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Phase Transformations in Metals and Alloys Solutions PDF
Phase Transformations in Metals and Alloys Solutions PDF
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
.
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
s-Fe
E-Fe
4
5 5
110 120
Six distinguishable configurations.
Schematic free energy-pressure curves for pure Fe.
; !
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
dG
Equation 1.39: G - AAGA + A'bGb + QXAXB + /?r(A'Aln,VA
Thus - = nA -
'
f A pln e)
dXB
(1.6.1)
= AaGa -
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
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
+ 0 307
Hb Ha .
dXB
0 231
.
0 307
i e . .
= OS +- - .
Thus jiB = OS + UV = TV
i .
e . point V represents the quantity b- = 4 66 J K
.
mol "1
= 1 -
43 J K"'
V
CD
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
= -1 .
83 kJ mor1 m
k
. n
f
e 9 h
(g) For a very small addition of Au S
0)
T2- a
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
-
. .
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
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 !
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.
.
ACA and ACb are as defined in (b) and (c). fd) Free energy curves for the A-B system at 7 F .
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 <
2lVm
.
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)
r) + vm(p - p0)
and
LAT 2yVm
The accuracy of this equation decreases as (T - Tq) and (P - P0)
increase.
T
1 m r
Ar> 27Vmrg
i .
e .
a = 80% A, 5% B 15% C;
,
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
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
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
.
actIvlty = __.ex
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
.
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
4 -
v
2
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
4Cor . kx 1 . 37rxl
C(x) = - nT + -slnTJ
v
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
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,
(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 .
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. ,
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
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
below
'
D
D2n
0
A a b c d B
XB
%Zn a
Cu
Solubility limit for a t
LJ
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
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
.
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
*
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.
LA/aJ .
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
32 Ew
one bubble diameter).
.
de
(-sin 9 + cos e)~ *
1.53
2a D °
8 0 mm
.
sin 11
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
. .
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
.
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.
"
39
.
2*2 1 26 - 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%
, ,
(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 .
= 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
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 .
!
Mass flow perpendicular to BC = u x h. A
-
X .
A
3 19.
X X,p
A X B
'
hb = GB + RT In Yi*t i
/ = 0
Hfc = Gb + RT\nycXc a a
r.
Aji'b = RT In Xc
X
A k = RTln X o
f = t3 > '2
= 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
~
Chapter 4 c
AGV + 47cr2YsL
.
c ,
47i/-::*AGv + 87rr/SL 4
dr
AGr = --7cr3AG + 47rr2YS[ v
0 = -4Trr *2
'AG v + 8nr*ySL .
r
*
=
2ysl cluster size increases somewhat.
AGy 4
.
4 From Equation 4 .
13
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
'
homogeneous nucleation. s
V nr
3
Thus
\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
e ~
AGh*hum
. .
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
V
maintain a negative radius of curvature which stabilizes the solid V
1 m S
(1 - 6) S
7777, 77777
Thus
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
,
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
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 -
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~]
ATf
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).
,
Tx-Ts (l-k)
where Tx > T2 > TE. For the phase diagram in Fig 4.21a. the .
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
,
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).
5
CO
J
f<X0
CD
Steady state
0
0 4
4
.
becomec
DdXL
v at the interface
dx
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
.
©
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
liquid ahead of the interface gives that the critical gradient, Ti, 0
0 38
. 0 97
.
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
,
(658.3 - 650.1)
,
Cm
-
= 0 17 x 2 wt% Cu
.
i
13.7 K mm
-
= 0 34 wt% Cu
.
488 Solutions to exercises Solutions to exercises 489
L
k T,-
a
c d
1
(-0 83) .
b
0 17
.
e 9
5 65
.
0 17
.
9 X / "0"83) 0 25
.
= 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
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
_
"
U :)X/e
v = kDATi
0 .
17 -
(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
/ « \;
_
f)
d2v 2c 6ca* Substituting X - 2a*
Differentiating a second time; - = - rj-.
dA~ A" A
d:Ar() 2Ari)
To / J1 1_\ A7n / J 6 \
:
dA2 a \4X*
c 2ca*
Hence - = -r- at the max. or min. urowth rate.
A
"
A"
Thus
d Ar,, is positive
dA
(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,
a 1
Thus: AH
AT,) \ k2 Substituting: Yap - 0.4 J m-". rE = 1000-K..-p = 8 x 10x J m '
- v
. jn
a dATi) 1 2X*
AT,
X2 3 X
Ar5 dl X
dAT. r2 i e
. . for a - 0.2 \xm. ATE = 5 K
~
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
.
(Xp - XQ)
Assuming the molar volume is independent of composition ,
this
will also be the volume fraction
P P P
.
(c)
50 nm
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
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
"
= 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
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
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
(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:) :
. .
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;
.
*
- 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
a E
0)
. .
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
5 11
G o + AA ) = G(Xn) + - (AX) + -T1 + . . .
.
.
S (kv
, .
Miscibility
gap
= G(X0) + (AX)2
r
Chemical
spinodal
5 12
.
Equation 5.50 gives the minimum thermodynamically possible wave-
length m in
as
IK
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
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 several degrees in a given alloy.
at the Ms temperature. 6 .
5 The key to the phenomenological approach to martensitic trans-
The driving force for the martensitic transformation has been formations is to postulate an additional distortion which reduces the
shown to be proportional to the undercooling (r0 - A/s), where T{] is elongation of the expansion axis of the austenite crystal structure to
the temperature at which austenite and martensite have the same free zero. This second deformation can occur in the form of dislocation
energy, and Ms is the temperature at which martensite starts to form. slip or twinning as shown below:
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 s
2y
c
#
167n(S/2)2 T
a
(ACV)2
J
Substitution of the values given gives Twinning
*
a = 8 5 nm
.
508 Solutions to exercises Solutions to exercises 509
Dislocation glide or twinning of the martensite reduces the strain of content which means that the austenite is not as uniformly or as
the surrounding austenite. The transformation shear is shown as S. efficiently eliminated as with lath martensites. Plate martensite is
Both types of shear have been observed under transmission electron formed by a burst mechanism, this factor contributing to the fact that
microscopy. 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
,
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 . .
a
y
= 3.
56 A .\ - 7 = 2.52 A
Vertical movement of atoms = 3.56 - 3.15 A
= 0 41 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
1
Controlled transformation steels. 430 ,
migration. 171 Massive transformations, 263, 288, 349 Overageing, 306 Richard's rule 11 ,
free energy of, 110 Microstructure, 110 nucleation. 327 Segregation of carbon duirno temperins .
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 ,
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 ,
. .
rem
514 Index
jump frequency. 79
TTT diagrams, 287, 301 339. quenched-in, 303
Temper embrittlement. 427 Valency compounds 28 ,