Imperfections in Solids

ISSUES TO ADDRESS...
• What are the solidification mechanisms?

• 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?

Chapter 6 - 1
 Imperfections in Solids

• Solidification- result of casting of molten material

– 2 steps
• Nuclei form
• Nuclei grow to form crystals – grain structure

(now the National Institute of Standards

Bureau of Standards, Washington, DC

and Technology, Gaithersburg, MD.)]

• Start with a molten material – all liquid

[Photomicrograph courtesy of L. C.
Smith and C. Brady, the National
nuclei crystals growing grain structure
liquid Adapted from Fig. 6.20 (b), Callister & Rethwisch 9e.

• Crystals grow until they meet each other

Chapter 6 - 2
 Solidification
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 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.)

heat
flow

Shell of
Columnar in equiaxed grains
area with less due to rapid
undercooling cooling (greater
ΔT) near wall

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

Chapter 6 - 3
 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.

Chapter 6 - 4
 Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

Chapter 6 - 5
 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

Chapter 6 - 6
 Equilibrium Concentration:
Point Defects
• Equilibrium concentration varies with temperature!

No. of defects Activation energy

Nv −Q v
No. of potential = exp
defect sites N kT
Temperature
Boltzmann's constant
-23
(1.38 x 10 J/atom-K)
-5
(8.62 x 10 eV/atom-K)
Each lattice site
is a potential
vacancy site
Chapter 6 - 7
 Measuring Activation Energy

• We can get Qv from Nv - Qv

an experiment. = exp
N kT
• Measure this... • Replot it...

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

T 1/T
defect concentration
Chapter 6 - 8
 Estimating Vacancy Concentration
• Find the equil. No. of vacancies in 1 m3 of Cu at 1000C.
• Given:
ρ = 8.4 g /cm 3 Cu Mass No. =A Cu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
0.9 eV/atom
Nv = - Qv
exp -4
= 2.7 x 10
N kT
1273 K
8.62 x 10-5 eV/atom-K
NA
For 1 m3 , N= ρ x x 1 m3 = 8.0 x 1028 sites
A Cu
• Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
Chapter 6 - 9
 Point Defects
• Vacancies
-- vacancies exist in ceramics for both cations and anions
• Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites

Cation
Interstitial
Cation
Vacancy
Fig. 6.2, Callister & Rethwisch 9e.
(From W.G. Moffatt, G.W. Pearsall, and J.
Wulff, The Structure and Properties of
Materials, Vol. 1, Structure, p.78. Copyright
©1964 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley and
Sons, Inc.)

Anion
Vacancy Chapter 6 - 10
• Frenkel Defect is a form of point defect that is created when an
atom or cation leaves its original place in the lattice structure to
create a vacancy while occupying another interstitial position
within the solid crystal.

• Shottky Defect: is a point defect in which both cation and anion

remain missing from the lattice site in equal numbers.
-- a paired set of cation and anion vacancies.

Shottky
Defect:

Frenkel
Defect

Chapter 6 - 11
 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.

Chapter 6 - 12
 Imperfections in Metals (ii)
Conditions for substitutional solid solution (S.S.)
• W. Hume – Rothery rule
– 1. Δr (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

Chapter 6 - 13
 Imperfections in Metals (iii)
Application of Hume–Rothery rules – Solid
Solutions Element Atomic Crystal Electro- Valence
Radius Structure nega-
(nm) tivity
1. Would you predict Cu 0.1278 FCC 1.9 +2
C 0.071
more Al or Ag H 0.046
O 0.060
to dissolve in Zn? 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. 177, Callister & Rethwisch 9e.

Chapter 6 - 14
 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 O2- impurity with impurity
Chapter 6 - 15
 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

Chapter 6 - 16
 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: a dislocation in the lattice structure of a

crystal in which the atoms are arranged in a helical pattern that
is normal to the direction of the stress. b parallel () to
dislocation line.

• Burger’s vector, b: represents the magnitude and direction of

the lattice distortion resulting from a dislocation in a crystal
lattice.
Chapter 6 - 17
 Imperfections in Solids
Edge Dislocation

Fig. 6.9, Callister & Rethwisch 9e. (Adapted from

A. G. Guy, Essentials of Materials Science, McGraw-Hill
Book Company, New York, NY, 1976, p. 153.)

Chapter 6 - 18
 Imperfections in Solids
Screw Dislocation
Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 6.10, Callister & Rethwisch 9e.
[Figure (b) from W. T. Read, Jr.,Dislocations in Crystals,
McGraw-Hill Book Company, New York, NY, 1953.]

Chapter 6 - 19
 Imperfections in Solids
Dislocations are visible in electron micrographs

Fig. 6.12, Callister & Rethwisch 9e.

(Courtesy of M. R. Plichta, Michigan
Technological University.)

Chapter 6 - 20
 Planar Defects in Solids
• Twin boundary: A grain boundary whose lattice structures are
mirror images of each other in the plane of the boundary
– Essentially a reflection of atom positions across the twin plane.

• Stacking faults: when there is an error in the stacking or

packing sequence.
– For FCC metals an error in ABCABC packing sequence
– Ex: ABCABABC
Chapter 6 - 21
 Microscopic Examination
• Crystallites (grains) can be quite small (mm or less) –
necessary to observe with a microscope.
Optical Microscopy
• Useful up to 2000X magnification.
• Polishing removes surface features (e.g., scratches)
• Etching changes reflectance, depending on crystal
orientation.

crystallographic
planes

Micrograph of
brass (a Cu-Zn
0.75 mm alloy) Chapter 6 - 22
 Optical Microscopy
Grain boundaries...

• are imperfections,
• are more susceptible
polished surface
to etching,
• may be revealed as surface groove
dark lines, grain boundary
• change in crystal (a)
Fig. 6.20(a) & (b), Callister &
orientation across Rethwisch 9e.
[Fig. 6.20(b) is courtesy of L.C.
boundary. Smith and C. Brady, the National
Bureau of Standards, Washington,
DC (now the National Institute of
Standards and Technology,
Gaithersburg, MD).]

Fe-Cr alloy
(b)

Chapter 6 - 23
 Summary
• Point, Line, and Area defects exist in solids.
• The number and type of defects can be varied
and controlled (e.g., temperature controls vacancy
concentration).
• 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).

Chapter 6 - 24
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 6 - 25