Crystal Structures

Crystalline material
A 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.
Some of the properties of crystalline solids
depend on the crystal structure of the material,
the manner in which atoms, ion or molecules
are spatially arranged.

There is an extremely large number of different

crystal structures all having longrange atomic order;
these vary from relatively simple structures for
metals to exceedingly complex ones, as displayed
by some of the ceramic and polymeric
materials.
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.

Unit cells for most crystal structures are parallelepipeds

or prisms having three sets of parallel faces; one is drawn
within the aggregate of spheres, which in this
casehappens to be a cube.
 an aggregate of
many atoms. (FCC)
Two other important characteristics of a crystal structure are
1. Coordination number
For metals, each atom has the same number of
nearest-neighbor or touching atoms, which is the
coordination number.

2. Atomic packing factor (APF)

is the sum of the sphere volumes of all atoms within a
unit cell (assuming the atomic hard sphere model)
divided by the unit cell volume
METALLIC CRYSTAL STRUCTURES
The Face-Centered Cubic Crystal Structure
(FCC) – with atoms located at each of the
corners and the centers of all the cube faces.
ex. copper, aluminum, silver, and gold
Coordination No. = 12, APF = 0.74
- the cube edge length a and the atomic radius
R are
a = 2R (21/2 )
For the FCC crystal structure
each corner atom is shared among eight
unit cells, whereas a face-centered atom
belongs to only two. Therefore, one-eighth of
each of the eight corner atoms and one-half of
each of the six face atoms, or a total of four
whole atoms, may be assigned to a given unit
cell.
a hard sphere unit cell
2. The Body-Centered Cubic Crystal Structure
has a cubic unit cell with atoms located at all
eight corners and a single atom at the cube
center.
Center and corner atoms touch one another
along cube diagonals, and unit cell length a and
Atomic radius R are related through
a = 4R/31/2

APF = 8, APF = 0.68

3. The Hexagonal Close-Packed Crystal Structure (HCP)
Not all metals have unit cells with cubic symmetry;
The top and bottom faces of the unit cell consist of six
atoms that form regular hexagons and surround a single
atom in the center. Another plane that provides three
additional atoms to the unit cell is situated between the
top and bottom planes. The atoms in this midplane have
as nearest neighbors atoms in both of the adjacent two
planes.

APF = 12, APF = 0.74

POLYMORPHISM AND ALLOTROPY
Some metals, as well as nonmetals, may have more than one crystal
structure, a phenomenon known as polymorphism.

When found in elemental solids, the condition is often termed

allotropy.

The prevailing crystal structure depends on both the temperature

and the external pressure. One familiar example is found in carbon:
graphite is the stable polymorph at ambient conditions, whereas
diamond is formed at extremely high pressures.

Also, pure iron has a BCC crystal structure at room temperature, which
changes to FCC iron at 912 deg.C . Most often a modification of the
density and other physical properties accompanies a polymorphic
transformation.
Crystallographic Points, Directions, and Planes
When dealing with crystalline materials, it often becomes necessary to
specify a particular point within a unit cell, a crystallographic direction,
or some crystallographic plane of atoms. Labeling conventions have
been established in which three numbers or indices are used to
designate point locations, directions, and planes.

The basis for determining index values is the unit cell, with a right
handed coordinate system consisting of three (x, y, and z) axes
situated at one of the corners and coinciding with the unit cell edges.
For some crystal systems—namely, hexagonal, rhombohedral,
monoclinic, and triclinic—the three axes are not mutually
perpendicular, as in the familiar Cartesian coordinate scheme.
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). q, r, and s
where q is some fractional length of a along
the x axis,
r is some fractional length of b along the y axis,
and similarly for s.Thus, the position of P
is designated using coordinates q r s with
values that are less than or equal to
unity.
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.
CRYSTALLOGRAPHIC PLANES
The unit cell is the basis, with the three-axis coordinate
System. In all but the hexagonal crystal system,
crystallographic planes are specified by three Miller
indices as (hkl).
Any two planes parallel to each other are equivalent
and have identical indices.

The procedure employed in determination

of the h, k, and l index numbers is as follows:
1. If the plane passes through the selected origin,
either another parallel plane must be constructed
within the unit cell by an appropriate translation, or
a new origin must be established at the corner of
another unit cell.

2. At this point the crystallographic plane either

intersects or parallels each of the three axes; the
length of the planar intercept for each axis is
determined in terms of the lattice parameters a, b,
and c.
3. The reciprocals of these numbers are taken. A
plane that parallels an axis may be considered to
have an infinite intercept, and, therefore, a zero
index.

4. If necessary, these three numbers are changed to

the set of smallest integers by multiplication or
division by a common factor.

5. Finally, the integer indices, not separated by

commas, are enclosed within parentheses, thus:
(hkl).
CLOSE-PACKED CRYSTAL STRUCTURES
Cryst alline and Noncrystalline Materials

SINGLE CRYSTALS
For a crystalline solid, when the periodic and
repeated arrangement of atoms is perfect or
extends throughout the entirety of the
specimen without interruption, the result is a
single crystal.
Single crystals exist in nature, but they may also be produced
artificially. They are ordinarily difficult to grow, because the
environment must be carefully controlled.

The crystal will assume a regular geometric shape having flat

faces, as with some of the gem stones; the shape is indicative
of the crystal structure.

Within the past few years, single crystals have become

extremely important in many of our modern technologies,
in particular electronic microcircuits, which employ single
crystals of silicon and other semiconductors.
POLYCRYSTALLINE MATERIALS

Most crystalline solids are composed of a collection of many small crystals or

grains; such materials are termed polycrystalline.

Initially, small crystals or nuclei form at various positions.These have random

crystallographic orientations, as indicated by the square grids. The small
grains grow by the successive addition from the surrounding liquid of atoms
to the structure of each. The extremities of adjacent grains impinge on one
another as the solidification process approaches completion.

the crystallographic orientation varies from grain to grain. Also, there exists
some atomic mismatch within the region where two grains meet; this area,
called a grain boundary,
X-RAY DIFFRACTION: DETERMINATION OF
CRYSTAL STRUCTURES
Historically, much of our understanding
regarding
the atomic and molecular arrangements in
solids
has resulted from x-ray diffraction
investigations;

furthermore, x-rays are still very important in

developing new materials
The Diffraction Phenomenon
Diffraction occurs when a wave encounters a
series of regularly spaced obstacles that
(1) are capable of scattering the wave, and
(2) have spacings that are comparable in magnitude
to the wavelength.

Furthermore, diffraction is a consequence of

specific phase relationships established between
two or more waves that have been scattered by the
obstacles.
ANISOTROPY
The physical properties of single crystals of some
substances depend on the crystallographic
direction in which measurements are taken.

For example, the elastic modulus, the electrical

conductivity, and the index of refraction may
have different values in the [100] and [111]
directions.
This directionality of properties is termed
anisotropy, and it is associated with the variance
of atomic or ionic spacing with crystallographic
direction.

Substances in which measured properties are

Independent of the direction of measurement a
are isotropic. The extent and magnitude of
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.
Amorphous materialsare characterized by
atomic or molecular structures that are
relatively complex and become ordered only
with some difficulty.

Furthermore, rapidly cooling through the freezing

temperature favors the formation of a
noncrystalline solid, since little time is allowed for
the ordering process.