Struktur Atom dan

Ikatan

TOPIC 2:
ATOMIC STRUCTURE & BONDING
Properties
Materials Science

Structure

Materials Engineering

Processing

Electronic level (subatomic)

Atomic (molecular level, chemical
composition)
Crystal (arrangement of atoms or ions wrt
one another)
Microstructure (can study with microscopes)
Macrostructure (can see with naked eye)

TOPIC 2:
ATOMIC STRUCTURE & BONDING

Based on Chapter 2 (Callister)

OUTLINE
Electronic structure & bonding
(Review: freshman chemistry)
What promotes bonding?
What types of bonds are there?

Bonding material properties

(melting point, thermal expansion, elasticity)

BOHR ATOM
electrons:
n = principal
quantum number
1
n=3 2

Adapted from Fig. 2.1,

Callister 6e.

Nucleus: Z = # protons
= 1 for hydrogen to 94 for plutonium
N = # neutrons
Atomic mass A Z + N
n labels shells; shells are composed of sub-shells: s, p, d, f,

ELECTRON ENERGY STATES

Electrons...
have discrete energy states
tend to occupy lowest available energy state.

Maximum electrons
In sub-shells
s=2
p=6
d = 10
f = 14
Maximum electrons in
nth shell = 2n2

STABLE ELECTRON
CONFIGURATIONS
Stable electron configurations...
have complete s and p sub-shells 8 electrons (octet)
tend to be unreactive.
Z Element Configuration
2
He
1s2
Adapted from Table 2.2,
Callister 6e.
10
Ne
1s22s 22p6
18
Ar
1s22s22p63s23p6
36
Kr
1s22s22p63s23p63d104s24p6

SURVEY OF ELEMENTS
Element
Atomic # Electron configuration
Hydrogen
1
1s1
Helium
2
1s2
(stable)
Lithium
3
1s22s1
Beryllium
4
1s22s2
1s22s22p1
Boron
5
Adapted from Table 2.2,
Callister 6e.
1s22s22p2
Carbon
6
...
...
Neon
10
1s22s22p6
(stable)
1s22s22p63s1
Sodium
11
1s22s22p63s2
Magnesium
12
1s22s22p63s23p1
Aluminum
13
...
...
1s22s22p63s23p6
(stable)
Argon
18
...
...
...
Krypton
36
1s22s22p63s23p63d104s246 (stable)

Most elements: Electron configuration not stable. Why?

Valence (outer) shell usually is not an octet.

give up 1e
give up 2e
give up 3e

Columns: Similar Valence Structure

Li Be

Metal
Nonmetal
Intermediate

accept 2e
accept 1e
inert gases

THE PERIODIC TABLE

He

Ne

Na Mg

Cl Ar

K Ca Sc

Se Br Kr

Rb Sr

Te

Cs Ba

Adapted
from Fig.
2.6, Callister
6e.

Xe

Po At Rn

Fr Ra

Electropositive elements:
Readily give up electrons
to become + ions.

Electronegative elements:
Readily acquire electrons
to become - ions.

ELECTRONEGATIVITY
Ranges from 0.7 to 4.0,
Large values: tendency to acquire electrons.
H
2.1
Li
1.0
Na
0.9

Be
1.5
Mg
1.2

K
0.8
Rb
0.8

Ca
1.0

Cs
0.7
Fr
0.7

Ba
0.9
Ra
0.9

Cl
3.0
Br
2.8

He
Ne
Ar
Kr
-

I
2.5
At
2.2

Xe
Rn
-

F
4.0

Ti
1.5

Cr
1.6

Fe
1.8

Sr
1.0

Smaller electronegativity

Ni
1.8

Zn
1.8

As
2.0

Larger electronegativity

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell
University.

IONIC BONDING

Occurs between + and - ions.

Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl
Na (metal)
unstable

Cl (nonmetal)
unstable
electron

Na (cation)
stable

Coulombic
Attraction

Cl (anion)
stable

ELECTRONIC STRUCTURE:
Na & Cl atoms

Atomic number of Na = 11 (1 valence electron)

Atomic number of Cl = 17 (7 valence electrons)

EXAMPLES: IONIC
BONDING NaCl
H
2.1
Li
1.0
Na
0.9
K
0.8
Rb
0.8
Cs
0.7
Fr
0.7

MgO
CaF 2
CsCl

Be
1.5

O
F
3.5 4.0
Cl
3.0

Mg
1.2
Ca
1.0
Sr
1.0

Ti
1.5

Cr
1.6

Fe
1.8

Ni
1.8

Zn
1.8

As
2.0

Ba
0.9

Br
2.8
I
2.5
At
2.2

He
Ne
Ar
Kr
Xe
Rn
-

Ra
0.9

Give up electrons

Acquire electrons

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell
University.

Predominant bonding in Ceramics

COVALENT BONDING
Requires shared electrons
Example: CH4
C: has 4 valence e,
needs 4 more

CH 4

H: has 1 valence e,
needs 1 more

Electronegativities
are comparable.

shared electrons
from carbon atom
H
shared electrons
from hydrogen
atoms

Adapted from Fig. 2.10, Callister 6e.

H2

H
2.1
Li
1.0
Na
0.9
K
0.8

Be
1.5
Mg
1.2
Ca
1.0

Rb
0.8
Cs
0.7

Sr
1.0
Ba
0.9

Fr
0.7

Ra
0.9

column IVA

EXAMPLES: COVALENT
BONDING
H2O
C(diamond)
SiC
Ti
1.5

Cr
1.6

Fe
1.8

Ni
1.8

Zn
1.8

Ga
1.6

C
2.5
Si
1.8
Ge
1.8

F2
He
O
2.0
3.
5
As
2.0

Sn
1.8
Pb
1.8

GaAs

F
4.0
Cl
3.0
Br
2.8
I
2.5
At
2.2

Ne
Ar
Kr
Xe
Rn
-

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is

adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition,
Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

Molecules with nonmetals

Molecules with metals and nonmetals
Elemental solids (RHS of Periodic Table)
Compound solids (about column IVA)
Prevalent in ceramics and polymers

Cl 2

METALLIC BONDING
Arises from a sea of donated valence electrons
(1, 2, or 3 from each atom).

Adapted from Fig. 2.11, Callister 6e.

Primary bond for metals and their alloys

high electrical conductivity.
Why? What about ionic/covalent?

METALLIC VERSUS IONIC

BONDING

Much easier to deform materials with

metallic than with ionic bonding. Why?

Sliding atom planes over each other

(deformation) very unfavorable energetically in
ionic solids!
metals are ductile & ceramics (ionic) are brittle

SECONDARY BONDING
Arises from interaction between dipoles
Fluctuating dipoles
ex: liquid H2
asymmetric electron
H2
H2
clouds

- secondary +
bonding

H H

Adapted from Fig. 2.13, Callister 6e.

H H

secondary
bonding

Permanent dipoles-molecule induced

-general case:

+ -

secondary
bonding

-ex: liquid HCl

H Cl

secondary
bonding

-ex: polymer

+ H Cl

Adapted from Fig. 2.14,

Callister 6e.

Adapted from Fig. 2.14,

Callister 6e.

SUMMARY: BONDING
Type

Bond Energy

Comments

Ionic

Large!

Nondirectional (ceramics)

Variable
Directional
Covalent large-Diamond (semiconductors, ceramics
small-Bismuth
polymer chains)
Metallic
Secondary

Variable
large-Tungsten
small-Mercury

Nondirectional (metals)

smallest

Directional
inter-chain (polymer)
inter-molecular

PROPERTIES FROM BONDING:

Energy versus bond length

Bond length, r
F

r
Bond energy, Eo
Energy (r)
unstretched length
ro

E o=
bond energy

PROPERTIES FROM BONDING: TM

Melting Temperature, Tm
Energy (r)
ro
r
smaller Tm
larger Tm
Tm is larger if Eo is larger.

PROPERTIES FROM BONDING:

EElastic modulus, E cross
sectional
area A o

length, L o

undeformed

deformed

Elastic modulus
F
L
=E
Ao
Lo

E similar to spring constant

E ~ curvature at ro
Energy
unstretched length
ro

E is larger if curvature is larger.

smaller Elastic Modulus

larger Elastic Modulus

PROPERTIES FROM BONDING:

Coefficient of thermal expansion,

coeff. thermal expansion

length, L o

unheated, T1

L
=(T2-T 1)
Lo

heated, T2

~ symmetry at ro
Energy
ro

r
larger

smaller

is larger if Eo is smaller
and very asymmetric.

Why does thermal expansion

occur?Bond Energy vs. Distance Curve is
asymmetric

As atoms vibrate, easy to move apart, but

difficult to move closer
As temperature increases, average bond length
increases.

SUMMARY: BONDING IN
MATERIALS
Ceramics

Large bond energy

(Ionic & covalent bonding):

Metals
(Metallic bonding):

Polymers
(Covalent & Secondary):

large Tm
large E
small

Variable bond energy

moderate Tm
moderate E
moderate

Secondary bonding dominates

small Tm
small E
large

2 Metallic Crystal
Structures
How can we stack metal atoms to
minimize empty space?
2-dimensions

vs.

Now stack these 2-D layers to make 3-D structures

Metallic Crystal Structures

Tend to be densely packed.
Reasons for dense packing:

- Typically, only one element is present, so all atomic

radii are the same.
- Metallic bonding is not directional.
- Nearest neighbor distances tend to be small in
order to lower bond energy.
- Electron cloud shields cores from each other
Have the simplest crystal structures.
We will examine three such structures...

2.1 Face Centered Cubic Structure

(FCC)
Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

Coordination # = 12

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

(Courtesy P.M. Anderson)

Atomic Packing Factor:

APF for a face-centered cubic structure = 0.74
FCC
maximum achievable APF
Close-packed directions:
length = 4R =

2a

2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
=

a
Adapted from
Fig. 3.1(a),
Callister 7e.

atoms
unit cell
APF =

4 atoms/unit cell

( 2 a/4 ) 3

3
a3

volume
atom
volume
unit cell

Linear Density

Number of atoms

Linear Density of Atoms LD =

Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
a

LD
length

2
2a

3.5 nm1

FCC Stacking Sequence

ABCABC... Stacking Sequence
2D Projection
BB
A sites
BB sites
sites

BB

C
BB

C
BB

BB

BB

BB

C sites

FCC Unit Cell

A
B
C

2.2 Body Centered Cubic Structure

(BCC)
Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

ex: Cr, W, Fe (), Tantalum, Molybdenum

Coordination # = 8

Adapted from Fig. 3.2,

Callister 7e.

2 atoms/unit cell: 1 center + 8 corners x 1/8

(Courtesy P.M. Anderson)

Atomic Packing Factor:

APF for a body-centered cubic structure = 0.68
BCC
3a
a

2a
Close-packed directions:
R
atoms

unit cell
APF =

length = 4R =

Adapted from
Fig. 3.2(a), Callister
7e.

( 3 a/4 ) 3

3
a3

volume
atom
volume
unit cell

3a

Example

Iron foil can be used as a catalyst. The

atomic packing of the exposed planes is
important.
a) Draw (100) and (111) crystallographic
planes
for Fe.
b) Calculate the planar density for each of
these planes.

Planar Density of (100)

Iron
Solution: At T < 912C iron has the BCC
structure.

2D repeat unit
(100)

Planar Density =
area
2D repeat unit

a2

4 3
R
3

Radius of iron R = 0.1241 nm

Adapted from Fig. 3.2(c), Callister 7e.

atoms
2D repeat unit

1
4 3
R
3

= 12.1atoms=

nm2

atoms
1.2 x 10
m2
19

Planar Density of (111) Iron

Solution (cont): (111) plane
1 atom in plane/ unit surface
cell

2a

atoms in plane

at
un
it

atoms above plane

rep
e

atoms below plane

2D

3
a
2

4 3
16 3 2

area 2 ah 3 a 3
R
R

3
3

atoms
2D repeat unit

Planar Density =
area
2D repeat unit

16 3
3

R2

atoms =
7.0
nm2

0.70 x 1019

atoms
m2

2.3 Hexagonal Close-Packed Structure (HCP)

ABAB... Stacking Sequence
3D Projection

2D Projection
A sites

Top layer

B sites

Middle layer

A sites

Bottom layer

Adapted from Fig. 3.3(a),

Callister 7e.

Coordination # = 12
APF = 0.74
c/a = 1.633

6 atoms/unit cell
ex: Cd, Mg, Ti, Zn

f13_03_pg62

f14_03_pg62

f15_03_pg63

HCP Crystallographic
DirectionsAlgorithm
z

a2

a3
a1

Adapted from Fig. 3.8(a), Callister 7e.

ex:

, , -1, 0

=>

1.Vector repositioned (if necessary) to

pass
through origin.
2.Read off projections in terms of unit
cell dimensions a1, a2, a3, or c
3.Adjust to smallest integer values
4.Enclose in square brackets, no
a2
commas
-a3
a2
[uvtw]
[ 1120 ]

a3

a1
2

dashed red lines indicate

projections onto a1 and a2 axes

a1

HCP Crystallographic Directions

Hexagonal Crystals
4 parameter Miller-Bravais lattice coordinates
are related to the direction indices (i.e.,
u'v'w') as follows.
z

[ u 'v ' w ' ] [ uvtw ]

u
a2

v
-

a3
a1
Fig. 3.8(a), Callister 7e.

1
3
1
3

( 2 u ' - v ')

( 2 v ' - u ')

t - ( u +v )
w w'

Crystallographic Planes
(HCP)
In hexagonal unit cells the same idea is
used
example
1.
Intercepts
2.
Reciprocals
3.

Reduction

a1
1
1
1
1

a2

1/
0
0

a3
-1
-1
-1
-1

c
1
1
1
1

a2

a3

4.

Miller-Bravais Indices (1011)

a1
Adapted from Fig. 3.8(a), Callister 7e.

1.2.4 Simple Cubic Structure

(SC)
Rare due to low packing denisty (only Po has this structure)
Close-packed directions are cube edges.

Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

Atomic Packing Factor

(APF)
Volume of atoms in unit cell*
APF =

Volume of unit cell

*assume hard spheres

APF for a simple cubic structure = 0.52
volume
atoms
a

unit cell
R=0.5a

APF =

4
3
a3

close-packed directions
contains 8 x 1/8 =
1atom/unit cell
Adapted from Fig. 3.23,
Callister 7e.

(0.5a) 3

atom

volume
unit cell

1.3 Theoretical Density,

Density = =

where

Mass of AtomsinUnit Cell

Total Volume of Unit Cell
nA
VC NA

n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.023 x 1023 atoms/mol

Theoretical Density,

atoms
unit cell

=
volume
unit cell

2 52.00
a 3 6.023 x 1023

Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
a = 4R/ 3 = 0.2887 nm
g
mol

theoretical

= 7.18 g/cm3

actual

= 7.19 g/cm3

atoms
mol

Densities of Material
Classes

In general

metals > ceramics > polymers

30

Why?

20

Metals have...

less dense packing

often lighter elements

Polymers have...

(g/cm3 )

close-packing
10
(metallic bonding)
often large atomic masses

Ceramics have...

low packing density

(often amorphous)
lighter elements (C,H,O)

Composites have...
intermediate values

Metals/
Alloys

5
4
3
2

Platinum
Gold, W
Tantalum
Silver, Mo
Cu,Ni
Steels
Tin, Zinc
Titanium
Aluminum
Magnesium

Graphite/
Ceramics/
Semicond

Polymers

Composites/
fibers

Based on data in Table B1, Callister

*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
60% volume fraction of aligned fibers
in an epoxy matrix).
Zirconia
Al oxide
Diamond
Si nitride
Glass -soda
Concrete
Silicon
Graphite

Glass fibers
PTFE
Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE

0.5
0.4

GFRE*
Carbon fibers
CFRE *
Aramid fibers
AFRE *

Wood

0.3
Data from Table B1, Callister 7e.

t01_03_pg41

1.4 Crystals as Building Blocks

Some engineering applications require single crystals:

--diamond single
crystals for abrasives
(Courtesy Martin
Deakins,
GE Superabrasives,
Worthington, OH. Used
with permission.)

--turbine blades
Fig. 8.33(c), Callister 7e.
(Fig. 8.33(c) courtesy
of Pratt and Whitney).

Properties of crystalline materials

often related to crystal structure.

--Ex: Quartz fractures more

easily along some crystal
planes than others.
(Courtesy P.M. Anderson)

Polycrystals
Most engineering materials are polycrystals.

1 mm

Nb-Hf-W plate with an electron beam weld.

Each "grain" is a single crystal.
If grains are randomly oriented,

Anisotropic

Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)

Isotropic

overall component properties are not directional.

Grain sizes typ. range from 1 nm to 2 cm

(i.e., from a few to millions of atomic layers).

Single vs Polycrystals
Single Crystals

E (diagonal) = 273 GPa

-Properties vary with

direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
Polycrystals

-Properties may/may not

vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)

-If grains are textured,

anisotropic.

E (edge) = 125 GPa

200 m

Data from Table 3.3,

Callister 7e.
(Source of data is
R.W. Hertzberg,
Deformation and
Fracture Mechanics
of Engineering
Materials, 3rd ed.,
John Wiley and Sons,
1989.)

Adapted from Fig.

4.14(b), Callister 7e.
(Fig. 4.14(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].)

t03_03_pg66

f17_03_pg65

1.5 Polymorphism

Two or more distinct crystal structures for the

same material (allotropy/polymorphism)
iron system

titanium
liquid

, -Ti
1538C

carbon
diamond, graphite

BCC

-Fe
1394C

FCC

-Fe
912C

BCC

-Fe

1.6 X-Ray Diffraction

Diffraction gratings must have spacings comparable

to the wavelength of diffracted radiation.
Cant resolve spacings
Spacing is the distance between parallel planes of
atoms.

Measurement of
critical angle, c,
allows computation
of planar spacing,
d.

ou

tg

n
oi

ra
X

te
ct
or
reflections must
ys
2

1
g

in
2
m
co ys
in -ra
X

extra
distance
travelled
by wave 2

X-Rays to Determine Crystal

Incoming X-rays diffract from crystal planes.
Structure
de

be in phase for
a detectable signal
Adapted from Fig.
3.19, Callister 7e.

spacing
d between
planes

X-ray
intensity
(from
detector)

n
2 sinc

Figure 3.44 Photograph of a XRD

diffractometer. (Courtesy of H&M
Analytical Services.)

X-Ray
Diffraction
Pattern
z
z
z
Intensity (relative)

y (110)

c
y

b
(211)

(200)

Diffraction angle
Diffraction pattern2
for polycrystalline -iron (BCC)
Adapted from Fig. 3.20, Callister 5e.

Figure 3.46 Photograph of a

transmission electron microscope
(TEM) used for analysis of the
microstructure of materials. (Courtesy
of JEOL USA, Inc.)

Figure 3.47 A TEM micrograph of an aluminum alloy (Al7055) sample. The diffraction pattern at the right shows
large bright spots that represent diffraction from the main
aluminum matrix grains. The smaller spots originate from
the nano-scale crystals of another compound that is
present in the aluminum alloy. (Courtesy of Dr. Jrg M.K.
Wiezorek, University of Pittsburgh.)

SUMMARY

Materials can be single crystals or polycrystalline.

Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are
generally
non-directional (i.e., they are isotropic) in polycrystals
with randomly oriented grains.
There are 7 crystal systems and 14 crystal structures
(lattices). FCC, BCC and HCP are the three most
common crystal structures for metals.

Some materials can have more than one crystal

structure. This is referred to as polymorphism (or
allotropy).
X-ray diffraction is used for crystal structure and
interplanar spacing determinations.

CHAPTER 4:
DEFECTS IN SOLIDS
1 mole Fe = 55.85g; V= 7.10 cm3 (D=7.87g/cm3); 6 x
1023 atoms
It would be nearly impossible to arrange so many atoms in
exact
3D periodicity. So, formation of defects is not unexpected!

ISSUES TO ADDRESS...

What types of defects arise in solids?

How do defects affect material properties?
Are defects undesirable?

63

Defects 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.

64

Types of Imperfections
Vacancy atoms
Interstitial atoms
Substitutional atoms

Point defects

Dislocations

Line defects

Grain Boundaries

Area defects

65

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

Vacancy
distortion
of planes
Self-Interstitials:

-"extra" atoms positioned between atomic sites.

distortion
of planes

selfinterstitial

66

Equilibrium Concentration:
Point Defects
Equilibrium concentration varies with temperature!
Activation energy

No. of defects

No. of potential
defect sites.

Q v
Nv
exp
kT
N

unitless; probability

Boltzmann's constant
(1.38 x 10 -23
(8.62 x 10 -5
Each lattice site

Absolute
Temperature

J/atom-K)
eV/atom-K)

1 eV = 1.6 x 10-19 J

is a potential
vacancy site
67

Measuring Activation
Energy

Q v
Nv
=exp
N
kT

We can get Qv from

an experiment.
Measure this...

Replot it...

Nv
ln

Nv
N

slope
- Q v /k

exponential
dependence!
T

1/ T

defect concentration
68

Estimating Vacancy
Concentration
Find the equil. # of vacancies in 1 m of Cu at 1000C.
3

Given:
= 8.4 g / cm 3
Q

A Cu

= 0.9 eV/atom

NA

Q v
Nv
exp
kT
N
For 1 m

,N= x

NA

= 63.5 g/mol
= 6.02 x 1023

atoms/mol

0.9 eV/atom

Cu T =1083 C, so at T~T

-4~ 1/10 sites are vacant

=
2.7
x
10

(general rule)

1273K

8.62 x 10-5
x 1 m3

eV/atom-K

= 8.0 x 1028 sites

A Cu

Answer:
Nv

(2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies

69

Point
Defects
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 solid
soln.
(e.g., Cu in Ni)

Insterstitial site can

be calculated using
simple geometry.

Interstitial solid
soln.
(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.

70

Imperfections in Solids
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

71

Imperfections in Solids
Application of HumeRothery rules Solid
Solutions
Element Atomic Crystal Electro- Valence
1. Would you predictCu
C
more Al or Ag
H
O
to dissolve in Zn? Ag
2. More Zn or Al
in Cu?

Al
Co
Cr
Fe
Ni
Pd
Zn

Radius Structure nega(nm)

tivity
0.1278
0.071
0.046
0.060
0.1445
0.1431
0.1253
0.1249
0.1241
0.1246
0.1376
0.1332

FCC

1.9

+2

FCC
FCC
HCP
BCC
BCC
FCC
FCC
HCP

1.9
1.5
1.8
1.6
1.8
1.8
2.2
1.6

+1
+3
+2
+3
+2
+2
+2
+2

Table on p. 106, Callister 7e.

72

Imperfections in Solids

Specification of composition
weight percent

m1
C1
x 100
m1 m2

m1 = mass of component 1

atom percent

n m1
C
x 100
n m1 n m 2
'
1

nm1 = number of moles of component 1

73

Line Defects in Solids

One dimensional defect in which atoms are mispositioned.

Edge Dislocation

Fig. 4.3, Callister 7e.

74

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 to dislocation line

Screw dislocation:

spiral planar ramp resulting from shear deformation

b to dislocation line
Burgers vector, b: measure of lattice distortion

75

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.
materials can be deformed rather easily

Atomic view of edge

dislocation motion from
left to right as a crystal
is sheared.

(Courtesy P.M. Anderson)

76

Line Defects in Solids

Screw Dislocation
Screw Dislocation

Dislocation
line
Burgers vector
b

b
(b)
(a)

Adapted from Fig. 4.4, Callister 7e.

77

Edge, Screw, and Mixed

Dislocations Mixed

Edge

Adapted from Fig. 4.5, Callister 7e.

Screw

78

Imperfections in Solids
Dislocations are visible in electron
micrographs

Adapted from Fig. 4.6, Callister 7e.

79

Planar Defects in Solids

One case is a twin boundary (plane)

Essentially a reflection of atom positions across

the twin plane.

Adapted from Fig. 4.9, Callister 7e.

Stacking faults

For FCC metals an error in ABCABC packing

sequence
Ex: ABCABABC
80

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 7e.

81

Microscopic Examination

Crystallites (grains) and grain

boundaries. Vary considerably in size.
Can be quite large
ex: Large single crystal of quartz or diamond
or Si
ex: Aluminum light post or garbage can see the individual grains

Crystallites (grains) can be quite small

(mm or less) necessary to observe
with a microscope.
82

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 7e. (Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.

Micrograph of
brass (a Cu-Zn alloy)
0.75mm
83

Optical
Microscopy
Grain boundaries...
are imperfections,
are more susceptible
to etching,
may be revealed as
dark lines,
change in crystal
orientation across
boundary.

polished surface

(a)

surface groove
grain boundary

ASTM grain
size number
N = 2 n -1
number of grains/in2
at 100x
magnification

Fe-Cr alloy

Adapted from Fig. 4.14(a)

and (b), Callister 7e.
(Fig. 4.14(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].)

(b)
84

Microscopy
Optical resolution ca. 10-7 m = 0.1 m = 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.

85

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.

Carbon monoxide
molecules
arranged on a
platinum (111)
surface.

Iron atoms
arranged on a
copper (111)
surface. These
Kanji characters
represent the word
atom.
86

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.)

87

Homework
4.3, 4.5, 4.7, 4.16, 4.19, 4.23, 4.27
Due in one week

88