2 Crystal Structure Ch3

Copyright © The McGraw-Hill Companies, Inc.
Permission required for reproduction or display
Adapted by Clinton Bemont for UKZN from McGraw-

Hill‟s Foundations of Materials Science and Engineering by
Smith and Hashemi
CHAPTER
3
Crystal
and
Amorphous Structure
in Materials
Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display
Crystal Structure
Animation: The structure of crystalline solids
(this file opens in a new window and

contains audio commentary)
2
3
Atomic Order:
• No order
 monoatomic gases (He, Ar)
•Short-range order
water or water vapour (H20 molecules)
Amorphous glass (tetrahedral silica molecule)
•Long-range order
Crystalline quartz glass (regular, repetitive grid-
like structure)
4
a) Glassy or amorphous solids show no definite solidification / meting

temperature
b) Pure crystalline material with a single solidification / melting
temperature
c) Crystalline mixtures for example metal alloys
Solids arranged in short range order

are called amorphous materials
5
The hexagonal lattice of an ice crystal
6
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 a
space lattice (or crystal lattice).
Animation:
7
• Unit cell is that block of atoms which repeats itself

to form a crystal lattice (space lattice).
Crystal Lattice
Unit Cell
“Unit Cell”
-Definition from Merrian-Webster
“The simplest polyhedron that embodies all of the structural characteristics
of and by infinite repetition makes up the lattice of a crystal”
8
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
The lattice parameter of a unit cell describes its size and shape
completely. Thus the dimensions of the sides and the included
angles are denoted.
9
Types of Unit Cells
• Cubic Unit Cell

 a = b = c (=“a0”)
 α = β = γ = 900
Simple Body Centered

In a cubic unit cell, the lattice
parameter is the length of a side
Face centered measured at room temperature.
• Tetragonal
 a =b ≠ c
 α = β = γ = 900
Simple Body Centered

10
Types of Unit Cells (Cont..)
• Orthorhombic
 a≠ b≠ c
 α = β = γ = 900
Simple Base Centered
Body Centered
Face Centered
• Rhombohedral
 a =b = c
 α = β = γ ≠ 900
Simple
11
Types of Unit Cells (Cont..)
• Hexagonal
 a= b≠ c
 α = β = 120 γ = 900 Simple
• Monoclinic
 a≠ b≠ c
 α = β = γ = 900 Base
Centered
Simple
• Triclinic
 a≠ b≠ c
 α = β = γ = 900
Simple
12
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.
• HCP is denser version of simple hexagonal crystal
structure.
BCC Structure FCC Structure HCP Structure

Figure 3.3
14
Simple Cubic Crystal Structure

Animation:
Represented as one atom at

each corner of a cube
15
Simple Cubic Crystal Structure
Animation: Simple cubic crystal structure
•Each atom has 6 nearest

neighbors.
•Therefore the
coordination number is 6.
(file opens in a new window and

16
Body Centered Structure
Animation:
17
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.
• Examples :-
 Chromium (a0=0.289 nm)
 Iron (a0=0.287 nm)
 Sodium (a0=0.429 nm)
18
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, a = 4R
3
19
Atomic Packing Factor of BCC Structure
Volume of atoms in unit cell

Atomic Packing Factor =
Volume of unit cell
 4 R 3 
Vatoms = 2.  = 8.373R3
 
 3 
3
 4R 
V unit cell = a3 =   = 12.32 R3
 
 3 
8.723 R3
Therefore APF = = 0.68
12.32 R3
20
Body Centered Crystal Structure
Animation: Body centred cubic crystal structure

21
Face Centered Crystal Structure
Animation:
22
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)
23
FCC Crystal Structure (Cont..)
• Each unit cell has eight 1/8

atom at corners and six ½
atoms at the center of six
faces.
• Therefore each unit cell has
(8 x 1/8)+ (6 x ½) = 4 atoms
• Atoms contact each other

across cubic face diagonal
Therefore, lattice 4R
constant a =
2
24
Face centered crystal Structure
Animation: Face centred cubic crystal structure
The FCC crystal lattice

has a co-ordiation
number of 12!

25
Cubic Crystal Structures - Summary
Animation:
26
3-20 Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi
Ionically bonded complex crystal structures
27
Unit Cells – Example - NaCl
Animation:
28
... ionically bonded complex crystal structures
8 Cl atoms around each

Cs atom!
29
Unit Cells – Example - ZnS
Animation:
30
Covalently bonded complex crystal structures
http://www.chemtube3d.com/solidstate/_simplecubic(final).htm
31
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 (as with FCC)
• APF = 0.74 (as with FC)
32
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 ½) + 3 = 6 atoms
• Examples:- 1/2 atom
 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.

Whole atom
33
Structural Difference between HCP and FCC
Plane A
Consider a layer „a‟ void
of atoms (Plane „A‟) „b‟ void
Another layer (plane „B‟) Plane A

of atoms is placed in „a‟ Plane B
Void of plane „A‟ „a‟ void
„b‟ void
Third layer of Atoms placed Third layer of Atoms placed
in „b‟ Voids of plane „B‟. (Identical in „a‟ voids of plane „B‟. Resulting
to plane „A‟.) HCP crystal. In 3rd Plane C. FCC crystal.
Plane A Plane A
Plane B Plane B
Plane A Plane C
34
HCP FCC
38
39
Comparison of FCC and HCP crystals
• Both FCC and HCP are close packed and have

APF 0.74.
• FCC crystal is close packed in (111) plane while
HCP is close packed in (0001) plane.
40
41
SOME EQUATIONS:
Volume of atoms in unit cell

Atomic Packing Factor =
Volume of unit cell
Where,
Vol. of atoms in unit cell = (number of atoms / UC) x (vol. of each atom)
Mass of atoms in 1 UC
(atoms / UC) (molar atomic mass) _

Density =
(vol of UC) (Avogadro‟s number)
Mass of 1 atom
42
Polymorphism or Allotropy
• Many metals can exist in more than one crystalline

form. This is called 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.
Liquid
Iron
-2730C 9120C 13940C 15390C
α Iron γ Iron δ Iron

BCC FCC BCC
…Polymorphism or Allotropy
Polymorphism of carbon
4 common allotropes of carbon
are:
• Diamond (where the carbon
atoms are bonded together in a
tetrahedral lattice arrangement)
• Graphite (where the carbon
atoms are bonded together in
sheets of a hexagonal lattice)
• Graphene (single sheets of
graphite)
• Fullerenes (where the carbon
atoms are bonded together in
spherical, tubular, or ellipsoidal
formations).
Crystalline polymers
45
• HOMEWORK ASSIGNMENT 1
46
Atom Positions in Cubic Unit Cells
• Cartesian coordinate system is used 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.
• Atom positions are

located using unit
distances along the
axes relative to one
atomic lattice
parameter
47
Directions in Cubic Unit Cells
• In cubic crystals, Direction Indices are vector components

of directions resolved along each axis, resolved to smallest
integers.
• Direction indices are position coordinates of unit cell
where the direction vector emerges from cell surface,
converted to integers.
48
Procedure to Find Direction Indices

Produce the direction vector till it
z
emerges from surface of cubic cell
(1,1/2,1) (1,1/2,1) - (0,0,0)
Determine the coordinates of point = (1,1/2,1)
of emergence and origin y
(0,0,0) 2 x (1,1/2,1)
Subtract coordinates of point of x = (2,1,2)
emergence from that of origin
The direction indices are [212]
Are all are NO Convert them to
integers? smallest possible
YES integer by multiplying
Are any of the direction by an integer.
vectors negative?
NO
YES
Represent the indices in a square
Represent the indices in a square
bracket without comas with a
bracket without comas (Eg: [212] )
over negative index (Eg: [121])
49
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).
Subtracting origin coordinates

from emergence coordinates,
(1/4, 1/2, 1/2) - (3/4 , 0 , ¼)
= (-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 ]
50
Crystallographic Directions, Tutorial

• Please click on the image below to begin a short tutorial
on crystallographic directions.
(this file opens in a new window)
51
Miller Indices
• 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 the cubic unit cell.
z
Miller Indices =(111)
x
52
Miller Indices - Procedure
Choose a plane that does not pass If it does then move it one atomic
through origin lattice parameter in any direction
Determine the x,y and z intercepts

of the plane
Find the reciprocals of the intercepts
Clear fractions by
Fractions? Yes
multiplying by an integer
Place a „bar‟ over the to determine smallest set
Negative indices of whole numbers
Enclose in parenthesis (hkl)where h,k,l

are miller indices of cubic crystal plane
for x,y and z axes. Eg: (111)
53
Miller Indices - Examples
• Intercepts of the plane at x,

z
y & z axes are 1, ∞ and ∞
(100) • Taking reciprocals we get
y (1,0,0).
x • Miller indices are (100).
x *******************
• 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).
Some rules for plane and direction indices
• Planes and their negatives are identical

• Planes and their multiples are not identical
• A direction and its negative are in opposite

directions
• A direction and its multiple are identical
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.
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)
To show this plane in a
single unit cell, the (110) z
origin is moved along
the positive direction
of y axis by 1 unit.
y
58
Miller Indices – Important Relationship

• Direction indices of a direction perpendicular to a crystal
plane are same as miller indices of the plane (only
necessarily applies to cubic systems).
• Example:-
[110]
• Interplanar spacing between parallel closest planes with

same miller indices is given by
a
d hkl

k l
2 2 2
h
59
X & Y axes
swapped as
shown...
X & Y axes
normal
position...
(111) (111) (111)
Cubic crystal Planes, Tutorial

• Please click on the image below to begin a short tutorial on
cubic crystal planes.

62
• HOMEWORK ASSIGNMENT 2
63
Planes and Directions in Hexagonal Unit Cells
• Four indices are used (hkil) called 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.
64
Hexagonal Unit Cell - Examples
• Basal Planes:-
Intercepts a1 = ∞
a2 = ∞
a3 = ∞
c=1
(hkil) = (0001)
• Prism Planes :- Figure 3.17 a&b
For plane ABCD,
Intercepts a1 = 1
a2 = ∞
a3 = -1
c=∞
(hkil) = (1010)
67
Directions in HCP Unit Cells
• Indicated by 4 indices [hkil].

• 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.
2
69
Volume Density
• Volume density of metal = v =

Mass/Unit cell
Volume/Unit cell
• Example:- Copper (FCC) has atomic mass of 63.54 g/mol

and atomic radius of 0.1278 nm.
4R 4  0.1278nm
a= = = 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.
(4atoms)(63.54 g / mol)  106 Mg 
Mass of unit cell = m =   = 4.22 x 10-28 Mg
6.02 10 atmos / mol 
23
g 
 m 4.22 1028 Mg
 
vol. V 4.7 1029 m3
 8.98
Mg
m3
 8.98
g
cm 3
 8980
kg
m3
70
Planar Atomic Density

Portion of atoms whose centers are
• Planar atomic density = =
p
intersected by selected area within UC
Selected area
• Example: In Iron (BCC, a = 0.287nm), The (110) plane

intersects center of 5 atoms (four ¼ and 1 full atom).
 Equivalent number of atoms = (4 x ¼ ) + 1 = 2 atoms
Area of 110 plane = 2a  a  2a 2

2
=
2 0.287 
p 2
 17.2 at nm 2
 1.72 1013 at mm2
71
Linear Atomic Density

Number of atomic diameters
intersected by selected length of line

lin. = =
• Linear atomic density
in direction of interest within UC
Length of selected line
• Example:- For a FCC copper crystal (a=0.361), the [110]

direction intersects 2 half diameters and 1 full diameter.
 Therefore, it intersects ½ + ½ + 1 = 2 atomic diameters.
Length of line = 2  0.361nm
 lin.

2atoms
2  0.361nm
 3.92 at nm  3.92 106 at mm
72
73
Producing x-rays
• Information about crystal structure are obtained using

X-Rays.
• The X-rays used are about the same wavelength (0.05-
0.25 nm) as the distance between crystal lattice planes.
35 KV
(Eg: Molybdenum)
/ anode
/ cathode
3-34 After B.D. Cullity, “Elements of X-RayofDiffraction,

Foundations “ 2d ed.,
Materials Science Addison-Wesley,
and Engineering, 5th Edn. 1978, p.23.
Smith and Hashemi
(incoming
electron)
Important:
Atomic orbitals (as above) do not represent the orbit of electrons around the
nucleus. They represent the (quantum) energy state of the electron, with
increasing energy as the orbitals widen.
X-Ray Spectrum of Molybdenum
• X-Ray spectrum of Molybdenum is

obtained when Molybdenum is used
as target metal.
• Kα and Kβ are characteristic of an
element.
• For Molybdenum Kα occurs at a
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
X-Ray Diffraction
• Crystal planes of target metal act as mirrors reflecting

X-ray beam.
• If rays leaving a set of planes
are out of phase (as in case of
arbitrary angle of incidence)
no reinforced beam is
produced.
• If rays leaving are in phase,

reinforced beams are
produced.
79
80
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 λ .
nλ = MP + PN (n = 1,2…)
n is order of diffraction
If dhkl is interplanar distance,
Then MP = PN = dhkl.Sinθ
Therefore, λ = 2 dhkl.Sinθ
3-37 After A.G. Guy and J.J. Hren, “Elements

Foundations of Physical
of Materials Metallurgy,”
Science and 3d5thed.,
Engineering, Edn.Addison-Wesley,
Smith and Hashemi1974, p.201.)
X-Ray Diffraction Analysis
• 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 3.30
3-40 After A.G. Guy “Essentials of Foundations
Materials Science,”
of Materials McGraw-Hill, 1976. 5th Edn.
Science and Engineering, Smith and Hashemi
XRD Results
An example of XRD output for Silicon:

/intensity / brightness
Interpreting Diffraction Data

a
• We know that d hkl

h2  k 2  l 2
(accounting for eg. planes that are not parallel to the co-ordinate system axes)
Since   2dSin
2aSin
Substituting for d, 
h2  k 2  l 2
2 h 2  k 2  l 2
Therefore Sin  
2
4a 2
Note that the wavelength λ and lattice constant a are unchanged

for incoming and outgoing radiation.
Interpreting Diffraction Data (Cont..)
• For planes „A‟ and „B‟ we get two equations

2 ( h A 2  k A 2  l A 2 ) (For plane „A‟)
Sin 2 A 
4a 2
2 ( h B 2  k B 2  l B 2 )
Sin 2 B  (For plane „B‟)
4a 2
Dividing each other, we get
Sin 2 A (hA  k A  l A )
2 2 2

Sin 2 B ( hB  k B  l B )
2 2 2
Diffraction Condition for Cubic Cells
• 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.
Interpreting Experimental Data
• For BCC crystals, the first two sets of diffracting

planes are {110} and {200} planes.
Sin 2 A (12  12  02 )
Therefore   0.5
Sin 2 B (2 2  02  02 )
• For FCC crystals the first two sets of diffracting planes

are {111} and {200} planes
Sin 2 A (12  12  12 )
Therefore   0.75
Sin 2 B (2 2  02  02 )
Crystal Structure of Unknown Metal
Unknown
metal
Crystallographic
Analysis
Sin 2 A Sin 2 A
 0.75  0.5
Sin  B
2
Sin 2 B
FCC BCC
Crystal Crystal
Structure Structure
Amorphous Materials (XRD not usually useful)
• Random spatial positions of atoms

• Polymers: Secondary bonds do not allow
formation of parallel and tightly packed chains
during solidification.
 Polymers can be semicrystalline.
• Glass is a ceramic made up of SiO4 4- tetrahedron
subunits – limited mobility.
• Rapid cooling of metals (10 8 K/s) can give rise to
amorphous structure (metallic glass).
• Metallic glass has superior metallic properties.
Inter-planar spacing
Unit cell volumes
Plane and direction families
• Some planes are of a similar type, depending only how you

“dive in”, eg. (100), (010). These are called families of
planes and any one of the indices of a family may be
placed in curly {hkl} brackets to refer to the whole family.
• Some directions are of a similar

type , depending how you “dive
in”, eg. [100], [001]. These are
called families of directions and
any one of the indices of a family
may be placed in <hkl> brackets
to refer to the whole family.

2 Crystal Structure Ch3

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2 Crystal Structure Ch3

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Copyright © The McGraw-Hill Companies, Inc.

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Adapted by Clinton Bemont for UKZN from McGraw-

Animation: The structure of crystalline solids

(this file opens in a new window and

a) Glassy or amorphous solids show no definite solidification / meting

Solids arranged in short range order

The hexagonal lattice of an ice crystal

The Space Lattice and Unit Cells

• Atoms, arranged in repetitive 3-Dimensional pattern, in

• Unit cell is that block of atoms which repeats itself

Crystal Systems and Bravais Lattice

• Only seven different types of unit cells are

Types of Unit Cells

• Cubic Unit Cell

Simple Body Centered

Simple Body Centered

Types of Unit Cells (Cont..)

Types of Unit Cells (Cont..)

Principal Metallic Crystal Structures

• 90% of the metals have either Body Centered Cubic

BCC Structure FCC Structure HCP Structure

Simple Cubic Crystal Structure

Represented as one atom at

Simple Cubic Crystal Structure

Animation: Simple cubic crystal structure

•Each atom has 6 nearest

(file opens in a new window and

Body Centered Structure

Body Centered Cubic (BCC) Crystal Structure

• Represented as one atom at each corner of cube and one at

BCC Crystal Structure (Cont..)

• Each unit cell has eight 1/8

• Atoms contact each

Atomic Packing Factor of BCC Structure

Volume of atoms in unit cell

Body Centered Crystal Structure

Animation: Body centred cubic crystal structure

(this file opens in a new window and

Face Centered Crystal Structure

Face Centered Cubic (FCC) Crystal Structure

• FCC structure is represented as one atom each at the

FCC Crystal Structure (Cont..)

• Each unit cell has eight 1/8

• Atoms contact each other

Face centered crystal Structure

Animation: Face centred cubic crystal structure

The FCC crystal lattice

(this file opens in a new window and

Cubic Crystal Structures - Summary

Ionically bonded complex crystal structures

Unit Cells – Example - NaCl

... ionically bonded complex crystal structures

8 Cl atoms around each

Unit Cells – Example - ZnS

Covalently bonded complex crystal structures

Hexagonal Close-Packed Structure

HCP Crystal Structure (Cont..)

• Ideal c/a ratio is 1.633.

Structural Difference between HCP and FCC

Another layer (plane „B‟) Plane A

Comparison of FCC and HCP crystals

• Both FCC and HCP are close packed and have