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highchrom.

qxp 10/15/2004 8:57 AM Page 1

HIGH-CHROMIUM
RESISTS AQUEOUS
ALLOY CORROSION
Improvements in alloy metallurgy, Ni-Cr-Mo alloy 625, as shown
per ASTM G-48 testing. Its
melting technology, and thermo- uniform corrosion resistance
mechanical processing led to in sulfuric acid in the medium
development of Alloy 31, concentration range is supe-
rior to even that of Alloy C-
a relatively low-cost alloy with 276 and alloy 20. As a result,
high corrosion resistance. the 6Mo alloys have been ap-
plied extensively in pulp and
D.C. Agarwal* paper production, phos-
phoric acid production,
ThyssenKrupp VDM USA Inc.
copper smelters, and sulfuric
Houston, Texas
acid production/reclamation.
Weldability: The alloy

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

ADVANCED MATERIALS & PROCESSES/NOVEMBER 2004 25


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Corrosion properties ASTM coverage.


Alloy 31 has excellent resistance to localized NACE MRO-175 coverage to level 6.
corrosion in halide media, both pitting and crevice Excellent fabricability with good thermal
corrosion. It also provides: stability.
Outstanding resistance to sulfuric acid.
Excellent resistance to phosphoric acid. Resistance to acids
Good resistance to nitric and nitric/hydro- Sulfuric acid: Table 2 gives the uniform cor-
fluoric acid mixtures. rosion data at various concentrations and tem-
Excellent resistance to chlorine dioxide media peratures. As is evident , Alloy 31 exhibits ex-
in the pulp and paper industry. cellent corrosion resistance in dilute and medium
Excellent resistance to both oxidizing and re- concentration up to 100C (212F). At concentra-
ducing media. tions greater than 80% and at 100C (212F) and
Good resistance to stress corrosion cracking. over, the alloy becomes active. However, in the
ASME SCVIII Div 1 coverage to 430C presence of oxidizing species such as ferric ions,
(800F). 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 sea-water is pumped through pipe loops. Such
31 is resistant at room temperature up to a con- tests have been carried out with water from both
centration of 8%, with corrosion rates below the the Baltic Sea and the North Sea. In the Baltic Sea In the
0.13 mm/y (5 mpy). test, Alloy 31 was resistant at temperatures up to
From 8% HCl to 40% HCl, the corrosion rate at 40C (100F) and chlorine levels up to 2 ppm.
Baltic Sea
room temperature is between 0.13 and 0.5 mm/y Only at a temperature of 50C (120F) and a chlo- test,
(5 mpy to 20 mpy). rine level of 2 ppm did alloy 31 show slight crevice Alloy 31
At a higher temperature of 80C (175F), the corrosion on two out of the ten flange joints.
alloy is resistant up to 3% concentration. Hence, In contrast, when placed in North Sea water, was
in many chemical processes where only traces of which has much greater salinity, the alloy was re- resistant at
HCl are present, Alloy 31 presents a good alter- sistant up to 45C (110F) at a 1.5 ppm level. How- temperatures
native over more expensive nickel alloys of the ever, at a temperature of 50C (120F) and a chlo-
B or C family that contain higher amounts of rine level of only 0.5 ppm, it showed crevice attack up to 40C
molybdenum. on three out of the ten flange joints. (100F)
Nitric acid: Tests were conducted in 67% boiling and chlorine
HNO3 (Huey test). Even after ten boiling periods Intergranular corrosion resistance
of 48 hours each, Alloy 31 exhibited a very low cor- Resistance to intergranular attack has been de- levels up
rosion rate of only 0.1 mm/y (4 mpy). termined by the TTS (time-temperature-sensitiza- to 2 ppm.
On welded samples (filler metal was alloy 625), tion) plot when tested per the ASTM G28A test
the corrosion rate increased to 0.2 mm/y (8 mpy), method. Corrosion depth of greater than 0.002 in.
still an acceptable rate. Despite the high molyb- (50 microns) only develops after a few hours (be-
denum content of 6.5%, it exhibits excellent re- tween two and three hours) at the nose of the plot
sistance in strongly oxidizing media. (between 650 and 700C, 1200 and 1290F). To com-
Phosphoric acid: Laboratory tests in synthetic plement this result, welded samples of 6 mm plate
phosphoric acid media with no solids present were tested in the ASTM G28A test. The weld
(Table 3) did indeed confirm that the corrosion metal, heat affected zone, and the base metal were
resistance of Alloy 31 was superior to those of al- totally free from intergranular attack. Hence the
ternative alloy 926 (UNS N08926, a standard 6Mo alloy can be and is used in the welded condition
alloy) and alloy 28 (UNS N08028). It was compa- without the need for any post-weld heat treatment.
rable or even better than alloy G-30 (UNS
N06030). These tests also confirmed that corro- Stress corrosion cracking
sion of metals in phosphoric acid could increase Austenitic stainless steels are susceptible to
rapidly at or above a certain threshold tempera- stress corrosion cracking in chloride media. Alloy
ture, which appears to be around 120C (250F). 31 will also crack in boiling 45% MgCl2 solution.
Actual plant coupon tests in wet phosphoric However, this environment is not encountered in
acid also confirmed the superior behavior of Alloy real world situations. Alloy 31 was tested in
31 over alloy G-30. A current application with ap- boiling 62% CaCl2 solution, an environment more
proximately 780 tubes in concentrated 46% to 54% closely related to the real world, for more than
P2O5 is demonstrating excellent performance. The 2000 hours and exhibited total resistance to stress
plant saved over $100K by selecting Alloy 31 as corrosion cracking.
the heat exchanger material over alloy G30. Alloy 31 was also tested under sour gas condi-
tions (10 bar H2S at 232C, 450F). After 35 days,
Pitting/crevice corrosion the corrosion rate was 0.01 mm/y with no signs of
One of the key service criteria after uniform any pitting or stress corrosion cracking at a stress
corrosion is the ability to resist pitting and crevice of 95% of 0.2% yield strength. This alloy also com-
corrosion in the process side, which is primarily plies with the NACE MRO-175 up to level 6.
acidic low pH with chlorides. ASTM G48 is one
of the standard laboratory tests established to Fabrication and specifications
evaluate this type of corrosion, and it is being in- Alloy 31 is readily fabricated by the standard
creasingly applied in specifications for sea/off- methods for stainless steels. It is weldable by all
shore and sour gas applications. The higher the conventional processes, including GTAW, GMAW,
critical pitting temperature (CPT) and crevice cor- SWAW, and plasma arc welding. The recom-
rosion temperature (CCT), the better is the resist- mended filler metal is alloy 59, which has an AWS
ance to localized corrosion. Table 4 lists the CCT A5.14 designation ErNiCrMo-13 and AWS 5.11
and CPT for a variety of alloys. Alloy 31 in this designation ENiCrMo-13. Greater details on fab-
group had the highest localized resistance, even rication are listed in the Alloy 31 data sheet. This
better than the Ni-Cr-Mo alloy 625. alloy is covered in all the standard ASTM specifi-
Many tests over the years have been conducted cations, NACE MRO-175 specification, and ASME
on Alloy 31 at Laque Center for Corrosion Testing, SC II, Part D for pressure vessel applications. 
Wrightsville Beach, N.C. For example, up to 60
days of multiple crevice assembly tests in filtered For more information: D.C. Agarwal, ThyssenKrupp
seawater at 30C (86F) showed that the alloy has VDM USA, 11210 Steeplecrest Drive #120, Hous-
good resistance to crevice corrosion attack. ton, TX 77065-4939; tel: 281/955-6683; fax: 281/955-
Of the various test conditions, the real world 9809; e-mail: dcagarwal@pdq.net; Web site: www.
is most closely approximated when chlorinated thyssenkrupp.com.

ADVANCED MATERIALS & PROCESSES/NOVEMBER 2004 27