IMPERFECTION S

(DEFECTS) IN SOLIDS
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?
IMPERFECTIONS (DEFECTS) IN SOLIDS
Defects in Crystals

Introduction
What is a defect?
Types of defects in crystals
Why are defects important?


Defects in Crystals
Point Defects
Linear Defects
Planar Defects: Surfaces and Grain
Boundaries
Volumetric Defects: Precipitates and
Inclusions


Vacancy atoms
Interstitial atoms
Substitutional atoms
Dislocations
Grain Boundaries

Precipitates/inclusions

Point defects
Line defects
Area defects
Volume defects
TYPES OF IMPERFECTIONS
Vacancies:
-vacant atomic sites in a structure.
Vacancy
distortion
of planes
Self-Interstitials:
-"extra" atoms positioned between atomic sites.
self-
interstitial
distortion
of planes
POINT DEFECTS
Crystal Defects
Schottky Defect


Frenkel Defect
-another possibility is for small
positive ion to move into an
interstice or interstitial site
-leaves a vacancy plus an
interstitial ion Frenkel defect
-formation energy is lower than
that for a Schottky defect
Recall:
-ionic crystals tend to form vacancies in pairs to preserve
charge neutrality Schottky defect
- e.g., NaCl both positive ion and negative ion migrate to
surface

vacancy
Interstitial ion
Both ions are removed
Defects can be categorized as either

Intrinsic: Defects required to be present because of physical
laws.
Extrinsic: Defects present because of the environment and/or
processing conditions. Most defects are extrinsic.

Crystal Defects
Substitutional Defect
(1) Metals


(2) Ionic Solids
limit to solubility for both interstitial or
substitutional atoms solubility limit
other phases form

- large impurity atoms that replace
host atoms on their lattice sites
may be either larger or smaller than
host atom produces compressive
or tensile strain fields respectively
-e.g., Ag dissolved in Au
-and dopant atoms in Si
- for ionic solids, must maintain charge
balance, which may lead to formation of
vacancy as well
- e.g., for Ca
2+
ions in NaCl, 2 Na
+
ions
are removed, which leaves a vacancy
- in compounds, may also get anti-site
defects
- ex; GaAs - Ga may be found on an
As site and vice versa (charge
balance must be maintained)
Ca
2+

replaces
Na
+

Space previously
occupied by the
second Na
+
ion
(vacancy)
Why are defects important?

Defects, even in very small concentrations,
can have a dramatic impact on the
properties of a material.
Without defects:
solid-state electronic devices could not exist
metals would be much stronger
ceramics would be much tougher
crystals would have no color
Boltzmann's constant
(1.38 x 10
-23
J/atom K)
(8.62 x 10
-5
eV/at om K)
|
N
D
N
=
exp

Q
D
kT
|
\

|
.
|
No. of defects
No. of potential
defect sites.
Activation energy
Temperature
Each lattice site
is a potential
vacancy site
Equilibrium concentration varies with temperature!
EQUIL. CONCENTRATION:
POINT DEFECTS
Depending on the units for Q, you
may use the Stephan Boltmann
constant k or R
We can get Q from
an experiment.
Measure this... Replot it...
1/T
N
N
D
ln
1
-Q
D
/k
slope
MEASURING ACTIVATION ENERGY
Find the equil. # of vacancies in 1m
3
of Cu at 1000C.
Given:
8.62 x 10
-5
eV/atom-K
0.9eV/atom
1273K
|
N
D
N
=
exp

Q
D
kT
|
\

|
.
|
For 1m
3
, N =
N
A
A
Cu
x x 1m
3
= 8.0 x 10
28
sites
= 2.7 10
-4
Answer:
ESTIMATING VACANCY CONC.
Crystal Defects
Example:
Assuming that 83.7 KJ/mole of energy is required to produce a vacancy in copper, what
heating temperature is required to increase the vacancy concentration of a wire to 1000
times the room temperature value?
For FCC copper a
Cu
= 0.36151 nm; 4 atoms/cell
# of Cu atoms per m
3
, N = 4 (atoms/cell)/(3.6151 x 10
-10
m)
3
= 8.47 x 10
28
atoms/m
3

At RT (T = 273 + 25 = 298
o
K)
Recall, n
v
= N exp[-Q/RT]
n
v
= (8.47 x 10
28
) exp[-83,700/(8.314)(298)] = 1.774 x 10
14
vacancies per m
3
(at RT)
Need to produce 1000 x n
v
or 1.774 x 10
17
vacancies/m
3
Therefore, n
v
= 1.774 x 10
17
= (8.47 x 10
28
) exp[-83,700/(8.314)(T)]
T = 375
o
K ( or 102
o
C)




By heating copper wire to 102
o
C and rapidly cooling back to RT,
these vacancies can be trapped in the metal!
Two outcomes if impurity (B) added to host (A):
Solid solution of B in A (i.e., random dist. of point defects)
Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)
OR
Substitutional alloy
(e.g., Cu in Ni)
Interstitial alloy
(e.g., C in Fe)
Second phase particle
--different composition
--often different structure.
POINT DEFECTS IN ALLOYS
are line defects,
cause slip between crystal plane when they move,
produce permanent (plastic) deformation.
Dislocations:
Schematic of a Zinc (HCP):
before deformation after tensile elongation
slip steps
LINE DEFECTS
Structure: close-packed
planes & directions
are preferred.
Comparison among crystal structures:
FCC: many close-packed planes/directions;
HCP: only one plane, 3 directions;
BCC: none
Mg (HCP)
Al (FCC)
tensile direction
Results of tensile
testing.
view onto two
close-packed
planes.
DISLOCATIONS & CRYSTAL STRUCTURE
Crystal Defects
2) Line Defects (1-D) Dislocations

Edge dislocation




- simplest line defect to visualize is
edge dislocation
- resembles an extra half plane of
atoms inserted into crystal (not actually
how it forms)
- form during processing thermal or
mechanical
Burgers vector is
equivalent to the
shortest distance
between 2
equivalent atoms
Extra plane
Burgers vector
Crystal Defects
1) Deformation




- only need to move dislocation and break bonds around dislocation
- do not need to break all bonds across slip plane at once
- strengthen metals and alloys by blocking dislocations (look at this later, time
permitting)
Recall analogies
Grain boundaries:
are boundaries between crystals.
are produced by the solidification process, for example.
have a change in crystal orientation across them.
impede dislocation motion.
grain
boundaries
heat
flow
Schematic
Adapted from Fig. 4.7, Callister 6e.
Adapted from Fig. 4.10, Callister 6e. (Fig.
4.10 is from Metals Handbook, Vol. 9, 9th edition,
Metallography and Microstructures, Am. Society for Metals,
Metals Park, OH, 1985.)
~ 8cm
Metal Ingot
AREA DEFECTS: GRAIN BOUNDARIES
Crystal Defects
Surface Defects (contd)
Free (or external) surface
Internal surface
Grain boundaries
Low angle
High angle
Grain size
Phase boundaries
Fully coherent
Incoherent
Partial or semi-coherent





Tend to increase energy of solid
Grain boundaries:
-most materials are not single crystal, but are composed of many small crystals or grains, 10
-4

to 10
-2
cm in diameter material is said to be polycrystalline
-boundary separating grains is an internal surface called a grain boundary energy is ~1/2 of
that for an external surface
-simplest type to visualize
is low angle or tilt boundary
two slightly misoriented
grains
-consists of parallel edge
dislocations equispaced by
a distance D
-angle of misorientation is
given by:
sin(u/2) = b/(2D)
u< 10 low angle
boundaries
u> 10 high angle
boundaries structure
more complicated but
similar
Useful up to 2000X magnification.
Polishing removes surface features (e.g., scratches)
Etching changes reflectance, depending on crystal
orientation.
close-packed planes
micrograph of
Brass (Cu and Zn)
Adapted from Fig. 4.11(b) and (c), Callister
6e. (Fig. 4.11(c) is courtesy
of J.E. Burke, General Electric Co.
0.75mm
OPTICAL MICROSCOPY (1)
Grain boundaries...
are imperfections,
are more susceptible
to etching,
may be revealed as
dark lines,
change direction in a
polycrystal.
Adapted from Fig. 4.12(a)
and (b), Callister 6e.
(Fig. 4.12(b) is courtesy of
L.C. Smith and C. Brady,
the National Bureau of
Standards, Washington, DC
[now the National Institute of
Standards and Technology,
Gaithersburg, MD].)

OPTICAL MICROSCOPY (2)
Point, Line, and Area 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 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.)
SUMMARY
Animations website
http://www.mhhe.com/engcs/
materials/schaffer/