440 Diffmionless transformations

i
are two different but equivalent ways of producing the lattice invariant
shear. Show exactly what is meant by this. What is the experimental
proof of both types of shear? Solutions to Exercises
6 .
6 Draw a diagram to illustrate Bain's homogeneous deformation model
for the fee -> bec diffusionless transformation. Assuming a7 = 3 56 A .

Compiled by John C .
Ion
and flu = 2.86 A, and that cia for martensite is 1.15 calculate the
maximum movement experienced by atoms during the transformation.
i
Assume that cia = 1.1.
6 7 .
What are the essential differences in martensite nucleation models based
(a) on changes at the core of a dislocation; (b) on dislocation strain field
interaction? Discuss the advantages and disadvantages of both models in
terms of the known characteristics of martensitic transformations.
6 .
8 Give possible reasons why the habit plane of martensite changes as a
function of alloying content in steels and Fe-Ni alloys. What factors
Chapter 1
influence the retention of austenite in these alloys?
6 .
9 What is the role of austenitic grain size in martensitic transformations? 1 1
. Cp = 22 64 + 6.28 x HrTJ moP'K
.

Is austenitic grain size important to the strength of martensite? What

fT-C
other factors are important to strength and roughness in technological Entropy increase AS = , - dT
hardened steels?
6 10 Suggest possible alloying and heat treatment procedures needed to
.

design the following steels: (a) a quenched and tempered steel; (b) a
AC _
300-13SS -
f358 22.64 +:-
6.28 x lO T dT
- MOO /
dual phase steel; (c) a maraging steel; id) a TRIP steel.
6 .
11 How would you characterize the unique properties of alloys which can * H,L22 641n r+ 6 28 x HrT]
.
.

be utilized as 'memory metals'. How would you design a TiNi alloy for 40.83 J mol-'K'1
use as. e.g., a self-locking rivet? Give instructions on how it is to be
used. 12
.

iquid Fe

1600

5-Fe

9 y-Fe

i 800

l
!
o
-
500-
a-Fe -Fe
300-

0 50 100 150

Pressure kbar ,
442 Solutions to exercises Solutions to exercises 443
i

Liquid Fe
1 .
4 Phases stable at low temperatures must have low enthalpies because
a-Fe the (-TS) term in the expression for G becomes negligible Phases .
. i 1

y-Fe stable at high temperatures, on the other hand have higher entropies
,

y-Fe
to compensate for higher enthalpies.

15 .

J
At 1600oC At 800oC
-
t -

24 22

2 3

LL <U
Pressure

kbar

a-Fe
At 5000C

y-Fe At 300oC a-Fe

s-Fe
E-Fe

4
5 5

110 120
Six distinguishable configurations.
Schematic free energy-pressure curves for pure Fe.

Theoretical number of distinguishable ways of arranging two black

balls and two white balls in a square is
1 . 3 From Equation 1.14
(/VB + yVw)! (2 + 2)!
/dP\ AH 6
2! 2!
TAV
cq

Assuming AH and AV are independent of T and P f the range of 1 .

6 Dividing both sides of Equation 1.30 by the number of moles of

interest, the equation may be rewritten as solution (nA + nB) gives
AP\ AH
dC7 A dB
TAV Ha + Mb
{nA + nB) ("a + nB) {nA + nB)
1
where: AH = HL - Hss = 13050 J mol
-

; !
The left-hand side of this equation is the free energy change per mole
AK = VL - Ks = (8.0 - 7.6) x 10-6rm , :

i
.
of solution and ean therefore be written dC.
T = (1085 + 273) K. dn A dn B
and
Thus if AP is 10 kbar, i.e. 109 Nm-2, the change in the equilibrium (A + b) (A + B)
melting temperature is given by the above equation as
are the changes in the mole fractions of A and B, dXx and dXB.
AT = 42 K The above equation can therefore be written as
444 ' Solutions to exercises Solutions to exercises 445

17 Equation 1.31: G = AXA + Ub b

dG = M a + b b .

dG
Equation 1.39: G - AAGA + A'bGb + QXAXB + /?r(A'Aln,VA
Thus - = nA -
'

f A pln e)
dXB
(1.6.1)
= AaGa -

f XBGB + Q(X\XB + AiYA)

= -nA + \iB
-

RT(XA\nXA -f A'BInA'B)
But using Equation 1.31 = XA[GA + fIA + /?rin,YA] + b[Gb
x G = \XaXa + I b b -

r QA
'

x -r RT\nXB]
Comparison with Equation 1.31 and using AA + XB - 1 gives
gives = XB
[iA = GA + Q(l - AA): + rin.Y .
x

dG G - Ha a B = GB + Q(.l - AB)2 + RT\nXH

giving
B
18
.
(a) Atomic weight of Au = 197
dG Atomic weight of Ag = 108
or uA = G - xYB
dA- B
1
No. of moles ot Au = - = 0 076 .

197
From the figure nA = PR - X* = PQ - OS
25
No. of moles of Au = - = 0 23! .

i .
e . point S, the extrapolation of the tangent to point R on the 108

G-curve represents the quantity |iA. no. of moles of solution = 0 307 .

Equation 1.6.1 gives

0 07b
.

dG (b) Mole fraction of Au = 0 248 .

+ 0 307
Hb Ha .

dXB
0 231
.

Uv Mole fraction of Ag = 0 752 .

0 307
i e . .
= OS +- - .

(c) Molar entropy of mixing. ASmix = -/ (A'AInAA -f ABlnArB}

But ITS = OT = 1
A5mix - -8.314(0.248-in 0.248 + 0.752 . In 0.752)
'

Thus jiB = OS + UV = TV
i .
e . point V represents the quantity b- = 4 66 J K
.
mol "1

(d) Total entropy of mixing = Molar entropy of mixing

x no .
of moles of solution
= 4 66 x 0.307
.

= 1 -
43 J K"'
V
CD

0) R (e) Molar free energy change at 500oC = AGmix

0) -
RT{XA\nXA + XB In ArB)
LL
rA5mix = -773 x 4.66 = -3.60 kJ mol"1
-

s
AG mix -

s u
(0 au = GAu + rin Au
I p T
= 0 + (8 314-773-In 0.248)
.

O
B -8 96 kJ mol
.

A X
446 Solutions to exercises Solutions to exercises 447

HAg = Gas + RT\nXAg

= 0 + (8 314-773-In 0.752)
.

= -1 .
83 kJ mor1 m
k
. n
f
e 9 h
(g) For a very small addition of Au S
0)
T2- a

dG' = HAu"dAu( P, nB constant) E a

0 T -

f b c
-
,
d o
.
At 500oC, Au = -8.96 kJ mor1.
Avogadro's Number = 6.023 x 1023 Fe3C
Graphite
1 eV = 1.6 x HT19 J

8
.
96 x 103 i
-8.% kJ mol"1 = Fe Fe3C Graphite
-

6 x lO-9 x 6.023 x 10" eV at0m

-

. .

1. %C

= -0 1 eV atom"1
. G-compositionand T-composition diagrams for the Fe-Fe3C
and Fe-C systems (not to scale).
Adding one atom of Au changes the free energy of solution
by -0.1 eV.

19
.

1
.
10 dC" = -nX dnA
Fe3C 8 dG = +\& dnA
At equilibrium dG" + dGp = 0
Graphite ie a + \i% dnA = 0
ncA
-

. .

1 = 1,
c
i e \i% =
19
- .

a b
d Similarly for B, C, etc.

1 11
.
Equilibrium vacancy concentration
AGV
f XI = exp -
RT
S? h
0)
c
CD
9 A5V AH,
0)
T = T2 = exp- -exp
03
e f
ul

1 eV = 1.6 x 10~i9 J
.
R = 8.63 x HT5 eV atom"1 K-1
-

.
'

.
Xt (933 K) = exp (2) - exp
/ \
n \8.63 x lO-5 x 933/
= 3 .
58 x HT4
m
T-T3
Q 8
k

(298 K) exp(2)-exp( 63 x : 5 298)

-

8 0 x

13
2 28 x 10
-

.
448 Solutions to exercises Solutions to exercises 449

2
L 12
.
Assume XSi
A 7V(Bi---
i
InXsi = In A - - !
S
.
rE !

At 550oC (823 K): In 1.25 = \nA - 2/(8.314 x 823)

A B
At 450oC (723 K): ln0.46 = \nA - (2/(8.314 x 723) -
Free energy of pure A Free energy of pure B
I
1
w hich can be solved to give
Q = 49.45 kJ moP1
A = 1721

Thus at 200oC (473 K)

/ 49450 \
Xsi = 1721 -exp -
\8.314 x 473/ T
Gk
= 0 006 atomic %
. G

According to the phase diagram, the solubility should be slightly

under 0.01 atomic %. Reliable data is not available at such low
temperatures due to the long times required to reach equilibrium. (d)
E
A B

1.
13 A sketch of the relevant phase diagram and free energy curves is
(a) Schematic phase diagram;
helpful in solving this problem. See p 449.
.

(b) G-Tcurves for pure A;

(c) G-Tcurves for pure B; "

ACA and ACb are as defined in (b) and (c). fd) Free energy curves for the A-B system at 7 F .

Since A and B are mutually immiscible, the tangent to the liquid

curve GL at = X will intercept the curves for the A and B phases
as shown, i.e. = GSA jib = G%.
,

Thus AGA ASm(A)-{Tm(A) - rE)

The liquid is assumed ideal, therefore from Fig. 1.12
AGB ASm(B)-(Tm(B) - 7E)
AGA -RTE\nX%
Finally therefore:
and
-

RTBlnX% = ASm(A)-(Tm(A) - TE)

E
AGb = ~RTE\nX% -

RTE\nX% = ASm(B)-(Tm(B) - TE)

But AGA and AGb can also be found from the relationships shown in or
Figs (b) and (c).
-

8 .314 rElnA = 8.4 (1500 - rE)

If Cp = Cp, Equation 1.17 gives -
8 314 TEH(1 - Xl) = 8.4 (1300 - TE)
.

AG = ~Ar
Solving these quations numerically gives
m
X% = 0.44
or Xl = 0.56
AG = ASm-AT TE = 826 K
 450 Solutions to exercises Solutions to exercises 451

1
.
14 If solid exists as a sphere of radius r within a liquid, then its free Let the mole fractions of a, (3 and y in the final microstructure be X <

energy is increased by an amount X$ and Xy respectively.

V

2lVm
.

s Balance on A: 0.4 = 0.8 Xa + 0.1 Xp + 0.1 Xy

(from Equation 1.58)
r Balance on B: 0.2 = 0.05 Xa + 0.7 Jfp + 0.2 Xy
Balance on C: 0.4 = 0.15 Xa + 0.2 + 0.7 JfY
where G] is the molar free energy of the sphere and GL is the molar
Solving these equations gives: Xa = 0.43; Xp - 0.13; 0 44
free energy in the absence of interfaces. 7
.

Growth of the sphere must lead to a reduction of the total free

i energy of the system, i.e. growth can occur when 1
.
16 From Equations 1.41 and 1.43 we have
GJ < GL
liA = Ga + RTlnyAXA
2yVm
i
. e .
G - Gl > where GA is the free energy of pure A at temperature T and pressure
r
P .

See figure below. Suppose GA is known for a given temperature and pressure T0 and
/\)
i e
. .
GA(r0, Po) = Ga
Growth occurs spontaneously with
a decrease in free energy From Equation 1.9 for 1 mole of A
dGA = -5Adr + VmdP
0)

0} Thus if SA and Vw are independent of T and P, changing temperature

G S from To to 7 and pressure from Pq to P will cause a total change in
CO GA of
O
2
mm AGA = -5A(r-r0) +vm(P-Po)
Gs
AT G
L
Ga = + AG
r = gSL + 5A(r0 -

r) + vm(p - p0)
and

Substituting Equation 1.17 for GL - Gi gives = GSL + 5A(To -

T) + Vm(P - Po) + RT\nyAXA

LAT 2yVm
The accuracy of this equation decreases as (T - Tq) and (P - P0)
increase.
T
1 m r

Ar> 27Vmrg
i .
e .

Substituting the numerical values given

AT(r = 1 im) > 0.2 K
AT{r = 1 nm) > 200 K
1 .
15 Composition = 40% A 20% By 40% C; ,

a = 80% A, 5% B 15% C;
,

p = 10% 70% B, 20% C;

Y = 10% A, 20% B, 70% C.
 i

452 Solutions to exercises Solutions to exercises 453

Chapter 2 Similarly, if C = C; at x = /, the thickness of the sheet gives

,

2 1
. (a) -

Jl = flC; + - C] - aC\ C]
Carburizing Sheet Decarburizing
n
gas

14 .
gas
i e
.
.
7 - |(C, - C:) + J (Ci - C \lL
The constants and b can be determined from
-

0 15 .
D] = a + bC\
D-
. = a + hC
Carbon concentration

from which a = D
l WTj
~

2
D, - >:
and 5 = - -
Thickness Li - (-2

Substitution of these expressions into the equation for / gives

(b) Under steady-state conditions, lux of carbon atoms into one side after simplification
f

= flux out of the other side = J .

D- + D,\Ci - C.
Z)cdC
/= -
i
Substituting: D, = 7.7 x 10 " irr s
[dCl fdC D2 = 2.5 x 10"" mV

I 1). 15 14
.

Ci = - x 60 kg m-"
08
.

0 32
jcUj, / IcLcLu 0,4
_

7.7 x 10-"
.

0 15
.

0 8
x 60 kg m
(c) Assume that the diffusion coefficient varies linearly with carbon
.

.
..
.

concentration 2 x Kr-1 m
y = 2.4 x 10~6 kg m-J2 ..-I
s
-

/> = a + gives

where a and b are constants that can be determined from the data
22
given. Pick's first law then gives .
.

1 2

/ = -(a + bC) -
dx

or J Jdx = -/ (a + bC) dC
bC2
i e
. . -Jx = aC + -

- + d
j
where d is an integration constant. If we define C = C, at x = 0

d = -ac, -1 q Consider two adjacent (111) planes in an f.c.c. crystal. A vacancy in

plane 1 can jump to one of three sites in plane 2. For the sake of
S9
 notations to exercises Solutions to exercises 455

generality, let this number of jumps be designated P ( = 3). In all there 2 3 The activity along the bar is described by the following equation
.

are 12 possible sites (nearest neighbours).

If nx and are the numbers of vacancies m 2 in planes 1 and 2 A ( x2 \
p(___j
~

actIvlty = __.ex

respectively, the number of jumps from 1 to 2 will be given by

P where An = initial activity;
7V = - Tvnx
"

m -

s
D = diffusion constant;
t = time;
where Vv is the jump frequency of the vacancies.
1 x = distance along the bar.
Lilcewise
Thus by plotting In (activity) vs jr a straight line of slope -(4D/)~ 1
.

is produced enabling D to be found since / is known.

,

x ]xm 10 20 30 40 50
Therefore following the same arguments as in Section 2.2.1 (p. 6) x 2 [im2 100 400 900 1600 2500
gives activity 83.8 66.4 42.0 23.6 8.74
In (activity) 4.43 4.20 3.74 3.16 2.17

where d is the perpendicular separation of the adjacent planes, i.e. we

can write

4 -

In f.c.c. metals the jump distance a is given by

a
a
'

v
2

where a is the lattice parameter.

For (111) planes

Putting P - 3 gives
2
1
0 1000 2000 x2
z
Z)v = 76 a2rv \im

For (100) planes, adjacent planes are in fact (200) From the graph: slope = -8 66 x 10~4 jiirr2.
.

a a
.
\ , " Hence: -777- -
8 66 x 10"4
.

2 v2
I
Since t = 24 h .

.
-

.
Dy = 76 a2rv D = 3.34 x 10-15 n s'1
\
!i
456 Solutions to exercises Solutions to exercises 457

The first two terms of the series are

24
. C = C + po sin
(t exp "

4Cor . kx 1 . 37rxl
C(x) = - nT + -slnTJ
v

For this equation to be a solution of Pick's second law, the following

condition must be met
Plotting this sum for the range 0 < v < / gives the curve plotted .

5C 52C opposite
57
"

Db &- (b) If the surface concentration is effectively zero, the solution to the
diffusion equation becomes
/tcxX 1 r
4C V 1
(2/ + 1) TLCj
-

C(x, t)
71 1=0 2/ + 1

= eXP " x7 C0S iyj [-(2/ + l)VDr]

52C r. ..
ir .
/7u:\
. exp
[ /= J
=-p(1exp -.-

The amplitude of the first term (A ) is obtained by putting jc = 1/2

and / = 0. i.e.
6C 52C r-
x
bt SX2 TT A
4C(, \-K2Dt]
i

But T
2D B
(Equation 2.21) The amplitude of the second term (Az) is obtained by putting x
k
1/6 and / = 1, i.e.
6C 52C
4Co r-97r:D/]
Of
~

Db 5x2 2

2 .
5 (a) If A2 < 0.05 Ax
(2/ + 1) 7U-
C(a-) sin 4Co \-9n2Dt] 4Ct) r-7t2D/l
7i 2/ + r / < 0.05 . --exp \ -p
3 exp rrn
'

K J
where / = thickness of sheet,

d = initial concentration. which gives / > 0.0240

D

(c) Assume that the time taken to remove 95% of all the hydrogen is
so long that only the first term of the Fourier series is significant .

Co The hydrogen concentration at this stage will then be given by

I
C{x, 0 = --sin y exp 1 /2
i.
e.
as shown in the figure on page 458.
CM
At the required time (tx) the shaded area in the figure will be 5% .
of the area under the concentration line at / = 0 i.e. ,

C(xi, /,) dr = 0.05 C,,/

0
0 31 4C0 /-7r2Df,\ (' tvc
4
X
2 4 - -expl-sin y dx = 0.05 CJ
458 Solutions to exercises Solutions to exercises 459

2 extrapolation of the tangents to the free energy curves at 1 and 2 to the

which gives = 0.282 - corresponding sides of the free energy diagram, as shown above.
All atoms diffuse so as to reduce their chemical potential.
t=0
Therefore, A atoms will have a tendency to diffuse from a to P (\iaA >
Co- \x%) and B atoms will have a tendency to diffuse from P to a >

The resultant composition changes are indicated in the diagram.

T
c
Diffusion stops, and equilibrium is reached, when |iA = nil and \i% =
ji . That this process results in a reduction in the total free energy of
the diffusion couple can be seen from the diagram below. The initial
free energy Gj can be reduced to G? by a change in the compositions
rr7777777777TT A of the a and P phases to and A , the equilibrium compositions
0 (provided < XBu]k < X%).
x

Note that this time is an order of magnitude larger than the time
derived in part (b). Consequently it is clearly justified to ignore all
terms of the Fourier series but the first.
/-13400\ P
From Table 2.1. D = 0.1 exp
RT CD
a

c Gi
2-1 Zl1\
i.
e
. D (20oC) = 4.08 x lO-4 mnrs ,

CD
Z
7
.

f
Thus for / = 10 mm: f, = 19.2 h, G2
f

for / = 100 mm: f, = 1920 h (80 days).

26
.

Mofar
free energy A X XBulk xz B
P

1
2
Ha
2
. 7 Substituting into Darken's Equations (2.47) and (2.51)
Zn
/ 5x
(equilibrium)
a
(equilibrium) Da = XC ll
DaZn + XZnD Cxi
we obtain
1
026 x lO"6 = (D n - Dacu) x 0.089 mm s
"

Ha 0.

A X B
4 .
5 x 10~7 0 .
+ 0.22
78 Dfin " a mnr2 s
.

From which
"1
DaZn 5 1 x 10
-
7
mm 2 s
At the initial compositions 1 and 2 of a and P respectively the
.

1
Dr 2 2 x UT7 mm 2 s
chemical potentials of A and B atoms in each phase can be found by Cu .
460 Solutions to exercises Solutions to exercises 461

The expected variation of Dzn, Dcu and Da are shown schematically 1 1

below

'
D
D2n
0
A a b c d B
XB

%Zn a

Cu
Solubility limit for a t

LJ

Since Zn has a lower melting point than Cu it diffuses faster of the

.

two, and since increasing the zinc content reduces the liquidus tem-
perature, all diffusivities can be expected to increase with increasing 0
Zn concentration.

28
.

JC

-
GB
P
U

Hb(2)

Ml)
a+(3 P+7 He

i M2)

Ml

A b c B
462 Solutions to exercises Solutions to exercises 463

(i)

t a

U
C
s
B
GO f = 3C
b
p P L
2

r
a t b A Bulk
05
.
o9
.
B

Bulk composition
B

The total distance the interface moves 5, can be calculated in terms of

,
(ii)
the total couple thickness, L, by writing down an equation describing
the conservation of B, i.e.

3
2
.

a
0.

9 |y + sj + ()[~ - s] - 0.5L
.
'

= 5.6 x lO-2
a

Chapter 3
29 3
.

.
1 Considering only nearest neighbours, if a surface atom has B 'broken*
bonds, it will have an excess energy of B. e/2, where is the bond
a
energy.
For f.c.c. crystals, each atom has twelve nearest neighbours in the
f = 0 bulk, so that 8 = Ls/6/Va, where Ls is the molar latent heat of sub-
P
limation and NLl Avogadro's number (no. of atoms per mole).
The surface energy per surface atom is therefore given by
B Ls
A XB B
7SV = -.- per surface atom
/Va
.

If each surface atom is associated with a surface area A, the surface

energy is
! a

o 1 >0
B
per unit area
iV 12A Na
Q
A can be calculated in terms of the lattice parameter a\

09 .
 464 Solutions to exercises Solutions to exercises 465
8
*
Each surface atom is connected to two nearest neighbours in the and sv (cos 9 - sin 9) , 9 < 0
27
{220} plane. Therefore it must be connected to ten others out of the
plane. Since the atoms are symmetrically disposed about the {220}
which gives | -r] "
~

2?
\ d9 /o.o
{hki} {111} {200) {220S
*

At 9 = 0 there is a cusp in the sv - 9 curve with slopes

Ge
a 3 3 For a two-dimensional rectangular crystal with sides of lengths /j and
V2
a
60 .

A and surface energies ji and 72 respectively the total surface energy

,

is given by
* a a V3 aV2
A _

a
\2 \'2 2 2 2
G = 2(/17, + /:Y2)

B 3 4 *
The equilibrium shape is given when the differential of G equals
5
zero. i.e.

dG = 2(/ldy, + y /, + /2d72 + y.d/,) = 0

Ysv 0 33 rf 0 42
.

LA/aJ .

Assuming that 71 and 72 are independent of length gives

Vsv 0 -

58[ 0 67.

a2/V;
0 59
.

[ 2W ]
a a
7id/, + y2dl2 = 0
But since the area of the crystal A = IJ2 constant
dA = /2d/2 + hdli = 0
plane, there must be five bonds above the plane of the paper and five
below (giving a total of 12) .

Giving
+ It can be shown that in general for f c c .
. .
metals

h ii
4

For the simple cases above however. A can be calculated directly

,

from a sketch as shown ,

.
3
.
4 (a) By measuring, the misorientation 9 = 11.
(b) By constructing a Burger- :ircuit around a dislocation, the
Burgers vector is found to be 1.53 mm in the photograph (i e . .

32 Ew
one bubble diameter).
.

= (cos 0 + sin |0|) ~

For a low-angle grain boundary, the spacing of the dislocations

2a
is given by
i .
. e
sv (cos 9 + sin 9) ~ e>0 D == -
b
2fl-
sin 9

de
(-sin 9 + cos e)~ *
1.53
2a D
8 0 mm
.

sin 11

( de /o =o 2a2 which is very close to the mean dislocation spacing in the

boundary.
466 Solutions to exercises Solutions- to exercises 467

3. 5 Like all other natural processes, grain boundary migration always (b) For nucleus growth, reduction in free energy due to annihilation
results in a reduction in total free energy. of dislocations must be greater than or equal to the retarding
force due to grain boundary curvature.

Grain growth Equating this with the driving force across a curved boundary

27
i e 1.96 x l(f
During the process of grain growth all grains have approximately the
. .

same, low dislocation density, which remains unchanged during the

grain growth process. '
27
. . r
Grain "boundaries move towards their centres of curvature in this 1.
96 x 106
case, because atoms tend to migrate across the boundaries in the
opposite direction (from the high pressure side to the low pressure Thus the smallest diameter = 1.0 fim
side), in order to reduce their free energy, or chemical potential.
The process also results in a reduction of the total number of grains
by the growth of large grains at the expense of smaller ones. The net 3 .
7 From the phase diagrams, the limit of solid solubility of Fe in Al is
result is a reduction in the total grain boundary area and total grain 0 04 wt% Fe, whereas that of Mg in Al is 17.4 wt% Mg. If one
.

boundary energy. element is able to dissolve another only to a small degree, the extent
of grain boundary enrichment will be large. (See for example Fig.
3 28, p. 138.) Thus grain boundary enrichment of Fe in dilute Al-Fe
.

alloys would be expected to be greater than that of Mg in Al-Mg

Recrystailization
alloys.

In this case, grain boundary energy is insignificant in comparison with

the difference in dislocation energy density between recrystallized 3 8
.
See Fig. 3.35, p. 145.
grain and surrounding deformed matrix. The small increase in total If d(t < dp, then in general the dislocation spacing (D) will span n
grain boundary energy that accompanies growth of a recrystailization atom planes in the P phase and (n + 1) planes in the a phase, i.e.
nucleus is more than compensated for by the reduction in total dis-
location energy. D = nd$ = (n + 1) d,
The boundaries of recrystailization nuclei can therefore migrate
away from their centres of curvature. From the definition of 8 we have

3 .
6 (a) The pulling force acting on the boundary is equivalent to the free (-ve)
energy difference per unit volume of material.
2 dv = (l + S)da
If the dislocations have an energy of j- J m and the
Substitution into the first equation gives
dislocation density is 1016 m~2, then the free energy per unit
volume, G, is given by n(l + 5) da = (n + 1) d(x
1
i e n = -
,
x
10-x(0.28x Y . .

G,10 ,1%MJ|n.3 o
4

and D = -
5
Thus the pulling force per unit area of boundary is 1.96 MN m~2.
"

468 Solutions to exercises Solutions to exercises 469

39
.
2*2 1 26 - 1.43
.

Hence zone misfit x 100%

1 43.

2*1
-

11.89%.
71
When the misfit is less than 5% strain energy effects are less
,

72
important than interfacial energy effects and spherical zones minimize
the total free energy. However when the misfit is greater than 5%
, ,

72 the small increase in interfacial energy caused by choosing a disc

shape is more than compensated by the reduction in coherency strain
energy.
The edges of the plate exert a force on the periphery of the broad Thus the zones in Al-Fe alloys would be expected to be disc-
face equal to 72 . 4 . 2t2 shaped.
This force acts over an area equal to (2X2)2 3
i .
12 Assuming that the matrix is elastically isotropic, that both Al and
Y2 ' 4 ' 2 272 Mg atoms have equal elastic moduli, and taking a value of 1/3 for
AP =

(2v2)2 x2 Poisson's ratio, the total elastic strain energy ACS is given by:
AGS - 4 jiS2!/ |i = shear modulus of matrix;
5 = unconstrained misfit;
V = volume of an Al atom.
\ 2x1
1 60 - 1.43
.

5 0 119
.

1 43 .

2x 2 V = 4/3 * tt (1 43 x 10~!0)3 = 1.225 x lO"29 m3

.

\xAl = 25 GPa = 25 x lO9 Nm"2

i
AGS = 4 x 25 x 109 x (0.119)2 x 1.225 x 10~29 J atom
-

= 1 .
735 x HT20 J atom"1
In 1 mol there are 6.023 x lO23 atoms
The periphery of each edge is acted on by a force of magnitude
2 -72 '2xx + 2-7, - 2x2 1 .
735 x HT20 x 6.023 x 1023 -
1
AG s kJ mol
1000
The area of each edge is 2xx . 2x2 10.5 kJ m-r'
2y2-2xl + '2 2 Y2 , Yi
AF = h - 6 x 10~19 J, thus
_

1 eV 1 .

1 735 x lO"20
From the Wulff theorem (p. 115) for an equilibrium plate shape: 1
.
-

AGS eV atom
1 .
6 x 10~19

- = (see also Exercise 3 3) .

0 .
1 eV atom"1

It is also implicitly assumed that individual Mg atoms are separated

by large distances, so that each atom can be considered in isolation,
Xi X2 i dilute solutions.
e
. .

3 . 10 See Section 3.4.1 (p. 143). The use of Equation 3.39 is also based on the assumption that the
matrix surrounding a single atom is a continuum.
3 .
11 Atomic radius of Al = 1.43 A
Atomic radius of Fe = 1.26 A 3 13
.
See Section 3.4.4. (p. 160).
 Solutions to exercises 471
470 Solutions to exercises
3 16
3 14 When a Shockley partial dislocation passes through an crystal f
.
c c
. .
.

B B B B
.
B B
the atoms above the glide plane in positions A are shifted to B
C C C C
positions, B into C positions, etc. C C

A A A A Fee
i.
e .
A B A A A

/////////
B B B B - A- B
,
v '

A B C C - C c C -
A B C 1

A B C C B B B B B B
C X

A A A
B C A A A A A A
1
B B B Fee
A B C C C C C C

C C C C Twin
C
Plane B B B B B B
B B B B
B 1
A A A A A A
A A A A
A

C C C C
C
If a single atom in crystal I attempts to jump into a crystal II position
B B B
8 B a ring of dislocation and an unstable A upon A situation results.
A Shockley partial dislocation in every {111} slip plane creates a
glissile interface between two twinned crystals:
The above series of diagrams shows the twinning process.
3 15 .

A i A
A
B " i
~ -

t
t
h
'
C
-
T ,D
B
I
J.
C

I
i
E F C B
JL
i I
A A 11
J .

Let the interface CD move with a velocity v perpendicular to the B

i
C
r
interface.
C B
Consider unit area of interface perpendicular to ooth BC and CD. !

!
Mass flow perpendicular to BC = u x h. A
-
X .
A

Mass flow perpendicular to CD = v x /.

From the conservation of mass: u x h = v x /. Note, however, that as a result of the shape change produced by the
u x h
transformation large coherency stresses will be associated with the
v - interface (see Fig. 3.62a).
I
Similar coherency stresses will arise as a result of the f.c.c./h.c.p.
interface in Fig. 3.61. Strictly speaking. Fig. 3.60 is an incorrect
representation of the stacking sequence that results from the passage
of the partial dislocations. In layer 10, for example, there will not be
'

a sudden change across the extra half-plane of A to B or B to C, but

'
472 Solutions to exercises Solutions to exercises 473

rather a gradual change associated with long range strain fields in 3 20

.

both crystals. r2.

3
. 17 Solid/vapour interfaces and solid/liquid interfaces in non-metals are
faceted and therefore migrate by ledge mechanisms .

Solid/liquid interfaces in metals are diffuse and migration occurs by

random atom jumps.
3 .
18 See-Section 3.3.4 p. 130.
,

3 19.

X X,p

Suppose the alloy had reached equilibrium at a temperature T[ and

consists of long plate-like precipitates. The bulk alloy composition is
Xih the equilibrium concentrations at 7, and 7 are Xx and
respectively, where 7% is the temperature to which the alloy is heated.

A X B

(i) Diffusion control (ii) Interface control

From equations 1.41 and 1 43 we can write
.

'
hb = GB + RT In Yi*t i
/ = 0

Hfc = Gb + RT\nycXc a a

r.

Aii = - (is = RTlnycXc X2-

Xo-
\ L
For ideal solutions: y; = y = 1 c

For dilute solutions (X 1): y, = yc = constant (Henry's Law)

} Distance
such that in both cases f = f1
X2

Aji'b = RT In Xc
X

This can also be written

A k = RTln X o
f = t3 > '2

If the supersaturation is small ,

i.e.

(X,- - Xe) Xe, then

= RT
X0
474 Solutions to exercises Solutions to exercises 475

(iii) Mixed control: similar to diffusion control except the interface Substituting Q - 1.6 x 10~29 m3
and y - 0.177 Jm : gives
~

concentration in the a-matrix will be less than A , the equi-

librium concentration at T2- '

AGr - (5.435 x l(r20)nl 3

For 1 mm3, n{i - 6.25 x 1019 atoms
Therefore when n = 10 atoms, nr - 9 x 1013 clusters mm 3:
"

Chapter 4 c

and when nQ = 60 atoms nx - 3 clusters mm-3; ,

4 1 * -47ir3 when n = 100 atoms nr = 4 x 10"8 clusters mm 3:

"

AGV + 47cr2YsL
.

c ,

3 or. alternatively. 1 cluster in 2.5 x 107 mm3 (251) .

Differentiating this equation with respect to r. 4 3

.
As the undercooling (AT) is increased there is an increasing con- ,

tribution from AG in the equation

dAGr V

47i/-::*AGv + 87rr/SL 4
dr
AGr = --7cr3AG + 47rr2YS[ v

At the critical radius, / *, this expression is equal to zero

whereas the interfacial energy is independent of AT Consequently
"

0 = -4Trr *2
'AG v + 8nr*ySL .

for a given r. AG decreases with increasing AT, and the 'maximum'

r

r
*
=
2ysl cluster size increases somewhat.
AGy 4
.
4 From Equation 4 .
13

In order to calculate the critical value of AG, AG* at this radius,

the value of r* is substituted into the original equation oCoeXp{ ILlkT
where 7 = 7m- bJ

From which the following values are obtained:

167rysL
=
AT K iVh om m"3 s""1 iVhom cm-3 s-1
3(AGV)2
180 07 7 x lO"7
4 2 From Equation 4.10. at the equilibrium melting temperature Tm
.

200 8 x 106 8
220 1 x 1012 1 x 10A

At the equilibrium melting temperature AGV = 0. so that Equation Note the large change in N over the small temperature range (see
4 4 becomes
.
Fig. 4.6).
AGr(r= Tm) = 4Ttr2ySL 4 5
.
AG* = i-F*-AG v

For a cluster containing nQ atoms with an atomic volume Q we have For homogeneous nucleation it has been shown (see 4.1) that
,

47173 2TSL
ncQ. *
_

3 AGV
Therefore the expression for AGr becomes Thus for a spherical nucleus
'

3QAic\2/3-r 4n7-*3 327tysL

V
3(AGV)3
 476 Solutions to exercises Solutions to exercises All

1 16Try3SL Heterogeneous nucleus

AG* - -- -AGv 2
3AG;
77777 L
This is identical to that derived in 4.1, and so the equation holds for /

homogeneous nucleation. s

For heterogeneous nucleation, it can be shown that

r Size of
> = 2ysL homogeneous
AGV nucleus
at same AT
The volume of a spherical cap on a flat mould surface is given by \ (same r')

,(2 + cose)(l - cos9)2 \

V nr
3

Thus

/2ysl\3 (2 + cos6)(l - cos e):

v* =

\AGv/ 3 The wetting angle between nucleus and mould wall (8) is fixed by the
' balance of surface tension forces (Equation 4.14). The activation
where 0 is the wetting angle.
energy barrier (AGhet) depends on the shape of the nucleus as deter-
Substituting into the given equation mined by the angles a and 0.
From Equation 4.23, for a given undercooling (AT), AGV and r*
4 yIl
.

i
AG* = - V*-AGV = -k- -(2 + cose)(l - cose)
7
are constant, such that the following equalities apply
2 j AGy
AGh,
he! het
S
Writing the normal free energy equation for heterogeneous nuclea- AGh*
horn hom
tion in terms of the wetting angle 0 and the cap radius r
AGh*et Volume of the heterogeneous nucleus
(2 + cos0)(l - cos0)2 i S

AGhet = j- AGv + 4nr2YSLj

_

e ~

AGh*hum
. .

Volume of a sphere with the same nucleus/

4
liquid interfacial radius
But from Equations 4.19 and 4.17 we have It can be seen that the shape factor {S) will decrease as a decreases ,

167ty|L (2 + cos0)(l - cos0)2 and on cooling below Tm the critical value of AG will be reached at
AG =W 4 progressively lower values of AT, i.e. nucleation becomes easier.
When a =S 90 - 0, S = 0 and there is no nucleation energy barrier.
which is identical to that obtained using AG* = tV *AG v (It can be seen that a = 90 - 0 gives a planar solid/liquid interface,
46 i e r = x even for a negligibly small nucleus volume.)
. See Section 4.1.3. . .

t
Once nucleation has occurred, the nucleus can grow until it reaches
4 7 Consider a cone-shaped crevice with semiangle a as shown below:
.

the edge of the conical crevice. However, further growth into the
liquid requires the solid/liquid interface radius to pass through a
minimum of R (the maximum radius of the cone). This requires an
>
'

-
undercooling given by
<

2ysl LbT
h R m

2YsiTm
i .
e
.
Ar
RL
I
i
478 Solutions to exercises Solutions to exercises 479

4 . 8 For conical crevices with a < 90 - 0 the solid/liquid interface can 1 m

2

V
maintain a negative radius of curvature which stabilizes the solid V

above the equilibrium melting temperature (rm): 6 L

1 m S
(1 - 6) S

7777, 77777
Thus

G(II) = Cs(l - 8) + CL8 4- ySL + yLV (8 > 0)

S
G(II) - Gs + 5(GL - Gs) + YSL + 7Lv (8 > 0)
LAT
At an undercooling AT below 7m, GL - Gs = --
*
m

LAT
i e
. . G(U) - Gs + --5 + 7sl + 7lv
/ rm

As the temperature is raised above rm the solid will melt back into
LAT
the crevice to maintain equilibrium with a radius given by or G(II) = G(I) - Ay + - --5
Tm
.

r
LAT where Ay = - 7SL - 7Lv

where { - AT) is now the superheat above r This is shown in the figure below:
m
.

4 .
9 If the situation described above is realized in practice it would explain
the observed phenomena. G(li
LA 7
4 .
10 (a) The values of the three interfacial energies are as follows: Gradient

el
Solid-liquid = 0.132 J m"2;
Liquid-vapour = 1.128 J m"2;
Ay
Solid-vapour = 1.400 J mT2.
Thus the sum of the solid-liquid and liquid-vapour interfacial
free energies is less than the solid-vapour free energy and there
,

is no increase of free energy in the early stages of melting .

Therefore, it would be expected that a thin layer of liquid should

form on the surface below the melting point because the dif-
,

0 6 max b
do
ference in free energies could be used to convert solid into liquid .

(b) Imagine the system I below. The free energy of this system is
given by: Note that as 5 -> 0. G(II) G(I), which means that in practice ySL +
G(I) = Gs + y sv
Ylv ~> Ysv a result of an interaction between the SiL and LIV
interfaces as they approach to within atomic dimensions of each
System II contains a liquid layer of thickness 5 and solid reduced other.
to a height (1 - 8). (The difference in molar volume between The optimum liquid layer thickness (5o) will be that giving a
liquid and solid has been ignored.) minimum free energy as shown. We cannot calculate this value
 480 Solutions to exercises Solutions to exercises 481

without a knowledge of the above interaction. However, it is reason- / -Ke" \

able to assume that the minimum will occur at a separation of a
few atom diameters, provided 5max in the above diagram is at least a
few atom diameters. 5max is defined by G(I) = G(II) But. AG 3c AT,, the undercooling at the interface, so for small
undercoolings we have
1 i .
e
. G(I) G(I) - Ay + 7m
,
-5 max

1
oc exp nuclei m 2 s
Ayrm
5 max
LAT
where k is approximately constant.
Each time a cap is nucleated, it should grow rapidly across the
Alternatively, AT
L5 max interface to advance a distance h. It seems reasonable to suppose
If Smax = 10 nm (say), then AT = 16 K. therefore that the growth rate will be proportional to N, i.e.
It seems therefore that surface melting is theoretically possible a few
degrees below 7m. v x exp
AT;
4.
11 (a) Repeated surface nucleation (see Section 4.2.2, p. 198).
I -

(b) Very roughly. Equation 4.28 can be seen to be reasonable as

follows:

i; r
Firstly, it is reasonable to suppose that the distance between
\ successive turns of the spiral (L) will be linearly related to the
*
minimum radius at the centre (r ) Thus we have
ii r h L .

t S
L r* * AT~]

Secondly, for small undercoolings, the lateral velocity of the

steps (w) should be proportional to the driving force, which in
turn is proportional to AT,
Suppose the edge of the cap nucleus is associated with an energy u ATj
e (J m 1) Formation of such a cap will cause a free energy
-

change given by Thus the velocity normal to the interface v is given by

uh
AG = -Kr2hAGv + lure v = -
i

ATf

The critical cap radius r* is given by = 0 where

r

is the step height.

dr
.

e
i
.
e .
r* = 4 .
12 Equilibrium solidification (see Figs, 4.19 and 4.20)
MGV
and From Fig. 4.19 the lever rule gives the mole fraction solid (/s) at T2
as
2
ne
AG*
hAG V XL - Xn (Xs/k) - X0
s
XL - Xs (Xs/k) - Xs
The rate at which caps nucleate on the surface should be
kX0
proportional to exp I-I s
1 - (1 - *)/s
482 Solutions to exercises Solutions to exercises 483

This expression relates the composition of the solid forming at the No diffusion in solid perfect mixing in liquid (see Fig. 4.21).
,

interface at T2 to the fraction already solidified. For the case shown in

Fig. 4.1, it will be roughly as shown below: Again, we have
2 ~~ T$ _
Xjy -
7\ - 7"} X; - k-X .

is now given by Equation 4.33 such that

Xo -
t
k-
.
t2-t3 i-k(i-fsy
_

Tx-Ts (l-k)

where Tx > T2 > TE. For the phase diagram in Fig 4.21a. the .

0 4 following variation is therefore obtained (k - 0.47. the exact form of

the curve depends on k, of course)

The temperature of the interface (7%) as a function of the fraction

solidified can be obtained using the following relationship which is
apparent from Fig. 4.19 To

T2 - T3 X{) - Xs T3-
r, - t3 xi} - kXo
Substituting for Xs gives

0 1

This will be a curved line roughly as shown below for the case
described for Fig. 4.19 (* - 0.47).
No diffusion in solid, no stirring in liquid (see Fig. 4.22)

t
Q)
T2 Initial transient
<5
Q .
T3-
E Final transient
52
Steady state
CD

CD

CD

T3
0 1
0 1 fs

i
484 Solutions to exercises Solutions to exercises 485

4. 13 No diffusion in solid, complete mixing in liquid Diagram (a), above is a typical phase diagram for k > 1. (In this
,

case, A- = 3.) The variation of composition along the bar can be

calculated using Equation 4.33

a)
i e
. .
Xs = kX(>(l -/s) <*-i)
L
ri The result for k = 3 is shown in diagram (b) /s is proportional to .

distance along the bar. Note that the final composition to solidify is
pure solvent (Xs = 0).

No diffusion in solid no stirring in liquid.

,

5
CO
J

f<X0
CD

Steady state

0
0 4

4
.

14 During steady-state growth the concentration profile in the liquid

must be such that the rate at which solute diffuses down the concen-
(b) tration gradient away from the interface is balanced by the rate at
which solute is rejected from the solidifying liquid i.e. ,

DCL = v(CL - Cs)

Assuming the molar volume is independent of composition this ,

becomec

DdXL
v at the interface
dx

The concentration profile in the liquid is given by

s
exp - m\
dXi
-X
= Xn I
o[ k II d exn
exp
-
-

: (D/
(D/v)

0
0 1
486 Solutions to exercises Solutions to exercises 487

Substituting this expression into the solute equation (d) For an Al-2 wt% Cu alloy;
v Interface temperature = 620 40C
-

D--(Xo-XO
9
3 x 10
-

Since = Xq/Ic at the interface, the expressions are equivalent, and Diffusion layer thickness re = 6 x 10
-

4
m
5 x 10
the profile satisfies the solute balance.
(653.2 - 620.4)
4 15
Temperature gradient 54.7 K mm
. 6 x 10
700"
4
.

16 Scheil equation: XL = X0fik-D

Since it is assumed that the soiidus and liquidus lines are straight ,
k is
constant over the solidification range and may be calculated usine
,

OS
a3 600- max and XE as follows
Q-

0) Xs
k = tt at a given temperature

At the eutectic temperature ,

s = Xmax and X{ = X
500
0 5 10 15 20 25 30 35
X solute

For an Al-0.5 wt% Cu alloy:

33-

(a) Interface temperature in the steady state is given by the soiidus

temperature for the composition concerned,
Interface temperature = 650, TC
6
(b) Diffusion layer thickness is equivalent to the characteristic width
of the concentration profile.
i
3 x lO"9
Thickness = - 6 x lO"4 m
v 5 x 10~6

(c) A planar interface is only staM: if there is no zone of constitu- 5 65-

.
- y

tional undercooling ahead of it. Under steady-state growth, con- 20 .

-

sideration of the temperature and concentration profiles in the 0 34'

.

liquid ahead of the interface gives that the critical gradient, Ti, 0
0 38
. 0 97
.

can be expressed as follows Distance along bar

where liquidus temp at The above plot may be constructed by considering the composition
L
DN soiidus temp at X0 of the initial solid formed (kX0) the position at which the solid has
,

the compositions X0 and X and the eutectic composition XR.

max,

(658.3 - 650.1)
,

Cm
-

1 Initial solid formed = kX0

ThUS = 6 x 10-
.

= 0 17 x 2 wt% Cu
.

i
13.7 K mm
-

= 0 34 wt% Cu
.
 488 Solutions to exercises Solutions to exercises 489

The volume fraction of liquid remaining, /L when the solid 4 .

17 Cells grow in the direction of maximum temperature gradient, which
deposited has a composition Xq is found from the Scheil equation. is upstream in a convection current.
4 18.

Thus when = XL = and the Scheil equation becomes

L
k T,-
a
c d
1
(-0 83) .

b
0 17
.

e 9

/l = 0.12. hence/s (position along bar) = 0.88

Similarly, when Xs = X max

5 .
65 wt% Cu, the Scheil equation
i becomes

5 65
.

0 17
.
9 X / "0"83) 0 25
.

Assume equilibrium conditions between <) and L

j_
0 .

175 65x 2y '0-83

.

= 0 03

\
.

2 T-p
Hence /s (position along bar) = 0.97
h
L
From the information given, X = 33 wt% Cu for positions along the 9
bar between 0.97 and L c .
b
(b) From the diagram, the fraction solidifying as a eutectic, fE = 0.03.
(c) For an Al-0.5 wt% Cu alloy solidified under the same conditions. e

the fraction forming as eutectic may be found from the Scheil

equation as before by putting equal to X miix
f

xL = x0f<-"
Temperature at which all
f S _ y ,(A-1) 6 disappeared

y
max v r(k-l)
4 . 19 It can be shown that the growth rate of a lamellar eutectic v. is given
k ~xofL
_

"

by the following equation

5 65.

U :)X/e
v = kDATi
0 .
17 -

/0.17 x 0.5\ 1/0.83 where k - proportionality constant;

/e D = liquid diffusivity;
\ 5.65 /
ATf, - interface undercooling;
0 006
.
X = lamellar spacing;
= minimum possible value of X .
490 Solutions to exercises Solutions to exercises 491

(i) When the undercooling is fixed, k, D and ATI, may be combined Differentiating a second time
to form a constant c. thus
'

-
a d AZi
-

dAT,, 2a 6a
-
r

A7n d>.- dA A To
;
-
a d Ar(i
Differentiating this equation with respect to X. A 7,) dA" AT

dv -c 2cX d2A7 2ATi)

ijji ii J.1 2a*\\ A/p / OA
V - = -H
dA A" X
r
d>.2 Ia '

/ \;
_

f)
d2v 2c 6ca* Substituting X - 2a*
Differentiating a second time; - = - rj-.
dA~ A" A
d:Ar() 2Ari)
To / J1 1_\ A7n / J 6 \

4> 2/ a 14;. : l(v. : '

_ _

:
dA2 a \4X*
c 2ca*
Hence - = -r- at the max. or min. urowth rate.
A
"

A"
Thus
d Ar,, is positive
dA

Hence undercooling is a minimum when /. = 2/.''

Substituting this value into the equation of the second differential
4 .
20 The total change in molar free energy when liquid transforms into
d2v 2c 6ca* lamella a + (3 with a spacing a is given by Equation 4 37. i.e. .
_
=

dx3 >7 " "x1-

2c 6ca*
AG(a) = -AG( ) +
A
4
16a *
The equilibrium eutectic temperature TE is defined bv X = * and
-c G(x) =0.
8/, We can define a metastable equilibrium eutectic temperature at
(7"E - ArE) such that at this temperature there is no change in free
Thus when /. = 2a*. the growth rate is a maximum. energy when L a + (3 with a spacing a. i.e. at TE - ATE ,

(ii) When the growth rate is fixed, the original equation may be AG{X) = 0.
rewritten as follows Also from Equation 4.38 at an undercooling of ArE
AHATe
a = A To . r AC( )
T,

where Finally, then, combining these equations gives

v
a 2ynfiVmTE
Li
AHX

a 1
Thus: AH
AT,) \ k2 Substituting: Yap - 0.4 J m-". rE = 1000-K..-p = 8 x 10x J m '

- v
. jn

Differentiating with respect to /. gives

-
6
10
-

a dATi) 1 2X*
AT,
X2 3 X
Ar5 dl X

dAT. r2 i e
. . for a - 0.2 \xm. ATE = 5 K
~

dX a \a2 a3 / X = 1.0 [im. ATB = 1 K

492 Solutions to exercises Solutions to exercises 493

Note that if these eutectics grow at the optimum spacing of 2X* the Chapter 5
total undercooling at the interface during growth (Ar0) will be given
by Equation 4.39 such that
5 1
.

AG,, = Rrf ln
for A. = 0.2 urn. X* = 0.1 \im. A To = 10 K
(a) By direct substitution into the above equation
and X = 1.0 (im, = 0.5 \xm. AT{) = 2 K
AGU = 420.3 J mor1
4 21
.

(b) Applying the lever rule to the system at equilibrium

U>-d -J
(X - X )
Mole fraction of precipitate = j- - = 0 08
.

(Xp - XQ)
Assuming the molar volume is independent of composition ,
this
will also be the volume fraction
P P P
.

(c)

50 nm

Lamellar eutectic Rod-like eutectic

For a lamellar eutectic the total interfacial area per unit volume of
eutectic is given by: 2/X. irrespective of volume fraction of p. Assuming a regular cubic array with a particle spacing of 50 nm .

For the rod eutectic, considering rods of unit length, and diameter the number of particles per cubic metre of alloy =
d the area of a/(3 interface per unit volume of eutectic is given by
.
1 21

nd 2nd (50 x w y
_

8 *10
X 3/2 X2V3 Let all the particles be of equal volume and spherical in shape
For the rod eutectic to have the minimum interfacial energy, then with a radius r. Then the total volume of particles in 1 m3 of
alloy =
2nd 2 d x3
7 < -
X < T' e.

8 x 1021 x 7tr3
' .

X A,
71

d depends on the volume fraction of p. (/)

Equating this with the volume fraction of precipitate
f~ 4 / 2
8 x 1021 x nr = 0.08 m3
v3
From which / < /c = - - 0 28.
.

r = 13.4 nm.
2n

4 22
.
See Sections 4.4 and 4.5. Thus in 1 m3 of alloy the total interfacial area =
4 23 .
See Section 4.5. 8 x 1021 x 47U-2 = 1.8 x 107 m2
I: 494 Solutions to exercises Solutions to exercises 495

2
(d) If Tap = 200 mJ m From Equation ] .40
"

total interfacial energy = 200 x 1.8 x 107 mJ m 3 alloy

"

GB + RT}nXq + D(l - Z,,)2

= 3 6 x 106 J m"3 alloy
. Mb GB + KTlnXe + na - Xe)2
= 36 J mol
"
1 GA + RT\n(l - X0) + QJCo2
HX = GA + RT\n (1 - Xe) + nx2
36
9% Combining the above equations gives
(e) The fraction remaining as interfacial energy
-
ir 420.3

(f) When the precipitate spacing is 1 im;

1
No of particles per m3
(1 x 10~6)3 53
.

(a) AGn RTln - per mole of precipitate

1 x 1018m"3
Thus for a precipitate with X{) 0 1 andZe - 0.02 at 600 K:
.

Using the same method as in (c), the particle radius is found to

be 267 nm.
AGn = 8.0 kJ mol
Thus in 1 m3 of alloy the total interfacial area =
(b) Assuming that the nucleus is spherical with a radius and ignor-
7
1 x 10i8 x 4n x (2.67 x 10 )2 ing strain energy effects and the variation of y with interface
~

= 8 .
96 x 105 m2 orientation, the total free energy change associated with nucieation
may be defined as
Total interfacial energy =1.8 x 10 J irT3 alloy
4
= 1 .
8 J mol"1 AG = --7W3-ACV + 4nr2y

Fraction remaining as interfacial energy = 0.4% where AGv is the free energy released per unit volume. Differ-
52
.
entiation of this equation yields the critical radius r*
m
r 0 50 nm
G
.

AG n
a

(c) The mean precipitate radius for a particle spacing of 50 nm was

calculated as 13.4 nm = 27 r*. For a 1 jam dispersion the
03
Go precipitate radius, 267 nm = 534 r*.
E3
54
.

Mi
CQ Gr a
O

P
A B
X ,

US

AG0 = G0 - Gf
G0 = XQv.l + (1 - Z0)nO
Gf = Zon| + (1 - x0) \i% Xe Xo
 496 Solutions to exercises Solutions to exercises 497

From Equation 1.68 5 f)

.
(a)
n = GB + rinyoZo
V
= Gb + RT\njcXc
i
where y0 and ye are the activity coefficients for alloy compositions X{)
and Xe respectively
Co
I AGn
0 e dti YO O
yeXe

For ideal solutions y0 = ye = 1

For dilute solutions yo = Ye = constant (Henry's Law)
In both cases

i
AG n RT\n
t (b)
t 5.
5 (a) Consider equilibrium of forces at the edge of the precipitate: a -

X
full

L
v

8
x

Using the simplified approach, above, the carbon concentration

gradient in the austenite, - may be expressed as
due

For unit area of interface

L
Yaa = 2ya(3COSe
For unit area of interface to advance a distance dr, a volume of
9 = cos"17"" = 53 1
.

material 1. dx must be converted from y containing CY to a
containing Ca moles of carbon per unit volume, i.e. (Cv - Ca)dbc
(b) The shape factor 5(0) is defined as moles of carbon must be rejected by diffusion through the y. . .
The flux of carbon through unit area in time dt is given by V
5(8) = ~(2 + cos8)(l - cos0)2 = 0 208 .
D{dCtdx) dt, where D is the diffusion coefficient. Equating the
two expressions gives

(Cy - Ca) dx dt
498 Solutions to exercises Solutions to exercises 499

(D ~ ?v )*s
*

dt
=
d(\dx ) l
-

(C7 - Ca)
Thus using the simple concentration profile obtained earlier where / is the volume fraction of austenite
, .

dr \; L J (CY-Cn:) :

The width of the diffusion zone L may be found by noting that

X
conservation of solute requires the two shaded areas in the
diagram to be equal 3 D
*max = (1 - f}.;>)-
'
,

. .

UCy - Co)
(Co - Ca)x
2

2(C0 - Ca)x D
L
(Cy - Co)
(The same answer is obtained for any polyhedron.) Approxi-
Substituting for L in the rate equation mately, f-, is given by
dx
_
"
D(C, - Cp)2 0 XfL
dr 2(Co - Ca)(CY - Ca)x Y
Xy - Xa
Assuming that the molar volume is constant, the concen- In the present case /7 = 0 .
43. such that for D - 300 jim;
trations may be replaced by mole fractions (X = CV ). Integration
*max = 36 5 fim
of the rate equation gives the half-thickness of the boundary
.

slabs as
This value will be approached more slowly than predicted by the
(Xy-X V Dt) parabolic equation, as shown schematically in the diagram below.
X
(xt) - xay*{xy - xa)
40-
Maximum half-thickness
(c) The mole fractions in the above equation can be replaced ap-
proximately by weight percentages. For ferrite precipitation from
austenite in an Fe-0.15 wt% C alloy at 800 0C we have ,
% 304 Parabolic equation
O? "1
\
i
.
:

xn 0 15;
.

Real variation (schematic)

0 02;
.
20-
"

*
- I
Dl 3 x HT12 m
"

1/2
giving x 1 .
49 x 10""6 t

10-
(d) The previous derivation of x(t) only applies for short times. At
longer times the diffusion fields of adjacent slabs begin to overlap
reducing the growth rate. The lever rule can be used to calculate
0
the maximum half-thickness that is approached for long times. 0 100 200 300 400 500 600 700
Assume the grains are spherical with diameter D. When the
Time (S)
transformation is complete the half-thickness of the ferritic slabs
Omax) is given by The exact variation would require a more exact solution to the
500 Solutions to exercises Solutions to exercises 501

diffusion problem. However, the approximate treatment leading 59 .

to the parabolic equation should be applicable for short times.

57
.
v

a E
0)

Nucleation or growth rate

Consider unit area of interface perpendicular to the diagram:

Mass flow in the direction of u = u x h: Civilian transformations that are induced by an increase in tempera-
ture show increasing nucleation and growth rates with increasing
Mass flow in the direction of v"= v x X.
superheat above the equilibrium temperature (Tc). This is because
From the conservation of mass: u x h = v x X both driving force and atom mobility (diffusivity) increase with
increasing AT.
u x h
v
5 .
10 (a) G = XAGA + XBGB + QXAXB + RKXA\nXA + XBlnXB)
GA = GB = 0 gives:
5.
8 /= 1 - exp(-tfO G = QXaXq + RT(XA\nXA + XBlnXB)
dG = ClXAdXB + nXBdXA
At short times this equation becomes
n
+ RT[dXA + dXB + \nXAdXA + \nXBdXB}
/= Kt
but
(a) Pearlitic nodules grow with a constant velocity, v. The voiume
fraction transformed after a short time t is given by XA + XB - 1
-

. .
d A + dXB = 0
dG
47t(v03 /4tcv3\ 3 = Q( A b) + RT(\nXB - \nXA)
/
-
_

d e
d2G
. e .

dZg
-

2Q + RT
{ + A)
xB
K = -r . n = 3
3d
3 d2G RT
-
2Q
dXi XAX]B
(b) For short times, slabs growing in from the cube walls will give
(b) This system has a symmetrical miscibilitv gap with a maximum at
i2-vt
6d- . /6v\ XA = XB = 0.5 for which
f
d3 Ui t
_
=

d2G
ART - in
i e . .

6v d2G
K = - . n = 1. It can be seen that as T increases changes from negative to
a d
502 Solutions to exercises Solutions to exercises 503

positive values. The maximum of the solubilitv gap (T = Tc) (d) The locus of the chemical spinodal is given by
d2G
corresponds to 0

dA-B
.
e
.

2R
RT
-

2O = 0
dG
A A A'b
(c) Equating --
dX
to zero in the equations gives
B
T
-

= 4 B(1 -

b)
Q(XA - XB) + RT(\nXQ - \nXA) 0

Putting Q = 2RTC gives

This is also shown in the figure.
T 2(1 - 2XB)
_

5 11
G o + AA ) = G(Xn) + - (AX) + -T1 + . . .
.
.

This equation can be used to plot the coordinates of the

miscibility gap as shown below:
G(X{) - AX) = G(X,) + (-AX) + !-p + . . .
Total free energy of an alloy with parts of composition (Xt) + AX)
and (Xu - AX) is given by
-

G(XI) + AX) G(Xn - OX) lnr,Y <? G ,

S (kv
, .

Miscibility
gap
= G(X0) + (AX)2
r

Original free energy = G(A',))

1 d2G 2
Change in free energy
2 dX
05
.
-

Chemical
spinodal
5 12
.
Equation 5.50 gives the minimum thermodynamically possible wave-
length m in
as

IK

0 Iv E'V is a positive constant, while d2G/dJt'2 varies with com-

0 0 5
.

position X& as shown below:

504 Solutions to exercises Solutions to exercises 505

d2G Chapter 6
dx2
6 1
.

0
05
.
B

At 7> T0
Chemical
spinodal

Coherent
spinodal

mm

"

0) G
03
0)
0)

At T = "r0
1
05
.
e

Thus Amin = * at the coherent spinodal, but decreases as XB

increases towards 0.5, as shown schematically above. The wavelength
that forms in practice will be determined by a combination of thermo-
dynamic and kinetic effects, but qualitatively it will vary in the same
'
G
way as A.mm.
5 13
.
(a) Massive transformations are classified as civilian nucleation and
growth transformations which are interface controlled. This is
because massive transformations do not involve long-range dif- A
fusion, but are controlled by the rate at which atoms can cross MT=M5(<TQ)
AG7
the parent/product interface (see also Section 5.9).
'
G
(b) Precipitation reactions can occur at any temperature below that B

marking the solubility limit, whereas massive transformations

cannot occur until lower temperatures at least lower than r0
(Fig. 5.74). Massive transformations therefore occur at lower
temperatures than precipitation reactions. However, at low tem-
peratures diffusion is slow, especially the long-range diffusion
required for precipitation. Massive transformations have the
advantage that only short-range atom jumps across the parent/
product interface are needed. Thus it is possible for massive
transformations to achieve higher growth rates than precipitation
reactions despite the lower driving force.
%Ni
X
For an alloy of composition X, at T > r0, the free energy curve for a
lies above that for y, thus austenite is stable at this composition and
temperature, and the martensitic transformation is unable to occur.
At a temperature T = T0 the a and a' free energy curve coincides
with that for y and so at this temperature and composition both the
,
506 Solutions to exercises Solutions to exercises 507

martensite and austenite have equal free energy, and there is no 6 .

4 The habit plane of martensite is a common plane between martensite
driving force for the martensitic transformation.
At a temperature T = Ms the y free energy curve lies above that for
a, therefore y is thermodynamically unstable, and there is a driving
force for the martensitic transformation proportional to the length
AB. The significance of the Ms temperature is that it is the maximum
temperature for which the driving force is sufficient to cause the
martensitic transformation. No such driving force is present at tem-
peratures above Ms.
At the equilibrium temperature Tq, AG for the transformation is
zero, thus
'
and the phase from which it forms which is undistorted and unrotated
during transformation. Thus all directions and angular separations in
the plane are unchanged during the rransformation.
The martensitic habit plane may be measured using X-ray diffrac-
tion and constructing pole figures. The figures are analysed and the
plane index may be determined by measuring the positions of diffrac-
tion spots from martensite crystals produced from austenite crystals.
The main reason for the scatter in the measurement of habit planes
is that the martensite lattice is not perfectly coherent with the parent
lattice, and so a strain is inevitably caused at the interface. This may

AGy~a = AHy-a - TcfiS = 0 act to distort the habit plane somewhat. Internal stress formed during
the transformation depends on transformation conditions. Habit
AH f~a
'

at Tn, AS
plane scatter has been observed to increase when the austenite has
To .
been strained plastically prior to transformation, indicating that prior
deformation of the austenite is an important factor.
For small undercoolings AH and AS may be considered to be Another reason for the scatter is that during the formation of
independent of temperature, thus the free energy change may be twinned martensite, the twin width may be varied to obtain adjacent
expressed in terms of the undercooling as follows: twin widths with very low coherency energies. Experimental studies
have shown that the lowest energy troughs are very shallow and quite
(Tp - Ms)
extensive, enabling the production of habit planes which may vary by
'

AGy-a = AHy-a
To
at the Ms temperature.
The driving force for the martensitic transformation has been
shown to be proportional to the undercooling (r0 - A/s), where T{] is
the temperature at which austenite and martensite have the same free
energy, and Ms is the temperature at which martensite starts to form.
In the Fe-C system both To and Ms fall with increasing carbon
content, with an equal and linear rate. Thus the difference (r0 - Ms)
remains constant for different carbon contents, which means that the
several degrees in a given alloy.
6 .
5 The key to the phenomenological approach to martensitic trans-
formations is to postulate an additional distortion which reduces the
elongation of the expansion axis of the austenite crystal structure to
zero. This second deformation can occur in the form of dislocation
slip or twinning as shown below:
s

driving force must remain constant. Z

7
6.
2 See Section '-.3.1 (p. 398). 7
i
i
t Z Slip
J nucleus
1
-

2y
c

#
167n(S/2)2 T
a
(ACV)2
J
Substitution of the values given gives Twinning

AG* - 3.0 x lO"18 J nucleus"1

c 0 23 nm
.
Austenite Martensite

*
a = 8 5 nm
.
 508 Solutions to exercises Solutions to exercises 509

Dislocation glide or twinning of the martensite reduces the strain of
the surrounding austenite. The transformation shear is shown as S.
Both types of shear have been observed under transmission electron
microscopy.
content which means that the austenite is not as uniformly or as
efficiently eliminated as with lath martensites. Plate martensite is
formed by a burst mechanism, this factor contributing to the fact that
the habit plane changes to {225}, and to {259} with even higher
carbon content.

66
.
Similar arguments may be used to explain the change in habit plane
with increasing Ni content in FeNi alloys since Ni acts in a similar
,

S5 way to C. lowering the Ms temperature and influencing martensite

morphology and amount of retained austenite.
C
The amount of retained austenite is also influenced by the austen-
itizing temperature since this influences the amount of dissolved iron
carbide. The quenching rate is also important an oil quench will
,

a ,, a
.
produce more retained austenite than a water quench.
V2 69
.
See Section 6.4 5 . .

Austenite Martensite

i
6 10
.
See Section 6 7
. .

6 11
.
See Section 6.7 4 . .

Assuming that ay = 3.56 A and aa = 2.86 A. and that da for

martensite is equal to 1.1, the movements of atoms in the c and a
directions may be calculated
} aa = 2.86 A . ca = 3.15 A
.

a
y
= 3.

56 A .\ - 7 = 2.52 A
Vertical movement of atoms = 3.56 - 3.15 A
= 0 41 A .

Horizontal movement of atoms = 2.86 - 2.52 A

= 0 .
34 A
Thus by vector addition, the maximum movement is found to be
0 .
53 A

6 7
.
See Sections 6.32 and 6.33.

6.
8 The habit plane of martensite is found to change with carbon and
nickel contents in FeC and FeNi alloys respectively. This may be
explained by considering the nature and the method of formation of
the martensite which is dependent on alloy content.
In low-carbon steels the Ms temperature is high and martensite
forms with a lath morphology growing along a {111} plane." Growth
occurs by the nucleation and glide of transformation dislocations.
However, as the carbon content is increased the morphology changes
to a plate structure which forms in isolation. The degree of twinning
is higher in this type of martensite. An important difference in this
process is that the Ms temperature is lowered with increasing alloy
 Index 511

relaxation time. 72 Gibbs-Duhem relationship. 54

self-diffusion, 75. 78. 79 Gibbs free energy, 1
short-circuits, 98 of grain boundaries. 122
steady-state. 69 of interphase interfaces, 146
substitutional, 61, 75 of mixing, 12
Index surface. 98 of solid/liquid interfaces. 171
ternary effects. 96 of surfaces, 113
X tracer. 94 of twin boundaries, 123
up-hill, 60, 96. 308 pressure effects. 7
Activation energy, 55, 67, 172 spinodal, 312 vacancy, 79 temperature effects, 4
barrier, 56 twin boundaries, 122 Diffusional transformations in solids, Gibbs phase rule, 36
interstitial diffusion. 68 Cold cracking, 376 263 Gibbs-Thomson effect, 46
substitutional diffusion, 75 Columnar zone, 235 Diffusionless transformations. 382 Glissile interfaces, 163. 172, 409. 413
Activity, 21 Common tangent construction. 31. 50 Discontinuous precipitation, 322 Gradient energy, 311
coefficient, 22 Components of a system, 1 Dislocations Grain boundaries. 116
Age hardening, single-component systems, 4 in martensite transformation, 401 high angle, 118
alloys. 291 two-component systems, 11 in precipitate nucleation. 274 in cellular precipitation. 322
aluminium-copper alloys, 307 Constitutional supercooling, 215 Shockley partials, 164 in nucleation. 271
Constrained misfit, 158 transformation, 409 low-angle, 116
i Antiphase domains, 363
Arrhenius rate equation, 56 Continuous casting, 238 Divorced eutectic, 229 special, 122
Avrami equations, 290 Continuous growth process, 198 Down-hill diffusion, 60, 309 Grain boundary
Driving force for precipitate nucleation aliotriomorphs, 317

1
Controlled transformation steels. 430 ,

Bain deformation, 391 Cooperative growth, 222 268 energy, 117

Bainite, 334 Coring, 229 junctions, 124
lower, 337 Correlation factor. 75 Enthalpy of formation migration, 130
upper. 334 Critical nucleus size of borides, 424, 425 mobility, 135
Binary phase diagrams. 33 for martensite nucleation. 400 of carbides, 424. 425 segregation, 138
Broken-bond model. 114 for precipitation, 267. 272 of nitrides. 424. 425 Grain coarsening, 131. 140
for solidification, 187. 193, 196 of vacancies. 43, 76 Grain growth. 131, 139
CCT diagrams, 346 abnormal, 142
Entropy. 1. 6
Carbides, 422 Darken's equations, 88 of fusion. 11 during tempering of steel, 426
Carbon equivalent, 376 Dendrites
of mixing, 13. 14 Growth fedges. 179 199, 285
Carburization, 73 cellular, 219
of vacancy formation. 43 Guinier-Preston (GP) zones, 149, 291
Cellular precipitation. 288, 322 columnar. 235
Epsilon carbide, 417, 421 equilibrium shape of. 158
Cellular solidification. 214 crystallography. 206 Epsilon martensite, 402
Cellular transformations, 288 equiaxed, 234, 236 Equiaxed zone, 236 Habit plane, 153
Cementite, 422 secondary-arm spacing, 221 Equilibrium, 1 of Widmanstatten plates 150, 152,
,

Chemical potential. 16 thermal, 206 317

freezing range, 216
gradient, 60 tip velocity, 207 heterogeneous systems, 28 of martensite laths and plates ,
390.
Chemical spinodal, 309 Diffuse solid/liquid interfaces, 169, 198 396
shape of crystal, 115
Chill zone, 234 Diffusion. 60
shape of precipitates, 149, 154, 179 Hardenability, 338
Civilian transformations, 172 atomic mechanisms, 61 solidification, 208 Heat flow, 203. 239
Classification of phase transformations, controlled growth. 105, 173, 175, 279 Eutectic solidification, 222 Helical dislocations, 303
173 controlled lengthening of plates and impurity effects, 229 Henry's law, 22
Clausius-Clapeyron equation, 9 needles, 283
Euteetojd transformations, 263, 326 Heterogeneous nucleation (see
Coarsening dilute substitutional alloys, 91 Extensive thermodynamic properties, 4 Nucleation, heterogeneous)
of grain size, 131 dislocation-assisted, 102 .
.
Homogeneous nucleation (see v
-

of particle dispersions, 314 down-hill, 60, 309 Nucleation, homogeneous)

Pick's laws, 65, 71, 88 Ferrite, 317 Homogenization, 71
Coherency, 143
loss, 161 grain boundary, 98 Fibrous precipitation, 349
strains. 155, 310. 398 interstitial, 61, 63 Pick's law of diffusion, 65, 71, 88 Ideal solutions, 13
Coherent multiphase systems, 103 First order transformations, 359 Ingot structure, 233
interfaces, 143 nonsteady state, 69 Free energy-composition diagrams, 15 Inoculants, 196
f
 512 Index Index 513

Intensive thermodynamic properties, 4 growth, 409 Order Raouh's law, 22

Interdiffusion coefficient. 88 habit planes, 389, 390, 396 long-range order parameter 358 ,
Recalescence. 346
Interface Mf temperature, 383, 386 short-range order parameter 24 ,
Recovery during tempering ,
426
coherence, 143 V/ temperature. 383, 386
; S
Order-disorder transformations 263. 358 , Recrystallization 138, 288 426
.

controlled growth, 106. 173 . 175, nucleation, 397 Orientation relationship144 .

Retained austenite 383, 426 ,

285 role of grain size. 416 of some martensites 390 .

Reversion 301 ,

migration. 171 Massive transformations, 263, 288, 349 Overageing, 306 Richard's rule 11 ,

mobility, 172 Mechanical properties

reaction, KS6 of age hardening alloys. 294 Partially coherent precipitates ,
151 Schaeffler diagram, 257
stability during solidification, 203 of controlled transformation steels, Particle coarsening 314
, Scheil equations, 212
Interfaces. 110 434 Pasty zone, 236 Second-order transformation 361 ,

coherent, 143 of titanium alloys, 372 Pearlite, 288 326

,
Secondary hardening in high-speed tool
complex semicoherent. 148 Metastable equilibrium, 2 growth, 330 steels, 423
effect on equilibrium, 44 Metastable (transition) phases, 2, 292 in off-eutectoid alloys ,
333 Segregation in ingots and castings 237 .

free energy of, 110 Microstructure, 110 nucleation. 327 Segregation of carbon duirno temperins .

incoherent, 147 Military transformations, 173 ,

382 Peritectic solidification 231 ,
420
interphase, 142 Miscibility gap, 33, 308 Phase diagrams, 33 Seif-diffusion, 75
S coherent, 312
"

irrational, 149, 167 Al-Cu, 291 activation energy of, 76

semicoherent, 145 incoherent, 313 binarv, 33 experimental data, 78
solid/liquid, 168. 197 Misfit dislocations. 145 Cu-Zn,353 Semicoherent interfaces 145 ,

solid/vapour, 112 Misfit parameters, 157 eutectic, 36. 51 Shape of inclusions and precipitates
Intermetailic compounds. 27 Mobility Fe-C,250. 318 coherent precipitates 155 .

Interphase precipitation, 349 of atoms, 92 Fe-Cr-C, 432. 433 grain boundary effects, 154
Interstitial of glissile interfaces. 172 Fe-Cr-Ni, 250. 257 incoherent precipitates and
compounds, 27 of grain boundaries, 135 Fe-Mo-C, 418 inclusions 159 ,

diffusion, 61, 63 of interphase interfaces 172

,
Fe-Cr-Mo-W-V-C 253 , interfacial energy effects. 149
sites in cubic crystals, 385 of twin boundaries, 136 Mg-Al. 326 misfit strain effects 155 ,

Invariant plane strain, 391 Mushy zone, 236 ternary, 48 plate-like precipitates. 160
tit Kinetics, 55
Ti-Ni/436
Phases, 1
Shape-memory. 431
Shockley partial dislocations 164
Nishiyama-Wasserman orientation ,

of grain growth. 139 relationship, 148. 317. 394

electron, 28 Short-range order, 24
of phase transformations. 287 Nitinol, 431 intermediate, 26 Shrinkage in ingots and castings ,
237
Kirkendall effect, 89 Laves, 27 Site saturation, 288
Non-equilibrium lever rule, 212
Kurd]umov-Sachs orientation metastable, 2, 292 Solid solutions
Nucleation, heterogeneous. 192
relationship, 148, 317 394 ,

activation energy barrier, 193, 195,

ordered, 24, 35 binary. 11, 52
272 transition. 292 carbon in iron, 285
Latent heat Plate martensite, 412 free energy of, 11
in liquids, 185
of fusion, 7, 112 170 .
in solids, 271 Polymorphic transformations 263 ,
ideal, 13
of melting, 7, 112 ,
170
of martensite, 400 Precipitate interstitial, 24
of sublimation 112, 170 coarsening, 314 ordered, 23, 24
,
on dislocations, 274
of vaporization 112 growth, 279, 283 quasi-chemical model, 18
on grain boundaries, 271
,

Lateral growth, 178 198, 285 ,

rate of, 194, 276 Precipitate-free zones 304 ,
real, 23
Lath martensite, 410 Precipitation, 263 regular. 18, 41
vacancy-assisted, 275
Laves phases, 27 in Al-Ag alloys, 302 solubility as a function of
Nucleation, homogeneous
Ledge mechanism 178, 198, 285 in Al-Cu alloys, 291 temperature, 41
,
activation energy barrier, 187, 266
Local equilibrium 97, 103, 177 210, of a from p brass. 349 Solidification, 185
in liquids, 185, 186
,

224, 279 of ferrite from austenite, 317

in solids, 265 alloy, 208
Long-range order, 358 of martensite, 397 Pre-martensitic phenomena. 416 carbon steels, 249
Lower bainite 337 Pro-eutectoid ferrite 317
,
rate of, 191, 267 , castings, 233
Pro-eutectoid cementite 322 , driving force for, 10
Martensite, 382 eutectic, 222
crystallography 389 , Off-eutectic alloys, 229 Quenched and tempered steels, 428 fusion welds, 243
effect of external stresses 415 , Off-eutectoid alloys, 333 Quenched-in vacancies, 303 high-speed steels, 251
. .

. .
 rem

514 Index

ingots, 233 recrystallization 138 ,

low-alloy steels, 249 Thermal activation 56, 66, 172

,

peritectic, 231 Thermodynamics, 1

rapid, 249 Ti-6V-4A1 alloys, 366
shrinkage, 237 Tie-lines, 50
single-phase alloys, 208 Torque term, 126
stainless steel weld metal, 256 Transformation shears, 337, 383
unidirectional, 208 Transformation dislocations, 409
Solubility product, 426 Transition phases, 292
Solute drag, 138 Twin boundaries, 122
Spinodal decomposition, 308 in solidification 202
,

Spiral growth, 201

Stabilization of austenite, 415
Stacking faults, 167
in martensitic transformations. 41)2
404
in precipitate nucleation. 273, 276
303
Stirling's approximation. 14
Substitutional diffusion, 75
Unconstrained misfit, 155
Up-hill diffusion, 60, 96, 308
, Upper bainite, 334
. Vacancy
Concentration, 43
diffusion, 79
formation enthalpy 43. 76 ,

Surface nucleation, 200 formation energy 43, 76 ,

Surface tension. Ill formation entropy 43 ,

jump frequency. 79
TTT diagrams, 287, 301 339. quenched-in, 303
Temper embrittlement. 427 Valency compounds 28 ,

Tempering of ferrous martensites .

417
Ternary alloys. 48 Weldability, 372
diffusion in, 96 Widmanstatten side-plates ,
317
Texture Widmanstatten structures. 153. 279 318 ,

deformation, 138 Wulff construction 115 ,