Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms 1-2 atoms

• Dislocations Line defects

1-dimensional

• Grain Boundaries Area defects

2-dimensional

1
•
Point
Vacancies:
Defects in Metals
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

• Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self-interstitial
distortion
of planes

2
 Self Interstitials

• In metals, a self interstitial introduces

relatively large distortions (strain) in the
surrounding lattice since the atom is
substantially larger than the interstitial
site.
 Point Defects in Ceramics
• 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

Adapted from Fig. 5.2, Callister & Rethwisch 3e.

(Fig. 5.2 is from W.G. Moffatt, G.W. Pearsall, and
J. Wulff, The Structure and Properties of
Materials, Vol. 1, Structure, John Wiley and Sons,
Inc., p. 78.)

Anion Vacancy
4
Point Defects: Impurities
 Point Defects: Frenkel and Schottky
• Frenkel Defect
To maintain the charge neutrality, a cation vacancy-cation interstitial
pair occur together. The cation leaves its normal position and moves to the
interstitial site.

• Schottky Defect
To maintain the charge neutrality, remove 1 cation and 1 anion;
this creates 2 vacancies.

Schottky
Defect

Adapted from Fig. 5.3, Callister & Rethwisch 3e.

(Fig. 5.3 is from W.G. Moffatt, G.W. Pearsall, and
J. Wulff, The Structure and Properties of
Frenkel Materials, Vol. 1, Structure, John Wiley and Sons,
Inc., p. 78.)
Defect

6
 Imperfections in Ceramics
• Since there are both anions and cations in ceramics, a substitutional
impurity will replace the host ion most similar in terms of charge.
•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 7
 Point Defects in Polymers
• Defects due in part to chain packing errors and impurities such
as chain ends and side chains

Adapted from Fig. 5.7,

Callister & Rethwisch 3e.

8
 Imperfections in Metals
What are the outcomes if impurity (B) is added to host (A)?
• Solid solution of B in A (random distribution of point defects)

OR

Substitutional solid solution. Interstitial solid solution.

(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.

9
 Hume - Rothery Rules
The Hume-Rothery rules are basic conditions
for an element to dissolve in a metal, forming a
substitutional solid solution.
1. The atomic radius of the solute and solvent atoms
must differ by no more than 15% (r < 15%).
2. The solute and solvent should have similar
electronegativities.
3. Same crystal structure for “pure” metals.
4. Maximum solubility occurs when the solvent and
solute have the same valence. Metals with lower
valence will tend to dissolve metals with higher
valence.
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Substitutional Solid Solution Example:
Copper and Nickel

Element Atomic Crystal Electro- Valence

Radius Structure nega-
(nm) tivity
Cu 0.1278 FCC 1.9 +2
C 0.071 2.5
H 0.046
O 0.060
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
Fe 0.1241 BCC 1.8 +2
Ni 0.1246 FCC 1.8 +2
Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
 Interstitial Solid Solution
• Carbon forms an interstitial solid solution when
added to iron; the maximum concentration of
carbon that can be added is roughly 2%.
• The atomic radius of the carbon atom is much
less than that of iron (0.071nm vs 0.124 nm).
• For interstitial solid solutions, the Hume-Rothery
rules are:
– 1. Solute atoms must be smaller than the pores in the
solvent lattice.
– 2. The solute and solvent should have similar
electronegativity.

12
 Types of Imperfections
• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms 1-2 atoms

• Dislocations Line defects

1-dimensional
200px-Dislocation_edge_b

13
 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 that cause
misalignment of nearby atoms.
Linear defects are associated primarily with mechanical deformation.
Types of dislocations: edge, screw, mixed.

Edge dislocation:
▪ extra half-plane of atoms
inserted in a crystal
structure; the edge of the
plane terminates within
the crystal.
▪ Around the dislocation
line there is some
localized distortion.
▪ b perpendicular (⊥) to
dislocation line

Burger’s vector, b: measure of lattice distortion 15

 Motion of Edge Dislocation
• Dislocation motion requires the successive bumping
of a half plane of atoms (from left to right).
• Bonds across the slipping planes are broken and
remade in succession.
• The (plastic) permanent deformation of most crystalline
materials is by dislocation movement.
• Most contain some dislocations that were introduced
during solidification, plastic deformations, and rapid
cooling (thermal stresses).
• To deform plastically means to slide atomic planes past
each other.
Atomic view of edge
dislocation motion from
left to right as a crystal
is sheared.
16
 Imperfections in Solids
Screw dislocation:
– Named for the spiral stacking of crystal planes around
the dislocation line; results from shear deformation
– b parallel () to dislocation line

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 Dislocation Motion
• Produces plastic deformation, Plastically
• Depends on incrementally breaking stretched
bonds. zinc
single
crystal.

• If dislocations don't move,

deformation doesn't happen!
Dislocations During Cold Working

• Ti alloy after cold working.

• Dislocations entangle with one
another during cold work.
• Dislocation movement becomes
more difficult.
• Dislocations are visible in
electron micrographs

19
 Polycrystalline Materials

Grain Boundaries
▪ regions between crystals
▪ transition from lattice of one
region to another
(a) The atoms near the boundaries
of the 3 grains do not have an
equilibrium spacing or
arrangement; slightly disordered.
(b) Grains and grain boundaries in a
stainless steel sample. low
density in grain boundaries

20
 Planar Defects in Solids - Twinning
• A shear force that causes atomic displacements such that
the atoms on one side of a plane (twin boundary) mirror the
atoms on the other side. A reflection of atom positions
across the twin plane.
• Displacement magnitude in the twin region is proportional
to the atom’s distance from the twin plane.
• Takes place along defined planes and directions
depending upon the system.
• Ex: BCC twinning occurs on the (112)[111] system
 Twinning
(c) 2003 Brooks/Cole Publishing / Thomson Learning

Applied stress to a perfect crystal (a) may cause a displacement of the

atoms, (b) causing the formation of a twin. Note that the crystal has
deformed as a result of twinning.

• Stacking faults
– For FCC metals an error in ABCABC packing sequence
– Ex: ABCABABC
 Slip systems

• FCC and BCC materials have large numbers of slip

systems (at least 12) and are considered ductile.
• HCP systems have few slip systems and are quite brittle.
Slip systems
 (c) 2003 Brooks/Cole Publishing / Thomson Learning

A micrograph of twins within a grain of brass (x250).

Brass (90 micron scale bar)

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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

Micrograph of
brass (a Cu-Zn alloy)

0.75mm
27
 Optical Microscopy
Grain boundaries...
• are imperfections,
• are more susceptible
to etching, polished surface
• may be revealed as
surface groove
dark lines,
• change in crystal grain boundary
(a)
orientation across
boundary.
ASTM grain
size number

N = 2n-1 Adapted from Fig. 5.19(a) and (b), Callister

& Rethwisch 3e. (Fig. 5.19(b) is courtesy

Fe-Cr alloy of L.C. Smith and C. Brady, the National

Bureau of Standards, Washington, DC
number of grains/in2 [now the National Institute of Standards
and Technology, Gaithersburg, MD].)

at 100x (b)

magnification 28
Change in Microstructure due to Cold Work
Polycrystalline Deformation
 Microscopy
Optical (light) resolution (0.1 m = 100 nm = 10-7 m)
For higher resolution need higher frequency
– X-Rays are difficult to focus.
– Electrons
• wavelengths are roughly 3 pm (0.003 nm)
–(Magnification - 1,000,000X)
• Atomic resolution possible
• Electron beam focused by magnetic lenses.

31