Chapter 4: Imperfections in Solids

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
• ___________ - result of casting of molten material
– 2 steps
• _________ of the solid phase form
• _________ grow until their boundaries meet each other – the
crystals become grains
• Start with a ___________ 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 - _______ (roughly the same dimension in all directions)
- _______ (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.)

_____
_____

Shell of
Columnar in _______ 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

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Chapter 4: Imperfections in Solids

Grains and Grain Boundaries

Grain Boundaries
• regions between ______
(crystals)
• crystallographic
misalignment across a
______ boundary
• Slight atomic disorder
– high _______________
– 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 ______ defects
• Substitutional impurity (0-Dimensional)
atoms
• Dislocations _______ defects
(1-Dimensional)

• Grain Boundaries _______ defects

(2-Dimensional)

Chapter 4 - 6

2
Chapter 4: Imperfections in Solids

Point Defects in Metals

• Vacancies:
-vacant ____________ sites.

__________
distortion
of planes

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

self-
interstitial
distortion
of planes

Chapter 4 - 7

Vacancies – Computation of
Equilibrium Concentration
• Equilibrium ________________ varies with temperature!

Number of vacancies ___________ energy

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

Note: Each _________ 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 _______
ln
N N
-Qv /k
__________
dependence!

T
1/ T
defect ______________
Chapter 4 - 9

3
Chapter 4: Imperfections in Solids

Computation of Equilibrium Vacancy

Concentration
• Find the equilibrium number of vacancies in 1 m3 of Cu
at 1000°C.
• Given:
ρ = ___________ A Cu = ________________
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 ) ⎛ 106 cm3 ⎞

N= = ⎜⎜ 3
⎟⎟
A Cu 63.5 g/mol ⎝ m ⎠
= 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 _________
microscope.
• Increasing ________________
causes surface island of
atoms to grow.
(View animation)
• Why? The equil. vacancy
conc. ______________; new
vacancies diffuse to the crystal
surface and become part of Reprinted with permission from Nature (K.F. McCarty, J.A. Nobel,
and N.C. Bartelt, "Vacancies in Solids and the Stability of Surface
the island. Morphology”, Nature, Vol. 412, pp. 622-625 (2001). Image is
5.75 mm by 5.75 mm. Copyright (2001) Macmillan Publishers, Ltd.
I sland grows/shrinks to maintain
equil. vancancy conc. in the bulk.

Chapter 4 - 12

4
Chapter 4: Imperfections in Solids

Impurities in Metals
Two outcomes if impurity B atoms are added to a solid
composed of host A atoms:
• _____________ of B in A (i.e., _____________ 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, ________________ of a new
phase (usually for larger concentrations of B)
Second phase particle
-- different ____________
-- often different structure.
Chapter 4 - 13

Impurities in Metals (continued)

Conditions for _________ of substitutional solid
solutions
W. Hume – Rothery rules
– 1. Δr (atomic radius) < 15%
– 2. Proximity in ______________ table
• i.e., similar electronegativities
– 3. Same crystal ___________ 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
soluble so favors Al Pd 0.1376 FCC 2.2 +2
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

5
Chapter 4: Imperfections in Solids

Specification of Composition

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

nm1
– atom percent C1' = x 100
nm1 + nm2

nm1 = number of moles of component 1

Chapter 4 - 16

Linear Defects—Dislocations
Dislocations
– Are one-dimensional defects around which atoms are
___________________
• Edge dislocation:
– extra half-plane of atoms inserted in a _________________
– b perpendicular ( ) to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear ____________
– 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

6
Chapter 4: Imperfections in Solids

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

7
Chapter 4: Imperfections in Solids

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 ___________ are applied,
• permanent (plastic) _________ results from dislocation motion.

Schematic of a __________________
• 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
w normal sequence is ABCABC
w becomes ABCABABC when there is a packing fault
Chapter 4 - 24

8
Chapter 4: Imperfections in Solids

Catalysts and Surface Defects

• A catalyst increases the
rate of a _________
_________ without being
consumed Fig. 4.11, Callister & Rethwisch 10e.

• ____________ 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

• _____________ 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 _______ or
Si; individual grains visible in aluminum light
posts and garbage cans
– Grain sizes can be quite small (< mm);
necessary to observe with a ___________.

Chapter 4 - 26

Optical Microscopy
• Uses light – useful up to __________ magnification.
• __________ removes surface features (e.g., scratches)
• Etching changes ______________, 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

9
Chapter 4: Imperfections in Solids

Optical Microscopy (cont.)

Grain boundaries...
• are more ____________
to etching
• after etching, grain
boundaries appear as polished surface
___________
_______________
_______________
(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).]

_________ 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 ___________ is ≈ 0.1 µm
(100 nm)
For higher resolution need to use _________
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)
• _________ resolution possible
• Electron beams focused by ____________ lenses.

Chapter 4 - 30

10
Chapter 4: Imperfections in Solids

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 ⎛ ⎞ Q
NV = N exp ⎜ − v ⎟
⎝ kT ⎠

• 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

11