2.

14 Heat-Treating Copper and Nickel Alloys

AK Bhargava and MK Banerjee, Malaviya National Institute of Technology, Jaipur, India
r 2017 Elsevier Inc. All rights reserved.

2.14.1 Introduction 398

2.14.2 Copper and Copper Alloys 398
2.14.2.1 Copper Alloys 399
2.14.2.2 Homogenization 400
2.14.2.3 Annealing 401
2.14.2.4 Stress Relieving Treatment 405
2.14.3 Heat Treatment of Copper 405
2.14.3.1 Heat Treatment of Brasses 406
2.14.3.2 Heat treatment of Bronzes 409
2.14.3.2.1 Tin bronzes 409
2.14.3.2.2 Aluminum bronzes 409
2.14.3.2.3 Beryllium bronzes 410
2.14.3.2.4 Silicon bronze 414
2.14.3.3 Cupronickels 414
2.14.3.4 Chromium Coppers 414
2.14.3.5 Zirconium–Copper Alloys 414
2.14.3.6 Copper–Chromium–Zirconium Alloys 415
2.14.3.7 Copper–Nickel–Silicon–Chromium Alloy 415
2.14.3.8 Copper-Base Shape Memory Alloys 415
2.14.4 Heat Treatment of Nickel Alloys 416
2.14.4.1 Annealing 416
2.14.4.2 Solution Annealing 417
2.14.4.3 Stress Relieving 417
2.14.4.4 Stress Equalizing 417
2.14.4.5 Precipitation Hardening 417
2.14.4.6 Nickel-Base Superalloys 418
References 419

2.14.1 Introduction different compositions and property requirements. It is for this

reason, a detailed analysis of heat treatment practice, princi-
Various heat treatment practices are employed for different ples behind the evolution of microstructures, and the purpose
copper alloys. In case of single-phase copper alloys, cold work- thereof are presented in this chapter.
ing is followed by recrystallization annealing for improvement Nickel alloys, in general, contain alloying elements like
of properties. However heat treatment of copper alloys is quite copper, iron, chromium, etc. The single-phase alloys are sub-
often critical. There are alloys like bronzes where micro- jected to recrystallization annealing following cold working.
segregation attracts special attention to the heat treater. Due to On the other hand solution treatment followed by aging is a
wide gap between liquidus and solidus lines the solidification of very common heat treatment for important alloys like Monel,
alloys like tin bronzes exhibits coring and so under such cir- Inconel, Hastelloy, and others. In each case, there are specific
cumstances the homogenization treatment is called for. Again criticalities with respect to proper microstructure achievement
there are important duplex alloys like alpha–beta brass which through heat treatment and a thorough understanding of the
may be subjected to hardening treatment. Annealing as a final phenomenological issues concerning the above is required. It
heat treatment or as a means for stress relieving is not uncommon is for this reason the present chapter has dealt with the heat
in copper alloys. Several copper alloys like copper–aluminum, treatment practices of nickel alloys, the anticipated difficulties,
copper–zinc–aluminum, and copper–aluminum–nickel show and the required precautions to achieve the desired set of
martensitic transformation. Also there are possibilities of for- properties. Also the heat treatment of nickel-base superalloys
mation of precipitates of intermetallics in many of these are highlighted.
martensitic alloys; hence heat treatment of these alloys is
judiciously decided depending upon the target microstructures
and thus the properties. For example, in a shape memory alloy 2.14.2 Copper and Copper Alloys
aging precipitate formation is not welcome in many cases
whereas aging precipitates in similar alloys are made to be Copper is well known for its outstanding electrical con-
formed deliberately under demand of situations. So a wide ductivity which is just next to silver. Copper and its alloys
variety of heat treatments are employable in copper alloys of possess excellent corrosion resistance and ease of forming and

398 Comprehensive Materials Finishing, Volume 2 doi:10.1016/B978-0-12-803581-8.09196-7

 Heat-Treating Copper and Nickel Alloys 399

finishing. Its face-centered cubic (f.c.c) structure accounts for 2.14.2.1 Copper Alloys
its good ductility. Other distinguishing properties exhibited by
The major copper alloys are the following:
copper include very good thermal conductivity and non-
magnetic properties. The heat treatment and consequent 1. Brass:
changes in properties of copper and its alloys are elaborately A. Single-phase alpha brasses (up to 36% Zn). There are
discussed in subsequent sections. The major commercial two categories of alpha brasses namely; red brass
grades of copper are: (5–20% Zn) and yellow brass (20–36% Zn).
B. Two phase a–b brasses (54–62% Zn).
• oxygen free high conductivity copper (OFHC);
2. Bronzes:
• tough pitch copper; and
A. tin bronze,
• phosphorous deoxidized copper.
B. silicon bronze,
‘OFHC’ is the highest purity copper with at least 99.98% C. aluminum bronze, and
purity. Its electrical conductivity is equivalent to 101% Inter- D. beryllium bronze.
national Annealed Copper Standard (IACS). It is also called as 3. Cupronickel.
electrolytic tough pitch copper with oxygen content of 4. Nickel–silver alloys – these are also called nickel brasses.
0.02–0.05% as Cu2O. Figure 1 is the microstructure of cast These are the alloys containing copper, nickel, and zinc.
wire bar of tough pitch electrolytic copper (99.95% Cu; 0.03% Though they do not contain silver, they have an attractive
O2) showing the presence of Cu2O in the interdendritic region. silver luster and therefore termed as nickel–silver alloys.
Because of its high purity,electrolytic tough pitch copper is the They have moderately high strength and good corrosion
most expensive among all grades of copper and therefore its resistance.
applications are limited to electrical industries.
‘Tough pitch copper’ is produced by the process of fire The term bronze is used to any alloy of copper containing
refining. It contains about 0.04–0.08% oxygen in the form of principal alloying element (up to 12%) other than zinc or
Cu2O (0.4–0.8% Cu2O). Its electrical conductivity is equiva- nickel. The term was originally applied to those copper alloys
lent to 100% IACS conductivity. This copper is tough. The which contained tin as the sole or principal alloying element.
lower the oxygen content of this copper, the higher the so- Commercial bronzes are principally the alloys of copper with
called ‘pitch’ and vice versa, hence the term ‘tough pitch.’ tin, silicon, aluminum, or beryllium as alloying element.
Tough pitch copper is susceptible to hydrogen embrittlement. The commonly employed heat treatment processes to
‘Phosphorous deoxidized copper’ is another grade of fire copper and its alloys are:
refined copper which is deoxidized by phosphorous. As small
as 0.04% phosphorous is retained in this copper which lowers
• homogenizing,
the conductivity of copper to 85% IACS. This grade of copper
• annealing,
has good hot and cold workability and is not susceptible to
• stress relieving, and
hydrogen embrittlement.
• precipitation hardening.
The other grades of copper include silver-bearing copper Most of the copper alloys are single-phase solid solutions
(7–30 oz t
1 of silver), arsenical copper (about 0.3% As) and and are non hardenable by heat treatment. Therefore first three
free cutting copper (about 0.6% tellurium). heat treating processes are used for these alloys as the case may

Figure 1 Microstructure of cast tough pitch electrolytic copper showing (a) cells of dendrites (the intersections of dendritic arms with surface of
polish) and Cu2O particles outlining the dendritic cells. The black spots are pores or holes in the cast metal;  50, (b) same as in (a) at higher
magnification (  500). Cu2O particles are resolved clearly and are seen to be of globular morphology.1
400 Heat-Treating Copper and Nickel Alloys

be. A brief account of these heat treatments in context with

copper alloys is given in the subsequent sections with reference
to the corresponding phase diagrams.

2.14.2.2 Homogenization
Homogenization treatment is very commonly applied to
castings and cast billets of copper alloys. In this treatment, the
cast alloy is heated to a temperature high enough so that dif-
fusion of atoms within the alloy is relatively rapid, but still
safely below the nonequilibrium solidus, so that burning of
the alloy does not occur. The nonequilibrium solidus tem-
perature depends on the composition of the alloy, its nature,
so on. If burning occurs, the shape of the casting is impaired
and physical properties also deteriorate. The alloy is held at
this temperature for a long period of time depending on the
freezing range of the alloy and massiveness of the casting so
that the micro-segregation or the so-called coring is eliminated
or at least reduced to a great extent. The alloys having wide
freezing ranges such as tin (phosphor) bronzes, silicon bron-
zes, and copper–nickel alloys are invariably cored after Figure 2 Microstructure of as cast 70:30 brass; cored crystals of
solidification under industrial practice. Though commercial a-solid solution throughout.2
copper-base alloys such as a-brasses, a-aluminum bronzes,
and beryllium bronzes are also cored, the degree of micro-
segregation is less. In these alloys, coring is generally elimi- equilibrated and thus ductility, toughness, and corrosion resis-
nated during primary mill processing followed by normal tance are improved. Also properties become uniform across the
annealing process. Formation of a cored dendritic structure section of the casting.
during solidification of castings under nonequilibrium con- The process of homogenization involves diffusion of atoms
ditions, as in industrial practice, is very common in solid across concentration gradient. Diffusion of atoms occurs in
solution alloys. Solid solution crystals usually grow as den- both the directions, that is, from core to surface of dendrite and
drites. There is large concentration gradient of alloying ele- vice versa. Diffusion of atoms is thermally activated process and
ments from interior of the dendrite (called core which forms at it increases exponentially with increasing temperature. Higher
higher temperature) to its surface which is lastly solidified at the temperature less will be the time of homogenization. Since
lower temperature. This results in coring. The core is enriched diffusivity of atoms varies from alloy-to-alloy, the time and
with respect to high melting constituent that raises the solidus temperature required for homogenization also vary with the
point while the surface of the dendrite is richer in low melting type of alloy. In addition, both these parameters vary with
constituent of the alloy that lowers the solidus point. That is, degree of segregation and grain size of the casting. High tin–
during nonequilibrium cooling solidification range is widened. bronzes (above 8% Sn) are well known for extreme segregation.
Because of the large difference in composition of alloy con- Diffusion and homogenization are both slower and rather dif-
stituents these portions tend to etch differently and an etched ficult in tin (phosphor) bronzes, silicon bronzes and copper–
microsection may reveal inhomogeneous composition within a nickel alloys as compared to most other copper alloys. There-
dendrite or grain. Figure 2 is the microstructure of as-cast 70:30 fore these alloys are usually subjected to prolonged homo-
brass (cartridge brass) showing cored crystals of alpha-solid genization treatment. In these alloys, temperatures of
solution throughout. Apart from segregation of low melting homogenization are generally kept about 50 1C below the
alloy constituent in interdendritic region, a brittle excess phase solidus temperature (Figure 3) and the soaking time varies from
may also appear which is a characteristic defect commonly 3–10 h or even more.
associated with cast alloys. This inhomogeneity in composition Figure 4 illustrates the effect of homogenization tempera-
increases with increasing cooling rate and it also depends on ture on ductility, tensile strength (T.S.), and yield strength
freezing range of the alloy. Such an inhomogeneous cast struc- (Y.S.) of phosphor bronze containing 92 wt% Cu, 8% tin, and
ture lowers several properties, viz., mechanical, physical, and small amount of phosphorous and traces of other elements.
chemical properties of the alloy. This structure leads to poor The improvement of ductility with increasing temperature is
ductility and toughness due to frequent brittle phase formation apparent from this figure. Being a thermally activated process,
in the interdendritic region. A concentration gradient between the progress of homogenization is a function of both tem-
dendritic core and dendritic surface leads to the formation of perature and time. This effect has been illustrated by taking an
galvanic microcouples which make the many commercial cast- example of another as cast copper alloy namely, 85% Cu–15%
ings susceptible to intergranular corrosion. Because of the non- Ni in Figure 5.
uniformity of composition across the casting, properties are also The microstructure of the chill-cast 85% Cu–15% Ni alloy
nonuniform. Coring can be eliminated by homogenization presented in Figure 5 is composed of dendrites of single-phase
treatment during which the composition of the alloy is a-solid solution. The dendritic coring is apparent in this
 Heat-Treating Copper and Nickel Alloys 401

microstructure. When this alloy is homogenized at 750 ºC for

3 h only a slight change in cored dendritic structure took place
as shown in Figure 5. During annealing, the counter diffusion
of atoms of nickel and copper between the nickel-rich cores
and copper-rich surfaces of dendrites results in decrease of
composition differences to some extent and thus slightly
reduced the height of the hills and depth of the valleys. When
both the temperature and time of homogenization of the
above alloy increased to 950 1C and 9 h, a remarkable change
in microstructure occurred as shown in Figure 5(c). The as cast
dendritic structure is completely eliminated and a homo-
geneous grain structure has been developed. Grain boundaries
are irregular in shape and are frequently encountered in the
cast and homogenized solid solutions. Dark particles are
inclusions of copper oxide or nickel oxide.
An initial cold work treatment is often given to cast ingot or
billet. This helps in speeding up the homogenization process.
Table 1 gives the schedule of homogenization treatment for
some typical copper-base alloys.

2.14.2.3 Annealing
The principal heat treatment applied to pure copper and solid
2 solution copper alloys is the recrystallization annealing fol-
Figure 3 Copper-rich end of the copper–tin phase diagram. lowing the cold working. Cold working is generally carried out

Figure 4 Effect of homogenization temperature on mechanical properties of C52100 (phosphor bronze, 92% Cu–8% Sn) alloy annealed for 4 h.3
402 Heat-Treating Copper and Nickel Alloys

Figure 5 Copper–15% Ni alloy (a) chill cast;  50, (b) same alloy heated for 3 h at 750 1C;  50, and (c) heated for 9 h at 950 1C.1

Table 1 Schedule of homogenizing treatment for some copper alloys

Material Temperature (1C) Time (h) Remarks

Copper–nickel–chromium alloy billets (alloy 1040–1065 4–9 To prevent cracks and seams
C71900) to prevent cracks, seams, etc.
Phosphor bronzes (8–10% Sn) C52100 and 775 5 To reduce embrittlement in billets and slabs that are to
C52400 be cold formed
Cast cupronickels (70:30 Cu:Ni) C96400 1000 2 Protective atmosphere is to be used. The alloy is cooled
to 400 1C in furnace and then in air

Source: Ref. [3].

below 0.4Tm, where Tm is the melting temperature of the metal may vary with the type of deformation process such as rolling,
or alloy in Kelvin. Plastic deformation of polycrystalline swaging, forging, etc. Of the total energy expended in cold
metallic material not only causes a permanent change in its working, about 10% remains stored within the crystalline
external shape but also brings about changes in internal metal and the remaining is lost as heat. The major contributor
structure. The internal structural change may be a change in to the stored energy (called inherent energy) is increased dis-
shape and size of grains, generation of lattice imperfections, location density. All these imperfections give rise to internal
and development of a texture and so on. The principal kind of stresses. The increased internal energy makes the metal ther-
lattice imperfections generated during cold working are the modynamically unstable at any temperature. The free energy
dislocations. Of the lattice imperfections generated, disloca- of such a metal is higher than it is in as-annealed state. The
tions are of great concern. Dislocation density is increased change in size and shape of individual crystals (or grains)
from as low as 1010 m
2 in annealed state to as high as occurs through processes called slip and twinning. The prin-
1016 m
2 in heavily deformed crystals.4 All these imperfec- cipal process of plastic deformation is slip. Multiplication of
tions produce a lot of lattice distortion and raise the internal dislocations on several slip systems upon plastic deformation
energy of the metal or alloy. The type of distortion produced leads to their interaction with each other and this restricts their
 Heat-Treating Copper and Nickel Alloys 403

The basic purpose of annealing is to soften and improve

ductility of the copper and its alloys which has been work
hardened so that further deformation can be facilitated. The
process involves heating the cold worked metal to a tem-
perature that produces recrystallization. Recrystallization
temperature generally ranges from 0.3 to 0.6Tm, where Tm is
the melting temperature in Kelvin. Generally recrystallization
process is carried out at about 0.4Tm or higher where migra-
tion of high-angle grain boundaries is possible. The factor
0.3Tm is common for pure metals after considerable amount
of deformation. Recrystallization temperature is an indicator
of the temperature at which a metal must be annealed to get
the desired softness. This temperature depends principally on
degree of prior cold working. Higher the degree of cold
working, lower is the temperature of recrystallization. As the
degree of cold working increases, the number of lattice defects
also increases which in turn makes the metal thermo-
dynamically more unstable as mentioned earlier. Hence
recrystallization occurs at a lower temperature and in shorter
time. Figure 7 illustrates the effect of prior cold work on
annealing behavior of pure copper. If the degree of cold
working is less than about 10%, recrystallization generally
does not occur. The recrystallization temperature is high if the
Figure 6 Effect of cold work on strength and ductility of copper and degree of cold working falls in between 10 and 20%. A
brass. The lower curves are for copper and the upper ones are for minimum of 20% cold reduction is normally required for
brass. recrystallization. In many instances a high degree of cold
working is desirable to achieve a fine grain structure after final
annealing. Since the rate of diffusivity of atoms increases with
motion. The consequent effect is that for further plastic increasing annealing temperature, a shorter annealing time (t)
deformation to take place, higher magnitude of load or stress is required for a given degree of cold working at higher
is required. The material is said to be work (or strain) har- annealing temperature (T). The incubation period is also
dened. Thus cold working results in increase of hardness, Y.S., shorter at higher annealing temperature and high degree of
T.S. but also reduction in ductility (or % elongation) and cold working. This time t of recrystallization is expressed as5:
toughness of a ductile material. Figure 6 illustrates the effect of
percent cold work on strength and ductility of copper and t ¼ t 0 expðQ=RT Þ ½1
brass. It also increases electrical resistivity because the
increasing number of point and line defects incoherently where t0 is a constant, Q is activation energy for recrystalliza-
scatters the movement of free electrons. In addition, the che- tion and R is universal gas constant. Both t0 and Q vary with
mical reactivity also increases due to cold working. temperature. During recrystallization, strain-free new crystals
In order to relieve internal stresses and to improve properties are formed at the expense of distorted grain structure. The
by way of microstructural refinement, the metal or alloy is process comprises of two steps, namely, nucleation and
subjected to annealing heat treatment. Stored internal energy is growth. Nucleation of new crystals takes place preferentially at
the driving force for a cold worked metallic material to undergo grain boundaries and twin boundaries. Higher the degree of
structural changes and to restore strain-free grains due to cold working higher will be the rate of nucleation (N) and less
annealing heat treatment. Once the metal or alloy is annealed it will be the rate of growth (G) of new nuclei. Hence finer will
becomes soft and ductile and is capable of deforming further if be the grain size. Similarly a higher rate of heating results in
so required. When a series of cold reductions are needed, higher N and therefore favors the formation of fine grain size
intermittent annealing processes are also required. One or more after recrystallization gets over. After recrystallization, a uni-
number of intermittent annealing may be required depending form grain structure is obtained. Grain size is the standard
on the extent of reductions needed. Annealing may be a final means of evaluating a recrystallization anneal in copper and
heat treatment for the concerned metal or alloy in the final brass mill alloys. This process of recrystallization is often called
product form. When series of cold reductions are required, the primary recrystallization.
first intermittent annealing is preferred to carry out at a tem- The presence of impurities also affects recrystallization
perature well above the recrystallization temperature to cause temperature. Very pure metals have a lower recrystallization
grain growth and achieve extra softness so that less work is temperature than impure metals.4 Even a very small con-
required in the next cycle of cold reduction. But in such case, the centration of solute atoms raises the recrystallization tem-
temperature of subsequent annealing must decrease to attain a perature, the degree of rise being dependent significantly on
fine grain structure after last annealing process. For copper and the nature and concentration of solute atoms. As the solute
brass mill alloys, grain size is the standard means of evaluating concentration increases, recrystallization temperature rises to a
a recrystallization annealing. maximum at certain value of solute content. With further
404 Heat-Treating Copper and Nickel Alloys

Figure 7 Effect of degree of cold working on the annealing process of pure copper.3

Figure 8 Illustration of effect of zinc content in copper on annealing process. The alloys were cold worked to 60% reduction in thickness at 25 1C.3

increase of solute concentration, the recrystallization tem- The increase in recrystallization temperature at lower solute
perature decreases. This is illustrated in Figure 8. It can be content is believed to be due to strain aging effect.
noted from this figure that as the concentration of zinc At low concentration, solute atoms form Cottrell atmo-
exceeded about 10%, recrystallization temperature decreased. spheres around dislocations. These atmospheres restrict the
 Heat-Treating Copper and Nickel Alloys 405

Figure 10 The relationship between hardness and annealing

temperature for cartridge brass.2

nature and are of sufficient magnitude, these may cause stress

1 corrosion cracking while the parts are stored in warehouse for
Figure 9 Copper–zinc phase diagram.
relatively long periods of time or otherwise exposed to specific
environments during service.
movement and rearrangement of dislocations, which is required
For instance, in brasses containing more than 15% zinc,
for the formation of recrystallization nuclei. Solute atoms are
stress corrosion cracking (also popularly known as season
also attracted toward grain boundaries. Atoms at grain bound-
cracking) can occur if sufficient magnitude of residual tensile
aries also retard their movement and thereby retard nucleation
stresses is left from the previous cold forming operation and if
and growth of recrystallization nuclei. When solute concentra-
the part is exposed to an environment containing traces of
tion increases, saturation occurs at these sites and further
ammonia. The problem of season cracking is more pro-
increase of recrystallization temperature becomes improbable.
nounced with the cold formed brass parts such as caps, car-
Melting temperature of Cu–Zn alloys decreases with increasing
tridge cases for rifles, caps for incandescent lamps, pipes for
concentration of zinc (Figure 9). This is the reason for lowering
air-coolers, etc. Stress relieving heat treatments are carried out
of recrystallization temperature of brasses when zinc content
by heating the parts, generally, to below the annealing tem-
exceeds about 20%. Thus a small concentration of solute atoms
perature that do not cause recrystallization and hence soft-
is able to raise recrystallization temperature. For instance, an
ening of metal. The properties that are derived due to cold
addition of 0.05% silver to copper is able to raise the recrys-
working should not be affected significantly following stress
tallization of temperature of pure copper from 140 1C to about
relieving treatment. For this, the temperature of the stress
340 1C. In case of copper–zinc alloys, addition of zinc up to
relieving treatment must be kept low but then time must be
about 10% raises the activation energy for mobility of solute
prolonged to achieve relief of residual stresses. In fact lower
atoms and thereafter it decreases as its concentration is increased
temperature stress relieving treatment (generally up to the
up to 20% in copper.
partial recovery stage of annealing during which excessive
point imperfections are eliminated) causes a slight improve-
ment of hardness and strength of heavily deformed alloy. This
2.14.2.4 Stress Relieving Treatment is illustrated for cold worked 70:30 brass in Figure 10. See-
As the name implies, stress relieving treatment is applied to mingly, this is due to strain aging effect. Percentage elongation
shaped articles in which the stresses are introduced during remains unaffected. Stress relieving treatment allows higher
fabrication processes. These stresses called residual stresses are external loads to be applied, increases fatigue resistance and
frequently tensile in nature and may be introduced during impact strength, lowers the susceptibility to brittle fracture,
machining, cutting, welding, brazing, casting, or mechanical intercrystalline corrosion, and prevents warpage.
shaping processes of fabrication. In context of copper and its
alloys, this treatment is very commonly used for relieving
residual stress of cold formed parts. Cold forming is done to 2.14.3 Heat Treatment of Copper
improve strength and hardness of the part or component due
to strain hardening effect but at the same time ductility is The principal heat treatment applied to pure copper is
reduced. Since cold forming is associated with generation of recrystallization annealing following the cold working.
host of crystal imperfections, in particular, the dislocations, the Though recrystallization temperature of pure copper is taken
elastic strain, and residual stresses are left in the part after as 270 1C (0.4Tm), in practice the recrystallization of pure
forming operation. If these residual stresses are tensile in copper is carried out at much higher temperature. The
406 Heat-Treating Copper and Nickel Alloys

principal reason is to reduce the time of recrystallization and lead to work softening and to avoid this, low temperature
hence to economize the process. In practice, most recrystalli- annealing is carried out. Since alloying elements raise the
zation treatments of pure copper are carried out in air in the recrystallization temperature, cold worked alpha brasses are
temperature range of 375–700 1C. The intermediate tempera- generally recrystallized in the temperature range of 700–730 1C.
ture, that is 600 1C, is very common. The temperatures used In case the temperature of recrystallization annealing exceeds
for annealing various grades of cold worked copper are given in 700 1C, the furnace atmosphere must be controlled to over-
Table 2. In the annealed state electrolytic tough pitch copper come the problem of excessive oxidation as well as dis-
(C11000) possesses Y.S. of 69 MPa, T.S. of 220 MPa and per- coloration of the surface. The recrystallization annealing
cent elongation of 45 (in 50 mm gage length of specimen).6 temperatures of some representative brasses (wrought) are
However, time and temperature must be controlled to given in Table 3. Figure 12 illustrates the microstructural
avoid danger of grain growth. A temperature greater than
700 1C is avoided to prevent excessive oxidation of copper
(Figure 11). Once recrystallization gets over, copper is quen-
ched in cold water such that the oxide scales formed at the
surface may completely flake off, leaving behind a very clean
shiny surface of pure reddish copper. In case of annealing
oxygen bearing copper, hydrogen in the furnace atmosphere
must be maintained to a minimum value to avoid any
embrittlement. For instance, when annealing temperature is
less than about 480 1C the hydrogen content of the atmo-
sphere should not exceed 1%.

2.14.3.1 Heat Treatment of Brasses

Like pure copper, single-phase alpha brasses are frequently
subjected to recrystallization annealing treatment. In fact a
single-phase alloy does not undergo any phase transformation;
therefore structural refinement through recrystallization of
cold worked alloy remains the only means of toughening.
Controlled degree of recrystallization or recovery fixes the
magnitude of hardening by cold working. It is to be under-
stood that intensive strengthening of single-phase alloy can

Table 2 Annealing temperatures for various grades of cold

worked copper

Wrought copper Common name Temperature

(1C)

C10100–C10300 Oxygen free high conductivity 375–650 Figure 11 Effect of annealing temperature upon oxidation of copper.7
copper (99.9% Cu)
C10400–C10700 Oxygen free silver-bearing 475–750
copper
Table 3 Annealing temperatures for some representative cold
C10800 Oxygen free low phosphorous 375–650
worked brasses
copper
C11000 Electrolytic tough pitch copper 250–650 Alloy Temperature
C11100 Electrolytic tough pitch, 475–750 (1C)
anneal-resistant copper
C11300, C11400, Silver-bearing tough pitch 400–475 Gilding metal (95Cu–5Zn): C21000 425–800
C11500, copper Commercial bronze (90Cu–10Zn): C22000 425–800
and C11600 Red brass (85Cu–15Zn): C23000 425–725
C12000 Phosphorous deoxidized 375–650 Low brass (80Cu–20Zn): C24000 425–700
copper, low residual copper Cartridge brass (70Cu–30Zn): C26000 425–750
C12200 Phosphorous deoxidized 375–650 Yellow brass (Cu–20–36 Zn): C26800, C27000, and 425–700
copper, high residual copper C27400
C12500, C12700, Fire refined, tough pitch 400–650 Muntz metal (60Cu–40Zn): C28000 425–600
and C1300 copper with silver Free cutting brass (61.5Cu–35.5Zn–3Pb): C36000 425–600
C14500 Phosphorous deoxidized, 425–650 Forging brass (60Cu–38Zn–2Pb): C37700 425–600
tellurium copper Naval brass (60Cu–39.25Zn–0.75Sn): C46200, 425–600
C14700 Sulfur copper 425–650 C46400, and C46700

Source: Ref. [3]. Source: Ref. [3].

 Heat-Treating Copper and Nickel Alloys 407

Figure 12 Alpha brass cold-rolled 60% and annealed for 30 min at (a) 300 1C,  75, (b) same at higher magnification (  500) where the
structure of new crystals is somewhat better resolved, (c), (d), (e), and (f) at 400, 500, 650, and 800 1C, respectively at  75.1

changes that occurred in cold-rolled (60%) a-brass with magnification (  500) showing that new crystals resolved
increasing temperature of annealing for a fixed time of somewhat better. The average grain diameter of the new
30 min. It can be noted that recrystallization is almost crystals found to be 2 mm. Figure 12(c) is the microstructure
completed after annealing at 400 1C. Further increasing of of the same specimen reheated for 30 min at 400 1C. At this
temperature of annealing resulted in grain coarsening. temperature recrystallization has been completed and some
Figure 12(a) shows tiny new crystals which are not resolved grain growth has occurred. The grain size estimated to be
very well here and some areas of the cold deformed structure about 20 mm. Same specimen when reheated for 30 min at
containing strain markings are also evident. Figure 12(b) is 500 1C, the microstructure shows an additional grain
the same microstructure as in Figure 12(a) with higher growth with grain diameter of about 45 mm (Figure12(d)).
408 Heat-Treating Copper and Nickel Alloys

On annealing the same specimen at 650 and 800 1C, Alpha phase is quite soft and ductile. Most widely used
further grain coarsening is apparent from Figures 12(e) and a–b0 brass is well known Muntz metal. Hardening of
12(f). Grain size increased to about 150 and 250 mm, this alloy involves heating to about 850 1C where single-
respectively. phase b exists. This is followed by quenching to room
Often a low temperature stress relieving annealing treat- temperature. Quenching results in suppression of most of
ment is applied to alpha brass articles to relieve internal resi- the a-phase while most b-phase is retained as is apparent
dual stresses generated during cold forming process. It has from the microstructure of water-quenched Muntz metal
been observed that sometimes cold-formed alpha brass articles shown in Figure 14. Subsequent tempering treatment in the
crack spontaneously without the influence of external stress, as temperature range of 100–500 1C results in more of the
for instance, when such articles are stored in warehouse. a-phase precipitated out from the supersaturated solid
Examples of such articles include cartridge cases of rifles, brass solution. Tempering curve shows a hardening peak at
caps, aircooler pipes, caps for incandescent lamps, etc. In the about 300 1C (Figure 15). Thus it is possible to heat treat
cold formed articles or parts, the residual stresses are mostly alpha–beta brasses.
tensile in nature. When exposed to corrosive atmosphere, in
particular, the atmosphere containing small amount of
ammonia and sulfur dioxide (as usually found in industrial
atmosphere), cracking in brass articles takes place at the grain
boundaries. Such type of cracking is called season cracking.
Figure 13 exhibits microstructure delineating stress corrosion
cracking in an a-brass.
In order to eliminate the problem of season cracking, brass
articles are often subjected to stress relieving at low tempera-
ture. However, this treatment is frequently accompanied with
some reduction of hardness of brass; so the time and tem-
perature of annealing is properly controlled to minimize
reduction of hardness.
Dual-phase alpha–beta brasses are generally given a hard-
ening treatment followed by tempering treatment. These alloys
consist of 38–46% Zn (Figure 9). These alloys at ambient
temperature have two phases namely a and b0 . b0 phase is
ordered CuZn intermetallic compound characterized by high
hardness coupled with brittleness. b-phase, which is high
temperature disordered CuZn is soft and allows hot working
of the alloy.

Figure 14 Microstructure of water-quenched Muntz metal. b0 -phase

is light and a-phase is dark.8

Figure 13 Stress corrosion cracking in alpha brass.8 Figure 15 Tempering curve for a–b brass quenched from 850 1C.7
 Heat-Treating Copper and Nickel Alloys 409

2.14.3.2 Heat treatment of Bronzes 2.14.3.2.2 Aluminum bronzes

Like brasses, aluminum bronzes also fall in two categories: single-
2.14.3.2.1 Tin bronzes phase alpha-aluminum bronzes with less than about 8% alumi-
Tin bronzes are also called as ‘phosphor bronzes’ due to the num and dual-phase alpha–beta aluminum bronzes with
presence of small amount (0.01–0.5%) of phosphorous used aluminum 8–12% plus small amounts of iron (0.5–5.0%),
as deoxidizer in casting. The wrought alloys usually contain silicon (up to 2%), nickel (up to 5%), and manganese. Both iron
1–10% tin. Copper containing up to about 6% tin are soft and nickel improve strength and hardness and refines the grain
alloys whereas those containing more than 6% tin are hard. but nickel is less effective than iron. Silicon imparts machinability
The copper-rich end of equilibrium phase diagram of Cu–Sn while manganese promotes soundness in the casting. alpha-
alloy shown in Figure 3 indicates a long freezing range over aluminum bronzes are ductile and therefore are cold workable.
useful compositions. When an alloy containing about 6% tin Cold working improves strength and hardness. Moreover, these
is solidified under normal industrial conditions to ambient bronzes possess good corrosion resistance against atmosphere
temperature, a high degree of coring results. This heavy coring and water. Single-phase alpha-aluminum bronzes containing iron
arises due to very low diffusivity of copper and tin into each up to about 3% are effectively strengthened by cold working. The
other. This low diffusivity of copper and tin into each other structure consists of iron-rich particles in alpha phase. Annealing
leads to formation of copper-rich a-dendrites surrounded by of alpha-bronzes is carried out in the temperature range of 550–
small particles of tin-rich δ-phase (Cu31Sn8) which is hard and 870 1C. Iron containing alloys require annealing temperature at
brittle. The equilibrium e-phase (Cu3Sn) is suppressed due to higher end of the range. Alloys without iron, are annealed in the
sluggishness of structural changes below about 400 1C. As a temperature range of 595–650 1C. Aluminum bronze castings are
result ductility of the casting is greatly reduced. In order to annealed at 620–670 1C.
make this alloy amenable to cold working, prolonged homo- Alpha–beta aluminum bronzes are heat treatable. Their
genization treatment is applied to castings. Phosphor bronzes heat treatment can be explained with reference to copper-rich
with 8–10% tin are homogenized in the temperature range of portion of the Cu–Al phase diagram (Figure 16). Consider the
700–775 1C for a period of 5–6 h to promote diffusion of slow cooling of Cu–10% aluminum. Slow cooling to ambient
copper and tin atoms. Eventually the δ-phase is dissolved and temperature yields a dual-phase microconstituent composed
uniform a-phase is produced. Subsequent cooling is done of a and g2 (Cu9Al4). Upon reheating the alloy, the eutectoid
quite rapidly to prevent the precipitation of e-phase (Cu3Sn). a þ g2 start transforming to a þ b above eutectoid temperature
Thus uniform single-phase a is retained at ambient tempera- of about 565 1C. Further heating results in dissolution of a
ture. The homogenized alloys are ductile and therefore can be until at about 910 1C where the structure is composed of
cold worked. The cold worked tin bronze (C50500) is completely single-phase b solid solution. Quenching the alloy
annealed in the temperature range of 475–675 1C while other from this single-phase region from about 960 1C produces a
phosphor bronzes (C51000, C52100, and C52400) are nonequilibrium phase named b0 called martensite; Figure 17
annealed at 475–675 1C. micrograph showing needle like martensitic microstructure.

Figure 16 Cu–Al equilibrium phase diagram (copper-rich end). The microstructural sketches indicate the types of structures normally produced commercially.2
410 Heat-Treating Copper and Nickel Alloys

This martensite is similar to the martensite produced in steel (Figure 19). This suggests that Cu–Be alloy is amenable to
and exhibit similar characteristics. Tempering of b0 phase at precipitation hardening. These alloys are also called beryllium
about 500 1C results in precipitation of a fine aggregate of a bronzes or beryllium copper. The alloys of copper containing
and g2 phases (Figure 18). beryllium are perhaps the strongest among the family of
copper-base alloys known. The T.S. of these alloys may
2.14.3.2.3 Beryllium bronzes range from 1300 to 1400 MPa after heat treatment. The high
The solubility of beryllium in copper decreases from about strength together with good electrical conductivity makes
2.7% at about 870 1C to about 0.2% at ambient temperature copper–beryllium alloys particularly suitable for electrical
applications such as electrical contacts and relays. The high
strength in these alloys is derived from heat treatment. Heat-
treated alloys find wide applications as structural members
in spacecraft and aircraft. These alloys are also used as non-
sparking tools and springs. Spring properties of Cu–2.25Be-
–0.25Ni alloy approach those of steel springs together
with nonrusting characteristics. Beryllium bronze containing
about 2.25% Be are used where high strength is required.
The response to precipitation hardening in these alloys is
enhanced when a small amount (from 0.5 to about 2%) of
nickel or/and cobalt is added to these alloys. The small
amounts of elements act as grain refiners and they also
increase the stability of the supercooled solid solution. A study
carried out on Cu–(0.77–4.0%) Be alloys solution treated
at 800 1C and aged at 350 1C for several hours shows that
the alloy containing as low as 0.77 % beryllium does not
respond to age hardening (Figure 20). On increasing the ber-
yllium concentration a hardening peak is observed only when
beryllium content is 2.39% or more. This suggests that
copper–beryllium alloys with about 2.25% or more respond
to effective age hardening. For this reason most of the com-
mercial beryllium bronzes generally contain about 2% or
more of beryllium though a significant hardening has been
Figure 17 Microstructure of 90:10 aluminum bronze water-quenched
from 900 1C (showing martensitic b0 structure).2

Figure 18 Microstructure of the same alloy as in Figure 17 after

tempering at 500 1C showing tempered martensite. Martensitic b0 Figure 19 Equilibrium phase diagram of copper–beryllium alloy
transformed to a fine aggregate of a þ g2 structure.2 (copper-rich end).2
 Heat-Treating Copper and Nickel Alloys 411

Figure 20 Aging curves of Cu–Beryllium alloys quenched from

800 1C and aged at 350 1C for various times.9

shown by Cu–1.82% beryllium after 4 h of aging. Commer-

cially, copper–beryllium alloys are available in two basic
classes, namely, high-strength copper beryllium and high-
conductivity copper–beryllium alloys. The former alloys
develop moderately high strength with good conductivity
while the latter alloys develop good ductility with slightly
lower level of strength after heat treatment. For high-strength
beryllium bronzes, solution treatment is performed at a rela-
tively lower temperature of 790 1C while high-conductivity
beryllium bronzes are solution annealed at higher tempera-
ture, that is, at about 900 1C. Generally, the minimum speci-
fied solutionizing temperature is 700 1C (Figure 21, top). Any
temperature less than the minimum specified may result in
lower hardness after precipitation hardening treatment; this
may be due to incomplete dissolution of alloy content in
alpha phase. The alloys containing higher amount of cobalt
are solution annealed in the temperature range of 750–950 1C
(Figure 21, bottom). An excessive temperature above the upper
specified limit may cause grain coarsening in wrought pro-
ducts and overheating in both wrought and cast products.
Coarse grain size impairs the formability while overheating
introduces brittleness and makes the alloy poor responsive
to precipitation hardening. Solution annealing of beryllium
copper requires careful control. Figure 21 Effect of solution treatment temperature on hardness of
Soaking time is also of prime concern as it affects the C17200 and C17500 alloys after aging.3
enrichment of alpha-solid solution with respect to beryllium.
Shorter times may result in undissolved beryllium rich phase
in the a-solid solution. As a consequence the solid solution
will be less enriched with respect to beryllium which in turn
lowers the strength and hardness of the alloy after precipita-
tion hardening treatment. Figure 22 is a microstructure of
97.5% Cu, 2.25% Be, and 0.25% Ni alloy quenched from the
solution treatment temperature of 800 1C. The presence of
undissolved b-constituent is evident in this microstructure. On
the contrary, longer times may result in excessive grain growth,
in particular, in thin sections of wrought alloys and oxidation
as well.
It is recommended to allow a soaking time of 3–5 min for
thin sections such as fine wire, 15 min–1 h for thin-walled Figure 22 Microstructure of Cu–2.25Be–0.25Ni alloy after quenching
tubes and small castings. Heavy sections (usually above showing presence of undissolved b-phase.1
412 Heat-Treating Copper and Nickel Alloys

about 25 mm) requires a soaking time of 1–3 h at the rate of Table 4 Solution treating and precipitation hardening schedule of
1 h duration for each 25 mm section thickness. As the cast some beryllium bronzes
structure contains large amounts of micro-segregation within
Alloy Solution treatment Ageing treatment
the dendrites a prolonged time may be used for cast products
to homogenize the structure. A minimum of 3 h of soaking at Temperature (1C) Time (h) Temperature (1C) Time (h)
solution annealing temperature is recommended for castings.
Often a nonoxidizing atmosphere, such as hydrogen, is C17000 775–800 1/2–3 300–330 1–3
desirable if solution annealing temperature is 800 1C or C17200 775–800 1/2–3 300–330 1–3
C17300 775–800 1/2–3 300–330 1–3
more. Under oxidizing atmosphere, oxygen may diffuse
C17500 900–925 1/2–3 455–480 1–3
inward and oxidize beryllium, thereby cause the surface to
C17510 900–925 1/2–3 455–480 1–3
remain soft after subsequent aging. The soft surface severely
lowers fatigue strength, which is particularly detrimental Source: Ref. [3].
when the alloy is used for corrosion resistant springs sub-
jected to reversed stresses that are of highest in magnitude at after solutionizing. The time of aging varies from 2 to 3 h. The
the surface. Thus a careful solution annealing treatment is lower time is preferred for cold-formed alloys. The standard
required to attain a desirable combination of mechanical age hardening cycle for high-strength castings alloys comprises
properties, grain size, and dimensional tolerances without of aging for 3 h at 320–340 1C. The standard precipitation
excessive oxidation. The oxide layer formed on the pre- hardening schedule for both wrought and cast high-conductivity
cipitation hardened parts can be removed by chemical beryllium bronzes is 2–3 h of aging at 480 1C. Solution
treatment or by abrasive cleaning. treating and precipitation hardening treatment temperature
Following soaking, quenching operation constitutes the and time for some beryllium bronzes are given in Table 4.
most important part of heat treatment in beryllium bronzes. All these alloys are rapidly quenched from the solution
Once soaking is over, the alloy is quenched immediately treating temperature. Thin sections such as strips can be
without any quench delay. Any delay may lead to partial cooled in circulating air. Heavier sections need water
precipitation. Quenching is recommended to be carried out at quenching. Further, shorter times at solution temperature
the highest possible rate so that there is minimum chance for are desirable to minimize the danger of grain coarsening, in
precipitation of second phase; at the same time quenching particular for thin sections.
must be not so high to cause distortion or warpage of the alloy The wrought alloys are frequently subjected to cold
part. In the as-quenched condition the alloy is supersaturated forming after the solution treatment and quenching. This
with respect to alloy content and is soft so that any cold influences the attainable strength after subsequent precipita-
forming (e.g., by forging, swaging, or machining), if needed tion hardening treatment. The final attainable strength fur-
can be performed at this stage. Most of the commercial ber- ther varies with the degree of cold working carried out. The
yllium bronzes are supplied in solution annealed or as- cold-work hard temper produces maximum strengthening
annealed and cold worked condition. effect after aging. Figure 23 illustrates the aging time required
The copper–beryllium alloys are finally precipitation har- for development of maximum strength in solution annealed,
dened by aging to attain the desired combination of 1/4 hard, 1/2 hard, and hard C17200 (Cu–1.9% Be–0.2%
mechanical and physical properties. The high-strength ber- Co þ Ni) strip aged at various temperatures in a recirculating
yllium bronzes are generally aged to peak hardening condi- air furnace.
tion. The alloys not aged to maximum strength and hardness Table 5 gives the precipitation treatment and the resulting
are regarded as underaged while the alloys aged beyond the properties attainable in C17200 flat products. It can be noted
maximum achievable strength and hardness are termed over- that the strength properties of the solution-annealed alloy
aged. Under aging (UA) copper–beryllium alloys results in increases with increasing amount of cold deformation (1/4
improvement of toughness, uniform elongation, and fatigue hard, 1/2 hard, and hard) and concurrently the ductility
strength. Overaging of the alloy increases its electrical and property reduces significantly. There is not much decrease of
thermal conductivities and dimensional stability as well. electrical conductivity. The strength properties are superior
Copper–beryllium alloys are not amenable to natural aging when the alloy is aged at lower temperature for longer period
even after prolonged holding at room temperature. This is of time than when aged at higher temperature for shorter
indicative of the fact that either Guinier–Preston (GP) zones times.
are not formed in this alloy or the GP solvus is below room The above discussion shows that copper–beryllium alloys
temperature; however further study in this regard is warranted. containing small amount of cobalt and nickel display a sig-
The allowable time of aging depends on the temperature of the nificant precipitation strengthening effect. However, their plasti-
furnace as well as on the requirement of properties. If the city and toughness decrease significantly with improvement of
motive is to produce maximum hardness, at high aging tem- strength after aging process, which compromises the safety of
perature, a precise control of aging time is essential to avoid these alloys. Under different working conditions, there are often
overaging. The aging temperatures for high-strength wrought special requirements for the fatigue properties, toughness, form-
copper–beryllium alloys generally vary from 260 to 370 1C. ability, creep properties, and other properties of alloys. In order
The time required to reach peak properties is lower at higher to meet these special requirements, a multistage aging process
aging temperature than at the lower temperature. The time at has been applied to Cu–(1.7–2.0%)Be–(0.2–0.3%)Ni–(0.1–
aging temperature further depends on whether the alloy is 0.2%)Co alloy by Yanchuan Tang et al.6 to obtain multiple
only in as solution treated condition or it is cold worked too precipitation strengthening phases instead of single-stage peak
 Heat-Treating Copper and Nickel Alloys 413

Figure 23 Aging temperature and time relationship for C17200 Cu–Be alloy strip showing aging time required to attain maximum strength in
annealed, ¼ hard, ½ hard, and hard C17200 strip aged at various temperatures.3

Table 5 Mechanical properties of C17200 flat products after aging treatment

Initial condition Standard aging Properties

treatment
Tensile strength Yield strength % Elongation Hardness Electrical conductivity
(MPa) (MPa) (BHN) (% IACS)

Annealed None 415–540 195–380 35–60 47–78 17–19

1/4 hard None 515–605 415–550 10–40 68–90 16–18
1/2 hard None 585–690 515–655 10–25 88–96 15–17
Hard None 690–825 620–770 2–8 96–102 15–17
Annealedd 3, 315 1C 1140–1345 865–1205 4–10 35–40 HRC 22–25
Annealed 1/2 , 370 1C 1105–1310 895–1205 3–10 34–40 HRC 22–25
1/4 hard 2, 315 1C 1205–1415 1035–1275 3–6 37–42 HRC 22–25
1/4 hardd 1/3, 370 1C 1170–1380 965–1275 2–6 36–42 HRC 22–25
1/2 hardd 2, 315 1C 1275–1485 1105–1345 2–5 39–44 HRC 22–25
1/2 hard 1/4, 370 1C 1240–1450 1070–1345 2–5 38–44 HRC 22–25
Hardd 2, 315 1C 1310–1575 1140–1415 1–4 40–45 HRC 22–25
Hard 1/4, 370 1C 1275–1480 1105–1415 1–4 39–45 HRC 22–25
d
Heat treatment that provide maximum strength.
Abbreviations: BHN, Brinell hardness number; IACS, International annealed copper standard; HRC, Rockwell C-scale hardness.
Source: Ref. [3].

aging process. In this study, they solution annealed the alloy

samples at 780 1C for 20 min, quenched in water to room
temperature and applied three aging treatments: (1) UA at
320 1C for 30 min and quenched to room temperature, (2)
normal aging (NA) at 320 C for 180 min and (3) interrupted
aging (IA). Results of the tensile testing showed that the alloy
under IA condition exhibited a marked hardening response
though the yield and T.S. have been still slightly lower (only
about 3%) than those of NA condition. However, the uniform
elongation has been found to increase significantly (about 17%)
after IA treatment as against the NA condition. The IA condition
also increased the tension toughness of the Cu–Be–Ni–Co alloy
suggesting its ability to resist crack propagation. Furthermore, the
same alloy in the IA-treated condition displayed much superior
fracture toughness than in NA condition as can be noted from
the load–displacement curves shown in Figure 24.6 Both the load
Figure 24 Load–displacement curve for the alloy Cu–Be–Ni–Co in required for fracture and the total energy absorbed during frac-
interrupted aging (IA) and normal aging (NA) conditions.6 ture have been found to increase by about 20% and more.
414 Heat-Treating Copper and Nickel Alloys

2.14.3.2.4 Silicon bronze In the precipitation hardened state these alloys display a
The solubility of silicon in copper is maximum (that is 5.3%) reasonably good T.S. coupled with good electrical conductivity
at about 852 1C and it decreases with decreasing temperature (80% IACS). These alloys are solution treated in the tempera-
(Figure 25). The eutectoid reaction at about 555 1C is very slow ture range of 950–1010 1C where a single-phase is obtained and
and therefore under normal cooling conditions a single-phase cooled rapidly after soaking. However due to differential melt-
a-solid solution is retained at ambient temperature in copper ing temperatures of copper and chromium, there is a preferred
alloys containing less than 5% silicon. These alloys are termed chromium–chromium coordination in the solidified alloy
as silicon bronzes. Being single-phase, these alloys are not which influences the subsequent aging treatment in a great way.
susceptible to precipitation hardening. Mechanical properties Unless proper care is taken, nonuniform distribution of pre-
of these alloys are comparable to those of mild steel and the cipitates may quite often result in the final microstructure.
corrosion resistance exhibited by these alloys is comparable to Solution treatment is generally carried out in a controlled
that of copper. The popular heat treatment applied to silicon atmosphere or in salt bath in order to prevent scaling and
bronzes is annealing treatment after cold working which is internal oxidation. In the solution treated condition the alloys
performed at 475–700 1C. are soft and ductile and therefore can be cold formed if desired.
Following this, aging is carried out in the temperature range
2.14.3.3 Cupronickels 400–500 1C for several hours (typically 4 h or even more)
depending on the combination of strength and electrical con-
Cupronickels are binary alloys of copper and nickel. Copper ductivity required. A typical aging cycle is 450 1C, 4 h or more.
and nickel form a series of solid solutions. Accordingly these
are single-phase alloys. Hence they are not susceptible to heat
treatment. They can be hardened only by cold working. 2.14.3.5 Zirconium–Copper Alloys
Commercial cupronickels generally contain up to 30% nickel. Copper alloys containing 0.13–0.3 % zirconium are solution
Cupronickels have high corrosion resistance together with treated at 900–980 1C and quenched rapidly (as in water).
resistance to corrosion fatigue. They also resist corrosive and Aging is performed at 500–550 1C for 1–4 h. The strengthening
erosive actions of rapidly moving seawater. The corrosion is imparted by coherent Cu3Zr-type precipitates. It is recom-
resistance of cupronickels increases with increasing nickel mended to minimize the holding time at solution annealing
content. The electrical resistivity of these alloys also increases temperature so as to eliminate the danger of excessive grain
with increasing nickel concentration. Cupronickels are mod- growth which may occur due to high diffusivity of zirconium
erately hard also but tough and ductile. Cupronickels with 10 at this temperature. Because of the high diffusivity of zirco-
and 30% nickel are very commonly employed for condenser, nium at solutionizing temperature, it requires less time for
distiller, evaporator, and heat exchanger tubes. The very dissolution and hence there is no need for longer soaking
common heat treatment applied to cupronickels is annealing time. Moreover, excessive time of soaking may cause internal
after cold working. Annealing after cold working of cupro-
nickels containing up to 30% nickel (Alloys C70600, C71000,
and C71500) is performed at 600–825 1C.

2.14.3.4 Chromium Coppers

The phase diagram of copper–chromium (Figure 26) shows
that the alloys containing chromium from 0.4 to 1.0% are
characterized as precipitation hardening alloys.

Figure 26 Equilibrium phase diagram of copper–chromium alloy

Figure 25 Copper-rich portion of the copper–silicon alloy system.8 (copper-rich end).2
 Heat-Treating Copper and Nickel Alloys 415

oxidation by reaction of zirconium with the furnace atmo- dispersion of Cu5Zr and chromium precipitates which develop
sphere. If desired, cold working can be done before aging. In during aging treatment. This microstructure imparts resistance
such condition, aging temperature may be reduced to the level to softening at elevated temperatures. These alloys find
between 375 and 475 1C. Prior cold working provides more applications in resistance welding electrodes, spot welding
nucleation sites for precipitation at dislocations and thus adaptor shanks, and others where high electrical conductivity
accelerates aging. and good resistance against softening are required.
Other single-phase copper alloys namely cupronickels
(10–30% Ni) and nickel–silver alloys are generally annealed
after cold working in the temperature range 600–825 1C. 2.14.3.7 Copper–Nickel–Silicon–Chromium Alloy
Silicon bronzes are annealed at 475–700 1C.
Apart from the advantageous properties mentioned earlier,
beryllium–copper alloys suffer from some drawbacks. Ber-
2.14.3.6 Copper–Chromium–Zirconium Alloys yllium present in the beryllium bronze is detrimental to
human life as well as to environment. The alloys are difficult to
Copper–chromium–zirconium alloys are precipitation hard-
recycle after use. In this context, researchers have been studying
ening alloys developed for high temperature applications
various other copper alloys as substitute for toxic beryllium
where material must meet an optimum combination of
bronzes. One such alloy investigated by Huei-Sen Wang et al.
mechanical properties coupled with high electrical and ther-
is Cu–7.4Ni–1.3Si–1.2Cr. This alloy is developed for mold
mal conductivities. These alloys derive the best combination of
tooling application. When cast conventionally, this alloy
physical and mechanical properties through precipitation
exhibits a coarse grain structure (grain size of about 200 mm)
hardening treatment. The heat treatment consists of solution
embedded with large size precipitates and substantial micro-
treatment followed by rapid quenching (as in water bath),
segregation of the alloying elements. Huei-Sen Wang et al.
cold working, and aging. The schedules of heat treatment of
processed this alloy through powder metallurgy route. The
two Cu–Cr–Zr alloys are given in Table 6 and the resultant
powder of the alloy was produced by argon atomization
properties are given in Table 7. Both these alloys exhibit
process with average size of 25 mm. The powder was con-
comparable mechanical property values but the latter alloy
solidated to bulk form by hot pressing followed by sintering to
displays high electrical conductivity after identical heat treat-
obtain dense mass. The average grain size of the hot pressed
ment. Strengthening in these alloys results due to fine
and sintered product has been found to be 100 mm. The alloy
samples were solution treated at 970 1C for times up to 10 h
and subsequently quenched in water. The samples were pre-
Table 6 Schedule of heat treatments of Cu–Cr–Zr alloys
cipitation hardened at 450 1C for up to 6 h. The best results
Alloy designation and Solution annealing Ageing were observed at 8 h solution treatment at 970 1C followed by
composition treatment treatment 6 h aging at 450 1C. After aging a subgrain structure with grain
size less than 30 mm was observed.11 The alloy was found to
ZollernCuCrZr 970 1C, 20 min/water 475 1C, 2 h exhibit average T.S. of up to 820 MPa and average thermal
(Cu–0.85Cr–0.09Zr) quench
conductivity of 110 W m
1 K
1. The strengthening was pro-
KabelmetalCuCrZr 980 1C, 60 min/water 475 1C, 2 h
duced due to fine dispersion of nanometer size b-Ni3Si and
(Cu–0.65Cr–0.10Zr) quench
δ-Ni2Si precipitates in fine grain size matrix as shown in
Source: Ref. [10]. Figure 27. Based on the thermal conductivity and the T.S.
developed in the Cu–Ni–Si–Cr alloy Huei-Sen Wang et al. sug-
gested the potential application of this alloy for mold tooling.
Table 7 Room temperature mechanical properties and electrical
conductivity
2.14.3.8 Copper-Base Shape Memory Alloys
Alloy and heat Yield Tensile Elongation at Electrical
Cu–Zn–Al alloys are known to produce thermoelastic mar-
treatment strength strength fracture (%) conductivity
(MPa) (MPa) tensite. When the alloy is deformed to a different shape in
martensitic and then heated to parent state, the original shape
Zollern CuCrZr is regained; this is called shape memory effect (SME). In gen-
Solution 118 243 52 35.7% IACS eral Cu–xZn–yAl and Cu–xAl–yNi are quenched from high
quenched temperature b-phase field to produce martensites. These mar-
Solution 310 418 25 76.4% IACS tensites are soft and can be deformed at a small force. Since
quenched
volume change ‘ΔV’ accompanying martensitic transformation
and aged
is very small these martensites are internally twinned; these
Kabelmetal reversible defects play important role for SME. The reversible
CuCrZr internal faults enable the transformation of martensite to
Solution 316 414 24 83.4% IACS parent phase along the same path as that of the forward
quenched transformation (b–M). Influence of a rare earth element,
and aged
Gd on microstructure on this shape memory alloy has
Abbreviation: IACS, International Annealed Copper Standard. been reported in the literature.12 Stabilization of martensite
Source: Ref. [10]. is observed in memory alloys.13 The inherent reversibility
416 Heat-Treating Copper and Nickel Alloys

Figure 27 Bright field images of the Cu–Ni–Si–Cr alloy after 6 h aging showing microsize Cr3Si and Ni2Si precipitates at the grain boundaries
((a) and (b)), microsize Ni31Si12 precipitate within the grain (c), and (d) large number of precipitate particles within copper matrix.11

characteristics of martensitic transformation in Cu–Zn–Al and given by International Nickel Company (INCO) and these are
Cu–Al–Ni alloy are envisaged due to low thermal hysteresis. Monels, Inconels, Nimonics, and Hastelloys.
The repetitive use of these shape memory alloys leads to aging Since nickel is attacked by sulfur, an important considera-
effect; this leads to the formation of precipitates of inter- tion during heat treatment of nickel alloys is the furnace
metallics which adversely affect the SME. However controlled atmosphere which must be free of sulfur. Embrittlement due
aging of some shape memory alloys may accentuate SME to sulfur, if occurs, cannot be remedied.
behavior although in most of the cases chemical degradation is The types of heat treatment applied to nickel alloys are as
reported to have deteriorated SME in copper alloys.14–17 follows.

2.14.4.1 Annealing
2.14.4 Heat Treatment of Nickel Alloys
The aim of annealing of cold worked nickel alloys is to make
Nickel is one of the most important engineering metals. It has them soft for further cold reduction. This treatment is per-
FCC structure and does not show any polymorphic changes formed by heating the alloy to a temperature where recrys-
even up to the melting temperature. It possesses good com- tallization takes place. This temperature for nickel alloys falls
bination of physical and mechanical properties apart from in the range of 700–1200 1C depending on the type of alloy
outstanding corrosion resistance against many corrosive media and its composition, as well as the degree of cold working.
and good oxidation resistance. However, nickel is prone to Higher annealing temperature is used where greater softening
attack by sulfur. Sulfur makes nickel embrittled due to the is desired. The alloy is generally slowly cooled from the
formation of brittle Ni3S2 at the grain boundaries.18 Nickel is annealing temperature. Effects of heat treating temperature on
principally alloyed with copper, iron, chromium, silicon, and some room temperature mechanical properties of cold drawn
molybdenum. Based on these principal alloying elements, Monel 400 alloy are represented in Figure 28. As stated earlier,
nickel-base alloys are categorized as: nickel–copper alloys, the heat treatment temperatures for various nickel alloys are
nickel–chromium alloys, nickel–iron alloys, nickel–chromium– also decided by the corresponding phase diagrams. A repre-
molybdenum alloys, nickel–iron–chromium alloys, and so on. sentative phase diagram of nickel–copper alloy (Monel) is
Nickel alloys are also popularly known by their trade names shown in Figure 29 that describes its annealing temperature.
 Heat-Treating Copper and Nickel Alloys 417

The annealing schedule for several nickel and nickel alloys is

given in Table 8.

2.14.4.2 Solution Annealing

It is a high temperature annealing treatment applied to some
specific nickel alloys so as to bring second phase into solution
and cause some grain coarsening which is desirable to improve
creep rupture properties. This treatment is applied at a tem-
perature lower than the upper annealing temperature range
prior to precipitation hardening. The solution treating tem-
peratures for some nickel alloys are given in Table 9.

2.14.4.3 Stress Relieving

This treatment is applied to cold worked nickel and non-age-
hardenable nickel alloys. The alloy is heated to a temperature in
the range 425–870 1C and soaked without any recrystallization
to occur. Only recovery part of annealing remains effective. The
true temperature of annealing depends on the alloy composi-
tion and degree of prior cold working. The stress relieving
temperatures used for some nickel alloys are given in Table 10.

2.14.4.4 Stress Equalizing

It is a kind of stress relieving treatment performed on cold
drawn nickel alloys at lower temperature of annealing so that
partial recovery takes place with the elimination of excess
lattice defects, in particular, the point imperfections. The
consequent effect is the restoration of electrical conductivity
while there is no deteriorating effect on improved hardness
Figure 28 Effect on room temperature properties of cold drawn
and strength produced by cold working. The exact temperature
Monel 400 rod held for 3 h at various temperatures.3
of stress equalizing cold drawn alloys depends on their com-
position and the degree of prior cold reduction. For instance,
an optimum temperature range of 230–315 1C is used for cold
drawn Monel 400 rod. The applications of stress equalizing
include coil springs, wire forms, and flat spring stampings.
Table 10 gives the schedule of stress equalizing treatment of
Nickel 200, Nickel 201, and Monel 400.

2.14.4.5 Precipitation Hardening

Alloying elements such as Al, Si, Ti, Nb, and others are added
in very small concentrations either singly or in combination
to make nickel and its alloys susceptible to precipitation
hardening. The strength and hardness properties are
improved after proper age hardening treatment. Solution
treatment is carried out at a temperature where the pre-
cipitation hardening constituents dissolve into solid solution
and form a single-phase. The temperature at which solution
treating is performed varies widely within the temperature
interval between 980 and 1315 1C. The upper limit of tem-
perature is preferred when carbides are required to dissolve
into solid solution. The time of solution treatment varies
from 2 to 4 h. The exact temperature of solutionizing
depends on the alloy composition. Subsequently the alloy
is cooled rapidly such that supersaturated solid solution is
retained at ambient temperature. In this condition the alloy is
Figure 29 Phase diagram of Cu–Ni system.19 soft and ductile and it can be fabricated by cold forming
418 Heat-Treating Copper and Nickel Alloys

Table 8 Annealing treatment schedule for some representative nickel and nickel alloys

Material with composition Temperature (1C) Time Cooling method

Nickel 200: 99.5 Ni–0.06 C–0.25 Mn–0.15 Fe–0.05 Si–0.05 Cu 705–760 B 2–6 h AC (air cool)
815–925 C 1/2–5 min AC or WQ (water quench)
Nickel 201: 99.5 Ni–0.01 C–0.20 Mn–0.15 Fe–0.05 Si–0.05 Cu 705–760 B 2–6 h AC
760–870 C 1/2–5 min AC or WQ
Monel 400: 66 Ni–0.12 C–0.90 Mn–1.35 Fe–0.15 Si–31.5 Cu 760–815 B 1–3 h AC
870–980 C 1/2–15 min AC or WQ
Monel R-405: 66 Ni–0.18 C–0.90 Mn–1.35 Fe–0.15 Si–31.5 Cu–0.04 S 760–815 B 1–3 h AC
870–980 C 1/2–15 min AC or WQ
Monel K-500: 65 Ni–0.15 C–0.60 Mn–1.00 Fe–0.15 Si–29.50 Cu 870–1040 B 1–3 h WQ
870–1040 C 1/2–20 min WQ
Carpenter nickel–copper 400: (63–70)Cu–0.03 C–2.0 Mn–2.5 704–980 1–3 h –
(maximum) Fe–0.50 Si–Balance Cu 870–980 most typical
sulfur free atmosphere
Inconel 600: 76 Ni–0.04 C–0.20 Mn–7.20 Fe–0.20 Si–0.10 Cu–15.8 Cr 925–980 B 1–3 h AC
925–1040 C 1/2–60 min AC or WQ
Inconel 601: 60.50 Ni–0.05 C–0.50 Mn–14.10 Fe–0.25 Si–23.00 1095–1175 B 1–3 h AC
Cr–1.35 Al 1095–1175 C 1/2–60 min AC or WQ
Inconel 617: 54.00 Ni–0.07 C–22.00 Cr–1.00 Al 9.00 Mo–12.5 Co 1120–1175 B 1–3 h AC
1120–1175 C 1/2–60 min AC or WQ
Inconel 625: 61.00 Ni–0.05 C–0.25 Mn–2.50 Fe–21.50 Cr–1.00 980–1150 B 1–3 h AC
Al–9.00 Mo–3.65 Nb 980–1150 C 1/2–60 min AC or WQ
Inconel 718: 52.50 Ni–0.04 C–0.20 Mn–18.00 Fe–0.20 Si–0.10 955–1065 B 1–3 h AC
Cu–19.00 Cr–0.8 Ti–0.60 Al–3.00 Mo–5.20 Nb 955–1065 C 1/2–60 min AC
Inconel X-750: 73.00 Ni–0.04 C–0.70 Mn–6.75 Fe–0.30 Si–0.05 955–1150 B 1–3 h AC
Cu–15.00 Cr–2.508 Ti–0.80 Al–3.00–0.85 Nb 955–1150 C 1/2–60 min AC
Hastelloy B-2: 69.00 Ni–0.01C–1.00 Fe–28.00 Mo 1095–1175 B 1h AC or WQ
1095–1185 C 5–10 min AC or WQ
Hastelloy C-276: 57.00 Ni–0.01 C–5.50 Fe–15.50Cr–16.00 Mo 1215 B 1h WQ
1215 C 5–10 min WQ
Hastelloy X: 48.00 Ni–0.10 C–18.50 Fe–22.00 Cr–9.00 Mo–1.00 1175 B 1h AC or WQ
Co–0.60 W 1175 C 1/2–15 min AC or WQ

Note: B stands for batch annealing and C stands for continuous annealing. Time given in minutes represent the actual ranges that thin sheet/strip products and heavy cross-sections
would receive in continuous furnaces.
Source: Ref. [3].

Table 9 Solution treating and precipitation hardening schedules for some representative nickel alloys

Alloy Solution treatment schedule Precipitation hardening schedule

Monel K-500 980 1C, 1/2–1 h hold, air cool (AC) Heat to 595 1C, hold 16 h; furnace cool (FC) to 540 1C, hold 6 h; FC to 480 1C; AC
Inconel 718 980–1065 1C, 1 h hold, AC Heat to 720–760 1C, hold 8 h; FC to 620–650 1C, hold until furnace time for entire
precipitation hardening cycle equals 18–20 h; AC
Inconel X-750 1150 1C, 1–2 h hold, AC Heat to 845 1C, hold 24 h; AC, reheat to 705 1C, hold 20 h; AC
Hastelloy X 1175 1C, 1 h hold, AC Heat to 760 1C, hold 3 h; AC; reheat 595 1C, hold 6 h; FC to 480 1C; AC
Inconel 901 1095 1C, 2 h hold, WQ Heat to 790 1C, hold 2 h; AC; reheat 720 1C, hold 24 h; AC
Nimonic 90 1080 1C, 8 h hold, AC Heat to 705 1C, hold 16 h; AC
Udimet 500 1080 1C, 4 h hold, AC Heat to 850 1C, hold 24 h; AC; reheat 760 1C, hold 16 h; AC
Waspaloy 1080 1C, 4 h hold, AC Heat to 845 1C, hold 24 h; AC; reheat 760 1C, hold 16 h; AC

Source: Ref. [3].

process if required. The alloy is finally precipitation hardened 2.14.4.6 Nickel-Base Superalloys
at 425–870 1C depending on the alloy type and its compo-
sition. Sometimes a double aging treatment is applied. The Nickel-base superalloys have an austenitic matrix structure.
solution annealing and precipitation hardening cycles Many of these contain molybdenum and/or tungsten, which
of some representative nickel alloys are given in Table 9. are soluble in the matrix and act as solid-solution strength-
Figure 30 is a typical representative microstructure of pre- eners. In nickel-base superalloys, g0 and g00 lead to precipitation
cipitation hardened alloy Monel K-500 showing fine pre- strengthening; The g0 phase, is identified as Ni3(Al,Ti) with its
cipitate of Ni3(Al,Ti) as black spots.8 crystal structure as ordered f.c.c of L12-type ordering and is
 Heat-Treating Copper and Nickel Alloys 419

Table 10 Stress relieving and stress equalizing cycle of heat treatment for some representative nickel and nickel alloys

Material Stress relieving Stress equalizing

Temperature (1C) Time (min) Cooling method Temperature (1C) Time (h) Cooling method

Nickel 200 480–705 1/2–120 AC (air cool) 260–480 1–2 h AC

Nickel 201 480–705 1/2–120 AC 260–480 1–2 h AC
Monel 400 540–650 1/2–20 AC 230–315 1–3 h AC
Carpenter nickel–copper 400 540–570 60–120 AC
Inconel 600 760–870 5–60 AC – – –

Note: Time given in minutes represent the actual ranges that thin sheet/strip products and heavy cross-sections would receive in continuous furnaces.
Source: Ref. [3].

as TiC, TiN, Ti(C, N), M6C, and M23C6 have also been iden-
tified in the structure of many nickel-base alloys. Major type of
nickel-base superalloys include Ni–Cr–Fe-based (e.g., Incon-
els), Ni–Mo–Fe-based (e.g., Hastelloy A and B), and Ni–Cr–
Mo–Fe-based (e.g., Hastelloy C and Hastelloy X). Examples of
a few nickel-base superalloys along with their heat treatment
schedule are given in Table 9.

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