BMFG 1213

ENGINEERING MATERIALS

Sem/Session : 1/2022-2023
Week 5
Chapter 5

Title : Diffusions in Solids

1
 Course Learning Outcomes
Upon completion of this subject, students should be able to:

1. Explain the basic concepts of engineering materials in terms of

interatomic bonding and crystal structure
2. Analyze the properties of engineering materials based on its
structure.
3. Describe the processing methods for engineering materials.

2
 Learning Objectives

 Name the two types of diffusions and

their mechanism.
 Macroscopic description in steady
state diffusion and non-steady state
diffusion.
 Predict the factors that influence
diffusion.
 Discuss the Industrial application.

3
 Chapter Outlines

1. Introduction
2. Diffusion mechanisms
3. Steady state diffusion
4. Non steady state diffusion
5. Factors that influence diffusion
6. Industrial Application

4
Diffusion
Diffusion of dye throughwater
 1.0 Introduction

Outer layer

Inner layer
 Why we need to studydiffusion???
• Material are often heat treated to improve their
properties.
• The phenomena that occur during a heat treatment
always involve atomic diffusion.
Often predictable
• Heat treating: temperature using the
mathematics of
time diffusion and
diffusion constant
cooling rate

• E.g. a steel gear has been case hardened; that is

hardness and resistance to failure by fatigue have
been enhanced, by diffusing excess carbon or
nitrogen into the outer surface layer.
• Many reactions and processes that are important in the
treatment of materials rely on the transfer of mass either
within a specific solid or from a liquid, gas or another solid
phase

Diffusion: phenomenon of material transport by

atomic motion

• The phenomenon of diffusion may be demonstrated with the

use of a diffusion couple, which is formed by joining bars of 2
different metals together so that there is intimate contact
between the 2 faces (e.g. copper & nickel)
 A copper- nickel diffusioncouple

Atom locations

Concentrations

Before heat treatment After heat treatment

• This copper- nickel couple is heated for an
extended period at an elevated
temperature (but below the melting
temperature of both metals) and cooled to
RT

• Copper atoms have migrated or diffused

into the nickel and that nickel has diffused
into copper.

• The process where atoms of one metal

diffuse into another is termed ->
interdiffusion or impurity diffusion

• Interdiffusion: changes in concentration

which occur over time. There is a net drift
or transport of atoms from high to low
concentration region (e.g. Cu- Ni diffusion
couple).

• Self- diffusion: diffusion which occurs for

pure metals, where all atoms exchanging
positions are of the same type
Carbon gaseous diffuse into ametal
 Interdiffusion
•Interdiffusion (impurity diffusion): In an alloy,
atoms tend to migrate from regions of high
concentration to regions of low concentration.
After some time

Initially

12
 Self-Diffusion
•Self-diffusion: In an elemental solid,
atoms also migrate.

Specific atom movement After some time

C
C
A D
A
D
B
B

13
 Diffusion

• How does diffusion occur?

• Why is diffusion 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?

14
 2.0 Diffusion Mechanisms
• Diffusion is stepwise migration of atoms from lattice site to lattice
site.
• Atom in solid materials are in constant motion rapidly changing
positions.
• 2 conditions must be met for an atom to move:

(1) There must be an empty adjacent site

(2) The atom must have sufficient (vibrational) energy to break
bonds with its neighboring atoms and then cause lattice
distortion during the displacement. At a specific temperature,
only a small fraction of the atoms is capable of motion by
diffusion. This fraction increases with rising temperature.

• There are 2 dominant models for metallic diffusion:

1. Vacancy Diffusion
2. Interstitial Diffusion
 Vacancy Diffusion
• atoms exchange with vacancies
• applies to substitutional impurity atoms
• rate depends on:
-- number of vacancies (significant concentrations of vacancies
may exist at elevated temperature)
-- activation energy to exchange.
• both self- diffusion and interdiffusion occur by this mechanism

increasing elapsed time 16

 Interstitial Diffusion
• Involves atoms that migrate from an interstitial position to a
neighboring one that is empty
• for interdiffusion of impurities (H, C, O, N), which atoms are small
enough to fit into the interstitial positions.
• More rapid than vacancy diffusion due to more mobile small atoms
and more empty interstitial sites

.
17
 3.0 Steady- State Diffusion
• Diffusion is a time- dependent process;
the quantity of an element that is
transported within another is a function
of time.
• It is necessary to know how fast
diffusion occurs ->rate of mass transfer
Diffusion Flux (J)

• Diffusion flux (J): defined as the mass

(or number of atoms) M diffusing/
passing through a plane of unit area
per unit time.

moles (or mass) diffusing mol kg

J  Flux   or
surface area time  cm2s m2s
• In differential form, the expression becomes; M 1 dM
J 
• Unit J, are kg/m2.s or atoms/m2.s At A dt
• If the diffusion flux does not change with time -> Steady- state condition

• Steady- state condition: is when 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

The concentration profile shows the concentration (C) vs the position within the
solid (x); the slope at a particular point is the concentration gradient.
 dC
Flux proportional to concentration gradient =
dx

C1 Fick’s first law of diffusion

C1

dC
J  D
C2 C dx
2

x1 x2 D  diffusion coefficient (m2/s)

x
dC C C2  C1 Fick’s first law: it postulates that the
if linear   solute will move from a region of high
dx x x2  x1 concentration to a region of low
concentration across a concentration
gradient

20
 Example 1: 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 are worn.
• If butyl rubber gloves (0.04 cm thick) are used, what is
the diffusive flux of methylene chloride through a
glove?
• Data:
– diffusion coefficient for butyl rubber:
D = 110 x10-8 cm2/s
– surface concentrations: C1 Surface concentration at
= 0.44 g/cm3 the beginning process

C2 = 0.02 g/cm3 Surface concentration at

the end process
22
 Example 1 (cont).
• Solution – assuming linear conc. gradient
glove
C1 dC C2  C1
tb 
2 J -D  
dx D x2  x1
6D
paint skin C2
remover
Data: D = 110x 10-8 cm2/s
x1 x2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

(0.02 g/cm 3
 0.44 g/cm3 ) g
J   (110 x 10-8 cm2/s)  1.16 x 10 -5
(0.04 cm) cm2s

23
Example 2:
Solution:
 4.0 Non- steady State Diffusion
• The concentration of diffusing species is a function of both time and
position C = C(x,t). More likely scenario than steady state.

Fick's second law: predicts how diffusion

causes the concentration to change with
respect to time

• In this case, Fick’s Second Law is used.

Fick’s Second Law

This law states that the rate of compositional change is equal to the
diffusivity times the rate of change of the concentration gradient
 Or can also use this
equation

Diffusion of a gas into a solid. (a) Gas A diffuses into solid B at the surface where x
= 0. The gas maintains a concentration of A atoms, called Cs, on this surface.
(b) Concentration profiles of element A at various times along the solid in the x
direction. The solid contained a uniform concentration of element A, called Co
before diffusion started.
The error function, erf, is a mathematical function existing by agreed definition
and is used in some solutions of Fick’s second law. The error function can be
found in standard tables in the same way as sines and cosines. Table 5.1 is an
abbreviated table of the error function.
 Difference between steady state and non- steady state diffusion
Steady state diffusion Non-steady state diffusion
1. Definition Steady state diffusion is a form of Unsteady state diffusion or non-steady
diffusion that takes place at a constant state diffusion is a form of diffusion in
rate. which the rate of diffusion is a function of
time.

2. Rate of diffusion The rate of diffusion is constant for steady The rate of diffusion is not constant for
state diffusion. unsteady state diffusion. It varies with
time.
3. Dependence on Steady state diffusion does not vary with Unsteady state diffusion is a function of
time. time (it changes with time).
time
4. Relationship to Steady state can be quantitatively Unsteady state diffusion can be
determined by Fick’s first law. quantitatively determined by Fick’s
Fick’s Law second laws.

or;
Example 3:
Solution:
Example 4:
 Carburizing process
 Carburizing is a heat treatment process in
which iron or steel absorbs carbon while the
metal is heated in the presence of a carbon-
bearing material, such as charcoal or carbon
monoxide, to make the metal harder.
 Longer carburizing times and higher
temperatures typically increase the depth of
carbon diffusion.
 When the iron or steel is cooled rapidly by
quenching, the higher carbon content on the
outer surface becomes hard due to the
transformation from austenite to martensite.

Austenite
microstructure

Martensite
microstructure
Solution:
 5.0 Factors That Influence Diffusion
(a) The type of diffusing species (@ mechanism)

The magnitude of the diffusion coefficient (D) is indicative of the rate at

which atoms diffuse
The diffusing species and host material influence the diffusion
coefficient (self- diffusion and interdiffusion also influence D )

Self- diffusion
(Fe in Fe)

Inter-
diffusion (C
in Fe)

D value for C
inter- diffusion
is greater than
self- diffusion
(Fe in Fe)
(b) Temperature

 Temperature has a most profound influence on the coefficients &

diffusion rates
 As the temperature is increased, the diffusion coefficient also
increases.

Activation energy - energy

required to produce the
movement of 1 mole of atoms by
diffusion.
Example 5:
 Example (cont.)
 Qd  1 1 
D2  D1 exp   
 R  T2 T1  

T1 = 273 + 300 = 573K
T2 = 273 + 350 = 623K

11 2   41,500 J/mol  1 1 

D2  (7.8 x 10 m /s) exp    
8.314 J/mol - K  623 K 573 K 

D2 = 15.7 x 10-11 m2/s

37
(c) The type of crystal structure of the solvent lattice

The diffusivity of carbon in BCC iron is 10-12 m2/s at 500 oC, which is much
greater than 5 x 10-15 m2/s, the value for the diffusivity of carbon in FCC iron at
the same temperature.

The reason for this difference is that the BCC crystal structure has a lower
atomic packing factor of 0.68 as compared to that of the FCC crystal
structure, which is 0.74.

Also, the interatomic spaces between the iron atoms are wider in the BCC
crystal structure than in the FCC one, and so the carbon atoms can diffuse
between the iron atoms in the BCC structure more easily than in the FCC one.
(d) The type of crystal imperfection present

More open structures (surface defects) allow for more rapid

diffusion of atoms.
For example, diffusion takes place more rapidly along grain
boundaries than in the grain matrix in metals and ceramics.
Excess vacancies will increase diffusion rates in metals and
alloys.
(e) The concentration of the diffusing species

 It is important in that higher concentrations of diffusing solute

atoms will affects the diffusivity.
 This aspect of solid-state diffusion is verycomplex.
6.0 Industrial Applications of Diffusion
 (a) Case Hardening
• Case hardening or surface hardening
is the process of hardening the surface
of a metal, often a low carbon steel, by
diffusing elements into the material's
surface, forming a thin layer of a harder
alloy.
• Carbon atoms diffuse into the iron
lattice atoms at the surface.
• This is an example of interstitial
diffusion.
• The C atoms make iron (steel) harder. Fe atom

C atom

42
A modern computerised gas carburising furnace

•Furnace for heat treating steel using carburization.

•Carburizing is the addition of carbon to the surface of low-
carbon steels at temperatures ranging from 850°C (1560°F)
to 950°C (1740°F).
•Hardening is achieved when a high carbon martensitic case
with good wear and fatigue resistance is superimposed on a
tough, low-carbon steel core.
http://www.americanmetaltreatinginc.com/carburizing.htm
 Example 6:

• 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  x 
• Solution:? Cs  C o
 1 erf
 2 Dt 
45
Solution (1):
C( x,t )   1 erf x 

Co Cs   2 Dt 
Co
– t = 49.5h x = 4 x 10-3 m
– Cx = 0.35 wt% Cs = 1.0wt%
– Co = 0.20 wt%

C(x,t )  C o 0.35  0.20  x   1 erf

  1erf (z)
Cs  Co 1.0  0.20  2 Dt  

 erf(z) = 0.8125

46
 Solution (2):
We must now determine from table the value of z for which the
error function is 0.8125. An interpolation is necessary as follows

z erf(z) z 0.90 0.8125  0.7970


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

 x2  (4 x103m)2 1h
D     2.6 x 1011 m2/s
 4z2t  (4)(0.93)2(49.5 h) 3600 s
 
48
 Solution (3): Qd 

D Doexp RT
• To solve for the temperature
 Q
at which D has the calculated T d

value, we use a rearranged R(lnDo  lnD)

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

49
 (b) Sintering in ceramic
 Sintering is the process of compacting and
forming a solid mass of material by heat or
pressure without melting it to the point of
liquefaction.
 Sintering happens naturally in mineral
deposits or as a manufacturing process
used with metals, ceramics, plastics, and
other materials.
 The atoms in the materials diffuse across
the boundaries of the particles, fusing the Iron powder
particles together and creating one solid
piece.

Cross section of a sintering tool and the

sintered part
 (c) Impurity Diffusion (Doping)
• Integrated circuits (ICs), found
in numerous electronic
devices have been fabricated
using doping techniques.
• The base material for these
ICs is silicon that has been
“doped” with other materials.
• More precisely, controlled
concentrations of impurities
have been diffused into
specific regions of the device
to change the properties
(improve electrical
conductivity).
 Microchip fabrication process
1.Making wafers: We grow pure silicon
crystals into long cylinders and slice them
(like salami) into thin wafers.
2.Masking: We heat the wafers to coat
them in silicon dioxide and use ultraviolet
light (blue) to add a hard, protective layer
called photoresist.
3.Etching: We use a chemical to remove
some of the photoresist, to areas of n-type
and p-type silicon.
4.Doping: We heat the etched wafers with
gases containing impurities to make the
areas of n-type and p-type silicon.
5.Testing: Long metal connection leads run
from a computer-controlled testing
machine to the terminals on each chip. Any
chips that don't work are marked and
rejected.
6.Packaging: All the chips that work OK
are cut out of the wafer and packaged into
protective lumps of plastic, ready for use in
computers and other electronic equipment
 Impurity Diffusion (Doping)

Diffusion method for diffusing boron into

silicon wafers Impurity diffusion into a silicon wafer from one
face. (a) A silicon wafer with thickness greatly
exaggerated having an impurity concentration
that diminishes from the left face toward the
interior. (b) Graphical representation of the
same impurity distribution
 Processing Using Diffusion
Doping silicon wafer with phosphorus for n-type semiconductors:

• Process: 0.5mm
1. Deposit P rich
layers on surface.
magnified image of a computer chip

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

light regions: Al atoms

silicon
54
 Thomson Learning™ is a trademark used herein under license.
©2003 Brooks/Cole, a division of Thomson Learning, Inc.
Schematic of the
microstructure of the Co-
Pt-Ta-Cr film after
annealing.
Most of the chromium
diffuses from the grains to
the grain boundaries after
the annealing process.
This helps improve the
magnetic properties of the
hard disk.
http://www.asylumresearch.com/Gallery/Materials/Materials.shtml
 CHECKLIST
 Diffusion
 Self-diffusion
 Interdiffusion
Make sure you understand  Vacancy diffusion
 Interstitial diffusion
 Diffusion flux
 Steady-state
diffusion and
Non- steady
diffusion
 Fick’s first and
second laws
 Factors influence
diffusion
56  Diffusion coefficient
 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

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Inspirational Quotes for Today…

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