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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-
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
Chapter 5-
C
A
D
B
C
A
D
B
DIFFUSION MECHANISMS
Substitutional Diffusion:
applies to substitutional impurities
atoms exchange with vacancies
rate depends on:
--number
number of vacancies
--activation energy to exchange.
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
size
i off solute
l t atoms
t
melting point of solvent
packing efficiency of solvent
number of vacancies
Chapter 5-
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
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]
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
C CB
J = D A
XA XB
2 0 .8
11
) (5 1.10
J = (3 10 11
3
) 10
C/t = -Jx/x
C/s area=unity
y
Chapter 5-
Chapter 5-
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
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 %)
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-
Chapter 5-
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