Material 2

BITS Pilani
Pilani Campus
ENGG ZC 232 ENGINEERING MATERIALS. Lecture 2
( Bonding in solids and Crystal Structure)

Prof.P.Srinivasan.
Mechanical Engineering.
BITS Pilani
Pilani Campus
Bonding in solids and Crystal
strcuture.
BITS Pilani, Pilani Campus
Primary and secondary bondings
Miller indices for Planes and directions.
Cubic crystals.
Single crystal and polycrystalline materials.
Details of presentation
08/08/2013
ENGG ZC 232 Engineering Materials.
(Bonding and crytals structure)
3
4
The Periodic Table
08/08/2013
Columns: Similar Valence Structure
From Fig. 2.6
Callisters
Materials
Science and
Engineering,
Adapted
Version.

Electropositive elements:
Readily give up electrons
to become + ions.
Electronegative elements:
Readily acquire electrons
to become - ions.
g
i
v
e

u
p

1
e

g
i
v
e

u
p

2
e

g
i
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
Se
Te
Po At
I
Br
He
Ne
Ar
Kr
Xe
Rn
F
Cl S
Li Be
H
Na Mg
Ba Cs
Ra Fr
Ca K Sc
Sr Rb Y
5
Electronegativity
08/08/2013
Ranges from 0.7 to 4.0,
Smaller electronegativity Larger electronegativity
Large values: tendency to 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.

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s
2
2s
2
2p
6
3s
2
O 1s
2
2s
2
2p
4

[Ne] 3s
2

6
Ionic bond metal + nonmetal
08/08/2013
Mg
2+
1s
2
2s
2
2p
6
O
2-
1s
2
2s
2
2p
6

[Ne] [Ne]
7
Ionic Bonding
08/08/2013
Occurs between + and - ions.
Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl
Na (metal)
unstable
Cl (nonmetal)
unstable
electron
+
-
Coulombic
Attraction
Na (cation)
stable
Cl (anion)
stable
Energy minimum energy most stable
Energy balance of attractive and repulsive terms
8
Ionic Bonding
08/08/2013
Attractive energy E
A

Net energy E
N

Repulsive energy E
R

Interatomic separation r
r
A
n
r
B
E
N
= E
A
+ E
R
=

From Fig. 2.8(b), Callisters
Materials Science and
Engineering,
Adapted Version.

9
Examples: Ionic Bonding
08/08/2013
Predominant bonding in Ceramics
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.
Give up electrons Acquire electrons
NaCl
MgO
CaF
2
CsCl
10
Covalent Bonding
08/08/2013
C: has 4 valence e
-
,
needs 4 more
H: has 1 valence e
-
,
needs 1 more
Electronegativities
are comparable.
From Fig. 2.10
Callisters Materials Science and Engineering, Adapted Version.
similar electronegativity share electrons
bonds determined by valence s & p orbitals dominate bonding
Example: CH
4
shared electrons
from carbon atom
shared electrons
from hydrogen
atoms
H
H
H
H
C
CH
4
Metallic Bond -- delocalized as electron cloud

Ionic-Covalent Mixed Bonding

% ionic character =

where X
A
& X
B
are Pauling electronegativities

11
Primary Bonding
08/08/2013
%) 100 ( x

1 e

(X
A
X
B
)
2
4
|
\

|
.
|
|
|
ionic 70.2% (100%) x e 1 character ionic %
4
) 3 . 1 5 . 3 (

2
=
|
|
|
.
|
\
|
=

Ex: MgO X
Mg
= 1.3
X
O
= 3.5
12
SECONDARY BONDING
08/08/2013
Arises from interaction between dipoles
Permanent dipoles-molecule induced
Fluctuating dipoles
-general case:
-ex: liquid HCl
-ex: polymer
From Fig. 2.13
From Fig. 2.14
Callisters Materials Science and
Engineering
Adapted Version.
asymmetric electron
clouds
+ - + -
secondary
bonding
H H H H
H
2
H
2
secondary
bonding
ex: liquid H
2
H Cl H Cl
secondary
bonding
secondary
bonding
+ - + -
secondary bonding
13
Summary: Bonding
08/08/2013
Type
Ionic
Covalent
Metallic
Secondary
Bond Energy
Large!
Variable
large-Diamond
small-Bismuth
Variable
large-Tungsten
small-Mercury
smallest
Comments
Nondirectional (ceramics)
Directional
(semiconductors, ceramics
polymer chains)
Nondirectional (metals)
Directional
inter-chain (polymer)
inter-molecular
14
Properties From Bonding: T
m

08/08/2013
Bond length, r
Bond energy, E
o
Melting Temperature, T
m

T
m
is larger if E
o
is larger.
r
o
r
Energy
r
larger T
m

smaller T
m

E
o
=
bond energy
Energy
r
o

r
unstretched length
15
Properties From Bonding : o
08/08/2013
Coefficient of thermal expansion, o
o ~ symmetry at r
o
o is larger if E
o
is smaller.
=
o
( T
2
- T
1
)
A L
L
o
coeff. thermal expansion

A L
length, L
o
unheated, T
1
heated, T
2
r
o
r
larger o
smaller o
Energy
unstretched length
E
o

E
o

16
Summary: Primary Bonds
08/08/2013
Ceramics
(Ionic & covalent bonding):
Metals
(Metallic bonding):
Polymers
(Covalent & Secondary):
Large bond energy
large T
m
large E
small o
Variable bond energy
moderate T
m
moderate E
moderate o
Directional Properties
Secondary bonding dominates
small T
m

small E
large o
17
Chapter 3: Fundamentals of Structure of
Crystalline Solids
08/08/2013
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?
When do material properties vary with the
sample (i.e., part) orientation?
How do we distinguish between single crystals
and polycrystalline materials?
18
Energy and Packing
08/08/2013
Non dense, random packing
Dense, ordered packing
Dense, ordered packed structures tend to have
lower energies.
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
19
Materials and Packing
08/08/2013
atoms pack in periodic, 3D arrays
Crystalline materials...
-metals
-many ceramics
-some polymers
atoms have no periodic packing
Noncrystalline materials...
-complex structures
-rapid cooling
crystalline SiO2
"Amorphous" = Noncrystalline
From Fig. 3.10(a)
Callisters Materials Science and Engineering,
Adapted Version.
Si
Oxygen
typical of:
occurs for:
noncrystalline SiO2
From Fig. 3.10(b)
Adapted Version.
20
Section 3.3 Crystal Systems
08/08/2013
7 crystal systems

14 crystal lattices

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

Unit cell: smallest repetitive volume which contains
the complete lattice pattern of a crystal.
a, b, and c are the lattice constants
Point coordinates for unit cell center are

Point coordinates for unit cell corner are 111

Translation: integer multiple of lattice constants identical
position in another unit cell
21
Point Coordinates
08/08/2013
z
x
y
a b
c
000
111
y
z
-
2c
-
-
-
b
b
22
Crystallographic Directions
08/08/2013
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

[uvw]
ex: 1, 0,
=> 2, 0, 1 => [ 201 ]
-1, 1, 1
families of directions <uvw>
z
x
Algorithm
where overbar represents a negative index [ 111 ]
=>
y
23
HCP Crystallographic Directions
08/08/2013
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of unit
cell dimensions a
1
, a
2
, a
3
, or c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

[uvtw]
[ 1120 ] ex: , , -1, 0 =>
From Fig. 3.6(a)

dashed red lines indicate
projections onto a
1
and a
2
axes
a
1

a
2

a
3

-a
3

2
a
2
2
a
1
-
a
3

a
1

a
2

z
Algorithm
Hexagonal Crystals
4 parameter Miller-Bravais lattice coordinates are
related to the direction indices (i.e., u'v'w') as follows.
24
HCP Crystallographic Directions
08/08/2013
=
=
=
' w w
t
v
u
) v u (
+ -
) ' u ' v 2 (
3
1
-
) ' v ' u 2 (
3
1
- =
] uvtw [ ] ' w ' v ' u [

Fig. 3.6(a)
Adapted Version.

-
a
3

a
1

a
2

z
25
Crystallographic Planes
08/08/2013
From Fig. 3.7
Adapted Version.

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)

26
08/08/2013
27
08/08/2013
z
x
y
a b
c
4. Miller Indices (110)
example a b c
z
x
y
a b
c
1. Intercepts 1 1
2. Reciprocals
1/1 1/1 1/
1 1 0
3. Reduction 1 1 0
1. Intercepts 1/2
2. Reciprocals 1/ 1/ 1/
2 0 0
3. Reduction 2 0 0
example a b c
28
08/08/2013
z
x
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
(001) (010),
Family of Planes {hkl}
(100), (010), (001), Ex: {100} = (100),
In hexagonal unit cells the same idea is used
29
Crystallographic Planes (HCP)
08/08/2013
example a
1
a
2
a
3
c
4. Miller-Bravais Indices (1011)
1. Intercepts 1 -1 1
2. Reciprocals 1 1/
1 0
-1
-1
1
1
3. Reduction 1 0 -1 1
a
2

a
3

a
1

z
From Fig. 3.6(b)
Adapted Version.
30
Crystals as Building Blocks
08/08/2013
Some engineering applications require single crystals:
Properties of crystalline materials
often related to crystal structure.
(Courtesy P.M. Anderson)
--Ex: Quartz fractures more easily
along some crystal planes than others.
--diamond single
crystals for abrasives
--turbine blades
Fig. 11.33(c)
Science and Engineering,
Adapted Version.
(Fig.11.33(c) courtesy
of Pratt and Whitney).
(Courtesy Martin Deakins,
GE Superabrasives,
Worthington, OH. Used with
permission.)
31
Polycrystals
08/08/2013
Most engineering materials are polycrystals.
Nb-Hf-W plate with an electron beam weld.
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).
From Fig. K, color inset
pages of Callister 5e.
(Fig. K is courtesy of Paul E.
Danielson, Teledyne Wah
Chang Albany)
1 mm
Isotropic
Anisotropic
32
Single vs Polycrystals
08/08/2013
Single Crystals
-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.
(E
poly iron
= 210 GPa)
-If grains are textured,
anisotropic.
200 m
Data from Table 3.2,
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),
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].)
E (diagonal) = 273 GPa
E (edge) = 125 GPa
33
SUMMARY
08/08/2013
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.

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