CHAPTER 6:
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?
Imperfections in Solids (Defects): Introduction
Real crystals are never perfect,
there are always defects
Defects have a profound
impact on the macroscopic
properties of materials
The processing determines the defect
type and defect concenration:
TYPES OF IMPERFECTIONS
• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms
• Dislocations Line defects
• Grain Boundaries Area defects
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
Schematic representation
of different point defects:
(1) Vacancy;
(2) Self-interstitial;
(3) Interstitial impurity;
(4,5) Substitutional impurities
EQUIL. CONCENTRATION:
POINT DEFECTS
• Equilibrium concentration varies with temperature!
No. of defects Activation energy
ND Q
exp
D
N kT
No. of potential Temperature
defect sites. 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
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
ESTIMATING VACANCY CONC.
• Find the equil. # of vacancies in 1m3 of Cu at 1000C.
• Given:
0.9eV/atom
NV QV
D exp
D
= 2.7 · 10-4
N kT
1273K
8.62 x 10-5 eV/atom-K
NA
For 1m3, N = x x 1m3 = 8.0 x 1028 sites
ACu
• Answer:
V
IMPERFECTIONS 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 alloy Interstitial alloy
(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
• 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
POINT DEFECTS IN CERAMICS (I)
• 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
Anion
Vacancy
POINT DEFECTS IN CERAMICS (II)
• Frenkel Defect
-- a cation vacancy-cation interstitial pair.
• Shottky Defect
-- a paired set of cation and anion vacancies.
Shottky
Defect:
Frenkel
Defect
• Equilibrium concentration of defects
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
LINE DEFECTS: DISLOCATIONS
Dislocations: • are line defects,
• cause slip between crystal plane when they move,
• produce permanent (plastic) deformation.
Schematic of a Zinc (HCP):
• before deformation • after tensile elongation
slip steps
Number of dislocations and their interaction with the
applied load and forces determine the deformation
behavior of metals. (CHAPTER 8)
Line Defects 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
• Mixed dislocation:
– A mixture of Edge and Screw Dislocations on the same plane.
– b is inclined (with an angle) to dislocation line
Burger’s vector, b: measure of lattice distortion
Edge Dislocations
Edge Dislocation Movement
Atomic rearrangements that accompany the motion of an edge
dislocation as it moves in response to an applied shear stress.
BOND BREAKING AND REMAKING
• 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.
INCREMENTAL SLIP
• Dislocations slip planes incrementally...
• The dislocation line (the moving red dot)...
...separates slipped material on the left
from unslipped material on the right.
Simulation of dislocation
motion from left to right
as a crystal is sheared.
Screw Dislocations Mixed Dislocations
Ex. Dislocations Observed in Metals
Dislocations are visible in electron micrographs
DISLOCATIONS & CRYSTAL STRUCTURE
Extra planes of dislocations do not form and move randomly
rather
they prefer to move
on close-packed planes & in close packed directions
view onto two
close-packed
planes.
Comparison among crystal structures:
•FCC: many close-packed planes/directions (4x3=12);
• HCP: only one plane, 3 directions;
• BCC: 6x2 =12
tensile testing of HCP and FCC crystals.
F F
Mg (HCP)
F F
Al (FCC)
AREA DEFECTS: GRAIN BOUNDARIES
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
Pure Pb
heat
flow
OPTICAL MICROSCOPY (1)
• Useful up to 2000X magnification.
• Polishing removes surface features (e.g., scratches)
• Etching changes reflectance, depending on crystal
orientation.
Micrograph of
Brass (Cu and Zn)
Light
0.75mm
OPTICAL MICROSCOPY (2)
Grain boundaries...
• are imperfections,
• are more susceptible
to etching,
• may be revealed as
dark lines,
• change direction in a
polycrystal.
OTHER AREA DEFECTS
External surfaces where crystal structure terminates.
Twin Boundaries (Mirror lattice image)
Stacking Faults (in FCC distortion in ABCABC stacking)
Phase Boundaries (Boundaries between two chemically different
grains)
Domain Walls (in Ferromagnetic and Ferrimagnetic materials,
boundaries between regions with different direction of magnetization)
Summary
TYPES OF IMPERFECTIONS
• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms
• Dislocations Line defects
• Grain Boundaries Area defects
• 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.)
