CHAPTER 2

FUNDAMENTALS OF
CRYSTALLOGRAPHY
In the previous chapter various types of atomic bonding
have been concerned. They are determined by the electron
structure of the atoms.The present discussion is devoted to
the next level of the structure of materials,specifically, to
some of the arrangements that may be assumed in the
solid state. Within this framework, concepts of crystallinity
and noncrystallinity are introduced.

The properties of some materials are directly

related to their crystal structures.
 CRYSTAL STRUCTURES

FUNDAMENTAL CONCEPTS

Solid materials may be classified according to the regularity

with which atoms or ions are arranged with respect to one
another. 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.
 All metals, many ceramic materials, and certain polymers
form crystalline structures under normal solidification
conditions.
Some of the properties of crystalline solids depend on the
crystal structure of the material, the manner in which atoms
ions, or molecules are spatially arranged.

When describing crystalline structures, atoms (or ions) are

thought of as being solid spheres having well-defined
diameters. This is termed the atomic hard sphere model in
which spheres representing nearest-neighbor atoms touch
one another.
 Sometimes the term lattice is used in the context of crystal
structures; in this sense lattice means a three-dimensional
array of points coinciding with atom positions (or sphere
centers).

UNIT CELLS
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.
That is the smallest unit of volume that permits identical
cells to stocked together to fill a space.
Different types of unit cell are possible and they are
classified based on their level of symmetry (translation,
rotation, reflection, inversion)

The position of any atoms are given by

rxyz = ax + by + cz (a,b,c are called lattice parameters).

Based on their length equality or inequality and their

orientation, the angle between them is
These indications are sometimes termed lattice parameters
of a crystal structure.
Total of seven crystal systems can defined based on
different possible combinations of a, b, and c, and a, b,
and g,
Bravais lattices
Although there are seven crystal systems, we have a total
of 14 distinct arrangements of lattice points. These unique
arrangements of lattice points are known as Bravais lattices
named after Auguste Bravais. Lattice points are located at
the corners of the unit cells, and in some cases, at either
faces or the center of the unit cell.
 The 14 distinct Bravais lattices

(c) 2003 Brooks/Cole Publishing / Thomson Learning™

 CRYSTALLOGRAPHIC POINTS AND
DIRECTIONS AND PLANES
POINT COORDINATES
The position of any point located within a unit cell may be
specified in terms of its coordinates as fractional multiples of the
unit cell edge lengths (i.e., in terms of a, b, and c).
Example: For the unit cell shown in the accompanying sketch (a),
locate the point P having coordinates ¼, 1, ½,.
CRYSTALLOGRAPHIC DIRECTIONS
A crystallographic direction is defined as a line between two
points, or a vector. The following steps are utilized in the
determination of the three directional indices:

1.A vector of convenient length is positioned such that it passes through the
origin of the coordinate system. Any vector may be translated throughout the
crystal lattice without alteration, if parallelism is maintained.
2.The length of the vector projection on each of the three axes is determined;
these are measured in terms of the unit cell dimensions a, b, and c.
3.These three numbers are multiplied or divided by a common factor to reduce
them to the smallest integer values.
4.The three indices, not separated by commas, are enclosed in square brackets,
thus: [uvw]. The u, v, and w integers correspond to the reduced projections
along the x, y, and z axes, respectively.
The [100], [110], and [111] directions within a unit cell
For each of the three axes, there will exist both positive and
negative coordinates. Thus negative indices are also possible,
which are represented by a bar over the appropriate index.
For example, the [1-11] direction would have a component in
the -y direction.

Example : Determine the indices for the

direction shown in the accompanying figure.
CRYSTALLOGRAPHIC PLANES
Plan in a crystal are described by notations called Miller indices.

Miller indices of a plane indicated by hkl are given by the

reciprocal of the intercepts of the plan of the axe.

The distance of spacing between planes in a crystal for a cubic

system is know as interplanar spacing and is denoted as :
(a is the lattice parameter)

the integer indices, not separated by commas, are enclosed within

parentheses, thus: (hkl).
CRYSTALLOGRAPHIC PLANES

Example: Determine the Miller indices for the

plane shown in the accompanying sketch (a).
 DESCRIPTION OF VARIOUS CRYSTAL
STRUCTURES IN METALS
The Face-Centered Cubic Crystal Structure
In this structure, there are atoms located at each of the
corners and the centers of all the cube faces. Some of the
familiar metals having this crystal structure are copper,
aluminum, silver, and gold.

A cube has 8 corners and 6 faces. So, the number of atoms

in one FCC unit cell is
 1  1
 8x    6 x   4
 8  2
  Face-Centered Cubic Crystal Structure

the cube edge length a and the

atomic radius R are related by
Another important characteristic of a crystal structure is the
coordination number . Coordination number is the number of
nearest-neighbor or touching atoms for a particular atom.

For FCC system, the coordination number is 12. The front face
atom has 4 corner nearest-neighbor atoms surrounding it, 4
face atoms that are in contact from behind, and 4 other
equivalent face atoms residing in the next unit cell to the front.
One final important characteristic of a crystal structure is the
atomic packing factor(APF) .The atomic packing factor is
the fraction of solid sphere volume in a unit cell (or it is the
fraction of space occupied by atoms).
Vatoms
APF 
Vtotal

where Vatoms is the volume of atoms in a unit cell and Vtotal is

the total unit cell volume.
For the FCC structure, the APF is 0.74, which is the
maximum packing possible for spheres all having the same
diameter.
The Body-Centered Cubic Crystal Structure

In this structure, atoms are located at all 8 corners and a

single atom is located at the cube center. Some of the
familiar metals having this crystal structure are chromium,
iron, and tungsten.
The number of atoms in one BCC unit cell is

 1   1
 8x   1x   2
 8   1
 Body-Centered Cubic Crystal Structure

the cube edge length a and the

atomic radius R are related by
The coordination number for the BCC crystal structure is 8;
each center atom has as nearest neighbors its 8 corner
atoms. Since the coordination number is less for BCC than
FCC, so also is the atomic packing factor for BCC lower−
0.68 versus 0.74.
The Hexagonal Close-Packed Crystal Structure
Not all metals have unit cells with cubic symmetry; the final
common metallic crystal structure to be discussed has a unit
cell that is hexagonal.
The top and bottom faces of the unit cell consists of 6 atoms
that form regular hexagons and surround a single atom in the
center. Another plane that provides 3 additional atoms to the
unit cell is situated between the top and the bottom planes.
The atoms in this midplane have as nearest neighbor atoms in
both of the adjacent two planes.
Hexagonal Close-Packed Crystal Structure
Each corner atom at the top and bottom planes is shared by 6
unit cells, so corner atoms contribute 1/6 of a point, top and
bottom face center atoms contribute 1/2, and the midplane
interior atoms contribute 1/1.
The number of atoms in one HCP unit cell:

Top corners: =1
Bottom corners: =1
Top and bottom centers:
Interior:
Total=1 + 1 + 1 + 3 = 6
The coordination number and the atomic packing factor for
the HCP crystal structure are the same as for FCC : 12 and
0.74 respectively.

The HCP metals include cadmium, magnesium, zinc, and

titanium.
HARD-SPHERE MODELS OF METALLIC
CRYSTAL STRUCTURES

BCC FCC HCP

 Theoretical density for metals
A knowledge of the crystal structure of a metallic solid permits
computation of its theoretical density through the relationship

Where Example: Determine the

n : number of atoms associated with density of BCC iron (atomic
each unit cell weigth is (55.847 g/mol), which
has a lattice parameter of
A : atomic weight 0.2866 nm.
NA : Avogadro’s number (6.023x1023
Answer; 7.882g / cm3
atoms/mol)
VC : volume of the unit cell
 Interstitial Sites
 Interstitial sites - Locations between the ‘‘normal’’ atoms or ions in a
crystal into which another - usually different - atom or ion is placed.
Typically, the size of this interstitial location is smaller than the atom or
ion that is to be introduced.
 Cubic site - An interstitial position that has a coordination number of
eight. An atom or ion in the cubic site touches eight other atoms or
ions.
 Octahedral site - An interstitial position that has a coordination number
of six. An atom or ion in the octahedral site touches six other atoms or
ions.
 Tetrahedral site - An interstitial position that has a coordination number
of four. An atom or ion in the tetrahedral site touches four other atoms
or ions.
 Structures of Ionic Materials
 Factors need to be considered in order to understand crystal
structures of ionically bonded solids:
 Ionic Radii
 Electrical Neutrality
 Connection between Anion Polyhedra
 Structures of Ionic Materials
The blende structure (ZnS)

(a) The zinc blende unit cell, (b) plan view.

 Structures of Ionic Materials
Example: potassium chloride (KCl) have NaCl structure. calculate
the Atomic packing factor for the compound.
From Appendix B, rK+ = 0.133 nm and rCl- = 0.181 nm

The ions touch along the body diagonal of the unit cell, so:

a0 = 2rK+ + 2rCl- = 2(0.133) + 2(0.181) = 0628 nm

a0 = 0.363 nm

4 3 4 3
rK  (1 K ion)  rCl  (1 Cl ion)
Packing factor  3 3
a03
4 4
 (0.133)   (0.181)3
3

 3 3
3
 0.725
(0.363)
 NONCRYSTALLINE SOLIDS

Noncrystalline solids lack a systematic and regular

arrangement of atoms over relatively large atomic
distances. Sometimes such materials are also called
amorphous(meaning literally without form), or supercooled
liquids, inasmuch as their atomic structure resembles that
of a liquid.
Crystalline and noncrystalline
structures of silicon dioxide(SiO2)

crystalline SiO2 noncrystalline SiO2

(two-dimensional) (two-dimensional)
 X-RAY DIFFRACTION: DETERMINATION OF
CRYSTAL STRUCTURES
 Diffraction - The constructive interference, or reinforcement, of a
beam of x-rays or electrons interacting with a material. The
diffracted beam provides useful information concerning the
structure of the material.
 Bragg’s law - The relationship describing the angle at which a
beam of x-rays of a particular wavelength diffracts from
crystallographic planes of a given interplanar spacing.
 In a diffractometer a moving x-ray detector records the 2y angles
at which the beam is diffracted, giving a characteristic diffraction
pattern
Diffraction of x-rays by planes
of atoms

SQ  QT  n

SQ  QT  2d sin
This equation is known as
n  2d sin  Bragg’s law
From the measured angle  , which yields the maximum
intensity for the scattered x rays, and the x-ray wavelength
(  ), we can calculate the spacing (d) between atomic planes.
With different orientations of the crystal, we can determine
atomic spacings and electron densities for different directions
through the crystal, in short, the crystal structure.

The diffraction pattern obtained

Photograph of a from a sample of gold powder
XRD diffractometer

(c) 2003 Brooks/Cole Publishing / Thomson Learning