Chapter 6

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?

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 Diffusion
Diffusion - Mass transport by atomic motion
• Diffusion Mechanisms
- Gases & Liquids – random (Brownian) motion
- Solids – vacancy diffusion and interstitial
diffusion
• Interdiffusion - diffusion of atoms of one material into
another material

• Self-diffusion – atomic migration in a pure metal

2
 Diffusion
• Atoms tend to migrate from regions of high concentration to
regions of low concentration.
Before diffusion After diffusion

Figs. 5.1,
Callister &
Rethwisch 10e.

Concentration Profiles 3
 Diffusion
• Self-diffusion: Migration of host atoms 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

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 Diffusion Mechanism I
Vacancy Diffusion
• atoms and vacancies exchange positions
• applies to host and substitutional impurity atoms
• diffusion rate depends on:
-- number of vacancies
-- activation energy to exchange.

increasing elapsed time

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

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

More rapid than vacancy diffusion

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 Processing Using Diffusion
Case hardened
• Case Hardening: region
- Example of interstitial diffusion
- Outer surface selectively hardened by
diffusing carbon atoms into surface
- Presence of C atoms makes
iron (steel) harder

• Example: Case hardened 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.)

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 Processing Using Diffusion

Diffusion in Semiconducting Devices

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

1. Deposit P rich 2. Heat treat 3. Result is P doped

layers on surface the sample to semiconductor
drive in P regions

silicon silicon

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 Rate of Diffusion
• Diffusion is a time-dependent process.
• Rate of Diffusion- expressed as diffusion flux, J
mass of diffused species M º kg º
J º Flux º = ç 2 ÷
(area)(time) At è m -s º
• Measured experimentally
– Use thin sheet (or membrane) – cross-sectional area A
– Impose concentration gradient across sheet
– Measure mass of diffusing species (M) that passes through
the sheet over time period (t)

M=
mass J µ slope
diffused
time
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 Steady-State Diffusion
The mathematics of steady-state diffusion in a single (x) direction is
relatively simple, in that the flux is proportional to the concentration
gradient, dC/dx through the expression
dC C = concentration
Jµ x = diffusion direction
dx

C1 Fick’s first law of diffusion

C1
C
dC
J = -D
C2 C2 dx
x1 x2 D = diffusion coefficient
x

dC DC C2 -C1
if linear @ =
dx Dx x2 - x1 10
11
 Diffusion Example
Chemical Protective Clothing (CPC)
• Methylene chloride is a common component 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 (0.04 cm
thick) commonly found in the kitchen can be used as
protective gloves.
• Note: The maximum allowable flux for a 150 lb person is
less than 3.5 x 10-7 g/cm2/s
• Compute the diffusion flux of methylene chloride
through the gloves.
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 CPC Example (cont.)
• Solution – diffusion flux of methylene chloride
assume linear conc. gradient
glove dC C2 -C1
J = -D @ -D
C1
tb =
2 dx x 2 - x1
6D
paint skin
remover Data: D = 110 x 10-8 cm2/s
C2 C1 = 0.44 g/cm3
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 cm /s)
-8 2
= 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. 13
 Influence of Temperature on Diffusion

• Diffusion coefficient increases with increasing T

Qd
D = Do exp -
RT

D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]

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15
 Influence of Temperature on Diffusion
(cont.)

D transform ln D
data

Temp = T 1/T

º Q º Qd
D = D0 exp ç - d ÷ take natural log
lnD = lnD0 -
è RT º of both sides RT

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Influence of Temperature on Diffusion (cont.)

Derive an equation relating the diffusion coefficients at

two temperature T1 and T2 using the equation derived
on slide 16.

Subtracting equation at T1 from equation at T2

D2 Qd º 1 1 º
lnD2 - lnD1 = ln = - çç - ÷÷
D1 R èT2 T1 º
Take the exponential of each side to get the final equation
é Q º 1 1 ºù
D2 = D1 exp ê- d çç - ÷÷º
êë R èT2 T1 ºº
û
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 Example Diffusion Problem
At 300°C the diffusion coefficient and activation energy
for Cu in Si are
D1(300°C) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
Compute the diffusion coefficient D2 at 350°C?
é Q º 1 1 ºù T1 = 273 + 300 = 573 K
D2 = D1 exp ê- d çç - ÷÷º
êë R èT2 T1 ºº
û T2 = 273 + 350 = 623 K

-11
é -41,500 J/mol º 1 1 ºù
D2 = (7.8 x 10 m /s) exp ê
2
ç - ÷º
ë 8.314 J/mol-K è 623 K 573 K ºû

D2 = 15.7 x 10-11 m2/s

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 Non-steady State Diffusion

• The concentration of diffusing species is a function of

both time and position C = C(x,t)
• For non-steady state diffusion, we seek solutions to
Fick’s Second Law

¶C ¶2C
Fick’s Second Law =D 2
¶t ¶x

This form of the equation assumes D is independent

of concentration

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 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 = ∞
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 Non-steady State Diffusion (cont.)

( )
C x,t - Co º x º
= 1- erf ç ÷
Cs -Co è 2 Dt º

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

time t
erf(z) = error function

z and erf(z) values are given

in Table 5.1

Fig. 5.5, Callister & Rethwisch 10e.

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 Non-steady State Diffusion

Example Problem
An FCC iron-carbon alloy initially containing 0.20
wt% 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
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.

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 Example Problem (cont.):
C(x,t) - Co º x º
Solution: use Eqn. 5.5 = 1- erf ç ÷
Cs -Co è 2 Dt º
Data for problem tabulated as follows:
– 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 º x º

= = 1- erf ç ÷ = 1- erf(z)
Cs -Co 1.0 - 0.20 è 2 Dt º

erf(z) = 0.8125

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 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 - 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

º x2 º (4 x 10-3 m)2 1h -11

\D = çç 2 ÷÷ = 2
= 2.6 x 10 m2
/s
è 4z t º (4)(0.93) (49.5 h) 3600 s
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 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 = 1027°C
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