Crystal structure of Solids Crystal structure of Solids

Crystalline Solid
a solid that contains a regular and g
repeating atomic or molecular arrangement
over large atomic distances (long-range g ( g g
order)
ex. metals, ceramics and some polymers ex. metals, ceramics and some polymers
Non-crystalline Solid
lid ith t l d i t a solid without long-range ordering atoms
or molecules
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also termed amorphous
Definitions Definitions
L tti Lattice
a three dimensional network of imaginary
lines connecting points (atoms) in space lines connecting points (atoms) in space
Basis
t f t tt h d t an atom or group of atoms attached to every
lattice point
every basis is identical in composition every basis is identical in composition,
arrangement and orientation
Crystal Structure Crystal Structure
the manner in which atoms, ions or molecules
are spatially arranged
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are spatially arranged
Crystal Structure = Lattice + Basis
Definitions Definitions
U it ll (P i iti C ll) Unit cell (Primitive Cell)
the smallest group of atoms possessing the
s mmetr of the cr stal hich hen repeated symmetry of the crystal which, when repeated
in all directions, will develop the crystal lattice
Parameters used to describe a unit cell: Parameters used to describe a unit cell:
lattice constants/parameter : edge lengths
alongthe major axes (a b c) along the major axes (a,b,c)
interaxial angles : angles between axes
(,,) (,,)
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Types of unit cells: Types of unit cells:
1) Si l t l iti d t th 1) Simple atoms are only positioned at 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-centered atoms are positioned at 4) Base centered atoms are positioned at
the corners, as well at two opposite faces of
the cube (usually at the top and bottom
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the cube (usually at the top and bottom
faces)
Crystal systems Crystal systems
h b hi h t l t t a scheme by which crystal structures are
classified according to unit cell geometry;
i l ifi d di t l ti hi i.e., classified according to relationships
between edge lengths and interaxial angles
there is a total of seven crystal systems:
cubic, hexagonal, tetragonal, rhombohedral, g g
orthorhombic, monoclinic, triclinic
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1) Cubic 1) Cubic
Axial relationships: a = b = c
Interaxial angles: = = = 90 g
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2) Hexagonal 2) Hexagonal
A i l l ti hi b Axial relationships: a = b c
Interaxial angles: = = 90 ; = 120
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3) Tetragonal 3) Tetragonal
A i l l ti hi b Axial relationships: a = b c
Interaxial angles: = = = 90
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4) Rhombohedral/Trigonal 4) Rhombohedral/Trigonal
A i l l ti hi b Axial relationships: a = b = c
Interaxial angles: = = 90
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5) Orthorhombic 5) Orthorhombic
A i l l ti hi b Axial relationships: a b c
Interaxial angles: = = = 90
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6) Monoclinic 6) Monoclinic
A i l l ti hi b Axial relationships: a b c
Interaxial angles: = = 90
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7) Triclinic 7) Triclinic
A i l l ti hi b Axial relationships: a b c
Interaxial angles: 90
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Bravais lattice Bravais lattice
th ti l d i ti f th ibl mathematical derivation of the possible
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
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Bravais lattices Bravais lattices
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Bravais lattices Bravais lattices
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Principal Metallic Structures 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
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(Hard sphere model) (Point model)
FCC structure FCC structure
Ex Cu Al Ex. Cu, Al,
Ag, Au
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Principal Metallic Structures Principal Metallic Structures
2. Body-centered cubic (BCC)
atoms are situated at the corners, as well as at
the (body) center of the cube
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(Hard sphere model) (Point model)
BCC structure BCC structure
Ex Cr Fe W Ex. Cr, Fe, W
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Principal Metallic Structures Principal Metallic Structures
3.Hexagonal close-packed (HCP)
has two basal planes in the form of regular hexagons with
an atomat each corner of the hexagon and one atomat the 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
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(Hard sphere model) (Point model)
HCP structure HCP structure
Ex. Cd, Co, Ti, Zn
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Characteristics of a crystal structure Characteristics of a crystal structure
1. Coordination number
number of nearest neighbor atoms 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, a
o
and
the atomic radius, r
expression relating the lattice constant,
a
o
with the atomic radius, r
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a
o
with the atomic radius, r
Characteristics of a crystal structure Characteristics of a crystal structure
4. Atomic Packing Factor (APF)
fraction of space filled by spherical atoms fraction of space filled by spherical atoms
ratio of the volume occupied by atoms to the
total available volume total available volume
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Summary of crystal structure characteristics Summary of crystal structure characteristics
Structure
CN Atoms/
cell
Equivalent
of a
APF
cell of a
o
BCC 8 2 0.68
3
4R
2
4R
FCC 12 4 0.74
3
HCP 12 6 2R 0.74
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Polymorphism and allotropy Polymorphism and allotropy
Polymorphism
phenomenon wherein solids can possess p p
more than one crystal structure
Allotropy Allotropy
polymorphism in elemental solids
E P F Ex. Pure Fe
- BCC at room temperature
- FCC at 912C
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Density computations Density computations
knowledge of the crystal structure permits
computation of theoretical density, :
where,
n = number of atoms per unit cell p
A = atomic weight
V
C
= volume of unit cell
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N
A
= Avogadros number (6.023x10
23
atoms/mol)
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Sample problem 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.
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