CHAPTER 5:

DIFFUSION IN SOLIDS
Why study diffusion?
Diffusion plays an important role in
Alloying
Strengthening and heat treatment processes (Ch. 7)
High temperature mechanical behavior (Ch. 8)
Phase transformations (Ch. 10)
Environmental degradation (Ch. 17)

K. M. Flores
Materials Science & Engineering

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.
x (mm)

time (s)

K. M. Flores
Materials Science & Engineering

5-2

DIFFUSION
Interdiffusion:
Initially

After some time

Adapted from Figs. 5.1

and 5.2, Callister 6e.

100%

Cu

Ni

100%

Concentration Profiles

0
Concentration Profiles

K. M. Flores
Materials Science & Engineering

5-3

DIFFUSION
Self-diffusion:

Label some atoms (e.g. isotopes)

After some time

C
A
D

C
A

K. M. Flores
Materials Science & Engineering

5-4

PROCESSING USING DIFFUSION

Fig. 5.0, Callister 6e.
(Fig. 5.0 is
courtesy of
Surface Division, MidlandRoss.)

Case Hardening:
Diffuse carbon atoms into the
host iron atoms at the surface
Example: 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.
K. M. Flores
Materials Science & Engineering

5-5

PROCESSING USING DIFFUSION

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

0.5mm

magnified image of a computer chip

silicon
Fig. 18.0, Callister 6e.

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

silicon
K. M. Flores
Materials Science & Engineering

light regions: Si atoms

light regions: Al atoms

5-6

PROCESSING USING DIFFUSION

Diffusion Bonding
Solid state joining process
Apply heat & pressure
across interface to be
joined
Local plastic deformation +
diffusion = joint!
Useful for joining difficult to
weld metals, dissimilar
materials, metals and
ceramics

B-1B
Image from http://www.user.lasercom.net/normajean/prod02.htm, downloaded October 3, 2005.

K. M. Flores
Materials Science & Engineering

5-7

DIFFUSION MECHANISMS
Substitutional Diffusion:
Applies to substitutional impurities
Atoms exchange with vacancies

K. M. Flores
Materials Science & Engineering

increasing elapsed time

5-8

DIFFUSION SIMULATION
Simulation of
interdiffusion
across an interface:
Rate of substitutional
diffusion depends on:
--vacancy concentration
--frequency of jumping.
Results in mixing up of
red and blue atoms.
(Courtesy P.M. Anderson)

K. M. Flores
Materials Science & Engineering

5-9

DIFFUSION MECHANISMS
Interstitial Diffusion:
Small atoms move through interstitial sites
Large concentration of interstitial vacancies

Simulation:
smaller atom jumps between
interstitial sites in a BCC
structure. The interstitial
sites are at the midpoints of
the unit cell edges.
(Courtesy P.M. Anderson)

K. M. Flores
Materials Science & Engineering

5-10

MODELING DIFFUSION: FLUX

Flux, J:

Directional Quantity
y J
y

x-direction
Unit area A
through
which
atoms
move.

Jx
x

Jz

z
Flux can be measured for:
--vacancies
--host (A) atoms
--impurity (B) atoms
K. M. Flores
Materials Science & Engineering

5-11

CONCENTRATION PROFILES & FLUX

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

Ni flux

Concentration
of Cu [kg/m3]

Adapted from Fig. 5.2(c),

Callister 6e.

Concentration
of Ni [kg/m3]

Position, x

Steady-state diffusion described by Fick's First Law:

dC
Jx = D
dx
The
steeper the concentration profile, the greater the flux!
K. M. Flores
Materials Science & Engineering

5-12

DIFFUSION AND TEMPERATURE

Diffusivity, D, increases with T:
pre-exponential

[m2/s]

For data on D0 and QD see

Table 5.2, Callister 6e

QD activation energy [J/mol],[eV/mol]

diffusivity D = D0 exp
RT
gas constant [8.31 J/mol-K]

300

600

1000
in
Fe
-

D has exp. dependence on T

Recall: Vacancy conc. does also!

0.5

Al
in
Al
Cu
Cu in -Fe
in uin
C
Fe Fe
-

10 -20

n
-Fe

Dinterstitial

Zn

10 -14

Ci

C in -Fe
C in -Fe

in
Fe

D (m2/s)

T(C)

10 -8

1500

Experimental Data:

1.0

K. M. Flores
Materials Science & Engineering

1.5

2.0

Dsubstitutional

1000K/T

Cu in Cu
Al in Al
Fe in -Fe
Fe in -Fe
Zn in Cu

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., ButterworthHeinemann, Oxford, 1992.)

5-13

STEADY STATE DIFFUSION

Steady State: the concentration profile doesn't change with time.

J x(left)

J x(right)

x
Concentration, C, in the box doesnt change with time.

Apply Fick's First Law:

J x = D

dC
dx

dC
dC

=

If Jx(left) = Jx(right) , then
dx left dx right
K. M. Flores
Materials Science & Engineering

5-14

STEADY STATE DIFFUSION EXAMPLE

1.2 kg/m3
0.8 kg/m3

Steel plate at 700C with one

side exposed to C-rich gas:

At steady state,
conc. gradient is
straight line.

C1
C2

Carbon
rich
gas

Adapted from Fig. 5.4,

Callister 6e.

Carbon
deficient
gas

Diffusivity of C in steel at 700C:

D = 3 x 10-11 m2/s

0 x1 x2
5 mm

10 mm

What is the flux of C

diffusing from the C-rich to
the C-deficient side?
K. M. Flores
Materials Science & Engineering

5-15

NON STEADY STATE DIFFUSION

dx

Concentration profile,
C(x), changes w/ time.

J (left)

J (right)
Concentration in
the box, C = f(t)

To conserve matter:

Fick's First Law:

J (right) J (left)
dC
=
dx
dt
dJ

= dC
dx
dt

J = D dC
dx
dJ
dx

= D

d2C
dx2

Differentiate both
sides, assume D does
not vary with x

equate

Governing Eqn.:

Ficks
2nd Law
K. M. Flores
Materials Science & Engineering

5-16

NON STEADY STATE DIFFUSION EXAMPLE

Copper diffuses into a bar of aluminum.
Surface conc. of
Cu atoms, Cs

Al bar
pre-existing concentration of Cu in bar, C0

Cs

(steady state!)

C(x,t)
Co

t0 t1

t2

t3

Adapted from Fig. 5.5, Callister

6e.

position, x
General solution:

x
C(x, t ) Co =
1 erf 2 Dt
Cs Co

K. M. Flores
Materials Science & Engineering

5-17

PROCESSING EXAMPLE
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?
Given: D500 = 4.8 x 10-14 m2/s, D600 = 5.3 x 10-13 m2/s

x
Cx Co
= 1 erf

Cs Co
2 Dt

K. M. Flores
Materials Science & Engineering

5-18

DIFFUSION DEMO: ANALYSIS

The experiment: we recorded combinations of
t and x that kept C constant.

x i
C(x i , t i ) Co
= 1 erf
2 Dt i
Cs C o

= constant

K. M. Flores
Materials Science & Engineering

5-19

DATA FROM DIFFUSION DEMO

K. M. Flores
Materials Science & Engineering

5-20

10

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
bonding

materials w/covalent
bonding

smaller diffusing atoms

larger diffusing atoms

cations

anions

lower density materials

higher density materials

K. M. Flores
Materials Science & Engineering

5-21

11