Crystal Structures of Solids

Questions to Answer:
What is the difference in atomic
arrangement between crystalline and
noncrystalline solids?
What are the common crystal structures for
metals?
How do we estimate density from crystal
structure information?
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Crystal structure of Solids

Crystalline Solid
a solid that contains a regular and
repeating atomic or molecular arrangement
over large atomic distances (long-range
order)
ex. metals, ceramics and some polymers

Crystal structure of Solids

Non-crystalline Solid
a solid without long-range ordering atoms
or molecules
also termed amorphous or vitreous
ex. Some ceramics and most polymers

Short-Range vs. Long-Range Order

Definitions
Lattice
a three dimensional array of imaginary
lines/points connecting points (atoms) in space

Definitions
Basis/Motif
an atom or group of atoms attached to every
lattice point
every basis is identical in composition,
arrangement and orientation

Definitions
Crystal Structure
the manner in which atoms, ions or molecules
are spatially arranged
Crystal Structure = Lattice + Basis

Definitions
Unit cell (Primitive Cell)
the smallest group of atoms possessing the
symmetry of the crystal which, when repeated
in all directions, will develop the crystal lattice

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Unit Cells

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Description of Unit Cells

Parameters used to describe a unit cell:
lattice constants/parameter : edge lengths
along the major axes (a,b,c)
interaxial angles : angles between axes
(,,)

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Types of unit cells:

1) Simple/Primitive (P) atoms are only
positioned at the corners
2) Body-centered (I) an additional atom is
positioned at the center of the unit cell
3) Face-centered (F) atoms are positioned
at the corners, as well at the faces of the
unit cell
4) Base-centered (C) atoms are positioned
at the corners, as well at two opposite faces
of the cube (usually at the top and bottom
faces)
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Types of Unit Cells

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Crystal systems
a scheme by which crystal structures are
classified according to unit cell geometry;
i.e., classified according to relationships
between edge lengths and interaxial angles
there is a total of seven crystal systems:
cubic, hexagonal, tetragonal, rhombohedral,
orthorhombic, monoclinic, triclinic

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1) Cubic
Axial relationships: a = b = c
Interaxial angles: = = = 90

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2) Tetragonal
Axial relationships: a = b c
Interaxial angles: = = = 90

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3) Orthorhombic
Axial relationships: a b c
Interaxial angles: = = = 90

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4) Monoclinic
Axial relationships: a b c
Interaxial angles: = = 90

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5) Triclinic
Axial relationships: a b c
Interaxial angles: 90

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6) Hexagonal
Axial relationships: a = b c
Interaxial angles: = = 90 ; = 120

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7) Rhombohedral/Trigonal
Axial relationships: a = b = c
Interaxial angles: = = 90

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THE SEVEN CRYSTAL SYSTEMS

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Bravais lattice
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

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Bravais lattices

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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)

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FCC structure

Ex. Cu, Al,

Ag, Au

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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)
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BCC structure

Ex. Cr, Fe, W

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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)

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HCP structure

Ex. Cd, Co, Ti, Zn

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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
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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

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Summary of crystal structure characteristics

Structure

CN

BCC

Atoms/
cell
2

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FCC

Equivalent
of ao

4R
3

APF

0.68
0.74

4R
2

HCP

12

2R

0.74

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Polymorphism and allotropy

Polymorphism
phenomenon wherein solids can possess
more than one crystal structure
Allotropy
polymorphism in elemental solids
Ex. Pure Fe
- BCC at room temperature
- FCC at 912C
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Density computations
knowledge of the crystal structure permits
computation of theoretical density, :

where,
n = number of atoms per unit cell
A = atomic weight
VC = volume of unit cell
NA = Avogadros number (6.023x1023 atoms/mol)

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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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Summary
Atoms may assemble into crystalline or
amorphous structures.
Common metallic crystal structures are FCC,
BCC, and HCP. Coordination number and atomic
packing factor are the same for both FCC and
HCP crystal structures.

We can predict the density of a material, provided

we know the atomic weight, atomic radius, and
crystal geometry (e.g., FCC, BCC, HCP).
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