MMEE 210: MATERIALS SCIENCE

Presenter: Dr Babatunde Abiodun Obadele CONSULTATION: TUESDAYS 16-18:00 h

Date: 11th November 2020
Office: Block 108: Room 021
E-mail: [email protected]

Chapter 6 -
 Lecture 6: Chapter 6

Diffusion

Imperfections in Solids Chapter 6 - 2

 Chapter 6: Diffusion
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 6 - 3
 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 6 - 4
 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.

Diffusion - Mass transport by atomic motion

Mechanisms
• Gases & Liquids – random (Brownian) motion
• Solids – vacancy diffusion or interstitial diffusion

Chapter 6 - 5
 Diffusion
• 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. 6.1 and
6.2, Callister &
Rethwisch 4e.

The process by which atoms of one metal diffuse into

Chapter 6 - 6
another is termed interdiffusion, or impurity diffusion.
 Diffusion
• Self-diffusion: In an elemental solid, atoms also migrate.

Label some atoms After some time

C
C
A D
A
D
B
B

Diffusion also occurs for pure metals, but all atoms exchanging positions are of the same type; this is
termed self-diffusion. Chapter 6 - 7
 Diffusion Mechanisms
Diffusion is the stepwise migration of atoms from lattice site to lattice
site.

Atoms in solid materials are in constant motion, rapidly changing

positions.

For an atom to make such a move, two conditions must be met:

A. There must be an empty adjacent site.

B. The atom must have sufficient energy to break bonds with
its neighbour atoms and then cause some lattice distortion during the
displacement.

This energy is vibrational in nature

Temperature dependent
Chapter 6 - 8
 Diffusion Mechanisms
Vacancy Diffusion:
Involves the interchange of an atom from a normal lattice position to
an adjacent vacant lattice site or vacancy.
• Atoms exchange with vacancies
• Applies to substitutional impurities atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.

increasing elapsed time

Chapter 6 - 9
 Diffusion Simulation
• Simulation of This slide contains an animation that requires Quicktime
interdiffusion and a Cinepak decompressor. Click on the message or
image below to activate the animation.
across an interface:
• Rate of substitutional
diffusion depends on:
-- vacancy concentration
-- frequency of jumping

(Courtesy P.M. Anderson)

Chapter 6 - 10
 Diffusion Mechanisms
Interstitial diffusion
The second type of diffusion involves atoms that migrate from an interstitial
position to a neighbouring 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.

Adapted from Fig. 6.3 (b), Callister & Rethwisch 4e.

•In most metal alloys, interstitial diffusion occurs much more rapidly than diffusion by the vacancy
mode because the interstitial atoms are smaller and thus more mobile. Chapter 6 - 11
 Processing Using Diffusion
• Case Hardening: Adapted from
chapter-opening
-- Diffuse carbon atoms photograph,
Chapter 6,
into the host iron atoms Callister &
at the surface. Rethwisch
(Courtesy of
4e.

-- Example of interstitial Surface Division,

Midland-Ross.)
diffusion is a case
hardened gear.

• Result: The presence of C atoms makes iron (steel) harder.

Chapter 6 - 12
 Processing Using Diffusion
• Doping silicon with phosphorus for n-type semiconductors:
0.5 mm
• Process:
1. Deposit P rich
layers on surface.
magnified image of a computer chip

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

light regions: Al atoms

silicon
Adapted from Figure 12.27, Callister &
Rethwisch 4e. Chapter 6 - 13
 Diffusion Mechanisms
Involves the interchange of an atom from a normal lattice position to an adjacent vacant lattice
site or vacancy.

Involves atoms that migrate from an interstitial position to a neighbouring one that is empty

Chapter 6 - 14
Adapted from Fig. 6.3 (a) Vacancy diffusion and (b) Interstitial diffusion Callister & Rethwisch 4e.
 Diffusion
• How do we quantify the amount or rate of diffusion?
Diffusion is a time-dependent process. The quantity of an element that is transported within another is a
function of time. The rate of mass transfer is frequently expressed as a diffusion flux (J), 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.

moles (or mass) diffusing mol kg

J º Flux º = or
(area)(time) cm2s m2s
• Measured empirically
– Make thin film (membrane) of known cross-sectional area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane

M=
M l dM mass J  slope
J= = diffused
At A dt
time Chapter 6 - 15
 Steady-State Diffusion
Rate of diffusion independent of time
dC
Flux proportional to concentration gradient =
dx

C1 C1 Fick’s first law of diffusion

dC
C2 C2 J = -D
dx
x1 x2
x
D  diffusion coefficient
dC DC C2 - C1
if linear @ =
dx Dx x2 - x1

Chapter 6 - 16
 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.
• If butyl rubber gloves (0.04 cm thick) are used, what
is the diffusive flux of methylene chloride through the
glove?
• Data:
– diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
– surface concentrations: C1 = 0.44 g/cm3
C2 = 0.02 g/cm3

Chapter 6 - 17
 Example (cont).
• Solution – assuming linear conc. gradient
glove
C1 dC C2 - C1
tb =
2
J =-D @ -D
paint skin
6D dx x2 - x1
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x 2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

-8 2 (0.02 g/cm3 - 0.44 g/cm3 ) -5 g

J = - (110 x 10 cm /s) = 1.16 x 10
(0.04 cm) cm2s

Chapter 6 - 18
 Diffusion and Temperature
• Diffusion coefficient increases with increasing T

 Qd 
D = Do exp

-
 RT 

D = diffusion coefficient [m2/s]

Do = temperature-independent preexponential [m2/s]
Qd = activation energy for diffusion [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]

Chapter 6 - 19
 Diffusion and Temperature
D has exponential dependence on T

Dinterstitial >> Dsubstitutional

C in a-Fe Al in Al
C in g-Fe Fe in a-Fe
Fe in g-Fe

Adapted from Fig. 6.7, Callister & Rethwisch 4e. (Date for Fig. 6.7
taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
Chapter 6 - 20
Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)
Example: At 300ºC the diffusion coefficient and
activation energy for Cu in Si are
 Qd 
D(300ºC) = 7.8 x 10-11 m2/s D = Do exp

-
Qd = 41.5 kJ/mol  RT 

What is the diffusion coefficient at 350ºC?

D transform ln D
data

Temp = T 1/T
Qdæ1ö Q æ1ö
lnD2 = lnD0 - çç ÷÷ and lnD1 = lnD0 - d çç ÷÷
R è T2 ø R è T1 ø
D2 Qd æ 1 1 ö
\ lnD2 - lnD1 = ln =- çç - ÷÷
D1 R è T2 T1 ø
Chapter 6 - 21
 Example (cont.)

é Qd æ 1 1 öù
D2 = D1 expê- çç - ÷÷ú
ë R è T2 T1 øû

T1 = 273 + 300 = 573K

T2 = 273 + 350 = 623 K

-11 2 é - 41,500 J/mol æ 1 1 öù

D2 = (7.8 x 10 m /s) expê ç - ÷ú
ë 8.314 J/mol - K è 623 K 573 K øû

D2 = 15.7 x 10-11 m2/s

Chapter 6 - 22
 Non-steady State Diffusion
Most practical diffusion situations are nonsteady-state ones, i.e.
the diffusion flux and the concentration gradient at some
particular point in a solid vary with time, with a net accumulation
or depletion of the diffusing species resulting

• The concentration of diffusing species is a function of

both time and position C = C(x,t)
• In this case Fick’s Second Law is used

¶C ¶ 2C
Fick’s Second Law =D 2
¶t ¶x

Chapter 6 - 23
VMSE: Screenshot of Diffusion
Computations & Data Plots

Chapter 6 - 24
 Non-steady State Diffusion
• Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms
Cx represents the
concentration at Cs
depth x after time t

Adapted from
Fig. 6.5,
Callister &
Rethwisch 4e.

Initial Condition: at t = 0, C = Co for 0  x  

Boundary Condition: at t > 0, C = CS for x = 0 (constant
surface conc.)
at t > 0, C = Co for x =  Chapter 6 - 25
 Solution:

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

C(x,t) = Conc. at point x at CS

time t
erf (z) = error function
C(x,t)
ò
2 z -y 2
= e dy
p 0
Co
erf(z) values are given in
Table 6.1
Adapted from Fig. 6.5,
Callister & Rethwisch 4e.

Chapter 6 - 26
 Non-steady State Diffusion
• Sample Problem: An FCC iron-carbon alloy initially
containing 0.20 wt% C is carburized at an elevated
temperature and in an atmosphere that gives a surface
carbon concentration constant 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.

C( x, t ) - Co æ x ö
• Solution: use Eqn. 6.5 = 1 - erf ç ÷
Cs - Co è 2 Dt ø

Chapter 6 - 27
 C( x ,t ) - Co æ x ö
Solution (cont.): = 1 - erf ç ÷
Cs - Co è 2 Dt ø

– 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 6 - 28
Chapter 6 - 29
Solution (cont.):
We must now determine from Table 6.1 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 x x2

z= D=
2 Dt 4z 2t

æ x2 ö -3 2
( 4 x 10 m) 1h
\D = ç ÷ = = 2.6 x 10 -11 m2 /s
ç 4z 2t ÷ ( 4)(0.93)2 ( 49.5 h) 3600 s
è ø
Chapter 6 - 30
 Solution (cont.):
• To solve for the temperature at Qd
T=
which D has the above value, R(lnDo - lnD )
we use a rearranged form of
Equation (6.9a);
from Table 6.2, 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 2.3x10 -5 m2 /s - ln 2.6x10 -11 m2 /s)

T = 1300 K = 1027°C

Chapter 6 - 31
Chapter 6 - 32
 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.
• If butyl rubber gloves (0.04 cm thick) are used, what is the
breakthrough time (tb), i.e., how long could the gloves be used
before methylene chloride reaches the hand?
• Data
– diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s

Chapter 6 - 33
 CPC Example (cont.)
• Solution – assuming linear conc. gradient
glove Breakthrough time = tb
C1 2 Equation from online CPC
Case Study 5 at the Student
paint skin tb = Companion Site for Callister &
Rethwisch 4e (www.wiley.com/
remover 6D college/callister)
C2
x1 x 2
= x2 - x1 = 0.04 cm
D = 110 x 10-8 cm2/s

(0.04 cm)2
tb = = 240 s = 4 min
-8 2
(6)(110 x 10 cm /s)

Time required for breakthrough ca. 4 min

Chapter 6 - 34
 Summary

Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

Chapter 6 - 35
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Slides from Callister and Rethwisch, Fundamentals of Materials Science and Engineering, An Integrated Approach,
International Student Version Fifth Edition Chapter 6 - 36
Thank you for your attention!

For more information contact:

E-mail: [email protected]
Office: Block 108; Room 021

Chapter 6 -