MODULE

The Chemistry of
Engineering Materials

Contents:
Chapter 4: Basic Concepts of Crystal Structure
Chapter 5: Metals
Chapter 6: Polymers
Chapter 7: Engineered Nanomaterials
 MODULE 2: THE CHEMISTRY OF ENGINEERING MATERIALS

CHAPTER 4: Basic Concepts of Crystal Structure

Solids and Modern Materials

Modern devices like computers and cell phones are built from solids with very
specific physical properties. For example, the integrated circuit that is at the heart of
many electronic devices is built from semiconductors like silicon, metals like copper, and
insulators like hafnium oxide. Hard drives, which store information in computers and
other devices, consist of a thin layer of a magnetic alloy deposited on glass substrate.

Scientists and engineers turn almost exclusively to solids for materials used in
many other technologies: alloys for magnets and airplane turbines, semiconductors for
solar cells and light-emitting diodes, polymers for packaging and biomedical
applications. Chemists have contributed to the discovery and development of new
materials either by inventing new substances or by developing the means for processing
natural materials to form substances that have specific electrical, magnetic, optical, or
mechanical properties. In this chapter, we explore the structures and properties of solids.
As we do so, we will examine some of the solid materials used in modern technology.

Classifications of Solids

Solids can be as hard as diamond or as soft as wax. Some readily conduct

electricity, whereas others do not. The shapes of some solids can easily be manipulated,
while others are brittle and resistant to any change in shape. The physical properties as
well as the structures of solids are dictated by the types of bonds that hold the atoms in
place. We can classify solids according to those forces (see Figure 4.1).
Metallic solids are held together by a delocalized “sea” of collectively shared valence
electrons. This form of bonding allows metals to conduct electricity. It is also responsible
for the fact that most metals are relatively strong without being brittle.
Ionic solids are held together by the mutual attraction between cations and anions.
Differences between ionic and metallic bonding make the electrical and mechanical
properties of ionic solids very different from those of metals.
Covalent-network solids are held together by an extended network of covalent bonds.
This type of bonding can result in materials that are extremely hard, like diamond, and
it is also responsible for the unique properties of semiconductors.
Molecular solids are held together by the intermolecular forces. Intermolecular forces
hold molecules together in a liquid or solid.
 Figure 4.1

Structures of Solids

Solids have different structures contributing to their different physical and

chemical properties. These structures are classified into two (2) mainly:

1) Crystalline Solids

2) Amorphous Solids

Solids in which atoms are arranged in an orderly repeating pattern are called crystalline
solids. These solids usually have flat surfaces, or faces, that make definite angles with
one another. The orderly arrangements of atoms that produce these faces also cause
the solids to have highly regular shapes (See figure 2). Examples of crystalline solids
include sodium chloride, quartz, and diamond.

Amorphous solids (from the Greek words for “without form”) lack the order found in
crystalline solids. At the atomic level the structures of amorphous solids are similar to
the structures of liquids, but the molecules, atoms, and/or ions lack the freedom of
motion they have in liquids. Amorphous solids do not have the well-defined faces and
shapes of a crystal. Familiar amorphous solids are rubber, glass, and obsidian (volcanic
glass).
Figure 2. Examples of crystalline and amorphous solids. The atoms in crystalline solids
repeat in an orderly, periodic fashion that leads to well-defined faces at the macroscopic
level. This order is lacking in amorphous solids like obsidian (volcanic glass).

Crystals

Because a crystalline solid, oftentimes called crystals consists of repeating patterns, we

can draw these patterns in a three-dimensional figure (Crystal Lattice).

We can represent the entire crystal by drawing the structure of smallest identical unit
that, when stacked together, form the crystal.
Unit Cell

In a crystalline solid there is a relatively small repeating unit, called a unit cell, that is
made up of a unique arrangement of atoms and embodies the structure of the solid. The
structure of the crystal can be built by stacking this unit over and over in all three
dimensions.

There are seven fundamentally different kinds of unit cells, which differ in the relative
lengths of the edges and the angles between them (see Figure 6). Each unit cell has six
sides, and each side is a parallelogram.

2) 3)
1)

5) 6) 7)
4)

Figure 6. The General Features of the Seven Basic Unit Cells. The lengths of the
edges of the unit cells are indicated by a, b, and c, and the angles are defined as follows:
α, the angle between b and c; β, the angle between a and c; and γ, the angle between
a and b.

We will focus primarily on the cubic unit cells, in which all sides have the same length,
and all angles are 90°, but the concepts that we introduce also apply to substances
whose unit cells are not cubic.
Cubic Unit Cell

Let us place certain points in each of the cubic unit cell to introduce the 3
subtypes of a unit cell.

Figure 7

If we place a lattice point at each corner of a unit cell, we get a simple/primitive lattice.
All seven lattices in Figure 6 are primitive lattices. It is also possible to generate what
are called centered lattices by placing additional lattice points in specific locations in the
unit cell. This is illustrated for a cubic lattice in Figure 8. A body-centered cubic
lattice has one lattice point at the center of the unit cell in addition to the lattice points
at the eight corners. A face-centered cubic lattice has one lattice point at the center of
each of the six faces of the unit cell in addition to the lattice points at the eight corners.
Centered lattices exist for other types of unit cells as well. Examples include body-
centered tetragonal and face-centered orthorhombic. Counting all seven primitive
lattices as well as the various types of centered lattices, there are a total of 14 three-
dimensional lattices.

Figure 8. The three types of cubic lattices.

Packing of Spheres

Our discussion of the three-dimensional structures of solids has considered only

substances in which all the components are identical. As we shall see, such substances
can be viewed as consisting of identical spheres packed together in space; the way the
components are packed together produces the different unit cells. Most of the
substances with structures of this type are metals.
1) Simple Cubic Structure

The arrangement of the atoms in a solid that has a simple cubic unit cell was
shown in n part (a) in Figure 7. Each atom in the lattice has only six nearest
neighbors in an octahedral arrangement. Consequently, the simple cubic lattice is
an inefficient way to pack atoms together in space: only 52% of the total space is
filled by the atoms. The only element that crystallizes in a simple cubic unit cell is
polonium.

2)

The arrangement of atoms in a simple cubic unit cell. Each atom in the lattice has six
nearest neighbors in an octahedral arrangement.

2) Body-Centered Cubic Structure

The body-centered cubic unit cell is a more efficient way to pack spheres together
and is much more common among pure elements. Each atom has eight nearest
neighbors in the unit cell, and 68% of the volume is occupied by the atoms. As
shown in part (b) in Figure 7, the body-centered cubic structure consists of a single
layer of spheres in contact with each other and aligned so that their centers are at
the corners of a square; a second layer of spheres occupies the square-shaped
“holes” above the spheres in the first layer. The third layer of spheres occupies the
square holes formed by the second layer, so that each lies directly above a sphere
in the first layer, and so forth. All the alkali metals, barium, radium, and several of
the transition metals have body-centered cubic structures.

3) Closed-Packed Structure

The most efficient way to pack spheres is the close-packed arrangement, which
has two variants. A single layer of close-packed spheres is shown in part (a) in
Figure 10. Each sphere is surrounded by six others in the same plane to produce
a hexagonal arrangement. Above any set of seven spheres are six depressions
arranged in a hexagon. In principle, all six sites are the same, and any one of them
could be occupied by an atom in the next layer. Actually, however, these six sites
can be divided into two sets, labeled B and C in part (a) in Figure 10. Sites B and
C differ because as soon as we place a sphere at a B position, we can no longer
place a sphere in any of the three C positions adjacent to A and vice versa.

Figure 10. Close-Packed Layers of Spheres.