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CHAPTER 4:

IMPERFECTIONS IN SOLIDS
Why study imperfections?
Crystalline defects drive most material
behaviors, both good and bad.
Diffusion/alloying (Ch. 5)
Deformation/strengthening (Ch. 6, 7, 8)
Corrosion (Ch. 17)
Semiconductors (Ch. 18)
Optical properties (Ch. 21)
Control defects control properties!
K. M. Flores
Materials Science & Engineering

4-1

TYPES OF IMPERFECTIONS
Vacancy atoms
Interstitial atoms
Substitutional atoms
Dislocations
Grain Boundaries
Surfaces

K. M. Flores
Materials Science & Engineering

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Vacancies:

POINT DEFECTS

Vacancy

distortion
of planes

Self-Interstitials:

selfinterstitial

distortion
of planes
K. M. Flores
Materials Science & Engineering

4-3

EQUILIBRIUM CONCENTRATION:
POINT DEFECTS
Equilibrium concentration varies with temperature!

-QD
ND

= exp kT
N

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

K. M. Flores
Materials Science & Engineering

4-4

MEASURING ACTIVATION ENERGY


We can get Q from
an experiment.

-Q
ND
= exp D
kT
N

Measure this...

Replot it...

ND

ln

ND

slope

exponential
dependence!

-QD/k

1/T

K. M. Flores
Materials Science & Engineering

4-5

ESTIMATING DEFECT
CONCENTRATION
Find the equil. # of vacancies in 1 m3 of Cu at 1000C (1273 K)
Given:
= 8.4 g/cm3

ACu = 63.5 g/mol

QV = QD = 0.9 eV/atom

NA = 6.02 x 1023 mole-1


0.9 eV/atom

-QD
ND =

exp
kT

1273K
8.62 x 10-5 eV/atom-K

# potential defect sites N =

Answer: ND =
K. M. Flores
Materials Science & Engineering

4-6

OBSERVING EQUILIBRIUM VACANCY


CONCONCENTRATION
Low energy electron microscope
view of a NiAl single crystal surface.
Increasing T causes surface island
of atoms to grow.
Why? T (NVac/N)
atoms pushed from the crystal
bulk to the surface, where they join
the island, making it grow.
Island grows/shrinks to maintain
equil. vacancy conc. in the bulk.

Reprinted with permission from Nature (K.F. McCarty, 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
5.75 m by 5.75 m.) Copyright (2001) Macmillan Publishers, Ltd.

K. M. Flores
Materials Science & Engineering

4-7

POINT DEFECTS IN ALLOYS - IMPURITIES


Two outcomes if impurity (B) added to host (A):
1. Solid solution of B in A (i.e., random dist. of point defects)

OR

2. Solid solution of B in A and particles of a new phase (more


likely as concentration of B increases)
Second phase
--different composition
--often different structure.
K. M. Flores
Materials Science & Engineering

4-8

ALLOYING AT A SURFACE
Low energy electron
microscope view of a single
crystal Cu surface in vacuum at
17C.
As Sn islands move along the
Cu surface, Sn dissolves into
Cu to make bronze, a
substitutional solid solution alloy
of Sn in Cu.
The Sn islands continually
move onto "unalloyed" regions
and leave tiny bronze particles
in their wake.
Eventually, the islands
disappear.

Reprinted with permission from: A.K. Schmid, N.C. Bartelt, and R.Q. Hwang, "Alloying at Surfaces by
the Migration of Reactive Two-Dimensional Islands", Science, Vol. 290, No. 5496, pp. 1561-64 (2000).
Field of view is 1.5 m and the temperature is 290K.

K. M. Flores
Materials Science & Engineering

4-9

COMPOSITION
Definition: Amount of impurity (B) and host (A) in the system.
Two descriptions:
Weight %

Atom %
CB =

CB =

Conversion between wt% and at% in an A-B alloy:


CB =

CBAB
CAAA + CBAB

x 100

CB =

CB/AB
CA/AA + CB/AB

x 100

Basis for conversion:


mass of A = moles of A x AA
mass of B = moles of B x AB

K. M. Flores
Materials Science & Engineering

AA: atomic weight of A


AB: atomic weight of B
4-10

LINE DEFECTS: MOTIVATION


Metal deformation occurs by crystal planes slipping past each other:
Schematic of -Zinc crystal (HCP):
before deformation

after tensile elongation


Crystal planes
offset

Crystal planes
aligned

slip steps
at surface

Whole crystal planes do not slip past each other at once!

K. M. Flores
Materials Science & Engineering

4-11

LINE DEFECTS: DISLOCATIONS


Edge dislocation: line of imperfect bonds at the bottom of an extra half plane:
= shear stress

extra half plane

Adapted from Fig. 7.1, Callister 6e. (Fig. 7.1


is adapted from A.G. Guy, Essentials of
Materials Science, McGraw-Hill Book
Company, New York, 1976. p. 153.)

Dislocation line

slip plane

Material permanently deforms as dislocation moves through the crystal.


Bonds break and reform, but only along the dislocation line at any point in time, not
along the whole plane at once.
Dislocation line separates slipped and unslipped material.
K. M. Flores
Materials Science & Engineering

4-12

LINE DEFECTS: DISLOCATIONS


Screw dislocation: line of imperfect bonds along axis of a corkscrew in crystal

Adapted from Fig. 4.4, Callister 6e.

AFM images of graphite, downloaded from http://www.phy.mtu.edu/~jaszczak/namibia-2.html,


November 22, 2004. (Rakovan & Jaszczak (2002) American Mineralogist 87, 17-24. )

K. M. Flores
Materials Science & Engineering

4-13

DISLOCATIONS & CRYSTAL STRUCTURE


view onto two
close-packed
planes.

close-packed plane (bottom)

close-packed directions
close-packed plane (top)

Comparison of different crystal structures:


FCC:
HCP:
BCC:
Results of tensile
testing.

Mg (HCP)
tensile direction

Al (FCC)
K. M. Flores
Materials Science & Engineering

4-14

DISLOCATIONS & MATERIALS CLASSES


Metals:

+
+

+
+

+
+

+
+

+
+

+
+

+
+

+
+

ion cores

electron
cloud

Covalent Ceramics (Si, diamond):

Ionic Ceramics (NaCl):

K. M. Flores
Materials Science & Engineering

4-15

AREA DEFECTS: GRAIN BOUNDARIES


Grain boundaries:
are boundaries between crystals with different orientation (planes go
in different directions).
are produced by the solidification process, for example.
have a change in crystal orientation across them.
impede dislocation motion.

Schematic

Metal Ingot
~ 8 cm

grain
boundaries
heat
flow

Adapted from Fig. 4.7, Callister 6e.

K. M. Flores
Materials Science & Engineering

Adapted from Fig. 4.10, Callister 6e. (Fig. 4.10 is from Metals
Handbook, Vol. 9, 9th edition, Metallography and Microstructures, Am.
Society for Metals, Metals Park, OH, 1985.)

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OBSERVATION OF GRAINS
Optical microscopy (up to 2000x) can be used to see grains
Sample surface first polished to mirror finish
Acid etch attacks grain boundaries and gives surface reflectance that
varies with crystal orientation.
microscope

microscope
polished surface

close-packed
planes

surface groove
grain boundary

micrograph of
Brass (Cu and Zn)

Fe-Cr alloy
0.75mm

Adapted from Fig. 4.11(b) and (c),


Callister 6e. (Fig. 4.11(c) is courtesy
of J.E. Burke, General Electric Co.

Adapted from Fig. 4.12(a) and (b), Callister 6e.


(Fig. 4.12(b) is courtesy
of L.C. Smith and C. Brady, the National Bureau of
Standards, Washington, DC [now the National Institute of
Standards and Technology, Gaithersburg, MD].)

K. M. Flores
Materials Science & Engineering

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OBSERVATION OF GRAINS
Focused Ion Beam (FIB) and Scanning Electron Microscopy (SEM)
can combine to produce 3D images of grains/defects
ion beam
(e.g. Ga+)

e- beam
Images courtesy R. Williams, OSU.

to e- detector
atoms removed
from specimen
Cantilever beams
for sectioning

Polycrystalline
Ni-superalloy

35 m

Movie courtesy M. Uchic, AFRL.

K. M. Flores
Materials Science & Engineering

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SUMMARY
Point, Line, and Area defects arise 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 affect 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.)

K. M. Flores
Materials Science & Engineering

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