Chapter4 Imperfectiondiff. - Bda10803 28i 20212022 29

BDA 10803
Materials Science
Sessi on 2021/2022
Sem ester I
Chapter 4:
IM PERFECTION AND DIFFUSION
IN SOLID
PM Ts. Dr. HAMIMAH BINTI ABD.RAHMAN

Dept. of Manufacturing Engineering
FKMP, UTHM
CHAPTER 4 – BDB 10803
4.1 Defects (Point Defects, Line/Linear Defects,

Area/Planar Defects, Bulk/Volume Defects)
4.2 Diffusion Mechanisms
4.3 Steady-State Diffusion
4.4 Non-Steady State Diffusion
4.5 Factors That Influence Diffusion
HUMAN’S GENE DEFECT
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ISSUES TO ADDRESS...
• What types of defects arise in solids?
• Can the number and type of defects be varied

and controlled?
• How do defects affect material properties?
• Are defects undesirable?

 The properties of some materials – influenced by the
presence of imperfections.
 In reality crystals – never perfect and contains various types
of imperfections or defects,
 affect many of their important physical and
mechanical properties such as the cold formability of
alloys, the electronic conductivity of semiconductors etc.
 Crystal lattice imperfections are classified according to their

geometry and shape :
1. point defects (zero-dimension)
2. line/linear defects (one-dimension)
3. area/planar defects (two-dimension)
4. bulk/volume defects
4.1 Defects

4.1.1 POINT DEFECTS
(1) Vacancy
– an atom site from which an atom is missing.
- all crystalline solid contain vacancies.
- produces during solidification or by atomic rearrangements.
Figure 3.1 : Vacancy point defect

(2) Self-Interstitial
– an atom in a crystal occupied an interstitial site, a small void that
under ordinary circumstances is not occupied.
- introduce relatively large distortion in the crystal lattice.
Figure 3.2 : Self-interstitial point defect

-ve ion
+ve ion
Figure 3.3 : Ionic crystal illustrating a Schottky defect and a Frenkel defect.
(3) Schottky Imperfection – when two oppositely charged ions

are missing from an ionic crystal (a cation-anion divacancy)
(4) Frenkel Imperfection – a cation moves into an interstitial site

in an ionic crystal, created cation vacancy in the normal ion
site.

Point Defects in Alloys - Impurities
◼ Two outcomes if impurity (B) added to host (A):
(5) Solid solution of B in A (i.e. random dist. of point defects)
Figure 3.4 : (a) Substitutional solid solutions (b) Interstitial solid solutions
– solute or impurity atoms replace or – impurity atoms fill the voids
substitute for the host atoms or interstices among the host
Factors that determine the degree of atoms (concentration <10%).
solvent dissolved (Hume-Rottery Rules) ;
1. Atomic size factor (< 15%)
2. Crystal structure – the same
3. Electronegativity
4. Valences
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Point Defects in Alloys - Impurities
◼ Two outcomes if impurity (B) added to host (A):
(6) Solid solution of B in A and particles of a new phase

(more likely as concentration of B increases)
Figure 3.5 : Occurrence of a new phase in solid solution

4.1.2 LINE/LINEAR DEFECTS
Metal deformation occurs by crystal planes slipping past each

other:
Whole crystal planes do not slip past each other at once!

(1) Dislocation
- a linear or one dimensional defect around which some of
the atoms are misaligned.
- move under the action of a shear stress, τ.
- motion involves bonds breaking and reforming, but only along

the dislocation line at any point in time, not along the whole
plane at once.
- Net result of dislocation moving across a crystal plane is same

as if whole plane moved, but less energy is needed to break a
single row of bonds.

Types of Dislocations :-
(1a) Edge Dislocation - termination of an extra portion

of a plane of atoms, or half-plane within the crystal
structure.
Figure 3.6 : Edge dislocation in a crystalline lattice.

(1b) Screw dislocation – the shifted of atomic plane in
the crystal structure
Figure 3.7 : Screw dislocation in a cubic

crystal lattice.

(1c) Mixed dislocation – mixed of screw and edge
dislocation.
Figure 3.8 : Mixed dislocation in a

crystal.
Dislocation line AB – pure screw type
(when it enters crystal) and pure
edge type (when it leaves crystal).

4.1.3 AREA/PLANAR DEFECTS
(1) Grain boundaries
- are boundaries between crystals with different orientation
(planes go in different directions).
- are produced by the solidification process, for example.
- have a change in crystal orientation across them.
- impede dislocation motion.
Figure 3.9 : Schematic diagram of grain boundaries and microstructure of metal ingot

Grain boundaries...
• are imperfections,
• are more susceptible to etching,
• may be revealed as dark lines,
• change direction in a polycrystal.
N = 2n-1 where N = no. grains/in2 at 100x magnification

n = ASTM grain size number

4.1.4 BULK/VOLUME DEFECTS
❖ This defect is much larger than previous defects that have

been discussed.
❖ Normally introduced during processing and fabrication
steps.
 Examples of bulk defects ;
1. Pores
2. Cracks
3. Foreign inclusions
4. other phases

SUMMARY of Defects
• Point, Line, Area and Volume defects arise in solids.
• The number and type of defects can be varied and controlled

(e.g., T controls vacancy conc.)
• Defects affect material properties (e.g., grain boundaries affect

crystal slip).
• Defects may be desirable or undesirable (e.g., dislocations may

be good or bad, depending on whether plastic deformation is
desirable or not.)

4.2 Diffusion Mechanism

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?

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.

4.3 DIFFUSION MECHANISMS
▪ Diffusion – the phenomenon of material transport by

atomic motion.
• Types of diffusion process.

1. Interdiffusion (impurity diffusion)
2. Self-diffusion

1. Interdiffusion (impurity diffusion)
– atoms of one metal diffuse into another.
Figure 3.10 : A copper-nickel diffusion couple before a high-temperature heat

treatment.

2. Self-diffusion – diffusion occurs for pure metal,
but all atoms exchanging positions are of the
same type.
Figure 3.11

 Two conditions must be met for diffusion process :
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.
 Temperature , the fraction of the total number of atoms

capable of diffusion motion .
 Two dominate models for atomic DIFFUSION

MECHANISIM in metal;
1. Substitutional/Vacancy diffusion
2. Interstitial diffusion

1. SUBSTITUTIONAL/VACANCY DIFFUSION
 One mechanism involves the interchange of an atom from a
normal lattice position to an adjacent vacant lattice site or
vacancy.
 Diffusion of atoms in one direction corresponds to the motion of
vacancies in the opposite direction.
 Both self-diffusion and interdiffusion occur by this mechanism;
for the latter, the impurity atoms must substitute for host atoms.
 Rate of substitutional diffusion depends on:
i) vacancy concentration
ii) frequency of jumping. Motion of a host or
substitutional atom
Vacancy
Figure 3.12 : Vacancy Diffusion

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2. INTERSTITIAL DIFFUSION
 The mechanism involves atoms that migrate from an interstitial position

to a neighboring one that is empty.
 Example : interdiffusion of impurities such as hydrogen, carbon, nitrogen
and oxygen.
 This mechanism occurs more rapidly than diffusion by the vacancy mode;
 interstitial atoms are smaller and more mobile.
 large ‘concentration’ of interstitial vacancies.
Figure 3.13 : Interstitial Diffusion

– the rate of mass transfer
M
J= (kg/m 2s or atoms/m2s)
At

Concentration profile – plot of curve for concentration C versus
position within the solid x
The steeper the concentration profile, the greater the flux!
Diffusion is a time-dependent process – the quantity of an element

that is transported within another is a function of time.

4.3 Steady-State Diffusion

4.3 STEADY-STATE DIFFUSION
 Steady-state diffusion – the concentration profile doesn't change with
time.
Example : the diffusion of atoms of a gas through a plate of metal for
which the concentration of the diffusing species on both surfaces of
the plate are held constant.
Steady-state diffusion described by Fick's First Law:

dC
J = −D
dx
where D - diffusion coefficient (m2/s)  Q 
D = Do exp − D 
 RT 
 The – ve sign → the direction of diffusion (flux direction) is from a

high to a low concentration.
 In this case, the driving force is the concentration gradient.
dC
J = −D
dx
Diffusivity, D depends on:
1. Diffusion mechanism
2. Temperature of diffusion
3. Type of crystal structure
4. Crystal imperfections
5. Concentration of diffusing
species
Recall: Solvent – the majority atom type (or host atoms); Solute – the element with lower concentration
Substitutional – a solid solution in which the solvent atoms are replaced by solute
Interstitial - solute atoms are located in gaps between host atoms

Figure 3.14 :
(a) Steady-state
diffusion across a thin
plate
(b) A linear concentration
profile for the diffusion
situation in (a).
Concentration gradient – the slope at a particular point on this curve.

dC CA − CB
Concentration gradient = =
dx xA − xB

Example Problem 1 :
Calculate the diffusivity D in square meters per second for the diffusion of nickel in
FCC iron at 1100ºC. Use values of D 0 = 7.7 × 10–5 m2/s; Q = 280 kJ/mol; R =
8.314 J/ (mol· K).
 Q 
D = Do exp − D 
 RT 

Example Problem 2 :
A plate of iron is exposed to a carburizing (carbon-rich) atmosphere
on one side and a decarburizing (carbon-deficient) atmosphere on
the other side at 700C (1300  F). If a condition of steady state is
achieved, calculate the diffusion flux of carbon through the plate if
the concentrations of carbon at positions of 5 and 10 mm (5 x 10-3 and
10-2 m) beneath the carburizing surface area is 1.2 and 0.8 kg/m3,
respectively. Assume a diffusion coefficient of 3 x 10-11 m2/s at this
temperature.
SOLUTION
CA − CB (1.2 - 0.8)kg/m3 = 2.4x10-9 kg/m 2s

J = −D = −(3x10 m / s)
-11 2
xA − xB (5x10-3 − 10− 2 )m

Example Problem 3 :
2.0 kg/m3
1.5 kg/m3
6.0 mm
J = 3.75 x 10-9 kg/m2s

Example Problem 4 :
Calculate the diffusivity in m /s of carbon in HCP titanium at 700ºC. Use

2
D 0 = 5.10 × 10– 4 m2/s; Q = 182 kJ/mol; R = 8.314 J/ (mol· K).
Example Problem 5 :
The diffusivity of manganese atoms in the FCC iron lattice is 1.5 × 10–14 m2/s at
1300ºC and 1.5 × 10–15 m2/s at 400ºC. Calculate the activation energy in kJ/mol
for this case in this temperature range. Data: R = 8.314 J/(mol·K).

Solution Problem 4 :

Solution Problem 5:

Exercise 1:
1. Calculate the diffusivity in m2/s for the diffusion of zinc in copper

at 350°C. Use D0 = 3.4 × 10-5 m2/s; Q = 191 kJ/mol.
2. The diffusivity of iron atoms in the BCC iron lattice is 4.5 × 10–23
m2/s at 400ºC and 5.9 × 10–16 m2/s at 800ºC. Calculate the
activation energy in kJ/mol for this case in this temperature
range. [R = 8.314 J/(mol·K).]

Solution:
1.
2.

Exercise 2:
1. Calculate the value of the diffusivity D in m2/s for the diffusion of carbon
in  iron (FCC) at 927C (1700F). Use the values of Do = 2.0 x 10-5
m2/s, Q = 142 kJ/mol, and R = 8.314 J/mol.K.
2. Calculate the diffusivity D in square meters per second for the diffusion of
nickel in FCC iron at 1100ºC. Use values of D0 = 7.7 × 10–5 m2/s; Q = 280
kJ/mol; R = 8.314 J/ (mol· K).
3. The diffusivity of silver (Ag) atoms in solid silver metal is 1.0 x 10-17 m2/s
at 500C and 7.0 x 10-13 m2/s at 1000C. Calculate the activation energy
(joules per mole) for the diffusion of Ag in Ag in the temperature range
500 to 1000C .
4. The diffusivity of copper atoms in the aluminum lattice is 7.5 × 10–13 m2/s
at 600ºC and 2.5 × 10–15 m2/s at 400ºC. Calculate the activation energy
for this case in this temperature range. [R = 8.314 J/(mol·K).]

5. Determine the rate at which helium (He), held at 5 atm and 200°C in a
Pyrex glass bulb of 50 cm diameter and a wall thickness (x) of 0.1 cm,
diffuses through the Pyrex to the outside. Assume that the pressure outside
the tube at all times remains negligible. Permeation constant, K = 1 x 10–9
cm2/s.atm. Give the rate of mass transfer in cm3/s.
(Flux equation - operates

with pressures instead of
concentrations)
Conditions for outdiffusion of He from a glass bulb

SOLUTIONS :
1.  - 142,000J/mol 
D = D o e −Qd / RT = (2.0 10−5 m 2 / s)exp 
 8.314 J/molK(1200K) 
D = (2.0 10−5 m 2 / s)(e −14.23 )
D = 1.32 10−11 m 2 / s
2.

3. D1000 C = exp(-Q / RT2 ) − equation(1)
D500 C = exp(-Q / RT1 ) − equation(2)
eq.(1)  eq.( 2)
D1000 C  Q  1 1 
= exp −  − 
D500 C  R  T2 T1 
7.0 10−13  Q  1 1  
= exp  −  −  
1.0 10−17  8.314 1273 773  
Q = 183,000J/mol = 183 kJ/mol
4.

5.
J = 3.927 x 10-4 cm3/s

4.4 Non Steady-State
Diffusion

4.4 NONSTEADY-STATE DIFFUSION
 Non Steady-State - Concentration profile, C(x), changes with time.
C  2C (Fick’s Second Law)

=D 2
t x
 The following assumption are made :

1. Before diffusion, any of the diffusing solute atoms in the solid
are uniformly distributed with concentration of Co.
2. The value of x at the surface is zero and increases with distance
into the solid.
3. The time is taken to be zero the instant before the diffusion
process begins.

Figure 3.16 : Concentration
Figure 3.15 :Diffusion of a gas into a profiles for nonsteady-state
solid. diffusion taken at three
different times t1, t2 and t3

NON STEADY STATE DIFFUSION
• Concentration profile, C(x),

changes w/ time.
• To conserve matter: • Fick's First Law:
• Governing Eqn.:
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 These boundary conditions are simply stated as
For t = 0, C = Co at 0  x  
For t > 0, C = Cs (the constant surface concentration)at x = 0
C = Co at x = 
 Application of these boundary conditions to Fick’s Second Law equation;

Cx − Co  x 
= 1 − erf   OR
Cs − Co  2 Dt 
where Cs = surface concentration of element in gas diffusing

into the surface
Co = initial uniform concentration of element in solid
Cx = concentration of element at distance x from
surface at time t
D = diffusivity of diffusing solute element
t = time
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Table 4.1 : Tabulation of Error Function Values
x
= z = constant
2 Dt

EXAMPLE PROBLEM 1 :
Consider an alloy which is undergoing carburizing process,

initially has a uniform carbon concentration of 0.25 wt%
and is to be treated at 950C (1750F). If the concentration
of carbon at the surface is suddenly brought to and
maintained at 1.20 wt%, how long will it take to achieve a
carbon content of 0.80% at a position 0.5 mm below the
surface? The diffusion coefficient for carbon in iron at this
temperature is 1.6 x 10-11 m2/s; assume that the steel piece
is semi-finite.

SOLUTION ;
Co = 0.25 wt%
Cs = 1.20 wt%
Cx = 0.80 wt%
x = 0.50 mm = 5 x 10-4m
D = 1.6 x 10-11 m2/s
C x − Co 0.80 − 0.25  (5x10-4 m) 

= = 1 − erf  
Cs − Co 1.20 − 0.25  2 (1.6 10 m / s)(t ) 
-11 2
 62.5s 1/2 
0.4210 = erf  
 t 

We must now determine from Table 4.1 the value of z for
which the error function is 0.4210.
z erf (z)
An interpolation is necessary, as
0.35 0.3794
z - 0.35 0.4210 − 0.3794 z 0.4210
=
0.40 - 0.35 0.4284 − 0.3794 0.40 0.4284
z = 0.392
62.5 s1/2
Therefore, = 0.392
t
t = 25,420s = 7.1 h

EXAMPLE PROBLEM 2 :
• Copper diffuses into a bar of aluminum.

• 10 hours at 600°C gives desired C(x).
• How many hours would it take to get the same C(x) if we
processed at 500°C?
Given: D500 = 4.8 x 10-14 m2/s, D600 = 5.3 x 10-13 m2/s
C x − Co  x 
= 1 − erf  
Cs − Co  2 Dt 

Answer for PROBLEM 2 :
Key point 1: C(x,t500C) = C(x,t600C).

Key point 2: Both cases have the same Co and Cs.
• Result: Dt should be held constant.
Note: values
• Answer:
of D are
provided here.

EXERCISE: Non Steady-State Diffusion
Solve the below questions.
1. If boron, B, is diffused into a thick slice of Si with no previous B in it at a

temperature of 1100°C for 5 h, what is the depth below the surface at
which the concentration is 1017 atoms/cm3 if the surface concentration is
1018 atoms/cm3? D = 4 × 10-13 cm2/s for B diffusing in Si at 1100°C.
2. Indium (In) is to be diffused into pure silicon such that the In

concentration at a depth (x) of 2.3 x 10–4 cm below the surface will be
half of the surface concentration (maintained constant throughout
diffusion). How long must diffusion be conducted at 1600K if
D = 8 x 10–12 cm2/s?

4.5 Factors That Influence
Diffusion

4.5 FACTORS THAT INFLUENCE
DIFFUSION
1. Diffusing Species

2. Temperature
- Temperature has a most profound influence on the coefficients and
diffusion rates.
- The temperature dependence of the diffusion coefficient, D
(diffusivity) is
 Qd  (m2/s)
D = Do exp − 
 RT 
where Do = a temperature-independent preexponential (m2/s)
Qd = the activation energy for diffusion (J/mol, cal/mol or eV/atom)
R = the gas constant, 8.314 J/mol-K, 1.987 cal/mol-K or
8.62 x 10-5 eV/atom-K
T = absolute temperature (K)
Qd  1 
ln D = ln Do −  
R T 
or
Qd  1 
log D = log Do −  
2.3R  T 
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SUMMARY:
STRUCTURE & DIFFUSION
Diffusion FASTER for... Diffusion SLOWER for...
• open crystal structures • close-packed structures
• lower melting T • higher melting T materials

materials
• materials with • materials with covalent

secondary bonding bonding
• smaller diffusing atoms • larger diffusing atoms
• cations • anions
• lower density materials • higher density materials


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BDA 10803

PM Ts. Dr. HAMIMAH BINTI ABD.RAHMAN

4.1 Defects (Point Defects, Line/Linear Defects,

har/jkp/fkmp/2021 BDA 10803 3

• What types of defects arise in solids?

• Can the number and type of defects be varied

• How do defects affect material properties?

• Are defects undesirable?

har/jkp/fkmp/2021 BDA 10803 5

 Crystal lattice imperfections are classified according to their

har/jkp/fkmp/2021 BDA 10803 10

Figure 3.1 : Vacancy point defect

har/jkp/fkmp/2021 BDA 10803 11

Figure 3.2 : Self-interstitial point defect

har/jkp/fkmp/2021 BDA 10803 12

(3) Schottky Imperfection – when two oppositely charged ions

(4) Frenkel Imperfection – a cation moves into an interstitial site

har/jkp/fkmp/2021 BDA 10803 13

(5) Solid solution of B in A (i.e. random dist. of point defects)

(6) Solid solution of B in A and particles of a new phase

Figure 3.5 : Occurrence of a new phase in solid solution

har/jkp/fkmp/2021 BDA 10803 15

Metal deformation occurs by crystal planes slipping past each

Whole crystal planes do not slip past each other at once!

har/jkp/fkmp/2021 BDA 10803 16

- move under the action of a shear stress, τ.

- motion involves bonds breaking and reforming, but only along

- Net result of dislocation moving across a crystal plane is same

har/jkp/fkmp/2021 BDA 10803 17

(1a) Edge Dislocation - termination of an extra portion

Figure 3.6 : Edge dislocation in a crystalline lattice.

har/jkp/fkmp/2021 BDA 10803 18

Figure 3.7 : Screw dislocation in a cubic

har/jkp/fkmp/2021 BDA 10803 19

Figure 3.8 : Mixed dislocation in a

har/jkp/fkmp/2021 BDA 10803 20

har/jkp/fkmp/2021 BDA 10803 22

N = 2n-1 where N = no. grains/in2 at 100x magnification

har/jkp/fkmp/2021 BDA 10803 23

❖ This defect is much larger than previous defects that have

har/jkp/fkmp/2021 BDA 10803 24

• Point, Line, Area and Volume defects arise in solids.

• The number and type of defects can be varied and controlled

• Defects affect material properties (e.g., grain boundaries affect

• Defects may be desirable or undesirable (e.g., dislocations may

har/jkp/fkmp/2021 BDA 10803 25

har/jkp/fkmp/2021 BDA 10803 26

• How does diffusion occur?

• Why is it an important part of processing?

• How can the rate of diffusion be predicted for

• How does diffusion depend on structure

har/jkp/fkmp/2021 BDA 10803 27

• Glass tube filled with water.

har/jkp/fkmp/2021 BDA 10803 29

▪ Diffusion – the phenomenon of material transport by

• Types of diffusion process.

har/jkp/fkmp/2021 BDA 10803 31

Figure 3.10 : A copper-nickel diffusion couple before a high-temperature heat

har/jkp/fkmp/2021 BDA 10803 32

har/jkp/fkmp/2021 BDA 10803 33

1. there must be an empty adjacent site

 Temperature , the fraction of the total number of atoms