Chapter 3 Crystalline Structure

Chapter Outline
✓ Types of solids
✓ Unit cells
✓ Metallic Crystal structures
✓ Polymorphism and Allotropy
✓ Seven Crystal Systems and Fourteen Lattices
✓ X-ray diffraction

Types of Solids
✓ Crystalline material: atoms self-organize in a periodic array (regular and repeating manner).
✓ Amorphous: lacks a systematic atomic arrangement
✓ Single crystal: are materials in which the atomic order extends uninterrupted over the entirety of the
specimen.
✓ Polycrystalline material: comprised of many small crystals or grains. The grains have different
crystallographic orientation.

Crystalline Amorphous

* There exists atomic mismatch within the regions where grains meet in polycrystalline materials. These regions are
called grain boundaries.

Fig. Atomistic model of a nanocrystalline solid

Crystal Structure
To discuss crystalline structures, it is useful to consider atoms as being hard spheres. In this hard-sphere model, the
shortest distance between two like atoms is one diameter.
For crystalline solids, crystal structure is just the spatial arrangement of hard spheres (atoms).

Face-centered cubic (fcc) structure for metals showing

Left) the representation of the actual packing of atoms
within the unit cell; Middle) An aggregate of many
atoms; Right) a reduced-sphere unit cell.
Unit Cell
The unit cell is the smallest structural unit or building block that can describe the crystal structure. Repetition of the
unit cell generates the entire crystal.

Metallic Crystal Structures

✓ Metals are usually (poly)crystalline; although formation of amorphous metals is possible by rapid cooling.
 ✓ Atomic bonding in metals is non-directional ⇒ no restriction on numbers or positions of nearest-neighbor
atoms ⇒ large number of nearest neighbors and dense atomic packing
✓ Atom (hard sphere) radius, R, defined by ion core radius - typically 0.1 - 0.2 nm
✓ The most common types of unit cells are the faced-centered cubic (FCC), the body-centered cubic (FCC)
and the hexagonal close-packed (HCP).

Two features of a crystal structure are

✓ Coordination number: number of nearest-neighbor atoms.
✓ atomic packing factor: fraction of solid sphere volume in the unit cell.

Face-Centered Cubic (FCC) Crystal Structure (I)

Atoms are located at each of the corners and on the centers of all the faces of cubic unit cell
Cu, Al, Ag, Au, Ni, Pt, Au have this crystal structure
✓ The hard spheres (ion cores) touch one another across a face diagonal; the cube edge length, a=2R√2

✓ The coordination number, CN = the number of closest neighbors to which an atom is bonded = number of
touching atoms, CN = 12
✓ Number of atoms per unit cell, n = 4. (For an atom that is shared with m adjacent unit cells, we only count a
fraction of the atom, 1/m). In FCC unit cell we have:
- 6 face atoms shared by two cells: 6 x 1/2 = 3
- 8 corner atoms shared by eight cells: 8 x 1/8 = 1
✓ Atomic packing factor, APF = fraction of volume occupied by hard spheres = (Sum of atomic
volumes)/(Volume of cell) = 0.74 (maximum possible)
✓ FCC crystal has APF of 0.74, the maximum packing for a system equal-sized spheres ⇒ FCC is a cubic
close-packed (ccp) structure.
✓ FCC can be represented by a stack of close-packed planes (planes with highest density of atoms)

Body-Centered Cubic (BCC) Crystal Structure (I)

✓ Atom at each corner and at center of cubic unit cell
✓ Cr, α-Fe, V, W, Mo have this crystal structure
✓ the presence of alloying elements diminishes crystalline perfection.
Figure 3-4 Body-centered cubic (bcc) structure for metals showing (a) the arrangement of lattice points for a unit
cell; (b) the actual packing of atoms (represented as hard spheres) within the unit cell; and (c) the repeating bcc
structure, equivalent to many adjacent unit cells.

✓ The hard spheres touch one another along cube diagonal⇒ the cube edge length, a= 4R/√3
✓ The coordination number, CN = 8
✓ Number of atoms per unit cell, n = 2
✓ Center atom (1) shared by no other cells: 1 x 1 = 1
✓ 8 corner atoms shared by eight cells: 8 x 1/8 = 1
✓ Atomic packing factor, APF = 0.68
✓ Corner and center atoms are equivalent

Hexagonal Close-Packed Crystal Structure (I)

✓ HCP is also a common structure of metallic crystals
✓ Six atoms form regular hexagon, surrounding one atom in center. Another plane is situated halfway up
unit cell (c-axis), with 3 additional atoms situated at interstices of hexagonal (close-packed) planes
✓ Cd, Mg, Zn, Ti have this crystal structure

Figure 3-6 Hexagonal close packed (hcp) structure

for metals showing (a) the arrangement of atom
centers relative to lattice points for a unit cell.
There are two atoms per lattice point (note the
outlined example). (b) The actual packing of atoms
within the unit cell. Note that the atom in the
midplane extends beyond the unit cell boundaries.

✓ Unit cell has two lattice parameters a and c. Ideal ratio c/a = 1.633
✓ The coordination number, CN = 12 (same as in FCC)
✓ Number of atoms per unit cell, n = 6.
✓ 3 mid-plane atoms shared by no other cells: 3 x 1 = 3
✓ 12 hexagonal corner atoms shared by 6 cells: 12 x 1/6 = 2
✓ 2 top/bottom plane center atoms shared by 2 cells: 2 x 1/2 = 1
✓ Atomic packing factor, APF = 0.74 (same as in FCC)
✓ All atoms are equivalent
Both HCP and FCC structures have atomic packing factors of 0.74, which raises two questions:
(1) In what other ways are the FCC and HCP structures alike?
(2) How do they differ?

✓ Both FCC and HCP crystal structures have atomic packing factors of 0.74 (maximum possible value)
✓ Both FCC and HCP crystal structures may be generated by the stacking of close-packed planes
✓ The difference between the two structures is in the stacking sequence
 HCP: Stacking Sequence ABABAB...
FCC: Stacking Sequence ABCABCABC...

Third plane is placed above the “holes” of the Third plane is placed directly above
first plane not covered by the second plane the first plane of atoms

This subtle difference can lead to significant differences in material!!!

properties.
Crystal systems and Lattices
✓ Crystal systems: the seven-unique unit-cell shapes that can be stacked together to fill three-dimensional
space.
✓ Lattice point: one of a set of theoretical points that are distributed in a periodic fashion in three-
dimensional space.
✓ Point Lattices: arrays of points with identical surroundings in three-dimensional space.
✓ These lattices are skeletons upon which crystal structures are built by placing atoms or groups of atoms
on or near the lattice points.

Some of the simple metal structures are of this type.

Figure 3-3 The simple cubic lattice becomes the simple cubic
crystal structure when an atom is placed on each lattice point.

Polymorphism and Allotropy

✓ Polymorph: chemical compound with different forms: a chemical compound that has several crystalline
forms
✓ Allotropy: occurrence of element in different forms: the existence in more than one form (allotrope) of
the same chemical element, each form differing in physical properties but having the same chemical
properties.
The minerals diamond (shown here cut and uncut) and graphite are different allotropes, or forms, of the
element carbon. Polymorphs form at different depths, and therefore different temperatures and pressures,
within the earth. This produces minerals with very different crystal structures and physical properties.

Seven Systems and Fourteen Lattices

- Seven unique unit-cell shapes that can be stacked together to fill three-dimensional space.

Table 3.1 The Seven Crystal Systems

Table 3.2 The 14 Crystal (Bravais) Lattices

How are atoms stacked together within a given unit cell?
✓ Consider Lattice points (theoretical points arranged periodically in three-dimensional space, rather
than actual atoms or spheres.
✓ Point Lattices: arrays of points with identical surroundings in three-dimensional space. These lattices
are skeletons upon which crystal structures are built by placing atoms or groups of atoms on or near
the lattice points.

Anisotropy
Anisotropic: exhibiting different values of a property in different crystallographic directions.
Isotropic: having direction-independent properties; having physical properties that do not vary with direction
✓ Polycrystalline materials with random grain orientations: Isotropic.
✓ Polycrystalline materials have grains with preferred orientations (texture): Anisotropic.

X-Ray Diffraction: method of determining atomic and molecular structures by measuring patterns of scattered
X rays after they pass through a crystalline substance. Also, the reinforced scattering of x-ray photons by an
atomic structure. Bragg’s law indicates the structural information available from this phenomenon.
✓ Can be used to determine the structure of a new material
✓ The known structure of a common material can be used as a source of chemical identification.

Diffraction: is the result of radiations being scattered by a regular array of scattering centers whose spacing is
about the same as the wavelength of the radiation.