NICKEL

ALLOYS
Meet Corrosion Challenges
Nickel and nickel alloys have useful
resistance to a wide variety of corrosive
environments encountered in various
industrial processes. This report is
based on a paper presented at the
NACE Corrosion 2001 conference in
March in Houston, Texas.

D.C. Agarwal*
Krupp VDM Technologies
Houston, Texas

T
he latter half of the 20th century saw a
phenomenal growth in the development
of nickel-base corrosion resistant alloys,
primarily due to the excellent metallur-
gical compatibility of nickel with alloying elements
such as chromium, molybdenum, cobalt, iron,
copper, tantalum, tungsten, and nitrogen. These el-
ements impart unique and very specific corrosion-
resistant and high-temperature properties for han-
dling the corrosive environments of chemical
process, petrochemical, marine, pulp and paper,
agrichemicals, oil and gas, heat treat, energy con- This piping in a European sulfuric acid plant of a copper refinery distribution
version, and many other industries. Improved system is made of Krupp VDM alloy 33. The temperature ranges from 70 to 90°C,
melting and thermo-mechanical process innova- and H2SO4 purity ranges from 97.5% to 99.5%.
tions, and a better fundamental understanding of
the role of these alloying elements and their physical Table 1 — Austenitic alloys that resist aqueous corrosion
metallurgy, were key factors in the development
of binary, ternary, and other complex nickel base Alloy group Generic description Typical alloys
alloy systems. I Fe-base 18-8 austenitic SS 304, 316, 317 & L
The intent of this article is to present the major and LM grades
nickel alloy systems, their major characteristics, the II High-performance 904L, 20, 28, 825
effects of alloying elements, and their strengths, austenitic SS alloys
limitations, and applications. III Ni-base general purpose alloys 200, 400, 600, 800
and H grades
IV 6% Mo super-austenitic SS alloys 1925hMo, AL-6XN,
Nickel and nickel alloy systems 254SMO, 654SMO*, 31*
Table 1 lists some of the major corrosion-resis- V Ni-base special Ni-Mo Controlled chemistry
tant alloys available to the materials engineers and family alloys B-2*, B-3*, B-4*, B-10*
designers today, grouped according to their met- VI Nickel-base high-performance G-3, N06030, 625, C-276,
allurgy/performance. Moving upward from type alloys C-4,22, 2000*, 686*, 59*,
304 stainless steel (304SS/group 1) to higher alloys m MAT 21*
such as groups II, III, IV, V, VI, and VII, corrosion VII Chromium-base austenitic alloy Alloy 33*
*Member of ASM International * Newer developments in the 1990s.

ADVANCED MATERIALS& PROCESSES/JUNE 2001 29

Table 2 — Typical composition of austenitic corrosion-resistant alloys nickel is more noble than that
of iron, and less noble than
UNS # Alloy Ni Cr Mo Fe Others PRE* copper. Because of nickel’s high
S31603 316L 12 17 2.3 66 — 24 over-potential for hydrogen
N08904 904L 25 21 4.8 48 Cu 37 evolution, hydrogen is not
N08926 1925hMo 25 21 6.5 46 Cu, N-0.2 48 easily discharged from any of
N08020 20 38 20 2.4 34 Cu, Cb 29 the common non-oxidizing
N08825 825 40 22 3.2 31 Cu 32 acids, and a supply of oxygen
N08028 28 31 27 3.5 36 Cu 38 is necessary for rapid corrosion.
N08031 31 31 27 6.5 32 Cu, N-0.2 54
Hence, in the presence of ox-
N06985 G-3 48 23 7 20 Cu, Cb 45
R20033 33 31 33 1.6 32 Cu, N-0.4 50 idizing species such as ferric or
N06625 625 62 23 9 3 Cb 52 cupric ions, nitrates, peroxides,
N10276 C-276 57 16 16 5 W 69 or oxygen, nickel can corrode
N06022 22 57 22 13 3 W 65 rapidly. Nickel’s outstanding
N06686 686 56 21 16 2 W 74 corrosion resistance to alkalis
N06200 2000 57 23 16 2 Cu- 1.6 76 has led to its successful appli-
N06059 59 59 23 16 1 — 76 cation in caustic evaporator
* PRE = Pitting Resistance Equivalent = % Cr + % ( 3.3 Mo ) + 30N tubes. However, when nickel
is to be utilized at temperatures
above 316°C (600°F), the low carbon version (alloy
201) is recommended to guard against graphitiza-
tion at the grain boundaries, which leads to pos-
sible loss of ductility and causes embrittlement.
Nickel is very resistant to chloride stress corro-
sion cracking, but may be susceptible to caustic
cracking in aerated solutions in severely stressed
conditions. Ni-Cr-Fe alloys such as alloy 600 may
be more resistant under such conditions. Nickel has
a high resistance to corrosion by most natural fresh
waters and rapidly flowing seawater. However,
under stagnant or crevice conditions, severe pitting
is possible. While nickel’s corrosion resistance to
oxidizing acids such as nitric acid is poor, it is suf-
ficiently resistant to most non-aerated organic acids
and organic compounds. Anhydrous ammonia or
very dilute ammonium hydroxide solution (2%)
does not attack nickel. Higher concentrations may
cause rapid attack due to formation of a soluble
(Ni-NH4) complex corrosion product.
The pickling tanks at Krupp Thyssen Nirosta in Germany are made of Krupp Nickel has good resistance to elevated tempera-
VDM alloy 33 to handle a mixture of hot nitric acid and hydrofluoric acids. tures in halogenic environments such as in chlori-
nation or fluorination reactions. This property has
resistance improves in specific corrosive environ- been utilized in many modern day chemical
ments as evidenced by the increasing alloy content processes, largely due to the fact that the nickel-
and the calculated Pitting Resistance Equivalent halide films have relatively low vapor pressures
(PRE) shown in Table 2. Higher PREs indicate im- and high melting points.
proved resistance to uniform corrosion, localized Nickel has been successful in the production of
corrosion, and environmental cracking in a variety high purity caustic in the 50% to 75% concentration
of environments. The alloys can be basically di- range, in the petrochemical industry, in the chemical
vided into various binary and ternary alloy systems process industry, in handling of food, and in the
with very specific properties and applications. production of synthetic fibers. Other useful appli-
Some of the alloying elements are common to cations are based on its magnetic and magneto-
both aqueous and high temperature corrosion re- strictive properties, high thermal and electrical con-
sistance, but impart different property characteris- ductivity, and low vapor pressure.
tics. Some may be detrimental for aqueous corro-
sion alloys, but beneficial for high temperature Nickel-copper alloys
corrosion alloys, and vice versa. The two main alloys in this system are alloy 400
and its age-hardenable version, alloy K-500. Alloy
Unalloyed nickel 400 was developed in the beginning of the 20th cen-
Commercially pure alloy 200 and alloy 201 have tury and even after approximately 100 years, con-
useful resistance at low to moderate temperatures tinues to be applied in the modern day chemical,
to corrosion by dilute un-aerated solutions of the petrochemical, marine, refinery, and many other
common non-oxidizing mineral acids, such as HCl, industries. Alloy 400 has many characteristics sim-
H2SO4, and H3PO4. The reason for its good service ilar to those of commercially pure nickel, while
is the fact that the standard reduction potential of others have been improved.
30 ADVANCED MATERIALS & PROCESSES/JUNE 2001
 Addition of some iron significantly im- Nickel-copper alloys
proves the resistance to cavitation and ero-
sion in condenser tube applications. This Alloy / UNS # Ni + Co Cu Fe Mn C Al , Ti
resistance is important under conditions of 400 / N04400 63.0 min 31 2.5 2.0 0.30 —
high flow velocity and erosion, as in pro- K500 / N05500 63.0 min 30 2.0 1.5 0.18 2.8 , 0.6
peller shafts, propellers, pump-impeller
blades, casings, condensers, and heat- Nickel-molybdenum alloys
exchanger tubes. The corrosion rate in
moving seawater is generally less than 0.025 Alloy / UNS # Ni Mo Fe Cr C
mm/year. The alloy can pit in stagnant sea- B / N10001 Bal 28 5 0.5 0.03
water; however, the rate of attack is con- B – 2 / N10665 Bal 28 1.8 0.7 0.005
siderably less than in commercially pure B –3 / N10675 Bal 28 1.5 1.5 0.005
nickel. Due to its high nickel content (ap- B – 4 / N10629 Bal 28 3 1.2 0.005
prox. 65%), the alloy is generally immune B –10 / N10624 Bal 24 6 8.0 0.005
to chloride stress corrosion cracking.
The general corrosion resistance of alloy Unalloyed nickel
400 in non-oxidizing mineral acids is better Alloy / UNS # Ni Cu Fe Mn C
than that of nickel. However, it exhibits the
same very poor corrosion resistance to oxi- 200 / N02200 99.0 min 0.25 0.40 0.35 0.15
dizing media such as nitric acid, ferric chlo- 201 / N02201 99.0 min 0.25 0.40 0.35 0.02
ride, cupric chloride, wet chlorine, chromic condensation units, and overhead condenser pipes
acid, sulfur dioxide, and ammonia. in refineries and petrochemical industries.
In un-aerated dilute hydrochloric and sulfuric The nickel
acid solution, the alloy has useful resistance up to Nickel-iron alloys alloys
concentrations of 15% at room temperature and up The nickel alloys containing 36 to 80% nickel are
to 2% at somewhat higher temperature, not ex- generally selected for their special physical prop- containing
ceeding 50°C. Because of this specific characteristic, erties, such as low expansion coefficient of thermal 36 to 80%
alloy 400 is also selected for processes in which chlo- expansion and/or magnetic properties. Higher
rinated solvents may form hydrochloric acid due nickel alloys containing 76 to 80% nickel with some nickel are
to hydrolysis, which would cause failure in stan- iron and some molybdenum, have the highest mag- generally
dard stainless steel. netic permeability and serve as inductive compo- selected
Alloy 400 possesses good corrosion resistance at nents in transformers, circuit breakers, low fre-
ambient temperatures to all HF concentrations in quency transducers, relay parts, and screens. Alloys for their
the absence of air. Aerated solutions and higher with 36% nickel have extremely low expansion special
temperatures increase the corrosion rate. The alloy characteristics. Due to applications in cryogenic en- physical
is susceptible to stress corrosion cracking in moist vironments, this alloy has undergone extensive cor-
aerated hydrofluoric or hydrofluorosilicic acid rosion testing. The nickel-iron alloys also have mod- properties,
vapor, but this can be minimized by de-aeration of erately good resistance to a variety of industrial such as
the environments, or by stress relieving anneal of environments.
the component in question.
low
Neutral and alkaline salt solutions such as chlo- Nickel-silicon alloys coefficient
ride, carbonates, sulfates, and acetates have only Cast Ni-Si alloys, which typically contain 8 to of thermal
minor effects, even at high concentrations and tem- 10% silicon, were developed for handling hot or
peratures up to boiling. Hence, it is widely favored boiling sulfuric acid of most concentrations. They
expansion
in plants for crystallization of salts from saturated also resist strong nitric acid above 50% concentra- and/or
brine. tion along with nitric-sulfuric acid mixtures. A few magnetic
Alloy K-500 is an age-hardenable alloy that also wrought Ni-Si alloys with 4 to 5 % silicon have also
contains aluminum and titanium. It combines the been developed in the last century to handle the properties.
excellent corrosion resistance of alloy 400 with the high-temperature, high-concentration sulfuric acid
added benefits of increased strength and hardness, environments. One of their weaknesses is the in-
and maintains its strength up to 600°C. The alloy creased corrosion rates when the concentrations of
has low magnetic permeability and is non-mag- sulfuric acid falls below 95%. Also their resistance to
netic to –134°C. Some of the typical applications of localized attack is poor in chloride-containing
alloy K-500 are for pump shafts, impellers, doctor cooling waters.
blades and scrapers, oil-well drill collars and other
completion tools, electronic components, springs, Nickel-molybdenum alloys
and valve trains. This alloy primarily serves in ma- • Alloy B: The original alloy in the Ni-Mo family
rine and oil and gas industrial applications. was developed in the 1920s. It is susceptible to HAZ
In contrast, alloy 400 is more versatile, and is corrosion in non-oxidizing acids (acetic, formic, and
found in roofs, gutters, and architectural parts on hydrochloric) because of its higher carbon content.
a number of institutional buildings, tubes of boiler In the decade of the 1960’s, improved AOD melting
feed water heaters, and seawater applications technology led to development of Alloy B-2. This
(sheathing, others). It is selected for equipment in alloy solved the HAZ corrosion problem, but has
the HF alkylation process, production and handling poor fabricability.
of HF acid, and in refining of uranium, distillation, Recent development of the controlled-chemistry
ADVANCED MATERIALS& PROCESSES/JUNE 2001 31
 alloys B-2, B-3, and B-4 solved both of these prob-
lems by eliminating or reducing formation of detri-
Alloy B-10 mental intermetallic phases such as the ß phase
has already Ni4Mo, and further improving corrosion resistance.
Controlled chemistry alloys B-2, B-3, and B-4 are
been recommended for service in handling all concen-
successful trations of HCl in the temperature range of 70 to
100°C, and the handling of wet HCl gas. They have
in the very excellent resistance to pure H2SO4 up to the boiling
specific point in concentrations below 60%.
crevice These alloys are limited by their lack of
chromium and the resulting very poor corrosion
corrosion resistance in the presence of oxidizing species. Alloy
conditions B-2 has been successfully applied in the production
in waste of acetic acid, pharmaceuticals, alkylation of ethyl
benzene, styrene, cumene, organic sulfonation re-
incinerators. actions, melamine, herbicides, and many other
products.
• Alloy B-4: This improved version of alloy B-2
is being tested in various applications. It has already
served successfully in resin production equipment,
where it encounters hydrochloric acid (resulting
from the presence of aluminum chloride) in the
temperature range of 120 to 150°C. In one chemical
company in Spain, alloy B-4 was tested and speci-
fied for production equipment for pesticides, where
severe corrosive conditions are caused by hy-
drochloric acid. (The “C” family alloys were totally
inadequate under these conditions.) Alloy B-4 has
solved both the fabricability problems encountered
32 Circle 15 or visit wwwadinfo cc ADVANCED MATERIALS & PROCESSES/JUNE 2001
with alloy B-2, and the susceptibility to stress cor-
rosion cracking.
• Alloy B-10: A very recent development in the
Ni-Mo family has been the introduction of alloy B-
10. One of the major weaknesses of the B, B-2, B-3,
and B-4 alloys was their inability to handle oxi-
dizing species in corrosive media. Unacceptable
and very high corrosion rates resulted. Under such
conditions, the “C” family alloys with their higher
chromium contents, such as alloy C-276, or alloy
59, could easily handle the oxidizing species, but
lacked sufficient molybdenum to counteract the
highly acidic hydrochloric or sulfuric acid reducing
conditions. Alloy B-10 was an intermediate alloy
between the “C” family and “B” family, in which
the molybdenum level was significantly higher than
the “C” family, but somewhat lower than the “B”
family. Also, the chromium and iron levels were
increased to 8% and 6% respectively to counteract
the oxidizing corrosive species, which may be pre-
sent in the environment. This alloy has already been
successful in the very specific crevice corrosion con-
ditions in waste incinerators. Many other field tests
are under way with this alloy.
Ni-Cr-Fe-Mo-Cu alloys
Fortification of Ni-Cr-Fe alloys with molyb-
denum and copper resulted in a series of alloys
with improved resistance to corrosion by hot re-
ducing acid such as sulfuric, phosphoric, and hy-
drofluoric acids, and those containing
oxidizing species. Copper content
should be about 2% or less, chromium
content from 20 to 33%, and molyb-
denum levels from 1.5 to 7.0%. If some
of the nickel is replaced with iron to
reduce cost, the result is a group of al-
loys that have useful corrosion resis-
tance in a wide variety of both oxi-
dizing and reducing acids (except
hydrochloric), organic compounds,
and to acid, neutral, and alkaline salt
solutions. ■
For more information: D.C.Agarwal,
Krupp VDM Technologies, 11210 Steeple-
crest Drive, #120, Houston, TX 77065-4939;
tel: 281/955-6683; fax: 281/955-9809; e-mail:
dcagarwal@pdq.net.
This article is based on paper #01325,
“Nickel Base Alloys: Corrosion Challenges
in the New Millennium.” It is available from
NACE International, Conferences Division,
P.O. Box 218340, Houston, TX 77218-8340;
tel: 281/228-6200; fax: 281/228-6300; Web
site: www.nace.org.
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