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Chapter 1 - Introduction
What is materials science?
Why should we know about it?
Materials drive our society
Stone Age
Chapter 1 - 7
Bronze Age
Iron Age
In the 1970s and 80s Metallurgy
became Materials Science,
In the 90s Materials Science
Materials Science Now
Chapter 1 - 8
increasingly shifts focus to
semiconductor industry.
In the 21st century Materials
Science increasingly focuses on the
atomic and molecular scale control.
Teaching Materials Science
Chapter 1 -
Engineers make things out of materials, using processes.
Philosophy of the approach
What do they need to know to do this successfully?
An ability to select those that best meet requirements of a design
Access to information and tools for comparison and
selection
An understandi ng material properties and their origins
The Materials Selection Process
Performance requirements
efficiency, cost, environmental impact, safety
Properties necessary to meet
performance requirements
mechanical, electrical, thermal, magnetic, Processing
Properties
Structure
Performance
Chapter 1 - 10
optical, deteriorative
material Structure to achieve required properties
single crystal, polycrystal, amorphous, single phase, multiphase
Processing methods to obtain required structure
casting, sintering, vapor deposition, doping, joining, annealing
Todaysclass:
Atomicbondings
Crystalstructures
Chapter 2 - 11
Tailored(Designed)MaterialAge
Compositions
Atomic arrangements
Properties
Chapter 2 -
Tailormaterialsfromatomicscaleupwardsto
obtaindesiredproperties.
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Atomic Structure (Freshman Chem.)
atom electrons 9.11 x 10
-31
kg
protons
neutrons
atomic number =#of protons in nucleus of atom
#of electrons of ne tral species
}1.67 x 10
-27
kg
Composition DifferencesinAtomicStructures
=#of electrons of neutral species
A [=] atomic mass unit =amu = 1/12 mass of
12
C
Atomic wt =wt of 6.023 x 10
23
molecules or atoms
1 amu/atom =1g/mol
C 12.011
H 1.008 etc. 13
ElectronicStructure
Electronshavewavelikeandparticulateproperties.
Thismeansthatelectronsareinorbitals definedbya
probability.
Eachorbitalatdiscreteenergyleveldeterminedby
quantumnumbers.
14
Quantum# Designation
n =principal(energylevelshell) K,L,M,N,O (1,2,3,etc.)
l=subsidiary(orbital) s,p,d,f (0,1,2,3,,n1)
#oforbitalseachsubshell 1,3,5,7(lto+l)
m
s
=spin ,
ElectronEnergyStates
3d
4p
4d
N-shell n = 4
have discrete energy states
tend to occupy lowest available energy state.
Electrons...
1s
2s
2p
K-shell n = 1
L-shell n = 2
3s
3p M-shell n = 3
4s
Energy
15
ElectronicConfigurations
ex: Fe - atomic # = 26
valence
electrons
3d
4s
4p
4d
N-shell n =4
1s
2
2s
2
2p
6
3s
2
3p
6
3d
6
4s
2
1s
2s
2p
K-shell n =1
L-shell n =2
3s
3p M-shell n =3
4s
Energy
16
ElectronConfigurations
Valenceelectrons thoseinunfilledshells
Filledshellsmorestable
Valenceelectronsaremostavailablefor
bondingandtendtocontrolthechemical
properties
17
properties
example: C (atomic number =6)
1s
2
2s
2
2p
2
valence electrons
Electronic configuration
Valenceelectronsdetermineallofthe
followingproperties
1) Chemical
2) Electrical
Chapter 2 -
3) Thermal
4) Optical
18
Mostdifferentpropertiesresultfromdistinct
electronicstructuresofmaterials.
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Most elements: Electron configuration not stable.
SURVEY OF ELEMENTS
Electron configuration
(stable)
...
Atomic # Element
1s
1
1 Hydrogen
1s
2
2 Helium
1s
2
2s
1
3 Lithium
1s
2
2s
2
4 Beryllium
1s
2
2s
2
2p
1
5 Boron
1s
2
2s
2
2p
2
6 Carbon
...
Valence (outer) shell usually not filled completely.
...
...
1s
2
2s
2
2p
6
3s
2
3p
6
(stable)
...
1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
(stable)
18
...
36
...
1s
2
2s
2
2p
6
(stable) 10 Neon
1s
2
2s
2
2p
6
3s
1
11 Sodium
1s
2
2s
2
2p
6
3s
2
12 Magnesium
1s
2
2s
2
2p
6
3s
2
3p
1
13 Aluminum
...
Argon
...
Krypton
19
ThePeriodicTable
Columns: Similar Valence Structure
g
i
v
e

u
p

1
e
g
i
v
e

u
p

2
e
v
e

u
p

3
e
i
n
e
r
t

g
a
s
e
s
a
c
c
e
p
t

1
e
a
c
c
e
p
t

2
e
O
He
Ne F Li Be
H
Adaptedfrom
Fig. 2.6,
Callister 7e.
Electropositive elements:
Readily give up electrons
to become +ions.
Electronegative elements:
Readily acquire electrons
to become - ions.
g
i
vO
Se
Te
Po At
I
Br
Ne
Ar
Kr
Xe
Rn
F
Cl S
Li Be
Na Mg
Ba Cs
Ra Fr
Ca K Sc
Sr Rb Y
20
Ranges from 0.7 to 4.0,
Large values: tendency to acquire electrons.
Electronegativity
Smaller electronegativity Larger electronegativity
21
Occurs between +and - ions.
Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl
Ionic Bonding
Na (metal) Cl (nonmetal)
Chapter 2 - 22
( )
unstable
( )
unstable
electron
+
-
Coulombic
Attraction
Na (cation)
stable
Cl (anion)
stable
Ionic bond metal + nonmetal
donates accepts
electrons electrons
Dissimilar electronegativities
Chapter 2 - 23
ex: MgO Mg 1s
2
2s
2
2p
6
3s
2
O 1s
2
2s
2
2p
4
[Ne] 3s
2
Mg
2+
1s
2
2s
2
2p
6
O
2-
1s
2
2s
2
2p
6
[Ne] [Ne]
Predominant bonding in Ceramics
Examples: Ionic Bonding
NaCl
MgO
CaF
2
CsCl
Chapter 2 - 24
AdaptedfromFig. 2.7, Callister 7e. (Fig. 2.7 is adaptedfromLinus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939and 1940, 3rd edition. Copyright 1960by Cornell University.
Give up electrons Acquire electrons
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Covalent Bonding
similar electronegativity share electrons
bonds determined by valence s & p orbitals
dominate bonding.
Bond is directional.
Example: CH
4
shared electrons
from carbon atom
H
CH
4
Chapter 2 - 25
C: has 4 valence e
-
,
needs 4 more
H: has 1 valence e
-
,
needs 1 more
Electronegativities
are comparable. AdaptedfromFig. 2.10, Callister 7e.
shared electrons
from hydrogen
atoms
H H
H
C
Examples: Covalent Bonding
H
2
O
C (diamond)
SiC
F
2
Chapter 2 -
GaAs
Molecules with non-metals
Molecules with metals and nonmetals
Elemental solids (RHS of Periodic Table)
Compound solids
Arises from interaction between dipoles
Fluctuating dipoles
AdaptedfromFig 2 13 Callister 7e
SECONDARY BONDING
asymmetric electron
clouds
+ - + -
secondary
bonding
H H H H
H
2
H
2
secondary
bonding
ex: liquid H
2
Chapter 2 - 27
Permanent dipoles-molecule induced
-general case:
-ex: liquid HCl
-ex: polymer
AdaptedfromFig. 2.13, Callister 7e.
AdaptedfromFig. 2.14,
Callister 7e.
bonding
bonding
H Cl H Cl
secondary
bonding
secondary
bonding
+ - + -
secondary bonding
Type
Ionic
Covalent
Bond Energy
Large!
Variable
large-Diamond
ll Bi th
Comments
Nondirectional (ceramics)
Directional
(semiconductors, ceramics
l h i )
Summary: Bonding
Chapter 2 - 28
Metallic
Secondary
small-Bismuth
Variable
large-Tungsten
small-Mercury
smallest
polymer chains)
Nondirectional (metals)
Directional
inter-chain (polymer)
inter-molecular
Ceramics
(Ionic & covalent bonding):
Metals
(Metallic bonding):
Large bond energy
large T
m
large E
small o
Variable bond energy
moderate T
m
moderate E
Summary: Primary Bonds
Chapter 2 - 29
Polymers
(Covalent & Secondary):
moderate E
moderate o
Directional Properties
Secondary bonding dominates
small T
m
small E
large o
Atomicarrangements:electronicstructuresof
materialsaredeterminedbyinteractionsoftheirvalence
electronswiththeirnucleiandcoreelectrons.
Crystalstructures:atomsarrangedinregular,repeating
manner,andthereisalongrangeorder.
Allcrystalshavediscretetranslationalsymmetry:Ifdisplaced
byaproperlyselectedlatticevector,everyatommovestothe
positionofanidenticalatominthecrystal.
Acrystalcanbeconstructedbyrepeatingthebasisatevery
Bravaislatticepoint.
Thebasisisthe``buildingblock"ofthecrystal,itmaycomprise
of1ormoreatoms.
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Crystal Systems
7 crystal systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
Chapter 3 - 31
14 crystal lattices
a, b, and c are the lattice constants
7 crystal
systems
14 crystal
lattices
(b i (bravais
lattices)
32
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
Metallic Crystal Structures
Chapter 3 - 33
- 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...
Rare due to low packing denisty(only Po has this structure)
Close-packed directions are cube edges.
Coordination #=6
(#nearest neighbors)
Simple Cubic Structure (SC)
Chapter 3 - 34
(CourtesyP.M. Anderson)
APF for a simple cubic structure =0.52
volume
Atomic Packing Factor (APF)
APF =
Volume of atoms in unit cell*
Volume of unit cell
*assume hard spheres
Chapter 3 - 35
APF =
a
3
4
3
t (0.5a)
3
1
atoms
unit cell
atom
volume
unit cell
volume
AdaptedfromFig. 3.23,
Callister 7e.
close-packed directions
a
R=0.5a
contains 8 x 1/8 =
1 atom/unit cell
Coordination #=12
Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
Face Centered Cubic Structure (FCC)
ex: Al, Cu, Au, Pb, Ni, Pt, Ag
Chapter 3 - 36
AdaptedfromFig. 3.1, Callister 7e.
(CourtesyP.M. Anderson)
4 atoms/unit cell: 6 face x 1/2 +8 corners x 1/8
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APF for a face-centered cubic structure =0.74
Atomic Packing Factor: FCC
maximum achievable APF
Close-packed directions:
length =4R = 2 a
Unit cell contains:
2 a
Chapter 3 - 37
APF =
4
3
t ( 2a/4)
3
4
atoms
unit cell
atom
volume
a
3
unit cell
volume
6 x1/2 +8 x1/8
=4 atoms/unit cell
a
Adaptedfrom
Fig. 3.1(a),
Callister 7e.
Coordination #=8
Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atomis shaded
differently only for ease of viewing.
Body Centered Cubic Structure (BCC)
ex: Cr, W, Fe (o), Tantalum, Molybdenum
Chapter 3 - 38
AdaptedfromFig. 3.2,
Callister 7e.
(CourtesyP.M. Anderson)
2 atoms/unit cell: 1 center +8 corners x 1/8
Atomic Packing Factor: BCC
a
APF for a body-centered cubic structure =0.68
a 2
a 3
Chapter 3 - 39
APF =
4
3
t ( 3a/4)
3
2
atoms
unit cell
atom
volume
a
3
unit cell
volume
length =4R =
Close-packed directions:
3 a
a
R
Adaptedfrom
Fig. 3.2(a), Callister 7e.
Theoretical Density,
Density = =
V
C
N
A
n A
=
Cell Unit of Volume Total
Cell Unit in Atoms of Mass
Chapter 3 - 40
where n =number of atoms/unit cell
A =atomic weight
V
C
=Volume of unit cell =a
3
for cubic
N
A
=Avogadros number
=6.023 x 10
23
atoms/mol
Ex: Cr (BCC)
A =52.00 g/mol
R =0.125 nm
n =2
Theoretical Density,
Chapter 3 - 41

theoretical
a =4R/ 3 =0.2887 nm

actual
a
R
=
a
3
52.00 2
atoms
unit cell
mol
g
unit cell
volume atoms
mol
6.023x10
23
=7.18 g/cm
3
=7.19 g/cm
3
Densities of Material Classes

metals >

ceramics >

polymers
Why?
)
Graphite/
Ceramics/
Semicond
Metals/
Alloys
Composites/
fibers
Polymers
20
30
Basedon data inTable B1, Callister
*GFRE, CFRE, &AFRE are Glass,
Carbon, &Aramid Fiber-Reinforced
Epoxycomposites (values basedon
60%volume fractionof aligned fibers
inanepoxy matrix). 10
5
Steels
Cu,Ni
Tin, Zinc
Silver, Mo
Tantalum
Gold, W
Platinum
Zirconia
Metals have...
close-packing
(metallic bonding)
often large atomic masses
C i h
In general
Chapter 3 - 42
Data fromTable B1, Callister 7e.

(
g
/
c
m


3
1
2
3
4
5
0.3
0.4
0.5
Magnesium
Aluminum
Titanium
Graphite
Silicon
Glass -soda
Concrete
Si nitride
Diamond
Al oxide
HDPE, PS
PP, LDPE
PC
PTFE
PET
PVC
Silicone
Wood
AFRE*
CFRE*
GFRE*
Glass fibers
Carbon fibers
Aramidfibers
Ceramics have...
less dense packing
often lighter elements
Polymers have...
low packing density
(often amorphous)
lighter elements (C,H,O)
Composites have...
intermediate values
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Crystallographic Directions
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
z Algorithm
y
Chapter 3 - 43
[uvw]
ex: 1, 0, => 2, 0, 1 => [201]
-1, 1, 1
families of directions <uvw>
x
where overbar represents a
negative index
[111] =>
Crystallographic Planes
Chapter 3 - 44
AdaptedfromFig. 3.9, Callister 7e.
Crystallographic Planes
Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions &
common multiples. All parallel planes have
same Miller indices.
Algorithm
Chapter 3 - 45
Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)
Crystallographic Planes
z
x
y
a b
c
4. Miller Indices (110)
1. Intercepts 1 1
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0
example a b c
Chapter 3 - 46
x
example a b c
z
x
y
a b
c
4. Miller Indices (100)
1. Intercepts 1/2
2. Reciprocals 1/ 1/ 1/
2 0 0
3. Reduction 1 0 0
Crystallographic Planes
z
y
a b
c
-
-
-
example
1. Intercepts 1/2 1 3/4
a b c
2. Reciprocals 1/ 1/1 1/
2 1 4/3
3 Reduction 6 3 4
Chapter 3 - 47
x
a b
4. Miller Indices (634)
3. Reduction 6 3 4
(001) (010),
Family of Planes {hkl}
(100), (010), (001), Ex: {100}=(100),
ex: linear density of Al in [110]
direction
a =0.405 nm
Linear Density
Linear Density of Atoms LD =
[110]
Unit length of direction vector
Number of atoms
Chapter 3 - 48
a 0.405 nm
a
#atoms
length
1
3.5 nm
a 2
2
LD

= =
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Planar Density of (100) Iron
Solution: At T <912C iron has the BCC structure.
(100)
R
3
3 4
a =
2D repeat unit
Chapter 3 - 49
Radius of iron R =0.1241 nm AdaptedfromFig. 3.2(c), Callister 7e.
= Planar Density =
a
2
1
atoms
2D repeat unit
=
nm
2
atoms
12.1
m
2
atoms
=1.2 x 10
19
1
2
R
3
3 4 area
2D repeat unit
Types of Materials
Metals: Metallic bonds-cationssurrounded by e clouds
Strong, ductile
high thermal & electrical conductivity
opaque, reflective.
Polymers/plastics: Covalent bonding sharing of es
Soft, ductile, low strength, low density
Chapter 1 - 50
thermal & electrical insulators
Optically translucent or transparent.
Ceramics: ionic bonding compounds of metallic & non-
metallic elements (oxides, carbides, nitrides, sulfides)
Brittle, glassy, elastic
non-conducting (insulators)