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CHAPTER 5:

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-

DIFFUSION: THE PHENOMENA ((1))


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

The diffusing atoms have enough energy to


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-

DIFFUSION: THE PHENOMENA ((2))


Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms

C
A
D
B

After some time

C
A

D
B

Activation energy for self diffusion = act. Energy of


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.

increasing elapsed time


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

FACTORS INFLUENCING DIFFUSION


Temperature

size
i off solute
l t atoms
t
melting point of solvent
packing efficiency of solvent
number of vacancies

Chapter 5-

MODELING DIFFUSION: FLUX


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 PROFILES & FLUX


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 steeper the concentration profile,


the greater the flux!
Chapter 5- 11

STEADY STATE DIFFUSION


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

EX: STEADY STATE DIFFUSION

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

Diffusion Flux computation


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

= 2.4 x 10-9 kg/m2s


Chapter 5-

NON-STEADY STATE DIFFUSION


The flux is not same at different sections
perpendicular
p
p
to the diffusion

The flux through a given cross-section varies with


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-

NON STEADY STATE DIFFUSION


C/t = -/x(-D(C/x)
If D does not depend on concentration
C/t = D(2C/x2)

Ficks second Law


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-

NON STEADY STATE DIFFUSION


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

Tabulation of Error function Table 5.1


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)

C(x,0) = Co for 0<x<

(0.25 wt %)

At t>0

C(x
C(x,t)
t) = Cx

(0 80 wt %)
(0.80

for 0<x<

C(0,t) = Cs for x=0

(1.20 wt %)

C(-x,t) = Cs for x=-

(1.20 wt %)

(Dc in steel = 1.6 x 10-11 m2/s, x = 0.5 mm ) t =Chapter


? 5-

PROCESSING USING DIFFUSION ((1))


Case Hardening:
--Diffuse carbon atoms
into the host iron atoms
at the surface.
--Example of interstitial
diffusion is a case
hardened gear.

Result: The "Case" is


--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-

PROCESSING USING DIFFUSION (3)


( )
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-

Factors that influence diffusion


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...

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
l
d
density
it materials
t i l

higher
hi h d
density
it materials
t i l
Chapter 5- 20