Diffusion

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Diffusion

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THERMALLY ACTIVATED

PROCESSES AND DIFFUSION IN

SOLIDS

Chapter 5-

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 DEFINED :

The phenomenon of material transport by

movement of atoms.

atoms

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.

theory

s

e

c

to

t1

t2

t3

xo

x1

x2 x3

mm

Chapter 5-

Interdiffusion: In an alloy, atoms tend to migrate

from regions of large concentration.

I iti ll

Initially

100%

0

Cu

Aft some ti

After

time

Ni

100%

C

Concentration

t ti P

Profiles

fil

0

C

Concentration

t ti P

Profiles

fil

Chapter 5- 3

DIFFUSION MECHANISMS

Takes place in presence of vacancies and

i t

interstitial

titi l voids

id off suitable

it bl size.

i

break the bonds with neighboring atoms

There are vacant sites where the diffusing atoms

can move.

move

Diffusion rate increases at elevated temperature.

mechanisms:

h i

self,

lf vacancy, interstitial

i t

titi l etc.

t

Chapter 5-

Self-diffusion: In an elemental solid, atoms

also migrate.

Label some atoms

C

A

D

B

C

A

D

B

y formation + activation energy

gy of movement

vacancy

of vacancy

Chapter 5- 4

DIFFUSION MECHANISMS

Substitutional Diffusion:

applies to substitutional impurities

atoms exchange with vacancies

rate depends on:

--number

number of vacancies

--activation energy to exchange.

Chapter 5- 5

DIFFUSION SIMULATION

Simulation of

interdiffusion

across an interface:

Rate of substitutional

diffusion depends on:

--vacancy concentration

--frequency of jumping.

Chapter 5-

INTERSTITIAL DIFFUSION

Applies to interstitial

impurities.

impurities

More rapid than

vacancy diffusion.

-- shows the jumping of a

smaller atom (gray) from

one interstitial site to

another in a BCC

structure. The

interstitial sites

considered here are

at midpoints along the

unit cell edges.

Chapter 5- 7

Temperature

size

i off solute

l t atoms

t

melting point of solvent

packing efficiency of solvent

number of vacancies

Chapter 5-

Flux:

atoms

1 dM kg

J=

or

2

2

A dt

m s

m s

Directional Quantity

y J

y

Jz

Jx

x

z

Flux can be measured for:

--vacancies

--host

host (A) atoms

--impurity (B) atoms

x-direction

di

ti

Unit area A

through

which

atoms

move.

Chapter 5- 10

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

Cu flux Ni flux

Concentration

of Cu [[kg/m

g 3]

Fick

Fick's

s First Law:

flux in x-dir.

[kg/m2-s]

Concentration

of Ni [[kg/m

g 3]

Position, x

Diffusion coefficient [m2/s]

dC

Jx = D

dx

concentration

gradient [kg/m4]

the greater the flux!

Chapter 5- 11

Steady State: the concentration profile doesn't

change with time.

Steady State:

Jx(left)

Jx(right)

Jx(left) = Jx(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

Steel plate at

700C with

geometry

g

y

Carbon

shown:

rich

gas

3

m

g/

k

2

3

.

m

=1

/

kg

C1

8

.

=0

C2

Steady State =

straight line!

Carbon

deficient

gas

D=3x10

D

3x10-11m2/s

5m

J = D

Q: How much

carbon transfers

from the rich to

the deficient side?

m

10

0 x1 x2

C2 C1 =

9 kg

2.4 10

x2 x1

m2s

Chapter 5- 13

A pplate of iron is exposed

p

to carburizingg ((carbon-rich))

atmosphere on one side and a decarburizing atmosphere on the

other side at 7000C.

C If a condition of steady state is achieved,

achieved

calculate the diffusion flux of carbon through the plate if the

concentrations

t ti

off carbon

b att positions

iti

5 andd 10 mm beneath

b

th

carburizing surface are 1.2 and 0.8 kg/m3, respectively.

C CB

J = D A

XA XB

2 0 .8

11

) (5 1.10

J = (3 10 11

3

) 10

Chapter 5-

The flux is not same at different sections

perpendicular

p

p

to the diffusion

time

There is a net accumulation or depletion of

diffusing species.

x

Jx Jxx+x

(

)

x=(C/t)x

x

C/t = -Jx/x

C/s area=unity

y

Chapter 5-

C/t = -/x(-D(C/x)

If D does not depend on concentration

C/t = D(2C/x2)

The solution to 1D equation is

C(x,t) = A B erf(x/2Dt)

A,B are constants determined from initial and

final boundary conditions of the problem.

Chapter 5-

General solution:

x

C(x, t) Co =

1 erf

2 Dt

Cs Co

"error function"

Boundary conditions

the two media are considered to be semi-infinite

concentrations on either side of the interface

change abruptly and are uniform

x=0 at the interface

t=0 when diffusion begins

Chapter 5- 15

NON STEADY

ST A Y STATE

STAT DIFFUSION

IFFUSION

Cs

C(x,t)

to t1

Co

t

t2 3

position, x

At t=0(to)

(0.25 wt %)

At t>0

C(x

C(x,t)

t) = Cx

(0 80 wt %)

(0.80

for 0<x<

(1.20 wt %)

(1.20 wt %)

? 5-

Case Hardening:

--Diffuse carbon atoms

into the host iron atoms

at the surface.

--Example of interstitial

diffusion is a case

hardened gear.

--hard to deform: C atoms

"lock"

lock planes from shearing.

shearing

--hard to crack: C atoms put

the surface in compression.

Chapter 5- 8

Carburization of steel

C(x,0)=c1 x> 0

C(0,t)=cs

Steel

Carburizing atmosphere

Cs

C1

0

x

C(x,0)=c2 x< 0

C(0,t)=cs

Steel

Decarburizing atmosphere

C2

Cs

0

x

Chapter 5-

( )

Corrosion resistance of duralumin

Alloy of Al with 4% Cu

Much higher strength

than Al

Corrosion resistance

poor compared to Al

Duralumin sheets covered with thin Al sheets on both

sides

ALCLAD

Chapter 5-

Diffusing Species

Self and interdiffusion

e.g.

g self and C interdiffusion in -iron diffusion coefficient varies ((3 x 10-21

vs 2.4 x 10-12 m2/s)

Temperature

Diffusion coefficient changes with temperature

The temperature dependent D is given by

Qd

D = DO exp

RT

DO = Temperature independent pre-exponential (m2/s)

Qd = Activation energy in J/ mol, eV/ atom

R = Gas constant (8.31 J/mol-K or 8.62 x 10-5 eV/ atom- K)

T = absolute temperature (K)

Chapter 5-

Chapter 5-

Chapter 5-

SUMMARY:

STRUCTURE & DIFFUSION

Diffusion FASTER for...

close-packed structures

materials w/secondary

bonding

materials w/covalent

bonding

cations

anions

lower

l

d

density

it materials

t i l

higher

hi h d

density

it materials

t i l

Chapter 5- 20

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