Exercise 1.

4: Enthalpies of allotropes

[Problem]

For a single component system, why do

the allotropes stable at high temperatures
have higher enthalpies than allotropes
stable at low temperatures,
e.g. Hg-Fe > Ha-Fe ?

Thermodynamics and Kinetics of Materials E-1

 Exercise 1.4: Enthalpies of allotropes

G = H - TS
G
 G 
   S
a  T  P
stable @
lower T
Gg steeper than Ga @ T0

Sg > Sa
g
stable @ Gg = Ga @ T0
higher T

T0 T hence: Hg > Ha

Thermodynamics and Kinetics of Materials E-2

Exercise 1.13: Eutectic Point

[Problem]
A, B: ideal solution in liquid
almost immiscible in solid
if :
DSm(A) = DSm(B) = 8.4 J·mol-1·K-1
Tm(A) = 1500 K, Tm(B) = 1300 K
CPS  CPL

? : xE, TE Richard’s Rule:

DSm ~ R (8.314 J·mol-1·K-1)
Thermodynamics and Kinetics of Materials E-3
 Exercise 1.13: Eutectic Point
T T
TmA
TmB
GL GL
TE
GS GS
GA A xE B GB
L
G @ TE
A
GBL
D GA D GB
S
G S
A
G B

A xE B
Thermodynamics and Kinetics of Materials E-4
 Exercise 1.13: Eutectic Point

considering the ideal liquid,

(see: Fig. 1.16 in page 21)

GAL @ TE
GBL
 L
A
 BL
RTE ln aA A xE B RTE ln aB
 RTE ln (1-xE)  RTE ln xE

comparing with the previous figures 

Thermodynamics and Kinetics of Materials E-5
 Exercise 1.13: Eutectic Point
T T
TmA
TmB
GL GL
TE
GS GS
GA A xE B GB
L
G @ TE
A
GBL
D GA D GB
S
G S
A
G B

A xE B
Thermodynamics and Kinetics of Materials E-6
 Exercise 1.13: Eutectic Point

L
G A @ TE L
G B

G 
S L
A
  GBS
L
B
A

RTE ln aA A xE B RTE ln aB
 RTE ln (1-xE)  RTE ln xE

DGA  RTE ln (1-xE)

DGB  RTE ln xE

Thermodynamics and Kinetics of Materials E-7

 Exercise 1.13: Eutectic Point

DGA  RTE ln (1-xE) DGB  RTE ln xE

since C PS  C PL, DG = DSm DT
( cf. Eq.(1.16) and (1.17) )

RTE ln (1-xE) = DSm(A)·(Tm(A)-TE)

RTE ln xE = DSm(B)·(Tm(B)-TE)
2 equations for 2 unknown quantities: TE and xE

xE = 0.56, TE = 826 K

Thermodynamics and Kinetics of Materials E-8

Exercise 1.14: Melting point of nano materials

[Problem]
1. Gr = f(r) ? for Cu sphere in liquid Cu
2. DTr = (Tmr  Tm) = ?

[Known]
d = 2 m, 2nm (r = 106 m, 109 m)
Tm = 1358 K, Vm = 63.5/8900000 m3
g = 0.144 J m2, L = 13300 J mol1

Thermodynamics and Kinetics of Materials E-9

 Exercise 1.14: Effect of radius

Gr = G + DGg = G + 2gVm / r (cf. Eq. 1.58)

Gr  GL (so that the sphere can grow in the liquid)

i.e.: GL  G  2gVm / r
= LDT / Tm (Eq. 1.17)
2gVmTm
hence: DT 
rL
DT (r = 1 m) > 0.2 K
DT (r = 1 nm) > 200 K

Thermodynamics and Kinetics of Materials E-10

 Exercise 2.1: Diffusion of carbon in iron sheet
[known] 1.4 wt% iron @ 1000°C
steady-state diffusion
C (wt.%) C (kg m-3) DC (10-11 m2s-1)
0.15 11.25 2.5 0.15 wt%
2 mm
1.4 105.0 7.7
[problem] dC
? J=? 0.8 wt% = 60 kg m-3
dy
assume: (linear)
D = a + bC D (10-11 m2s-1)  1.876 + 0.0555C (kg m-3)
0.002 105.0

 1.876  0.0555C dC

dC
J  D  const. 
11
J dy  10
dy 0 11.25

Thermodynamics and Kinetics of Materials E-11

 Exercise 2.1: Diffusion of carbon in iron sheet

J  2.4  10-6 kg m-2 s-1 solution of problem (c)

dC J

dy D
 dC   dC  D0.15 2.5
       0.32 prob. (b)
 dy  1.4  dy  0.15 D1.4 7.7
C y

 1.876  0.0555C dC   2.4  10 5

 dy (C in kg m-3 , y in m)
105 0
C y

 140  312C dC  240 dy

1.4 0
(C in wt%, y in mm)

C  3.43  1.52 y  0.45 (C in wt%, y in mm)

Thermodynamics and Kinetics of Materials E-12

 Exercise 2.1: Diffusion of carbon in iron sheet

C  3.43  1.52 y  0.45

1.4
C wt %

1.0
The concentration is not
linear distributed due to
0.5
the dependence of DC on
0.15 the carbon concentration
0 1 2
distance in mm

Thermodynamics and Kinetics of Materials E-13

 Exercise 2.5: Application of the sine-solution
C
C0
4C 0 
1 2i  1x
C ( x) 


i  0 2i  1
sin
l top-hat distribution
[problem]
(a) plot the first two terms
(b) t for A2 < 5% A1 0 l x
(c) t for C = 5% C0 at 20°C if: (i) l = 10 mm, (ii) l = 100 mm
Table 2.1 (p.68): D  0.1 exp 13400 RT 
D(20°C) = 4.0810-4 mm2s-1

Thermodynamics and Kinetics of Materials E-14

 Exercise 2.5: Application of the sine-solution
C 1st harmonic 1st+2nd
solution of (a) harmonics

C0

t=0
4C0 x sum of the
C1  sin
 l first 100
harmonics
4C0 3x
C2  sin
3 l
0 l/4 l/2 3l/4 l x
2nd harmonic

Thermodynamics and Kinetics of Materials E-15

 Exercise 2.5: Application of the sine-solution
amplitude
solution of (b)

C ( x, t )  
4C0  ( 2i  1) 2  2 Dt 
 exp   sin
2i  1x

i 0 ( 2i  1) 
2
 l  l

4C0   2 Dt 
A1   exp  2  A2 < 0.05A1
  l 
 2 Dt 9 2 Dt
4C0  9 2 Dt    ln 0.15
A2   exp   l 2
l 2
3  l 2

t > 0.024 l2/D

Thermodynamics and Kinetics of Materials E-16

 Exercise 2.5: Application of the sine-solution
C
solution of (c) C0
t very long  t=0
only the 1st harmonic is significantly
4C0   2 Dt  x
C ( x, t )   exp  2   sin t = t1
  l  l
l 0 l x
 C ( x, t )dx
0
1 = 0.05 C0l

t1 = 0.282 l2/D D(20°C) = 4.0810-4 mm2s-1

for l = 10 mm: t1 = 19.2 h
for l = 100 mm: t1 = 1920 h (80 days)

Thermodynamics and Kinetics of Materials E-17

 Exercise 2.8: Information from a phase diagram
T
L

For the system in Fig.2.29 at T1:

T1
T G-xB curves
a) Draw possible a b c d
L a b g
b) Derive B-xB, aB-xB diagram
0 xB 1
c) Sketch diagrams to show aA, A, B across the diffusion
couple
T1
a b c d
d) Sketch the final composition profile if x0 lies
a b g
i) in ab phase-zone
ii) in a phase-zone
0 xB 1

Thermodynamics and Kinetics of Materials E-18

Exercise 2.8: Information from a phase diagram

T
L

a b g
T1
a b c d

0 xB 1

Thermodynamics and Kinetics of Materials E-19

Exercise 2.8: Information from a phase diagram

T
a b g
T1

Gg
Ga

Gb

a ab b bg g
0 xB 1

Thermodynamics and Kinetics of Materials E-20

 Exercise 2.8: Information from a phase diagram

T T
a b g a b g
T1 T1
B aB
GB 1

q q

p p


0
0 xB 1 0 xB 1

Thermodynamics and Kinetics of Materials E-21

 Exercise 2.8: Information from a phase diagram

1
A GB
GA B

a
a b g

a b g
- -
0
Distance Distance

Thermodynamics and Kinetics of Materials E-22

 Exercise 2.8: Information from a phase diagram

g
d
a b

c xB
b
b
L

x0
a
a

0
T

T1

Distance

Thermodynamics and Kinetics of Materials E-23

 Exercise 2.8: Information from a phase diagram

g
d
a
c xB
b
b
L

x0
a

0
T

T1

Distance

Thermodynamics and Kinetics of Materials E-24

 Exercise 3.5: Moving direction of GBs

Why grain boundaries move towards their centre of

curvature during grain growth but away from their
centre of curvature during recrystallization ?

Grain B deformed grain 1

recryst. grain
Grain A

deformed grain 2

Thermodynamics and Kinetics of Materials E-25

Exercise 3.5: Moving direction of GBs
 grain boundary migration always results in
a reduction in total free energy
 GG: 1) same GV for all grains
2) GBs move to reduce total GB area
3) larger grains grow, smaller ones shrink
4) a larger grain: concave GBs
so that GBs move towards the curvature centre
 Recryst.: 1) deformed matrix : higher GV
2) rectst. nuclei : lower GV
3) g much smaller than DGV
4) rectst. nuclei: convex boundaries
so that GBs move away from the curvature centre

Thermodynamics and Kinetics of Materials E-26

 Exercise 3.12: Misfit strain energy

Mg (rMg = 1.60Å) dissolve in Al (rAl = 1.43Å) to form a

substitutional solid solution.
To estimate the misfit strain energy for each Mg atom
DGS = 4d2V (3.39)
 : shear modules (= 25 GPa for Al)
d : misfit
V : volume of an Al atom

1) express the answer in kJ mol-1 and eV atom-1

2) what assumptions are implicit ?

Thermodynamics and Kinetics of Materials E-27

Exercise 3.12: Misfit strain energy
DGS = 4d2V
 = 25 GPa = 25  109 Nm2
d = (1.60  1.43) / 1.43  0.119
V = 4/3··(1.43  10 10 )3  1.225  10 29 m3
DGS = 4d2V  1.73  10 20 J atom1
 10 kJ mol1 N0 = 6.0231023
 0.1 eV atom1 1 eV = 1.610-19 J
implicit assumptions:
1) dilute solutions (Mg atoms separated by large distances)
2) continuum matrix

Thermodynamics and Kinetics of Materials E-28

 Exercise 5.6: Growth of ferrite slabs in austenite

Fe-0.15wt%C alloy:
austenitized above A3 and then quenched to 800°C,
ferrite nucleates & covers the austenite grain boundaries.

a) draw profile: composition ~ distance

b) derive expression: ferrite thickness ~ time
c) plot curve: thickness ~ time, when D is given
d) try to extend the above curve to long times ?

Thermodynamics and Kinetics of Materials E-29

Exercise 5.6: Growth of ferrite slabs in austenite

temperature, C 900 A3 g
800
a b
727C
700 A1 0.76

600 a

500
0 0.5 1
weight percent carbon

Thermodynamics and Kinetics of Materials E-30

Exercise 5.6: Growth of ferrite slabs in austenite
problem (a)
C

a g

0.4
b

Cg
g

0.2
C0
a

Ca
a

y
900

800

700

600

500
T

Thermodynamics and Kinetics of Materials E-31

 Exercise 5.6: Growth of ferrite slabs in austenite
problem (b)
For unit area of interface
to advanced dl, a volume
of 1·dl must be converted
a g
from g (Cg) to a (Ca), i.e.
Cg 2l (C0  Ca )
L (CgCa)·dl moles carbon
Cg  C0
l must be rejected, which is
equal to the diffusion flux
C0
through unit area in g in
L dC C g  C0
 time dt: D(dC/dy)dt
Ca dy L
y

Thermodynamics and Kinetics of Materials E-32

 Exercise 5.6: Growth of ferrite slabs in austenite

carbon rejected from a = diffusion flux in g dC C g  C0


dy L
( Cg  Ca ) ·dl = D ( dC/dy ) dt
2l (C0  Ca )
L
Cg  C0
dl D (C g  C 0 ) 2
 
dt 2l (C0  C a )( C g  C a )
integration yields:
C g  C0
l  Dt
(C0  C a )( C g  C a )
x g  x0
if Vm is constant l   Dt
( x0  xa )( x g  xa )
Thermodynamics and Kinetics of Materials E-33
 Exercise 5.6: Growth of ferrite slabs in austenite
problem (c)
C g  C0
l  Dt D = 3  10 12 m 2 s 1
(C0  C a )( C g  C a )
Ca = 0.02 wt%
T C0 = 0.15 wt%
900 g
Cg = 0.32 wt%
800
a
700
l  1.5 10  6 t 1/2
600

500
0 0.2 0.4
C

Thermodynamics and Kinetics of Materials E-34

 Exercise 5.6: Growth of ferrite slabs in austenite
problem (d) 40 lmax = 36.5 m

half-thickness, m
at longer times, the diffusion
30
fields of adjacent slabs begin
to overlap reducing dl/dt. 20

when the transformation is 10

complete, volume fraction 0
0 200 400 600
of g : time, s
f g  1  lmax R  R = 150 m
3


fg  C0  Ca  Cg  Ca 
a
lmax = 36.5 m g
lmax

Thermodynamics and Kinetics of Materials E-35