Chapter 5: Diffusion

Chapter 5: Diffusion

ISSUES TO ADDRESS...
• What is diffusion?

• By what atomic mechanisms does diffusion occur?

• What are examples of diffusion in materials processing?

• What equations do we use to solve diffusion problems?

• How does the rate of diffusion depend on
temperature?

Chapter 5 - 1

Diffusion
Diffusion - Mass transport by atomic motion
• ______________________
- Gases & Liquids – random (___________) motion
- Solids – ______ diffusion and _________ diffusion

• Interdiffusion - diffusion of atoms of one material into

another material

• Self-diffusion – atomic migration in a pure metal

Chapter 5 - 2

Diffusion
• Atoms tend to _________ from regions of ____ concentration to
regions of ____ concentration.
Before diffusion After diffusion

Figs. 5.1,
Callister &
Rethwisch 10e.

Concentration Profiles Chapter 5 - 3

1
Chapter 5: Diffusion

Diffusion
• Self-diffusion: Migration of __________ in pure metals

Locations of 4 labeled Locations of 4 labeled

atoms before diffusion atoms after diffusion
C
C
A D
A
D
B
B

Chapter 5 - 4

Diffusion Mechanism I
Vacancy Diffusion
• ___________________ exchange positions
• applies to host and ___________________ impurity atoms
• diffusion rate depends on:
-- number of ___________
-- activation _________ to exchange.

increasing elapsed time

Chapter 5 - 5

Diffusion Mechanism II
____________ Diffusion
• Small, _____________ atoms move from one
interstitial position to an adjacent one

Fig. 5.2 (b), Callister & Rethwisch 10e.

More rapid than ___________ diffusion

Chapter 5 - 6

2
Chapter 5: Diffusion

Processing Using Diffusion

Case hardened
• Case _______________: region
- Example of ____________ diffusion
- Outer surface selectively hardened by
diffusing carbon atoms into surface
- Presence of C atoms makes
iron (steel) harder

• Example: __________________ gear

- Case hardening improves wear
resistance of gear
- Resulting residual compressive
stresses improve resistance to
fatigue failure
Chapter-opening photograph, Chapter 5,
Callister & Rethwisch 10e. (Courtesy of
Surface Division, Midland-Ross.)

Chapter 5 - 7

Processing Using Diffusion

Diffusion in Semiconducting Devices

• _______ – Diffusion of very small concentrations of atoms
of an impurity (e.g., P) into the semiconductor silicon.
• Process:

1. Deposit ___ rich 2. __________ 3. Result is P doped

layers on surface the sample to ______________
drive in P regions

silicon silicon

Chapter 5 - 8

Rate of Diffusion
• Diffusion is a time-dependent process.
• Rate of Diffusion- expressed as diffusion flux, J
mass of diffused species M ⎛ kg ⎞
J ≡ Flux ≡ = ⎜ ⎟
(area)(time) At ⎝ m2 -s ⎠
• Measured experimentally
– Use thin sheet (______________) – cross-sectional area A
– Impose _________________ gradient across sheet
– Measure mass of diffusing species (M) that passes through
the sheet over time period (t)

M l dM M=
J= = mass J ∝ slope
At A dt diffused
time

Chapter 5 - 9

3
Chapter 5: Diffusion

Steady-State Diffusion
Rate of ___________ (or flux) independent of time
dC
Flux (J) proportional to ___________ gradient: J ∝
dx
C = concentration
x = diffusion direction
C1 C1
____________ of diffusion
C
C2 dC
C2 J = −D
dx
x1 x2
x
D = diffusion coefficient
dC ΔC C2 − C1
if linear ≅ =
dx Δx x 2 − x1
Chapter 5 - 10

Diffusion Example
Chemical Protective Clothing (CPC)
• ________________ 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.
• Lets investigate whether butyl rubber gloves (_____ cm
thick) commonly found in the _______ can be used as
protective gloves.
• Note: The maximum allowable flux for a 150 lb person is
less than _______________________
• Compute the diffusion flux of methylene chloride
through the gloves.
Chapter 5 - 11

CPC Example (cont.)

• Solution – diffusion flux of methylene chloride
assume __________ conc. gradient
glove dC C − C1
J = −D ≅ −D 2
C1 2 dx x 2 − x1
tb =
6D
paint skin
remover Data: D = ____________
C2 C1 = _____________
x1 x2 C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

(0.02 g/cm3 − 0.44 g/cm3 ) g

J = − (110 x 10-8 cm2 /s) = 1.16 x 10-5
(0.04 cm) cm2 -s

Note: this is more than 30 times the allowable flux.

Unsafe to use these gloves for paint removal. Chapter 5 - 12

4
Chapter 5: Diffusion

Influence of Temperature on Diffusion

• Diffusion coefficient increases with increasing _____

Qd
D = Do exp -
RT

D = __________ coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = __________ energy [J/mol]
R = gas constant [____________]
T = absolute temperature [K]

Chapter 5 - 13

Influence of Temperature on Diffusion

(cont.)

D transform ln D
data

Temp = T 1/T

⎛ Q ⎞ Qd
D = D0 exp ⎜ − d ⎟ take natural log
lnD = lnD0 −
⎝ RT ⎠ of both sides RT

Chapter 5 - 14

Influence of Temperature on Diffusion

(cont.)
D has _________________ dependence on T
1500

1000

600

300

T(°C)
10-8
C

D (m2/s)
in

C in
Dinterstitial >> Dsubstitutional
γ-

α-F
Fe Fe i

e
C in α-Fe Al in Al
Fe

10-14 C in γ-Fe Fe in α-Fe

n
in

Al
α-

Fe in γ-Fe
Fe
γ

in
-Fe

Al

10-20
0.5 1.0 1.5 1000 K/T

Adapted from Fig. 5.6, Callister & Rethwisch 10e.

(Data for Fig. 5.7 taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)

Chapter 5 - 15

5
Chapter 5: Diffusion

VMSE: Screenshot of Diffusion Plots

Chapter 5 - 16

Influence of Temperature on Diffusion (cont.)

Derive an equation relating the ________ coefficients at

two temperature T1 and T2 using the ________ derived
on slide 14.
Q "1% Q "1%
lnD2 = lnD0 − d $$ '' and lnD1 = lnD0 − d $$ ''
R # T2 & R # T1 &

______________ equation at T1 from equation at T2

D2 Q ⎛ 1 1⎞
lnD2 − lnD1 = ln = − d ⎜⎜ − ⎟⎟
D1 R ⎝ T2 T1 ⎠
Take the ___________ of each side to get the final equation
⎡ Q ⎛ 1 1 ⎞⎤
D2 = D1 exp ⎢− d ⎜⎜ − ⎟⎟⎥
⎢⎣ R ⎝ T2 T1 ⎠⎥⎦
Chapter 5 - 17

Example Diffusion Problem

At 300°C the diffusion coefficient and _______________
for Cu in Si are
D1(300°C) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
Compute the _____________________ D2 at 350°C?
⎡ Q ⎛ 1 1 ⎞⎤ T1 = 273 + 300 = 573 K
D2 = D1 exp ⎢− d ⎜⎜ − ⎟⎟⎥
⎢⎣ R ⎝ T2 T1 ⎠⎥⎦ T2 = 273 + 350 = 623 K

⎡ −41,500 J/mol ⎛ 1 1 ⎞⎤
D2 = (7.8 x 10−11 m2 /s) exp ⎢ ⎜ − ⎟⎥
⎣ 8.314 J/mol-K ⎝ 623 K 573 K ⎠⎦

D2 = _____________
Chapter 5 - 18

6
Chapter 5: Diffusion

Non-steady State Diffusion

• The ___________ of diffusing species is a function of

both time and position C = C(x,t)
• For non-steady state diffusion, we seek solutions to
____________________

____________ Law ∂C ∂2C

=D 2
∂t ∂x

This form of the equation assumes D is independent

of concentration

Chapter 5 - 19

Non-steady State Diffusion

• Consider the diffusion of copper into a bar of aluminum
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms

Cs

Fig. 5.4,
Callister &
Rethwisch 10e.

Boundary/Initial Conditions
at t = 0, C = Co for 0 ≤ x ≤ ∞
at t > 0, C = CS for x = 0 (constant surface conc.)
C = Co for x = ∞
Chapter 5 - 20

Non-steady State Diffusion (cont.)

( )
C x,t − Co ⎛ x ⎞
= 1− erf ⎜ ⎟
Cs − Co ⎝ 2 Dt ⎠

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

time t
erf(z) = error ___________

z and erf(z) values are given

in Table _______

Fig. 5.5, Callister & Rethwisch 10e.

Chapter 5 - 21

7
Chapter 5: Diffusion

Non-steady State Diffusion

Example Problem
An FCC iron-carbon alloy initially containing ______
% C is carburized at an elevated temperature and in
an atmosphere in which the surface carbon
concentration is maintained at 1.0 wt%. If, after
_____, the concentration of carbon is 0.35 wt% at a
position ________ below the surface, determine the
temperature at which the treatment was carried out.

Chapter 5 - 22

Example Problem (cont.):

C(x,t) − Co ⎛ x ⎞
Solution: use Eqn. 5.5 = 1− erf ⎜ ⎟
Cs − Co ⎝ 2 Dt ⎠
Data for problem tabulated as follows:
– t = 49.5 h x = ________
– Cx = 0.35 wt% Cs = 1.0 wt%
– Co = __________

C(x,t) − Co 0.35 − 0.20 ⎛ x ⎞

= = 1− erf ⎜ ⎟ = 1− erf(z)
Cs − Co 1.0 − 0.20 ⎝ 2 Dt ⎠

erf(z) = ______

Chapter 5 - 23

Example Problem (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 erf(z) z − 0.90 0.8125 − 0.7970

=
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 4z 2t

⎛ x2 ⎞ (4 x 10−3 m)2 1h
∴D = ⎜⎜ 2 ⎟⎟ = 2
= 2.6 x 10−11 m2 /s
⎝ 4z t ⎠ (4)(0.93) (49.5 h) 3600 s
Chapter 5 - 24

8
Chapter 5: Diffusion

Example Problem (cont.):

}
• To solve for the temperature at
which D has the above value, Qd
T=
we use a rearranged form of R(lnDo − lnD)
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 x 10−5 m2 /s) − ln (2.6 x 10−11 m2 /s)]

T = 1300 K = _______

Chapter 5 - 25

Summary
• Solid-state diffusion is mass transport within solid
materials by stepwise atomic motion
• Two diffusion mechanisms
- Vacancy diffusion
- Interstitial diffusion
dC
• Fick’s First Law of Diffusion J = −D
dx

• Fick’s Second Law of Diffusion ∂C ∂2C

=D 2
- non-steady state diffusion ∂t ∂x

• Diffusion coefficient ⎛ Q ⎞
D = D0 exp ⎜⎜ − d ⎟⎟
- Effect of temperature ⎝ RT ⎠
Chapter 5 - 26