CHAPTER 5:

DIFFUSION IN SOLIDS

ISSUES TO ADDRESS...
How does diffusion occur?

Why is it an important part of processing?

How can the rate of diffusion be predicted for

some simple cases?

How does diffusion depend on structure

and temperature?

Chapter 5- 1
 DIFFUSION DEMO
Glass tube filled with water.
At time t = 0, add some drops of ink to one end
of the tube.
Measure the diffusion distance, x, over some time.
Compare the results with theory.

to x (mm)
t1
t2
t3
time (s)
xo x1 x2 x3

Chapter 5- 2
 DIFFUSION: THE PHENOMENA (1)
Interdiffusion: In an alloy, atoms tend to migrate
from regions of large concentration.
Initially After some time

Adapted
from Figs.
5.1 and
5.2,
Callister 6e.

Cu Ni
100% 100%

0 0
Concentration Profiles Concentration Profiles
Chapter 5- 3
 DIFFUSION: THE PHENOMENA (2)
Self-diffusion: In an elemental solid, atoms
also migrate.

Label some atoms After some time

C
C
A D
A
D
B
B

Chapter 5- 4
 DIFFUSION MECHANISMS
Substitutional Diffusion:
applies to substitutional impurities
atoms exchange with vacancies
rate depends on:
--number of vacancies
--activation energy to exchange.

increasing elapsed time

Chapter 5- 5
 DIFFUSION SIMULATION
Simulation of
interdiffusion
across an interface:

Rate of substitutional
diffusion depends on:
--vacancy concentration
--frequency of jumping.

(Courtesy P.M. Anderson)

Chapter 5- 6
 INTERSTITIAL SIMULATION
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 (Courtesy P.M. Anderson)

at midpoints along the

unit cell edges. Chapter 5- 7
PROCESSING USING DIFFUSION (1)
Case Hardening:
--Diffuse carbon atoms Fig. 5.0,
Callister 6e.
into the host iron atoms (Fig. 5.0 is
courtesy of
at the surface. Surface
Division,
--Example of interstitial Midland-
Ross.)
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.

Chapter 5- 8
 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
Fig. 18.0,
2. Heat it. Callister 6e.

3. Result: Doped
light regions: Si atoms
semiconductor
regions.

light regions: Al atoms

silicon
Chapter 5- 9
 MODELING DIFFUSION: FLUX
Flux:
1 dM kg atoms
J or
A dt 2
m s 2
m s
Directional Quantity x-direction
y J
y

Jx Unit area A
Jz x through
z which
Flux can be measured for: atoms
--vacancies move.
--host (A) atoms
--impurity (B) atoms
Chapter 5- 10
 CONCENTRATION PROFILES & FLUX
Concentration Profile, C(x):
[kg/m3] Cu flux Ni flux

Concentration Concentration Adapted

of Cu [kg/m3] of Ni [kg/m3]
from Fig.
5.2(c),
Callister 6e.

Position, x
Fick's First Law:
flux in x-dir. Diffusion coefficient [m2/s]
[kg/m2-s] dC
J x D concentration
dx gradient [kg/m4]
The steeper the concentration profile,
the greater the flux!
Chapter 5- 11
 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.
dC
Apply Fick's First Law: J x D
dx
dC dC
If Jx)left = Jx)right , then dx
left dx right

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

(i.e., slope doesn't vary with position)!
Chapter 5- 12
 EX: STEADY STATE DIFFUSION
Steel plate at
700C with
geometry
shown: Carbon Steady State =
rich straight line! Adapted
gas Carbon
from Fig.
5.4,
deficient Callister 6e.

gas
D=3x10-11m2/s
0 x1 x2
Q: How much
carbon transfers
from the rich to C2 C1 9 kg
J D
2.4 10
the deficient side? x2 x1 m2s

Chapter 5- 13
 NON STEADY STATE DIFFUSION
dx
Concentration profile,
C(x), changes J (left) J (right)
w/ time.
Concentration,
C, in the box
To conserve matter: Fick's First Law:
J (right) J (left) dC dC
J D or
dx dt dx
dJ dC dJ d2 C (if D does
D not vary
dx dt dx dx2 with x)
equate
Governing Eqn.:
dC d2C
=D 2
dt dx Chapter 5- 14
EX: NON STEADY STATE DIFFUSION
Copper diffuses into a bar of
aluminum.
Surface conc.,
C s of Cu atoms bar
pre-existing conc., C o of copper atoms
C(x,t)
Cs

t3 Adapted from
t2 Fig. 5.5,
t1 Callister 6e.
t
Co o
position, x
General solution: C(x, t) C x
o 1 erf
Cs Co 2 Dt
"error function"
Values calibrated in Table 5.1, Callister 6e.
Chapter 5- 15
 PROCESSING QUESTION
Copper diffuses into a bar of aluminum.
10 hours at 600C gives desired C(x).
How many hours would it take to get the same C(x)
if we processed at 500C?
Key point 1: C(x,t500C) = C(x,t600C).
Key point 2: Both cases have the same Co and Cs.
Result: Dt should be held constant.
C(x,t) Co x
=1 erf (Dt)500C =(Dt)600C
Cs Co 2Dt

5.3x10-13m2/s 10hrs
(Dt)600 Note: values
Answer: t 500 110hr of D are
-
D500 provided here.
14
4.8x10 m /s2
Chapter 5- 16
 DIFFUSION DEMO: ANALYSIS
The experiment: we recorded combinations of
t and x that kept C constant.
to
t1
t2
t3
xo x1 x2 x3
x
C(xi,ti ) Co
1 erf i
= (constant here)
Cs Co 2 Dti

Diffusion depth given by:

xi Dti

Chapter 5- 17
 DATA FROM DIFFUSION DEMO
ln[x(mm)]
4
BB
BBBB
3.5 BB
BB
BB
3 B
B
2.5
2 Linear regression fit to data:
1.5 ln[x(mm)] 0.58ln[t(min)] 2.2
1 R2 0.999
0.5
0
0 0.5 1 1.5 2 2.5 3
ln[t(min)]
Experimental result: x ~
t0.58
Theory predicts x ~ t0.50
Reasonable agreement!
Chapter 5- 18
 DIFFUSION AND TEMPERATURE
Diffusivity increases with
T. pre-exponential [m2/s] (see Table 5.2, Callister 6e)
activation energy
Q [J/mol],[eV/mol]
diffusivity D Doexp d (see Table 5.2, Callister 6e)
RT
gas constant [8.31J/mol-K]
Experimental
Data:
1500
1000
600

300 T(C)
10-8 D has exp. dependence on T
D (m2/s) Recall: Vacancy does also!
Dinterstitial >> D
substitutional
10-14 C in -Fe Cu in Cu
C in -Fe Al in Al
Fe in -Fe
Fe in -Fe
Zn in Cu
10-20
0.5 1.0 1.5 2.0 1000K/T
Adapted from Fig. 5.7, Callister 6e. (Date for Fig. 5.7 taken

from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
Reference Book, 7th ed., Butterworth-Heinemann, Oxford,
Chapter 5- 19
 SUMMARY:
STRUCTURE & DIFFUSION
Diffusion FASTER for... Diffusion SLOWER for...

open crystal structures close-packed structures

lower melting T materials higher melting T materials

materials w/secondary materials w/covalent

bonding bonding

smaller diffusing atoms larger diffusing atoms

cations anions

lower density materials higher density materials

Chapter 5- 20