Chapter 3.

The structure of crystalline solids

3.2. Crystallography
3.2.1. Crystal systems 3.2.2. Crystallographic directions and planes 3.2.3. Linear and planar density 3.2.4. Closed-packed crystal structures

3.3. Crystalline and noncrystalline materials

3.3. Crystalline and noncrystalline materials 3.3.1. Single crystal Single crystal is a crystalline solid, when the periodic and repeated arrangement of atoms is perfect or extends throughout the entirety of the specimen without interruption. Single crystals exist in nature and may also be produced artificially. Examples: gem stone, silicone and other semiconductors (electronic microcircuit purposes)

3.3.2. Polycrystalline materials Polycrystalline is a solid which is composed of a collection of many small crystals or grains.

Physical properties of single crystals of some substances depend on the crystallographic direction which measurements are taken. Substances in which measured properties are dependent of the direction of measurement are anisotropy. Example: elastic modulus, electrical conductivity and index of refraction have different values in the [100] and [111] directions. Substances in which measured properties are independent of the direction of measurement are isotropy. Triclinic structures normally are highly anisotropic. The degree of anisotropic increases with the decreasing structural symmetry. The grains in polycrystalline materials have a preferential crystallographic orientation (texture). The magnitude of a measured property represents some average of the directional values.

3.3.3. X-ray diffraction The diffraction phenomenon Diffraction occurs when a wave encounters a series of regularly spaced obstacles that 1. are capable of scattering the wave, 2. have spacings that are comparable in magnitude to the wavelength. The diffraction concept The phase difference between the scattered waves depend on the path length difference and the path length difference is an integral number of wavelength (). Constructive interference (same phase and l = ) Destructive interference (l = )

The Braggs Law The atomic spacings for solids is in the order of X-rays. X-rays are a form of EM radiation that have high energies and short .

Braggs Law

n = 2d sin
hkl

The magnitude of the distance between 2 adjacent and parallel planes of atoms (dhkl) is a function of the Miller indices (h, k, and l) and the lattice parameters

d =
hkl

a h +k +l
2 2

(Cubic system)

where d is the interplanar spacing, a is the lattice parameter

l = SQ + QT = d sin + d sin

Diffraction technique Powder or polycrystalline specimens (C), consisting of many fine and randomly oriented particles, are exposed to monochromatic X-rays (T). A diffractometer (D) is an apparatus used to determine the angles at which diffraction occurs for powder specimens. D is mounted on a movable carriage that may also be rotated about the O axis. Carriage and specimen are mechanically coupled in a way that a rotation of the specimen through is accompanied by a 2 rotation of D. A recorder automatically plots the diffracted beam intensity as a function of 2.

Interplanar spacings for different crystal system

Cubic

Tetragonal

h2 + k2 + 2 2 c a

1 l2 2

Orthorhombic

h2 k2 2 + 2 + 2 b c a

1 l2 2

Hexagonal

4(h 2 + k 2 + kh) + 2 2 3a c

1 l2 2

The high-intensity peaks result when the Bragg diffraction condition is satisfied by some set of crystallographic planes.

3.3.4. Noncrystalline solids Noncrystalline solids or amorphous are materials with lack a systematic and regular arrangement of atoms over relatively large atomic distances. Silicon dioxide (SiO2) may exist in crystalline and noncrystalline structures. Each silicon ion bonds to four oxygen ions for both states, but the structure is more irregular for the noncrystalline structure.

Silicon dioxide (SiO2) in the noncrystalline state is called fused silica or vitreous silica. Other oxides, such as B2O3 and GeO2, may also form glassy structures and polyhedral oxide structures. These materials are called network formers. Network modifiers are usually added to silica glasses to form common glass (for containers, windows etc). Intermediates are also usually added to silica glasses to stabilize the network. Both modifiers and intermediates lower the melting point and viscosity of a glass so that it is easier to form in lower temperatures.