upon plant
preference), but alwlYs the ferric sulfate test for Type
316L unless the material represented IS to be used in service
mvolving nitric acid (very seldom). Other grades are
subjected direc:tly to evaluation lests since Insumdent
InfarmBtlon has been developed to classify oxalic etch
Structures. The maximum acceptable corrOSlQn rates for the
most common lus-temllC wades as currently listed in Du
Pont specifications are $hown in Table 2.
Compariso n of Eyaluation Tesl Data

From lime to Lime, tabulations of Du Pont evaluation
test data hive been made ovef some period for some
speCIfic purpost. Such tabulation covering approximately
10,000 tests an Clst 18S (now CF-S), 18..g Mo (CF8M),
and FA-20 (eN.7M) which ilIustrllted the effect o f compo51110n variables on nitric test rates for Slaul1ess caslings was
published in 1949.5 A recent summary of nuric and ferric
test data on wrought minim Illoys broken down into
corrosion rate incremen ts is available for use in thls paper.
Thts includes 7732 incom ing sa mples of which 5466 were
Type 304 l and 1454 were Type 3 16L Of the 10111
sampes, 3 139 were Icceptd a n the basis of the: oxalic elch
tW, 2624 were subjected to nildc tests. and 1969 to ferric
tests. The lime periods represented were January, 19 64
Vol. 30, No. I , Jan'*Y, 197.
through MlY, 1965; AuguSt, 1966 through April, 1967;

January, 1968 throuah December, 1969; plus 1970 and
197 1 data for grades olhCT than Type 304L.
Since Ou Pont data are from specimens representing
purchased material specified to meet evaluat ion test
reqUirements, It an be ugued that they are biased to .1
least some extent through special handling actarded the
material by the producers. Consequently, producers were
Isked to supply evaluation teSI data from their own mill or
laboratory records for comparison. Such information was
submitted by the AUeghney Ludlum Steel Corp., Armco
Steel Corp., C. O. CarlSon, Inc., Carpenter Technology
Corp., Crucible Stamleu Steel Division. EaSiern Stainless
Slee] Co., and the United States Steel Corp. The combmed
data from these sources are lhown under the he.dmg
Producers. They include 2296 nitric tesls (1613 on Type
304L) and 179 ferric sulfate tests. In eomparing Du Pont
and Producers data, II should be underslood thll there are
severallmpolwn differences In the makeup of the teSlS.
For Types 304, 304L. and 316 in both teStS and for
Types 316l and 3171111 the ferric sulflle test, Du Pont
test results include only samples which were nat ac:cept.ble
on the basis of the oxahc etch test . I.e., I lalge propaJ1ion
of the specimens which would ihow the lowest corrosion
rates were screened out and not tested.
For a considerable propOrtion Df Du Pont nitric tests
on Type 304L .nd for aU ferric rulflle lests on Types
3041., 3l6L, and 317L. I "scns.ili7inl treatment of 20
minutes at 611 C in a salt bath (inSle-ad of I hour in 9n air
furnace) was used In order to increue Ihe proportion which
could be screened by the oxaJic elch test. The resulls from
20 minutes and 1 hour 5enSitiZUlg IreatmenlS are shown
separately. Where sensititing treatme:nU arc lllvolved, Producers data are ,II for I hour treatments.
The specimen! represented b~ PrOducers data all faJl
within the classificatiOns of plate, sheet, and strip, tube and
pipe, and rod, bar Ind hex. Ou Pont data fOf all fanns also
includes I large miscellaneous category consistmg princi
pally of vanous types of nltjngs and forgings. Test resulls
for castings and all weJd me tal pads lie not included In
some cases whtre the numbers repre~nted are sufficiently
large to have Slatistical significance, dati for the different
forms are shawn separately.
A major proportion of incoming Du Pant specimens are
transmi tted by fabricators or ~lehouses rather than
directly from the producers so thai the passibUlly of mixup
In material or heat treatment is increued. As In extreme
example, in one lot of seven Type 316 rod specimens of
different sizeS. five failed the evalualion test and one WIS
found by rou tine spot lest to (onlain no molybdenum.
As an aid in inlerprel'tion of the paphs of corroslon
dati which faDow, Table 3 presen ts PJodUCfrs and Du Pont
nitric acid tesl data for Type 304L (after 1 hour.t 677 C)
in numerical farm as the result s were orilinally tabulated.
DistributiOn o f corrosion rates is shown IS Ihe number of
samples falling wi thin sdected rale increments. Producers
data inclucX ttst rates for aJl sample., bu' .,. previously
sl.led . Du Panl tcsled only specuMns ...Mch wele not
TABLE 1 - ou Pont Dati on Proportion of Simples Screened (ACCt!pted)

By the Oxalic Etch Tnt
Type 304l Iher 1 Hr .ll 677 C
."
AI ftclrvlld
As receIVed
20 min, 611 C
1 ht,617C
AI t-.:IIiYed
,..'"
".
26.6
?II. 1
62.'
Col"r'MlOn Ru,
DDD4D
D ....
D""
D.DD4D
D.....
D ....
D.....
240 Hour NIUK TtIt IASTM A-252. Pt'X'ttce CI
A I~.:j
605
717
1454
CF~M
IDOl
1111
CF"
'"
26.D
36D6
As rtc.iwd
20 min, 671 C
AI ,ece,.,.-cj
20 mtn, 617 C
20 min, 617 C
As received
CF-8M
63
51<
All Fotml
120 Hour F.tlC T_ IASTM A262, Pratiu 8)
CF"
2211
51.5
47.4
lin/mol
lhr,677C
Al ftCIlved
"
26.'
".1
14.2
58'
316 H CommlttCially Ann.led

P1Ite, 1hHI, Ind IIlr,p
All Forms
AI'~I"'"
58
"39
~1I'mum
".
258
Misc.lI."'01Jl
T,,,
3D9S
41 .1
6.6
''''..,
TABLE 2 - Maximum Acceptable Evalu. tion Tut Rates

Specified by Do Pont for Services Where Susceptible
Material Would Be Intergranulatly Attacked
3D<
3D<L
3D<L
'"29
"'.S
Typtl304" Commltfl:llUy An.-c

Plllte, shet!t, 100 strip
All Forms
316L
311L
S26
""-
'7.
Type 316L 1ft. 20 Min II m

Platl, th.II, Ind strip
All Forms
3D<L
Percent
Screen"
..",
Type 304L .trer 20 Min It tr77 C

Pllt., shHl,.net striP
Tube Ind P'PI
Rod, blr,.oo h,1I
FMglngl
""
31.
Num b...
89'
"'11, "'eet. end strip

Tube Ind pipit
Rod, blr,.nd hll(
Fofgingl
MJ_Il.n8O\.l1
All forml
Ty~
Number
of s.mpl.
0.0015
0.0010
0.0020
0.0(110
0.0015
D.DD2D
D.DD2D
D.DD2S
15'
58'
57.5
47.0
10<
68.D
I.'
61.5
lDO
54
'"
109
... ,
32D
.. D
accepted on Ihe baSIS of the oxalic etch ICst Con~ucnll)' .

for Du Pont dall, the percent of teSts shOWing ralcs above
the specIfied maximum rale of 0.0020 in/ mo is considerably higher than the percent of total Jllmples above thlt
rale. ThIS differe:nce is eve:n greater for Du Pont data based
on 20 minute: sensitizing IreatmenlS, since as shown In
Table I, the proportio n screened by the oxahc eh:h test IS
substantially higher.
In making comparisons. it must be recognlud thai the
Producers data is a compoSIte ftOm seven JOurees. In some
instances, there were major differences between sources.
For cum pie, in Table 3, I [J of 770 plate, ihee.t, and SlrIp
samples (14.4%) had rates above OJlp20 tn /mo. However ,
one of the four sources represented in this case (w{lIch we
Will call Source A) reported 97 of 516 samples (18.8%)
above 0.0020 in/rna, whUe. the other three reported only 14
of 254 sample.s (5.5") .bo\le this rale. This difference is SO
great thai exclusion of these 5 16 plate, sheet, and strip
samples from the all fornu tOtals would decrease the

percentage o f samples with rtlles above 0.0020 in/mo from
12.6~ to 7.3%. Where such major differences in the data
ftom different sources exist, they will be mentioned in
discussion of the figures.
CORROSION- NACE
"
The nitric test data given in Table 3 for 01/ fo rms of

Type 304L tested after a sensitizing treatment of I hour at
677 C are also shown In graphic IQrm in Figure 1. in which
the percentage of samples above the indicated corrosion
rate IS ploued fOT the selected rate increments.. The number
of samples represented m each case Is shown in parentheses
following the symbol Identification. In view of the situation
describeQ In the preceding paragraph. Producers data are
shown b~th for lotal-samples and excluding Source A. In
order to provide II betfer basis of comparison on the graphs,
Du Pont data ale shown both as: (1) peJ'cent of rem above
the indicated corrosion rate, and (2) percent of total
SlImpfes above the indjeated corrosion rate. For this
purpose, it is assumed thnt the samples SCreened by the
oxalic acid elch test will not show nitric test rates above
0.0010 in/mo (or ferric test rales above 0.0030 in/mo).
Experience has indicated these limits to be approximately
correct, and that most screened samplel will give consider
ably lower conosion rales. As shown in Figure 1. the
percentage of samples above the selected rate incremenTS up
to and iJlcluding the 0.0020 in/rna limit is considerably
higher for Producen total samples than for Du POnt total
samples or even Du Pont tests only. However, when the
results from Source A are excluded, the data are in quite
reasonable agreement. Du Pont data show a larger (bUI still
small) proportion of specimens with rates above 0.0050
In/ rna, which is at least partially due to mixups in material
(Le.. Type 304 instead of Type 304L).
Figure 2 shows Du Pont nitric test dlla for aU forms
and plate, sheet. and strip of Type 304L tested after
sensilizallon fOI 20 minutes al 671 C. Differences between
the tests only and tott.! sample basis are greater with the
shorter sens.itizing lime, since the proportion screened by
the oxalic etch lesl is almost doubled . The specified
maximum ule ror specimens sensitized 20 minutes 01' 671
C was originally set at 0.0010 in/rna and has not been
changed. It can be argued that a value of 0.0015 in/ mo as
allowed ror Type. 304 wouJd be more oonsisu!nI . The dala
indicate that the effeCI of such a change would be sliiht.
With 1he 0.1)010 mlmo limit. Ihe proportion of total
specimens (all forms) above the specified maximum was
slighll) lower than wilh the 0.0020 in/ rna rale for I hour
sensiliz.alions (7.5% vs 8.6%); with a 0.0015 inl mo limit for
20 minute sensi.til.Jtion. the 7.5% would have been reduced
only to 6.5%. The rdative behavior of various forms is also
quile similar to thllt With the longer senSItizing time. No
Producers dllta art available for 20 minUle sensitizing
treatments.
Figure 3 presents nhoc lest dalll (or all forms ofTypt
304 as commercially annealed. The number of samples
represented is much smaller than for Type 304L but is
sufficient to be ItatlsticaJly significant. The proportion
screened by Du Ponl with the oxalic etch tcst by Du Ponl is
much highe.r (64~) than ro r Type 304L Agreement
between Producers and Du POllt d:lIa on the tOlal $lImples
baSIS is quite good.
Figure 4 covers nitric test dilla for all forms of Type
316 as commercially annealed. Here, the differem'ts
Vol. 3D, No. 1, Jan uary. 1974
7. _ _ __
' . . ._ _ _--~::_==-"T!'m
__
_
_
~_
04II ......
_
_ _
...
~
_
1:I.
i.
j"
FIGU RE 1 _ Nitric: Kid tat
diU ,,1"1
Type 304L ;111 .. one
hour ;It 677 C taU formsj.
FIGURE 2 _ Ou p"I"I' l"I;ul(: Kid lest cYU "" Type 304l

1ft. 20 mlnUIU It f'i17 C.
belween Producers and Du Ponl data on the total samples

baSIS are large and if plale. sheet, a.nd strip are considered
separately. they are extreme. For plale. sheel. and strip.
two of four SOUTces reponed that 52 of 100 samples gave
rate! above 0.0015 in/mo. In contrast. another source
reported no samples of 30 tesled abo ..e 0.0015 in/mo.
while Du Ponl had 4 of 21 teSIS leprestn1ing 63 samples of
which 42 wele passed by the oxalic etch teSt . As previously
explained, Du Pont currently runs very- few nitric lem on
Type 316: for services where intergranular corrolion is 10
be feared, Type 316l is normally specified and tested by
the ferric sulfate lest. However, Du POni mn thousands of
nitric tem on 18-8-S-Mo (specified as 0.07% carbon ma.""<)
in the early days before Type 316L became avoUable and
before the ferric sulfate test was denloped. Unfortunately.
delailed records of Ihese tests are no longer av:tibble.
However. the proportion of Sped mens ..... llh mtes O\tt
0.0015 in/mo was not e"CSIVt', amounting to abouI7..or
8%. including the inevit:lble insl3nct's of C:lrburiz:nion. end
gram lIuack. and tTIlXUpS in moterial. SubmkroSl:opil: sigma
was unknown 3fld bel.-:lme :1 signifi.::anl r:a~lor ollly orler
tesls were made on sensitized spedlllt'1l5 of Types J I6l and
316 Cb. Annealing pr.h:IIC1!S in those days generally
TABLE 3 - Nitric Add Test Resulu on Type 304L After One Hour at 677 C
IASTM A-262, Practice C)
PI.II. snMI_ lOCI Sulp
PToducer.(I}
0... Porol
Totill s.mpl"
770
Nunber O)r.lic s.c:r-..:l

try ASTM 1.262 Pl'ktice A
Number of T"a
O,nributron of Comuion
R.la In 'nJMo
0.00050 .nd below
0.00051 to 0.00075
0.00076100.0010
0.0011 10 0.0015
0.0016100.0020
0.0021 100.0030
0.0031 to 0.0060
o.oosl to 0.010
0.011 end.,.,.."
,. of Tem Above 0.00050
,,"of Tftb Abo .... 0.0010
"of Tut. Above 0.0015
"of T.rtI AboVtl 0.0020
893
TuM .nd PIp'P.odu-utl

Du Pont
".
>n
770
145
203
167
.
59
36
12
'"
13
200
180
8'
"89
99.2
48.8
97.5
24.6
21.0
14.4
85
5.8
14.4
3.'
.,.
Rod. e ....nd Hu
Proch.IC....
Du Ponl
220
29
126
21
54
17
13
10
3
0
497
40
20'
117
"118
,.
17
17
220
..
30
2.
"9
3
3
258
190
53
54
32
8
"
10
AJI Form.
Ou Pont(2)
Produo:.,.(1)
1116
22 "
57'
1116
.,
1637
205
B2
.14
'64
233
122
54
72
42
20
7
48
53
285
306
.
..
....
813
92.0
21.0
16.6
274
17.0
86'
26.4
15.0
113
8.
247
205
23.1
87
".
".".
87
12.5
8 .
15.1
12.6
B.
91.9
415
"9
949
292
'I. 0' Toa.1 Simp/II:!. AboYI
0.0020
(I)()QIU 001 indudo: 4117 pbte iheet .nd s trip amp ... which were brohn dow" onl,. inlo
(56) eoffO,lon .. ft: ,ncr"m91",
(l)lndudlU OIlier form. JUeh u fillinp .nd forJInp..
involved longer holding times and rugher temperatules than

often used today. It IS possible that variations in annealing
pr.Ct1ce may be an appreciable factor in the erratic nitric
telt resuits reponed. It is known that higher annealing
temperatures and longer holding limes can substantially
reduce (but not eliminate) the submicroscopic sigm4 ~ff~Cl
in rutric tests on sensitlled Type 316L.2l However, as
previously stated, the mtnc test is not recommended for
the evaluation of Type 316l urness the material Is actuaUy
10 be used in scrvice Involving nitric aCid.
Figure S shows nitric test data on all forms of Type
347 after .sensitlLing one hour at 617 C and rlgUTe 6 for all
forms of Type 309S. For Type 347; Producers and Du Pont
data are m good agreement. The pro port ion of specimens
excu:dmg the specined maximum nte is higher for Type
347 than for Type 304L. and it is probable that secondary
phases are sometimes involved, although to a much lesser
extent than with Type 316L For 3095, the Producers data
consiSlS of only five tests. In Ihis grade, more thin 80':Jt of
the nitric test rates are below 0.00050 in/mg.
InsuffiCient data are available on Type 321 to Justify
plotting_ A limiting rate of 0.oe)30 m/mo In the nitric acid
test afler one hour at 677 C has sometimes been specified
In Ihe past .The cunent tabula tions include only 13 tests,
with Du Pont reporting two of seven samplu Ind Producers
< 0.0010 (1'9). 0.0011 10 0.0010 (152), .nd > 0.0010
four of six samples above this rate, Streicher}) has shown

that sensitizing treatments tn some cues resulted In the
formation of secondary phases which caused increased rates
m the mtric acid test and also, to a lesstr degree, in the
ferric sulfate test. These were nOI reVelled by the Quilc
etch test , the HNO,HF test, or the copper sulfatesulfulle
aad test. i1 has also been shown that TIC and Ti(C,N)
particles are subject to direct a1lack by boiling 65%
HNOJ.H,lS For plITuciesSCIuered throughout the matrix,
Uus results in only superficial surface .Itu.:k. lIowever, m
the fUsion zone of welds, it is poSSible to develop a
continuous gram boundluy network of TiC, which Is
soluble in hot HNO] and causes a speCialized form of
inter granular or interdendrilic corrosion referred 10 as
.,.
I
fi1SUr~ Quack_ l ',11
Figures 7 and 8 present Du Pom ferric test dtra on

Types 304L and 317L, respectively, iested after :liscnsitWng tIeatment of 20 minutes at 677 C Differences
between dats for alJ forms and plate, sheet, and strip lire
less than in the nllnc test, rince the ferric test is not
sensitive to end grain attack The limited Producers ferric
test data submitted for both Types 304L and 316l are
shown in Figure 9. The specimens were all plate, sheet, and
strip and were lested after a senSitizing treatmcnt of one
hour at 677 C_ For Type 304L. the resuJ ts differ only
slightly frum the Do Pont data based on 10 minute
CORROSION- NACE
... _--..-
0"_
,_",.
a __ .............
1:
1:
J
j.
--
,--
. . .. '.:
"
:
:
'
..~;
- :;::~~~~~:;~::::::~:;~
-- -
. ...
~
~-
~-~--
c-- ..... ~ ....
FIGURE 3 - Nitric: acid lest dar. on TVI"I 304 ..

eomm.,cl.Uv .nnM'" '_II lornul.
FIGURE _ Nonie .cod teJ1 dlt' on Type 316 n

comm.ttllllly .n,....ltd 1"1 form.l.
I:J.
1
J
j
j.
0-.., __
.u
l"
_-
I
j
l .
.._
_
...... ---,..
........
r----,~~""""T""....,
- ..... ..
~
- .....'-_
FIGUFIE 5 - Nitric: Kid IWI data on TVPlc 347 _her on.

hoUr.l 671 C 1.tllolfNI).
FIGURE 6 - NlIIie Kid I", dille on TyPl' 309S ..

comrMl'd.Uy .n'*lltd 1.11 form.' .
sensitizing IrealmenlS. For Type 3161... the Producers raftS

are considerably higher, bUI only 17 lests were reporttd.
Figures 10 and II cover Ihe limited ferric leSI data available
fOI Types 304 Ind 316. respectively. In the commercially
anneale-d condition. The Produceu data show a subSlan.
tlaiJy higher propoTllon of the gmples tested above the
sdecled rate tnCJcmenls .t the lower levels, bUI only
slightly more above the 0.0040 in/mo maximum (10.0% 'IS
6.2% for Type 304 and 3.0% 'IS 2.4~ (0' Type 316).
by the Ihree test methods are quue coniislenf fOf plate.

respecti\'e1y) where
sheet, and strip (3.4%, 3.4%. and
the complicating effects of end grain allade ;md localized
carburiz8ILon Ire rarely encounter~d. Also, tht chance for
mixup in malerial Is minimized as compared. for instanct.
to small Jots of rod, bar, and ht'( which frequently COJTl('
from warehouse or fabricator stocks. On the all forms basis.
tht correspondmg values for Ih~ thrtt leSt mtlhods art
8.6%,7.6%, and 4.B':l. rtsptClively. The Iowtr v31ue for lhe
felne sulfate lest rC'Sull$ is to be exptcted sinct the ftrrie
tesl is not SC'nullvt to end grain attack \\hich Is sonltllmes
found on bar and tubul:u products in nilde 3cid. The
proportion of lube and pipe specimens abm"e the specified
maximuhl rlllt apptars to be appreciably higher for nitric
ttsts with one hour stnsitillitions Ihan for nitric tesll wnh
20 minute sensitiulion&. This may be :11 least partially
explamed on the bas.is that interior carbunz:llion is frt
quently found in small bort tubing (tspeclally ~ ITlch 00
or less), and thai one plant using larg~ qU3n1 it its of such
tubmg preftrs thlll n:IlUlliiolis bt madt by nil l"ic add tUIS
with one hour stnslIizations: ,:onSt'~uently. Ihe dala are
Figure 12 compares Du Pont results on Type 304L as

obtained by: (I) nitric lUIS after one hour at 677 C. (2)
mtric Itsls aru~r 20 minutes al 617 C, and (3) f~nic sulfat~
tuls afler 20 minutes at 677 C. Th~ differ~nl forms are
shown Stparalely IS well 115 the combined totals (ir.. all
forms). The dall 8re ploued on the total umples basis (i.e..
samples screened by the oxalic etch test are Included as
OJ)()IO infmo maximum). Since no rale Incrtmenn below
0.0010 infmo are included, the scale isupanded 10 enable
benet separation of the curves for the diHerent fo rms. The
proportion of samples above Ihe specified maximum rales
Vol. 30. No. I . January. 1974
3.n.
TABLE 4 - Average Corrosion Ralet for Passing Samples
.....
""L
"'300'
"
300'
300'
"od~
F~m
,
Plall. ShMt,
andSUlP
Tube IIOd Pipe
Rod, Blr,
.nd Hex
M,_llan)ul
lhr,677C
lhr,617C
'"
All Forms
(Total)
1 hr, 617 C
300
All Forms
All Forms
AU Forrm
All Forms
Du Pont
"iMo
T_.
,,-
Nitrk Acid T HII (ASTM A262, PJltC1iee CI
254
p,,~, ShlNt,
.nd Strip
Tubt.nd P,pe
Rod, Bar,
nd Hlx
M,tce:llanlfOUl
AU Frm
ITlltall
3'.
3<7
T....
I hr. 617 C
lhr,611C
"'"
"'"
"'"
30"
"'"
309.
Condition
115
...
0.00093
0.00081
0.00015
0.000B6
20 min, fS77 C
20 min, 617 C
Comm, An,..I"
Conwn. AIl.-led
Comm. All_led
1 hr,671C
0.00084
0.00Il05
374
IS'
0.00092
0.00084
'047
0.00085
58
.,
.
5
276
0.00085
0,00056
0.00112
0.00120
0.00011
,.7
0.00072
0.00073
558
000068
72
""
0.00016
0.00037
0.00097
0.00126
25'
000252
0.00231
35
25'
20 min, a17 C
20 min, 677 C
2Om,n, 677 C
491
'31
36
78
000064
Flrric Sulfll ..Sulfurlc Acid Tfttt IASTM A262, Prat;1icl 81
"'"
300'
"'"
"'"
300'
"'"
316l
316l
"'.,
316l
316l
316l
317L
300
300
PI,I., Sheet,
and Sl1ip
PIII Sh... ,
.nd Su,p
T . ""d Pipe
Rod,S,.,..
1 hr,rrnC
59
0,00257
20 min, 671 C
2Omill,877C
330
MlIctll,twIOlJJ
20 mill, 677 C
20 min,677 C
323
0.00254
0.00244
All Forrm
ITIlUl!l
20 m,n, 617 C
50
0.00257
951
0.00'244
1 hr,677C
17
0,00297
20 /TIIn, 611 C
2Omm,mC
29'
255
0.00209
2Om,n, 677 C
74
113
O'(l0232
0.00218
........
PIlI', 5twet,
.nd Stnp
Ptalf. Sheet,
and Strip
Tubtand Pip'
Rod, BIIr,
.1Id Hex
M,ICeIl.neotn;
All Forms
(Total)
All Forms
Pl.II. ShIft,
.1'Id Strip
AU Forms
31'
Pllltl.~,
31.
.nd Strip
All Forml
2Omm, mc
2Om,n,
mc
17
0.00297
2Om,n.8nC
Comm.An,..I"
Comm.. Ar....--I..
54
54
0.00274
OJXl274
Comm. MII8II.cI
Comm. Atm8lI.cI
32
32
0.00202
0.002fi2
..
,."
.."
737
0.00224
0.00224
0.00194
000204
O.oom
0.00228
0.00207
NOTE, The I ....~ rale for 101.1 lelU hu IIlde rnqnlnlli nci only I rew utopia willi waf1 hi&h ralts un distort tIlll OY~1
reMIl! wfnde:nll)' 10 m-lltc II mblndlnl- Ho ___ , u, order 10 ....swcr the question, Oycrln.Yenl,e ralQ were QI(ulllt\t rOt
aU nitric add lUll on Type 304L lutcd .ncr ooc bllur a' 6'77 C rOt wbich lxeCI ..11!1 wert ....il.bl". Th. oy",..lInaap for
SSrProdu(..... luts _. 0.00138 in/mo and for 1631 Ou Ponl taU wu O.OOIS6In/mo.
10
CORRQSIOIll- NACE
........
.".. _.------
"'-
_ _ ....._
nII
6 ...........
_ ._
-._
'"
*
J:
J
j.
,
),
-'
J:
I,
lp
,j.
+
j
------ - -
j'
...-
o.- ..... ~ ..
FIGURE 7 - Ou Pont ferric lftl diltl on

m1nll'" ill 671 C.
T'I~
_.'-_
304L .ft... 20
0 _____
...
....
-- .._............-
........""""~ "",!P''!l"'""::___ ~wl-' ....
...
FIGURE 8 _ Ou Pont t...,1c II1St diltll on Typtl316l aft ... 20

minut" ilt 671 C.
......... ,...
0 . . . . '_
_.
.....
a_ _ _
"
l'
l.
J.
I'
I'
I.
j.
,
,j:
1,
,
,
....
-~
..
-- .. -- .... -
--.~
FIGURE 9 - Producers 'a..1e lest cia" on Types 304L .nc!

3 16L .her onllHlur at f!i77 C 1.11 pllll, u,NI..net nrip!.
FIGURE 10 - Ferric: len d.11 oro T'f1N 304 Hcommlfc:ially

.ronulld 1.11 for"",l.
biased in that respect 10 an appreciable degree. Otherwise,

the results with the: two sensitizing limes 3re in quite
test, can be used 10 advantage fOI certain grades to screen

out a large proportion of the specimens which can be safely
accepted without th~ necessity of furtherl~sting.
satisfactoryagreemenl.
In order 10 provide some basis of typical performance
evaluation leSIS, average corrosi9n nlteJ have also been
calculated for speCimens of the various grlIdes which mel
the maximum aCct!pubJe values listed in Table 2 and for
which exact TBLC~S wer~ available In the data as suppli~d. Du
Pont data are on Ih~ testS only basis, Le.. . ~cimens which
wer~ screen~d by th~ oxalic etch test were not included.
The results are mown in T3bl~ 4.
In
General Conclusions
I. Practices B, C, D, and E .as described in ASTM
A262 ate reliable methods of simIlar sensitivity for the
det~ction of su$Ceptibility to intergranuJar allack In aus.
tenitic stainless steels due to lhe precipitation of chromium
rich carbides. The preferred method depends upon the
grade and intended use. Practice A, the oxalic acid etch
Vol. 30, No. I, JanWU'}', 1974
2. Correlation of thou~nds of nuric acid and fenic

sulfate lesl.$ with many years of service experience has
demonstrated that the acceptance limits listed in Table 2
are r~aliSlic and effective in guarding against the installation
of equipment which wouJd fail in service environments
capable of intergranularly attacking susc~plib )e matedal.
3. There is no justification for lhe specification of
th~se evaluatJon t~s1S as a basis for accepTance unless the
material represented is to be used und~r service conditions
..... htre it is known or stlspecl~d that susceplible mQ.I~,ia1
wouJd be inwgr.nularly attacked.
References
I. Recommended
granutar
PraetlCt
for Del1in& Susc:eptililit)' 10 Inler-
Atllclt In SlIinle5$ Steels. loST&.! .Dedarntion :
1.262-70. Published by Amedc:an SodeIY

~Ierials.
rOI
TwiJ'll. and
Phibdelphbl. P:J..
II
-'.
,.
I'
I:I,
l"
I:
j.
J
J
I
I.
FIGURE 11 - F.nlC lISt ula on Type 316

'.nn.-led (,II 10fmll.
*' oo",m.,(a.lly
.. - ..
---
FIGURE 12 - Du Pont d.lt. on Typ. 3041.. COmpB'lJOn 01

1_ m~hod, holAl .,nplI'SJ.
2. J, R. Auld. Effed OrHUI Ttalmc:ntlnd Wekhlllon Corrosion

Rc:dstancc of AltStenilic Stainlc:u Sleeb. P1oc. Sond bturtmriONlJ COlII'm 011 ,\ftttlllir Corrorton. I'll- 4"$-461 (1963).
1. Subeommitfee on Field !:Dnollon Testl; IntelJ.l1lnuw Corro
lIOn of Quomlum-NickeJ Suinless Sleet Final Report, WcldifW
Re_rch Council Bulletin t4o. 138 (1969) Fc:bnwy.
4. Rocommend!d PrtCI~ for CondUCIm, Addifted CoPpcf SuIr.lte Test for IntcJpam1lu Attack in Aultc:nltic 5wnlw Steel,
ASTM Ocsl,pulion 1\393-63. Published by American ,sc,c!ety
for Testing and Materiab. Pltibdc/phia, PL
S. M H Brown, W 8. DeLons. and W. R. Myers, An APPlllA! of
Methodl for E...1ualIn& tho Corrosion ReJisllnce of Stalnlc:u
SleelJ.ASTM STINo. 93, pp. 103-1 20 (1949).
6. L R. Sdwrftem and C. M Elsenbrown. An [n1ultlon of
Accelerated Stnuu Tutml. ASTM STP No. 369. pp. 235-239
(1963).
7. H. J. Roeha. Diseuwon of I PIper by . Bnll!.ns and C. Pier,
SuM WId EIsm, 75,519 (1955).
8. W. R. HueI'. Corrosion Test for ReSC:lrdl and In5ptction of
AUoY'. Thlnf. Am. Soc. Sud TrttJrllll. HI, 1126 C1930).
9. Report of Subcommittee IV on Method. of Corrosion TeRml,
hoc. Am. ,sot. Taulff .~/lItUUJ/f, 33, 187 (193]).
10. IN B OtLcn&- Teslinl Multiple Specimens or SlainIe:U Sleeis m
a lo4odlfied BoihTIJ Nillic Ten APPllf1l1US, ASTM STP No. 91.
pp. 211-2 14 (1949).
11. J. J. HtJel and J. L Hamiltoll. Couoffon. J I, 6 (1955).
11_ A. J. Ltna. DiKilUIOtt III: ThlIU. A&I,. 45,446 (195))_
I
I
I
I
I). M. A. Suekhtr. J. f/ffuochenl. Soc., 106. 161 (1959).

J4 M.. A. Sue.cher. IntelJllnu.lar CorrOMOn RCSI$t;linl.c of Auttenitk Slainl"I Sleds' A I'elrie SulfateSulfur .... Aod TCSI.
AS7,11 Huller/II /110. 219, pp. 17-86 f 1958) Api'll
U. D Wltren. Nitric-HydrofluorIc E.YIIllnluon Ten fur Type ]16l
Stainless Sleel, ASTM BullelUl No. ] If). pp. 4556 fl1I58) M~)'
16. M A Streithef. Screenl", Siainleu Steeh (rom thl: 240-Huul
Nitric Acid Tut by electro!),!lI. ltdll"l In O,~t<; A~td, AST.tl
IMlttlll No. 188, p. 15 (195]) Ftbl UIII)
11. Resulls or COOPCTltl'iC Tc\ul\I. PJOIf.m Cor b,lIlDlIl.ln or I~
Onhc: ACKI Etdl Test. ASTM /lI<flrftn
195, p. 6) (l9S4)
Janu:uy.
"'0.
18 R. S. Blenllln. E. '- du Pont de Ncm<JulSand Cu., V,llmirlf'on.

Deilwart, unpublished data.
19 J. S. Armijo. OJ/ tOf/On. 14, 1,14 (968).
20. K T, Ausl, J. S. AlmljO, and 1. H. Weubfook. AS.JI TnWL
QUlIrl.. 59.544 (966).
21 K. T AU51. T"'S-AJAlt, 24S, 2 111 11969),
22. M. H Bro .... n. 1::.. I. du Pont de Nemours I.nd Co . WllmillllOn.
Dclall.'l1c. unpublUhcd dall.
l). M. A, Strch:hef. ('omwotl,. 20.571 (964).
24 A. P W~Its. PhD Thc:s1S, Ohio SIIII: UnlH:fsity (1952).
25 s. M. 80" Ind F G, WiIJon. 1. 11'011 and Slnt 11111 2 10.118
(1972).
26. V Cihal, I. Kuova, and 1 Kubclu . 1. "'1.'11'111)( CorroJlrJn
Ifldusuln, 529, 281 (1969) September.
21. P. 5c:hwub, \10' Schwenk. and II Ternes.. Wt,blOf!r und
Konuliofl, 16,844 (1965).
...
12
CORROSION- N,\ CE
-'.
,.
I'
I:I,
l"
I:
j.
J
J
I
I.
FIGURE 11 - F.nlC lISt ula on Type 316

'.nn.-led (,II 10fmll.
*' oo",m.,(a.lly
.. - ..
---
FIGURE 12 - Du Pont d.lt. on Typ. 3041.. COmpB'lJOn 01

1_ m~hod, holAl .,nplI'SJ.
2. J, R. Auld. Effed OrHUI Ttalmc:ntlnd Wekhlllon Corrosion

Rc:dstancc of AltStenilic Stainlc:u Sleeb. P1oc. Sond bturtmriONlJ COlII'm 011 ,\ftttlllir Corrorton. I'll- 4"$-461 (1963).
1. Subeommitfee on Field !:Dnollon Testl; IntelJ.l1lnuw Corro
lIOn of Quomlum-NickeJ Suinless Sleet Final Report, WcldifW
Re_rch Council Bulletin t4o. 138 (1969) Fc:bnwy.
4. Rocommend!d PrtCI~ for CondUCIm, Addifted CoPpcf SuIr.lte Test for IntcJpam1lu Attack in Aultc:nltic 5wnlw Steel,
ASTM Ocsl,pulion 1\393-63. Published by American ,sc,c!ety
for Testing and Materiab. Pltibdc/phia, PL
S. M H Brown, W 8. DeLons. and W. R. Myers, An APPlllA! of
Methodl for E...1ualIn& tho Corrosion ReJisllnce of Stalnlc:u
SleelJ.ASTM STINo. 93, pp. 103-1 20 (1949).
6. L R. Sdwrftem and C. M Elsenbrown. An [n1ultlon of
Accelerated Stnuu Tutml. ASTM STP No. 369. pp. 235-239
(1963).
7. H. J. Roeha. Diseuwon of I PIper by . Bnll!.ns and C. Pier,
SuM WId EIsm, 75,519 (1955).
8. W. R. HueI'. Corrosion Test for ReSC:lrdl and In5ptction of
AUoY'. Thlnf. Am. Soc. Sud TrttJrllll. HI, 1126 C1930).
9. Report of Subcommittee IV on Method. of Corrosion TeRml,
hoc. Am. ,sot. Taulff .~/lItUUJ/f, 33, 187 (193]).
10. IN B OtLcn&- Teslinl Multiple Specimens or SlainIe:U Sleeis m
a lo4odlfied BoihTIJ Nillic Ten APPllf1l1US, ASTM STP No. 91.
pp. 211-2 14 (1949).
11. J. J. HtJel and J. L Hamiltoll. Couoffon. J I, 6 (1955).
11_ A. J. Ltna. DiKilUIOtt III: ThlIU. A&I,. 45,446 (195))_
I
I
I
I
I). M. A. Suekhtr. J. f/ffuochenl. Soc., 106. 161 (1959).

J4 M.. A. Sue.cher. IntelJllnu.lar CorrOMOn RCSI$t;linl.c of Auttenitk Slainl"I Sleds' A I'elrie SulfateSulfur .... Aod TCSI.
AS7,11 Huller/II /110. 219, pp. 17-86 f 1958) Api'll
U. D Wltren. Nitric-HydrofluorIc E.YIIllnluon Ten fur Type ]16l
Stainless Sleel, ASTM BullelUl No. ] If). pp. 4556 fl1I58) M~)'
16. M A Streithef. Screenl", Siainleu Steeh (rom thl: 240-Huul
Nitric Acid Tut by electro!),!lI. ltdll"l In O,~t<; A~td, AST.tl
IMlttlll No. 188, p. 15 (195]) Ftbl UIII)
11. Resulls or COOPCTltl'iC Tc\ul\I. PJOIf.m Cor b,lIlDlIl.ln or I~
Onhc: ACKI Etdl Test. ASTM /lI<flrftn
195, p. 6) (l9S4)
Janu:uy.
"'0.
18 R. S. Blenllln. E. '- du Pont de Ncm<JulSand Cu., V,llmirlf'on.

Deilwart, unpublished data.
19 J. S. Armijo. OJ/ tOf/On. 14, 1,14 (968).
20. K T, Ausl, J. S. AlmljO, and 1. H. Weubfook. AS.JI TnWL
QUlIrl.. 59.544 (966).
21 K. T AU51. T"'S-AJAlt, 24S, 2 111 11969),
22. M. H Bro .... n. 1::.. I. du Pont de Nemours I.nd Co . WllmillllOn.
Dclall.'l1c. unpublUhcd dall.
l). M. A, Strch:hef. ('omwotl,. 20.571 (964).
24 A. P W~Its. PhD Thc:s1S, Ohio SIIII: UnlH:fsity (1952).
25 s. M. 80" Ind F G, WiIJon. 1. 11'011 and Slnt 11111 2 10.118
(1972).
26. V Cihal, I. Kuova, and 1 Kubclu . 1. "'1.'11'111)( CorroJlrJn
Ifldusuln, 529, 281 (1969) September.
21. P. 5c:hwub, \10' Schwenk. and II Ternes.. Wt,blOf!r und
Konuliofl, 16,844 (1965).
...
12
CORROSION- N,\ CE
CORROSION
PolythionicAcid
POLYTHIONIC ACID
Skeletal formula of polythionic acid
Polythionic acid is an oxoacid which has

a straight chain of sulfur atoms and has the
chemical formula H2SnO6 (n > 2).
Trithionic acid (H2S3O6), tetrathionic acid
(H2S4O6) are simple examples. The
compounds of n < 80 are expected to exist,
and those of n < 20 have already been
synthesized. Dithionic acid (H2S2O6) does
not belong to polythionic acid due to the
difference in the property.
behaviour of H2S in aqueous solutions of

SO2 (1808). This solution now has the
name of Heinrich Wilhelm Ferdinand
Wackenroder, who conducted a systematic
study (1846). Over the next 6080 years,
numerous studies have shown the presence
of ions, in particular tetrathionate and
pentathionate anion (S4O62- and S5O62-,
respectively).
Preparation and Properties

Nomenclature
All polythionates anion contains chains of
sulfur atoms attached to the terminal
SO3H-groups. Names of polythionic acids
are determined by the number of atoms in
the chain of sulfur atoms:
H2S2O6 - dithionic acid

H2S3O6 - trithionic acid
H2S4O6 - tetrathionic acid
H2S5O6 - pentathionic acid, etc.
History
Numerous acids and salts of this group
have a venerable history, and chemistry
systems, where they exist, dates back to
the studies John Dalton devoted to the
In the last few decades in the work of

Schmidt and other scientists in Germany, a
new idea formed: as H2S can react with
SO3 or HSO3Cl, forming thiosulfuric acid
H2S2O3, as the analogous reaction with
H2S2 forms disulfonmonosulfonic acid
H2S2SO3H; similarly polysulfanes H2Sn (n
= 2-6) give HSnSO3H. Reactions from both
ends of the polysulfane chain lead to the
formation of polysulfondisulfonic acid
HO3SSnSO3H.
There are many known methods for the
synthesis of these acids, but the reaction
mechanism is unclear because of the large
number of simultaneously occurring and
competing reactions such as redox, chain
CORROSION
transfer, and disproportionation. Typical

examples are:
Interaction between hydrogen sulfide

and sulfur dioxide. This yields a
complex mixture of various oxyacids
of sulfur of different structures, called
Wackenroder solution.
H2S + H2SO3 H2S2O2 + H2O
H2S2O2 + 2H2SO3 H2S4O6 + 2H2O
H2S4O6 + H2SO3 H2S3O6 + H2S2O3
Reactions of sulfur halides with HSO3or HS2O3-, for example :

1. SCl2 + 2HSO3- [O3SSSO 3]2- +
2HCl
2. S2Cl2 + 2HSO3- [O 3SS2SO3]2 +
2HCl
3. SCl2 + 2HS2O3- [O3SS3SO3]2- +
2HCl
The oxidation of thiosulfate with mild
oxidizing agents such as I2, Cu2+,
S2O82-, H2O2, MnO2.
Various special methods of synthesis.
Dithionate ion is obtained by oxidation of

aqueous sulfur dioxide in a powder
suspension of manganese or iron oxide
(MnO2, Fe2O3):
MnO2 + 2SO2 MnS2O6
Trithionate ion synthesized by oxidation of
thiosulfate ions with hydrogen peroxide:
2S2O32- + 4H2O2 S3O62- + SO42- + 4H2O
Tetrathionate ion can be obtained by
oxidation of thiosulfate ion with iodine
(reaction is used in iodometry):
S2O32- + I2 S4O62- + 2IPentathionate ion is obtained by the action
of SCl2 on the thiosulfate ion and
Wackenroder solution by adding to it
potassium acetate. Initially prismatic
PolythionicAcid
crystals of potassium tetrathionate fall,

then lamellar crystals of potassium
pentathionate, from which the influence of
tartaric acid makes an aqueous solution of
pentathionic acid.
For potassium hexathionate K2S6O6 the
best synthesis action is combining KNO2
and K2S2O3 in concentrated HCl at low
temperatures.
Anhydrous polythionic acids can be
formed in diethyl ether solution by the
following three general ways:
1. HSnSO3H + SO3 H2Sn+2O6 (n = 1, 2
8)
2. H2Sn + 2SO3 H2Sn+2O6 (n = 1, 2
8)
3. 2HSnSO3H + I2 H2S2n+2O6 + 2HI (n
= 1, 2 6)
More complex polythionates, with the
number of sulfur atoms being 23, form by
reacting thiosulfate with SCl2 and S2Cl2.
Polythionic acids with a small number of
sulfur atoms in the chain (x = 3 - 6) are the
most stable. Polythionic acids are stable
only in aqueous solutions, and are rapidly
destroyed at higher concentrations with the
release of sulfur, sulfur dioxide and sometimes - sulfuric acid. Acid salts of
polythionic
acids
do
not
exist.
Polythionate ions are significantly more
stable than the corresponding acids.
Under the action of oxidants (potassium
permanganate, potassium dichromate)
polythionic acids and their salts are
oxidized to sulfate, and the interaction
with strong reducing agents (amalgam of
sodium) converts them into sulfites and
dithionites.
Occurrence
Polythionic acids are often found in crater
lakes. There are various kinds of ions
CORROSION
containing sulfur atoms derived by

hydrogen sulfide and they make the
strongly acidic conditions. It is observed
that polythionates in crater lakes are
PolythionicAcid
drastically decreased before an eruption

occurs. The phenomenon may be useful to
predict volcanic activity.
*********
Source:
ScrapedfromWikipedia
CORROSION
PolythionicAcidSCC
POLYTHIONIC ACID STRESS COROSSION CRACKING

The most common fluid causing intergranular
corrosion in hydrocarbon plants is polythionic
acid (they are weak sulfuric acids with the
formula H2SxO6, where x is usually 2 to
5). Both austenitic and straight chromium
grades of stainless steels can be attacked by
polythionic acid. This phenomenon is usually
an internal problem, occurring on the processexposed side of a piping run, vessel shell,
exchanger bundle, heater tube, etc. The
phenomenon usually starts with the stainless
steel surface forming a thin iron sulfide film
because of exposure to small amounts of sulfur,
usually from hydrogen sulfide in the process
stream. During a shutdown, in the presence of
air and liquid water, often dew point water, the
sulfides convert to polythionic acid. The
polythionic acid then corrodes the chromiumdepleted grain boundaries of the sensitized
alloy. Since stainless steels are usually supplied
to fabricators in the solution-annealed condition,
sensitization is usually confined to weld affected
zones.
ASTM G35 describes procedures for testing SS
in polythonic acids at room temperature to
determine relative susceptibility to intergranular
SCC.
POLYTHIONIOC ACID CORROSSION
CRACKING
DETERIORATION
MECHANISM
Heaters
used
in
hydrodesulfurization,
hydroforming, hydrocracking, and similar
processes often have austenitic stainless steel
tubes and usually process reactor feed or
recycled gas containing hydrogen sulfide and
sulfur compounds. The austenitic stainless steel
tubes in these services can be susceptible to
polythionic acid stress corrosion cracking.
Polythionic acids form from sulfide scales
exposed to oxygen and water in the stainless
steel that are sensitized which can occur in most
stainless-steel tube materials after exposures to
temperatures in excess of 700F to 1500F
(371C to 815C) during manufacturing,

fabrication or in service. Relatively short
exposure times are necessary to sensitize
stainless steels at the high end of the temperature
range while prolong exposure is necessary to
sensitize stainless steels at the lower end of the
temperature range. Generally, the risk of
cracking increases during downtime when water
and air are present. Cracking can be rapid as the
acid corrodes along the grain boundaries of the
stainless steel.
Cracking can initiate from either the inside or
outside of the tube. Cracking from the process
side is more common because the process often
contains sulfur compounds resulting in sulfide
scales. However, cracking can occur from the
tube OD if the firebox operates fuel rich and
there is sufficient sulfur in the fuel.
Preventive measures include using materials less
susceptible to sensitization, preventing acid from
forming, and neutralizing the acids. Specific
details are as follows.
a. Stabilized grades of stainless steel (e.g., Type
321 or Type 347) are more resistant to
sensitization but even these materials can
become sensitized after a longer exposure to
slightly higher temperatures. A thermal
stabilization heat treatment of a stabilized
grade of stainless has been shown to
significantly
improve
resistance
to
sensitization and thereby minimize the
potential for cracking.
b. Preventing oxygen and moisture exposure
will not allow the polythionic acid to form.
This can be accomplished by purging with an
inert gas, like nitrogen, and keeping the tubes
pressurized with it. When blinding is
required, a positive flow of inert gas should
be maintained while the flanges are open and
a blind is being installed. If desired, a small
amount of ammonia can be added to the inert
gas as a neutralizing agent. Maintaining a
CORROSION
PolythionicAcidSCC
positive flow of inert gas excludes air and

moisture.
c. A wash with a soda ash solution can
effectively neutralize acids and maintain a
basic pH. Soda-ash wash tubes crossovers,
headers, or other parts of the heater which
must be opened. The usual solution is a 2 wt.
% soda ash (Na2CO3) with a suitable wetting
agent. The solution should be circulated so
that all gas pockets are moved and all
surfaces are wetted. Sodium nitrate at 0.5 wt.
% may also be added to the solution to inhibit
chloride cracking. The solution may then be
drained and reused in piping or another
heater. The 2-percent solution contains
enough soda ash to leave a film, but a weaker
solution may not. The film is alkaline and can
neutralize any reaction of iron sulfide, air,
and water. It is important to remember that
the film, the residue from the soda-ash
solutions, must not be washed off during

downtime. Most units are put back on stream
with the film remaining. If the film must be
removed, flushing during start-up followed
by inert gas may be acceptable.
d. Preventing moisture exposure by maintaining
tube temperatures above the dew point will
also prevent acid from forming. This is
typically applied to external tube surfaces
which are not neutralized. Depending on the
dew point temperature, this may be
accomplished either by keeping pilots
burning during down times or keeping a
burner at minimum fire when access is not
needed and safety procedures allow. Tube
temperatures should be monitored to (Part 2)
ensure they are above the target dew point
temperature. These preventive measures are
described in detail in NACE RP 0170.
*********
CORROSION
PolythionicAcidSCCfromASMSpecialityHandbook

In the 1950S a form of Inter granular SCC
became recognized as a technological problem
in catalytic reformers used in the petroleum
Industry. Earlier studies (Ref. 132, 133) showed
that this form of attack occurred in the aqueous
condensates of reforming furnaces when
polythionic acids (H2SxO5 where X = 3, 4 or 5)
were present. Subsequently, this form of attack
became known as Polythionic Acid SCC. More
recent studies (Ref 134) have shown that of all
the polythionic acids, only tetrathionic acid
(H2S4O6) induces SCC in sensitized type 304.
Tetrathionic acid has also been shown to be the
critical species causing SCC of sensitized type
304 in tests employing sulfurous acids solutions
(Ref 135).
A Laboratory test for resistance to polythionic
acid cracking has been standardized as ASTM G
35. The solution is prepared by bubbling sulfur
dioxide and then Hydrogen sulfide through
distilled water. Stressed U-bend specimens are
often used in such tests, although any type of
SCC test specimen can be used. Excellent
correlation has been shown (Ref 133) between
polythionic acid cracking resistance as
determined by ASTM G 35 and inter granular
corrosion resistance, as determined by the
Strauss test (ASTM A 393) for a dozen different
austenitic stainless steels and higher alloys. An
example of this correlation in terms of cracking
topography surface diagram is shown in figure
38 (Ref 133). As a result of this study it is now
generally accepted that polythionic acid cracking
is a form of inter granular SCC linked to
sensitization. Accordingly, attempts to mitigate
this form of attack have included the
metallurgical remedies used to minimize
sensitization.
The technological problem encountered in the
petroleum industry is essentially as follows.
Stainless steel components are used at operating
temperatures that may be high enough to
sensitize the material. On subsequent shut down
of a refinery unit, polythionic acids may form by
the interaction of sulphur components, moisture

and air at low temperatures and attack the
chromium depleted boundaries. A combination
of operational procedures and metallurgical
remedies has been used to minimize polythionic
acid cracking during shutdowns. The operation
procedures
are
described
in
NACE
Recommended practice P-0107-85 and are based
on preventing the condensation of water vapour
or maintaining and alkaline environment by
additions of ammonia or sodium carbonate.
Among the metallurgical remedies that have

been tried is the use of low carbon grades (eg.
Type 304 L), the use of stabilized grades (type
321 or 347), and the use of higher nickel content
alloys such as Incoloy alloy 801. However, the
stabilized and the low carbon grades of stainless
steel can be sensitized at certain time
temperature combinations (Ref 1). Accordingly,
it has been recommended that low carbon grades
be used for operating temperatures below 4000C
(7500F), and that stabilized grades be thermally
CORROSION
PolythionicAcidSCCfromASMSpecialityHandbook
treated at temperatures of 9000C to 9250C

(16500F to 17000F) to ensure maximum
precipitation of carbon as titanium or niobium
carbides prior to services. In cases where
welding is necessary, a British practice has been
to weld the thermally stabilized (9200C or
16900F) type 321 and locally anneal the welds at
9200C (16900F). Higher nickel content alloys,

such as the titanium stabilized Incoloy alloy 801,
have been used in the United States. Weld
overlays, in the as deposited states, of several
austenitic stainless steels have been reported to
be resistant to Polythionic Acid SCC.
*********
Source:
Reproduced from ASM Specialty Handbook Stainless Steels by Joseph R. Davis
CORROSION
PolythionicAcidSCCQ&A
-Q&A
Question:
Answer:
Dear Experts,
Mr. Gandhi,
In one of our client project spec., it is specified

that SS 321 pipes shall be in a stabilized HT
condition. Stabilizing HT shall be carried out
subsequent to the normal solution annealing.
Soaking temp. & holding time for stabilizing HT
shall be 900 0C & 4 hrs respectively.
You may follow this earlier discussion on the

same subject in this forum.
(2) This stabilized HT pipe shall be solution

annealed after bending in coil form. Is it
allowed or again we shall have to carry out
stabilized HT after solution annealing?
Client Spec. asks for solution annealing HT
only after bending in coil form.
Stabilized /Non-stabilized Austenitic stainless

steels experience Polythionic Acid Stress
Corrosion Cracking (PASCC) in refinery
service. PASCC is a type of stress corrosion
cracking which occurs in refinery or even in coal
fired plant (burning high sulfur coal). PASCC
normally occurs during shutdowns, start-ups or
during operation when air and moisture are
present. Cracking is due to sulfur acids forming
from sulfide scale, air and moisture acting on
sensitized
austenitic
stainless
steels.
Sensitization is common in austenitic stainless
steels following welding or after prolonged
exposure to service.
Your prompt response on the above shall be

highly appreciated.
1. It usually occurs adjacent to welds or high

stress areas.
Thanks & regards,
2. Cracking may propagate rapidly (in a matter

of minutes or hours) through the wall
thickness of piping and component
My questions are
(1) What is the purpose of stabilizing HT?
C. R. GANDHI
The critical levels of sensitization and tensile

stress required to initiate PTA SCC are not well
understood. Therefore, austenitic stainless steel
and other austenitic alloy process equipment that
may be exposed to PTA should be protected
using one or more of the PTA SCC mitigation
methods presented in NACE-SP-170-2012(see
below).
(QCM)
Dye penetrant inspection showing extensive

O.D. cracking around weld
Equipments which will operate below the

sensitizing temperature range and the austenitic
material which has not been sensitized by any
prior fabrication practices (e.g., hot forming,
CORROSION
PolythionicAcidSCCQ&A
corrosion/sensitization test, i.e. ASTM A262

Practice C. or A262 Practice E (as
minimum) If not specified earlier, meeting
A 262 practice C would be really tough,
while practice E could be relatively easy.
welding, heat treatment) would not be the

suspects for PASCC.
A thermal stabilization heat treatment at 900C
(1650 0F) may be applied to chemically
stabilized austenitic stainless steels after welding
to
reduce
sensitization
and
PASCC
susceptibility.
For 321 stainless steels, the Ti:C stabilization

ratio shall be greater than or equal to 8.
Thermal stabilization heat treatment is

recommended for heater tubes and welds.
For 347 stainless steels, the Nb:C stabilization

ratio shall be within the range 10 to 12.
Between 321H and 347, the later performs

better in service following stabilization.
Stabilizing anneal fixes Ti (in 321H) or Nb (in

347) through formation of stable carbides e.g.
TiC or NbC. It leaves Cr in the solution, thus
without any deterioration of overall corrosion
resistance of 321 & 347 S.S.
As per ASTM (SA 213, S2), the stabilization

cycle is subjected to mutual agreement between
the purchaser and the supplier. However the
following is the recommended cycle to follow
(as per one of the oil giants).
It would be advisable to get material with

stabilization anneal done in the mill with the
MTR. Otherwise it may be a problem later.
Apply the following heat treatments:

Pradip Goswami, P. Eng, IWE
0
a) Solution annealing at 1040 1070 C for 1

hour per inch followed by water quenching
for 321/321H and 347/347H, and
Welding & Metallurgical Specialist

Ontario, Canada
b) Stabilization 850 900 0C for 4 hours

followed by rapid air cooling.
c) The adequacy of the above heat treatments
must be verified by an intergranular
pgos...@quickclic.net
pgos...@sympatico.ca
*********
Source:
web
CORROSION
SulphidationResistanceofSS
SULPHIDATION RESISTANCE OF STAINLESS STEELS
For practical considerations, sulphidation in

relation to high temperature attack of stainless
steels is more a consideration of the effects of
sulphur containing atmospheres, rather than a
specific attack mechanism. Both oxides and
sulphides may be formed depending on the
atmosphere, but generally the resistance to
sulphur containing gasses is related to chromium
content, in the same way as oxidation.
The combustion of high sulphur level fuel oils is
not normally considered hazardous to stainless
steels, provided there is sufficient oxygen
present to make conditions sufficiently
oxidising.
(446) and austenitic 1.4845 (310) heat resisting

grades can be considered up to 1025C and
1050C, respectively.
Affect of sulphur containing gas conditions hydrogen and hydrogen sulphide

Stainless steels with less than 20% chromium
may form less stable chromium sulphide 'scales'.
The 1.4845(310) grade (24-26% Cr in BS EN
10095) can be considered for hydrogen sulphide
environments.
Combustion atmospheres with sulphur

Affect of sulphur containing gas conditions sulphur dioxide
Dry sulphur dioxide is normally not considered a
hazard to stainless steels, although the scaling
rates are higher for a given temperature than in
dry air.
Damp sulphur dioxide is more aggressive, which
may be similar to the comparison of dry and
damp air oxidation.
Higher levels of chromium are beneficial in
resisting attack. Although there may be little
difference between grades like 1.4301 (304),
1.4401 (316) and 1.4845 (310) at around 7000C
in damp sulphur dioxide, these conditions can be
expected to compromise the resistance of 1.4301
(304) at 850C. Generally grades 1.4016 (430),
1.4301(304) and 1.4541 (321) can be considered
up to 800C in sulphur dioxide. Ferritic 1.4749
The sulphur levels in fuels such as natural gas

are low and so the combustion products of these
fuels are not a hazard to stainless steels, from the
point of view of sulphur content. High sulphur
oil combustion products may be a hazard and it
is not sensible to generalize on these.
Liquid sulphur and sulphur vapour

Liquid sulphur at up to 240C should not attack
stainless steels, but at its boiling point (445C),
liquid sulphur is very aggressive to 1.4301 (304)
type. Grades such as 1.4401(316) have some
resistance and may be useful under certain
conditions.
Sulphur vapour is very aggressive to stainless
steels but the higher chromium 1.4845(310)
grade may be worth considering.
*********
Source:
Web

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CORROSION

G31 calculating corrosion rates requires

Inches per month

Pressure Vessel Engineering

Millimeters per year

Micrometers per year

Milligrams per square Decimeters per day (mdd)

Grams per square meter per day

Table 3: Corrosion rate units with appropriate value of K

Mils per year (mpy)

Inches per year (ipy)

Inches per months (imp)

Millimeters per year (mm/y

Micrometers per year (m/y)

Picometers per second (pm/s)

Grams per square per hour (g/m2h)

Milligrams per square Decimeter per day (mdd)

Micrograms per square meter

Per second (g/m2 s)

Pressure Vessel Engineering

Monograph for mpy, ipy, ipm and mdd

involved. Density is given as grams per

Pressure Vessel Engineering

corrosion coupon material.

loss coupon method, but enjoys the great

Scraped from Corrosion of Austenitic Stainless Steels: Mechanisms, Mitigation

Pressure Vessel Engineering

INTERGRANULAR AND TRANSGRANULAR SCC

These zones also act as local galvanic couples,

The ASTM A923, ASTM A262, and other

Pressure Vessel Engineering

KNIFELINE ATTACK (KLA)

Aluminium-based alloys may be sensitive to

Pressure Vessel Engineering

orientation of atoms in each grain. In other

In this type of corrosion, a small volume of

Pressure Vessel Engineering

COMMON STRESS CORROSION CRACKING SYSTEMS

Water (Y.S > 1200 MPa)

Chloride (Y.S > 800 MPa )

Sulphide (Y.S > 600 MPa )

Pressure Vessel Engineering

Chloride (usually + H2S)

Pressure Vessel Engineering

Scraped from Stress Corrosion Cracking National Physical Laboratory

Pressure Vessel Engineering

Intergranular corrosion (IGC), also

or an improper heat treatment. When zones

Pressure Vessel Engineering

made of such steels have to be heated in a

grains, are especially prone to intergranular

Aluminium-based alloys may be sensitive to

Rapid attack at the grain boundaries can

Other kinds of alloys can undergo

Figure 1: Intergranular corrosion grain

Anisotropic alloys, where extrusion or heavy

Pressure Vessel Engineering

lines consist of carbides and corrosion

Heavily sensitized microstructure

Intergranular corrosion is generally

Pressure Vessel Engineering

Because the chromium is the primary

With austenitic stainless steels, intergranular

Figure 2: Chromium depletion at the grain