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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:

(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

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

diffusion than for interstitial diffusion (G

term only)

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

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