ME F213 & MF F213

Materials Science & Engineering

Learning Objectives
Learn to classify materials

ISSUES TO ADDRESS...
What promotes bonding?
What types of bonds are there?
What properties are inferred from bonding?

Atomic Structure (Freshman Chem.)

atom

electrons 9.11 x 10-31 kg

protons
1.67 x 10-27 kg
neutrons

atomic number = # of protons in nucleus of atom

= # of electrons of neutral species

C
H

12.011
1.008 etc.

1 atomic mass unit (amu) = (1/12 mass of 12C)/NAv

Atomic Structure
Valence electrons determine all of the
following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical

Electronic Structure
Electrons have wavelike and particulate
properties.
This means that electrons are in orbitals defined
by a probability.
Each orbital at discrete energy level determined
by quantum numbers.
Quantum #

Designation

n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)

l = subsidiary (orbitals)
s, p, d, f (0, 1, 2, 3,, n -1)
ml = magnetic
1, 3, 5, 7 (-l to +l)
ms = spin

, -
5

Electron Energy States

Electrons...

have discrete energy states

tend to occupy lowest available energy state.
4d
4p

N-shell n = 4

3d
4s
Energy

3p
3s

M-shell n = 3
Adapted from Fig. 2.4,
Callister 7e.

2p
2s

L-shell n = 2

1s

K-shell n = 1
6

SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Element
Hydrogen
Helium
Lithium
Beryllium
Boron
Carbon
...

Atomic #
1
2
3
4
5
6

Electron configuration
1s 1
1s 2
(stable)
1s 2 2s 1
1s 2 2s 2
1s 2 2s 2 2p 1
1s 2 2s 2 2p 2
...

From Table 2.2

Callisters Materials Science
and Engineering,
Adapted Version.

Neon
Sodium
Magnesium
Aluminum
...

10
11
12
13

1s 2 2s 2 2p 6
(stable)
1s 2 2s 2 2p 6 3s 1
1s 2 2s 2 2p 6 3s 2
1s 2 2s 2 2p 6 3s 2 3p 1
...

Argon
...
Krypton

18
...
36

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)

Why? Valence (outer) shell usually not filled completely.

7

Electron Configurations
Valence electrons those in unfilled
shells
Filled shells more stable
Valence electrons are most available for
bonding and tend to control the chemical
properties
example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

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

Columns: Similar Valence Structure

accept 2e
accept 1e
inert gases

The Periodic Table

He

Li Be

F Ne

Na Mg

Cl Ar

K Ca Sc
Rb Sr

Cs Ba

Se Br Kr
Te

Xe

Po At Rn

From Fig. 2.6

Callisters
Materials
Science and
Engineering,
Adapted
Version.

Fr Ra

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

Electronegative elements:
Readily acquire electrons
to become - ions.
9

Electronegativity
Ranges from 0.7 to 4.0,
Large values: tendency to acquire electrons.

Smaller electronegativity

Larger electronegativity

From Fig. 2.7, Callisters Materials Science and Engineering, Adapted Version.
(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.
10

Ionic bond metal

donates
electrons

nonmetal
accepts
electrons

Dissimilar electronegativities
ex: MgO

Mg

1s2 2s2 2p6 3s2

[Ne] 3s2

Mg2+ 1s2 2s2 2p6

[Ne]

1s2 2s2 2p4

O2- 1s2 2s2 2p6

[Ne]
11

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

12

Ionic Bonding
Energy minimum energy most stable
Energy balance of attractive and repulsive
terms
A

EN = EA + ER =

B
rn

Repulsive energy ER

Interatomic separation r
Net energy EN

Attractive energy EA

From Fig. 2.8(b),

Callisters Materials
Science and Engineering,
Adapted Version.

13

Examples: Ionic Bonding

Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons

Acquire electrons

From Fig. 2.7, Callisters Materials Science and Engineering, Adapted Version.
(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.
14

f09_02_pg27

Covalent Bonding
similar electronegativity share electrons
bonds determined by valence s & p orbitals
dominate bonding
Example: CH4
C: has 4 valence e-,
needs 4 more
H: has 1 valence e-,
needs 1 more
Electronegativities
are comparable.

CH 4
H

shared electrons
from carbon atom

H
shared electrons
from hydrogen
atoms

From Fig. 2.10

Callisters Materials Science and Engineering, Adapted Version.

16

Primary Bonding
Metallic Bond -- delocalized as electron cloud
Ionic-Covalent Mixed Bonding

% ionic character

(X A -X B )2

4
1e
=
x (100%)

where XA & XB are Pauling electronegativities

Ex: MgO

XMg = 1.3
XO = 3.5

(3.5 -1.3)2

4
% ionic character 1 - e

x (100%) 70.2% ionic

17

SECONDARY BONDING
Arises from interaction between dipoles
Fluctuating dipoles
asymmetric electron
clouds

+
secondary
bonding

ex: liquid H 2
H2
H2

H H

H H
secondary
bonding

From Fig. 2.13

Callisters Materials Science and Engineering, Adapted Version.

Permanent dipoles-molecule induced

-general case:
-ex: liquid HCl
-ex: polymer

H Cl

secondary
bonding

secondary
bonding

H Cl

From Fig. 2.14

Callisters Materials Science and
Engineering
Adapted Version.

secondary bonding
18

Summary: Bonding
Comments

Type

Bond Energy

Ionic

Large!

Nondirectional (ceramics)

Covalent

Variable
large-Diamond
small-Bismuth

Directional
(semiconductors, ceramics
polymer chains)

Metallic

Variable
large-Tungsten
small-Mercury

Nondirectional (metals)

Secondary

smallest

Directional
inter-chain (polymer)
inter-molecular
19

Properties From Bonding: Tm

Bond length, r

Melting Temperature, Tm
Energy

Bond energy, Eo

ro

Energy

r
smaller Tm

unstretched length
ro

Eo =
bond energy

larger Tm
Tm is larger if Eo is larger.

20

Properties From Bonding : a

Coefficient of thermal expansion, a
length, L o
coeff. thermal expansion
unheated, T1

DL
= a(T2 -T1)
Lo

DL

heated, T 2

a ~ symmetry at ro
Energy
unstretched length
ro

E
o

E
o

a is larger if Eo is smaller.

smaller a
larger a
21

Summary: Primary Bonds

Ceramics
(Ionic & covalent bonding):

Metals
(Metallic bonding):

Polymers
(Covalent & Secondary):

Large bond energy

large Tm
large E
small a

Variable bond energy

moderate Tm
moderate E
moderate a

Directional Properties
Secondary bonding dominates
small Tm
small E
large a

22

Fundamentals of Structure of
Crystalline Solids
ISSUES TO ADDRESS...
How do atoms assemble into solid structures in
crystalline and non-crystalline materials?
How do we specify directions and planes in
unit cells?
How do we distinguish between single crystals
and polycrystalline materials?
When do material properties vary with the
sample (i.e., part) orientation?
23

Linus Pauling (1901-1994)

Nobel prize in
Chemistry in
1954

24

Platonic Solids

25

Penrose tilings

26

Energy and Packing

Non dense, random packing

Energy
typical neighbor
bond length

typical neighbor
bond energy

Dense, ordered packing

Energy
typical neighbor
bond length

typical neighbor
bond energy

Dense, ordered packed structures tend to have

lower energies.
27

Materials and Packing

Crystalline materials...
atoms pack in periodic, 3D arrays
typical of: -metals
-many ceramics
-some polymers

crystalline SiO2
From Fig. 3.10(a)
Callisters Materials Science and Engineering,
Adapted Version.

Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline

Si

Oxygen

noncrystalline SiO2
From Fig. 3.10(b)
Callisters Materials Science and Engineering,
Adapted Version.
28

Quasi-crystals

Daniel Shchetman
Nobel prize in Chemistry (2011)

29

Section 3.3 Crystal Systems

Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems

14 crystal lattices

a, b, and c are the lattice constants

Fig. 3.2
Callisters Materials
Science and
Engineering,
Adapted Version.

30

Section 3.5 Point Coordinates

z

Point coordinates for unit cell

center are

111

a/2, b/2, c/2

y

000

a
x

Point coordinates for unit cell

corner are 111

2c

b
b

Translation: integer multiple

of lattice constants
identical position in
another unit cell
31

Crystallographic Directions
z

Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

[uvw]

ex: 1, 0, => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ]

where overbar represents a

negative index

families of directions <uvw>

32

HCP Crystallographic Directions

z

Algorithm

a2

a3
a1

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 commas
[uvtw]
a
2

ex:

, , -1, 0

=>

[ 1120 ]

-a3

a2
2

From Fig. 3.6(a)

Callisters Materials Science and Engineering, Adapted Version.

a3

dashed red lines indicate

projections onto a1 and a2 axes

a1
2

a1
33

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 ]

a2

a3
a1

1
u (2 u ' - v ')
3
1
v (2 v ' - u ')
3
t - (u +v )
w w'

Fig. 3.6(a)
Callisters Materials Science and Engineering,
Adapted Version.
34

Crystallographic Planes

From Fig. 3.7

Callisters Materials Science and Engineering,
Adapted Version.

35

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
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)

36

Crystallographic Planes
z
example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1
1/1
1
1

4.

Miller Indices

(110)

example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1/2
1/
2
2

4.

Miller Indices

(100)

b
1
1/1
1
1

1/
0
0

c
y
b

a
x

1/
0
0

1/
0
0

z
c

y
a

x
37

Crystallographic Planes
z
example
1. Intercepts
2. Reciprocals
3.

Reduction

4.

Miller Indices

a
1/2
1/
2
6

b
1
1/1
1
3

(634)

c
c
3/4
1/
4/3

4 a
x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)
38

Crystallographic Planes (HCP)

In hexagonal unit cells the same idea is
z
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
From Fig. 3.6(b)
Callisters Materials Science and Engineering,
Adapted Version.

39

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. 11.33(c)
Callisters Materials
Science and
Engineering,
Adapted Version.
(Fig.11.33(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)

40

Polycrystals
Most engineering materials are polycrystals.

Anisotropic

From Fig. K, color inset

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

1 mm
Nb-Hf-W plate with an electron beam weld.
Each "grain" is a single crystal.
If grains are randomly oriented,

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).

41

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 mm

Data from Table 3.2,

Callisters Materials
Science and
Engineering,
Adapted Version.
(Source of data is R.W.
Hertzberg, Deformation
and Fracture Mechanics
of Engineering
Materials, 3rd ed., John
Wiley and Sons, 1989.)

From Fig. 5.19(b),

Callisters Materials
Science and
Engineering,
Adapted Version.
(Fig. 5.19(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].)
42

SUMMARY
Atoms may assemble into crystalline or
amorphous structures.
Crystallographic points, directions and planes are
specified in terms of indexing schemes.
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.

43