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onlinuing advances in mClallurgical reserved largely for ultrahigh-strength
techniques and manufacturing tech- Nickel alloys offer a combina- applications sllCh as those encountered in
nologies have spurTed the develop- deep oiVgas production and extreme high-
ment of nickel alloys and their broader tion of excellent corrosion resis- pressure processes.
utilization in the chemical industry. Except for selected components in
Nickel alloys offer a combination of tance, strength, toughness, met- valves and TOtating machinery. precipita-
excellent corrosion resistance. strength, tion-hardened nickel alloys find limited
toughness. metallurgical stability. fabrica- allurgicaJ stability, fabricability application in chemical plants. Included in
bility and weldability. Many nickel alloys this alloy class are heat-resistant superal-
additionally possess outstanding heal loys employed in gas turbines. combus-
and weldabilit)'.
resiSllmce. making them ideal choices for tion chambers and aerospace applications,
applications requiring chemical resistance
and strength at elevated temperatures. nificantly lowcr than 300 series stainless Corrosion-resistance
This survey of wrought nickel-based steels. Nickel alloys represent a step up from
alloys (here defined as containing more Though the thermal conductivity of conventional slainless steels and super-
than 45% nickel) covers a range of pure nickel exceeds that of carbon steel. austenitic iron-based alloys in resisting
wrought corrosion-resistant 3110ys com- most nickel alloys have markedly lower corrosion by a wide spectrum of acids.
monly used in chemical plant applications. conductivities. in some instances even alkalis and salts. An outstanding attribute
Chemical compositions and Unified lower than austenitic stainless steels. of nickel alloys is exceptional resistance
Numbering System (UNS) designations Except for pure nickel. the nickel 10 aqueous solutions containing halide
of these alloys are shown in Table I. To alloys used in chemical processing are ions, In that regard, nickel alloys are far
aid the reader, 3.nd not as an endorsement. considerably stronger than the 300 Series superior 10 auslenitic stainless steels.
some familiar trade names are identified stainless steels. Nickel alloys also have which are notoriously prone to attack by
in the sidebar. very good ductility (as illustrated by the wei chlorides and fluorides.
room temperature mechanical properties This superior corrosion behavior of
Properties of alloys listed in Table 2) and toughness. nickel alloys manifests ilself not only in
Nickel alloys are more expensive than Maximum allowable design Stresses for terms of lower metal loss. but in the abili-
stainless steels. However. economic com- most of the alloys used in chemical plant ty to better withstand localized auack,
parisons on a first-cost. rather than on a equipment are published in Section vm notably pining/crevice corrosion, inter-
life-cycle basis. can be: deceiving. For of the ASME Boiler and Pressure Vessel granular auack and Stress corrosion crack-
instance. Ni-Cr-Mo alloys cost roughly Code. ing. These forms of localized allack. more
five times as much as ISCr-8Ni stainless Nickel alloys have fully austenitic so than general thinning. account for the
steels and about twice as much as super- microstructures. Nearly all of the grades majority of corrosion-induced failures in
austenitic stainless steels. employed in the chemical industry are the chemical industry,
Owing to the exceptional corrosion solid-solution strengthened. They derive Nickel alloys owe their corrosion
resistance of nickel alloys. the initial COSt their enhanced strength properties from resistance partly 10 the inherent lower
premium can often be recouped through the addition of effective hankners such as reactivity of nickel relative to iron. as
long-term savings due to prolonged molybdenum and tungsten. rather than measured by its more noble oxidation
equipment life. reduced maintenance and from carbide formation. Like austenitic potential in the EMF Series. Similar to
fewer shutdowns. stainless steels, solid solution nickel stainless steels. chromium-containing
Physical properties of nickel alloys are alloys cannot be strengthened by heat nickel alloys have the capability to passi-
quite similar to those of the 300 Series treatment. only by cold working. vate (i,e.. to spontaneously form an ultra-
austenitic stainless steels. As a class, nick- Another broad class of nickelbased thin but tenacious surface oxide that func-
el-based alloys have thermal expansion alloys are strengthened by a precipitation- tions as an effective corrosion barrier).
rotes about equal to carbon steel. but sig. hardening heat treatment, These are
is the ..bilit)' to accept large fractions of the greater sluggishness of Ni-rich weld wrought counterparts.
alloying elements wilhout fonning briule puddles and the lower penetration charac- Nickel alloys are generally classified
phases. Common alloying additions for teristics of nickel alloys. the production according to their principal alloying con-
enhanced corrosion resistance are chromi- of full penctration welds may require stilUents. The families of nickel alloys
um. molybdenum and copper. Their roles modification of joint configurations and extensively utilized in chemical plant
are addressed in the brief chamcterizations welding techniques. Nickel alloys are equipment are briefly characterized
of nickel alloy syStems thaI follow. less tolerant than ferrous materials to con- below;
Comparative resistance ratings of nick- tamination that could cause weld embril- Pure nickel. Pure nickel (Alloy 200)
el alloys in common chemical planl cov;- tlemenl. has very good resistance to a wide ronge
ronlTl('nlS are shown in Table 3. These gen- The combinatioo of high ductility, low of reducing acids and salts. but is not a
eral guidelines are nOi intended for specifi- thennal expansion and the ability to toler- suiw.bte choice for strongly oxidizing
calion purposes but only as a starting point ate dilution by numerous metallic ele- environments such as nitric acid. The
in the materials selection process. ments h:ts made nickel-rich welding coo- most significant allribute of pure nickel is
sumables universally 3CCepied for joining unexcelled resistance to caustic alkalis,
Welding guidelines dissimilar metals. This includes not only even when molten. Though outstanding in
The majority of nickel alloy welds are per- welds of nickel-based alloys to iron-based its resistance to dry halogen environ-
formed by shielded metal arc welding alloys. but also for welds of stainlcss ments, nickel is not adequately resistant
(SMAW). gas tungsten arc welding steels to carbon and alloy steels. below the water dewpoint. For applica-
(GTAW) and gas metal arc welding Similarly. nickel alloys can be weld- tions m~ than 600"F. a lowcarbon vari-
(GMA W). Nickel alloy weldmcnts are deposited on carbon steel without the risk ant, designated Nickel 201 (UNS
very ductile. and their low thennal expan- of crocking. N02201), is the preferred choice.
sion characteristics reduee residual stresses NiCu Alloy 400. The corrosion
and warpage. Post weld heat treaunent is Types of nickel alloys behavior of nickel-copper Alloy 400. like
generally required only for precipitation- Nickel alloys are commercially available that of nickel. is best under reducing con-
hardcnablc grades. Specifications issued in a broad variety of product forms ditions and can be compromised by aera-
by the American Welding Society (AWS) including plate. sheet. strip. tubes. pipe. tion and oxidizing chemicals. Alloy 400
for nickel alloy welding electrodes and fittings and forgings. Selected ASTM possesses very good resislance to halogen
filler metals are liSlOO in Table 4. specifications for some of these are noted acids and compounds. particUlarly hydro-
Welding procedures for nickel alloys in Table 5. Some nickel alloys arc also fluoric acid and hot gases rich in fluorine
are fairly similar to those used for produced as castings. These generally or hydrogen fluoride.
austenitic stainless steels. Howevcr. due to have different charactcristics from their The alloy is used widely for handling
Alloy Sulfuric Phosphoric Hydrochloric Hydrofluoric Nitric Organic Strong Reducing Oxidizing
acid acid acid acid acid acids alkalis salts salts
.. ... ...
200
400
600
.
..
.
..
. .
.
.
625
690
825
G3
......
.
.
C276
B2
Excellent 10 good;
... Good to satisfactory;
Not recommended.
sulfuric acid solutions. sea water and Alloy 625 is a very strong material with thai. as with Alloy 20, were major devel-
brines. For applications requiring higher excellent resistance to fatigue. Alloy opment targets. Though reasonably resis-
strength. such as thaI demanded for valve 625LCF. a bellows.quality version of tantto hydrochloric acid, Alloy 825 is sub-
and pump components, use is made of Alloy 625. lays claim to exceptionally ject to chloride pitting and crevice corro-
Alloy K-500 (N05500), a precipitation- good resistance to low.cycle and thermal sion. panicularly in stagnant. unaerated
hardenable variant of Alloy 400. fatigue. solutions. Its high iron content makes
.NiCrFe Alloy 600. The addition of Like Alloy 600. Alloy 625 serves Alloy 825 less resistant than higher nickel
chromium to the nickel matrix extends the effectively both as a corrosion-resislant containing alloys to alkalis and halogens.
suitability of Alloy 600 imo the oxidizing and heat-resistant material. The combina- .Ni-Cr-Fe-Mo "G" alloys. Alloy G-3
range. Though only mediocre for mil'leral tion of eltcellenl high.temperature offers improved corrosion resistance over
acids. Alloy 600 has cltccllcnt resislallCe 10 strength and resistance to halogen attack, alloys 400, 600 and 825 in a wide range of
organic acids and is used e:uensively in oxidation and carburization has made applications. The: alloy is especially resis-
fatty acid processing. It is also employed Alloy 625 a favored choice for chemical tant to sulfuric acid and contaminated
widely in the production and handling of and petrochemical process equipment phosphoric acid. and can withstand both
caustic and alkali chemicals. exposed to hoslile, high-temperalllre envi reducing and oltidizing conditions. The
Alloy 600 also qualifies as an excellent ronments. more recently developed Alloy G-30 has
m:lleriaJ for high-temperature applications Ni-Cr Alloy 690. Alloy 690 has the better weldability and offers improved a11-
requiring a combination of heat and COfTO- highest chromium content among nickel round corrosion resistance. TlOtably in weld
sion resistance. The alloy's excellent perfor- alloys suilable for fabrication of pressure heat-affected zones.
mance in hol halogen environments makes equipment. which confers eltceptional Ni-CrMo ''C'' alloys. Alloy C-276
it a favorite choice for organic chlorination resistance to oxidizing media. It is effec- is considered [he preeminent alloy
processes. Other elevated temperature tively used for hot concentrated sulfuric employed in the chemical industry for
degradation processes against which Alloy acid, nitric acid and nitric,1lydrofluoric acid exceptionally corrosive environments that
600 has demonslrated excellenl resistance mixtures, as well as for oxidizing salts. are beyond the capability of stainless
are oltidation. carburizalion and nitridation. The high chromium content also improves steels. It has outstanding resistance to
NiCrMo Alloy 625. The addition of resislance in hot sulfidizing environments. acids. acid salts and a wide spectrum of
molybdenum to the Ni-Cr systems broad- NiCrFe Alloy 825. Because of its other aggressive substances encountered in
ens resistance to mineral acids and salts. near 30% iron content. Alloy 825 is s0me- chemical processing.
both oxidalion and reducing. Molybdenum times included in the family of super- Alloy C276 is particularly effective in
additionally confers resistance to pilling austenitic stainless steels. The alloy excels such punishing environments as wet chlo-
and crevice corrosion by wet chlorides. in sulfuric and phosphoric applicalions rine and hypochlorites. Owing to its
molybdenum content, Alloy C-276 is high- Recently introduced alloys 8-3 and 8-4
ly resislant 10 chloride-induced pitting and offer improved properties over Alloy B-2.
crevice corrosion. A practical advantage of these new grades
The quest for materials possessing bet- is minimized formation of undesirable
lcr metallurgical propenies and corrosion microstructures during fabrication that can
resistance than Alloy C-276 has spurred cause embritllemenl.
the development and commercialization of
several proprietary (.type alloys. repre- By G. Sorell. president of G. Sorell
sented by alloys C-22. 622, 59. 686 and C- Consiliting St'rvius. North Calm.,t'll. NJ.
2000. Sorell is a mott'rialS/CQrrosion engineer with
All have roughly comparable molybde- more toon 40 years of/lIdlUlrial experience.
num content but significantly higher Preparation oftlJis artielt' ...as sllpported by
chromium content than Alloy C-276. Some (ht' Nickel DeI'tlopmt'rtI Institute.
grades also contain tungsten and copper.
The effect of these minor alloying con-
SlilUents on metallurgical propenies and
corrosion resislance is complex and
beyond the scope of this anicte.
NiMo "B" alloys. Alloy B-2 has
exceptional resistance 10 sulfuric. phos-
phoric and hydrochloric acids under reduc-
ing conditions. It is panicularly suited for
equipment handling hydrochloric acid at
all concentrations and temperatures up to
the boiling point.
Oxidizing chemicals adversely affect its
corrosion resistance. notably such strong
oxidizers as ferric and cupric salts thai may
be present as contaminants.
he ability to withstand the combined Alloys 600. 601 and 625 are commonly strengthened (ODS) alloys produced by
..
2. Nicrofe,e AllOy 45 ftl , Nicrofer 6025tfTaIIoy 602CA (Krupp VDM GmbH)
For example. generic
useful srrengm at temperatures of 2,()()()IlF Alloy Amblotd 1,0lIII'f 1,2OO'f 1,6OO'F 1,BOD'F
and above. nickel alloys can still function
effectively for moderately stressed compo- 30455 42 18 16 10
nents. For example. the I.QOO-hr rupture 30955 45 26 23 18
strength at 2,ooooF is about 1.0 ksi for 310 SS 45 25 21 IS
Alloys 600. 601. 214. 230 and 333. and 1.4 600H 29 17 15 13 9
ksi for Alloys 617 and 602CA. 600 50 40 37 20 9
The ASME Boiler and Pressure Vessel 601 40 32 28 20 7
Code contains allowable stresses for the 617 45 32 34 35 18
alloys surveyed. except for Alloys 214, 625 48 32 35 38 18
242 aod 45TM. X 49 33 30 26 18
214 82 72 76 81 8
MetallUfJ1cai stability 230 57 40 39 21
Al10Iher important property in alloy selec- 242 113 70 76 50 28
tion for high-temperature applications is 333 43 25 25 24 10
metallurgical stability, which is also 45TM 53 36 34 28
known as thennal stability. The tenn refers 602CA 50 38 37 31 13
to the resistance to fonn brinle micr05U\1c-
tural phases or precipitates upon aging. i.e.,
after prolonged ellposure 8t elevated tem- about 1.2000F to 1,4()(pF. At higher tem- ments is gaseous corrosion. principally
peratures. That so-called "age embrittle- peratures, those properties are partly oxidation, sulfidation and halogenation
ment" manifests principally as reduced restored because brittle precipitates tend to (chloridation and fluoridation). Other
ductility and toughness. and may also redissolve. Equipment failures attributable fonns of deterioration encountered in hos-
impair corrosion resistance. to reduced ductility and toughness are tile elevated-temperature environments are
While some alloys. such as 600 and infrequent. which can be ascribed 10 the carburization, nitridation and hydrogen
601. are vinually immune to age embrittle very high starting properlies typical of attack. Those are not classed as corrosion
ment. most undergo varying degrees of unaged nickel alloys. in the conventional sense of the word.
impairment. Among those adversel)' because there is no metal loss or surface
affected is Alloy 625, which may suffer a Chemical resistance recession. Rather. damage manifests as
marked drop in ductility and impact The most prevalent form of attack in high metallurgical/mechanical impairment-
..
strength when exposed in the range of temperature chemical processing environ-
The directional effect of alloying con- lion modes may occur simullafleOUsly. For Forms of IIttaek
SlilUents on either retarding or exacerbating example. many industrial environments c0n- The common fOMs of high-temperature
high-tempernture chemical altack of nick- tain both oxygen and chlorine. subjecting chemical attack are brieny characterized
el-base alloys is shown in Table 5. exposed mcIaIs to ol(ychlorination, a highly below. Hydrogen attack is omitted because
The effect of Cr. Mo, Co. w. 5i and AI virulent fonn of corrosion. Exceptionally nickel alloys are highly resistant.
may be either favorable or detrimental, se~ COITOSion can also be caused by liquid Oxidation. Oxidation, the most com-
depending on the specific exposure condi- phases. such as molten salts, ash Of metals. mon fonn of corrosion at elevated temper-
matrix IlI1d ronn metal carbides. ThaI form ly welded by Ihe common welding (GMA W). Nickel alloy weldmenlS typical-
of lIt1ack, called carburizlIlion. can cause processes. inclUding shielded metal arc ly exhibit excellent duclility. and their low
severe impainnent of me<:hllnical proper- welding (SMA W). gas tungsten arc weld- thermal expansion characteristics tend to
ties. notably duclility and impact strength. ing (GTAW) and gas melal arc welding reduce residual slresses and diSlortion.
Nickel alloys exhibit good carburization
resistance because nickel. unlike iron. is Table 6. AWS speCifications for recommended weldmg materials
no! a strong carbide fonner.
Nitridation. Nitridation. orten called Alloy Welding electrode (AS.11) Filler m.lal (A5.14)
nilriding. refers to nitrogen diffusion into
the metal lanice to form metal nilrides. In 600 ENiCrFe-3 ERNiCrFe3
the chemical industry. it is encountered 601 ENiCrFe3 ' ERNiCrFe31,2
primarily in high-temperature ammonia- 617 ENiCrt:oMo-1 ERNiCrt:oMo-1
rich atmospheres. As in carburization. 625 ENiCrMo3 ERNiCrMo3
damage manifeslS no! as metal loss but as X ENiCrMo-2 ERNiCrMo-2
embrittlement. Nickel does not form 214 ENiCrMo2\ ERNiCrMo-2\.2
nitrides. which accounlS for the excellent 230 ENiCrWMo-1 1 ERNiCrWMol 1,2
nilridalion resislance of nickel-rich alloys. 242 ENiMo-3\ ERNiMo-3 1,2
Inlernal attack. Carburizalion and 602CA ENiCrCoMo-1 1 ERNiCrCoMol l ,2
nilridation are by no means the only high-
temperature degradation modes character- 1. These consumables are not exact matches to the loose metal composnions and the result-
ized by inlemal damage. Vinually all high ing weld deposits may not have the same high-lemperature corrosion resistance as the base
temperature corrosion is diffusion driven metal.
and characterized by substantial subsurface 2. Matching filler metals are available but are not Included in AWS specifications.
attack. predominanlly along grain bound-
aries. That applies to oxi-
dation. sulfidation. and
especially 10 halogenation.
Table 7. ASTM specifications for selected llroducl forms
In many instances. internal
attack penetrales deeper Alloy PI....... SUml. . plp. Woldedplp. SlImlns tube Welded tube
into the metal than surfoce
melal loss. Evaluation of BOO 8168 8167 8517 8167 8516
high temperature corrosion 601 8168 8167 8167
should therefore be based 617 8168 854li
not solely on thickness or 625 8443 B444 8705 B444 8704
weight loss. but additional X 8435 8622 8619 8622 8626
lyon metallographic 230 843S 8622 8619 8622 8626
examination. 333 8718 8722 8723 8722 8726
45TM 8168 8167 8517 8167 8516
Welding guidelines
Nickel alloys can be: readi- L.
602CA 8168 8167 8517 8167 8516 J
PostweJd heal treatment is generally not oxidation. chloridation. carburiz.ation and for combined chloridationloxidation,lsulfi
required for solution strengthened alloys. nitridation, but poor resistance to sulfida- dationjcarburization resistance. The alloy
RCl:ommended welding consumables tion. Alloy 600 is widely used for hOI chlo- excels in incineration and gasification
for the alloys surveyed. as covered by rine/hydrogen chloride and for ammonia proo=.
American Welding Society (A WS) specifi. atmospheres. Alloy 602CA has ex.ceptional resis-
cations AS.II and A5.14. are listed in Alloy 601 has excellent resistance to tance to cyclic oxidation (up to 2.2CJ01'F)
Table 6. Although not included in AW$ carburization and cyclic oxidation. It has and carburization and also provides good
AS.II and A5.14, matching filler melals moderate strength but excellent thennal resistance to oxidizinglsulfidizing gases.
for Alloys 601, 214. 230. 242 and 602CA stability. Alloy 601 is widely used in cont- It offers high creep strength at extreme
are commercially available. Matching filler aminated combustion environments. tcmperatures.
melals are the preferred choice for welds Alloy 617 has an exceptional combi-
exposed to aggressive high-temperalUre nation of high-temperature strength, ther- Cost fa<tors
environments because they provide greater mal stability and resistance to oxidation The alloys surveyed are about two times to
assurance that the weld metal will have the and carburization. The alloy is used in five times costlier than Type 310 stainless
same corrosion resistance as the base nitric acid and petrochemicals production. steel. The cost differentials are consider-
metal. Nickel-rich weld materials are wide Alloy 625 has the favoroble combina- ably lower on an installed--equipment basis.
Iy used also for dissimilar metal weld tion of high strength and good all-around largely because the cost of fabrication does
joints between nickel-base and iron-base corrosion resistance. including aqueous not vary greatly between nickel alloys and
alloys and for depositing weld overlays on environments. II has excellent fatigue stainless steels.
fenuus subslrJles. resistance but only moderate thennal sta- Another imponant consideration in ec0-
Welding procedures for nickel alloys are bility. Alloy 625 is used extensively in nomic analysis is the greater capabilities,
broadly similar to those for stainless steels. chemicaVpetrochemical plant services. lower maintenance and looger life of high-
However. modifications of joint designs and Alloy X has an outstanding combina perfomlance materials. On the basis of life-
tion of strength. fabricability and resistance cycle cost. nickel alloys often prove the
Welding procedures are broad- to oxidizing. carburizing and nitriding best economic choice.
gllse~. It is a popular alloy for stressed
componems in aggressive combustion
Iy similar for nickel alloys and
environments.
Alloy 214 has superb resistance to By G. Sorell, prtsidel1l ofG. Sorell
stainless steel.
oxidation (up to 2.2WF), chloridation. Conslliting Sn-,,icts. NOrlh Call"'n!!l. NJ.
carburiZlition and nitridation. It has Sorell is a materials/carrosiOrl erlgirleer ....ilh
welding techniques may be indicated to mediocre thermal stability, fllbricability mort Ihan 40 years ofintlllSlrial experimce.
achieve full penetration welds, conditioned and welJability. Alloy 214 is a niche alloy Preporo/iOrl of/his Or/ide ....a s s/lPporied by
by the sluggish flow characteristics of high- for ex.ceptionally cOfTOsh'e environments. /lie Nickel Derefopmem IIlS/i/llte.
nickel weld puddles. Nickel alloys are There is limited availability of product
inherently more sensitive than iron-base fonns and quantity.
metals to weld embriulemeOl by contami- Alloy 230 has the beSt balance of
nants. Exercise special care to shield the strength. thermal stability and fatigue resis-
wcld zone from foreign substances. tastce, oxidation resistance and fabricability
Wrought heat- and corrosion-resistant among major high-temperature alloys. It is
nickel alloys come in a wide range of prod- favored for high-strength components in
uct forms. including plate/sheet and both punishing combustion environments.
seamless and welded tubular goods. Alloy 242 is the best among nickel
ASTM specifications covering those are alloys for fluorine and fluoride resistance.
listed in Table 7. Most of the alloys in It has very high strength and good !hennal
Table I can also be produced as castings. stability. Alloy 242 is nOt TC<:ommended
albeit with minor chemistry modifications. for applications above 1.5WF. It is used in
fluoropolymers production.
Alloy characlerlstics .Alloy 333 has ex.cellent oxidation and
This brief rundown highlights the attributes carburization resistance. as well as good
of each of the alloys discussed that affect sulfidation resistance and mechanical prop-
their suitability for corrosive high tempera- enies. It is used in diverse chemical/petro-
ture environments in chemical plants. chemical plant applications.
Alloy 600 has excellent resistance to Alloy 45TM is the optimum choice