Structural 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. 5.19 (b), Callister & Rethwisch 3e.

Crystals grow until they meet each other

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
Adapted from Fig. 5.12,
Callister & Rethwisch 3e.

Solidification
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 8 cm

heat
flow

Shell of
Columnar in equiaxed grains
area with less due to rapid
undercooling cooling (greater
Adapted from Fig. 5.17,
T) near wall
Callister & Rethwisch 3e.

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

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.

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

6
 Equilibrium Concentration:
Point Defects
Equilibrium concentration varies with temperature!

No. of defects Activation energy

Nv  Q
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
7

Measuring Activation Energy

We can get Qv from Nv -Qv

an experiment.
= exp
N T
Measure this... Replot it...

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

T 1/T
defect concentration

Estimating Vacancy Concentration

Find the equil. # of vacancies in 1 m3 of Cu at 1000C.
Given:
 = 8.4 g/cm3 A Cu = 63.5 g/mol
Qv = 0.9 eV/atom N A = 6.02 x 1023 atoms/mol
0.9 eV/atom
Nv
-Q
exp = 2.7 x 10-4
N kT
1273 K
8.62 x 10-5 eV/atom-K
NA
For 1 m3 , N = 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
9
 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
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
10 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: 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 Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)
Frenkel
Defect

QD

kT
Equilibrium concetration of defects=e

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.

12
 Imperfections in Metals (ii)
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

13

Imperfections in Metals (iii)

Application of HumeRothery 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. 159, Callister & Rethwisch 3e.

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
O 2-

Cl - Cl -
without impurity O2- impurity with impurity
15
 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.

Adapted from Fig. 5.7,

Callister & Rethwisch 3e.

16

Impurities in Solids
Specification of composition
m1
weight percent C1
x 100
m1  m 2
m1 = mass of component 1

nm 1
atom percent C1'
x 100
nm 1  nm 2

nm1 = number of moles of component 1

17

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

18
 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:
spiral planar ramp resulting from shear deformation
b parallel (||) to dislocation line
Burgers vector, b: measure of lattice distortion

19

Imperfections in Solids
Edge Dislocation

Fig. 5.8, Callister & Rethwisch 3e.

20

Motion of 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.

21
 Imperfections in Solids
Screw Dislocation
Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 5.9, Callister & Rethwisch 3e.

22

Edge, Screw, and Mixed Dislocations

Mixed

Edge

Adapted from Fig. 5.10, Callister & Rethwisch 3e.

Screw

23

Imperfections in Solids
Dislocations are visible in electron micrographs

Fig. 5.11, Callister & Rethwisch 3e.

24
 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)

25

Planar Defects in Solids

One case is a twin boundary (plane)
Essentially a reflection of atom positions across the twin
plane.

Adapted from Fig. 5.14,

Callister & Rethwisch 3e.

Stacking faults
For FCC metals an error in ABCABC packing sequence
Ex: ABCABABC
26

Catalysts and Surface Defects

A catalyst increases the
rate of a chemical
reaction without being
consumed Fig. 5.15, Callister & Rethwisch 3e.

Active sites on catalysts

are normally surface
defects

Single crystals of
(Ce0.5Zr0.5)O2
used in an automotive
catalytic converter
Fig. 5.16, Callister & Rethwisch 3e.

27
 Summary
Point, Line, and Area defects exist in solids.

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.)

28