Caustic Stress Corrosion Cracking | No.
13
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 40-50% 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 Figure 1. Caustic service chart for carbon steel.
containing approximately 25-35 wt. % nickel, and
include such non-patented and proprietary alloys
as 904L, Sanicro 28, alloy 20Cb-3, alloy 800, Al6- Recommended Reference:
XN etc. With these alloys, resistance to aggressive MTI Publication MS-6, Material Selector for
(high temperature) caustic solutions increases Hazardous Chemicals -Ammonia and Caustic
significantly compared with the 300-series The technical contributions of Hira Ahluwalia for MTI are
stainless steels. graciously acknowledged.

Nickel Alloys. Commercially pure nickel, alloy 200 Originally published: November 2008
(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)

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.
 Figure 3. Caustic stress corrosion cracking susceptible
regions of 300 series SS

Figure 4. Caustic stress corrosion cracking range of Nickel

and other 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.