Phase Transformation I I

Phase Transformation II
Instructor: Kazuhiro Hono
Professor,
f
Program
g
off Materials Science and Engineering,
g
g
Grad. School of Pure and Applied Sciences, Univ. Tsukuba
and
National Institute for Materials Science
http://www.nims.go.jp/apfim/
Main Textbooks:
D. A. Porter and K. E. Eastering,
g, and M. Y. Sherif,, Phase Transformations in
Metals and Alloys 3rd Edition, CRC Press
T. Nishizawa, Thermodynamics of Microstructures, ASM Intermational, 2008
JJ. W.
W Martin,
Martin R.
R D.
D Doherty,
Doherty and B.
B Cantor,
Cantor Stability of microstructure in metallic
systems, 2nd edition, Cambridge Univ. Press, 1997.
Many of the figures in this lecture note are copied from the above textbook and they are copyrighted by
the original author(s) and publisher(s).
publisher(s) Permission of use for the class room is deeply appreciated.
appreciated
Ai
Aim
To gain basic knowledge on how to control microstructure of
materials - in both bulk and thin films
Contents
1. Brief review of thermodynamics and phase transformation
2. Diffusional Transformations in Alloys and Relevant Topics
3 Diff
3.
Diffusionless
i l
T
Transformations
f
ti
iin All
Alloys
4. Solidifications of Alloys
Brief review of thermodynamics and

phase diagrams
Free energy
Fe @ 1 atm
liquid
1539
C
1400
C
(bcc)
(bcc)
(fcc)
(bcc)
l
(fcc)
910
C
910
C
(bcc)
Free energy: G
G = H TS
H: enthalpy
S: entropy
Potential energy
1400
C
1539
C
Entropy, enthalpy and free energy

Entropy increases in
nature
Enthalpy: H
HAB=nAAeAA+nBBeBB+nABeA
G = H - TS
S kBlnW
S=k
l W
B
HB
HABmix>0
HA
H=(1-x)HA+xHB
HB
HA
HABmix=0
xB
SA
GB
HB
HABmix<0
HA
GA
xB
xB
Phase separation
H
T=T1
G
G=H-T1S
G1
Gm
G2
-T1S
A x1
x2 B
Gm
T1>T2
T=T2
G>Gm=x1G1+x2G2
G
GB
GA
SB
Smix
Ideal solid
solution
GA
entropy S
GB
(n n )!
W 1 2
n1!n2 !
G=H-T2S
-T2S
A
Spinodal decomposition
G
G2
Gm
G1
x2
x1
XB
distance
Free energy and phase diagram
T3>T2>T1
T=T3
HABmix~0: ideal solid solutionn
e.g., Cu-Ni, Au-Ag
T3
T3
T=T2
l+
T2
T2
l
+l
T1
T1
T=T1
l
G
x
B

T=T4
HABmix>0: AB repulsive
T4
e.g. Au-Ni
T4
T=T3
T2
+l
+l
T2
T1
T=T2
l
G
T3
l
l+
T3
1+2
T=T1
l
T1
x
B
2 1
B A
Free energy and phase diagram 3

T=T4
G
HABmix>>0: AB strongly repulsive
e.g. Cu-Ag, Al-Si

T4
T4
l+
T=T3
T3
+l
+l
T3
T2
T=T1
l
x
B
B A
1+2
2
T2
T1
B
T=T2
l 1 + 2
l +
T=T4
HABmix<0: AB attractive
e.g. Au-Cu
l
A
T4
B
T=T3
G
l
+l
+l
T=T1
l
T1
B
T=T2
l+
T2
T3
B A
Enthalpy and phase diagram

Intermetallic compound
TiAl, NiAl, Ni3Al
Hms<Hml<0
Hms<Hml<<0
Hms>Hml>0
Hms>Hml>>0
L10
L12
Diffusional Transformations in Solids

Poter and Eastering 2nd edition
Page 251
Types of Diffusional Transformations

precipitation
p
p
eutectic
ordering
massive
polymorphic
(disordered)(ordered)
Fig. 5.1
Homogeneous Nucleation in Solids

G = -VGv + A + VGs
4
G r 3 Gv Gs 4r 2
3
r*
2
(Gv Gs )
G*
16 3
3( Gv Gs ) 2
Homogeneous nucleation rates

Gm
G *
N hom C0 exp
exp
kT
kT
G*
16 3
3( Gv Gs ) 2
constant
If a small amount of materials with the composisition XB is
removed from , the total free energy of the system decrease by
G1 A (1 X B ) B X B
If a small amount of b is created in , the total free energy of

the system increase by
G2 A (1 X B ) B X B
Driving force for nucleaton
Gn G2 G1
Gn
G v
Vm
For dilute solution,
total driving force for

the transfromation
Gv X X 0 X e
The driving force for nucleation increases as
supersaturation increases
Gv with X as T
Homogeneous nucleation rate for T

Gv X X 0 X e T
G*
16 3
3( Gv Gs ) 2
St i energy
Strain
Temp
perature (T)
conc.nuclei
atomic mobility
Gm
G *
N hom C0 exp
exp
kT
kT
Transformation
Time (t)
Assumptions:
p
1. nucleation rate is constant but not true
2. nuclei are spherical : Al-Ag, Cu-Co - not applicable for rArB, e.g. Al-Cu
Nucleation
Nucleation will be dominated by whatever nucleus has the minimum activation
energy
gy barrier G*
G*
16 3
3( Gv Gs ) 2
Reduction of is most effective

incoherent nuclei
homegeneous nucleation vertually impossible
orientation relationship (OR) to form coherent
i t f
interface
Formation of coherent nuclei Gs
S it bl shape
Suitable
h
will
ill change
h
Gs
and have different structure
GP zones (metastable coherent precipitates or
atomic cluster)
fcc
fcc
Heterogeneous nucleation
suitable nucleation sites:
excess vacancies, dislocations, grain boundaries, stacking faults, inclusios,
free surfaces
Ghet V (Gv Gs ) A Gd
Nucleation on grain boundaries
ignoring misfit strain energy, embrio shape would be that minimize A
incoherent GB
2 cos
the excess free energy
G VGv A A
Homework 2: derive the critical nuclei can be expressed as
r* 2 / Gv
Heterogeneous Nucleation II
Let's define a shape factor as
*
*
Ghet
Vhet
S ( )
*
*
Vhom
Ghom
o
o
Home Works 2: derive the following shape factor:

1
S ( ) (2 cos ) 2 (1 cos ) 2
2
Shape factor for more complicated case:
triple
p p
point
grain corner
G*hom
G*het
Heterogeneous nucleation (contd)

nucleation at prior precipitate
with OR
S. Q. Xiao et al. p
phys.
y Stat. sol. 131, 333 ((1992).
)
Ti2AlC in Ti-52Al-3C alloy.
(0006)Ti2AlC//(111)TiAl, [11-20]Ti2AlC//[01-1]TiAl
Heterogeneous Nucleation III

1. homogeneous sites
2 vacancies
2.
3. dislocations
4. stacking faults
5. GBs and interphase interface
6. free surface
Dislocations
reduction of lattice distortion

G*
16 3
3( Gv Gs ) 2
S. P. Ringer, K. Hono, I. J. Polmear and T. Sakurai, Acta Mater 44,
1883 (1996).
(1996)
Stacking faults
a
a
a[110] [121] [211]
6
6
(0001) ' //(111)
[1120] ' //[110]
L. Reich, S. P. Ringer and K. Hono, Phil

Mag Lett 79, 639 (1999).
J. M. Howe, U. Dahmen, and R. Gronsky, Phil. Mag. A 56, 31 (1987).
Heterogeneous Nucleation Rate

Gm
G *
N hom C0 exp
exp
kT
kT
C0: the number of atoms per unit volume
Gm
G *
N het C1 exp
exp
kT
kT
C1: concentration of heterogeneous nucleation sites
heterogeneous nucleation can occur at very

low driving force
*
*
Ghom
N het
Ghet
C
1 exp
N hom C0
kT
For small driving force, heterogeneous N

become dominant, but for large driving force,
homogeneous N becomes dominant
for GB nucleation
C1
C0 D
C1

C0 D
: GB thickness, D: grain size

2
for grain edges
C1

C0 D
for grain corners
see Table 5.1 in p. 278
Further reduction of interfacial energy by faceting

see page 111 for -plot
Faceting in homogeneous nuclei
K. B. Alexander et al. Acta Metall. 32, 2241 (1984).
Precipitate Growth
Nuclei will have the shape to achieve the lowest interfacial energy at the absence
of strain energy.
How about the growth of precipitates? See Section 5.3.1
Ledge Mechanism
hcp
A A A A A A A A A A
A A A A A A A A A A
A A A A A A A A A A
B B B B B B B B B B
C C C C C C C C C C
B B B B B B B B B B
C C C C B C C C C C
B B B B B B B B B B
C C C B B B B C C C
A A A A A A A A A A
A A A A A A A A A A
A A A A A A A A A A
B B B B B B B B B B
A A A A A A A A A A
B B B B B B B B B B
A A A A A A A A A A
B B B B B B B B B B
A A A A A A A A A A
fcc
G. C. Wetherly, Acta Metall. 19, 181 (1971).
Widmanstaeten morphology
after Wikipedia
Growth of incoherent interfaces

Fi k' 1st
Fick's
1 t law
l off diffusion.
diff i
eq 2.4
24
J B DB
C B
x
(C Ce )dx D
dx
dC
dt
dx
dx
D dC
dt C Ce dx
since dC/dx is time dependent,

p
it
cannot be solved analytically!
dC/dx can be approximated by C0/L

(C C 0 ) x
L C 0
2
D ( C 0 ) 2
2(C Ce )(C C0 ) x
Let Ce~C0
X 0
Dt
X X e
X 0
D
2( X X e ) t
where X0=(X0Xe)
Precipitate Growth
x
X 0
Dt
X X e
X 0
D
2( X X e ) t
1. x(Dt): paraboric law

2 vX0: growth rate is proportional to supersaturation
2.
3. v(D/t):
S. Y. Hu et al. Computer Coupling of Phase

Diagrams and Thermochemistry 31 (2007) 303
The paraboric law applies to spheroidal precipitates, too.
Reduction of growth rates due to the reduction of

supersaturation
t ti
The diffusion field to separate the

precipitates begin to overlap, the growth
rate no longer follow the above rule, and
the growth stops when the supersaturation
is lost.
Grain boundary precipitates

Particle growth by GB diffusion:
growth
g
o t rate
ate is
s much
uc faster
aste tthan
a tthat
at by tthe
e
volume diffusion
Grain boundary allotriomorph
L. Chen et al. ISIJ International, 48 (2008), 830.
Growth of plates or needles

Cr: increased Ce due to Gibbs-Thompson effect
L kr
L=kr
v
dx
D C
dt C Cr kr
r *
X X 0 1
r
dC/dx can be approximated by C0/L
(C C0 ) x
LC
2
DX 0 1 r *
1
k X X r r
r
The legthening rate is constant, i.e.,

xt:
t liner
li
growth
th
December 12, 2011
Growth rate of plates by ledge

v
DX 0
u
k X X e h
DX 0
v
k X X e
uh
Diffusion field do not overlap, so the

thickening rate is inversely proportinal
to the interledge spacing
Thickening
constant supply
g require
q
pp y
(nucleation) of ledges, but this cannot
be achievable, so the growth rate
show discrete change, indicating
ledge nucleation is rate controlling
TTT Diagram
f 1 exp( kt n )
f(t,T): fraction of transformed

1.
1
2.
3.
4
4.
5.
nucleation
l ti rate
t
growth rate
the density and distribution of h-nucleation sites
overlap of diffusion filed from adjacent particles
impingement of adjacent particles
1&2
3&4
site saturation
5
F. Katsuki et al. JAP 89, 4643 (2001).
discontinuous
precipitation
impingement
Kinetics for precipitation
cellular
ll l ttransformation
f
ti ((massive
i ttransformation)
f
ti )
4 3 4
V r (vt ) 3
3
3
The volume of the cell that does not nucleate until
4
4
V r 3 v 3 (t )3
3
3
The number of nuclei in a time increment d will be Nd
Nd. If particles do not
impinge each other
4
f V ' Nv 3 (t ) 3 d Nv 3t 4
3
3
0
t
for ff<<1 before impingement

p g
For randomly distributed nuclei,

f 1 exp((
For t<<1
f
Nv 3t 4 )
N
Nv 3t 4
N
In general, the kinetics for nucleation and growth follows
f 1 exp(( kt n )
J h
Johnson-Mehl-Avrami
M hl A
i equation
ti
n ranges from 1 to 4 depending on the nucleation mechanism
Kinetics for precipitation

f 1 exp( kt n )
Nv 3
Since exp(-0.7)=0.5, the time for 50% transformation t0.5 is

kt0n.5 0.7
t0.5
0. 7
k1/ n
Nv 3
rapid transformations are associated with large values of k, i.e., rapid nucleation
and
d growth
th rates
t
Precipitation in age-hardening alloys

Al-Cu alloys
Guinier Preston (G. P.) zones
Precipitation in Al-Cu alloys
T<150C
+GP zones +"
+"
+'
+'
+
150<T<180C
+'+
180<T<200C
+
Precipitation in Al-Cu alloy

"
GP
"+'
"
"
after T. Sato
Al-Cu contd.
GP
T<150C
+GP zones +"+'+
150<T<180C
150<T<180
C
+'+
180<T<200C
+
Precipitate size and density at different aging temperatures
T. Honma, Ph.D. thesis, Univ. Tsukuba 2005
Origin of GP zones
metastable miscibility gap
after H. Ohtani, Kitakyushu Inst. Tech.
Ground state of fcc alloys

P 4 / mmm D41h
13
Pmmn D2h
I 4 / mmm D417h
Ground state phase in Al-Cu alloys and

GP zone
Metastable miscibility gaps for the binary

systems in which GP zones were reported
Heterogeneous
g
nucleation at prior precipitates
Al-2.5Cu-0.5Si-0.5Ge
160C 0.5, 3, 10 h
190C 180s and 10 h
T. Honma, Ph.D. thesis, Univ. Tsukuba 2005
Al-Ag alloy
a0 1 GP
0 1 + GP zones 2 +' 3 +
(0001) ' //(111) a[110] a [121] a [211]

6
6
[1120] ' //[110]
K. T. Moore and J. M. Howe,

Acta mater. 48, 4083 (2000)
R. B. Nicholson and J. Nutting, Acta. Metall. 9, 332 (1961).
Quenched-in Vacancies
Cv (T ) exp( Ev / kT )
Ts
T
Cv (T1 ) exp( Ev / kT1 )
exp 0
Cv (T0 ) exp( Ev / kT0 )
T1
420K
D(T=420) D(Ts)
D(T=420)~D(Ts)
373K
T2T0
T2
T1
Hv
T1T0
T0
t
A
B
A
t
Hv
Two step aging
Precipitate Free Zone

GB
cB
Al G alloy
Al-Ge
ll
K. Oh-ishi, Acta Mater. 2009
cB
Al-Zn-Mg-Cu alloy
Age hardening
Cutting
O
Orowan
morphology
Cutting
f
Gb 1 1
2
ln
4 1 r0
Orowan
for spherical particles
Shape factor and precipitate shape
Nabarro curve for precipitate shape af

cuntion of shape factor
Shape effect of age hardening
J. F. Nie et al. Mat. Sci. Forum. 217, 1257 (1996).
Age-hardenable Mg-0.3Ca-0.6Zn alloy

Mg-0.3Ca peak aged (200C-28h)
Mg2Ca
Addition of Zn cause enhanced precipitation hardening

and creep resistance:
J.F. Nie, B.C. Muddle, Scripta Mater. 37 (1997) 1475.
Best
Hv~25
Hv~10
Mg-0.3Ca-0.6Zn peak aged (200C-1.4h)

K. Oh-ishi et al. MSEA, 25, 177 (2009).
Microstructure of peak aged Mg-0.3Ca-0.6Zn

HAADF image
High resolution HAADF
(0001)
(00
001)
BD // [1010]
BD // [1120]
1 60
M 1.60
Mg
[1010]
-6
Mg
Ca/Zn
1.97
Ca
-4 kJ/mol
Zn
-22
1.48
[1120]
Monolayer ordered G.P. zones form on the basal planes.
Effective precipitate morphology in Mg alloys
J. F. Nie, Scrita Mater. 48, 1009 (2003).
Prismatic plates in Mg-Ca-In alloy
Mg 1.60
-6
6
1 97
1.97
Ca
-4
4 kJ/mol
-35
35
In
1.62
C. L. Mendis et al. Scripta Mater. (2010)
Spinodal and Nucleation-Growth
d 2G
0
dx 2
d 2G
0
dx 2
d 2G
0
dx 2
Spinodal
d 2G
0
dx 2
D<0: uphill diffusion
Nucleation & Growth

d 2G
0
dx 2
D>0: downhill diffusion
Spinodal Decomposition
If x0 composition decomposes to x0x, the total chemical free energy change will be
Gc
1 d 2G
( x ) 2
2 2dx 2
x cause interfacial energy gradient energy G

x
G

if size of atoms are different, x causes strain energy Gs

Gs 2 (x) 2 E Vm
1 da
a dx
E
a
fractional change in lattice parameter per unit composition change

: Poisson's
P i
' ratio,
ti Vm: molar
l volume
l
d 2G 2 K
( x ) 2
G 2 2 2 2 E Vm
dx
2
2K
d G / dx
d 2
2
d G 2K
2 2 2 E Vm
dx 2
when
h =
d 2G
2 2 E Vm
dx 2
Experimental work on spinodal

K. B. Rundman and J. E. Hilliard, Acta
Metal. 15, 1025 (1967).
E Vm
Applications of spinodal decomoposition in permanent

magnets
FeCo-rich and NiAl-rich '
Fe-rich phase
NiAl-rich phase
850 2h then quenching
Coercivity
y by
y Shape
p Anisotropy
py
Hc I ( N 2 N1 )
I I I '
FexCo1-xNiAl
N d
N:
demagnetization
ti ti ffactor
t
Anisotropic (Alnico)
Alnico 8 DG
Orientated particles
p
View H
H
View // H
8009h in a magnetic field
Fe-Cr-Co pemanent magnets

Spinodal decomposition between Cr-rich and FeCo-rich
Half of Co with comparable magnetic properties with Alnico
Cold rolling and drawing are possible
Fe-(24-28)Cr-(8-15)Co-1.5Ti
Fe
(24 28)Cr (8 15)Co 1 5Ti
Br: 8-1.5 T, Hc: 48- 60 kA/m, (BH)max: 40 - 76 kJ/m3
Effect of magnetic trasition on phase diagram
T. Nishizawa, Thermodyanmics of Microstructures, ASM, 2008.
T. Nishizawa, Thermodyanmics of Microstructures, ASM, 2008.
Sm2Co17/SmCo5 sintered magnet

Sm(Co0.72Fe0.20Cu0.055Zr0.025)7.5
Co63.5Fe17.7Sm11.8Cu4.9Zr2.2
Coercivity
y Hci, kOe
15
Sm(Co
( 0.72
Fe0.20
Cu0.055
Zr0.025
)7 5
0 72
0 20
0 055
0 025 7.5
Isothermal aging at 820Cx6h.
10
0
300
400
500
600
700
800
900
Quenching Temperature Tq, C
T
1200C
1150C
800C
sintering
solution treatment
aging
slow cooling
400C
Time
TEM
Tq = 820C
[01 1 0]
0.071/nm
[21 3 0]
[0001]
Tq = 520C
0.070/nm
Sm(Co0.72Fe0.20Cu0.055Zr0.025)7.5
Sm2Co17
SmCo5
Z-phase
Z-phase
Sm5Co1
0001
Sm2Co17
Reasons for the coercivity increase

1. Hc of SmCo5, increased with the Cu content.
Sm(Co0.71Fe0.15Cu0.13)5 Sm(Co0.62Fe0.13Cu0.24)
2.
3.
From Lectard etal.
Dynamic phase separation in thin films

C C
Co-Cr
*3
3K
K. Hono et al.
al Appl.
Appl Phys
Phys. Lett.
Lett 66,
66 1686 (1995)
*4 K. Hono, Prog. Mater. Sci. 47, 621 (2002)
Ts: 227, 75 at.% Co
At
Atoms
are mobile
bil only
l on surface
f
*4
*3
Ts ~ 327
CoCrTa thin films
Phase separation in Cu-Ni thin films

*1
Tm/2
*1 T. B. Massalski, Binary Alloy Phase Diagrams, 2nd Ed. (ASM, Metals Park, OH, 1990)
*2 H. Katayama-Yoshida et al., Jpn. J. Appl. Phys. 46 L777 (2007)
Miscibility gap below 356C. Phase separation is thermodynamically

possible but kinetically impossible.
Cu30Ni70: CPP~ 50 mV
~ 50 nm
~ 50 nm
~ 70 nm
60
50
~ 70 nm
Concentration of Cu (at.%)
40
30
20
10
60
1.0
Binominal
Composition
Average comp.
0.6
Binominal
Cu30Ni70
0.4
Comp.
02
0.2
Cu-rich
Normalized C
N
Count
Normalized C
Count
1.0
0.8
16 / 20
Ni-rich
0.0
Concentration of Cu (at.%)
40
30
20
50
Cu46Ni54
0.8
10
Binominal
Composition
Average comp.
Binominal
0.6
Comp.
0.4
02
0.2
Cu-rich
Ni-rich
0.0
40
50
60
70
80
Concentration of Ni (at.%)
90
40
50
60
70
80
Concentration of Ni (at.%)
90
17 / 20
+ 5 at.%
t % + 5 at.%
t%
+ 5 at.%
t % + 5 at.%
t%
Cu-rich
C
i h face
f
Average Ni-rich
A
Ni i h face
f
Cu25Ni75
Cu20Ni80
Cu15Ni85
Cu-rich
C
i h face
f
Average Ni-rich
A
Ni i h fface
Cu45Ni55
Cu40Ni60
Cu35Ni65
Cu-rich region form pseudo-one-dimensional structure.
18 / 20
~ 30 at.%
~ 15 nm Cu-rich
Ni-rich
~ 65 nm
Cu30Ni70 CPP~ 50 mV
Cu46Ni54 CPP~ 480 mV
High property sample contains clear Cu enrichment

surrounded by Ni-rich region.
Phase separation in 8mol% Y2O3 stabilized ZrO2

- ion conductor for SOFC
8mol%Y2O3 stabilized ZrO2

As sintered
2 20 85
22085nm
1000Cx2000h
22085nm
Y>5 at.%
Particle Coarsening
N-G
Coarsening
2Vm
X r ~ X 1
RTr
t
N-G
Coarsening
(1.61)
GVm/r
t1/3
t
3
r r 3 kt
where
k D xe
for diffusion controlled growth
d r
k
2
dt
r
when coarsening is controlled by pipe or grain boundary diffusion, coaresening deviate from t1/3
Important for heat resistant alloys! Decrease D, , xe
Example: particle coarsening
r3~k(fe)t
D.M. Kim, A.J. Ardell / Acta Materialia 51 (2003) 4073.
Fe-C binary phase diagram

A4
A3
(a) (b)
A1
A3
A1
(a)
(b)
A2
Precipitation of ferrite from austenite

grain boundary allotriomorph
(a)
(b)
coherent
(c)
habit p
plane irrational
4-20from {111}
OR: Nishiyama-Wasserman or Kurdjumov-Sachs
incoherent
intragranular
g
ferrite
(d)
at large supercooling only

incoherent interface can migrate
intragranular ferrite
(DGB dependence)
Widmansttten sideplate
austenite()ferrite() transformation
(a)
(b)
OR
(c)
Fe-0.34C
(a) Grain boundary allotriomorphs:
nucleate
l t att BGs.
BG At high
hi h T,
T curved;
d att
low T, facet.
(d)
(b) Widmansttten side plates: nucleate

at BGs, but grow along well defined
matrix.
(c) Intragranular idiomorphs: roughly
equi-axed nucleate within grains.
(d) Intragranular plates: nucleate within
g
grains.
(e)
(f)
Fe-1.2C steel
(e) GB allotriomorphs and intragranular
idiomorphs of Fe3C
(f) Widmansttten Fe3C
R. W. K. Honeycombe and H. K. D. H. Bhadeshia, Steels- microstructure and properties, 2nd ed. Edward Arnold, 1995.
TTT of
f 1 exp(kt n )
grain size
since exp(-0.7)=0.5
0.7
t0.5 1/ n
k
hypoeutectoid
T>Tw: grain boundary allotriomorph

T<Tw: Widmansttten
0.23 wt%C, 1.2%Mn
1150C air-cooled
900C air-cooled
1150C air
1150C furnace
cooled
microstructure changes
depending on cooling rate
0.4 wt%C
Cellular Precipitation
Mg17Al12

Mg-9at.%Al
(a)
(b)
1 h@ 220C-> 2 min@310C
20 min @ 220C->90s@277C
discontinous precipitation
the reason why cells develop in some alloys and not in others is not fully understood
not desirable in view of mechancial properties
Discontinuous precipitation
F. Findik, J. Mater. Sci. Lett. 17, 79 (1997)
Prangnell et al. Acta Metall. Mater. 42, 419 (1994).
Pearlite Reaction in Fe-C: eutectoid
Fe3C
Nucleation and growth of pearlite

coherent immobile
OR
coherent mobile
OR
which phase appear first depends on GB

structure and composition
proeutectoid
phase
S0 S *
1
T
v kDc (T ) 2
experimental
calculated for the

volume diffusion of C
v kDB (T )3 : boundary diffusion controlled
Bainite: mixture of ferrite and carbides
direct
transformation to
pearlite
Bainitic Transformation
>550C
550C
350-550C
Upper Bainite
pearlitic and bainitic growth

no OR
austenite
pearlite
OR
bainite
Pearlite: cementite and ferrite have no spcific OR to the

austenitic grain in which they grow
Bainite: cementite and ferrite have an OR within the grain
KS
mixture of ferrite
and carbides
Lower Bainite
diffusivity of carbon is low
austenite and carbides precipitate with OR
carbides either cementite or metastable ones ()
cementite or
-carbides
austenite
bainite growth is controlled by C diffusion

even though surface relief appears
Effect of alloying elements in Fe-C

Ni, Mn, Co
Si, Al, Be, P

Ti, V, Mo, Cr
c
H
exp
c
RT
ln
H H H a
austenitic
steel
C, N, Cu, Zn
c
H
ln
c
RT
H is the differencce between the heat absorved per unit of

solute dissolving in g and a phases
B, Ta, Nb, Zr
ferrite formers: H<H so H>0

austenite
t it formers:
f
H>H
H so H<0
H 0
solid
solution
R. W. K. Honeycombe and H. K. D. H. Bhadeshia, Steels- microstructure and properties, 2nd ed. Edward Arnold, 1995.
Effect of microalloying
Addition of alloying elements is to increase the hardenability
hardenability, ii.e.
e to delay the time
required for pearlitic reaction to obtain bainite and martensite, allowing slower cooling
rate to obtain fully martensite
aistenite
i t it stabilizer:
t bili
M
Mn, Ni
Ni, C
Cu
ferrite stabilizer: Cr, Mo, Si
carbide former: Cr
Cr, Mo
Mo, Mn - partition in
carbides
ferrite stabilizer: Si - partition in ferrite
X: uniform in austenite
X must partition in pearlite reaction reduce pearlite growth
Partitioning
g of X
Cr: carbide former
At equilibrium, X will have different Cx in (Fe) and (Fe3C)

Partitioning
carbide former, Cr, Mo, Mn:
Si:
ferrite stabilizer must

partition
T~A1
equilibrium partitioning: diffusion of X control the growth of pearlite
T~nose (600C)
X: ferrite stabilizer partitions
X: austenite stabilizer Ni
pearlite grows without partitioning
X: carbide former Mo, Cr
solute drag effect at interface
pearlite w/o partitioning
Effect of alloying elements on the kinetics of

the ferrite reaction
solute
l t d
dragg effect
ff t
interface dragg Mo
(a) growth with partition of solute X between a/g under local equilibrium donditions:
Mn, Ni - controlled diffusivity of X
(b) growth with no partition of X between a/g under local equilibrium conditions: Si,
Mo, Co, Al, Cr, Cu - diffusivity of C - solute dragg effect
TTT of low alloy steels

carbide former: Mo,
Cr: solute dragg effect
0.4C-1.0Cr-0.2Mo-1.0 Mn
0.4C-1.0
0.4C
1.0 Mn
pearlite
bainite
0.4C,-0.9Cr-1.0 Mn
0.4C-0.8Cr-0.3Mo-1.8Ni-1.0 Mn
poisonin of ferrite
nucleation sites by th
eprecipitation of Xcarbide clsters
austenite stabilizer does not have

to be partitioned
Continuous Cooling Transformation (CCT) diagrams
Seels with carbide forming elements

Steels
St
l with
ith carbide
bid fforming
i elements,
l
t
Mo, W, Cr, Ti, V that form carbides more stable than
cementite
Fe-4%Mo-0.2%C
Fe 4%Mo 0 2%C transformed 2 h at 650C
interphase precipitation
Fe-0.75V-0.15C 5 min @ 725C
Massive Transformation
Massive Transformation
Cu Al
Cu-Al
pure Fe
Only
jump
O l a ffew atomic
t i distance
di t
j
No change in composition of phases
Interface is incoherent
Similar to recr
stalli ation
Similar
recrystallization
Martensitic Transformation
The effect of cooling rate

on the transformation
temperature of pure Fe
Fe.
massive ferrite
Ordering transformation
Intermetallic compound
TiAl, NiAl, Ni3Al
Hms<Hml<0
rA x A
1 xA
derivatives of bcc
Hms<Hml<<0
L10
L12
Let xA=0.5 and rA=1, then L=1

So this equation is valid regardless of alloy compositions
1st and 2nd order phase transformation

2nd order
A2B2
S
T
refer 1.2.7 for s
1st order
A1 L10
A1L1
AlL12
G
V
Cp
2G
1 H
S
2

T P T T P T
T P
Ferromagnetic transition
Ferromagnetic transition is also 2nd order transition in which the spin direction
is aligned by exchange interfaction, and it can be regarded as ordering of spins
Detection of order-disorder transformation

Note the integrated intensity of x-ray by a diffractometor
2
2 1 cos 2 2 M
e
I F p 2
sin cos
F: structure factor, p: multiplicity factor

1 cos2 2
2
sin cos
: Lorentz-polarization factor
e 2 M
: temperature factor
Fhkl f n e 2i ( hun kvn lwn )

1
For simple cubic, there is only one atom at (000) in a unit cell
F fe2i ( 0 ) f
F2 f 2
F2 is independent of h, k, and l and is the same for all reflections
s h2 k 2 l 2
x-ray diffraction appear for s=1,2,3,4, 5, 6, 8,9, 10, 11, 12, 13, 14, 16, ...
Detection of order-disorder transformation 2

N
Fhkl f n e 2i ( hun kvn lwn )

1
For body
F
b d centered
t d cubic,
bi th
there are ttwo atoms
t
att 0 0 0 and
d 1/2 1/2 1/2 iin a unit
it
cell
F fe2i ( 0 ) fe2i ( h / 2k / 2l / 2 ) f [1 ei ( h k l ) ]
F 2f
for (h+k+l) is even
F 0
for (h+k+l) is odd
F2 4 f 2
for (h+k+l) is even
111
222
F2 0
f (h
for
(h+k+l)
k l) iis odd
dd
s h2 k 2 l 2
x-ray diffraction appear for s=2,4, 6, 8, 10, 12, 14, 16, ...

N
h n kv
k n lw
l n)
Fhkl f n e 2i ( hu
1
For face centered cubic,, there are 4 atoms at 0 0 0,, 0 1/2 1/2,, 1/2 0 1/2,, 1/2 1/2 0
in a unit cell
F fe2i ( 0 ) fe2i ( h / 2 k / 2 ) fe2i ( h / 2l / 2 ) fe2i ( k / 2l / 2 )

f [1 ei ( h k ) ei ( h l ) ei ( k l ) ]
F 4f
for unmixed indeces (111), (200), (220)
F 0
for mixed indeces (100), (210), (112)
F 2 16 f 2
F2 0
for unmixed indeces
f mixed
for
i d indeces
i d
s h2 k 2 l 2
x-ray diffraction appear for s=3, 4, 8, 11, 12, 16,...

N
h n kv
k n lw
l n)
Fhkl f n e 2i ( hu
1
Simple Cubic:
F2 is independent of h, k, and l and is the
same for all reflections
s h2 k2 l2
s=1,2,3,4, 5, 6, 8,9, 10, 11, 12, 13, 14, 16, ...
bcc
F2 4 f 2
for (h
(h+k+l)
k l) is even
F2 0
for (h+k+l) is odd
s=2 4 6,
s=2,4,
6 8,
8 10,
10 12,
12 14
14, 16
16, ...
fcc
F 2 16 f 2
F2 0
for unmixed indeces

for mixed indeces
s=3, 4, 8, 11, 12, 16,...

Disordered A1 Cu3Au
The average atomic scattering factor fav
1
3
f Au f Cu
4
4
f av x Au f Au xCu f Cu
F f av e2i ( 0 ) f av e2i ( h / 2 k / 2 ) f av e2i ( h / 2l / 2 ) f av e2i ( k / 2l / 2 )

f av [1 ei ( h k ) ei ( hl ) ei ( k l ) ]
F 4 f av ( f Au 3 f Cu ) for unmixed indeces (111), (200), (220)
F 0
f mixed
for
i d indeces
i d
(100),
(
) (210),
(
) (112)
( )
F 2 16 f av
F2 0
for unmixed indeces
for mixed indeces
The diffraction intensity for disordered Cu3Au will be the same as the fcc alloy
Ordered A1 Cu3Au
F f Au e2i ( 0 ) f Cu e2i ( h / 2 k / 2 ) f av e2i ( h / 2l / 2 ) f av e2i ( k / 2l / 2 )
F f Au 3 f CCu
F f Au f Cu
XRD of A1 and L12 Cu3Au

Intensity (%)
1,1,1
100
90
80
70
60
50
2,0,0
40
3,1,1
30
2,2,0
20
2,2,2
10
0
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Intensity (%)
1,1,1
100
90
80
70
60
50
superlattice diffractions
2,0,0
40
1,0,0
30
1,1,0
3,1,1
2,2,0
20
2,1,0
2,1,1
10
3,0,0
2,2,1
2,2,2
3,1,0
3,2,0
0
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Phase Transformations II: Home work

due: January 24
24, 2011
Home work 1
Calculate F2 for B2 ordered CoAl using atomic factor for Co and Al as
fCo and fAl and discuss the XRD intensities for B2 ordered phase.
Discuss the XRD intensities for the B2 ordered FeCo, too.
B2
Home work 2
Calculate F2 for L10 ordered FePt using atomic factor for Fe and Pt
as fFe and fPt and discuss the XRD intensities for L10 ordered and A1
di d d alloy.
disordered
ll
Home work 3
Sh
Show
th
the method
th d tto d
determine
t
i th
the llong range order
d parameter
t using
i
the experimentally measured I100 and I111 for L12 ordered Cu3Au alloy.
You can ignore the Lorenz-Polarization, absorption and temperature
factors.
factors
L10 FePt
L12 Cu3Au
Phase Transformations II: Home work

Home work 1
Calculate F2 for B2 ordered CoAl using atomic factor for Co and Al as fCo and
fAl and discuss the XRD intensities for B2 ordered and A2 disorded alloy.
Discuss the XRD intensities for the B2 ordered FeCo, too.
B2
F f Co e 2i ( 0 ) f Al e 2i ( h / 2 k / 2 l / 2 )
F f Co f Al
for (h+k+l) is even
F f Co f Al
1
2
3
4
5
6
0.2862
0.2024
0.1652
0.1431
0.1280
0.1168
1
2
3
4
5
6
0.2868
0.2028
0.1656
0.1434
0.1283
0.1171
31.220
44.740
55.580
65.140
74.000
82.480
for ((h+k+l)) is odd
173.4
1000.0
37.4
147.5
39.8
281.6
31.160
44.640
55.440
64.980
73.820
82.280
100
110
111
200
210
211
0.2
1000.0
0.1
143.6
0.2
269.8
6
12
8
6
24
24
100
110
111
200
210
211
6
12
8
6
24
24
Long range order parameter

Long range parameter S
S
rA x A
1 xA
rA: fraction of A sites occupied by the right atoms

xA: fraction of A atoms in the alloy
For perfect long range order, rA=1, so S=1

When atomic order is completely random, rA=xA, so S=0
Consider
C
id 100 atoms
t
iin A
AuCu
C 3, xA=0.25
0 25
If 25 Au atoms are at the right sites, S=1
If only 22 Au are in the Au sites and 3 atoms are in the Cu sites, then
rA=22/25=0.88,
=22/25=0 88 so S=(0
S=(0.88-0.25)/(1.00-0.25)=0.84
88 0 25)/(1 00 0 25)=0 84
Any departure from perfect LRO causes the superlattice diffraction intensity
weaker Structure factors of partially disordered AuCu3 alloy is given (after
weaker.
Wallen)
F f Au 3 f Cu
F S f Au f Cu

Note that only superlattice diffractions are affected by S.

S2
I100 ( S )
I100 ( S 1)
Disorderorder phase transformation

1. Continuous change from sort range order to long range ordering (no
nucleation barrier, spontaneous) - only in 2nd order transformation or with a
very high spercooling
2. Nucleation and growth of ordered domains from disordered matrix
Antiphase boundary
Measurement of degree of order from XRD

I = L2 ((fA - fB) 2
Home work:
Draw the XRD intensity profile for strongly (001) textured L21 ordered Co2MnSi
alloy and discuss whether or not one can determine the degree of order from the
(001) textured film.
film
D03 and L21

Fe3Si
Cu2MnAl
Continuous ordering
S=0
S=0.3, L=0
S=1, L=1
Free energy as function of ordering

Landau theory
Heterogeneous and homoegeneous ordering

disorder
continuously
metastable ordered
state
disorder by
nucleation and
growth
order by
nucleation and
growth
spinodal ordering
W. A. Soffa and D. E. Laughlin, Acta Mater. 37, 3019 (1989)
order
continuously
Phase separation and ordering
2V ( k )c(1 c )
kB
1 i
i
i
Vi E AB
( E AA
E BB
)
2
Ti
Phase separation and ordering

T=T1
nucleation and growth of ordered

phase wihin the disordered phase
Precipitation of ordered from disordered

T=T2
congruent ordering: ordering

w/o change iin composition
continous ordering ot
->continous
-> precipitation of from
Congruent ordering
ordering without change in composition

Ordering and phase separation
spinodal decomposition of ordered

-> one of phase decomposed disorder
ordering and precipitation by NG

as-quenced disordered solid
solution is unstable with respect to
continuous
ti
ordering.
d i
Th
The ordered
d d
state is unstable with respect to
phase separation.
Spinodal decomposition after
ordering conditional spinodal
Spinodal decomposition of disordered phase and

subsequent ordering
M. Kompatscher et al. / Acta Materialia 51 (2003) 165175
Multitwin structure by A1L10 ordering

0.382 nm
Disordered A1 phase
0 382 nm
0.382
Ku=7107 erg/cc
Ms=1140 emu/cc
HA=120 kOe
Domain wall width: 4 nm
SDP: 34 nm
(BH)maxtheor: 51 MGOe
Tc~1300C
72.3
c
APB
c
(011) transformation twin
(111) deformation or
annealing twin
Discontinuous ordering
Coercivity of FexPt100-x bulk alloy
Bulk Alloy
K. Watanabe and H. Masumoto, Trans Jpn Inst
)
Met. 24,, 627 ((1983).
High coercive (001) thin film
M. Watanabe and M. Honma, Jpn. J. Appl. Phys.
Part 1 35, 1264 (1996).
ASQ
Y. Tanaka et al. J. Mag. Mag. Mater. 170, 289 (1997).
Microstructure & Hc of Fe-39.5Pt alloy
3.4 kOe
(BH)max=100 kJ/m3
2.5 kOe
Y. Tanaka et al. JMMM 170, 289 (1997).
Introduction of {111} twin by strain
M. H. Hong, K. Hono, M. Watanabe, JAP, 84, 4403 (1998).
FePt nanogranular materils

1 Tbit/in2
Size of FePt particles < 10 nm
FePt-Al2O3 granular film
Thermal instability
10 nm
KuV<kBT
KuV>kBT
High Ku materialsFePt, CoPt
Size dependence of ordering

FePt-Al2O3 granular thin films
SAED pattern
FePt 0.5 nm/Al2O30.5nm, 600C 54h
I(110)/I(111)
s2
I(110)/I(111)S=1
I(hkl) : the intergrated intensity of
the (hkl) diffraction ring
(110)
(111)
s2 = 0.64
ref. Y.K. Takahashi et al. J. Appl. Phys., 95, 2690 (2004)
Depression of Tc in nano sized particles

Helmholtz free energy
F = U - TS
where
h
U : iinternal
t
l energy Lennard-Jones
L
dJ
potential
t ti l
T : absolute temperature
S : entropy
kBlnW
1.0
Tc / Tc bulk
0.8
Uorder = Udisorder-kBNTln2
T = Tc
0.6
disorder
free surface with

vacuum
A1
Tc
annealing temp.
Ta
Tcnano
0.4
order
L10
0.2
0
0.5
10
Grain size (nm)

ref. Y.K. Takahashi et al. J. Appl. Phys., 93, 7166 (2003).
Phase-Field calculation
Critical size of ordering < 4 nm

depend on the matrix.
T. Miyazaki et. al Phys. Rev. B, 72, 144419 (2005)
5 nm
High Ku ferromagnets
Areal density and
bit size
4 Tbits/in2
500GB/p
500GB/
(750 GB/in2)
D=6.9 nm
bit size S = 10 nm10 nm = 100 nm2
670GB/p
670GB/
(1 TB/in2)
D~5 nm
S/N
Ferro
d ~ 4 nm for n=16
Superpara
750 GB/in2
A1
L10-FePt
600
K1~10 J/m4
(001)
Ku~7 x 106 J/m3

Superparamagnetic limit : 4 nm
A1 B2 ordering of FePt nanogranular films
K1~10 J/m4
Tm/2
Di d d F
Disordered
FePt
Pt
as sputtered A1
Ku~7 x 106
J/m3
H. Okamoto: Phase diagram for binary alloys p. 371,

1995.
L10-FePt
As-depo.
650C anneal
Order temp. > Tm/2

coarsening and coalescence
of the nanoparticles
D.H. Ping et al. J. Appl. Phys., 90, 4708 (2001)
Technical Target
Current CoCrPt media
5 nm
FePt-X
D~4 nm
aspect ratio > 1.5
Interlayer
Heat Sink or Soft underlayer
Heat Resistant Glass
Early work: MgO/FePt-SiO2 granular films

Tsub=500 C
200
220
Tsub=600 C
110
Dav 6.2 nm
T. O. Seki, Y. K. Takahashi, K. Hono, JAP (2008)
200
220
110
Dav 9.9 nm
Tsub=700 C
220
200
110
Dav 15 nm
FePt-C granular film

Oxi Si Subs / MgO(10)/ FePtC(50
Oxi.Si.Subs./
FePt C(50 vol%)
6 7 1.5
6.7
1 5 nm
FePt
C axis
MgO
a-SiO2
Hc = 10.6 kOe
Ku = 8106 erg/cc
A. Perumal, Y. K. Takahashi, K. Hono, APEX, 1 (2008) 101301.
Higher Hc FePt-C granular films

for heat assisted magnetic
g
recording
g (HAMR)
(
)
for continuous films
C.L. Platt et al, J. Appl. Phys. 92 (2002) 6104.

Ag reduces the ordering temperature for continuous FePt films
Oxi. Si/ MgO(5)/ (FePt)1-xAgx-50vol.%
Lowering L10 temperature: (FePt)Ag-C
L. Zhang Y.K. Takahashi, A. Perumal, and K. Hono, JMMM, 322, 2658 (2010).
Ag 20%
%
Ag 1
10%
Ag
g 0%
(FePt)1-xAgx-50vol.%C granular films @ 450C
L. Zhang Y.K. Takahashi, A. Perumal, and K. Hono, JMMM 322, 2658 (2010).
Recording by HAMR static tester

previsou work by HGST
A. Hirotsune et al, IEEE Trans. Magn. 46 (2010) 1569
Tc
RT
Co/Pd-B Film HC=11kOe,

=11kOe TC=300oC
Heat Assisted Magnetic Recording (HAMR)

B.C. Stipe et al. Nature Photonics 4, 484 (2010)
Track width 80nm

Min. bit length 25nm,
i.e. areal density of
325Gbits/in2
Write Field 5kOe
FePtAg-C HAMR Meida

800
600
HC.perp = 35kOe
HC.inp = 7kOe
Ku = 4.3107erg/cc
HC = 6kOe
perp
inp
M (emu
u/cc)
400
200
0
-200
-400
-600
800
-800
-40
-20
20
40
H (kOe)
Grain Size
6.21.4nm
6
21 4
120
Co
ount
100
80
60
40
20
0
10
12
D (nm)
RT
Tc
Heat Assisted Magnetic

Recording (HAMR)
Track width 92nm

Min. bit length 15nm
Areal density ~ 550Gbits/in2
(TAR static test HGST)
L. Zhang, Y. K. Takahashi, K. Hono, B. C. Stipe, J.-Y. Juang, and M. Grobis, IEEE Trans. Magn. 47, 4062 (2011).
Amorphous alloys and their

crystallization
Amorphous alloys by rapid solidification

melt spinning
melt-spinning
Ar gas
Induction coil
0.2 nm
A1
A2
A3
A4
A5
A6
A7
A8
Cu roll
~104 K/s
Other methods for amorphous formation

Gass atomization
Electron beam deposiiton
Sputtering
B. L. Zheng et al. Metall. Mater. Trans. B 40 (2009)
http://www.ourpromesse.com/Service.aspx
Mechanical milling/alloying
L. Schltz, Mat. Sci. Eng. 97, 15, (1988).
T0 lines
l
T0 line
1+2
xB
A
l
c c0
cl
+
xB
l
A
xB
segregation free solidification

is possible below T0
+
xB
Glass transition temperature (Tg)

T
viscosity
G
G
T
Tg
cooling rate
Tg0
Tm
Tg1
Tg2
Tm
glass forming range
Tg: the temperature at which the liquid

phase solidify with the amorphous
structure
t t
- viscosity
i
it ~10
1011 poise
i
Glass forming ability (GFA)

GFA: the critical cooling rate at which amorphous structure is frozen
Bulk forming metallic glass
mixing enthalpy Hmix<<0 (SRO)

atomic raius r/r
r/r>0.12
0.12 (dense packing)
atomic
multicomponet alloy (confusion rule)
composition cluse to eutectic
viscosity
amo
mg
Marginal glass former and bulk forming glass

crystal
Rc
T
amorphous
Amorphous alloy
metallic glass
time
Metallic glass
Tx Tg Tx Tm
QN: small
Tx<Tg
x
amo
mg
Tx
rN: small
QN: large rN: large

Tx>Tg
Tg
Tx
Structure characterization of amorphous alloys:

pair distribution function
p
g(r)
1.
0
2ro
4ro
ro
2ro
g(r)
1.
0
24 24
N( )
N(r)
12
6
2r
8 6
4ro
TEM images of amorphous alloy
no diffraction contrast in bright field image

halo p
pattern in SAED
XRD shows halo for the average

nearestt neighbor
i hb di
distance
t
Zr36Ti26Be40
isotropic maze pattern in HREM image
Magnetizatic properties of Fe based amorpous alloys
Applications of amorphous alloys

no crystal structure - zero magnetocrystalline anisotropy
soft magnetic materials
Ru
transformer and coke coil cores

20nm
MgO
g
Ta
FeCoB
FeCoB
Ta
CoZrTasoftunderlayer
soft magnetic underlayer for magnetic recording media
Ru
magnetic tunnel junction
Crystallization of amorphous alloy

primary
crystallization
Pi
Primary
crystallization
t lli ti
Condition for nanocrystallization

1.
Fast nucleation rate
2.
A number of het. nucl. sites
3.
growth is diffusion controlled
Polymorphic crystallization
AxBy
amorphous
or
amorphous
h
AxBy
phase transformation w/o change in
composition
p
M. Blank-Bewersdorff and U. Kster, MSE 97, 313 (1988).
similar to massive transformation
Eutectic crystallization
AxBy
amorphous AxBy
di
discontinous
ti
precipitation
i it ti
Primary crystallization
amo
G
A
B
C
D
AxBy
amo amo'+AxBy
volume diffusion controlled growth
Nanocrstalline soft magnetic materials

5 x 105
2 x 105
Co-based
Amorphous
New FINEMET
FeSiBNbCu FINEMET
Hitach Metals
Fe-M-B NANOPERM
Tohoku and ALPS
1 x 105
5 x 105
(Fe,Co)-M-B
HITPERM
CMU
e 2 x 105
100
After G. Herzer
1 x 105
10
Hc
(A/cm)
1/D
Silicon Steels
D6
FeSi6.5
0.1
0.001
amorphous
2 x 105
50NiFe
nanocrystal
y
0.01
Fe based
Fe-based
Amorphous
5 x 105
permalloy
1 m
1 nm
Mn-Zn Ferrite
Fe-Co alloy
1 x 105
0.5
1.0
1.5
2.0
2.5
Bs (T)
1 mm
Courtesy of Vacuumschmeltz
Grain Size D
Alloy name
Typical composition
FINEMET
FINEMET2
NANOPERM
HITPERM
Primary phase
Fe73.5Si13.5B9Nb3Cu1
Fe76.9Si11B9Nb2.5Cu0.6
Fe88Zr7B4Cu1
Fe44Co44Zr7B4Cu1
Bs(T)
Tc(C)
FeSi(D03) 1.0 - 1.2

FeSi(D03) 1.45
-Fe
1.5 - 1.8
-FeCo(B2) 1.6-2.1
<770
<770
770
>965
Phase separation in an amorphous

Fe77.5
77 5Si13.5
13 5B9Nb3Cu1 alloy
HREM
3DAP Cu map
ASQ
60 min@ 400C
K. Hono et al., Acta mater. 47, 997 (1999).
Amorphous phase decomposition and nanocrystallization of

-Fe from an Fe77.5Si13.5B9Nb3Cu1 alloy
Fe77.5Si13.5B9Nb3Cu1 alloy
Hmix=13 kJ/mol
f liquid
for
li id F
Fe-Cu
C
Convex upwards
with two minima
K. Hono et al., Acta mater. 47, 997 (1999).
Bulk amorphous alloys

Pd40Cu30Ni10P20
Zr41.2Ti13.8Cu12.5Ni10Be22.5
Zr52.5
52 5Ti5Cu17.9
17 9Ni14.6
14 6Al10
rather expesive alloys
MG
Metal
strong (hard) but brittle
http://www.liquidmetal.com/technology/default.asp
Liquidmetal
Zr41.2Ti13.8Cu12.5Ni10Be22.5
http://www.liquidmetalgolf.com/
Plasticity of bulk metallic glasses

metallic glass
crystal
A. Inoue et al. Acta Mater. 49 (2001), 2645.
Zr47.5Cu47.5Al5
G. Kumar et al., Scripta Mater. 57, 173 (2007).
Cu60Zr30Ti10
Cu60Zr30Ti10
A. Inoue et al., Mater.Trans. 2001,42(6),1149.

crystal
T
metallic glass
time
Is plasticity due to nanocrystalline microstructure?

Cu50Zr50
Cu60Zr30Ti10
Cu47.5Zr47.5Al5
A. Inoue et al. Acta Mater. 49 (2001),

(
) 2645.
M. Kasai et al. J. Phys. Condens.

Matter 14 (2002),
Matter.
(2002) 13867.
13867
Das et al. PRL(2005)

Inoue et al. PML 85 (2005) 221
Shear bands in melt-spun ribbons

Zr45Cu45Al10
367 kJ/mol
Zr47.5Cu47.5Al5
Poissons ratio:0.36-0.37
330 kJ/mol
G. Kumar et al., Scripta Mater. 57, 173 (2007).
Amorphous alloys >> Metallic Glass

crystal
Rc
T
amorphous
Amorphous alloy
metallic glass
time
Metallic glass
Tx Tg Tx Tm
QN: small
Tx<Tg
x
amo
mg
Tx
rN: small
QN: large rN: large

Tx>Tg
Tg
Tx
Eutectic crystallization of Pd40Ni40P20

metallic glass
A. J. Drehman and A. L. Greer, Acta metall. 32, 323 (1984).
Amorphous Phase Decomposition
G
a
spinodal
i d l
xB
Hlmix
i >0
after T
T. Koyama
Koyama, NIMS
Conditions for good glass forming ability

mixing enthalpy Hmix<<0
atomic
t i raius
i r/r>0.12
/ 0 12
multicomponet alloy (confusion rule)
composition
iti cluse
l
tto eutectic
t ti
dense packing
short range order
difficult to rearrange
amo
mg
bulk forming glasses are unlikely to phase separate in amorphous
Competition between glass formation and phase separation
miscibility gaps calculated

by CALPHAD
after T. Koyama, NIMS
773K
673K
573K
473K
Tg~800K
H. Kimura et al. Mater. Trans. 44, 1167 (2003).
Glass phase separation?
Zr36Ti24Be40
HZrTimix= 0 kJ/mol
HZrBemix=-43 kJ/mol
HTiBemix=-30 kJ/mol
L. Tanner, R. Ray, Scripta Metall. 14, 657 (1980).
Zr36Ti24Be40 - revisit
XRD pattern of Zr36Ti24Be40 As-Q
DSC curve of Zr36Ti24Be40 As-Q

Tg1
L. Tanner, R. Ray
Scripta Metall. 14, 657 (1980).
Tg2
Heating rate : 20K/min
TEM images of as-quenched Zr36Ti24Be40 ribbon
-10 24V 84mA
-2524V 36mA
200nm
L. Tanner, R. Ray,
Scripta Metall. 14, 657 (1980).
-2024V 53mA
D. Nagahama et al., Scripta Mater. 49, 729 (2003).
EF-TEM ASQ Zr36Ti24Be40 ion-milling
Be map
Ti map
Zr map
EF-TEM
Zr36Ti24Be40 heated to 390 at 20 K/min
HREM
Bright Field Image
Eutectic crystallization of Zr36Ti24Be40

20 K/min
B map
Be
Z map
Zr
Ti map
Be
Ti
Zr
200 nm
200 nm
200 nm
amorphous -(Zr,Ti)+Be2(Zr,Ti) eutectic crystallization
Distance , nm
Enthalpy of mixing and phase

separation of ternary metallic glass
T. Nishizawa, Thermodynamics of microstructures, ASM, 2008.
Miscibility gap island
T. Nishizawa, Thermodynamics of microstructures, ASM, 2008.
When mixing enthalpies are largely differnt

A - B, B - C : large negative
A-C
: small negative
A-A
C-C
B-B
Nu
umber of B
Bonds
A-B
B-C
A-C
T ~ Tg
Tg
M. Shimono and H. Onodera

NIMS
Tm
Temperature
Possibility of metallic glass nanostructure

control by phase separation
A - B, B - C : large negative
A-C
T ~ Tg
: large positive
C-C
B-C
A-B
A-A
A-C
Tg
Temperature
Number o
of Bonds
B-B
Two distinct p
phases in
supercooled liquid state
Tm
M. Shimono and H. Onodera

NIMS
Glass formation and phase separation

A
HAB<<0
HAC>0
miscibility gap
glass
B
HBC<<0
Two phase metallic glass

LaCuNiAl+ZrCuNiAlLa27.5Zr27.5Cu15Ni15Al15
100 nm
Hmix
Zr
La
Al
Cu
Ni
Zr
+13
-44
-23
-49
-38
-21
-27
La
Al
Cu
Ni
Zr51.3La5.2Cu7.2Ni20.6Al15.4
La43.7Zr10.6Cu22.3Ni9.5Al13.9
<0
-22
+4
100 nm
A. A. Kundig et al. Acta Mater. 52, 2441 (2004).
La27.5Zr27.5Cu15Ni15Al15
10 nm
Phase separation during solidification surface

f
fractal
f t l
Tg
Tg
T
Zr-rich
Ni-rich comp
La-rich
Cu-rich
Cu
rich
All sizes present from m to ~5 nm

Surface fractal dimension: 2.4
Nanoporus structure by selective dissolution
After dissolution of the La-based phase
Metallic Vycor
y
Porus metallic g
glass
A. Gebert, A. A. Kundig, L. Schultz, and K. Hono, Scripta Mater. 51, 961 (2004).
Cu43Zr43Al7Ag7 BMG with a large plastic deformation

Metallic glass
Metal
En
ngineering streess (MPa)
2000
1500
1000
Cu43Zr43Al7Ag7
500
KIST
0
0
10
Engineering strain (%)
D-S. Sung,
g O-J Kwon, E. Fleury,
y K-B Kim, J. C. Lee, D. H. Kim, and Y-C
Kim, Metals and Materials International 10, 575 (2004).
What is the reason for the large elongation?
Cu-Ag system
Phase separated Cu43Zr43Al7Ag7

Cu
After E. Fleury, KIST

3000
Cu43Zr43Al7Ag7
Zr
2500
Al
2000
~6 nm
m
4mm
1500
Ag
1000
7mm
~50 nm
500
8mm
0
20
30
40
50
60
70
80
Diffraction angle, 2
60
Cu
40
20
80
Compo
osition (%)
Relative Intensity (a.u.)
melt spun
60
Zr
40
20
20
Al
10
0
20
Ag
10
0
0
10
15
20
Distance (nm)
Selected volume : 1.7x2.5x23 nm
J.Oh et al. Scripta Mater. 53, 165 (2005).
Forced alloying by intense strain

Cu-Zr system fcc-bcc
Cu-Ag system
Hmix:Negative
Hmix: + 6
fcc-fcc
150 pass
Zr/Cu/Ni/Al cold rolling
Cu/Ag cold rolling
A. Sagel et al, Acta Mater. 46, 4233 (1998).
H. W. Sheng, G. Wilde, E. Ma, Acta Mater. 50, 475 (2002)
Accumulative roll bonding

Cu39.5Ag60.5 (at%) Eutectic composition
Casting, Swaging
1.2mm2
Cold rolling
=6.8
=6 8 (5cycles)
Cu71Zr29 (at%)
Cu t=0
t=0.2mm5
2mm5
Zr t=0.2mm4
Stacking
Cu
Zr
Y.Saito. et al. Acta Mater.47(1999) 579
=13.6 (9cycles)
SEM BSE images of ARB Cu/Ag and Cu/Zr
Cu39.5Ag60.5 (at%)
1cycle =3.5
3cycles =5.0
4cycles =5.95
5cycles =6.8
C 71Zr
Cu
Z 29 (at%)
( t%)
3cycles =4.8
=4 8
5c cles =8.0
5cycles
80
7c cles =11.2
7cycles
11 2
9cycles =13.6
=13 6
S. Ohsaki et al. Acta Mater. 55, 2885 (2007).
TEM images
Cu39.5
39 5Ag60.5
60 5 (at%)
Cu71Zr29 (at%)
1cycle
y
=3.5
3cycles =4.8
4.8
R
D
5cycles =6.8
=6 8
shear
band
9cycles =13.6
=13 6
HREM image of shear bands
100nm
5nm
Cu-L2,3 image
Forced alloying of Cu/Ag =6.8

Elemental mapping of Ag and Cu atoms
13nm
110nm
Composition profile
Cu layer
Ag layer()
ND
Ag
Cu
Ag layer()
90
Cu layer()
95at%Ag
Ag
95at%Ag
80
60at%Cu
70
at%
60
50
40
Cu
40at%Ag
30
Light Ag
Dark Cu
FIM image
g from TD
9.2kV, 60K, Ne
20
5 t%C
5at%Cu
5at%Cu
10
1
10
Depth distance (nm)
Intermixing of Ag and Cu layers

Does amorphous form by forced alloyin of Cu/Ag?

5cycles =6.84
BF iimage
HREM image
Nanobeam Dp (0.5nm)
No amorphous
Does amorphous form by forced alloyin of Cu/Ag?

3cycles
5cycles
7cycles
Cu
Zr
Cu
Cu map White: Cu
Black: Zr
Alloying and amorphization of Cu/Zr

C map
Cu
1
White: Cu
Black: Zr
Amorphous
Crystal
HREM image of Cu/Zr nanolayer

Aft 9cycles
After
9
l
Cu
Cu
Amo
Cu
Amo
Zr
Cu
Cu
Zr
Amo
Amorphization of some of the Zr lamellae

Amorphization
p
of Cu/Zr by
y forced alloying
y g
Instability lines and amorphous formation

Cu-Zr
Ag-Cu
T0
T0
T0
Amorphous (liquid) phase becomes stable in Cu-Zr if solid solution is forced to be

made, whle no amorphous phase formation is expected in the Ag-Cu system.
Chapter 6
Diffusionless Transformations
Variant 2
Displacive Transformation
or
Variant 1
The name martensite is after the German scientist

M t
Martens,
which
hi h was used
d originally
i i ll tto d
describe
ib th
the
hard microconstitutent found in quenched steels. Many
materials other than steel exhibit the same type of
transformation,, known as martensitic transformation.
Features of martensite
invariant lattice plane
Surface relief due to a martensitic

transformation in an Fe-24.5%Pt alloy.
y
habit planes for Fe-7Al-1.5C martensite
C. W. Wayman and H. K. D. H. Bhadeshia, Physical Metallurgy, Ed. IV
Microstructural feature of a martensite in steel

low C steel (lath)
coherent
mid rib
martensite spans
within 10-7 sec, nearly
equal to the velocity of
sound- no thermal
activation (athermal)
OR
e.g.
(111) //(011) '
(111)//(011)'
[10-1]//[-11-1]'
Fe-Ni (p
(plate))
Unlike ferrite or pearlite, martensite forms by a deformation of the austenite
lattice (fcc) to ferrite (bcc) without any diffusion of atoms.
fractio
on of martens
site
Martensite reaction is athermal transformation; the fraction of transformed

depends on the undercooling below a martensitic start temperture, Ms.
10
1.0
1 - x = exp{(Ms Tq)}
The athermal
Th
th
l character
h
t iis d
due tto
very rapid nucleation and growth
Mf
T
Ms As
Af
Ms
Mf: xx=0.95
0.95
grwoth rate of martensite: ~1100 m/s
c f solidification rate <80 m/s
c.f.
Te
Martensitic transformation in Fe-C steel
+ retained
G ' H '
T0 M S
T0
Undercoolings for MT
G ' H '
T0 M S
T0
Martensite in steels- Solid Solution of C in Fe

preferred
f
d site
it for
f C
fcc
hcp
octa
0.155D
tetra
0.291D
Tetrahedral site: dt=0.225D

Octahedral site: do=0.414D
iron: D=0.252 nm
dt=0.057, do=0.104
DC=0.154
considerable distortion occur by
the carbon dissolution in
c/a=1.005 + 0.045 (wt%C)
Martenseite Crystallography
invariant plane strain
The growth of habit plane or martensite is

obsrved to be macroscopically undistored, i.e.,
the habit plane is a plane which is common to
both the austenite and martensite in which all
directions and angular separations in the plane
are unchanged during the transformation.
(111)
[112]
The habit plane remains undistorted.

invariant plane
Bain Modal of fccbcc

C occupy 1/50 x for 1at.%C
x'
y'
12%
20%
(111) //(011)
[101] //[1 11]
12%
[1 10] //[100]
[112] //[01 1]
20%
fcc bct transformation
slip
li
twinning
habit plane is a plane in the austenite which

undergoes no net distortion
N-W and K-S OR
U. Dahmen, Acta Metall. 30, 63 (1982).
Crystallography in steel MS
a high dislocation density lath
morphology, or consist of bundles of
needles lying on {111}
twinned plate or lens
lath
twinned
any exact morphological description of martensite is not possible, because it is rather

irregular after growth
Martensite nucleation
martensite grow at velocities of sound, i.e. 800 - 1100 m/s
G A V Gs V Gv
initial strain of the austenite lattice by

martensite nucleus - coherent
small
large
shear
s 2(2 ) c 4 2
G 2 a 2 2 V
a cGv
2 (1 ) a 3
: Poisson ratio of austenite
: shear modulus of austenite
Putting =1/3
16
G 2 a 2
3
s 4 2
a cGv
2 3
4
G*
512 3 s 2

3 Gv 4 2
~20 eV too high for thermal activation
c*
2
Gv
a*
16 ( s / 2)2
Gv2
thin plate is favorable

for large Gv, i.e. for
large T
However, most martensitic transformations

are heterogeneous - dislocations
Role of dislocations in martensite nucleation

abcabcabc
a2 110 a6 [ 211] a6 [ 1 2 1]
abcababca
12 b 12a [ 211]
fcc/bcc/fcc
1
futhr thickening by
pile ups
p
dislocation p
a
110 a [ 211] a [ 1 2 1 ]
2
6
6
twinning shear
1
a
b1 [ 2 11]
2
12
fcc two atomic layer bcc

twin + jump
Zener's model of two atomic layer martensite
Role of dislocations in martensite nucleation

fcc
hcp
martensite
bcc
this model has not been supported
experimentally
Venables' model
Martensitic transformation of Co
fcc hcp @ 390C
fcc
hcp
a
(111)//(0001)
11 2 on{111}
6
only with low stacking fault energy
abcabcabcabc
a
110 a [ 2 11] a [ 1 2 1 ]
2
6
6
abababababab
Dislocation strain energy assisted transformation

nucleation barrier can be reduced by the elastic strain field of a dislocation
not necessary that the habit plane correspond to the glide plane of austenite
coherent nuclei are generated by a pure Bain strain
strain field associated with a dislocation can provide a faborable interaction
with the strain field of martensite nucleus
G=A+V(Gs-Gv)-Gd
dislocation interaction energy which reduced the nucleation energy barrier
Gd 2 s ac b
b: Burgers vector
s: shear strain of nucleus
G 2 a 2
16
4 2
( s / 2) 2 ac 2 Gv
a c 2 s ac b
3
3
Nucleation and growth of martensite

~20 nm
2-3 thickness
twin or slip
whether twin or slip occurs for growth

depends on alloy content and Ms
c*
2
G v
a*
16 ( s / 2)2 thin plate is favorable for large

Gv, i.e. for large T
Gv2
max shear stress
2 sc
a
s: shear strain of nucleus
threshold for nucleation at dislocations
Bain
twinned plate
Plate martensite
{225}
{259}
U. Dahmen et al. Acta Metall. 1984
Ms, Mf, As, and Af
fraction of martens
site
1.0
cooling
Mf
As Ms
Af
Stress induced martensitic transformation
K. Oishi and L. C. Brown, Metal.

Trans. 2 (1972),
Shape memory and superplasticity

deformation of M
stress induced M
stress induced M
Ms
on heating -pseudelastic
shape memory
Af
pseudelastic=superelastic
residual strain
Critical stress as function of temperature

dor inducing martensite (T>Ms) and for
yielding (T<Ms).
(T<Ms)
Af: reverse transformation finish
Stressstrain curves of Ti50.6Ni alloy.

Miyazaki et al. Scripta Metal. 15 (1981), 287.
Ms<T<Af: shape memory

Ms>Af: superelastic
Shape memory and superelasticity
stress induced
M is possible
M deformation is
possible
After Otsuka and Shimizu, Inter. Met. Rev. 93 (1986), 21.
Shape memory
li and
d
slip
twinning
stress
induced M
and slip
stress induced M
http://www.grc.nasa.gov/WWW/RT/2003/5000/5120noebe.html
S. Miyazaki et al. Scripta Met. 18 (1981), 883.
Tempering of ferrous martensite

Martensite steels are hard
hard, but brittle
brittle. To give toughness
toughness,
martensite steels are heat treated before use tempering
martensite
t
it ferrite
f it supersaturated
t t d with
ith carbon
b (bct)
(b t)
' + -carbide (Fe2.4C)
' + Fe3C
Carbide formers: T, Nb, V, Cr, W, or Mo
diffusion of substitutional elements are
slower
MCx formation
f
ti is
i sluggish
l
i h compared
d tto
and
Tempering of ferrous martensite
Tempering of martensite
-cabide (Fe2-3C)
observed only when c > 0.2wt.%
where Ms is low
100 - 250C
hexagonal
(10-11)//(101)
[0001]//[011]
cementite (Fe3C) or (FeM)3C

habit {1011}'
250 - 700
700C
C
orthorhombic
(
(001)c//(211)
) (
)
[100]c//[0-11]
Alloy carbides
alloy
ll carbides
bid fform >~500C
500C where
h
substitutional
b tit ti
l diffusion
diff i occurs
the carbides replace less stable cementite
nucleate at cementite/ferrite interface

or
nucleate heterogeneously within the ferrite on dislocations, lath boundaries,
and prior austenite boundaries - grow at the expence of cementite
Secondary hardening
Fe-0.1%C-x%Mo
high speed tool steels
secondary hardening
complex structure
fne dispersion
Precipitation
p
of carbides
concentration of M and C in Fe
q
with MmCn
in equilibrium
m
[M] [C]n=K
K=K0exp(-H/RT)
Retained austenite
steels containing >0.4%C, austenite
is retained
on aging at 200 - 300C, austenite

decomposes to bainite
Morito et al.
Summary
Phase transformation is the basic science based on
thermodynamics to understand how microstructure evolve in
materials in certain conditions.
Quite useful for designing materials with structural and
functional properties.
F further
For
f th reading
di
R. Cahn and P. Haasen, Physical Metallurgy 4th edition, I-III, Elsevier
H. I. Aaronson, M. Enomoto, and J. K. Lee, Mechanisms of Diffusional Phase
Transformations in Metals and Alloys, CRC Press, 2010.
R. W. Balluffi, S. M. Allen, W. C. Carter, Kinetics of Materials, Wiley, 2005.
T. Nishizawa,, Thermodynamics
y
of Microstructures,, ASM Intermational,, 2008
R. A. Swalin, Thermodynamics of Solids, John Wiley & Sons, 1972.

Phase Transformation I I

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Phase Transformation I I

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Phase Transformation II

Instructor: Kazuhiro Hono

Brief review of thermodynamics and

Entropy, enthalpy and free energy

Free energy and phase diagram

HABmix~0: ideal solid solutionn

e.g., Cu-Ni, Au-Ag

Free energy and phase diagram

Free energy and phase diagram 3

HABmix>>0: AB strongly repulsive

e.g. Cu-Ag, Al-Si

Free energy and phase diagram

Enthalpy and phase diagram

Diffusional Transformations in Solids

Types of Diffusional Transformations

Homogeneous Nucleation in Solids

Homogeneous nucleation rates

If a small amount of b is created in , the total free energy of

total driving force for

Homogeneous nucleation rate for T

Reduction of is most effective

the excess free energy

Home Works 2: derive the following shape factor:

Heterogeneous nucleation (contd)

Heterogeneous Nucleation III

reduction of lattice distortion

L. Reich, S. P. Ringer and K. Hono, Phil

J. M. Howe, U. Dahmen, and R. Gronsky, Phil. Mag. A 56, 31 (1987).

Heterogeneous Nucleation Rate

C0: the number of atoms per unit volume

C1: concentration of heterogeneous nucleation sites

heterogeneous nucleation can occur at very

For small driving force, heterogeneous N

: GB thickness, D: grain size

for grain edges

for grain corners

see Table 5.1 in p. 278

Further reduction of interfacial energy by faceting

Faceting in homogeneous nuclei

K. B. Alexander et al. Acta Metall. 32, 2241 (1984).

G. C. Wetherly, Acta Metall. 19, 181 (1971).

Growth of incoherent interfaces

since dC/dx is time dependent,

dC/dx can be approximated by C0/L

1. x(Dt): paraboric law

S. Y. Hu et al. Computer Coupling of Phase

The paraboric law applies to spheroidal precipitates, too.

Reduction of growth rates due to the reduction of

The diffusion field to separate the

Grain boundary precipitates

L. Chen et al. ISIJ International, 48 (2008), 830.

Growth of plates or needles

The legthening rate is constant, i.e.,

Growth rate of plates by ledge

Diffusion field do not overlap, so the

f(t,T): fraction of transformed

Kinetics for precipitation

for ff<<1 before impingement

For randomly distributed nuclei,

In general, the kinetics for nucleation and growth follows

n ranges from 1 to 4 depending on the nucleation mechanism

Kinetics for precipitation

Since exp(-0.7)=0.5, the time for 50% transformation t0.5 is