Corrosion of Carbon Steels in Caustic Soda

Corrosion of Carbon Steels in Caustic Soda
Graph showing corrosion resistance of carbon steel, stainless steel and nickel alloys
in caustic solutions, based on temperature and concentration.
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, both with regard to caustic stress corrosion
cracking (CSCC) and corrosion. Stainless steels are more resistant to general
corrosion compared with carbon steel; however, they can suffer CSCC at
approximately 250oF/121oC.
As a general rule, the resistance to caustic solutions increases with increasing nickel
content. Susceptibility to caustic SCC is dependent 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.
Literature corrosion data for other nickel-based alloys is more difficult to find. This is
partly due to the fact that many nickel-based alloys, (i.e., alloys 625, C-276, B-2),
contain significant quantities of molybdenum for resistance to aggressive acid
solutions. As the molybdenum containing nickel-based alloys are more expensive
than comparable nickel content alloys without molybdenum (alloy 600), and
molybdenum does not significantly contribute to caustic resistance, they have not
been studied much.Another difficulty with ranking alloys for caustic service based
strictly on nickel content is the dual problem one has with caustic, i.e., it can cause
general corrosion and well as SCC.
Also, depending on caustic concentration, temperature and other environmental

factors, including whether oxygen is present or not, ranking of alloys can change.
This is true of alloys 800 and 600. Table 1 shows alloys with useful resistance to
caustic, categorized by resistance limits. The table is based on literature corrosion
information and is believed to represent conservative maximum temperature and
concentration limits. However, when in determining whether a specific alloy will
provide resistance in caustic service, the environment must be known well or testing
should be conducted.
Corrosion Resistance of Alloys to Caustic Solutions

Carbon and Low Alloy SteelsSodium 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
caustic stress corrosion cracking (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 150oF/65oC,
although cracking has occurred at temperatures as low as 120oF/48oC.
The Caustic Soda Service Graph 1 is a widely used guide for determining safe
operating temperatures with respect CSCC of carbon steels at various
concentrations of caustic. Ferritic Stainless SteelsThe 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 2. This superior resistance in some caustic
solutions has been attributed to the presence of hypochlorates or chlorates
comtaminants, which are detrimental to nickel alloys 3.
One source reports that 26-1 is useful up to 300oF/148oC to 350oF/177oC 4. Another

reports good resistance at 350oF/177oC - 400oF/204oC and 45% NaOH 5. 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 inherent poor toughness of welded joints and low
strength at elevated temperatures; therefore, they are used not normally used for
pressure vessel applications.
Austenitic Stainless SteelsAustenitic (300 series) stainless steels possess good

resistance to caustic up to approximately 50% and temperatures about 200 oF/93oC.
At, and above 200oF/93oC, the austenitics exhibit unstable passivity and can suffer
severe general corrosion if activated. Above approximately 250 oF/121oC they are
susceptible to SCC (see Figure).
No distinction is made between 304SS and 316SS regarding resistance to caustic as

their behaviors are similar. They are also susceptible to chloride SCC if substantial
chlorides are present in low grade caustic.
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 316SS in certain
environments. High Nickel Austenitic Stainless SteelsThe high nickel family of
stainless steels are those containing approximately 25-35 wt. % nickel, and include
such non-patented and proprietary alloys as 904L, Sanicro 28, alloy 20 Cb-3, alloy
800, etc. With these alloys, resistance to aggressive (high temperature) caustic
solutions increases significantly compared with the 300-series stainless steels.
Meaningful corrosion resistance data is available for alloy 800, much less for the
other alloys listed here; therefore, the discussion on the resistance of this family of
alloys will concentrate on alloy 800.
Although it is not possible to rank the above alloys listed, and resistance will vary
between them, based on their similar nickel contents, similar order-of-magnitude
resistance between the alloys can be inferred. Most studies of the highly alloyed
stainless steels and nickel-based alloys have been based on determining
susceptibility to caustic SCC.
This would infer that, with these alloys, CSCC is more important as a potential failure
mechanism than general corrosion at moderate temperatures. CSCC is also more
critical as general corrosion can be observed and monitored, while CSCC is
insidious, causing unexpected failures.
Based on limited data, alloy 800 should possess satisfactory resistance to caustic
solutions of 50% up to 225oF/107oC 6 . It has been made to crack in molten caustic at
600oF/315oC. Between these two temperatures, the data becomes more muddled.
According to one source 2, the general corrosion rate of alloy in simulated first-effect
caustic liquor (43% caustic) at 300oF/148oC is excessive (>39mpy) 7. Other, non
published data, suggests that alloy 800 may be resistance to SCC at 500 oF/260oC in
10% caustic but not in a 50% solution.
Another source suggests that the corrosion rate of alloy 800 in boiling 50% caustic
(300oF/148oC) is excessive (39 mpy).Based on the above data, a recommended safe
use of alloy 800 is 50% caustic at approximately 250oF/121oC, based on general
corrosion. It may exhibit a higher temperature limit, based on CSCC. Its use,
predicated on periodic inspection for SCC, is not recommended as are alloys 400,
600 and 690, because when it has cracked the time to cracking was very short (14
days), while the time to cracking of alloys 600 and 690 were much longer.Nickel-
based AlloysThe nickel based alloys under consideration include alloys 400, 600,
200, 625, C-276 and B-2. Alloys 200, 400, 600 and 690 have historically been the
materials of choice for aggressive caustic service and possess excellent resistance
to caustic over a wide range of temperatures and concentrations.
Based on nickel content, all of the listed alloys should possess good resistance to
high-temperature, concentrated caustic solutions. However, little data is available for
alloys 625, C-276 and B-2. Available data for alloy B-2 suggests that it is resistant to
all concentrations of caustic up to 70% at 250oF/121oC, with corrosion rates of less
than 2 mpy 8. In boiling 60% caustic (328oF/164oC) and boiling 70% caustic
(375oF/190oC) the corrosion rate was less than 20 mpy. C-276 suffered CSCC in
boiling 50% caustic (300oF/148oC) when cold reduced to 60% and did not crack in
the mill annealed condition. In 30% caustic at 550oF/287C, C-276 experienced high
corrosion rates (>42 mpy). The same data suggests that alloys C-22, C-276 and B-2
should be resistant to CSCC in boiling 50% caustic.Above 70% caustic at
temperatures greater than 300oF/148oC nickel is the preferred choice, as alloys 400,
600, and 690 may experience excessive general corrosion rates.

Corrosion of Carbon Steels in Caustic Soda

Uploaded by

Copyright:

Available Formats

Corrosion of Carbon Steels in Caustic Soda

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Corrosion of Carbon Steels in Caustic Soda

Uploaded by

Copyright:

Available Formats

What materials are suitable for handling caustic solutions at room temperature?

What is the safe temperature limit for carbon steel in caustic solutions?

Corrosion of Carbon Steels in Caustic Soda

Corrosion in Caustic Solutions

Also, depending on caustic concentration, temperature and other environmental

Corrosion Resistance of Alloys to Caustic Solutions

One source reports that 26-1 is useful up to 300oF/148oC to 350oF/177oC 4. Another

Austenitic Stainless SteelsAustenitic (300 series) stainless steels possess good

No distinction is made between 304SS and 316SS regarding resistance to caustic as

Duplex Stainless Steels:

You might also like