MIAE 221 – Materials Science

IMPERFECTIONS IN SOLIDS
Chapter 4

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 CHP 4: 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?

Notes# 4A - MIAE 221 (adapted from Callister) 2

 Imperfections in Solids
• Solidification- result of casting of molten material
– 2 steps
• Nuclei of solid phase start to form
• Nuclei grow to form crystals – when crystal
boundaries meet form grain structure
• Start with a molten material – all liquid

nuclei crystals growing grain structure

liquid

Notes# 4A - MIAE 221 (adapted from Callister) 3

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?

Notes# 4A - MIAE 221 (adapted from Callister)

 Types of Imperfections
• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area (interfacial)

defects

Notes# 4A - MIAE 221 (adapted from Callister) 5

 Point Defects
• Vacancies:-vacant atomic sites in a structure.

Vacancy
distortion
of planes

• Self-Interstitials: -"extra" atoms positioned between

atomic sites. Very rare as big distortion.
self-
interstitial
distortion
of planes

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Notes# 4A - MIAE 221 (adapted from Callister)
VACANCY

Vacancy - Missing atom from lattice

site.
Sometimes produced during
solidification, sometimes by physical
factors, (heating, neutrons, working)
but present in all crystals (increases
the randomness- entropy-of the Vacancy on
crystal). silicon surface
Usually low in number but reaches 1
vacancy per 10,000 atoms as
temperature rises to melting point.

Notes# 4A - MIAE 221 (adapted from Callister) 7

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

No. of vacancies Activation energy

Nv  −Q 
No. of potential = exp  v 
N  kT 
defect sites.
Temperature
Boltzmann's constant
(1.38 x 10 -23 J/atom-K) (depending
(8.62 x 10 -5 eV/atom-K) on units)

Each lattice site is a potential vacancy site

Notes# 4A - MIAE 221 (adapted from Callister) 8
 MEASURING ACTIVATION ENERGY, QD
We can get Q from an experiment; taking natural logs of both sides….

Nv - Qv  ND  QD 1
= exp ln   =−
N kT  N  k T
 ND  1
• Measure ND as a function of T. Then: Plot ln
 N  versus T

ND slope
1
ln
N
-QD/k

1/T
Notes# 4A - MIAE 221 (adapted from Callister) 9
0

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
N= =
ACu

N = 8.0 x 1028 sites/m3

Notes# 4A - MIAE 221 (adapted from Callister)

 Computation 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)

NV = (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

Notes# 4A - MIAE 221 (adapted from Callister) 11

IMPURITIES IN SOLIDS

“Pure” metals are very difficult to make and not often

used.
Refining may give 99.9999% purity but this still means
billions (1022) of impurity atoms in 1 m3 of metal.

Gold (is usually alloyed with Cu, Ni, Pt)

24 carat gold = 99.98%-99.95% gold,
thus 14 carat = 14/24th

High purity Copper (99.99%) is used for electronics as

impurities reduce electrical conductivity.

High purity “Pure” Platinum is used for thermo-electric

applications.

Notes# 4A - MIAE 221 (adapted from Callister) 12

METAL “ALLOYS”

Usually engineering metals are combined with other metals or

elements to give ALLOYS.

Usually for increased strength.

e.g.
STEEL → Iron (Fe) + Carbon (C)
BRASS → Cu + Zn (zinc)
BRONZE → Cu + Sn (tin)
TITANIUM Alloy → Ti + 4 Al + 6 V (vanadium)
Ni-Based SUPERALLOYS → up to 10 elements

Notes# 4A - MIAE 221 (adapted from Callister) 13

 SOLID SOLUTIONS

Simplest alloy is a SOLID SOLUTION.

Atoms of Element B are dissolved randomly into Element A (host)

usually when they are in the liquid state.
"SOLVENT" - major element (host)
"SOLUTE" - minor element (impurity)
After freezing, they now form a Solid Solution.

One phase (all crystals/grains are the same as the next except for
orientation i.e. same composition). (We can also get 2-phase
mixtures – Chapter 9)
e.g.. Liquid solutions - water + alcohol

We can have both:

SUBSTITUTIONAL AND INTERSTITIAL SOLID SOLUTIONS

Notes# 4A - MIAE 221 (adapted from Callister) 14

SUBSTITUTIONAL SOLID SOLUTIONS
A host atom is replaced by a different type of atom. The
substitutional atom can be either slightly larger or smaller than
the host atom but occupies its position. Causes a distortion to
surrounding lattice.

INTERSTITIAL SOLID SOLUTIONS

Impurity atoms go into spaces (interstices) between host
atoms. Usually spaces are small so interstitial atoms have to
be small.

E.g. Hydrogen atoms in iron (from poor welding) – not good.

Carbon atoms added to iron to produce steel – very good.

Notes# 4A - MIAE 221 (adapted from Callister) 15

Notes# 4A - MIAE 221 (adapted from Callister) 16
 Point Defects in Alloys
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.

Notes# 4A - MIAE 221 (adapted from Callister) 17

COMPOSITIONS
In industry usually use weight% for alloys: easier to add 5 kgs
of Mg to 10 tonnes of Aluminum than add 4 million atoms of Mg
to 67 billion atoms of Al.
m1
C1 = x100
m1 + m2
C1 is the wt% of element 1 where m1 and m2 are the weights of
elements 1 and 2.

For chemical/scientific measures often need atomic %.

nm1 m1′
′
C1 = x100 nm1 = (g/g.mol-1) → mol.
nm1 + nm 2 A1
nm1 is the number of moles of element 1, m'1 is the mass
(grams) and A1 is the atomic weight of element 1 (g/mole) etc.

Notes# 4A - MIAE 221 (adapted from Callister) 18

 Imperfections in Solids

Conditions for substitutional solid solution (S.S.)

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

Notes# 4A - MIAE 221 (adapted from Callister) 19

A slight difference in size can be tolerated (a slight distortion to
lattice), but there is a limit to this, e.g.

Copper (FCC) - Nickel (FCC) Size%

r = 0.128 nm 0.125 nm 2.3%

Similar electronegativites, valence: Cu: +1, (+2), Ni: +2.

There is 100% solubility between Cu and Ni.

Whereas for Copper and Lead system:

Copper (FCC) Lead (FCC) Size%
r = 0.128 0.175 36.7

There is only 0.1% solubility (only 1 in 1000 atoms can be

replaced)

Notes# 4A - MIAE 221 (adapted from Callister) 20

 Line Defects
Dislocations:
• are line defects,
• under force, dislocations can move and produce permanent
(plastic) deformation.

Schematic of Zinc (HCP):

• before deformation • after tensile elongation

slip steps

Notes# 4B - MIAE 221 (adapted from Callister) 21

Notes# 4B - MIAE 221 (adapted from Callister) 22
 Imperfections in Solids
Linear Defects (Dislocations)
– Are one-dimensional defects around which atoms are
misaligned
• Edge dislocation:
– Looks like an extra half-plane of atoms have been inserted into
a crystal structure
– b ⊥ to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b || to dislocation line

Burger’s vector, b: this is a measure of lattice distortion

Dislocations make metals weaker than they should be,

BUT also allow metals to be deformed (ie. allow plastic
deformation). (Chp. 6)

Notes# 4B - MIAE 221 (adapted from Callister) 23

 Imperfections in Solids
Edge Dislocation

Notes# 4B - MIAE 221 (adapted from Callister) 24

 Screw
Dislocation

Notes# 4B - MIAE 221 (adapted from Callister) 25

 Edge, Screw, and Mixed Dislocations

Mixed

Edge

Adapted from Fig. 4.5, Callister 7e.

Screw

Notes# 4B - MIAE 221 (adapted from Callister) 26

 Imperfections in Solids

Dislocations
are visible in
electron
micrographs

Notes# 4B - MIAE 221 (adapted from Callister) 27

 INTERFACIAL DEFECTS
Defects between crystals or materials

Surface Defects
Material surface: boundary between material and atmosphere.
Atomic bonding disrupted. More reactive.

Grain Boundaries (GBs)

Regions where grains (crystals) join. Because adjacent grains
(crystals) have different orientations then some disorder at
boundaries. Atomic bonding disrupted. GBs are more reactive
chemically.
If a solid is made of only one crystal called: Single Crystal
If solid has many Crystals → Polycrystalline.

Most materials/metals are Polycrystalline. i.e. composed of

many crystals/grains joined together.

Notes# 4B - MIAE 221 (adapted from Callister) 28

 Grain Boundaries in Polycrystalline Materials

Grain Boundaries
• regions between crystals
• transition from lattice of
one region to that of the
other
• slightly disordered
• low density in grain
boundaries
– high mobility
– high diffusivity
– high chemical reactivity

Notes# 4B - MIAE 221 (adapted from Callister) 29

 GRAIN BOUNDARIES cont.
Grain boundaries:
• are boundaries between crystals.
• are produced by the solidification process, for example.
• have a change in crystal orientation across them.
• impede dislocation motion. Metal Ingot
Schematic ~ 8cm

grain
boundaries

heat
flow

Notes# 4B - MIAE 221 (adapted from Callister) 30

BULK/VOLUME DEFECTS
Larger defects such as cracks, pores (holes), other stuff.

These are usually formed or introduced during casting or

material fabrication.
They are not really seen as being part of the atomic or crystal
structure but as defects introduced during a particular forming
process, eg.
• Sand particles from a sand mould during sand-casting.
• Pores (holes/gas bubbles) formed during solidification of
molten metal.
• Surface oxide trapped in metal when it is forged

Notes# 4B - MIAE 221 (adapted from Callister) 31

How to observe GRAINS and GRAIN BOUNDARIES

Grains, grain boundaries can be observed in metals/ceramics:

• Section (cut in half) and Grind sample.
• Polish (diamond paste).
• Etch (chemical attack) Occurs preferentially depending upon
crystal orientation and in grain boundaries.
• View MICROSTRUCTURE with microscope.

Can also use: Scanning Electron Microscope, SEM

Can measure properties such as GRAIN SIZE. This effects
strength, toughness etc.

Notes# 4B - MIAE 221 (adapted from Callister) 32

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

0.75mm

micrograph of
Brass (Cu and Zn)
Notes# 4B - MIAE 221 (adapted from Callister) 33
Grain boundaries...

• are imperfections,
• are more susceptible
to etching,
• may be revealed as
dark lines,
• change direction in a
polycrystal.

Notes# 4B - MIAE 221 (adapted from Callister) 34

Notes# 4B - MIAE 221 (adapted from Callister) 35
 Unetched vs etched gray cast iron

Notes# 4B - MIAE 221 (adapted from Callister) 36

Grain Size Determination
Grain size in metals can affect several mechanical properties
especially strength. Can measure grain size by:
Intercept method:
• Draw equal length lines randomly across photomicrograph. (l )
• Count number of grains intercepted per line. (ng)

• Line length is divided by average no. of grains per line (l / ng)

• This is then divided by magnification of photo to give average

grain diameter. (l /ng)/M = Avg. g.d.

𝑙𝑙
Average grain diameter =
𝑛𝑛𝑔𝑔 𝑀𝑀

Notes# 4B - MIAE 221 (adapted from Callister) 37

Photomicrograph Mag: 100X
7 randomly oriented straight lines labeled, (60 mm long) Line No. of grains
intersected
1 11
2 10
3 9
4 8.5
5 7
6 10
7 8
AVG 9.1

Avg. Grain Dia. = (l /ng)/M

(60 /9.1)/100= 6.59 x 10-2mm

Notes# 4B - MIAE 221 (adapted from Callister) 38

 Grain Size (cont)
ASTM Grain size Number
Take photo at 100X and compare with ASTM standard charts of
grain size. Each chart shows particular grain size (G). As G
increases, grain size decreases. Select chart that is closest
match to actual structure.

Current Edition n = 2G-1

where n is the average number of grains per square inch at
Magnification X100
G = ASTM grain size number

Notes# 4B - MIAE 221 (adapted from Callister) 39

Notes# 4B - MIAE 221 (adapted from Callister) 40
 Microscopy
Optical resolution ca. 10-7 m = 0.1 µm = 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

Notes# 4B - MIAE 221 (adapted from Callister) 41

Notes# 4B - MIAE 221 (adapted from Callister) 42
 Scanning Tunneling Microscopy (STM)

• Atoms can be arranged and imaged!

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

molecules arranged on a copper (111)
on a platinum (111) surface. These Kanji
surface. characters represent
the word “atom”.

Notes# 4B - MIAE 221 (adapted from Callister) 43

 SUMMARY

• When liquids solidify they can form crystals

which grow until the solid is many “grains” joined
together.
• These crystals are not perfect.
• Different defects can be seen.
• POINT DEFECTS:
• Vacancies
• Solid solutions
• Substitutional
• Interstitial

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