MODULE II

THE CHEMISTRY OF
ENGINEERING MATERIALS

The hard drive of a

computer is made from an
extremely smooth glass disc
coated with a thin layer of a
magnetic alloy of cobalt. To store
and retrieve information, the
read/write head must glide over
the disc at a height of ~1 μm (less
than 1/200 the width of a human
hair) while the disc moves at
speeds in excess of 7000 rpm.
Devices such as this would not
be possible without advanced
solid-state materials.

Modern devices like computers and cellphones 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 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 lesson, we explore the structures and properties of solids. As we do so, we will
examine some of the solid materials used in modern technology.
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LESSON 4 BASIC CONCEPTS OF CRYSTAL STRUCTURE

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).
Above is a pyrite and
obsidian sculpture. Iron
pyrite (FeS2), a
crystalline solid and
obsidian (typically
KAlSi3O8), an amorphous
solid.

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:

• Metallic solids (or simply metals) – held together by a

delocalized “sea” of collectively shared valence
electrons; form of bonding allows metals to conduct
electricity, responsible for the fact that most metals are
relative strong without being brittle
The positive metallic ions are held together by a “glue” of
delocalized electrons. ►

• Ionic solids – held together by the mutual attraction between cations and anions

• Covalent – network solids – held together by an extended network of covalent

bonds; this type of bonding can result in materials that are extremely hard, like
diamond, and is also responsible for the unique properties of semiconductors

• Molecular solids – held together by intermolecular forces: dispersion forces,

dipole-dipole interactions, and hydrogen bonds; these forces are relatively weak
and tend to be soft and have low melting points

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Classifications of solids according to predominant bonding type.

Two classes of solids that do not fall neatly into the preceding categories:

• Polymers – contains long chains of atoms, where the

atoms within a given chain are connected by covalent
bonds and adjacent chains held to one another largely
by weaker intermolecular forces

Formation of Teflon molecule through polymerization from C2F4

monomer. ►

• Nanomaterials – solids in which the dimensions of individual crystals have been

reduced to the order of 1 – 100 nm

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A scale to show the relative dimensions of various objects.

4.1. STRUCTURE OF SOLIDS

The structures of many solids have patterns that repeat over and over in three
dimensions. We can visualize the solid as being formed by stacking a large number of
small, identical structural units, like a wall can be built by stacking identical bricks.

• Crystalline Solids (or true solids) – atoms arranged in an orderly repeating

pattern; usually have flat surfaces, or faces, that make definite angles with one
another
Exists as small crystals, each crystal having a characteristic geometrical shape.

• Amorphous solids – Greek words for “without form”; at atomic level, the
structures are similar to the structures of liquids, but the molecules, atoms, and/or
ions lack the freedom of motion they have in liquids
These solids do not have the well-defined faces and shapes of crystal. Familiar
amorphous solids are rubber, glass and obsidian (volcanic glass)

◄ two-dimensional
representation of
crystalline solid and
an amorphous solid.
Each substance has
the formula A2O3. A is
shown by ● and O is
shown by

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➢ Amorphous substances are said to be isotropic because they exhibit the

same value of any property in all directions. Thus, refractive index, thermal and
electrical conductivities, coefficient of thermal expansion in amorphous solids are
independent of the direction along which they are measured.
➢ Crystalline substances are anisotropic and the magnitude of a physical
property varies with directions. For example, velocity of light in a crystal may
vary with direction in which it is measured. Thus, a ray of light passing through a
Nicol prism splits up into two components, each travelling with different velocity
(double refraction).

Isotropic refers to the properties of a material which is independent of the direction whereas
anisotropic is direction-dependent. The mechanical and physical properties can be easily
affected based on the atom orientation in crystals.
Some examples of isotropic materials are cubic symmetry crystals, glass, etc. Some examples of
anisotropic materials are composite materials, wood, etc.

The Habit of a Crystal

• Habit of the crystal – the external shape

• Faces – the plane surfaces of the crystal
• Interfacial angles – the angles between faces; the interfacial angles for a given
crystalline substance are always the same
► The consistency of interfacial angles is an essential characteristic of crystalline
solids.
Different crystals of the same substance may not look alike. In the presence of certain
impurities, different faces grow at different rates and give rise to many forms
For example, refer to the figure below, if sodium chloride is crystallized from its
supersaturated solution, it forms cubic crystals. But if urea is added as impurity, it gives
octahedral crystals.

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The habit of a crystal of a given compound depend on the rate of development of the
different faces. The external appearance or size of crystals of a substance may be
different but the interfacial angles are always the same.

Symmetry of Crystals
Symmetry in crystals may be due to a plane, a line or a point. Accordingly, there are three
types of symmetry elements associated with a crystal.
Elements of Symmetry
1. Plane of Symmetry – A crystal is said to have a plane of symmetry if it can be
divided by an imaginary plane into two equal parts, each of which is the exact
mirror image of the other.
2. Axis of Symmetry – An imaginary line drawn through the crystal such that
during rotation of the crystal through 360o-, the crystal presents exactly the
same appearance more than once.

Diad axis – also called

as an axis of two-fold
symmetry, if similar view
appears twice

Triad axis – an axis of

three-fold symmetry, if it
appears thrice

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3. Center of Symmetry – it is a point at the center of the crystal so that any line
drawn through it will meet the surface of the crystal at equal distances on either
side.
A crystal may have a number of planes of symmetry or axis of symmetry but it
can have only one center of symmetry.
Crystal Structure
The particles (atoms, ions or molecules) in crystals are highly ordered as is evident from
their geometrical shapes, smooth surfaces and specific interfacial angles.

• Crystal Lattice / Space Lattice / Simply

Lattice – overall arrangement of particles
in a crystal; the geometrical pattern of
points on which the unit cells are arranged
- it is an abstract scaffolding for the
crystal structure
• Unit Cell – the simple basic unit or building
block of the crystal lattice

Structure of Crystalline solid is defined by:

(a) The size and shape of the unit cell; and (b) the location of atoms within the unit cell

A unit cell has one atom or ion at each corner of the lattice, also there may be atoms or
ions in faces and interior of the cell

• Primitive lattice – a regular three-dimensional unit cell with atoms or ions located
at its corner only

• Body-centered cubic lattice – one lattice point at the center of the unit cell in
addition to the lattice points at the eight corners

• Face-centered cubic lattice – one lattice point at the center of the six faces of the
unit cell in addition to the lattice points at the eight corners

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Filling the Unit Cell

The lattice by itself does not define a crystal structure. To generate a crystal structure, we
need to associate an atom or group of atoms with each lattice point.
In most crystals the atoms are not exactly coincident with the lattice points. Instead, a
group of atoms, called motif, is associated with each lattice point.
The crystal structure of graphene below illustrates two important characteristics of
crystals:
(a) No atoms lie on the lattice points (while most of the structures do have atoms on
the lattice points), thus, to build up a structure we must know the location and
orientation of the atoms in the motif with respect to the lattice points.
(b) The bonds can be formed between atoms in neighboring unit cells. This happens
in many crystals, particularly metallic, ionic, and network-covalent solids.

Keep in mind that only elements can form structures of this type. For compounds, even if we were
to put an atom on every lattice point, the points would not be identical because the atoms are not all
of the same.

4.2. METALLIC SOLIDS

- The bonding in metals is too strong to be due to dispersion forces, and yet there
are not enough valence electrons to form covalent bond between atoms.
- Metals also have high electrical conductivity, which means that electrically charged
particles flow easily through them. The thermal conductivity of a metal usually
parallels its electrical conductivity.
- Most metals are malleable, which means that they can be hammered into thin
sheets, and ductile, which means that they can be drawn into wires

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Structures of Metallic Solids

The crystal structures of many metals are simple enough that we can generate the
structure by placing a single atom on each lattice point.
► Each structure can be generated by the combination of a single-atom motif and the
appropriate lattice.
The structures corresponding to the three cubic lattices are shown:

The table summarizes how the fractional part of each atom that resides within a unit cell
depends on the atom’s location in the cell.
Note: A unit cell, represented by a cube, has eight corners.

Fraction of Any Atom as a Function of Location Within the Unit Cell*

Atom Location Number of Unit Cells Fraction of Atom Within
Sharing Atom Unit Cell
Corner 8 1/8 or 12.5%
Edge 4 1/4 or 25%
Face 2 1/2 or 50%
Anywhere else 1 1 or 100%
*It is only the position of the center of the atom that matters. Atoms that reside near the boundary of the
unit cell but not on a corner, edge, or face are counted as residing 100% within the unit cell.

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Number of Atoms or point in a Unit Cell

In counting the number of atoms (or points) per unit cell, we must keep in mind that atoms
on corners of faces are shared with adjoining cells. Therefore, the number of atoms in a
cubic unit cell may be computed as follows:
(1) Simple cubic unit cell contains the equivalent of one atom.
At each corner we have = 1/8 atom
At 8 corners we have = 1/8 x 8 = 1 atom
(2) Face-centered unit cell contains the equivalent of four atoms.
At 8 corners, 1/8 each = 1 atom
6 face-centered sites, ½ each = 3 atoms
Total equivalent atoms = 1 + 3 = 4 atoms
(3) Body-centered unit cell contains the equivalent of two atoms.
At 8 corners, 1/8 each = 1 atom
Central unshared = 1 atom
Total equivalent atoms = 1 + 1 = 2 atoms

Calculation of Mass of the Unit Cell

Mass of the unit cell can be calculated from the number of atoms in the unit cells.
Molar mass of the substance
Mass of one atom =
Avogadro′ s Number

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Sample Problem. The unit cell of metallic gold is FCC (face-centered cubic).
(a) How many atoms occupy the gold unit cell?
(b) What is the mass of a gold unit cell?
Solution
At 8 corners, 1/8 each = 1 atom
Six faces at ½ atom each = 3 atoms
∴ 4 atoms occupy the gold unit cell
molar mass 197 g/mol 1
Mass of gold atom = = ×
Avogadro′ snumber 6.022 × 1023 Au atoms/mol 4
= 8.178 x 10-23 g

Sample Problem. By X-ray diffraction, it is found that nickel crystals are face-centered
cubic. The edge of the unit cell is 3.52 Å. The atomic mass of nickel is 58.7 and its density
is 8.94 g/cm3. Calculate the Avogadro’s number from the data.
Solution
Number of atoms in nickel unit cell = 4 atoms
Let Avogadro’s number = N
58.7
The mass of one Ni atom =
𝑁
58.7
The mass of one-unit cell = 4 ( )g
𝑁
The volume of one-unit cell = (3.52 × 10−8 )3 cm3
58.7
4 ( 𝑁 )g g
Density of Nickel cell = = 8.94 (𝑔𝑖𝑣𝑒𝑛)
(3.52 × 10−8 )3 cm3 cm3
N = 6.02 x 1023

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4.3. CLASSIFICATION OF CRYSTALS ON THE BASIS OF BONDS

Crystals can also be classified on the basis of the bonds that hold the ions, molecules or
atoms together in the crystal lattice. Thus, we have: Ionic crystals, Molecular crystals,
Network covalent crystals, and Metallic crystals.

Ionic Crystals
- Lattice is made of positive and negative ions held together by ionic bonds – the
strong electrostatic attractions between oppositely charged ions.
- Consequently, the cations and anions attract one another and pack together in an
arrangement so that the attractive forces maximize.
- Since the ions are fixed in their lattice sites, typical ionic solids are hard and rigid
with high melting points.

- Ionic solids are brittle and they shatter easily by hammering. A layer of ions slips
away from their oppositely charged neighbors and brings them closer to ions of
like charge
► The increase of electrostatic repulsions along the displaced plane causes to break.
- Ionic solids are non-conduction because the ions are in fixed positions. However,
in the fused state, the ions are allowed freedom of movement so that it becomes
possible for them to conduct electricity.

Molecular Crystals
- In molecular crystals, molecules are the structural units, held together by van der
Waal’s forces.
- The molecules are packed together in a tightly packed pattern because the forces
of attraction are non-directional
- Weak van der Waals forces is the only need to overcome, thus, molecular solids
have low melting points.

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Network Covalent Crystals

- Or also simply called covalent solid – atoms are bonded to one another by
covalent bonds and interlocked by a network of covalent bonds, produces a crystal
which is considered to be a single giant molecule
- These crystals are very hard and have very high melting points.

Structure of Diamond. Diamond offers the best example of a network covalent solid. It
consists of carbon atoms bonded to one another in a three-dimensional pattern to form the
crystal. The diamond crystal made of carbon atoms joined by a network of strong covalent
bonds is the hardest substance known and has an extremely high melting point (3550OC).
Since the bonds between two carbons cannot be distorted to any great extent, the diamond
crystal cannot be distorted but is rather brittle and gives way in the face of a shearing force.

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Metallic Crystals
- The atoms are arranged in different patterns, often in layers placed one above the
other.
- The electrostatic attractions between the metal ions and the electron cloud
constitute the metallic bond.
► A metal crystal may be described as having positive ions at the lattice
positions surrounded by mobile electrons throughout the crystal.
- The mobile electrons in the crystal structure make metals excellent conductors
of heat and electricity.

- On application of force, metals can be deformed. The metal ions in the crystal
change positions without making material difference in the environments. The
attractive force between ions and the electron cloud remains the same, thus
it does not break.

Positive kernels of metallic atoms can be moved within the sea of electrons without materially
changing the environments. That is why metals can be worked into sheets or foils without cracking.

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4.4. STRUCTURE OF METAL CRYSTALS

The spherical atoms are packed together in the lattice very efficiently in geometrical
arrangement as to leave minimum interspaces.
Three dimensional metallic crystals consist of closely packed layers stacked one over the
other. Depending upon the geometrical arrangement of spheres in three layers, the
closed-packed metallic crystals are of two types:

(a) Hexagonal Close-Packed Structure (hcp)

- consists of three layers of spherical atoms packed one
over the another
- The three spheres in the top and the bottom layer fit
into the same voids on either side of the middle layer
► Each sphere in the structure is in contact with 12
neighboring spheres, six in its own layer, three in the
layer above and three in the layer below.
- Coordination number of the close-packed structure is
12
In the overall close-packed structure, the layers repeat in
the manner ABABAB

(b) Cubic Close-Packed Structure (ccp)

- Like hcp structure, it consists of three layers of
spherical atoms lying over one another;
coordination number is also 12
- The three spheres in the top layer do not lie
exactly on the spheres in the bottom layers; the
layers are repeated in the order ABCABCABC
- By turning the whole crystal, you can see that the
ccp structure is just the fcc structure.

The coordination number of a crystal structure is the number of

particles (ions, atoms, or molecules) immediately adjacent to each
particle in the lattice. It is characteristic of a given space lattice
and is determined by inspection of the model.

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▼ Close packing of equal-sized spheres. Hexagonal (left) close packing and cubic
(right) close packing are equally efficient ways of packing spheres.

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◄ The unit cells for (a) a hcp and (b)

a ccp metal. The solid lines indicate the
unit cell boundaries.

Body-Centered Cubic Structure

- About one-third of the meals pack in a bcc structure in which the coordination
number is only 8.
- Each atom touches four atoms in the layer above and four atoms in the layer below

- When a square-packed
layer (non-close packed) is
packed on another layer, a
simple cubic pattern of
spherical atoms results

► the large holes remaining in

the middle of each cube on
slight expansion can
accommodate another
sphere to form a body-
centered cube.

(a) Layers of non-close spheres stacked one on the other. (b) Fifth atom when inserted
in a simple cubic structure forms a body-centered cubic pattern.

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Sample Problem.
It is not possible to pack spheres together without leaving some void spaces between the
spheres. Packing efficiency is the fraction of space in a crystal that is actually occupied
by atoms.
Determine the packing efficiency of a fcc metal.
Solution
A fcc has four atoms per unit cell
4𝜋r 3 16𝜋r 3
Occupied volume = 4 × ( )=
3 3
A fcc metal, the atoms touch along the diagonal of a face of the
unit cell
A diagonal across a face of the unit cell is equal to 4 times the atomic radius, r
Using simple trigonometry,

√2
𝑎 = 4 𝑟 cos(45°) = 4 𝑟 ( ) = (2√2)𝑟
2
We can calculate packing efficiency by dividing the volume occupied by atoms by the
volume of the cubic unit cell, 𝑎3
16
volume of atoms ( 3 ) 𝜋𝑟 3
Packing efficiency = = = 0.74 𝑜𝑟 𝟕𝟒 %
volume of unit cell (2√2)3 𝑟 3

ES CHEM 101 Chemistry for Engineers First Semester AY 2021-2022