Dislocations & Crystal Structures

• Structure: close-packed view onto two

planes & directions close-packed
planes.
are preferred.
close-packed directions
close-packed plane (bottom) close-packed plane (top)

• Comparison among crystal structures:

FCC: many close-packed planes/directions;
HCP: only one plane, 3 directions;
BCC: none
• Specimens that Mg (HCP)
were tensile
tested. tensile direction
Al (FCC)
Chapter 5 - 1
 Planar Defects in Solids
• One case is a twin boundary (plane)
– Essentially a reflection of atom positions across the
twin plane.

Adapted from Fig. 4.9,

Callister & Rethwisch 8e.

• Stacking faults
– For FCC metals an error in ABCABC packing
sequence
– Ex: ABCABABC Chapter 5 - 2
 Polycrystalline Materials

Grain Boundaries
• regions between
crystals
• transition from lattice
of one region to that of
the other
• slightly disordered
• low density in grain
boundaries
– high mobility
– high diffusivity
Adapted from Fig. 4.7,
– high chemical reactivity Callister & Rethwisch 8e.
Chapter 5 - 3
 Imperfections in Solids

• Solidification- result of casting of molten

material
– 2 steps
• Nuclei form
• Nuclei grow to form crystals – grain structure
• Start with a molten material – all liquid

nuclei crystals growing grain structure

liquid Adapted from Fig. 4.14(b), Callister & Rethwisch 8e.

• Crystals grow until they meet each other

Chapter 5 - 4
 Solidification
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 8 cm

heat
flow

Shell of
Columnar in equiaxed grains
area with less due to rapid
undercooling cooling (greater
Adapted from Fig. 5.17, T) near wall
Callister & Rethwisch 3e.

Grain Refiner - added to make smaller, more uniform, equiaxed grains.

Chapter 5 - 5
 Defects and dislocations
• b-b defects
• https://www.youtube.com/watch?v=O3Rs
DIWB7s0
• bubble rafts
• https://www.youtube.com/watch?v=UEB39
-jlmdw
• start at 1:30 to ~ 6:15
• https://www.youtube.com/watch?v=TW2k1
TYKAEk

Chapter 5 - 6
Bubble raft analogy

Chapter 5 - 7
Bubble raft analogy

Chapter 5 - 8
 Summary

• Point, Line, and Area defects exist 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 control 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.)

Chapter 5 - 9
 Chapter 5: 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 5 - 10
 Diffusion
Diffusion - Mass transport by atomic motion

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

Chapter 5 - 11
 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. 5.1 and
5.2, Callister &
Rethwisch 8e.

Chapter 5 - 12
 Diffusion
• 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 - 13
 Diffusion Mechanisms
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurities atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.

increasing elapsed time

Chapter 5 - 14
 Diffusion Simulation

• Simulation of
interdiffusion
across an interface:

• Rate of substitutional
diffusion depends on:
-- vacancy concentration
-- frequency of jumping.

(Courtesy P.M. Anderson)

Chapter 5 - 15
 Diffusion Mechanisms
• Interstitial diffusion – smaller atoms can
diffuse between atoms.

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

More rapid than vacancy diffusion

Chapter 5 - 16
The (UC) LA description of diffusion

• Vacancy Diffusion

• Interstitial Diffusion

Chapter 5 - 17
 Processing Using Diffusion
• 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.

Chapter 5 - 18
 Processing Using Diffusion
• 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: P atoms

silicon
Adapted from Figure 18.27, Callister &
Rethwisch 8e. Chapter 5 - 19
 Diffusion
• How do we quantify the amount or rate of diffusion?

moles (or mass) diffusing mol kg

J  Flux   or
surface area time  2
cm s m2s
• Measured empirically
– Make thin film (membrane) of known surface 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 5 - 20
 Diffusion and 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 (or kB) = gas constant [8.314 J/mol-K] or 8.62x10-5 eV/K)
T = absolute temperature [K]

Chapter 5 - 21
 Diffusion and Temperature
D has exponential dependence on T
1500

1000

600

300
T(C)
10-8

D (m2/s) D interstitial >> Dsubstitutional

C in a-Fe Al in Al
10-14 C in g-Fe Fe in a-Fe
Fe in g-Fe

10-20
0.5 1.0 1.5 1000 K/T

Adapted from Fig. 5.7, Callister & Rethwisch 8e. (Date for Fig. 5.7
taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)

Chapter 5 - 22
Example: At 300 ºC the diffusion coefficient and
activation energy for Cu in Si are
D(300 ºC) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350 ºC?

D transform ln D
data

Temp = T 1/T

Qd 1 Qd  1
lnD2  lnD0 -   and lnD1  lnD0 -  
R  T2  R  T1 
D Q  1 1
 lnD2 - lnD1  ln 2  - d  - 
D1 R  T2 T1 
Chapter 5 - 23
 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

Chapter 5 - 24
 Steady-State Diffusion
Rate of diffusion independent of time
dC
Flux proportional to concentration gradient =
dx

C 1 C1 Fick’s first law of diffusion

dC
C2 C2 J  -D
dx
x1 x2
x
D  diffusion coefficient
dC C C2 - C1
if linear  
dx x x2 - x1

Chapter 5 - 25
 Non-steady State Diffusion

• 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

Fick’s Second Law C  2C

D 2
t x

Chapter 5 - 26
 Concept of diffusion length
Effective Diffusion Length based on a
random walk

finish

This is the total distance

an average atom / defect
will move during a start

diffusion process
Chapter 5 - 27
 Non-steady State Diffusion
• Copper diffuses into a bar of aluminum.
Surface conc.,
C s of Cu atoms bar
pre-existing conc., Co of copper atoms

Cs

Adapted from
Fig. 5.5,
Callister &
Rethwisch 8e.

B.C. at t = 0, C = Co for 0  x  
at t > 0, C = CS for x = 0 (constant surface conc.)
C = Co for x = 
Chapter 5 - 28
 Solution:
C x ,t  - Co  x 
 1 - erf  
Cs - Co  2 Dt 

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

time t
erf (z) = error function
2 z -y 2 C(x,t)

  0
e dy
Co
erf(z) values are given in
Table 5.1
Adapted from Fig. 5.5,
Callister & Rethwisch 8e.

Chapter 5 - 29
 Log scale vs linear scale

1 1
0.8
0.1
0.6
y( x) y( x) 0.01
0.4
-3
1 10
0.2
-4
0 1 10
0 0.01 0.02 0 0.01 0.02

x x

Chapter 5 - 30
 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  x 
• Solution: use Eqn. 5.5  1 - erf  
Cs - Co  2 Dt 

Chapter 5 - 31
 C( x ,t ) - Co  x 
Solution (cont.):  1 - erf  
Cs - Co  2 Dt 

– 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  x 
  1 - erf    1 - erf ( z )
Cs - Co 1.0 - 0.20  2 Dt 

 erf(z) = 0.8125

Chapter 5 - 32
Solution (cont.):
We must now determine from Table 5.1 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 4 z 2t

 x2  -3 2
( 4 x 10 m) 1h
D     2.6 x 10-11 m2 /s
 4z 2t  ( 4)(0.93)2 ( 49.5 h) 3600 s
 
Chapter 5 - 33
 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 (5.9a);
from Table 5.2, 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 ºC

Chapter 5 - 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

exception: metal atoms in
• lower density materials semiconductors (open
structure)

• higher density materials

Effective Diffusion Length
Chapter 5 - 35