COLLEGE OF Engineering

GENG211:
Material Science

Lecture 5:

chapter 5: Diffusion

• Dr. Hamdan Hamdan

• [email protected]
https://www.youtube.com https://www.youtube.com/watch?v=FaMWxLCGY0U
/watch?v=z4TVnbuy4Lw

https://www.youtube.com/watch?v=IZkzxWZETds
 • How does diffusion occur?
ISSUES TO • Why is it an important part of processing?

ADDRESS... • How can the rate of diffusion be predicted

for some simple cases?
• How does diffusion depend on structure
and temperature?
Diffusion

• Diffusion -
• Mass transport by atomic motion
• Mechanisms
1. Gases & Liquids – random
(Brownian) motion
• Brownian motion is the characteristic
random wiggling motion of small
airborne particles in still air, resulting
from constant bombardment by
surrounding gas molecules.

2. 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

 Diffusion

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

Label some atoms After some time

C
C
A D
A
D
B
B
 Diffusion Mechanisms
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurities atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.

increasing elapsed time

 Diffusion Simulation
• Simulation of
interdiffusion
across an interface:

• Rate of substitutional
diffusion depends on:
-- vacancy concentration
-- frequency of jumping.
 Diffusion Mechanisms
•Interstitial diffusion – smaller atoms can
diffuse between atoms.

Adapted from Fig. 5.3(b), Callister & Rethwisch 8e.

More rapid than vacancy diffusion

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

• Result: The presence of C

atoms makes iron (steel) harder.
Processing Using 0.5 mm

Diffusion
• Doping silicon with phosphorus for n- magnified image of a computer chip
type semiconductors:
• Process:
1. Deposit P rich
layers on surface.
light regions: Si atoms

silicon
2. Heat it. light regions: Al atoms
3. Result: Doped
semiconductor
regions.

silicon
 Diffusion
• How do we quantify the amount or rate of diffusion?

moles (or mass) diffusing mol kg

J  Flux  = or
(surface area)(time ) cm s m2s
2

• 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= = diffused
At A dt
time
 Steady-State Diffusion
Rate of diffusion independent of time
dC
Flux proportional to concentration gradient =
dx

C1 C1 Fick’s first law of diffusion

dC
C2 C2 J = −D
dx
x1 x2
x
D  diffusion coefficient
dC C C2 − C1
if linear  =
dx x x2 − x1

13
 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
 Example (cont).
• Solution – assuming linear conc. gradient
glove
C1 dC C2 − C1
tb =
2 J = -D  −D
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

-8 2 (0.02 g/cm3 − 0.44 g/cm3 ) g

J = − (110 x 10 cm /s) = 1.16 x 10 -5
(0.04 cm) cm2s
 Diffusion and Temperature
• Diffusion coefficient increases with increasing T.

 Qd 
D = Do exp− 
 RT 

D = diffusion coefficient [m2/s]

Do = temperature-independent pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]
 Diffusion and Temperature
D has exponential dependence on T
1500

1000

600

300
T(C)
10-8

D (m2/s) Dinterstitial >> Dsubstitutional

C in a-Fe Al in Al
10-14 C in g-Fe Fe in a-Fe
Fe in g-Fe

10-20
0.5 1.0 1.5 1000 K/T
Example: At 300ºC the diffusion coefficient and activation
energy for Cu in Si are
D(300ºC) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350ºC?

D transform ln D
data

Temp = T 1/T

Qd1 Qd  1
lnD2 = lnD0 −   and lnD1 = lnD0 −  
R  T2  R  T1 
D Q  1 1
 lnD2 − lnD1 = ln 2 = − d  − 
D1 R  T2 T1 
 Example (cont.)
 Qd  1 1 
D2 = D1 exp−  − 
 R  T2 T1 

T1 = 273 + 300 = 573 K

T2 = 273 + 350 = 623 K

−11 2  − 41,500 J/mol  1 1 

D2 = (7.8 x 10 m /s) exp  − 
 8.314 J/mol - K  623 K 573 K 

D2 = 15.7 x 10-11 m2/s

 Non-steady State Diffusion
• The concentration of diffusing species is a function of both time and
position C = C(x,t)
• In this case Fick’s Second Law is used

Fick’s Second Law C  2C

=D 2
t x
 VMSE: Student Companion Site
Diffusion Computations & Data Plots

21
 Non-steady State Diffusion
• Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms

Cs

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 = 
 Solution:
C (x , t ) − Co  x 
= 1 − erf  
Cs − Co  2 Dt 

C(x,t) = Conc. at point x at CS

time t
erf (z) = error function
2 z −y 2 C(x,t)
= 
 0
e dy
Co
erf(z) values are given in
Table 5.1
 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.

C ( x , t ) − Co  x 
• Solution: use Eqn. 5.5 = 1 − erf  
Cs − Co  2 Dt 

24
 C( x , t ) − Co  x 
Solution (cont.): = 1 − erf  
Cs − Co  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 ) − Co 0.35 − 0.20  x 
= = 1 − erf   = 1 − erf ( z )
Cs − Co 1.0 − 0.20  2 Dt 

 erf(z) = 0.8125

Chapter 5 - 25
Solution (cont.):
We must now determine from Table 5.1 the value of z for which the
error function is 0.8125. An interpolation is necessary as follows

z − 0.90 0.8125 − 0.7970

z erf(z) =
0.95 − 0.90 0.8209 − 0.7970
0.90 0.7970
z 0.8125 z = 0.93
0.95 0.8209

Now solve for D x x2

z= D=
2 Dt 4 z 2t

 x2  −3 2
( 4 x 10 m) 1h
D =   = = 2.6 x 10 −11 m2 /s
 4z 2t  ( 4)(0.93)2 ( 49.5 h) 3600 s
 
Chapter 5 - 26
 Solution (cont.):
• To solve for the temperature at Qd
T =
which D has the above value, R(lnDo − lnD )
we use a rearranged form of
Equation (5.9a);
from Table 5.2, for diffusion of C in FCC Fe
Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol

148,000 J/mol
 T =
(8.314 J/mol - K)(ln 2.3 x10 −5 m2 /s − ln 2.6 x10 −11 m2 /s)

T = 1300 K = 1027ºC

Chapter 5 - 27
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
breakthrough time (tb), i.e., how long could the gloves be
used before methylene chloride reaches the hand?
• Data
• diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
 CPC Example (cont.)
• Solution – assuming linear conc. gradient
glove Breakthrough time = tb
C1
2 Equation from online CPC

tb =
Case Study 5 at the Student
paint skin Companion Site for Callister &
remover 6D Rethwisch 8e (www.wiley.com/
college/callister)
C2
 = x2 − x1 = 0.04 cm
x1 x2
D = 110 x 10-8 cm2/s

(0.04 cm) 2
tb = = 240 s = 4 min
-8 2
(6)(110 x 10 cm /s)

Time required for breakthrough ca. 4 min

 Summary
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

Questions