CORROSION-

RESISTANT PART 4
NICKEL ALLOYS
Nickel alloys provide levels of
corrosion resistance not possible
with other alloys. This is part four
of a four-part series about
corrosion-resistant nickel alloys.
Paul Crook*
Haynes International Inc.
Kokomo, Indiana

N
ickel is an ideal base for corrosion-
resistant alloys. Not only is it inher-
ently resistant to certain chemicals, but
also it can be highly alloyed with ele-
Corrosion-resistant nickel alloys are used in the structures of chemical pro-
ments known to enhance corrosion performance, cessing plants such as this chlorine/EDC/VCM complex. Image courtesy Uhde,
such as chromium, copper, and molybdenum, a company of ThyssenKrupp Technologies.
while retaining its ductile face-centered cubic
structure. Iron is not as accommodating; thus high
Boiling point curve Boiling point curve
levels of such elements are not possible in the 120
Over 0.5 mm/year
120
stainless steels without structural instability. 0.1 to 0.5
mm/year
In addition to commercially pure nickel, three
Temperature, C

Temperature, C

binary alloy systems also provide exceptional cor- 80 80

rosion resistance. These include nickel-chromium
(Ni-Cr), nickel-copper (Ni-Cu), and nickel-molyb-
denum (Ni-Mo). Chromium enhances the resist-
ance of nickel to oxidizing acids by encouraging
the formation of passive films. Copper is very
helpful in seawater, brackish water, and reducing
acids, in particular hydrofluoric. Molybdenum is
extremely beneficial in all reducing acids.
This article focuses on the effects on various
nickel alloys of industrially important acids, bases,
and salts. These include nitric acid, phosphoric
acid, sulfuric acid, and caustic alkalis.
Nitric acid
Unlike the three halogen acids discussed last
month, nitric acid causes a high potential (oxi-
dizing) cathodic reaction that readily induces pas-
sive films on high-chromium stainless steels. In
fact, the stainless steels are very resistant to nitric
acid and the nickel alloys are not needed unless
there are extenuating circumstances, such as the
additional presence of halogen acids or halide salts.
Some nickel alloys exhibit good resistance to
nitric acid, notably those Ni-Cr and Ni-Cr-Mo ma-
terials with high chromium contents. Nitric acid
iso-corrosion diagrams are shown for C-2000 and
*Member of ASM International
ADVANCED MATERIALS & PROCESSES/SEPTEMBER 2007
Under 0.1 mm/year
Under 0.1 mm/year
40 40
20 40 60 20 40 60
Acid concentration, wt% Acid concentration, wt%
Fig. 1 Iso-corrosion diagram for Fig. 2 Iso-corrosion diagram for
C-2000 alloy in nitric acid. G-35 alloy in nitric acid.
G-35 alloys in Fig. 1 and 2. From these, the strong
influence of chromium content can be deduced.
The G-35 alloy, with a chromium content of 33
wt%, exhibits corrosion rates of less than 0.1
mm/y at all temperatures up to the boiling point
curve, at acid concentrations up to 70 wt%.
Phosphoric acid
About ten million tons of phosphoric acid are
produced annually in the United States, 80% of
which is used in the production of agricultural
fertilizers. Most of this acid is made by the wet
process, which involves a reaction between sul-
furic acid and phosphate rock.
Iso-corrosion diagrams do not exist for fertil-
izer-grade phosphoric acid. This is partly because
impurity contents vary from country to country
45
 G-35 in acid 1 31 in acid 1
0.4 G-35 in acid 2 31 in acid 2 160 160
G-30 in acid 1 28 in acid 1 Over 0.5 mm/year
Corrosion rate, mm/year G-30 in acid 2 C-2000 in acid 1 0.1 to 0.5 mm/year 0.1 to 0.5 mm/year
0.3 120 Boiling point curve 120 Boiling point curve

Temperature, C

Temperature, C
0.2 80 80
Under 0.1 mm/year
Under 0.1 mm/year
0.1 40 40

38 40 42 44 46 48 50 52 54 20 40 60 80 20 40 60 80
Acid concentration, wt% Acid concentration, wt% Acid concentration, wt%

Fig. 3 Corrosion rates in wet process phosphoric acid
(Source: Florida. Test temperature 121C).
and from plant to plant due to variations in the com-
position of phosphate rock. In addition, the corro-
sivity of a particular solution can vary with time of
storage, as a result of impurity interactions. Im-
purities include fluoride ions, chloride ions, silica,
aluminum, iron (which serves to increase the oxi-
dizing potential of the acid), calcium, and sodium.
Instead, it is customary to test alloys at specific
concentrations and temperatures typical of the
production process. Within the fertilizer industry
it is also customary to define phosphoric acid con-
centrations in terms of P2O5 content. Corrosion
rates for G-30 and G-35 alloys in several concen-
trations of P2O5 (supplied by plants in Florida) at
121C are shown in Fig. 3.
Pure phosphoric acid, which is added to foods,
is made by oxidizing elemental phosphorus de-
rived from phosphate rock, then adding water.
This type of phosphoric acid is much less corro-
sive than the fertilizer grade, as indicated by the
250 250
Boiling point curve
200 200
Boiling point curve
Temperature, C
Fig. 4 Iso-corrosion diagram for Fig. 5 Iso-corrosion diagram for
B-3 alloy in phosphoric acid. C-2000 alloy in phosphoric acid.
iso-corrosion diagrams for B-3 and C-2000 alloys
in Fig. 4 and 5. Indeed, 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/y in pure phosphoric acid.
Sulfuric acid
Sulfuric acid is one of the most important in-
dustrial chemicals. Not only is it used in the man-
ufacture of fertilizer-grade phosphoric acid, but
also it serves as a catalyst in the petroleum in-
dustry and as a reactant in the production of de-
tergents, polymers, and pigments.
Provided that the acid is pure, the Ni-Mo ma-
terials are the most resistant nickel alloys; second
best are the Ni-Cr-Mo alloys. Impurities of an oxi-
dizing nature are extremely detrimental to the func-
tion of the Ni-Mo materials, whereas the Ni-Cr-Mo
alloys generally benefit from such impurities. Iso-
corrosion diagrams for B-3, C-2000, 400, and 625 al-
loys are shown in Fig. 6 to 9. A 0.1 mm/y line com-
parison between C-2000 alloy, 316L, 254SMO alloy,
and 20Cb-3 alloy (designed especially for service
in sulfuric acid) is shown in Fig. 10.

Temperature, C

Over 0.5 mm/year Sulfuric acid is reducing to the nickel alloys at

0.1 to 0.5 mm/year concentrations up to about 60 wt% (meaning that
150 150
0.1 to 0.5 mm/year Over 0.5 the cathodic reaction is hydrogen evolution). At
mm/year
100 100 higher concentrations, other cathodic reactions
0.1 to 0.5 mm/year
Under 0.1 mm/year
0.1 to 0.5 mm/year are possible, and some materials exhibit sharp
50 50 Under 0.1 mm/year dips in performance. Concentrated, industrial-
grade sulfuric acid is known to contain impuri-
20 40 60 80 20 40 60 80 ties of an oxidizing nature; indeed, at tempera-
Acid concentration, wt% Acid concentration, wt% tures in excess of about 90C (194F), the oxidizing
Fig. 6 Iso-corrosion diagram for Fig. 7 Iso-corrosion diagram for potential of this acid is beyond the scope of the
B-3 alloy in sulfuric acid. C-2000 alloy in sulfuric acid. chromium-bearing nickel alloys.
250
250 250 316L
200 254SMO
Boiling point curve Boiling point curve 20Cb-3
200 200
Temperature, C
Temperature, C

Temperature, C

C-2000
150 BP curve
150 150
Over 0.5 0.1 to 0.5 mm/year
mm/year 100
100 100 Over 0.5 mm/year
0.1 to 0.5 mm/year
50 50 0.1 to 0.5 mm/year 50
Under 0.1 mm/year
Under 0.1 mm/year
20 40 60 80 20 40 60 80 20 40 60 80
Acid concentration, wt% Acid concentration, wt% Acid concentration, wt%

Fig. 8 Iso-corrosion diagram for Fig. 9 Iso-corrosion diagram for Fig. 10 Comparison of 0.1 mm/year lines of several
alloy 400 in sulfuric acid. alloy 625 in sulfuric acid. nickel alloys in sulfuric acid.

46 ADVANCED MATERIALS & PROCESSES/SEPTEMBER 2007

 A nickel alloy designed for such situations is the chemical process industries, several other in-
a high-silicon Ni-Cr material known as D-205 dustries take advantage of their corrosion be-
alloy. However, the mechanical properties of D- havior. These include Food: Commercially pure
205 weldments are such that it can only function nickels are easy to form and provide inherent re-
safely in the form of plate heat exchangers. sistance to mild corrosives; Marine: Ni-Cu alloys
enable resistance to corrosion and cavitation ero-
Caustic alkalis sion; Power: Ni-Cr-Mo alloys line flue gas desul-
Sodium hydroxide (known also as caustic soda) furization systems; and Metal finishing: Ni-Cr
and potassium hydroxide (known also as caustic and Ni-Cr-Fe alloys serve as pickling fixtures.
potash) are widely used chemicals. Applications
include the manufacture of soap, paper, and alu- For more information: Paul Crook is Product R&D
minum. They also serve to neutralize acids, espe- Manager at Haynes International, 1020 W. Park Avenue,
cially in the petrochemical industries. Molten Kokomo, IN 46904-9013; tel: 765/456-6241; pcrook@
sodium hydroxide functions to descale stainless haynesintl.com; www.haynesintl.com.
steels and other alloys in the metals
industry.
As indicated earlier, the commer-
cially pure nickels are the premier
materials for service in caustic al-
kalis. They are resistant over very
wide ranges of concentration and
temperature. Alloys 400 (from the
Ni-Cu group) and 600 (from the Ni-
Cr group) are also favored in caustic
alkalis. For situations involving
caustic alkalis on the one hand and
chlorinated compounds on the other,
the Ni-Cr-Mo alloys are candidates.
However, it has recently been discov-
ered that high-molybdenum nickel
alloys are susceptible to caustic
dealloying in strong, hot, caustic so-
lutions. This means that elements
other than nickel are selectively
leached from surfaces. Field testing
is therefore important prior to
placing Ni-Cr-Mo materials into
service in caustic alkalis.

Welding nickel alloys

Three processes are typically
chosen to weld the nickel alloys. For
sheets and plate root passes, gas tung-
sten arc (TIG) welding is favored. For
plate welds, the gas metal arc (MIG)
process is preferred. For field welding,
the shielded metal arc process with
coated electrodes is favored.
To minimize the precipitation of
second phases in regions affected by
the heat of welding, a maximum in-
terpass temperature of 90C is rec-
ommended for the nickel alloys.
Also, welding of cold-worked ma-
terials is strongly discouraged, since
they sensitize more quickly and in-
duce residual stresses. A full solu-
tion anneal, followed by water
quenching, is recommended for
cold-worked structures prior to
welding.

Applications
While the corrosion-resistant
nickel alloys are used primarily in
ADVANCED MATERIALS & PROCESSES/SEPTEMBER 2007 47