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NBS MONOGRAPH 106

Nickel and Its Alloys

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS
THE NATIONAL BUREAU OF STANDARDS

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UNITED STATES DEPARTMENT OF COMMERCE . C. R. Smith, Secretary

NATIONAL BUREAU OF STANDARDS • A. V. Astin, Director

Nickel and Its Alloys

National Bureau of Standards Monograph 106

Issued May, 1968

(Supersedes NBS Circular 592)

For sale by the Superintendent of Documents, U.S. Governme nt Printing Office Washington, D.C., 20402 - Price $1.25

Samuel J. Rosenberg

Institute for Materials Research

National Bureau of Standards Washington, D.C. 20234
Foreword

Publications by the National Bureau of Standards include a series of Monographs (previously designated as Circulars), each of which represents a compilation and critical review of available information on a particular subject. Metallurgical Circulars, each dealing with a particular metal and its alloys, have

been prominent in this series. Circular 100, entitled "Nickel and its Alloys," authored by P. D. Merica, was published in 1921 when

expansion and growth of the nickel industry were becoming noticeable. A second edition (revised by E. C. Groesbeck) was issued in 1924. At the close of World War II the subject was again reviewed and Circular

485, written by M. R. Meyerson, was published in 1950. However, much information about the strategic ele- ment, nickel, had been developed during World War II but was not yet available for publication in Circular

485. The phenomenal expansion of the North American nickel industry since 1950, the release of some of

the previously restricted information, the development of new theories of alloying and heat treatment, and

the development of new alloys to meet industrial requirements of ever-increasing severity made it desir- able again to revise the Nickel Circular. That revision. Circular 592, was written by J. G. Thompson and

published in 1958. During the relatively few years since the publication of the last nickel circular, development of nickel

alloys and steels has continued so that considerable information needed to be incorporated in a revised edition, and much old data needed to be updated. This task was assigned to S. J. Rosenberg, formerly Chief of the Engineering Metallurgy Section, Metallurgy Division, Institute for Materials Research, of the National

Bureau of Standards.

The current revision, like the previous one, was sponsored by The International Nickel Company, In- corporated, and was written at the National Bureau of Standards under the Bureau's Research Associate

plan. This revision represents a review of the literature through 1965 and includes some 1966 references.

A. "V. ASTIN, Director

Library of Congress Catalog Card Number: 67-62384
Trademarks

A number of alloys discussed in this compilation are marketed under the following various trademarks:

Trademark Owner

ALUMEL

CARPENTER STAINLESS NO. 20

CARPENTER 426 CHROMEL

COBENIUM

CONPERNIK

COR-TEN

CUFENLOY

DISCALOY

DURANICKEL

DYNALLOY

DYNAVAR

ELGILOY

ELINVAR

GEMINOL

HASTELLOY

HI-STEEL

HIPERNIK

HP

HY-TUF

ILLIUM

INCOLOY

INCONEL

INVAR

KANTHAL

KOVAR

MAGARI-R

MANGANIN

MINOVAR

MONEL

MONIMAX

NICROTUNG

NIMOCAST

NIMONIC

NISILOY

NI-SPAN-C

PERMALLOY

PERMANICKEL

REFRACTALOY

RENE 41 RODAR

SD

SIMINEX

SEALMET

STAINLESS STEEL W

STAINLESS STEEL 17-4PH

SUPERMALLOY

T-1 TRI-TEN

TRW

UDIMET

I UNITEMP

USS STRUX

WASPALLOY

WELCON

WEL-TEN

YOLOY

Hoskins Manufacturing Company

The Carpenter Steel Company

The Carpenter Steel Company

Hoskins Manufacturing Company

Wilbur B. Driver Company

Westinghouse Electric Corporation

United States Steel Corporation

Phelps Dodge Corporation

Westinghouse Electric Corporation

The International Nickel Company, Inc. Alan Wood Steel Corporation

Precision Metals Division

Elgin National Watch Company

Hamilton Watch Company

Driver-Harris Company

Union Carbide Corporation

Inland Steel Corporation

Westinghouse Electric Corporation

Republic Steel Company

Crucible Steel Company

Stainless Foundry & Engineering Inc. The International Nickel Company, Inc. The International Nickel Company, Inc. Soc. Anon, de Commentry-Fourchambault et Decaziville (Acieries d'Imphy)

The Kanthal Corporation

Westinghouse Electric Corporation

Bethlehem Steel Corporation

Driver-Harris Company

The International Nickel Company, Inc. The International Nickel Company, Inc. Allegheny Ludlum Steel Corporation

Westinghouse Electric Corporation

The International Nickel Company, Inc. The International Nickel Company, Inc. The International Nickel Company, Inc. The International Nickel Company, Inc. Allegheny Ludlum Steel Corporation

The International Nickel Company, Inc. Westinghouse Electric Corporation

Allvac Metals Corporation (Division of Teledyne)

Wilbur B. Harris Company

The International Nickel Company, Inc. Allegheny Ludlum Steel Corporation

Allegheny Ludlum Steel Corporation

United States Steel Corporation

Armco Steel Corporation

Allegheny Ludlum Steel Corporation

United States Steel Corporation

United States Steel Corporation

TRW, Inc. Special Metals Corporation

Universal Cyclops Specialty Steel Division, Cyclops Corporation

United States Steel Corporation

Pratt and Whitney Aircraft

Japanese Steel Works, Ltd. Yawata Iron & Steel Company, Ltd. Youngstown Sheet & Tube Company

iii
Contents

Page Foreword ii Trademarks iii 1. Introduction 1 1.1. History 1 1.2. Occurrence, minerals, ores 2

1.3. Recovery of nickel from its ores 4

1.4. Statistics of production and consumption 6

1.5. Available forms of nickel 6

2. Nickel—Properties and uses 9

2.1. Physical properties 9

a. General 9

(1) Atomic number and weight—isotopes 9

(2) Nuclear properties 10

(3) Crystal form and lattice constant 10

(4) Density 10

(5) Miscellaneous physical properties 12

b. Optical properties 12

c. Thermal properties 14

(1) Melting and boiling points; heat of fusion; vapor pressure 14

(2) Specific heat and heat capacity 14

(8) Thermal expansion 15

(4) Thermal conductivity 17

(5) Thermionic properties 17

(6) Recrystallization temperature 18

d. Electrical properties 19

(1) Electrical resistivity 19

(2) Thermal electromotive force 21

e. Magnetic properties 22

(1) General 22

(2) Curie point 22

(3) Saturation 24

(4) Permeability 24

(5) Coercivity 24

(6) Magnetostriction 25

2.2. Chemical properties 26

a. Behavior in corrosive media 26

(1) Water 27

(2) Mineral acids, alkalies, and salts 27

(3) Organic acids and compounds 28

(4) Atmospheres 28

(5) Wet and dry gases 29

(6) Oxidation 29

b. Adsorption and diffusion of gases and metals. 30

c. Catalytic action 34

d. Electrolytic solution potential—passivity 36

e. Hygienic significance 36

2.3. Mechanical properties 37

a. Tensile and compressive properties 37

b. Elastic properties 41

c. Hardness 41

d. Impact 44

e. Fatigue 46

f. Creep 46

g. Ductility 47

h. Friction 48

2.4. Effect of minor constituents on properties 48

a. Carbon 48

b. Cobalt 48

c. Copper 48

d. Iron 48

e. Magnesium 49

f. Manganese 49

g. Oxygen 49

h. Silicon 49

i. Sulfur 49

3.2.

a.b.

2.5. Technology

a. Melting and casting

b. Hot-forming (forging, rolling, extrusion)

c. Cold-forming (drawing, shearing, punching,

spinning)

d. Welding, brazing, soldering

e. Annealing

f. Pickling

g. Machining

h. Grinding, polishing, buffing

2.6. Metallography of nickel

a. Selection of specimens

b. Preparation of specimens

(1) Grinding

(2) Rough polishing

(3) Final polishing

(4) Electropolishing

c. Etching

2.7. Uses of nickel

a. Coatings

(1) Electroplating

(2) Electroless plating

(3) Electroforming

(4) Nickel cladding

(5) Sprayed and vapor-deposited coatings

b. Nickel powders

c. End uses of nickel and nickel-surfaced materials

, Nonferrous alloys

3.1. General

High-nickel alloys

Nickels

Nickel-chromium alloys

c. Nickel-chromium-iron alloys

d. Other high-nickel alloys

e. Superalloys

f. Nickel-copper alloys

(1) Monel alloys

3.3. Low-nickel alloys

a. Copper-nickel alloys

(1) Coinage alloys

(2) Corrosion-resistant and engineering al- loys

(3) Thermocouple and electrical resistance

alloys; alloys for electrical use

b. Copper-nickel-zinc alloys (nickel brasses)

3.4. Miscellaneous alloys

4. Ferrous alloys

4.1. General

4.2. Wrought steels

a. Low alloy steels

b. Ultra high-strength structural steels

c. Maraging steels

d. Special steels

4.3. Cast steels and irons

a. Cast steels

b. Cast irons

4.4. Stainless steels

a. General

b. Martensitic stainless steels

c. Austenitic stainless steels

d. Precipitation-hardening stainless steels

4.5. Thermal expansion and constant modulus

alloys

4.6. Magnetic alloys

a. Magnetically soft materials

b. Permanent magnets

5. Multicomponent systems

6. References

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IV
Nickel and Its Alloys

Samuel J. Rosenberg*

This monograph reviews available information on the production, properties, and

uses of high-purity and commercial forms of nickel, and on the properties and applications

of its important alloys, both ferrous and nonferrous. It is a revision of National Bureau

of Standards Circular 592, issued in 1958.

Key Words: Alloys, corrosion-resisting alloys, copper-nickel alloys, electroplating,

electrical resistance alloys, heat resisting alloys, magnetic alloys,

maraging steels, nickel, stainless steels, steels.

' Research Associate from The International Nickel Company, Inc., at the National Bureau of Standards, Washington. D.C. 20234, 1965-1967.

1. Introduction

1.1. History

Alloys of nickel had been known and used for

thousands of years before its identification as

a metallic element was established. There is reliable evidence that prehistoric man made use

of iron-nickel alloys of meteoric origin [1].^

The earliest authenticated artifact from such a source is what is believed to be a portion of a dagger found at Ur of the Chaldees (c. 3100

B.C.) ; analysis has shown it to contain 10.9

percent Ni [2].

The first manmade alloy containing nickel,

believed to date back to 3500-3100 B.C., is a bronze reamer containing 2.73 percent nickel

found in the plain of Antioch in Syria [3] . The

earliest copper-nickel alloy objects which are known to have survived to the present day are

coins minted in Bactria, an ancient kingdom

situated north of present-day Afghanistan [4].

Coins (c. 200-190 B.C.) issued during the reign

of the Greek sub-king Euthydemus II analyzed

20.038 percent nickel and 77.585 percent copper

[5]. It is interesting to note that this composition is very near that of the 75/25 Cu/Ni alloy

used for minting the U. S. five-cent coin.

Nickel was first identified as an element by

Cronstedt in 1751 [6], although he did not name

it until 1754 [7] . Its identity was confirmed by

Bergman in 1755 [8]. According to Fourcroy

[9] , the nickel prepared by Bergman was much

purer than Cronstedt's. Richter [10] apparently was the first to obtain pure nickel. His description of its characteristics is interesting

:

"Its color is half-way between that of silver

and pure tin. "It is not affected by air or atmospheric

water, that is, it does not rust. "It is perfectly ductile; rods can be made

from nickel when it has been heated and

one can beat them into very thin plates

when cold. Because of this property, nickel

canno!; be considered a semi-metal and takes

its place amongst 'perfect' metals.

"Its specific weight or density is 8.279 for

molten nickel and 8.666 for wrought nickel. "Its strength is considerable.

"It has a high melting point and so is ex- tremely difficult to melt, at least as difficult as manganese.

"The metal oxidized very little on being

heated until red, when it becomes a little duller than platinum, gold or silver. Thus

nickel is not only a perfect metal but also a

noble one. "The action of magnets on nickel is very

great, only slightly less than their action on

iron."

The earliest recorded use of nickel in modern

times (i.e., the last few hundred years) was in

"white copper" or "pai-thung," - first mentioned in 1597 [11]. von Engestrom [12] gave

its analysis as 40.60 percent copper, 18.75 percent nickel, and 31.25 percent zinc. A basin and

ewer made in China of "white copper" was

analyzed by Fyfe [13] as containing 40.4 percent copper, 31.6 percent nickel, 25.4 percent

* Figrures in brackets indicate the literature references at the end

of this paper.

- Variations of this term are petong, pehtong, paaktong, packtong,

pak-fong, and packfong.

1
zinc, and 2.6 percent iron. These utensils were

so attractive that Thomason [14] began the

manufacture of an alloy based on the above

composition ; his alloy was mixed in the following proportions: 40 percent copper, 31 percent

nickel, 26 percent zinc, and 3 percent iron.

Although many attempts were made to incorporate nickel in cast iron, wrought iron, and

steel, it remained for Riley [15] to be the first to describe the improved mechanical properties

of nickel steel in 1889. These nickel steels found

their first extensive use in ordnance material in

the 1890's and the role of nickel as an alloying

element in steel to develop strength and toughness became firmly established. An historical

review of nickel steels was written by Yeo and

Miller [15a]. The twentieth century witnessed

the development and tremendous growth of a

large variety of corrosion- and heat-resistant

alloys, including stainless steels ar d superalloys, as well as numerous nonferrous alloys. There

are many uses where the importance cannot be

evaluated in terms of tonnage involved, for ex- ample, in magnetic alloys, in alloys with controlled rates of thermal expansion, and in alloys

for monitoring neutron doseage.

1.2. Occurrence, Minerals, Ores

In his classic work, Clarke [16] estimated the

average nickel content of the earth's crust to a depth of 10 miles as 0.019 percent. A reestimate

by Wells [17] changed this figure slightly, to 0.016 percent, whicn indicates an abundance

greater than the total of copper, zinc, and lead. Sandell and Goldich [18] estimated that nickel

constitutes 0.008 percent of the uppermost crust

of the earth. Fraser [19] stated that nickel is the 23d element in the order of abundance in the

lithosphere and that the average nickel content

of all igneous rock is about 0.009 percent.

Queneau and Roor'da [20] note that nickel ranks

24th in the earth's crust in the order of abundance of the elements. They report that geochemists estimate that the earth's crust averages

about 0.01 percent of nickel.

Although nickel is widely distributed over

the face of the earth, the igneous rocks in which

it occurs are not readily susceptible to concentration of the contained minerals by weathering.

Hence there are workable deposits of nickel

minerals in relatively few localities, and even

in these the concentration of nickel is so low

that economic exploitation usually depends upon

the recovery of valuable by-products.

The presence of nickel has been identified in

the spectrum of the sun [21] and many of the

stars, in deep sea silt [22,23], and it has long

been known that nickel is an important constituent of metallic meteorites. It is interesting, as a

future possibility, to consider that the nickel

content of sea water, reported by Ishibashi [24]

to be 0.7 to 0.8 microgram per liter, can be

expressed as 3 tons of nickel contained in each

cubic mile of sea water.

A large number of nickel-bearing minerals

have been identified but relatively few are abundant enough to be industrially significant.

Nickel minerals that are or have been important

are classified as sulfides, oxides, silicates (including nickeliferous iron ores), and arsenides.

Of these, the most important present-day ores are sulfides and oxides.

In the sulfide ores, nickel occurs chiefly as

the mineral pentlandite, (FeNi)9S8, in association with large amounts of pyrrhotite, Fe„_iS„,

commonly FejSs, and usually with a significant

amount of chalcopyrite, CuFeS2. In addition to

nickel, iron, and copper, these ores contain varying amounts of cobalt and precious metals : the

platinum group, gold and silver. Their chemical

composition falls in the general range 0.4-3 percent Ni, 0.2-3 percent Cu, 10-35 percent Fe,

5-25 percent S, with the balance being substantially SiOs, AI2O3, MgO, and CaO. The nickel

content of pentlandite is normally close to 34

percent, although it has been found to range up

to 36 percent, and its cobalt content varies between about 1 percent and 5 percent of the con- tained nickel. Pyrrhotite, about 57 percent iron,

accounts for most of the ore's iron content. This

mineral often contains a small portion of nickel,

partly as a very fine dispersion of pentlandite,

partly SiS Si solid solution, with a combined minimum nickel content varying around 1 percent

of the contained iron. Chalcopyrite is usually

the only important copper mineral, although

cubanite, CuFe2S3, may also occur. The chief minerals of nickel are given in

table 1. Some other nickel minerals are polydymite, Ni3S4; ullmanite, NiSbS; parkerite,

Ni3Bi2S2 ; and trevorite, NiO • Fe203.

Table 1. Nickel Minerals

Ideal formula % Ni Color Crystal system

Sulfides: Pentlandite (Fe.NDsSs 34.22 Bronze- Isometric Yellow

Millerite NiS 64.67 Brass- Hexagonal YeUow

Heazlewoodite NisSa 73.30 Bronze- Isometric (?) Yellow Polydymite Ni3S4 57.86 Steel-Gray Isometric Violante (Ni.Fe) 3S4 38.94 Violet-Gray Isometric

Siegenite (Co.Ni) sSi 28.89 Steel-Gray Isometric

Arsenides:

ISIiccolite NiAs 43.92 Copper-Red Hexagonal

Mauclierite NiuAss 51.85 Platinum- Tetragonal Gray

Ramniels- NiAsa 28.15 Tin-White Orthorhombergite bic (?) Gersaorffite NiAsS 35.42 Steel-Gray Isometric

Arsenate: Annabergite NisAszOs'SHjO 29.40 Apple- Monoclinic Green

Silicate and

Oxide:

Garnierite (Ni.Mg)6Si40io(OH)8 Variable up Green- Amorphous

to 47% Gray

Nickeliferous (Ni.FejaOj.nHjO Low but

limonite variable
Nickel is found also in a number of less com- mon secondary silicate minerals and it is known

to substitute for magnesium in certain primary

minerals (olivene, hypersthene, hornblende,

biotite) . Native nickel approaching purity is un- known. Small quantities of nickel combined with

iron have been found in meteorites.

In addition to the famous sulfide nickel ores

of northern Ontario, important tonnages of similar ore are now being mined at Thompson and

Lynn Lake in northern Manitoba. Russia produces nickel from sulfide deposits in the

Pechenga (formerly Finnish Petsamo) and

Monchegorsk areas near Murmansk and at Norilsk, near the mouth of the Yenisey in

Siberia.

Oxide ores, commonly called laterites, are

residual concentrates of chemical action by

weathering in place of basic igneous rocks high

in magnesium and iron and with a small amount

of nickel, e.g., 0.2 percent in peridotite, mainly

associated with magnesium-rich minerals such

as serpentine, olivine, and pyroxene. Nickel can

substitute for magnesium in the crystal lattices

of these minerals because its atomic radius

(0.69 A) is about equal to that of magnesium

(0.66 A). Depending upon the extent of weathering, two main types of oxide ore can be distinguished: silicate-type ore, in which nickel

is contained in the lattice of hydrated magnesium-iron-silicates, of which garnierite

(Ni,Mg)6Si40io(OH)8 is the most common, and

limonitic-type ore, predominately the hydrated

mineral goethite, Fe^Oa • H2O, in which nickel

is dispersed, and iron oxide such as hematite

Fe203. The chemical composition of oxide ores

varies widely and, in addition to 1-3 percent

nickel, they contain significant amounts of co- balt and chromium. Silicate-type ore in New

Caledonia analyzes about 2-3 percent Ni, 0.1 percent Co, 2 percent Cr203, and 20-25 percent

MgO. Cuban ore, primarily of the limonitic type,

analyzes in the range of about 1.2-1.4 percent

Ni, 0.1-0.2 percent Co, 3 percent Cr^Os, and 35-

50 percent Fe.

Oxide ores are widely distributed, but occur mainly in the tropical areas of the world and

form the largest nickel reserves. Nickel is produced in important quantities from oxide deposits in Cuba, New Caledonia, the USSR, and

the United States. Extensive deposits are known

in Indonesia, the Philippines, and Central and

South America.

The nickel arsenides are of minor importance

today as sources of nickel, but are of historical

interest. Niccolite (NiAs) is still the principal

nickel-arsenide mineral. Others that have re- ceived attention at one time or another include

bravoite (arsenide of nickel and iron), chloanthite and smaltite (arsenides of nickel and co- balt), gersdorffite (nickel-iron-cobalt sulfarsenide), annabergite (hydrous nickel arsenate),

and breithauptite (antmonide of nickel).

Additional information on the mineralogy and

geology of nickel is presented by Coleman [25]

,

Lindgren [26] , Mellor [27] , Dana [28] , Hall

[29], in a report by the U. S. Bureau of Mines

[30], and by Boldt and Queneau [36].

Table 2 gives estimates of known deposits of

nickel ore, as quoted by Queneau and Roorda

[20], and figure 1 illustrates the geographical

distribution of the principal nickel deposits of

the world. The Canadian ores of the Sudbury

District in Ontario have been the dominant fac- tor in the nickel industry for many years. These

ores consist mainly of lenses of mixed pentlandite, pyrrhotite, and chalcopyrite. There is considerable variation from mine to mine, but the

average content of the ore is about 1.5 percent

each of both nickel and copper. These deposits were discovered in 1884 as a result of excavations made during the building of the Canadian

Pacific Railroad [29,29a,31] and subsequent

prospecting in the vicinity. Originally the ores were valued primarily for their copper content,

and copper today is second only to nickel in

importance of products recovered from these

ores. Valuable by-products include the platinum

metals, cobalt, gold, silver, selenium, tellurium,

sulfuric acid, liquid sulfur dioxide, and highgrade iron ore, in the form of sintered pellets.

Table 2. Nickel ore bodies and estimated reserves "

Ore Reserve, Grade Tons

Occurrence Type Tons % Ni Contained

Nickel "

Canada:

Int. Nickel Co Sulfide 325,000,000 1.5 4,875,000

Falconbridge Sulfide 56,000,000 1.4 785,000

Sherritt Gordon Sulfide 11 ,400,000 0.8 90,000

Finland _ . _ _ _ Sulfide 3,000,000 0.6 • 20,000 Cuba Oxide 3,000,000,000 0.8 24,000,000 New Caledonia- Oxide 1,400,000,000 1-5 20,000,000

Indonesia.- - Oxide 850,000,000 0.5-2 10,000,000

Philippines Oxide 550,000,000 0.8 4,000,000

\ enezuela . Oxide 40,000,000 1.7 700,000

Brazil Oxide 20,000,000 1-3.5 500,000 Japan . Oxide 30,000,000 0.5 150,000

Greece . Oxide 10,000,000 0.5-1 75,000 Malagasy- .- .- _- Oxide 900,000 5 50,000

L'SA Sulfide, Oxide 54,000,000 0.3-1.5 400,000 USSR--. Sulfide, Oxide 300,000,000 0.3-1.5 3,000,000

Others'' .-. ... Sulfide, Oxide 1,000,000,000 0.5-2 10,000,000

"Estimate from recent publications. ''Important tonnages of nickel ore occur in other countries such as in the Dominican Republic, Guatemala, Solomon Islands, Australia, etc. "^Figures rounded off.

Sulfide ore similar to the ore of the Sudbury

district was found in the Lynn Lake area in

northern Manitoba in 1941 [32,33], and was

brought into production by Sherritt Gordon

Mines, Ltd. in 1953. Deposits of nickel ore have

been reported in New Brunswick, Quebec, British Columbia, Northwest Territories, Yukon

Territories, and Saskatchewan.

The nickel silicate ores of New Caledonia were discovered by Garnier in 1865, and were

the principal source of the world's supply of

nickel from 1875 to 1903. The nickel minerals

are usually associated in the ore with considerable iron, which is present as hydrated oxide or

3
X REFINERY • MINE 8 REFINERY

o MINE o POTENTIAL SOURCE

Figure 1. Principal sources of nickel ore in 1965.

silicate. The ores originally exploited were variable in composition but appreciably richer in

nickel than the Canadian ores. Subsequently,

attention was paid to ores that were not so rich,

and Hall [29] reported that the New Caledonia

ores ran 4 to 6 percent of nickel.

The nickel-bearing iron ores of Cuba, in the

districts of Mayari, Moa Bay, and San Felipe, are an important group of ores. According to Moldenke [34], the dried Mayari ore contained

49 percent Fe, 11 percent AI2O3, 3 percent Si,

1 percent Ni, and 1.5 percent Cr. Williams [35]

noted that there are two types of ores in the

Nicaro deposits ; surface occurrences of limonite

containing about 1.25 percent of nickel and 45

percent of iron, underlain by altered serpentine

that contains up to 1.6 percent of nickel and

down to 12 percent of iron. In contrast to the

Nicaro ores, most of the nickel in the Moa Bay

ores is in limonite.

In the United States, the silicate and nickelbearing ores near Riddle, Douglas County, Oregon, are the source of the only appreciable production of nickel. Other locations of nickel ores

in the United States are near Fredericktown,

Missouri, the Lancaster Gap area in Pennsylvania, in Lake County, Minnesota, in Grant

County, New Mexico, and in Alaska.

Minor production comes from the sulfide ores

of Africa and the oxide or silicate ores of Greece

and the Central Celebes. The sulfide and ar- senide ores of southern Norway were the most

important nickel ores until competition developed from New Caledonia. An important European source of nickel, according to Boldt and

Queneau [36], is in Greece, particularly the

magnesium-silicate ores, with the chromiumnickel iron ore (similar to the Mayari ore of

Cuba) of less importance. There are sulfide ores

in the Transvaal area of the Union of South

Africa, and cobalt ores in Morocco.

Other ore bodies are known to exist in Borneo,

Solomon Islands, the Philippines, Australia,

Malagasy, Brazil, Venezuela and Guatemala.

1.3. Recovery of Nickel from Its Ores

In sulfide-type nickel ores, the sulfides of

nickel, copper, and iron occur as distinct minerals, and beneficiation methods such as flota- tion and magnetic separation generally can be

employed after the ore has been crushed and

ground suflSciently fine to liberate the sulfide

particles from the worthless gangue. With oxide

ores, however, the fine chemical dissemination

of the nickel content precludes the application

of such beneficiation procedures, and except for

minor screening or sorting out of barren lumps,

the entire ore must be treated by either pyro-, hydro-, or vapo-metallurgical procedures, or by

a combination of them.

Electrolytic refining is the final purification

step for over half of the world's nickel production. The electrorefining process not only yields

nickel of high purity, but facilitates the recov- ery of elements associated with nickel in the

ores, such as the precious metals and cobalt. A

variety of beneficiation and extractive metallurgical procedures are employed to prepare

crude metal or sulfide anodes for electrorefining.

Some higher-grade sulfide ores may be

smelted directly, but usually flotation or magnetic concentrates are produced in the initial beneficiation step. To keep slag losses to a minimum, subsequent smelting operations are con- ducted in three phases; roasting, smelting, and

converting, respectively, which progressively in- crease the valuable metal content. The concentrates are first roasted in multi-hearth furnaces,

sintering machines, or fluidized-bed reactors, to oxidize part of the iron and sulfur constituents. In the ensuing smelting operation, for which

4
blast, reverberatory, or electric furnaces are employed, the iron oxide combines with silice- ous flux to form a molten slag which is skimmed

off and discarded, while the more valuable

metals are collected by the sulfur into a molten

'furnace' matte, which usually contains about

15 to 20 percent nickel-copper, 50 percent iron,

and 25 percent sulfur.

The furnace matte is further up-graded by a converting (or Bessemerizing) process, in

which molten matte is charged to Pierce-Smith

horizontal type converters and air or oxygenenriched air is blown through it to selectively

oxidize the iron and a part of the remaining

sulfur. Slag formed in the converters is re- turned to the primary furnaces to be cleaned

of its metal content. The Bessemer matte produced contains about 47 percent nickel, 30 percent copper, and 22 percent sulfur. Several

methods are employed by the various nickel

companies to separate nickel and copper in the

Bessemer matte and produce refined nickel.

At The International Nickel smelter at Copper

Cliff, converting is continued until the matte is slightly deficient in sulfur to form sulfides with

all the nickel and copper that are present. The

molten converter matte is then cast into insulated moulds and cooled slowly over a period of

several days, during which time it solidifies and

forms discrete grains of copper sulfide, nickel

sulfide, and a small amount of a nickel-copper

metallic phase. These constituents can be separated by standard beneficiation procedures of

crushing, grinding, magnetic separation, and

flotation. The metallic phase serves to collect the

major portion of the precious metals and, being

magnetic, is readily removed for separate treat- ment. Part of the nickel sulfide flotation con- centrate from the matte separation process is roasted in fluidized beds to make nickel oxide

sinter containing 75 percent or 90 percent

nickel, for direct use by the steel industry. Part

is melted and cast into nickel sulfide anodes for

direct electrorefining. The major portion is fluid-bed roasted to oxide, a part of it is sent to Clydach, Wales, for refining by the carbonyl

process, and the remainder is reduction smelted

to crude metal and cast into metal anodes for

electrorefining.

At Thompson, Manitoba, where smelter feed

contains much less copper, the converter (Bessemer) matte containing about 76 percent

nickel, 20 percent sulfur, and small amounts of

copper, cobalt, and iron, is cast directly into

nickel sulfide anodes which are then electrorefined in the same manner as crude metal anodes.

In Falconbridge practice, the converter matte is roasted to oxide, copper is removed from the

calcine by acid leaching, and the leached calcine

is smelted to nickel anode metal.

Electrorefining is conducted in divided cells,

which are separated by porous diaphragms into

anode and cathode compartments, respectively.

Impure anolyte obtained from dissolution of the

crude metal or sulfide anodes is constantly re- moved from the cells, pumped to a purification

section where impurities are removed by chemical treatment, and returned as purified electrolyte to the cathode compartments. Flow through

the porous diaphragm from the cathode com- partment to the anode compartment is suffi- ciently restricted to maintain a small hydrostatic head in the former. The constant outflow

prevents impurities from reaching the cathodes,

where nickel of 99.9+ percent purity is deposited. Pure nickel starting sheets become fin- ished cathodes in about ten days. The purity of

nickel from sulfide anodes is similar to that

obtained from metal anodes. Sulfur, selenium,

tellurium, and the precious metals do not dissolve anodically and may be recovered from the

anode sludge. When sulfide anodes are used, this

sludge contains about 95 percent sulfur.

As previously mentioned, nickel is also refined at Clydach, Wales, by the carbonyl process discovered by Langer and Mond in 1899. The

nickel oxide from Copper Cliff is reduced to crude metal, which is then reacted with carbon

monoxide to form gaseous nickel carbonyl. Upon

heating, the carbon gas decomposes into its constituents, carbon monoxide and pure nickel,

and the latter deposits upon seed nickel pellets

in a decomposer. The carbonyl process produces

a very high purity nickel in which cobalt is essentially absent.

Nickel is also produced commercially by gas- eous reduction of nickel leach solutions derived

from both sulfide and oxide ores. While preparatory treatments and leaching procedures vary,

nickel is precipitated from a purified aqueous

solution by reduction with hydrogen at elevated

pressure and temperature.

As practiced by Sherritt Gordon, pentlandite

concentrates analyzing about 10 percent nickel,

2 percent copper, 0.5 percent cobalt, 38 percent

iron, and 31 percent sulfur are dissolved under

elevated temperature and pressure in an aerated

ammoniacal solution. The base metals are con- verted to soluble amines, while the iron remains

in the residue as a hydrated ferric oxide. The

leach solution is then boiled to recover part of

the ammonia and precipitate the copper as sulfide, unsaturated sulfur compounds are destroyed by oxidation and hydrolysis, and the

solution is reacted with hydrogen at 30 atm

and 200 °C to precipitate nickel powder which

analyzes about 99.9 percent nickel. Some of the

powder is briquetted and sintered for market.

The Freeport Nickel Company developed a pressure acid leaching process to recover nickel

and cobalt from the limonitic type oxide ores of Cuba. The ore is leached with sulfuric acid

at elevated temperatures and pressures selected

to enhance preferential solution of nickel and

cobalt, while leaving most of the iron undissolved. After separation from the residue, the

5
leach solution is treated with hydrogen sulfide to precipitate nickel and cobalt as sulfides. The

sulfide slurry is shipped from Cuba to Louisiana,

where it is redissolved in acid solution, impurities are removed, and the nickel precipitated as a 99.8 percent nickel powder by reduction with

hydrogen at high pressure. The powder is then

briqueted for market.

Nickeliferous oxide ores of the silicate type

are smelted to ferronickel in several countries,

notably in New Caledonia, Japan, Greece, Brazil, and at Hanna Nickel Smelting Company in

Oregon. Blast furnaces, rotary kilns, and electric furnaces are used by various producers,

with carbonaceous material or ferrosilicon as the reducing agent. Crude ferronickel is refined

generally in two stages (oxidizing and reducing) , the oxidizing stage removing carbon, sili- con, chromium, and phosphorus, and the re- ducing stage any residual sulfur.

The distribution of nickel ore deposits in the

world and their geological background, mining

methods for their recovery, and the various

beneficiation, pyrometallurgical, hydrometallurgical, and vapometallurgical methods that are presently in use throughout the world for

extraction of nickel and associated metals, are

described in considerable detail in a recent book

by Boldt and Queneau [36], which was produced under the sponsorship of The International Nickel Company.

1.4. Statistics of Production

and Consumption

World production of nickel was less than 100

tons per year in 1850 and it did not reach 1000

tons per year until the 1880's. Production began

to become commercially important during the

1890's. As shown in figure 2, the production of

nickel has increased at a phenomenal rate during the last decade.

In the early years of the century, New Caledonia was the principal source of supply of

nickel. Canadian output became greater than

that of New Caledonia in 1903. Today approximately 57 percent of the world's production of

nickel comes from Canada [42]. The estimated

world production capacity for nickel in 1965 is given in table 3. Expansion of productive capacity is in progress by several major nickel

producers.

Table 3. Estimated world nickel production capacity [20a]

Country Million pounds

Type of ore

Canada. . 538

19038

11428

36 944

Sulfide

Sulfide and oxide Oxide Oxide

Oxide

Sulfide and oxide

Soviet Union- . . Cuba _ . France (New Caledonia) . _ United States. . . ...

Others (South Africa, Finland, Brazil, etc.).. Total

The price of nickel [4] varied from about

$1.70 per pound in 1840 to about $3.10 per

pound in 1845-1846. From then it dropped to about $1.10 per pound in 1862, then increased

to about $2.30 per pound in 1864, dropped to

less than $1.30 per pound in 1870, and then in- creased markedly to over $3.80 per pound, an

all-time high. The price of nickel since 1890 is plotted in figure 2. The price as of Nov. 1, 1966 was 85.25^'/lb; this was increased to 94fi/lb on

Sept. 15, 1967.

As shown in figure 3, the consumption of

nickel in the United States has increased at a

steady rate since the end of World War II. Of

this total, the stainless steels now consume the

largest amounts of nickel. The approximately

350 million pounds of nickel consumed in the

United States in 1965 were used as follows

[42]

Stainless steels 30.0%

Other steels 15.7

Cast irons 4.0

Nonferrous 21.6

High temperature and electrical

resistance alloys 10.7

Electroplating 11.3

All other uses 6.7

Under this last heading are such uses as catalysts, ceramics, chemicals (other than electroplating), iron-nickel alloys, magnets, metal

powder products, welding rods, etc.

1.5. Available Forms of Nickel

The primary forms of nickel that are available to meet the various demands of industry

are indicated in table 4. A listing of alloys and

forms is given in the Handbook of Huntington

Alloys [43] and in a booklet issued by The In- ternational Nickel Company, Ltd. [44].

Nickel is marketed in various forms, as fol- lows: (1) nickel pellets, produced by decomposition of nickel carbonyl; (2) electrolytic cathode sheets cut into various sizes; (3) shot, obtained by remelting electrolytic nickel and then

casting it into pig molds or pouring it into water

without deoxidation; (4) malleable nickel, produced by pouring into ingot molds after deoxidation; (5) nickel rondelles, reduced from the

oxide without fusion; (6) nickel salts; (7)

nickel oxide; (8) ferronickel; (9) nickel powder; and (10) special alloys for addition to cast

irons.

Electrolytic nickel and pellets constitute the

most widely used forms of primary metallic

nickel. Nickel oxide sinter and ferronickel (of

varying Ni content) are also widely used in

the steel and foundry industries as alternate

forms of primary nickel. These are used in approximately equivalent proportions. Electrolytic

nickel, including SD nickel, has gained rapid

6

Fit

ilili M(

! Hil

ike

Sit

1948 1952 1956 I960 1964 1968

YEAR

Figure 3. Consumption of nickel in the United States [37,38,39,A0,il'i.

and widespread usage as anode material in

electroplating when contained in titanium baskets. Rolled bars and, to a lesser extent, cast anodes, are also used as anode materials in

electroplating. Briquetes (as produced from

compacted CP powder) , XX shot, and rondelles are also utilized to a smaller degree as metallic

forms of primary nickel. F shot, nickel-magnesium alloy, and nickel-magnesium-silicon al- loy are used for additions to cast iron and for

the production of ductile iron. Carbonyl powders find usage in sintered porous plates for

batteries and in powder metallurgy parts.

Carbonyl nickel is especially low in cobalt content. The principal impurities are varying

amounts of carbon and oxygen from the decomposition of the carbonyl radical.

Electrolytic nickel supplies about one-half of

the industrial demand for the metal. The commercial electrolytic refining processes permit the

recovery of valuable by-products, such as the

platinum metals, and reduce or eliminate most

of the impurities. The residual cobalt, less than

0.05 percent, is traditionally counted as nickel

because of the chemical and metallurgical similarities of the two metals. Electrolytic nickel is available in full-sized cathodes as deposited,

approximately 28 by 38 by % in and 145 lb in

weight, and in smaller sizes, down to 1 by 1 by

% in, prepared by shearing the electrolytic

plates.

Nickel shot was used for alloying purposes

before the electrolytic refining process was developed, and is still used in small-scale alloy

^ t

8
production. Shot is produced today by pouring

melted electrolytic nickel into water or by highI pressure steam shotting. "XX" shot passes

(through a 1-in opening and is retained by an

10.053 in opening; the low-sulfur and high-sulfur

[grades are steam-shotted, with the maximum

particle size 0.053 in for the low-sulfur and

j 0.071 in for the high-sulfur grade.

Malleable or wrought nickels are produced

by treating the molten metal with magnesium

and manganese to combine with the sulfur and

thereby prevent the formation of brittle films

!of nickel sulfide. Furnace practice may be

varied and additions may be made to meet the

I requirements of particular uses.

American Society for Testing and Materials

recently revised Specification B39 which covers

refined nickel primarily produced from ore or matte or similar raw material. The principal

commercial forms are cathodes and briquetes.

The chemical composition shown in B39 is as

follows

Ni

Co

Cu

C

Fe

S

99.80 min

.15 max

.02 max

.03 max

.02 max

.01 max

P, Mn, Si, As, Pb, Sb,

Bi, Sn, Zn, less than

0.005 each

Table 4. Primary forms of nickel

Type Producer Approx. Ni content Main uses Description

Electrolytic (cathode)

Pellets Briquetes

Rondelles

Ferronickel XX shot F shot

Nickel oxide sinter 75

Nickel oxide sinter 90

Powder, carbonyl

Powder, chem. pptn. (CP)

Nickel magnesium additive Nickel magnesium silicon additive Nickel oxide acid soluble

1,3

2546,4

1

1

1

1

2

%

99.9

99.9 99.9

99.3 20 min

99.6

92

7590

99.9

99.9

82

5177

Alloy production, electroplating Alloy production

Alloy production

Alloy production Ferrous alloy production

Alloy production (ferrous casting) Cast iron addition alloy

Ferrous alloy production

Ferrous alloy production

Nickel and nickel-containing alloys, via powder metallurgy. Nickel and nickel-containing alloys, via powder metallurgy. Production of ductile (nodular) iron Production of ductile (nodular) iron Production of chemicals, ferrites, enameling frits.

Sheared cathodes. Carbonyl nickel. Compacted hydrogen reduced powder. Carbon-reduced molded nickel oxide. Pyrorefined ingots. Molten electronickel shotted in water. Cast or shotted pyrorefined nickelsilicon additive. Product from roasting of refined nickel

sulfides. Product from roasting of refined nickel

sulfides. Powder from decomposition of nickel carbonyl. Powder obtained by chemical precipita- tion methods.

Ingot, crushed to various sizes. Ingot, crushed to various sizes. Refined form of nickel oxide.

1. The International Nickel Co. of Canada, Ltd., Toronto, Ontario.

2. The International Nickel Co., Ltd, Clydach, England.

3. Falconbridge Nickel Mines Ltd., Toronto, Ontario.

4. La Societe " Le Nickel." Le Havre, France.

5. Sherritt-Gordon Mines Ltd., Toronto, Ontario,

e. Hanna Mining Co., Cleveland, Ohio.

2. Nickel—Properties and Uses

Although nickel can be produced commercially to a purity of 99.99 percent, most of the

data reported in the literature are concerned

with nickel (plus cobalt) of 99.95+ percent.

This degree of purity is satisfactory for the

determination of many properties, but certain

properties, for instance, electrical resistivity, are very sensitive to impurities in solid solution.

A general review of the properties of nickel and

its alloys was given by Manly and Bridges [46]

.

For compositions of the various commercial

nickels, see table 31.

2.1. Physical Properties

a. General

(1) Atomic number and iveight—Isotopes.

Nickel is number 28 in the periodic tabulation

of the elements. The three metals, iron, nickel.

and cobalt constitute the transition group in the

fourth series in the periodic table. The atomic weight of nickel is 58.71, representing a composite of the five stable isotopes.

The natural abundances of the stable isotopes, as reported by White and Cameron [47] and by

Brosi [48], are 67.7 percent for Ni^^, 26.2 per- cent for Ni"", 1.25 percent for Ni*^i, 3.66 percent

for Ni**-, and 1.16 percent for Ni^'^. The isotope

with mass 61 has an odd number of neutrons

and is probably the only stable isotope that has

a nuclear spin other than zero. Ni*^^ is about 10

percent heavier than Ni^**, enough to cause appreciable shifts in the energy levels of the

atoms as indicated by the values for packing

fraction and nuclear binding energy reported

by White and Cameron [47], Duckworth and

co-workers [49,50], and Wapstra [51]. The

technique for separating the stable isotopes was

developed by Kelm, and electromagnetically

9
concentrated samples of each isotope are available through the Isotopes Division of the

Atomic Energy Commission at Oak Ridge.

Seven radioactive isotopes of nickel have been

identified [48,52], with mass numbers 54, 56,

57, 59, 63, 65, and 66. The radioisotopes are produced by cyclotron bombardment of iron, nickel, or cobalt, and have half-lifes as follows

Ni54_0.16 second

Ni56—about 6 days

Ni5T—36 hours

Ni59—approximately 100,000 years

Ni63—about 85 years

Ni65_2.6 hours

Ni^e—56 hours

Brosi [48] discussed the decay mechanisms and

predicted that Ni^^ probably will be one of the

most valuable radioisotopes; the softness of the

radiation is an inconvenience in some respects

but a very valuable property in others, e.g., in

the study of surface reactions, diffusion, and

homogeneity in solids containing nickel.

(2) Nuclear properties. The reactions of

nickel and its principal isotopes to neutron bombardment were summarized by Bradford [53]

from Atomic Energy Commission publications, as shown in table 5. The reaction cross sections

(1 barn 10"-*cm-) refer to cases in which the

neutron is not reemitted, that is, to in,y) re- actions. The absorption cross sections are the

particular reaction cross sections that are measured by observing the reaction in which the

neutron is absorbed. The activation cross sec- tions are those determined from the radioactivity of the product nucleus as the result of the

{n,y) reaction. The scattering cross sections are

usually constant with energy in the thermal

region, are averaged over the Maxwell distribution, and will depend on the crystalline form of

the sample and even upon the size of the crystal

grains.

Values for neutron absorption cross section

of nickel and some of its isotopes under bombardment by neutrons of different velocities

Table 5. Thermal neutron cross sections of nickel and

its isotopes [53]

Element Isotope

Reaction cross sections

(for neutron velocity

of 2,200 m/sec)"

Scattering

cross sections average Absorption Activation

Nickel- -- -- - harns 4.5±0.2 4.2±0.3

2.7±0.2

1.8=hl.3

15 ±3

Barns I7.5±1.0

Ni's

Ni60 Ni" Ni"

Ni61 Ni65

l.OiO.l

9 ±1

» L. Goldring has stated that bombardment of Ni** with fast neutrons produces an absorption reaction cross section of 0.055 barn and yields Co'8.

were reported by Harris, et al. [54], Hildebrand

and Leith [55], Grimeland, et al. [56], Pomerance [57], Chilton, Cooper, and Harris [58],

and Nereson and Darden [59]. Scattering of

1-MeV neutrons were discussed by Walt and

Barschall [60] and inelastic scattering of monoenergetic neutrons by Kiehn and Goodman [61]. ^ The eflfect of bombardment, by neutrons,

gamma rays, and beta particles, on the physical

and mechanical properties of metals used in

reactors was discussed by Convey [62].

(3) Crystal form and lattice constant. The

normal crystal form of nickel is face-centered

cubic. The Metals Handbook [63] gives the

value of the lattice constant as 3.5238 A at 20

°C, although Wise [64], in the same handbook,

gives 3.5167 A. Swanson and Tatge [65] re- ported the value of 3.5238 in 1953 in recording

the x-ray diffraction patterns obtained from

powdered nickel. Values given by other investi

gators are as follows

Unit cell in angstroms, 25 °C

1931 Phragmen [66]. _ 3 5255

1932 Owen and Iball [67] 3 5254

1934 Jesse [68]- - - -- 3 525

1935 Jette and Foote [69, 70, 71] 3 5239

1936 Owen and Yates [72].. 3 5247

1941 Lu and Chang [73].- ... 3 5247

1941 Fricke [74] 3 5239

1954 von Batchelder and Raeuchle [75]. 3 5238 ±0.0003

The closest approach of the atoms is given as

2.491 A by the Metals Handbook [63].

Hazlett and Parker [76] showed that the

addition of the solid solution alloying elements

tungsten, titanium, iron, and cobalt to nickel

effected an expansion of the lattice that was

directly proportional to the amount of the added

element (fig. 4)

Another crystal form of nickel, hexagonal

close-packed, has been observed in thin films

of nickel prepared by cathode sputtering or by

vacuum distillation [77,78,79], in the mixed

structure of certain electrodeposits [80] , and as a result of the bombardment of cubic nickel

with energy of the order of 12 kV [81]. Thomson [77] reported the values of the axes as being c = 4.06 A and a = 2.474 A. This gives a ratio of 1.64, which is near enough to the

ratio 1.633 for closest packing. Finch et al.[82],

identified a body-centered cubic structure in

translucent nickel films deposited from hot

nickel-coated tungsten onto surfaces maintained at 300 to 340 °C. Mild heating, e.g., 1 hr at 400 °C, caused both of these crystal forms

unusual for nickel to revert to the normal facecentered cubic form.

(4) Density. The Metals Handbook [63]

gives the density of nickel as 8.902 g/cm^ at 25 °C. The density, as computed from atomic

10
I- 3.5300

»< o<

I i 3.5200

I-O

U

liJ u

Ih-•<

_J 3.5100

TUNGSTEI"

TANIUM

/

IRON

COBALT

2 4 6 8 ALLOYING ELEMENT IN ATOMIC 7o

]0

Figure 4. Effect of alloying elements on the lattice constant of nickel at 25° C [7-6].

8.5

o 8.0

> 7.5

7.0

6.5

D,'^' = 9.908 - 1 1.589 X lO'^T^K i

1600 1800 2000 2200 2400 2600 2800

TEMPERATURE, °K

Figure 5. The density of liquid nickel [56],

>- U

o

-J

UJ>

4800

4600

4400

^NNEALEC

100 200 300

TEMPERATURE °C

400 500

Figure 6. Effect of temperature on the velocity of sound in annealed nickel

191}.

11
data, is 8.908 g/cm^ at 20 °C, according to Fraser [19]. Direct determinations of the density of nickel are affected by the composition,

physical condition, and prior treatment of the

material; for example, Jordan and Swanger

[83] reported the density of 99.94 nickel as 8.907 g/cm^ at 23 °C in the cast condition, and

as 8.900 to 8.903 g/cm^ for the same material

cold swaged and annealed. Subsequent investigations [84,85] showed that two sudden increments in density, observed on heating plastically deformed nickel, may be attributed to the

disappearance of vacancies and to recrystallization.

The density of liquid nickel at its melting

point is 7.9 g/cm^. The effect of temperature

on the density of liquid nickel is shown by the curve in figure 5. (5) Miscellaneous physical properties. The

surface tension of pure nickel was determined

by Kozakevitch and Urbain [87] , who reported a value of 1924 d/cm at 1550 °C. Smirnova and

Odmont [88] reported that the surface tension

of nickel at the melting point was 1756 d/cm,

A study was made of the microwave reso- nance absorption at a wavelength of 0.86 cm in a single crystal of nickel and in polycrystalline

nickel by Barlow and Standley [89]. At 20 °C,

the anisotropy constants Ki and K2 of the single

crystal were both equal to —6.06 X 10* ergs

cm"^. The spectroscopic splitting factor, g, was

determined as 2.19 ± 0.02 both for the single

crystal and polycrystalline nickel. This same

value was also obtained for nickel-copper alloys

containing up to 26 a/o of copper. For nickelmanganese alloys, the gf-value decreased with in- crease in manganese, reaching 2.12 at 13.5 a/o

of manganese.

The speed of sound in a longitudinal bar of

commercial nickel (99.51%) was reported as

4.7 X 10° cm/sec [79]. For ultrasonic frequencies, the transmission rate in electrolytic nickel

has been given as 5660 m/sec [90]

The effect of temperature on the velocity of

sound in pure nickel was studied by Bell [91].

His results on annealed nickel are shown in

figure 6. The sharp maximum at 358 °C is at- tributed to the Curie temperature, but no ex- planation was given for the minimum at about

175 °C.

The electron binding energies in metallic

nickel are given by Hagstrom et al. [92], as

follows

K 8333

Li 1012

L„ 872

Liii 855

Mi 113

Mii.iii 69

Miv.V 4

Bearden [93] gives a listing of the x-raji

properties of nickel as follows:

Principal x-ray emission lines

KLii--_: —. Ka2 1.661747 A±8

KLin 1.657910 A±8

KMii.iH Kgi.3 1.500135 A±8

KMivv---- - --- -- - K35 1.48862 A±4

LiMn.iii 13.16 A±2

L„Mi L„ 16.27 A±3

LiiMiv 14.271 A±6

LiiiMi 16.693 A ±9

LiiiMiv.v Lai,

14.561 A±3

Mii.iii Miv.v 190. A±2

' Probable error in last digit.

X-ray absorption edges

K 1.4887 A

L„ 14. 242 A

Liii 14.525 A

Mill 188.4 A

b. Optical Properties

The ability of polished nickel to reflect a large percentage of the light incident upon it was summarized by Meyerson [94] as follows:]

Values for the reflectivity of various forms o:^ nickel increase with increasing wavelength of

light, from about 10 percent reflectivity at wavelengths of about 1000 A to about 90 per-|

cent for wavelengths of about 40,000 A. Some

data presented by the Mond Nickel Co., Ltd.

[79], are reflectivities of 41.3 percent for 3000

A wavelength (ultraviolet), 64 percent for

5500 A (yellow-green), 83.5 percent for 2000

A, and 87 percent for 3000 A, the last two representing wavelengths in the infrared region.

Roberts [95] reported optical data for nickel at

88, 298, and 473 °K.

The temperature coefficient of reflectivity of

nickel was determined by Ward [96], who

found that the change in reflectivity was a

straightline function of temperature and that

there was no significant change at the Curie

point. Figure 7 shows his results for wavelengths in the near infrared region of the

spectrum.

The emissivity of nickel (and other metals)

varies with surface conditions, including the

presence of oxide films, and with temperature.

The total emissivity of nickel increases approximately linearly with temperatures from 0.045

at 25 °C to 0.19 at 1000 °C. The emissivity for

monochromatic light of 0.65 fx wavelength is

12
XIO-3

\

2A/JL

Figure 7. Change in reflectivity of nickel as a function of temperature for

several wave lengths of light [56].

(Ro = room temperature reflectivity and AR = the change over T".)

0.355 [79] and this value is also given by Wise

[64]. Lund and Ward [97] presented data for

variations in the emissivity of nickel from 1,000

to 1,300 °C. The total emissivity at 1,000 °C was given as 0.19 by Barnes [98].

Nickel films thicker than 100 A have very

nearly the same transmission values for all

Table 6. Refractive index (n) and absorption coefficient (k) of nickel for different wavelengths of light [94]

Wavelength n k Wavelength n k

A A

4200 1 42 1 79 7500 2 19 1 99 4358 1 41 2 56 7800 2 13 4 43 4600 1 40 2 77 8600 2 24 4 69 5000 1 54 1 93 9400 2 45 4 92 5400 1 54 3 25 10000 2 63 2 00

5461 1 66 3 39 12500 2 92 2 11 5780 1 70 3 51 15000 3 21 2 18 5800 1 73 1 98 17500 3 45 2 25 6200 1 .82 1 99 20000 3 70 2 31 6600 1 .95 1 98 22500 3 95 2 33 7000 2 .03 1 97

wavelengths of light in the visible range, but

with thinner films there is a slight maximum

in transmission at 5000 A wavelength, imparting a green color to the film [99]

.

Values for the refractive index and absorption coefficient of nickel for various wavelengths

of light are shown in table 6 [94]

.

The radiation spectrum of nickel is highly

complex and contains thousands of individual

lines. The most persistent, with a maximum

intensity in both arc and spark sources, is at 3414.77 A. Burns and Sullivan [100] measured

230 lines, in the vacuum-arc spectrum, between

1981 and 221 A, and Gatterer et al. [101], presented charts of the arc and spark spectra of

nickel and other metals.

A tabulation of the wavelengths, between

2000 and 10000 A, of approximately 500 of the

principal lines in the emission spectrum of

nickel, is presented in the Handbook of Chemistry and Physics [102]. Moore [103] computed

13
atomic energy levels from analyses of the optical spectrum of nickel.

Spectral lines of short wavelength are emitted

from nickel cathodes in an x-ray tube operated

at a sufficiently high potential. The most important of these are the K series, with wavelengths of the order of 1.5 A [104].

c. Thermal Properties

(1) Melting and boiling points; heat of fusion; vapor pressure. The Metals Handbook

[63] gives the melting (or freezing) point of

nickel as 1453 °C (2647 °F). This generally ac- cepted value is based on determinations made

at the National Bureau of Standards on 99.94

percent nickel, as reported by Jordan and

Swanger [83]. Although they reported 1455 ±

1 on the International Temperature Scale

of 1927, the value of 1453 °C was assigned to the freezing point as a secondary fixed point on

the International Temperature Scale of 1948

[105] because of slight changes in the constants

of the radiation equations. The value of 1452 °C

(2645 °F) was given by Honig [106]. The pres- ence of the usual impurities or alloying elements

tends to lower the melting point of nickel and

to change the melting point to a melting range.

The boiling point of nickel is too high to permit direct determinations and is estimated by

extrapolation of vapor-pressure data. Wise [64]

reported 2730 °C (4950 °F) for the boiling

point of nickel. Strangely enough, Honig [106]

reported 2839 °C (5142 °F) from vapor pres- sure data. His vapor pressure data for nickel are shown in figure 8. Some other values for

the vapor pressure of nickel are 1.2 X

10"*^ mm

of mercury at 1000 °C, 9.4 X lO ^' at the melting

point, and 213 mm at 2000 °C [79].

The latent heat of fusion of nickel is given as

73.8 cal/g for 99.95 percent nickel [64]. Geoffray et al. [107], gave the value of 4176 ± 54

cal/g-at for the latent heat of fusion.

(2) Specific heat and heat capacity. The specific heat of nickel at any temperature represents a combination of lattice vibration, a magnetic effect, and a residual portion. The Metals

Handbook [63] gives the value of 0.105 cal/g/

°C for the specific heat of nickel at 20 °C. Sykes

and Wilkinson [108] determined the specific

heat of vacuum-melted Mond pellets from 60 to 600 °C. Busey and Giaque [109] reviewed the

low-temperature results reported by others and

presented results obtained from very pure

nickel over the range 294 down to 12.95 °K.

1000 1200 1400 1600 1800 2000 2200 2400 2600 2800

TEMPERATURE °K

Figure 8. Vapor pressure of nickel

14
They give a heat capacity at 15 °K of 0.183 J

mole'i deg -. Krauss and Warncke [110] used

vacuum-melted carbonyl nickel of 99.97 percent

purity and covered the range from 180 to 1150

°C. The work of these authors has been combined in figure 9, and some of the numerical

values used in plotting the curve are recorded in

table 7. The sharp maximum at the Curie Doint occurs at 358 °C according to Sykes and Wilkinson [108], and at 357.2 °C according to Krauss

and Warncke [110].

-200 0 200 400 600 800 1000 1200 TEMPERATURE, °C

Figure 9. Specific heat of high-purity nickel

[108,109,110'i.

Table 7. Specific heat of high-purity nickel [108, 109, 110]

Temperature Specific heat

°C cal/grC -260 0.00061 -200 .00355 0 .1025 200 .1225 357.5 .1592 500 .1260 700 .1328 900 .1397 1150 .1525

Values for the specific heat of pure nickel, as reported by Valentiner [111], and by Pawel and

Stansbury [112], are plotted in figure 10.

Heat capacity measurements have been made

below 4.2 °K on 99.9 percent nickel bv Rayne

and Kemp [113]. They give the curve shown in

figure 11, from which they deduce the y value

of 7.02 ± 0.06 J mole (deg ^ x 10^). According

to these authors, the Debye temperature for

nickel (6) is 441 ± 15 °K. They calculate the

heat capacity a'- 15 °K as 0.183 J mole ' deg"-.

Rosenberg [114] gives the value for nickel of

440 °K for e, and 72.8 X 10" J mole i deg i for y, the coefficient of the electronic specific heat.

De Nobel [115] gave the following values for

the specific heat resistance (Wspei) and the

specific heat conductivity (Asp,,c) for 99.4 percent nickel

Temperature

°K

spec watt~* cm

degree

X spec watt cm~i

degree" 1

15.12 5.55 0. 180 18.15 4.52 .221 21.50 3.65 .274

77.1 1.64 .610 93.1 1.51 .661

Hultgren and Land [116] measured the ef- fect of chromium additions on the heat capacity

of nickel; their values for the heat capacity of

nickel are given in table 8.

Table 8. Heat capacity of nickel \116]

Temperature—°K Heat capacity —cal per g-atom deg

800 7.44 900 7.60

1000 7.70

1100 7.85

1200 8.08

1300 8.35

1400 8.60

1500 8.80

(3) Thermal expansion. Nickel expands with

increasing temperature at a regular rate except

0.1600

111 o 0.1400

o<

U-CC — o

^"1 0.1200

0.1000

40 160 280 400 520

TEMPERATURE, ''C

Figure 10. Specific heat of high-purity nickel [111, 112].

15

640
16 18

T^(DEGREE^)

Figure 11. Atomic heat of nickel [113].

for a sharp maximum at the Curie temperature.

Numerical values for thermal expansion are

affected by the composition and by physical fac- tors such as the presence of strains, etc. The

thermal expansion characteristics of nickel al- loys are of much greater practical importance

than those of pure nickel and many alloys of

closely controlled expansion characteristics depend upon nickel additions.

20

16 ^ —

-200 0 200 400 600 800 1000

TEMPERATURE,

Figure 12. Thermal expansion of nickel [83,117']. Figure 12 records results obtained on 99.9

percent nickel at low temperatures by Nix and

MacNair [117], combined with results obtained

by Hidnert for 99.94 percent nickel over the

range 25 to 900 °C. The determinations made by

Hidnert at the National Bureau of Standards, as reported by Jordan and Swanger [83] and summarized in table 9, have been the basis for numerous summaries of the average coefficient over specific temperature ranges. Owen and

Yates [72] reported higher numerical values as

a result of x-ray measurements of the lattice

constant of 99.98 percent nickel, but a later determination [75] of the lattice constant over the

range from 24 to 455 °C confirmed Hidnert's

results.

Table 9. Thermal expansion of 99.91t percent nickel [83]

Temperature Average Temperature Average

range coefficient range coefficient

Millionths Millionths "C per °C °C per °C

25 to 100 13.3 25 to 100 13.3 100 to 200 14.4 25 to 300 14.4 200 to 300 _ . _ 15.4 25 to 600 15.5 300 to 350 17.2 25 to 900 16.3 350 to 400- . - 16.4 300 to 600 16.5 400 to 500 15.9 600 to 900 17.8 500 to 600 16.9 600 to 700 17.1 700 to 800 17.7 800 to 900 18.6

Same values for the spot coefficient at specific

temperatures, according to Fraser [19], are

at 20 °C, 12.5 X 10-« per °C

at 100 °C, 13.5 X 10"*^ per °C

at 300 °C, 16.3 X lO"** per °C

at 400 °C, 16.3 X 10'*' per °C

The Metals Handbook [63] gives the value of

13.3 X

10"*' per °C and 7.39 X lO'^ per °F for

the temperature range of 0 to 100 °C (32 to 212 °F).

Arp, et al. [118], made a careful study of the

linear contraction relative to 293 °K of several

materials, one of which was "A" Nickel (now

termed Nickel 200). His values are given in

table 10. Corruccini and Gniewek [119] presented a compilation from the literature of the

thermal contraction and coefficients of thermal

expansion of various metals and alloys at low

temperatures. Their values for nickel are given

in table 11.

16
Table 10. Linear contraction of Nickel 200 [118]

Temperature "K

Contraction

L293

Temperature "K

Contraction

L293

293 0 160 149 280 lb 140 170

273 25 120 188 260 39 100 203 240 63 80 215 220 85 60 223 200 107 40 228

180 129 20 230

rABLE 11. Linear thermal contraction and coefficients of

linear thermal expansion of nickel [119]

I TemI perature

020

30

40

50

60

7080

90

100

120

Ij293 — Lt X 10=

224

224 224

223

221 219 216

211 206

201

187

dL

XIO*

deg ' K

0

0.2

.5 1.0

1.9 2.8

3.8

4.7

5.5

6.1

Temperature

"K

140 160

180 200

220

240

260

273 280

293 300

L293

Lt

X10»

171 152

132

11188

65

4125

160 -9

dL

LisidT X 10«

9.8

10.5

11.0

11.5

11.9

12.2

12.3 12.4

12.6

12.6

Owen et al. [120], reported on the effect of

iron on the thermal expansion of nickel at temjperatures up to 500 °C.

i; (4) Thermal conductivity. The thermal conductivity of nickel is lowered by the presence

of impurities and irregularities occur near the

Curie temperature. The effect of impurities is particularly noticeable at very low temperatures in the varying results reported in 1956 by

Kemp et al.[121], who concluded that at these

8 -

O

o

o

<

Ui ' I

-200 0 200 400

TEMPERATURE, ° C

600

Figure 13. Thermal conductivity of high-purity (solid

lines) and commercial-purity ( dashed lines) nickel [121,122,123].

Ibw temperatures thermal conduction in pure

nickel is almost completely electronic.

Figures 13 shows results obtained by Van

Dusen and Shelton [122] for 99.94 percent

nickel over the range 25 to 575 °C and by Kemp

et al.[121], for 99.99+ percent nickel at very

low temperatures. The two dashed curves for

commercial-purity nickel show that the effect of

impurities on thermal conductivity is most pronounced at extremely low temperatures. The

low-temperature curve for commercial-purity

nickel represents data from low-carbon nickel

by Powers, Schwartz, and Johnson of Ohio State

University according to Powell and Blanpied

[123]. The other commercial-purity curve was

reported by Van Dusen and Shelton as representing commercial malleable nickel. Some val- ues based in those of Van Dusen and Shelton

for 99.94 percent nickel, but expressed [19,79]

in calories per second rather than in watts are

at 100 °C, 0.198 cal per cm sec °C

at200 °C, .175 cal per cm sec °C

at300 °C, .152 cal per cm sec °C

at400 °C, .142 cal per cm sec °C

at500 °C, .148 cal per cm sec °C

The Metals Handbook [63] gives the thermal

conductivity of nickel as 0.22 cal/cm-/cm/sec/

°C at 25 °C, which expression may be written as

0.22 cal per cm sec °C. This value is repeated by

Wise [64], who also gives the values of 0.198,

0.152, and 0.148 at 100, 300, and 500 °C, re- spectively.

(5) Thermionic properties. Thermionic properties of nickel are those properties that make

it useful for ion emission in vacuum tubes. The

cathodes used in electron tubes consist of a base

material—a nickel alloy having a thin layer

of oxides of alkaline-earth elements. When

heated to about 700 °C, they emit the stream of

electrons used in the amplification process.

Nickel sheet is used for anodes in low-power

tubes [129]. Cathodes usually are oxide-coated

nickel, but cathodes formed by powder metallurgy techniques from sintered nickel powder

and alkaline earth oxides [130] or from car- bonyl nickel powder, nickel plus about 4 percent

tungsten, or nickel plus 2 percent titanium

[131] have been recommended.

Caldwell [132] reported that the thermionic

properties of a spectroscopically pure nickel fila- ment became stable only after heat treatment

for 1500 hr at temperatures up to 1200 °C.

Wohlfarth [133] associated the thermionic

emission of nickel with the fact that, with an

overlapping s-band, there is an increasing transfer of electrons from the d-band as the temperature rises. The secondary electron emission of

nickel was discussed by Favorin [134] and by

Blankenfeld [135]. The amount of carbon present and the rate of its diffusion in nickel are of

interest in the activation of oxide-coated ther17
mionic tubes. Lanter ct al.[13G], reported thrt

the solubility of carbon in nickel between 700

and 1300 °C is expressed by the equation log

S = 2.480 - 4880/r, where S is the solubility

of carbon in grams per 100 g of nickel and T is the temperature in degrees centigrade. The diffusion rate of carbon in nickel is expressed by

the equation log D = 0.909 — 20,200/T, where

D is the diffusion coefficient in square centimeters per second.

A review of work carried out to attain precise

control over cathode material was written by

Acker [137]. The Bell Laboratories developed a method of producing very pure nickel with controlled additions of single alloying elements

[138] and material so prepared was used to evaluate the effect of other elements upon the

transconductance and total emission of nickel

[139].

The thermionic properties of nickel were summarized by Wright [129] as follows:

Work function, *, — 5.0 eV,

Temperature, Te, where vapor pressure is 10-5 mm = 1330 °K,

ioo

(300

Te X 10^=3.78

Fomenko [140] gives 4.50 eV as the recom- mended value for the work function of nickel.

He notes that the value varies with crystal face

and with temperature.

(6) Recrystallization temperature. As with

other metals that do not undergo an allotropic

transformation, some extraneous factor, such as

1 cold work, is necessary in order for nickel to'"'''' recrystallize during subsequent heating.

Pure nickel recrystallizes in the temperature^ , range of approximately 300 to 350 °C. The dia-W

gram in figure 14 from work by Bollmann [141] ' ^ shows three general regions for pure nickel coldfj

worked 80 percent; (1) recovery up to 250 °C;

(2) primary recrystallization between 250 and

400 °C; and (3) secondary recrystallization

above 400 °C. During secondary recrystallization the hardness remains practically un- changed. This figure also shows the recrystallization diagram for two grades of electrolytic

nickel.

As a matter of interest, the recrystallization

diagram for TD nickel as determined by Inman

et al.[142], is included in figure 14. TD nickel

consists of a 2 volume percent dispersion of fine

thoria particles in a pure nickel matrix. This

material was cold worked 93 percent. Its re- crystallization diagram indicates that recrystallization occurs at higher temperatures than in

pure nickel and that the resultant minimum

hardness is considerably higher than that of

pure nickel.

Bartuska and Kufudakis [143] presented a

recrystallization diagram for nickel showing

grain size as a function of temperature and*

amount of cold work. These authors note that! up to about 1050 °C the increase in grain size

is very slow and becomes appreciable only above!

this temperature.

Olsen [144] studied the effect of trace ele- ments on the recrystallization temperature of

nickel and noted that the greater the increase

in atomic diameter of an added element in relarec

CO

• cvl

UJ

£r< 2

X X

UJ

:^o

300

250

200

150

100

50

0

NICKE L

ME

P(

_TING

DINT

1

lEGUL/

99.9<

\R ELE

9% EL

:CTROL

.ECTRC

.YTIC

)LYTIC

V^PURE Nl(:kel

'0 200 400 600 800 1000 1200 1400 1600

ANNEALING TEMPERATURE °C

Figure 14. Recrystallization diagram for pure nickel [J-4-Z], TD nickel [H2'[, 99.99 percent electrolytic nickel [tfi], and regular electrolytic nickel [64].

18

idME

red

•; crvsl

)(1)

3 itivil

tmpei

111

( iirie

ciiipei

..](
pt)n to that of nickel, the higher is the recrystalitation temperature. His study showed that the

/eatest rise resulted from addition of the

^rgest atoms, magnesium and zirconium. The

jost pronounced retardation of recrystalliza-

[pn was produced by addition of 0.1 w/o of

bconium, which caused approximately 400 °C

(Se in reerystall ization temperature over that

,f pure nickel. Figure 15 shows the effect of

500

! 300

[ 100

Zr

Solid Solubility

0——o Extensive

+ Limited

o-—0 Very Limited

7*—

1 0"

Ti 1^ + '

1

1 ^^L-—

—•—

Co,

Wri 1 1—#_J i \ 1 1 1—•

0 0.10 0.20 0.30 0.40

t Atomic % of Additive

I'gtjre 1.5. Increase in recrystallization temperature of

I high-purity nickel resulting from additions of indi- [cated elements

1

•ace elements on the recrystallization temperare of high-purity nickel.

. Abrahamson [145] reported that data on the

];crystallization temperature of binary solidj'lution alloys of nickel with up to 0.7 a/o of the

.irious transition elements showed that all the

Iditions increase the recrystallization temperaire of nickel.

d. Electrical Properties

1 (1) Electrical resistivity. The electrical restivity of pure nickel is negligible at extremely

| w temperatures but increases with increasing

j mperature and with increasing amounts of

fipurities. The resistivity of 99.68 and 99.84

j';rcent nickel was determined by Pallister

j.46), who combined his results with those of

[ veral other investigators to yield the curve

i lown in figure 16. The marked change at the

; urie temperature is evident when values of

>/dT, derived from the values of p (resistivity) near temperatures, are plotted against the

mperature (fig. 17).

' On the basis of his work and that of others,

allister [146] presents estimates for pure

ckel as shown in table 12. The ideal electrical resistivity of 99.997 pernt nickel, according to the data of White and

'oods [147], is shown in figure 18. Rider and Brooks [148] studied the effect of

Id work on the electrical resistivity of 99 per- nt nickel. Their data gave the curve shown in

I

Table 12. Estimate for electrical resistivity of pure nickel

Temperature Resistivity P/P273 dp/dT

"A' Microhm cm

0 <0 03 <0 005 <0.0005

20 < 04 < 006 .001 50 < 18 < 029 .008 100 <1 02 < 16 .023 200 3 70 60 .031

273 6 15 1 00 .0365 300 7 16 1 165 .0385 400 11 55 1 88 .0505 500 17 5 2 85 .068 550 21 05 3 42 .077 600 25 2 4 10 .0905 650 29 6 4 815 .050 700 31 7 5 16 .0365 800 35 0 5 70 .031 900 38 0 6 18 .0285

1000 40 75 6 62 .027 1100 43 35 7 05 .0255 1200 45 85 7 45 0245

1300 48 3 7 85 !0235 1400 50 6 8 23 .023

1500 52 85 8 59 .0225 1600 55 05 8 95 .022 1700 57 25 g .30 .0215

figure 19, where the logarithmic reduction rj is defined by t; = ln(Ao/A), where Ao is the initial cross-sectional area (i.e., as annealed) and

A is the cross-sectional area after cold reduction.

Wise [64] gives the value of 6.84 microhmcm for the resistivity of nickel at 20 °C, and

25.2 percent lACS for the electrical conductivity. The marked effect of slight impurity is indicated by the value of 9.5 microhm-cm for the

electrical resistivity at 20 °C and 18 percent

lACS for the electrical conductivity for "A"

nickel [149]. Figure 20 depicts the ratio of

electrical resistance of nickel to the resistance

at 0 °C.

Reichelt [150] noted that the resistivity of

very thin films, for example, vapor deposited on

glass, is 3 to 10 times that of bulk metal.

Bridgman [151] found that the resistivity of a single crystal of high-purity nickel decreased

with increasing pressure, as follows:

Pressure Relative resistivity

kg/crrfi R/Ro

0 1.000

10,000 .982 50,000 .918 80,000 .880 100,000 .858

Changes in the electrical resistivity of a

stressed nickel wire can be used to determine

Poisson's ratio [152], and the strain coefficient

of resistivity of nickel can be qualitatively ex- plained by the free-electron theory [153].

Broom [154] found that the resistivities in the

longitudinal and transverse directions in coldrolled nickel are equal. According to Potter
60

50

o 40

u

I >-

ILU

a:

30

1 1

1 T —I—r^- '-f

I I 1

1

1—1

1 1 L_Ji 1 1

1 1 1 1 1 0 5 30 10 00 1500

TEMPERATURE - °K.

Figure 16, Electrical resistivity of nickel [i^fi].

O

LUQ

015

010

X

§005

o

^1 0 /Till 1 1 1 1

1 1 1 0 500 1000

TEMPERATURE, °K

1500

Figure 17. Change in electrical resistivity of nickel as a function of tempero/- ture \_lJt6}.

[155] and Matuyama [156], increases in the

resistivity of nickel because of the presence of

longitudinal magnetic fields are most noticeable

at very low temperatures and fade out as the

temperature rises above ambient. Smit [157]

reported that the resistivity of pure nickel at low temperatures increases with increasing

strength of the magnetic field. Tabulated data

for the increase of resistivity of nickel due to transverse magnetic fields are presented in

tables 488 and 489 of the Smithsonian Physical

Tables [158].

Values for the temperature coefficient of elec- trical resistance of high-purity nickel, from 0 to 100 °C, range from 0.00658 to 0.00692 per °C

[19]. Wise [64] gives the value of 0.0069 mfct

crohm-cm per °C for the temperature coefficiei |2 of resistivity. That of "A" nickel is given i\ rmoi 0.00474 microhm-cm per °C [149]. The tempelfimp

ature coefficient of very thin films of nickel

negative, passing through zero and becominilmt

positive as the thickness of film increases [15i,il,s 160,161]. Belser and Hicklin [162] reportel

that the temperature coefficients of resistance (f h

substantially pure metallic films (nickel was iis It of eluded) were in the range of 1/3 to 2/3 those ( the respective bulk metals, irrespective of th' substrate used.

Impurities have a marked effect upon ttt iples, electrical resistivity of nickel. The increase 'k\^

20
••a

e 2

0 50 100 150 200 250 3C

TEMPERATURE ''K

FiGXJRE 18. Ideal electrical resistivity of pure nickel \_H7'\.

istivity caused by small amounts of other

mients is indicated in figure 21.

(2) Thermal electromotive force. Nickel is rmoelectrically negative to platinum, i.e., in

simple thermoelectric circuit of these two

tals the current at the cold junction flows

:im the platinum to the nickel. Iron, copper,

|d, silver, and numerous other metals, which

positive to platinum, all develop higher emf

;h nickel than they do with platinum, but in

te of this, nickel is not one of the most com- n thermocouple elements because of excessive

dation at the higher temperatures. It is, howr, an alloying element in many thermo-

-iples.

/alues for the thermal emf of nickel with

tinum, silver, and iron at various temperatures are shown in figure 22. Values for nickelcopper thermocouples, reported by Pecheux

[165], are very similar to the values shown for

nickel-silver. Mortlock [166] observed the ef- fect of elastic tensile strain on the thermoelectric power of high-purity nickel from 20 to 400

°C. Bridgman [167] showed that pressures up

to 12,000 kg/cm2 had a slight but consistent ef- fect on the thermal emf of nickel. The eifect of

magnetic fields of different intensities was studied by Yamanaka [168]. The effect of magnetization on the thermoelectric power of a single

crystal of 99.2 percent nickel is always positive near the Curie point, but varies with different

orientations within the crystal [169].

Effects associated with the development of

thermal emf in nickel and other metals, i.e., the

21
u

a

>->

10.2

10.1

10.0

9.9

S 9.8

9.7

p =1( 1-112- 0.37^ EXP (-1.61 /)

0 0.25 0.5 0.75 1.0 1.25 1.5 1.75 2.0

LOGARITHMIC REDUCTION rt

Figure 19. Effect of cold work on the electrical resistivity of 99 percent

nickel

Peltier and Thomson effects, are discussed in

the Smithsonian Physical Tables [158].

Berry and Martin [170] studied the thermoelectric stability of various thermocouple materials and found that the high-purity grade of

nickel was quite stable in air up to 780 °C.

Considerable information exists in the literature on the compositions, properties, and uses

of thermocouples in which nickel is either a major or a minor alloying element. Potts and

McElroy [171] investigated the effects of cold

working, heat treatment, and oxidation on the

thermal emf of the nickel-base thermoelements

indicated in table 13.

Table 13. Nickel-base thermoelements investigated by

Potts and McElroy [171]

Material

Hoskins Alloy No. 875_ Hoskins Alloy No. 827_ Hoskins Alloy No. 717. Chromel A

Geminol P

Chromel P

Chromel P + Nb

Kanthal P

.Vlumel Oeminol N

Kanthal N

.\lumel special Nickel Nickel-1% Si Nickel-2% Si Nickel-3% Si Nickel-4% Si Nickel 5% Si

Al

%

6.0

Cr

%

22.5

20

2020

189.46

9.41 9.11

Fe

%

8.0

.7

.2

.2.05 .10

%

0.5 2.0

.25 1.5

.8

.4.35

.37 1.2 2.75

2.4

1.23

Ni

%

bal

bal

bal

bal

bal

bal

bal

bal bal

bal

bal

bal bal99

98

97

96

95

Other

elements %

1.0 Nb

""2"Nb^ i^75"Mn

e. Magnetic Properties

(1) General. Nickel is one of the three ele- ments (iron and cobalt are the others) that are

strongly ferromagnetic at ambient temperature.

Typical normal induction curves of annealt

samples of the elements iron, nickel, and coba

of comparatively high purity are shown in fi ure 23. Pure nickel is seldom used itself as magnetic material except for certain sped

purposes, such as magnetostriction applicatio]|i

and as a calibration standard in susceptibili

measurements. However, many nickel alloys a exceedingly important and often are superior

all other magnetic materials for many applici

tions. The magnetically preferred axes of sing

crystals are the body diagonals (111), as shov^j

in figure 24. Bozorth discussed the theories | ferromagnetism as applied to nickel in his boc

[174] and in a subsequent paper [175] ar showed Beth's curve relating the exchange e: ergy of magnetization of nickel to the distan(

between atom centers, with fixed diameter < active shell. The formation of ferromagnet

domains in single crystals of nickel, their ident

fication through Bitter patterns, and the effe- of grain boundaries have been reported by se' eral other investigators [176,177,178,179,180]

The magnetic properties of thin films of pui

nickel have been studied by several investig;

tors. Although their conclusions are inconsi

tent, the latest studies indicate that the maj

netic properties of really clean and pure filn are the same as for the bulk nickel [181].

(2) Curie point. The Curie point for nicke

the temperature at which the change from fe: romagnetism to paramagnetism occurs, is a- fected by numerous factors, including the pric

mechanical and thermal treatment of the spec

men, the nature and amount of impurities prei

ent, and the method of determination.

The Curie point for high-purity nickel occulfiw

between 350 and 360 °C. A value of 353 °C w£

22
-400

121

TEMPERATURE, °F

400 800 1200 1600°F

0.72

tr

lij 0.70

0.68

0.66

CO <

tr 7 064

X

o 0.62

0.05 OlO OI5 O20 025 0.30 035 0.40 045

ADDED ELEMENT ATOMIC PER CENT

Figure 21. Effect of trace elements on the change in electrical resistivity of high-purity nickel wire (annealed V2 hour at 800 °C)

30

10

10

1 ....

1 N

-200 0 200 400 600 800 1000

TEMPERATURE °C

(Figure 22. Thermal electromotive force of nickel against

platinum [83'\, silver {103] and iron il6Jf'\.

reported for 99.94 percent nickel, 360 °C for

"A" nickel [19,79,182], and 357 or 358 °C for

high-purity nickel [108,110]. Wise [64] gives

the value of 353 °C for 99.95 percent nickel. The

Curie point is lowered slightly by tensile stresses [183] and is raised by pressure at the

rate of 0.35 °C per 1,000 atm [184]. Bader

[185] correlated pressure effects on the Curie

temperature with the introduction of rf-elec- trons and the accompanying changes in interatomic distances. Most alloying elements lower

the Curie point of nickel but cobalt and iron are exceptions, as shown in figure 25, Small

heat changes accompany the magnetic transition [187] and this effect for nickel has been

reported by various observers as 0.65, 1.33, and

2.01 cal/g [188]. At relatively high field in23
(3) Saturation. The intrinsic saturation in- duction value for high purity nickel (99.98%)

is approximately 6170 ^nd for "A" nickel is approximately 600 G [19,79]. The saturation in- duction of nickel at various temperatures is shown in figure 26 according to Bozorth [174] | The effect of tension in decreasing the magnetic

saturation of nickel was explained by Buh"'

[190] on theoretical grounds.

(4) Permeability. The initial permeability oii high-purity nickel is approximately 200 and th€

maximum permeability is 2,000 to 3,000 with

H = 1 Oe. For "A" nickel the initial permeability is approximately 200 and the maximum

permeability, H = 20 Oe, is approximatelj;

1,000 [19,79]. The theoretical effect of tempera-i

ture on the permeability of nickel was compared

by Kersten [191] with the vaulting of the Block

walls.

(5) Coercivity. The coercivity of nickel is given from 0.7 to 2.7 Oe [19,175]. It is greatly

affected by its fabrication and heat treatment.

The effect of plastic deformation on the tem-

•' This value, not yet published, was obtained by R. E. Mundy a1 the National Bureau of Standards in 1966.

7000

1000

0 I 1 I I I I 0 40 80 120 160 200

MAGNETIZING FORCE, H, OERSTEDS

Figure 24. Crystal structure of nickel and types of magnetization curves ob- tained in crystallographic directions [J ?"<?].

24

wl5

OQ 5

CO

Nl r/

u

0 50 100 150 200

H, OERSTEDS

Figure 23. Typical normal induction curves of annealed

samples of iron, nickel, and cobalt [172'\.

tensities the magnetocaloric effect is mainly re- versible ; in low positive fields there is a marked

cooling effect, which is associated with large

irreversible changes in magnetization [189].
500

4 00

300 oo

0

-100

^^-^^ 1 lW xKsJ ^SW v^Os. ^^>»* !\\N —\v v\-\—

V

\VVvl\ \

\ V \\! \

'\\\

I \ Mn

--Sn

Zn\

\ \v' \\

^ V \\

^ \^ \\

rV

\mo

- Al \Sb

\ \ \

Tl

\ 1

0 5 10 15 20 25 ALLOYING ELEMENT,

%

Figure 25. Effect of single alloying elements on the Curie point of nickel [186].

perature dependence of the coercivity, through

the temperature range —195 to +360 °C, is reversible on annealing [192]. Nickel rods sintered above 1,000 °C show an increase in co- ercivity with decreasing temperature, and the

increase is proportional to the square root of

the crystal energy or the anisotropy constant

[193].

(6) Magnetostriction. Magnetostriction is the

change in dimensions of a body resulting from

magnetization. The most important magnetostrictive effect is the fractional change in length

of the order of a feiv parts in a million on magnetization, known as the Joule effect. The re- verse phenomenon, in which change of magnetization is produced by the application of

mechanical strain, is known as the Villari effect. Pure nickel has, in conjunction with other desirable properties, one of the largest magnetostrictive effects available in commercial materials and is extensively used in devices when

this effect is required.

According to the domain theory of magnetization, magnetostriction develops in nickel as

follows: each small domain is always magnetized to saturation in any one of the six easy

directions of magnetization. In the absence of

0-273 -200 -100 0 100 200

TEMPERATURE, °C

300 400

Figure 26. Saturation induction of nickel at various temperatures [17^].

25
an external field, the random orientation of the

100,000 domains in a crystal of average size

results in a net magnetic effect of zero for the

crystal. However, if a weak magnetic field is applied, some of the favorably oriented domains

grow in size at the expense of others. As the

field is increased the growth process continues

until each crystal becomes one domain, magnetized along an easy direction of magnetization

that approximates the direction of the field. On

further increase of the applied field, the large

domain rotates until it is parallel to the field,

and it is during this process that the material

expands or contracts its dimensions, thus ex- hibiting magnetostriction.

Nickel contracts in all magnetic fields whereas

iron expands in a low field and contracts slightly

in a high field as shown by figure 27. The nickeliron alloy system is interesting in the wide

range of magnetostrictive properties available, as shown in figure 28. A few percent of nickel

makes iron exhibit positive magnetostriction at

all magnetic field strengths. At about 30 percent

nickel the longitudinal magnetostriction drops

to zero, but the volume magnetostriction reaches

its maximum in alloys containing about 35 percent of nickel. At about 45 percent nickel there

is a peak in positive magnetostriction that is comparable in size to the negative magnetostriction of pure nickel. The 63-percent nickel alloy

is the most strain-sensitive of these alloys, i.e., it shows the greatest change in magnetization

for a given change in stress, and the effect can

be further increased by special heat treatment.

At 81 percent nickel the magnetostriction goes

through zero, and at higher nickel contents the

negative magnetostriction ultimately reaches its maximum value at pure nickel.

Ferromagnetic iron-nickel alloys lose their

magnetism as the temperature is increased to the Curie point, and this loss of internal magnetism causes the alloy to contract if the magnetostriction is positive. In the Invar alloys, the volume contraction due to loss in magnetization al40X10 -6

20X10

g

O -20

COo

6

Fe

Ni

1 1 1 <

200 400 600

H, OERSTEDS

800

<1 20

o

0

-20

1 230 H*250

/

/ Aw

-\—/-

H*IO

10

^2S0

Figure 27. Effect of field strength on the magnetostriction of nickel and iron

0 20 40 60 80 100

NICKEL, %

Figure 28. Magnetostriction in iron-nickel alloys at dif- ferent field strengths

most neutralizes the thermal expansion due to the forces of thermal agitation, with the result

that these alloys have extremely low thermal

expansion over a considerable temperature

range.

The actual change in length that accompanies

magnetostriction is small; even in nickel the

maximum change in length is less than 40 ppm.

However, even this small dimensional change is sufficient to make nickel very important in the

construction of transducers for the conversion

of electrical to mechanical energy, particularly

in the ultrasonic range. The magnetostrictive

properties of nickel or its alloys make it useful

for transducers vibrating in the range of 10-100

kHz and of vital importance in equipment used

in many and diverse fields, including Sonar and

related devices for echo sounding and underwater detection; electrical filters, e.g., a band

pass filter for use in commercial receiving sets

the purification of water and killing of bacteria

acceleration of chemical reactions and cavitation effects; strain gages, vibration and engine

detonation ; phonograph pickups ; frequency control of oscillators; dust precipitation; the drill- ing and machining of hard materials like tool steels and refractories; detection of flaws, and

many other uses. An extended discussion of the theory and

practice of magnetostrictive effects, with an appendix of pertinent references, is contained in

two booklets of The International Nickel Company, Inc. [194,195]

2.2. Chemical Properties

a. Behavior in Corrosive Media

The resistance of nickel to tarnish and corrosion in the atmosphere and in many corrosive

media was established in the early history of

the nickel industry and was responsible for the

first large use of nickel in nickel plating. Nickel

requires the presence of an oxidizing agent,

such as dissolved air, for most of its corrosion

reactions. Reducing conditions usually retard

26
the corrosion of nickel, while oxidizing conditions usually accelerate it. However, nickel has

the ability to protect itself against certain forms

of attack by development of a corrosion resisting, or passive, oxide film and consequently, oxidizing conditions do not invariably accelerate

corrosion.

The surface finish and the use of polishing

agents, such as chalk, tripoli, and the oxides of

iron, chromium, and aluminum, have effects on

the initial rates of corrosion but the differences

disappear as corrosion proceeds [196]. Yamaguchi [197] found that nickel lapped to a mirror finish with an aqueous colloidal suspension

of aluminum oxide exhibits remarkable corro- sion resistance, retaining its finish even after

longtime immersion in a saturated aqueous solution of hydrogen sulfide. In contrast, a chemically or electrochemically polished surface was

immediately attacked in the hydrogen sulfide

solution. A bibliography of the literature con- cerned with the corrosion products on nickel and

its alloys was published in 1960 [198].

(1) Water. Nickel is highly resistant to cor- rosion by waters, such as distilled water, ordinary tap water, and natural fresh waters (including those containing hydrogen sulfide or

free carbon dioxide) . It is resistant to corrosion

by water even at 500 °F under pressure of 2000

psi and at velocities up to 30 fps [199].

In sea water, conditions of agitation or flow are favorable to nickel, but local attack may

occur under barnacles or other attached solids

in low-velocity exposure. In general, salt and

brackish waters are more corrosive than fresh

waters, but nickel alloys find many uses under

marine conditions. An evaluation of nickel and

many nickel-containing materials for marine

usage was made by Tuthill and Schillmoller

[200]

.

Although Friend [201] reported, on the basis

of 4-year exposure tests, that 99.84 percent

nickel was second only to tin in resistance to Bristol Channel waters, other sea water exposures have shown that nickel is subject to pitting [201a]. A report by May and Humble

[202] stated that crevice corrosion of nickel in

quiet sea water can be prevented by cathodic

protection.

(2) Mineral acids, alkalies, and salts. Nickel

is fairly resistant to sulfuric acid in concentrations of less than 80 percent at room temperature, the rates varying from less than 5 mpy in

air-free acid to about 50 mpy in air-saturated

acid. It is not useful in contact with hot sulfuric

acid of concentrations greater than about 15

percent [203]. Aeration increases corrosion

rates, particularly in dilute acids; in concentrated acids aeration decreases corrosion rates. Increasing temperature increases corrosion

rates and hot aerated solutions are very corrosive. In boiling solutions the use of nickel should

be confined to concentrations below 5 percent.

At 5 percent concentration, the corrosion rate of Nickel 200 in boiling (216 °F) sulfuric acid

is 34 mpy [204]. At 10 percent, the rate in- creases to 120 mpy. The kinetics of nickel cor- rosion in sulfuric acid were reported by Pitt

and Wadsworth [205]. Nickel is corroded se- verely by sulfurous acid, except the very dilute

solutions such as are used to preserve foods.

With cold hydrochloric (muriatic) acid, the

rates of attack vary according to the air content, from 10 to 40 mpy in dilute acid to 60 to 80 mpy in concentrated acid. Figure 29 shows

the effect of hydrochloric acid concentrations

and aeration on the corrosion rates of nickel at 86 °F. Nickel may find some applications in low

concentrations of acid, especially in unaerated

solutions at room temperature. Nickel is rarely

useful in handling hot hydrochloric acid of more

than 2 percent concentration [203,206].

Nickel is resistant to pure unaerated phosphoric acid at room temperature but is cor160

E 120

LiJ <

o

(f) o

01

cr. oo

80

40

0

NICKEL 200-AIR

SATURATED

NICKEL 200-AIR FREE

(NITROGEN-SATURATED)

J I \ \ 0 5 10 15 20 25 30 35

ACID CONCENTRATION, % BY WT

40

Figure 29. Corrosion of Nickel 200 in hydrochloric acid solutions at 86

[204].

27
roded when the acid contains oxidizing impurities such as ferric compounds. In hot phosphoric

acid, corrosion rates are liigh.

Nickel 200 shows excellent resistance to an- hydrous hydrofluoric acid even at elevated temperatures [204]. In aqueous solutions, however,

exposure is usually limited to temperatures below 180 °F.

Strongly oxidizing acids, such as nitric acid,

corrode nickel. Berg [207] showed that the rate of solution in nitric acid was proportional to the

square root of the concentration up to 3.5 N,

but at higher concentrations the equation is complex and results are difficult to reproduce.

Nitric acid of greater than 0.5 iV concentrations

rapidly attacks Nickel 200.

Nickel is strongly resistant to alkali solutions.

For example, in boiling 50 percent sodium hydroxide (caustic soda) the rates of corrosion are less than 1 mpy [203,208,209], and in con- centrations greater than 75 percent, nickel is second only to silver in resisting attack. The

resistance of nickel to corrosion by molten

sodium hydroxide was used by Probst et al. [210] , as a base for attempting to develop nickel

alloys having similar corrosion resistance but

having greater high-temperature strength. Anhydrous ammonia does not corrode nickel, but

ammonium hydroxide is appreciably corrosive

in concentrations greater than about 1 percent.

Molten carbonates are corrosive to nickel [211].

The well-known abilitj'' of molten sodium hydroxide containing about 2 percent of sodium

hydride to remove oxide scale from nickel without attacking the underlying metal led to nu- merous investigations of the possibility of using

nickel to contain sodium hydroxide as a heat

transfer agent in nuclear reactors [212,213,214,

215]. These investigations showed that molten

sodium hydroxide can be handled in nickel containers at all temperatures up to about 1000 °F,

but at 1200 to 1500 °F the circulating system

becomes plugged with deposited nickel. The Research and Development Department of The In- ternational Nickel Company, Inc., reports that,

in commercial production of caustic, nickel containers are useful at 1200 °F.

Nickel resists corrosion by neutral and alkaline salt solutions, with rates usually less than

5 mpy. Nonoxidizing acid salts are only moderately corrosive, with rates seldom higher than

2 mpy. Oxidizing acid salts, such as ferric chloride, and mixtures of oxidizing salts with mineral acids, are likely to corrode nickel severely,

and the same is true of oxidizing alkaline salts,

such as hypochlorites, with which nickel should

not be used when the available chlorine content

exceeds 3 g per liter, Gurovich [216] reported

that the magnitude and rate of corrosion in

molten alkali chlorides varied with the cation

ratio; nickel lost 1.3 g/m-/hr in KCl and 4

g/m-/hr in LiCl. He also reported on reactions

of nickel with molten nitrates of the alkali

metals [217]. Treseder and Wachter [218]

stated that the use of nickel is required when

a liquid mixture of AICI3 and SbCla is used as a

catalyst in petroleum processes.

Alkaline solutions containing hydrogen peroxide do not corrode nickel and are not decomposed by it. (3) Organic acids and compounds. With a few exceptions, organic acids are weak and nonoxidizing. Nickel 200 has excellent resistance

to organic acids of all concentrations if the

aeration is not high. Natural and alkaline or- ganic compounds have virtually no effect on

nickel.

Nickel is not attacked by fatty acids or soap

and is widely used in their processing [219,

220]. The corrosion of nickel by acetic acid is very slight [219]. In the production of low- and

medium-priced jewelry, watch bracelets, for

example, Mairs and Williams [221] note that no single substitute has yet been found with

the general usefulness of nickel in resistance to synthetic and natural perspiration.

Steverding [222] reported that rapid intergranular corrosion of nickel by kerosene-type

fuels does not occur below 550 °C, and that

cold-worked metal offers greater resistance to corrosion than nickel of equiaxed grain structure. Nickel is not corroded appreciably by chlorinated solvents or by mixtures of these with

water. j (4) Atmospheres. Wlaen exposed indoors.

Nickel 200 will remain reasonably bright and

free of tarnish, being superior to silver, copper,

and brass in this respect. Outdoors, it becomes

dull and acquires a thin adherent corrosion film

which is usually a sulfate. Rate of corrosion is extremely slow although corrosion does increase

with increases in the sulfur dioxide content of

the atmosphere. Marine atmospheres and rural

atmospheres cause comparable corrosion rates,

both very slow.

The 20-year atmospheric exposure tests con- ducted by the American Society for Testing and

Materials included exposure of plates of 99 +

nickel at industrial locations (Altoona, Pa., and

New York City), a marine location receiving

Table 14. Results of ASTM 20-year atmospheric exposures

of 99 + nickel [223] (Specimen size 9 x 10 x 0.035 in.)

Location Original weight, avg

Loss in weight, avg Corrosion rate

10 yr 20 yr 10 yr 20 yr

g y % a % mil/yr m.il/yr Altoona . .

566 47 90 8.5 140.73 25.2 0.164 0.222 New York 564 40 56 7.2 93.28 16.6 .137 .144 Sandy Hook 562 9 35 1.7 .0313 Key West _ _ . 562 1 49 .3 2.55 .5 .0050 .0041 La Jolla_ . - 564 1 38 .2 3.32 .6 .0047 .0058

State College 565 1 95 .3 5.44 1.0 .0066 .0085 Phoenix . 563 38 .1 .88 .2 .0013 .0015

28
considerable industrial pollution (Sandy Hook,

N. J.), marine locations (La Jolla, Calif., and

Key West, Fla.), and two rural locations (State

College, Pa., and Phoenix, Ariz.). The results

of these long-duration exposures, reported by

Copson [223] and summarized in table 14 and

figure 30, showed that nickel is very resistant

to corrosion at marine and rural locations. In all cases the corrosion was constant with time, and

the corrosive attack was essentially uniform in

nature, i.e., nonpitting.

Copson's report of the ASTM tests contained

supplementary data from exposures of sheet

and screen specimens in the industrial atmosphere of Bayonne, N. J., for periods ranging

up to 20 years. The corrosion rates corresponded

with those of the ASTM locations, but the

Bayonne results showed that sheltered specimens corroded more than unsheltered exposed

specimens, and that screen and wire corrode

faster than sheet. Pitting was not observed in

any of the screen specimens but was observed

in two of the sheet specimens ; the average maximum pit depth was 3.4 mils for a sheet exposed

12 years in the exposed vertical position and

1.4 mils for a sheet exposed for 20 years in the

sheltered vertical position. The faster corrosion

of screen and wire, because of such factors as increased pickup of pollution per unit area, was

discussed by Copson in another publication

[224].

(5) Wet and dry gases. Dry gases are not

actively corrosive to nickel at atmospheric temperatures, but wet gases such as nitric oxide,

chlorine and other halogens, sulfur dioxide, and

ammonia are appreciably corrosive. Nickel is resistant to dry chlorine and hydrogen chloride

at temperatures up to about 1,000 °F [203].

The approximate temperature at which a given

corrosion rate is exceeded in short-time tests in

dry chlorine for Nickel 201 is as follows [204]

30 mpy

60 mpy

120 mpy

600 mpy

1200 mpy

950

1000

1100

1200

1250

8 12 16 TIME.yr

FiGl'RE 30. ASTM 20-year atmospheric exposures of 99+ nickel plate [223].

In wet hydrochloric acid vapor, corrosion begins at isolated points, which increase in number with increasing time [225]. Nickel is re- sistant to fluorine and fluorides, but this re- sistance is decreased in the presence of moisture

and the consequent formation of hydrofluoric

acid [226,227]. At temperatures above 375 °C,

nickel is subject to general and intergranular

attack by gases that contain sulfur and sulfur

compounds. The extent of the attack is less in an oxidizing environment (SO9) than in a re- ducing environment (HoS), and the resistance

of nickel to attack by sulfur is considerably improved by the presence of up to about 5 percent

of manganese [203]. Nickel begins to react with

sulfur dioxide at about 460 °C to form nickel

sulfide, Ni3S2; the reaction goes nearly to completion at about 700 °C, and may reverse at higher temperatures [228]. The reaction of

nickel and molten sulfur follows a parabolic law

between 205 and 445 °C, forming Ni3S2 or NieSs [229].

(6) Oxidation. When heated in oxidizing at- mospheres, nickel forms a superficial, tightly

adherent scale at temperatures below 1400 °F,

and its resistance to excessive oxidation makes

nickel useful at higher temperatures [203] . The

rate of oxidation of nickel in air or oxygen

essentially follows a parabolic law, and the

purer the nickel the lower the rate [230,231,

232].

Gulbranson and Andrew reviewed the early

literature relating to the oxidation of pure

nickel [233] and reported studies on oxidation

at temperatures up to 1050 °C [234]. They re- ported that protective oxidation failed at about

900 °C, at which temperature the parabolic law

constant has a value of 1.88 X 10 " (g/cm-)^/

sec and a film thickness value of 400 to 600

/xg/cm^. Their curves for the oxidation of nickel are shown in figure 31.

Many studies of the oxidation of nickel have

been reported [235,236,237,238,239,240,241,242,

243,244]. Uhlig et al.[237] ascribed the discontinuity in oxidation rate at the Curie temperature to a slightly higher work function

above the Curie temperature, which explains a

slightly higher activation energy for oxidation

above the Curie temperature. Doerr [240] re- ported that for 99.99 percent nickel heated in

oxygen at 1200 °C, the parabolic-rate constant was 2 mg cm -hr"'^. Baur et al.[242] studied the

eflfect of oxygen pressures ranging from 6.5 X

10'^ atm to 20.4 atm at temperatures up to

29
2000

1600

E

u

cn 1200

•i 800

o

60 80

TIME(MIN.)

Figure 31. Effect of temperature on the oxidation of nickel in oxygen; pres- sure = 7.6 cm Hg {23A^.

1200 °C; they found the oxidation rate to be

proportional to the one-fifth power of the oxygen pressure. Fueki and Wagner [243] determined activation energies for oxidation ranging

from 36.3 to 43.6 kcal/mole, depending on the

test atmosphere.

Zima [245] combined his data (at 76 cm of

Hg) with those of Gulbranson and Andrew

[233] (at 7.6 cm of Hg) to give the oxidation

rates at temperatures from 550 to 1260 °C as presented in table 15. The combined data yielded an activation energy of 45.1 kcal/mole for the

oxidation of nickel. Rosenberg [246] reported

that TD nickel wire exhibited parabolic oxidation kinetics, with the resultant formation of a

tenacious oxide (NiO) film on the surface. No

internal oxidation, or effects of stress on oxidation, were noted. The effect of small amounts

of lithium in decreasing the oxidation of nickel was studied by Hagel [247] . He determined a

parabolic rate constant (at 1200 °C) of 2.75 X

IQ-io g2 cm * sec"^ for nickel containing 0.6 a/o

lithium, as compared with one of 2.00 X lO"** g^

cm"* sec"^ for carbonyl nickel ; i.e., the oxidation

Table 15. Rates of oxidation of 99.95% nickel [233, 21^5]

Temperature Oxygen pressure Parabolic rate law constant

"C cm of Hg 0^ cm~* sec"' 550 7.6 1. 08X10-"

600 7.6 5.23 X 10-"

625 7.6 6.83X10-H

650 7.6 1. 46X10-"

700 7.6 5.08X10-"

980 76 1.14X10-1"

1096 76 5.48X10-'"

1260 76 34.1X10-1"

rate was decreased by a factor of seven. Even a

barely detectable amount of lithium (<0.4 a/o)

provided a rate constant of 5.65 X lO"^** g^ cm"*

sec * (rate-reduction factor, 3.5).

Fueki and Ishibashi [248] showed that the

addition of small amounts of aluminum (about

1 % ) improves the oxidation resistance of nickel

at temperatures from 700 to 900 °C.

b. Adsorption and Diffusion of Gases and Metals

Hydrogen is strongly adsorbed and other

gases, such as carbon monoxide, carbon dioxide,

and ethylene, are adsorbed by nickel. This ability of nickel to combine with certain gases without forming stable compounds is important in

electroplated nickel and is particularly important in the use of nickel as a catalyst. In general, the amount of gas taken up by nickel in- creases markedly with increasing temperature

and mildly with increasing pressure, but the

mechanism of the adsorption and absorption re- actions has not been completely clarified. Baker

et al.[249] concluded that the contact of nickel

with hydrogen, at temperatures from -f20 to —183 °C, results in dissociation at the surface

with subsequent solution of atoms in the bulk

phase. This involves activation energy and the

existence of lattice vacancies or macrocrystalline spaces, but probably does not involve lattice

solution. Baker and Rideal [250] reported that

at —183 °C carbon monoxide is absorbed by

nickel, but at higher temperatures, surface re- actions form carbon dioxide and nickel carbide

(or carbon). Carbon dioxide can replace hydrogen chemisorbed by nickel, but hydrogen cannot

30
replace carbon monoxide. Gundry and Tompkins [251,252] studied the equilibrium properties of the hydrogen plus nickel and carbon

monoxide plus nickel systems and the kinetics

of sorption of these two gases on nickel films

below —78 °C. They concluded that the slow

I'ate of sorption was due to an activated diffusion process over the nonuniform surface of the

metal film. The ratio of amount of carbon monoxide adsorbed to that of hydrogen, under comparable conditions, was about 1.5. The amounts of hydrogen and other gases adsorbed by nickel are greatly in excess of their

true solubilities. Meyerson [94] presented results from numerous sources to show that the

solubility of hydrogen in solid nickel varies from

10-^ I

1

about 0.0002 w/o at 300 °C to 0.0008 w/o at 900 °C.

Edwards [253] determined that the diffusion rate of hydrogen in nickel followed the equation

D = Do exp (-"/T), where Do = 1.07 X 10-2 cm - sec'i and b = 5100 °K, His plot of the variation of diffusion rate with temperature is shown in figure 32, Olsen and Larkin [254]

found the diffusion coefficient of hydrogen in

nickel at 25 °C to be 3.9 X 10"io cmVsec and re- ported that the diffusion constants showed the

activation energy to be about 9500 calories per

mole. They found that the total amount of hydrogen liberated at this temperature was approximately 0.0001 percent. Wortman et al, [255], reported that the diffusion of hydrogen

Figure 32. Variation of diffusion rate of hydrogen in nickel with temperature

[253'\.

31
in nickel occurs with an activation energy of

7000 ± 1000 calories per mole in the chemisorbed layer.

Some gases, notably hydrogen, can diffuse

through solid nickel. It is reported [256] that

hydrogen at a pressure differential of 1 atm

diffused through certain thin-walled nickel

tubes at 950 °C at a rate of 250 ml/min. Hill

and Johnson [257] studied the diffusion of hydrogen through nickel at temperatures from

380 to 1,000 °C. They concluded that the en- tropy of activation was negative and that the

diffusion was accompanied by little, if any, distortion of the nickel lattice. Grimes [258] observed that deformations up

to 10 percent caused no significant change in

the diffusion coefficient for hydrogen through

unstrained nickel, which he gave as 0.0095 exp

(~10,S00/RT) cm-' sec. He noted that this finding agrees with theoretical analysis of interstitial diffusion in strained systems.

The permeability of hydrogen through nickel

is rapid, even at temperatures approaching room temperature [259]. Gorman and Nardella

[260] measured the hydrogen permeation rate

in nickel and reported the following values for

the permeation coefficient (U) : at 700 °K, U

atm-'^^ 19.1 X 10-2 ^ liters cm'^ sec~i

at 1000 °K, U = 3.32 X lO^ liters cm"^ sec^

Their curves for hydrogen permeation through

nickel are shown in figure 33.

Weinstein and Elliott [261] reported that, at 1600 °C and 1 atm, 40.7 ppm of hydrogen was

soluble in liquid nickel. The effect of temperature on the solubility of hydrogen, according to these authors, is shown in figure 34. Busch and

Dodd [262] found that, at 1600 °C and one

atmosphere, 3.82 X 10'^ w/o of hydrogen was

soluble in nickel.

Selwood [263] discussed the theory of nitrogen adsorption on nickel at low temperatures

and demonstrated that there is no true chemisorption of nitrogen on nickel. However, Kokes, I and Emmett [264] reported that pure nickel

catalysts will chemisorb nitrogen to a slight ex- tent at about 250 to 300 °C. Amounts chemisorbed at high temperatures correspond to 5

percent surface coverage calculated as molecular nitrogen ; the low temperature chemisorption

corresponds to as much as 28 percent surface

coverage. The nitrogen absorbed at —195 °C is easily removed by evacuation at room temperature. Busch and Dodd [262] reported that nitrogen was insoluble in pure liquid nickel, but Humbert and Elliott [265] note some slight solubil

ity at 1600 °C and 1 atm (0.001 ± 0.001 w/o)

The solubility of oxygen in molten nickel, ac- cording to Wriedt and Chipman [266], varies

from 0.294 w/o at 1450 °C to 1.63 w/o at 1691

°C. In a later paper [267], these authors dis- cuss equilibrium of hydrogen and oxygen with

molten nickel, iron, and their alloys. Tankins

-1

-2

-3

-4

-5

-6

-7

-8

1000 900 800 700 600 500 400

I I I 1 T 1 I

1 1 1

3.0

0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7

lOVT

Figure 33. Hydrogen permeation through nickel l260'\.

Solid line—heavy-walled sample. Dotted line—thin-walled sample.

32
46.0

X

o

lu 44.0

>-

CO

on

liJ

a:<

Q.

36.0

1440 1480 1520 1560 1600 1640 1680 1720

TEMPERATURE °C

Figure 34. Effect of temperature on the solubility of hydrogen at one at- mosphere pressure in pure nickel 1261],

et al.[268], gave the following figures for the

j maximum solubility of oxygen in nickel:

0.44% at 1550 °C

.62 at 1600

.88 at 1650

1.23 at 1700

Sedles and Danielson [124] computed the

thermal difFusivity of 99.95 percent nickel at 25 °C as almost 0.23 cmVsec, and of 97.92 percent nickel as 0.12. Hoffman et al.[125], studied

the self-diffusion coefficient of high-purity

] nickel over the range 870 to 1248 °C and found

; that the measured activation energy correlated

I with the melting point and the heats of fusion

I and sublimation. Studies of the diffusion rates

j of nickel in other metals, and vice versa, have

i been reported [126,127,128].

Surface self-diffusion measurements on

nickel between 800 and 1200 °C were made by

Blakely and Mykura [269] . They found that

1 the self-diffusion constant (D.,) depended

} strongly on surface orientation, the dependence

being greatest at the lower temperatures. Variation of diffusion constants with temperature for

surfaces orientated within 25° of the (111)

surface was given by D, — Do exp C'^/KT),

with Do ^ 5 (±3) X 10 cmVsec and Q =

0.62 (±0.08) eV.

Upthegrove and Sinnott [270] studied the

grain boundary self-diffusion of nickel. They

reported that the lattice self-diffusion coefficient

of nickel in the temperature range 850 to 1100

is Dl = 0.48 exp {-Q5,S00/RT) . The ratio

of the grain boundary diffusion coefficient to the

lattice diffusion coefficient (Db/Dl) varies from

10'^ to 10' for boundary angles from 5° to 80° over the temperature range 700 to 1100 °C. The

ratio increases with increasing angular misfit

and with decreasing diffusion temperature. The

activation energy for grain boundary diffusion

is independent of misfit angle for 20° < 0 < 70°; the value is 26.0 ± 1.5 kcal/g mole.

Beyond these limits the activation energy approaches 65.9 kcal/g mole, the lattice diffusion

activation energy.

The surface self-diffusion coefficient on nickel

single crystals was measured by Pye and Drew

[271] over the temperature range 400 to 1000

°C. They found that the activation energy for

surface diffusion was the same on the (111),

(110), and (100) planes, amounting to about

0.60 eV. The values for the diffusion coefficient

(Dg) at constant temperature varied with crystallographic orientation as follows:

D, (111) > D., (110) > Ds (100). Their data

are plotted in figure 35.

Murarka et al.[272], gave the diffusion coefficient of chromium in nickel in the range 600

to 900 °C as:

Z>cr/Ni = 0.03 exp ( — 40,800 R/T cm^ sec and

in the range 350 to 600 °C as Dcr/^i = 5.45 X

lO--* exp ( - 13,700 R/T) cm' sec. The diffusion rates of magnesium, silicon, and

molybdenum in nickel were measured as a function of temperature by Swalin et al.[273], and

are shown in figure 36.

33
EuQ

i X 103 (K-1)

Figure 35. The temperature dependence of the self surface diffu^on of

nickel [271'^.

Barnes and Mazey [274] reported no change

in the rate of diffusion of copper into nickel as a result of pressure up to 2500 Ib/in^.

The interdiffusion of uranium and nickel was

studied by Aas and Steinegger [275] who found

that at 500 and 600 °C the penetration of nickel

into uranium was about four times more rapid

than that of uranium into nickel. The activation

energy for the temperature range 400 to 600 °C was determined as 17.1 kcal.

c. Catalytic Action

About 1818 Thenard observed the catalytic

effect of nickel in a study of the decomposition

of hydrogen peroxide, and Marchand in 1842

decomposed ethylene over heated nickel. Mond

and Langer produced hydrogen in commercial

quantities by the action of nickel catalysts on

mixtures of carbon monoxide, hydrocarbons,

and steam. In 1896 Sabatier and Senderens

started their classical work on the catalytic

hydrogenation of unsaturated hydrocarbons and

other organic compounds. Most of the reactions

catalyzed by nickel involve hydrogenation or dehydrogenation of organic compounds. The

preparation of edible oils and fats accounts for

more than two-thirds of the consumption of

nickel as a catalyst. Fraser [276] in 1937 listed

approximately 40 fields in which nickel catalysts

34
Figure 36. Relation between temperature and diffusion of molybdenum, sili- con, and magnesium in nickel 1273].

I" were used, and the list was still growing. Among

these fields are the artificial aging of liquors,

drying oils, bleaching, waste-water purification,

the removal of organic sulfur compounds from

coal gas, the manufacture of alcohol from gas

i^oil, cracking of ammonia, reactions of carbon

{monoxide with aromatic halogen compounds,

I and the manufacture of hydrazine from urea. iDinickel phosphide, prepared by reduction of

nickel orthophosphate in excess hydrogen, is a

highly active heterogeneous catalyst for the

vapor-phase reduction of nitrobenzene with hydrogen to analine and water [277]. Alloys of

nickel and copper are used as catalysts to hydrogenate carbon dioxide to methane rather

than to carbon monoxide [278].

The catalytic action of nickel is primarily a

surface reaction and consequently maximum

surface with respect to mass is desirable in

nickel catalysts. The traditional procedure,

from the days of Sabatier's experiments, was to disperse small particles or flakes of nickel

throughout the reacting mixture, but the modern Raney catalyst is much more active than

Sabatier's flake nickel. To prepare the Raney

catalyst, according to Adkins and Billica [279]

,

a nickel-aluminum alloy is digested in aqueous

NaOH at 50 °C, producing a sludge, which is washed successively with distilled water, ethanol, and absolute alcohol. The centrifuged

sludge may be stored wet in a refrigerator for

about two weeks before its activity becomes

appreciably affected. Ipatieff and Pines [280]

reported that catalysts thus prepared contained

35
about 21 percent of AloO.j, instead of being: simply nickel and residual aluminum as reported by

Adkins and Billica. Raney catalysts prepared

from nickel-magnesium, instead of from nickelaluminum, were reported by Pattison and Degering [281] . The mechanisms of the reactions of

Raney catalysts, particularly in hydrogenation

reactions, has been thoroughly studied. The fac- tors affecting the catalytic activity were discussed by Pattison and Degering [281] and were reviewed by Yasumura [282], who cited some 60 references. Baker, Jenkins, and Rideal

[249] believed that chemisorption and energy

of activation were important factors and that

solution in the lattice was not involved, although

vacancies might be. Smith et al. [283] reported

that the catalytic activity is highest for those

freshly prepared catalysts that have the highest

hydrogen contents, and assumed that the hydrogen atoms are attached to nickel in metastable

fashion. In film catalysts, available evidence indicates the presence of a catalytically active

nickel-hydrogen layer [284].

The catalytic activity of Raney catalysts may

be reduced, i.e., the catalysts may be "poisoned"

by sulfur, chlorides, or bromides, and particularly by iodides [281] or by an excess of alkali

[285].

d. Electrolytic Solution Potential—Passivity

Values for the electrolytic solution potential

of nickel are -0.227 ± 0.002 V at 20 °C [286],

and -0.231 ± 0.002 V at 25 °C [287]. Values

of -0.2508 V at +18 °C and -0.2496 at 25 °C were reported for powdered nickel in lA^ solution of nickel sulfate [288].

Under most conditions the tendency for nickel

to become passive, i.e., to behave like a noble

metal, is not dependable and is not of practical

importance. The passivity developed by simple

immersion may be destroyed by slight changes

in the composition or concentration of the solution, or by mechanical means such as scratching

the surface. Anodic passivity is affected by the

presence of impurities in the metal or electrolyte; chloride ions are particularly effective in

destroying anodic passivity, and use is made of

this in maintaining the activity of nickel in

electroplating.

The passivity of nickel in acid solution was

studied by Markovic and Ahmedbavic [289],

who concluded that in the case of acid solution,

the dissolution mechanism and formation of the

passive film are explicable by the reaction Ni304

+ Ni.Oa + Ni2^ + OH- where the basic

potential Uh = +0.38 V. Osterwald and Uhlig

[290] found that the critical potential for

passivity of nickel in deaerated 17V sulfuric

acid at 25 °C followed the relation Eh =0.125 +

0.059 pH. The critical current density (ma/cm-)

followed the relation log i = —0.76 pU. + log

27. Sato and Okamoto [291] also studied the

passivation of nickel in sulfuric acid solutions

and proposed that the mechanism for formation

of passive film involves the successive reactions

Ni + OH- NiOH^ + 2e;

3NiOH^ + OH- NisOi + 4H^ + 2e. Markovic [292] found that, in neutral andi

alkaline solutions, the formation and dissolution:

of the surface film involves the mechanism

Ni304 + H^ ^ NiaOa + Ni^* + OH- with Uh =

0.38 V. I Davis and Barker [293] reported that nickel

becomes passive in alkaline solutions by the

formation of about one layer of Ni(0H)2 on the,: surface. In borate solutions, 1-2 molecular layers' are necessary for passivation. Further polariza-j^.

tion causes the Ni(0H)2 to become oxidized to NisOa. , Kronenberg et al.[294], determined the en-[

ergy of activation for the anodic dissolution,

process to be approximately 15 kcal/mole. j' Janz and Conte [295] conducted potentio-j;

static studies to establish data on the electrochemical behavior of nickel over the range 600,

to 700 °C. The steady state potential for nickel was — 1166 mV when referred to a Ag/Ag!

reference half-cell. The anodic potentiostaticj

polarization curve at 600 °C was characteristiqj

of metal passivation; a primary passive potenHjj

tial was observed at —1015 ± 5 mV, but the proj'

tection conferred appeared to be far from com^j

plete.

[ Other studies on the passivity of nickel havel

been made by Piontelli and Serravalle [296],

Piontelli, Seravelle, and Sternheim [297],'

Schwabe and Dietz [298], Okamoto, et al.[299] J and Greene [300].

e. Hygienic Significance j The hygienic significance of nickel is con-.' fined to industrial operations for the production*

and utilization of nickel and its salts or compounds, and is further confined to poisoning

from nickel carbonyl or to dermatitis produced

in individuals sensitive to nickel, for example;

in electroplating operations [301]. It was showtf over 40 years ago [302] that the preparation of' food in nickel or nickel-plated utensils is en-' tirely safe, and the extensive use of nickel ir pasteurizing equipment and in commercial fooc

processing has never created any problems'

[303]. The small amounts of nickel that art' naturally present in food products, or may b^- introduced by processing or cooking operations' are in general promptly and completely ex'' creted [304]. Early in the 20th century nicke

sulfate, chloride, and bromide were sometimes

prescribed for tonic purposes, although in som<

cases overdoses produced nausea and vomiting!

[302].

36
Some operators of industrial electroplating

equipment have suffered from eczematous dermatitis in varying degrees from contact with

nickel-containing solutions and fumes [302,

305], and there have been occasional reports of

nickel poisonmg resulting from the inhalation

of dust, for example, in polishing operations

[302], or in the production of alkali-cadmiumnickel storage batteries [306]. Modern knowledge of industrial hygiene, improved ventilation, and the use of protective equipment have

practically eliminated the danger of nickel poisoning in such operations.

An extremely toxic industrial nickel com- pound is nickel carbonyl, Ni(C0)4, which is prepared in large quantities for subsequent

thermal decomposition to yield a high-purity

nickel powder. It has found extensive industrial

application as a carbonylation reagent for producing acrylic acid from acetylene. When nickel

carbonyl is present in human lungs, the pres- ence of moisture causes the compound to dissoci- ate into carbon monoxide and finely divided

nickel. Small amounts of the dissociation products are readily eliminated by the human sys- tem, i.e., the effects are not cumulative, but a number of fatalities have occurred because of

single exposures to lethal doses in producing

plants and in laboratories [301,302,307]. The

threshold limit of one part of nickel carbonyl per

billion parts of air has been established by the

American Conference of Governmental Industrial Hygienists. The compound known as BAL

(2,3-dimercaptopropanol) has been found to be an excellent antidote for nickel-carbonyl poison-

' ing [308] . An excellent review of the toxicity

of nickel carbonyl was prepared by Rea [309]

.

The utilization or handling of radioactive

forms of nickel obviously requires observance

of the precautions used in handling any radioactive material. The tissue-damaging properties

I of gamma and beta radiation from irradiated

, nicKel (and other metals) are discussed by

Wise [310]

.

2.3. Mechanical Properties

The mechanical properties of nickel, in com- mon with other metals, are greatly influenced by

the purity, temperature, and the previous thermal and mechanical history of the specimen. As

in the case with pure metals in general, the

values for many of the mechanical properties

of pure nickel are lower than those of commercially pure or alloyed metal, particularly the

low-alloy, age-hardening nickels. With decreasing temperature below room temperature there

is a marked increase in tensile strength, and a

less pronounced increase in yield strength, hardness, modulus of elasticity, elongation, and fatigue resistance. The effects on the reduction in area, impact values, and compressibility are in- consistent.

^ Nickel, with its face-centered cubic lattice,

does not show the embrittlement and abrupt

change from ductile to brittle behavior with

decreasing temperature that is encountered in so many ferritic materials with body-centered

cubic lattices. Elevated temperatures produce

softening and weakening of most metals, including nickel. The previous thermal and mechanical history affect the grain size, structure,

and physical condition, including the presence

of strains, all of which affect mechanical properties. For these reasons, values cited in the

ensuing paragraphs are general. A comprehensive coverage of the mechanical properties of

nickel is contained in a booklet published by

The International Nickel Company, Inc. [86].

Slunder and Hall [311] summarized the mechanical properties of wrought nickel in various

forms and conditions.

a. Tensile and Compressive Properties

The tensile strength of annealed nickel of

high purity, 99.99 percent [186] and 99.94 percent [83] was reported as 46,000 psi. Brenner

[312] gives a value of 1.8 percent elastic strain

for nickel whiskers, which, using a modulus of

elasticity of 30,000,000 psi, converts to a tensile stress of 540,000 psi. Wise and Schaefer [186]

summarized the tensile strengths of commercial

nickel as follows : by suitable choice of hot roll- ing, annealing, and cold drawing or cold rolling,

tensile strengths ranging from 65,000 to 115,-

000 psi can be had in rods and bars, as high as 130,000 psi in strip, and 160,000 psi in wire.

ASTM Specifications B160-61 for nickel rods

and bars, B161-61 for pipe and tubing, and

B162-61 for plate, sheet, and strip require minimum tensile strengths of 55,000 psi for annealed 99 percent nickel and 50,000 psi for annealed low-carbon (0.02% max.) 99 percent

nickel, with higher values for worked material.

Studies of annealed 99.85 percent nickel, with an average grain diameter of 0.045 mm, have

been reported by the National Bureau of Standards in a series of papers [313,314,315]. Fig- ure 37, plotted from the data of Jenkins et al. [315] shows that the tensile strength of 99.85

percent nickel decreases smoothly and rapidly

with increasing temperature. The value at room

temperature was 51,800 psi. Small irregularities in the vicinity of the Curie temperature were reported by Zackay and Hazlett [316].

Foley [317] reported that the tensile strength

of nickel increased with decreasing temperature, from 65,000 psi at room temperature to 97,500 psi at —120 °C. Additional data at temperatures down to —320 °F are given by Inter- national Nickel [86]. At this low temperature

the tensile strength of annealed Nickel 200 is given as 103,000 psi. Wessel [319] investigated

the tensile properties of commercially pure

nickel over a wide range of temperatures. Mc37
Table 16.

Temperature Tensile strength

Yield strength (0.2% offset) Elongation

in 2 in

op Room

200 300 400

500

600

650

700 800

900

1000

1100

1200 1400

1500 1600

1800 2000

Effect of temperature on the tensile properties Clintock and Gibbons [319] reviewed the literaof annealed Nickel 200 [86] ^= ture on the mechanical properties of materials

at low temperature ; their curves for nickel are

^ofarea" rcproduced in figure 38. Table 16 gives the tensile properties of annealed Nickel 200 as listed

% by The International Nickel Co., Inc. [86] . Their

data for annealed Nickel 201 are shown in

table 17. Anker and Parker [320] reported that the

tensile strength of nickel increased regularly

[I'llWllW with increasing amounts of deformation at room

temperature followed by a recovery anneal at 800 °C. They believed that the hardening effect

of the recovery treatment, i.e., the sharpening

" "98^5 " " of the angular dislocations produced by the

room-temperature deformation, was greater

99 '.6 than the softening effect resulting from the

annihilation of internal barriers. The temperapsi 67,000

66,500

66 , 700 66,500

67,500

66 , 200

62 , 000

52 , 500 44,000

37,000

31,500

26,500

21,500

14,000 12,200

8,200 5,400

3,500

21,500

22,300 21,700

20,200

19,600 20,200

18,100

17,000 16,500

15,000

13,500

11 ,500 10,000 7,000 6,300

3 , 600 2,300

1,400

%

47.0

46.0

44.5 44.0

45.0

47.0

47.0

61.5 65.0 66.0

69.0

72.0 76.0 89.0

98.5 110.0

198.0 205.0

-320 212

100

90

80

70

Q.

§ 60

a:o 50

LU 40

ILI Q30

20

10

1 REpu CT mi 0 F AR EA

1 H

1

1

1

1 EL-Oh GA Til )N

r

Re

Oc

cry cur

sta

s

Iliz ati on

1 TEN 5IL E 5Tf lEhIG7

1

1

t

Yl ELD : ;Tf ?Ehig: H

0-400 -200 0 20 0 400 600 800 100 0 1 200 1400

TEMPERATURE, °F

Figure 37. Effect of temperature on the tensile properties of annealed 99.85 percent nickel 1315}.

38
Table 17. Effect of temperature on the tensile properties of annealed Nickel 201 [86]

Temperature •t Yield strengtli ii^longation JMouulus oi

[ij.^yo onseij ID 2 in elasticity

ont psx 07

/O psi Room 50 0 200 oo , lUU 20 700 45 0

on Ann onn

300 nan 1 o , / uu riO . O OQ 1 nn nnn 400 54 , 000 43 5

9fi Rnn nnn . ouu , yjuu 500 54.000 16,200 41.0 28,000,000

600 52,500 18,700 42.0 27,400,000

700 47.000 14,000 26,900,000

800 41,500 13,500 26,200,000

900 37,500 13,000 25,600,000

1000 33,000 12,000 25,000,000

1100 27,000 11,500 24,300,000

1200 22,000 9,000 23,700,000

ture of heating after cold working has a marked

effect on the room temperature tensile properties of nickel, as shown in table 18. Makin [321] investigated the effect of neutron irradiation at 100 °C with 5 X lO^^ neu- trons/cm- on the mechanical properties of nickel over a range of temperatures; he reported a

small increase in tensile strength but a large

increase in yield stress as a result of irradiation. At room temperature, the tensile strength was increased about 5,000 psi and the yield

strength about 25,000 psi; these increases became proportionately greater at the lower temperatures. The increase in strength was re150x10

140

130

120

110

a.

<)"" UJ

100

90

80

70

60

50

40

30

20

10

0,

— ALED

] tu —ANNE

>

N

ELONG

•

0 50

u

70

60

50

40 i

30

20

10

<

o

z

o

_l

t-z

UJu

on

UJ

250

0 100 150 200 300

TEMPERATURE,°K

Figure 38. Effect of temperature on the tensile properties of nickel \_319'\.

39
Table 18. Effect of heating on room-temperature tensile properties of hot-rolled and annealed Nickel 200 after 22

percent stretching at room temperature [86]

Temperature Tensile Yield Elongation

Reduction

strength strength in 2 in of area

pai psi % %

No heating 89,400 82 , 500 20.5 61.3 89,200 80,400 25.0 68.1 200 89,300 81 ,600 22.5 90.5 89,400 81 , 700 21.5 70.5 400 97,300 80,700 21.0 62.1 97,300 81,900 18.5 60.2 600 98,200 78,900 21.0 62.4 99,000 78 , 200 20.0 65.3

800 95,000 70 , 700 22.0 68.3 95,800 70,600 23.0 70.6

1,000 89,800 58,000 26.0 70.6 89,600 57 , 700 25.0 71.4

1,200 83 , 700 42 , 700 30.5 68.3 84,400 42,400 32.0 69.1

moved by annealing between 340 and 400 °C.

His curves are reproduced in figure 39. Paine,

Murphy, and Hackett [322] reported that, after

irradiation at fast flux levels of the order of

lO-*' nvt, increases in yield strength of Nickel

200 were as high as 500 percent. Tensile

strength was increased up to 70 percent. The

rate of change in these properties decreased

with increased radiation. For the flux levels

tested, irradiation generally leaves Nickel 200

in a more ductile condition than does cold working to a comparable strength.

The yield strength of annealed 99.95 nickel,

according to Wise [64] is 8,500 psi. Jenkins

et al. [315] reported values of 11,100 and 12,500

psi at 75 °F for annealed 99.85 percent nickel;

their data for the effect of temperature are

plotted in figure 37. ASTM Specifications B160-

61, B161-61, and B162-61 require minimum

120

o

if)

100

80

o 60

40

20

ULTIM

YIELD

ATE TENSILI

STRESS

E STRENGTH

^^.^NICKEl. IRRADIATE.D

NICKEL

IRRADIAT ED

^

NICKEL UNIRRADIA

0

-200 -100 0 100

TEMPERATURE, ^'C 200

Figure 39. Effect of neutron irradiation on the tensile properties of commercially pure nickel \_321'].

40
yield strengths of 15,000 psi for annealed commercial nickel and 10,000-12,000 psi for annealed low-carbon nickel, depending upon the

product. The effect of temperature on the yield

strength of nickel is also shown in figure 38 and

in tables 16 and 17. Rosenberg [323] reported that the yield

strength of cold-drawn commercial 99.4 percent

nickel was 97,000 psi at room temperature and

112,000 psi at — 78 °C. Meyerson [94] quoted

values for yield strength in compression (0.2%

offset) of "A" nickel as 23,000 psi for hot rolled,

58,000 psi for cold drawn and stress relieved,

and 26,000 psi for annealed material. Slunder

and Hall [311] give the following values in

compression

Hot rolled Cold drawn 24%

Annealed

Yield strength

(0.2% offset) Proportional

limit

psi

23,000

58,000

26,000

psi

18,000

41,000

15,000

The yield point in stress-strain curves of single

crystals of nickel was discussed by Haasen and

j Kelly [324]. The marked effect of irradiation

f on the yield strength has already been noted

(fig. 39).

The strength of "A" nickel in double shear

is given as 52,300 psi annealed, 57,550 psi halfi hard, and 75,300 psi hard [149]. Data on the

shear and bearing strengths of Nickel 200 are given in tables 19 and 20.

Table 19. Shear strength of Nickel 200 bars [86\

Temper Shear strength (double shear) Tensile strength Hardness, Rockwell B

Annealed

pai 52,000

58,000

75,000

psi 68,000

79,000

121,000

46

Half-hard 90

FiUl-hard 100

Table 20. Bearing strength of Nickel 200 sheet " [86\

Condition

Tensile properties Bearing

properties

Ratio of bearing to

tensile properties

Tensile strength

Yield

strength (0.2%)

Elongation

in 2 in

Ultimate

strength

(tearing out)

Yield

strength Tensile Yield

Soft

pai 59,600

67 , 600 99,000

pai 28,700

55,500

88,900

%

39.0

30.0

18.0

pai 125,500

151,500 179,000

pai 50,300

97,900

133,500

2.11 2.24

1.81

1.75

1 .77

1 .50 Half-hard... FuU-hard...

• 0.062 % 1.25 X 2.5 in material having a \a in hole at a hole center-to- edge distance of % in. 2 percent enlargement of hole diameter in sheet.

b. Elastic Properties

Studies of single crystals revealed pronounced

anisotropy in the elastic properties of nickel

[325,326,327,328] . For example, the anisotropy

factor is 2 C44/(Cii — C12) = 2.63, according

to Bozorth [325], and values for Young's modulus, according to Yamamoto [328], are

E(ioo) = 1.198, £\no) = 2.008, and E(iu) = 2.592

X 10^- d/cm-. Measurements made on polycrystalline specimens with random orientation represent a balance between anisotropic

values ; computations made by Yamamoto [327]

showed good agreement between his results obtained from single crystals, by magnetostrictive

vibration methods, and measured values for

polycrystalline nickel.

Average values for Young's modulus of elas- ticity are 30,000,000 psi for 99.95 percent nickel

[64] and also for annealed "A" nickel [149] ; 31,200,000 psi for cold-drawn nickel [323], and

21,500,000 psi for sand-cast "A" nickel [149].

Bennett and Davies [329] concluded, from a comparison of their own results with those of

other investigators, that purity had less significant effect tnan thermal treatment (there was

no significant difference in results from 99.97

and 99.2 nickel), that the temperature of an- nealing was more significant than the time, and

that Young's modulus decreased regularly with

increasing temperature, except in the vicinity

of the Curie temperature, until the value at 600

°C was about 80 percent of the value at room

temperature. The effect of temperature on the

elastic modulus, according to several investigators, is shown in figure 40. Additional data are given in table 17. Young's modulus of nickel is dependent on

magnetization as well as temperature. Figure

41 [174] shows the effect of various degrees of

magnetization on the modulus of nickel.

The modulus of elasticity in compression is the same as in tension, about 30,000,000 psi for

all commercial forms of nickel [94].

The modulus of elasticity in torsion, also

known as the modulus of rigidity and the modulus of shear, was reported as 11,000,000 psi

for "A" nickel [79] ; 12,000,000 psi for an- nealed 99.2 percent nickel and 11,600,000 psi

for the same material before annealing [333]

;

and as 11,270,000 for hot-rolled nickel [334].

Poisson's ratio, i.e., the ratio of transverse

contraction to longitudinal extension under tensile stress, is 0.31 for nickel [158].

c. Hardness

Values as low as 35 Rockwell B and 64 Vickers have been reported for the indentation hardness of annealed high-purity nickel [94]. The

hardness of annealed Nickel 200 rod and bar

has been given as 45-70 Rockwell B [86]. Cold

work and the presence of impurities increase

the hardness. ASTM Specification B162-61 for

41
34

32

30

°

28 X

26

S

24

22

20

18

1.00

UJ

.95

.90

.85

.80

-

—

LECTf lOLYT C

- K A URE N ICKEL

- \

^ ICKEL 200

- V

-

-

URE N CKEL

1 1 r 1 1 1

1 1 200 400 600 800 1000 1200 1400 1600

TEMPERATURE, °C

Figure 40. E^ect of temperature on the elastic modulus of nickel [329,330,331,332'].

nickel plate, sheet, and strips lists Rockwell B

numbers ranging from 64 maximum for an- nealed "A" nickel (Nickel 200) and 55 maximum for annealed low-carbon nickel (Nickel

201) to 90 minimum for hard cold-rolled and

95 minimum for spring-temper cold-rolled

strip. The effect of cold work on the hardness

of nickel is shown in figure 42.

The hardness of electrolytic nickel as deposited ranges from 100 to 425 Vickers [335].

The effect of annealing temperature on the

Vickers hardness is slight up to about 300 °C;

above this temperature the hardness drops

sharply as shown in figure 43.

Pile irradiation of lO^" nvt increased the

Brinell hardness of annealed nickel by 110. The

increase in Brinell hardness was smaller for

partially hardened material [336] . i A general relationship exists between the

hardness and the tensile properties of nickel, as shown in figure 44. \

42
C-.C-Kj

2.15

UJ 2.10

>-Q

z 2.Co

UJ ? 00

CO3

_l3

1

1 . »7 J

O

o 1 90

enCD 1.85

o

> 1.80

1.75

Nil:kel

(SATLJRATE[

— 0.^

D.6 ^

0.4,

02

0

5NITIZEID)DEMAC

0 50 100 150 200 250 300 350 400

TEMPERATURE IN DEGREES CENTIGRADE

Figure 41. Young's modulus of nickel as dependent on magnetization and

temperature

43
250

200

150

100

.50

VICKEFIS HARD

1

' NESS NT JMBER

' '1

ELECl

'.99% ^ ROLYT

Pr

\

ELE

EGULAI

CTROL\Tiq

is

100 200 300 400 500 600

ANNEALING TEMPERATURE, °C

Figure 43. Effect of annealing temperature on the hardness of electrolytic nickel [6^].

lO 15 20

Rockwell C

Figure 44. Relationship between hardness and tensile properties of nickel 200

d. Impact

Nickel is an extremely tough metal as measured by the notched-bar impact test, and it maintains this toughness even at low temperatures. For "A" nickel at room temperature,

Charpy values were reported as 222 ft-lb annealed, 197 ft-lb hot rolled, 195 ft-lb cold

drawn, and 60 ft-lb as sand cast; Izod values were 120 ft-lb for annealed, hot-rolled, or colddrawn material, and 85 ft-lb for sand cast [149]. Some low-temperature Charpy impact

values for "A" nickel are recorded in table 21.

Rosenberg [323] reported similar Charpy Vnotch values for cold-drawn commercial nickel,

204 ft-lb at room temperature and 216 ft-lb at —78 °C.

Table 21. Charpy impact values of 99.51 percent nickel

at low temperature [79]

Temperature Hot rolled Cold drawn Annealed

"C ft-lb ft-lb ft-lb Room 195 185 216 -80 236 205 235 -190 227 210 234

McClintock and Gibbons [319] published the

graph shown in f.gure 45 to illustrate the effect of temperature on the impact properties of commercial nickel.

Additional data on the impact properties of

Nickel 200 are presented in table 22.

44
CO

-J

I

11.

300

280

260

240

220

200

180

160

140

120

100

80

60

40

20

0

CHARPY V

IZOD

AN ^^EALED

HOT ROLLE

COLD I OUNT NC

D

DRAWN

(AW )T STATE:d)

Ah^NEALED

(N01

AS CAST

rCH NOT GIVEN)

0 50 100 150 200 250 300

TEMPERATURE ^ K

Figure 45. Effect of temperature on the impact energy of commercial nickel [3191.

Table 22. Impact values of Nickel 200 [86]

Condition

Brinell hardness number

Izod impact Charpy V

notchimpact

Charpy torsion Charpy tension

ft-lb ft-lb/in.

2

ft-lb ft-lb twist-degree ft-lb Elong.in 3.54

in.

Reduction

of area % %

iot rolled . _ 107 120 932 200 29 103}4 98 20.0 83.1

'old drawn 24% reduction, stress re- lieved . 177 120 966 204 35 102 88 19.5 71.2

^old drawn, annealed 3 hr at 1.350 °F._. 109 120 980 228 29 103 113 33.0 75.1

45
e. Fatigue

Results for the endurance limit for 100,000,-

000 cycles were compiled for "A" nickel by

Meyerson [94] as follows: 24,000 psi annealed,

30,000 psi hot rolled, and 42,500 psi cold drawn.

Greenall and Gohn [337] found that rolling

24-gage "A" nickel sheet to reductions of 4 or 8 B and S numbers raised the endurance limit

from 25,000 to 40,000 psi. Betty [338] found

that polishing the surface of a cold-drawn nickel

specimen increased the endurance limit almost

50 percent. Alternate tension and compression

softened cold-drawn nickel but produced strainhardening in annealed specimens [339]

The combined effects of corrosion in several

waters and fatigue on the endurance limit (10*

cycles) of annealed "A" nickel were determined

by McAdam [340] to be 21,000 to 24,000 psi in

carbonated tap water, and 20,000 to 22,000 psi

in brackish water, in comparison with 33,000

psi in air. Gideon et al. [341] observed that the fatigue

life of "A" nickel, at both 10^ and lO** cycles, increased as the temperature decreased below

room temperature. The effect of elevated temperatures and of vacuum on the fatigue life of

nickel has been studied at temperatures as high

as 1500 °F [342,343]. In vacuum, the fatigue

strength initially increases with increasing

temperature, due to greater ductility, up to 600

°C. The fatigue strength subsequently decreases

and the mechanism of damage and crack initiation undergoes a transition in this temperature

range due to the appearance of diffusion-controlled processes such as dislocation climb and

grain-boundary sliding.

f. Creep

Creep curves for nickel, as for metals in general, exhibit three stages: an initial rapid rate

of primarily elastic extension, a second stage

where the combination of elastic and plastic

behavior produces a low and fairly constant

rate of extension, and a final stage where the

extension increases rapidly until fracture oc- curs. Because of the complicated nature of

these curves and the difficulty of deriving

equations to describe such curves completely

it has been the practice to summarize the re-' suits obtained from a family of curves in terms' of the stress required to produce a specified

strain in a specified number of hours. Recent

investigations have been concerned with the

behavior in certain portions of the curves, and

with the explanation of these behaviors in

terms of atomic forces, dislocations, etc' [343a].

Jenkins, Digges, and Johnson [344] con-' ducted an exhaustive study of the creep behavior of 99.85 percent nickel in tension at temperatures up to 650 °C (1200 °F). They

found that discontinuous flow occurred in each

of the three stages and was affected by temperature, strain rate, and prior strain history.

Strain aging was especially prominent at 300 °F, producing an appreciable creep life in specimens stressed in excess of the shorttime tensile strength at this temperature. The

influence of stress on the average creep rate

is shown in figure 46. Some of their results

may be summarized as follows: at 300 °F the

rate of extension in the second stage was very

low for all stresses up to slightly above the

normal tensile strength; at higher temperatures fracture occurred as follows:

Temperature Stress Time to fracture

"F psi hr 700 21,330 21,000

700 32,000 22 900 18,670 153 900 20,000 57 1,200 4,010 6,800

1,200 6,670 224

1,200 9,330 32

50000

40000

^, 30000

on^ 20000

_i

<

I

10000

o

z

300°F

900

0

0.01 0.1 1 10 100 1000

CREEP RATE, PERCENT PER 1000 HR

Figure 46. Influence of stress on the average creep rate of nickel during the second stage of creep [544].

46
For hot-rolled nickel rod, it was reported

that at 427 °C a stress of 20,000 psi produced an extension of 0.25 percent in 1,000 hr; at 538 °C a stress of 10,000 psi produced an

extension of 0.28 percent in 1,000 hr [345].

The creep of annealed nickel was studied by

Jenkins and Johnson [346].

Jenkins and co-workers [347,348] found that

cold drawing increased the creep resistance of

nickel below the recrystallization temperature,

but had little effect above that temperature.

Golden et al. [349] noted that, at relatively low

temperatures, internal strain induced by cold

work can raise the creep strength of nickel

substantially. As the test temperature in- creases, strain becomes less important. The

recrystallization temperature is the limiting

factor for improving strength by this mechanism. Davies et al. [350,351] , also reported that

prestrain increases resistance to creep. Yim

and Grant [352] observed that the creep

strength at 700 and 1300 °F of prestrained

nickel appears to be related to the arrangement

and density of preinduced dislocations. The

greater the dislocation density, the stronger was the nickel during creep. In contrast to tensile prestrain, compressive prestrain de- creases both the creep resistance and fracture

life [353]. Davies [354] reported that in pure

nickel the creep rate in compression at 500 °C was between two and three times as rapid as

in tensile creep at the same stress. Weertman and Shahinian [355] measured

minimum creep rates of nickel in the stress region 2.5 X 10^ to 2.8 X 10« d/cm^ in the

temperature range 400 to 1100 °C. They re- ported that the creep rate appeared to be

proportional to the 4.6 power of the stress at stresses below 7 X 10** d/cm- and that the

activation energy of creep is approximately

65,000 cal/mole. Landon, et al.[356], reported

that the activation energy for creep increased

with rising temperature from a low value of

about 3,000 to 5,000 cal/mole at 78 °K (-195

°C) to that for self-diffusion at the highest

temperatures.

The effect of environment on the creep of

nickel has been studied extensively [357,358,

359,360,361,362]. The stress-rupture life at 1500 °F was slightly less in sodium hydroxide

than in argon, and somewhat less in argon than

in air [357] . At low rates of strain and at high

temperatures, the strength of nickel was higher

in air than in vacuum ; at high strain rates and

low temperatures the strength was higher in

vacuum [358]. It was found that at high temperatures an oxidizing atmosphere gave the

highest strength but that it gave a lower

strength at lower temperatures [360]. It was

also reported that the strength in nitrogen was

lower than in vacuum [360] . Cass and Achter

[361] explained the higher strength in oxidizing atmospheres as being due to an oxide bonding.

Dennison and Wilshire [363] found that

both the creep resistance and rupture life of

nickel increased with decrease in purity.

g. Ductility

Values for elongation and reduction in area

are the usual indications of ductility, with cer- tain other determinations to show ductility or deformability under particular conditions.

Nickel, being a face-centered metal, is inherently ductile. Tensile tests have shown highpurity nickel to have elongation in 2 inches of

56 percent at room temperature and 72 percent

at —320 °F [315] ; corresponding values for

reduction in area were 88 percent and 78 per- cent; true strain at complete fracture was

2.173 and 1.543. Additional values for elongation and reduction of area are shown in tables

16, 17, 18, and figure 44.

The amount of cold work that may be done

without intermediate annealing is indicated by

the Olsen (Erickson) test. Using a ys-in diam

ball and a 1%-in diam die, the following values were reported for nickel [86]

Thickness Condition Depth to fracture Load to fracture

in lb 0.062 Annealed

0.650 10,000

.062 Hard .325 7,000

.031 Annealed- . _ .500 3,400

.031 Hard .300 3,000

Kramer and Macklin [364] reported that

subzero ductility of nickel decreases linearly

with increase in prior strain history.

Ellis [365] determined the malleability of

cold-drawn nickel rods at various temperatures

by measuring the reduction in height caused by

forging blows of known energy. His results

showed that the malleability increased slowly

up to 600 °C and rapidly thereafter up to 1,100 °C, with irregularities at about 850 °C.

In the practice of the International Nickel

Company, the temperature range for hot roll- ing and hot forging is 650 to 1260 °C. Brittle- ness at elevated temperatures has been shown

to be due to minor amounts of sulfur [366,

367].

Bridgman [368] reported that nickel re- mained ductile under pressures up to 30,000

kg/cm-.

The flexure of nickel wire was determined

by MacBride [369] by cantilever tests in a Tour-Marshall tester. The results showed that

the load to produce a given angular deflection

increased progressively with cold-drawing 1 and 3 B&S numbers, and that this stiffening

47
effect was reduced by annealing at 500 °C and

eliminated by annealing at 700 °C.

h. Friction

The coefficient of friction in rubbing contact was reported by Tichvinsky [370] as fol- lows: With nickel as the moving contact, the

coefficient with nickel was 0.53, with glass

0.56, and with mild steel 0.66. With nickel

stationary and mild steel moving, the coeffi- cient was 0.49. Tamai [371] found the coeffi- cient of friction of nickel on nickel to be 0.60. Simon et al. [372] determined the coefficient

of static friction of two unlubricated surfaces

of nickel as 0.51 at 4.2 °K (liquid helium) and

0.65 at 77 °K (liquid nitrogen). Higher values were obtained in vacuum, 0.82 at 4.2 °K, 0.77

at 77 °K, and 0.69 at 300 °K. The results were

cited as substantiating the adhesion theory of

friction.

2.4. Effect of Minor Constituents

on Properties

In general, minor constituents or impurities

that exist in solid solution in nickel tend to increase the hardness, strength, and electrical

resistivity, decrease the thermal expansion and

thermal conductivity, and except for iron and

cobalt, lower the Curie temperature. According to Kornilov [373], nickel will form solid

solutions with elements whose atomic radii

differ from that of nickel by not more than

11 percent. Impurities that are present in excess of the solid solubility in nickel chiefly

affect the workability, particularly the hot

workability, and may affect the resistance to corrosive attack. When impurities or alloying

elements are deliberately added to produce

specific effects, the product is technically an

alloy even though the alloy content is small,

for example, in the age-hardening nickels or high-sulfur shot.

a. Carbon

Carbon exists in nickel in solid solution or

as graphite formed by the decomposition of

the carbide, NigC, which exists at temperatures above 1500 °C but is exothermic and

unstable. The solubility of carbon in nickel is as follows [136,374] :

0.03 w/o at 500 °C

.14 w/o at 780

.245 w/o at 1,030

.65 w/o at 1,318 (the eutectic

temperature)

The solubility of carbon in liquid nickel is given by Elliott [375] as follows:

12.5 a/o at 1,550 °C

11.9 a/o at 1,500

10.9 a/o at 1,450 . 9.5 a/o at 1,350

' 8.9 a/o at 1,314 (which he gives as bhe

eutectic temperature)

The diffusion coefficient of carbon in nickel

ranges from 4.0 X 10"» cm-/sec at 727 °C to

4.1 X 10-^ at 1,020 °C [136].

Carbon in solid solution in nickel increases

the ease of hot working because of increased

toughness and lower susceptibility to edgei

cracking at these temperatures. However, the

initial hardness, strength, and tendency to'; work harden, as a result of the presence of

carbon, increase the difficulty of cold working.

The low-carbon malleable nickel (Nickel 201) was developed to facilitate spinning and deep

drawing operations.

Small amounts of carbon do not appreciably i affect the Curie temperature [374] , but the ^ diffusion of even small amounts of carbon in ^ nickel is of interest in the activation of ther- ^ mionic oxide-coated cathodes [136]. The malleability of nickel is adversely affected by the ' presence of graphite or carbon in excess of : the solid solubility.

b. Cobalt li The great bulk of nickel, i.e., nickel pro- . duced from Canadian ores by processes other

than the carbonyl process, has had an average I cobalt content of about 0.5 percent. Such

amounts of cobalt produce slight increases in

electrical resistivity and in the Curie temperature but otherwise have no appreciable effect j on the properties of nickel. Consequently, it has been the accepted commercial practice to count the cobalt as nickel and to express ana-

'

lytical results in a single value for nickel plus

cobalt. The current demand for cobalt, and the

development of improved processes for recov- ering nickel from its ores, have resulted in

lowering the average content of cobalt in

nickel to about 0.1 percent, from the 0.5 percent which had previously represented the

practical economic limit of separation of nickel

and cobalt in commercial production.

It has been reported [376] that cobalt in- creases the oxidation rate for nickel but the

effect is small below 11 percent of cobalt.

c. Copper

Copper usually is present in nickel in

amounts less than 0.1 percent and such

amounts do not have a noticeable effect on

the properties.

d. Iron Iron is present in commercial nickel either

because it was present in the ore, or because

of contamination from iron equipment during

the recovery and refining processes. The iron

48
content of electrolytic cathodes usually is less

' than 0.05 percent, whereas melted electrolytic

^ nickel and the malleable nickels may contain

up to 0.25 percent. Such amounts of iron have

j no appreciable effect on the properties of nickel.

e. Magnesium

: Magnesium was the first metal used to con1 trol the harmful effects of sulfur and it is still

; important for this purpose. It has the indirect

i effect, through fixing of sulfur by the forma-

) tion of the high melting point compound MgS,

f of increasing the ductility of nickel and of

. decreasing the tendency for hot shortness.

) f. Manganese

, j The equilibrium diagram of the nickel-man-

, 'ganese system according to Lacy [377] indiI cates a solubility of at least 20 percent of

. manganese in solid nickel.

In the production of malleable nickel, small

I j'l amounts of manganese and magnesium are

i added to combine with the sulfur present as

nickel sulfide, and thereby to improve the malleability, surface characteristics, and appearance of ingots. Additions of manganese in

! excess of the requirements for sulfur fixation

mildly increase the strength and hardness

without appreciable effects on the ductility,

increase the resistance to oxidation, and de- crease the susceptibility of nickel and its alloys

! to damage from sulfur in the fuels used to heat these materials for hot-working and heatI; treating operations.

Additions of 10 to 20 percent of manganese

markedly increased the electrical resistance of

annealed nickel [378]. Ten percent of mangaj nese lowers the Curie temperature to about

[ 200 ^C, as shown in figure 25. In the common

, commercial alloys, each percent of manganese

up to 15 percent reduces the density of nickel

by about 0.02 g/cm^.

( g- Oxygen

* Oxygen is the only gaseous element that has

any significance in nickels that have been

melted. Electrolytic nickel, as deposited, contains variable amounts of hydrogen and other

gases, which contribute to the hardness and

brittleness of some electrodeposits, but these

gases are greatly diminished by heat treat1 ment and disappear on melting, particularly

' when melting is done under oxidizing condii tions.

Oxygen is soluble in molten nickel in increasing amounts as the temperature rises above

the melting point. According to Wriedt and

Chipman [266], the solubility is 0.294 w/o of

oxygen at 1,450 °C and 1.63 w/o at 1,691 °C.

The presence of oxygen lowers the melting

point of nickel progressively until the eutectic

composition (0.22% of oxygen) is reached,

with a melting point 20 °C lower than that

of pure nickel [379]. According to Seybolt

[380], the solubility of oxygen in solid nickel

is exceptional in that it increases with decreasing temperature as follows:

0.012% at 1,200 °C

.014 at 1,000

.019 at 800

.020 at 600

Oxygen has little effect on the properties of

nickel, even when it is present in amounts in excess of the solid solubility. Merica and Waltenberg [381] showed that nickel may contain up to 1.1 percent of nickel oxide and still be malleable hot or cold. Agents such as titanium and boron may be added to correct the

minor effects on the malleability of oxides and

of gases such as carbon monoxide, nitrogen,

and hydrogen. Nickel oxide, which is readily

detectable microscopically, may be encountered in nonmailable nickels, such as shot for

alloy additions, but is generally eliminated in

the preparation of malleable nickels.

h. Silicon Additions of silicon lower the melting point

of pure nickel until the eutectic composition

(about 11.5% of silicon) melts at 1,152 °C.

The solubility of silicon in solid nickel de- creases with decreasing temperature from 9.3

percent at 1,125 °C to about 6 percent at 600 °C [382].

Silicon is present in furnace-melted nickels,

up to 0.10 percent in electrolytic shot, and up

to about 0.25 percent in some of the malleable

nickels. Age-hardening nickels contain up to 0.50 percent of silicon, and casting nickels

contain up to 1.5 percent. The amounts of sili- con present in the malleable and electrolytic

nickels have little, if any, effect on the properties, but amounts in excess of 1 percent in- crease the hardness and stiffness, and reduce

the malleability. According to Okamoto and

Iwase [383], 1 percent of silicon lowers the

Curie temperature from 362 to 320 °C and

6 percent lowers it to —45 °C.

i. Sulfur

Sulfur lowers the melting point of nickel;

the eutectic composition (21.5% of sulfur)

melts at 644 °C [384]. The solubility of sulfur

in solid nickel is about 0.005 percent [381].

Amounts in excess of the solid solubility exist as sulfides which can be identified by metallographic procedures [385].

I'he only property of nickel that is appreciably or seriously affected by the amounts of

sulfur ordinarily present is the malleability,

both hot and cold. The brittleness of nickel

49
encountered in the very early days of the industry, and the discovery by Fleitman in 1879

that additions of manganese and magnesium

improved the malleability of nickel, were ex- plained by Merica and Waltenberg [381].

These investigators found that sulfur, if present in excess of about 0.005 percent, formed

grain-boundary films of nickel sulfide or the

low-melting eutectic of nickel-nickel sulfide.

Additions of manganese converted the films of

nickel sulfide to globules or particles of manganese sulfide. These particles often occurred

in grain boundaries; however, additions of

manganese did have a moderately beneficial

effect on hot and cold malleability. Additions

of magnesium caused the formation of magnesium sulfide particles, which because they had

a higher melting point than that of nickel, were distributed randomly throughout the microstructure and thereby caused a marked

increase in hot and cold malleability. In modern practice manganese is added to nickel that

has been treated with magnesium to enhance

hot workability and to extend the hot-working

range.

In adition to residual sulfur from the original ore, sulfur may be present in nickel

because of reaction with sulfur gases, particularly sulfides and reducing compounds, in

heat treatment and annealing operations.

2.5. Technology

Much of the industrial working and fabrication of nickel is closely parallel to the operations performed on steel. The information in

the following paragraphs is based on articles, as indicated in the text, which should be consulted for information about nickel alloys and

for more detailed information about nickel.

a. Melting and Casting

Nickel may be melted in electric, oil, or gasfired furnaces, but coke-heated pit melting is not recommended because of possible contamination by sulfur. For small melts, the nickel is melted under a thin limestone slag, with additions of nickel oxide and carbon to cause a

boil to eliminate gases. When the solidification

characteristics of a small sample show that the

boil has been effective, the metal is killed with

silicon, the carbon content is adjusted, manganese is added, and the melt is allowed to remain quietly in the furnace to allow en- trapped oxides to rise to the slag. After final

deoxidation in the ladle with silicon and magnesium, the metal is poured at temperatures

between 1,500 and 1,600 °C, depending upon

the size of the casting and the type of mold.

Pattern equipment should provide for a linear

shrinkage of in/ft and gates and risers

should be larger than those used for steel [386]

Large melts, in the range from 9,000 ti 23,000 lb, are usually made in acid-lined opei;

hearth or basic electric furnaces. In the opeihearth, no slag is added intentionally bu, some is formed from the silica-alumina refrae

tories. In basic electric furnace melting, smal

amounts of lime and fluorspar are added earlj'

in the heat to avoid excessive oxidation durinj

melt-down and to minimize gas pickup fron!

the furnace atmosphere. Carbon and nicke

oxide are added to produce a degasifying boif

after which the carbon content is adjusted;

manganese is added, and final "deoxidation'

is carried out in the ladle by additions of tita

nium, boron, and magnesium. The metal h

then poured into cast iron molds equipped witlJ

hot tops, to produce standard ingots approxi?

mately 18 in sq by 40 in long and 4,600 lb ir^ weight, or larger ingots up to 14,000 lb fofi large forgings or heavy plates. Special gradef^

of nickel, for example, for electronic applicafj

tions or for oxidized or carbon-bearing anodej

for the electroplating industry, are produced

by modifications of the forgoing procedure [387i

388].

b. Hot-Forming (Forging, Rolling, Extrusion)

After suitable treatment to remove surface

defects, the ingots are reheated in furnaces

fired by low-sulfur fuels. Natural gas, lowsulfur city gas, propane, and butane are desirable fuels; oil is generally used in the larger

operations. The furnace atmosphere should be

sulfur-free and always slightly reducing; flue-: tuation between reducing and oxidizing condi-i tions is most harmful. The temperature range

for good forging of nickel is between 870 and

1,160 °C, with heavy forging and drop forging

operations carried on in the upper two-thirds

of this range and light forging in the lowerl

third [389].

* Hot-rolling of nickel usually starts at about[

1,150 °C. Finishing temperatures vary with the|

dimensions of the product, but nickel generallyj can be hot-worked to 650 °C, or even lower,

temperatures. Rolling mills of the same design' as for rolling steel are suitable for rolling

nickel [387]. | Extrusion of nickel and high-nickel alloys,

requires more power than that normally used

for the softer extrudable alloys because of the

high strength and resistance to deformation,

^ and the narrow range of temperature in which

^ plastic deformation can be accomplished. Bar-|

clay [390] 20 years ago pointed out that pres-^ sures for extrusion of nickel might be 30 tO|

50 percent higher than for copper alloys, even^

when a heated container was used. Neverthe-,

less, Betteridge and Cound [391] reported that i the extrusion of bars of nickel, Monel nickel

copper alloys, and the softer alloys had been

carried on for many years, and that extrusion

50
of the harder alloys had been facilitated by the

'-I use of glass as a lubricant. ASTM Specification

''I B161-61, Nickel Seamless Pipe and Tubing,

h states that hct-finished (extruded) tubing is

I'' available in some of the sizes provided for in

the specification (up to S^s in 0. D. with wall

^1 thicknesses up' to Y-) in).

i

!j c. Cold-Forming (Drawing, Shearing,

d Punching, Spinning)

ji The equipment and procedures used for cold-

[' forming nickel resemble those used for similar

'; operations on steel.

il In drawing operations, gray cast semisteel

j dies give good results on high-nickel materials

i for comparatively short runs of a few hundred

. pieces. However, these die materials are comj paratively soft and consequently wear rapidly,

i which makes them unsuitable for precision

I work or large production runs without frequent redressing. Satisfactory die materials

sj. for steady production are hard alloy bronze,

heat treated nickel chromium cast iron, chrom-

, ' ium plated hardened steel, and tungsten car- bide [392,393]. New dies or punches, when

required, should be made from these materials rather than from plain carbon steel because nickel and high-nickel alloys have a strong tendency to gall against carbon steel. Dies and punches should be kept smooth at

•r all times [392].

It requires more power to form the high- " nickel materials than is required for aluminum

^[ or brass, so die components should be designed

T for greater strength.

j Beef tallow and castor oil are satisfactory

j lubricants ; so also are water-soluble oil or oil-

, soluble lubricants compounded in correct balII ance from these two substances. In general,

pigmented type lubricants are preferred [392].

Lubricants containing lead or sulfur should

generally be avoided, and should never be used if

" the pieces being pressed are to be annealed. For

^ ; that matter, any lubricant, regardless of its

'

' nature, should be removed thoroughly before ^ annealing.

, Monel nickel-copper alloys, nickel, and In-

^

' conel nickel-chromium alloys require better lu-

. bricants than the light oils and thin soapy

J

I solutions frequently used on steel and the

I"

; softer metals. The high-nickel materials do

not form thin oxide films, such as are found

^

\ on steel sheets, which prevent actual metal-to-

^ ; metal contact, and allow the steel to flow be-

'' tween the die and pressure plate with rela-

'

' tively low frictional resistance. Copper flashing

; the surface of materials gives added lubrication

^ " for drawing operations but material so pre-

^ pared is used only for difficult jobs. To reduce

^ ; to a minimum the factors conducive to galling,

' lubricants with high film strength, lubricity,

^ ' and wetting characteristics are required. Most

il ^

^of the satisfactory lubricants contain a filler of some inert material.

In drawing wire, tungsten carbide dies are used for all sizes down to 0.032-in wire and

diamond dies are used for sizes smaller than

0.032-in diameter [394]. Lubricants for drawing the softer materials are flour, hard soap,

and tallow; harder alloys, for example, nickelchromium and nickel-chromium-iron alloys,

may be lead coated or copper flashed prior to drawing. Mineral oil is a satisfactory lubricant

for fine sizes, and water-soluble oil for superfine sizes [391].

The shearing of high-nickel alloys in sheet

and plate form requires slightly more power

than is needed for shearing soft steel of the same thickness. Although the additional power

requirement is real, neither it nor the strength

of the shear need be considered unless the job

involved is close to the capacity of the equipment.

Monel alloy 400, Nickel 200, and Inconel alloy

600 sheet may be perforated to practically the same limits of hole diameters for various thick- nesses of sheet as are considered commercial

for soft steel, as indicated in table 23.

Table 23. Relation between thickness of sheet and minimum

permissible hole diameter for punching Monel alloy 1^00, Nickel 200, and Inconel alloy 600 [392]

Thickness of sheet Approximate minimum

diameter of hole

0.018 to 0.034 in, incl. Sheet thickness x 1 5 .037 to .070 in, incl. Sheet thickness x 1 3 .078 to .140 in, incl. Sheet thickness x 1 2

in and heavier Sheet thickness x 1 0

In spinning operations, the strength . and

work-hardening tendency of nickel require

more power and more frequent annealing than

are required for most of the nonferrous metals

generally spun. Broad, flat, tools, preferably

made of hard alloyed bronze, are recom- mended. Yellow soap, beeswax, or tallow lubricants should be removed prior to annealing.

d. Welding, Brazing, Soldering

Nickel and high-nickel alloys can be welded

by most of the fusion and resistance welding

processes. The manual metal-arc (covered

electrode) and the MIG processes are most

widely used for joining heavy sections and

making overlays but the TIG process has

nearly replaced gas welding for joining sheet

thicknesses. When properly made, the as- welded joints are equal to the parent metal in

strength and resistance to corrosion and only

in the case of age-hardening alloys is a postweld heat treatment needed to develop full strength. All foreign matter should be cleaned

from the joint area prior to welding. Arcwelded nickel joints have an average tensile

51
strength of 70,000 psi with minimum elongation of 30 percent, whereas gas-welded joints

show an average tensile strength of 60,000 psi

with 35 percent minimum elongation [395].

See also Pease [396]. The welding of nickel

and nickel alloys, and welding materials, has

been described in publications of the Huntington Alloy Products Division of The International Nickel Company, Inc. [397,398,399]

Spot, seam, and flash resistance-welding of

nickel and high-nickel alloys is much the same

as for steel, with allowance for the differences

in electrical and thermal conductivities.

Nickel and its alloys may be brazed with commercially available silver brazing alloys. Fluxes

are required for torch brazing and may be used

in furnace brazing depending on furnace atmosphere. Special care must be exercised to prevent overheating with brazing alloys containing

phosphorus and cadmium. The use of boroncontaining brazing alloys is restricted to joints

in heavier sections.

Soldering can be effectively used to join nickel

to itself and to other alloys. A relatively highstrength solder is preferred and the joint should

be so designed that the solder is not depended

upon for structural strength. Solder is frequently used to seal riveted, lock-seam., or spotwelded joints. An acid-base flux yields best

results. Useful booklets describing the brazing

and soldering of nickel and high-nickel alloys are available [400,401].

e. Annealing

In all annealing operations of nickel, the fur- nace atmosphere should be free from sulfur

compounds and should not fluctuate between

oxidizing and reducing conditions because nickel

alloys are sensitive to attack by sulfur and oxygen at elevated temperatures. Open annealing

usually requires subsequent cleaning or pickling, whereas a bright surface results from box

or pot annealing and from open annealing in

controlled neutral or slightly reducing atmospheres.

A list of satisfactory and unsatisfactory heat

sources for annealing are as follows [392] :

Satisfactory Unsatisfactory

Electric Coal

Acetylene Coke

Natural ga,s High sulfur oil Butane Unwashed producer gas Propane Unwashed blast furnace gas Washed producer gas Any fuel with sulfur over Washed blast furnace gas 0.5%

Oil with sulfur under 0.5% Gas containing more than 30

grains of sulfur per 100

cu ft

The three types of annealing treatments

given nickel and its alloys are (1) stress equalizing, (2) stress relieving, and (3) complete

annealing.

The stress-equalizing anneal for work-hardened nickel and high-nickel alloys is carried out

at low temperatures (525 to 900 °F), depending upon their composition [402]. This lowtemperature treatment does not produce soft- ness or any visible change in microstructure,

but it does equalize, balance, or homogenize

the principal residual stresses. The optimum

temperature for such equalization depends

upon the manner in which the metal or alloy

has been work hardened. Cold-worked materials, possessing greater intrinsic energy than

hot-worked materials, can be stress-equalized

at a lower temperature. This thermal treat- ment effects what is known as a partial re- covery. This recovery consists of a considerable increase in proportional and elastic limits, a slight increase in hardness and tensile

strength, no significant change in elongation

and reduction of area, balancing of internal

stresses, and return of electrical conductivity

towards its characteristic value for the metal

or alloy in the annealed condition.

The stress-relieving anneal requires moderate temperatures, 1000 to 1300 °F, for coldworked and hot-worked nickel and high-nickel

alloys, depending upon their composition. The

purpose of this treatment, sometimes referred

to as temper annealing or partial annealing, is to reduce or relieve the internal macrostresses

that exist in the metal as a result of coldworking, machining, casting or welding operations.

Complete annealing (sometimes termed soft

annealing, or just annealing) is applied to metals and alloys that have been hardened by

cold-working operations such as rolling, drawing, spinning, bending, etc., and which require

softening before further cold work can be continued. The temperatures required are high

(1400 to 2000 °F), depending upon the alloy.

This anneal will soften the cold-worked struc- ture by effecting recrystallization, sometimes

accompanied by grain growth. In age-hardenable alloys, annealing will effect softening by

dissolving the secondary precipitated phases

and keeping them in a supersaturated solid

solution by rapid cooling from the annealing

temperature. This type of anneal is more properly called a solution heat treatment. A complete anneal is the only thermal treatment that

will completely relieve both macro and micro

internal stresses existing in a metal or alloy.

Figure 47 is a schematic representation of

the effect of annealing temperature on coldworked metals and alloys.

It must be recognized that time, as well as temperature, is important during annealing

52

i
STRESS EQUALIZE

RANGE

STRESS RELIEF

RANGE

RECOVERY 1 Q

1 < 1 M

1 _l

> >-

1

1

GRAIN GROWTH / UJ

Nj

<

o

TEMPERATURE

Figure 47. Schematic representation of effect of temperature on cold-worked

metals and alloys [-402].

operations. Within certain limits, the same

results may be obtained at lower temperatures

with longer periods of time as are obtained at higher temperatures with shorter periods of

time. The relationship between time and temperature during annealing of cold-worked

nickel is shown in figure 48.

f. Pickling

The resistance of nickel to corrosion makes

its pickling more difficult than that of iron,

carbon and low alloy steels, or copper alloys.

Oil and grease must be removed by appropriate

procedures prior to pickling, and discolorations from the presence of residual lubricants

may be removed by proprietary chemical solutions or by soaking in a cold solution of 10

percent by volume sodium cyanide.

All the various pickling baths for nickel

and its alloys contain acid [403]. After pickling, the metal should be rinsed in hot water

and the acid neutralized in a 1 to 2 percent

(by volume) ammonia solution.

Pretreatment baths of fused salts have been

developed to aid in the pickling of many

alloys. They are particularly effective in handling nickel-chromium and nickel-chromium53
100

5 10 15 20 25

TIME AT TEMPERATURE, MIN.

30

6 iK Figure 48. Effect of time at various annealing temperatures on the hardness

of cold-worked nickel [i02'\.

iron alloys and their use for this application

is strongly recommended. These baths are patented and the manufacturer should be consulted regarding their use. There are two

types, reducing and oxidizing. The sodium

hydride process (E. I. duPont de Nemours and

Company, Inc.) and the two Kolene processes

(Kolene Corporation) are reducing processes.

The Virgo process (Hooker Chemical Corpotion) is an oxidizing process.

Light oxide films may be removed by elec- trolytic pickling [403].

g. Machining

The tools, lubricants, etc., used in machining nickel are similar to those used for steel. Details of tool design and the procedures for

various machining operations (turning, drill- ing, broaching, threading, reaming, planing,

tapping, cutting, milling, and grinding) are

described in a booklet by The International

Nickel Company, Inc. [404]. This booklet also

describes electrochemical machining (ECM),

electrical discharge machining (or spark ero- sion), chemical milling, electron-beam machining, plasma-arc cutting and welding, ultrasonic machining, cold machining, and hot machining.

h. Grinding, Polishing, and Buffing

For heavy grinding, where the finish is not

important, grinding wheels of No. 14 and 24

grit should be used and finer wheels, for example. No. 36 grit, may be used when better

finishes are desired.

Various operations under the general heading of polishing include roughing, dry finishing, greasing, and grease coloring. Ordinarily

there should be from 40 to 60 grit numbers

difference between successive polishing operations.

In bufiing operations, tripoli compounds are used for the removal of polishing scratches,

and unfused aluminous oxide or green chromium oxide for color buffing. For the highest

mirror finish, chromic oxide is used. High

quality white lime compounds are very satisfactory for color buffing pure nickel and nickel

plate.

Detailed information about the grinding,

polishing, and buffing of nickel and its alloys was presented by Burchfield [389].

2.6. Metallography of Nickel

The primary object of metallographic examination is to reveal, by means of the microscope, the constituents and structure of metals

and their alloys. The selection and preparation

of the specimen is of major importance, but

the preparation of metallographic specimens is essentially an art because of the diversity of

available equipment, the variety of problems

encountered, and the personal aptitudes, skills,

and preferences of the metallographer. The en- suing discussion of the metallography of nickel

and its alloys was prepared mostly by personnel of the Huntington Alloy Products Division,

The International Nickel Company, Inc., and

represents their normal laboratory practice.

a. Selection of Specimens

The primary requirement is that the specimen should be representative of the material

being studied, but the actual selection of a

54
Table 24. Recommended conditions for electropolishing nickel and some nickel-base alloys

Solution Alloy Current density (amp/in2) Time Remarks

tjP04 37 ml_.

i lvcerin. .- - 56 mlIjO 7 ml-.

INOJ .-33 ml--

Sethanol .66 ml-.

Nickel 270«

Nickel 2001' Monel aUoy 400

Inconel alloy 625.

Incoloy aUoy 800 Monel alloy 400 Monel alloy 404

10-12 9-10

6-7 8—10

20

10-15

1 min

1 min

1-2 min

2—4 min

2—4 min

25 sec

The water must be distilled. Used for nickels, Monel alloys, some Inconel alloys and some

Incoloy alloys; not Inconel alloy 718 and Inconel alloy 600.

Used for most Monel alloys. Faster than the 37-56—7 polish. A black film is formed prior to

polishing.

Water must be distilled. Used for Inconel alloys. Use maximum cooling and stirring.

IjPOi 25 ml--

[s'Oj 25 ml-.

::0 50 ml-.

Monel alloy 405

iVlonel alloy il—out)

Inconel alloy 600 . . Inconel alloy X-750

115

115 5—10 sec 5-10 sec

» High purity nickel.

^ Comn 1 il nickel.

peciri en depends upon the size and shape of

he m, terial, the portion or section of the ma-

|erial that is of interest, and the purpose for

vhich the study is being made. For more deailed discussion of this subject, see ASTM

jl^pecification E3-62.

b. Preparation of Specimens

The degree of surface preparation to be

jfiven to a sample is largely dependent on the

lature of the examination and the type of

tchant to be used. Rough grinding on an abraive wheel or on a coarse emery cloth belt is isually adequate for small specimens. Large

lections, such as cross sections of ingots,

jilooms, etc., lend themselves to preparation on

Ij. surface grinder.

A suitable specimen, either unmounted or nounted in plastic with a flat surface, is prepared as follows:

(1) Grinding. Hand or power-driven disk

•rinding should be carried through a series of

mery papers of successively increasing fineness. The commonly used papers are No. 3, 2,

, 0, 00, and 000. The papers used will depend

In the starting condition of the sample. After

ompletion of a grinding operation, the sample must be thoroughly rinsed to wash away

11 traces of the emery before proceeding to

'he next finer grade. Each successive cut should

•e at right angles to the preceding cut, and

rinding with each grit should be continued

ntil all scratches left by the preceding coarser

rit have been removed.

I (2) Rough polishing. Specimens ground

Ihrough No. 000 paper can be wet polished on

broadcloth-covered wheel, using levigated

lumina abrasive powder (particle size about

' fi) suspended in water.

A much faster method utilizes a silk- or ylon-covered wheel impregnated with dialond dust paste (particle size about 3 /x). If

lis method is used, preparation need consist

nly of grinding through No. 1 paper, thereby

liminating three grinding steps.

(3) Final polishing. Fine scratches remaining after the rough polishing can be removed

on a microcloth- or duracloth-covered wheel

using gamma aluminum abrasive powder (less

that 0.1 fi size) suspended in water.

(4) Electropolishing. In general, better elec- tropolishing can be obtained by starting with

mechanically polished specimens. For the solutions given in table 24, most any flat, rough

grind may be used as a starting point. These

solutions are used as water cooled and stirred.

Platinum is usually used as a cathode. All acids are concentrated.

c. Etching

In general, polished metal does not reveal

the crystalline structure and etching must be

used to delineate the structure and to produce

optical contrast between the various constituents. Nickel is generally resistant to corrosive

media and its etching involves the use of vig- orous reagents which tend to form etch pits

and to dissolve out the inclusions. The diffi- culty of etching increases with increasing purity of the metal and alternate polishing and

etching frequently are required in order to obtain the desired development of the microstructure. The etchants most frequently used for macroetching of nickel and some of the nickel-base

alloys are given in table 25, and for microetchTable 25. Macroetehing of nickel and some nickel-base alloys

Solution

HNO3 50 ml.. HCzHaOj 50 ml-- HNO3 50 ml-. H2O 50 ml-- HCl 40 ml.- H2O2 (30%) 40 ml.- H2O 20 ml-.

(NH4)2S204 15 gm-- H2O 75 ml-. FeCh 250 gm-- HCl 100 ml.. HNO3 30 ml-.

Alloy

Nickels

Monel alloys.

Inconel alloys.

Weld structures of nickel-base alloys.

Remarks

The water does not have to be distilled. H2O2 may be added

as needed. Fresh solutions are

required. Time 30-120 seconds

(Lepito's Reagent).

55
ing in table 26. For electrolytic etching, Inconel alloy 600 is used as the cathode and where

water is indicated, tap water is used. Additional useful reagents are given by Smithells [405].

The microstructure of high-purity nickel is shown in figure 49.

1 ,<

'

-J

Figure 49. Microstructure of high-purity nickel (Nickel

200) as forged. Etched with NaCN — (NHi)2S20s.

a. X 100. b. X 500.

2.7. Uses of Nickel

Topics discussed in this section include the

production of nickel coatings by various pro- cedures and the end uses of nickel-plated anc„

solid-nickel objects. '

a. Coatings

(1) Electroplating. Nickel is one of the- most important metals applied by electrodeposition [406]. Nickel electrodeposits are used

extensively as a foundation for a highly lus- trous finish on many manufactured metallic

articles. Protection of the basis metal and per- manence of a stain-free surface are the primary requisites of such decorative coatings.

These are obtained by an adequate thickness

of nickel and a comparatively thin layer of chromium over it. Nickel coatings alone are

also used industrially to protect the basis metal

from corrosion or to prevent contamination of a chemical product. Although surface improve^

ment and corrosion resistance are the principal objectives of nickel electroplating, it is also

used for building up worn parts [407] and for

electroforming of printing plates, tubes, and

many other articles [408,409]. Williams [410]

reported that steel sheet or plate up to 80 in

wide and up to 20 ft long can be coated with

0.006 to 0.020 in of nickel by electroplating

Nickel electroplating was originally used oh

iron, steel, and copper alloys but has been ex- tended to zinc-base die castings, aluminum,

magnesium, and many other metals and plas

tics. An undercoat of copper is frequently em

ployed to create a better surface for the deposition of nickel and the good appearance and

tarnish resistance of the nickel coating may be

further improved, for particular applications,

by a final coating of other metals, including

gold.

According to Gray [335] , the history of elec

troplating goes back to the production of the

first good nickel plate by Boettger in 1843, ob- tained from a bath containing nickel and amo- nium sulfates. Adams [411] in 1869 was probably the first to do nickel plating on a truly

commercial basis, thereby establishing elec- troplating as one of the major consumers of

nickel. Developments in nickel electroplating

led to the installation in about 1890 of elec

trolytic refining in the production of nickel,

and this in turn contributed to the furtherl

improvement of nickel electroplating by sup- plying better anode material. Developments in

electroplating have been rapid since early in

the present century, with improved baths that

permitted plating at high speeds, with improved understanding and control of operating

variables and the use of addition agents, and

with the development of improved and auto56 t
Table 26. Microetching of nickel and some nickel-base alloys

Alloy

Nickel and Monel alloys.

Inconel alloy 600

j Inconel alloy X-750.

Inconel alloy 700.

m

ifr^ Inconel alloy 718_ m

Inconel alloy 625-

Incoloy alloy 800

Incoloy alloy 825

Nickels and Monel alloys

High purity Nickel

Inconel alloys

Solution

H3PO4 H2O

NaCN

{NH4) 28203 H2O

HNO3

Methanol HCl

HNO3

CuCls HNO3

Methanol HCl HNO3

H2SO4 HC2H 3O2 HCl H2O

H2SO4 HNO3

H3PO4

CrOj

H2O

CrOa H2O

HC2H 3O2 HCl HNO3

Glycerin

Glycerin HCl HNOi

Oxalic H2O

Oxalic HzO HNO,

HC2H302 HNO3 HF

HNO3

HF

20 ml

80 ml

10 ml

10 ml

20 ml

5 ml

95 ml

30 ml

10 ml

Saturated 20 ml

80 ml

92 ml

3 ml

5 ml

10 ml

3 drops 90 ml

47 ml

41 ml

12 ml

5 gm

100 ml

25 gm

7 ml

133 ml

50 ml

10 ml

10 ml

30 ml

20 ml

10 ml

20 ml

80 ml

10 ml

90 ml

50 ml

50 ml

20 ml

3 ml

20 ml

3 ml

Voltage

(volts)

20

10

30

3-4

5-10

10

10

10

10

Time

10-15 sec

5-10 sec

15-30 sec

10-20 sec

8-10 sec

7-10 sec

5-15 sec

1 0-15 sec

5-10 sec

2-6 sec

1-3 sec

1-3 sec

Remarks

General structure.

Swab: The NaCN and (NH4)2 S2O3 additions are made from 20%

stock solutions.

Swab: Let stand 5 min before using, good for Inconel alloy 600 but

not Inconel alloy X-750.

Swab: Add H2SO4 last and slowly.

This alloy is difficult to etch but one of these two solutions should work for most conditions of heat treatment.

Dip in 100 ml HNO3 +4 drops of HF to remove the stain.

To dissolve the CrOs, the solution should be heated in hot water

only. Add HC2H3O2 last. No staining.

Swab.

Swab or immerse and stir.

Oxalic is mixed from a 20% stock solution.

Oxalic is mixed from a 20% stock solution.

Good for grain size determinations, tends to pit.

Good for grain size determination, tends to pit.

Good for grain size determination, tends to pit. Rinse sample

thoroughly.

matic equipment for conducting the operations [412,413].

Since 1915, the rate of development of nickel

plating has been quite rapid. Among the highlights are high-speed plating, begun by Watts

with his famous "Watts bath" [414] ; control

quality of deposits, first emphasized by Watts

and DeVerter [415] ; accurate pH. control, in- troduced by Thompson [416] ; low pB. baths,

suggested by Phillips [417] ; commercial introduction of modern bright nickel plating begun

by Schlotter [418] and the many later developments of it; design of baths for deposition

of leveling, semibright and bright nickel coat- ings; growing appreciation of the importance

of high-purity electrolytes and of high ductility and low stress in deposits; and the development of automatic plating equipment that

makes possible today's high production rates and low costs. According to Pinner, Knapp, and Diggin

[406] a survey of recent information shows

that the composition of the modern Watts

bath can be represented reasonably well by

the following:

Nickel sulfate (NiS04'7H20) 240-340 g/1

Nickel chloride (NiCls'eHaO) 30- 60 g/1

Boric acid (H3BO.3) 30- 40 g/1

An all-chloride bath was developed by Blum

and Kasper [419]. The better-buffered halfchloride, half-sulfate bath of Pinner and Kinnaman [420] has advantages of both the Watts

and the high-chloride baths and has been

found to be especially suitable for high-speed

plating.

Information of value on the electroplating

of nickel is contained in several publications

of The International Nickel Company, Inc.,

[421,422,423,424,425].

Improvements in the nickel anode material

have kept pace with improvements in the bath

and in the operating procedure. Nickel con57
Table 27. Examples of industrial nickel-plating baths and operating conditions

Nickel sulfate oz/gal_ Sodium sulfate oz/gal_ Nickel sulfamate oz/gal_ Nickel chloride oz/gal. Ammonium chloride oz/gal. Boric acid oz/gal_ pHTemperature °F. Current density Amp/ft^,

Watts bath

(High pH)

32

4 4.5 to 6.0

115 to 160 20 to 100

(Low pH)

5

1.5 to 4.5

115 to 140 25 to 100

All chloride bath

40

42.0

140

25 to 100

Inter- mediate bath

26

235.3

1.5

115 100

Hard

plating bath

24

3.3 4.0

5.6 to 5.9 110 to 140

25 to 50

Special purpose bath

16

2

2 5.0 to 5.5 Room

5 to 10

Nickel sulfamate bath

60

1.0

5

4 11050

Sulfate bath

38.5

3.2

4.8

2.5

95 20 to 30

ay ID'

top

(rteil

\i it

aial w ni

In a(

lbs 8

loped

ii]

sve 1

I! redes

!( 'M CO

i tidso

(111 a

; idel

! erent

lapf

!i iin u]

Fil

, sn

" iei'at( ik

liiver

i loy

[

' ia?!ie

3 itiel

taining up to 10 percent of impurities was

acceptable as an anode material in the early

baths. The development of the Watts bath,

containing chlorides, permitted the use of the

99-percent, chill-cast nickel anode, and later,

of the 99-percent, rolled anode that contained

small amounts of nickel oxide for depolarizing

purposes. A later development, for particular

applications, was the cast or rolled carbonsilicon-nickel anode, which under some conditions forms an adherent, porous, carbon-silica

iilm that acts as a bag. Anodes cut from elec- trolytic nickel sheet have been used to a limited

extent, and several patents have been issued

for introducing sulfur into nickel anodes to promote corrosion of the anodes.

Several special baths are cited by Gray

[335]. In addition, references to the use of

sulfamate [425a], fluoborate [426,427], and

pyrophosphate [428] baths, and to the electrodeposition of nickel from molten salt baths

[429] have been noted. The brightening action

of cadmium salts has long been known, and a great number of organic addition agents have

been proposed and used to control the surface

appearance (brightness) of the deposit, and

sometimes for other reasons [335,430,431]. A

black nickel deposit, containing nickel sulfide, can be obtained [432]. Indira et al. [433] described a solution for black nickel plating and

showed that a high sulfur content was a prerequisite for achievement of jet-black coatings.

Wesley and Knapp [434] patented a method of

black nickel plating. McCarthy [435] described

the production of various colors on several

basis metals using a black nickel plating elec- trolyte. Wesley [436] reported the production

of malleable sheets up to 6 mm thick of nickel

that contained only 34 ppm of detectible impurities, by electrodeposition from a purified

nickel chloride-boric acid solution, using iridium-platinum electrodes.

Electroplating on aluminum requires special

treatment because of interference by the sur- face oxide film, but procedures have been developed for plating nickel directly on aluminum [437,438,439,440,441,442,443,444] . Likewise, special treatments have been developed

so that nickel can be plated on beryllium [445]

,

on magnesium [446,447], on molybdenum

[448,449], on titanium [450] , on uranium

[451], on zinc [452], and on zirconium [453].

Numerous processes have been developed for

the plating of nickel alloys. A review of recent

developments in nickel plating was written by

Castell [454].

Examples of industrial nickel-plating baths

and operating conditions are shown in table

27, without reference to brightening agents

and other possible additions. In many industrial operations, the nickel plating may be

applied over an undercoat of copper and may

be followed by a final thin coating of chromium. Recommended practice for the preparation of nickel for electroplating with nickel

is discussed in ASTM Specification B 343-60T.

The requirements of ASTM Specifications for

minimum thickness of coatings for service

conditions of varying severity are summarized

in table 28. More recent ASTM specifications are being issued; however these specifications

will adhere to the same standards.

The physical and mechanical properties of

electroplated nickel are affected by the composition of the bath, by all the variables in

bath operation, and by the presence of metallic and gaseous impurities. These effects have

been reviewed in many articles [455,456,457,

458]. The mechanical properties of nickel deposits for engineering uses are summarized in

table 29.

Table 28. ASTM standards for nickel coatings

On steel (ASTM A 166-61T) Copper plus nickel Nickel (if copper is used)... Chromium (if required) On copper and its alloys (ASTM B 141-58)

Nickel Chromium (if required) On zinc and its alloys (ASTM B 142-61) Copper plus nickel Copper

Final nickel Chromium (if required)

Thickness of coating, in (min)

Type D Type F Type K Type Q

0.0020

.00100 .000010

.0020 .00020

.0010 .000010

0.0012

. 00060

.000010

.00050 .000010

.0012 .00020

.00050 .000010

0.00075

.00040 .000010

. 00030

.000010

.00075 .00020

.00030 .000010

0.00040

. 00020

.000010

.00010

.000010

.00050

.00020

.00030 .000010

58
=ijABLE 29. Mechanical properties of nickel deposits for engineering uses U59]

i'il

Type of bath

Watts, low pH Chloride Hard,

as plated

Sulfa- mate,

as As plated

plated Annealed As

plated Annealed

bnsile strength,

[psi longation, % in

11 in Ickers hardness

j numbers

ockwell hardness63.00031

137

75 B

50,00050

63

17 B

100,000

21 240

99 B

58,00048

8136 B

100 ,uuu

6 400

42 B

yu.uuu

10 200

J Hammond [458] noted that nickel plating

a -nay involve risk of hydrogen embrittlement in

]. iteels of 180,000 psi or higher, but that this

r lay be obviated by low-temperature baking

M tfter plating. Beck and Jankowsky [460] relyjlorted that hydrogen embrittlement of 4340

teel induced by chromium plating was sub-

'o tantially reduced by an undercoat of Wattsieivpe nickel.

^! In addition to electroplates of nickel alone,

5-l^aths and operating conditions have been deiclfeloped for the deposition of nickel alloys.

J lome of these are nickel-aluminum [461]

,

> ickel-boron [462], nickel-chromium [463],

i- (ickel-cobalt [464], nickel-iron [465], nickel-

;1 lolybdenum [466], nickel-phosphorus [467],

!.

j lickel-rhenium [468], nickel-tin [469], and

r tickel-zinc [470]. Some ternary alloys that

e ave been plated are nickel-iron-chromium

i 471] and nickel-cobalt-copper [472]. Couch

1 t al. [473] patented the production of nickel3 luminide coatings.

The various processes used for plating nickel

^ re described in a booklet by The International

• fickel Company, Inc. [474].

3 (2) Electroless plating. Brenner and Rid-

• ell [475] decribed a process developed at the

2 ifational Bureau of Standards in 1946 for the

- eposition of nickel from an ammoniacal solu-

• on containing hypophosphite by chemical re1 iuction. The following year the process was

fXpanded to include deposition of nickel from

icid solutions and the deposition of cobalt from

oth alkaline and acid solutions. Reduction of

ickel salts by hypophosphite had been long

nown as a chemical reaction, but Brenner and

.iddell were the first to develop a controlled

. utocatalytic reaction to produce a sound, co- erent metallic coating that could be built up

) appreciable thicknesses. The coatings conjiin up to 6 or 7 percent of phosphorus, probbly in the form of finely dispersed phosphides,

.s deposited, the coatings have a Vickers hard-

: ess number as high as 700, but heating at levated temperatures reduces the hardness,

nd heating for at least 4 hr at 725 to 800 °C

inverts the plated coating into an iron-nickel

Hoy [476]. The deposits are somewhat less lagnetic, but are similar to electrodeposited

ickel in resistance to rusting as indicated by

the salt spray test. The electroless process has

three advantages over electroplating:

1. Coatings deposit with uniform thickness

in recesses as well as on exposed surfaces.

2. There is no buildup of coating on points or edges.

3. No electrical equipment is required.

Electroless nickel plating can be deposited

directly upon surfaces that catalyze the reaction, for example, on aluminum, cobalt, copper,

gold, iron, nickel, palladium, platinum, and sil- ver. A method of electroless nickel plating of

magnesium and thorium was patented by Puis

and Vincent [477] and electroless nickel plating of beryllium was described by Roberts

[478]. Titanium, zirconium, and hafnium have

also been chemically plated with nickel [479].

Semiconductors, such as graphite and silicon

carbide, may be electroless plated by touching

the semiconductor with a piece of aluminum

or steel to start the reaction, and nonconductors, such as glass, plastics, and ceramics, may

be electroless plated after dipping in palladium

solution or being otherwise treated to form an

absorbed film of palladium or a palladium compound. However, cadmium, manganese bronze,

lead and its alloys, and silicon cannot be elec- troless plated, according to Panchenko and

Krokhina [480].

The compositions of various baths for elec- troless nickel plating and the operating procedures have been described by Krieg [481] and

by Aitken [482].

Patents for the electroless deposition of

nickel-boron [483] and nickel-vanadium [484]

alloys have been issued.

The history of the electroless plating process was reviewed by Brenner [485]. MacLean and

Karten [486] reported that small fuse parts

with deep blind holes could be plated with 0.1 mil of nickel. Rich [487] reported that the use

of ultrasonic vibrations from stainless steel transducers increased the rate of electroless

nickel plating. Gutzeit and Landon [488] described operations of a large-scale, electroless,

custom plating shop. Chinn [489] reviewed the

subject of electroless plating and cited numerous examples of its practical use. (3) Electroforming. Nickel electroforming,

accomplished by the use of electroplating processes, is defined as the production or the reproduction of articles by electrodeposition upon a mandrel or mold that is subsequently separated

from the deposit. It is a low-cost production

method for forming complex assemblies or in- tricate internal contoured shapes which re- quire high dimensional accuracy and smooth

surface finish. The process is sometimes re- ferred to as "cold casting." Inasmuch as the

electrodeposit that constitutes an electroformed

article is used as a separate structure, its mechanical properties are a matter of major importance.

59
Nickel ordinarily is electroformed in a Watts-type solution or a nickel sulfamate bath,

such as shown in table 30. The pB. of all nickel

solutions should be maintained within a relatively narrow range of about 0.5 unit for good

control of physical and mechanical properties,

but a relatively low pB. of about 3 is preferred

for some applications, whereas a pH of 4 to 4.5

is preferred for others.

Table 30. Composition and operating conditions for two

nickel electroforming baths H90]

Cla

Watts bath Sulfamate bath

Nickel sulfate or 30 to 50 oz/gal 30 to 60 oz/gal sulfamate a 44 " 50

Nickel chloride _ 4 to 8 0 4 to 0.8

• 6 « 0.6

Nickel 10 to 12 8 to 14

• 11 « 10

Boric acid 4 to 5 4 to 6

« 5 • 4 pH 2 Oto 4.5 3 5 to 4.2 Temperature-- -- - to 140 °F 80 to 140 °F

Current density - 25 to 50 A/ft2 20 to 150 A/ft2

» Typical or average operating condition. The structure and properties of electroformed nickel (or alloy) depend on electrodeposition conditions as follows: kind and con- centration of the nickel salts, concentration of

chloride or other anion employed for assisting

the dissolution of anodes, pH. of the solution,

impurity concentrations, solution temperature,

cathode current density, kind and amount of

solution agitation, and interrelation of these

factors. The kind and concentration of organic

chemical agents added to the electrodeposition

solution for avoiding pitting, reducing stress, or refining the grain structure frequently have

profound effects on properties.

Kura et al.[491], in a review of the literature, gave the following ranges for the physical and mechanical properties of electroformed

nickel

Density

Modulus of elasticity Coefficient of linear expansion near room temperature. Ultimate tensile strength _ Yield strength

Elongation in 2 in

0.321 to 0.327 lb/in.3 23,000,000 to 28,000,000 psi

3.1 to 6.3 microinch/°F

55,000 to 215,000 psi

32,000 to 128,000 psi 2 to 27 percent

These authors noted that as a rule, an in- crease was observed in the tensile and yield

strengths for electroformed nickel, and a de- crease in ductility was evident when the temperature for the electrodeposition bath was

lowered. They note further that, of the various

baths used for electroforming, stronger nickel

with a higher yield strength was obtained

with the nickel chloride and nickel sulfamate

solution than with any other. Modern electroforming solutions were discussed by Diggin

ft

[492] and the physical and mechanical proj

erties of electroformed nickel at both elevate

and subzero temperatures were reported bf Sample and Knapp [493]. | Electroforming is particularly applicabi

to the manufacture of phonograph recor stampers [494] , printing plates [495] , screer, [496], etc. Even pressure vessels have bee;

electroformed [497].

(4) Nickel cladding. Nickel cladding, lil* electroplating, supplies corrosion resistant

nickel-surfaced material that is cheaper tha

solid metal. In this process the cladding mett

is pressure welded to one or both sides of a.. open-hearth steel slab in a rolling mill at aboi,

2,200 °F. If the bonding surfaces have bee

properly cleaned and protected during heav

ing, excellent bonding through the formatio

of an iron-nickel solid solution is accomplishe|iFith

during hot reduction to between one-eighti

and one-sixteenth of the original thickness, n The ratio of cladding material to the bas. plate is usually expressed as a percentage c, the total thickness of the plate. For exampld

a i/2-in plate clad 10 percent on one side onl

consists of about 0.45 in of steel and 0.05 in

nickel; clad 10 percent on both sides, it woul,

be 0.40 in of steel and 0.05 in of nickel on eaci

side. When both sides are clad, the same thicli; ness of nickel usually is applied to each sid(

but different thicknesses on the two sides ma,

be developed if desired. Nickel-clad steels ar

regularly supplied with 5-, 10-, 15-, or 20-per

cent cladding on a 55,000-psi minimum tensil

strength steel as base material. According t Theisinger and Huston [498], nickel claddinj

does not affect the mechanical properties of thi clad material, as illustrated by the followinj

data of i/2-in steel with and without 10-percen

nickel cladding. ,

Tensile strength Yield

point

Elongation

in 8 in

Reductior

in area

Clad

psi

60,600

60,800

psi

40,400

40,200

%

30.0 30.5 %57.2

Plate.- 59.0

peri

Chi

Ni(

A relatively new process for metallurgicallj

bonding a pore-free coating onto mild stee consists of applying carbonyl nickel powder ir, slurry form directly to the surface of a movinjj

strip of hot rolled steel [498a]. The slurry is then dried and sintered to a porous nickel,

layer which is densified to a nonporous coat by'|

passing between the rolls of a hot compaction

mill. Nominal nickel coating thicknesses on the

order of 0.0005 to 0.0025 in have been achieved

after cold rolling.

' Metals have also been clad with nickel Wi

explosive bonding techniques.

h

60
(| Cladding is not restricted to the use of nickel

ionly. Steel may be clad with Monel alloy 400,

Inconel alloy 600, stainless steel, etc. In welding the clad surface of a plate, a covered elec- :trode of approximately the same composition

:ias the cladding is used. ASTM Specification

: A265-62 covers nickel and nickel-base alloy

i clad steel plate.

(5) Sprayed and vapor-deposited coatings.

'- Protective coatings of nickel or of nickel alloys

:may be applied by metal-spray processes, n which are particularly adapted for coating

-

: large objects of irregular shape [499] . Pure

nickel can be sprayed with either a wire or ^powder gun. Nickel alloys are usually sprayed

*i in a powder gun because they are more readily

1; available in powder form. After spraying, the

immaterial is fused to form a metallurgical bond

: : with the base material, which may be steels,

' irons, nickel and nickel alloys, copper and copper alloys, and refractory alloys. A self-bondi iing material that does not have to be fused

after spraying is nickel aluminide, which has

> been decribed by Sheppard [500] . Kura et al. [491] summarized the process of metal spraying of nickel and its alloys. A patent for ob-

- taining a smooth uniform coating of nickel

= 'by spraying with an aqueous solution was

issued to Carlson and Prymula [501].

.' Chemical vapor deposition (CVD) is accom-

^plished by causing gaseous molecules to react chemically at, or near, a heated surface under

;conditions such that one, and only one, of the

'reaction products is a solid and is deposited on the heated surface. As the reaction con-

'tinues, atoms (or molecules) are added to the

-growing metal lattice one at a time. Such a

• procedure has been called a "molecular formling" process. Considerable detail concerning

the mechanism of deposition at low pressures

=and the properties of nickel coatings was given

jby Owen [502]. Nickel can also be vapor de4)0sited by electron beam p rays. Nickel can be deposited by the thermal de-

-composition of nickel carbonyl, of nickel acetyl

'acetonate, or by the hydrogen reduction of

'nickel chloride. According to Owen [503],

nickel carbonyl is used because it is highly

•volatile. The plating temperature is under

!)0

°C and rates of deposition as fast as 0.030

i/hr are achieved without difficulty.

Tewes et al. [504] studied four potential

italytic agents and found that the use of the

/drogen sulfide/oxygen catalytic mixture

:hieved the same plating rate at 100 °C as

as obtained at 150 °C without a catalyst.

The strength of vapor-deposited nickel films

' 700 to 4360 A thickness was studied by

'Antonio et al.[505], who concluded that a

gnificant contribution to the high strength

: thin metal films can be attributed to the

ipor-deposition process which, owing to its (vere quenching effect, is believed to promote

the formation of many point defects which

inhibit the motion of dislocations.

Recent developments in the technique of

nickel plating from the vapor of nickel car- bonyl have been reviewed by Owen [506].

Gas plating of nickel has been used to coat

synthetic fibers such as nylon, rayon, glass,

etc. [507,508,509]. The protection afforded ura- nium by the thermal decomposition of nickelcarbonyl vapor was reported by Owen [510]

to be considerably superior to electrodeposited

coatings of the same thickness.

According to Cummins [511], the addition

of ammonia gas to nickel carbonyl plating gas

results in the production of nickel-containing

films of relatively high electrical resistance.

These coatings are applied to the preparation

of electrical resistance units.

Breining [512] obtained a patent on the

deposition of nickel-phosphorus alloys by gas

plating.

b. Nickel Powders

By varying the conditions of electrodeposition, nickel may be deposited as a powder

rather than as a continuous plate [513,514,

515,516]. Nickel powder has been produced

by electrolysis of fused salts [517], grinding

of sulfurized nickel shot, hydrogen reduction

of nickel oxide, and in the ammonia-leach

process for the recovery of nickel from its ores [518], but the principal production of

nickel powder for powder metallurgy uses is by decomposition of nickel carbonyl or by the

ammonia-leach process. Various types of car- bonyl-nickel pK)wders are also available [519].

The properties of sintered carbonyl nickel

powder compacts were reported by Prill and

Upthegrove [520].

Nickel powder may be used by itself to form

all-nickel parts, or in combination with other

metal powders to produce alloys or compounds [45,521,522,523,524]. Pure nickel strip can be produced from powder [525,526,527,

527a].

Carbonyl nickel powders of irregular particle shape and low bulk density are used in

the production of porous nickel electrodes for

nickel-cadmium storage batteries and hydrogen-oxygen fuel cells employing alkaline elec- trolytes [528,529,530,530a,530b]

.

Nickel powder parts are particularly valuable in the field of electronics, and controlledexpansion and magnetic alloys formed by

powder-metallurgy techniques have advantages

over melted metal [531]. Cathode-base materials for the electron tube industry have been

made by the powder rolling of nickel powder

with controlled alloy additions to achieve

unusual combinations of properties, such as

electrical passivity and mechanical strength

at high temperature [531a]. Nickel-silver con61
tact materials have been made by powder

metallurgy [532], as have nickel-base alloy

turbine blades [533]. Nickel alloyed with up

to 40 percent of tungsten is useful for thermionic valve construction [182].

Sintered nickel steel engineering components have been made by the pressing and sintering of mixtures of iron and nickel powders [533a] . Nickel-chromium alloy powders

added to iron powder produce compacted parts

with tensile strengths between 80,000 and

120,000 psi [533a,534].

Nickel or nickel-alloy objects infiltrated with

silver or a silver alloy have effective resistance

to wear at elevated temperatures [535]. The

compound NiAl, formed by powder metallurgy

technique, has refractory properties which

make it useful in the temperature range from

850 to 1,150 °C [536]. Forming of stainlesssteel powders by slip casting instead of the

more conventional pressing has been reported

[537], and this technique should be applicable

to other alloys and to nickel itself, particularly for the production of thin-walled and

special shapes.

Tungsten-nickel-copper compositions, com- monly called "heavy alloys," have found commercial applications requiring high specific

gravities. Nickel powder mixed with copper

powder is used to bond the tungsten particles.

Nickel powder may be used to bond carbides

of titanium, tantalum, and columbium in the

formation of sintered carbide objects. Nickel,

like cobalt, wets the carbide particles and

forms extensive interlocking bonds [538,539].

Nickel-chromium-boron powders have been

used as a hard-facing overlay [540].

c. End Uses of Nickel and Nickel-Surfaced Materials

The tarnish resistance and corrosion resist- ance of nickel make nickel and nickel plate

useful in many industries, including the paper

and pulp industry, food, dairy and beverage

industries, and the petroleum, textile, and plastic and automotive industries [541,542]. These

properties plus electrical and magnetic properties make nickel useful in the electrical and

electronic industries. The following list of

ASTM Specifications indicate the form and

shapes of nickel that are available for the

construction of equipment or parts for these

conditions of use: B 39-22

B 160-61

B161-61

B162-61

B163-61T

B295-54T

Nickel.

Nickel rod and bar.

Nickel pii>e and tube, seamless.

Nickel plate, sheet, and strip.

Nickel and nickel alloy, seamless,

condenser and heat-exchanger

tubes.

Nickel and nickel-base alloy cov- ered welding electrodes.

B 141-58 Electrodeposited coatings of nickel and chromium on copper and

copper-base alloys.

^ B 142-61 Electrodeposited coatings of nick- i el and chromium on zinc and zincbase alloys.

B355-60T Nickel-coated soft or annealed

copper wire.

A166-61T Electrodeposited coatings of nickel and chromium on steel. Nickel finds a variety of uses in the elec- trical industry [543] , including the use of very

thin films sputtered or vapor deposited, as

resistance thermometers at very low temperatures [150], A thin film of nickel, which transmits 30 percent of the incident light to the

germanium semiconductor, improves the performance of a photoelectric cell [544].

In the field of electronics, nickel forms the

base of the cathodes in practically all small

and moderate size radio and television tubes,

and in the deep-sea portion of the TransAtlantic telephone cable. The use of nickel and

its alloys with aluminum, tungsten, and rhodium in cathodes, grids, and other parts of elec- tronic tubes, has been the subject of numerous

articles and patents [295,545,546,547].

In the chemical industry, nickel is widely

used for handling caustic soda and other alkalies, even at elevated temperatures.

The use of nickel in nuclear power plants was discussed by Convey [62], Koenig [548],

and Dalzell [549]. Fuller [550] reported that

more than 1,200 miles of piping internally

plated with 0.003 to 0.005 in of nickel would

be used in the Atomic Energy Commission's

gaseous diffusion plant at Portsmouth, Ohio.

Heavy electrodeposits of nickel, for resist- ance to wear and corrosion or to build up worn

ports, have some advantages over chromium

plating [551] and are used in transportation

equipment, in paper and textile mills, in equipment and tools for oil drilling, in food processing, and in the printing industry.

Nickel combustion boats and crucibles for

laboratory use may be made from sheet metal

[552]. Nickel tubes with walls 0.1 mm thick were used for diffusion purification of hydrogen [553] and tubes of pure nickel 0.015 in

thick are used as a protective material for

beryllium rod during drawing to wire of 0.005

in diam [554]. Nickel is an activator of phosphors [555]. Nickel powder is pyrophoric

under some conditions and finds use in incendiaries, tracer ammunition, igniters, primers,

etc. [556]. Nickel-plated silk was used in England as a wartime substitute for fine copper

gauze for straining gasoline [557], and nickelplated wires produced a superior Fourdriner

cloth [558]. Nickel was recommended as a

container for bromine [559], and for use as a spinneret in the production of acetate and

62
cuproammonium fibers [560] . According to Atkinson [561], about 500,000 lb of nickel is used

annually in precious metal jewelry, including

gold-filled and rolled-gold plate and the white

and colored golds.

About 1 percent of the world consumption

of nickel represents uses of nonmetallic forms,

i.e., compounds such as sulfates, chlorides, carbonates, oxides, and hydroxides. These compounds are used in the electroplating industry,

in the production of alkali storage batteries,

and in the production of nickel catalysts other

that Raney catalysts. Nickel compounds are

used, as a dip bath and in ground coats, for

applying vitreous enamel to steel [562,563,

564].

3. Nonferrous Alloys

3.1. General

The nonferrous alloys of which nickel constitutes either a major or minor percentage

are so numerous that it is impossible to present

a comprehensive coverage in this circular. An

attempt has been made to group these alloys

into certain classes and attention will be directed to the more representative materials.

There are many general reviews of the properties and uses of high nickel alloys that are

of interest [565,566,567,568,569,570]

.

3.2. High Nickel Alloys

a. Nickels

Table 31 gives the nominal chemical composition of a group of nickels containing a minimum of 94 percent nickel. Except for four

alloys, the minimum nickel content is 99 percent. Each of these alloys is manufactured for

particular usage because of certain inherent

properties.

Nickel 200 (99.00% Ni min, 0.15% C max,

0.35% Mn max, 0.40% Fe max, 0.010% S

max, 0.35% Si max), is commercially pure

wrought nickel and has been discussed in a previous section. It has good mechanical properties and excellent resistance to many corrosive environments. Much of its strength is retained at high temperatures and it is tough

and ductile at subzero temperatures. Its corrosion resistance makes it particularly useful for

manufacturing product purity in the handling

of foods, synthetic fibers and caustic alkalies.

Nickel 201 is similar to Nickel 200 except

that the carbon content is held to a maximum

Table 31. Commercial nickel alloys H.3]

Designation Nominal chemical composition—percent

Ni C Mn Fe S Si Cu

Nickel 200 99 5 0.06 0.25 0 15 0.005 0 .05 0.05

Nickel 201 99 5 .01 .20 15 .005 .05 .05 Nickel 204 95 2 .06 .20 05 .005 .02 .02 Nickel 205 99 5 .06 .20 10 .005 .05 .05 Nickel 211 95 0 .10 4.75 05 .005 .05 .03 Nickel 220 99 5 .06 0.12 05 .005 .03 .03 Nickel 230 99 5 .09 .10 05 .005 .03 .01 Nickel 233 99 5 .09 .18 05 .005 .03 .03 Nickel 270 99 98 .01 <.001 < 001 <.001 < .001 <.001

Permanickel alloy 300 98 6 .25 .10 10 .005 06 .02 Duranickel alloy 301 94 0 .15 .25 15 .005 55 .05 Monel alloy 400 66 0 .12 .90 1 35 .005 15 31.5 Monel alloy 401 44 5 .03 1.70 0 20 .005 01 53.0 Monel alloy 402 58 0 .12 0.90 1 20 .005 10 40.0 Monel alloy 403 57 5 .12 1.80 50 .005 25 40.0 Monel alloy 404 55 0 .06 .01 05 .005 02 44.0 Monel alloy R-405 66 0 .18 .90 1 35 .050 15 31.5 Monel alloy 406 84 0 .12 .90 1 35 .005 15 13.0 Monel alloy 474 54 0 .01 trace 0 01 .001 < 01 46.0 Monel alloy K-500 65.0 .15 .60 1 00 .005 15 29.5 Monel alloy 501 65.0 .23 .60 1 00 .005 15 29.5

Inconel alloy 600 76 0 .04 .20 7 20 .007 20 0. 10 Inconel alloy 604 74 0 .04 .20 7 20 .007 20 .10 Inconel alloy 625 61 0 .05 .15 3 00 .007 30 .10

Inconel alloy 700 46 0 .12 .10 0 70 .007 30 .05

Inconel alloy 702 79 5 .04 .05 35 .007 20 .10

Inconel alloy 718 52 5 .04 .20 18.5 .007 30 .07

Inconel alloy 721 71 0 .04 2.25 20 .007 12 .10

Inconel alloy 722 75 0 .04 0.55 6 50 .007 20 .05 Inconel alloy X-750 73 0 .04 .70 6 75 .007 30 .05 Inconel alloy 751 72 5 .04 .70 6 75 .007 30 .05

Incoloy alloy 800 32 0 .04 .75 46 0 .007 35 .30 Incoloy alloy 801 32 0 .04 .75 44 5 .007 35 .15 Incoloy alloy 804 42 6 .06 .85 25 4 .007 50 .40 Incoloy alloy 825 41 8 .03 .65 30 0 .007 35 1.80 Hi-Span-C alloy 902 42 0 .02 .40 48 5 .008 50 .05

Al Ti Others

Previous designation

<.001

15.8

15.8 22.0

15.0

15.6

18.6

16.0 15.0

15.0

15.0 20.5 20.5

29.3

21.5 5.4

0.02 CoMg

4.50

0.04

4.60

.02 .003

.003 <.001

.50

.50

Mg

Mg

Mg

CoMg

Mg

0.04 0.06

0.07 <0.001

<0.001

0.35

Co 0.50

0.02

trace 2.80

2.80

.50

.50

3.00

3.40

0.40

- .60 .80 1.20 0.30

.25

.15 .65

2.20 0.70

.90 3.00

2.40

2.50 2.50

.30 1.00

.40

.90 2.40

Nb 2 0 Nb 4 0 Mo 9 0 Co 28 5 Mo 3 75 Nb 5 0 Mo 3 1

Nb 0 85 Nb 1 00

Mo 0.30

"A" Nickel. Low Carbon Nickel. Nickel 204. "A" Nickel (elec- tronic grade). "D" Nickel. "220" Nickel. "230" Nickel. "330" Nickel.

Permanickel alloy. Duranickel alloy. Monel alloy. Monel "401" alloy. Monel "402" alloy. Monel "403" alloy. "R" Monel alloy. LC Monel alloy. "K" Monel alloy. "KR" Monel aUoy.

Inconel alloy. Inconel "600" alloy.

Inconel "700" alloy.

Inconel "702" alloy. Inconel "718" alloy.

Inconel "M" alloy. Inconel "W" alloy. Inconel "X" alloy. Inconel "X-550"

alloy. Incoloy alloy. Incoloy "T" alloy. Incoloy "804" alloy. Ni-O-Nel alloy. Ni-Span-C alloy.

63
of 0.02 percent. It is particularly suited for

spinning and cold forming operations because

of its low base hardness and low work-hardening rate. It is also preferred to Nickel 200 for

applications involving exposure to temperatures above 600 °F.

Nickel 204 (0.20% C max, 0.35% Mn max,

0.30% Fe max, 0.008% S max, 0.20% Si max,

0.20% Cu max, 0.05% Ti max, 4.00/4.60% Co,

remainder Ni) is characterized by its excellent

magnetostrictive properties. At optimum bias,

its electromechanical coefficient is 0.5/0.6 ; sat- uration magnetostriction is about min 38 ppm.

Transducers utilizing this alloy exhibit high

efficiency, are rugged, and have excellent cor- rosion resistance.

Nickel 205 (99.00% Ni min, 0.15% C max,

0.35% Mn max, 0.20% Fe max, 0.008% S max,

0.15% Si max, 0.15% Cu max, 0.01/0.05% Ti,

0.01/0.08% Mg) is designed especially for elec- trical and electronic components. Its modulus

of elasticity and damping factor are sufficiently

high to minimize vibrational and microphonic

effects. Sufficient strength is maintained at normal bombardment temperatures to prevent

deformation during outgassing. In addition,

it has a high Curie temperature and a high

magnetostrictive coefficient.

Nickel 211 (93.70% Ni min, 0.20% C max,

4.25/5.25% Mn, 0.75% Fe max, 0.015% S

max, 0.15% Si max, 0.25% Cu max) is designed to resist sulfur compounds at elevated

temperatures. This alloy maintains much of

its strength when exposed to degassing temperatures. It is useful for supports sealed into

glass where embrittlement from sulfur in the

heating flame is a factor. Electron emission is low enough to make it useful for grid wires

in electron tubes even when the wire becomes

contaminated with barium.

Nickel 220 (99.00% Ni min, 0.08% C max,

0.20% Mn max, 0.10% Fe max, 0.008% S

max, 0.01/0.05% Si, 0.10% Cu max, 0.01/

0.05% Ti, 0.01/0.08% Mg) is widely used for

cathodes in electronic receiving tubes. It is effective where fairly easy activation is re- quired without liberating excessive amounts of

barium.

Nickel 230 (99.00% Ni min, 0.10% C max,

0.15% Mn max, O.lO^o Fe max, 0.008% S

max, 0.010/0.035% Si, 0.10 % Cu max, 0.005%

Ti max, 0.04/0.08% Mg) is designed for use

in active cathodes. Its closely controlled composition makes it useful for certain special

electron-tube applications.

Nickel 233 (99.00% Ni min, 0.10% C max,

0.30% Mn max, 0.10% Fe max, 0.008% S max,

0.10% Si max, 0.10% Cu max, 0.005% Ti max,

0.01/0.10% Mg) is used for plates (anodes)

in vacuum tubes, and oxide-coated and cold

cathodes and structural parts of tubes.

Nickel 270 (99.97% Ni min, 0.02% C max,

0.001% Mn max, 0.005% Fe max, 0.001% S

max, 0.001% Si max, 0.001% Cu max, 0.001% i Ti max, 0.001% Co max, 0.001% Mg max) is a high-purity product exceptionally free from j nonmetallic inclusions. Its low base hardness { and good ductility permit heavy cold deforma- i tion without reannealing.

Duranickel alloy 301 (93.00% Ni plus Co

min, 0.30% C max, 0.50% Mn max, 0.60% Fe ' max, 0.01% S max, 1.00% Si max, 0.25% Cu

max, 4.00/4.75% Al, 0.25/1.00% Ti) is an age-

^ hardenable alloy employing aluminum and tita- * nium as the age-hardening elements. It combines the excellent corrosion resistance characteristic of nickel with the additional advantages of greater strength and hardness. Alloy

301 is age hardened by heating in the temperature range of 800 to 1300 °F; the time and

temperature depend upon the properties desired. Tensile strengths in excess of 200,000

psi can be obtained in this material [565].

Permanickel alloy 300 (97.00% Ni plus Co

min, 0.40% C max, 0.50% Mn max, 0.60% Fe , max, 0.01% S max, 0.35% Si max, 0.25% Cu

max, 0.20/0.60% Ti, 0.20/0.50% Mg) is an

age-hardenable alloy similar to Duranickel al- : loy 301 in its strength and corrosion resistance,

but has higher thermal and electrical conductivity. It is somewhat difficult to heat treat and Duranickel alloy 301 is recommended in

preference to Permanickel alloy 300 except for

applications requiring Permanickel's superior

conductivity or magnetic properties [571].

Data on the physical properties of these and

other high-nickel alloys are given in table 32.

b. Nickel -Chromium Alloys

Nickel-chromium alloys (and Ni-Cr-Fe al- loys) have many applications ranging from ^ thermocouples to structural units, depending

upon their electrical and mechanical properties and their resistance to heat, oxidation,

and corrosion. Perhaps their most outstanding characteristic is their heat resistance, al- though they do not qualify as superalloys,

which are treated in a subsequent section.

However, many nickel-chromium base alloys, even though treated in this section, are actually superalloys.

Accordmg to the nickel-chromium constitution diagram (fig. 50) [572], nickel is capable

of formmg a solid solution with up to about 30

percent ot chromium. The two most important

nickel-chromium alloys contain 10 and 20 per- cent of chromium.

I'he 90 percent Ni-10 percent Cr alloy, known

as Chromel alloy P, is used as a heating element

up to 2400 °F. However, its most important use

is as the positive wire of a base-metal thermocouple with the 95 percent Ni, balance Si, Mn,

Al alloy known as Alumel. Roeser, Dahl, and j Gowens [573] reported the values shown in

table 33 for the thermal emf of this thermo64
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65
WEIGHT % NICKEL

5 15 25 35 45 55 65 75 85 95

2000

1800

1600

o

0£.

m

Q.

U

1400

600

200

—r—

1880<^

1 1 "T—1 1 T—

n—

1 1 r T" -1 T 1

: *

>l\C N 46(49] 1455°

c

17(19:

32(35)

-51.-1(54.4:

55 (5i

[^0 (; V

3)

!)\-

(Ni)

-jlJ

\

7 (8)-

(3)— 1 (64) 6

\

i

1

1 —

V

\

40°

\ —

U

M/ GN/

1 RANSF/

1/

353*

li.iSi

3 Si,:

(i.iSi.

1

Si,

II fl Hi,

li Xi,

'( Si,

il Si,

SS Si,

iiimi

c prei

0 10 20 30 40 50 60 70 80 90 100

ATOMIC % NICKEL

Figure 50. Nickel-chromium constitution diagram, [5721. Numbers refer to atomic (weight) percent at the temperatures indicated.

couple at temperatures up to 1,400 °C. The life of the thermocouple is short in oxidizing atmospheres above about 1,100 °C, and the emf is subject to change in an alternately oxidizing and

reducing atmosphere.

The 80 percent Ni-20 percent Cr alloy, known

as Chromel alloy A, was developed in 1906 by

A. L. Marsh for use as an electrical resistance

alloy [574]. The use of the drawn or rolled

alloy for electrical heating elements is discussed

in ASTM Specification B344-65. Properties of

Table 33. Thermal electromotive force of chromel-alumel thermocouple with cold junction at 0 °C [573]^

m

nicke

of si

Temperature Electromotive

force Temperature Electromotive

force

°C mV °C mV

-200 -5.75 700 29.14 -100 -3.49 800 33.31 0 0 900 37.36

100 4.10 1,000 41.31 200 8.13 1,100 45.14 300 12.21 1,200 48.85

400 16.39 1 ,300 52.41 500 20.64 1,400 55.81 600 24.90

" More detailed tables are presented in NBS Circular 561, published

in 1955.

interest of the nickel-chromium and related al loys are summarized in tables 34 and 35 [57^|Z

and 576]. The effect of increasing temperatur^j on the resistivity of 80-20 alloy is shown ir; figure 51 [577]. Values for the specific heat o^

80 Ni-20 Cr, as reported by Douglas and Devei

[578] and shown in figure 52, show a discontinuity in the vicinity of 600 °C that has not yel

been fully explained. ' The maximum temperature to which a heat-: ing alloy is subjected is one of the most im-j

portant factors governing service life. WhetheJj

the temperature is constant or intermittent alsci has a marked effect. Data from accelerated

laboratory tests (fig. 53) [575] illustrate the

effects of temperature on heating elements made

from 80-20 alloy.

Resistance to oxidation is important in heat

ing units. Zima [579] reported that the rate ot

oxidation of 80-20 alloy at 2000 °F, in oxygen^

at atmospheric pressure, was only a little more

than 1 percent of the oxidation rate of pure

nickel under the same conditions. Rates of oxi^

dation of 80 Ni-20 Cr and of nickel are appreciably less in air than in oxygen. Gulbransei;,

and Andrew [233] reported ttiat pure chrom

lu 2 £

0

2

Ficu

66
Table 34. Physical properties of electric resistance heating elements [575]

Typical composition, %

Resistivity at 68

°F, ohm

per cir mil-ft

Specific gravity

Density, lb/in'

Average percent change in resistance from 68 °F to Thermal expansion, micro in/in/ °F from 68 °F to Tensile strength

at 68 "F, 1000 psi

Approximate

melting

point, °F

Maxifurnace

operating temperature

in air, °F 500 °F 1000 °F 1500 °F 2000 "F 212 °F 1060 "F 1485 °F

78.5Ni, 20Cr, 1.5 Si, (80-20) 73.5 Ni, 20 Cr, 5 Al, 1.5 Si 650

830 700

675 610

8.41 7.90

8.33

8.25

7.95

0.3039

.2854 .3010

.2979 .2870

-1-4.2

-1-2.5 -t-3.9

-1-5.9 -1-8.4

+ 7.0

-1- 2.8

-1- 6.7

-1-10.9

-1-16.7

-1- 6.3 - 1.6

-1- 6.0

-f-12.4 -t-21.8

-1- 7.7 - 3.7 + 7.1

-1-16.2 -1-24.8

7.5 7.0

"7^5

'

8.7

8.4 9.8 100/200

130/180

130/180 95/175

70/150

2550

2540

2540

2462 2515

2100

2200 2100

1850

1700

68 Ni, 20Cr, 8.5 Fe, 2 Si 60 Ni, 16 Cr, 22.5 Fe, 1.5 Si 35 Ni, 20 Cr, 43.5 Fe, 1.5 Si

7.0

8.4

8.7

Table 35. Physical properties of electrical resistance alloys [576]

Typical composition, %

^99.8 Ni

'*71 Ni, 29 Fe

(80 Ni, 20 Cr

175 Ni, 20 Cr, 3 Al-|-Cu or Fe

!76 Ni, 17 Cr, 4 Si, 3 Mn

i60 Ni, 16 Cr, 24 Fe

•35 Ni, 20Cr, 45Fe

Resistivity at 68 °F. ohms per cir mil-ft

48

120 675 800

800

675 610

Temperature coefficient of resistance, microhm/ohm/''C

-1-6000 ( 20 to 35 "O

-1-4500 ( 20 to 100 °C)

-I- 85 ( - 55 to 100 °C) ± 20 (-55 to 100 °C) ± 20 {-55 to 100 °C) + 150 ( 20 to 100 °C)

-I- 350 ( 20 to 100 °C)

Thermal emf

vs copper, microvolts/°C

-22 -39 + 5 + 1 - 1 +

(0 to 75 °C)

(0 to 100 °C)

(0 to 100 °C)

(0 to 100 °C)

(0 to 100 °C) 0.8(0 to 75 °C)

3 (0 to 100 °C)

Thermal

expansion,

micro- in/^C

Tensile strength

at 20 °C, 1000 psi

50/110

70/150

100/200

130/180

175/200 95/175

80/160

Specific gravity

at 20 °C

8.9

8.5

8.4

8.1 7.8

8.3

7.9

Density,

lb/in3

0.32

.31

.31 .29 .28

.30

.29

ium oxidized 4 times as fast, and pure nickel

12 times as fast, as the 80-20 alloy at temperatures from 500 to 950 °C under an oxygen

pressure of 7.6 cm. In another publication

[580], these authors reported that the rates of

oxidation at about 900 °C were lower for con- tinuous exposure than for hot-cold cycling. The

mechanism of oxidation of nickel-chromium al- loys (up to 80% Cr) has been studied by Birks

and Rickert [581] at temperatures up to 1100

°C. Hopkinson and Copson [582] evaluated the

effect of additions of niobium, titanium, and

silicon on the internal oxidation of several

nickel-chromium and nickel-chromium-iron al- loys. Carburization and oxidation in industrial

gases at 900 to 1,000 °C is avoided if 2 percent

of silicon is added to the 80 Ni-20 Cr alloy

[583].

0 400 800 1200 1600 2000

TEMPERATURE, °F

Figure .51. Effect of temperature on the electrical resist- ance of Chromel A (80 Ni^20 Cr) [577].

Osipov and Miroshkina [584] reported that

the highest resistance to short-time plastic deformation of nickel-chromium alloys at temperatures up to 1,000 °C was obtained with the

highest chromium content tested (23.82%), but

that the creep rate in long-time tests at high

temperatures was increased. The effect of minor

elements and of atmosphere on the creep-rupture properties of 80 Ni-20 Cr alloys was re- ported by Widmer and Grant [585,586]. Haynes

[587] found that the addition of niobium to lowzoo 400 600 800 I 000 TEMPERATURE, °C

Figure 52. Specific heat of Chromel A (80 Ni-20 Cr)

[578].

67
600

on

ui" 400

Uu- 200

LU

80

1 NI-20 C:r

ME -TING PC INT-y

2000 2200 2400

TESTING TEMPERATURE, F

II

Figure 53. Effect of temperature on the useful life of 80 Ni-20 Cr alloy [575]

carbon nickel-chromium alloys can confer

marked precipitation-hardening capacity. The

room-temperature yield strength was raised and

creep resistance at elevated temperatures was

improved. Further improvement resulted from

additions of molybdenum and/or tungsten. Roster and Christ [588] conducted a systematic

study of the effect of varying additions of cobalt,

aluminum, and titanium on the mechanical and

physical properties of 80 Ni-20 Cr and 60 Ni-20

Cr-20 Co alloys.

The properties enumerated for the nickelchromium alloys, plus their resistance to various

corrosive media, make wrought 80 Ni-20 Cr

suitable for engineering construction, particularly for use at temperatures higher than those

that the less expensive nickel-chromium-iron

alloys can withstand. However, the 80-20 alloy

is subject to plastic flow under relatively light

loads at high temperatures and, therefore, does

not appear in lists of superalloys.

According to Bagger [589], 80 Ni-20 Cr

forgings have good corrosion resistance, moderate strength characteristics, and are used for

high-temperature applications. The alloy forges

readily at 2,200 °F and is annealed at 1,600 to 1,900 °F.

The series of alloys known as Nimonic alloys are nickel-chromium and nickel-chromium-cobalt base alloys specifically developed to meet

strict limitations on permissible creep of vital

components under given conditions of stress and

temperature. There are also available complementary casting alloys, known as Nimocast al- loys, for high-temperature service. Detailed

data on these alloys are given in publications

by Henry Wiggin and Co. [590,591] and additional data are given by Forrest and Armstrong

[592], Forrest and Smith [593], and Franklin

et al.[594]. The forgeability of the Nimonics was studied by Yoda et al. [595] , and spot-welding techniques were reported by Waller and

Knowlson [596]. Compositions of the Nimonic

alloys are given in table 36.

Nimonic alloy 75 is basically an 80-20 nickelchromium alloy, stiffened by a small addition of

titanium. The alloy combines the inherent oxidation resistance of the nickel-chromium alloys

with improved mechanical properties at ele- vated temperatures. It is comparatively ductile at room temperature, permitting forming by

spinning, pressing, or rolling, and is weldable

by all conventional methods.

Nimonic alloy 80A is an 80-20 nickel-chromium alloy hardened by closely controlled additions of titanium and aluminum. In addition to

its good creep properties, its resistance to hightemperature fatigue is noteworthy. These properties, combined with the oxidation resistance

inherent in the nickel-chromium alloys, make it an ideal material for gas-turbine blades and

other highly stressed components operating

Table 36. Chemical composition of the Nimonic alloys [590]

Percent

C Si Cu Fe Mn Cr Ti Al Co Mo B Ni

Nimonic alloy 75. __ Nimonic alloy 80A

Nimonic alloy 90--. Nimonic alloy 105__ Nimonic alloy 115..

0.08/0.15

. 1 max

. 13 max

. 2 max

.20 max

1.0 max

1.0 max

1.5 max

1.0 max

1.0 max

0.5 max

.2 max

5.0 max

3.0 max

3.0 max

2.0 max

1.0 max

1.0 max

1.0 max

1.0 max

1.0 max

1.0 max

18 /21

18 /21

18 /21 13.5/15.75

14 /16

0.2/0.6

1.8/2.7

1.8/3.0 0.9/1.5 3.5/4.5

bal

bal

bal

bal bal

i. 6/1.8

.8/2.0 4.5/4.9

4.5/5.5

2.0 max

15 /21

18 /22

13.5/16.5

0.008 max

.5 max

.2 max

4.5/5.5

3 /5

68
within the recommended limits of temperature

and stress. Nimonic alloy 90 has a nickel-chromiumcobalt base resulting in a material which has

generally superior properties to Nimonic 80A,

enabling it to be used successfully at temperatures up to 900 °C.

Nimonic alloy 105 is a nickel-chromium-cobalt alloy with an addition of molybdenum to- gether with modified titanium and aluminum

contents. It has outstanding resistance to creep

at temperatures higher than those at which

Nimonic alloy 90 can be used.

Nimonic alloy 115 was developed to have even

better high-temperature properties than Nimonic alloy 105. When melted in vacuum, it has

li a temperature advantage of about 40 °C over

I' Nimonic 105.

The physical and mechanical properties of

cast 40 Ni-60 Cr alloy were investigated by

McDowell and Mihalisin [597] and the superior

resistance of this alloy to residual oil-ash corroi sion has been described [598].

c. Nickel -Chromium-Iron Alloys

The nickel-chromium alloys, modified by the

addition of iron and other elements, form a

I large group of materials characterized generally

by excellent heat and corrosion resistance and

good strength at moderately elevated temperatures. The Huntington Alloy Products Division

of The International Nickel Company, Inc. markets a family of nickel-chromium-iron alloys

under the trademarks "Inconel" and "Incoloy."

Nominal compositions of these alloys are given

in table 31 and physical constants are given in

table 32. Additional alloys, analyses of which

have been standardized by the Alloy Casting

Institute, are discussed in the section dealing

with cast heat-resisting steels. The constitution

of the ternary system nickel-chromium-iron at 650 °C (1200 °F) is shown in figure 54.

The 80 Ni-14 Cr-6 Fe alloy, made by adding

ferrochromium to nickel and originally designated as Inconel, was first offered in 1932 to the dairy industry for its resistance to corrosion

by milk [600]. It is now designated as Inconel

alloy 600 with a slightly different composition.

Nickel contributes in high degree to its resist- ance to corrosion by many inorganic and or- ganic compounds throughout wide ranges of

acidity and alkalinity. Chromium confers re- sistance to sulfur compounds in the atmosphere

or in many other corrosives; it also provides

resistance to oxidizing atmospheres at elevated

temperatures, and to oxidizing conditions in

corrosive solutions. Its chromium content

makes it superior to pure nickel under oxidizing
conditions, while at the same time its high

nickel content enables it to retain a considerable

corrosion resistance under reducing conditions.

Inconel alloy 600 has been used for the alkaline

digesters in paper making [601], in petroleum

refineries [602] , and in the soap and fatty acids

industry [220], as well as many other applications. It shows excellent resistance to sulfur

dioxide but is corroded by hydrogen sulfide

[603]. Moore and Mason [604] reported that

Inconel alloy 600 was more resistant than stainless steel to lead bromide vapor at 1,350 to 1,650

°F, and Farber et al. [605] found that it was

the most resistant, of all the metals tested, to

nitric acid at temperatures up to 1,700 °F. According to Johnson et al.[606], the wear and

sliding fraction properties of cast Inconel alloy

610 against ball-bearing steel (SAE 52100)

compared favorably with the performance of

nodular iron. Weldments made in inert gas with

Inconel filler metal 62 welding rod were better

than those made with a metal-arc coated elec- trode when the weldments were tested at 1,800

°F, but both procedures were equally good when

the weldments were tested at 1,400 and 1,600

°F [607].

Some of the room-temperature mechanical

properties of Inconel alloy 600 are tensile

strengths ranging from 80,000 to 100,000 psi

for annealed rod and bar to 165,000 to 185,000

psi for spring-temper wire. Corresponding yield

strengths are 25,000 to 50,000 psi and 150,000

to 175,000 psi, with elongations in 2 in of 50 to 35 percent and 10 to 2 percent, respectively

[608] . The strength properties at elevated temperatures are summarized in tables 37, 38 and

39.

Inconel alloy 600 has excellent properties at subzero temperatures. The strength factors in- crease considerably without appreciable change

in ductility factors and toughness. Some low

temperature properties are summarized in

table 40.

The addition of aluminum and titanium to Inconel alloy 600 confers the ability to age

harden, and additions of niobium further stiffen

the matrix and stabilize the carbides. Inconel

alloy X-750, formerly designated Inconel X al- loy, is the age-hardening variety of Inconel

alloy 600. This alloy was developed to have a

Table 37. Tensile properties of hot-rolled Inconel alloy 600 al elevated temperatures [608]

Temperature Tensile strength Yield strength (0.2%)

Elongation

in 2 in Modulus of

elasticity

op psi psi % 10^ psi 70 90,500 36,500 47 31.0

600 90,500 31,000 46 29.5 800 88,.500 29 , 500 49 28.0

1000 84,000 28,500 47 26.8

1200 65,000 26,500 39 25.5

1400 27,500 17,000 46 24.0

1600 15 , 000 9,000 80 22.5

1800 7,500 4,000 118 21.0

Table 38. Creep properties of Inconel alloy 600 [608]

Temperature. °F

Stress (psi) for secondary creep rate of

0.01% per 1000 hr 0.1% per 1000 hr

Cold

drawn,

annealed

Hot

rolled Coarse

grained" Colddrawn, annealed

Hot

rolled Coarse

grained"

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800 1900 2000

2100

30,000

18,000 6,000 3,400

2,200

1,400 970

660 450

47,000

29,000

13,000

7,800 8,000 4,700

2,300

770 460

260

340

40,000

28 , 000

12,500 6,800

54,000

40,000

25,000

12,000 9,500

6,200

3,600

1,500 750 420

560

4,666

3,500

2,800

1,700 810

350

5,000

880

3,200 2,000

1,100 340 560 560

160

100

160 100160

100 270

170 270170 270170

» 2 hr at 2050 °F, air cooled.

Table 39. Stress rupture properties of Inconel alloy . 600 bar [608]

Temperature, °F

Stress (psi) to produce rupture in

10 hr 100 hr 1,000 hr 10,000 hr 100,000 hr

Cold-drawn, annealed

1000 1200

1400 1600

1800 2000

74,000

34 , 000

13,000

7,500 4,400 2,100

50,000

23,000

8,400

4,800

2,800

1,400

34,000

14,500 5,600

3,000

1,800

« 920

» 23 , 000 "9,400

» 3 , 600

" 1,900

1 ,150

» 620

" 16,000 "6,000

"2,400

"1,200

» 730

" 400

Hot rolled, annealed (2 hr at 1650 °F)

1350

1600 1800 2000

20,000

8,100 4,400

2,100

13,500 5,300 2,800

1,400

9,200

« 3,500

1,800

» 920

"6,400

"2,200

1,150 "620

"4,400

• 1,500

" 730

» 400

Coarse grained (2 hr at 2050 °F, air cooled)

13.50 1500

1600

1800 2000 2100

19,000

11 ,500 8,000

4,400

2,100

1,600

14,800 8,000

5,300 2,800

1,400

1,100

9,800

5,600

" 3 , 500

1,800

» 920

" 7,000 "4,000

" 2,300

1,150

" 620

"5,000

« 2,800

" 1 , 500

" 730 "400

" Extrapolated

Table 40. Mechanical properties of Inconel alloy 600 bar

at low temperatures [608]

Yield Elon- Reduc- Chirpy

Condition Temper- Tensile strength. gation tion impact.

ature strength (0.2%) in of (V- 2 in area notch)

op psi psi % % fl-lb Annealed 70 93 , 800 36,800 37.3 64.1 236 -110 106,400 42,400 39.8 64.0 206 Hot rolled 70 87,000 42.5 71.9 213 -315 116,800 51.0 72.7 169 Cold drawn 70 145,000 10.0 35.1 69 50% -315 182,000 10.0 49.5 61
Table 41. Some properties of age-hardened " Inconel alloy X-750 bar stock [608]

Temperature

Tensile properties Creep strength,

stress (psi) to produce an elongation of

Stress-rupture strength,

stress (psi) for rupture in Modulus

of

elasticity

Endurance

limit Tensile (10« cycles) strengthYield

strength CO.2%)Elongation

in 2 in Reductionin area 0.1% per

1,000 hr 0.01% per1,000 hr 100 hr 1,000 hr

70 600

1000

1200 1350

1500

psi 162,000

154,000

140,000 120,000 92,000

52.000

psi 92,000 88,000

84,000

82,000

74,000 44,000

%

2428

22

9

7 22

%

30

3430

11

1234

10« psi 31.0

28.7

26.7 25.5

24.4

23.1

psi

115,000 80,000

50,000 28,000

110,000 68,000

40,000

18,000

63,000 38,000

18,000

54,000 30,000

14 , 000

55.0

48.5 36.0

« Solution treated 2100 "F for 4 hr, aged 1550 "F for 24 hr, and re-aged 1300 °F for 20 hr, air cooled.

low creep rate under high stresses at 1200 to 1500 °F after suitable thermal treatment and a

considerable portion of its high-temperature

strength is retained at temperatures up to 1500

°F. It may be used as spring material at moderately elevated temperatures. Above 1500 °F

:he creep strength falls off rapidly and the re- sistance to oxidation is inferior to that of alloy

300. Some properties of alloy X-750 are sumpiarized in table 41.

Inconel alloy 625 is a high strength corrosion

resistant material in which the nickel-chromLum matrix is solid-solution strengthened by

additions of molj^bdenum and columbium

[608a] . Figures 55 and 56 show the tensile and

itress-rupture properties, respectively, of this

alloy.

Inconel alloy 700 has excellent high-tempera-

;ure strength characteristics and good oxidation

and corrosion resistance. Its major use is for

Dlades in aircraft jet engines, but the material is jseful in many additional applications because

)f its unusual high-temperature properties

|X609].

|i Inconel alloy 702 is a nickel-chromium base

ijalloy that contains relatively high aluminum

160

140

120

•g. 100 g

d 60

40

20

i 0

Tttnatle S trength

Yiel S Strang th.CL2^( Offset

Elon gotion

0 200 400 600 800 1000 1200 1400 1600 1800 2000 TEMPERATURE .°F

IGURE 55. Tensile properties of Inconel alloy 625 [609],

(Hot roiled 9/16 in rod. annealed 1 hr at 1600 °F.)

content for excellent resistance to oxidation at

elevated temperatures. At high temperatures

the surface of a nickel-rich, nickel-chromium

alloy becomes covered with a compact layer of

uniformly thick oxide; the presence of aluminum improves the protective action of the oxide.

Inconel alloy 718 is a nickel-chromium-ironmolybdenum alloy made age-hardenable by the

addition of niobium. It has a number of unique

characteristics which distinguish it from the

family of nickel-chromium-iron alloys hardened

by aluminum and titanium. These are exceptionally high yield, tensile, creep, and rupture

strengths at temperatures up to 1300 °F; good

ductility in the temperature range of 1200 to 1400 °F, and sluggish response to age hardening, which permits annealing and welding without spontaneous hardening during heating and

cooling. It may be pickled in the age-hardened

condition without intergranular attack and can

be repair welded in the age-hardened condition.

Inconel alloy 718 is annealed at about 1750 °F

and aged 1325 °F. The ageing time is quite

long—16 hr. Some of the mechanical properties are summarized in figure 57. IN-102 is essentially a nickel-chromium-iron

base alloy (15% Cr, 7% Fe) solid-solution

strengthened with 3 percent columbium, 3 percent molybdenum, and 3 percent tungsten. It

olOO

OHot Rolle AHot Rollec Hot Rollef

i+ I6C I+2IC

iO°F/llir. )0°F/lhr.

—-^O-n

n

00°F

I500° F

00° F

I 10 100 1000 10,000 100,000 RUPTURE LIFE, HOURS Figure 56. Stress^upture strength of Inconel alloy 625

[609].

(Hot tolled 9/16 in rod, annealed 1 hr at 1600 °F.)

71
200

180

._ 160

1/1 °- 140 o

8 120

i" iOO i 80

uj^ 60

CO 40

20

0

Tensile Strength

1% Yield Str( ngtt %

(

\ l_J

Cl2%Yield Streng h -

' ptur e-l(DOG Hrs" Totol P iQSti c Cr sep- 100 0 Hrs ^

% RA

i

.1 %

60 t

40 P

20 Q

0 200 400 600 800 1000 1200 1400 1600 TEMPERATURE,°F

Figure 57. Tensile, creep, and rupture properties of Inconel alloy 718

(Bar stock annealed 1 hr at 1700 °F and aged 16 hr at 1325 T.)

was developed to meet the need for stronger

materials for steam turbine applications at 1200

°F. At this temperature, its 10,000-hr rupture

strength is 40,000 psi.

As may be seen from table 31, the Incoloy

nickel-iron-chromium alloys are characterized

by a much lower nickel content than the In- conel alloys, but the chromium contents are

higher. Incoloy alloy 800 is an austenitic solid

solution alloy and was developed to provide a

material of good strength and resistance to oxidation and carburization at elevated temperatures. Some of its more important uses are in

the industrial heating field for furnace equipment, baskets, trays, muffles, radiant tubes, etc.

in the petrochemical field for reformer and

cracker tubes; in the domestic appliance field as a sheath material for electrical resistance

heating elements; and in the food industry for

process equipment. Its corrosion resistance has

led to its use in a variety of corrosive environments. Incoloy alloy 825 (formerly designated

Ni-O-Nel alloy) was developed to handle a wide

variety of corrosive solutions, some of unusual

severity. Many of the successful applications of

Incoloy alloy 825 are in the handling of sulfuric

acid solutions in a variety of processes where

few other materials have adequate corrosion

resistance.

The various Inconel alloys and Incoloy alloys are amenable to fabrication by forging, machining, and welding. Typical stress-rupture values are shown in figure 58. A condensed review of

nickel-base alloys was written by Kihlgren

[611].

Wick [612] patented an alloy suitable for

valve-seat-insert castings containing 0.85-3.5

percent total carbon, 0.5-3.0 percent Mn, 1.5- 3.5 percent Si, 5-20 percent Cr, 4-12 percent

Mo, 4-12 percent Co, 4-12 percent W, 0.2-6.0

percent Cu, 0.2-4.0 percent Al, 5-35 percent Fe,

remainder Ni. The alloy is stated to be resistant

to thermal cracking at temperatures in the region of 1500 °F, to have good hot-hardness properties and high-temperature impact resistance,

and to be stable at high temperatures. Its expansion characteristics are compatible with

those of the engine block in which the valve seat

is inserted, it retains a good seal, is resistant tc corrosion by the hot exhaust gases of an internal

combustion engine, and it can be used for heavyduty applications if required.

d. Other High-Nickel Alloys

The first of the high nickel corrosion-resistant

alloys known as Hastelloy alloys were nickelmolybdenum-iron alloys, but in subsequent al- loys the composition was considerably changed

The nominal compositions of some of the Hastelloys as given by Fritzlen [613] are shown in

table 42.

Table 42. Nominal compositions of Hastelloy alloys [613, 613a]

Alloy Percent

Ni Mo Fe Cr W Si Cu Others

Hastelloy alloy B_

Hastelloy alloy C_

Hastelloy alloy D_

Hastelloy alloy F_

Hastelloy alloy G.

Hastelloy alloy N.

Hastelloy alloy W.

Hastelloy alloy X_

62 28 5 54 17 5 15 4 85 10 3 47 7 17 22 44

70

6.5

17

20

5

22.2

7

1.0 max 2.0 Co 2.5 max.

2.1 Cb +Ta

62 24.5

9 5.5 5 47 18 22

The Hastelloy alloys are not high-strength al- loys, although many of them retain such a high

percentage of their room-temperature strength

at very high temperatures that structural applications at high temperatures are not unusual.

Their strengths vary, depending on composition

and form, but generally these alloys have tensile

strengths in the neighborhood of 100,000 psi

and yield strengths of approximately 50,000 psi.

They are used, however, primarily for applications requiring exceptional corrosion resistance.

The Hastelloy alloys are amenable to fabrication

by forming and welding.

Hastelloy alloy B is notable for its unusually

high resistance to all concentrations of hydrochloric acid at temperatures up to the boiling

point. It is also resistant to other nonoxiding

acids and salts, and has valuable high-temperature properties in that it retains over two-thirds

of its room temperature strength at 1600 °F in

oxidizing atmospheres (not oxidizing solutions)

It may be used at high temperatures in reducing

atmospheres. It should not be used for strongly

oxidizing acids or salts. Hastelloy alloy C possesses an unusual degree

of resistance to oxidizing solutions, especially

those containing chlorides, and to hypochlorite

solutions and moist chlorine. It resists nitric,

hydrochloric, and sulfuric acids at moderate

72
Typical Stress for 1000 Hour Rupture Life At Various Temperatures

INGONEL

INCONEL

INCONEL

INCOLOY

INCONEL

INCONEL

NI-O-NEL

INCONEL

INCOLOY

INCOLOY

INCONEL

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

700

718

X-750

901

625

702

825

604

800

804

600

1200° F.

Str 10^ INCONEL

INCONEL

INCONEL

INCOLOY

INCONEL

INCONEL

INCOLOY

INCOLOY

INCONEL

INCOLOY

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

700

X-750

718

901

702

604

825

804

600

800

1350°F.

Stress X 10 psi INCONEL

INCONEL

INCONEL

INCONEL

INCONEL

INCOLOY

INCONEL

INCOLOY

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

700

751

x-750

702

604

804

600

800

1500°F.

0.5 1 1.5 2.5 3 Stress X 10* psi

3.5 4.5 INCONEL

INCONEL

INCONEL

INCONEL

INCOLOY

INCONEL

INCONEL

INCOLOY

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

Alloy

700

751

X-750

702

804

604

600

800

1600°F.

2.5 5 7.5 10 12.5 15 17.5 Stress X 10^ psi INCONEL

INCONEL

INCONEL

INCOLOY

INCOLOY

Alloy

Alloy

Alloy

Alloy

Alloy

700

702

600

804

800

1800°F.

0.5 1 1.5 2 2.5 3 3.5 Stress X 10'' psi

4 4.5

Figure 58. Typical stress for 1000-hr rupture life of nickel alloys at various temperatures lAS"]. temperatures, has excellent resistance to many

corrosive organic acids and salts, and is re- sistant to oxidizing and reducing atmospheres

up to 2000 °F. It should not be used above 120

°F in nitric and hydrochloric acid and salt combinations. An extensive study of the effect of

heat treatment on the corrosion resistance of

this alloy was reported by Streicher [614].

The most important property of Hastelloy al- loy D is its resistance to all concentrations of

hot sulfuric acid. It is also resistant to hydrochloric acid under mild conditions and to other

nonoxidizing acids and salts. It should not be

used under oxidizing conditions at elevated

temperatures.

Hastelloy alloy F withstands the corrosive ef73
feet of acid and alkaline, and oxidizing and re- ducing conditions. It is especially resistant to stress-corrosion cracking in chloride solutions.

A major use has been for lining sulfite pulp

digesters and in semichemical pulping processes.

Hastelloy alloy G is used primarily for nuclear fuel applications [613a]

Hastelloy alloy N (also designated INOR-8)

was developed for use as a container material

for molten fluoride salts. It has good oxidation

resistance in air up to 1800 °F. It is not recom- mended for nitric acid service.

Hastelloy alloy W is primarily a high-temperature alloy for extended structural applications

up to 1400 °F. It also has excellent short-time

strength at temperatures as high as 75 to 90

percent of its melting temperature.

Hastelloy alloy X has exceptional strength

and oxidation resistance up to 2200 °F and is useful for many industrial furnace applications

because of its resistance to oxidizing, neutral,

and carburizing atmospheres. It has had wide

use for aircraft parts such as jet engine tail- pipes, after-burners, turbine blades and vanes. Donachie and Shepheard [615] studied the

creep-rupture behavior of this alloy; their

stress-rupture curves are shown in figure 59.

Another group of high-nickel corrosion-resisting alloys are the Illium alloys [615a]. The

nominal compositions of some of these alloys as given by Johnson [616] are shown in table 43.

Table 43. Nominal compositions of some Illium alloys [616]

AUoy

Percent

Ni Cr Mo Cu

Illium B 50 28 8.5 5.5

Illium G 5668 22.5 6.5 6.5 lUium R 21 5 3

Illium 98 55 28 8.5 5.5

Illium R alloy is a wrought alloy, but the others are cast. All may be machined and welded.

The Illium alloys are characterized by high

resistance to sea water and to many fluorine

compounds. They should never be used for halogens, halogen acids, or halogen salt solutions.

e. Superalloys

The line of demarcation between heat-resistant (or high-temperature) alloys and superalloys is rather tenuous; as indefinite, indeed, as the dividing line between ferrous and nonferrous. Many of the superalloys are modifications

of the heat-resistant, corrosion-resistant alloys

and many of the nickel alloys already discussed

fall into the general category of superalloys.

Although attention will be directed mainly to those superalloys having nickel as a major, or

at least a significant, part of their composition,

it must be emphasized that the number of superalloys is legion, that most of them contain nickel,

and that a systematic approach to their classifi- cation has never been developed.

Grant [617] pointed out that single-phase al- loys such as Nichrome and Inconel alloy 600 are weak above about 1250 °F, but that their hightemperature strength and resistance to creep

are materially improved by the introduction of a stable, hard phase or phases, i.e., precipitated

carbides or intermetallic compounds. Most of

the high-nickel superalloys are of the Al-Ti

age-hardenable type. In these alloys, chromium

is present to provide oxidation resistance along

with some auxiliary strengthening. Columbium,

molybdenum, tungsten, and tantalum are often

present, separately or together, to provide solid

solution strengthening of the matrix. The major

part of the strengthening at high temperatures,

however, is due to the precipitation of the

Ni3(Al,Ti) compound, generally designated the

CLO

I CO

</) UJ

\-

(f)

100

I 10 100 1000

TIME FOR RUPTURE-HOURS

Figure 59. Stress-rupture curves for Hastelloy alloy X [tfJ5].

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NICROTUNG

ALLOY 713C

CAST ALLOYS

M-252

IN-100

UDIMET 700 UDIMET 600

_ WROUGH

ALLOYS

- INCONEL

ALLOY 722

UDIMET 500 NIMONIC ALLOY 105 'INCONEL ALLOY 700

''HASTELLOY ALLOY R-235

^NIMONIC ALLOY 90 INCONEL ALLOY X-750

J \ I

I I I 0 1 5 6 7

Al + Ti, %

8 9 10 11 12

Figure 60. The effect of aluminum plus titanium content on the 100-hr rupture life at 1600 °F of several high-temperature nickel alloys \_618'\.

gamma prime phase. The remarkable strengthening effect of this compound on commercial

high-strength nickel alloys is indicated in figure

60. The improvement in the stress-rupture properties of some nickel-base alloys modified by

600 800 1000 1200 1400 1600 1800 TEMPERATURE, °F, FOR RUPTURE IN 1000 hr

Figure 61. Effect of modified compositions on the stress- rupture properties of some nickel-base alloys [57^].

Curve Additional elements Typical alloys

12 None - _ - Inconel alloy 600; 80 Ni-20 Ci- Inconel alloy 722 W; Nimonie

alloy 80. Hastelloy alloy C

M252, Waspalloy

Inconel alloy 700; Udimet alloy 500.

2.5 Ti, 0.6 Al

i 19 Mo, 5 W

4

5

2.5 Ti. 1 AI, 10 Co, 3 to 10 Mo2.5 Ti, 3 Al, 13,3 Co, 3 Mo

precipitation-hardening and alloying additions,

according to Ver Synder [574] , is shown in fig- ure 61. In some of the alloys cobalt is often present, replacing substantial amounts of nickel (or

iron) . In many alloys boron and zirconium are purposeful addition elements, importing improvements in high temperature creep properties and/or increased malleability. The status of

the cobalt- and nickel-base high-temperature al- loys was discussed by Sharp [618].

The high-temperature strengths of the superalloys increase the difficulty of hot working, and

alloys with extra-special properties require

extra-special care in forging. The selection of

tools, cutting fluids, and machinability data for

machining superalloys was discussed by Halverstadt [619]. Because of forming difficulties, some of the nonferrous superalloys, especially

those high in aluminum, titanium, cobalt, tungsten, and molybdenum, are used in cast or investment-cast forms [620].

Table 44 gives a listing of the names and

compositions of many nickel-bearing superalloys as listed by the International Nickel Company [621] and their strengths at elevated temperatures are summarized in figure 62. This

reference contains considerable additional in- formation on both the physical and mechanical

properties of the alloys noted in table 44.

An extensive compilation of the compositions

and strengths of superalloys was prepared by

Simmons and Metzger [622] and a review of

the properties and treatments of nickel-chromium high-temperature alloys was written by

Young [623]

Maxson [624] described a general purpose

alloy (45% Ni, 25% Cr, 3% W, 3% Mo, 3% Co,

1.25% Si, 0.08 % C max, bal Fe) for use in a

76
TEMPERATURE, °F

Figure 62. Temperature to produce rupture in various high temperature

alloys in 100 and 1000 hr at a stress of 20,000 psi [6211^.

' broad high-temperature range. He gives the fol- lowing 100-hr stress rupture values:

I 1350 °F 23,000 psi

1400 18,500

1450 14,500

1500 10,500

I 1550 9,050

; 1600 7,200.

Freche et al. [625] reported that the strongest

" alloy obtained in their investigation (8% Ta,

6% Cr, 6% Al, 4% W, 4% Mo, 2.5 7f V, 1% Zr,

0.125% C, bal Ni) had as-cast rupture lives at a

stress of 15,000 psi as follows:

1800 °F 1,200 hr

1850 560

1900 185.

Ultimate tensile strengths of 80,000, 54,300,

and 49,200 psi were obtained at 1800, 1900, and

2000 °F, respectively. This alloy also exhibited

extremely limited workability.

77
TD nickel is pure nickel strengthened by a dispersion of 2 percent thorium oxide. Anders

et al. [626] describe its characteristics as fol- lows : "Stress-rupture and creep strength better

than superalloys from 1900 to 2400 °F.

"Properties insensitive to overheating.

"Easily fabricated.

"Notch insensitive, good impact and fatigue

properties.

"Physical properties similar to wrought

nickel; high thermal conductivity.

"Lack of intergranular attack in oxidizing

and corrosive media.

"Resistant to oxidation and corrosion."

Stress-rupture data for TD nickel are shown in

figure 63. The metallurgy and properties of

thoria-strengthened nickel were reviewed by

Rice [627].

Mechanical properties at high temperatures

are the principal basis for evaluating superalloys, but physical properties such as coefficient

of expansion, thermal conductivity, and emissivity are important in many high-temperature

applications. Thermal stresses due to differential expansion of single parts subject to different temperatures, or of different parts at a joint,

may comprise 50 percent of the total load and

have been responsible for many cases of failure

[628] . In general, a low coefficient of expansion

is desired ; in the case of dissimilar metal joints,

the two coefficients may be high or low as long

as they are equal. Thermal conductivity be- comes critical in applications such as combustion chambers, especially when uneven combustion produces hot spots. Since most high-temperature alloys have comparatively low thermal

conductivity, differential heating and hot spots can easily lead to severe distortion and actual

burning through of the metal [628] . The Inter- national Nickel Company, Inc. has tabulated

1200 1600 2000

Temperoture (°F) 2400

Figure 63. lOO-hr stress-rupture strength of TD nickel [626].

(few

lidiice

Sty an

fflrfe

data on the physical properties of interest oJ the various nickel superalloys [621].

T f. Nickel -Copper Alloys

Nickel and copper form a continuous series f of solid solutions, as indicated by the phase

diagram established by Guertler and Tammann

[629] in 1907 and subsequently confirmed by'

other investigators ; Pilling and Kihlgren [630]'

presented the diagram shown in figure 64. ThCj,

solid solution alloys have a face-centered cubic' structure and the lattice constant varies linearly

with atomic concentration from 3.60 A for cop- per to 3.54 A for nickel. The only transition ir the solid alloys is the magnetic transition, which

varies with the weight percent of nickel from

353 °C for nickel to 25 °C for 70/30 Ni-Cu tc' about -170 °C for 50/50 Ni-Cu.

Impurities affect the physical and mechanical ^ properties of the high-nickel alloys in much the* same manner is they affect nickel. The carbon"

content must be kept low to avoid precipitationof free graphite with consequent intercrystal-- " line brittleness. Additions of carbide-formingf®^

elements, such as manganese or titanium, reduce

the amount of graphite precipitation. Sulfur is extremely harmful in these alloys and must be

kept low. Lead in the presence of silicon coarsens

the structure and causes cracking, particularly'

in sand-cast materials. Controlled additions of

silicon, manganese, magnesium, and zinc ard

beneficial in most of the alloys.

The corrosion resistance of the nickel-copper

alloys that contain more than 50 percent nickel are benefited by the high degree of nobility of

copper and by the ability of nickel to protect

itself, frequently through the development offTM

passive oxide films. Such alloys are, in general,

more resistant than nickel under reducing con-i ditions and more resistant than copper under

oxidizing conditions.

(1) Monel alloys. The most important of the

high nickel-copper alloys are the Monel alloys

According to Mudge [631], in the early days of

the nickel industry attempts were made to prO'

duce alloys from the Sudbury ores directly,

without separating the copper and nickel. R. C

Stanley in 1905 perfected a process of oxidizing

i. cm

iiiiiti

iteri!

1600

40 60

NICKEL,

H2800 o.

UJ 2600 5

2400 <

cr 2200 ^

2000

p

00

Figure 64. The nickel-copper phase diagram 1630}.

78

iiric

lii

tomi

«1
4ne matte, which contained roughly twice as

j^uch nickel as copper, reducing the oxidized

I jiatte with charcoal, and adding magnesium to toduce a wrought alloy that was silvery white

g.nd brighter than nickel, stronger than mild

^tee\, and notably resistant to sulfuric acid and

rtO sea water. The new alloy was named Monel

honor of Ambrose Monell, then president of

fr'fhe International Nickel Company.

a The first large order for this alloy was for

piieet which was installed in 1909 as roofing for

inrie Pennsylvania Railroad station in New York

ity and was still free from trouble in 1955

^;631]. Intensive research developed everi^'idening use of this engineering material and

^^<y 1955, according to Mudge, there were 800

tt-iBcorded uses of Monel alloys, with corrosion

esistance responsible for the majority of them.

2^ij!*hroughout the development of the family of

jfLIonel nickel-copper alloys, additions of chrojLiiium, manganese, aluminum, iron, molybT^enum, tungsten, titanium, and other metals

ll'ere tried for increased strength and for other

v^easons. In the 1920's it was found that addill ons of about 4 percent of aluminum made the

Uasic alloy age hardenable [632]. It is now

j^jiown that 16 different elements confer age-

^i^rdening characteristics on nickel and highi^^ ickel alloys, the most important being alumiVum, titanium, columbium, and silicon, with

.|iiagnesium, molybdenum, tungsten, and berylj um used to a lesser extent. The age-hardened

:,[;Ionel alloys are readily fabricated in the soft

jj;,ondition and can be hardened to strength levels

" Dmparable to those of quenched and tempered

Hoy steels and still retain their resistance to orrosion. Nominal compositions of the various

"lonel alloys that are currently available from

nternational Nickel are shown in table 31 and

,ieir physical properties are shown in table 32.

The Monel nickel-copper alloy metals have

jSeful resistance to neutral and alkaline salts,

-xidizing alkaline salts (except hypochlorites),

^ulfuric, hydrochloric, hydrofluoric and phosphoric acids (the alloys have useful resistance

O corrosion by all acids except those that are

ighly oxidizing) , organic acids and compounds,

..end alkalies. The alloys are not resistant to 'xidizing acid salts, nitric and nitrous acids,

nd sulfurous acid. They are resistant to corro-

.ion by all common dry gases at room temperajre. They are not resistant to such gases as jromine, chlorine, nitric oxides, ammonia, and

rulfur dioxide in the presence of appreciable

(mounts of water.

Monel alloy 400 is available in all commer-

;ial forms and tempers. It is characterized by

ood strength and ductility combined with

xcellent resistance to many corrosive environlents. The alloy is notable for its toughness

laintained over a wide temperature range,

losenberg [323] reported a Charpy V-notch

Tipact value of 180 ft lb at -78 =C. Sixty years

af experience has established this alloy as a standard engineering material. It is a general

purpose alloy used in many industries. Some

typical applications are crude petroleum stills, process vessels, piping, pump and propeller

shafts, gasoline and fresh water tanks, boiler

feed water heaters, heat exchangers, deaerating

heaters, valves and pumps, chemical processing

equipment, marine fixtures, and electrical and

electronic components.

Monel alloy 400 gives excellent service in sea or brackish water under high-velocity conditions, as in propellers, impellers, and condenser

tubes, where resistance to the effects of cavitation and erosion are important. Corrosion rates

in strongly agitated and aerated sea water

usually do not exceed 1 mpy. Another important

consideration in the use of the alloy in corrosive

environments is its general freedom from

stress-corrosion cracking. The limiting temperatures for use of alloy 400 in various environments are given in table 45.

Table 45. Limiting tem-peratures for Monel alloy 1^00

Service or environment

Air Carbon monoxide Hydrogen

Chlorine

Fluorine Hydrogen chloride Hydrogen Huoride Sodium, potassium, sodium-potassium (static) Steam

Temperature, °F

1000

1500 •2000 800

900

450

1200

1100 800

» Sulfur free. Do not exceed 500 to 600 °F if appreciable amounts of

^sulfur are present.

The results of the ASTM 20-year atmospheric

exposure tests of Monel alloy 400 as reported

by Copson [223], are shown in figure 65. Comparison with the results reported for nickel in

figure 30 shows that alloy 400 is equally excellent in resisting the less corrosive atmospheres

and is markedly superior to nickel in resistance

to the industrial atmospheres of Altoona and

New York City. In the ASTM 20-year tests, specimens of the alloy exposed at Altoona decreased 16 percent from the preexposure tensile

strength of 80,000 psi, those at New York 11

percent, those at Sandy Hook 5.5 percent, and

the changes in tensile strength at the other

four stations were of the order of ±1 percent.

According to Grant and Bucklin [634], Monel

alloy 400 has very good resistance to oxidation

at temperatures up to about 900 °F. From 900

to 1300 °F the surface scale is still thin and very

adherent, but grain boundary penetration of

oxide is evident. Above 1500 °F the bulk oxide

grows rapidly, remains adherent and apparently

quite dense, but is poorly protective.

According to Jenkins and associates [315],

the 70/30 Ni/Cu alloy has the best high-temperature strength of the straight nickel-copper

alloys, as shown in figure 66. This alloy also has

79
E

-a

O

Ul STAT

jolla\

E COLLEGE

KEY WEST

;^HOENIX

8 12 16

EXPOSURE TIME, yr

20

Figure 65. ASTM 20-year atmospheric exposure tests of Monel Alloy hOO

[223].

NICKEL, ATOMIC %

100 0

I I I 30000

20000 - -150000

25000

75 100 0 25

NICKEL % BY WEIGHT

Figure 66. Effect of nickel content and test temperature on the yield and

tensile strengths of initially annealed specimens of the copper-nickel system

[315].

the greatest resistance to creep [346,348]. The

stress required to produce equal second-stage

creep rates at different temperatures is significantly higher for the 70/30 Ni/Cu alloys as annealed (fig. 67) or as cold drawn 40 percent

(fig. 68) than for any other of the nickel-copper

alloys. Creep rupture curves for Monel, from

data by Grant and Bucklin [634] , are shown in

figure 69.

The effect of temperature on the elastic constants of Monel alloys 400 and K-500 is shown

in figure 70.

Monel alloy 401 has a low temperature coefl^cient of electrical resistivity. It ii used in

the manufacture of wire-wound resistors.

Monel alloy 402 is used for fixtures in operations for pickling steel and copper alloys. It is resistant to hot sulfuric acid pickling solutions

and to hydrogen embrittlement when it is galvanically coupled to steel. In Monel alloy 403, the nickel, iron, and manganese contents are so adjusted that the alloy

remains nonmagnetic at the freezing point of

80
70000

60000

50000

z

_J 40000

on

LU 30000

q:

h- 20000

10000

K

0

loi 1000 HR 10d%/l'000'HR

50 100 0 50 100 0 NICKEL, % BY WEIGHT

50 100

Figure 67. Variation of stress with nickel content in Ni-Cu alloys to produce

equal second-stage creep rates at different temperatures of the annealed

metals [346].

50 100 0 50 100 NICKEL, PERCENT BY WEIGHT

Figure 68. Variations of stress ivith nickel content in Ni-Cu alloys to produce

equal second-stage creep rates at different temperatures of the cold-drawn

(40%) metals [3^8].

81
0.01 I 10 CREEP-RUPTURE TIME.hr

000

Figure 69. Stress versus creep-rupture life for annealed Monel alloy 400 at 700 to 1300 °F [634}.

sea water (27 °F). It was developed for use in

mine-sweepers.

Monel alloy 404 is characterized by low magnetic permeability and excellent brazing characteristics. Residual elements are controlled at low levels to provide a clean wettable surface even after prolonged firing in wet hydrogen.

Its permeability (typically 1.004 at room temperature, 200-Oe field strength) is not significantly affected by processing and fabrication.

This property makes it particularly suitable for

electronic applications. The alloy has low vapor

pressure, thermal expansion characteristics

compatible with other metals, and strengths at outgassing temperatures. It finds use as wave

guides, transitor capsules, metal-to-ceramic

seals, and power tubes.

Monel alloy R-405 is similar to Monel alloy

200

TEMPERATURE, °F

400 600 800 1000

0.6 o

0.4

0.2 o

If) —o

a. 0 100 200 300 400 500 600 700

TEMPERATURE,

Figure 70. Effect of temperature on the modulus of

elasticity (E), the modulus of rigidity (G), and Poisson's ratio (tJ-) of Monel alloy 400 and Monel alloy

K-500 [635].

400 in all respects except that a controlled

amount of sulfur is added to improve machining

characteristics. It is designed particularly for use with automatic screw machines. Typical applications are for water meter parts, valve seat

inserts, screw machine products, and fasteners

for nuclear applications.

Monel alloy 406 is used particularly for its resistance to corrosion from some mineral

waters. It finds application in hot-water tanks.

Monel alloy 474 is a relatively new highpurity nickel-copper alloy. It is essentially free

from nonmetallic inclusions. It is nonmagnetic

and its low permeability is not substantially affected by processing and fabrication. The alloy

has good formability and superior brazing characteristics even in a wet hydrogen (high dew

point) atmosphere. Its typical applications are

the same as those for Monel alloy 404.

Monel alloy K-500 is an age-hardenable

nickel-copper alloy with a long history of successful industrial use. Heating the solutiontreated alloy at 1080 °F precipitates small particles of Ni3(Al, Ti), which increase strength

and hardness. Higher properties are achieved

when the alloy is cold worked prior to age hardening. This alloy has good mechanical properties over a wide temperature range. Strength,

toughness, and ductility are retained at —423

°F as indicated in table 46, and it is nonmagnetic to temperatures below —210 °F.

Monel alloy 501 is similar to alloy K-500 in

all respects except that it has improved machinTable 46. Tensile properties of Monel alloy K-500 {aged

sheet) [43]

Room

temp. -100 °F -320 °F -423 "F

Tensile strength psLVield strength psi-- 154,000 97,000

22

166,000

107,000

24

183,000 120,000 30

200,000

136 , 000

28

82
ling characteristics. This is achieved through use

I of a higher carbon content and controlled heatiing which results in precipitation of graphite

j particles in the material. It is designed particui larly for use at high production rates with automatic screw machines.

' The nominal range of mechanical properties

for some of the Monel nickel-copper alloys is

I given in table 47.

ITable 47. Nominal range of mechanical properties of Monel alloys (wrought rods and bars) U3]

1000 psi

Jiilon- Bnnell Monel Temper gation hardness

Tensile 0.2% in 2 number.

strength yield in, % 3.000 kg

strength

Hot finished. 80- 95 40- 65 45-30 140-185 |400 Cold drawn, stress relieved. 84-120 55-110 35-22 16J-225 Annealed . 70- 85 25- 40 50-35 110-140

[402 Hot finished 70- 95 25- 65 45-30 130-185

land Cold drawn, stress relieved. 75-120 45-100 35-15 150-225

J403 Annealed.. 65- 85 23- 40 50-35 100-140

R-405 Hot finished.. . . 75- 90 35- 60 45-30 130-170 Cold drawn - . 85-115 50-100 35-15 160-240 Annealed. . . -. 70- 85 25- 40 50-35 110-140

jK-500 Hot finished-- .. 90-135 40-110 45-20 140-160 Hot finished, age hardened 140-170 100-125 30-17 265-330 Annealed .- .. 90-110 40- 60 45-25 140-185

Annealed, age hardened- 130-160 85-110 30-20 250-auo

Cold drawn. 100-135 70-100 35-13 175-26J

Cold drawn, age hardened. 135-180 95-130 30-15 255-3:^5

3.3. Low-Nickel Alloys

a. Copper-Nickel Alloys < The copper-nickel alloys find a variety of uses because of their combinations of physical and

mechanical properties and their excellent re-

' iisistance to saline water corrosion. The oldest use

^

! "was for coinage, the largest use today is in

marine applications, particularly heat-exchange

equipment. Some other uses depend upon the

nonmagnetic characteristics of the alloys, their

electrical resistance, and their thermal electromotive force in relation to other metals or al-

' |ioys. A comprehensive review of the properties,

^ 1 'fabrication, and applications of copper-nickel al-

; j'loys was written by Nothing [636] . In a general

fashion, the strength properties decrease as the

) nickel content decreases [637,713]. Electrical

^ iiresistivity follows the same pattern. The prop-

' 'erties of cupronickels at temperatures from

'—300 to +1500 °F were surveyed by Pritchard

" f[638].

(1) Coinage alloys. Feely [639] reported that

^ Ithe total use of nickel in coinage from 1850 to

' 1955 was 65,646 tons. The alloy that accounted

for the great bulk of the nickel consumed was

7 the traditional coinage alloy of 75 percent copper and 25 percent nickel. The 1954 uses of this

0 ' * The copper industry has recently adopted a standard numbering

t system for all copper-base alloys. In line with this arranuement.

BO/IO Cu-Ni is OA (copper alloy) 706; 80/20 is OA 710, 75/25 is

, CA 713, and 70/30 is OA 715.

alloy included the United States 5-cent piece,

the French 100-franc coin, and the United Kingdom's half-crown, florin, shilling, and sixpence.

Commercially pure nickel was used for some

coins in India and the Netherlands, and nickelclad steel was used in Israel. Low-nickel alloys

also were used, for example, 95 percent copper5 percent nickel in some of the coins of Columbia; silver-copper-zinc-5 percent nickel al- loys in Sweden and Australia; copper-aluminum-2 percent nickel in Finland and Denmark

;

and a copper-zinc-1 percent nickel alloy was

used in Pakistan, Paraguay, and the United

Kingdom. Because of the shortage of silver, the

dimes and quarters of the United States are now copper sandwiched between a 75/25 Cu/Ni

alloy—the overall nickel content of the coins is 8.33 percent.

(2) Cor7'Osion-resistant and engineering al- loys. All of the cupronickels have desirable

physical and mechanical properties and are re- sistant to corrosion in many media. Consequently, almost every possible composition from

1 to 50 percent nickel has been marketed under

one or more trade names, but the most widely

used alloys are classed, for specification purposes, in three groups:—the 70/30 (CA 715),

the 80/20 (CA 710), and the 90/10 (CA 706)

copper-nickel groups.

Cupronickels containing 10 to 30 percent of

nickel have long been noted for their resistance

to sea water, which led to many marine applications, particularly in the field of heat exchanger

tubes, condensers, etc. For use in marine and

heat exchanger environments, the beneficial effects of small amounts of iron on the erosioncorrosion behavior have been well established

[640,641]. The iron contents for 70/30 and

90/10 copper-nickel have been standardized at

0.4-0.7 percent and 1.0-1.8 percent, respectively.

Addition of slightly less than 1 percent of manganese is useful for deoxidation and desulfurization during casting. Improvement in the resist- ance of the cupronickels to sea water, through

additions of iron, also was evident as improved

resistance to a variety of fresh and industrial

waters, well waters high in carbon dioxide,

boiler feed waters, etc. This led to improved

performance in powder plant applications, such

as steam condensation from turbines, and to ex- tended use in heat exchangers in the chemical

and petroleum industries. As LaQue [641]

pointed out, when alloys are used in heat ex- changer tubes with one side exposed to corrosives at high temperatures, reaction on the side

in contact with the corrosive is fully as significant as the attack on the water side. LaQue's

review of the resistance of the cupronickels to a variety of corrosive media included the fol- lowing : they resist sulfuric acid very well ; they

are resistant to brines in salt-plant operations

and to sodium hydroxide solutions but are at- tacked by fused sodium hydroxide at 750 °F;

83
they are superior to other copper-base alloys in

resisting ammonia and its compounds. The pres- ence of sulfides in high temperature hydrocarbon strains has limited use of copper nickels to the 70-30 copper nickel grade in refinery condensers. The presence of sulphides (from decay

of organic wastes in sea water) has led to wider

use of both the 90-10 and the 70-30 grades in

coastal power plant condensers in preference to other less resistant copper base condenser tube

alloys. In certain locations the concentration of

organic wastes is so great as to limit the service

life of copper nickel though they are often con- tinued in service under even these most adverse

conditions. Data were presented on their re- sistance to halogens and halogen compounds

other than brines. Ordinarily the cupronickels

have good resistance to chlorinated solvents, and

the 90:10 alloy is better than the 70:30 in re- sistance to miscellaneous organic compositions.

Their resistance to pulp and paper stock suspensions is superior to that of phosphor bronze ; in

miscellaneous uses in petroleum refineries their

performance is generally good at ordinary and

moderate temperatures, but the presence of hydrogen sulfide at elevated temperatures results

in severe attack.

Tice and Venizelos [642] reported that the

70:30 alloy showed the highest corrosion re- sistance of all the alloys they tested for use in

condenser tubes and Donachie [643] found that

the 70 :30 alloy offered usable strength above the

normal service range of 300 to 500 °F. Hopkinson [644] found that the addition of several

other metals increased the resistance of 70:30

to scale exfoliation, but that only silicon, beryllium, and columbium produced significant improvement. Simmons et al. [645] concluded that

the combination of strength, ductility, and cor- rosion resistance of Cufenloy 30 (30% Ni, 0.5%

Fe, 0.6% Mn, bal Cu) rendered it suitable for use in unfired pressure vessel applications at temperatures up to about 850 to 900 °F. Cufenloy 40 (56% Cu, 41% Ni, 2% Fe, 1% Mn) was

described as having properties sufficiently improved over those of Cufenloy 30 so that design

lilis

si

factors could be significantly increased [646]

An evaluation of the resistance to stress corro! sion of 28 common copper-base alloys le(^ Thompson [647] to the conclusion that the high;

J est resistance to stress corrosion was offered bj

tough pitch copper and 70:30 cupronickel

Szabo [648] showed that the 80/20 Cu/Ni allojl'^ was superior to aluminum brass, Admiraltjj jijfj brass, and 70/30 brass in resistance to stres; corrosion. The characteristics, properties, anc

applications of the cupronickels have been disj L cussed by Everhart [649] and by Shephen

[650], and the physical and mechanical proper

ties of the 70/30 alloy have been described bj

The International Nickel Company, Inc. [651]

The compositions and mechanical properties ai outlined in ASTM Specification Blll-66a foij copper and copper alloy seamless condense]

tubes and ferrule stock are given in table 48; Copper-nickel tubing has been commonly sup^jj^jj

plied and used in the as drawn condition, taking

advantage of its superior resistance to stresi cracking to gain practical advantages in den,

resistance and handling.

Mechanical properties of the cupronickels, ai was the case for the Monel alloys, improve a low temperature. For example, Geil and Car

wile [314] reported that the tensile strength o: annealed, high-purity 70/30 Cu/Ni increased ir almost linear fashion from 54,000 psi at roon temperature to 83,000 psi at —196 °C. The me

chanical properties of the cupronickels fall ofl at moderately elevated temperatures. Port anc Blank [652] discussed the creep characteristic; at 300, 400, and 500 °F of the 70 :30, 80 :20, anc 90 :10 alloys. They reported that the 90 :10 alloj was affected more than the others by increas

ing temperature within this range, anc

that the creep strength of the 90:10 alloj

containing 1.08 percent iron was double thai

of the 90:10 alloy containing 0.68 perceni

iron. Jenkins and co-workers [315,346,348]

studied the tensile and creep properties of highpurity 70/30 Cu/Ni alloys and some of theii

results have already been presented in the dis- cussion of the Monel nickel-copper alloys. Fig-

(-rit(

Table 48. Composiiions and mechanical properties of copper alloy condenser tubes as listed in ASTM specification Blll-66i

Composition, percent Minimum tensile requirements

Alloy Cu Pb Zn Mn Tensile Yield Elongation

(min) Ni max Fe max max Temper strength, strength. in 2 in., psi psi" percent

60-40

65-35-5

70-30

70-30 80-20

90-10

90-10

95-5

52.5

6065.0

65.0

74.0 86.5

86.5

91.2

40.0/43.0

29 . 0/33 .

29.0/33.0 29.0/33.0

19.0/23.0 9.0/11.0

9.0/11.0

4.8/ 6.2

0.05

.05

.05 .05

.05

.05

.05

.05

1.5 /2.5 4.75/5.75 0.40/0.70

.40/0.70

.5 /l.O

1.0 /I.

1.0 /I. 1.3 /I.

0.3

1.0

1.0 1.0

1.0

1.0 1.0

1.0

0.5 /I.

1.0

1.0

1.0

1.0

1.0

1.0 0.30/0.80

Drawn, stress relieved- Annealed . . . - - -- Annealed. _ .

.

. Drawn, stress relieved. _ Annealed . _ - - - Annealed . _ . Light drawn

Light drawn. . _ . . . . .

85,000

74,000 52,000

72 , 000 45,000 40,000

40,000

65,000

36,000

18,000 50,000

16,000

15,000 30,000

»>12 or 1530

^12 or 15

" At 0.5 percent extension under load. The lower value is for wall thickness up to 0.048 in., inclusive; the higher value is for wall thickness over 0.048 in.

*• No minimum properties established.

84 v. i
I^fbre 71, from the work of Jenkins, Digges, and

'"jiohnson [315], shows that the strengthening

;f¥ect of cold work upon the yield and tensile

: ; .trengths of the 70/30 Cu/Ni alloy is completely

•liminated at 1200 °F and above.

In Powell and Blanpied's review [123] of

hermal conductivities at low temperatures, the

"^/alues cited for the cupronickels are: for the

f-DO/lO alloy, 470 mW/cm deg K at room tem-

^ oerature, 380 at 80 °K, and 12 at 4.2 °K; for

^'-}he 80/20 alloy, 4.5 mW/cm deg K at 9 °K and

";.9 at 1.9 °K; for the 70/30 alloy, 290 mW/cm

? 'leg K at room temperature,

'r Hawthorne and Borth [653] describe a spedualized type of welding applicable to CA 715

fi:70/30 Cu/Ni) and The International Nickel

ompany. Inc. publishes a more general bulledn on welding and brazing [653a]

.

Bouillon and Stevens [654] observed that the

O xidation resistance of copper was improved by

5 -he addition of 5 and 10 percent nickel. A high-

''trength 70/30 copper-nickel contains 5 percent

"'ron [655]. Higher strength copper-nickel al- oys for military service have been described by

^orkin [655a]. Precipitation-hardening 70/30

]u/Ni containing beryllium is available in cast

r wrought form [655b]

.

The advantages offered by the 90/10 Cu/Ni

s a material of construction for seawater pipeines have been described [656,657]. Its use as sheathing material for wood piling in seawater has been advocated by Hunt and Schillmoller [658]

.

The 70/30, 80/20, and 90/10 alloys are used

as castings, as well as in the wrought form.

Vanick [659] and Shepherd [650] discussed the

production, processing, and use of castings.

The alloys that are called cupronickels in the

United States are called Kunifers in England,

with numbers to indicate the nickel content, for

example, Kunifer 30, Kunifer 10, Kunifer 5. Mechanical properties of the low-nickel cupronickels make them suitable for some ordnance

uses, for example, alloys containing 2.5 to 5

percent of nickel are used as driving bands and

the 15-percent alloy as bullet jackets.

(3) Thermocouple and electrical resistance al- loys; alloys for electHcal icse. The cupronickel

that contains 45 percent of nickel and generally

known as constantan, but marketed under a number of trade names, is useful as a thermocouple element. It has the highest thermal emf

against platinum of any of the copper-nickel al- loys [660] . It is used with copper and especially

with iron [661]. According to Roeser and Dahl

[662], the emf of the platinum-constantan

thermocouple increases regularly with increasing temperature to about 43 mV at 1800 °F (although the maximum temperature for this thermocouple use is 1650 °F) ; the iron-constantan

thermocouple produces higher emf values at any

particular temperature, for example, 57 mV at

100000

REDUCTION IN AREA BY COLD-DRAWING, %

Figure 71. Effect of cold drawing and test temperature on the yield and

tensile strength of 30:70 Ni:Cu alloy [SIS'].

85
1800 °F; the copper-constantan thermocouple

up to 750 °F produces emfs only slightly lower

than those of iron-constantan.

The curve of electrical resistivity versus composition reaches a maximum at 50 to 55 percent

of nickel, according to Shibuya [663] . Constantan has about the maximum resistivity of the

cupronickels and has been used as a heating ele- ment and as a resistance unit in rheostats and

electrical instruments. According to Guettel

[660], eonstantan has the highest electrical resistivity (50 microhm-cm) and the lowest temperature coefficient of resistance (±0.00002

from 68 to 300 °F) of any of the copper-nickel

alloys. The change in resistance may be either

positive or negative, depending on small variations in composition and on variations in the

amount of cold work. The maximum temperature for use as a resistor is 930 °F. Cupronickels

with lower nickel contents and correspondingly

lower resistivities are used for heating applications such as radiant heating panels, electric

blankets, etc., but the 45-percent nickel alloy is the outstanding cupronickel for this use. The nickel-base electrical resistance alloys

have been considered previously, but there are

several copper-nickel and copper-manganesenickel alloys that should be noted in this section.

The Metals Handbook [576] lists the alloys

shown in table 49 for use in electrical resistors.

Of these, manganin has been almost universally

adopted for use in the construction of precision

resistors, slide wires, and other components for

electrical measuring and control instruments.

Manganin is a stable solid solution. Its electrical

stability, verified by several decades of experience, is such that there is no more than 1 ppm

change per year when the alloy is properly heat

treated and protected.

Recently announced very pure 70/30 cupronickel [663a] is used for special electronic applications where residual metallic impurities

could interfere with the proper functioning of

the alloy.

b. Copper-Nickel-Zinc Alloj's (Nickel Brasses)

The copper-nickel-zinc alloys are of very old

origin, dating back to the paktong of ancient

a IS

Ciif

K

China. Early in the 19th century two alloys,'

"Neusilber" and "Argentan," which resembled

silver in appearance and were suitable for table- ware and culinary purposes, were developed in Germany and the name German silver was in general use until after World War I, when it was supplanted in the trade by the name nickel,

silver. The alloys also have been known as. nickelene. Inasmuch as the alloys do not contain

any silver whatever, the use of such designations as German silver or nickel silver is misleading, particularly to the layman, but the term

nickel silver has been firmly established in in- dustry. The alloys are properly and accurately

designated as copper-nickel-zinc alloys or as nickel brasses and are covered by the Copper'

Development Association numbers CA 730-790,

inclusive.

The addition of nickel to brass gradually

changes the normally yellow color to white sa

that at about 12 percent of nickel the typically

brass appearance is practically gone. According

to Grosvenor [664] , the alloys contain the three

major elements in the approximate ranges of! 45 to 75 percent copper, 5 to 30 percent nickel,'

and 5 to 45 percent zinc. The principal functions^

of nickel are to whiten the alloys, to increase'' the strength properties for given zinc contents,' to improve the resistance to corrosion, and to decrease the susceptibility of copper-zinc

brasses to stress corrosion. The single (alpha)

phase alloys have excellent ductility at rooni

temperature but only fair hot-working properties, whereas the two-phase (alpha-beta) alloys are hot workable over a wide temperature rangeji

but are not sufficiently ductile at room tempera-;'

ture to be cold worked extensively. Lead is oftens added to improve the machinability. [, The compositions and properties of selected^ nickel silvers, according to The Internationalt|iit

Nickel Co., Inc. [665], are given in table 50

The density of the alloys is about 0.31 Ib/in^j

the coefficient of thermal expansion is about/

9.1 X 10"*'/° F, thermal conductivity varies between 17 and 27 Btu/sq ft/ft/hr/°F, electrical!

conductivity varies between 5.5 and 10 percentj aJS lACS, the modulus of elasticity is about 18,000,-((

000 psi and the modulus of rigidity is about

6,800,000 psi.

me

Table 49. Physical properties of copper-nickel electrical resistance alloys [576]

Composition

Resistivity, ohms per eir mil-ft at 20 "CTemperature coefficient

of resistance, microhm/ohm/°C

Thermal emf

versus copper, microvolts per °C

Thermal

expansion, micro-in/°C

Tensile strength

at 20 °C, 1000 psi

Specific gravity

at 20 °C

Density,

lb per cu in

98 Cu-2 Ni

94 Cu-6 Ni

89 Cu-11 Ni

78 Cu-22 Ni

55 Cu-45 Ni (eonstantan) . _ . — 87 Cu-13 Mn (manganin) _ 83 Cu-13 Mn-4 Ni (manganin).

85 Cu-10 Mn-4 Ni (shunt manganin)

70 Cu-10 Mn-20 Ni

67 Cu-27 Mn-5 Ni

30

6090

180 300 290

290 230

294 600

-f 1500 ( 0 to 100 °C) + 800 ( 0 to 100 °C)

-1- 400 ( 0 to 100 °C) + 300 ( 0 to 100 °C) ± 40 (20 to 100 °C) ± 15 (15 to 35 "O

± 10 (20 to 35 °C) ± 10 (20 to 45 °C) ± 20 (20 to 35 °C) ± 20 (20 to 35 °C)

- 14 (0 to 75 °C) - 12 (0 to 75° C) - 24 (0 to 75 °C) -36 (0 to 75 °C) -42 (0 to 75 °C) + 1 (0 to 50 °C) - 1 (0 to 50 °C) - 1.5 (0 to 50 °C) -10 (Oto50°C) + 2 (0 to 50 °C)

17

1717

17

15

1919

19

1620

30 to 60 40 to 85 35 to 75 50 to 100

66 to 125 40 to 90 40 to 90

50 to 100

70 to 120

67 to 110

8.9 8.9

8.9

8.9

8.9

8.2

8.4

8.4

8.2 8.5

0.32

.32

.32

.32

.32 .30

.31 .31 .30

.31

il

]
I Table 50. Corn-position and mechanical properties of some

! nickel silvers {nickel brasses) [665]

i

Copper

Composition, percent

X leiQ strength (0.5% Tensile Elongation Rockwell

alloy No. Cu Ni Zn

Condition extension under

load), 1,000 psi

strength.

1,000 psi

in 2 in, percenthardness, B scale

CA 735 72 18 10 Annealed Hard

23 to 28

72 50 to 5879 40 to 50

4 38 to 5285 CA 752 65 18 17 Annealed

Half-hard Hard

25 to 30

62

74

58 to 60

74

85

32 to 40

8

3

40 to 55

8387 CA 754 65 15 20 Annealed

Half-hard Hard

18 to 28

62

75

53 to 61 74

85

34 to 43

10

3

22 to 55 80

87 CA 7fi6 56

- 12 31.5 Annealed Hard

24 to 29

82

56 to 63 98

32 to 43

3 40 to 55 88 CA 770 ">5 18 27 Annealed Hard

27

85 60

100 403 55

• 91 CA 774 45 10 45 Forged 36 83 25 73

lit!

I[ i

55,1 Kihlgren et al. [666] studied the physical

51 properties of cast nickel silvers and Vanick

il [667] reviewed the compositions, properties,

Si. and uses of leaded casting alloys. He reported

that tin strengthens and hardens the alloys,

2

; lead promotes machinability, zinc is a useful

I > deoxidizer, and that nickel is progressively beneli y ficial to the corrosion resistance, color, and mejj f; chanical properties.

I I The three most common copper-nickel-zinc alr

• loys contain 72, 65, and 55 percent copper, 18

- percent nickel and the remainder zinc. These

1 1 alloys have good resistance to corrosion by both

J ; fresh and salt waters. The resistance to corro-

-1 ] sion by saline solutions is usually much better

than that of brasses of the same copper content

a > because the relatively large amount of nickel ini 1 hibits dezincification.

<l 'i The mechanical properties, corrosion resisti' ' ance, and attractive appearance of these alloys

; i have led to a variety of engineering, decorative,

le i and architectural uses. They are used in spring

3

\ applications, in food-handling equipment, gift

5 \ and tableware usually silver plated, marine fitj, . tings, in the chemical industry, in musical, deni tal, and drafting instruments, slide fasteners,

and as the base metal for moderate priced jewI elry with or without plated coatings. The im-

: proved machinability and performance in blanka ing operations of the leaded alloys results in uses as parts of fishing reels, in cigarette lightj ers, and in grills and keys. According to Dume

[668], the electrical resistivity of the alloys con-

^ taining 5 to 30 percent of nickel increases with

increasing percentage of nickel, leading to their use in rheostats.

The cast alloys have many uses, including

ornamental plaques, architectural parts, fittings,

plumbing fixtures, valves, hardware, dairy and

soda fountain equipment, etc.

3.4 Miscellaneous Alloys

There are any number of nickel alloys that do

not fall into any of the categories discussed in

this report. Many of these were developed for

specific applications.

An alloy intended to satisfy the demand for a corrosion-resistant nongalling, nonseizing al- loy suitable for use at room temperature or at high temperatures in bearing and seal applications, even if lubrication is temporarily deficient, was patented by Parana [669]. Composition was given as 3 to 8 percent Ag, 3 to 9 percent Zn, 6 to 9 percent Sn, 3 percent Mn max,

0.3 percent C max, remainder Ni.

Teasel and Hoffman [670] patented a nickelbase alloy for spark-plug electrodes. The alloy

displays high resistance to erosion by electrical

discharge and to inter- and intragranular attack

when exposed to the temperatures and corrosive

conditions involved in operation or fabrication

of spark-plug electrodes. The range of composition is 90 percent Ni min, 0.5-3 percent Mn, 0.1- 2 percent Zr, 0.5-3 percent Cr, 0.2 to 1.5 percent

Si, 0.5 percent Fe max, 0.5 percent C max, 0.25

percent impurities max.

Foerster and Kopituk [671] described a series

of brazing and coating alloys with compositions

as follows

Alloy 50—93% Ni, 3.5% Si, 2.25% B, 1%

other.

Alloy 52—91% Ni, 4.5% Si, 3.25% B, 1%

other.

Alloy 53—82% Ni, 4.5% Si, 2.9% B, 7% Cr,

3% Fe, 0.5% other.

Alloy 56—71% Ni, 4% Si, 3.75% B, 16% Cr,

4% Fe, 1% other.

The alloys are intended for use in steam and

other valves, high-temperature jet and rocket

parts, roller parts, honeycomb mats, etc. Long [672] reported an investigation to develop nickel-base brazing alloys having good

ductility. The most promising alloys are shown

in table 51.

Table 51. Nickel-base ductile brazing alloys [672]

Composition—percent Liq- uidus temper- ature

Braze

flow temper- ature

Hardness, Ni Mo Si Mn Cr Sn Fe Rc

op op

61.0" 10.7 4.76 18.2 4.5 0.8 2080 2150 30-33

66.0" 16.2 7.65 5.9 3.5 .7 2050 2150 40

54.7" 14.0 5.8 25.0 1925 44

69.7>> 13.7 6.9 8.3 1.3 2100 44

82.01= 8.7 4.2 5.0 .5 2200 33

82. 3» 8.7 1.7 5.0 2.3 "2356" 2400 Rb72

" Produced in powder form by atomization.

1= Produced in shot-cast form.

87
Table 52. Nickel-base wide-gap brazing alloys [673]

Composition, percent

Ni

Bal 28.0

Bal

Cr

20.0 10.0 2.0

2.0

Cu

Bal 60% J8100+40% nickel powder.

70% J8100+30% NSB powder..

80% J8590 +20% iron powder..

_

Mn

10.0

0.8

Temperature, °F

Solidus

20.30 1850 1980

Liquidus Brazing

2075 2000 >2300

2125-2175 2050-2100 >2300

2240 2125-2175 2050-2100

Remarks

Capillary brazing alloy. Capillary brazing alloy. Used for filler alloy for wide-gap brazing. Wide-gap brazing material. Wide-gap brazing material. Wide-gap brazing material.

The application of furnace brazing to the

fabrication of large sheet-metal structures has

been inhibited in the past by the joint clearances

required to insure the necessary capillary at- traction (0.002-0.006 in). Mobley and Hoppin

[673] developed a series of capillary and widegap brazing alloys, the compositions of which

are given in table 52. Two high temperature

brazing alloys for joining materials such as high-alloy steels, stainless steels, and nickelchromium alloys were patented by Evans and

Pattee [674,675]. Compositions were given as 30-60 percent Ni, 20-45 percent Sn, 10-30 percent Pd, 4-8 percent Si, and 58-68 percent Ni,

25-40 percent Sn, 3-10 percent Co. Hoppin

[676] also patented a high-temperature brazing

alloy (10-30% Cr, 8-12% Si, 7-15% Mn, re- mainder Ni), and Cape [677] patented a lowmelting (1700-1750 °F) alloy having the preferred composition of 65 percent Ni, 25 percent

Fe, 3.5 percent B, 4.5 percent Si, 1.25 percent P. Witherell [678] described an all-position welding electrode for producing sound nonporous

crack-free welds on copper-containing alloys by

means of a welding electrode, the core wire of

which contains 25 to 35 percent Ni, up to 1 percent Fe, up to 1 percent Si, up to 3 percent Mn,

up to 1 percent Ti, <0.15 percent C, remainder

Cu.

Nickel-tungsten alloys, containing 60 to 95

percent of nickel, produced by powder metallurgy techniques, exhibit several of the desirable qualities of cathode core metal for radio

tube construction [182]. Tungsten-nickel and

ternary alloys were suggested as heavy alloys

for use as high-inertia masses or for x-ray protection [679]. Nickel-chromium-gold-cobalt al- loys were suggested as platinum-colored alloys

for dentures [680] and nickel-chrominummolybdenum-cobalt alloys were recommended

for pen nibs [681]

Beryllium-nickel alloys containing 2-3 percent of beryllium exhibit good castability, a hardness similar to that of steel, resistance to heat checking, crazing, and corrosion, and good wear resistance [682].

Buehler and Wiley [683] described the unique

properties of Nitinol, a 55-percent nickel-titanium alloy.

Uranium-nickel alloys approximating the

formula UcNi have better resistance than ura- nium metal to corrosion in reactors [684].

Grala [685] reported that the intermetallic

compound NisAl homogenized at 1,800 °F, had

tensile strengths of 32,100 psi at room temperature and 19,600 psi at 1,500 °F. Heat treatment

at 2,200 °F increased the grain size and re- duced the strength.

The presence of 1 percent of nickel produces

hard particles of NisTi which are responsible

for the superior wear resistance of titaniumbearing zinc-alloy forming dies [686].

4. Ferrous Alloys

4.1. General

As indicated in figure 3, more than half of

the nickel consumed in the United States in

1964 was used in steel and cast irons, thus bearing evidence to its importance as an alloying

element.

Nickel is unique among elements added to

steel in that it forms a continuous series of solid

solutions with iron (fig. 72). A peritectic re- action occurs at 1512 °C (2754 °F) and 4.3 a/o

Ni. The solidification interval of the entire sys- tem is very narrow. The temperature of the

minimum in the liquidus curve, which occurs at about 67 a/o nickel, has been reported as high

as 1436 °C (2616 °F) [687] and as low as

1420 °C (2606 °F) [688]. Both the alpha and

delta solid solutions have a body-centered cubic . lattice, whereas the gamma phase is face-centered cubic. i Nickel is one of the two common alloying ele- ] ments (manganese is the other) that lowers the i As transformation temperature of iron. When

carbon is present, nickel also lowers the Ai

temperature and reduces the carbon content of < the eutectoid. Because of the effectiveness of o nickel in depressing the gamma- to-alpha trans- '( formation in iron, the austenitic solid solutions

existing at elevated temperatures are stable at : room temperature under any condition of cool- ing when the nickel content exceeds about 30 ' percent. Many of these austenitic alloys possess

38
iinusual magnetic, expansion, and thermoelastic

jjroperties that make them of great value to industry. Although frequently referred to as

ligh-nickel steels, they are more properly dekcribed as iron-nickel alloys.

Because of the formation of metastable structural states which vary widely according to comiOosition and heat treatment, and the extreme

luggishness of diffusion at temperatures below

ibout 500 °C (932 °F), the exact location of

he equilibrium phase boundaries has met with

?reat experimental difficulties. The boundaries

if the alpha and gamma phases shown in figure

r2 are those reported by Owen and Liu [689]

.

The Curie temperatures of the iron-nickel alloys decrease steadily up to about 42 percent

nickel. With higher nickel, the magnetic trans- formation of the gamma phase increases to a maximum of 612 °C (1134 °F) at about 64 to 68 a/o of nickel.

Hansen [572] notes that with the exception

of the ordered FeNis structure, which is of the

Cu.sAu (Llo) type, only the body-centered-cubic

alpha structure (A2 type) and the face-centered

cubic gamma structure (Al) type have been

found in the iron-nickel system. He notes further that this disproves the existence of compounds such as FeoNi, FcaNio, FeNio, and FeNi4

which had been previously suggested on the

basis of curves of physical properties versus

89
U) 30

O.zo

28

26

U. 24 O

Ui

_lQ 22 O

20

\ -t \-z ^\ ("^

20 40 60 NICKEL,%80 100

Figure 73. Modulus of elasticity of iron-nickel alloys

[696^.

composition. According to neutron-diffraction

work [690] , ordered FeNis possesses a magnetic

superstructure.

The addition of nickel to iron, and of iron to nickel, expands the lattice. The parameter of

the gamma phase was found to reach a maximal

value at 37 [66] or 39 a/o of nickel [71,691,

692].

Wakelin and Yates [693] reported lattice

parameters of the disordered and ordered states

in the region of 50 to 80 a/o nickel. The 75 a/o

nickel alloy was found to have a parameter of a = 3.5544 A and a = 3.5522 A in the disordered and ordered states, respectively.

Nickel is ordinarily found only in the solidsolution phase. It does not combine with carbon

or oxygen, nor does it form intermetallic con pounds in simple steels. It does not greatly affe

the diffusion rate of carbon in austenite, a though the diffusion rate of nickel itself, whic

is very much slower than that of carbon,

affected markedly by variation in carbon coi tent [694,695].

Nickel decreases the modulus of elasticity < iron and iron, in turn, decreases the modulus ( nickel. The modulus of elasticity of iron-nick'

alloys are shown by Marsh [696] from selects data (fig. 73).

4.2. Wrought Steels

Excluding the austenitic alloys, the maj(

contributions of nickel to steel result from

effects of nickel (1) on ferrite, (2) on the har*

ening reactions, (3) on the transformation ten perature ranges, and (4) on resistance to en brittlement at low temperatures.

In the ferritic alpha range, it appears fairl well established that strength is increased aboi

4200 psi and hardness about 16 Brinell numbei

for each 1 percent of nickel (fig. 74) . With moi

than 5 percent nickel, even slowly cooled alloj

begin to assume a martensite-like structure an when the nickel content reaches 15 to 20 pe: cent, slowly cooled alloys appear to consist ei tirely of martensite even though the carbo

content is extremely low [698,699] . The relati\

effectiveness of nickel as a ferrite strengthens

is shown in figure 75. Nickel retards both the pearlite and bainil

transformation while steel is cooling from tH austenitic state; the bainite transformation i influenced more markedly than the pearlite. Aj

indication of the effectiveness of nickel in r< tarding these transformations may be obtaine

by a comparison of figure 76 with figure T

Even though the carbon content of the nick(

steel is lower than that of the carbon steel, thi

facilitating the transformation, the start of th

pearlite transformation is delayed by a facte of more than ten.

I

100

% NICKEL

Figure 74. Effect of nickel on the hardness of annealed pure iron \_697'].

90
llll'l

LU

CO

I/O »>

LUZ

o

<

LUZ

a:

00

0 2 4 6 8 10 12 14 16 18 20 22

% ALLOYING ELEMENT IN a-IRON

Figure 75. Relative effectiveness of the alloying elements as ferrite strengtheners [700].

1050

c-o.so Mn-0.91

Austenitlzed at 1670 F Grain Size: 7-8

Starting Criterion: 0.1% Transformation

Legend A = Austenite

F = Ferrite C = Carbide M = Martenslte

Data from

U.S. Steel Atlas

0.5 1 2 5 10

Figure 76. Isothermal transformation diagram for AISI 1050 steel (0.50% C) [701}.

91
800

700

600

500

g 400

300

1400

1200

1000

800

600

200 - 400

100 200

0 -

1 1 1 1 1 1

A

I III \ 1 1 1

— -Ae,-

A

A+F

C

A+ F + C

F +

A

A + F+C F + c -

1 1

1 Min

1 1

1 Hou

1 1

1 Da y 1 VVeeklil

2340

C-0.40 Mn-0.89

Ni-3.34

Austenitized at 1500

Grain Size: 8

Starting Criterion: 1% Transformation

Legend A = Austenite

F = Ferrite C = Carbide M= Martenslte

Data by

A. R. Troiano for The International

Nickel Company, Inc.

57

0.5 1 2 5 10 10^

Time, seconds

Figure 77. Isothermal transformation diagram for 23i0 steel (040% C, 3.SU% Ni) [T'Oi].

0 .40 .80 1.20 1.60 2.00 2.40 2.80 3.20 3.60 4.00

WEIGHT % OF ELEMENT

Figure 78. Multiplying factors for the common alloying elements [rOO].

6 Iti

lint Hi

itiie

92
FiGxniE 79. Effect of nickel on the Acs transformation in steel [705].

) Despite this, however, the hardenability of

Jj! steel is increased only moderately by nickel.

Multiplying factors for hardenability for several alloying elements are shown in figure 78.

Related data are given in references [702,703,

1 704].

Because nickel lowers the transformation

ranges of steels, nickel steels may be hardened

by quenching from lower temperatures than

their nickel-free counterparts. The effect of

nickel on the Acs transformation temperature is shown in figure 79. Nickel increases the volume

change occurring during the a y transformation in steel [706].

Nickel has no unusual effects on the tempering of martensite. No secondary hardening oc- curs in plain nickel steels and, consequently,

there is no exceptional resistance to softening.

It has no effect on the temperature range over

' which martensite decomposes [707]

.

I When nickel steels are tempered for long

' periods of time, as is often necessary in treat- ing heavy sections, care must be taken not to exceed the true Aci temperature, which has

been shown to be considerably lower (as much

as 80 °F) than the apparent Aci temperature

indicated by conventional tests made under conditions of continuous heating [708] . This precaution is unnecessary when tempering periods

' do not exceed about two hours, but longer holding at temperatures slightly higher than the

true Aci may result in the formation of suffi- cient austenite to produce a hardening of the

steel during subsequent cooling, thereby necessitating a second tempering operation to decompose the transformation products so formed.

Nickel depresses the temperature of both the

martensite and bainite reactions. Steven and

Haynes [709] studied a variety of low-alloy

steels and concluded that the start of the martensite (Ms) and bainite (BJ reactions can be

calculated to within ± 25 °C with a 90 percent

certainty from the following equations:

M,(°C) = 561 - 474 (% C) - 33 (% Mn) - 17 (% Ni) - 17 (% Cr) - 21 (% Mo)

Bs(°C) = 830 - 270 (% C) - 90 (% Mn) - 37 (% Ni) - 70 (% Cr) - 83 (% Mo).

The Ms temperature of high-nickel steels (up to about 31% nickel) is given by Clark [710] as:

Ms^ (°K) = 70.1 X 10^ - 2.90 X 10* (% Ni)

+ 2.60 X 102 Ni)-.

The Ms temperatures calculated by Clark agreed

fairly well with the temperatures deterniined

experimentally. The resulting curve is shown in

figure 80.

Nickel is widely accepted as a specific for

ameliorating the deterioration in toughness suffered by all ferritic steels at subzero temperatures. Generous amounts of nickel appear in- dispensable for the very lowest temperatures

[711,712]. Nickel is particularly effective in applications where quenching is not feasible and

where normalized or normalized and tempered

steels must be used. Lisner [713] reported that

low-carbon nickel steel could be used at temperatures down to —75 °F for 2V2 percent

nickel, to —150 °F for 31/2 percent nickel, and

to —320 °F for 9 percent nickel. The toughness

of the austenitic nickel steels at very low temperatures is well known.

Thermal conductivity of steel is reduced by

nickel and electrical resistivity is increased

93
0 5

Figure 80. Effect of nickel content on the Ms temperatures of steels [710']

TO 15 20 25 30 35

NICKEL CONTENT, %

[714,715]. Specific heat appears to be unaffected

[715]. Nickel decreases slightly the coefficient

of thermal expansion of steels [716]. The density of nickel steels is essentially the same as for

unalloyed steels of comparable carbon content. Nickel improves somewhat the resistance to corrosion of steels in the atmosphere (fig. 81)

and other environments. It is particularly ef- fective in supplementing and intensifying the

effects of other elements on resistance to cor- rosion.

a. Low-Alloy Steels The first interest in nickel steels was shown

by manufacturers of ordnance and armor and was a direct result of the work reported by

Riley [15]. According to Hall [29], bridge designers were among the first to specify nickel

steels, and the 1906 specifications for the 3i/o

percent nickel steel used for eye bars, stif- fening trusses, and other highly stressed units

of the Manhattan Bridge in New York City are similar to a modern specification, ASTM

A8-54 (discontinued in 1962) for structural

nickel steel for use in main stress-carrying

structural members, as follows:

Yield Elonga- ReducTensile strength, tion in tion of strength mini- 8 inches. area, mum mini- mum

mini- mum

psi psi % %

1906. Manhattan 85,000 55,000 17 40

Bridge. to 95,000

1961. ASTM A8- 90,000 55,000 14 30

54. to 115,000

There was almost immediate acceptance of

these steels for general engineering purposes

because of their improved strength, toughness,

and response to heat treatment in comparison

with plain carbon steels. At the beginning of

the 20th century many nickel steels were available, with nickel and carbon contents adjusted

to meet the requirements of a variety of uses, both with and without heat treatment. Actually, these nickel steels were the first of the numerous alloy steels to be introduced for

general engineering usage.

Until comparatively recently, nickel alloy

steels of 3 1/2 and 5 percent nickel were listed

94
0.25 0.5 1 1.5 2 15 3

% NICKEL

Figure 81. Effect of nickel content on the corrosion of steel in marine and

industrial atmospheres [717}.

Table 53. American Iron and Steel Institute low-alloy nickel steels [718]

Chemical composition ranges and limits, percent number C Mn P (max.) S (max.) Si Ni Cr Mo

3140 0.38/0.43 0.70/0.90 0.035 0.040 0.20/0.35 1.10/1 40 0.55/0.75 E3310 .08/ .13 .45/ 60 .025 .025 .20/ .35 3 . 25/3 75 1.40/1 75 4320 .17/ .22 .45/ 65 .035 .040 .20/ .35 1.65/2.00 0.40/0.60 0.20/0.30

4337 .35/ .40 .60/ 80 . 035 .040 .20/ .35 1.65/2.00 .70/ 90 . Zif/ . oU E4337 .35/ .40 .65/ 85 . 025 .025 .20/ .35 1.65/2 00 .70/ .90 4340 .38/ .43 .60/ 80 .035 .040 .20/ .35 1.65/2.00 .70/ .90 .20/ .30 E4340 .38/ .43 .65/ 85 .025 .025 .20/ .35 1.65/2.00 .70/ .90 4615 .13/ .18 .45/ 65 .035 .040 .20/ .35 1.65/2.00 .20/ .30 4317 .15/ .20 45/ 65 .035 .040 .20/ .35 1 .65/2 00 .20/ .30 4620 .17/ .22 .45/ 65 .035 .040 .20/ .35 1.65/2 00 .20/ .30 4321 .18/ .23 .70/ 90 .035 .040 .20/ .35 1.65/2 00 .20/ .30 4S26 .24/ .29 .45/ 65 .035 .040 .20/ .35 0.70/1 00 .15/ .25 4718 .16/ .21 .70/ 90 .035 .040 .20/ .35 .90/1 20 .35/ .55 .30/ .40 4720 .17/ .22 .50/ 70 .035 .040 .20/ .35 .90/1 20 .35/ .55 .15/ .25 4815 .13/ .18 .40/ 60 .035 .040 .20/ .35 3.25/3 75 .20/ .30 4817 .15/ .20 .40/ 60 .035 .040 .20/ .35 3 . 25/3 75 .20/ .30 4820 .18/ .23 .50/ 70 .035 .040 .20/ .35 3 . 25/3 75 .20/ .30 8115 .13/ .18 .70/ 90 .035 .040 .20/ .35 0.20/0.40 .30/ .50 .08/ .15

8315 .13/ .18 .70/ 90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8317 .15/ .20 .70/ 90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8320 .18/ .23 .70/ 90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8322 .20/ .25 .70/ .90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8825 .23/ .28 .70/ .90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8527 .25/ .30 .70/ .90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8630 .28/ ..33 .70/ .90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8837 ..35/ .40 .75/ .90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8640 .38/ .43 .75/ .90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8342 .40/ .45 .75/ .90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8345 .43/ .48 .75/. 90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8350 .48/ .53 .75/ .90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8655 ..30/ .60 .75/ .90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8660 .55/ .65 .75/ .90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .15/ .25 8720 .18/ .23 .70/ .90 .035 .040 .20/ .35 .40/ .70 .40/ .60 .20/ .30 8735 .33/ .38 .75/1 .00 .035 .040 .20/ .35 .40/ .70 .40/ .60 .20/ .30 8740 .38/ .43 .75/1 .00 .035 .040 .20/ .35 .40/ .70 .40/ .60 .20/ .30 8742 .40/ .45 .75/1 .00 .035 .040 .20/ .35 .40/ .70 .40/ .60 .20/ .30

8822 .20/ .25 .75/1 .00 .035 .040 .20/ .35 .40/ .70 .40/ .60 .30/ .40 E9310 .08/ .13 .4.5/0.65 .025 .025 .20/ .35 3.00/3.50 1.00/1 .40 .08/ .15 9840 .38/ .43 .70/ .90 .035 .040 .20/ .35 0 85/1 .15 0.70/0.90 .20/ .30 9850 .48/ .53 .70/ .90 .035 .040 .20/ .35 .85/1 .15 .70/ .90 .20/ .30 •81B45 .43/ .48 .75/1 .00 .035 .040 .20/ .35 .20/0.40 .35/ .55 .08/ .15 •94817 .15/ .20 .75/1 .00 .035 .040 .20 , .35 .30/ .60 .30/ .50 .08/ .15 •94B30 .28/ .33 .75/1 .00 .035 .040 .20/ .35 .30/ .60 .30/ .50 .08/ .15

' These steels can be expected to have 0.0005% minimum boron couteni. 95
;je a:

t :iteii

a imprc

\ to,

Nickel, Figure 82. Expected properties of normalized nickel steels treated in small sizes (V2 to lV2-in diam or thickness)

[719].

by the American Iron and Steel Institute as standard steels. The most recent listing of

alloy steels [718], however, does not include

these straight nickel steels as standard compositions (table 53).

In complex steels, the effects of nickel and

other alloying elements are complementary in a balanced composition and frequently are mutually intensifying. The contributions of nickel

to hardenability are increased by the presence

of manganese, chromium, and molybdenum.

and the contributions of the latter three are

materially increased by the presence of nickel

[702,703]. The synergistic effect of alloying

elements was a guiding factor in the development of the "National Emergency Steels" during World War II when the element nickel was

in such short supply as to be critical. Many of

the resultant lean triple-alloy steels proved to be

of such merit as to warrant retention as standard steels (the 8000 and 9000 series, table 53).

The mechanical properties of the alloy steels

96
re affected by the carbon content, the alloy

ontent, and by heat treatment. Although hardening and tempering are usually desirable,

iand even necessary, to develop the maximum

potential of alloy steels, there are many uses Kvhere normalized, or normalized and tempered

Bteels, are suitable. The latter are used v^^here improvement over carbon steel is desired but

liquid quenching is either impractical or not

[required. Applications include some large forgjings, some steels for low-temperature service,

fend structures fabricated so that liquid

iquenching is not feasible. An indication of

jthe properties to be expected from normalized

nickel steels (no other alloying element) may

be obtained from figure 82. The change in

strength and toughness conferred on normalized straight carbon steels by the addition of

31/2 percent nickel is show^n in figure 83. At

0.40 percent carbon, tensile strength is increased from about 90,000 psi to 110,000; the

yield point from about 56,000 to 75,000 psi.

This increase in strength is accompanied by

a slight decrease in ductility; however, if the

steels are compared on the basis of equal tensile strengths, the nickel steels show better

ductility. For instance, the following values are taken from figure 83

I50,000r400

NORMALIZED

100,000

CO

Q.

O

O

cn

(J)

Ixl

I-to 50,000

CARBON STEELS

3-1/2% NICKEL STEELS

0 0.20 0.40

CARBON,

%

Figure 83. Effect of 3 Vz percent nickel on the tensile properties of normalized

steels treated in small sizes (V2 to lV2-in diam or thickness) [HS].

97
Plain carbon steel 33^% nickel steel

Tensile

strength,

psi Percent Percent

C Elong. R.A. C Elong. R.A.

70,000

100,000 0.23

.48 34

23

62

43

0. 18 .33 35

25 68

54

In heat-treating alloy steels, it must be realized that transformation of austenite is re- tarded because of alloy content. With sufficient

alloy and carbon content, steels become air

hardening- and the softening of such steels, for

machining and forming operations, may necessitate subcritical or isothermal transformation

after austenitizing. A list of sUi gested treat- ments for softening wrought nickel alloy steels,

together with resultant structures and hardness, is given in reference [720].

When low-alloy steels are quenched and tempered, their resultant room-temperature mechanical properties are quite similar, provided

the initial transformation was completely tc martensite. The average expected properties are shown in figure 84. These curves can be

used to predict the properties of any of the

common alloy steels to within about ±10 per- cent if the hardenability and heat treatment

are such as to obtain a microstructure essen-* tially of tempered martensite.

The low-carbon alloy steels are used mainly

as carburizing steels; here the principal function of nickel is to strengthen and toughen the core whereas the principal benefits of chromium and molybdenum are in improved hardness and wear resistance of the case. The higher carbon alloy steels are used for a variety of structural purposes. The mechanical properties of a few of these steels at a carbon content of 0.40 percent are shown in figure 85. Hardenability bands for these same

steels are shown in figure 86.

oao

REDUCTION

OF AREA

MisceHaneous low-a!loy

steels containing

0.30 to 0.50% C,

quenched and tempered

120 130 140 150 160 170 180

TENSILE STRENGTH, 1000 PSI

Figure 84. Normally expected mechanical properties (heavy line) and average

variation (hatched band) of quenched and tempered low-alloy steels containing 0,30 to 0.50 percent carbon [721 J,

mn

98
9-

TEMPERING TEMPERATURE, "C

100 200 300 400 500 600 700 100 200 300 400 500 600 700 100 200 300 400 500 600 700

250

a- 200

K 150

100

1 i

'

OIL C

1-IN.

1 1 31 40 UENCHED

SECTION

1 1 1 Ivj-I

1 1 434 OIL QUEh

1-IN. SEC

1

1 CHED

TION

1 1 98 OIL QUE

I-IN. SE

\

1 10 _l NCHED

CTION t?/

!^ \\

\ A

/ R^

\ EL y^

100 '

600 200 600 1000 200 TEMPERING TEMPERATURE, °F

600 1000

Figure 85. Tensile and impact properties of oil-quenched and tempered lAn

sections of alloy steels as indicated [722'].

The low-alloy engineering- steels as a class

; retain their room-temperature properties up

to about 500 °F, but thereafter the tensile and

yield strengths begin to fall off rapidly with

further increases in temperature. Nevertheless, these steels are sometimes used at temperatures up to 1000 °F and the elevated temperature properties are of interest [724] . At

subzero temperatures, the limitation on the use

of these steels is their brittleness. This lowtemperature brittleness is reduced by nickel

but for use at very low temperatures, nickel

in excess of the amounts present in the lowalloy structural steels is required. Parker and

Sullivan [725] indicate that the lowest temperature at which a Charpy keyhole notch impact

strength of 15 ft-lb may be specified is —75

and —150 °F for 214 and 31/2 percent nickel

steel, respectively. The beneficial effect of nickel

in improving the impact resistance of steels is

, indicated in figure 87.

I Beginning in the early 1930's, there has been

a concerted effort on the part of the steel producers to develop high-strength low-alloy struc- tural steels with mechanical properties that

would permit substantial savings in weight in

various types of construction, together with

increased resistance to atmospheric corrosion

that would permit the use of thinner sections

I without impairment of service life or safety.

High-strength constructional steels previously

had been carbon steels containing nickel, manganese, or silicon; in 1933 the first of the new

steels appeared for use in railroad rolling

stock. Applications of the high-strength lowalloy steels have been extended to include a

variety of industrial equipment.

The required mechanical properties for sec- tions of up to 14 inch in thickness, 70,000 psi

minimum tensile strength and 50,000 psi minimum yield strength in the hot-rolled condition, were met by various combinations of alloying

elements, some of which also improved the

resistance to corrosion. For low alloy steels,

functions of the different elements have been

stated [727] to be as follows:

"Carbon is generally maintained at a level to insure freedom from excessive hardening

after welding and to retain ductility.

"Manganese is used principally as a strengthening element.

"Phosphorus is sometimes employed as a strengthening element and to enhance resist- ance to atmospheric corrosion.

"Copper is commonly used to enhance re- sistance to atmospheric corrosion and as a

strengthening element.

"Silicon, nickel, chromium, molybdenum,

vanadium, aluminum, titanium, zirconium and

other elements are used, singly or in combination, for their beneficial effects on strength,

toughness, corrosion resistance and other desirable properties."

Some of these alloys are nickel free, or contain only residual amounts of nickel, but many

include nickel as an alloying element. The

nickel-containing steels as tabulated by Hall

[29] are listed in table 54. For all, the minimum tensile and yield strengths are 70,000

and 50,000 psi, respectively, with elongations

of about 20 percent for sections up to 1/2 in. in thickness. Other properties for these steels may be summarized as follows

Fabrication and joining—satisfactory.

Notch toughness—better than carbon steels. Resistance to fatigue and abrasion—trend

toward superiority over carbon steels. Resistance to corrosion—Resistance to atmospheric corrosion is substantially superior to carbon steels. Results of nine years of expo99
Table 54. Representative low-alloy high-strength steels containing nickel [29]

Trade name

Composition—percent

C Mn P S Si Cu Ni Cr Mo

Cor-Ten _ . _

'0. 12 '.12 '.20

'.12 '.12

'.25 '.15

0.20/0.50

.50/1.00

'1.25

.50/ .90 .50/1.00

'1.30 "0.60

0.07/0.15

'0.04

'.10

.05/ .12 .08/ .12 '0.45

.05/ .10

'0.05

'.05

'.05 '.05

'.05 '.05 '.05

0.25/0.75 0.25/0.55

.50/1.00

'.60 .95/1.30

.50/ .70 .30/ .60 .75/1.25

'0.65 .50/1.10

'1.00

.45/ .75 .25/ .75 .50/1.00 1.50/2.00

0.30/1.25 Double Strength 6.10 min. '.10

.08/. 18

Dynalloy '.30

'.15

.10/ .50

.10/ .30

Hi-Steel Magari-R_ .40/1.00 Tri-Ten Yoloy

» Maximum.

sure of 71 low-alloy steels in industrial and

marine atmospheres led Copson [738] to the

conclusion that nickel additions produced low

initial weight losses and, on long exposures, were particularly effective in decreasing pit

depths. In sea water the average loss in weight

is about the same, but the depth of pitting is about half that of carbon steels. Hudson and

Stanners [729] concluded that copper, nickel,

and chromium were the most useful alloying

elements for resistance to atmospheric and sea- water corrosion. In inland waters the low-alloy

steels are at least equal to carbon steels and

are superior in some contaminated, corrosive

river waters. In soils the results are variable

and about the same as for carbon steels. Protective coatings, such as galvanizing, for ex- ample, are readily applicable to these steels. Manufacturing details for the low-alloy

high-strength steels are given by the American Iron and Steel Institute [727].

More recently the demand for structural

steels of still higher strengths resulted in the

development of steels that were either precipitation hardened (held at 1000-1100 °F for 2 to 4 hr) or heat treated by quenching and tempering. A listing of some of the nickel-containing steels as compiled from various sources is given in table 55. Some of these steels have

strengths as high as 140,000 psi tensile and

100,000 psi yield.

b. Ultra High -Strength Structural Steels

Until the end of World War II, the maximum strength at which steels were used for

highly stressed structural components was less than 200,000 psi. Although steels could easily

be treated to much higher strength levels than

this, the assumption that the reduced ductility -; accompanying the higher strengths rendered

the steels susceptible to brittle fracture prevented their use as very high strengths.

During the past twenty years the aircraft

industry became particularly active in explor-ji

ing the use of steels at higher strength levels,

mainly because of the necessity of increasing

the strength-weight ratio of structural parts

in order to obtain greater efficiency of aircraft. Attempts to develop steels combining

tensile strengths above 200,000 psi with suffi- cient ductility and toughness for safe usage

have followed several courses—modification of

the normal quench and temper heat treatment,

modification of composition, martempering,

ausforming, austempering, prestraining and

retempering (also called mar-straining), and

mar-aging.

Probably the first of the ultra high-strength

steels was Hy-Tuf (0.25% C, 1.3% Mn, 1.5%

Si, 1.8% Ni, 0.4% Mo) [730] developed by the

Crucible Steel Company. The development of

this steel was based on the finding by Allten

Table 55. Representative low-alloy high-strength heat-treatable nickel-containing steels

Trade name

Composition—percent

C Mn P S Si Cu Ni Cr Mo V B

Republic "65" 0.12

.14

. 15 .10

.10/. 20

'.22

'. 15 .10/. 18

.10/. 20

.13 '.18

'.18

.08/. 16

.08/. 16 '.18

0.45

.75

.95 .50 .60/1.00

.10/ .40

.5 .60/1.00

.60/1.00

.65/ .95 '1.00

.90 .60/1.20

.60/1.20

.60/1.20

0.20

.25

.22

.17

.15/. 35

.15/. 35

'.25

.15/. 35

. 15/. 35

'.35

. 15/. 35

.30 '.55

'.55

. 15/. 35

1.00

1.15

.65 1.00 .15/0.50

1.30

1.50

1.35

1.82 .70/1.00 2.00/2.75 H.OO

.70/1.00

.70/1.00 1.10/1.60

'1.00 1.50

'1. 00

'1.50 '1.50

0.20

.22 .25 Republic "70" .-- Cu-Ni-Mo - Yoloy "S" "T-1" HY-80

80 HLES

'0.040

'.035 '.025 '.030

'.030 '.030

'.035

.030 '.035

'.035 '.035

'0.050 '.040

'.020 '.030

'.030

'.030

'.040

.025 '.040

' . 040

'.040

0.40/0.65

.90/1.40

'.5 .40/ .80 .40/ .80

.40/ .70 '.80 1.30

'.5

'.8 .40/ .80

.40/. 60

. 23/ . 35

'.4

.40/. 60

.40/. 60

. 40/ . 60

'.60

.25

'.4

'.7 '.60

0.03/0.08

''io' .03/ .10 .03/ .10 .04/ .10 '.10

0.002/0.006

HI-Z K-O MTR

NK-HITEN 80

Superelso

.15/ .50

.15/ .50 '.25

.15/ .50

.20

.002/ .006 .002/ .006 Tooe

Welcon 24 Super Welcon 2H Ultra Wei-ten 80

.15/ ..50 .15/ .50 '.10 '.10

'.006 '.006

• Maximum. Minimum. Where no ranges are given, values are approximate or average.

100
1 40 H

1 340 H

9 840 H

4 6 8 10 12 14 16 18 20 DISTANCE FROM QUENCHED END, SIXTEENTHS OF AN INCH22

Figure 86. Hardenability bands for alloy steels as indi- cated [723].

and Payson [731] that silicon retards the softening of steels tempered in the range of 400

to 600 °F (fig. 88) and also that it raises the

temperature at which the so-called "500 °F"

embrittlement occurs, thus permitting the use

of a higher tempering temperature resulting in increased toughness with no significant loss in

strength. When combined with reduction in

carbon content, adequate toughness for struc- tural use was developed at a tensile strength

of 230,000 psi.

Testing programs in many laboratories

showed that toughness values could be shaded

to allow the use of steel at still higher strength

levels and a tensile strength of 300,000 psi

became the magic number. Practically all of

the steels developed to meet this goal contained

nickel. A listing of some of these steels whose

high strength may be obtained by a quench and

temper heat treatment is given in table 56.

Many of these steels are also susceptible to strengthening by some of the other processes

noted previously.

The use of steel at very high strength and

hardness levels involves careful consideration

of certain factors that are relatively unimportant at lower strength levels. These include

sensitivity to hydrogen embrittlement in plating operations, to damage in grinding, to the

effects of surface decarburization during heat

treatment, and diflficulties in welding, machining, and forming. Careful handling and meticulous inspection are required, and particular effort must be made to design and fabricate

to minimize notch effects and other stress

raisers.

c. Maraging Steels The term "maraging" was coined to describe

the hardening process in a series of ultra

high-strength steels developed by The Inter- national Nickel Company during the past several years. Essentially, the process consists of

transforming a highly alloyed low-carbon austenite to martensite, which is subsequently

aged to induce hardness and strength, hence

the term "maraging." These steels contain

large amounts of nickel (12 to 25%) plus

other elements. The physical metallurgy of the

maraging steels is discussed by Hall [734],

Decker et al. [739], and The International

Nickel Company, Inc. [739a].

The addition of such large amounts of nickel

to iron depresses the « ^ y transformation

markedly. However, the transformation on

cooling is depressed to a much greater degree

than that on heating and this temperature

hysteresis increases with increasing nickel content. A plot of the metastable transformation

diagram is shown in figure 89. At the lower nickel contents and, hence, the

higher tansformation temperatures, the transformation process is controlled by diffusion.

At higher nickel contents and correspondingly

lower transformation temperatures, the ex- tremely low diffusion rates discourage diffusion-controlled transformation and transformation occurs by shear. The result of this

transformation is martensite. It is important

to note that the formation of such martensite

101
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102
-200 -150 -100 -50 0 50 100

TEMPERATURE °F

Figure 87. Effect of nickel on low temperature impact properties of nor- malized and tempered 0.16 percent C steel treated with 0.80 percent Al 1726'].

is not dependent upon cooling rate, but only

upon composition and temperature. In the

presence of low carbon, the martensite so formed has a body-centered cubic structure,

but unlike the martensite of heat-treated steels,

it is cubic and not tetragonal. Because of this,

the volume change resulting from the formation of high-nickel martensite is much less than that in heat-treatable steels. Furthermore, because the martensite is very low in

carbon, it is relatively soft and readily workable. According to Gilbert and Owen [736], the

transformation temperature (Mr) is suffi- ciently depressed so that martensite forms under all conditions of cooling at a minimum content of about 18 percent nickel. Nevertheless,

maraging steels with 12 percent nickel have

been developed [737]. Maraging steels con- taining as much as 28 percent nickel have been

studied [738].

The martensitic transformation is not disturbed by the addition of substantial amounts

of other elements, such as molybdenum, cobalt, and titanium, the presence of which provides the 18 percent nickel maraging steels

Avith their distinguishing characteristics. The

M; temperature of these steels appears to be

in the vicinity of 310 °F, while their Mf temperature is about 210 °F [739].

As shown in figure 89, a considerable hysteresis exists in the a ^ y transformation,

which permits reheating of the martensite to

fairly high temperatures before reversion to austensite takes place. This, in turn, provides

considerable opportunity to develop aging and

precipitation reactions within the martensite.

When the maraging steels are heated to ele- vated temperatures below that at which reversion to austensite occurs, their hardness and

strength increase markedly. Moreover, the

hardening response of these steels during

aging is rapid. The hardening mechanism of

these steels has been the subject of considerable study [740,741,742,743] . Heat treatment

of the 18 percent nickel steel has been investigated by Floreen and Decker [744].

Initially, three main types of maraging

steels, containing 18, 20, and 25 percent nickel, were developed. However, only the 18 percent

nickel grade has found widespread commercial

usage. This steel is produced commercially at three strength levels; 200, 250, and 280 KSI.

The alloy additions to the 18 percent nickel

steel are mainly cobalt, molybdenum, and titanium; those to the 20 and 25 percent nickel

103
60

55

1^50

LU<

X

^45

u

§40

35

30

X

A

Time

5 Minutes

2 Hours

88 Hours

200 400 600 800

TEMPERATURE °F

A 1000

Figure 88. Effect of silicon upon the hardness of 0.6 percent C, 3.0 percent Ni

steel after oil quenching, subzero cooling (to —320 °F), and tempering as

indicated [731].

steels were mainly titanium, aluminum, and

columbium. The 12 percent nickel steel (12-5-

3) is a more recent development, as is a new

18 percent nickel grade at 350 KSI. Compositions of the most popular commercial grades

are given in table 57. These steels may be aged

either in the as-rolled condition, or as annealed

at 1500 °F. Details on the 20 and 25 percent

nickel maraging steels can be found in refer- ences 745 and 748.

The effect of residual elements on the properties of maraging steels has been reported

by Novak and Diran [746]

The 18 percent nickel steel has been the most

important member of the maraging steels. By

minor variations in composition, it can be made

Table 57. Compositions of maraging steels [73U, 737, 737a, 737b]

Chemical composition—percent

C'' Mn" pa Si" Ni Co Mo Ti Al Cr

18 Ni 350 0.01

.03 .03

.03 .03

.03

0.10

. 12 .12 .12 .10

.10

0.005

.01

.01

.01

.01

.01

0.005

.01

.01

.01 .01

.01

0.10

.12

.12

.12 .10

.12

17.0/18.0 18.0/19.0

17.0/19.0

17.0/19.0

16.0/17.5

11.5/12.5

12.0/13.0

8.0/ 9.5

7.0/ 8.5

8.0/ 9.0

9.5/11.0

3.5 /4.0

4.6 /5.2

4.6 /5 .

3.0 /3.5 4.4 /4.8 2.75/3.25

1.6 /2.0

.5 / .8

.3 / .5 .15/ .25 .15/ .45

.10/ .35

0 10/0.20

.05/ .15 .05/ .15 .05/ .15 .02/ .10 .20/ .50

18 Ni 280 - 18 Ni 250

18 Ni 200 Cast -- 12-5-3 '4^75/5^25

Maximum.

104
10 15 20 25

NICKEL,

%

'I Figure 89. The iron-nickel metastable transformation

diagram [735].

Table 58. Physical and environmental properties of maraging steels [758]

Density lb/in. Modulus of elasticity 1& psi-- Modulus of rigidity 10« psi-- Poisson's ratio Coefficient of thermal expansion (70-900 °F) 10-«/°F__

Nil ductility transition temperature °F-. Change in length during maraging %--

Electrical resistivity ^ ohm-em-

_

As annealed Annealed plus maraged"

Intrinsic induction gauss.

H = 250 oersteds H = 5000 oersteds Remanence gauss -_ Coercive force oersteds--

ytress corrosion—minimum life at stress equal to yield strength days-- U bends in sea water

3-point loaded in Bayonne atmosphere

18% Ni«

0.290

26.5

10.2 0.30

5.6

-800.06

60-61 38-39

16,550

18,500 5,500

28.1

35<i >360

' 250.000 grade. Elastic modulus for 200,000 and 300,000 grades is 27.5 X 106 psi.

b At 1500 °F for 1 hr.

t At 900 °F for 3 hr. 200,000 grade showed no failures in 6 months.

Table 59. Mechanical properties of annealed maraging

steel [758]

Yield strength (0.2%) psi-- Tensile strength psi-- Elongation in 1 in percent-- Reduction of area percent-

Hardness, Rc

18% Ni»

110,000

140,000

1775 28-32

' Bar specimen, 0.252-in. diam, 1-in. gage length.

to three different yield strength levels

200,000, 250,000, and 300,000 psi. The lowest

strength level was designed to provide maximum toughness with good strength at ambient

and cryogenic temperatures; the intermediate

strength level was designed to optimize high

strength with good toughness, and the highest

strength level was designed to obtain the highest strength-to-weight ratio with adequate

toughness. The new 350,000 psi grade represents the highest strength practically obtainable with this hardening mechanism to date.

The 18 percent nickel steels can be aged

either as hot rolled or as annealed at 1500 °F.

Optimum properties are obtained by aging at 900 The low distortion and small volume

change accompanying this simple heat treat- ment make this steel attractive for large components. They are weldable without preheat

in both the solution annealed and in the fully

aged condition. Only a post-weld aging treat- ment is required to restore properties in the

heat-affected zone and to develop good strength

in the weld metal [747,748,749,750,751].

Many studies have been made of the mechanical and physical properties of the maraging steels [752,753,754,755,756,757,758,759]. A

tabulation of some properties is given in tables

58, 59 and 60.

Dean and Copson [760] reported that the

maraging steels are somewhat better than

high-strength low alloy steels in general cor- rosion behavior. Scharfstein [761] noted that

susceptibility to stress-corrosion cracking was

greatest in the highest-strength condition.

As cast, the maraging steels are reported to respond to the same simple heat treatments as

the wrought steels and to have mechanical

properties [762,763,764] comparable to those

of the wrought steels.

d. Special Steels There are many special nickel-containing

steels that have been designed for specific purposes and whose compositions do not fall into

any regular grouping. An example of such a

steel is the 9 percent nickel steel designed for

low-temperature service.

As has been mentioned previously, nickel

increases the toughness of steel. At low temperatures, the 9 percent nickel steel shows

toughness significantly superior to any of the

ferritic steels. It may be used either as quenched

and tempered (1475 °F, water; 1050 ° F, air or water) or as double normalized and tempered (1650 °F, air; 1450 °F, air; 1050 °F,

air or water). Its excellent toughness at subzero temperatures is indicated in figure 90.

Information on the properties of this steel is

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-400 -300 -200 -100 0 100 TEMPERATURE, °F

Figure 90. Impact properties of 9 percent nickel steel [765].

Table 61. Some properties of 9 percent nickel steel [765]

Composition, % Mechanical properties (double normalized and tempered)

C 0.13 max. Mn .90 max. P .035 max.

S .040 max.

Si .15 / .30 Ni 8.50 /9.50

Tensile strength —100,000/120,000 psi Yield strength — 75,000 min. Elongation in 2 in. — 22.0 min. Endurance limit — 65,(X)0 psi

Thermal conductivity Modulus of elasticity

Temperature — °F

-.320 -243 -189 -99-9

81

Btu/in/hr/sq

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91 134

149

172 190 203

at 70 °F 27,000,000 psi at -320°F 30,000,000 psi Density 0.284 lb/in." Electrical resistivity at 70° F—33.0 microhms cm

Specific heat (double normalized and

tempered) (mean -320 to 80 °F)—0.088 BTU/lb/ °F (mean 80 to 700 °F)—0.119 BTU/lb/ °F

Thermal expansion (double normalized and tempered)

Temperature.°F

Instantaneous

coefficient per °F

Temperatuie

interval °F Mean

coefficient per °F

-260 0. 0000040 -325 to 75 0.0000049 -150 .0000047 -200 to 75 .0000051 -50 .0000055 -100 to 75 .0000054 50 .0000058 -100 to 200 .0000058

150 . 00000d4 75 to 200 .000006.'")

Magnetic properties (double normalized and tempered)

Temperature. °F Magnetic saturation" (Bs) Gauss

-303 21,360 -148 20,830

32 20,300

68 20,210

212 19,850

•Magnetic field strength (h) of 16,700 Oe, Bs = niaxiinuni po.ssiljle intrinsic induction. The Curie temperature on heating is :ibout 13U1 °1'

;

on cooling about 968 °F.

given in table 61. The strength properties in- crease as the temperature of test decreases;

elongation remains essentially unchanged, being about 30 percent at temperatures as low

as —300 °F.

Considerable information on the metallurgy

and properties of the 9 percent nickel steel is available and its suitability for low temperature service has been well documented [766,

767,768,769,770,771,772,773]. It is readily

amenable to fabrication , by welding [774,775,

776,777] and as welded, its properties are sufficiently good to allow its use for cryogenic

pressure vessels without subsequent stress relief [778]. The ASME has approved its use in

welded vessels down to —320 °F without stress

relief in plates up to 2 in thick [779]. The 9

percent nickel steel is covered by ASTM Specification A353-64 for double normalized and

tempered, A553-65 for quenched and tempered,

and A522-65 for forgings.

Schumann [780] described a low-carbon 13

percent nickel steel that is characterized by

greater low-temperature ductility and by a

considerably higher yield point and tensile

strength than the 9 percent nickel steel. Nonmagnetizable (austenitic) steels for use under service conditions that necessitate a higher performance than that usually demanded of conventional austenitic steels are

described by Kroneis and Gattringer [781].

These are very high alloy steels, many susceptible to precipitation hardening by incorporation of vanadium, titanium or aluminum.

Composition ranges are carbon 0.2/0.65 percent, manganese 6/18 percent, nickel 4/10

percent, and chromium 3.5/12 percent.

A nitriding steel that can be age hardened

to a tensile strength of 200,000 psi has compositional limits of carbon 0.20/0.25 percent,

manganese 0.25/0.45 percent, nickel 4.75/5.25

percent, aluminum 1.8/2.2 percent, chromium

0.4/0.6 percent, molybdenum 0.2/0.3 percent,

vanadium 0.08/0.15 percent [782,783]. The re- sistance to tempering exhibited by both the

core and nitrided case makes this steel particularly suitable for use in cams, gears, shafts

and bearings required to exhibit fatigue and wear resistance at temperatures up to 1000 °F.

A variation of the Hadfield manganese steel [784] with compositions of carbon 0.95/1.1

percent, silicon 1 percent maximum, 13/18

percent manganese, and 7/11 percent nickel are stated to exhibit high yield and tensile

strengths, exceptionally uniform elongation

and ductility, a high degree of notch toughness, and excellent energy dissipation characteristics without failure. Heat treatment consists of water-quenching from 2000 °F.

The properties of HP 9-4-25 steel were

described by Savas [785]. This steel contains

approximately 8 percent nickel, 4 percent cobalt, and 0.25 percent carbon. When double

107
tempered at 1000 °F, it has yield and tensile

strengths of 190,000 and 200,000 psi, respectively, over 50 percent reduction of area, and

14 percent elongation. Charpy V-notch impact

is 45 ft-lb. Steels with a coefficient of expansion approaching that of aluminum alloys have been

developed. One analysis is 0.55/0.65 percent

carbon, 1.00 percent silicon maximum, 5.00/

6.00 percent manganese, 8.50/10.50 percent

nickel [786]. Another analysis is 0.4/0.6 percent carbon, silicon 0.3 percent maximum, 4.6

percent manganese, 11/13 percent nickel, 3

percent chromium and 0.5 percent molybdenum [787].

4.3. Cast Steels and Irons

a. Cast Steels Casting represents the most direct method

of producing steel parts to final form and

nickel increases the strength and ductility of

steel castings in much the same manner as it does for wrought products. By 1910 the properties of cast steel containing about 31/2 percent nickel were well known and the steel was widely used for cast sections in heavy

ordnance. In early work on cast gun tubes at Watertown Arsenal, a 0.40 percent carbon,

2.96 percent nickel steel was used [788]. Burgess [789] reporting on tests of similar steels,

noted that "certain of these treated steel cast- ings would appear to compare very favorably

in the properties with those of forged material

of the same composition." Cone [790] called

attention to an important characteristic of cast nickel steels, i.e., the relatively high ratio of

yield to tensile strength as compared with that

of carbon steels of approximately the same

ductility. It is now known that the beneficial

effects of nickel in cast steels result from the

fact that nickel depresses the pearlite nose of

the S-curve and shifts it to the right to produce a finer structure and higher yield strength

when normalized.

In amounts of 2 to 314 percent, nickel is useful alone, and in smaller amounts, 0.4 to 1.5

percent, it is effective in combination with

manganese and other alloying elements. The

most favorable combination of properties in cast steels, just as in wrought steels, is developed by heat treatment. Liquid quenching, fol- lowed by tempering, is usually the best treat- ment and is widely used when the size and

shape of the casting permit. Castings of intri- cate shape and with sharp changes in section

size may be used in the normalized or normalized

and tempered condition. Cast steels, like

wrought steels, may be martempered, austempered, isothermally quenched, flame hardened,

induction hardened, and case hardened.

Data of early investigators on the mechanical properties of cast plain nickel steels were

reviewed by Lorig and Williams [791] and

the results of a number of investigations in the

1930's, together with some more recent data, are summarized in table 62. Armstrong [792,

793] reported typical properties of 30-ton naval castings and large railroad frames, made

of steel containing 0.30 percent carbon, 0.90

percent manganese, and 3 percent nickel, to be as follows

liDllI

lesist

Normalized

Annealed and

tempered

Tensile strength . . . psi - 85,000 87,000

Yield strength psi 53,000 55,000

Elongation in 2 in 30 30 Reduction of area 54 50

As was the case with wrought steels, uses

of cast nickel steels led to interest in cast ( steels containing additional alloying elements.

Mechanical properties of some of these steels in comparison with plain nickel steels, as re- ported by Lorig [794], are given in table 63. Chrominum functions as a ferrite strength- ener in low-carbon steels and also has a strong

tendency to form hard carbides; it therefore

increases the strength and hardness of cast

nickel steels but the increase in strength is

Table 62. Typical properties of some cast nickel steels [29, 791a]

Composition, %

0.17

.17

.09 .24

.16

.30 .30

.39 .09

.33

Mn Ni

0.80

.40

.65 .60

.57 1.00

.60

.75 .65

.60

2.05

2.50

2.50

2.40

2.65 2.00

3.25

50

50 3.25

Treatment

Double normalized and tempered Double normalized and tempered Double normalized and tempered Double normalized and tempered

Normalized, oil quenched and tempered

Normalized and tempered

Annealed Annealed Double normalized and tempered Water (luenched and tempered

Psi

Tensile strength

80,000 80,000

82,000

82,000

81,000

94,000

95,500

115,000 80,000

134,000

Yield

strength

53,000

.56,000 62.000

60 , 000 65,500

58,000

61,000

65,000

.54,000 120,000

%

Elongation

in 2 in.

29

3132

3129

26

22

22

32

17

Reduction

of area

60

5954

5558

48

48

35

60

40

Charpy

impact,

ft lb

"58

30

t 2533

37

'•30

» Izod. i>At -150 °r.

108
Table 63. Mechanical properties of^some cast steels containing nickel [791a, 79^]"^

Composition, %

Mn Ni Cr Mo

Psi

Tensile strength Yield

strength Elongationin 2 in. Reduction

of area

Izod

impact,

ft-lb

.31 [3024

30

.30 .20 max

1.15 1.60

.90

.74

.90 .90

.90 1.00 max

.65

0.39

.35

.35

.29

.35 .35

.35 .80 max

.50 max

0.67

1.37 2.15

1.29

1.33 1.82

1.45

.60 2.80

0.79

0.10

.54

.60

1..50

0.35

.21 .23

.45

94,500

101,000

103,000 81,500

100 , 000

92,000 104,000

115,000 112,000

57,000

68,000

62,.500 64,000 60,000

65 , 000 79,000

96,000

90,000

24.5

24.5

2530.5

22.5 22.5

2220

23

48

56

50

6143

47

46

5258

71

''40

'>, = 80

» .\11 steels were normalized and tempered, except the last two, which were quenched and tempered. Charpy V-notch impact.

' At - 100 °F.

accompanied by some loss in ductility. Molybiienum in the usual range of 0.10 to 0.30 perIbent, but sometimes as high as 0.50 percent, is effective in increasing the hardenability and

Resistance to some types of corrosion. Vanadium is an effective grain refiner and is frequently added to cast nickel steels, usually in

^mounts between 0.08 and 0.15 percent, to improve ductility and the yield to tensile

strength ratio. Manganese is the cheapest of

the alloying elements and its use in combinaition with nickel produces good ductility and

high ratios of yield to tensile strength. Armistrong [795] concluded that the benefits of

[manganese in low-alloy steels were most apparent when the manganese content was above

1 percent.

Elman and Schelleng [796] found nickel to be essential in raising low-temperature toughness of nickel-manganese steels. Its effective- ness was found to be dependent on the particular manganese content. At a carbon level of 0.30 percent, optimum tensile and low-temperature impact properties were obtained with

1.50 percent nickel, 1.60 percent manganese.

The interplay of nickel and manganese on the

15 ft-lb transition temperature of this steel as normalized and tempered is shown in fig- ure 91.

1.0 1.5 % NICKEL

Figure 91. Effect of nickel and manganese upon the 15 ft-lb transition tem- perature of 0.30 percent carbon cast steel [756].

109
A low-alloy cast steel with an exceptionally

good combination of strength and toughness was developed by Knoth and Schelleng [797].

Its composition is 0.25/0.29 percent carbon,

0.20/0.40 percent silicon, 0.40/0.70 percent

manganese, 3.7/4.2 percent nickel, 1.9/2.1

percent chromium, 0.38/0.45 percent molybdenum, and 0.10/0.14 percent vanadium. With

so much alloy, transformation from austenite

is sufficiently retarded so that the steel transforms to bainite during air cooling even in

heavy sections. As normalized and tempered,

this steel develops a minimum yield strength

of 100,000 psi in combination with 15 ft-lb Charpy V-notch transition temperatures below

—70 °F and an NDT below -90 °F.

A cast steel, air hardenable in thick sections

for use in armored vehicles, was developed by

Rostoker [798]. The following two analyses were found to be capable of providing, in a

5-in section, an impact strength of 18/20 ft

lb at —40 °F at a hardness, after tempering,

of Re 22/24

(1) (2)

Carbon

0. 18% 0. 18%

Manganese . 1.9 . 5

Silicon .5 .5 Chromium 1.0 1.0 Nickel . 5 2.5 Molybdenum

.5 .5

A cast steel containing 9 percent nickel was

reported to have a 15 ft-lb Charpy V-notch

transition temperature lower than liquid nitrogen temperature [799].

The design, treatment, and properties of

steel castings are covered in the Steel Castings

Handbook [800]

b. Cast Irons One of the first attempts to improve cast iron by means of additions of nickel was made

by Hickling [801] in 1799 when he patented

the use of 2.5 to 25 percent of nickel in making

hollow cast iron vessels. In 1845 Poole [802]

patented an oxidation-resistant cast iron with

2-10 percent nickel. The first published paper on nickel cast iron is attributed to Fairbairn

[803], who reported on the properties of vari- ous mixtures of cast iron and nickel in 1860.

The use of nickel to improve the properties

of cast iron were developed empirically during

the 19th century and it was not until the 20th

century that the complex nature of cast iror,

and the interrelation of carbon, silicon, alloy

content, and heat treatment began to be understood, with an accompanying rapid expansion

in uses and applications. The early history of

nickel cast iron was summarized in 1923 I Merica [804] and additional data were pr< sented by Wickenden and Vanick [805]. Sul

sequent reviews include those of Merica [806

in 1937, Bairot and Berthelier [807] in 195:

and Hall [29] in 1954.

Even today the iron-nickel-carbon system i not well understood and very little is known o equilibria in the iron-silicon-nickel-carbon sys i tem. According to Hall [29], nickel decrease:]

the solubility of carbon in molten iron, lower i the eutectic carbon content and raises the eu

tectic temperature, acts graphitizer wit!

about one-half the effectiveness of silicon

lowers the critical temperatures and thereby

extends the austenite field, decreases the eutec

toid carbon content by approximately 0.04 per

cent of carbon for each 1 percent of nickel

and moves to the left, i.e., toward lower carbor

contents, the boundaries of the field in whic?

plain cast iron has a wholly pearlitic matrix

Because nickel is a graphitizer, it acts to de-: crease the amount of eutectic cementite in the; structure, thereby reducing or eliminating hardj

spots and chill and promoting uniformity in

the distribution of graphite. Nickel refines the

pearlitic matrix in cast iron by delaying the

austenite pearlite reaction (by displacement to the right of the upper nose and lower

portions of the T-T-T curve), as well as by

lowering the eutectoid temperature. As with

steels, increasing amounts of nickel tend to make the structure martensitic or austenitic on slow cooling. The acicular structures have

proved to be very desirable from the standpoint of mechanical properties.

Schelleng [808] evaluated the influence of

nickel up to 37 percent in combination with

silicon on the carbon content of the eutectic

and proposed the following formula:

% C (eutectic) = 4.30 - 0.33 (% Si) - 0.47 (%Ni) + 0.0055 (% Ni) (% Si).

The effect of nickel on the eutectic in ironcarbon alloys according to Schichtel and Piwowarsky [809] is shown in figure 92. Wickenden and Vanick [805] reported that, as the nickel content of cast iron is increased

to between 5 and 12 percent, a series of alloyed

irons is produced that are martensitic when

cooled at ordinary rates and quite hard, particularly if chromium is present. Norbury and

Morgan [810] observed that when the silicon

content was increased from 0 to 7 percent, the

amount of nickel required to render the matrix

martensitic increased from about 5 percent

to about 12 percent. They also found that additions of chromium up to about 1.8 percent

slightly reduced the amount of nickel required

to produce a martensitic matrix, but further

110
o

CO< -> O

0 10 20 3 0 4 0. 50

% NICKEL

1400

uo

S'

<

(U

11200

1100

)

) —

)

•

0 1 0 20 30 40 50

2500

u. 2400^

2300H

LU 2200 Q.

Ill 2100'

2000

% NICKEL

FiGtJRE 92. Effect of nickel on the carbon content and temperature of the

eutectic in iron-nickel alloys [809'\.

additions of chromium caused no change in the

t

I required nickel content. Acicular irons, accord-

^'

I dng to Flinn and Reese [811], are capable of

J /developing 105,000 psi tensile strength. Eight- een percent of nickel is sufficient to make cast irons completely austenitic [810].

j Cast irons with such high alloy contents are

llintended for special purposes such as resist- ance to corrosion, heat, and wear. The engineering cast irons have a total alloy content

that normally does not exceed about 3 or 4

(percent.

As has been mentioned before, nickel is effective as a graphitizer. As such, it acts to reduce or eliminate the amount of white iron

in a chilled bar. The following data are indicative of its effectiveness in a cast iron of base

composition about 3.55 percent total carbo:i

and 1.05 percent silicon

Effect of nickel on depth of chill [805]

Depth of white Depth of white

Nickel iron in chilled and mottled

bar iron in chilled bar

% in. in. 0. 12 0.70 1.30

.32 .60 1.05

.94 . .5.5 1. 10

1. 10 .45 1. 15 2.47 .30 . 75 3.90 0 0

111
400

350

1/1 HIZ

Q

<

Ulz

CQ

300

250

200

TC 3.15

Si 1.15 Mn 0.4

\&\ -< \m\o

S 0.05

P 0.3

SECTION THICKNESS, IN. Figure 93. Influence of nickel in equalizing the hardness of cast iron \_812'i. Base composition: TC 3.15 percent, Si 1.15 percent, Mn 0.4 percent, S 0.05 percent, P 0.3 percent.

The marked effect of nickel in equalizing the

hardness of cast iron is indicated in figure 93. The influence of nickel on the structure and

properties of gray iron has been summarized

by Form and Wallace [813].

Chromium is a powerful carbide stabilizer,

thereby increasing tensile strength, transverse

strength, and hardness. Molybdenum is a mild

carbide stabilizer and an effective strengthener. Examples of typical compositions of

high-strength irons, assembled by Hall [29]

from various sources, are presented in table

64. These properties often may be improved

by heat treatment.

The size, shape, and uniformity of distribution of graphite flakes have important ef- fects on the mechanical properties of cast iron^

particularly for the so-called high-duty irons

that are low in carbon and silicon. Consequently, inoculants are added to cast iron in

the ladle to promote the formation of graphite

and its uniform distribution. Nickel itself has no inoculating properties, but a nickel-silicon

alloy, Nisiloy, was at one time widely used for

this purpose [814,815].

The graphite phase in cast iron may be al- tered completely from its usual lamellar-flake

form by special ladle additions and caused to

form as spheroidal nodules. In 1948 Mor

rogh [816] described a method of obtaining

nodular graphite in hypereutectic iron by

making a ladle addition of cerium or misch

metal. In 1949 a patent, originally filed in

1947, was granted to Millis et al. [817] cover- ing controlled magnesium additions to hypo

eutectic or hypereutectic irons that would

cause the graphite to precipitate in spheroidal

form. It was also found at that time that the

nodular form of graphite could be produced

in austenitic as well as pearlitic iron by the

magnesium addition.

Magnesium is not readily added to liquid

iron because it is extremely reactive and, in

addition, boils at the temperature of molten

iron. However, it can be added satisfactorily

when it has been alloyed with a metal like

nickel or copper, which will reduce its reactivity and raise the boiling point. Nickel-magnesium and copper-magnesium alloys containing

10-20 percent magnesium are very satisfactory

for this purpose [818]. Iron-silicon-magnesium

alloys are also used commercially and occasionally pure magnesium is used with the aid of

special devices.

The spheroidal or spherulitic graphite (S.G.) or ductile cast irons possess high tensile

fives

teiisi

I at

torn

112
Table 64. Typical compositions and properties of some high-strength cast irons [29]

Composition, percent

Tensile strengthBrinell hardness

Transverse

strengtli 1.25 in. bars, 12 in. span

Deflection TC 1 CC Si Mn P S Ni Cr Mo

Niclcel cast irons

2.73 3.02 2.98

2.89

3.07 2.86

2.89

2.78

1.68 1 13 0.11 0.073 0 98

1.65 0 91 .11 .073 75 1.66 1 17 .16 .074 1 02

1..58 0 77 .097 .090 1 21 1.64 95 .13 .077 1 03

1.41 88 .13 .096 0 97

2.02 53 .033 .097 2 44

1.79 49 .029 .087 2 88

psi lb inch 48,500 228 4,900 0.17 49,100 228 5,100 .21 50 , 000 217 5,270 .24 50,800 228 5,390 .187 51,000 217 5,060 .19 52 , 600 217 5,210 .24 66,200 269 6,200 .1.53 68,000 269 5,920 .142

Nickel-chromium automotive cylinder irons

i . 10

3 . 35 3.15

1 . 05 0.82

.90

1.13 2.32

1.76

1.21 0.86

1.13

0.39

.41 .45

31,5,50 34,600 44,450286

217

262

4,130

3,715 5,030

0.107

.123

.159

Nickel-molybdenum irons, as-cast

2 26 0.72 2 27

2 30 .75 2 31

2 28 .74 2 31

2 31 .76 2 30

2 30 .77 2 32

1.09

1.03 2.06

1.04 2.03

0 33 71 ,000 286 4,0.50 "0.26

1 36 71,800 321 4,700 ».33 0 82 74 , 400 340 4,600 ".36

81 80,600 321 4,600 ".32

1 31 82,000 387 4.800 ".35

Nickel-chromium-molybdenum cast irons, cupola produced

3.36 2 04 0.87 0.105 0.063 1 52

3.21 1 85 .85 .087 .0.56 1 61 3,24 1 99 1.00 .093 .067 1 52 3.20 1 97 0.93 .089 .064 1 53 3,24 1 75 .93 .087 .0.57 1 42 3.24 1 87 .84 .089 .066 1 56 3.28 1 88 1.09 .072 .064 1 55 2.97 2 01 0.93 .087 .069 1 63

3 . 12 1 74 .92 .080 ,084 1 63 2.94 1 78 1.00 .080 .0,54 1 62

" On 18-in. span.

ly, strength and ductility and at the same time

J.

. retain the machinability and much of the castj

I ability of the standard gray irons. Tensile

f. I strengths of 70,000-120,000 psi can be obtained

yU by the nodularizing treatment without heat

ijjj treatment in irons that normally would have

J j 20,000-40,000 psi tensile strength, and annealing 1 hr at 1650 "F, followed by slow cooling,

d j gives an elongation of about 20 percent with a

e i tensile strength of about 70,000 psi [818].

High ductility can also be achieved by a sub-

(j I critical heat treatment when no carbide exists

jjj in the iron. Heat treatment (quenching and

[jj tempering) will give even higher strengths, as

J

I much as 175,000 psi. In nickel ductile irons, the

{

I nickel content is relatively low (about 0.4 to

. j2%), but the austenitic type of ductile iron

.

j contains about 18 to 22 percent of nickel. Inj

• deed, it is this high nickel content that makes

'j

I it austenitic. This iron has excellent heat and

J

: corrosion resistance. The seven generally rec-

. ognized grades of ductile iron are tabulated in

[

. table 65. It will be observed that types 100-

75-04 and 120-90-02 are identical in composiI tion. The higher strength of the latter type is

; attained by heat treatment. The ASTM lists

0.29 0.74 .56,750 248 5 , 220

.24 .78 61,0.50 248 5,575

.19 .73 63 , 350 269 5 , 280

.19 .74 65 , 550 262 5,335

.25 .82 66 , 100 262 5,640

.28 .80 67 , 400 269 5,770

.26 .73 70,3,50 293 6,120

.29 .77 74,900 286 5,785

.28 .90 77,000 302 5 , 930

.28 .79 79,150 286 5,990

five grades of ductile irons by properties only, as indicated in table 66. The cast irons generally have better corrosion resistance than steels. Greene and Sefing

[820] reported that low-alloy irons could be

used up to about 1100 °F as grate bars, annealing boxes, etc., whereas higher alloyed irons

could be used at higher temperatures. Wilks,

Mathews, and Kraft [821] reported that ductile high-nickel irons were useful up to 1200

or 1300 °F.

The compressive strength of cast irons con- taining nickel extends over a range of 80,000-

200,000 psi [29]. As a rule, the ratio of compressive to tensile strength becomes smaller

as the tensile strength increases, varying from

4.5 to about 2.5 times the tensile strength.

Shock resistance is somewhat better than for

unalloyed iron ; the ratio of shear strength

to tensile strength decreases as the tensile

strength increases, from about 1.6 or 1.7 for

low-strength irons to about 1.0 for highstrength irons ; the torsional strength generally

bears a linear relation to the tensile strength;

the high damping capacity of gray iron varies

with the amplitude of vibration, and the fa113
OD O c U

03 E if u

C J2

^S3 >i © o

=3 C5 £2 J.-

+^ > —

= Ji: S =3 ° o £ 5

CJ «) g g 3 g

= s S s c-S-? 5 C._ — O .o si

-g,oi=:sf o|

in

« C S £

4) C '''%-\

J3 3

c OS ^ ^3 0) o —

0) C g

J) 53 S

^ o g

a). 2 =3 o- — s c s =8 ? S o o

S.2

«.2

5 us tS c ES °

-2 = 2-^

c c —

O 0(N

6?5

E

^5

114
Itable 66. Tens^ile requirements for ductile iron castings {ASTM A336-65T)

Grade Orade Grade Grade Grafle (50-40-18 6.5-i5-12 80-.5.5-03 100-70-03 120-90-02

tfTisile streimth. niin

psi. 60.000 6.5,000 80,000 100.000 120,000

'iplil strength, min

psi 40,000 4.5,000 5.5,000 70,000 90,000

loneation in 2 in, min- percent - 18 12 6.0 3.0 2.0

tigue strength increases with increasing tensile

strength, although both drop off rapidly when

the temperature exceeds about 800 °F.

Gray irons containing nickel are widely used

for automobile engine cylinder blocks, diesel

engine cylinder liners, piston rings, crankishafts, camshafts, couplings, gears, machinery

'.frames, and a variety of uses involving metaljto-metal contact and resistance to w^ear and

abrasion. Many of the properties, and particularly the resistance to wear and abrasion, are improved by increasing the carbon and alloy content. For instance, Ni-Hard is a generic

designation for a martensitic white cast iron

that is widely used in applications requiring

I resistance to abrasion, particularly in such

I severe service as in grinding and crushing

equipment. Its composition is 2.8-3.6 percent

carbon, 0.5-0.7 percent manganese, less than

0.4 percent phosphorus, 4 to 5 percent nickel,

and 1.8 to 2.6 percent chromium [822]. A sum- maiy of its properties is given by The Inter- national Nickel Company, Inc. [823].

Many cast irons with higher alloy contents

have been developted since about 1930 for improved heat and corrosion resistance to meet

the increasingly severe requirements of service in the chemical industry and as annealing

retorts, grate bars, and other furnace parts.

Hallett [824] reviewed established and experimental materials with varying combinations

of increased nickel, chromium, and silicon with

additions of other elements, including copper

t and molybdenum. Some of these are gray irons,

' but in many instances the alloy content is high

enough to make the irons austenitic.

Ni-Resist is a generic name applied to a group of high-nickel alloy cast irons containing sufficient nickel to produce an austenitic

structure as well as a complete change in

chemical and physical characteristics. Ranges

of chemical compositions are given in table 67

I and are covered by ASTM Specification A436-

63. By reason of their high alloy content and

austenitic structure, they provide a unique

combination of engineering properties: resist- ance to corrosion, erosion, heat and oxidation

;

strength and toughness, resistance to wear,

good mechinability, high electrical resistance,

and, by suitable choice of the nickel content,

non-magnetic characteristics and varying

thermal expansivities. Types 1 and 2 are corrosion resistant, the heat resistance of type 3

is considerably improved over that of types 1 and 2, and types 4 and 5 are notably resistant

to both heat and corrosion, although the latter

is used primarily for parts requiring high dimensional stability and low thermal expansion.

Considerable information on Ni-Resist is given by Barton [826] . Ni-Resist can be treated

with magnesium to change the graphite from

flakes to spheroids [827] with improvement in

strength, elongation, and toughness at room

and elevated temperatures. This iron is cov- ered by ASTM Specification A439-62. According to Wilks, Mathews, and Kraft [821], tensile, rupture, and creep tests show that the

utility of the standard ferritic and pearlitic

grades of cast iron is limited to about 1000 °F

for long-term load-carrying applications when

both scaling resistance and strength are considered, but the high-nickel austenitic irons

should be useful to about 1200 to 1300 °F.

Their results for the effect of temperature on

the tensile strength and ductility of ductile cast irons are showni in figure 94. The development of a special Ni-Resist ductile cast iron for use at low temperatures was

described by Rickard [828]. A ductile austenitic cast iron was patented by Schelleng

and Abbott [828a]

.

400 800 1200

TEMPERATURE, °F

I 600

Figure 94. Effect of temperature on the tensile strength

and elongation of ductile cast irons \_821'].

115
Table 67. Composition ranges of Ni-Resist irons [825]

Chemical composition, percent

-1 ypc

1 otal Manga- Silicon Nickel Copper Chro- carbon nese mium

1 >3.00 1.00/1 50 1 00/2.80 13.50/17.50 5.50/7 50 1 75/2.50

lb » 3 . 00 1.00/1 50 1 00/2.80 13.50/17.50 5.50/7 50 2 75/3.50

» 3 . 00 .80/1 50 1 00/2.80 18.00/22.00 ».50 1 75/2..50 2b » 3 . 00 .80/1 50 1 00/2.80 18.00/22.00 ».50 3.00/6.00

3 "2.60 .40/ 80 1 00/2.00 28.00/.32.00 ".50 2 50/3 . 50

4 "2.60 .40/ 80 5 00/6.00 29.00/32.00 "..50 4 50/5 . 50

5 > 2.40 .40/ 80 1 00/2.00 34.00/36.00 «.50 10

' Maximum.

4.4. Stainless Steels

a. General

The outstanding characteristic of the stainless steels (more properly termed corrosionresisting steels) is their ability to resist at- tack by oxidizing media. This property is con- ferred by the addition of chromium and the

presence of large amounts of this element is a common characteristic of all of the many stainless steels. The minimum content of chromium

in any of the stainless steels is about 11.5 percent. Standard compositions of the nickelbearing stainless and heat-resisting steels are given in table 68. The stainless steels can be divided into four

general classes, namely, martensitic, ferritic,

austenitic, and precipitation-hardening. None

of the ferritic stainless steels contain nickel and

are not, therefore, included in this discussion.

b. Martensitic Stainless Steels Only two of the standard martensitic stainless steels (and none of the ferritic type) contain nickel (table 68). Type 414 is not used a

great deal, but type 431 (frequently referred

to as 16-2) finds extensive use as high-strength

stainless forgings and fittings. It is normally

used as heat treated to a strength level of

about 200,000 psi. When properly made and

processed, this steel exhibits amazing toughness at high strength levels. Charpy V-notch

values in excess of 70 ft-lb have been recorded on steels treated to a hardness of Rockwell C36

and 40 ft-lb at a hardness level of C43. It is important that this steel should never be tempered in the range of 600 to 1000 °F as tempering in this range results in excessive brittleness. The constitution of 16-2 has been

studied by Johnson and Rosenberg [831] and

the properties of 16-2 have been discussed by

Angstadt [832]. The function of the nickel

content is to decrease, or even eliminate, the

delta ferrite in the microstructure.

Two modifications of the 16-2 steel, one for

forgings and one for cold-rolled sheet, were

described by Morley [833]. The compositions

are as follows:

FV520(B) FV520(S)

-

Carbon 0.07% max 0.04/0.089^

Manganese 1 . 0 max .8 /I. 8

'

Silicon . 6 max . 6 max

Chromium 13.5/14.5 15.3/16.0

Nickel 5.0/ 5.8 5.0/ 5.8 Molybdenum 1.2/ 2.0 1.2/ 3.0 - Copper 1.2/ 2.0 1.5/ 2.2 Niobium, .2/ .9 Titanium . 2 max :

1 A steel of somewhat similar composition wasl

patented by Irvine [834] (carbon 0.07-0.16%,|

chromium 14-17.5%, nickel 3.5-4.5%, nitrogen

0.05%). It is characterized by a content of

manganese, with or without one or more of the,

elements silicon, tungsten, and molybdenum, in

certain specified proportions. Another hardenable nickel-bearing stainless steel was patented

by Aktiebolaget Bofors [835] (carbon 0.03-

0.25%, manganese 0.25-2.00% silicon 0.10-" 0.70%, chromium 11-14%, nickel 4-8%, molyb-;

denum 0.5-3.5%). Mott [836] described a

hardenable stainless steel resistant to erosion,;

corrosion, and abrasion by acid and other cor- rosive slurries (carbon 0.07% max, manga-j; nese 0.2-4%, silicon 0.2-7%, chromium 15-

32.5%, nickel 25-35%, molybdenum 2-20 %,i

copper 1-5%). This steel is hardened by proper

adjustment of the alloying elements and not

by heat treatment.

c. Austenitic Stainless Steels The chromium-nickel (austenitic) stainless

steels are widely used because of their resist- ance to corrosion, ease of formability, desirable

mechanical properties, and the ability to re- tain these properties at temperatures above

and below ambient. Although chromium is the

principal alloying element, the austenitic stain-3

less and heat-resisting steels account for about*

one-fourth of all the nickel consumed (fig. 3)

in the United States. The addition of substantial amounts of

nickel to high-chromium steels effects a marked change in both mechanical and physical properties. Nickel enhances fabricating

characteristics and increases corrosion resist- ance significantly in the presence of chromium,

but the principal function of nickel in stainless'

steel is to stabilize the austenitic structure nor-! mally existent only at high temperatures. Ther

austenitic stainless steels originally developed',

during the 1920's contained about 18 percent

chromium and 8 percent nickel and this led to the use of the term "18-8" to decribe these'

steels. During times of national emergencies, the

shortage of nickel presented a serious problem

to the producers and consumers of the 300

.Hill

ICilj

t.Hi.. M..

M..

CB-iCi CM..

CWSI

CH..

«...

tf-!...

tl-iO..

ii-ni

IT-ISl wc.

tF-KF

tt-lM

CH-!1

CS-M. tS-IM M..

SI-!)...

1.1.

»c,.

'

116
Table 68. Nickel bearing standard stainless and heat-resisting steels [829, 830]

Chemical composition AISI type

/o ^ % Mn % P 1 % s % Si % Cr % Ni Other

(max) (max) (max) (max) (max)

Austenitic steels

|201 0.15 5.50/ 7 .50 0.060 0.030 1 .00 16 00/18 .00 3 50/ 5 50

^02 _ . 15 7.50/10 00 .060 .030 1 .00 17 .00/19 00 4 00/ 6 00

. xo 2 nnKJU . u-io . nQn uou 1 00 16 00/18 .00 6 00/ 8 00

15 2 uu . \j-±o . UoU 1 00 17 00/ 19 00 8 00/ 10 00

Lj 15 UU . U40 . UoU 2 .00/3 00 17 00/19 00 8 00/10 00

|303 .15 2 00 .20 ".15 1 00 17 00/19 00 8 00/10 00

15 00 20 060 1 uu 17 00/19 00 00/ 10 00

304 !08 2 00 .045 !030 1 00 18 00/20 00 8 00/12 00

304 L 030 2 00 045 030 I 00 18 00/20 00 00/12 00

l305 !l2 2 00 .045 .030 1 00 17 00/19 00 10 00/13 00

308 .08 2 00 .045 .030 1 00 19 00/21 00 10 00/12 00

309 .20 2 00 .045 .030 1 00 22 00/24 00 12 00/15 00

309 S .08 2 00 .045 .030 1 00 22 00/24 00 19 00/22 00 aio .25 2 00 .045 .030 1 50 24 00/26 00 19 00/22 00 310S .08 2 00 .045 .030 1 50 24 00/26 00 19 00/22 00

1314 .25 2 00 .045 .030 1 . 50/3 00 23 00/26 00 19 00/22 00

Bl6 .08 2 00 .045 .030 1 00 16 00/18 00 10 00/14 00 316 L .030 2 00 .045 .030 1 00 16 00/18 00 10 00/14 00

317 .08 2 00 .045 .030 1 00 18 00/20 00 11 00/15 00

321 .08 2 00 .045 .030 1 00 17 00/19 00 9 00/12 00

347 .08 2 00 .045 .030 1 00 17 00/19 00 9 00/13 00 348 .08 2 00 .045 .030 1 00 17 00/19 00 9 00/13 00

N 0.25% max. N 0.25% max.

Mo 0.60% max (optional). Se 0.15% min.

Mo 2.00/3.00%. Mo 2.00/3.00%. Mo 3.00/4.00%. Ti 5 X C min. Cb-Ta 10 X C min. Cb-TalOxCmin Ta 0.10% max Co 0.20% max.

Martensitic steels

Uu.. . 15 1.00 .040 .030 1.00 11.50/13.50 1.25/ 2.50

|431 .20 1.00 .040 .030 1.00 15.00/17.00 1.25/ 2.50

Cast steels

f,CA-15 . 15 1 .00 .04 .04 1.50 11 5 /14 b 1 Mo 0.5% max''. ICA-40 .20/ .40 1 .00 .04 .04 1.50 11 5 /14 b 1 Mo 0.5% max''. !CB-30 .30 1 .00 .04 .04 1.50 18 /22 b 2 -CB-7 Cu.... .07 1 .00 .04 .04 1.00 15 5 /17 3.6 / 4.6 Cu 2.3/3.3%. lCC-50 .50 1 .00 .04 .04 1.50 26 /30 b 4 CD-4 M Cu. .040 1 00 .04 .04 1.00 25 /27 4 75/ 6.00 Mo 1.75/2.25; Cu 2.75/3.25. CE-30 .30 1 50 .04 .04 2.00 26 /30 8 /II CF-3 .03 1 50 .04 .04 2.00 17 /21 8 /12 iCF-8 .08 1 50 .04 .04 2.00 18 /21 8 /II CF-20 .20 1 50 .04 .04 2.00 18 /21 8 /II CF-3 M .03 1 50 .04 .04 1.50 17 /21 9 /13 Mo 2.2/3.0. CF-8 .M .08 1 50 .04 .04 2.00 18 /21 9 /12 Mo 2.0/3.0. CF-8 C .08 1 50 .04 .04 2.00 18 /21 9 /12 Cb 8 X C min, 1.0% max. CF-16 F .16 1 50 .17 .04 2.00 18 /21 9 /12 Mo 1.5% max, Se 0.30/0.35%,. CG-8 M...- .08 1 50 .04 .04 1.50 18 /21 9 /13 Mo 3.0/4.0%. CH-20.._... 20 1 50 .04 .04 2.00 22 /26 12 /15 CK-20 .20 1 50 .04 .04 2.00 23 /27 19 /22 CN-7 M.... 07 1 50 .04 .04 18 /22 21 /31 Mo-Cu<^. 'CY-40 40 1 50 .015 .015 3.00 14 /17 Bal Fe 11.0% max. CZ-100 1 00 1 50 .015 .015 2.00 " 95 Fe 1.50% max. M-35 35 1 50 .015 .015 2.00 Bal Cu 26/33%, Fe 3.50% max. HA 20 .35/ 65 .04 .04 1.00 8 /lO Mo 0.90/1.20%. HC 50 1 00 .04 .04 2.00 26 /30 b4 Mo 0.5"^ max"!. HD 50 1 50 .04 .04 2.00 26 /30 4 / 7 Mo 0.5'% max'i. HE .20/ 50 2 00 .04 .04 2.00 26 /30 8 /II Mo 0.5% max''. HF .20/ 40 2 00 .04 .04 2.00 19 /23 9 /12 Mo 0.5% max"). HH .20/ 50 2 00 .04 .04 2.00 24 /28 11 /14 Mo 0.5% max''; N 0.2% max. HI .20/ 50 2 00 .04 .04 2.00 26 /30 14 /18 Mo 0.5% max''. HK .20/ 60 2 00 .04 .04 2.00 24 /28 18 /22 Mo 0.5'% max''. HL .20/ 60 2 00 .04 .04 2.00 28 /32 18 /22 Mo 0.5% max''. HN .20/ 50 2 00 .04 .04 2.00 19 /23 23 /27 Mo 0.5% max''. HT .35/ 75 2 00 .04 .04 2.50 13 /17 33 /37 Mo 0.5%, max''. HU .35/ 75 2 00 .04 .04 2.50 17 /21 37 /41 Mo 0.5% max-i. HW .35/ 75 2 00 .04 .04 2.50 10 /14 58 /62 Mo 0.5% max''. HX .35/ 75 2 00 .04 .04 2.50 15 /19 64 /68 Mo 0.5% max''.

» Minimum. b Maximum. There are several proprietary alloy compositions falling within the stated chromium and nickel ranges, and coni taining varying amounts of silicon, molybdenum, and copper. '' Molybdenum not intentionally added. For the cast steels, designations with the initial letter "C" indicate alloys generally used to resist corrosive attack at temperatures less than 1200 °F. Designations with the initial letter "H" indicate alloys generally used under conditions where the metal temperature is in excess of 1200 °F. The second

letter represents the nominal chromium-nickel type, the nickel increasing in amount from ".V" to "Z". Numerals following the letters indicate the maximum

- carbon content of the corrosion-resistant alloys.

117
series of stainless steels. Since the main function of nickel in the 300 series steels is to form

austenite at high temperatures, retain it at ambient temperatures, and to retard its trans- formation during cold working, and since nitrogen is effective in forming austenite at high

temperatures and manganese serves to retain

austenite at room temperature and retard its transformation during cold-work, substitute

stainless steels containing nitrogen and manganese (the 200 series) were developed. Experience with these steels was described by Spencer [837] and Paret [838].

As the chromium-nickel stainless steels are

austenitic at room temperature, they cannot

be hardened by heat treatment. However, they can be hardened by cold work. Part of this

strengthening results from the cold work itself and some from the transformation of the austenite. The degree to which austenite can be

decomposed by cold work is largely dependent

on its chemical composition. Both the percentages of the alloying elements and the ratios in

which they are present have an important in- fluence on the response to cold working. Elements tending to stabilize austenite and thereby decrease the work-hardening rate differ in

their relative effect. As the nickel content is increased up to the limit permitted by the specification for a given stainless steel, the steel becomes more stable and shows a lower rate

of strengthening by cold work. The effect of

chromium depends on the nickel and chromium

content. With nickel contents of 9 to 10 percent

or greater, increasing the chromium content

increases the rate of work hardening. On the

other hand, if the nickel content is below 7

percent, the rate of work hardening decreases

as the chromium content is increased from 17

to 20 percent. Depending on the amount of

cold work, the tensile strength of austenitic

stainless steels varies from about 80,000 psi

for fully annealed to as high as 300,000 psi

for severely work-hardened steel ; the highest

strengths can be secured only with small cross

sections.

Chromium itself causes a significant de- crease in the thermal conductivity of steel and

this characteristic of the straight chromium

martensitic or ferritic steels is accentuated

in the austenitic chromium-nickel steels; in

addition, the coeflflcient of thermal expansion of

the austenitic steels is considerably higher

than that of the martensitic or ferritic steels. Inasmuch as these steels are austenitic, they

are also nonmagnetic. However, many of the

compositions are somewhat marginal so that

partial transformation of the austenite may

occur during cold working or exposure to sub- zero temperatures ; this tendency may be counteracted by increasing nickel, manganese, or carbon, or by decreasing chromium or molybdenum.

The austenitic stainless steels can be hoi

worked readily, although more power is re quired than for unalloyed steels. In some oJ the highly alloyed stainless steels the hot

working properties are improved by smal

amounts of rare earth metals of the cerium

group [839] or of boron [840]. ' Other common characteristics are high re^ sistance to shock, good weldability, and betteij

strength and resistance to scaling at high temperatures and better corrosion resistance thar

the martensitic or ferritic stainless steels. They

are somewhat difficult to machine unless they

contain sulfur or selenium (types 303 and

303Se). When heated in the temperature rangf

of about 800 to 1400 °F, they are susceptible

to carbide precipitation and consequent intergranular corrosion unless they have been sta- bilized by additions of titanium or columbium

(types 321 and 347). Metallographic etching

methods and reagents for the detection of austenite, ferrite, sigma phase, and carbides were

reviewed by Braumann and Pier [841]. Commercial procedures for cleaning, grinding,

pickling, descaling, polishing, buffing, plating,

coloring, etc., were discussed by DuMond [842].

The physical and mechanical properties of

the wrought stainless steels are of interest

for their engineering applications in corrosive

environments. The literature on this subject is extremely voluminous.

Considerable information from various

sources on the physical and mechanical properties of the austenitic stainless steels has been

summarized in publications of The International Nickel Company, Inc. [843,844,845] . The

effect of temperature on some physical properties of selected steels is shown in figures 95

to 99, inclusive.

0.2905

0.2895

0.2885

N2 CH4

77 112

Temperature, K

195

'2 "2'' 233 273 300

• lilt

1 0.2875

0.2865

0.2855 -400

1 1

316^

1 1 1 L

301

347 s,,^

8.04

8.03

8.02

8.01

8.00

7.99

7.98

7.97

7.96

7.95

7.94

7.93

7.92

7.91 7.90

M t

, ii a> ' - Q E

-300 -200 -100

Temperature, F

100

Figure 95. Effect of temperatures on the density of some

stainless steels [844}.

118
I

(!

lOttj

ici

u. 0.125

o

tr

ijj ^ 0.100

_locS 0.075

•-

CQ

. -0.050

<

UJX

o 0.025

u.oUJ Q

^-459.4 -400 -300 -200 -100

3()i,3i6,;547^

504

ai25

0.100

id

ocrLd

a.

o> a:

0.075 _i

<

0.050^

X

0.025 t

oUJ

Q.CO 0

0

100

Figure 96. Effect of temperature on the specific heat of some stainless steels

The austenitic stainless steels find many

ises because of their nonma^etic charactersties. The effect of temperature on the perj-neability of selected steels is shown in figure

'lOO. An interesting use of stainless steels is :or standards of mass. Necessary qualities

'A'ere specified density and low magnetic perTieability. Steels have been developed for den-

"[sities of 8.4 g/cm^ [846] and 8.0 g/cni' [847]

,

:ontaining 32 and 25 percent nickel, respec-

:ively.

As with other metals, the strength of the

'austenitic stainless steels increases at subzero

.:emperatures. Because of its austenitic struc2 X 10'^ -100

Temperature, C

200 400 600 800

^ 10

1

1 1 1

1

1 -300 0 200 400 600 800 1000 1200 1400 1600 1800

Temperature, F

Figure 97. Effect of temperature on the coefficient of expansion of some stainless steels [8.45].

ture, however, ductility is not greatly affected

;

neither is toughness. It is for this reason that

these steels are such favorites for low-temperature use [848]. The effect of low temperature on the tensile and impact properties of

a type 304 stainless steel is shown in figure

101. The mechanical properties of many materials have been surveyed in two monographs

by the National Bureau of Standards [319,

849]. Watson and Christian reported on the

low-temperature properties of cold rolled stainless steel sheet [850].

At elevated temperatures the strength of

the austenitic stainless steels falls off. Typical

properties of some are shown in figures 102,

103, and 104. Many of these data were taken

from the work of Simmons and Cross [851].

The strength-rupture values of the various

steels tend to merge at about 1200 °F. Freeman

and Voorhees' summary [852] of relaxation

properties showed that the replacement of

initial elastic strain by the plastic strain of

creep occurs at approximately this temperature, with resultant reduction in stress level. Improvement in the properties from cold working is still evident up to about 800 °F, provided

that the degree of cold working and the conditions of exposure are not conducive to extensive recrystallization [853].

Recent work on the elevated temperature

properties of the austenitic stainless steels was

presented at the 1963 Joint International Conference on Creep [854,855,856,857] . An ex- haustive series of stress-rupture tests was

made on a type 304 stainless steel to evaluate

its potential as a so-called "standard" stress- rupture specimen [858].

Pfeil and Harries [859] studied the effect of

neutron irradiation on austenitic stainless

119
Q CO o cc

UJ I200

175

150

125

100

75

50

25

0

TY

3C 4,321,347

<

rPE 31 6

E 310

-400 0 400 800 1200

TEMPERATURE°F

1600

Figure 98. Effect of temperature on the thermal conductivity of some stainless steels [5-45].

steels and reported an adverse effect on the

tensile ductility at test temperatures above

600 °C (1110 °F) and a detrimental effect on

the stress-rupture properties. Irvin, Bement,

and Hoagland [860] also reported a marked

650

600 E

550

a>

C3L

(/» 500 Bo

>^ 450

|>

a> 400

cr

"«o

350 oaa UJ 300

250

He H2 4 20

N2

77

Temperature, K CH4 CO2

112 135

CHCIF2 233

H2O

273 300

1 1 1

1

1 1 1 L

/304 _

-316-^

347 _

303

105

100 95 E

90 ^

85 I

80" t

70 I

65 f

o

60 'B 55 lIj 50

-459.4 -400 -300 -200 -100

Temperature, F

100

Figure 99. Effect of temperature on the electrical resistivity of some stainless steels [SH'].

reduction in ductility with increasing exposure

and test temperature. Confirmatory evidence

of the damaging effect of neutron irradiation on the ductility has been given by Martin and

Weir [861] and by Venard and Weir [862].

The tendency of some austenitic stainless

steels to become embrittled at high temperatures, through the formation of the intermetallic sigma phase [863,864,865], is detrimental

to some of the properties. However, heating

sigma-embrittled steels to about 1800 °F eliminates sigma and restores the original toughness. Aborn [839] reported that sigma rarely occurs in plain 18-8 stainless steel. It would

be expected that increase in chromium in- creases the susceptibility to sigma formation,

especially if ferrite is present. This was found

to be so by Rosenberg and Irish [866], who

found sigma to be a stable phase in highpurity 18 percent Cr-10 percent Ni alloys.

Sigma formation in commercial nickel-chromium-iron alloys was summarized by Foley

and Krivobok [867].

As a group, the modulus of elasticity in ten- sion or compression of the annealed wrought

stainless steels is about 29,000,000 psi. Poisson's ratio is about 0.30. The resistance to corrosion of stainless

steels with chromium contents in excess of

about 11-12 percent is due to the presence of

ban

1 Wf

3 icrf

Epo:

otl

(

120
0.001

-423 -321 -108

TEMPERATURE, °F

+ 80

Figure 100. Effect of temperature on the permeability of some annealed stainless steels [5^4].

passive oxide film that is richer in chromium

lhan the underlying metal [839]. Protection

Ifforded by this film is complete at room and

loderately elevated temperatures, but the film

icreases in thickness as the temperature

icreases and becomes a scale at very high

emperatures. Eiselstein and Skinner [868]

sported that scaling of stainless steels did

ot become pronounced until temperatures of

800 or higher were reached. Paret [838]

eported that the scaling resistance of the high-

'langanese types 201 and 202 was equivalent

0 that of types 301 and 302 up to about

1550 but that above that temperature the

high-manganese steels scaled faster. Keith,

Siebert, and Sinnot [869] reported that intergranular oxides formed by 100 hours exposure

at 1900 °F had the same composition as the

external scale, both being high in chromium

and manganese, and low in nickel as compared with the underlying metal.

In some of the early uses of austenitic stainless steel at elevated temperatures, it was

observed that they became embrittled and

subject to intergranular corrosion. This intergranular embrittlement was the result of the

precipitation of chromium carbides at the

grain boundaries of steels heated in the range

121
280

240

g 200

160

UJH 120

80

40

1 b

RA,

YS

ELONC

80 9

70

60

50

40

lij UJ

a: O UJ z Q.

< > _ <

O

5-

UJ

X

120 o

-500 -400 -300 -200 -100

TEMPERATURE, °F

100 I !^

100 <^X _ u

Figure 101. Effect of low temperature on the tensile and impact properties of type 302 stainless steel [84i'\.

of 800 to 1400 °F and became evident when

such steel was subsequently subjected to acidic

environments. This problem was attacked in

two ways: (1) by reduction in the amount of

carbon available to form carbides, i.e., by the

development of low-carbon steels such as 304L

and 316L, and (2) by the addition of titanium

or columbium (types 321 and 347) that formed

their own stable carbides and thus prevented

the formation of chromium carbides. Testing

procedure to determine the susceptibility of

austenitic stainless steel to intergranular at- tack, using acidified copper sulfate solution,

is covered by ASTM Specification A393-63.

The susceptibility to intergranular embrittlement was explored in detail by Rosenberg and

Darr [870], by Binder, Brown, and Franks

[871], by Tupholme and Bouchier [872], and

by Schwaab, Schwenk, and Temes [873].

The resistance of austenitic stainless steel to corrosion in a great many media has re- sulted in extensive uses in the chemical, transportation, and petroleum industries; in food

i ESS

ESis

ion

ElM

m

wit

IDt

processing and dairy equipment; in hospitali

surgical, and pharmaceutical equipment; ir the fatty acid industry; in the production oi

atomic power ; in the paper making and textik^

industries; in domestic uses, and many others

The resistance to a particular corrosive me- dium may vary with the concentration of the li corrodent; the presence of impurities, includ- w

ing oxygen; the temperature, composition!

prior history, and surface condition of thelit steel ; contact with dissimilar metals ; and with' !raf other factors. Stainless steel has been studied! k

for use in the human body; Fischer and Zit-< ter [874] suggested the use of slightly modified type 316 for implants.

The low-carbon stainless steels generally!

show improved resistance to corrosion, as dci the steels with increased alloy content. The

addition of molybdenum (types 316 and 317)i|etj

improves the resistance of 18:8 to many media, including sulfurous, sulfuric, phosphoric,

formic, and various hot organic acids [875].

The 18:8 steels have good resistance to nitric^

122
Figure 102. Effect of temperature on the short-time tensile properties of several annealed austenitic stainless steels [8^51.

I cid, but have no resistance to hydrochloric.

I'^sukamoto [876] described a special stainjess steel, designated NTK-M7, that has good

' fesistance to hydrochloric acid ; its composiI ion is carbon 0.06 percent max, manganese

l.'.O percent max, silicon 1.0 percent max, chrojnium 9-11 percent, nickel 16-18 percent, molybdenum 6-8 percent. Types 316 and 317 are

I esistant to pitting corrosion and give useful

alJilervice at room temperature in sulfuric acid

ijr'f concentrations lower than 20 percent and

oi(iigher than 85 percent. Between these limits

-ilhey are subject to rapid attack. The Carpenriker Steel Company developed a steel of comJ^iosition carbon 0.07 percent max, manganese

)j|!».75 percent, silicon 1 percent, chromium 20

,(l]?)ercent, nickel 29 percent, molybdenum 2 perijjient min, copper 3 percent min, that is resistifti nt to sulfuric acid ; recent work by Class and

t^Trafen [877] indicates that this steel with 1

e(r)ercent columbium added (Carpenter Stainrt jess 20 Cb) exhibits satisfactory resistance to

iiiulfuric acid.

A comprehensive review of the effect of

Ijijilloying elements upon the corrosion resistihnce of stainless steels was published by Class

|(ii'878]. A review of the literature relating to

fjinetallurgical factors involved in welding the

e?.8-8 steels was prepared by Ball [879].

t; Many of the stainless steels are subject to

I |.tress-corrosion cracking and this has been

i)he subject of considerable research. A compilation of case histories was published in

1960 [880] and many recent papers are of

interest [881,882,883,884,885]. Hochmann and

Bourrat [886] reported that the addition of

3.3 to 4.1 percent silicon significantly in- creased the resistance of 18: 10 to stress corrosion. Snowden [887] noted that the more

stable austenite resulting from increased

nickel content has greater resistance to stress- corrosion cracking, and Eckel [888] reported

that the nucleation of stress-corrosion cracking was delayed by an increase in nickel content.

• According to Truman and Kirby [889],

stress-corrosion cracking of the stainless steels

is not the hazard it might seem to be from the

number of papers that have been published.

They indicate that it is likely to occur only

under certain specific conditions, the limits

of which are fairly well defined. Fairman [890]

reported that stress-corrosion cracking may

be prevented by suitable cathodic protection.

The effect of irradiation on the stress-corrosion

cracking of type 316 and a 20 percent Cr-25

percent Ni-1 percent Nb stainless steel developed specifically for reactor applications was

studied by Davies, Landsman, and Seddon

[891]. They found that the susceptibility to stress-corrosion cracking of the former steel was greatly increased, whereas the latter steel proved to be immune both in the unirradiated

and in the irradiated conditions.

Considerable data on the corrosion resist-

[ 123
65

800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800

TEMPERATURE, F

Figure 103. Stress-rupture curves for several annealed austenitic stainless

steels [845].

ance of the austenitic stainless steels have been

summarized by The International Nickel Company, Inc. [892,893,894,895].

Stainless steel is expensive and for many

applications the use of carbon or low-alloy

steels, clad with stainless, represents a successful compromise betv^^een cost and corrosion

resistance. Stainless clad steels are described by

Ma [896].

The cast stainless steels, as indicated in

table 68, fall into two broad groups—the cor- rosion-resistant and the heat-resistant. Many

of the compositions correspond generally to those of the wrought steels. Resistance to both

corrosion and heat increases as the total alloy

increases; maximum resistance is obtained

with castings extremely high in nickel.

Detailed and specific information on the

physical constants and mechanical properties,

as well as heat treatment and fabricating pre

cedures and design consideration, are givei

for all of the cast steels in the form of dat,

sheets issued by the Alloy Casting Institut

[897]. Criteria for the selection of the heat

resisting grades, as well as their short- an(

long-time strength characteristics at tempera

tures up to 1880 °F, are given by Schoeffe

[898,899]. The effect of low temperatures oi _

the mechanical properties of cast stainless stee has been studied by Mayer and Balajva [900

and by Hall [901], both of whom reported tha

the cast steels retained useful ductility ancf^

toughness down to the lowest test temperature

(-430 °F for Hall).

d. Precipitation-Hardening Stainless Steels The precipitation hardenable stainless steels are a series of iron^chromium-nickel alloys t

124
1100 1200 1300

TEMPERATURE, °F

1600

Figure 104. Creep rate curves for several annealed austenitic stainless steels

which additional elements have been added to provide hardening by precipitation reactions.

The steels are divided into three broad groups

martensitic, semi-austenitic, and austenitic

steels. Nominal compositions are given in table

69. Development work in this field has been

extremely active and there are literally dozens

of other precipitation-hardening stainless

steels. The compositions of the martensitic steels are so adjusted that the Ms transformation is above ambient. Actually, both stainless W and

Table 69. Nominal compositions of some of the precipitation hardening stainless steels \902\

Designation Producer Chemical composition, %

C Mn P s Si Cr Ni Cu Mo Ti Al Cb+Ta N V

Martensitic steels

stainless W U.S. Steel 0.07

.04 0.50.25 0.010.020 0.010

.010 0.60.60 17.016.0 7.0 4.0

0.70 0.20

17-4 PH -Vrmco 3.2 0.25

Semiaustenitic steels

VM-350 .\llegheny Ludlum .10

.13

.07

.07

.80

.95 .60

.60

.020

.020

.020

.020

oooo oooo

.25

.25 .40

.40

16.5

15.5 17.0 15.0

4.3

4.3 7.0

7.0

2.75

2.75 0.10 VM-355 .\lleghenv Ludlum .10

.

1^15""

1.15

17-7 PH .Vrmco PH 15-7 Mo -Vrmco 2.20

Austenitic steels

HN'M Crucible .30

.12

.12

.06

3..50

.75

.75 1.50

.25

.25 .020 .020

.025 .030

.010

.020

.50 .60

..50 .70

18.5 17.0

16.0 15.0

9.5

10.0

14.0 26.0

17-10 P Armco - 17-14 Cii Mo

V-286

.\rmco

.Vllegheny Ludlum

3.0 2.5

1.2

.25 1.8.50 .020 0.30

125
17-4 PH are severely unbalanced AISI 301

types. The austenite in both steels is so unstable that it transforms to martensite at about

200 to 300 °F upon cooling from the solution

annealing temperature (about 1900 °F). In

this condition it has relatively high strength

and \ow ductility. A simple aging treatment

at about 900 to 1000 °F promotes the precipitation of intermetallic compounds and causes

full hardening.

The semiaustenitic stainless steels are essentially similar to those in the martensitic group

except that the composition is so adjusted that

the Ms temperature is depressed. Solution annealing below 1700 °F results in transformation above room temperature; annealing at higher temperatures depresses the Ms transformation to subzero temperatures. As annealed, these steels are soft and ductile and

therefore are amenable to fabricating operations.

These characteristics permit the use of a variety of heat treatments. The steels can be

transformed by conditioning the austenite at about 1700 °F, followed by refrigeration at —100 °F, or by conditioning at 1300 to 1400 °F

followed by cooling to about 60 °F. This conditioning treatment allows some of the carbon

originally in solution in the austenite to precipitate as chromium carbides. The depletion

of chromium and carbon from the austenite

reduces its stability, i.e., it raises the Ms temperature. Upon cooling to room temperature or below, the austenite-to-martensite transformation reaches completion. The transformation can also be effected by severely cold working

the steel as annealed at 1950 °F. Full hardening

is then effected by a subsequent aging treat- ment at 900 to 1050 °F.

The compositions of the austenitic steels are adjusted so as to assure retention of the austenitic structure under all conditions of heat

treatment. These steels are solution annealed

at temperatures above 2000 °F. As so annealed,

the steels are soft and ductile and therefore

amenable to fabricating operations. Complete

hardening is effected by aging at 1300 to 1450 °F.

The physical metallurgy of the precipitationhardening stainless steels has been discussed

by Ludwigson and Hall [903], by Dulis [904],

and by Lena [904a]. Data on physical and

mechanical properties are given by Roach and

Hall [905], Brisbane [906], Roberts, Roach,

and Hall [907] , Holmberg [908] , and Inter- national Nickel [902].

The strengths and ductilities of the precipitation-hardening stainless steels vary over a

considerable range, depending on treatment.

Maximum strengths are approximately as fol- lows [902]

Martensiti-c steels _ _ _

Tensile Yield i

psi

210,000

265 000

150,000

C psi

200,000 -

100,000

Spim-a 1 ic;t.PTn t,i f* tstppic; Austenitic steels

i

itii

One of the semiaustenitic steels (AM-355)1

can be treated to as high as 350,000 psi tensile

and 335,000 psi yield by very severe cold work-^

ing prior to aging [903]. As with other ma-5

terials, the higher strengths in all these steels usually are obtained at some sacrifice in ductility. ^ The strength properties increase as the tem-J_

perature decreases [319,849,902] . Ductility and

toughness decrease, but Campbell and Rice

[909] note that many of these steels have

reasonably good ductility and toughness down

to —108 °F (the temperature of CO2). Below

this, ductility and toughness decrease rapidly,

An important attribute of the precipitatior

hardenable stainless steels is retention ol|

strength at moderately elevated temperatures

(600 to 1000 °F). Since this temperature,

range extends into the precipitation hardening

range, additional aging can occur in servicejj

This may or may not be beneficial. In several

of the grades, long time aging can impair tint] usefulness of the alloy for service in the range

600 to 800 °F because of embrittlement.

These steels also have excellent stress rupture and creep properties at moderatelj^

elevated temperatures [672]. At higher tem

peratures (up to 1300 °F), the austenitic prej

cipitation-hardening stainless steels retail]

their strength properties to a greater degree:

than the other types of precipitation-hardening

steels. Data on the mechanical properties of the precipitation-hardening stainless steels are contained in the booklet of International Nickelj

[902]. Additional data have been reported by,

Pearl, Kappelt, and King [910].

The corrosion resistance of these steels is inferior to that of the 300 series (the 18-8

steels), but is still markedly superior to thai; of the 400 series (the straight chromiunq.

steels).

Precipitation-hardening stainless steels may

be used in the cast condition, although compo-[

sitions may vary somewhat. Thus, CB-7Cifi

(table 68) is somewhat similar to 17-4 Pd

(table 69). Data on the mechanical properties{

of castings of this steel are given by Ekey and

Black [911], and of CD-4M Cu by Schoefei,

[912,913]. Four precipitation-hardening stain-, less steels for casting were described by Mott

[914]. I The semiaustenitic precipitation hardening

stainless steel designated PH 14-8 Mo [915J:

is a modification of PH 15-7 Mo. It gives betf

126
ter toughness at high strength levels and also

possesses increased stability at high temperaitures. Its composition is carbon 0.05 percent

max, manganese and silicon 1.0 percent max,

phosphorus 0.015 percent max, sulfur 0.010

percent max, chromium 13.5 to 15.5 percent,

I nickel 7.5 to 9.5 percent, molybdenum 2.0 to

1 3.0 percent, aluminum 0.75 to 1.5 percent,

j The weldability of the precipitation hardenj ing stainless steels varies with composition,

' but all of them except those high in phosphorus

can be readily welded by conventional methods [916,917].

' Two stainless maraging steels designated as iAM 362 and AM 363 combine the mechanical

properties of nickel maraging steels with the

corrosion resistance of stainless steels [918].

' These two steels are readily weldable.

14.5. Thermal Expansion and Constant Modulus Alloys

I The fact that iron-nickel alloys containing

about 36 percent of nickel have extremely low

coefficients of thermal expansion was observed

by Guillaume [919] in 1897 in a search for less expensive materials than the platinum-iridium

alloy that was then the standard for metrology. Additional data were published subsequently [920] . Because the 36 percent alloy

had such a low coefficient of expansion at room

temperature that the linear dimensions were

almost invariable over ordinary changes in

temperature, Guillaume named it Invar. In a

' study of the elastic properties of this alloy,

' Guillaume found that the addition of 12 percent of chromium produced an alloy that had

' an invariable modulus of elasticity over a considerable range of temperature, as well as rea-

' sonably low thermal expansion. This alloy he

I named Elinvar. It is now known that these low

coefficients of expansion represent an approximate balance between expansion from thermal

agitation and contraction from magnetostriction.

Subsequent investigations here and abroad

confirmed and extended Guillaume's original

observations. Owen, Yates, and Sully [120]

showed that increasing the temperature above room temperature increased the minimum coefficient of expansion and shifted it toward

that of the higher nickel contents. Figure 105

shows their data for alpha and for gamma al- loys. Compositions between about 18 and 28

percent of nickel are mixtures of alpha and

gamma. Atomic precentages of nickel in ironnickel alloys are approximately the same as weight percentages; for instance, 36 atomic

percent is 35 weight percent.

Scott [921] showed that, as the nickel content is increased above 36 percent, the coeffi- cients of expansion increase but are retained

to higher temperatures. This is important

20X10

20 40 60 80

NICKEL, ATOMIC %

Figure 105. Coefficient of thermal expansion of iron- nickel alloys at temperatures up to 500 °C [120'].

where a low-expansion material is needed at temperatures in excess of that at which the

36 percent alloy is eflfective. Figure 106, ac- cording to Hunter [922], shows the eflfect of

temperature on the thermal expansion of alloys

containing 36 to 52 percent of nickel, in comparison with a plain carbon steel. The 36 percent nickel alloy Invar (also marketed under the designation Nilvar) is the

most widely used alloy for applications requiring low thermal expansivity up to about 400 °F.

This alloy finds extensive use as the low expansion side of thermostatic bimetals, measuring

devices, electronic equipment, and other applications requiring extreme dimensional stability over temperature ranges up to 400 °F. SuperInvar (also sold under the designation SuperNilvar) has near zero expansivity over the

Invar temperature range. It contains 31 percent nickel plus cobalt.

1.000 200 400 600

TEMPERATURE, C

Figure 106. Thermal expansion of iron-nickel alloys

[922}.

127
Table 70. Approximate physical and mechanical properties of three low-expansion alloys in the annealed condition [923]

36% Nickel 42% Nickel 49% Nickel

Average coefficient of expansion per °F between -200 and 0 °F

0 and 200 'P 200 and 400 °F 400 and 600 °F 600 and 800 °F 800 and 1000 °F

Curie temperature °F_.

Tensile strength psi_. Yield point psi-- Elongation in 2 in %--

Reduction of area %

Urinell hardness Modulus of elasticity psi__ Temperature coefficient of the modulus of elasticity per °F-- Modulus of rigiaity psi-- Temperature coefficient of the modulus of rigiditj' per °F--

Poisson's ratio Electrical resistance: ohms/mil-ft microhm-cm

Temperature coefficient of electrical resistance per °F--

Specific heat between 77-212 °F Btu/lb/°F or cal/g/''C__ Thermal conductivity between 68-212 °F Btu/hr/ft Vin/°F_-

cal/sec/cm Vcm/°C--

Density:

lb/ft g/cm '

1,1X10-6

l!5 . 6.4

8.6 9.5

3.4X10-6

3.2 3.0

3.2

5.5 8.6

5.4xl0-«

5.6

5.6 5.6

5.6

7.3 530 71,000

40,000

43

75

132

21 ,000,000 + 270X 10- 8,100,000 +300X10-

755 68,000

35 , 000

45

75

138 22,000,000 + 150X10-«

8,500,000 + 50X 10-«

965 77,000 33,000

45

75

144 24,000,000 -130X10-

9,300,000 -50X10-

0.290

490

810.67X10-"

0.123

93

.0323

508

8.13

0.290 420

700.66X10-

0.121

106

.0366

507

8.12

0.290

290481.66X10-'

0.120

124 .0428

5148.23

From 400 to 650 °F, the 42 percent nickel

alloy is used, and from 650 to 1000 °F, the al- loys containing 47 to 50 percent of nickel are

used. These alloys are generally designated by

their nickel content, such as "52 Alloy." They

find extensive use a,s the low expansion side

of thermostatic bimetals operating at temperatures above the Invar range, as glass sealing

alloys suitable for use in conjunction with

many soft glasses, and other applications re- quiring low but not minimum expansivity.

Practical experience has shown that these

three compositions will satisfy most requirements. The approximate physical and mechanical properties of these three alloys are shown

in table 70. The physical and mechanical propTable 71. Effect of heat treatment and impurities on the thermal expansion of Invar [925]

Compositon, percent

Coefficient of expansion,

niillionths per °C from -40 to +40 °C

c Mn Si Ni Annealed" Water

quenched'' Quenchedand

stabilized "

Commercial Invar

0.07 0.44 0.24 36.8 1.9 0.9 1.1

Experimental alloys

0.02

.10

.15 .25

0.09

.12 .08

.05

0.01

.08

.17

.20

36.0

36.1 36.0

36.6

0.8

1.0

1.5

1.4

0.1

.1

.1.1

0.0

.0

.0 1.0

>' Furnace cooled after 30 min at 830 ° C.

>> Water quei.ched after 30 min at 830 ° C.

o Treatment b, then stabilized by reheating at 95 "C for 48 hr, followed by air cooling.

erties of the Invar type alloys are discussed

in detail by McCain and Maringer [924].

The linear expansion of Invar, and particularly the minimum expansion values, are affected by the presence of impurities and by

additions of alloying elements. The expansivity of fully annealed Invar is appreciably

higher than that of quenched or cold-worked

material. These extremely low expansion val- ues of quenched or cold-worked material are

unstable with respect to time and temperature,

but the alloys can be stabilized by low-temperature annealing. The effect of heat treatment

and of minor changes in composition is shown

by the data of Lement, Roberts, and Averbach [925] in table 71. The water-quenched

high-purity alloys have coefficients of expansion close to that of fused quartz for the temperature range indicated. Additions of manganese,

chromium, silicon, tungsten, or molybdenum

tend to shift the area of minimum expansivity

toward higher nickel contents, whereas copper and carbon have the reverse effect [94]. Some of the aging effects observed in

Invars are attributed to the precipitation of

carbon or carbides, others to intermetallic

compounds. Cobalt lowers the coefficient of

Invar at ordinary temperatures [921,926], and

titanium raises the minimum value of the coefficient and shifts it toward that of the higher

nickel contents [927].

A series of age-hardening alloys with a constant modulus of elasticity, each containing

about 2.5 percent of titanium, was reported by

Mudge and Talbot [927] . Three of these alloys are called Ni-Span-Lo with appropriate numbers to designate their, nickel contents of 42, 45,

128
md 52 percent. With proper cold working and

Ifieat treatment these alloys have tensile

strengths approaching 200,000 psi. Other alloys

reported by Mudge and Talbot were a relatively

fiigh expansion alloy, Ni-Span-C alloy 902, containing 8 to 9 percent of chromium, and a constant modulus alloy, Ni-Span-C that contains 42

percent of nickel and 5.5 percent of chromium.

The constant modulus alloys generally contain

B6 to 42 percent of nickel plus one or more of

the following: Cr, W, Mo, Ti, Al. The use of

constant modulus alloys as spring materials was

reviewed by Carlson [928] as follows, with

compositions as listed by Woldman [929] : "Elinvar—the first of the constant modulus

materials and used for horological springs,

weighing scales, tuning forks, bourdon tubes,

and other applications requiring invariant

elasticity with temperature variations. The

original composition of 36% Ni, 12% Cr,

balance iron was austenitic and hardenable

only by cold work; modern Elinvar Extra

contains 42% Ni, 5% Cr, 2.5% Ti, 0.5% Al,

balance iron.

"Ni-Span-C alloy 902—42 percent Ni, 5.5 percent Cr, 2.4 percent Ti, 0.6 percent Al,

balance iron alloy developed by the International Nickel Company. Most popular of the

constant modulus alloys. Usually formed in

the 50% cold-worked condition and precipitation hardened at 900 °F for 8 hr, or at 1250

°F for 3 hr to produce a hardness of 40 to 44 R^., permitting safe torsional loads of

60,000 to 80,000 psi. The alloy is ferromagnetic up to 400 °F and nonmagnetic at higher

temperatures. Its thermal expansion at room

temperature is 3.8 to 4 X 10 ^ per °F.

"Iso-Elastic—36% Ni, 8% Cr, 4% Mn-Si-V,

0.5% Mo, balance iron alloy developed by

John Chatillon and Sons. Easier to fabricate

than Ni-Span-C and popular for scales, dynamometers, and instruments. Used at 30 to 40

Ro to withstand torsional stresses of 40,000 to 60,000 psi.

"Elgiloy—40% Co, 20% Cr, 15% Ni, 7% Mo,

15% Fe, 2% Mn, 0.05% Be alloy also called

8J alloy, Durapower, and Cobenium. Developed at Battelle Memorial Institute [930] for

the Elgin Watch Company in cooperation

with wire producers. The alloy is nonmagnetic. It is worked and precipitation hardened

at 900 ^F to produce a hardness of 48 to 50

R,.. It is used in Elgin watches and instruments for torsional stresses below 75,000 psi

from subzero temperatures to about 1,000 °F.

"Dynavar—Fe, Ni, Cr, Co, alloy developed by

the Hamilton Watch Company. Nonmagnetic

;

precipitation hardened at 900 °F. Useful from

subzero temperatures to about 1,000 °F."

Clark [931] patented an alloy with the de-

;ired composition of 42.2 percent Ni, 2.8 percent Ti, 6.5 percent Cr, remainder iron, that

exhibits a substantially zero thermoelastic coefficient and low mechanical hysteresis in the

age-hardened condition. Eiselstein and Bell

[932] patented an age-hardenable iron-nickelcobalt base alloy stated to have a constant thermoelastic coeflicient over a wide range of temperature. The composition is 16 percent Ni min,

12.5 percent Co min, 0-6 percent Cb and/or 0-12

percent Ta, 0.5-1.5 percent Ti, 0-1 percent Si,

0-1 percent Mn, 0-1 percent Al, 0-0.2 percent C,

0-0.1 percent Ca, remainder (at least 31%) Fe. Several of the iron-nickel and modified al- loys are used for making glass-to-metal seals for

electrical connections into vacuum tubes, laboratory apparatus, etc. For stress-free and vacuumtight joints the expansion curves of the metal

and glass must be close together, and any particular alloy cannot be used above its Curie

temperature, where an inflection in the expansion occurs. The presence on the surface of some

metallic oxide, produced during heating, probably is essential to the production of a good seal,

and preoxidation of the metal frequently facili- tates the sealing operation. Copper has been

added to some of the alloys or used as a coating

to facilitate the formation of a good seal. The

alloy known as Dumet, which is 42 percent Ni

(25% Cu clad) is used as leads to electric light

bulbs and electronic tubes, and other glass seal- ing applications requiring high electrical conductivity.

The alloys of 42 percent Ni, 5.5 percent Cr,

balance iron, known as Sylvania HC4, Sealmet

HC4, Carpenter 426, are suitable for seals in

many soft glasses. Alloys of 29 percent nickel

plus 17 percent cobalt are suitable for sealing

hard, heat resistant glasses. Fernico (28%, Ni,

18% Co, 54% Fe) and Kovar (29% Ni, 17%

Co, 0.3% Mn, balance Fe), are two of these

alloys. Others are known as Therlo and Rodar.

Grosvenor [664] reported that the 42-percent

nickel irons were used with soft glasses, the 52

percent nickel iron and Kovar or Fernico with

certain hard glasses, and cited data supplied by

G. V. Luerssen to illustrate the close match in

expansion of a 42-percent nickel alloy with soft

glass, as shown in figure 107. For borosilicate

50X10" ^ 40 CP

a> T3 ^,3 0 £

o

Tn 20 z

<t5< 10 -no/. ^

200 400 600 800

TEMPERATURE, °F 1000

Figure 107. Thermal expansion curves of i2 percent

nickel-iron alloy and soft glass [66Jf~\.

129
Table 72. Iron-nickel sealing alloys according to ASTM Specification F30-63T

Composition—percen t Average linear

coefficient of thermal

expansion

cm/cm/^C X 10~^

Temperatur

range, °C Ni Mn Si C Ci- Co P

• S Al Fe

42 alloy 41 0.80 0.30 0.05 0.10 0.50 0.025 0.025 0.10 bal 4.0— 4 .

30-3C 6.7— 7.4 30-45 46 alloy 46 .80 .30 .05 .10 .50 .025 .025 .10 bal 7.1— 7.8 30—35 8.2- 8.9 30-50 48 .80 .30 .05 . 10 .50 .025 .025 .10 ba! 8.2- 9.2 30-40 9!6-10!3 30-55

52 alloy 50.5 .60 .30 .05 .10 .50 .025 .025 .10 bal 9.6-10.1 30-45

10.2-10.7 30-55

The nickel contents are nominal. All others, except iron, are maximum.

glasses, an alloy containing 30 percent Ni, 17

percent Co, and 53 percent Fe has been recom- mended [933,934]

The American Society for Testing and Materials lists the chemical requirements and ex- pansion characteristics of glass-to- metal sealing

alloys in Specification F30-63T, as shown in

table 72. This society also lists Specification

F31-63T, covering the 42% Ni-6% Cr-Fe seal- ing alloy. The composition is given as

« oei'si

Nickel

Chromium

Carbon

Manganese

Phosphorus

Sulfur

Silicon

Aluminum

Iron

42% (nominal)

5.6 (nominal)

.07 (max)

.25 (max)

.025 (max)

.025 (max)

.30 (max)

.20 (max)

remainder.

The average linear coefficient of expansion, ex- pressed as cm/cm/°C, falls within the following

limits: 9.7 to 10.4 X IQ-^ for 30 to 425 °C, and

8.5 to 9.2 X 10-« for 30 to 350 °C.

Patents covering sealing alloys have been is- sued to Williams [935] for a zirconium-containing glass-to-metal sealing alloy producing bubble-free seals; to Smith [936] for an ironnickel-cobalt alloy for sealing to high-alumina

ceramics ; to Wloka [937] for alloys for sealing

to both soft and hard glass; to Scott [938] for an alloy capable of withstanding a wide range

of temperature variation, and to the Pittsburgh

Plate Glass Company [939] for an alloy known

as "4750" suitable for sealing to lead-borosili- cate plate and window glass. The characteristics

and applications of 8 sealing alloys (7 of which

contain nickel) were described by Eberly [940].

A technique for producing reliably air-tight

seals between nickel and glass was described by

Certa [941].

Minovar is an austenitic iron that contains

36 percent Ni, 1.5 percent Si, 0.5 percent Cr,

and 2.40 percent maximum total carbon [942].

Its coefficient of expansion is 2.2 X 10"^ per °F,

about one-third that of ordinary irons, and

Minovar therefore is useful for such applications as spindle housings of precision drilling,

boring, and grinding machines. Alloys contain-] m

ing 27 percent Ni, 5 percent Mo, 67 percent Fe, or 42 percent Ni, 5 percent Mo, 53 percent FeJsi have been used for the high-expansion side of

thermostatic bimetals [943].

4.6. Magnetic Alloys

A

Useful magnetic materials either have higKlpj,., permeability and are magnetized and demag-|

netized easily, or are permanent magnets and

magnetize with difficulty but retain their magnetism tenaciously [944]. Most of the ferro-,

magnetic substances are alloys containing one

or more of the elements iron, nickel and cobalt; some are nonmetallic compounds of these three

elements, sometimes plus others; and some are, alloys that contain no iron, nickel, or cobalt but

are composed of manganese and other elements

that are individually nonmagnetic. This discus-i

sion will be confined to the magnetically soft

and permanent magnet ferrous materials in

which nickel is a major constituent. An excel-i lent condensation of this subject has been pre-1

pared by The International Nickel Company,^

Limited [945]. For applications of magnetic

nickel-iron alloys, see Smith [946]. For discussions for magnetic alloys, see Stanley [173,

947].

a. Magnetically Soft Materials

It became generally recognized about 1920, c as a result of the work of Arnold and Elmen

[948], that nickel-iron alloys containing from

35 to 90 percent of nickel had high permeabilities at low field strengths and several of these

alloys were called Permalloys, with numerical

prefixes to indicate the nickel content. The 78-

Permalloy (78% nickel) developed maximum

permeabilities approaching 100,000, together

with low hysteresis losses, low saturation values, very low magnetostriction, and low elec- trical resistivity. These properties were obtained after heating the alloy to 900 °C and

cooling it slowly, followed by reheating to 600

°C with final rapid cooling to room temperature [696]. Even more remarkable properties were exhibited by Permalloys when the material was exposed to a magnetic field of several

130
Table 73. Magnetic properties of some iron-nickel alloys [917]

Alloy Composition, percent Hj'drogen

heat treatment

Relative permeability

Coercivity Saturation Electrical

restivity Curie temperature

Density Ni Fe Other Initial Maximum

induction

45 Permalloy 4550

78

79

7579

5450

21

16

18

15

°C

1,050

1,200 1,050+600

1,100

1,100

1,300

2,500

4,000

8,000

20,000

20,000

100,000

25,000

80,000

100,000

150,000 150,000 1,000.000

Oersteds 0.30

.05

.05 .05

.03 .004

Gausses 16,000

16,000

10,000 8,700

7,200 8.000

MicTofiTfi-cm 50

35

165760

60

°C 440

500

580 420

430

400

g/cTfl ^ 8. 17 8.25 8.60

8.72 8.58

8.87

Hiperink 78 Permalloy 4-79 Permalloy. Mu metal

Su[>ermalloy . . .

4 Mo

2 Cr, 5 Cu

5 Mo

2 1

oersteds during the reheating to 600 °C. This

magnetic anneal greatly increased the maximum permeability, diminished the coercive

force, and converted the hysteresis loop to a substantially rectangular shape, the effects being at a maximum for alloys containing 65 to 70 percent of nickel, as shown in figure 108.

During World War II a gi'eat improvement was made in the Permalloys by heat treating them

in pure hydrogen at about 1,200 °C. The 78-

Permalloy has been widely used in transformers

transmitting weak signals of communication apparatus, whereas Hypernik, which contains 50

percent of nickel and was developed by Yensen,

has been used in the transmission of power

[944].

Additions of chromium, copper, molybdenum,

or vanadium reduce the sensitivity of the ironnickel alloys to heat treatment variables and

thereby simplify the control of cooling rates to obtain high permeabilities. These elements also

increase electrical resistivity, which is desirable

for alternating current applications. Of the al- loys summarized in table 73, the 4-79 Permalloy

and Mumetal alloys are the most widely used

and Supermalloy is the most responsive to the

hydrogen anneal, with initial permeabilities of more than 1,000,000 obtainable commercially

even in thin sheets [174,944].

Elmen [949] found that iron-nickel-cobalt al- loys, which he called Perminvars, had permeabilities that were independent of field strength

over a relatively large range, particularly when

the usual heat treatment at about 1,000 °C was

300X lO200

100

X

1

MAGNET

ANNE/

icfV

L \

/ a\ / RAPID' iS SLOW

20 40 60

NICKEL, 7o

80 100

followed by about 24 hr at about 400 °C. The

Perminvar containing 45 percent Ni, 30 percent Fe, and 25 percent Co is a good example ; a

permeability of 300 is obtainable for a field of

about 3 Oe, corresponding to a flux density of

1,000 G. The resistivity of Perminvars is low

but can be increased by additions of molybdenum or chromium [173]. Useful alloys in the

Perminvar class include the nickel-iron-alloys

Conpernik (50% Ni) and Isoperm (40% Ni).

Iron-nickel-manganese alloys containing 5 to 15 percent of manganese generally have lower

permeabilities than the iron-nickel-chromium or iron-nickel-molybdenum alloys, but have been

used commercially. Addition of 1 or 2 percent

of manganese improves the forging and mechanical properties of iron-nickel alloys [173].

Other useful alloys in the Permalloy or Hypernik class include Sinimax (43% Ni, 3.25%

Si, Fe), Nicalloy (47% Ni, Fe), Monimax

(47% Ni, 3% Mo, Fe), and 1040 (72% Ni,

14% Cu, 3% Mo, Fe). Gyorgy and Nesbitt

[950] found that the coercive force of Permalloy could be raised to the level desirable for

magnetic memory devices, without adverse ef- fects on the rectangularity of the hysteresis

loop, by the addition of gold and patented an

alloy with the following ranges: 0.5-20.0 percent gold, 35-85 percent (preferably 63-85%)

nickel, remainder iron, the ratio of nickel to iron

being between 2:1 and 6:1.

Many of the iron-nickel alloys have anisotropic magnetic properties, that is to say, properties which are different along the different crystallographic axes. By suitable alignment of structure, properties can be obtained

which are distinct from those of the material

in the random condition. These effects can be

produced either by cold work or by heat treat- ment, or by a combination of the two.

Magnetically soft materials generally are used as solid metals. For some uses, for ex- ample, inductances in telephonic and radio frequency circuits, cores made of finely divided

material are required to minimize eddy current

losses. To facilitate the preparation of powders

with particle diameters in the range from

0.0002 to 0.0004 in, the alloys frequently are

embrittled by the addition of a few tenths of

1 percent of sulfur. The powder is annealed,

mixed with a suitable bonding agent such as

131
Eakelite, and molded in a die under pressure.

The permeability of the compact depends upon

the particle size and shape, thickness, and molding pressure. Useful permeabilities are 20 to 80 for telephonic use and 5 to 20 for radio frequencies. The ferromagnetic oxides or ferrites are also used in powdered form for high-frequency applications because of their high elec- trical resistance and consequent low eddy losses. Typical examples are NiO • FeoOa, MgO • Fe203,

and NiO • ZnO • FesOa, but many oxides with

low loss and high permeability have been identified, for example, by Snoek [951]. All Fe20.<i ferrites have negative magnetostriction, but

magnetite (Fe304) is positive, and mixtures of

the negative magnetostriction materials with

magnetite readily produce substances with zero magnetostriction [173].

The magnetically soft nickel-irons have been

established for some time. Consequently, recent

literature has been more concerned with the

theory of magnetic behavior than with the development of new alloys. Bozorth [952] studied

the effect of cooling rate on the magnetic anisotropy, magnetostriction, and permeability of

single crystals of Permalloy and other compositions. The behavior of a cold-rolled single

crystal of the intermetallic compound NiaFe was studied by Chikazumi and Suzuki [953] in

connection with the strong magnetic anisotropy

developed by cold rolling iron-nickel alloys.

Schindler and Salkovitz [954] reviewed published data on the Hall coefficients of binary

alloys and offered explanations for anomalous

behavior. The galvanomagnetic properties and

Goldhammer effect in iron-nickel alloys were

discussed by Grum-Grzhimailo [955]

Clark and Fritz [956,957] conducted a comprehensive investigation of the influence of temperature on the magnetic properties of ironnickel alloys and Schindler et al. [958] reported on the effect of irradiation on the magnetic

properties of iron-nickel alloys.

b. Permanent Magnets

Magnetically hard or permanent magnet materials have a large coercive force sometimes

because of internal stress involving lattice distortions. In the martensitic steels that were the

early permanent magnets, internal stress developed during the heat treatment that produced the martensitic structure. In later permanent magnets, the internal stresses developed

from the precipitation-hardening and aging

processes.

The quality of a permanent magnet is characterized not only by the residual induction, Br,

and coercive force, He, but also by the so-called

energy product, the product of B and H for

various points on the demagnetization curve. The maximum energy product is probably the

best single criterion of magnetic quality for

these materials. Factors that produce undesirable demagnetization of permanent magnets in- clude high temperatures, vibration and impact, i stray magnetic fields, and accidental contact

with another magnet to produce new poles [173,

944].

Uses of permanent magnets are (a) convert- , ing mechanical to electrical energy, e.g., dy- || namic microphones, phonograph pickups, etc., (b) converting electrical to mechanical or

acoustical energy, i.e., electric motors, electrical [I instruments, radio loudspeakers, etc., (c) trac- ' tive efforts to attract or repel other magnets or magnetic materials, e.g., magnetic chucks, magnetic separators, pressure controls, switches,

thermostats, etc., (d) control of charged particles, i.e., focusing of electrons and ions in some

types of scientific apparatus, and (e) modification of the normal characteristics of matter.

The first permanent magnets were martensitic plain carbon steels. The tungsten magnet

steels, introduced after 1855, were an improvement over the plain carbon steels, both the remanence and coercive force being increased.

When tungsten became difficult to obtain, chromium was found to be a cheaper and almost

equivalent substitute and the iron-chromiumcarbon alloys were developed during World War

I. In 1916, Honda and Saito, in Japan, introduced the KS magnet steel, which contained 35

to 41 percent Co, 2.0 to 3.75 percent Cu, 3.75 to

7.0 percent W, and 0.9 percent C. In the early

1930's it was found that excellent permanent

magnets could be made from carbon-free alloys,

j notably the iron-nickel-aluminum alloys discovered by Mishima [959] and developed by Ruder

[960,961] in this country. These iron-nickel- - aluminum alloys and their modifications are the

most popular and most widely used for all permanent magnet materials. They were named " Alnico, which is a generic term describing the

ternary alloys of aluminum, nickel, and iron.

These alloys (25 to 30 percent Ni, 10 to 15 percent Al, remainder Fe) correspond roughly to Fe2NiAl, and are precipitation hardening. Compositions and properties of the Alnicos and other

j nickel-containing permanent alloys are given in j table 74.

The Alnico alloys are glass-brittle and diffi- cult to fabricate; however, they have sufficient

strength for most applications. They are usually

fabricated by sand or shell mold casting ; a few

j are fabricated by powder metallurgy techniques. The cast alloys are unmachinable and

must be finished by grinding. They can be pulverized, and magnets can be pressed from this

powder, bonded with Bakelite or other suitable

binders. Such bonded cores are inferior to cast ones in that the residual induction is greatly . reduced, but this difficulty can be partly over- come by increasing the cross-sectional area. By

heating some Alnico compositions close to the

melting point, it has been possible to hot work

them. In general, vacuum-melted alloys hot

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work more easily than air-melted. The alloys

have been extruded, rollad, and swaged. Properties of hot-worked Alnico are similar to those

of the cast product. Ritzow [962] evaluated the

temperature regions for complete homogenization of the structures in sintered Alnicos.

The Alnico alloys are age hardening because

of the precipitation of the Ni-Al or Ni-Ti compounds or complexes like (Fe, Ni, Co)3Ti [963,

964,965]. In general, the heat treatment given

these alloys is to quench from about 1,200 °C

and then age them for the proper time at about

650 °C. Geisler [963] reported that overaging

appreciably reduced all of the magnetic properties, for example, the energy product for Alnico

V was reduced from 5.00 to 0.09 X 10'^ and for

Alnico IV from 1.30 to 0.02 X 10^ The principal

function of the cobalt is to decrease the cooling

rate necessary to obtain optimum properties,

thus permitting the casting of larger magnets.

According to Stanley [947], the Alnicos are

the most popular and most widely used of all permanent magnet materials. Hadfield [966]

suggested that magnetically anisotropic Alnicos

may be about the maximum obtainable in solid

magnets, but that further improvement may

result from powder metallurgy techniques.

Sugiyama and Shida [967] reported that the

addition of 0.5 to 2.0 percent of columbium improved the properties of cast Alnico V.

Nickel-copper-iron alloys (Cunifes) can be

hot and cold worked and machined. Their properties in very small wire sizes were studied by

Cooter and Mundy [968]. Legat [969] found

optimum magnetic properties at 15 percent

nickel and 15 percent copper. The copper-nickelcobalt alloys (Cunicos) have magnetic and

physical properties similar to those of the

Cunifes. They are used as castings, sintered

powder metallurgy products, and in wrought

condition. They are malleable when cold, but

cannot be hot worked.

Precipitation hardening gold-nickel magnets,

with compositions in the vicinity of 70 percent

gold and 30 percent nickel, are of interest on

theoretical grounds [970].

The stability of nickel-containing permanent

magnets, both at ambient and elevated temperatures, has been the subject of numerous investigations [971,972,973,974,975] . The effect of

radiation on permanent magnets was reported

by Sery et al.[976]. A review tabulating available data on various permanent magnet materials was written by Fabian [977].

Cliroir

]aii(

5. Multicomponent Systems

In the review of recent technical literature,

references pertaining to the phase diagrams of

systems of which nickel is a component were

noted as follows:

Binary systems, nickel and

Aluminum [978,979,980]

Beryllium [981,982]

Boron [983,984]

Chromium [980,985,986,987,988,989,990]

Cadmium [991]

Cobalt [992]

Columbium [993]

Gadolinium [994,995]

Gallium [996]

Gold [997]

Hafnium [998]

Indium [999]

Iron [689,992,1000,1001,1002,1003]

Lead [1004,1005]

Manganese [1003,1006,1007]

Molybdenum [1008,1009,1010]

Osmium [1011]

Palladium [1012,1013,1014]

Phosphorus [1015]

Platinum [1016]

Rhenium [1017]

Ruthenium [1018]

Silicon [1019,1020]

Sulfur [1021]

Tantalum [1022]

Tin [1023]

Titanium [980,1024,1025,1026,1027,1028,1029,

1030,1031]

Tungsten [182,980,1032,1033]

Uranium [1034,1035]

Vanadium [1036,1037]

Yttrium [1038,1039]

Zinc [1040,1041]

Zirconium [998,1017,1042,1043]

Ternary systems, nickel with

Aluminum and boron [1044]

Aluminum and chromium [1045]

Aluminum and copper [1046]

Aluminum and Iron [1048,1049,1050,1051,

1052]

Aluminum and molybdenum [1047]

Aluminum and nitrogen [1053]

Aluminum and silicon [1054]

Aluminum and titanium [1055]

Aluminum and zinc [1056]

Boron and zinc [1057]

Cadmium and nitrogen [1053]

Carbon and chromium [1058]

Carbon and indium [1059]

Carbon and iron [1060,1061,1062]

Carbon and manganese [1063]

Carbon and titanium [1064]

Carbon and zinc [1065]

Stri

134
Chromium and cobalt [1066]

iChromium and copper [1067]

jchromium and iron [8b6,1068]

[Chromium and molybdenum [1066]

jchromium and nitrogen [1069]

IChromium and palladium [1014]

Chromium and silicon [1054]

Chromium and titanium [1070,1071]

Cobalt and manganese [1072]

Cobalt and sulfur [1073]

Cobalt and zinc [1074]

Copper and lead [1075]

Copper and manganese [1014,1076]

Copper and palladium [1014]

Copper and sulfur [1014]

Copper and tin [1077]

Gold and iron [1078]

|Iron and lead [1061]

Iron and molybdenum [1062,1079]

Iron and nitrogen [1080,1081,1082,1083]

Iron and phosphorus [1084]

Iron and silicon [1085]

Iron and zinc [1086]

Magnesium and copper [1087]

Magnesium and nitrogen [1053]

Magnesium and zinc [1087]

Manganese and palladium [1014,1088]

Molybdenum and cobalt [1089]

Molybdenum and iron [1089]

Molybdenum and silicon [1047]

^Molybdenum and titanium [1054]

Nitrogen and zinc [1053]

Palladium and silver [1014]

Palladium and titanium [1047]

Quaternary systems, nickel with

Aluminum, chromium and titanium [1090]

|,i Aluminum, copper, and iron [1091]

l[ Aluminum, copper, and manganese [1092]

Carbon, chromium, and iron [831,866,1093]

Carbon, iron, and lead [1061]

Chromium, iron and molybdenum [1094]

Chromium, iron and nitrogen [1095]

Quinary systems, nickel with

Aluminum, chromium, iron, and titanium

[1096]

Systems with intermetallic compounds

Cr-NiAl [1097]

CrgNb^-Ni [993]

Ni-NiAl [1097]

Ni3Cr-Ni3Al [1098]

Ni-NiCl [1099]

TiC-Ni [1100]

Ni-Cr-NiAl [1097]

The author is indebted to the Director and

technical staff of the National Bureau of Standards and to members of the Development and

Research Department of The International

Nickel Company, Inc., for cooperation and as- sistance in the preparation of this Monograph

under the National Bureau of Standards Research Associate Plan. Particular thanks are due T. E. Kihlgren, R. J. Knoth, R. V. LaMaire

and the library staif of International Nickel,

whose valued cooperation aided materially in

the preparation of the manuscript. The staff of

the NBS library was ever ready to lend their

talents and resources in locating reference material. Dr. M. R. Meyerson, Chief of the Engineering Metallurgy Section and author of one

of the previous circulars, generously placed the

facilities of his section at the disposal of the

author. Finally, the grateful thanks of the author are due Mrs. G. M. Davis, who so conscientiously prepared the manuscript.

135
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