Materials of Construction

Selecting Nickel Alloys

for
Corrosive Applications
Nickel and its alloys offer resistance to
Paul Crook attack by a wide range of chemicals,
Haynes International, Inc.
including acids, alkalis and salts,
making these materials suitable for
many CPI applications.

N
ickel alloys are vitally important industrial materi-
als. In a corrosion sense, they fall between stain-
less steels and exotic materials, such as tantalum.
They are commonly used in applications involving aggres-
sive inorganic acids and chloride-bearing environments,
where many of the stainless steels are prone to stress-cor-
rosion cracking, pitting and crevice attack. Commercially
pure nickel is the material of choice for service in caustics.
Zirconium and titanium alloys lie within the same per-
formance band as the corrosion-resistant nickel alloys;
however, these so-called “reactive metal” alloys have
more specific uses and are intolerant of certain ionic
species, such as fluorides.
Nickel alloys are available to resist most forms of corro-
sion. Most possess high resistance to chloride-induced
stress corrosion cracking. Many resist aggressive reducing
acids, such as hydrochloric (HCl), hydrofluoric (HF), and
low-to-medium concentrations of sulfuric (H2SO4). Some
withstand both strong reducing acids and strong oxidizing
acids. Many exhibit high resistance to the alkalis. Some
have high resistance to localized attack (pitting and crevice
corrosion). All are ductile and easily formed, and weldable.
Nickel itself is inherently resistant to certain chemicals, and
it can be highly alloyed with elements known to enhance
corrosion performance, including chromium, copper,
molybdenum and tungsten.
The role of chromium in nickel alloys is the same as in
stainless steel — in the presence of oxygen, it enhances the
formation of passive films, which impede the corrosion
process. Iron, if added to the nickel alloys, also influences
the formation of passive films.
Copper, molybdenum and tungsten enhance the nobility
of nickel under active corrosion conditions. In addition, due
to their large atomic sizes, molybdenum and tungsten are
significant strengtheners of the nickel alloys, as is niobium.
In addition to commercially pure nickel, there are several
nickel alloy families. There are three binary alloy systems,
namely nickel-chromium (Ni-Cr), nickel-copper (Ni-Cu) and
nickel-molybdenum (Ni-Mo). Chromium encourages the
formation of passive films. Copper is very helpful in seawa-
ter, brackish water and reducing acids, particularly HF.
Molybdenum is extremely beneficial in all reducing acids.
There are also three ternary alloy systems. The most
versatile of these is the nickel-chromium-molybdenum
(Ni-Cr-Mo) system. Not only do the chromium and molyb-
denum provide resistance to oxidizing and reducing acids,
respectively, but also they act synergistically to provide out-
standing resistance to the chloride-induced phenomena of
pitting, crevice attack and stress corrosion cracking. The
nickel-chromium-iron (Ni-Cr-Fe) and nickel-iron-chromium
(Ni-Fe-Cr) families were designed to bridge the performance
and cost gaps between the Ni-Cr alloys and the austenitic
stainless steels. One of their benefits over the stainless steels
is their enhanced resistance to stress corrosion cracking.
Table 1 provides the nominal compositions of the most
common nickel alloys. The next sections of this article
describe these alloys. After that, guidance on selecting
materials for various chemical services is provided.

CEP May 2007 www.aiche.org/cep 45

Materials of Construction

Table 1. Nominal compositions (wt.%) of nickel alloys resistant to aqueous corrosion.

Alloy UNS No.† Form‡ Ni Cu Mo Cr Fe W Mn Si C Al Ti Other

Ni
200 N02200 W 99.5 0.1 — — 0.2 — 0.2 0.2 0.08 — — —
201 N02201 W 99.5 0.1 — — 0.2 — 0.2 0.2 0.01 — — —
301 N03301 W 96.5 0.1 — — 0.3 — 0.2 0.5 0.2 4.4 0.6 —
CZ-100 N02100 C 95** 1.25* — — 3* — 1.5* 2* 1* — — —

Ni-Cu
400 N04400 W 66.5 31.5 — — 1.2 — 1 0.2 0.2 — — —
K-500 N05500 W 66.5 29.5 — — 1 — 0.8 0.2 0.1 2.7 0.6 —
M-35-1 N24135 C Bal 29.5 — — 3.5* — 1.5* 1.25* 0.35* — — Nb 0.5*

Ni-Mo
B-2 N10665 W 69 0.5* 28 1* 2* 0.5* 1* 0.1* 0.01* — — —
B-3 N10675 W 65** 0.2* 28.5 1.5 1.5 3* 3* 0.1* 0.01* 0.5* — —
N-7M N30007 C Bal — 31.5 1* 3* — 1* 1* 0.07* — — —
N-12MV N30012 C Bal — 28 1* 5 — 1* 1* 0.12* — — Co 2.5*, V 0.4

Ni-Cr
600 N06600 W 76 0.2 — 15.5 8 — 0.5 0.2 0.08 — — —
625 N06625 W 61 — 9 21.5 2.5 — 0.2 0.2 0.05 0.2 0.2 Nb + Ta 3.6
690 N06690 W 58** 0.5* — 29 9 — 0.5* 0.5* 0.05* — — —
725 N07725 W 57 — 8 21 7.5 — 0.35* 0.2* 0.03* 0.35* 1.5 Nb 3.5
G-35 N06035 W 58 0.3* 8.1 33.2 2* 0.6* 0.5* 0.6* 0.05* 0.4* — —
Allcorr N06110 W Bal — 10 31 — 2 — — 0.02 0.25 0.25 Nb 0.4

Ni-Cr-Mo
C-4 N06455 W 65 0.5* 16 16 3* — 1* 0.08* 0.01* — 0.7* —
C-22 N06022 W 56 0.5* 13 22 3 3 0.5* 0.08* 0.01* — — V 0.35*
C-22HS — W 61 0.5* 17 21 2* 1* 0.8* 0.08* 0.01* 0.5* — —
C-276 N10276 W 57 0.5* 16 16 5 4 1* 0.08* 0.01* — — V 0.35*
C-2000 N06200 W 59 1.6 16 23 3* — 0.5* 0.08* 0.01* 0.5* — —
59 N06059 W Bal — 16 23 1.5* — 0.5* 0.1* 0.01* 0.25 — —
686 N06686 W Bal — 16 21 5* 3.7 0.75* 0.08* 0.01* — 0.15 —
CW-2M N26455 C Bal — 16.25 16.25 2* 1* 1* 0.8* 0.02* — — —
CW-6M N30107 C Bal — 18.5 18.5 3* — 1* 1* 0.07* — — —
CW-12MW N30002 C Bal — 17 16.5 6 4.5 1* 1* 0.12* — — V 0.3
CX-2MW N26022 C Bal — 13.5 21.5 4 3 1* 0.8* 0.02* — — V 0.35*

Ni-Cr-Fe
G-3 N06985 W 44 2 7 22 19.5 1.5* 1* 1* 0.015* — — Co 5*, Nb 0.5*
G-30 N06030 W 43 2 5.5 30 15 2.5 1.5* 0.8* 0.03* — — Co 5*, Nb 0.8
G-50 N06950 W 50** 0.5* 9 20 17 1* 1* 1* 0.02* 0.4* Co 2.5*, Nb 0.5*

Ni-Fe-Cr
825 N08825 W 42 2.2 3 21.5 30 — 0.5 0.2 0.05* 0.1 0.9 —
925 N09925 W 44 2.2 3 21 22** — 1* 0.5* 0.03* 0.3 2.2 Nb 0.5*

* Maximum ** Minimum † Unified Numbering System for Metals and Alloys ‡ C = Cast, W = Wrought

46 www.aiche.org/cep May 2007 CEP

Commercially pure nickels
Numerous materials are sold under the guise of commer-
cially pure nickel. Most contain in excess of 99% nickel, and
most contain small, elemental additions to control specific
properties. Many were designed for use in the electronics
industry, where the electrical and magnetic properties of pure
nickel are advantageous.
From a corrosion standpoint, the pure nickels are impor-
tant for two reasons. First, they possess outstanding resist-
ance to the caustic alkalis over wide ranges of concentration
and temperature (1, 2). Second, they are very easy to form
into complex shapes with inherent resistance to mild corro-
sives, making them suitable for food processing equipment.
Ni-Cu alloys
Nickel and copper, neighbors on the periodic table, share
the same atomic structure (face-centered cubic), which is
retained in all mixtures of the two elements at all tempera-
tures in the solid range. This has given rise to several impor-
tant nickel-copper and copper-nickel alloys. This article is
concerned with the nickel-copper alloys, which contain
approximately 30–45 wt.% copper and are closely associated
with the Monel trademark.
At the other end of the spectrum, copper alloys contain-
ing approximately 30 wt.% nickel have been commercially
successful, albeit under less-aggressive conditions. In fact,
these copper-nickel alloys have the best general resistance to
aqueous corrosion of all the commercially important copper
alloys, being particularly useful in HF.
The primary attribute of the nickel-copper Monel alloys is
their resistance to seawater and brackish water; indeed, they
are known for their resistance to biofouling in such environ-
ments. They also possess excellent resistance to HF and mod-
erate resistance to other non-oxidizing acids. They withstand
cavitation erosion and are therefore ideally suited to applica-
tions in flowing water, such as propellers and pumps (1, 3).
Ni-Mo alloys
The nickel-molybdenum, or Hastelloy B-type, alloys
have a long history of use in the chemical process industries
(CPI), their chief benefit being high resistance to pure HCl
and H2SO4 over large ranges of concentration and tempera-
ture. They also resist pure HF, hydrobromic acid (HBr),
Trademark Acknowledgements
Allcorr is a trademark of Allegheny Technologies Inc.
254SMO is a trademark of Outokumpu.
20Cb-3 is a trademark of Carpenter Technology Corp.
Hastelloy, B-3, C-22, C-22HS, C-2000, G-30, and G-35 are trademarks of
Haynes International, Inc.
Monel and Inconel and are trademarks of Special Metals Corp.
food-grade phosphoric acid (H3PO4), acid chlorides, and
other non-oxidizing halide salt solutions.
The primary limitation of the Ni-Mo alloys is that they
cannot tolerate either oxidizing acids, such as nitric (HNO3),
or acids that contain oxidizing species, such as oxygen, hydro-
gen peroxide, chlorine, bromine, ferric ions and cupric ions.
Ni-Cr alloys
Early experiments involving the addition of chromium to
nickel not only resulted in materials resistant to oxidizing
acids, but also paved the way for the development of a wide
range of oxidation-resistant high-temperature alloys.
The most common corrosion-resistant wrought Ni-Cr
materials are the Inconel 600-series alloys. The primary
corrosion-related attributes of Alloy 600 include excellent
resistance to sodium hydroxide (NaOH) and good resist-
ance to stress corrosion cracking (SCC) relative to many
stainless steels.
Ni-Cr-Mo alloys
The chief attribute of the nickel-chromium-molybdenum
alloys is their versatility. This stems from the fact that they
contain high levels of both chromium and molybdenum.
Chromium induces passivation in oxidizing acids, as it does
in the stainless steels. Molybdenum provides resistance to
reducing acids, in particular HCl.
HCl and the chloride salts are the chemicals most respon-
sible for the commercial success of the Ni-Cr-Mo alloys.
These compounds are encountered throughout the CPI and
can be very damaging to stainless steel. The Ni-Cr-Mo
alloys are particularly resistant to pitting, crevice attack and
stress corrosion cracking, insidious and unpredictable forms
of corrosion caused by chlorides. In heat exchangers, not
only is the process stream important, but the cooling medi-
um must also be taken into account. Cooling waters, for
example, are often chlorinated to combat biofouling, and
seawater (perhaps the most common chloride solution) is
used as a coolant at many coastal locations.
Just as the Ni-Cr-Mo alloys resist HCl and associated
salts, they also resist the corresponding compounds of
bromine and fluorine. Indeed, the Ni-Cr-Mo alloys are
among the few metallic materials that withstand warm, wet
HF. Among their other attributes, the Ni-Cr-Mo alloys resist
H2SO4 and H3PO4, and moderate concentrations of caustic
soda (NaOH) and caustic potash (KOH).
Ni-Cr-Fe alloys
The nickel-chromium-iron alloys were originally
designed to fill the performance gap between the high-
molybdenum stainless steels and the nickel-chromium-
molybdenum alloys. Thus, they possess good resistance to
CEP May 2007 www.aiche.org/cep 47
Materials of Construction

chloride-induced phenomena, such as pitting, crevice corro- SELECTING NICKEL ALLOYS

sion and stress corrosion cracking, and exhibit moderate
resistance to the halogen acids, in particular HCl. Some con-
tain copper to enhance their resistance to H2SO4 and HF.
These alloys evolved from Hastelloy G alloy, which was
conceived as a copper-bearing variant of a prior Ni-Cr-Fe
alloy, Hastelloy F alloy.
Ni-Fe-Cr alloys
With iron contents as high as about 30 wt.%, these
alloys are compositionally close to the high-nickel austen-
itic stainless steels. The negative aspects of such a high
iron content are reduced solubilities of key elements, such
as molybdenum, and reduced resistance to environmental
cracking. On the other hand, a high iron content reduces
the cost of producing the alloys.
120
100 Boiling Point Curve
Temperature, ºC
The corrosion resistance of a material is often summa-
rized in an iso-corrosion chart, which plots the material’s
expected corrosion rates over wide ranges of concentration
and temperature, based on laboratory tests. A material’s
resistance to chloride-induced pitting and crevice attack can
be gauged by its critical pitting temperature (CPT) and criti-
cal crevice temperature (CCT) in acidified ferric chloride.
These charts and data are useful in material selection.
Hydrobromic acid (HBr)
HBr is one of the strongest mineral acids. It is a more-
effective solvent for some ore minerals than HCl because
of its higher boiling point and stronger reducing action.
Of the nickel alloys, those with a high molybdenum
content have the greatest resistance to HBr and the other
halogen acids. Iso-corrosion diagrams for B-3 and C-2000
alloys, as representatives of the Ni-Mo and Ni-Cr-Mo
groups, are shown in Figures 1 and 2, respectively.
Figure 1 indicates that B-3 alloy (Ni-Mo) can be used in
HBr up to the boiling point, although corrosion rates exceed-
ing 0.1 mm/yr (the accepted limit for thin structures, such as

80
plate heat exchangers and rupture discs) are expected at tem-
0.1 to 0.5 mm/yr
peratures above about 40°C.
60
The diagram for C-2000 alloy (Ni-Cr-Mo) is quite differ-
ent. This material exhibits corrosion rates of less than 0.1
40
mm/yr over a wider range of temperatures. However, rates
over 0.5 mm/yr (the accepted limit for thick structures, such
20
Under 0.1 mm/yr as reactors and shell-and-tube heat exchangers) are anticipat-
ed within a significant area below the boiling point curve.
0
0 10 20 30 40 These diagrams were created by analyzing numerous
Acid Concentration, wt.% corrosion rates generated in pure HBr in the laboratory. For
industrial applications, any impurities or residuals present

Figure 1. B-3 alloy (Ni-Mo) in hydrobromic acid. in the process streams must be considered; if these are of
120 120
Boiling Point Curve
Under 0.1 mm/yr
100 Boiling Point Curve
100
Over 0.5 mm/yr
Temperature, ºC

Temperature, ºC

80 0.1 to
0.5 mm/yr 80
0.1 to 0.5 mm/yr 0.1 to 0.5 mm/yr
60

60
40

Under 0.1 mm/yr 40

20
Under 0.1 mm/yr
0 20
0 10 20 30 40 0 4 8 12 16 20
Acid Concentration, wt.% Acid Concentration, wt.%

Figure 2. C-2000 alloy (Ni-Cr-Mo) alloy in hydrobromic acid.
Figure 3. B-3 alloy (Ni-Mo) in hydrochloric acid.

48 www.aiche.org/cep May 2007 CEP

 120 120
Boiling Point Curve Boiling Point Curve
100 100
Temperature, ºC

Temperature, ºC
80 Over 0.5 mm/yr 80
Over 0.5 mm/yr

60 60

40 40
0.1 to 0.5 mm/yr
0.1 to 0.5 mm/yr
20 20
Under 0.1 mm/yr
Under 0.1 mm/yr
0 0
0 4 8 12 16 20 0 4 8 12 16 20
Acid Concentration, wt.% Acid Concentration, wt.%

Figure 4. Alloy 400 (Ni-Cu) in hydrochloric acid.
an oxidizing nature, they are detrimental to the Ni-Mo
materials. The Ni-Cr-Mo alloys, on the other hand, are tol-
erant of, and even benefit from, species of an oxidizing
nature, such as ferric ions, cupric ions, oxygen, chlorine
and hydrogen peroxide.
Hydrochloric acid (HCl)
HCl is very aggressive to stainless steels. Furthermore, it
is indirectly responsible for the insidious effects of chloride
salts on metallic materials.
Figures 3–6 are iso-corrosion diagrams for alloys repre-
senting the Ni-Mo (B-3 alloy), Ni-Cu (Alloy 400), Ni-Cr
(Alloy 625), and Ni-Cr-Mo (C-2000 alloy) groups.
Figure 3 indicates that the Ni-Mo alloys can be used
in 0–20 wt.% HCl up to the boiling point curve, without
the corrosion rates exceeding 0.5 mm/yr. Indeed, rates of
0.3 mm/yr or less are typical above 40°C.
The Ni-Cr-Mo alloys (Figure 6) are the next best option
120
Boiling Point Curve
100

Figure 5. Alloy 625 (Ni-Cr) in hydrochloric acid.
for HCl service. They are preferred at low concentrations
and elevated temperatures. High-molybdenum Ni-Cr
alloys, such as Alloy 625 (Figure 5) also offer considerable
resistance to HCl.
To put this into perspective, Figure 7 compares the per-
formance of the Ni-Cr-Mo materials (represented by C-2000
alloy) and three types of austenitic stainless steel (Type
316L, 254SMO and 20Cb-3), presenting the concen-
tration/temperature combinations at which a corrosion rate of
0.1 mm/yr would be expected. Not surprisingly, the stainless
steel with the highest molybdenum content (254SMO alloy)
is the most resistant of the stainless steels, but it falls well
short of the performance of C-2000 alloy.
Hydrofluoric acid (HF)
HF is among the most dangerous of chemicals, being
highly damaging to skin and mucous membranes. Con-
tainment of the acid is also a problem, especially at elevated
120
Boiling Point Curve
100

0.1 to Over 0.5 mm/yr C-2000

Temperature, ºC
Temperature, ºC

80 80 316L
0.5 mm/yr 254SMO
20Cb-3
60 60

0.1 to 0.5 mm/yr

40 40

Under 0.1 mm/yr

20 20

0 0
0 4 8 12 16 20 0 4 8 12 16 20
Acid Concentration, wt.% Acid Concentration, wt.%

Figure 7. Comparison of 0.1-mm/yr lines for C-2000 and three

Figure 6. C-2000 alloy (Ni-Cr-Mo) in hydrochloric acid.
stainless steels in hydrochloric acid.

CEP May 2007 www.aiche.org/cep 49

Materials of Construction
120
Boiling Point Curve
100
Temperature, ºC
80 Ran
ge
for
59,
200
, 68
60 6, C
40
20 G-30
316L
0 fluoric acid.
0 20 40
Acid Concentration, wt.%

Figure 8. Comparison of 0.5-mm/yr lines for various nickel
alloys in hydrofluoric acid. Source: (4).
temperatures and intermediate concentrations. The reactive
metals (notably titanium, zirconium, niobium and tantalum),
for example, are readily attacked by HF, and the stainless
steels generally exhibit high corrosion rates.
Fortunately, the nickel alloys exhibit low to moderate
corrosion rates in HF, over wide ranges of concentration
and temperature, and are thus suitable for many pieces of
equipment involved in the manufacture and use of this acid.
It is believed that the resistance of the nickel alloys to HF is
due, in part, to the formation of protective surface films, in
particular nickel fluoride.
The laboratory characterization of the nickel alloys in HF
has not been as extensive as it has for other common inor-
ganic acids, largely because of its dangerous nature. The lim-
ited amount of information available suggests the following:
• Monel Alloy 400 and Hastelloy C-2000 alloy are
among the most resistant. Alloy 400 is most suitable when
fully immersed; C-2000 alloy excels in vapor spaces above
hot HF solutions.
• In laboratory tests, the length of the test is important.
This probably relates to the time it takes for protective fluo-
ride films to form on the different alloys.
• The nickel alloys are susceptible to stress corrosion
cracking in HF, and (in some cases) in the associated
vapor spaces. Care should be taken, therefore, to avoid
applied or residual stresses in nickel alloy components
exposed to the chemical.
Iso-corrosion diagrams of the 0.5 mm/yr lines for several
nickel alloys were published recently (4) and are summa-
rized in Figure 8. Despite the scatter at some concentrations
and temperatures, undoubtedly due to different test times
and conditions, they do provide a good, general guide to the
performance of the nickel alloys in HF.
Stress corrosion cracking in HF is a fascinating subject,
50 www.aiche.org/cep May 2007
400
B-2
-22
and
C-2
76
Figure 9. Stress corrosion
825 cracking in U-bend samples of
690
625 C-22 (top left), C-276 (above)
600 and C-2000 (left) alloys (Ni-Cr-
Mo) after immersion in hydro-
60 80 100
because the cracks are unlike those caused by chloride salt
solutions. Rather than individual deep cracks, HF tends to
induce fine craze-cracking, which progresses in broad-front
fashion (Figure 9). Interestingly, the alloys that suffered
considerable weight loss during recent tests (involving an
acid concentration of 20 wt.%, a temperature of 79°C and a
test duration of 240 h), namely 625 and G-35, did not
exhibit stress corrosion cracking, suggesting that the uni-
form corrosion front was propagating more rapidly than
the crack front. Of those materials that did exhibit cracking,
C-2000 alloy was the least susceptible, in terms of depth of
cracking and crack width; in fact, it was difficult to resolve
the cracks optically.
Nitric acid (HNO3)
Unlike the three halogen acids discussed so far, HNO3
causes a high-potential (oxidizing) cathodic reaction, which
readily induces passive films on high-chromium stainless
steels. In fact, the stainless steels are very resistant to HNO3
and there is no need for the nickel alloys, unless there are
extenuating circumstances, such as the additional presence
of halogen acids or halide salts.
Some nickel alloys exhibit good resistance to HNO3,
notably those Ni-Cr and Ni-Cr-Mo materials with a high
chromium content. The iso-corrosion diagrams for C-2000
(Ni-Cr-Mo) and G-35 alloys (Ni-Cr) in Figures 10 and 11
illustrate the strong influence of the chromium content. G-35
alloy, with a chromium content of 33 wt.%, exhibits corro-
sion rates of less than 0.1 mm/yr at all temperatures up to the
boiling point curve, at acid concentrations up to 70 wt.%.
Phosphoric acid (H3PO4)
About 10 million tons of H3PO4 are produced annually
in the U.S., 80% of which is used in the production of fertil-
izers. Most of this acid is made by the wet process, which
involves a reaction between H2SO4 and phosphate rock.
CEP
 120 120 Over 0.5 mm/yr

Boiling Point Curve 0.1 to

Boiling Point Curve 0.5 mm/yr
Temperature, ºC

Temperature, ºC
80 80

Under 0.1 mm/yr

Under 0.1 mm/yr
40 40

0 0
0 20 40 60 0 20 40 60
Acid Concentration, wt.% Acid Concentration, wt.%

Figure 10. G-35 alloy (Ni-Cr) in nitric acid.
Figure 11. C-2000 alloy (Ni-Cr-Mo) in nitric acid.

Iso-corrosion diagrams do not exist for fertilizer-grade
H3PO4. This is partly because impurity contents vary from
country to country and from plant to plant, due to variations
in the composition of phosphate rock. In addition, the corro-
sivity of a particular solution can vary with time of storage
due to impurity interactions. Impurities include fluoride ions,
chloride ions, silica, aluminum, iron (which serves to increase
the oxidizing potential of the acid), calcium and sodium.
Instead, it is customary to test alloys at specific concen-
trations and temperatures typical of the production process.
It is also customary in the fertilizer industry to define phos-
phoric acid concentrations in terms of P2O5 content.
Corrosion rates for G-30 (Ni-Cr-Fe) and G-35 (Ni-Cr) alloys
in several concentrations of P2O5 (supplied by plants in
Florida) at 121°C are shown in Figure 12.
Pure phosphoric acid (which is used in foods) is made by
oxidizing elemental phosphorus, derived from phosphate
0.4
rock, then adding water. This type of H3PO4 is much less cor-
rosive than the fertilizer grade, as indicated by the iso-corro-
sion diagrams for B-3 (Ni-Mo) and C-2000 (Ni-Cr-Mo)
alloys in Figures 13 and 14. Only at high concentrations and
temperatures do the Ni-Mo, Ni-Cr and Ni-Cr-Mo alloys
exhibit corrosion rates in excess of 0.1 mm/yr in pure H3PO4.
Sulfuric acid (H2SO4)
H2SO4 is one of the most important industrial chemi-
cals. Provided that the acid is pure, the Ni-Mo materials
are the most resistant nickel alloys; second-best are the
Ni-Cr-Mo alloys. Impurities of an oxidizing nature are
extremely detrimental to the performance of the Ni-Mo
materials, whereas the Ni-Cr-Mo alloys generally benefit
from such impurities.
Iso-corrosion diagrams for B-3 (Ni-Mo), C-2000
(Ni-Cr-Mo), 400 (Ni-Cu) and 625 (Ni-Cr) alloys are shown
160

0.1 to 0.5 mm/yr

Corrosion Rate, mm/yr

C-2000 in Acid 1
0.3 120
Boiling Point Curve
Temperature, ºC

G-30 in Acid 1
0.2 80

G-30 in Acid 2
Under 0.1 mm/yr
G-35 in Acid 1
0.1 40
G-35 in Acid 2

0 0
36 48 40 42 44 46 48 50 52 54 0 20 40 60 80
Acid Concentration, wt.% Acid Concentration, wt.%

Figure 12. Corrosion rates for G-35 (Ni-Cr) and G-30

Figure 13. B-3 alloy (Ni-Mo) in phosphoric acid.
(Ni-Cr-Fe) alloys in wet-process phosphoric acid.

CEP May 2007 www.aiche.org/cep 51

Materials of Construction

160
Over 0.5 mm/yr in Figures 15 to 18, respectively. Figure 19 compares the
0.1-mm/yr lines for C-2000 alloy, Type 316L stainless
120 steel, 254SMO alloy, and 20Cb-3 alloy.
Boiling Point Curve 0.1 to H2SO4 is reducing to the nickel alloys at concentrations up
Temperature, ºC

0.5 mm/yr
to about 60 wt.% (meaning that the cathodic reaction is
80 hydrogen evolution). At higher concentrations, other cathodic
reactions are possible and some materials exhibit sharp dips
in performance. Concentrated, industrial-grade H2SO4 is
Under 0.1 mm/yr
40
known to contain impurities of an oxidizing nature; indeed,
above about 90°C, the oxidizing potential of this acid is
beyond the scope of the chromium-bearing nickel alloys.
0
0 20 40 60 80
Caustic alkalis
Acid Concentration, wt.% As noted earlier, the commercially pure nickels are the
premier materials for service in caustic alkalis such as sodi-

Figure 14. C-2000 alloy (Ni-Cr-Mo) in phosphoric acid. um hydroxide and potassium hydroxide. They are resistant

250 Over 0.5 mm/yr 250

200 200 Boiling Point Curve

Boiling Point Curve
Temperature, ºC

Temperature, ºC

150 0.1 to 150

0.5 mm/yr
Over 0.5 mm/yr
100 100

Under 0.1 mm/yr 0.1 to 0.5 mm/yr

50 50

Under 0.1 mm/yr

0 0
0 20 40 60 80 0 20 40 60 80
Acid Concentration, wt.% Acid Concentration, wt.%

Figure 15. B-3 alloy (Ni-Mo) in sulfuric acid.
Figure 17. Alloy 400 (Ni-Cu) in sulfuric acid.

250 250

200 200 Boiling Point Curve

Boiling Point Curve
Temperature, ºC

Temperature, ºC

150 150
0.1 to 0.5 mm/yr 0.1 to 0.5 mm/yr
Over 0.5 mm/yr
100 100
Over 0.5 mm/yr

50 Under 0.1 mm/yr 50

Under 0.1 mm/yr
0 0
0 20 40 60 80 0 20 40 60 80
Acid Concentration, wt.% Acid Concentration, wt.%

Figure 16. C-2000 (Ni-Cr-Mo) in sulfuric acid.
Figure 18. Alloy 625 (Ni-Cr) in sulfuric acid.

52 www.aiche.org/cep May 2007 CEP

over very wide ranges of concentration and temperature. fied 6 wt.% ferric chloride, in accordance with the procedures
Alloys 400 (from the Ni-Cu group) and 600 (Ni-Cr) are also defined in ASTM Standard G 48. These values represent the
favored in caustic alkalis. lowest temperatures at which crevice attack and pitting are
For situations involving caustic alkalis and chlorinated encountered in acidified ferric chloride within 72 h. CCT and
compounds, the Ni-Cr-Mo alloys are good candidates. How- CPT values for several nickel alloys and stainless steels are
ever, it has recently been discovered that in strong, hot caus- given in Table 2. From these data, the superiority of the
tic solutions, high-molybdenum nickel alloys are prone to chromium-bearing nickel alloys over the stainless steels in
caustic dealloying, whereby elements other than nickel are resisting these forms of localized attack is evident.
selectively leached from surfaces (5). Field testing is, there- A common way to evaluate the resistance of metallic
fore, important prior to placing Ni-Cr-Mo materials into materials to chloride-induced stress corrosion cracking is
service in caustic alkalis. to immerse them in boiling 45 wt.% magnesium chloride,
as defined in ASTM Standards G 30 and G 36. Typically,
Salts U-bend samples are tested in this environment for periods
While many salts pose few problems for nickel alloys, up to 1,008 h, with interruptions to check for cracking.
some are of concern because they can induce insidious and Data for several nickel alloys and stainless steels are pre-
unpredictable forms of attack. Water solutions of chloride sented in Table 3, which shows that low-iron nickel alloys,
salts, for example, cause pitting, crevice attack and stress cor- such as the Ni-Cr-Mo materials, offer the highest resistance
rosion cracking, particularly of stainless steel. Other halide to stress corrosion cracking.
salts (notably bromides and fluorides) induce similar effects.
Not only are anions of concern when salts are present in Seawater
aqueous systems, but cations can also be influential. For Seawater is encountered in CPI facilities in coastal
example, ferric ions and cupric ions can substantially alter regions, which often use seawater as a coolant. As a
the electrochemistry of acid systems, resulting in cathodic chloride, seawater can induce pitting, crevice attack and
reactions of higher potential, and significant corrosion of
alloys that would otherwise be inert. The Ni-Cu and Ni-Mo Table 2. Critical crevice temperatures (CCT) and
critical pitting temperatures (CPT) data.
materials are particularly prone to such effects.
Fortunately, the nickel alloys in general are very resistant Alloy CCT, °C CCT, °F CPT, °C CPT, °F
to chloride-induced stress corrosion cracking and some
316L 0 32 15 59
(notably the Ni-Cr-Mo materials) possess high resistance to 254SMO 30 86 60 140
pitting and crevice attack as well. Much of their success in 28 17.5 64 45 113
chemical industry applications is due to these attributes. 31 42.5 109 72.5 163
To assess the resistance of alloys to crevice attack and pit- G-30 37.5 100 67.5 154
ting, it is customary to measure their critical crevice tempera- G-35 45 113 95 203
625 40 104 100 212
tures (CCT) and critical pitting temperatures (CPT) in acidi- 725* 25 77 85 185
250 C-22 80 176 >120 >248
C-22HS** 100 212 >120 >248
C-2000
316L C-22HS* 75 167 110 230
200 254SMO C-276 55 131 >120 >248
20Cb-3 C-2000 80 176 >120 >248
Temperature, ºC

150 * Age-hardened ** Annealed

Boiling Point
Curve Table 3. Time required to induce stress corrosion cracking.
100
Time to Time to
Alloy Cracking, h Alloy Cracking, h
50
316L 2 G-35 None*
254SMO 24 625 None*
0
28 36 C-22 None*
0 20 40 60 80
31 36 C-276 None*
Acid Concentration, wt.%
G-30 168 C-2000 None*

Figure 19. Comparison of 0.1-mm/yr lines for C-2000
(Ni-Cr-Mo) and three stainless steels in sulfuric acid. * No cracking was observed during the 1,008-h test.

CEP May 2007 www.aiche.org/cep 53

Materials of Construction

stress corrosion cracking, as well as uniform attack, of
metallic materials. Furthermore, equipment exposed to sea-
water can become encrusted, leading to a form of crevice
attack known as under-deposit corrosion. Biofouling is
also an issue.
The nickel alloys possess good seawater resistance. In
particular, those with a high copper content, such as Alloy
400, resist biofouling because copper is poisonous to
microbes. For stagnant or low-velocity conditions, chromi-
um- and molybdenum-bearing nickel alloys are favored due
to their higher resistance to pitting and crevice attack.
Some recent crevice corrosion data for seawater, generat-
ed as part of a U.S. Navy study at the LaQue Laboratories
in Wrightsville Beach, NC, are presented in Table 4 (6).
Crevice tests were performed in both still (quiescent) and
flowing seawater, at 29°C ± 3°C, for 180 days. In quiescent
seawater, the results mirror those generated in acidified fer-
ric chloride, with C-22 and C-2000 alloys as the most resist-
ant. In flowing seawater, crevice attack of the stainless
steels was shallower, and none of the Ni-Cr-Mo alloys
exhibited crevice corrosion.
Conclusion
In summary, there are seven types of nickel alloys, each
with specific technical and/or cost benefits.
The commercially pure nickels, such as Alloy 200, are
the primary materials choice for caustic alkalis. They are
also well-suited to food processing applications. The Ni-Cu
materials (e.g., the Monels) are favored in seawater, brackish
water and hydrofluoric acid.
The Ni-Mo alloys possess outstanding resistance to pure
non-oxidizing acids, such as hydrochloric. However, they are
intolerant of oxidizing impurities and residuals.
On the other hand, the Ni-Cr alloys possess outstanding
resistance to oxidizing acids, and moderate resistance to
chloride-induced effects, such as pitting, crevice attack and
stress corrosion cracking. Adding iron to the Ni-Cr alloys
reduces their cost, but negatively influences their resistance
to environmental cracking, particularly in the presence of
chlorides and hydrogen sulfide. Nevertheless, the Ni-Cr-Fe
and Ni-Fe-Cr nickel alloys fill the important performance
and cost gaps between the Ni-Cr materials and the high-
nickel austenitic stainless steels.
Finally, the Ni-Cr-Mo materials are the most versatile
nickel alloys. They withstand both oxidizing and non-oxidiz-
ing acids, and are extremely resistant to chloride-induced
corrosion phenomena. CEP
Literature Cited
1. Special Metals Corp., “High Performance Alloys for
Resistance to Aqueous Corrosion,” Publication No. SMC-
026, Special Metals Corp. (2000).
2. “Nickel 200/201,” Alloy Digest, No. Ni-539, ASM
International (1998).
3. Special Metals Corp., “MONEL Alloy 400,” Publication
No. SMC-053, Special Metals Corp. (2005).
4. Crum, J. R., et al., “Characterization of Corrosion Resistant
Materials in Low and High Temperature HF Environments,”
Paper 382, Presented at Corrosion 99, NACE International,
San Antonio, TX (Apr. 1999).
5. Crook, P., et al., “The Caustic Dealloying of Molybdenum-
Bearing Nickel Alloys,” Proceedings of Eurocorr 2005,
Lisbon, Portugal, organized by the Portugese Corrosion
Society (Sept. 2005).
6. Aylor, D. M., et al., “Crevice Corrosion Performance of Can-
didate Naval Ship Seawater Valve Materials in Quiescent and
Flowing Natural Seawater,” Paper 329, Presented at Corro-
sion 99, NACE International, San Antonio, TX (Apr. 1999).
Further Reading
ASM International, “Specification for Castings, Nickel and
Nickel Alloys, A 494 / A 494M,” Annual Book of ASTM
Standards, Vol. 01.02, ASM International, Materials Park,
OH (1999).
Crook, P., and M. L. Caruso, “A New Nickel Alloy Resistant to
‘Wet Process’ Phosphoric Acid,” Paper 04221, Presented at
Corrosion 2004, NACE International, New Orleans, LA
(Mar. 2004).
Krivsky, W. A., “Preparation of Metals and Alloys,” U.S. Patent
3,252,790 (May 1966).
Special Metals Corp., “INCONEL Alloy 690,” Publication No.
SMC-079, Special Metals Corp. (2003).

Table 4. Seawater crevice corrosion results.

Quiescent Seawater Flowing Seawater PAUL CROOK is manager of product R&D at Haynes International, Inc.
Number of Depth, Number of Depth, (1020 W. Park Ave., P.O. Box 9013, Kokomo, IN 46904-9013; Phone:
Alloy Attack Sites mm Attack Sites mm (765) 456-6241; Fax: (765) 456-6925; E-mail: pcrook@haynesintl.com).
Throughout his career at Haynes (and at Deloro Stellite before its wear-
resistant alloys business was purchased by the Haynes Stellite Div. of
316L 2 1.80 2 0.32
Cabot Corp.), he has been involved in the development of new, wear-
254SMO 2 1.25 2 0.01 resistant alloys and corrosion-resistant alloys. His inventions include
625 2 0.11 2 <0.01 the alloys: Ultimet; Hastelloy C-2000; and Hastelloy G-35. While
C-22 0 0 0 0 primarily a technical specialist, he has held a number of management
C-276 1 0.12 0 0 positions at Haynes as well. Crook earned BS, MS and PhD degrees in
C-2000 0 0 0 0 physics and metallurgy from the Univ. of Manchester, England. He holds
11 U.S. patents and has authored many publications, including the
Source: (6). cobalt and nickel chapters of the “ASM Handbook 13B” on corrosion.

54 www.aiche.org/cep May 2007 CEP