Materials Science and Engineering

Edition
Eighth
Eighth Edition

MATERIALS SCIENCE AND

CHAPTER
ENGINEERING :

5 William D. Callister, Jr.

David G. Rethwisch

Lecture Notes:
Solomon B.
Addis Ababa University
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Diffusion
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Contents

• Learning Objectives • Steady-State Diffusion

• Why Study Diffusion ? • Non-steady-State Diffusion
• Factors That Influence
• Introduction
Diffusion
• Diffusion Mechanisms • Summary
• Vacancy diffusion
• Interstitial diffusion
• Substitutional Diffusion
• Processing using diffusion
• Modeling Diffusion: Flux

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Learning Objectives
After studying this chapter you should be able to do the
following:
1. Name and describe the two atomic mechanisms of diffusion.
2. Distinguish between steady-state and non-steadystate
diffusion.
3. (a) Write Fick’s first and second laws in equation form and
define all parameters. (b) Note the kind of diffusion for which
each of these equations is normally applied.
4. Calculate the diffusion coefficient for some material at a
specified temperature, given the appropriate diffusion
constants.

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INTRODUCTION
• 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.

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Why Study Diffusion ?

Diffusion plays a crucial role in…

Alloying metals => bronze, silver, gold
Strengthening and heat treatment processes
• Hardening the surfaces of steel

High temperature mechanical behavior

Phase transformations
• Mass transport during FCC to BCC
Environmental degradation

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Diffusion couple

• Diffusion couple, is formed by joining bars of two

different metals together so that there is intimate contact
between the two faces

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INTRODUCTION
Diffusion transport by atomic
motion.
• Inhomogeneous material can
become homogeneous by
diffusion. Temperature should
be high enough to overcome
energy barrier.
Inter-diffusion
• Concentration Gradient 
(Heat) Interdiffusion (or Impurity
Diffusion).
Self-diffusion:
• one-component material, atoms
are of same type

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Diffusion mechanisms
• From an atomic perspective, diffusion is just the stepwise
migration of atoms from lattice site to lattice site.
• For an atom to make such a move, two conditions must
be met:
1. there must be an empty adjacent site, and
2. the atom must have sufficient energy to break bonds
with its neighbor atoms and then cause some lattice
distortion during the displacement.
There are three mechanisms of diffusion
 Vacancy diffusion
 Interstitial diffusion
 Impurities

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Vacancy diffusion
One mechanism involves the interchange of an atom from a
normal lattice position to an adjacent vacant lattice site or
vacancy
Atom migration Vacancy migration

Before
After
To jump from lattice site to lattice site, atoms need energy to break bonds with
neighbors, and to cause the necessary lattice distortions during jump.
Therefore, there is an energy barrier.
Energy comes from thermal energy of atomic vibrations (Eav ~ kT)
Atom flow is opposite to vacancy flow direction.
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Interstitial diffusion
Interstitial atom Interstitial atom
after diffusion
before diffusion

Generally faster than vacancy diffusion because bonding of

interstitials to surrounding atoms is normally weaker and there are
more interstitial sites than vacancy sites to jump to. Smaller energy
barrier
Only small impurity atoms (e.g. C, H, O) fit into interstitial sites.
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Substitutional Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.

increasing elapsed time

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Processing Using Diffusion

• Case Hardening: Fig. 5.0,
--Diffuse carbon atoms Callister 6e.
(Fig. 5.0 is
into the host iron atoms courtesy of
Surface
at the surface. Division,
Midland-
--Example of interstitial 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.

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Processing Using Diffusion

• Doping Silicon with P for n-type semiconductors:
• Process:
0.5mm
1. Deposit P rich
layers on surface.

magnified image of a computer chip

silicon
2. Heat it.
3. Result: Doped
light regions: Si atoms
semiconductor
regions.

light regions: Al atoms

silicon
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Modeling Diffusion: Flux

• Flux:

1 dM  kg  atoms 
J   or  2 
A dt 2
m s   m s 
• Directional Quantity
x-direction
y J MODELING DIFFUSION: FLUX
y

Jx Unit area A
Jz x through
z which
• Flux can be measured for: atoms
--vacancies move.
--host (A) atoms
--impurity (B) atoms

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Concentration Profiles & Flux

• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux

Concentration Concentration Adapted from

of Cu [kg/m 3 ] of Ni [kg/m 3 ]
Fig. 5.2(c),
Callister 6e.

Position, x
• Fick's First Law:
Diffusion coefficient [m 2 /s]
flux in x-dir.
[kg/m 2 -s] dC
Jx  D concentration
dx gradient [kg/m 4 ]
• The steeper the concentration profile,
the greater the flux!

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Steady State Diffusion

the concentration profile doesn't
• Steady State:
change with time.
Steady State:
J x(left) J x(right) J x(left) = J x(right)
x
Concentration, C, in the box doesn’t change w/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)!

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Non Steady State Diffusion

• Concentration profile, dx
C(x), changes
w/ time. J (left) J (right)

Concentration,
C, in the box
• To conserve matter: • Fick's First Law:

J (right)  J (left)  d C dC
 J  D or
dx dt dx
dJ  dC dJ  d 2 C (if D does
 D not vary
dx dt dx dx 2 with x)
equate
• Governing Eqn.:
dC d 2C
=D 2
dt dx
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Diffusion – Thermally Activated Process

Atom needs enough thermal energy
to break bonds and squeeze through
its neighbors.
Energy needed energy barrier
Called the activation energy Em
(like Q)

Diagram for Vacancy and Interstitial Diffusion

Diffusion Thermally Activated Process

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Room temperature (kBT = 0.026 eV)

Typical activation energy Em (~ 1 eV/atom) (like Qv)

Therefore, a large fluctuation in energy is needed for a jump.

 orEfrequency
Probability of a fluctuation
R j  R0 exp    of jump, Rj
k BT 
m

R0 = attempt frequency proportional to vibration frequency
Swedish chemist Arrhenius

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Calculate Activated Diffusion

1. Probability of finding a vacancy in an adjacent lattice site (Chap. 4) : times
2. Probability of thermal fluctuation

P  Const.exp   v 
Q
k T   Em e
 B 
D  Const.exp  
k T 
 B 

R j  R0 exp   m 
E
k T 
 B 

The diffusion coefficient = Multiply

D  Const.exp   m  exp   QV 
E
 k BT  
 k BT 
D  D0 exp   d 
Q
k T 
 B 

Arrhenius dependence.
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Diffusion And Temperature

• Diffusivity increases with T.
pre-exponential [m 2 /s] (see Table 5.2, Callister 6e )
activation energy
 Q  [J/mol],[eV/mol]
diffusivity D  D exp  d  (see Table 5.2, Callister 6e )
o  RT 
• Experimental Data: gas constant [8.31J/mol-K]
1500
1000

600

300
T(C)
10 -8 C i D has exp. dependence on T
n
- Recall: Vacancy does also!
2
D (m /s) Fe Ci
n
-Fe Dinterstitial >> D substitutional
10 -14 C in -Fe Cu in Cu
Zn

C in -Fe Al in Al
Fe

in Cun -

Al

Fe in -Fe
Cu in Fe
F
in

in
ei e

Fe in -Fe
Al
 -F

Zn in Cu
Cu

10 -20
0.5 1.0 1.5 2.0 1000K/T
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.,
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Factors that Influence Diffusion

 Temperature - diffusion rate increases very rapidly with

increasing temperature

 Diffusion mechanism - interstitial is usually faster than

vacancy

 Diffusing and host species - Do, Qd is different for every solute,

solvent pair

 Microstructure - diffusion faster in polycrystalline vs. single

crystal materials because of the rapid diffusion along grain
boundaries and dislocation cores.

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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

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Summary
Make sure you understand

Activation energy
Concentration gradient
Diffusion
Diffusion coefficient
Diffusion flux
Driving force
Fick’s first and second laws
Interdiffusion
Interstitial diffusion
Self-diffusion
Steady-state diffusion
Vacancy diffusion
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