Diffusion

Introduction
Diffusion: Material transport by atomic
motion.
Self diffusion: For pure metals, atoms (of the
same type) exchange positions.
Impurity diffusion (interdiffusion): Atoms
of one metal diffuse in another.

Diffusion phenomena (1)

Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms

C
A
D
B

After some time

C
D

A
B

Diffusion phenomena (2)

Interdiffusion: In an alloy, atoms tend to migrate
from regions of large concentration.
Initially

100%
0

Cu

After some time

Ni

Concentration Profiles

100%
0
Concentration Profiles

Processing using diffusion (1)

Case Hardening:
--Diffuse carbon atoms
into the host iron atoms
at the surface.
--Example of interstitial
diffusion is a case
hardened gear.

Result: The "Case" is

--hard to deform: C atoms
"lock" planes from shearing.
--hard to crack: C atoms put
the surface in compression.

Processing using diffusion (2)

Doping Silicon with P for n-type semiconductors:
Process:
0.5mm
1. Deposit P rich
layers on surface.

magnified image of a computer chip

silicon
2. Heat it.
3. Result: Doped
semiconductor
regions.

silicon

light regions: Si atoms

light regions: Al atoms

Diffusion mechanisms
Conditions for an atom to diffuse:
There must be empty neighboring site.
Atom must have sufficient energy to break bonds
with its neighbor atoms and then cause some
lattice distortion during the displacement.

Diffusion mechanisms
(a) Substitutional (vacancy) Diffusion:
Applies to substitutional impurities (or self diffusion
Atoms exchange with vacancies
Rate depends on:
--number of vacancies
--activation energy to exchange.

increasing elapsed time

Vacancy diffusion
Simulation of
interdiffusion
across an interface:
Rate of substitutional
diffusion depends on:
--vacancy concentration
--frequency of jumping.

(Courtesy P.M. Anderson)

Diffusion mechanisms
(b) Interstitial Diffusion:
Applies to interstitial
impurities.
More rapid than
vacancy diffusion.
Simulation:
--shows the jumping of a
smaller atom (gray) from
one interstitial site to
another in a BCC
structure. The
interstitial sites
considered here are
at midpoints along the
unit cell edges.

(Courtesy P.M. Anderson)

Modeling diffusion: Flux

Flux:
atoms
1 dM kg
J

or

2
2
A dt
m s
m s
Directional Quantity
y J
y
Jz

Jx
x

z
Flux can be measured for:
--vacancies
--host (A) atoms
--impurity (B) atoms

x-direction
Unit area A
through
which
atoms
move.

Concentration profiles and flux

Concentration Profile: C(x): [kg/m3]
Cu flux Ni flux
Concentration
of Cu [kg/m3]

Concentration
of Ni [kg/m3]

Position, x
Fick's First Law:
flux in x-dir.
[kg/m2-s]

Diffusion coefficient [m2/s]

dC
J x D
dx

concentration
gradient [kg/m4]

The steeper the concentration profile,

the greater the flux!

Steady state diffusion

Steady State: the concentration profile doesn't
change with time.
Steady State:
J x(left)

J x(right)

J x(left) =J x(right)

x
Concentration, C, in the box doesnt change w/time.

Apply Fick's First Law:

If Jx)left = Jx)right , then

dC
J x D
dx
dC
dC

dx left dx right

Result: the slope, dC/dx, must be constant

(i.e., slope doesn't vary with position)!

Steady state diffusion (example)

Steel plate at
700C with
geometry
shown:

Carbon
rich
gas

Steady State =
straight line!

Carbon
deficient
gas

0 x1 x2
Q: How much
carbon transfers
from the rich to
the deficient side?

J D

D=3x10-11m2/s

C2 C1
9 kg

2.4 10
x2 x1
m2s

Diffusion and temperature

Diffusivity increases with T.
diffusivity D Do

pre-exponential [m2/s] (see Table 5.2, Callister 6e)

activation energy
Q [J/mol],[eV/mol]
exp d (see Table 5.2, Callister 6e)

RT

gas constant [8.31J/mol-K]

300

10-8
D (m2/s)

600

1500
1000

Experimental Data:

10-14

10-20

0.5

1.0

1.5

T(C)

D has exp. dependence on T

Recall: Vacancy does also!
Dinterstitial >> D
substitutional
Cu in Cu
C in -Fe
Al in Al
C in -Fe
Fe in -Fe
Fe in -Fe
Zn in Cu
2.0 1000K/T

Diffusion data

BTE 2210

Dr. M. Hassan

Summary
Diffusion FASTER for...

Diffusion SLOWER for...

open crystal structures

close-packed structures

lower melting T materials

higher melting T materials

materials w/secondary
bonding

materials w/covalent
bonding

smaller diffusing atoms

larger diffusing atoms

cations

anions

lower density materials

higher density materials