Diffusion in Solids

p. 8.1

Diffusion is

The transport of atoms through matter

The mechanism by which many important

processes occur in materials:

Case hardening of steel

Doping of semiconductors

Oxidation of metals

Solid-state formation of compounds from

individual components

Sintering the process by which an object

made from powders becomes dense and
strong

Types of diffusion in solids

Self-diffusion movement of atoms through their

own lattice

Interdiffusion (a.k.a. impurity diffusion) e.g.,

movement of Ni through the lattice of Cu

Mechanisms

Vacancy diffusion

Interstitial diffusion

Typically, interstitial diffusion is much faster than vacancy

diffusion
EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03

Diffusion in Solids

p. 8.2

VACANCY DIFFUSION vs. INTERSTITIAL DIFFUSION

Vacancy diffusion: a host or substitutional
atom exchanges places with a vacancy
Before jump
After jump

Vacancy

Callister, Fig. 5.3 schematic illustration of diffusion

Interstitial diffusion: an interstitial atom jumps
into an adjacent unoccupied interstice
Before jump
After jump

EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03

Diffusion in Solids

p. 8.3

MACROSCOPIC DESCRIPTION OF DIFFUSION

Ficks first law (in one dimension)

dC
J = D dx

number

J: flux, area time or

mass

area time

1 dM
J = A dt

dC
number/volume

or
:
concentration
gradient,

distance

dx

mass/volume

distance

driving force for diffusion

D: diffusion coefficient for diffusing species in

distance2
solid, time

Minus sign denotes flux is toward lower

concentrations, i.e. down the concentration
gradient

EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03

Diffusion in Solids

p. 8.4

MACROSCOPIC DESCRIPTION OF DIFFUSION (cont.)

Ficks second law

(in one dimension)

[rate of accumulation] = [flux gradient]

C
J
=

t
x
dC
J = D dx

C
C
t = x D x

C
number/volume

or
:
rate
of
accumulation,

time

J
flux in - flux out
:
flux
gradient;
x
distance

Cases

Steady state

mass/volume

time

Flux out = flux in

=
0

Zero accumulation

=
0

Unsteady state

Flux in flux out

Accumulation or depletion

C
2 C
D D(x) t = D x 2

EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03

Diffusion in Solids

p. 8.5

STEADY STATE DIFFUSION

Starting from
Fick's 2nd law in 1-D
with D D(x),

and

assuming steady state,

2 C
C
D x 2 = t

we find:
2 C
x 2 = 0
i.e., the concentration profile is linear
( only a line has a second derivative equal to zero)
J in

J out

steady state: J in = J out

C(x)
conc'n gradient
= slope
= C/ x
x
and the flux J can be calculated from Fick's 1st law simply as
C
Jin = Jout = D x
EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03

Diffusion in Solids

p. 8.6

SOLUTIONS TO FICKS SECOND LAW (start)

C
2 C
=
D
t
x 2
[for D D(x); 1-D]

General comment:
Many functions
C(x,t)
will satisfy this differential equation.
To correctly describe the concentration profile C(x,t)
that occurs in a particular physical situation,
a function must also satisfy the pertinent
initial condition what prevails at t=0
and boundary conditions that hold at some interface or
boundary in our system.

EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03

Diffusion in Solids

p. 8.7

SOLUTIONS TO FICKS SECOND LAW (cont.)

Example thin film solution (start)

S g/cm 2 of solute between two semi-infinite bars

solute layer, S g/cm2

two semi-infinite bars

x
0

i.c.: C(x,0) = 0

b.c. #1: C(,t) = C(,t) = 0

(composition at ends of bars x > 10

Dt will
not change)

b.c. #2: C dx = S
holds for all t

(constant total amount of solute)

Solution:
x 2
S
C(x,t) =
exp 4Dt

4Dt

EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03

Diffusion in Solids

p. 8.8

SOLUTIONS TO FICKS SECOND LAW (cont.)

Example thin film solution (end)

x 2
S
C(x,t) =
exp 4Dt

4Dt

C
t1
t 2 = 2t 1
t 3 = 4t 1

Gaussian distribution (bell-shaped curve)

Finite supply of diffusing species

area under curves remains constant for all t

Useful exercise:

Where does 2C/x 2 = 0? Why is that significant?

EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03

Diffusion in Solids

p. 8.9

SOLUTIONS TO FICKS SECOND LAW (cont.)

Example semi-infinite solid; constant surface

composition CS

i.c.: C(x,0) = CO

b.c. #1: C(,t) = CO

(composition at endof bars x > 10
Dt will not
change)
surroundings maintain

constant surface concn

b.c. #2: C(0,t) = CS

Solution: (see Callister, Eq. 5.5 and Figs. 5.5-5.6)

C(x,t) CO
x

= 1 erf

CS CO
2
Dt

erf(z)
1.0

0.5

z
3

0.5

1.0

EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03

Diffusion in Solids

p. 8.10

SOLUTIONS TO FICKS SECOND LAW (end)

erf solution also gives C(x,t) for two joined semi-infinite

solids:
Callister Figs. 5.1, 5.2

EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03

Diffusion in Solids

p. 8.11

FACTORS INFLUENCING D
A diffusing atom needs
1)

2)

a new site to occupy

Vacancy concentrations and hence

substitutional and self-diffusion depend
strongly on temperature: NV = Nexp(GV/RT)

In contrast, interstitial sites are ~always

available (but only for dilute solutes) number
of available interstitial sites is ~T-independent

energy to leave its current location

b.

Free energy

a.

c.

high solute concn

higher energy

low solute concn

lower energy

a.

b.
Distance, x

c.

Diffusion requires an activation energy

probability of a successful jump exp(G/RT)
EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03

Diffusion in Solids

p. 8.12

FACTORS INFLUENCING D (cont.)

D = DO exp

RT

1
Q
Plot of lnD vs. T will be linear, with slope Rd

Q d, apparent activation energy for diffusion

Increases with size of diffusing atom

Is typically larger (GV + G terms) for vacancy

diffusion than for interstitial diffusion (G term only)

Callister, Figure 5.7 log D vs. 1/T for several metals

EMSE 201 Introduction to Materials Science & Engineering

2003 Mark R. De Guirerev. 2/10/03