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Mechanisms
Gases & Liquids random (Brownian) motion
Solids vacancy diffusion or interstitial diffusion
Diffusion
Interdiffusion: In an alloy, atoms tend to migrate
from regions of high conc. to regions of low conc.
Initially After some time
Adapted from
Figs. 6.1 and
6.2, Callister &
Rethwisch 3e.
Diffusion
Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms After some time
C
C
A D
A
D
B
B
3
Diffusion Mechanisms
Vacancy Diffusion:
atoms exchange with vacancies
applies to substitutional impurities atoms
rate depends on:
-- number of vacancies
-- activation energy to exchange.
Diffusion Mechanisms
Interstitial diffusion smaller atoms can
diffuse between atoms.
hardened gear.
6
Processing Using Diffusion
Doping silicon with phosphorus for n-type semiconductors:
Process: 0,5 mm
1. Deposit P rich
layers on surface.
magnified image of a computer chip
silicon
2. Heat it.
3. Result: Doped light regions: Si atoms
semiconductor
regions.
Diffusion
How do we quantify the amount or rate of diffusion?
moles or mass diffusing mol kg
J Flux = 2 or 2
surface area time cm s m s
Measured empirically
Make thin film (membrane) of known surface area
Impose concentration gradient
Measure how fast atoms or molecules diffuse through the
membrane
M=
M l dM mass J slope
J
At A dt diffused
time
Steady-State Diffusion
Rate of diffusion independent of time
dC
Flux proportional to concentration gradient =
dx
dC
C2
J D
C2 dx
x1 x2
x
D diffusion coefficient
dC C C2 C1
if linear
dx x x2 x1
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Example: Chemical Protective
Clothing (CPC)
Methylene chloride is a common ingredient of paint
removers. Besides being an irritant, it also may be
absorbed through skin. When using this paint
remover, protective gloves should be worn.
If butyl rubber gloves (0,04 cm thick) are used, what
is the diffusive flux of methylene chloride through the
glove?
Data:
diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
surface concentrations: C1 = 0,44 g/cm3
C2 = 0,02 g/cm3
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Example (cont).
Solution assuming linear conc. gradient
glove
C1 dC C C1
tb
l2 J - D D 2
paint
6D dx x2 x1
skin
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x2 C1 = 0,44 g/cm3
C2 = 0,02 g/cm3
x2 x1 = 0,04 cm
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Qd
RT
D=D0 e
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Diffusion and Temperature
D has exponential dependence on T
1500
1000
300
600
T(
C)
10-8
C
in
D (m2/s) - C in
Fe Dinterstitial >> Dsubstitutional
-F
e
C in -Fe Al in Al
Fe
Fe
10-14
in
C in -Fe Fe in -Fe
in
-
Al
-F
Fe in -Fe
Fe
in
Al
e
10-20
0.5 1.0 1.5 1000 K/T
Adapted from Fig. 6.7, Callister & Rethwisch 3e. (Date for Fig. 6.7
taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)
13
D transform ln D
data
Temp = T 1/T
ln D2 =ln D 0
Qd 1
R T2 and ln D1 =ln D 0
Qd 1
R T1
ln D 2 ln D1 =ln
D2
D1
Q 1 1
= d
R T2 T1 14
Example (cont.)
D2 =D1 exp
[ Qd 1
1
R T2 T 1 ]
T1 = 273 + 300 = 573 K
T2 = 273 + 350 = 623 K
D 2 = 7,810 11 m 2 /s exp
[ 41500 J/mol 1
1
8,314 J/mol.K 623 K 573 K ]
D2 = 15,7 x 10-11 m2/s
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Non-steady State Diffusion
2
C C
Ficks Second Law =D
t x2
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Cs
Adapted from
Fig. 6.5,
Callister &
Rethwisch 3e.
B.C. at t = 0, C = Co for 0 x
at t > 0, C = CS for x = 0 (constant surface conc.)
C = Co for x =
17
Solution:
C x , t C o
C s C o
=1 erf
x
2 Dt
C(x,t) = Conc. at point x at CS
time t
erf (z) = error function
z
2 C(x,t)
e y dy
2
=
0
Co
erf(z) values are given in
Table 6.1
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Non-steady State Diffusion
Sample Problem: An FCC iron-carbon alloy initially
containing 0.20 wt% C is carburized at an elevated
temperature and in an atmosphere that gives a
surface carbon concentration constant at 1.0 wt%. If
after 49.5 h the concentration of carbon is 0.35 wt%
at a position 4.0 mm below the surface, determine the
temperature at which the treatment was carried out.
Solution (cont.):
C x , t C o
C s C o
=1 erf
x
2 Dt
t = 49,5 h x = 4 x 10-3 m
Cx = 0,35 wt% Cs = 1,0 wt%
Co = 0,20 wt%
C x , t C o 0 , 35 0 ,20
C s C o
=
1 , 0 0 , 20
=1 erf x
2 Dt
=1 erf z
erf(z) = 0,8125
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Solution (cont.):
We must now determine from Table 6.1 the value of z for which the
error function is 0.8125. An interpolation is necessary as follows
2 3 2
x 410 m 1h 11 2
= 2
= 2
=2,610 m /s
4z t 4 0,93 49,5 h 3600 s
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Solution (cont.):
To solve for the temperature at Qd
T
which D has the above value, R(lnDo ln D )
we use a rearranged form of
Equation (6.9a);
from Table 6.2, for diffusion of C in FCC Fe
Do = 2,3 x 10-5 m2/s Qd = 148,000 J/mol
148,000 J/mol
(8. 314 J/mol - K)(ln 2.3x10 5 m2 /s ln 2.6 x10 11 m2 /s)
T = 1300 K = 1027C
22
23
0 , 04 cm 2
t b= -8 2
=240 s = 4 min
6 110 x 10 cm /s
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Summary
Diffusion FASTER for... Diffusion SLOWER for...
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