CHAPTER

Kinetics—Heat
10
Treatment

The microstructure of a rapidly cooled “eutec-

tic” soft solder ( ≈ 38 wt % Pb − 62 wt %
Sn) consists of globules of lead-rich solid so-
lution (dark) in a matrix of tin-rich solid solu-
tion (white), 375X. The contrast to the slowly-
cooled microstructure at the opening of Chap-
ter 9 illustrates the effect of time on microstruc-
tural development. (From ASM Handbook,
Vol. 3: Alloy Phase Diagrams, ASM Interna-
tional, Materials Park, Ohio, 1992.)
T

Completion of reaction

T
t

Tmp

x t

(a) (b)

Figure 10-1 Schematic illustration of the approach to equilibrium. (a) The time for solidi-
fication to go to completion is a strong function of temperature, with the minimum time
occurring for a temperature considerably below the melting point. (b) The temperature–
time plane with “transformation curve.” We shall see later that the time axis is often plot-
ted on a logarithmic scale.
 Liquid

Solid

(a) (b)

Crystal
Crystal growth
nucleus

(c) (d)
Figure 10-2 (a) On a microscopic scale, a solid precipitate in a liquid matrix. The pre-
cipitation process is seen on the atomic scale as (b) a clustering of adjacent atoms to
form (c) a crystalline nucleus followed by (d) the growth of the crystalline phase.
 Surface energy addition

+
Net energy change

Net energy change

0 r
rc

Volume energy reduction

Figure 10-3 Classical nucleation theory involves an energy balance
between the nucleus and its surrounding liquid. A nucleus (clus-
ter of atoms) as shown in Figure 10–2(c) will be stable only if
further growth reduces the net energy of the system. An ideally
spherical nucleus will be stable if its radius, r , is greater than a
critical value, rc .
 Tm
Contribution of diffusion (clustering of atoms)
Temperature, T

Net nucleation rate (= product of two dashed lines)

Contribution of liquid phase instability

Nucleation rate, N (s–1)

Figure 10-4 The rate of nucleation is a product of two curves that represent two
opposing factors (instability and diffusivity).
 Tm
Temperature, T

Overall transformation rate

Rate, (s–1)
Figure 10-5 The overall transformation rate is the product of the nucleation
rate Ṅ (from Figure 10–4) and the growth rate Ġ (given by Equation 10.1).
Temperature, T

Tmp

1 50 100 % completion of reaction

Curve shown in Figure 10-1

Time, t (logarithmic scale)

Figure 10-6 A time–temperature–transformation diagram for the solidification reac-
tion of Figure 10–1 with various percent completion curves illustrated.
 ˚C

800

727˚
700

Coarse pearlite
600

500 Fine pearlite

400

Bainite
300

200

100
1 sec 1 min 1 hour 1 day

0
0.1 1 10 102 103 104 105 0 0.77
Time, seconds wt % C

Figure 10-7 TTT diagram for eutectoid steel shown in relation to the Fe–Fe 3 C phase
diagram (see Figure 9–39). This shows that, for certain transformation tempera-
tures, bainite rather than pearlite is formed. In general, the transformed microstruc-
ture is increasingly fine-grained as the transformation temperature is decreased. Nu-
cleation rate increases and diffusivity decreases as temperature decreases. The solid
curve on the left represents the onset of transformation ( ∼ 1% completion). The
dashed curve represents 50% completion. The solid curve on the right represents
the effective ( ∼ 99%) completion of transformation. This convention is used in
subsequent TTT diagrams. (TTT diagram after Atlas of Isothermal Transforma-
tion and Cooling Transformation Diagrams, American Society for Metals, Metals
Park, Ohio, 1977.)
Temperature

Coarse pearlite

Time (logarithmic scale)

Figure 10-8 A slow cooling path that leads to coarse pearlite formation is superimposed
on the TTT diagram for eutectoid steel. This type of thermal history was assumed,
in general, throughout Chapter 9.
Figure 10-9 The microstructure of bainite involves extremely fine
needles of α -Fe and Fe 3 C, in contrast to the lamellar structure
of pearlite (see Figure 9–2), 535 × . (From Metals Handbook,
8th Ed., Vol. 7: Atlas of Microstructures, American Society
for Metals, Metals Park, Ohio, 1972.)
Temperature

Coarse pearlite

Coarse pearlite remains upon cooling

Time (logarithmic scale)

Figure 10-10 The interpretation of TTT diagrams requires consideration
of the thermal history “path.” For example, coarse pearlite, once formed,
remains stable upon cooling. The finer-grain structures are less stable
because of the energy associated with the grain boundary area. (By
contrast, phase diagrams represent equilibrium and identify stable phases
independent of the path used to reach a given state point.)
 ˚C

800

727˚
700

Coarse pearlite
600

500 Fine pearlite

400

Bainite
300

Ms
200
M50
M90
100
1 sec 1 min 1 hour 1 day

0
0.1 1 10 102 103 104 105 0 0.77
Time, seconds wt % C

Figure 10-11 A more complete TTT diagram for eutectoid steel than was given
in Figure 10–7. The various stages of the time-independent (or diffusion-
less) martensitic transformation are shown as horizontal lines. Ms repre-
sents the start, M50 50% transformation, and M90 90% transformation. One
hundred percent transformation to martensite is not complete until a final
temperature ( Mf ) of − 46 ◦ C.
 a0
c

a0|! 2 a

(a) (b)
Figure 10-12 For steels, the martensitic transformation involves the sudden reorientation of C and Fe atoms from
the fcc solid solution of γ -Fe (austenite) to a body-centered tetragonal (bct) solid solution (martensite). In (a),
the bct unit cell is shown relative to the fcc lattice by the h 100 iα axes. In (b), the bct unit cell is shown before (left)
and after (right) the transformation. The open circles represent iron atoms. The solid circle represents an inter-
stitially dissolved carbon atom. This illustration of the martensitic transformation was first presented by Bain in
1924, and while subsequent study has refined the details of the transformation mechanism, this remains a useful
and popular schematic. (After J. W. Christian, in Principles of Heat Treatment of Steel, G. Krauss, Ed., Ameri-
can Society for Metals, Metals Park, Ohio, 1980.)
Figure 10-13 Acicular, or needlelike, microstructure of martensite 1000 × . (From
Metals Handbook, 8th Ed., Vol. 7: Atlas of Microstructures, American So-
ciety for Metals, Metals Park, Ohio, 1972.)
 ˚C

800

727˚
3 Continuous cooling
700 transformation
1 2

Isothermal
600 transformation

500 1 Rapid cooling rate

400 2 Moderate cooling rate

3 Slow cooling rate

300

Ms
200
M50
M90
100
1 sec 1 min 1 hour 1 day

0
0.1 1 10 102 103 104 105
Time, seconds

Figure 10-14 A continuous cooling transformation (CCT) diagram is shown superimposed

on the isothermal transformation diagram of Figure 10–11. The general effect of contin-
uous cooling is to shift the transformation curves downward and toward the right. (After
Atlas of Isothermal Transformation and Cooling Transformation Diagrams, American
Society for Metals, Metals Park, Ohio, 1977.)
 ˚C

900 880˚

800
727˚
700

600

500

400

300

200 Ms

M50
100
M90
1 sec 1 min 1 hour 1 day
0
0.1 1 10 102 103 104 105 0 1.13
Time, seconds wt % C

Figure 10-15 TTT diagram for a hypereutectoid composition (1.13 wt % C) compared

to the Fe–Fe 3 C phase diagram. Microstructural development for the slow cooling
of this alloy was shown in Figure 9–40. (TTT diagram after Atlas of Isothermal
Transformation and Cooling Transformation Diagrams, American Society for Met-
als, Metals Park, Ohio, 1977.)
 ˚C

900

800 770˚
727˚
700

600

500

400

Ms
300
M50
M90
200

100
1 sec 1 min 1 hour 1 day

0.1 1 10 102 103 104 105 0 0.5

Time, seconds wt % C

Figure 10-16 TTT diagram for a hypoeutectoid composition (0.5 wt % C)

compared to the Fe–Fe 3 C phase diagram. Microstructural development
for the slow cooling of this alloy was shown in Figure 9–41. By compar-
ing Figures 10–11, 10–15, and 10–16, one will note that the martensitic
transformation occurs at decreasing temperatures with increasing car-
bon content in the region of the eutectoid composition. (TTT diagrams
after Atlas of Isothermal Transformation and Cooling Transformation
Diagrams, American Society for Metals, Metals Park, Ohio, 1977.)
Temperature
Thermal history for center of part being heat-treated
Thermal history for surface of part being heat-treated

Tempering temperature

Ms

Transformation

Mf

Tempered martensite
Martensite

Time (logarithmic scale)

Figure 10-17 Tempering is a thermal history [ T = f n(t) ] in which marten-

site, formed by quenching austenite, is reheated. The resulting tempered
martensite consists of the equilibrium phase of α -Fe and Fe 3 C but in a mi-
crostructure different from both pearlite and bainite (note Figure 10–18).
(After Metals Handbook, 8th Ed., Vol. 2, American Society for Metals,
Metals Park, Ohio, 1964. It should be noted that the TTT diagram is, for
simplicity, that of eutectoid steel. As a practical matter, tempering is gener-
ally done in steels with slower diffusional reactions permitting less severe
quenches.)
Figure 10-18 The microstructure of tempered martensite, although
an equilibrium mixture of α -Fe and Fe 3 C, differs from those
for pearlite (Figure 9–2) and bainite (Figure 10–9), 825 × . This
particular microstructure is for a 0.50 wt % C steel comparable
with that described for Figure 10–16. (From Metals Handbook,
8th Ed., Vol. 7: Atlas of Microstructures, American Society for
Metals, Metals Park, Ohio, 1972.)
Temperature
Surface
Center

Tempering temperature

Transformation

Tempered martensite
Martensite

Time (logarithmic scale)

Figure 10-19 In martempering, the quench is stopped just above Ms . Slow cool-
ing through the martensitic transformation range reduces stresses associ-
ated with the crystallographic change. The final reheat step is equivalent to
that in conventional tempering. (After Metals Handbook, 8th Ed., Vol. 2,
American Society for Metals, Metals Park, Ohio, 1964.)
Temperature
Surface
Center

Transformation

Bainite

Time (logarithmic scale)

Figure 10-20 As with martempering, austempering avoids the distortion and

cracking associated with quenching through the martensitic transforma-
tion range. In this case, the alloy is held long enough just above Ms to al-
low full transformation to bainite. (After Metals Handbook, 8th Ed., Vol.
2, American Society for Metals, Metals Park, Ohio, 1964.)
(a)

(c) (b)
DT

DT
Quench rate =
t

t
 Specimen

Water spray

Figure 10-21 Schematic illustration of the Jominy end-quench

test for hardenability. (After W. T. Lankford et al., Eds.,
The Making, Shaping, and Treating of Steel, 10th Ed., United
States Steel, Pittsburgh, Pa., 1985. Copyright 1985 by United
States Steel Corporation.)
 Distance from quenched end, inches
1 1 1 1
8 4 2
1 1 2
2
1000
500
Cooling rate at 700˚C, C/sec

200
100
50

20
10
5

2
0 10 20 30 40 50 mm
Distance from quenched end, Dqe
(Jominy distance)
Figure 10-22 The cooling rate for the Jominy bar (see Figure 10–21) varies along
its length. This curve applies to virtually all carbon and low-alloy steels. (Af-
ter L. H. Van Vlack, Elements of Materials Science and Engineering, 4th Ed.,
Addison-Wesley Publishing Co., Inc., Reading, Mass., 1980.)
 60

55

50

45
Rockwell hardness C scale

40

35

30

25

20

15

10

0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32
Distance from quenched end – sixteenths of an inch

Figure 10-23 Variation in hardness along a typical Jominy bar. (From W. T.

Lankford et al., Eds., The Making, Shaping, and Treating of Steel, 10th
Ed., United States Steel, Pittsburgh, Pa., 1985. Copyright 1985 by United
States Steel Corporation.)
 65

60

55
Rockwell hardness C scale

50

45

40 4340
35 9840
30 4140

25 8640
20
5140
15
10
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32
Distance from quenched end—sixteenths of an inch

Figure 10-24 Hardenability curves for various steels with the same carbon con-
tent (0.40 wt %) and various alloy contents. The codes designating the alloy
compositions are defined in Table 11.1. (From W. T. Lankford et al., Eds.,
The Making, Shaping, and Treating of Steel, 10th Ed., United States Steel,
Pittsburgh, Pa., 1985. Copyright 1985 by United States Steel Corporation.)
 ˚C
700

600

500

400

Slow cool
300

200

100

0
90 95 100 Time
wt % Al

Figure 10-25 Coarse precipitates form at grain boundaries in an Al–Cu (4.5 wt

%) alloy when slowly cooled from the single-phase ( κ ) region of the phase
diagram to the two-phase ( θ + κ ) region. These isolated precipitates do little
to affect alloy hardness.
 ˚C
700

600 Solution treatment

500
Quench
400
Fine dispersion of
precipitates within grains
300 taging (retained upon cooling)

200

100

0
90 95 100 Time
wt % Al

Figure 10-26 By quenching and then reheating an Al–Cu (4.5 wt %) alloy, a fine dispersion of precipi-
tates forms within the κ grains. These precipitates are effective in hindering dislocation motion and,
consequently, increasing alloy hardness (and strength). This is known as precipitation hardening, or
age hardening.
 Temperature

Coarse precipitates
within grains
taging

Time
(a)

Hardness
(arbitrary units)

0.01 0.1 1 10 100 1000

taging (hours)
(b)

Figure 10-27 (a) By extending the reheat step, precipitates coalesce and become
less effective in hardening the alloy. The result is referred to as “overaging.”
(b) The variation in hardness with the length of the reheat step (“aging time”).
Figure 10-28 Schematic illustration of the crystalline ge-
ometry of a Guinier–Preston (G.P.) zone. This struc-
ture is most effective for precipitation hardening, and
is the structure developed at the hardness maximum
in Figure 10–27b. Note the coherent interfaces length-
wise along the precipitate. The precipitate is approxi-
mately 15 nm × 150 nm. (From H. W. Hayden, W. G.
Moffatt, and J. Wulff, The Structure and Properties
of Materials, Vol. 3: Mechanical Behavior, John Wi-
ley & Sons, Inc., New York, 1965.)
 (a)

(b)
Figure 10-29 Examples of cold-working operations: (a) cold-rolling of a bar
or sheet and (b) cold-drawing a wire. Note in these schematic illustrations
that the reduction in area caused by the cold-working operation is associ-
ated with a preferred orientation of the grain structure.
 (a) (b) (c)

(d) (e)

Figure 10-30 Annealing can involve the complete recrystallization and subsequent
grain growth of a cold-worked microstructure. (a) A cold-worked brass (de-
formed through rollers such that the cross-sectional area of the part was reduced
by one-third). (b) After 3 s at 580 ◦ C, new grains appear. (c) After 4 s at 580 ◦ C,
many more new grains are present. (d) After 8 s at 580 ◦ C, complete recrystal-
lization has occurred. (e) After 1 h at 580 ◦ C, substantial grain growth has oc-
curred. The driving force for this is the reduction of high-energy grain bound-
aries. The predominant reduction in hardness for this overall process had oc-
curred by step (d). All micrographs at magnification of 75 × . (Courtesy of J. E.
Burke, General Electric Company, Schenectady, N.Y.)
 Temperature, ˚F
200 400 600 800 1000 1200 1400
120

C26000
110
Hardness, HRH

100

90

80
0 100 200 300 400 500 600 700 800
Temperature, ˚C
Figure 10-31 The sharp drop in hardness identifies the recrystallization tem-
perature as ∼ 290◦ C for the alloy C26000, “cartridge brass.” (From Met-
als Handbook, 9th Ed., Vol. 4, American Society for Metals, Metals Park,
Ohio, 1981.)
 2000

1 15000
2
Melting temp.

Recrystallization temperature, ˚C
Recrystallization temperature, K

W
Ta 1000
Mo
1000
Be
Ni Ti
500
Fe Pt
1
As 3
Melting temp.
Al
Mg Au Cu
Cd Zu
Sn 0
Pb

0
0 2000 4000
Melting temperature, K
Figure 10-32 Recrystallization temperature versus melting points for various
metals. This plot is a graphic demonstration of the rule of thumb that atomic
mobility is sufficient to affect mechanical properties above approximately 13
to 12 Tm on an absolute temperature scale. (From L. H. Van Vlack, Elements
of Materials Science and Engineering, 3rd Ed., Addison-Wesley Publishing
Co., Inc., Reading, Mass, 1975.)
 60% cold work

200
40% cold work
Hardness, BHN

20% cold work

100

65 Cu–35 Zn

0
0 100 200 300 400
Temperature, ˚C
Figure 10-33 For this cold-worked brass alloy, the recrystallization temperature drops
slightly with increasing degrees of cold work. (From L. H. Van Vlack, Elements
of Materials Science and Engineering, 4th Ed., Addison-Wesley Publishing Co.,
Inc., Reading, Mass. 1980.)
 600 60

Tensile strength
50
Tensile strength (MPa)

500

Ductility (%EL)
40

400 30

Ductility
20

300
Recovery Recrystallization Grain growth

Cold worked
and recovered
grains

0.040 New
Gain size (mm)

grains
0.030

0.020

0.010

100 200 300 400 500 600 700

Annealing temperature (˚C)
Figure 10-34 Schematic illustration of the effect of annealing temperature on the
strength and ductility of a brass alloy shows that most of the softening of the
alloy occurs during the recrystallization stage. (After G. Sachs and K. R. Van
Horn, Practical Metallurgy: Applied Physical Metallurgy and the Industrial
Processing of Ferrous and Nonferrous Metals and Alloys, American Society
for Metals, Cleveland, Ohio, 1940.)
 0.5 2.00

0.4 2.50
Rate, hr–1

0.3 3.33

Time, hr
0.2 5.00

0.1 10.0
20.0
0 ∞
–60 –40 –20 0 20
Temperature, ˚C
Figure 10-35 Rate of crystallization of rubber as a function of temperature. (From L.
A. Wood, in H. Mark and G. S. Whitby, Eds., Advances in Colloid Science, Vol. 2,
Wiley Interscience, New York, 1946, pp. 57–95.)
Figure 10-36 TTT diagram for (a) the 100
fractional crystallization (10−4 vol
%) of a simple glass of composition
Na 2 O · 2SiO 2 and (b) the fractional

Undercooling (K)
200
crystallization (10 −1 vol%) of a glass
of composition CaO · Al 2 O 3 · 2SiO 2 .
[Part (a) from G. S. Meiling and D.
R. Uhlmann, Phys. Chem. Glasses 300
8, 62 (1967) and part (b) from H.
Yinnon and D. R. Uhlmann, in Glass:
Science and Technology, Vol. 1, D.
400
R. Uhlmann and N. J. Kreidl, Eds., 1 10 102 103 104 105 106 107 108
Academic Press, New York, 1983, Time (sec)
pp. 1–47.] (a)
1550 Tmelt

1450

1350
Temperature (˚C)

1250

1150

1050

950

850
102 103 104 105
Time (sec)
(b)
T
Glass formation

Crystallization
Melting

Forming

Growth

Nucleation

t
Figure 10-37 Typical thermal history for producing a glass ceramic by the controlled nu-
cleation and growth of crystalline grains.
Figure 10-38 Transmission electron micrograph of monoclinic zirconia
showing a microstructure characteristic of a martensitic transforma-
tion. Included in the evidence are twins labeled T. See Figure 4–15
for an atomic-scale schematic of a twin boundary and Figure 10–13
for the microstructure of martensitic steel. (Courtesy of Arthur H.
Heuer)
Figure 10-39 An illustration of the sintering mech-
anism for shrinkage of a powder compact is
the diffusion of atoms away from the grain
boundary to the pore, thereby “filling in” the
pore. Each grain in the microstructure was
originally a separate powder particle in the
initial compact.
Figure 10-40 Grain growth hinders the densifi-
cation of a powder compact. The diffusion
path from grain boundary to pore (now iso-
lated within a large grain) is prohibitively long.