Chapter 4: Imperfections in Solids

ISSUES TO ADDRESS...

• What types of defects exist in solid materials?

• How does the number of vacancies depend on
temperature?
• What are the two types of solid solutions?
• What are the three types of dislocations?

• What kinds of information come from

microscopic examinations?

Chapter 4 - 1
 Solidification
• Solidification- result of casting of molten material
– 2 steps
• Nuclei of the solid phase form
• Crystals grow until their boundaries meet each other – the
crystals become grains
• Start with a molten material – all liquid

(now the National Institute of Standards

Bureau of Standards, Washington, DC

and Technology, Gaithersburg, MD.)]

[Photomicrograph courtesy of L. C.
Smith and C. Brady, the National
nuclei crystals growing grain structure
liquid Adapted from Fig. 4.15 (b), Callister & Rethwisch 10e.

Chapter 4 - 2
 Solidification (continued)
Grains can be - equiaxed (roughly the same dimension in all directions)
- columnar (grains elongated in one direction)
~ 8 cm Adapted from Fig. 5.17,
Callister & Rethwisch 3e.
(Reproduced with permission
from Metals Handbook, Vol. 9,
9th edition, Metallography and
Microstructures, ASM
International, Materials Park,
OH, 1985.)

heat
flow

Shell of
Columnar in equiaxed grains
region with due to rapid
slower cooling cooling (greater
ΔT) near wall

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

Chapter 4 - 3
 Grains and Grain Boundaries

Grain Boundaries
• regions between grains
(crystals)
• crystallographic
misalignment across a
grain boundary
• Slight atomic disorder
– high atomic mobility
– high chemical reactivity

Fig. 4.8, Callister & Rethwisch 10e.

Chapter 4 - 4
 Imperfections in Solids
There is no such thing as a perfect crystal.
Crystalline imperfections (or defects) are
always present.
• Many of the properties of materials are sensitive to the
presence of imperfections.
• Crystalline defect refers to a lattice irregularity with
dimensions on the order of an atomic diameter.
• What kinds of crystalline imperfections exist in solids?

Chapter 4 - 5
 Types of Imperfections

• Vacancies
• Interstitial atoms Point defects
• Substitutional impurity (0-Dimensional)
atoms
• Dislocations Linear defects
(1-Dimensional)

• Grain Boundaries Interfacial defects

(2-Dimensional)

Chapter 4 - 6
 Point Defects in Metals
• Vacancies:
-vacant atomic sites.

Vacancy
distortion
of planes

• Self-Interstitials:
-Host atoms positioned in interstitial positions between atoms.

self-
interstitial
distortion
of planes

Chapter 4 - 7
 Vacancies – Computation of
Equilibrium Concentration
• Equilibrium concentration varies with temperature!

Number of vacancies Activation energy

Nv - Qv
Total number of = exp
lattice sites N kT
Temperature
Boltzmann's constant
-23
(1.38 x 10 J/atom-K)
-5
(8.62 x 10 eV/atom-K)

Note: Each lattice site is a potential vacancy.

Chapter 4 - 8
 Determination of Activation Energy
for Vacancy Formation
• Qv can be determined Nv - Qv
experimentally.
= exp
N kT
• Data may be plotted as... • Replot data as follows...

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

T 1/ T
defect concentration
Chapter 4 - 9
 Computation of Equilibrium Vacancy
Concentration
• Find the equilibrium number of vacancies in 1 m3 of Cu
at 1000°C.
• Given:
ρ = 8.4 g/cm3 ACu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.022 x 1023 atoms/mol

Solution: The first step is to determine the total number of

lattice sites N using Equation 4.2

NA ρ (6.022 ´ 1023 sites/mol)(8.4 g/cm3 ) æ106 cm3 ö

N= = çç 3
÷
÷
ACu 63.5 g/mol è m ø
= 8.0 x 1028 sites/m3
Chapter 4 - 10
 Computation of Equilibrium Vacancy
Concentration (continued)
The second step is to determine the equilibrium vacancy
concentration NV using Equation 4.1.

- Qv - 0.9 eV/atom
Nv = N exp = N exp
kT (8.62 x 10-5 eV/atom-K)(1273 K)

= (2.7 x 10-4) N

• Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites/m3
= 2.2 x 1025 vacancies/m3
Chapter 4 - 11
Observing Changes in Equilibrium Vacancy Conc.
• The (110) surface of NiAl
viewed through an electron
microscope.
• Increasing temperature
causes surface island of
atoms to grow.
(View animation)
• Why? The equil. vacancy
conc. Increases; new
vacancies diffuse to the
crystal Reprinted with permission from Nature (K.F. McCarty, J.A. Nobel,
and N.C. Bartelt, "Vacancies in Solids and the Stability of Surface
surface and become part of Morphology”, Nature, Vol. 412, pp. 622-625 (2001). Image is
5.75 mm by 5.75 mm. Copyright (2001) Macmillan Publishers, Ltd.
the island.
Island grows/shrinks to maintain
equil. vancancy conc. in the bulk.

Chapter 4 - 12
 Impurities in Metals
Two outcomes if impurity B atoms are added to a solid
composed of host A atoms:
• Solid solution of B in A (i.e., random dist. of B atoms)

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (e.g., C in Fe)
• Solid solution of B in A, plus particles of a new
phase (usually for larger concentrations of B)
Second phase particle
-- different composition
-- often different structure.
Chapter 4 - 13
 Impurities in Metals (continued)
Conditions for formation of substitutional solid
solutions
W. Hume – Rothery rules
– 1. Δr (atomic radius) < 15%
– 2. Proximity in periodic table
• i.e., similar electronegativities
– 3. Same crystal structure for pure metals
– 4. Valences
• All else being equal, a metal will have a greater
tendency to dissolve a metal of higher valence than one
of lower valence

Chapter 4 - 14
 Impurities in Metals (continued)
Application of Hume–Rothery rules – Solid
Solutions Element Atomic Crystal Electro- Valence
Radius Structure nega-
(nm) tivity
Ex: Would you predict Cu 0.1278 FCC 1.9 +2
more Al or Ag to C 0.071
H 0.046
dissolve in Zn? O 0.060
Ag 0.1445 FCC 1.9 +1
1. Δr – slightly favors Al Al 0.1431 FCC 1.5 +3
Co 0.1253 HCP 1.8 +2
2. Electronegativity – favors Al Cr 0.1249 BCC 1.6 +3
3. Crystal structure – tie Fe 0.1241 BCC 1.8 +2
4. Valences –higher valance more Ni 0.1246 FCC 1.8 +2
Pd 0.1376 FCC 2.2 +2
soluble so favors Al
Zn 0.1332 HCP 1.6 +2

This suggests Al is more soluble Table on p. 135, Callister & Rethwisch 9e.

in Zn. This agrees with experimental observations.

Chapter 4 - 15
 Specification of Composition

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

n m1
– atom percent C1' = x 100
nm 1 + nm 2

nm1 = number of moles of component 1

Chapter 4 - 16
 Linear Defects—Dislocations
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

Chapter 4 - 17
Edge Dislocation

Fig. 4.4, Callister & Rethwisch 10e.

Chapter 4 - 18
 Screw Dislocation
(a) Schematic of screw (b) Top view of screw
dislocation in a crystal dislocation in (a)
Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 4.5, Callister & Rethwisch 10e .
[Figure (b) from W. T. Read, Jr.,Dislocations in Crystals,
McGraw-Hill Book Company, New York, NY, 1953.]

Chapter 4 - 19
Edge, Screw, and Mixed Dislocations
Mixed

Edge

Adapted from Fig. 4.6, Callister & Rethwisch 10e.

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

Chapter 4 - 20
VMSE Screenshots of a Screw Dislocation
• In VMSE:
– crystal region containing screw dislocation—rotated by clicking-and-
dragging
– dislocation motion may be animated

Front View Top View

Chapter 4 - 21
Observation of Dislocations
Dislocations appear as dark lines
in this electron micrograph

Fig. 4.7, Callister & Rethwisch 10e.

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

Chapter 4 - 22
 Linear Defects—Dislocations
Dislocations:
• move when stresses are applied,
• permanent (plastic) deformation results from dislocation motion.

Schematic of a single crystal metal

• unstressed • after tensile elongation
(undeformed) (after plastic deformation)

Steps correspond to
plastic deformation:
each step is produced
by dislocations that
have moved to the
crystal surface.

Chapter 4 - 23
 Interfacial (Planar) Defects
• Twin boundaries (or planes)
– Mirror reflections of atom positions of one side of twin plane to
the other side.
Twin plane (boundary)
Fig. 4.10, Callister &
Rethwisch 9e.

• Stacking faults
– Occur when there is an error in the planar stacking sequence
– Ex: for FCC metals
 normal sequence is ABCABC
 becomes ABCABABC when there is a packing fault
Chapter 4 - 24
 Catalysts and Surface Defects
• A catalyst increases the
rate of a chemical
reaction without being
consumed Fig. 4.11, Callister & Rethwisch 10e.

• Catalytic reactions
normally occur at surface
defect sites
Single crystals of
(Ce0.5Zr0.5)O2
used in an automotive
catalytic converter
Fig. 4.12, Callister & Rethwisch 10e.
[From W. J. Stark, L. Mädler, M. Maciejewski, S. E.
Pratsinis, and A. Baiker, “Flame Synthesis of
Nanocrystalline Ceria/Zirconia: Effect of Carrier
Liquid,” Chem. Comm., 588–589 (2003). Reproduced
by permission of The Royal Society of Chemistry.] Chapter 4 - 25
 Microscopic Examination
• Grain size is an important microscopic
characteristic.
• Grain size can vary from one material to
another.
– Grain sizes can be quite large
• ex: large single crystal of quartz or diamond or
Si; individual grains visible in aluminum light
posts and garbage cans
– Grain sizes can be quite small (< mm);
necessary to observe with a microscope.

Chapter 4 - 26
 Optical Microscopy
• Uses light – useful up to 2000X magnification.
• Polishing removes surface features (e.g., scratches)
• Etching changes reflectance, depending on grain
orientation.

crystallographic planes
Fig. 4.14(b) & (c), Callister &
Rethwisch 10e.

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

Microstructure of
a brass alloy
(a Cu-Zn alloy)

grain
0.75 mm
Chapter 4 - 27
 Optical Microscopy (cont.)
Grain boundaries...
• are more susceptible
to etching
• after etching, grain
boundaries appear as polished surface
dark lines
surface groove
grain boundary
(a)
Fig. 4.15(a) & (b), Callister &
Rethwisch 10e.
ASTM grain [Fig. 4.15(b) is courtesy of L.C.
Smith and C. Brady, the National
size number Bureau of Standards, Washington,
DC (now the National Institute of
Standards and Technology,

n = 2 G-1 Gaithersburg, MD).]

number of grains/in2 Fe-Cr alloy

at 100x (b)
magnification
Chapter 4 - 28
 Optical Microscopy
• Polarized light
– metallographic scopes often use polarized
light to increase contrast
– Also used for transparent samples such as
polymers

Chapter 4 - 29
 Electron Microscopy
Best resolution for optical microscopes is ≈ 0.1 μm
(100 nm)
For higher resolution need to use shorter
wavelength radiation
– X-Rays? Difficult to focus.
– Electron beams
• Wavelengths as short as 3 pm (0.003 nm) possible
– (Magnification as high as 1,000,000X are achievable)
• Atomic resolution possible
• Electron beams focused by magnetic lenses.

Chapter 4 - 30
 Scanning Tunneling Microscopy
(STM)
• Surface atoms imaged using a microprobe that
tapers to a single atom at its tip.
• Surface atoms can be rearranged by pushing them into
the desired position using the probe tip.
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 on a

molecules arranged on a copper surface to form the
platinum surface in the Japanese Kanji characters
form of a human. that represent the word
“atom”.
Chapter 4 - 31
 Summary
• Point, Linear, and Interfacial defects exist in solids.
• Point defects • Linear defects
- Vacancies - Dislocations
- Interstitial atoms • Interfacial defects
- Substitutional impurity - Grain boundaries
atoms - Twin boundaries
- Stacking Faults
• The equilibrium number vacancy defects depends
on temperature æ Q ö
NV =N exp ç- v ÷
è kT ø

• Dislocation types include edge, screw, and mixed

Chapter 4 - 32
 Summary (continued)

• Metallic grain sizes can be quite small (< mm);

necessary to observe with a microscope.

• Optical microscopy can provide up to ≈ 0.1 μm resolution.

• Higher magnifications, better resolution, with electron

microscopes.

Chapter 4 - 33
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 4 - 34