CHAPTER 2

2.1

Atomic structure and bonding

2.2

Crystal system and Bravais lattice

2.3

Metallic crystal structure

2.4

Crystallographic directions and planes

2.5

Crystal structure analysis (X-Ray Diffraction)

1

Prologue
Dalam bentuk dan rupa apa sahaja yang
dikehendakiNya, Ia menyusun kejadianmu.

In whatever Form He wills, does He put thee

together.
(Al-Infitaar 82:8)

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?

2.1 ATOMIC AND BONDING

STRUCTURE
Fundamental concepts atomic number, atomic
weight, atomic mass unit (amu), mole etc.
Electron in atoms atomic models, quantum
numbers, electron configurations, periodic table.
Primary interatomic bonds ionic bonding,
covalent bonding, metallic bonding.
Secondary bonding (Van Der Waals) hydrogen
bonding, polar-molecule-induced dipole bonds,
permanent dipole bonds.
4

2.2 CRSYTAL SYSTEMS & BRAVAIS

LATTICE SYSTEM
Crystal a solid composed of atoms, ions or molecules
arranged in a pattern that is repeated in three
dimensions.
Solid materials classified according to the regularity
with which atoms or ions are arranged.
Atomic arrangement determine the solid materials
microstructure and properties.
Examples : ductility and strength
5

ENERGY AND PACKING

MATERIALS AND PACKING

SOLID
MATERIALS

CRYSTALLINE
- Atoms are positioned/situated in
an orderly and repeated pattern,
3D arrays
- Examples : all metals, many
ceramic and some polymers

NONCRYSTALLINE
(AMORPHOUS)
- Atoms are distributed randomly
and disordered.
-Occurs for complex structure
- rapid cooling
- Examples : polymer & a few
ceramics
7

METALLIC CRYSTALS
have the simplest crystal structures.
tend to be densely packed.
have several 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.
8

CRYSTAL SYSTEM
Crystal structure a regular three-dimensional
pattern of atoms or ions in space.
Space lattice a three-dimensional array of points
coinciding with atom positions (or sphere centers).
Lattice point atom position in the crystal lattice
Unit cell small groups of atoms form a repetitive
pattern (Figure 1)

Figure 1 : Crystal Structure

Space
lattice

Geometry of a
unit cell
10

7 systems of unit cell for metallic crystal structures

(Table 1 & Figure 2) :

Cubic
Tetragonal
Orthorhombic
Rhombohedral
Hexagonal
Monoclinic
Triclinic

These systems can be divided into 14 types of standard

unit cell geometries Bravais Unit Cell System
11

Table 1 : Lattice parameter for the 7 Crystal Systems

12

Figure 2 :14 unit cell geometries (Bravais Unit Cell)

13

2.3

METALLIC CRYSTAL STRUCTURE

Most of the metallic materials - 3 types of

crystal structure :

Face-centered cubic (FCC)

example : Fe, Cu, Al, Arg, Au
Body-centered cubic (BCC)
example : Fe, Cr, W
Hexagonal close-packed (HCP)
example: Mg, Ti, Zn, Cd.
14

Atomic packing factor (APF);

(Total sphere volume)

Vs
Vc

nVa
Vc

Coordination number;
number of nearest-neighbor or touching
atoms for each atom in the crystal structure

15

THE SIMPLE CUBIC STRUCTURE

Rare due to poor packing (only Po has this structure)

16

THE FACE-CENTERED CUBIC STRUCTURE

2a 4R
a 4R
2R 2
2
where
a = unit cell length
R = atomic radius
17

Atoms located at each of the corners and the centers of all

the cube faces
Example : aluminium, silver, gold, copper etc
Number of atoms per unit cell = 4
Total sphere volume, Vs

Vs

(4) 4

R3

Unit cell volume, Vc

a3

Vc

(4 R 2 ) 3
Atomic Packing Factor, (APF)
APF

Vs
Vc

4( 4

3
(4 R

R3 )
2

)3

0.74

74% of the unit cell space is packed with atoms.

18

THE BODY-CENTERED CUBIC STRUCTURE

a 4R

where

a = unit cell length

R = atomic radius

19

Number of atoms per unit cell = 2

Total sphere volume, Vs

Vs (2) 4

R3

Unit cell volume, Vc

a3

Vc

(4 R 3 )3
Atomic Packing Factor, (APF)
APF

Vs
Vc

2( 4

3
(4 R

R3 )
3

0.68

68% of the unit cell is occupied with atoms.

20

HEXAGONAL CLOSE-PACKED

21

a 2r
c

h (a

1.633
a
c 1.633a

1
2 2
1
( a) )
2

1
2 2
3
( a )
4
( 3 )a
2

No. of atoms per unit cell = 6

Area of triangle ABC
=
=

Area of base = 6 x area of triangle ABC

1 a h
2
1

a (( 3 )a)
2
2

1
a ( 3 a)
2
2
3a 2 3
2

22

 Volume of unit cell, Vc= Base area x c

3a 2 3
c
2

3a 2 3
1.633a
2
3

3
2

Atomic volume, Va =

4 3
r
3

Atomic packing factor, APF =

1.633(2r )3

6( 4

r3)

3( 3 ) 1.633(2r 3 )
2

= 0.74

74% of the unit cell is occupied with atoms and 26% is empty
space.
23

24

 Theoretical density, =

n x A
Vc x NA

where

n = number of atoms associated with

each unit cell
A = atomic weight
Vc = volume of the unit cell
(NA) = Avogadros number(6.023x 1023
atoms/mol)

25

Example :
Copper has the FCC crystal structure with atomic radius, R =
0.1278nm. Assume the atoms to be hard spheres and packed as
close together as possible along the FCC unit cell cross-section.
Calculate the theoretical volume density of copper in mg/m3.
(Atomic mass of Cu = 63.54 g/mol)

SOLUTION :
For FCC,

2a 4R
a 4R
2
4(0.1278 )nm
2
0.361nm
26

Mass / unitcell
Volume / unitcell

Theoretical volume density, Pv

6.02 x 1023 atoms

4 atoms

63.54 g

63.54(4)
6
(
10
mg )
23
6.02 10

Mass of unit cell, m = 4.22 10

Volume of unit cell, V =

a3

Pv

mg

(0.361 10 9 )3
4.70 10

m
v

28

4.22 10
4.70 10

29

28

mg
3
29
m

8.98mg / m3

8.98 g / cm3

27

28

2.4

CRYSTALLOGRAPHIC PLANES AND

DIRECTIONS

Deformation in metal such as forging, drawing

etc. moves according to certain planes and
directions in the crystal structure.
Example : Ferum (Fe) Magnetic effect is strong
in [100] direction compare to [111] direction.
Miller Indices used to explain the planes and
directions position in crystal.

29

Atomic position in cubic unit cell

Atomic position in BCC unit cell

30

CRYSTALLOGRAPHIC DIRECTIONS

A line or vector between 2(two) points.

Steps in determination of the three directional indices :

1. A vector of convenient length is positioned such that it
passes through the origin of the coordinate system. Any
vector may be translated throughout the crystal lattice
without alteration, if parallelism is maintained.
2. The length of the vector projection on each of the three
axes is determined; they are measured in terms of the unit
cell dimensions a, b and c.
3. These three numbers are multiplied or divided by a common
factor to reduce them to the smallest integer values.
4. The three direction indices are enclosed by square
brackets with no separating commas, thus : [
].
uvw +ve

uvw

-ve
31

All parallel direction vectors have the same

direction indices.

Crystallographically equivalent directions the

atom spacing along each direction is the same.

100

[100], [010], [001], [100], [010], [001]

other directions of a family <110> and <111>

- INDICES OF A FAMILY

32

111

110

221

201
Z

1
2

1
2
Y

X
33

203

122

1
2

0
2
3

X
Z

102
0

1
2

201

1
2

X
34

Problems
Determine the direction indices of the cubic direction
shown in figure below.
z

Solution :
(a)

(a)[110]

1
2

(b)

(b)[212]

(c)
(d)

(c)[661]

1
3

(d )[121]
x

1
2

1
2

35

CRYSTALLOGRAPHIC PLANES
The reciprocals of the fractional intercepts (with fractions cleared)
which the plane makes with the crystallographic x, y and z axes of
the three nonparallel edges of the cubic unit cell.

Procedure for determining the Miller indices for a cubic crystal plane
is as follows :
1.
Choose the plane that does not pass through the origin at
(0,0,0).
2.
Determine the intercepts of the plane in terms of the
crystallograhic x, y and z axes for a unit cube. These
intercepts may be fractions.
3.
Form the reciprocals of these intercepts. A plane that
parallela an axis may be considered to have an infinite
intercept, and therefore, a zero index.
4.
If necessary, these three numbers are changed to the set of
smallest integers by multiplication or division by a common
factor.
5.
Finally, the integer indices, not separated by commas, are
enclosed with parentheses, thus : (hkl)
36

(1 0 1)

( 1 1 1)
y

x
37

Problems
Draw the following crystallographic planes in cubic unit cells:

(a)(101)
(b)(110)
(c)(221)
(d )(234)

z
(a)
y

z
x
(b)

x
38

PLANES OF A FAMILY sets of equivalent lattice

planes are related by the symmetry of the crystal
system.

{100}

100 , 010 , 001

An important relationships for the cubic system (only)

the direction indices of a direction perpendicular to a
crystal plane are the same as the Miller indices of that
plane.

Example : the [100] direction is perpendicular to the

(100) crystal plane.

39

Determine the planes indices of the cubic direction shown

in figures below.

(a)

(d)

(b)

(e)

(c)

(f)

40

CRYTALLOGRAPHIC PLANES IN HEXAGONAL

UNIT CELLS
The HCP crystal planes
indices, are donated by the
letters h, k, i and l.
Enclosed in parentheses

as (hkil )

a1, a2 and a3 basal

axes which make 120 with
each other.
c axis the vertical axis
located at the center of
the unit cell.

The four coordinate axes (a1, a2, a3

and c) of he HCP crystal structure
unit cell
41

Miller-Bravais indices of
hexagonal crystal planes

Basal planes very important

planes for this unit cell.
The basal plane on the top of
the HCP unit cell is parallel to
the a1, a2 and a3 axes the
intercepts of this plane with
these axes will all be infinite.
The c axis is unity since the top basal plane intersects the
c axis at unit distance.
Taking the reciprocals of these intercepts gives the MillerBravais indices for the HCP basal plane (0001)
42

Prism planes
The front prism plane (ABCD)
has the indices (1 0 1 0)
Similarly, the ABEF prism
plane has the indices (1 1 0 0)
All HCP prism planes can be
identified - as the {1 0 1 0}.

Sometimes HCP planes are

identified only by three indices
(hkl) since h + k = -i.
However, the (hkil) are used
commonly.
43

Exercise :
Determine the Miller indices for these HCP planes.
(a)
(b)

(b)
(a)
(c)

(c)

1 a = (0 1 1 0) ,

b=( 2200) ,

c = (10 1 2)

2 a = (0 1 1 0) ,

b = ( 1 1 0 1) ,

c = (1 1 0 1)
44

PLANAR ATOMIC DENSITY ( P)

Number of atoms centered on a plane

Area of plane

The units of planar density = m-2 , nm-2

Example Problem
Calculate the planar atomic density p on the plane of the iron
BCC lattice in atoms per square millimeter. The lattice constant,
a of iron is 0.287 nm.

45

Figure : (a) A BCC atomic-site unit cell showing a shaded (110) plane
(b) Areas of atoms in BCC unit cell cut by the (110) plane.

46

Solution :

Equivalent number of atoms intersected by the (110) plane ;

1 atom at the center + (4 x atoms at four corners of plane) = 2
atoms
Area of the plane (110) ;

(2 a)(a) = 2 a2
The planar atomic density is
2 atoms
P
P

2 (0.287nm)
2
17.2atoms/nm

2
13
2
17.2x10 atoms/mm

47

LINEAR ATOMIC DENSITY ( l)

Number of atoms centeredon direction vector

Length of direction vector

The units of linear density = m-1 , nm-1

Example Problem
Calculate the linear atomic density l in the [110] direction in the
copper crystal lattice in atoms per millimeter. Copper is FCC and
has a lattice constant of 0.361 nm.

48

Figure :

Diagram for calculating the atomic linear density in the

[110] direction in an FCC unit cell

49

Solution :
The number of atomic diameters intersected by this length of line are
+ 1 + = 2 atoms.
Length of the direction vector = 2 a
The linear atomic density is

2 atoms
l
l

2 (0.361nm)
3.92 atoms/nm

6
3.92 x 10 atoms/mm

50

2.5

Crystal Structure Analysis

(X-Ray Diffraction)

Spacing between planes distance between 2 parallel

planes having similar miller indices, given by d hk (hkl is
miller indices for plane).
The analysis is done by using the X-Ray Diffractometer
Machine.

51

Atoms can be arranged and imaged!!!

Carbon monoxide
molecules arranged
on a platinum (111)
surface.

Iron atoms arranged

on a copper (111)
surface. These Kanji
characters represent
the word atom.

SCANNING TUNNELING MICROSCOPY

52

SUMMARY
Atoms may assemble into crystalline or amorphous
structures.
We can predict the density of a material, provided
we know the atomic weight, atomic radius, and
crystal structure (e.g., FCC, BCC, HCP).
Material properties generally vary with single
crystal orientation (i.e., they are anisotropic), but
properties are generally non-directional (i.e., they
are isotropic) in polycrystals with randomly
oriented grains.
53