Chapter 3

Crystal Structure
 The Space Lattice, Unit Cells& lattice
• 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
• Unit cell: is that block of
atoms which repeats itself
to form space lattice.

Unit Cell
• Lattice :means a three dimensional array of points
coinciding with atom position/sphere centers,

• The four basic types of unit cells are

 Simple
 Body Centered
 Face Centered
 Base Centered
 Simple and base center cubic

Simple

Base Centered
 a=b=c
 α = β = γ = 900  a≠ b≠ c
 α = β = γ = 900
 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 FCC Structure HCP Structure

 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 (a=0.289 nm)
 Iron (a=0.287 nm)
 Sodium (a=0.429 nm)
 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 4R
constant a =
3
 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)
 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
 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.

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

After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
 Atomic Packing Factor of metallic Structure

Volume of atoms in unit cell

Atomic Packing Factor of BCC =
Volume of unit cell

 4R 3 
Vatoms = 2.  = 8.373R3
 
 3 
3
 4R 
V unit cell = a3 =   = 12.32 R3
 
 3 

Therefore APF = 8.723 R3 = 0.68

12.32 R3
 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.

• Atom positions are

located using unit
distances along the
axes.
 Directions in Cubic Unit Cells
• In cubic crystals, Direction Indices are vector
components of directions resolved along each axes,
resolved to smallest integers.
• Direction indices are position coordinates of unit cell
where the direction vector emerges from cell surface,
converted to integers.
 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 by that of origin
The direction indices are [212]
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])
 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 , 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 ]
 Miller Indices
• 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.
z Miller Indices =(111)

x
 Miller Indices - Procedure

. Choose a plane that does not pass

through origin

Determine the x,y and z intercepts

of the plane

Find the reciprocals of the intercepts

Clear fractions by
Fractions?
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 indicesof cubic crystal plane
forx,y and z axes. Eg: (111)
 Miller Indices - Examples
• Intercepts of the plane at
z
x,y & z axes are 1, ∞ and ∞
(100) • Taking reciprocals we get
y (1,0,0).
• Miller indices are (100).
x
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).
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.
 Hexagonal Unit Cell - Examples
• Basal Planes:-
Intercepts a1 = ∞
a2 = ∞
a3 = ∞
c=1
(hkli) = (0001)
• Prism Planes :-
For plane ABCD,
Intercepts a1 = 1
a2 = ∞
a3 = -1
c=∞
(hkli) = (1010)
 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.

After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.51.)
 Structural Difference between HCP and FCC
Consider a layer Plane A
of atoms (Plane ‘A’) ‘a’ void
‘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

Figure 3.20
 Density computations

Density of metal =  =
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 = 23
  = 4.22 x 10-28 Mg
6.023 10 atmos / mol  g 

 
m

4.22 10  28 Mg
8.98
Mg
8.98
g

V 4.7 10  29 m 3 m3 cm 3
 Planar Atomic Density
Equivalent number of atoms whose
• 
Planar atomic density= =
p
centers are intersected by selected area
Selected area

• Example:- In Iron (BCC, a=0.287), 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

17.2atoms 1.72 1013

 
nm 2 mm 2
 Linear Atomic Density
Number of atomic diameters
intersected by selected length
• Linear atomic density =  l
=
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 ½ + ½ + 1 = 2 atomic diameters.

Length of line = 2 0.361nm

3.92 106 atoms

 l

2atoms

3.92atoms

2 0.361nm nm mm

Figure 3.23
 Polymorphism or Allotropy

• Some metals as well as non metals may

have more than one crystal structure, this
phenomenon is called polymorphism.
• When found in elemental solids that
condition is called allotropy.
• The prevailing crystal structure depend on
both the temperature & external pressure.
 Polymorphism or Allotropy
• Metals exist in more than one crystalline form.
• 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
 Crystal systems

• Crystal structures are grouped according to unit cell

configuration and/or atomic arrangements.
• The unit cell geometry is completely defined in terms of six
lattice parameters;
The three edge length a , b & c and the three interaxial
angles α, β & γ .
• Based on this there are seven different possible combination of
a , b & c and α, β & γ, each of which represents a distinct crystal
system.
 Seven crystal systems

1 Cubic Unit Cell

 a=b=c
 α = β = γ = 900

Simple Body Centered

Face centered

2 Tetragonal
 a =b ≠ c
 α = β = γ = 900

Simple Body Centered

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

3 Orthorhombic
 a≠ b≠ c
 α = β = γ = 900

Simple Base Centered

Body Centered
Face Centered

4 Rhombohedral
 a =b = c
 α = β = γ ≠ 900

Simple
After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.47.)
 Crystal systems (Cont..)

5 Hexagonal
 a≠ b≠ c
 α = β = γ = 900 Simple

6 Monoclinic
 a≠ b≠ c
Base
 α = β = γ = 900
Centered
Simple

7 Triclinic
 a≠ b≠ c
 α = β = γ = 900
Simple
After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.47.)
 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  0 2 )
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

• Random/ irregular arrangement of atoms over

relatively atomic distance.
• Polymers: Secondary bonds do not allow
formation of parallel and tightly packed chains
during solidification.
 Polymers can be semi crystalline.
• 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.
THANK YOU
 Quiz

1. Define crystal and amorphous structure of solids

(2point)

2. Briefly explain the difference between;

 SC,(2point)
 BCC, (2point)
 FCC and (2point)
 HCP structures (2point)