Chapter 4: Imperfections in Solids

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.

2
 Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

3
 Point Defects in Metals
• Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

• Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes

4
 Equilibrium Concentration:
Vacancy
• Equilibrium concentration of vacancy varies with temperature!

No. of vacancy Activation energy

Nv −Q v
= exp
No. of atomic sites N kT
Temperature
Boltzmann's constant
-23
(1.38 x 10 J/atom-K)
-5
(8.62 x 10 eV/atom-K)

Each lattice site

For most metal just below Nv
is a potential melting temperature ≈ 10−4
N
vacancy site
5
 Measuring Activation Energy

• We can get Qv from Nv - Qv

an experiment. = exp
N kT
• Measure this... • Replot it...

Nv Nv slope
ln
N N
-Qv /k
exponential
dependence!

T
1/T
vacancy concentration

6
 Estimating Vacancy Concentration
• Find the equil. # of vacancies in 1 m3 of Cu at 1000°C.
• Given:
ρ = 8.4 g /cm 3 A Cu = 63.5 g/mol
Q v = 0.9 eV/atom N A = 6.02 x 1023 atoms/mol
0.9 eV/atom
Nv - Qv
= exp = 2.7 x 10-4
N kT
1273 K
8.62 x 10-5 eV/atom-K
1× ρ
=
for 1 m3 N = 8.0 ×1028 sites/m3
ACu / N A
• Answer:
N v = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies

7
 Point Defects in Ceramics (i)
• Vacancies
-- vacancies exist in ceramics for both cations and anions
• Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites

Cation
Interstitial
Cation
Vacancy

Anion
Vacancy 8
 Point Defects in Ceramics (ii)
• Frenkel Defect
-- a cation vacancy-cation interstitial pair.
• Shottky Defect
-- a paired set of cation and anion vacancies.
Shottky
Defect:

Frenkel
Defect

• Equilibrium concentration of defects

9
 Point Defects in Ceramics (iii)

Stoichiometry: ratio of cations to anions is not altered

by defects

Nonstoichiometry

10
 Equilibrium number of defects

Q fr
Number of Frenkel =
N fr N exp(− )
defect 2kT

Qs
Number of Schottky =
N s N exp(− )
defect 2kT

11
 example
Calculate Schottky defect per cubic meter in potassium chloride at
500 ℃. Qs = 2.6 eV, KCl density = 1.955 g/cm3 at 500 ℃.

N Aρ
N=
AK + ACl
(6.022 ×1023 atoms / mol )(1.955 g / cm3 )
=
(39.10 + 35.45) g / mol
= 1.58 ×1028 atoms / m3

2.6eV
Ns =
(1.58 ×1028 ) exp(− )
2(8.62 ×10−5 eV / K )(500 + 273) K
= 5.31×1019 defects / m3

12
 Impurities in Metals (i)
Two outcomes if impurity (B) added to host (A):
• Solid solution of B in A (i.e., random dist. of point defects)

OR

Substitutional solid solution. Interstitial solid solution

(e.g., Cu in Ni) (e.g., C in Fe)
• Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)
Second phase particle
-- different composition
-- often different structure.

13
Interstitial site in BCC

14
Interstitial site in FCC

15
 Impurities in Metals (ii)
Conditions for substitutional solid solution (S.S.)
• Hume – Rothery rules
– 1. Δr (atomic radius) < 15% (atomic size factor)
– 2. Same crystal structure for pure metals
– 3. Proximity in periodic table
• i.e., similar electronegativity factor
– 4. Valency
• If other conditions being equal, a metal will have a
greater tendency to dissolve a metal of higher valency
than one of lower valency

16
 Impurities in Metals (iii)
Application of Hume–Rothery rules – Solid
Solutions Element Atomic Crystal Electro- Valence
Radius Structure nega-
(nm) tivity
1. Would you predict Cu 0.1278 FCC 1.9 +2
more Al or Ag C 0.071
H 0.046
to dissolve in Zn? O 0.060
Ag 0.1445 FCC 1.9 +1
More Al because size is closer and val. Is
Al 0.1431 FCC 1.5 +3
higher – but not too much – FCC in HCP
Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
Fe 0.1241 BCC 1.8 +2
2. More Zn or Al Ni 0.1246 FCC 1.8 +2
in Cu? Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
Surely Zn since size is closer thus
causing lower distortion (4% vs 12%)

17
 example

Compute the radius r of an impurity atom that just fits into a BCC
octahedral site

4R
2 R + 2r =
3

r = 0.155 R

Figun_06_p152

18
 Impurities in Ceramics
• Electroneutrality (charge balance) must be maintained
when impurities are present
• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca 2+
Na +
Na +
Ca 2+
without impurity Ca 2+ impurity with impurity
• Substitutional anion impurity anion vacancy
O2-

Cl - Cl -
without impurity O2- impurity with impurity
19
 Point Defects in Polymers
• Defects due in part to chain packing errors and impurities such
as chain ends and side chains

20
 Specification of composition

– weight percent
m1
C1 = x 100
m1 + m2
m1 = mass of component 1
m2 = mass of component 2

n m1
– atom percent C =
'
x 100
n m1 + n m 2
1

nm1 = number of moles of component 1

nm2 = number of moles of component 2

21
Composition conversion

22
Composition in mass per unit volume

23
 example

m1
C1 = x 100
m1 + m2
24
example

25
example

26
 Line Defects
Dislocations:
• are line defects,
• slip between crystal planes result when dislocations move,
• produce permanent (plastic) deformation.

Schematic of Zinc (HCP):

• before deformation • after tensile elongation

slip steps

27
 Linear Defects in Solids
Linear Defects (Dislocations)
– Are one-dimensional defects around which atoms are
misaligned
• Edge dislocation:
– extra half-plane of atoms inserted in a crystal structure
– b perpendicular (⊥) to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b parallel (||) to dislocation line

Burger’s vector, b: measure of lattice distortion

28
 Imperfections in Solids
Edge Dislocation

Fig. 6.9, Callister & Rethwisch 9e. (Adapted from

A. G. Guy, Essentials of Materials Science, McGraw-Hill
Book Company, New York, NY, 1976, p. 153.)
29
 Imperfections in Solids
Screw Dislocation
Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 6.10, Callister & Rethwisch 9e.
[Figure (b) from W. T. Read, Jr.,Dislocations in Crystals,
McGraw-Hill Book Company, New York, NY, 1953.]

30
 VMSE: Screw Dislocation
• In VMSE:
– a region of crystal containing a dislocation can be rotated in 3D
– dislocation motion may be animated

Front View Top View

VMSE Screen Shots
31
Edge, Screw, and Mixed Dislocations
Mixed

Edge

Adapted from Fig. 6.11, Callister & Rethwisch 9e.

Screw [Figure (b) from W. T. Read, Jr., Dislocations in Crystals,
McGraw-Hill Book Company, New York, NY, 1953.]

32
 Imperfections in Solids
Dislocations are visible in electron micrographs

Fig. 6.12, Callister & Rethwisch 9e.

(Courtesy of M. R. Plichta, Michigan
Technological University.)

33
 interfacial Defects in Solids
• External surface
• Grain boundaries
• Phase boundaries

34
 interfacial Defects in Solids

• twin boundary (plane)

– Essentially a reflection of atom positions across the twin
plane.

Adapted from Fig. 6.15,

Callister & Rethwisch 9e.

• Stacking faults
– For FCC metals an error in ABCABC packing sequence
– Ex: ABCABABC
35
 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 or garbage can - see the
individual grains
• Crystallites (grains) can be quite small (mm
or less) – necessary to observe with a
microscope.

36
 Optical Microscopy
• Useful up to 2000X magnification.
• Polishing removes surface features (e.g., scratches)
• Etching changes reflectance, depending on crystal
orientation.

crystallographic planes
Fig. 6.19(b) & (c), Callister &
Rethwisch 9e.

Courtesy of J.E. Burke, General Electric Co.

Micrograph of
brass (a Cu-Zn alloy)

0.75 mm
37
 Optical Microscopy
Grain boundaries...
• are imperfections,
• are more susceptible
to etching,
• may be revealed as polished surface
dark lines,
• change in crystal surface groove
orientation across grain boundary
(a)
boundary.
ASTM grain
size number

N = 2 n -1

number of grains/in2 Fe-Cr alloy

at 100x (b)
magnification
38
 Optical Microscopy

• Polarized light
– metallographic scopes often use polarized
light to increase contrast
– Also used for transparent samples such as
polymers

39
 Microscopy
Optical resolution ca. 10-7 m = 0.1 μm = 100 nm
For higher resolution need higher frequency
– X-Rays? Difficult to focus.
– Electrons
• wavelengths ca. 3 pm (0.003 nm)
– (Magnification - 1,000,000X)
• Atomic resolution possible
• Electron beam focused by magnetic lenses.

40
 Scanning Tunneling Microscopy
(STM)
• Atoms can be arranged and imaged!
Photos produced from the
work of C.P. Lutz,
Zeppenfeld, and D.M. Eigler.
Reprinted with permission
from International Business
Machines Corporation,
copyright 1995.

Carbon monoxide Iron atoms arranged

molecules arranged on a copper (111)
on a platinum (111) surface. These Kanji
surface. characters represent
the word “atom”.

41
 Grain size
• Linear intercept
• counting numbers of grain boundary intersections by
straight lines

LT
l =
PM
l : a measure of grain diameter
P: number of intersections
LT : total length of lines
M : magnification

42
 Grain size
• Comparison
• Compare grain structure with standard charts
(numbers of grains per unit area)
n = 2G −1
n : average number of grains per square inch
G: grain-size number
magnification=100

M 2
nM ( ) = 2G −1
100
nM : average number of grains per square inch
G: grain-size number
magnification=M

G=
−6.6457 log l − 3.298
( l in mm)
43
 example
Grain-size computation
(a) Intercept length
(b) ASTM grain-size number

16000
=M = 160
100
length of each line = 50mm
Figun_06_p173a

line no.
total length =7 × 50 =350mm 1 8
2 8
3 8
350 4 9
=l = 0.0377 mm 5 9
58 ×160
6 9
G= −6.6457 log l − 3.298 7 7
=58 Figun_06_p173b

= 6.16
44
 Summary
• Point, Line, and Area defects exist in solids.
• The number and type of defects can be varied
and controlled (e.g., temperature controls vacancy
concentration).
• 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).

45