Imperfections in Solids

Dr. Tariq Jamil

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 Materials and Metallurgy (ME-209)
(According to Course Outline)
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Crystallography: Types of crystal structures, atomic packing factor, Miller indices of

TJ crystallographic planes
TJ and directions Imperfections
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in solids: Classification of defects, TJ
types of point defects and their effects on material properties, dislocations, kinetics of
dislocations, dislocation interactions, significance of dislocations on material permanent
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deformation
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 Books
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• Textbook: “Materials Science and Engineering: An

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Introduction” byTJ TJ
William D. Callister and David G. TJ TJ

Rethwisch, 9th Edition

•TJChapter # 4 TJ TJ TJ

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• Internet resource
TJ • http://wordpress.engineering.iastate.edu/polycom
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p/files/2012/06/ch04.pdf
•TJMore similar links are
TJ also available. TJ TJ

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 Outline
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• What are the solidification mechanisms?

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• What types of defects arise in solids?
• Can the number and type of defects be varied and controlled?
• How
TJ do defects affect material
TJ properties? TJ TJ
• Are defects
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undesirable? TJ TJ TJ

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 Imperfections in Solids
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• Solidification- result of casting of molten material
TJ • 2 steps
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• Nuclei form
• Nuclei grow to form crystals – grain structure
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• Start with a molten material – all liquid
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TJ nuclei TJ crystals growing TJ grain structure TJ

liquid Adapted from Fig. 4.14(b), Callister & Rethwisch 8e.

• Crystals grow until they meet each other

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 Polycrystalline Materials
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Grain Boundaries
TJ • regions between
TJ crystals TJ TJ TJ
• transition from lattice of one
TJ region to that of the
TJ other TJ TJ
• slightly disordered
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• low density in grain
boundaries
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• high mobility TJ TJ TJ
• high diffusivity
TJ • high chemical reactivity
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Adapted from Fig. 4.7,

Callister & Rethwisch 8e.
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 Solidification
Grains can be - equiaxed (roughly same size in all directions)
TJ - columnar
TJ (elongated grains) TJ TJ
~ 8 cm

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TJ TJ TJ TJ
heat
TJ flow TJ TJ TJ

Shell of
TJ Columnar inTJ TJ equiaxed
TJ grains TJ
area with less due to rapid
undercooling cooling (greater
TJ Adapted from Fig. 5.17,
TJ TJ T) near wall
TJ
Callister & Rethwisch 3e.

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

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 Grain Structure of Ingot
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 Imperfections in Solids
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There is no such thing as a perfect crystal.
• What are these imperfections?
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• Why are they important?
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Many of the important properties of materials are due to
TJthe presence of imperfections.
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 Types of Imperfections
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• Vacancy atoms
TJ • Interstitial
TJ atoms TJ Point defectsTJ TJ
• Substitutional atoms
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• TJDislocations TJ
Line defects
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TJ • GrainTJBoundaries TJ
Area defectsTJ TJ

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 Point Defects in Metals
• Vacancies:
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-vacant atomic sites in a structure.
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Vacancy
TJ distortion TJ TJ TJ
of planes
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• Self-Interstitials:
TJ -"extra"TJ
atoms positioned between
TJ atomic sites. TJ TJ

self-
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interstitialTJ
distortion
of planes
 Equilibrium Concentration: Point Defects
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• Equilibrium concentration varies with temperature!
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No. of defects Activation energy
TJ TJ Nv  −TJQ v  TJ
No. of potential = exp  
TJdefect sites TJN  kT  TJ TJ
Temperature
Boltzmann's constant
TJ TJ TJ-23 TJ TJ
(1.38 x 10 J/atom-K)
-5
(8.62 x 10 eV/atom-K)
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Each lattice site
is a potential
vacancy site
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 Estimating Vacancy Concentration
• Find
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the equil. # of vacancies
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in 1 m 3 of Cu at 1000C.
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• Given:
r = 8.4 g/cm 3 A Cu = 63.5 g/mol
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Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
0.9 eV/atom
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 −Q v  TJ TJ
Nv = 
exp   -4
 kT  = 2.7 x 10
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N
1273 K
TJ TJ 8.62
TJ x 10-5 eV/atom-K TJ TJ
NA
For 1 m3 , N= r x x 1 m3 = 8.0 x 1028 sites
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A Cu TJ TJ
• Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
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 Observing Equilibrium Vacancy Conc.
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• Low energy electron
microscope view of Click once on image to start animation
TJ a (110)TJsurface of NiAl. TJ TJ TJ
• Increasing temperature
causes surface island of
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atoms to grow.
• TJ
Why? The equil. vacancy TJ TJ TJ
conc. increases via atom
motion from the crystal
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to the surface, where Reprinted with permission from Nature (K.F. McCarty,
they join the island. J.A. Nobel, and N.C. Bartelt, "Vacancies in
Solids and the Stability of Surface Morphology",
TJ TJto maintain Nature, Vol.TJ
412, pp. 622-625 (2001). Image is TJ
Island grows/shrinks 5.75 mm by 5.75 mm.) Copyright (2001) Macmillan
equil. vancancy conc. in the bulk. Publishers, Ltd.

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

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Substitutional solid soln. Interstitial solid soln.
(e.g., Cu in Ni) (e.g., C in Fe)
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• Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)
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Second phase particle
-- different composition
-- often different structure.
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 Imperfections in Metals (ii)
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Conditions for substitutional solid solution (S.S.)

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• W. Hume – Rothery rule
• 1. r (atomic radius) < 15%
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• 2. Proximity in periodic table
TJ • i.e., similar electronegativities
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• 3. Same crystal structure for pure metals
TJ • 4. TJValency TJ TJ TJ
• All else being equal, a metal will have a greater tendency
to dissolve a metal of higher valency than one of lower
TJ valencyTJ TJ TJ

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 Imperfections in Metals (iii)
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Application of Hume–Rothery rules – Solid
TJ Solutions
TJ TJ Atomic Crystal
Element TJ
Electro- Valence TJ
Radius Structure nega-
(nm) tivity
TJ 1. Would you TJ
predict TJ TJ
Cu 0.1278 FCC 1.9 +2
C 0.071
more
TJ Al or Ag TJ H 0.046 TJ TJ
to dissolve in Zn? O
Ag
0.060
0.1445 FCC 1.9 +1
TJ TJ Al TJ 0.1431 FCC 1.5
TJ +3 TJ
Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
2. More Zn or Al Fe 0.1241 BCC 1.8 +2
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Ni 0.1246 FCC 1.8 +2
in Cu? Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2

Table on p. 118, Callister & Rethwisch 8e.

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 Imperfections in Metals (iii)
TJ TJ TJ TJ
Application of Hume–Rothery rules – Solid
TJ Solutions
TJ TJ Atomic Crystal
Element TJ
Electro- Valence TJ
Radius Structure nega-
(nm) tivity
TJ 1. Would you TJ
predict TJ TJ
Cu 0.1278 FCC 1.9 +2
7.4% 8.4% C 0.071
more
TJ Al or Ag TJ H 0.046 TJ TJ
to dissolve in Zn? O
Ag
0.060
0.1445 FCC 1.9 +1
TJ TJ Al TJ 0.1431 FCC 1.5
TJ +3 TJ
Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
2. More Zn or Al Fe 0.1241 BCC 1.8 +2
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Ni 0.1246 FCC 1.8 +2
in Cu? Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2

Table on p. 118, Callister & Rethwisch 8e.

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 Imperfections in Metals (iii)
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Application of Hume–Rothery rules – Solid
TJ Solutions
TJ TJ Atomic Crystal
Element TJ
Electro- Valence TJ
Radius Structure nega-
(nm) tivity
TJ 1. Would you TJ
predict TJ TJ
Cu 0.1278 FCC 1.9 +2
C 0.071
more
TJ Al or Ag TJ H 0.046 TJ TJ
to dissolve in Zn? O
Ag
0.060
0.1445 FCC 1.9 +1
TJ TJ Al TJ 0.1431 FCC 1.5
TJ +3 TJ
4% 12% Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
2. More Zn or Al Fe 0.1241 BCC 1.8 +2
TJ TJ TJ TJ
Ni 0.1246 FCC 1.8 +2
in Cu? Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2

Table on p. 118, Callister & Rethwisch 8e.

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 Impurities in Solids
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• Specification of composition
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m1
• weight percent C1 = x 100
TJ TJ 1 + m2
mTJ TJ

TJ m1 = mass ofTJcomponent 1 TJ TJ

nm1
TJ TJ
– atom percent CTJ' = x 100 TJ TJ
nm1 + nm 2
1

TJ TJ TJ TJ
nm1 = number of moles of component 1

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 Line Defects
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Dislocations:
• are line defects,
TJ • slip between
TJ crystal planes result
TJ when dislocations
TJmove, TJ
• produce permanent (plastic) deformation.
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Schematic of Zinc (HCP):
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• before deformation • after tensile elongation

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slip steps
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 Defect Movement in Steps
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 Imperfections in Solids
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Linear Defects (Dislocations)
TJ • AreTJ
one-dimensional defects
TJaround which atoms are
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misaligned
• Edge dislocation:
TJ TJ of atoms inserted inTJ
• extra half-plane a crystal structure TJ

TJ • b perpendicular (⊥)TJ
to dislocation line TJ TJ
• Screw dislocation:
• spiral planar ramp resulting from shear deformation
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• b parallel () to dislocation line
Burger’s vector, b: measure of lattice distortion
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 Imperfections in Solids
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Edge Dislocation
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Fig. 4.3, Callister & Rethwisch 8e.

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 Motion of Edge Dislocation
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• Dislocation motion requires the successive bumping
of a half plane of atoms (from left to right here).
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• Bonds across the slipping planes are broken andTJ TJ

remade in succession.
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Click once on image to start animation Atomic view of edge dislocation motion
from left to right as a crystal is sheared.
(Courtesy P.M. Anderson)
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Imperfections in Solids
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Screw Dislocation
TJ Screw DislocationTJ TJ TJ TJ

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b
TJDislocation
line
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Burgers vector b (b)
(a)
Adapted from Fig. 4.4, Callister & Rethwisch 8e.

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 Edge, Screw, and Mixed Dislocations
TJ TJ Mixed TJ TJ

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Edge
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Adapted from Fig. 4.5, Callister & Rethwisch 8e.

Screw

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 Imperfections in Solids
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Dislocations are visible in electron micrographs
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Fig. 4.6, Callister & Rethwisch 8e.

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 Planar Defects in Solids
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• One case is a twin boundary (plane)
• Essentially a reflection of atom positions across the twin
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plane. TJ TJ TJ

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Adapted from Fig. 4.9,

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Callister & Rethwisch 8e.
TJ

TJ TJ TJ TJ
• Stacking faults
• For FCC metals an error in ABCABC packing sequence
• Ex: ABCABABC
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 Catalysts and Surface Defects
•ATJ catalyst increases
TJ the TJ TJ
rate of a chemical
TJ reaction
TJ without being TJ TJ TJ
consumed Fig. 4.10, Callister & Rethwisch 8e.

TJ • Active sites TJ
on catalysts TJ TJ

are
TJ normally surfaceTJ TJ TJ
defects
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Single crystals of
TJ (Ce0.5TJ
Zr0.5)O2 TJ TJ
used in an automotive
catalytic converter
Fig. 4.11, Callister & Rethwisch 8e.
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 Optical Microscopy
• UsefulTJup to 2000X magnification.
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• Polishing removes surface features (e.g., scratches)

TJ • Etching changes
TJ reflectance, depending
TJ on crystal orientation.
TJ TJ

TJ TJ TJ TJ

TJ TJ TJ
crystallographic planes TJ
Adapted from Fig. 4.13(b) and (c), Callister
& Rethwisch 8e. (Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.)
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Etch: to cut, bit or corrode with

an acid or the like
Micrograph of
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brass (a Cu-Zn alloy)TJ

Investigations of this
type are often termed metallographic 0.75mm
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 Optical Microscopy
Grain boundaries...
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• are imperfections,
• are more susceptible polished surface
TJ to etching,
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• may be revealed as surface groove
dark lines, TJ grain boundary
TJ (a)TJ TJ
• change in crystal Adapted from Fig. 4.14(a)
and (b), Callister &
TJ orientation across TJ TJRethwisch 8e. TJ
(Fig. 4.14(b) is courtesy
boundary. of L.C. Smith and C. Brady,
the National Bureau of
TJ ASTM TJgrain TJ Standards,TJWashington, DC TJ
[now the National Institute of
size number Standards and Technology,
Gaithersburg, MD].)
Fe-Cr alloy
TJ N = 2n-1 TJ TJ
(b)
TJ

number of grains/in2 ASTM grain size number(n) is related with the number of
grains that you can count in 100X magnification (N) by
at 100x
the relation, N=2(n-1). So ASTM grain size number
magnification increases with decreasing grain size. 32
 Optical Microscopy
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• Polarized light
TJ • metallographic
TJ scopes TJ
often use polarized light
TJ to TJ
increase contrast
TJ • Also usedTJfor transparent samples
TJ such as TJ
polymers
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 Microscopy
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Optical resolution ca. 10-7 m = 0.1 mm = 100 nm

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For higher resolution needTJhigher frequencyTJ TJ

• X-Rays? Difficult to focus.

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• Electrons
TJ • wavelengths ca. TJ 3 pm (0.003 nm) TJ TJ

• (Magnification - 1,000,000X)
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• Atomic resolution possible
• Electron beam focused by magnetic lenses.
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 Transmission Electron Microscopy
TJ• Frequently utilized inTJ
the study of dislocationsTJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ
The transmitted beam is
TJ TJ TJ
projected onto a fluorescent TJ
screen or a photographic film
so that the image may be
TJ TJ TJ viewed. TJ TJ

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High-resolution TEM of
Palladium nanocrystals
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 Scanning Electron Microscope
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A scanning electron microscope (SEM) is a type of electron
microscope that produces images of a sample by scanning the surface
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with a focused beam of electrons. The electrons interact with atoms in
TJ
the sample, producing various signals thatTJ
contain information about TJ TJ
the surface topography and composition of the sample
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BSEs come from deeper regions of the sample, whereas SE

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originate from surface regions. Thus, the two carry different
types of information. BSE images show high sensitivity to
differences in atomic number; the higher the atomic number,
the brighter the material appears in the image. SE imaging can
provide more detailed surface information. 36
 Scanning Probe Microscopy
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Scanning probe microscope (SPM) is a branch
of microscopy that forms images of surfaces using a
TJ TJ scans the specimen.
physical probe that TJ TJ TJ

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TJ TJ Scanning TJprobe microscopy image of graphene (Image

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credit: U.S. Army Materiel Command)

Magnifications as high as 109x are possible

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Structural
Features

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Microscopic TJ TJ TJ TJ
Techniques

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 Summary
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• Point, Line, and Area defects exist in solids.

TJ • The number
TJ and type of defects
TJ can be variedTJ TJ
and controlled (e.g., T controls vacancy conc.)
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• Defects affect material properties (e.g., grain
TJ boundaries control
TJ crystal slip). TJ TJ

• Defects may be desirable or undesirable

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(e.g., dislocations may be TJ
good or bad, dependingTJ TJ

on whether plastic deformation is desirable or not.)

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