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IMPERFECTIONS IN SOLIDS
ISSUES TO ADDRESS...
What are the solidification mechanisms?
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?
Chapter 4 - 1
Imperfections in Solids
Solidification- result of casting of molten material
2 steps
Nuclei form
Nuclei grow to form crystals grain structure
nuclei
liquid
crystals growing
grain structure
Adapted from Fig.4.14 (b), Callister 7e.
Heterogeneous nucleation
much easier since stable nucleus is already
present
Could be wall of mold or impurities in the liquid
phase
allows solidification with only 0.1-10C
supercooling
Chapter 4 - 3
r* = critical nucleus: nuclei < r* shrink; nuclei>r* grow (to reduce energy)
Adapted from Fig.10.2(b), Callister 7e.
Chapter 4 - 4
Solidification
2 Tm
r*
HS T
r* = critical radius
= surface free energy
Tm = melting temperature
HS = latent heat of solidification
T = Tm - T = supercooling
= weak function of T
r*
decreases as T increases
For typical T
r* ca. 100
Chapter 4 - 5
t10_01_pg318
Chapter 4 - 6
f10_06_pg320
Chapter 4 - 7
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
high chemical reactivity
Solidification
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 8 cm
heat
flow
Columnar in
area with less
undercooling
Shell of
equiaxed grains
due to rapid
cooling (greater
T) near wall
Imperfections in Solids
There is no such thing as a perfect crystal.
What are these imperfections?
Why are they important?
Many of the important properties of
materials are due to the presence of
imperfections.
Chapter 4 - 10
Free surface:
a 2D defect
Chapter 4 - 12
Surface Defects
Chapter 4 - 13
Chapter 4 - 14
Vacancy
Chapter 4 - 15
Defects Dimensionality
Examples
Point
Vacancy
Line
Dislocation
Surface
Free surface,
Grain boundary
Chapter 4 - 16
Vacancy
Crystal in equilibrium
Minimum Gibbs free energy G at
constant T and P
A certain concentration of vacancies
lowers the free energy of a crystal
Chapter 4 - 18
E internal energy
P pressure
V volume
2. Entropy S =k ln W
k Boltzmann constant
W number of microstates
G=HTS
T Absolute temperature
Chapter 4 - 19
H = n f
Chapter 4 - 20
Chapter 4 - 21
G of a
perfect
crystal
G = H TS
neq
TS
S k[( N n) ln( N n) n ln n N ln N ]
Chapter 4 - 23
Types of Imperfections
Vacancy atoms
Interstitial atoms
Substitutional atoms
Point defects
Dislocations
Line defects
Grain Boundaries
Area defects
Chapter 4 - 24
Vacancies:
Point Defects
Vacancy
distortion
of planes
Self-Interstitials:
-"extra" atoms positioned between atomic sites.
distortion
of planes
selfinterstitial
Chapter 4 - 25
Schottky
defect
Cation vacancy
+
anion vacancy
Chapter 4 -
26
Equilibrium Concentration:
Point Defects
Equilibrium concentration varies with temperature!
No. of defects
No. of potential
defect sites.
Activation energy
Q
Nv
v
exp
kT
N
Temperature
Boltzmann's constant
(1.38 x 10 -23 J/atom-K)
(8.62 x 10 -5 eV/atom-K)
Each lattice site
is a potential
vacancy site
Chapter 4 - 27
Q
Nv
v
= exp
N
kT
Measure this...
Replot it...
Nv
ln
N
exponential
dependence!
defect concentration
Nv
N
slope
-Qv /k
1/T
Chapter 4 - 28
Q
Nv
v
exp
kT
N
NA
For 1 m , N = x
A Cu
3
0.9 eV/atom
= 2.7 x 10-4
1273K
8.62 x 10-5 eV/atom-K
x 1 m3 = 8.0 x 1028 sites
Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
Chapter 4 - 29
Chapter 4 - 30
OR
Substitutional solid soln.
(e.g., Cu in Ni)
Imperfections in Solids
Conditions for substitutional solid solution (S.S.)
W. Hume Rothery rule
1. r (atomic radius) < 15%
2. Proximity in periodic table
i.e., similar electronegativities
Chapter 4 - 32
Imperfections in Solids
Application of HumeRothery rules Solid
Solutions
Element
Atomic Crystal
ElectroRadius Structure
(nm)
Cu
C
H
O
Ag
Al
Co
Cr
Fe
Ni
Pd
Zn
0.1278
0.071
0.046
0.060
0.1445
0.1431
0.1253
0.1249
0.1241
0.1246
0.1376
0.1332
Valence
negativity
FCC
1.9
+2
FCC
FCC
HCP
BCC
BCC
FCC
FCC
HCP
1.9
1.5
1.8
1.6
1.8
1.8
2.2
1.6
+1
+3
+2
+3
+2
+2
+2
+2
Imperfections in Solids
Specification of composition
weight percent
m1
C1
x 100
m1 m2
m1 = mass of component 1
atom percent
n m1
C
x 100
n m1 n m 2
'
1
Chapter 4 - 34
Line Defects
Dislocations
Chapter 4 - 35
Chapter 4 - 36
or a missing half
Chapter plane
4 - 37
What kind of
defect is this?
A line defect?
Or a planar
defect?
Chapter 4 - 38
No extra plane!
Chapter 4 - 39
Missing plane
No missing plane!!!
Chapter 4 - 40
Edge
Dislocation
or a missing half
Chapter plane
4 - 41
ab I f a
cr ru p
ys p t l a n
ta l y e
l w in en
e si d d s
ha e
de ve a
fe a
ct
.
g
n
i
d t
n
e ec
y
f
l
e
t
p ad
u
r t
b
a no
f
o
s
i
le n e
o
h pl a
w
e
n
e
a
l
p
e
h
Th
t
a
f
o
s
a
e
g
d
d
e
e
r
e
e
d
t
h
i
c
t
s
e
n
y
f
o
e
c
d
Onl
e
b
n
a
c
Chapter 4 - 43
Slip
Dislocations:
slip steps
Chapter 4 - 44
Glide of
an Edge
Dislocation
Chapter 4 - 45
Glide of
an Edge
Dislocation
crss
crss is
critical
resolved
shear stress
on the slip
crss
plane in the
Chapter 4
- 46
direction
of
Glide of
an Edge
Dislocation
crss
crss is
critical
resolved
shear stress
on the slip
crss
plane in the
Chapter 4
- 47
direction
of
Glide of
an Edge
Dislocation
crss
crss is
critical
resolved
shear stress
on the slip
crss
plane in the
Chapter 4
- 48
direction
of
Glide of
an Edge
Dislocation
crss
crss is
critical
resolved
shear stress
on the slip
crss
plane in the
Chapter 4
- 49
direction
of
Glide of
an Edge
Dislocation
crss
A surface
step of b
is created
if a
dislocation
sweeps
over the
entire slip
plane
Surface
step, not a
dislocation
crss
Chapter 4 - 50
Chapter 4 - 51
Slip plane
t
b
no slip
dislocation
slip
Dislocation: slip/no
slip boundary
b: Burgers vector
magnitude and
direction of the slip
t: unit vector
tangent to the
dislocation line
Chapter 4 - 52
Burgers vector
Johannes Martinus
BURGERS
Burgers vector
Burgers vector
Chapter 4 - 53
Dislocation Line:
A dislocation line is the boundary between
slip and no slip regions of a crystal
Burgers vector:
The magnitude and the direction of the
slip is represented by a vector b called the
Burgers vector,
Line vector
A unit vector t tangent to the dislocation
line is called a tangent vector or the line
vector.
Chapter 4 - 54
2 3
Burgers vector
b
Slip plane
slip
no slip
Chapter 4 - 55
ew
r
Sc
tio
a
c
o
l
is
e
n
i
nL
b || t
b
Chapter 4 - 57
Screw Dislocation
Chapter 4 - 58
If b || t
Positive
Edge
Dislocation
Screw
Dislocation
Extra half
plane above
the slip plane
Left-handed
spiral ramp
b parallel to t
Negative
Extra half
plane below
the slip plane
Right-handed
spiral ramp
b parallel to t
Chapter 4 - 60
Edge
Adapted from Fig. 4.5, Callister 7e.
Screw
Chapter 4 - 61
S
F
10
11
12
13
14
15
16
1
A closed
Burgers
Circuit in an
ideal crystal
7
6
5
4
4
5
6
7
2
1
9
16
15 14
13
12
11
10
Chapter 4 - 62
F b
9
10 11
12 13
14
15
16
1
2
7
6
5
4
4
5
6
7
2
1
9
16 15
14
13
12
11
10
Chapter 4 - 63
b is a lattice translation
b
Surface defect
Tension
Below the slip plane
N planes
Chapter 4 - 65
1
2
E b
2
Unit: J m1
Chapter 4 - 66
b is a lattice translation
100
BCC
1
111
2
FCC
1
110
2
NaCl
1
110
2
CsCl
100
Chapter 4 - 68
Slip plane
no slip
dislocation
slip
Dislocation:
slip/no slip
boundary
slip
no slip
Chapter 4 - 69
M
F
Grain
Boundary
Grain 1
Grain 2
Chapter 4 - 71
A dislocation loop
t
b t
t b
slip
No slip
The Burgers
vector b is
constant along a
dislocation line
Chapter 4 - 72
Dislocation node
b2
t
Node
t
t
b1
b3
b2
b1
b3
b1 + b2 + b3 = 0
Chapter 4 - 73
Chapter 4 - 74
close-packed directions
close-packed plane (top)
Specimens that
were tensile
tested.
Mg (HCP)
tensile direction
Al (FCC)
Chapter 4 - 75
Deformation Mechanisms
Slip System
Slip plane - plane allowing easiest slippage
Wide interplanar spacings - highest planar densities
+ + + + + + + +
+ + + + + + + +
+ + + + + + + +
ion cores
Covalent Ceramics
(Si, diamond): Movement
difficult.
-directional (angular) bonding
Chapter 4 - 77
Surface
Defects
Chapter 4 - 78
External
Surface Defects
Internal
Same
phase
Twin boundary
Interphase
boundary
Domain Wall
Different
phases
Chapter 4 - 79
Chapter 4 - 80
Grain 1
Grain 2
Chapter 4 - 82
Deformation by Twinning
Chapter 4 - 84
Chapter 4 - 85
Stacking faults
For FCC metals an error in ABCABC packing sequence
Ex: ABCABABC
Chapter 4 - 87
Optical Microscopy,
Experiment
Photomicrograph an iron
chromium alloy. 100X.
Concept Check!
Chapter 4 - 90
Microscopic Examination
Crystallites (grains) and grain boundaries.
Vary considerably in size. Can be quite large
ex: Large single crystal of quartz or diamond or Si
ex: Aluminum light post - see the individual grains
Chapter 4 - 91
Optical Microscopy
Useful up to 2000X magnification.
Polishing removes surface features (e.g., scratches)
Etching changes reflectance, depending on crystallographic
orientation.
crystallographic planes
Adapted from Fig. 4.13(b) and (c), Callister
7e. (Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.
Micrograph of
brass (a Cu-Zn alloy)
0.75mm
Chapter 4 - 92
Polarized Light
metallographic scopes often use polarized
light to increase contrast
Also used for transparent samples such as
polymers
Chapter 4 - 93
Optical Microscopy
Grain boundaries...
are imperfections,
are more susceptible
to etching,
may be revealed as
dark lines,
change in crystal
orientation across
boundary.
polished surface
(a)
surface groove
grain boundary
ASTM grain
size number
N = 2n-1
number of grains/in2
at 100x
magnification
Fe-Cr alloy
(b)
Chapter 4 - 94
Concept Check
Does the grain size number (n of Equation
4.16) increase or decrease with decreasing
grain size? Why?
Answer: Taking logarithms of Equation 4.16
and then rearranging such that the grain size
number n is the dependent variable leads to
the expression!
n = 1 + log N / log 2
In other words, the value of n increases with
decreasing grain size.
Chapter 4 -
Electron Microscopy
Optical resolution ca. 10-7 m = 0.1 m = 100 nm
For higher resolution need higher frequency
X-Rays? Difficult to focus.
Electrons
wavelengths ca. 3 pm (10-12m ~0.003 nm)
(Magnification - 1,000,000X)
Chapter 4 - 96
Imperfections in Solids
Dislocations are visible in electron micrographs
Pollen
Seed
Lead-Tin Solder
Fracture Surface
Chapter 4 - 98
Ants Head
Dislocations in Ti
Alloy at 51,450X
Zirconia/Alumina Interface
Chapter 4 - 99
Chapter 4 - 100
Quantum Tunneling
Chapter 4 -101
http://www.nobelprize.org/educational/physics/microscopes/scanning/stm.html
Chapter 4 -102
Carbon monoxide
molecules arranged
on a platinum (111)
surface.
Chapter 4 -103
(110) Surface of Ni
Chapter 4 -104
Fe atoms on a Cu surface
Chapter 4 -105
Chapter 4 -106
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 4 -107