Crystalline Structures
Assignment # 2
Submitted To: Sir Nadeem Khan
Crystalline Structures
Crystalline structure is a unique arrangement of atoms or molecules in a crystalline liquid or
solid. A crystal structure is composed of a pattern, a set of atoms arranged in a particular way,
and a lattice exhibiting long-range order and symmetry. Patterns are located upon the points of a
lattice, which is an array of points repeating periodically in three dimensions.
Unit Cell
The unit cell is a small box containing one or more atoms, a spatial
arrangement of atoms. The unit cells, stacked in three-dimensional space,
describe the bulk arrangement of atoms of the crystal. The crystal
structure has a three-dimensional shape. The unit cell is given by its lattice
parameters, which are the length of the cell edges and the angles between
them, while the positions of the atoms inside the unit cell are described by
the set of atomic positions (xi , yi , zi) measured from a lattice point.
Planes and Directions
The crystallographic directions are fictitious lines linking nodes (atoms,
ions or molecules) of a crystal. Likewise, the crystallographic planes are
fictitious planes linking nodes. Some directions and planes have a higher
density of nodes. These high density planes have an influence on the
behavior of the crystal as follows:[1]
Optical properties: Refractive index is directly related to density (or periodic density
fluctuations).
Adsorption and reactivity: Physical adsorption and chemical reactions occur at or near
surface atoms or molecules. These phenomena are thus sensitive to the density of nodes.
Surface tension: The condensation of a material means that the atoms, ions or molecules
are more stable if they are surrounded by other similar species. The surface tension of an
interface thus varies according to the density on the surface.
Microstructural defects: Pores and crystallites tend to have straight grain boundaries
following higher density planes.
Cleavage: This typically occurs preferentially parallel to higher density planes.
Plastic deformation: Dislocation glide occurs preferentially parallel to higher density
planes. The perturbation carried by the dislocation (Burgers vector) is along a dense
direction. The shift of one node in a more dense direction requires a lesser distortion of
the crystal lattice.
In the rhombohedral, hexagonal, and tetragonal systems, the basal plane is the plane
perpendicular to the principal axis.
Lattice systems
These lattice systems are a grouping of crystal structures according to the axial system used to
describe their lattice. Each lattice system consists of a set of three axes in a particular
geometrical arrangement. There are seven lattice systems. They are similar to but not quite the
same as the seven crystal systems and the six crystal families.
The 7 lattice
systems
The 14 Lattice Types
(From least to
most symmetric)
1. triclinic
(none)
simple base-centered
2. monoclinic
(1 diad)
face-
simple base-centered body-centered
centered
3. orthorhombic
(3 perpendicular
diads)
4. rhombohedral
(1 triad)
5. tetragonal simple body-centered
(1 tetrad)
6. hexagonal
(1 hexad)
body-centered face-centered
simple (SC)
(bcc) (fcc)
7. cubic
(4 triads)
The simplest and most symmetric, the cubic (or isometric) system, has the symmetry of a cube,
that is, it exhibits four threefold rotational axes oriented at 109.5° (the tetrahedral angle) with
respect to each other. These threefold axes lie along the body diagonals of the cube. The other
six lattice systems, are hexagonal, tetragonal, rhombohedral (often confused with the trigonal
crystal system), orthorhombic, monoclinic and triclinic.
Types of Crystalline structures based on Chemical Bonds
Covalent Crystals
A covalent crystals has true covalent bonds between all of the atoms in the
crystal. You can think of a covalent crystal as one big molecule. Many covalent
crystals have extremely high melting points. Examples of covalent crystals
include diamond and zinc sulfide crystals.
Metallic Crystals
Individual metal atoms of metallic crystals sit on lattice sites. This leaves
the outer electrons of these atoms free to float around the lattice. Metallic
crystals tend to be very dense and have high
Ionic Crystals
The atoms of ionic crystals are held together by electrostatic forces (ionic bonds).
Ionic crystals are hard and have relatively high melting points. Table salt (NaCl) is
an example of this type of crystal.
Molecular Crystals
These crystals contain recognizable molecules within their structures. A
molecular crystal is held together by non-covalent interactions, like van der
Waals forces or hydrogen bonding. Molecular crystals tend to be soft with
relatively low melting points. The crystalline form of table sugar or
sucrose, is an example of a molecular crystal.
Grain Boundaries
Grain boundaries are interfaces where crystals of different orientations
meet. A grain boundary is a single-phase interface, with crystals on
each side of the boundary being identical except in orientation. The
term "crystallite boundary" is sometimes, though rarely, used. Grain
boundary areas contain those atoms that have been perturbed from their
original lattice sites, dislocations, and impurities that have migrated to
the lower energy grain boundary.
Treating a grain boundary geometrically as an interface of a single
crystal cut into two parts, one of which is rotated, we see that there are
five variables required to define a grain boundary. The first two
numbers come from the unit vector that specifies a rotation axis. The
third number designates the angle of rotation of the grain. The final two
numbers specify the plane of the grain boundary (or a unit vector that
is normal to this plane).
Grain boundaries disrupt the motion of dislocations through a
material, so reducing crystallite size is a common way to improve
strength, as described by the Hall–Petch relationship. Since grain
boundaries are defects in the crystal structure they tend to decrease
the electrical and thermal conductivity of the material. The high
interfacial energy and relatively weak bonding in most grain
boundaries often makes them preferred sites for the onset of corrosion
and for the precipitation of new phases from the solid. They are also
important to many of the mechanisms of creep.
Grain boundaries are in general only a few nanometers wide. In
common materials, crystallites are large enough that grain boundaries
account for a small fraction of the material. However, very small grain sizes are achievable. In
nanocrystalline solids, grain boundaries become a significant volume fraction of the material,
with profound effects on such properties as diffusion and plasticity. In the limit of small
crystallites, as the volume fraction of grain boundaries approaches 100%, the material ceases to
have any crystalline character, and thus becomes an amorphous solid.
