CHAPTER 5:

DIFFUSION IN SOLIDS

ISSUES TO ADDRESS...
• How does diffusion occur?

• Why is it an important part of processing?

• How can the rate of diffusion be predicted for

some simple cases?

• How does diffusion depend on structure

and temperature?

Chapter 5- 1
 DIFFUSION DEMO
• Glass tube filled with water.
• At time t = 0, add some drops of ink to one end
of the tube.
• Measure the diffusion distance, x, over some time.
• Compare the results with theory.

Chapter 5- 2
 Cu-Ni Diffusion Couple
• Interdiffusion: In an alloy, atoms tend to migrate
from regions of large concentration.
Initially After some time

Adapted
from Figs.
5.1 and 5.2,
Callister 6e.

100%

0
Concentration Profiles
Chapter 5- 3
 Interdiffusion or Impurity Diffusion
The couple is heated at extended period at elevated
temperature
The concentrations of nickel and copper is a function of
position across the couple.
After some time
The concentration profile can
be determined by elemental
analysis.

This indicates that Cu atoms

have diffused into the Ni and
100% that Ni atoms have diffused into
the Cu

0
Concentration Profiles
Chapter 5- 3
Adapted from Figs. 5.1 and 5.2, Callister 6e.
 Self-diffusion
Occurs for pure metals, but all atoms exchanging positions
are of the same type
Not normally subject to observation by noting composition
change
Initially After some time
Note the labeled atoms Note the final positions
C
A
D
B
Cu Cu
100% 100%

0 0
Concentration Profiles Concentration Profiles
Chapter 5- 4
 DIFFUSION MECHANISMS
Stepwise migration of atoms from lattice/interstitial
site to lattice/interstitial site

Required conditions
• there must be an empty adjacent site
*vacancy or interstitial

• sufficient energy to break bonds with its neighbor

atoms and then cause some lattice distortion during the
displacement

Chapter 5- 5
 Metallic Diffusion Mechanisms
VACANCY Diffusion:
• applies to both
interdiffusion (substitutional impurities) and
self-diffusion
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.

Chapter 5- 5
 Metallic Diffusion Mechanisms
VACANCY Diffusion:
• applies to both
interdiffusion (substitutional impurities) and
self-diffusion
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.
Initially After some time

C
A
D
B
Chapter 5- 5
 DIFFUSION SIMULATION
• Simulation of
interdiffusion
across an interface:

• Rate of substitutional
diffusion depends on:
--vacancy concentration
--frequency of jumping.

(Courtesy P.M. Anderson)

Chapter 5- 6
 Metallic Diffusion Mechanisms
Interstitial Diffusion
• Applies to interstitial impurities.
• In most metal alloys, interstitial
diffusion occurs more rapidly than
vacancy mode.
• There are more interstitials the vacancies
• Applications
Steel manufacturing (C and Fe)
Purification of gas using thin sheet of
metal

(Courtesy P.M. Anderson)

Chapter 5- 7
 Metallic Diffusion Mechanisms
Interstitial Diffusion

(Courtesy P.M. Anderson)

Simulation:
--shows the jumping of a smaller atom (gray)
from one interstitial site to another in a BCC
structure. The interstitial sites considered here
are at midpoints along the unit cell edges.

Chapter 5- 7
SUBSTITUTIONAL vs INTERSTITIAL

Chapter 5- 7
 PROCESSING USING DIFFUSION
• Case Hardening:
--Diffuse carbon atoms Fig. 5.0,
Callister 6e.
into the host iron atoms (Fig. 5.0 is
courtesy of
at the surface. Surface
Division,
--Example of interstitial Midland-
Ross.)
diffusion is a case
hardened gear.

• Result: The "Case" is

--hard to deform: C atoms
"lock" planes from shearing.
--hard to crack: C atoms put
the surface in compression.

Chapter 5- 8
 PROCESSING USING DIFFUSION
• Doping Silicon with P for n-type semiconductors:
• Process:
1. Deposit P rich
layers on surface.

silicon
Fig. 18.0,
2. Heat it. Callister 6e.

3. Result: Doped
semiconductor
regions.

silicon
Chapter 5- 9
 DIFFUSION: FLUX
Diffusion is a time dependent process.
Rate of mass transfer is frequently expressed as FLUX (J).

In differential form

Definition:
amount of M (mass or number of atoms)
diffusing through and perpendicular to a
a unit cross sectional area A of solid per unit
of time t
Chapter 5- 10
 DIFFUSION: FLUX

• Directional Quantity Unidirectional

• Flux can be measured for:

--vacancies
--host (A) atoms
--impurity (B) atoms

Chapter 5- 10
 CONCENTRATION PROFILES & FLUX
• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux

Concentration Concentration Adapted

of Cu [kg/m3] of Ni [kg/m3]
from Fig.
5.2(c),
Callister 6e.

Position, x
• Fick's First Law:

• The steeper the concentration profile,

the greater the flux!
Chapter 5- 11
 STEADY STATE DIFFUSION
• Steady State: the concentration profile doesn't
change with time.

dC
• Apply Fick's First Law: J x  D
dx
dC  dC
• If Jx)left = Jx)right , then     
dx left dx right

• Result: the slope, dC/dx, must be constant

(i.e., slope doesn't vary with position)!
Chapter 5- 12
 STEADY STATE DIFFUSION
Linear Concentration Profile

Concentrat ion gradient

dC C C A  CB
 
Adapted from Fig. 5.4, Callister 6e. dx x x A  xB Chapter 5- 13
 STEADY STATE DIFFUSION
Linear Concentration Profile
PROBLEM: A plate of iron is exposed to a carburizing
(carbon-rich) atmosphere on one side and decarburizing
(carbon deficient) on the other side at 700°C. If a
condition of steady state is achieved, calculate the
diffusion flux of carbon through the plate.

Refer to the figure for

Additional information
about the system.

Chapter 5- 13
 STEADY STATE DIFFUSION
Linear Concentration Profile
• Steel plate at
700C with Adapted
geometry from Fig.
5.4,
shown: Callister 6e.

• Q: How much
carbon transfers
from the rich to
the deficient side?

Chapter 5- 13
 STEADY STATE DIFFUSION
Purification of Hydrogen Gas

N2 Palladium
H2O Mixture
O2 of
H gases Steady State =
2 straight line!
High Low
Concentration of Concentration of
H2 H2

0 x1 x2
Hydrogen gas selectively diffuses through the Palladium metal sheet
from the region of high to low concentration of hydrogen gas.

Chapter 5- 13
 STEADY STATE DIFFUSION
Purification of Hydrogen Gas
PROBLEM: Compute the kg of H2
that pass per hour through a 6
mm thick sheet of palladium
having an area of 0.25 m2 at
600°C. Assume the diffusion
coefficient of 1.7x10-8 m2/s, that
the concentrations at the high
and at the low pressure sides of
the plates are 2.0 and 0.4 kg
H2/m3 of palladium, and that
steady state conditions have
been attained.
Chapter 5- 13
 STEADY STATE DIFFUSION
Purification of Hydrogen Gas
GIVEN:
A = 0.25 m2
D = 1.7x10-8 m2/s @ T = 600°C
C1 = 2.0 kg H2/m3 of Pd
C2 = 0.4 kg H2/m3 of Pd
Δx = 6 mm

Compute the kg of H2 that pass

per hour or rate of transport

Chapter 5- 13
 STEADY STATE DIFFUSION
Linear Concentration Profile
PROBLEM: When -Fe is subjected to an atmosphere of
N2, the CN (in wt%) is a function of N2 pressure PN2 (in
MPa), and absolute temperature (T) according to
3  37.6 mol
kJ

C N  4.90 10 PN 2 exp   
 RT 

Furthermore, the values of D0 and

Qd for this diffusion system are
3.0x10-7 m2/s and 76.25 kJ/mol,
respectively. Consider a thin iron
Membrane 1.5 mm thick that is at
300°C. Compute the flux through this membrane if PN2 on
one side is 0.10 MPa and on the other side 5.0 MPa. 13
 DIFFUSION AND TEMPERATURE
• Diffusivity increases with T.

D has exp. dependence on T

Recall: Vacancy does also!

pre-exponential [m 2/s]
activation energy
[J/mol],[eV/mol]
 Q 
(Absolute Temperature)
diffusivity D  Do exp  d
 RT 
gas constant [8.31J/mol-K]

Chapter 5- 19
 DIFFUSION AND TEMPERATURE
• Experimental Data: D has exp. dependence on T
Recall: Vacancy does also!

Dinterstitial >> Dsubstitutional

C in -Fe Cu in Cu
C in -Fe Al in Al
Fe in -Fe
Fe in -Fe
Zn in Cu

Adapted from Fig. 5.7, Callister 6e. (Date 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
 DIFFUSION and TEMPERATURE
PROBLEM: Using the data below, compute the value of D
for the following:

a. magnesium in aluminum at 500°C

b. zinc in copper at 1000K
c. copper in nickel at 0°C
Solute Host metal Do (m2/s) EA or QD, (kJ/mol)
Zn Cu 2.4x10-5 189
Cu Ni 2.7x10-5 256
Mg Al 1.2x10-4 131

 Q 
D  Do exp  d
 RT 
Chapter 5- 13
 DIFFUSION and TEMPERATURE
PROBLEM: Using the data below, compute the value of D
for the following:

a. magnesium in aluminum at 500°C (Ans:1.7x10-13 m2/s)

b. zinc in copper at 1000K (Ans:3.2x10-15 m2/s)
c. copper in nickel at 0°C (Ans:2.8x10-54 m2/s)
Solute Host metal Do (m2/s) EA or QD, (kJ/mol)
Zn Cu 2.4x10-5 189
Cu Ni 2.7x10-5 256
Mg Al 1.2x10-4 131

 Q 
D  Do exp  d
 RT 
Chapter 5- 13
 DIFFUSION and TEMPERATURE
PROBLEM: The diffusion coefficient for carbon and
nickel are given at two temperatures

a. Determine the values of Do and QD.

b. What is the magnitude of D at 900°C?

Temperature, °C D (m2/s)
600 5.5x10-14
700 3.9x10-13

Chapter 5- 13
 DIFFUSION and TEMPERATURE
PROBLEM: The diffusion coefficient for carbon and
nickel are given at two temperatures

a. Determine the values of Do and QD.

Temperature, °C D (m2/s)
600 5.5x10-14
700 3.9x10-13

EA  1 
log D  log D0   
2.3R  T 

Chapter 5- 13
 DIFFUSION and TEMPERATURE
SOLUTION: Temperature, °C D (m2/s)
600 5.5x10-14
700 3.9x10-13

14 EA  1 
(1) log( 5.5 x10 )  log D0   
2.3R  873K 
13 EA  1 
(2) log( 3.9 x10 )  log D0   
2.3R  973K 

Chapter 5- 13
 DIFFUSION and TEMPERATURE
SOLUTION: Temperature, °C D (m2/s)
600 5.5x10-14
700 3.9x10-13

14 EA  1 
(1) log( 5.5 x10 )  log D0   
2.3R  873K 
13 EA  1 
(2) log( 3.9 x10 )  log D0   
2.3R  973K 

Chapter 5- 13
 DIFFUSION and TEMPERATURE
SOLUTION: Temperature, °C D (m2/s)
600 5.5x10-14
700 3.9x10-13

Linear Regression:

1
plot log D (in y ) vs (in x)
T
EA
slope    E A   slope(2.3R)
2.3R
y  int ercept  b  log D0  D0  10b
Chapter 5- 13
 DIFFUSION and TEMPERATURE
PROBLEM: The diffusion coefficient for carbon and
nickel are given at two temperatures

a. Determine the values of Do and QD.

Ans: Do = 1.04x10-5 m2/s and
Ans: QD = 138 kJ/mol

Temperature, °C D (m2/s)
EA  1 
600 5.5x10-14 log D  log D0   
700 3.9x10-13 2.3R  T 

Chapter 5- 13
 NON STEADY STATE DIFFUSION
• Concentration profile,
C(x), changes
w/ time.

• To conserve matter: • Fick's First Law:

• Governing Eqn.:
∂C ∂2C
=D 2
∂t ∂x Chapter 5- 14
NON STEADY STATE DIFFUSION
Diffusion of Cu in Al

C(x,t)
Cs
Adapted from
Fig. 5.5,

t3 Callister 6e.

t2
t t1
Co o
x1 position, x

"error function"
Values calibrated in Table 5.1, Callister 6e. Chapter 5- 15
 NON STEADY STATE DIFFUSION
Diffusion of Cu in Al
For semi-infinite solid (none of the diffusing atoms
reaches the bar end during the time over which
diffusion takes place),
at t<0 (before diffusion takes place)
C = C0 = uniform concentration of the solute
bar
pre-existing conc., C o of copper atoms
at t = or > 0 (during diffusion)
C x = 0 = Cs = constant surface concentration (Cs>C0)
C x > 0 = C(x,t) = unsteady concentration profile

Chapter 5- 15
 ERROR FUNCTION
General solution:

"error function”

Chapter 5- 15
 NON STEADY STATE DIFFUSION
Carburizing
PROBLEM: Consider a carbon iron alloy that initially has a
uniform carbon concentration of 0.25 wt% and is to be
treated at 950C. If the carbon concentration at the
surface is suddenly brought to and maintained at 1.20
wt%, how long will it take to achieve a carbon content of
0.80 wt% at the position 0.5 mm below the surface?

Assume D at this temperature is 1.6x10-11 m2/s and the

alloy is semi-infinite.
bar
Before diffusion, C0 = conc of C atoms
Surface conc.,
Cs of C atoms bar
During diffusion, C is a function of x and t
Chapter 5- 13
 PROCESSING QUESTION
• Copper diffuses into a bar of aluminum.
• 10 hours at 600C gives desired C(x).
• How many hours would it take to get the same C(x)
if we processed at 500C?
Key point 1: C(x,t500C) = C(x,t600C).
Key point 2: Both cases have the same Co and Cs.
• Result: Dt should be held constant.

Note: values
• Answer: of D are
provided here.
Chapter 5- 16
 DIFFUSION DEMO: ANALYSIS
• The experiment: we recorded combinations of
t and x that kept C constant.

C(x i , t i )  Co  x 
 1 erf  i  = (constant here)
Cs  Co 2 Dt 
 i 

• Diffusion depth given by:

Chapter 5- 17
 DATA FROM DIFFUSION DEMO

• Experimental result: x ~ t0.58

• Theory predicts x ~ t0.50
• Reasonable agreement!
Chapter 5- 18
 SUMMARY:
STRUCTURE & DIFFUSION
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• lower melting T materials • higher melting T materials

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• cations • anions

• lower density materials • higher density materials

Chapter 5- 20