MSE 225 INTRODUCTION TO

MATERIALS SCIENCE
(SECTION 01-02)

DIFFUSION IN SOLIDS

Assoc. Prof. Dr. İlkay KALAY

Materials Science and Engineering Department
Çankaya University Chapter 5 -
 What is Diffusion?
• 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.

Chapter 5 - 2
 What is Diffusion?

Ceramic Coating on a Metal substrate

Chapter 5 -
 Diffusion Couple
• Interdiffusion: In an alloy, atoms tend to migrate from
regions of high conc. to regions of low conc.
Initially After some time

Adapted from
Figs. 5.1 and
5.2, Callister &
Rethwisch 8e.

Chapter 5 - 4
 Diffusion Couple
Interdiffusion: In an
alloy, atoms tend to
migrate from regions of
large concentration.
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

Diffusion of copper
atoms into nickel.
Eventually, the copper
atoms are randomly
distributed throughout
the nickel

Chapter 5 -
 Diffusion Couple
• Self-diffusion: In an elemental solid, atoms also migrate.

Label some atoms After some time

C
C
A D
A
D
B
B

Chapter 5 - 6
 Diffusion Mechanisms

at T=room temperature
time=0

at T=Higher temperature
(lower than melting point)

time=t1

Inhomogeneous materials can become homogeneous by diffusion. For

an active diffusion to occur, the temperature should be high enough to
overcome energy barriers for atomic motion with time. Chapter 5 -
 Diffusion Mechanisms

©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

Diffusion mechanisms in material: (a) vacancy or substitutional

atom diffusion and (b) interstitial diffusion

Chapter 5 -
 Diffusion Mechanisms

Energy is needed to generate a vacancy, break bonds, cause

distortions. Provided by HEAT , kT !
Atom moves in the opposite direction of the vacancy !
Chapter 5 -
 Diffusion Mechanisms
Substitutional Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.

Chapter 5 - 5
 Diffusion Mechanisms
• Interstitial diffusion – smaller atoms can diffuse
between atoms.

Adapted from Fig. 5.3(b), Callister & Rethwisch 8e.

Much faster than vacancy diffusion, why ? Smaller atoms like

B, C, H, O. Weaker interaction with the larger atoms. More
vacant sites, no need to create a vacancy ! Chapter 5 - 11
 Applications
• Case Hardening:
Adapted from
-- Diffuse carbon atoms chapter-opening
into the host iron atoms photograph,
Chapter 5,
at the surface. Callister &
Rethwisch 8e.
-- Example of interstitial (Courtesy of
Surface Division,
diffusion is a case Midland-Ross.)

hardened gear.

Result: The presence of C

atoms makes iron (steel) harder.
The "Case" is hard to deform:
- C atoms "lock" planes from shearing.
- hard to crack: C atoms put the surface in
compression. Chapter 5 - 12
Applications

Parts carburized in nitrogen-methanol atmosphere

Chapter 5 -
Applications

Chapter 5 -
Applications
• Doping silicon with phosphorus for n-type semiconductors:
• Process: 0.5 mm
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
Chapter 5 - 15
Applications

Chapter 5 -
Applications

Chapter 5 -
Applications
Powder Metallurgy

Chapter 5 -
Applications

Chapter 5 -
Applications

Chapter 5 -
Applications

Chapter 5 -
 Diffusion
Diffusion is a time-dependent process: the quantity of matter
that is transported within another is a function of time.

Often it is necessary to know how fast diffusion occurs, or the

rate of mass transfer .

• How do we quantify the amount or rate of diffusion?

moles (or mass) diffusing mol kg

J  Flux   or
surface area time  cm s m2s
2

The flux during diffusion is defined as the

number of atoms passing through a plane of
unit area per unit time
Chapter 5 - 22
 Diffusion
Diffusion is a time-dependent process: the quantity of matter
that is transported within another is a function of time.

Often it is necessary to know how fast diffusion occurs, or the

rate of mass transfer .

• How do we quantify the amount or rate of diffusion?

Chapter 5 - 23
 Diffusion
The flux during diffusion is defined as the
number of atoms passing through a plane of
unit area per unit time

moles (or mass) diffusing mol kg

J  Flux   or
surface area time  2
cm s m2s

M=
M l dM mass
J= = J  slope
At A dt diffused
time
Chapter 5 - 24
 Fick’s First Law
• When concentration C is plotted vs position (or distance) plotted
with in the solid:
Concentration Profile, the slope will give us concentration gradient.
It is sometimes convenient to express conc. In terms of mass of
diffusing species per unit volume of a solid. C(x): [kg/m3]

• The steeper the concentration profile,

the greater the flux!

Concentration gradient is the DRIVING

FORCE !

Chapter 5 -
Concentration Gradient

Chapter 5 -
 Fick’s First Law
ADOLPH EUGEN FICK
In 1855 Fick published* “On liquid Diffusion” :

“ A few years ago Graham published an extensive

investigation on the diffusion of salts in water, in which he
more especially compared the diffusibility of different salts.
It appears to me a matter of regret, however, that in such an
exceedingly valuable and extensive investigation, the
development of a fundamental law, for the operation of
diffusion in a single element of space was neglected, and I
have therefore endeavored to supply this omission.”

“I’m going to quantify the diffusion process”

*Fick A., “On liquid diffusion”, Philosophical Magazine and Journal Science, 10, 31-39,Chapter
1855. 5 -
 Fick’s First Law
Pure Water

Depth under surface

B A

SALT
SOL. B
Fick’s experimental set-up
A: cylindrical tube (salt gradient)
B: vessel of pure water

Constant temperature
Steady State
J. Philibert., Diffusion Fundamentals, 4, 6.1-6.19, 2006. Chapter 5 -
 STEADY STATE DIFFUSION
• Steady State: The concentration profile doesn't change with time.

dC
• Apply Fick's First Law: J x  D Why is the
dx
dC  dC  minus sign ?
• 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
 Fick’s First Law
Steady State Diffusion

Carbon Steady State =

straight line!
rich
gas Carbon
deficient gas

0 x1 x2
Chapter 5 -
 Fick’s First Law
Steady State Diffusion

Carbon Steady State =

straight line!
rich
gas Carbon
deficient gas

0 x1 x2

Chapter 5 -
Factors that influence diffusion

Temperature

• 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 or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]
Chapter 5 - 32
Factors that influence diffusion

Temperature

interstitial
Chapter 5 -