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MATERIALS SELECTION & DESIGN

Corrosion of stainless steel by hot caustic

Research using solutions of


chemically pure caustic (sodium 600 8 &
1 1 I
hydroxide [NaOH]) led to the
development of a diagram that
attempts to delineate the param-
eters of concentration and tem- 500 - Stress cracking zone -
perature governing stress
corrosion cracking (SCC) of type
300 series austenitic stainless steels
(SS), such as types 304 (UNS
Apparent SCC boundary
S30400), 316 (S31600), and their
low-carbon forms, types 304L
(S30403) and 316L (S31603). This
diagram (Figure 1) is analogous to
a similar diagram for caustic
embrittlement of carbon steel un-
der stress from welding or cold-
forming. The term caustic
embrittlement is a misnomer be-
cause the phenomenon is simply
SCC of steel in the alkaline
solution.
The 1 mpy (0.0254 mm/y)
isocorrosion line in Figure 1 is
nearly constant at 100C (212F)
from -20% to 50% caustic. The
dashed line delineating SCC (la-
beled Apparent SCC boundary) is
U-shaped, with the minimum at
-40% caustic and -240F (115C).
In actuality, there is a real 0 20 40 60 80
possibility that type 300 series SS
NaOH (wt%)
may lose passivity and undergo
rapid general corrosion in hot FIGURE 1
40% to 50% caustic. Probable safe lsocorroslon diagram for type 300 series austenitlc SS in NaOH (caustic).

limits are well below those indi-


cated by the diagram, perhaps
70C (158F) for 50% caustic and Above 300C (570F), the dan- is encountered, there is a charac-
80C (177F) for 40% solution. ger of caustic SCC is very great. teristic gunmetal blueing of the
However, oxidizing contami- Bellows-type piping expansion surface.
nants can maintain passivity. joints made of type 321 (S32100, Fe- The role of chlorides in caustic
Extra-low interstitial ferritic SS 18% Cr-10% Ni-Ti stabilized) in cracking is often misunderstood.
grades, such as alloy 26-l 300-lb to 400-lb steam (-215C to Chlorides, if present, are not a
(S44627), have been used instead 230C [QOF to 445F]) are prone to factor. There have been failures of
of Ni (UNS N02200) in caustic rapid SCC if there is entrainment of alloys 800 (NOSSOO, Fe-30% Ni-20%
evaporators provided the chlor- caustic from boiler treatment. When
ate content is sufficiently high. high-temperature caustic SCC of SS

64 MP/January 1998
MATERIALS SELECTION & DESIGN
NACEREPORT
i Phorgotten Phenomena Reference
<Ollh,llrd frO,?l{"Z,yCbi I J K. .lelwn. M,~termls ot Cmstructmn tar Alka-
lies md Hypochlorites, in Process lndustms Cor-
Cr) and 825 (N08825, Fe-40% roz~n-k Throw mJ Practice. cds. 13.1.Llonu.
1Y.I. Poilock (Hw&, TX. -LACE. l%h), p. XIU.
Ni-2096 Cr-3% MO-~% Cu), high-
Ni alloys that are very resistant to
Corrosion Scientists,
chloride SCC, used as replace-
ments for type 300 series SS. Rus- Engineers, Practitioners...
Sian investigators reported that S/fare your Plmgotten Phe~mmerux
chlorides, a common contaminant iterlzs zuitll your colleayues. Articles
in concentrated caustic, do not sliodd be 1,000 zuords or 1ess;photos
md drmings me nppreciated. Srnd
Impressed Current
aggravate SCC and may even play
an inhibitive role. subnzissions to Warren 1. Pollock, MP
Alloy 600 (N06600, Ni-15% Tecllnicrzl Editor, NACE, P.0. Bus
Anodesfor Underground
215340, Houston, TX 77215-8340.
CathodicProtection
Cr-8% Fe ) is satisfactory in hot
caustic service. For bellows, alloy
625 (N06625, Ni-20% Cr-8% Mo-Cb Systems is now
available.
stabilized) is currently used almost C.P. Dillon is the 1998 NACE International T.J.
exclusively. Hull Award recipient for his outstanding con-
tributions In the field or puhlicatlons. He is the
C.P. Dillon, FNACE author oi Corrosion Control in the Chemical
C.P. Dillon 0 Associates Process Industries, 2nd Edition (St. Louis, IMO:
940 Park Street MTI, lYY;~, now in its second printing. This This new consensus-approved
St. Albans, WV 25177 book is available irom NACE. technical committee report pro-
vides an overview of impressed
current anode materials for those
new to the cathodic protection field
and serves as a reference for more
experienced personnel.

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