Structure of Materials I.

Crystalline Solids

The fundamental difference between single crystal, polycrystalline and amorphous solids is the length scale over which the atoms are related to one another by translational symmetry ('periodicity' or 'long-range order'). Single crystals have infinite periodicity, polycrystals have local periodicity, and amorphous solids (and liquids) have no longrange order. Crystalline solids have highly regular arrangement of atoms, ions, or molecules - periodic (repeating).

An ideal single crystal has an atomic structure that repeats periodically across its whole volume. Even at infinite length scales, each atom is related to every other equivalent atom in the structure by translational symmetry.

The symmetry exhibited by real single crystals is determined by the crystal structure of the material Gemstones are often single crystals. They tend to be cut artificially to obtain aesthetically pleasing refractive and reflective properties. This generally requires cutting along crystallographic planes. This is known as cleaving the crystal. A familiar example is diamond, from which decorative stones can be cleaved in different ways to produce a wide range of effects. The characteristic shape of some single crystals is a clue that the properties of the material might be directionally dependent. Single crystals form only in special conditions. The normal solid form of an element or compound is polycrystalline. As the name suggests, a polycrystalline solid or polycrystal is made up of many crystals. The properties of a polycrystal are notably different from those of a single crystal. The individual component crystallites are often referred to as grains and the junctions between these grains are known as grain boundaries. The size of a grain varies according to the conditions under which it formed. Galvanized steel has a zinc coating with visibly large grains. Other materials have much finer grains, and require the use of optical microscopy.

A polycrystalline solid or polycrystal is comprised of many individual grains or crystallites. Each grain can be thought of as a single crystal, within which the atomic structure has long-range order. In most polycrystalline solids, there is no relationship between neighboring grains. Therefore, on a large enough length scale, there is no periodicity across a polycrystalline sample.

The packing of soap bubbles is somewhat similar to the packing of crystals - both systems seek to minimize their surface area. Amorphous solids have no repeating pattern, only short range order. They are extensively disordered - non crystalline (e.g. glasses).

Amorphous materials, like window glass, have no long-range order at all, so they have no translational symmetry. The structure of an amorphous solid (and indeed a liquid) is not truly random - the distances between atoms in the structure are well defined and similar to those in the crystal. This is why liquids and crystals have similar densities - both have short-range order that fixes the distances between atoms, but only crystals have long-range order.

Many characteristic properties of materials, such as mechanical, optical, magnetic and electronic behavior, can be attributed to the difference in structure between these three classes of solid. II. Defects

Within a single crystal or grain, the crystal structure is not perfect. The structure contains defects such as vacancies, where an atom is missing altogether, and dislocations , where the perfection of the structure is disrupted along a line. Grain boundaries in polycrystals can be considered as two-dimensional defects in the perfect crystal lattice. Crystal defects are important in determining many material properties, such as the rate of atomic diffusion and mechanical strength. Even in a single crystal, or large-grained sample, there are still vacancies, as the shot model shows. The reason for this involves entropy: at all finite temperatures, there will be some disorder in the crystal. Note that the packing of atoms at the grain boundaries is disordered compared to the grains. At a grain boundary, the normal crystal structure is obviously disturbed, so the boundaries are regions of high energy. The ideal low energy state would be a single crystal.

Polycrystals form from a melt because crystallization starts from a number of centers or nuclei. These developing crystals grow until they meet. Since they are not usually aligned before meeting, the grains need not necessarily be able to fit together as a single crystal, hence the polycrystalline structure. After crystallization the solid tends to reduce the boundary area, and hence the internal energy, by grain growth. This can only happen by a process of atomic diffusion within the solid. Such diffusion is more rapid at a higher temperature since it is thermally activated. A grain boundary in a 2D lattice is the interface between two regions of crystalline order. Each region or 'grain' has a different orientation with respect to some arbitrary axis perpendicular to the plane of the lattice.

A vacancy is a point defect that arises when an atom is 'missing' from the ideal crystal structure.

A solute atom in a crystal structure is an atomic species that is different from the majority of atoms that form the structure. Solute atoms of similar size to those in the host lattice may substitute for host atoms - these are known as substitutional solutes. Solute atoms that are much smaller than the host atoms may exist within normally empty regions (interstices) in the host lattice, where they are called interstitial solutes.

A dislocation in a 2D close-packed plane can be described as an extra 'half-row' of atoms in the structure. Dislocations can be characterized by the Burgers vector which gives information about the orientation and magnitude of the dislocation.

Dislocation motion along a crystallographic direction is called glide or slip. There must be a local shear stress in an appropriate direction on the dislocation for glide to occur. Dislocation glide allows plastic deformation to occur at a much lower stress than would be required to move a whole plane of atoms past another In three dimensions, the nature of a dislocation as a line defect becomes apparent. The dislocation line runs along the core of the dislocation, where the distortion with respect to the perfect lattice is greatest. There are two types of three-dimensional dislocation. An edge dislocation has its Burgers vector perpendicular to the dislocation line. Edge dislocations are easiest to visualize as an extra half-plane of atoms. A screw dislocation is more complex - the Burgers vector is parallel to the dislocation line. Mixed dislocations also exist, where the Burgers vector is at some acute angle to the dislocation line. In a 2D model such as the bubble raft, only edge dislocations can exist. Dislocations can be observed by a number of methods. Only high-resolution TEM lattice images or STM surface images can show dislocations directly, but etching methods and optical microscopy can be used to elucidate the presence of dislocations, for example on sodium chloride crystal surfaces.

III.

Seven Crystal Systems

A lattice is "an infinite 1, 2, or 3-D regular arrangement of points, each of which has identical surroundings". There are 7 unique unit-cell shapes that can fill all 3-D space. These are the 7 Crystal systems. We define the size of the unit cell using lattice parameters (sometimes called lattice constants, or cell parameters). These are 3 vectors, a, b, c. The angles between these vectors are given by (angle between b and c), (angle between a and c), and (angle between a and b).

Although there are only 7 crystal systems or shapes, there are 14 different crystal lattices, called Bravais Lattices. (3 different cubic types, 2 different tetragonal types, 4 different orthorhombic types, 2 different monoclinic types, 1 rhombohedral, 1 hexagonal, 1 triclinic). Real crystals always possess one of these lattice types, but different crystalline compounds that have the same lattice can have different motifs and different lattice parameters (these depend upon the chemical formula and the sizes of the atoms in the unit cell). We will only concern ourselves with the cubic lattices and hexagonal lattices.

IV.

Bravais Lattices

V.

Cubic Lattices

3 types; simple cubic (also called primitive cubic), lattice points only at corners, body centered cubic (BCC), lattice points at corners and in middle of cube and face centered cubic (FCC) lattice points at the corners and in the middle of each face.

Simple Cubic

Body Centered Cubic (BCC)

Face Centered Cubic (FCC)

VI.

Lattice Planes and Miller Indices

Miller Indices are a method of describing the orientation of a plane or set of planes within a lattice in relation to the unit cell. These indices are useful in understanding many phenomena in materials science, such as explaining the shapes of single crystals, the form of some materials' microstructure, the interpretation of X-ray diffraction patterns, and the movement of a dislocation, which may determine the mechanical properties of the material. In crystallography there are conventions as to how the indices of planes and directions are written. When referring to a specific plane, round brackets are used: (hkl) When referring to a set of planes related by symmetry, then curly brackets are used: {hkl} Directions in the crystal can be labeled in a similar way. These are effectively vectors written in terms of multiples of the lattice vectors a, b, and c. They are written with square brackets: [UVW] A number of crystallographic directions can also be symmetrically equivalent, in which case a set of directions are written with triangular brackets: <UVW> The (100), (010), (001), (00), (00) and (00) planes form the faces of the unit cell. Here, they are shown as the faces of a triclinic (abc, ) unit cell. Although in this image, the (100) and (100) planes are shown as the front and back of the unit cell, both indices refer to the same family of planes, as explained in the animation Parallel lattice planes. It should be noted that these six planes are not all symmetrically related, as they are in the cubic system.

The (101), (110), (011), (10), (10) and (01) planes form the sections through the diagonals of the unit cell, along with those planes whose indices are the negative of these. In the image the planes are shown in a different triclinic unit cell.

VII.

X-ray Diffraction

Xray diffraction is a method of determining the crystal structure of a material. By interpreting the diffraction patterns as reflections from lattice planes in the material, the structure can be determined. X-radiation (X-rays) is the term used to describe electromagnetic radiation with wavelengths between roughly 0.01nm and 10nm. This is shorter than ultraviolet but longer than gamma radiation. The spacing of adjacent atoms in a crystal structure is typically about 0.3nm. The wavelengths of X-rays are therefore of the same order as the atomic spacing in a crystal. Braggs Law The Bragg law is the cornerstone of X-ray diffraction analysis; it allows us to make accurate quantification of the results of experiments carried out to determine crystal structure. An X-ray incident upon a sample will either be transmitted, in which case it will continue along its original direction, or it will be scattered by the electrons of the atoms in the material. All the atoms in the path of the X-ray beam scatter X-rays. In general, the scattered waves destructively interfere with each other, with the exception of special orientations at which Bragg's law is satisfied.

The extra distance that ray B must travel is the distance X-Y-Z. Thus X-Y-Z = n, But X-Y = Y-Z = dhkl sin . Hence, n = 2 dhkl sin Bragg's law, as stated above, can be used to obtain the lattice spacing of a particular cubic system through the following relation:

where a is the lattice spacing of the cubic crystal, and h, k, and l are the Miller indices of the Bragg plane. Combining this relation with Bragg's law:

One of the primary uses of x-ray diffractometry is for the determination of crystal structure. The unit cell size and geometry may be resolved from the angular positions of the diffraction peaks, whereas arrangement of atoms within the unit cell is associated with the relative intensities of these peaks.