What is Sensitization? | No.

26

What is Sensitization? Sensitization is a concern in the refining and

Sensitization refers to a zone of chromium chemical industries, and it also comes up in the
depletion at grain boundaries associated with nuclear industry.
carbide precipitation in certain corrosion resistant
alloys, causing the alloy to be susceptible to
intergranular corrosion and stress corrosion Carbide Precipitation – The Basics
cracking. When susceptible alloys are heated in the 800-
1500°F (425-815C) temperature range, chromium
A key thing to remember is that carbide and carbon in the alloy form chromium carbides
precipitation occurs only at high temperatures that precipitate in the grain boundaries typically as
where no aqueous phase can be present, but the Cr23C6.
resulting corrosion/cracking only happens at lower
temperatures in the presence of aqueous Chromium carbide formation ties up significant
conditions. The carbide precipitation associated amounts of Cr in and near the grain boundaries,
with sensitization has almost no effect on any high thus rendering the matrix in a narrow region at the
temperature mechanical properties or on high grain boundary low in Cr content, relative to the
temperature corrosion rates. Furthermore, room bulk composition, and susceptible to corrosion and
temperature ductility loss due to carbide SCC, see Figure 2.
precipitation is normally not significant.

All the 300-series austenitic stainless steels, 400-

series ferritic stainless steels, many other
chromium-containing austenitic alloys and some
nickel base alloys are susceptible.
Figure 2: Cr-carbide precipitation at grain boundaries
and Cr-depleted zones.

Carbide precipitation can occur during welding, hot

forming, heat treatment, or any other temperature
excursion into the sensitizing temperature range,
which varies from alloy to alloy.

Sensitization can occur within seconds-minutes for

standard versions of the austenitic stainless steels
(304, 316) as compared to the low carbon versions
(304L, 316L), see Figure 3 for the 304 stainless
steel alloy family. Alloys with higher carbon
Figure 1: Cracking of stainless steel due to sensitization.
Used with the kind permission of NACE. contents such as 304H and 347H, which are
optimized for high temperature creep strength,
sensitize even faster and more severely than lower
carbon versions such as 304, 304L and 347.
The distribution of MTI documents to non-member companies is done as a service to industry. MTI assumes no responsibility for the contents or for
results associated with implementing any recommendations. Copyright © 2019 Materials Technology Institute, Inc. All Rights Reserved 26-4/19
 than the chromium carbide precipitation
temperature range. The stabilizing carbides tie up
carbon in the alloy, thus reducing the amount of
carbon available to precipitate as chromium
carbides and hence reducing the formation of Cr-
depleted grain boundaries. When the stabilized
grades are given a stabilizing heat treatment, they
can resist sensitization for much longer time
Figure 3: Time-temperature-sensitization curves for periods (months to years). To achieve optimum
austenitic 304 family. Ref: Nickel Institute Publication. stabilization these steels are first given a full
solution anneal followed by a stabilizing anneal in
the temperature range of 1800 to 1600 °F (982 to
Effect on Corrosion Resistance
The real problem with sensitization is that the 871 °C).
precipitation of grain boundary chromium carbides Unfortunately, all the mentioned alloys will
removes chromium from the alloy immediately eventually sensitize to one degree or another on
adjacent to the grain boundaries. The resulting long-term heating (hours-years) in the sensitizing
chromium-depleted grain boundaries are temperature range. This includes 347 SS and 347H
susceptible to enhanced localized corrosion or SS. Prolonged heating in the lower part of the
cracking in very specific aqueous environments, sensitizing range is the most dangerous for
see Figure 4. sensitization.

Prolonged heating (months-years) in the upper part

of the sensitizing temperature range can lead to a
type of "healing" of the sensitized condition. This
healing occurs as chromium diffuses from farther
away into the chromium-depleted zones along the
grain boundaries. The infusion of chromium
restores grain boundary corrosion resistance. We
sometimes see this in stainless steel furnace tubes
Figure 4. Schematic of corrosion attack of sensitized that operate continuously for years in the
alloys. sensitizing temperature range.

Corrosive environments which can readily attack Detecting the Susceptibility of Intergranular
sensitized grain boundaries include hot strong Attack in Austenitic Stainless Steels
oxidizing acids, such as hot nitric acid and sulfuric When sensitization is a concern the material in
acid, and intermediately oxidizing sulfur acids, such question can be tested to determine its
as sulfurous acid and polythionic acids. susceptibility to intergranular attack. Test methods
for evaluating austenitic stainless steels include
Resistant Alloys metallographic methods such as ASTM A262
Stabilized alloys such as 347 SS (stabilized with Practice A, corrosion tests such as ASTM A262
niobium) and 321 SS and Alloy 825 (both stabilized Practices B, C, E, and F and electrochemical
with titanium) were developed to resist sensitization methods such as ASTM G108.
during short-term (1-2 hours) heating, such as
occurs during welding, hot forming and heat These tests are designed to detect sensitization in
environments that could cause corrosion or stress
treatment. Stabilizing additions of Nb, Ta, and Ti
corrosion cracking of equipment being placed into
readily form their own carbides when the material is service. Material that fails the selected test may not
heated into their precipitation temperature ranges, be safe to put into service.
which are generally at a little higher temperature
Updated August 2019
The distribution of MTI documents to non-member companies is done as a service to industry. MTI assumes no responsibility for the contents or for
results associated with implementing any recommendations. Copyright © 2019 Materials Technology Institute, Inc. All Rights Reserved 26-4/19