Chapter 4 ENG - Imperfections in Solids

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CHAPTER 4: IMPERFECTIONS IN
SOLID
1
MAIN ISSUES
• 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?
Imperfections in Solids 2
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 7e.
• Crystals grow until they meet each other
Solidification
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 8 cm
heat
flow
Columnar in Shell of equiaxed

area with less grains due to rapid
undercooling cooling (greater
T) near wall
Adapted from Fig. 4.12, Callister 7e.
Grain Refiner - added to make smaller, more uniform, equiaxed grains.
Imperfections of Solids 4
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
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.
Imperfections of Solids 6
Types of Imperfections
• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms
• Dislocations Line defects
• Grain Boundaries Area defects
Point Defects
• Vacancies:
-vacant atomic sites in a structure.
Vacancy
distortion
of planes
• Self-Interstitials:
-"extra" atoms positioned between atomic sites.
self-
interstitial
distortion
of planes
Point Defects
M M M X M X M
X • Frenkel defects:
X M Y X M X
M X M X M i  VM'  0
M
M X M X L M X X M
M
X M X X X M X
X, M: anion, cation with valency 1

Y, L: anion, cation with valency 2 • Schottky defects:
M X M X M X
VX  VM'  0
Abbreviation: X X M M
cations: 1  ; 2   
anions: 1  ; 2 Density of materials is affected by
Schottky defects
Point defects & Stoichiometry
Perfect crystal
Point defects:
Stoichiometric defect  Stoichiometric compound
Example: Fe3O4, Na2SiO3
Non- stoichiometric defect Non- stoichiometric compound
Example: FeO, TiOx
Equilibrium Concentration: Point Defects
• Equilibrium concentration varies with temperature!
No. of defects 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)
(8.62 x 10 -5 eV/atom-K)
Each lattice site
is a potential
vacancy site
Equilibrium Concentration: Point Defects
Calculate the equilibrium number of vacancies per cubic meter for copper
at 1000 C. The energy for vacancy formation is 0.9 eV/atom; the atomic
weight and density (at C) for copper are 63.5 g/mol and 8.4 g/cm3,
respectively. R= 8.31J/mol -K
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.
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. Valency
• All else being equal, a metal will have a greater tendency
to dissolve a metal of higher valency than one of lower
valency
Bonding and properties 15

• Specification of composition
m1
– weight percent C1  x 100
m1  m2
m1 = mass of component 1
' n m1
– atom percent C 
1 x 100
n m1  n m 2
nm1 = number of moles of component 1
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
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  to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b  to dislocation line
Imperfections in Solid 18
Motion of Edge Dislocation
Edge Dislocation
• Location of lattice distortion
• Represented by Burgers
vector
Burgers vector: represents the

magnitude and direction of the lattice
distortion resulting from a dislocation
Fig. 4.3, Callister 7e.
in a crystal lattice
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.
(Courtesy P.M. Anderson)
Screw Dislocation
• Formation by shear stress
• Atoms localized in distortion area
Screw Dislocation
are traced by screw
Dislocation
line
Burgers vector b
(a)
b
Adapted from Fig. 4.4, Callister 7e. (b)
Edge, Screw, and Mixed Dislocations
Mixed
Edge

Screw
Dislocations are visible in electron micrographs
27
Dislocations & Crystal Structures
• Structure: close-packed view onto two

planes & directions close-packed
planes.
are preferred.
close-packed directions
close-packed plane (bottom) close-packed plane (top)
• Comparison among crystal structures:
FCC: many close-packed planes/directions;
HCP: only one plane, 3 directions;
BCC: none
• Specimens that Mg (HCP)

were tensile
tested. tensile direction
Al (FCC)
28
THANK YOU
FOR YOUR ATTENTION
29

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.

• What are the solidification mechanisms?

• What types of defects arise in solids?

• Can the number and type of defects be varied

• How do defects affect material properties?

• Are defects undesirable?

• Solidification- result of casting of molten material

nuclei crystals growing grain structure

• Crystals grow until they meet each other

Columnar in Shell of equiaxed

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

Adapted from Fig. 4.7, Callister 7e.

There is no such thing as a perfect crystal.

• Dislocations Line defects

• Grain Boundaries Area defects

X, M: anion, cation with valency 1

• Equilibrium concentration varies with temperature!

No. of defects Activation energy

Substitutional solid soln. Interstitial solid soln.

• Solid solution of B in A plus particles of a new

Conditions for substitutional solid solution (S.S.)

Bonding and properties 15

nm1 = number of moles of component 1

Schematic of Zinc (HCP):

Adapted from Fig. 7.8, Callister 7e.

Linear Defects (Dislocations)

Burgers vector: represents the

Atomic view of edge

(Courtesy P.M. Anderson)

Adapted from Fig. 4.4, Callister 7e. (b)

Adapted from Fig. 4.5, Callister 7e.

Adapted from Fig. 4.6, Callister 7e.

• Structure: close-packed view onto two

• Specimens that Mg (HCP)

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