Crystal structure of Solids

Crystalline Solid
– a solid that contains a regular
g and
repeating atomic or molecular arrangement
over large
g atomic distances ((long-range
g g
order)
– ex. metals, ceramics and some polymers
Non-crystalline Solid
– a solid
lid without
ith t llong-range ordering
d i atoms
t
or molecules
– also termed “amorphous”
1
Definitions
Lattice
L tti
– a three dimensional network of imaginary
lines connecting points (atoms) in space
Basis
– an atom
t or group off atoms
t attached
tt h d to
t every
lattice point
– every basis is identical in composition
composition,
arrangement and orientation
Crystal Structure
– the manner in which atoms, ions or molecules
are spatially arranged
Crystal Structure = Lattice + Basis 2
Definitions
Unit
U it cellll (Primitive
(P i iti Cell)
C ll)
– the smallest group of atoms possessing the
s mmetr of the cr
symmetry crystal
stal which,
hich when
hen repeated
in all directions, will develop the crystal lattice
Parameters used to describe a unit cell:
• lattice constants/parameter : edge lengths
along the major axes (a (a,b,c)
b c)
•interaxial angles : angles between axes
(α,β,γ)

3
Types of unit cells:
1) Si
Simplel – atoms
t are onlyl positioned
iti d att th
the
corners
2) Body-centered – an additional atom is
positioned at the center of the unit cell
3) Face-centered – atoms are positioned at
the corners, as well at the faces of the unit
cell
4) Base
Base-centered
centered – atoms are positioned at
the corners, as well at two opposite faces of
the cube (usually at the top and bottom
faces) 4
Crystal systems
→ a scheme
h b
by which
hi h crystal
t l structures
t t are
classified according to unit cell geometry;
i
i.e., classified
l ifi d according
di to t relationships
l ti hi
between edge lengths and interaxial angles
→ there is a total of seven crystal systems:
cubic, hexagonal,
g tetragonal,
g rhombohedral,
orthorhombic, monoclinic, triclinic

5
1) Cubic
Axial relationships: a = b = c
g
Interaxial angles: α = β = γ = 90°

6
2) Hexagonal
Axial
A i l relationships:
l ti hi a=b≠c
Interaxial angles: α = β = 90° ; γ = 120°

7
3) Tetragonal
Axial
A i l relationships:
l ti hi a=b≠c
Interaxial angles: α = β = γ = 90°

8
4) Rhombohedral/Trigonal
Axial
A i l relationships:
l ti hi a=b=c
Interaxial angles: α = β = γ ≠ 90°

9
5) Orthorhombic
Axial
A i l relationships:
l ti hi a≠ b≠ c
Interaxial angles: α = β = γ = 90°

10
6) Monoclinic
Axial
A i l relationships:
l ti hi a≠ b≠ c
Interaxial angles: α = γ = 90° ≠ β

11
7) Triclinic
Axial
A i l relationships:
l ti hi a≠ b≠ c
Interaxial angles: α ≠ β ≠ γ ≠ 90°

12
Bravais lattice
→ mathematical
th ti l d
derivation
i ti off th
the possible
ibl
number of ways of arranging atoms in
space
→ arrived at by combining one of the seven
crystal systems with the basic types of unit
cells

13
Bravais lattices

14
Bravais lattices

15
Principal Metallic Structures
1. Face-centered cubic (FCC)
– atoms are situated at the corners of the unit cell,
as well as at the centers of each face; each
face atom touches its nearest corner atoms

(Hard sphere model) (Point model) 16

FCC structure

Ex. Cu
Ex Cu, Al
Al,
Ag, Au

17
Principal Metallic Structures
2. Body-centered cubic (BCC)
– atoms are situated at the corners, as well as at
the (body) center of the cube

(Hard sphere model) (Point model)

18
BCC structure

Ex Cr,
Ex. Cr Fe,
Fe W

19
Principal Metallic Structures
3.Hexagonal close-packed (HCP)
– has two basal planes in the form of regular hexagons with
an atom at each corner of the hexagon and one atom at the
center. In addition, there are three atoms in the form of a
triangle midway between the two basal planes

(Hard sphere model) (Point model) 20

HCP structure

Ex. Cd, Co, Ti, Zn

21
22
Characteristics of a crystal structure

1. Coordination number
→ number of nearest neighbor atoms
2. Number of atoms per unit cell
→ equivalent number of atoms enclosed
by the unit cell
3. Relationship of the cube side, ao and
the atomic radius, r
→ expression relating the lattice constant,
ao with the atomic radius, r
23
Characteristics of a crystal structure

4. Atomic Packing Factor (APF)

→ fraction of space filled by spherical atoms
→ ratio of the volume occupied by atoms to the
total available volume

24
Summary of crystal structure characteristics

Structure CN Atoms/ Equivalent APF

cell of ao
BCC 8 2 4R 0.68
3
FCC 12 4 4R 0.74
2
HCP 12 6 2R 0.74

25
Polymorphism and allotropy
Polymorphism
→phenomenon
p wherein solids can p
possess
more than one crystal structure
Allotropy
→ polymorphism in elemental solids
E P
Ex. Pure Fe
F
- BCC at room temperature
- FCC at 912°C

26
Density computations
→ knowledge of the crystal structure permits
computation of theoretical density, ρ:

where,
n = number of atoms pper unit cell
A = atomic weight
VC = volume of unit cell
NA = Avogadro’s number (6.023x1023 atoms/mol)

27
Sample problem
Copper has an atomic radius of 0.128 nm, an
FCC crystal structure, and an atomic weight
of 63.5 g/mol. Compute its theoretical density
and compare the answer with its measured
density.

28