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
WHY STUDY Diffusion?

Materials of all types are often heat treated to improve their properties. The
phenomena that occur during a heat treatment almost always involve atomic
diffusion. Often an enhancement of diffusion rate is desired; on occasion measures
are taken to reduce it. Heat-treating temperatures and times, and/or cooling rates
are often predictable using the mathematics of diffusion and appropriate diffusion
constants. The steel gear shown on this page has been case hardened (Section
8.10); that is, its hardness and resistance to failure by fatigue have been enhanced
Chapter 5- 1
by diffusing excess carbon or nitrogen into the outer surface layer.
 Diffusion?
Many reactions and processes that are important in the treatment of materials rely on the transfer
of mass either within a specific solid (ordinarily on a microscopic level) or from a liquid, a gas,
or another solid phase. This is necessarily accomplished by diffusion, the phenomenon of
material transport by atomic motion.

Figure 5.1 (a) A copper–nickel diffusion couple
before a high-temperature heat treatment.
(b) Schematic representations of Cu (red
circles) and Ni (blue circles) atom locations within
the diffusion couple. (c) Concentrations of copper
and nickel as a function of position across the couple.
Figure 5.2 (a) A copper–nickel diffusion couple
after a high-temperature heat treatment, showing the
alloyed diffusion zone. (b) Schematic representations
of Cu (red circles) and Ni (blue circles) atom
locations within the couple. (c) Concentrations of Chapter 5- 1
copper and nickel as a function of position across the couple.
 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
 DIFFUSION: THE PHENOMENA (1)
Interdiffusion : In an alloy, atoms tend to migrate from regions of large
concentration. There is a net drift or transport of atoms from high- to
low-concentration regions.
Initially After some time

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

100%

0
Concentration Profiles
The copper atoms have migrated or diffused into the nickel, and that nickel has diffused into 5-copper.
Chapter 3 This
process, whereby atoms of one metal diffuse into another, is termed interdiffusion, or impurity diffusion.
 DIFFUSION: THE PHENOMENA (2)
Self-diffusion: In an elemental solid, atoms also migrate. Diffusion also
occurs for pure metals, but all atoms exchanging positions are of the same
type.

Label some atoms After some time

C
A
D
B

Chapter 5- 4
 DIFFUSION MECHANISMS
From an atomic perspective, diffusion is just the stepwise migration of atoms from lattice site
to lattice site. In fact, the atoms in solid materials are in constant motion, rapidly changing
positions. For an atom to make such a move, two conditions must be met:
(1) there must be an empty adjacent site
(2) the atom must have sufficient energy to break bonds with its neighbor atoms and then cause
some lattice distortion during the displacement

• applies to substitutional impurities

Substitutional Diffusion: • atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.

Chapter 5- 5
DIFFUSION MECHANISMS

One mechanism involves the

interchange of an atom from a
normal lattice position to an adjacent
vacant lattice site or vacancy, as
represented schematically in Figure
5.3a. This mechanism is aptly
termed vacancy diffusion

The second type of diffusion involves

atoms that migrate from an interstitial
position to a neighboring one that is
empty. This mechanism is found for
interdiffusion of impurities such as
hydrogen, carbon, nitrogen, and
oxygen, which have atoms that are
small enough to fit into the interstitial
positions. This phenomenon is
appropriately termed interstitial
diffusion
Chapter 5- 5
 PROCESSING USING DIFFUSION (1)

• 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 (2)

• 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
 MODELING DIFFUSION: FLUX
Flux defined as the mass (or, equivalently, the number of atoms) M
diffusing through and perpendicular to a unit cross-sectional area of
solid per unit of time

• Flux:

• Directional Quantity

• Flux can be measured for:

--vacancies
--host (A) atoms
--impurity (B) atoms
Chapter 5- 10
 MODELING DIFFUSION: FLUX
If the diffusion flux does not change with
time, a steady-state condition exists. One
common example of steady-state
diffusion is the diffusion of atoms of a gas
through a plate of metal for which the
concentrations (or pressures) of the
diffusing species on both surfaces of the
plate are held constant
When concentration C is plotted versus
position (or distance) within the solid
x, the resulting curve is termed the
concentration profile; the slope at a
particular point on this curve is the
concentration gradient:
Chapter 5- 10
 CONCENTRATION PROFILES & FLUX
• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux

Concentration Concentration Adapted

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

Position, x
• Fick's First Law: Fick’s first law diffusion flux for steady-state
diffusion (in one direction)

Chapter 5- 11
The steeper the concentration profile, the greater the flux!
 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
 EX: STEADY STATE DIFFUSION
• Steel plate at
700C with
geometry
shown:
Adapted
from Fig.
5.4,
Callister 6e.

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

Chapter 5- 13
 NON STEADY STATE DIFFUSION

Fick’s second law

diffusion equation for
nonsteady- tate
diffusion (in one
direction)

• General solution: Equation 5.5

"error function"
Values calibrated in Table 5.1, Callister 6e.
Chapter 5- 15
Chapter 5- 16
Chapter 5- 16
 FACTORS THAT INFLUENCE DIFFUSION
Diffusing Species
The magnitude of the diffusion coefficient D is indicative of the rate at
which atoms diffuse

Chapter 5- 17
 FACTORS THAT INFLUENCE DIFFUSION
Temperature
Temperature has a most profound influence on the coefficients and
diffusion rates.

Chapter 5- 17
 FACTORS THAT INFLUENCE DIFFUSION
Dependence of the diffusion coefficient on temperature :

Energy required to produce the diffusive

motion of one mole of atoms.

Figure 5.7 Plot of the logarithm of

the diffusion coefficient versus the
reciprocal of absolute temperature
for several metals.

Chapter 5- 17
 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