27

Secondary Bonding
Secondary bonds are due to attractions of electric
dipoles in atoms or molecules.
Dipoles are created when positive and negative
charge centers exist.

Dipole moment= =q.d

+q

-q

d
There are two types of bonds
fluctuating.
2-30

q= Electric charge
d = separation distance
permanent and

28

Fluctuating Dipoles
Weak secondary bonds in noble gasses.
Dipoles are created due to asymmetrical distribution
of electron charges.
Electron cloud charge changes with time.

Symmetrical
distribution
of electron charge

Asymmetrical
Distribution
(Changes with time)

29

Permanent Dipoles

Dipoles that do not fluctuate with time are

called Permanent dipoles.
Examples:-

CH4

CH3Cl

Symmetrical
Arrangement
Of 4 C-H bonds

Asymmetrical
Tetrahedral
arrangement

No Dipole
moment

Creates
Dipole

30

Hydrogen Bonds
Hydrogen bonds are Dipole-Dipole interaction
between polar bonds containing hydrogen atom.
(Hydrogen is covalently bonded to F, O or N
atoms)
Example :H

In water, dipole is created due to asymmetrical

arrangement of hydrogen atoms.
Attraction between positive oxygen pole and
negative hydrogen pole.

105 0

Hydrogen
Bond

31

van der Waals bonds

Fluctuation-induced dipole bonds

Charge on atom in motion being redistributed
Electric dipole
Induced electric dipole
Polar molecule induced dipole bonds
Neutral atoms form dipole
Permanent dipole bonds: HCl

Van der Waal bonds

r
6

Attraction
Energy

B
+
r

n 12

Repulsion
Energy

32

Architecture of solids
Single crystals
The arrangement of atom is regular and repeated in 3D
pattern throughout the entirety of the crystalline solid
without interruption
Poly-crystals
Solids consisting of many crystals or grains, divided by
grain boundaries, where two grains meet
Amorphous (Non-crystalline)
Solids lack a systematic, repeated and regular arrangement of
atoms
Heat treatment usually would transform a random structure to an
ordered state

33

The Space Lattice and Unit Cells

Atoms or ions are arranged in repetitive 3Dimensional pattern, in long range order give rise to
crystal structure.
Properties of solids depends upon crystal structure
and bonding force.
An imaginary network of lines, with atoms at
intersection of lines, representing the arrangement of
atoms is called space lattice.
Space Lattice

Unit Cell
3-2

34

Atomic hard sphere model

Lattice: a three-dimensional array of points
coinciding with atomic sphere centers
Unit cell: a small repeat entity representing the
symmetry of the crystal structure
Coordination number (Z): the number of nearestneighbor atoms surrounding each atom in a
crystal structure
Atomic packing factor (APF): the volume fraction
of atomic spheres in a unit cell
d-spacing: distance between lattice planes

35

Crystal Systems and Bravais Lattice

3-3

36

Principal Metallic Crystal Structures

90% of the metals have either Body Centered Cubic

(BCC), Face Centered Cubic (FCC) or Hexagonal Close
Packed (HCP) crystal structure.

BCC Structure

3-7

FCC Structure

HCP Structure

37

Body Centered Cubic (BCC) Crystal

Structure
Represented as one atom at each corner of cube and
one at the center of cube.
Each atom has 8 nearest neighbors.
Therefore, coordination number is 8.

3-8

38

BCC Crystal Structure (Cont..)

Each unit cell has eight 1/8
atom at corners and 1
full atom at the center.
Therefore each unit cell has
(8x1/8 ) + 1 = 2 atoms

3-9

Atoms contact each

other at cube diagonal
Therefore, lattice 4 R
constant a =
3

39

Atomic Packing Factor of BCC Structure

Atomic Packing Factor =

Vatoms =

4 R 3

2.

V unit cell =

a3

Volume of atoms in unit cell

Volume of unit cell

= 8.373R3

4R

= 12.32 R3

3
8.723
R
Therefore APF = 12.32 R3 = 0.68

3-10

40

Face Centered Cubic (FCC) Crystal

Structure
FCC structure is represented as one atom each at the
corner of cube and at the center of each cube face.
Coordination number for FCC structure is 12
Atomic Packing Factor is 0.74
Examples :

Aluminum (a = 0.405)
Gold (a = 0.408)

41

FCC Crystal Structure (Cont..)

Each unit cell has eight 1/8
atom at corners and six
atoms at the center of six
faces.
Therefore each unit cell has
(8 x 1/8)+ (6 x ) = 4 atoms

3-12

Atoms contact each other

across cubic face diagonal
4R
Therefore, lattice
constant a
=
2

42

Atomic Packing Factor of FCC Structure

Atomic Packing Factor =

Vatoms =

4 R 3
4

V unit cell =

a3

Volume of atoms in unit cell

Volume of unit cell

= 16.755R3

4R

= 22.63 R3

3
16.755
R
Therefore APF = 22.63 R3 = 0.74

3-10

43

Hexagonal Close-Packed Structure

The HCP structure is represented as an atom at each
of 12 corners of a hexagonal prism, 2 atoms at top and
bottom face and 3 atoms in between top and bottom
face.
Atoms attain higher APF by attaining HCP structure
than simple hexagonal structure.
The coordination number is 12, APF = 0.74.

3-13

44

HCP Crystal Structure (Cont..)

Each atom has six 1/6 atoms at each of top and
bottom layer, two half atoms at top and bottom layer
and 3 full atoms at the middle layer.
Therefore each HCP unit cell has
(2 x 6 x 1/6) + (2 x ) + 3 = 6 atoms
Examples:

Zinc (a = 0.2665 nm, c/a = 1.85)

Cobalt (a = 0.2507 nm, c.a = 1.62)

3-14

Ideal c/a ratio is 1.633.

45

Atomic Packing Factor of HCP Structure

Atomic Packing Factor =

Vatoms =
V unit cell =

Volume of unit cell

4
6( R 3 ) =??
3
1
3 3 2
ac
6( a 2 sin 60o ) c =
2
2

Therefore APF = = 0.74

3-10

Volume of atoms in unit cell

R=??a

c=1.633a

46

Atom Positions in Cubic Unit Cells

Cartesian coordinate system is use to locate atoms.
In a cubic unit cell

y axis is the direction to the right.

x axis is the direction coming out of the paper.
z axis is the direction towards top.
Negative directions are to the opposite of positive
directions.

3-15

Atom positions are

located using unit
distances along the
axes.

47

Directions in Cubic Unit Cells

In cubic crystals, Direction Indices are vector
components of directions resolved along each axes,
reduced to smallest integers.
Direction indices are position coordinates of unit cell
where the direction vector emerges from cell surface,
converted to integers.

3-16

48

Direction Indices - Example

Determine direction indices of the given vector.

Origin coordinates are (3/4 , 0 , 1/4).
Emergence coordinates are (1/4, 1/2, 1/2).
(3/4 , 0 , 1/4) - (1/4, 1/2, 1/2)
= (-1/2, 1/2, 1/4)
reduced to smallest integers
4 x (-1/2, 1/2, 1/4) = (-2, 2, 1)

Therefore, the direction indices are

3-18

2 2 1

49

Miller Indices in Cubic Unit Cells

Miller Indices are are used to refer to specific lattice
planes of atoms.
They are reciprocals of the fractional intercepts (with
fractions cleared) that the plane makes with the
crystallographic x,y and z axes of three nonparallel
edges of the cubic unit cell.
Miller Indices =(111)
z

y
x
3-19

50

Miller Indices - Examples

z

(100)
y
x
x

3-21

Intercepts of the plane at

x,y & z axes are 1, and

Taking reciprocals we get

(1,0,0).
Miller indices are (100).
*******************
Intercepts are 1/3, 2/3 & 1.
taking reciprocals we get
(3, 3/2, 1).
Multiplying by 2 to clear
fractions, we get (6,3,2).
Miller indices are (632).

51

Miller Indices - Examples

Plot the plane (101)
Taking reciprocals of the
indices we get (1 1).
The intercepts of the plane are
x=1, y= (parallel to y) and z=1.
******************************
Plot the plane (2 2 1)
Taking reciprocals of the
indices we get (1/2 1/2 1).
The intercepts of the plane are
x=1/2, y= 1/2 and z=1.

3-22

52

Miller Indices - Example

Plot the plane (110)

The reciprocals are (1,-1, )
The intercepts are x=1, y=-1 and z= (parallel to z
axis)
(110)

To show this plane in a

single unit cell, the
origin is moved along
the positive direction
of y axis by 1 unit.

y
x

3-23

53

Miller Indices Important Relationship

Direction indices of a direction perpendicular to a
crystal plane are same as miller indices of the plane.
Example:

(110)

{110}

Interplanar spacing between parallel closest planes

with same miller indices {h k l} is given by

d
3-24

hkl

54

Crystallographic directions and planes

A crystallographic direction is
defined as a vector between two
lattice sites. Indices are vector
components of direction reduced to
smallest integer.
Miller indices for cubic crystals
(1,0,0) plane
{1,0,0} plane family
[1,0,0] direction
<1,0,0> direction family
Planes and directions of cubic
crystals having the same indices
are perpendicular to one another.

Ref: Ashby and Jones, 1980.

55

Structural Difference between HCP and

FCC
Consider a layer
of atoms (Plane A)

Plane A
a void
b void

Another layer (plane B)

of atoms is placed in a
Void of plane A

Plane A
Plane B
a void
b void

Third layer of Atoms placed

in b Voids of plane B. (Identical
to plane A.)
HCP crystal.

3-29

Third layer of Atoms placed

in a voids of plane B. Resulting
In 3rd Plane C.
FCC crystal.

Plane A
Plane B

Plane A
Plane B

Plane A

Plane C

56

Volume Density

Volume density of metal =

Mass/Unit cell
=
v Volume/Unit cell

Example:- Copper (FCC) has atomic mass of 63.54

g/mol and atomic radius of 0.1278 nm.
a=

4R
2

= 4 0.1278 nm = 0.361 nm
2

Volume of unit cell = V= a3 = (0.361nm)3 = 4.7 x 10-23 cm3

FCC unit cell has 4 atoms.
Mass of unit cell =

3-30

(4atoms )(63.54 g / mol )

= 4.22 x 10-22 g
23
6 10 atmos / mol

m 4.22 1022 g
g
= =
= 8.98 3
23
3
V 4.7 10 cm
cm
v

57

Volume Density, contd

Volumetric (material) density ():
nA
=
Vc N A
n: number of atoms associated with each unit cell
A: atomic weight
Vc: volume of the unit cell
NA: Avogadros number (6.023 x 1023 atoms/mol)

58

Planar Atomic Density

Planar atomic density=

Equivalent number of atoms whose

centers are intersected by selected area

Selected area

Example:- In Iron (BCC, a=0.287), The (110) plane

intersects center of 5 atoms (Four and 1 full atom).
Equivalent number of atoms = (4 x ) + 1 = 2 atoms
Area of 110 plane = 2a a = 2a 2

Figure 3.22 a&b

3-31

or

2 (0.287 )

2 ( R 2 )
2a

17.2atoms
=
nm 2
2 ( R 2 )
4R
2

= 0.833

59

Linear Atomic Density

Linear atomic density =

Number of atomic diameters

intersected by selected length
of line in direction of interest
Selected length of line

Example:- For a FCC copper crystal (a=0.361), the

[110] direction intersects 2 half diameters and 1 full
diameter.
Therefore, it intersects + + 1 = 2 atomic diameters.
Length of line =

or
3-32

2atoms
2 0.361nm

2 0.361nm

3.92atoms

nm

2(2 R)
4R
=
=1
4
R
2a
2
2

3.92 10 6 atoms
mm

60

Planer Density and Linear Density

Linear atomic density (LD): the fraction of line length in a
particular crystallographic direction that passes through
atom centers.
2R
EX: BCC along [110]
LD =

2a

Planer atomic density (PD): the fraction of total

crystallographic plane area that is occupied by atoms. The
plane must pass through an atoms center for the
particular atom to be included.
1

EX: BCC on (100)

2

4
PD =
aa

61

Density, contd
Density of materials depend on (1) packing
and (2) mass and size of atoms
Metals
Heavy atoms and closely packed

Ceramics
Light atoms and closely packed

Polymers
Light atoms and randomly packed