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 G
C
1400 (bcc) (fcc)
C (bcc)
(bcc)
l
(fcc)
910 1400 1539
C T C C
910 c
C Free energy: G
(bcc) G = H TS
H: enthalpy
S: entropy

Potential energy
 Entropy, enthalpy and free energy

Entropy increases in
nature
Enthalpy: H
HAB=nAAeAA+nBBeBB+nABeA
G = H - TS
B S kBlnW
S=k l W
GB
HB (n n )!
W 1 2 GA
HA HABmix>0 n1!n2 !

entropy S
A B A xB
H=(1-x)HA+xHB GB
HB
HABmix=0 SB GA
HA Smix
Ideal solid
solution SA
A B

HB GB

HA
HABmix<0 GA
A xB B

A xB B

Phase separation
T=T1 H

G
G G=H-T1S
Gm G2
G1
-T1S
A B
A x1 x2 B
T1>T2
T=T2 H
G>Gm=x1G1+x2G2

G Gm G=H-T2S

-T2S

A B
 Spinodal decomposition

G
G

G2
Gm
G1

A x1 x2 B

XB

distance

T3>T2>T1
Free energy and phase diagram
T=T3
HABmix~0: ideal solid solutionn
G e.g., Cu-Ni, Au-Ag
l
T3
A B T3 l
l
T=T2 l+
G T2
T2 l
l
+l l

T1
A B
T1
T=T1

l
G A x B
B

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

T2

T2
+l l +l

A B T1
T=T2 T=T1 1+2
l l T1
G G A x B
B

2 1

A B A B

Free energy and phase diagram 3

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

T=T3
T3
G l l
T3
1 2
+l l +l T2
T2
T1
A B 1+2

T=T2 T=T1

l l A x B
G G B


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

G
l
T2
+l +l l
l

A B T1
T=T2 T=T1
l
l
G G A x B

B

A B A B

Enthalpy and phase diagram

Intermetallic compound
TiAl, NiAl, Ni3Al

Hms<Hml<0 Hms<Hml<<0 L10 L12

Hms>Hml>0 Hms>Hml>>0
Diffusional Transformations in Solids

Poter and Eastering 2nd edition

Page 251

Types of Diffusional Transformations

precipitation
p p

eutectic

ordering
(disordered)(ordered)

massive

polymorphic
Fig. 5.1
Homogeneous Nucleation in Solids

G = -VGv + A + VGs

4
G r 3 Gv Gs 4r 2
3
r 2
r*
(Gv Gs )

16 3
G*
3( Gv Gs ) 2

Homogeneous nucleation rates

Gm G * 16 3
N hom C0 exp exp G*
kT kT 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,

Gv X X 0 X e
total driving force for
the transfromation
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

16 3
G*
3( Gv Gs ) 2
St i energy
Strain

conc.nuclei

perature (T)
Transformation

Temp
atomic mobility
Gm G * Time (t)
N hom C0 exp exp
kT kT

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
gy barrier G*
energy

16 3
G*
3( Gv Gs ) 2

Reduction of is most effective

incoherent nuclei
homegeneous nucleation vertually impossible
orientation relationship (OR) to form coherent fcc
i t f
interface
fcc
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)
 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 ( )
Ghom
*
o
*
Vhom o
G*hom

Home Works 2: derive the following shape factor: G*het

1
S ( ) (2 cos ) 2 (1 cos ) 2
2
Shape factor for more complicated case:

triple
p p point

grain corner
 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 Dislocations
4. stacking faults
5. GBs and interphase interface
6. free surface

reduction of lattice distortion

16 3
G*
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 J. M. Howe, U. Dahmen, and R. Gronsky, Phil. Mag. A 56, 31 (1987).
Mag Lett 79, 639 (1999).
 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 C1: concentration of heterogeneous nucleation sites
kT kT

heterogeneous nucleation can occur at very

low driving force

N het C Ghom
*
Ghet
*
For small driving force, heterogeneous N
1 exp
N hom C0 kT become dominant, but for large driving force,
homogeneous N becomes dominant
for GB nucleation
C1
: GB thickness, D: grain size
C0 D
2
C1 C1
2
for grain edges for grain corners
C0 D C0 D 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 B B B B B B B B B B B B B B B B B B B B
C C C C C C C C C C C C C C B C C C C C 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 B B B B B B B B B B B B B B B B B B B B
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
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
C B
J B DB
x

dC
(C Ce )dx D dt
dx

dx v
dx

D dC since dC/dx is time dependent,
p it
dt C Ce dx cannot be solved analytically!

dC/dx can be approximated by C0/L

L C 0
(C C 0 ) x
2
D ( C 0 ) 2
v
2(C Ce )(C C0 ) x Let Ce~C0

X 0
x Dt
X X e
X 0 D
v
2( X X e ) t where X0=(X0Xe)
 Precipitate Growth
X 0
x Dt X 0 D
X X e v
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
dx D C
v
dt C Cr kr

r *
X X 0 1
r
dC/dx can be approximated by C0/L
LC
(C C0 ) x
2

DX 0 1 r *
v 1
k X X r r r

The legthening rate is constant, i.e.,

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

Diffusion field do not overlap, so the
DX 0 DX 0
u v thickening rate is inversely proportinal
k X X e h k X X e
to the interledge spacing

Thickeningg require
q constant supply
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 nucleation
l ti rate t
2. growth rate
3. the density and distribution of h-nucleation sites
4
4. overlap of diffusion filed from adjacent particles
5. impingement of adjacent particles

1&2

3&4
site saturation

discontinuous impingement
F. Katsuki et al. JAP 89, 4643 (2001). precipitation
 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
t

f V ' Nv 3 (t ) 3 d Nv 3t 4 for ff<<1 before impingement
p g
3 0
3
For randomly distributed nuclei,

f 1 exp(( Nv 3t 4 )
N
3
For t<<1

f Nv 3t 4
N
3
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 ) k Nv 3
3

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

kt0n.5 0.7

0. 7
t0.5 k Nv 3
k1/ n 3
rapid transformations are associated with large values of k, i.e., rapid nucleation
and
d growthth 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

after H. Ohtani, Kitakyushu Inst. Tech.

Ground state phase in Al-Cu alloys and

GP zone

after H. Ohtani, Kitakyushu Inst. Tech.

 Metastable miscibility gaps for the binary
systems in which GP zones were reported

after H. Ohtani, Kitakyushu Inst. Tech.

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] K. T. Moore and J. M. Howe,

6 6 Acta mater. 48, 4083 (2000)
[1120] ' //[110]

R. B. Nicholson and J. Nutting, Acta. Metall. 9, 332 (1961).

Quenched-in Vacancies
Cv (T ) exp( Ev / kT )
Ts
Cv (T1 ) exp( Ev / kT1 ) T
exp 0
Cv (T0 ) exp( Ev / kT0 ) T1
420K
373K D(T=420) D(Ts)
D(T=420)~D(Ts)

T2
T2T0
T1 Hv T1T0

T0
t

A
B Hv B
A

t t
 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 Orowan
f

Gb 1 1 for spherical particles

2 ln
4 1 r0

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]

M 1.60
Mg 1 60
[1010]

-6 -4 kJ/mol

Mg Ca Zn
1.97 -22 1.48
Ca/Zn
[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 -4
4 kJ/mol

Ca In
1 97
1.97 -35
35 1.62

C. L. Mendis et al. Scripta Mater. (2010)

Spinodal and Nucleation-Growth

d 2G d 2G
0 0
dx 2 dx 2

d 2G
0
dx 2

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

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

Gs 2 (x) 2 E Vm

1 da
fractional change in lattice parameter per unit composition change
a dx
E
E : Poisson's
P i ' ratio,
ti Vm: molar
l volume
l
a
d 2G 2 K ( x ) 2
G 2 2 2 2 E Vm 2K
dx 2 2
d G / dx
2
d 2
2 2
E Vm
2
d G 2K
2 2 2 E Vm
dx 2

h =
when
d 2G
2 2 E Vm
dx 2

Experimental work on spinodal

K. B. Rundman and J. E. Hilliard, Acta
Metal. 15, 1025 (1967).
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
15
Co63.5Fe17.7Sm11.8Cu4.9Zr2.2 Sm(Co
( 0.72
0 72
Fe0.20
0 20
Cu0.055
0 055
Zr0.025)7 5
0 025 7.5
Isothermal aging at 820Cx6h.

y Hci, kOe
10

Coercivity
5

0
300 400 500 600 700 800 900
Quenching Temperature Tq, C

T sintering
1200C
1150C
solution treatment

800C
aging
slow cooling

400C

Time

TEM
Tq = 820C Tq = 520C

[01 1 0]
0.071/nm 0.070/nm

[21 3 0]

[0001]
 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.

From Lectard etal.

3.
 Dynamic phase separation in thin films

C C
Co-Cr *3
3KK. Hono et al.
al Appl.
Appl Phys
Phys. Lett.
Lett 66,
66 1686 (1995)
*4 K. Hono, Prog. Mater. Sci. 47, 621 (2002) At
Atoms are mobile
bil only
l on surface
f

Ts: 227, 75 at.% Co *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.
 16 / 20
Cu30Ni70: CPP~ 50 mV Cu46Ni54: CPP~ 480 mV
~ 50 nm

~ 50 nm
~ 70 nm
~ 70 nm
Concentration of Cu (at.%) Concentration of Cu (at.%)
60 50 40 30 20 10 60 50 40 30 20 10
1.0 1.0
Binominal Cu46Ni54 Binominal
0.8 Composition Binominal Composition
0.8
Count

Count
Average comp. Binominal Average comp.
Normalized C

Normalized C
0.6
Cu30Ni70 0.6

0.4 0.4 Comp.

Comp.
Cu-rich
N

02
0.2 02
0.2
Cu-rich Ni-rich Ni-rich
0.0 0.0
40 50 60 70 80 90 40 50 60 70 80 90
Concentration of Ni (at.%) Concentration of Ni (at.%)

17 / 20
Cu30Ni70: CPP~ 50 mV Cu46Ni54: CPP~ 480 mV
+ 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 Cu-rich
C i h face
f Average Ni-rich
A Ni i h fface
Cu25Ni75 Cu20Ni80 Cu15Ni85 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 (1.61)
RTr
N

t
N-G Coarsening GVm/r

r
t1/3

t
3
r r 3 kt for diffusion controlled growth
where
k D xe
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 A2

(a) (b)
 Precipitation of ferrite from austenite
grain boundary allotriomorph

(a) (b)

coherent

incoherent
intragranular
g
ferrite

(c) (d)
habit p
plane irrational
4-20from {111}
OR: Nishiyama-Wasserman or Kurdjumov-Sachs

at large supercooling only

incoherent interface can migrate

intragranular ferrite
(DGB dependence) Widmansttten sideplate

austenite()ferrite() transformation
(a) (b) Fe-0.34C
OR
(a) Grain boundary allotriomorphs:
l t att BGs.
nucleate BG At high
hi h T,
T curved;
d att
low T, facet.
(b) Widmansttten side plates: nucleate
at BGs, but grow along well defined
(c) (d) matrix.
(c) Intragranular idiomorphs: roughly
equi-axed nucleate within grains.
(d) Intragranular plates: nucleate within
g
grains.

(f) Fe-1.2C steel

(e)
(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
grain size f 1 exp(kt n )
since exp(-0.7)=0.5
0.7
t0.5 1/ n
hypoeutectoid k
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
0.4 wt%C depending on cooling rate

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

Prangnell et al. Acta Metall. Mater. 42, 419 (1994). F. Findik, J. Mater. Sci. Lett. 17, 79 (1997)

Pearlite Reaction in Fe-C: eutectoid

Fe3C

 Nucleation and growth of pearlite
coherent immobile coherent mobile

OR
OR

which phase appear first depends on GB

structure and composition

proeutectoid
phase

1
S0 S *
T experimental

v kDc (T ) 2
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
pearlitic and bainitic growth Upper Bainite

no OR
pearlite austenite

OR
bainite

Pearlite: cementite and ferrite have no spcific OR to the mixture of ferrite

austenitic grain in which they grow KS and carbides
Bainite: cementite and ferrite have an OR within the grain

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

c H
ln ln
c RT

H H H a
austenitic
c steel
H is the differencce between the heat absorved per unit of
c solute dissolving in g and a phases
C, N, Cu, Zn B, Ta, Nb, Zr

ferrite formers: H<H so H>0

austenite
t it formers:
f H so H<0
H>H 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
pearlite w/o partitioning
X: carbide former Mo, Cr
solute drag effect at interface

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-1.0
0.4C 1.0 Mn 0.4C-1.0Cr-0.2Mo-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 X-
carbide 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
O l a ffew atomic
t i distance
di t jump
j
No change in composition of phases
The effect of cooling rate
Interface is incoherent on the transformation
Similar to recr
Similar stalli ation
recrystallization temperature of pure Fe
Fe.

Martensitic Transformation
massive ferrite

Ordering transformation
Intermetallic compound
TiAl, NiAl, Ni3Al

Hms<Hml<0 Hms<Hml<<0 L10 L12

rA x A
L Let xA=0.5 and rA=1, then L=1
1 xA So this equation is valid regardless of alloy compositions

derivatives of bcc
1st and 2nd order phase transformation
G
S
T
2nd order
A2B2
refer 1.2.7 for s

1st order
A1 L10
A1L1
AlL12
G
V
P

2G S 1 H Cp
2
T P T P T T P T

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 1 cos 2 2 M
2
I F p 2 e
sin cos

F: structure factor, p: multiplicity factor

1 cos2 2
2 : Lorentz-polarization factor e 2 M : temperature factor
sin cos
N
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 ththere 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
111

F 0 for (h+k+l) is odd 222

F2 4 f 2 for (h+k+l) is even 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, ...
Detection of order-disorder transformation 3
N
Fhkl f n e 2i ( hu
h n kv
k n lw
l n)

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 for unmixed indeces F2 0 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,...

Detection of order-disorder transformation 4

N
Fhkl f n e 2i ( hu
h n kv
k n lw
l n)
Simple Cubic:
1 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 for unmixed indeces
F2 0 for mixed indeces

s=3, 4, 8, 11, 12, 16,...

Detection of order-disorder transformation 3
Disordered A1 Cu3Au
The average atomic scattering factor fav
1 3
f av x Au f Au xCu f Cu f Au f Cu
4 4

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)
( )
2
F 2 16 f av for unmixed indeces F2 0 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 for unmixed indeces (111), (200), (220)
F f Au f Cu for mixed indeces (100), (210), (112)

XRD of A1 and L12 Cu3Au

Intensity (%)
1,1,1
100

90

80

70

60

50 2,0,0

40

30 3,1,1
2,2,0

20

10 2,2,2

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
2,0,0 superlattice diffractions
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 2,2,2
2,2,1
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 L10 FePt

Sh
Show th
the method
th d tto d
determine
t i ththe 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

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.

F f Co e 2i ( 0 ) f Al e 2i ( h / 2 k / 2 l / 2 ) B2

F f Co f Al for (h+k+l) is even F f Co f Al for ((h+k+l)) is odd

1 0.2862 31.220 173.4 100 6

2 0.2024 44.740 1000.0 110 12
3 0.1652 55.580 37.4 111 8
4 0.1431 65.140 147.5 200 6
5 0.1280 74.000 39.8 210 24
6 0.1168 82.480 281.6 211 24

1 0.2868 31.160 0.2 100 6

2 0.2028 44.640 1000.0 110 12
3 0.1656 55.440 0.1 111 8
4 0.1434 64.980 143.6 200 6
5 0.1283 73.820 0.2 210 24
6 0.1171 82.280 269.8 211 24
 Long range order parameter
Long range parameter S
rA x A rA: fraction of A sites occupied by the right atoms
S
1 xA 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 for unmixed indeces (111), (200), (220)
F S f Au f Cu for mixed indeces (100), (210), (112)
Note that only superlattice diffractions are affected by S.
I100 ( S )
S2
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

order
continuously
W. A. Soffa and D. E. Laughlin, Acta Mater. 37, 3019 (1989)
 Phase separation and ordering

2V ( k )c(1 c )
Ti
kB
1 i
Vi E AB
i
( E AA E BBi
)
2
W. A. Soffa and D. E. Laughlin, Acta Mater. 37, 3019 (1989)

Phase separation and ordering

T=T1

nucleation and growth of ordered

phase wihin the disordered phase

W. A. Soffa and D. E. Laughlin, Acta Mater. 37, 3019 (1989)

Precipitation of ordered from disordered

T=T2

congruent ordering: ordering

w/o change iin composition

continous ordering ot
->continous
-> precipitation of from

W. A. Soffa and D. E. Laughlin, Acta Mater. 37, 3019 (1989)

Congruent ordering

ordering without change in composition

W. A. Soffa and D. E. Laughlin, Acta Mater. 37, 3019 (1989)

 Ordering and phase separation

spinodal decomposition of ordered

-> one of phase decomposed disorder

W. A. Soffa and D. E. Laughlin, Acta Mater. 37, 3019 (1989)

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

W. A. Soffa and D. E. Laughlin, Acta Mater. 37, 3019 (1989)

 Spinodal decomposition of disordered phase and
subsequent ordering

M. Kompatscher et al. / Acta Materialia 51 (2003) 165175

Multitwin structure by A1L10 ordering

Disordered A1 phase
Ku=7107 erg/cc
Ms=1140 emu/cc
0.382 nm

HA=120 kOe
Domain wall width: 4 nm
SDP: 34 nm
0 382 nm
0.382
(BH)maxtheor: 51 MGOe
Tc~1300C

72.3
c

APB
c
c

(111) deformation or
(011) transformation twin 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 FePt-Al2O3 granular film
Size of FePt particles < 10 nm
Thermal instability

10 nm
KuV>kBT KuV<kBT
High Ku materialsFePt, CoPt

Size dependence of ordering

FePt-Al2O3 granular thin films

SAED pattern I(110)/I(111)

s2 =
FePt 0.5 nm/Al2O30.5nm, 600C 54h 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
disorder order
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
free surface with
vacuum
1.0 Uorder = Udisorder-kBNTln2 A1
Tc
0.8
T = Tc
Tc / Tc bulk

Ta
0.6 annealing temp.
Tcnano
0.4 L10

0.2

0
0.5 1 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
500GB/p
500GB/ 4 Tbits/in2
Areal density and
bit size (750 GB/in2)
D=6.9 nm
bit size S = 10 nm10 nm = 100 nm2
670GB/p
670GB/
(1 TB/in2) S/N n d ~ 4 nm for n=16
D~5 nm
Ferro Superpara

750 GB/in2
A1 L10-FePt

600
(001)

Ku~7 x 106 J/m3

K1~10 J/m4
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.
As-depo. 650C anneal
L10-FePt

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

220
Tsub=500 C 200
220
Tsub=600 C 200
220 Tsub=700 C 200
110 110
110

Dav 6.2 nm Dav 9.9 nm

Dav 15 nm

T. O. Seki, Y. K. Takahashi, K. Hono, JAP (2008)

 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 Hc = 10.6 kOe
Ku = 8106 erg/cc
a-SiO2
A. Perumal, Y. K. Takahashi, K. Hono, APEX, 1 (2008) 101301.

Higher Hc FePt-C granular films

for heat assisted magnetic
g recordingg (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).

(FePt)1-xAgx-50vol.%C granular films @ 450C

g 0%
Ag10%
Ag 1
Ag 20%
%

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

RT Tc 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 m

FePtAg-C HAMR Meida

800
600
perp
inp
HC.perp = 35kOe
400
HC.inp = 7kOe
Ku = 4.3107erg/cc
200
u/cc)

HC = 6kOe
0
M (emu

-200
-400
-600
800
-800
-40 -20 0 20 40
H (kOe)

Grain Size
6.21.4nm
6 21 4
120
100
80
ount

60
Co

40
20
0
2 4 6 8 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
l 1 2

T
1+2
A xB B

A c c0 cl B
l

+
A xB B

A xB B

segregation free solidification

is possible below T0 +
A xB B

Glass transition temperature (Tg)

T
viscosity
G
G

T
Tg

x Tm
glass forming range

cooling rate Tg: the temperature at which the liquid

V phase solidify with the amorphous
structure
t t - viscosity
i it ~10
1011 poise
i

Tg0 Tm
Tg1
Tg2
 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
atomic r/r>0.12
0.12 (dense packing)
multicomponet alloy (confusion rule)
composition cluse to eutectic

viscosity
T
G

x
x amo mg

Marginal glass former and bulk forming glass

crystal

T Rc

amorphous metallic glass

Amorphous alloy
time
V Metallic glass

Tx Tg Tx Tm

rN: small QN: large rN: large

QN: small
Tx>Tg
Tx<Tg
G

x
Tx Tg Tx
amo mg
T T
Structure characterization of amorphous alloys:
pair distribution function
p

g(r)
1.
0

0 2ro 4ro r

g(r)
1.
0

0 ro 2ro r
N( )
N(r) 24 24
12
6 8 6

0 2r 4ro r
o

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 didistance
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 Ta
FeCoB
MgO
g
FeCoB
Ta

CoZrTasoftunderlayer Ru

soft magnetic underlayer for magnetic recording media 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

l
G

AxBy

amorphous AxBy

di
discontinous
ti precipitation
i it ti

Primary crystallization

amo
G
A C

B D

AxBy

amo amo'+AxBy

volume diffusion controlled growth

 Nanocrstalline soft magnetic materials

5 x 105

Co-based
2 x 105 Amorphous
New FINEMET

FeSiBNbCu FINEMET
1 x 105 Hitach Metals Fe-M-B NANOPERM
Tohoku and ALPS
5 x 105
(Fe,Co)-M-B

e 2 x 105
HITPERM
CMU
100
After G. Herzer
1 x 105
10 Fe based
Fe-based
1/D Amorphous
5 x 105
Hc Silicon Steels
1 D6
(A/cm) FeSi6.5
2 x 105
Mn-Zn Ferrite
0.1 50NiFe Fe-Co alloy
nanocrystal
y 1 x 105

0.01 amorphous permalloy

0 0.5 1.0 1.5 2.0 2.5
0.001
1 nm 1 m 1 mm Bs (T)
Grain Size D Courtesy of Vacuumschmeltz

Alloy name Typical composition Primary phase Bs(T) Tc(C)

FINEMET Fe73.5Si13.5B9Nb3Cu1 FeSi(D03) 1.0 - 1.2 <770
FINEMET2 Fe76.9Si11B9Nb2.5Cu0.6 FeSi(D03) 1.45 <770
NANOPERM Fe88Zr7B4Cu1 -Fe 1.5 - 1.8 770
HITPERM Fe44Co44Zr7B4Cu1 -FeCo(B2) 1.6-2.1 >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

Zr47.5Cu47.5Al5

A. Inoue et al. Acta Mater. 49 (2001), 2645. 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?

Cu60Zr30Ti10 Cu50Zr50 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

T Rc

amorphous metallic glass

Amorphous alloy
time
V Metallic glass

Tx Tg Tx Tm

rN: small QN: large rN: large

QN: small
Tx>Tg
Tx<Tg
G

x
Tx Tg Tx
amo mg
T T
 Eutectic crystallization of Pd40Ni40P20
metallic glass

A. J. Drehman and A. L. Greer, Acta metall. 32, 323 (1984).

Amorphous Phase Decomposition

l


G

a b

A spinodal
i d l xB B after T
T. Koyama
Koyama, NIMS

Hlmix
i >0
 Conditions for good glass forming ability
mixing enthalpy Hmix<<0
atomic
t i raiusi r/r>0.12
/ 0 12
multicomponet alloy (confusion rule)
composition
iti cluse
l tto eutectic
t ti

dense packing G

short range order

difficult to rearrange
x
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
Tg2

L. Tanner, R. Ray
Scripta Metall. 14, 657 (1980). 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

D. Nagahama et al., Scripta Mater. 49, 729 (2003).

 Zr36Ti24Be40 heated to 390 at 20 K/min

Bright Field Image HREM

D. Nagahama et al., Scripta Mater. 49, 729 (2003).

Eutectic crystallization of Zr36Ti24Be40

20 K/min

B map
Be Ti map Z map
Zr
Be

Ti

200 nm 200 nm 200 nm

Zr

amorphous -(Zr,Ti)+Be2(Zr,Ti) eutectic crystallization Distance , nm

D. Nagahama et al., Scripta Mater. 49, 729 (2003).

 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
H
A-C : small negative

A-B
B-C
A-C

Nu

umber of B
A-A
C-C
B-B

Bonds

T ~ Tg

Tg Temperature Tm M. Shimono and H. Onodera
NIMS

Possibility of metallic glass nanostructure

control by phase separation
A - B, B - C : large negative T ~ Tg
H
A-C : large positive

C-C

Number o

B-B

B-C
of Bonds

A-B

A-A Two distinct p

phases in
supercooled liquid state
A-C

Tg Temperature Tm M. Shimono and H. Onodera

NIMS
 Glass formation and phase separation
A

HAB<<0
HAC>0

miscibility gap

glass

B C
HBC<<0

Two phase metallic glass

LaCuNiAl+ZrCuNiAlLa27.5Zr27.5Cu15Ni15Al15

100 nm 100 nm

Hmix Zr La Al Cu Ni
Zr 0 +13 -44 -23 -49
La 0 -38 -21 -27
Al 0 <0 -22
Cu 0 +4
Ni 0

Zr51.3La5.2Cu7.2Ni20.6Al15.4
La43.7Zr10.6Cu22.3Ni9.5Al13.9 A. A. Kundig et al. Acta Mater. 52, 2441 (2004).
 La27.5Zr27.5Cu15Ni15Al15

10 nm

A. A. Kundig et al. Acta Mater. 52, 2441 (2004).

Phase separation during solidification -

surface
f fractal
f t l

Tg

Tg

T
La-rich
Zr-rich Cu-rich
Cu rich All sizes present from m to ~5 nm
Ni-rich comp Surface fractal dimension: 2.4

A. A. Kundig et al. Acta Mater. 52, 2441 (2004).

 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
2000
ngineering streess (MPa)

1500

Metal

1000
En

Cu43Zr43Al7Ag7
500

KIST
0
0 2 4 6 8 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
melt spun
Relative Intensity (a.u.)

2000
Al
4mm
m
~6 nm

1500

Ag
1000
7mm

500 ~50 nm
8mm

0
20 30 40 50 60 70 80

Diffraction angle, 2

60

40 Cu
20
80
osition (%)

60
40 Zr
20

20
Compo

10 Al
0

20

10 Ag
0
0 5 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 fcc-fcc

Hmix:Negative Hmix: + 6

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%) Stacking

Cu t=0
t=0.2mm5
2mm5 Cu
Y.Saito. et al. Acta Mater.47(1999) 579
Zr t=0.2mm4 Zr
=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 9cycles =13.6
=13 6
shear
band
S. Ohsaki et al. Acta Mater. 55, 2885 (2007).
 HREM image of shear bands

100nm

5nm
Cu-L2,3 image

S. Ohsaki et al. Acta Mater. 55, 2885 (2007).

Forced alloying of Cu/Ag =6.8

Elemental mapping of Ag and Cu atoms
13nm

ND
110nm Ag
Composition profile Cu

Ag layer() Cu layer Ag layer() Cu layer()

90
Ag 95at%Ag
80
95at%Ag
70 60at%Cu
60
at%

50

40 Cu

30 40at%Ag
20 5 t%C
5at%Cu
Light Ag 10 5at%Cu
Dark Cu
1 2 3 4 5 6 7 8 9 10
FIM image
g from TD Depth distance (nm)

9.2kV, 60K, Ne
Intermixing of Ag and Cu layers
S. Ohsaki et al. Acta Mater. 55, 2885 (2007).
Does amorphous form by forced alloyin of Cu/Ag?

5cycles =6.84

BF iimage
HREM image

Nanobeam Dp (0.5nm)
No amorphous

S. Ohsaki et al. Acta Mater. 55, 2885 (2007).

Does amorphous form by forced alloyin of Cu/Ag?

3cycles 5cycles 7cycles

Cu

Zr

Cu

Cu map White: Cu Black: Zr

S. Ohsaki et al. Acta Mater. 55, 2885 (2007).
Alloying and amorphization of Cu/Zr
White: Cu
C map
Cu
1
Black: Zr

2 1
2

Amorphous Crystal
S. Ohsaki et al. Acta Mater. 55, 2885 (2007).

HREM image of Cu/Zr nanolayer

Aft 9cycles
After 9 l

Cu Cu Cu Zr Cu Cu Zr
Amo Amo Amo

Amorphization of some of the Zr lamellae

S. Ohsaki et al. Acta Mater. 55, 2885 (2007).
 Amorphization
p of Cu/Zr by
y forced alloying
y g

S. Ohsaki et al. Acta Mater. 55, 2885 (2007).

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 Martensitic Transformation

The name martensite is after the German scientist

M t
Martens, which
hi h was usedd 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 OR
within 10-7 sec, nearly e.g.
equal to the velocity of Fe-Ni (p
(plate))
(111) //(011) '
(111)//(011)'
sound- no thermal
[10-1]//[-11-1]'
activation (athermal)

Martensitic Transformation
Unlike ferrite or pearlite, martensite forms by a deformation of the austenite
lattice (fcc) to ferrite (bcc) without any diffusion of atoms.

Martensite reaction is athermal transformation; the fraction of transformed

depends on the undercooling below a martensitic start temperture, Ms.
site

10
1.0
on of martens

1 - x = exp{(Ms Tq)}

The athermal
Th th l character
h t iis d
due tto
fractio

very rapid nucleation and growth

0
Mf Ms As Af
T Mf: xx=0.95
0.95
G
G grwoth rate of martensite: ~1100 m/s

c f solidification rate <80 m/s
c.f.

Ms Te T
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 (111)
[112]
are unchanged during the transformation.

The habit plane remains undistorted.

invariant plane
 Bain Modal of fccbcc
C occupy 1/50 x for 1at.%C

C 12%

x'
y'
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}

lath twinned
twinned plate or lens

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

initial strain of the austenite lattice by G A V Gs V Gv

martensite nucleus - coherent small large

shear

2
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
2
2 c* thin plate is favorable
16 s 4 2 Gv
G 2 a 2 a cGv for large Gv, i.e. for
3 2 3 16 ( s / 2)2 large T
4 a*
512 3 s 2 Gv2
G*
3 Gv 4 2
However, most martensitic transformations
~20 eV too high for thermal activation
are heterogeneous - dislocations

Role of dislocations in martensite nucleation

abcabcabc
a2 110 a6 [ 211] a6 [ 1 2 1]
abcababca
12 b 12a [ 211]
1

fcc/bcc/fcc
futhr thickening by
dislocation p
pile ups
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

abcabcabcabc
a
110 a [ 2 11] a [ 1 2 1 ]
2 6 6
abababababab
a
11 2 on{111} (111)//(0001)
6
only with low stacking fault energy
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

16 4 2
G 2 a 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
2 16 ( s / 2)2 thin plate is favorable for large
c* a*
G v Gv2 Gv, i.e. for large T

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

1.0
site
fraction of martens

cooling
0
Mf As Ms Af
T
 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

Ms<T<Af: shape memory

Stressstrain curves of Ti50.6Ni alloy. Ms>Af: superelastic
Miyazaki et al. Scripta Metal. 15 (1981), 287.
 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
slip d
stress twinning
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 comparedd 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
in equilibrium with MmCn
[M] [C]n=K
m

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.