highchrom.
qxp 10/15/2004 8:57 AM Page 1
HIGH-CHROMIUM
RESISTS AQUEOUS
ALLOY CORROSION
Improvements in alloy metallurgy,
melting technology, and thermo-
mechanical processing led to
development of Alloy 31,
a relatively low-cost alloy with
high corrosion resistance.
D.C. Agarwal*
ThyssenKrupp VDM USA Inc.
Houston, Texas
A
n advanced super-austenitic, high-
chromium 6 Mo alloy called alloy 31
(UNS N08031) bridges the cost/per-
formance gap between high-perform-
ance Ni-Cr-Mo alloys and the 300 series stainless
steels. It is especially suitable as a material of con-
struction for the modern chemical process and
petrochemical industries, where materials must
not only resist uniform corrosion caused by a
range of corrodents, but also must have effective
resistance to localized corrosion and stress corro-
sion cracking in halide and other media.
This article describes the development of Alloy
31, its physical metallurgy, corrosion resistance,
and a few of its many applications in various in-
dustries over the past 15 years.
Effects of molybdenum and nitrogen
Engineers have long known that chromium
and molybdenum improve resistance to localized
corrosion. They also have long known that in-
creased amounts of nickel and nitrogen enhance
resistance to chloride stress corrosion cracking.
This knowledge led to a class of alloys that were
very cost effective and provided corrosion resist-
ance that in many cases approached or equaled
the corrosion resistance of more expensive high
Ni-Cr-Mo alloys in many environments. Cronifer
1925hMo (UNS N08926) was derived from the
904L alloy, and Nicrofer 3127hMo (UNS N08031)
was derived from alloy 28 metallurgy, by in-
creasing the molybdenum content to 6.5% and
fortifying the composition with 0.2% nitrogen.
The addition of nitrogen provided the added ben-
efits of improved localized corrosion resistance,
stronger mechanical properties, and higher
thermal stability.
Alloy 31, known as the advanced 6 Mo alloy,
is the higher-chromium-and-nickel version, and
imparts significantly improved corrosion resist-
ance in a variety of media. Its localized corrosion
resistance is superior to many alloys, including the
*Member of ASM International
ADVANCED MATERIALS & PROCESSES/NOVEMBER 2004
Ni-Cr-Mo alloy 625, as shown
per ASTM G-48 testing. Its
uniform corrosion resistance
in sulfuric acid in the medium
concentration range is supe-
rior to even that of Alloy C-
276 and alloy 20. As a result,
the 6Mo alloys have been ap-
plied extensively in pulp and
paper production, phos-
phoric acid production,
copper smelters, and sulfuric
acid production/reclamation.
Weldability: The alloy
1925hMo, a standard 6Mo
alloy, is readily weldable
with over-alloyed filler metals
such as alloy 625, C-276, or 59.
These filler metals compen-
sate for the segregation of
molybdenum into the inter-
dendrite regions of weld-
ments. On the other hand,
Alloy 31 is welded only with
alloy 59, except for applica-
tions such as chlorine-dioxide
bleach washers in the pulp Tank truck is constructed of alloy 31 for
and paper industry. transporting extremely corrosive liquids.
Alloy 31 is also frequently selected for equip-
ment in pollution control and in the production
of phosphoric acid, rayon, and specialty chemi-
cals. Its resistance to salt water corrosion has made
it successful in marine and offshore applications,
pickling baths, and heat exchangers for which
seawater and brackish water act as coolants.
One recent application of Alloy 31 has been
in the pressure acid leaching process of recov-
ering nickel from the lateritic ore deposits in Aus-
tralia. Many hundreds of tons of this alloy have
been used in this technology.
Alloy optimization
Table 1 shows the basic chemical composition
of Alloy 31 compared with other alloys that mit-
igate aqueous corrosion. It has half the nickel con-
tent of alloy 625, with lower amounts of molyb-
denum. However, its localized corrosion
resistance is superior to that of alloy 625. Nickel
has been kept as low as possible for reasons of
cost, while retaining a fully austenitic structure.
At the same time, nitrogen has been added to im-
prove the stability of this austenitic structure, to
increase resistance to localized corrosion, and
to improve mechanical properties. The chromium
and molybdenum levels are the highest possible
to still be consistent with a fully austenitic alloy.
Continued
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Corrosion properties ASTM coverage.

Alloy 31 has excellent resistance to localized
corrosion in halide media, both pitting and crevice
corrosion. It also provides:
Outstanding resistance to sulfuric acid.
Excellent resistance to phosphoric acid.
Good resistance to nitric and nitric/hydro-
fluoric acid mixtures.
Excellent resistance to chlorine dioxide media
in the pulp and paper industry.
Excellent resistance to both oxidizing and re-
ducing media.
Good resistance to stress corrosion cracking.
ASME SCVIII Div 1 coverage to 430C
(800F).
NACE MRO-175 coverage to level 6.
Excellent fabricability with good thermal
stability.
Resistance to acids
Sulfuric acid: Table 2 gives the uniform cor-
rosion data at various concentrations and tem-
peratures. As is evident , Alloy 31 exhibits ex-
cellent corrosion resistance in dilute and medium
concentration up to 100C (212F). At concentra-
tions greater than 80% and at 100C (212F) and
over, the alloy becomes active. However, in the
presence of oxidizing species such as ferric ions,
the range of Alloy 31 passivity can be expanded.

Table 1 Metallurgical optimization of Alloy 31 vs. some other alloys

Alloy Ni Cr Mo Fe Others PRE*
316L 12 17 2.3 66 24
904L 25 21 4.8 48 Cu 37
1925hMo 25 21 6.5 46 Cu, N 48
20 38 20 2.4 34 Cu, Cb 29
825 40 22 3.2 31 Cu 32
28 31 27 3.5 36 Cu 38
31 31 27 6.5 32 Cu, N 54
G-3 48 23 7 20 Cu, Cb 45
G30 45 29 5 15 Cu,W,Cb, Ta 45.5
625 62 23 9 3 Cb 52
C-276 57 16 16 5 W 69
59 59 23 16 <1 76
*PRE = Pitting Resistance Equivalent = % Cr + % (3.3 Mo) + 30N

Table 2 Corrosion rate in sulfuric acid at various temperatures in mils/year

H2SO4 60C (140F) 80C (175F) 100C (210F)
Alloy Alloy Alloy Alloy Alloy Alloy Alloy Alloy Alloy
Percent, % 20 C276 31 20 C276 31 20 C276 31
20 <5 <1 <0.1 10 4 <0.1 >25 >1 0.3
40 <5 <2 <0.1 10 3 <0.2 >25 10 0.6
60 >5 <2 <0.1 11 4 0.4 >50 11 1
80 5 <1 0.2 18 15 0.8 >50 240 240

Table 3 Corrosion rate of various alloys in phosphoric acid in mm/year

Test media Temp., C Alloy 31 Alloy 926 Alloy 28 Alloy G-3 Alloy 30
52% P2O5 + Impurities 80 0.02 0.06 0.08
120 0.78
52% P2O5 Very pure 116 0.08 (1) 1.2 0.28 0.10
30% P2O5 + Impurities 80 0.015 0.03
44% P2O5 + Impurities 116 0.55 0.18
54% P2O5 + Impurities 116 0.05 (1) 1.4 0.40 0.20

Table 4 Critical pitting and crevice corrosion temperature

Critical pitting Critical crevice Pitting resistance
Alloy corrosion temp., C (F) corrosion temp., C (F) equivalent (PRE)**
316 15 (60) <0 (32) 24
904L 45 (113) 25 (77) 37
20 15 (59) <10 (50) 29
825 30 (86) <5 (41) 32
G-3 70 (158) 40 (104) 45
1925hMo 70 (158) 40 (104) 48
625 77.5 (171.5) 57.5 (135.5) 52
33 85 (1850 40 (104) 50
30 75 (167) 50 (122) 46
31 85* (185) 65 (149) 54
Per ASTM G-48 (10% FeCl3 ) * Above 85 C, the 10% FeCl3 solution chemically breaks down ** PRE = 5%Cr + 3.3(%Mo) + 30N

26 ADVANCED MATERIALS & PROCESSES/NOVEMBER 2004

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Hydrochloric acid: In hydrochloric acid, Alloy
31 is resistant at room temperature up to a con-
centration of 8%, with corrosion rates below the
0.13 mm/y (5 mpy).
From 8% HCl to 40% HCl, the corrosion rate at
room temperature is between 0.13 and 0.5 mm/y
(5 mpy to 20 mpy).
At a higher temperature of 80C (175F), the
alloy is resistant up to 3% concentration. Hence,
in many chemical processes where only traces of
HCl are present, Alloy 31 presents a good alter-
native over more expensive nickel alloys of the
B or C family that contain higher amounts of
molybdenum.
Nitric acid: Tests were conducted in 67% boiling
HNO3 (Huey test). Even after ten boiling periods
of 48 hours each, Alloy 31 exhibited a very low cor-
rosion rate of only 0.1 mm/y (4 mpy).
On welded samples (filler metal was alloy 625),
the corrosion rate increased to 0.2 mm/y (8 mpy),
still an acceptable rate. Despite the high molyb-
denum content of 6.5%, it exhibits excellent re-
sistance in strongly oxidizing media.
Phosphoric acid: Laboratory tests in synthetic
phosphoric acid media with no solids present
(Table 3) did indeed confirm that the corrosion
resistance of Alloy 31 was superior to those of al-
ternative alloy 926 (UNS N08926, a standard 6Mo
alloy) and alloy 28 (UNS N08028). It was compa-
rable or even better than alloy G-30 (UNS
N06030). These tests also confirmed that corro-
sion of metals in phosphoric acid could increase
rapidly at or above a certain threshold tempera-
ture, which appears to be around 120C (250F).
Actual plant coupon tests in wet phosphoric
acid also confirmed the superior behavior of Alloy
31 over alloy G-30. A current application with ap-
proximately 780 tubes in concentrated 46% to 54%
P2O5 is demonstrating excellent performance. The
plant saved over $100K by selecting Alloy 31 as
the heat exchanger material over alloy G30.
Pitting/crevice corrosion
One of the key service criteria after uniform
corrosion is the ability to resist pitting and crevice
corrosion in the process side, which is primarily
acidic low pH with chlorides. ASTM G48 is one
of the standard laboratory tests established to
evaluate this type of corrosion, and it is being in-
creasingly applied in specifications for sea/off-
shore and sour gas applications. The higher the
critical pitting temperature (CPT) and crevice cor-
rosion temperature (CCT), the better is the resist-
ance to localized corrosion. Table 4 lists the CCT
and CPT for a variety of alloys. Alloy 31 in this
group had the highest localized resistance, even
better than the Ni-Cr-Mo alloy 625.
Many tests over the years have been conducted
on Alloy 31 at Laque Center for Corrosion Testing,
Wrightsville Beach, N.C. For example, up to 60
days of multiple crevice assembly tests in filtered
seawater at 30C (86F) showed that the alloy has
good resistance to crevice corrosion attack.
Of the various test conditions, the real world
is most closely approximated when chlorinated
ADVANCED MATERIALS & PROCESSES/NOVEMBER 2004
sea-water is pumped through pipe loops. Such
tests have been carried out with water from both
the Baltic Sea and the North Sea. In the Baltic Sea In the
test, Alloy 31 was resistant at temperatures up to
40C (100F) and chlorine levels up to 2 ppm.
Baltic Sea
Only at a temperature of 50C (120F) and a chlo- test,
rine level of 2 ppm did alloy 31 show slight crevice Alloy 31
corrosion on two out of the ten flange joints.
In contrast, when placed in North Sea water, was
which has much greater salinity, the alloy was re- resistant at
sistant up to 45C (110F) at a 1.5 ppm level. How- temperatures
ever, at a temperature of 50C (120F) and a chlo-
rine level of only 0.5 ppm, it showed crevice attack up to 40C
on three out of the ten flange joints. (100F)
and chlorine
Intergranular corrosion resistance
Resistance to intergranular attack has been de- levels up
termined by the TTS (time-temperature-sensitiza- to 2 ppm.
tion) plot when tested per the ASTM G28A test
method. Corrosion depth of greater than 0.002 in.
(50 microns) only develops after a few hours (be-
tween two and three hours) at the nose of the plot
(between 650 and 700C, 1200 and 1290F). To com-
plement this result, welded samples of 6 mm plate
were tested in the ASTM G28A test. The weld
metal, heat affected zone, and the base metal were
totally free from intergranular attack. Hence the
alloy can be and is used in the welded condition
without the need for any post-weld heat treatment.
Stress corrosion cracking
Austenitic stainless steels are susceptible to
stress corrosion cracking in chloride media. Alloy
31 will also crack in boiling 45% MgCl2 solution.
However, this environment is not encountered in
real world situations. Alloy 31 was tested in
boiling 62% CaCl2 solution, an environment more
closely related to the real world, for more than
2000 hours and exhibited total resistance to stress
corrosion cracking.
Alloy 31 was also tested under sour gas condi-
tions (10 bar H2S at 232C, 450F). After 35 days,
the corrosion rate was 0.01 mm/y with no signs of
any pitting or stress corrosion cracking at a stress
of 95% of 0.2% yield strength. This alloy also com-
plies with the NACE MRO-175 up to level 6.
Fabrication and specifications
Alloy 31 is readily fabricated by the standard
methods for stainless steels. It is weldable by all
conventional processes, including GTAW, GMAW,
SWAW, and plasma arc welding. The recom-
mended filler metal is alloy 59, which has an AWS
A5.14 designation ErNiCrMo-13 and AWS 5.11
designation ENiCrMo-13. Greater details on fab-
rication are listed in the Alloy 31 data sheet. This
alloy is covered in all the standard ASTM specifi-
cations, NACE MRO-175 specification, and ASME
SC II, Part D for pressure vessel applications.

For more information: D.C. Agarwal, ThyssenKrupp
VDM USA, 11210 Steeplecrest Drive #120, Hous-
ton, TX 77065-4939; tel: 281/955-6683; fax: 281/955-
9809; e-mail: dcagarwal@pdq.net; Web site: www.
thyssenkrupp.com.
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