Diffusion in Solids p. 8.

1
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
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
Diffusion in Solids p. 8.2
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
VACANCY DIFFUSION vs. INTERSTITIAL DIFFUSION
Vacancy diffusion: a host or substitutional
atom exchanges places with a vacancy
Vacancy
Before jump After jump
Callister, Fig. 5.3 schematic illustration of diffusion
Interstitial diffusion: an interstitial atom jumps
into an adjacent unoccupied interstice
After jump Before jump
Diffusion in Solids p. 8.3
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
MACROSCOPIC DESCRIPTION OF DIFFUSION
Ficks first law (in one dimension)
J = D
dC
dx
J: flux,

_ number
area time
or

_ mass
area time
J =
1
A

dM
dt

dC
dx
: concentration gradient,

_ number/volume
distance
or

_ mass/volume
distance
driving force for diffusion
D: diffusion coefficient for diffusing species in
solid,

_ distance
2
time
Minus sign denotes flux is toward lower
concentrations, i.e. down the concentration
gradient
Diffusion in Solids p. 8.4
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
MACROSCOPIC DESCRIPTION OF DIFFUSION (cont.)
Ficks second law (in one dimension)
[rate of accumulation] = [flux gradient]

C
t
=
J
x
J = D
dC
dx

C
t
=

_
D
C
x

C
t
: rate of accumulation,

_ number/volume
time
or

_ mass/volume
time

J
x
: flux gradient;
flux in - flux out
distance
Cases
Steady state
Flux out = flux in

_

J
x
= 0
Zero accumulation

_

C
t
= 0
Unsteady state
Flux in flux out
Accumulation or depletion
D D(x)
C
t
= D

2
C
x
2
Diffusion in Solids p. 8.5
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
STEADY STATE DIFFUSION
Starting from
Fick's 2nd law in 1-D
with D D(x),
and assuming steady state,

D

2
C
x
2
=
C
t
= 0
we find:

2
C
x
2
= 0
i.e., the concentration profile is linear
( only a line has a second derivative equal to zero)
steady state:
C(x)
x
conc'n gradient
= slope
J
in
J
out
=
= C/ x
J
out
J
in
and the flux J can be calculated from Fick's 1st law simply as
J
in
= J
out
= D
C
x
Diffusion in Solids p. 8.6
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
SOLUTIONS TO FICKS SECOND LAW (start)
C
t
= D

2
C
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.
Diffusion in Solids p. 8.7
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
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/cm
2
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:
C(x,t) =
S

4Dt
exp

_
x
2
4Dt
Diffusion in Solids p. 8.8
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
SOLUTIONS TO FICKS SECOND LAW (cont.)
Example thin film solution (end)
C(x,t) =
S

4Dt
exp

_
x
2
4Dt
C
x
t
1
t
1
t
2
= 2
t
1
t
3
= 4
Gaussian distribution (bell-shaped curve)
Finite supply of diffusing species
area under curves remains constant for all t
Useful exercise:
Where does
2
C/x
2
= 0? Why is that significant?
Diffusion in Solids p. 8.9
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
SOLUTIONS TO FICKS SECOND LAW (cont.)
Example semi-infinite solid; constant surface
composition C
S
i.c.: C(x,0) = C
O
b.c. #1: C(,t) = C
O
(composition at endof bars x > 10

Dt will not
change)
b.c. #2: C(0,t) = C
S

'
surroundings maintain
constant surface concn
Solution: (see Callister, Eq. 5.5 and Figs. 5.5-5.6)
C(x,t) C
O
C
S
C
O
= 1 erf

_
x
2

Dt
erf(z)
1.0
0.5
0.5
1.0
1 2 3 1 2 3
z
Diffusion in Solids p. 8.10
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
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
Diffusion in Solids p. 8.11
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
FACTORS INFLUENCING D
A diffusing atom needs
1) a new site to occupy
Vacancy concentrations and hence
substitutional and self-diffusion depend
strongly on temperature: N
V
= Nexp(G
V
/RT)
In contrast, interstitial sites are ~always
available (but only for dilute solutes) number
of available interstitial sites is ~T-independent
2) energy to leave its current location
a. b. c.
a. b. c.
F
r
e
e

e
n
e
r
g
y
G

Distance, x

high solute concn

higher energy
low solute concn
lower energy
Diffusion requires an activation energy
probability of a successful jump exp(G

/RT)
Diffusion in Solids p. 8.12
EMSE 201 Introduction to Materials Science & Engineering 2003 Mark R. De Guirerev. 2/10/03
FACTORS INFLUENCING D (cont.)
D = D
O
exp

Q
d
RT
Plot of lnD vs.
1
T
will be linear, with slope
Q
d
R
Q
d
, apparent activation energy for diffusion
Increases with size of diffusing atom
Is typically larger (G
V
+ G

terms) for vacancy

diffusion than for interstitial diffusion (G

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