Diffusion in Amorphous Metals

Introduction
Production Of Metallic Glasses:
techniques & Procedure
Self Diffusion in Amorphous Metals:
Dominant mechanism
Diffusion of Small Interstitial Solute Atoms:
Dominant mechanism
Evaluate Equations
Production Of Metallic Glasses
Avoid Of Solidification By Crystallization With
Rapid Quenching below T
m
supercooled liquid
undergoes a glass transition to an amorphous glassy
Low Temp +Loss Free Vol
lose its characteristic fluidity
become relatively rigid
Production Techinques Of Amorphous Metals
1- Sputtering and PVD or CVD techniques:
Mainly used for amorphous thin films.
2- Solid state reactions:
Diffusion couples, Mechanical alloying.
3- Electrochemical deposition:
For amorphous surface coatings.
4- Production from the melt by casting techniques:
Splat quenching with R
C
10
6
Ksec
-1
Melt spinning with R
C
10
4
Ksec
-1
High-pressure die casting R
C
10
2
Ksec
-1
Suction mold casting with RC 10
2
Ksec
-1
Self Diffusion in Amorphous Metals
If a rapidly cooled
metallic glass
reheated and annealed
isothermally at Below T
g
excess free volume
will anneal out
the system attempts to relax and
equilibrate without crystallizing
Self-diffusion coefficient of
59
Fe in
amorphous Fe
40
Ni
40
B
20
during
isothermal annealing below T
g
, after
rapid quenching from liquid state
Time independent
Exhibit Arrhenius Behavior
(lnD
i
vs 1/T appear straight line)
Self Diffusion in Amorphous Metals
Self-diffusion occurs by a direct collective mechanism
and is not aided by point defects in thermal equilibrium
as in the vacancy mechanism for self-diffusion in crystals
Why?
Cause 1
Sudden changes in temperature during diffusion
Cause instantaneous changes in the diffusivity.
if diffusion occurs by a point-defect
mechanism significant time is required
Self-diffusion occurs by a direct collective mechanism
not point defects mechanism
Self Diffusion in Amorphous Metals
Cause 2
Activation Volume
for Diffusion
=
Activation Volume
of Defect formation
+
Activation Volume
of Defect Migration
As Mesured by
Experimental
Accuracy is ZERO
Why Self-diffusion occurs by a direct collective
mechanism not point defects mechanism?
ZERO
Self Diffusion in Amorphous Metals
Why Self-diffusion occurs by a direct collective
mechanism not point defects mechanism?
Cause 3
Computer simulations of the diffusion process in relaxed
Fe-Zr glasses reveal diffusion which takes place directly
via thermally activated displacement chains
Diffusion of Small Interstitial Solute Atoms
Small solute atoms in the interstices between the
larger host atoms in a relaxed metallic glass diffuse by
the direct interstitial mechanism.
An example is the diffusion of H solute atoms in
glassy Pd
80
Si
20
.
Diffusion of Small Interstitial Solute Atoms
*pk = fraction of all sites that are tracer-occupied type k sites
The following quantities will be of use in describing the
interstitial self-diffusion and intrinsic chemical diffusion:
N = total number of interstitial sites
p = fraction of all interstitial sites that are occupied
*p = fraction of all sites that are tracer-interstitial occupied
P
k
o
= fraction of all sites that are type k sites
P (k) = fraction of type k sites that are occupied
p
k
= fraction of all sites that are occupied type k sites
Diffusion of Small Interstitial Solute Atoms
Diffusion of Small Interstitial Solute Atoms
because each site can accommodate only one interstitial,
The Occupation Probability at the various sites should
follow Fermi-Dirac statistics ,therefore:
) ( ) (
1
1
) (
kT G
k
e
k p

+
=
G
k
= the energy corresponding to occupation of the type k site
P (k) = fraction of type k sites that are occupied
= chemical potential of interstitial
Diffusion of Small Interstitial Solute Atoms
The Fraction of all interstitial sites that occupied:

+
= =
k
kT G
o
k k
o
k
k
e
p
N
Np k p
k p
) ( ) (
1
) (
) (

The partial Concentration is:

=
+
= =

k
k
kT G
o
k
o
k
p p and
e
p
N
k Np p
k p
k
) ( ) (
1
) (
) (

Since the inert and tracer interstitials are randomly
intermixed in each local region
p
p
p
p
k
k
* *
=
(Eq 1)
(Eq 1)
) ( ) (
*
*
1
kT G
o
k
k
k
e
p
p
p
p

+
=
Diffusion of Small Interstitial Solute Atoms
Slab I Slab II
Unit area
C
X
C
X
X
X
The Jump rate of a tracer
interstitial from i site to
adjacent empty i site is:
) ( ) ( ' kT Gk Eo Go
ki
e
+
= I
X
0
Diffusion of Small Interstitial Solute Atoms
The net number of jumps all types crossing the x = x
0
plane per unit time in X direction is:
| | | | { }

A + A
I I A
O
=
i k
x x ki i
o
i k x x ki i
o
i k I
o o
p p p p p p x g J
2 /
' *
2 /
' * *
) ( ) (

g = a purely geometrical constant

= the ratio of interstitial sites to atoms
= the average atomic volume in the glass
= the number of interstitial sites per unit volume
O

O
(p
i
o
- p
i
) = the probability that a site is an empty i site
Diffusion of Small Interstitial Solute Atoms
During tracer self-diffusion, the total concentration
of inert and tracer interstitial atoms is constant
p & (p
i
o
- p
i
) ar Independent of X
With perform Taylor Expansion:

c
c
(

O
A
=

i k
kT G
kT G G o
i
i
o
i
kT E
I
x
p
p e
e p
p p e
x g
J
k
o k
o
*
) ( ) (
) ( ) (
) (
2
*
1
1
) (
) (

With using:
) /( ) (
1
, , 1 ) ( , 1
kT G
o
k
k
k
k
i
i
o
i
i
o
i
k
e
p
p p p p p p p

+
= = = =

Diffusion of Small Interstitial Solute Atoms
) ( ) ( ) ( ) (
) ( ) (
) ( ) (
) 1 ( ) (
1
kT G
k
k
o
k
kT G
k
kT G
kT G G o
i
o o
k
o k
e p p p e
e
e p

= =
(

x
p
e
p
p
e
x g
J
kT G kT E
I
o
o
c
c
O
A
=

*
) ( ) (
2
) (
2
*
) 1 ( ) (

Diffusion of Small Interstitial Solute Atoms

The Simpler Form of
*
J
I
is:
x
p
e
p
p
D J
kT G o
I I
o
c
c
O

=

*
) ( ) (
2
* *
) 1 (

Ficks Low
Equation
) ( ) (
2
* *
) 1 (
kT G o
I I
o
e
p
p
D D

=

) ( 2 *
) (
kT E o
I
o
e x g D

A =
Corresponding
to
Diffusion of Small Interstitial Solute Atoms
o
I I
D
p
D
*
ln
ln
1
|
|
.
|

\
|
c
c
+ =

is Activity Coefficient A function of Concentration
and Position
diffusivity vs
concentration
prbability of
H at different
temperatures
in Pd80Si20
*D
i
glassy Ni80Zr50 of
various solute atoms as
a function of their size
Diffusion of Small Interstitial Solute Atoms
D
I
H Concentration
Radius Metalic D
I
Small Interstitial
Solute atom is
Dominant
Discussion
Time independent
Exhibit Arrhenius Behavior
1- Self Diffusion in
Amorphous Metals
2-Diffusion of Small
Interstitial Solute Atoms
D
I
Interstitial
atom Concentration
Radius Metalic
D
I
Reference
1- KINETICS OF MATERIALS Robert W. Balluffi Samuel M. Allen
W.Craig Carter
2- AMORPHOUS MATERIALS Laboratory Class Tutorial by
R.Wunderlich University of Ulm Abteilung Werkstoffe derElektro
technic Version 20 Dec 2004
3- An Explanation of Anomalous Diffusion Patterns Observed in
Electroactive Materials by Impedance Methods Juan Bisquert,* Germa
Garcia-Belmonte, and Angeles Pitarch
4-Amorphous Semiconduncer Are denser M. Popescu, F. Sava, W. Hoyera
June 2006
5- Exciting New Coatings For Amprphous Glass Pulse CoresRichard H
Wood, and Richard Lathlaen* National-Arnold Magnetics 17030 Muskrat
Ave Adelanto, CA 92301