CH 04
CH 04
Imperfections in Solids
ISSUES TO ADDRESS...
What are the solidification mechanisms?
Chapter 4 - 1
Imperfections in Solids
Chapter 4 - 2
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. 4.7,
Callister & Rethwisch 8e.
Chapter 4 - 3
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.
Chapter 4 - 5
Types of Imperfections
Vacancy atoms
Interstitial atoms Point defects
Substitutional atoms
Chapter 4 - 6
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 4 - 7
Equilibrium Concentration:
Point Defects
Equilibrium concentration varies with temperature!
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 4 - 8
Measuring Activation Energy
Nv Nv slope
ln
N N
-Qv /k
exponential
dependence!
T 1/T
defect concentration
Chapter 4 - 9
Estimating Vacancy Concentration
Find the equil. # of vacancies in 1 m3 of Cu at 1000C.
Given:
r = 8.4 g /cm 3 A Cu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
0.9 eV/atom
Q
exp
Nv =
v -4
N kT = 2.7 x 10
1273 K
8.62 x 10-5 eV/atom-K
NA
For 1 m3 , N= r 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 4 - 10
Observing Equilibrium Vacancy Conc.
Low energy electron
microscope view of Click once on image to start animation
a (110) surface of NiAl.
Increasing temperature
causes surface island of
atoms to grow.
Why? The equil. vacancy
conc. increases via atom
motion from the crystal
to the surface, where Reprinted with permission from Nature (K.F. McCarty,
they join the island. J.A. Nobel, and N.C. Bartelt, "Vacancies in
Solids and the Stability of Surface Morphology",
Nature, Vol. 412, pp. 622-625 (2001). Image is
Island grows/shrinks to maintain 5.75 mm by 5.75 mm.) Copyright (2001) Macmillan
equil. vancancy conc. in the bulk. Publishers, Ltd.
Chapter 4 - 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
Chapter 4 - 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
Chapter 4 - 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
Chapter 4 - 14
Impurities in Solids
Specification of composition
m1
weight percent C1 = x 100
m1 m2
m1 = mass of component 1
n m1
atom percent C =
'
x 100
nm1 nm 2
1
Chapter 4 - 15
Line Defects
Dislocations:
are line defects,
slip between crystal planes result when dislocations move,
produce permanent (plastic) deformation.
slip steps
Chapter 4 - 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:
spiral planar ramp resulting from shear deformation
b parallel () to dislocation line
Burgers vector, b: measure of lattice distortion
Chapter 4 - 17
Imperfections in Solids
Edge Dislocation
Chapter 4 - 18
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.
b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 4.4, Callister & Rethwisch 8e.
Chapter 4 - 20
VMSE: Screw Dislocation
In VMSE:
a region of crystal containing a dislocation can be rotated in 3D
dislocation motion may be animated
Edge
Chapter 4 - 22
Imperfections in Solids
Dislocations are visible in electron micrographs
Stacking faults
For FCC metals an error in ABCABC packing sequence
Ex: ABCABABC
Chapter 4 - 25
Catalysts and Surface Defects
A catalyst increases the
rate of a chemical
reaction without being
consumed Fig. 4.10, Callister & Rethwisch 8e.
Single crystals of
(Ce0.5Zr0.5)O2
used in an automotive
catalytic converter
Fig. 4.11, Callister & Rethwisch 8e.
Chapter 4 - 26
Microscopic Examination
Chapter 4 - 27
Optical Microscopy
Useful up to 2000X magnification.
Polishing removes surface features (e.g., scratches)
Etching changes reflectance, depending on crystal
orientation.
crystallographic planes
Adapted from Fig. 4.13(b) and (c), Callister
& Rethwisch 8e. (Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.)
Micrograph of
brass (a Cu-Zn alloy)
0.75mm
Chapter 4 - 28
Optical Microscopy
Grain boundaries...
are imperfections,
are more susceptible
to etching,
may be revealed as polished surface
dark lines,
change in crystal surface groove
orientation across grain boundary
(a)
boundary. Adapted from Fig. 4.14(a)
and (b), Callister &
ASTM grain Rethwisch 8e.
(Fig. 4.14(b) is courtesy
size number of L.C. Smith and C. Brady,
the National Bureau of
Polarized light
metallographic scopes often use polarized
light to increase contrast
Also used for transparent samples such as
polymers
Chapter 4 - 30
Microscopy
Optical resolution ca. 10-7 m = 0.1 mm = 100 nm
For higher resolution need higher frequency
X-Rays? Difficult to focus.
Electrons
wavelengths ca. 3 pm (0.003 nm)
(Magnification - 1,000,000X)
Atomic resolution possible
Electron beam focused by magnetic lenses.
Chapter 4 - 31
Scanning Tunneling Microscopy
(STM)
Atoms can be arranged and imaged!
Photos produced from
the work of C.P. Lutz,
Zeppenfeld, and D.M.
Eigler. Reprinted with
permission from
International Business
Machines Corporation,
copyright 1995.
Chapter 4 - 32
Summary
Point, Line, and Area defects exist in solids.
Chapter 4 - 33
ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:
Chapter 4 - 34