Lecture 4

Imperfections in Solids

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 Imperfections in Solids
ISSUES TO ADDRESS...

• What types of defects arise in solids?

• Can the number and type of defects be varied

and controlled?

• How do defects affect material properties?

• Are defects undesirable?

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 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.

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Imperfections in Solids

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Imperfections in Solids

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 Imperfections in Solids
2D representation of a perfect
single crystal atomic arrangement

Structures of real material have

types of defects

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

nuclei crystals growing grain structure

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

• Crystals grow until they meet each other

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Types of Imperfections

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 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

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 Equilibrium Concentration:
Point Defects
• Equilibrium concentration varies with temperature!

No. of defects Activation energy

Nv Q v 
No. of potential = exp  
N  kT 
Temperature
-23
(1.38 x 10 J/atom-K)
-5
(8.62 x 10 eV/atom-K)
defect sites
Each lattice site
N
is a potential N= r x A
vacancy site ACu
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Boltzmann's constant
 Measuring Activation Energy

• We can get Qv from Nv Q v 

= exp 
 
an experiment. N  kT 
• Measure this... • Replot it...

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

T
1/T
defect concentration
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 Estimating Vacancy Concentration
Find the equil. # of vacancies in 1 m3 of Cu at room temp.
(27C) and at 1000C
r = 8.4 g/cm 3 A Cu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
Boltzmann constant =8.62 x 10-5 eV/atom-K
Temperature in Kelvin = 27C + 273 = 300 K

@ 1000C= 2.19 x 1019 vacancies/cm3

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Other Point Defects
1.Vacancy (from previous section)

2. Self interstitial:
Large distortion in the surrounding lattice
Needed energy is 3 times larger than vacancies,
eq. concentration is very low

3. Interstitial impurity
4.5.Substitutional impurity

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 Imperfections 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 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 a larger amount of B)
Second phase particle
-- different composition
-- often different structure.

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 Imperfections in Metals (ii)
Conditions for substitutional solid solution (S.S.)
• W. Hume – Rothery rule
– 1. r (atomic radius) < 15%
– 2. Proximity in periodic table
• i.e., similar electronegativities
– 3. Same crystal structure for pure metals
– 4. Valence
• All else being equal, a metal will have a greater tendency
to dissolve a metal of higher valence than one of lower
valence

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 Imperfections in Metals (iii)
Application of Hume–Rothery rules – Solid
Solutions Element Atomic Crystal Electro- Valence
Radius Structure nega-
(nm) tivity
1. Which elements Cu 0.1278 FCC 1.9 +2
C 0.071
completely dissolve H 0.046
O 0.060
in Cu and Fe? Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
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
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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 Interstitial Impurities
Carbon interstitial atom in
BCC iron

BCC, FCC and HCP

structures has small voids.
Interstitial atoms must be
small. Interstitial impurity
can’t be more than %10. In
case of carbon in iron it is
2%
Atomic radius of iron: 0.124 nm
Atomic radius of carbon: 0.071 nm

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 Composition

Average
Density of Alloy
Average Atomic Weight
of Alloy
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 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

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 Imperfections 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

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 Imperfections in Solids
Edge Dislocation

Fig. 4.3, Callister & Rethwisch 8e.

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

Atomic view of edge

dislocation motion from
left to right as a crystal
is sheared.

Click once on image to start animation

(Courtesy P.M. Anderson)
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 Imperfections in Solids
Screw Dislocation
Screw Dislocation

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

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 Edge, Screw, and Mixed Dislocations
Mixed

Edge

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

Screw

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 Dislocations
Dislocations are visible in electron micrographs

Fig. 4.6, Callister & Rethwisch 8e.

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Planar Defects in Solids

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

Adapted from Fig. 4.9,

Callister & Rethwisch 8e.

Stacking faults
– For FCC metals an error in ABCABC packing sequence
– Ex: ABCABABC 27
 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.

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

crystallographic planes
Adapted from Fig. 4.13(b) and (c), Callister
& Rethwisch 8e. (Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.)

Micrograph of
brass (a Cu-Zn alloy)

0.75mm
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 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. Adapted from Fig. 4.14(a)
and (b), Callister &
ASTM grain Rethwisch 8e.
(Fig. 4.14(b) is courtesy
size number of L.C. Smith and C. Brady,
the National Bureau of

N = 2n-1 Standards, Washington, DC

[now the National Institute of
Standards and Technology,
Gaithersburg, MD].)
number of grains/in2 Fe-Cr alloy
at 100x (b)
magnification 30
 Optical Microscopy

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

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 Microscopy
Optical resolution ca. 10-7 m = 0.1 m = 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.

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 Electron Microscopy
•Scanning Tunneling Microscopy (STM)
•Scanning Electron Microscopy (SEM)
•Transmission Electron Microscopy (TEM)

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

• The number and type of defects can be varied

and controlled (e.g., T controls vacancy conc.)

• 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.)

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