BONDING AND PROPERTIES

ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

Chapter 2 - 1
Atomic Structure (Freshman Chem.)
• atom – electrons – 9.11 x 10-31 kg
protons
neutrons } 1.67 x 10-27 kg

• atomic number = # of protons in nucleus of atom

= # of electrons of neutral species

• A [=] atomic mass unit = amu = 1/12 mass of 12C

Atomic wt = wt of 6.023 x 1023 molecules or atoms

1 amu/atom = 1g/mol
C 12.011
H 1.008 etc.

Chapter 2 - 2
 Atomic Structure

• Valence electrons determine all of the

following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical

Chapter 2 - 3
 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

Chapter 2 - 4
 The Periodic Table
• Columns: Similar Valence Structure

inert gases
give up 1e
give up 2e

accept 2e
accept 1e
give up 3e

H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister 7e.
K Ca Sc Se Br Kr
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
Chapter 2 - 5
 Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

[Ne] 3s2

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]

Chapter 2 - 6
 Ionic Bonding
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction

Chapter 2 - 7
 Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms
−
A −
B
EN = EA + ER =
r rn
Repulsive energy ER

Interatomic separation r

Net energy EN
Adapted from Fig. 2.8(b),
Callister 7e.

Attractive energy EA
Chapter 2 - 8
 Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister 7e. (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.

Chapter 2 - 9
 Covalent Bonding
• similar electronegativity ∴ share electrons
• bonds determined by valence – s & p orbitals
dominate bonding
• Example: CH4
shared electrons
H
C: has 4 valence e-, CH 4
from carbon atom
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10, Callister 7e.

Chapter 2 - 10
 Metallic Bonding
• Occurs between Metallic elements
• Ion Cores (+) surrounded by delocalized electrons (-)
• High electrical and thermal conductivity from “free
electrons”

Adapted from Fig. 2.11, Callister 7e.

Chapter 2 - 11
 Primary Bonding
• Metallic Bond -- delocalized as electron cloud

• Ionic-Covalent Mixed Bonding

 (X A −X B )2 
 − 
4
% ionic character = 1− e  x (100%)
 
 
where XA & XB are Pauling electronegativities
Ex: MgO XMg = 1.3
XO = 3.5

 (3.5 −1.3 )2 
 − 
% ionic character = 1 − e 4  x (100%) = 70.2% ionic
 
 
Chapter 2 - 12
 SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13, Callister 7e. bonding

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.14,
Callister 7e.
secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

Chapter 2 - 13
 Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
Chapter 2 - 14
 Properties From Bonding: Tm
• Bond length, r • Melting Temperature, Tm
Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
“bond energy”

Chapter 2 - 15
 Properties From Bonding : α
• Coefficient of thermal expansion, α
length, L o coeff. thermal expansion
unheated, T1
∆L ∆L
= α (T2 -T1)
heated, T 2 Lo

• α ~ symmetry at ro
Energy
unstretched length
ro
r α is larger if Eo is smaller.

E
smaller α
o
E larger α
o Chapter 2 - 16
 Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small α

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate α

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
large α

Chapter 2 - 17
 The Structure of Crystalline Solids

ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?
(for now, focus on metals)

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample (i.e., part) orientation?

Chapter 3 - 18
 Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have

lower energies.
Chapter 3 - 19
 Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.22(a),
Callister 7e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.22(b),
Callister 7e.

Chapter 3 - 20
 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. 3.4, Callister 7e.

Chapter 3 - 21
 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

Chapter 3 - 22
 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...

Chapter 3 - 23
 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)

Chapter 3 - 24
 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 atom
a 4
unit cell 1 π (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.23,
Callister 7e. Chapter 3 - 25
 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 (α), 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)
Chapter 3 - 26
 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
R length = 4R = 3 a
Adapted from
Fig. 3.2(a), Callister 7e.
a
atoms volume
4
unit cell 2 π ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell Chapter 3 - 27
 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)
Chapter 3 - 28
 Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2 a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 7e. atoms volume
4
unit cell 4 π ( 2a/4) 3
3 atom
APF =
3 volume
a
unit cell
Chapter 3 - 29
 Hexagonal Close-Packed Structure
(HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a Adapted from Fig. 3.3(a),
Callister 7e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 Chapter 3 - 30
 Theoretical Density, ρ

Mass of Atoms in Unit Cell

Density = ρ =
Total Volume of Unit Cell

nA
ρ =
VC NA

where n = number of atoms/unit cell

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

Chapter 3 - 31
 Theoretical Density, ρ
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
a a = 4R/ 3 = 0.2887 nm

atoms
g
unit cell 2 52.00 ρtheoretical = 7.18 g/cm3
mol
ρ= ρactual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol Chapter 3 - 32
 Densities of Material Classes
In general Graphite/
ρmetals > ρceramics > ρpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum
Based on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

ρ (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2 Carbon fibers
Polymers have... Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1 HDPE, PS
(often amorphous) PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3

Data from Table B1, Callister 7e.
Chapter 3 - 33
 Crystals as Building Blocks
• Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives Fig. 8.33(c), Callister 7e.
(Fig. 8.33(c) courtesy
(Courtesy Martin Deakins, of Pratt and Whitney).
GE Superabrasives,
Worthington, OH. Used with
permission.)

• Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)

Chapter 3 - 34
 Polycrystals Anisotropic
• Most engineering materials are polycrystals.

Adapted 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. Isotropic

• Each "grain" is a single crystal.
• If grains are randomly oriented,
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).
Chapter 3 - 35
 Single vs Polycrystals
• Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
E (diagonal) = 273 GPa
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.)
200 µm 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].)
Chapter 3 - 36
 Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
•
1538ºC
carbon
BCC δ-Fe
α, β-Ti
diamond, graphite 1394ºC
FCC γ-Fe
912ºC
BCC α-Fe

Chapter 3 - 37
 Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2 ½½½

000
y
a b
Point coordinates for unit cell
x • corner are 111
z 2c
•
Translation: integer multiple of
• • lattice constants  identical
b y position in another unit cell
b
Chapter 3 - 38
 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

x [uvw]

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a
negative index
families of directions <uvw>
Chapter 3 - 39
 Crystallographic Planes

Adapted from Fig. 3.9, Callister 7e.

Chapter 3 - 40
 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)

Chapter 3 - 41
 Crystallographic Planes
z
example a b c
1. Intercepts 1 1 ∞ c
2. Reciprocals 1/1 1/1 1/∞
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2 ∞ ∞ c
2. Reciprocals 1/½ 1/∞ 1/∞
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
Chapter 3 - 42
 Crystallographic Planes
z
example a b c c
1. Intercepts 1/2 1 3/4 •
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 • y
•
3. Reduction 6 3 4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

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

Chapter 3 - 43
 SUMMARY
• Atoms may assemble into crystalline or
amorphous structures.
• Common metallic crystal structures are FCC, BCC, and
HCP. Coordination number and atomic packing factor
are the same for both FCC and HCP crystal structures.
• We can predict the density of a material, provided we
know the atomic weight, atomic radius, and crystal
geometry (e.g., FCC, BCC, HCP).
• Crystallographic points, directions and planes are
specified in terms of indexing schemes.
Crystallographic directions and planes are related
to atomic linear densities and planar densities.

Chapter 3 - 44
 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.
• Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).

Chapter 3 - 45