TECHNICAL AWARENESS BULLETIN

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FOCUS ON CAUSTIC STRESS CORROSION CRACKING

Corrosion in Caustic Solutions
Corrosion by caustic (sodium or potassium hydroxide) at
all concentrations is easily handled at room temperature
with a variety of metals and alloys, including carbon steels.
It becomes increasingly more corrosive with increasing
temperature and concentration. The useful safe limit of
carbon steel is approximately 150oF/65oC, with regard to
corrosion. With regard to the safe temperature for carbon
steel, the reader should look at the curve in Figure 1.
Stainless steels are more resistant to general corrosion
compared with carbon steel; however, they can suffer
Caustic Stress Corrosion Cracking (CSCC) at
approximately 250oF/121oC.
As a general rule, the resistance to caustic solutions
increases with increasing nickel content. Susceptibility to
caustic SCC depends on several variables including alloy
content, caustic concentration, temperature, and stress
level. As with other cracking mechanisms, there is a
threshold stress level where cracking will not occur;
unfortunately, the threshold level for the high nickel alloys
in high-temperature caustic has not been determined
precisely. Much data has been obtained on alloy 600 in
caustic environments because of its extensive use as
steam generator tubing in pressure water reactors (PWR).
Alloy 200 (pure nickel) is considered to be immune to all
but the most severe caustic environments, including
molten caustic.

Corrosion Resistance of Alloys to Caustic

Solutions
Carbon and Low Alloy Steels. Sodium and potassium
hydroxides (both hereafter referred to as caustic) are
commonly handled and stored at ambient temperatures in
all concentrations with carbon steel equipment. At
temperatures above ambient, corrosion rates of carbon
steel become greater and is accompanied by a risk of
CSCC. Low concentrations of caustic can be safely
handled by carbon steel up to 180oF/82oC, where CSCC
starts to become a risk factor, while the safe upper limit for
a 50% solution is approximately 120oF/48oC. The Caustic
Soda Service Chart (Figure 1) is a widely used guide for
determining safe operating temperatures with respect
CSCC of carbon steels at various concentrations of
caustic. The photomicrograph in Figure 2 shows caustic
cracking of a carbon steel pipe.

Ferritic Stainless Steels. The high purity ferritic

stainless steels, such as E-Brite 26-1 (UNS S44627),
exhibit excellent resistance to aggressive caustic solutions

with performance far superior to the austenitic stainless

steels and, reportedly, at least as good as nickel. This
superior resistance in some caustic solutions has been
attributed to the presence of hypochlorates or chlorate
contaminants, which are detrimental to nickel alloys. One
source reports that 26-1 is useful up to 300oF/148oC to
350oF/177oC. Another reports good resistance at
350oF/177oC - 400oF/204oC and 45% NaOH Based on
their good resistance to caustic, particularly those
containing oxidizing contaminants, they see extensive use
as caustic evaporator tubes. However, the Achilles Heel of
the ferritic stainless steels is the inherent poor toughness
of welded joints and low strength at elevated temperatures.
They are, therefore, not normally used for pressure vessel
applications.

Austenitic Stainless Steels. Researchers using

solutions of commercially pure caustic developed a
diagram that attempts to delineate the parameters of
concentration and temperature governing caustic
embrittlement, i.e., SCC of the 300 series austenitic
stainless steels. Figure 3 shows the chart developed. The
1 mpy isocorrosion line is constant at approximately 100C
from 20-60% caustic and the delineation for SCC is slightly
higher in the 40-50% range.
In actuality, it has been observed that there is a real
possibility that the type 300 series grades may lose their
passivity and undergo rapid general corrosion in hot 4050% caustic. Probable safe limits are well below those
indicated in the curve, e.g., 70C for 50% caustic and 80C
for 40% solutions.
The common service maximum temperature limit for
304/316 type stainless steel is 100C. Caustic cracking
can occur at higher temperatures. SCC of the 300 series
stainless steels is classically transgranular.

Duplex Stainless Steels. The duplex stainless steels

were developed to exhibit comparable general corrosion
resistance as 316SS, but with reduced susceptibility to
chloride stress corrosion cracking. The higher alloyed
duplex stainless steel alloys, ones with significant
molybdenum and nitrogen additions, can be superior to
316 SS in caustic environments. Grades 2205 and 2906
are reported to have useful caustic cracking resistance.

High Nickel Austenitic Stainless Steels. The high

nickel family of stainless steels are those containing
approximately 25-35 wt. % nickel, and include such nonpatented and proprietary alloys as 904L, Sanicro 28, alloy
20Cb-3, alloy 800, Al6-XN etc. With these alloys,

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 2012 Materials Technology Institute, Inc. All Rights Reserved.

resistance to aggressive (high temperature) caustic

solutions increases significantly compared with the 300series stainless steels.

Nickel Alloys. Commercially pure nickel, alloy 200

(N02200) and alloy 201 (N02201) are the best materials
for resisting corrosion and stress corrosion cracking in
caustic environments. Alloy 400 (N04400) and alloy 600
(N06600) also have excellent stress corrosion resistance.
These alloys can however suffer from caustic stress
corrosion cracking at caustic concentrations above 70% at
temperatures above 290C (550F). The Ni-Cr-Mo alloys
such as C-276 (N10276) also have useful caustic cracking
resistance, however are susceptible to caustic cracking at
high concentrations and temperatures. Figure 4 shows the
SCC range of nickel and other nickel alloys.

Figure 2. Caustic stress corrosion crack in carbon

steel. (MSR Photo)

Figure 3. Caustic stress corrosion cracking

susceptible regions of 300 series SS

Figure 1. Caustic service chart for carbon steel.

Recommended Reference:
MTI Publication MS-6, Material Selector for
Hazardous Chemicals -Ammonia and Caustic

The technical contributions of Hira Ahluwalia for MTI are

graciously acknowledged.

Figure 4. Caustic stress corrosion cracking range of

Nickel and other alloys.

Originally published: November 2008

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 2012 Materials Technology Institute, Inc. All Rights Reserved.