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
• 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

Chapter 5 - 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 Chapter 5 - 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

Chapter 5 - 4
 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

Chapter 5 - 5
 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

Chapter 5 - 6
 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.)

Chapter 5 - 7
 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

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 æ kg ö
J º Flux º = ç 2 ÷
(area)(time) At è m -s ø
• 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 l dM M=
J= = mass J µ slope
At A dt diffused
time

Chapter 5 - 9
 Steady-State Diffusion
Rate of diffusion (or flux) independent of time
dC
Flux (J) proportional to concentration gradient: Jµ
dx
C = concentration
x = diffusion direction
C 1 C1
Fick’s first law of diffusion
C
dC
C2 C2
J = -D
dx
x1 x2
x
D = diffusion coefficient
dC DC C2 -C1
if linear @ =
dx Dx x2 - x1
Chapter 5 - 10
 Diffusion 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.
• 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.
Chapter 5 - 11
 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. Chapter 5 - 12
Chapter 5 -
 Example SS Diffusion
• Iron Plate Processed
at 700 °C under Carbon Steady State →
Conditions at Right rich CONST SLOPE
gas Carbon
▪ Find the Carbon
deficient
Diffusion Flux Thru the gas
Plate D=3x10-11 m2/s
▪ For SS Diffusion 0 x1 x2

J (x1 ) = − D = J (x2 ) = − D
dC dC
dx dx ▪ For const dC/dx
x1 x2
dC dC C C 2 −C1
▪  dC/dx  f(x) = = =
• i.e., The Gradient is dx x1 dx x 2 x x 2 − x1
Constant

Chapter 5 -
 Expl SS Diff cont
• Thus the Gradient Carbon Steady State →
C (0.8 − 1.2) kg m3 rich CONST SLOPE
= gas
x (0.01 − 0.005)m Carbon
deficient
kg m3 gas
= −80 = −80 kg m 4
m D=3x10-11 m2/s
0 x1 x2
▪ Use In Fick’s 1st Law
dC ▪ or
J x = −D
dx J x = +2.4 10−9 kg m 2  s
( )(
J x = − 3 10−11 m 2 s − 80kg / m4 ) J x = 2.4 g m 2  s

Chapter 5 -
Chapter 5 -
 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]

Chapter 5 - 17
 Influence of Temperature on Diffusion
(cont.)

D transform ln D
data

Temp = T 1/T

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

Chapter 5 - 18
 Influence of Temperature on Diffusion
(cont.)
D has exponential dependence on T
1500

1000

600

300
T(°C)
10-8

D (m2/s) Dinterstitial >> Dsubstitutional

C in α-Fe Al in Al
10-14 C in γ-Fe Fe in α-Fe
Fe in γ-Fe

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 - 19
VMSE: Screenshot of Diffusion Plots

Chapter 5 - 20
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 14.

Subtracting equation at T1 from equation at T2

D2 Qd æ 1 1 ö
lnD2 - lnD1 = ln = - çç - ÷÷
D1 R èT2 T1 ø
Take the exponential of each side to get the final equation
é Q æ 1 1 öù
D2 = D1 exp ê- d çç - ÷÷ú
êë R èT2 T1 øúû
Chapter 5 - 21
 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 æ 1 1 öù T1 = 273 + 300 = 573 K
D2 = D1 exp ê- d çç - ÷÷ú
êë R èT2 T1 øúû T2 = 273 + 350 = 623 K

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

D2 = 15.7 x 10-11
m2/s Chapter 5 - 22
Chapter 5 -
 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

Fick’s Second Law ¶C ¶2C

=D 2
¶t ¶x

This form of the equation assumes D is independent

of concentration

Chapter 5 - 24
 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 - 25
 Non-steady State Diffusion (cont.)

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

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.

Chapter 5 - 26
 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.

Chapter 5 - 27
 Example Problem (cont.):
C(x,t) - Co æ x ö
Solution: use Eqn. 5.5 = 1- erf ç ÷
Cs -Co è 2 Dt ø
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 æ x ö

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

erf(z) = 0.8125

Chapter 5 - 28
 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

æ x2 ö (4 x 10-3 m)2 1h -11

\D = çç 2 ÷÷ = 2
= 2.6 x 10 m2
/s
è 4z t ø (4)(0.93) (49.5 h) 3600 s
Chapter 5 - 29
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

Chapter 5 - 30
 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 æ Q ö
D = D0 exp çç - d ÷÷
- Effect of temperature è RT ø
Chapter 5 - 31
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 5 - 32