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Chapter 5: Imperfections in Solids: Issues To Address..
Chapter 5: Imperfections in Solids: Issues To Address..
Chapter 5: Imperfections in Solids: Issues To Address..
Chapter 5 - 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
Chapter 5 - 2
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Solidification (continued)
Grains can be - equiaxed (roughly the same dimension in all directions)
- columnar (grains elongated in one direction)
~ 8 cm 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
Chapter 5 - 3
Grain Boundaries
• regions between grains
(crystals)
• crystallographic
misalignment across a
grain boundary
• Slight atomic disorder
– high atomic mobility
– high chemical reactivity
Chapter 5 - 4
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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 5 - 5
Types of Imperfections
• Vacancies
• Interstitial atoms Point defects
• Substitutional impurity (0-Dimensional)
atoms
• Dislocations Linear defects
(1-Dimensional)
Chapter 5 - 6
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Vacancy
distortion
of planes
• Self-Interstitials:
-Host atoms positioned in interstitial positions between atoms.
self-
interstitial
distortion
of planes
Chapter 5 - 7
Vacancies – Computation of
Equilibrium Concentration
• Equilibrium concentration varies with temperature!
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)
Chapter 5 - 8
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Nv Nv slope
ln
N N
-Qv /k
exponential
dependence!
T 1/T
defect concentration
Chapter 5 - 9
NA ρ
N= =
A Cu
= 8.0 x 1028 sites/m3
Chapter 5 - 10
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- 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 5 - 11
Chapter 5 - 12
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Cation
Interstitial
Cation
Vacancy
Fig. 5.2, Callister & Rethwisch 5e.
(Fig. 5.2 is from W.G. Moffatt,
G.W. Pearsall, and J. Wulff, The
Structure and Properties of
Materials, Vol. 1, Structure, John
Wiley and Sons, Inc., p. 78.)
Anion
Vacancy Chapter 5 - 13
Frenkel
Defect
Chapter 5 - 14
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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
Chapter 5 - 16
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This suggests Al is more soluble Table on p. 181, Callister & Rethwisch 5e.
Imperfections 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 2-
O impurity with impurity
Chapter 5 - 18
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Chapter 5 - 19
Specification of Composition
m1
– weight percent C1 x 100
m1 m2
m1 = mass of component 1
nm1
– atom percent C1' x 100
nm1 nm 2
Chapter 5 - 20
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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
Chapter 5 - 21
Linear Defects—Dislocations
(continued)
Edge Dislocation
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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. 5.10, Callister & Rethwisch 5e.
[Figure (b) from W. T. Read, Jr.,Dislocations in Crystals,
McGraw-Hill Book Company, New York, NY, 1953.]
Chapter 5 - 23
Edge
Chapter 5 - 24
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Observation of Dislocations
Dislocations appear as dark lines
in this electron micrograph
Chapter 5 - 26
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Linear Defects—Dislocations
Dislocations:
• move when stresses are applied,
• permanent (plastic) deformation results from dislocation motion.
Steps correspond to
plastic deformation:
each step is produced
by dislocations that
have moved to the
crystal surface.
Chapter 5 - 27
• 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 5 - 28
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• Catalytic reactions
normally occur at surface
defect sites
Single crystals of
(Ce0.5Zr0.5)O2
used in an automotive
catalytic converter
Fig. 5.17, Callister & Rethwisch 5e.
[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 5 - 29
Microscopic Examination
Chapter 5 - 30
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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. 5.19(b) & (c), Callister &
Rethwisch 5e.
grain
0.75 mm
Chapter 5 - 31
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Optical Microscopy
• Polarized light
– metallographic scopes often use polarized
light to increase contrast
– Also used for transparent samples such as
polymers
Chapter 5 - 33
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 5 - 34
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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
Chapter 5 - 36
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Summary (continued)
Chapter 5 - 37
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