20/11/2009

The Space Lattice and Unit Cells

Atoms, arranged in repetitive 3-Dimensional pattern,
in long range order (LRO) 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

Lecture

Unit cell is that block of

atoms which repeats itself
to form space lattice.

Crystal Structures
and
Crystal Geometry

Materials arranged in short

range order are called
amorphous materials.
Unit Cell

3-1

3-2

a) Space lattice of ideal crystalline solid b) Unit cell showing lattice

constants

Crystal Systems and Bravais Lattice

Only seven different types of unit cells are
necessary to create all point lattices.
According to Bravais (1811-1863) fourteen
standard unit cells can describe all possible lattice
networks.
The four basic types of unit cells are
Simple
Body Centered
Face Centered
Base Centered

3-3

Types of Unit Cells

Types of Unit Cells (Cont..)

Cubic Unit Cell

Orthorhombic

a=b=c

a b c

= = = 900

= = = 900
Simple
Simple

Figure 3.2

Face centered

Body Centered
Face Centered

Tetragonal

Rhombohedral

a =b c

a =b = c

= = = 900

= = 900

Simple
3-4

Base Centered

Body Centered

Body Centered

Figure 3.2

Simple
3-5

After W.G. Moffatt, G.W. Pearsall, & J. Wulff, The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.47.)

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Types of Unit Cells (Cont..)

Classification of space lattices by crystal system

Hexagonal
a b c
= = 900, =120o

Simple

Monoclinic
a b c
= = 900

Base
Centered
Simple

Triclinic

Figure 3.2

a b c
900

Simple
3-6

After W.G. Moffatt, G.W. Pearsall, & J. Wulff, The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.47.)

Principal Metallic Crystal Structures

Body Centered Cubic (BCC) Crystal Structure

90% of the metals have either Body Centered Cubic

(BCC), Face Centered Cubic (FCC) or Hexagonal
Close Packed (HCP) crystal structure.
HCP is denser version of simple hexagonal 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.
Examples : Chromium (a=0.289 nm)
Iron (a=0.287 nm)
Sodium (a=0.429 nm)

BCC Structure

FCC Structure

HCP Structure

Figure 3.3

Figure 3.4 a&b

3-7

3-8

BCC unit cell showing relationship between the lattice constant a and
the atomic radius R

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

Atoms contact each

other at cube diagonal
Therefore, lattice
constant a =

4R

Figure 3.5

3
3-9

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BCC unit cells

Atomic Packing Factor of BCC Structure

a) atomic-site unit cell

b) hard-sphere unit cell
c) isolated unit cell

Volume of atoms in unit cell

Atomic Packing Factor =

Volume of unit cell

Vatoms =

4R 3

2 .

= 8.373R3

V unit cell = a3 = 4 R

Therefore APF =

= 12.32 R3

8.723 R3
= 0.68
12.32 R3

3-10

Selected metals that have BCC crystal structure

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 (the number of atomic or ionic
nearest neighbors) for FCC structure is 12
Atomic Packing Factor is 0.74
Examples : Aluminum (a = 0.405)
Gold (a = 0.408)

Figure 3.6 a&b

3-11

FCC unit cell showing relationship between the lattice constant a and
atomic radius R.

FCC Crystal Structure (Cont..)

Since the atoms touch across the face diagonals,

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

Atoms contact each other

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

Figure 3.7

2
3-12

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FCC unit cells

Selected metals that have FCC crystal structure

a) atomic-site unit cell

b) hard-sphere unit cell
c) isolated unit cell

HCP Crystal Structure (Cont..)

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.

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)

Ideal c/a ratio is 1.633.

Figure 3.8 a&b

3-13

After F.M. Miller, Chemistry: Structure and Dynamics, McGraw-Hill, 1984, p.296

HCP crystal structure

Figure 3.8 c
3-14

After F.M. Miller, Chemistry: Structure and Dynamics, McGraw-Hill, 1984, p.296

Selected metals that have the HCP crystal structure

a) schematic of the crystal structure

b) hard-sphere model
c) isolated unit cell shematic

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Example:
Calculate the APF of the zinc crystal structure by using the
following data: pure zinc has the HCP crystal structure
with lattice constants a = 0.2665 nm and c = 0.4947 nm.

Theoretical Density
Example:

Theoretical density =

nA
Vc N A

Question:
Niobium has an atomic radius of 0.143nm and
a density of 8.57g/cm3. Determine whether it
has an FCC or BCC crystal structure.

n = number of atoms associated with each unit

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

elements have more than one crystal structure, a

phenomenon known as polymorphism. When found in
element of solids, the condition is often termed allotropy.

Atom Positions in Cubic Unit Cells

Solution:
Density =
If FCC
If BCC

Cartesian coordinate system is use to locate atoms.

In a cubic unit cell

nA
Vc N A

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.

= 4 (92.19)/ (16)(2)0.5(1.43x10 -8)3(6.023x1023)

= 9.25g/cm3
= 2 (92.19)/ (16)(2)0.5(1.43x10 -8)3(6.023x1023)
= 4.62g/cm3

Negative directions are to the opposite of positive

directions.

Atom positions are

located using unit
distances along the
axes.

By comparison, Niobium has FCC crystal structure

Figure 3.10 b
3-15

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Directions in Cubic Unit Cells

a) Rectangular x, y and z axes for locating atom positions
in cubic unit cells
b) Atom positions in a BCC unit cell

In cubic crystals, Direction Indices are defined as a line

between two point, or a
Direction indices are position coordinates of unit cell
where the direction vector emerges from cell surface,
converted to integers.

Figure 3.11
3-16

Procedure to Find Direction Indices

Produce the direction vector till it
emerges from surface of cubic cell

Example

z
(1,1/2,1)

Determine the coordinates of point

of emergence and origin

y
2 x (1,1/2,1)
= (2,1,2)

(0,0,0)

Subtract coordinates of point of

Emergence by that of origin
Are all are
integers?
YES
Are any of the direction
vectors negative?

NO

YES
Represent the indices in a square
bracket without comas with a
over negative index (Eg: [121])

Draw the following direction vectors in cubic unit cells:

a) [100] and [110] b) [112] c) [110] d) [321]

(1,1/2,1) - (0,0,0)
= (1,1/2,1)

The direction indices are [212]

Convert them to
smallest possible
integer by multiplying
by an integer.

NO
Represent the indices in a square
bracket without comas (Eg: [212] )

3-17

Direction Indices - Example

Miller Indices

Determine direction indices of the given vector.

Origin coordinates are (3/4 , 0 , 1/4).
Emergence coordinates are (1/4, 1/2, 1/2).

Miller Indices 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.

Subtracting origin coordinates

from emergence coordinates,
(1/4 , 1/2 , 1/2) - (3/4, 0, 1/4)
= (-1/2, 1/2, 1/4)
Multiply by 4 to convert all
fractions to integers
4 x (-1/2, 1/2, 1/4) = (-2, 2, 1)
Therefore, the direction indices are [ 2 2 1 ]

y
Figure EP3.6

3-18

Miller Indices =(111)

x
3-19

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Miller Indices - Procedure

Miller indices of some important cubic crystal planes

Choose a plane that does not pass

through origin

a) (100) b) (110) c) (111)

Determine the x,y and z intercepts

of the plane
Find the reciprocals of the intercepts
Clear fractions by
multiplying by an integer
to determine smallest set
of whole numbers

Fractions?
Place a bar over the
Negative indices

Enclose in parenthesis (hkl)where h,k,l

are miller indicesof cubic crystal plane
forx,y and z axes. Eg: (111)
3-20

Miller Indices - Examples

Miller Indices - Examples

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).

z
(100)
y
x
x

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.

Figure EP3.7 a

Figure EP3.7 c

Figure 3.14
3-21

3-22

Miller Indices Important Relationship

Directions in HCP Unit Cells

Indicated by 4 indices [uvtw].
u,v,t and w are lattice vectors in a1, a2, a3 and c
directions respectively.
Example:For a1, a2, a3 directions, the direction indices are
[ 2 1 1 0], [1 2 1 0] and [ 1 1 2 0] respectively.

Direction indices of a direction perpendicular to a

crystal plane are same as miller indices of the plane.
z
Example:-

(110)

[110]
Figure EP3.7b

Interplanar spacing between parallel closest planes

with same miller indices is given by

d
3-24

hkl

Figure 3.18
3-27

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Miller-Bravais hexagonal crystal structure direction indices for principal

directions

Planes and Directions in Hexagonal Unit Cells

Four indices are used (hkil) called as
Miller-Bravais indices.
Four axes are used (a1, a2, a3 and c).
Reciprocal of the intercepts that a crystal
plane makes with the a1, a2, a3 and c axes
give the h,k,I and l indices respectively.

It has been agreed that u + v = -t

Figure 3.16
3-25

Hexagonal Unit Cell - Examples

The four coordinate axes (a1, a2, a3 and c) of the HCP crystal structure

Basal Planes:Intercepts a1 =
a2 =
a3 =
c=1
(hkli) = (0001)

Figure 3.12 a&b

Prism Planes :For plane ABCD,

Intercepts a1 = 1
a2 =
a3 = -1
c=
(hkli) = (1010)

3-26

Planar Atomic Density

Volume Density

Volume density of metal =

Example:- Copper (FCC) has

atomic mass of 63.54 g/mol
and atomic radius of 0.1278
nm.
4R

a=

Equivalent number of atoms whose

= centers are intersected by selected area

Mass/Unit cell
Volume/Unit cell

4 0.1278nm

Planar atomic density=

Selected area

Example:- In Iron (BCC, a=0.287), The (100) plane

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

= 0.361 nm

2
2
Volume of unit cell = V= a3 = (0.361nm)3 = 4.7 x 10-29 m3

FCC unit cell has 4 atoms.

Mass of unit cell = m =

m
V

3-30

(4 atoms)(63.54 g / mol ) 106 Mg = 4.22 x 10-28 Mg

(
)
6.23x10 23 / mol
g

4.22 1028 Mg
4.7 1029 m3

8.98

Mg
m3

8.98

17.2atoms
nm

2 0.287

1.72 1013
mm 2

Figure 3.22 a&b

cm3
3-31

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Linear Atomic Density

Linear atomic density =

Polymorphism or Allotropy

Number of atomic diameters

intersected by selected length
of line in direction of interest

Metals exist in more than one crystalline form. This is

caller polymorphism or allotropy.
Temperature and pressure leads to change in
crystalline forms.
Example:- Iron exists in both BCC and FCC form
depending on the temperature.

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 =

2atoms

3.92atoms

2 0.361nm

Liquid
Iron

2 0.361nm

nm

3.92 10 6 atoms

9120C

-2730C

mm

Iron
BCC

13940C 15390C

Iron
FCC

Iron
BCC

Figure 3.23
3-32

3-33

Allotropic crystalline forms of iron over temperature ranges at

atmosphere pressure

X-Ray Diffractometer

Crystal Structure Analysis

Information about crystal structure are obtained using
X-Rays.
The X-rays used are about the same wavelength (0.050.25 nm) as distance between crystal lattice planes.

35 KV
(Eg:
Molybdenum)
Figure 3.25
3-34

After B.D. Cullity, Elements of X-Ray Diffraction, 2d ed., Addison-Wesley, 1978, p.23.

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X-Ray Diffraction Analysis

X-Ray Spectrum of Molybdenum

X-Ray spectrum of Molybdenum
is obtained when Molybdenum is
used as target metal.
K and K are characteristic of
an element.
For Molybdenum K occurs at
wave length of about 0.07nm.
Electrons of n=1 shell of target
metal are knocked out by
bombarding electrons.
Electrons of higher level drop
down by releasing energy to
replace lost electrons

Powdered specimen is used for X-ray diffraction analysis as

the random orientation facilitates different angle of incidence.
Radiation counter detects angle and intensity of diffracted
beam.

Figure 3.26

Figure 3.30
3-40

3-35

After A.G. Guy Essentials of Materials Science, McGraw-Hill, 1976.

Energy levels of electrons in molybdenum

X-Ray Diffraction (Cont..)

For rays reflected from different planes to be in phase,
the extra distance traveled by a ray should be a integral
multiple of wave length .
(n = 1,2)

n = MP + PN

n is order of diffraction
If dhkl is interplanar distance,
Then MP = PN = dhkl.Sin
Therefore,

= 2 dhkl.Sin

Figure 3.28

3-37

Interpreting Diffraction Data

We know that

hkl

Interpreting Diffraction Data (Cont..)

For planes A and B we get two equations

h2 k 2 l 2

Sin 2 A

Since 2 dSin
Substituting for d,

After A.G. Guy and J.J. Hren, Elements of Physical Metallurgy, 3d ed., Addison-Wesley, 1974, p.201.)

2 ( h A 2 k A 2 l A 2 )

2aSin

Sin 2 B

h2 k 2 l2

Sin 2

(For plane B)

4a 2

2 h 2 k 2 l 2
Dividing each other, we get

4a 2

Sin 2 A

Note that the wavelength and lattice constant a are the same
For both incoming and outgoing radiation.

3-38

2 ( hB k B l B )

Therefore

(For plane A)

4a 2

Sin 2 B

( hA k A l A )
(hB k B l B )

3-39

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Diffraction Condition for Cubic Cells

Record of the diffraction angles for a tungsten sample obtained by XRD

For BCC structure, diffraction occurs only on planes

whose miller indices when added together total to an
even number.
I.e. (h+k+l) = even
Reflections present
(h+k+l) = odd
Reflections absent
For FCC structure, diffraction occurs only on planes
whose miller indices are either all even or all odd.
I.e. (h,k,l) all even
Reflections present
(h,k,l) all odd
Reflections present
(h,k,l) not all even or all odd
Reflections absent.

3-41

Interpreting Experimental Data

For BCC crystals, the first two sets of diffracting
planes are {110} and {200} planes.
Therefore

Sin 2 A

Sin 2 B

(12 12 0 2 )

0.5

( 2 2 02 02 )

For FCC crystals the first two sets of diffracting planes

are {111} and {200} planes
Therefore

Sin 2 A
Sin 2 B

(12 12 12 )

0.75

(22 02 02 )

3-42

Crystal Structure of Unknown Metal

Unknown
metal
Crystallographic
Analysis

Sin2 A

0.75

Sin B
FCC
Crystal
Structure

Sin2 A

0 .5

Sin2 B
BCC
Crystal
Structure

3-43

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