Structure of Materials

Dr. Kazi Hanium Maria

Course teacher
PH-407
 Crystallographic axes
Crystallographic axes: The lines drawn parallel
to the line of intersection of any three faces of the
unit Cell which do not lie in the same plane are
called Crystallographic axes X, Y and Z

Interfacial angles: The angles between three

Crystallographic axes represented by α, β, Ƴ are
called interfacial angles.

Primitives: The intercepts a, b, and c, which define the dimensions of the unit cell
on the respective Crystallographic axes are called primitives of the Unit Cell.

We can have 1D, 2D or 3D arrays (lattices)

 Crystal system
Crystals are grouped into seven crystal systems, according to the
characteristic symmetry of their unit cell. The characteristic symmetry of a
crystal is a combination of one or more rotations and inversions.

There are Seven Basic Crystal Systems

• Cubic Shape of Used as Unit Cell for
Lattice Parameters
• Tetragonal Unit Cell crystal:
• Orthorhombic Cube Cubic (a = b = c,  =  =  = 90)
• Monoclinic Square Prism Tetragonal (a = b  c,  =  =  = 90)
Rectangular Prism
• Triclinic Orthorhombic (a  b  c,  =  =  = 90)
• Rhombohedral
Parallelogram Prism Monoclinic (a  b  c,  =  = 90  )
(Trigonal) Parallelepiped
Triclinic (a  b  c,     )
• Hexagonal (general)
Parallelepiped
Rhombohedral
(Equilateral, (a = b = c,  =  =   90)
(Trigonal)
Equiangular)
120 Rhombic (a = b  c,  =  = 90,  =
Hexagonal
Prism 120)
 Bravas Lattice
• In 1848, Auguste Bravais demonstrated that in a 3-dimensional
system, there are fourteen possible lattices.

• Bravais showed that there are only 14 independent ways of arranging

points in space so that the environment looks the same from each
point. These lattices are called Bravais lattices

• A Bravais lattice is an infinite array of discrete points with identical

environment

• seven crystal systems + four lattice centering types = 14 Bravais

lattices

• Lattices are characterized by translation symmetry

 Crystalline Materials
• Atoms arranged in repeating and regular array
• Unit cells ® individual crystals ® structural part
– Unit cell - smallest repeating unit

Body-centered cubic (BCC)

Face-centered cubic (FCC)

Hexagonal-close-packed (HCP)
 Contributions per Unit Cell
Atoms that are entirely within a unit cell each contribute a full atom to the cell
stoichiometry, but the atoms in the faces, corners, and edges are shared by
more than one unit cell, and the number of atoms they contribute to each unit
cell is given below.

8 𝑐𝑜𝑟𝑛𝑒𝑟𝑠 1 𝑎𝑡𝑜𝑚 1 𝑎𝑡𝑜𝑚

× = = Atoms located on the corners of the unit
𝑈𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 8 𝑐𝑜𝑟𝑛𝑒𝑟 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
cell contribute 1 atom per unit cell.

6 𝑓𝑎𝑐𝑒𝑠 1 𝑎𝑡𝑜𝑚 3 𝑎𝑡𝑜𝑚

× = = Atoms located on the faces of the unit cell
𝑈𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 2 𝑓𝑎𝑐𝑒𝑠 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
contribute 3 atoms per unit cell.

12 𝑒𝑑𝑔𝑒𝑠 1 𝑎𝑡𝑜𝑚 3 𝑎𝑡𝑜𝑚

× = = Atoms located on the edges of the unit cell
𝑈𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 4 𝑒𝑑𝑔𝑒𝑠 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
contribute 3 atoms per unit cell.
The particles on the eight corners combine to contribute 1 particle to a unit cell.
Particles in the six face centers combine to contribute 3 particles to a unit cell.
Those on the twelve edges combine to contribute 3 particles per unit cell.
Problem: Three atoms A, B, C, crystallize in a cubic solid lattice where A atoms
are present at the body centre, B atoms are present at the edge centres as well
as the corners of the cube and C atoms are present at the face centres of the
cube .Now if all the atoms are removed from the two 4-fold axis and the one two
fold axis passing through the cube then what is the formula of the compound?

Solutions:
 Simple Cubic Structure (SC)
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination number # = 6
(# nearest neighbors)

The volume of atoms in unit cell* [*assume hard spheres]

Atomic Packing Factor, APF =
Volume of a unit cell

atoms
volume
a unit cell atom
4
1×3𝜋 0.5𝑎 3
R=0.5a APF =
𝑎3 volume
= 0.52
unit cell
close-packed directions contains 8 x 1/8 = 1 atom/unit cell
 Body-Centered Cubic Structure (BCC)
Atoms touch each other along cube diagonals. All atoms are identical; the
center atom is shaded differently only for ease of viewing. ex: Cr, W, Fe
(), Tantalum, Molybdenum.
Coordination number # = 8

R
a
Close-packed directions: length = 4R = 3𝑎
2 atoms/unit cell: 1 center + 8 corners x 1/8
atoms
volume
unit cell atom 3a
4 3𝑎
2×3𝜋( 4 )3
APF = a
𝑎3 volume
= 0.68 unit cell 2a
 Face Centered Cubic Structure (FCC)
Atoms touch each other along face diagonals. All atoms are identical; the face-
centered atoms are shaded differently only for ease of viewing. ex: Al, Cu, Au, Pb, Ni,
.
Pt, Ag.
Coordination # = 12

2
a

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8 Close-packed directions: length = 4R = 2𝑎

1 1 𝑎𝑡𝑜𝑚𝑠 atoms
𝑈𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑐𝑜𝑛𝑡𝑎𝑖𝑛𝑠: 6 × + 8 × = 4
2 8 𝑢𝑛𝑖𝑡
𝑐𝑒𝑙𝑙 volume
unit cell atom
4 2𝑎
4×3𝜋( 4 )3
APF = volume
𝑎3
= 0.74 unit cell
 FCC Stacking Sequence
• ABCABC... Stacking Sequence
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C
 Hexagonally Close Packed
• 6 around 1 on top
ABAB... Stacking Sequence • 6 around 1 on bottom
• 3 at mid-height
ex: Cd, Mg, Ti, Zn
Coordination number # = 12

A sites Top layer

c
B sites Middle layer
A sites Bottom layer
a

3D Projection 2D Projection
• APF = 0.74
• c/a = 1.633 6 atoms/unit cell
 Miller indices
The orientation of planes or faces in a crystal can be described in terms of their
intercepts on the three axes.

Miller introduced a system to designate a plane in a crystal.

He introduced a set of three numbers to specify a plane in a crystal.

This set of three numbers is known as the ‘Miller Indices’ of the concerned plane.
Procedure for finding Miller Indices
Step 1: Determine the intercepts of the plane along the axes X,Y, and Z in terms of
the lattice constants a,b, and c.
Step 2: Determine the reciprocals of these numbers.
Step 3: Find the least common denominator (lcd) and multiply each by this lcd.
Step 4:The result is written in parentheses. This is called the `Miller Indices’ of the
plane in the form (h k l).
This is called the `Miller Indices’ of the plane in the form (h k l).
 Miller indices
Step 1:The intercepts are 2,3 and 2 on the three axes.

Step 2:The reciprocals are 1/2, 1/3 and 1/2.

Step 3:The least common denominator is ‘6’.

Multiplying each reciprocal by lcd,
we get, 3,2 and 3.

Step 4:Hence Miller indices for the plane ABC is (3 2 3)

IMPORTANT FEATURES OF MILLER INDICES

For the cubic crystal especially, the important features of Miller indices are,
A plane parallel to any of the coordinate axes has an intercept of infinity (). Therefore,
the Miller index for that axis is zero; i.e. for an intercept at infinity, the corresponding index
is zero.
A plane passing through the origin is defined as a parallel plane with non-zero intercepts.
All equally spaced parallel planes have the same ‘Miller indices’ i.e. The Miller indices do
not only define a particular plane but also a set of parallel planes. Thus, the planes whose
intercepts are 1, 1,1; 2,2,2; -3,-3,-3 etc., are all represented by the same set of Miller indices.
 Miller indices
It is only the ratio of the indices which is important in this notation. The (6 2 2) planes
are the same as (3 1 1) planes.

If a plane cuts an axis on the negative side of the origin, the corresponding index is
negative. It is represented by a bar, like (1 0 0). i.e. Miller indices (1 0 0) indicate that the
plane has an intercept in the –ve X–axis.

𝑎
Spacing between planes in a cubic crystal, 𝑑ℎ𝑘𝑙 =
ℎ2 +𝑘 2 +𝑙 2
where dhkl = inter-planar spacing between planes with Miller indices h,k,and l.
a = lattice constant (edge of the cube)
h, k, l = Miller indices of cubic planes being considered.
Problem:
1. Calculate the miller indices for the plane with intercepts 2a, - 3b, and 4c
along the crystallographic axes.
2. The lattice constant for a unit cell of aluminum is 4.031Å Calculate the
interplanar space of (2 1 1) plane.
3. Find the perpendicular distance between the two planes indicated by the
Miller indices (1 2 1) and (2 1 2) in a unit cell of a cubic lattice with a lattice
constant parameter ‘a’.
 Types of Crystal Lattices
Bravais Lattice are the basic lattice arrangements. All other lattices can be
simplified into one of the Bravais lattices. Bravais lattices move a specific basis
by translation so that it lines up to an identical basis. In 3 dimensions, there are
14 Bravais lattices.

Non-Bravais Lattice: Not only the arrangement

but also the orientation must appear exactly
the same from every point in a Bravais lattice

✓ Bravais lattices assume that the basis is reduced to a

single point. Since atoms are also single points, many pure
elements have a crystal structure that is the same as its
Bravais lattice.
✓ To know which Bravais lattice fits a certain pattern, check
for translational symmetry. If we can exactly repeat the
entire structure by a set of translations, that is the lattice.
Another way to think about it is that an infinite lattice is
exactly the same, regardless of which particular point you
start at.
❖ The red side has a neighbor to its immediate left, the blue one instead has a
neighbor to its right.
❖ Red (and blue) sides are equivalent and have the same appearance.
❖ Red and blue sides are not equivalent. The same appearance can’t be obtained
by rotating the blue side 180°.
It is also possible to have larger lattices than the most basic lattice. The smallest
possible unit cell is called the “primitive” unit cell, but in many cases, it’s more natural to
use a larger unit cell that shows full symmetry. For example, the hexagonal Bravais
lattice can be simplified into a rhombus, but this image doesn’t show the full symmetry.

Why Bravais Lattices Matter in Crystallography?

Crystal structures are defined by a lattice and basis. The basis is what gets repeated in
the crystal structure. The lattice is how it gets repeated. Basically, most materials are
crystals, and crystals have a repeating pattern of atoms. Bravais lattices describe the
basic crystal structure The basic crystal structure can make a huge difference in a
material’s properties.
 Crystal Locations, Planes, and Directions
➢ In crystalline materials, it is necessary to specify points, directions, and
planes within unit cells and in the crystal lattice.
➢ Three numbers (or indices) used to designate points, directions (lines), or
planes, based on basic geometric notions.
➢ The three indices are determined by placing the origin at one of the corners
of the unit cell, and the coordinate axes along the unit cell edges.

Cell coordinates specify a position in the lattice and are indicated by the
variables u, v, and w, separated by commas with no brackets:
u distance along the lattice translation vector a
v distance along the lattice translation vector b
w distance along the lattice translation vector c

A unit cell with 𝑥, 𝑦, and 𝑧 coordinate axes

showing axial lengths ( 𝑎 , 𝑏 , and 𝑐 ) and
interaxial angles ( , , and )
 Crystal Locations, Planes, and Directions
A space lattice is a set of points such that a translation from any point in the lattice
by a vector ; 𝑅𝑛 = 𝑛1 𝑎 + 𝑛2 𝑏 locates an exactly equivalent point. This is
translational symmetry. The vectors 𝑎, 𝑏 are known as lattice vectors and (𝑛1, 𝑛2) is a
pair of integers whose values depend on the lattice point. The choice of lattice
vectors is not unique. Thus one could equally well take the vectors 𝑎 and 𝑏’ as a
lattice vectors.

An ideal three dimensional crystal is described by 3

fundamental translation vectors a, b and c. If there is
a lattice point represented by the position vector r,
there is then also a lattice point represented by the
position vector where u, v and w are arbitrary
integers.

Point D(n1, n2) = (0,2) 𝒓 = 𝑢𝒂 + 𝑣𝒃 + 𝑤𝒄

Point F (n1, n2) = (0,-1)
 Crystal Locations, Planes, and Directions
A cell direction is designated by the vector 𝒓, which is
a combination of the lattice translation vectors 𝒂, 𝒃,
and 𝒄 : 𝒓 = 𝑢𝒂 + 𝑣𝒃 + 𝑤𝒄
We choose one lattice point on the line as an origin,
say the point O. Choice of origin is completely
arbitrary since every lattice point is identical. Then we
choose the lattice vector joining O to any point on the
line, say point T.
A direction can also be specified with the cell
coordinates in square brackets, with commas and
fractions removed:
[1 1 1] ≡ [1/2 1/2 1/2] ≡ 1/2𝒂 + 1/2𝒃 + 1/2𝒄

Negative directions are indicated by an overbar 1ത .

All directions are relative to the origin where the three Fig. Shows [111] direction
lattice translation vectors originate.
Determining Miller indices of direction
Determining Miller indices of direction
 210

X=½ ,Y=½,Z=1
X=1,Y=½,Z=0 [½ ½ 1] [1 1 2]
[1 ½ 0] [2 1 0]

X=1,Y=0,Z=0 [1 0 0]
X = -1 , Y = -1 , Z = 0 [1ത 10]
ത
 Crystal Direction

X =-1 , Y = 1 , Z = -1/6
We can move the vector to the origin. [-1 1 -1/6] [6ത 61ത ]
The cell volume, 𝑉 , can be calculated using the lattice translation vectors:
𝑉 = 𝒂 × 𝒃. 𝒄
Mathematically, this is a triple scalar product and can be used to calculate the
volume of any cell, with only a knowledge of the lattice translation vectors.
If the lattice parameters and interaxial angles are known, then:
𝑉 = 𝑎𝑏𝑐(1 − 𝑐𝑜𝑠2𝛼 − 𝑐𝑜𝑠2𝛽 − 𝑐𝑜𝑠2𝛾 + 2𝑐𝑜𝑠𝛼𝑐𝑜𝑠𝛽𝑐𝑜𝑠𝛾)1/2
𝑉 = 𝑎𝑏𝑐 (in case of orthogonal systems (α, β, γ = 90◦ ))
 Problems on Crystal Direction
1.

2.
 Point Coordinates z
111
Any point within a unit cell specified as c
fractional multiples of the unit cell edge
lengths. Position P specified as q r s;
convention: coordinates not separated by
commas or punctuation marks.
000
y
a b
x ·
z 2c
·

· ·
b y
The manner in which the 𝑞, 𝑟, and 𝑠 coordinates at point b
𝑃 within the unit cell are determined. The q coordinate Point coordinates for the
(which is a fraction) corresponds to the distance 𝑞𝑎 unit cell center are
along the 𝑥-axis, where 𝑎 is the unit cell edge length. a/2, b/2, c/2 ½½½
The respective 𝑟 and 𝑠 coordinates for the 𝑦 and 𝑧 axes
are determined similarly. Point coordinates for
unit cell corner are 111
 Point Coordinates
Locate the point (1/4 1 ½)

Problem: Specify point coordinates for all the atom positions for a BCC unit cell.