Chapter 3

The Structure of Crystalline Solids

Course Conducted by-

Fatema-Tuz-Zahra
Lecturer,
Dept. of MSE, KUET.
Why Study the structure of Crystalline solids?
❑ The properties of some materials are directly related to their crystal
structures. For example, pure and undeformed magnesium and
beryllium, having one crystal structure, are much more brittle (i.e.,
Fracture at lower degrees of deformation) than pure and undeformed
metals such as gold and silver that have yet another crystal structure.

❑ Furthermore, significant property differences exist between crystalline

and noncrystalline materials having the same composition. For
example, noncrystalline ceramics and polymers normally are optically
transparent; the same materials in crystalline (or semicrystalline) form
tend to be opaque or, at best, translucent.
 Energy and Packing
Energy

• Non dense, random packing typical neighbor

bond length

typical neighbor r
bond energy

Energy

• Dense, ordered packing typical neighbor

bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend

to have lower energies.
 Crystal Structures
❑ Solid materials may be classified according to the regularity with which atoms or ions are
arranged with respect to one another. This is called Crystal Structure.
❑ A crystalline material is one in which the atoms are situated in a repeating or periodic array
over large atomic distances; that is, long-range order exists, such that upon solidification, the
atoms will position themselves in a repetitive three-dimensional pattern, in which each atom
is bonded to its nearest-neighbor atoms.
Example: All metals, many ceramic materials, and certain polymers form crystalline
structures under normal solidification conditions.

❑ For those that do not crystallize, this long-range atomic order is absent; these materials are
called noncrystalline or amorphous materials.
Example: Ceramics, Glass and many plastics.
Lattice: Sometimes the term lattice is used in the context of crystal structures.
“lattice” means a three-dimensional array of points coinciding with atom
positions (or sphere centers).

Unit Cell: The atomic order in crystalline solids indicates that small groups of
atoms form a repetitive pattern. Thus, in describing crystal structures, it is often
convenient to subdivide the structure into small repeat entities called unit cells.
7 Crystal Systems: Crystal structures are divided into groups according to unit cell
geometry (symmetry).
 Metallic Crystal Structures
❑ Tend to be densely packed.

❑ 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 to lower bond energy.
- Electron cloud shields cores from each other

❑ Have the simplest crystal structures.

❑ We will examine four such structures (those of engineering importance)

called: SC, FCC, BCC and HCP
 Simple cubic structure (SC)
• Rare due to low packing density (only Po: Polonium has
this structure)
• Close-packed directions are cube edges.

• Coordination No. = 6
(nearest neighbors) for
each atom as seen
 Atomic packing factor (APF)
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
a 4
unit cell 1 π (0.5a) 3
R=0.5a 3
APF =
a3 volume
close-packed directions
unit cell
contains (8 x 1/8) = Here: a = Rat*2
1 atom/unit
Adapted from Fig. 3.23, Where Rat is the atomic radius
Callistercell
7e.
 Body centered cubic structure (BCC)
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.
ex: Cr, W, Fe (α), Tantalum, Molybdenum
• Coordination # = 8

Adapted from Fig. 3.2,

Callister 7e.

2 atoms/unit cell: (1 center) + (8 corners x 1/8)

(Courtesy P.M.
Anderson)
 Atomic packing factor (BCC)
3a

2a
Close-packed directions:
R
a length = 4R = 3 a

atoms volume
4 3
unit cell 2 π ( 3a/4)
3 atom
APF =
3 volume
Adapted from
Fig. 3.2(a), Callister 7e.
a
unit cell
• APF for a body-centered cubic structure = 0.68
 Face centered cubic structure (FCC)
• Atoms touch each other along face diagonals.
--Note: 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

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: (6 face x ½) + (8 corners x 1/8)

(Courtesy P.M.
Anderson)
 Atomic packing factor (FCC)
• APF for a face-centered cubic structure = 0.74
The maximum achievable APF!
Close-packed directions:
2a length = 4R = 2 a
(a = 2√2*R)
Unit cell contains:
6 x 1/2 + 8 x 1/8
a = 4 atoms/unit cell
Adapted from
atoms volume
Fig. 3.1(a),
Callister 7e.
4 3
unit cell 4 π ( 2a/4)
3 atom
APF =
3 volume
a
unit cell
 Hexagonal Close- packed Structure (HCP)
Six atoms form regular hexagon surrounding one atom in center
Another plane is situated halfway up unit cell
(c-axis) with 3 additional atoms situated at interstices of hexagonal (close-packed)
planes
Cd, Mg, Zn, Ti have this crystal structure
❑ Starting Point → Hexagonal layer
❑ Three positions A (the first layer atomic positions), B & C
(Valleys) are shown
❑ The second layer (of hexagonal packing of atoms) can be
positioned in valley B (or equivalently in valley C)
Part of the hexagonal layer shown

Step-1

A Step-2

AB
❑ The third layer can be positioned with atoms directly above the A layer (Option-1) or with
atoms above the C layer (Option-2)

Layer-3
ABA
(Option-1)
Continuing this
ABAB sequence we
C-site vacant
get the HCP structure
Step-3

(Option-2)

ABC
Continuing this ABCABC
sequence we get the CCP structure
(Though not obvious!)
Hexagonal Close Packed Crystal Structure (HCP)
 Total number of atoms in HCP unit
cell
❑ Atoms per unit cell in HCP crystal system = (contribution of corner
atoms to the unit cell X no. Of corner position) + contribution of base
center position atoms X no. Of base center position) + no. Of atoms
inside the unit cell.
❑ Atoms per unit cell of HCP = 1/6 x 12 + 1/2 x 2 + 3
= 6 atoms/unit cell

Determination of APF-(Hand note)

 PROBLEMS

Worked Example
Zinc has HCP structure. The height of the unit cell is 4.935Å. Find
(i). How many atoms are there in a unit cell? and (ii). What is the
volume of the unit cell ?
Height of the unit cell, c = 4.935Å = 4.935 × 10-10m

In HCP structure, the number of atoms present in the unit cell is 6.

We know that, the ratio

a= , a = 4.935 × a = 3.022 Å
Crystal structure of metals – of engineering interest
 Density computation, Ρ

Mass o Atoms i Uni Cel

Density = ρ =
Tota f on Uni
t l
Cel
l Volume f t l
nA
ρ =
V C NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.023 x 1023 atoms/mol
 THEORETICAL DENSITY, Ρ

• EX: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
N=2
R
a ∴ a = 4R/√3 = 0.2887
nm
atoms ρtheoretical = 7.18 g/cm3
g
unit cell 2 52.00 = 7.19 g/cm3
mol ρactual
ρ=
a3 6.023 x 1023
volume atoms
unit cell mol
 3.5 LOCATIONS IN LATTICES: POINT
COORDINATES
z POINT COORDINATES FOR UNIT
111
CELL CENTER ARE
c
A/2, B/2, C/2 ½½½

000
y
a b POINT COORDINATES FOR UNIT
x CELL (BODY DIAGONAL)
CORNER ARE 111
z 2c

TRANSLATION: INTEGER
MULTIPLE OF LATTICE
b y CONSTANTS IDENTICAL
POSITION IN ANOTHER UNIT
b CELL
 3.6 CRYSTALLOGRAPHIC
DIRECTIONS
z Algorithm
1. Vector is repositioned (if necessary) to
pass through the Unit Cell origin.
2. Read off line projections (to principal axes
of U.C.) in terms of unit cell dimensions a, b,
y and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
x
[uvw]

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 where ‘overbar’ represents a
] negative index
families of directions <uvw>
 What is this Direction ?????

x y z
a/2 b 0c
Projections:
Projections in terms of a,b and c: 1/2 1 0
Reduction: 1 2 0
Enclosure [brackets] [120]
 DETERMINING ANGLES BETWEEN
CRYSTALLOGRAPHIC DIRECTION:

Where ui’s , vi’s & wi’s are the “Miller Indices” of the directions in
question

– also (for information) If a direction has the same Miller Indices as

a plane, it is NORMAL to that plane
 3.7 CRYSTALLOGRAPHIC
PLANES
• Miller Indices: reciprocals of the (three) axial intercepts for a
plane, cleared of fractions & common multiples. All parallel
planes have same miller indices.

• ALGORITHM (CUBIC LATTICES IS DIRECT)

1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no commas i.e., (hkl) → families {hkl}
CRYSTALLOGRAPHIC PLANES --
FAMILIES
CRYSTALLOGRAPHIC PLANES
z
example a b c
1. Intercepts 1 1 ∞ c
2. Reciprocals 1/1 1/1 1/∞
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2 ∞ ∞ c
2. Reciprocals 1/½ 1/∞ 1/∞
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
 CRYSTALLOGRAPHIC PLANES
z
example a b c c
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 y
3. Reduction 6 3 4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)

Determine the Miller indices for the plane shown in the sketch

x y z
Intercepts ∝a -b
Intercept in terms of lattice parameters ∝
c/2 -1
Reciprocals 01/2 -1 2
Reductions N/A
Enclosure (012)
 CRYSTALLOGRAPHIC PLANES
• WE WANT TO EXAMINE THE ATOMIC
PACKING OF CRYSTALLOGRAPHIC
PLANES – THOSE WITH THE SAME
PACKING ARE EQUIVALENT AND PART
OF FAMILIES
• IRON FOIL CAN BE USED AS A
CATALYST. THE ATOMIC PACKING OF
THE EXPOSED PLANES IS IMPORTANT.
a) DRAW (100) AND (111) CRYSTALLOGRAPHIC
PLANES
FOR FE.
B) CALCULATE THE PLANAR DENSITY FOR
EACH OF THESE PLANES.
LOOKING AT THE CERAMIC UNIT CELLS

ADDING IONIC COMPLEXITIES

Cesium chloride (CsCl) unit cell showing (a) ion positions and the two ions per lattice point
and (b) full-size ions. Note that the Cs+−Cl− pair associated with a given lattice point is not
a molecule because the ionic bonding is nondirectional and because a given Cs+ is equally
bonded to eight adjacent Cl−, and vice versa. [PART (B) COURTESY OF ACCELRYS, INC.]
 Sodium chloride (NaCl)
structure showing (a) ion
positions in a unit cell, (b)
full-size ions, and (c) many
adjacent unit cells. [Parts
(b) and (c) courtesy of
accelrys, inc.]
Fluorite (CaF2) unit cell showing (a) ion positions and (b) full-size ions. [PART
(B) COURTESY OF ACCELRYS, INC.]
 4.9 POLYMORPHISM AND
ALLOTROPY
• TWO OR MORE DISTINCT CRYSTAL STRUCTURES
FOR THE SAME MATERIAL
(ALLOTROPY/POLYMORPHISM)iron system:
liquid
TITANIUM 1538ºC
Α (HCP), Β(BCC)-TI BCC δ-Fe
1394ºC
FCC γ-Fe
CARBON:
912ºC
DIAMOND, GRAPHITE BCC α-Fe
 4.20 X-RAY DIFFRACTION

• Diffraction gratings must have spacings comparable to the

wavelength of diffracted radiation.
• Can’t resolve spacings < λ
• Spacing is the distance between parallel planes of atoms.
Sir William Henry Bragg:
•William Henry and William Lawrence Bragg Bragg’s law
(father and son) found a simple interpretation
of von Laue’s experiment.
• They assume that each crystal plane reflects radiation
as a mirror and analyze this situation for cases of
constructive and destructive interference.

Noble
prize
1915!

Conditions for reflection:

The most important thing in science is not so much to obtain
new facts as to discover new ways of thinking about them.
 DERIVATION OF BRAGG’S LAW

θ
dhkl
θ x

Path difference Δ= 2x => phase shift

Constructive interference if Δ=nλ
This gives the criterion for constructive interference:

Bragg’s law tells you at which angle θB to expect maximum

diffracted intensity for a particular family of crystal planes.
For large crystals, all other angles give zero intensity.
FIGURE 3.32 RELATIONSHIP OF THE BRAGG ANGLE (Θ) AND THE
EXPERIMENTALLY MEASURED DIFFRACTION ANGLE (2Θ).

X-ray
intensity nλ
d=
(from 2 sinθc
detector)
θ
θc
 X-RAY DIFFRACTION PATTERN
z z z
c c c

y (110) y y
a b a b a b
Intensity (relative)

x x x (211)

(200)

Diffraction angle 2θ

Diffraction pattern for polycrystalline α-iron (BCC)

Adapted from Fig. 3.20, Callister 5e.