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Big Picture 2

Week 4-5: Unit Learning Outcomes (ULO): At the end of the unit, you are
expected to

a. demonstrate understanding on the basic concepts of crystal structure;

b. differentiate metals and non-metals by understanding their
characteristics;
c. explain the concept of polymers;
d. show understanding of the concept of engineered nanomaterials.

Big Picture in Focus: ULO2a. demonstrate understanding on the basic

concepts of crystal structure

Metalanguage

In this section, the most essential principles and concepts relevant to the study of
crystal structure to demonstrate ULOa will be reviewed. Please refer to these
definitions in case you will encounter difficulty in the in understanding educational
concepts.

Amorphous an amorphous or non-crystalline solid is a solid that lacks the long-range

order that is characteristic of a crystal

Atomic Packing the ratio of volume occupied by the atoms in a unit cell to the total
Factor volume of the unit cell
Body-centered has lattice points at the eight corners of the unit cell plus an additional
cubic point at the center of the cell.
Bravais lattice the fourteen distinguishable ways of arranging the points independently
in three-dimensional space
Coordination defined as the number of equidistant nearest neighbors that an atom
number has in a given structure

Crystal lattice is the symmetrical three-dimensional arrangement of atoms inside a

crystal.

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Cystalline is a solid material whose constituents are arranged in a highly ordered

microscopic structure, forming a crystal lattice that extends in all
directions.
Crystallographic the lines drawn parallel to the lines of intersection of any three faces of
axes the unit cell which do not lie in the same plane

Density mass per unit volume

Face-centered has lattice points at the eight corners of the unit cell plus additional
cubic points at the centers of each face of the unit cell.
Hexagonal layers of spheres are packed so that spheres in alternating layers
close-packed overlie one another. As in cubic close packing, each sphere is
surrounded by 12 other spheres.
Interfacial the angles between three crystallographic axes
angles
Lattice collective term for primitives and interfacial angles
parameters
Primitives the dimensions of a unit cell

Simple cubic is the simplest repeating unit in a simple cubic structure. Each corner of
the unit cell is defined by a lattice point at which an atom, ion, or
molecule can be found in the crystal.

Space lattice defined as an infinite array of points in three dimensions in which every
point has surroundings identical to that of every other point in the array.

Unit cell the smallest group of atoms of a substance that has the overall
symmetry of a crystal of that substance, and from which the entire lattice
can be built up by repetition in three dimensions.
Void space vacant space left or unutilized space in unit cell , and more commonly
known as interstitial space

Essential Knowledge

BASIC CONCEPTS OF CRYSTAL STRUCTURE

In crystallography, crystal structure is a description of the ordered
arrangement of atoms, ions or molecules in a crystalline material. Ordered structures
occur from the intrinsic nature of the constituent particles to form symmetric patterns
that repeat along the principal directions of three-dimensional space in matter (Moore
& Smart, 2005).
The smallest group of particles in the material that constitutes the repeating
pattern is the unit cell of the structure. The unit cell completely defines the symmetry
and structure of the entire crystal lattice, which is built up by repetitive translation of

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the unit cell along its principal axes. The repeating patterns are said to be located at
the points of the Bravais lattice.
The lengths of the principal axes, or edges, of the unit cell and the angles
between them are the lattice constants, also called lattice parameters.
The symmetry properties of the crystal are described by the concept of space
groups. All possible symmetric arrangements of particles in three-dimensional space
may be described by the 230 space groups.
The crystal structure and symmetry play a critical role in determining many
physical properties, such as cleavage, electronic band structure, and optical
transparency.
Crystal structure is one of the most important aspects of materials science and
engineering as many properties of materials depend on their crystal structures. The
basic principles of many materials characterization techniques such as X-ray
diffraction (XRD), Transmission electron microscopy (TEM) are based on
crystallography. Therefore, understanding the basics of crystal structures is of
paramount importance.
Matter exist usually in solid or fluid (liquid, gas) state. According to modern
concept matter classification is specified as condensed state and gaseous state.
Solids and liquids come under condensed state. Any material whose position of
constituent particles is fixed can be regarded as solids.

Solids are characterized by incompressibility, rigidity and mechanical strength.

This indicates that the molecules, atoms or ions that make up as solid is closely
packed. Thus in solids we will have a well ordered molecular, atomic or ionic
arrangement.

In general solids can be classified into:

• Crystalline - particles are orderly arranged (long range order).

• Amorphous - particles are randomly oriented.

If the atoms or molecules are uniquely arranged in crystalline solid or liquid, we

call it a crystal structure. A crystal possesses long range order and symmetry. The
main property of crystal structure is its periodicity. This periodicity is due to the
arrangement of atoms/molecules in the lattice points. The crystal structure as a whole
can be considered as the repetition of unit cell. For a given crystal structure the shape
of unit cell is same but varies from crystal to crystal (Schaffer et al, 1999).

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Figure 1. General classification of solids

Unit Cell
Crystal structure is described in terms of the geometry of arrangement of
particles in the unit cell. The unit cell is defined as the smallest repeating unit having
the full symmetry of the crystal structure. The geometry of the unit cell is defined as
a parallelepiped, providing six lattice parameters taken as the lengths of the cell edges
(a, b, c) and the angles between them (α, β, γ). The positions of particles inside the
unit cell are described by the fractional coordinates (xi, yi, zi) along the cell edges,
measured from a reference point. It is only necessary to report the coordinates of a
smallest asymmetric subset of particles. This group of particles may be chosen so that
it occupies the smallest physical space, which means that not all particles need to be
physically located inside the boundaries given by the lattice parameters. All other
particles of the unit cell are generated by the symmetry operations that characterize
the symmetry of the unit cell. The collection of symmetry operations of the unit cell is
expressed formally as the space group of the crystal structure (Atkins & de Paula,
2006).

Figure 2. Unit cell

Unit cell can be of primitive as well as non-primitive type. A primitive cell is a
minimum volume unit cell and has only one lattice point in it and the latter contains
more than one.

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Figure 3. Primitive and non-primitive unit cell

In the given figure below, simple cube is a primitive cell. No. of atoms per unit
cell is one for it. The rest two is non primitive. No. of atoms per unit cell is 2 and 4
respectively.

Figure 4. Primitive cell (P) and Non-primitive cell (I and F)

Bravais Lattices
The number of lattices that can fill two- or three-dimensional space with
periodically repeating units without leaving gaps or causing overlaps is limited.
Therefore, there is a finite number of different crystal structures, and different
crystalline solids may crystallise according to the same pattern. The metrics of the
lattice may be different, but the symmetry is the same in such cases. Lattices which
fill space without gaps are called Bravais lattices. There are five of them in two
dimensions and 14 in three dimensions (Hermann, 2017).

Bravais Lattices in Two Dimensions

The most general and least symmetric Bravais lattice in two dimensions is
the oblique lattice. If the angle between the two lattice vectors is 90°, the higher
symmetry of the cell gives rise to a distinct Bravais lattice, either rectangular
or square depending on whether the unit cell vectors have different length or not. In
the case of a rectangular lattice, we can distinguish between a primitive

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rectangular lattice and a centred rectangular lattice, which has an extra lattice point
(atom) at the centre. The centred rectangular lattice could be set up as a primitive
lattice with lower symmetry (unit cell shown in green), but convention prefers the more
symmetric description. Finally, if the lattice vectors are the same length and the angle
is 120°, we have another special case with higher symmetry, the hexagonal lattice
(Ellis et al, 1995).

Figure 5. Bravais lattices in two dimensions

Bravais Lattices in Three Dimensions
Based on the lattice parameters a, b, c, α, β and γ and applying the restrictions
as above, only 14 types of lattices are possible in three dimensions. One general
(triclinic) and thirteen special. Only seven different systems of axis are found to be
sufficient to represent all Bravais lattice. This fourteen space lattice is divided into
seven crystal systems (Callister, 2002).

They are triclinic, monoclinic, orthorhombic, tetragonal, trigonal, hexagonal and

cubic.

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Lattice Simple Base- Body- Face- Example

System Centered Centered Centered
triclinic CuSO4.5H2O
K2Cr2O7

monoclinic CaSO4.2H2O
FeSO4
Na2SO4

orthorhombic KNO3
BaSO4

rhombohedral
As
Sb
Bi

tetragonal
TiO2
SnO2
NiSO4

hexagonal SiO2
Zn
Mg
Cd

cubic Au
Cu
NaCl

Table 1. Bravais lattices in three dimensions

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Atomic Coordination
In chemistry, crystallography, and materials science the coordination
number, also called ligancy, of a central atom in a molecule or crystal is the number
of atoms, molecules or ions bonded to it. The ion/molecule/atom surrounding the
central ion/molecule/atom is called a ligand. This number is determined somewhat
differently for molecules than for crystals.
By considering the arrangement of atoms relative to each other, their
coordination numbers (or number of nearest neighbors), interatomic distances, types
of bonding, etc., it is possible to form a general view of the structures and alternative
ways of visualizing them.
Simple cubic, face-centered cubic (FCC) and body-centered cubic (BCC) have
coordination numbers 6, 8, and 12 respectively (Atkins, 2006).
Atomic Packing Factor (APF)
Atomic packing fraction mainly gives us an idea about the arrangement of
atoms/ions in solids. It will give the efficiency with which the available space is being
filled by atoms (Callister, 2002).

Packing fraction is defined as the ratio of volume of atoms occupying the unit
cell to the volume of unit cell.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

𝐴𝑃𝐹 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

Examples:
1. Simple Cubic

Consider a cube of side 'a'. Atoms of radius ‘r’ is placed at the corner. So that
length of cube a=2r.

Figure 6. Simple cubic unit cell

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In a simple cubic structure, the atoms occupies at the eight corners. An atom
at the corner is equally shared by 8 unit cells. So the contribution of one atom to a unit
cell is 1/8. Therefore the no. of atoms per unit cell is (1/8)*8(corner atoms) =1.
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = 𝑎3 = (2𝑟)3 = 8𝑟 3
4 3
𝜋𝑟 𝜋
𝐴𝑃𝐹 = 3 3 = = 𝟓𝟐%
8𝑟 6
2. Body-centered Cube

Consider a cube of side ‘a’, and atoms of radius ‘r’ are placed at corners and at
the body centre. Length of body diagonal, √3a=4r.

Figure 7. Body-centered cubic unit cell

4 8
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = 2 ∗ 𝜋𝑟 3 = 𝜋𝑟 3
3 3
In a body centered cube, there will be one atom at the centre along with 8 corner
atoms. This corner atom is shared by 8 unit cell and the atom at the centre is not a
shared one. Therefore no. of atoms per unit cell= (1/8)*8(corner atoms)+1(body
centre)=2.
3
3
4𝑟64𝑟 3
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = 𝑎 = ( ) =
√3 3√3
8 3
𝜋𝑟 √3𝜋
𝐴𝑃𝐹 = 3 3 = = 𝟔𝟖%
64𝑟 8
3√3
3. Face-centered Cube

Consider a cube of length ‘a’ and atoms of radius ’r’ are placed at the corners
as well as at the face centre. Length of face diagonal √2a=4r.

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Figure 8. Face-centered cubic unit cell

4 16 3
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = 4 ∗ 𝜋𝑟 3 = 𝜋𝑟
3 3
In a face centered cube, each face possess one atom along with 8 corner
atoms. The atoms at the faces are equally shared by two unit cell. Corner atoms by 8
unit cells. So the no. of atoms per unit cell is=(1/8)*8(corner atoms)+(1/2)*6(atoms at
face)=4.
3
3
4𝑟
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = 𝑎 = ( )
√2
16 3
𝜋𝑟 𝜋
𝐴𝑃𝐹 = 3 3 = = 𝟕𝟒%
4𝑟 3√2
( )
√2
4. Hexagonal Close-Packed
For the hexagonal close-packed structure, the unit cell (equivalent to 3 primitive
unit cells) is a hexagonal prism containing six atoms (if the particles in the crystal are
atoms). Indeed, three are the atoms in the middle layer (inside the prism); in addition,
for the top and bottom layers (on the bases of the prism), the central atom is shared
with the adjacent cell, and each of the six atoms at the vertices is shared with other
five adjacent cells. So the total number of atoms in the cell is 3 + (1/2)×2 + (1/6)×6×2
= 6. Each atom touches other twelve atoms. Now let a be the side length of the base
of the prism and c be its height. The latter is twice the distance between adjacent
layers, i.e., twice the height of the regular tetrahedron whose vertices are occupied by
(say) the central atom of the lower layer, two adjacent non-central atoms of the same
layer, and one atom of the middle layer "resting" on the previous three. Obviously, the
8
edge of this tetrahedron is a. If a=2r, then its height can be easily calculated to be √3 𝑎,
2 3√3
and, therefore, 𝑐 = 4√3 𝑟. So the volume of the hcp unit cell turns out to be 𝑎2 𝑐,
2
that is 24√2𝑟 3 .
It is then possible to calculate the APF as follows:

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4 3
𝑁𝑎𝑡𝑜𝑚𝑠 𝑉𝑎𝑡𝑜𝑚 6 ∙ 3 𝜋𝑟
𝐴𝑃𝐹 = =
𝑉𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 3√3 2
2 𝑎 𝑐
4 4
6 ∙ 3 𝜋𝑟 3 6 ∙ 3 𝜋𝑟 3
𝐴𝑃𝐹 = =
3√3 2√ 2 3√3 √2 3
2 (2𝑟) 3 ∙ 4𝑟 2 3 ∙ 16𝑟
𝜋 𝜋
𝐴𝑃𝐹 = = = 0.74048048
√18 3√2

Figure 9. Hexagonal close-packed structure.

Density Calculation
The density of a solid is that of the unit cell, obtained by dividing the mass of
the atoms (n atoms x Matom) and dividing by Vc the volume of the cell (a3 in the case of
a cube). If the mass of the atom is given in amu (A), then we have to divide it by the
Avogadro number to get Matom. Thus, the formula for the density is:
𝑛𝐴
𝜌=
𝑉𝑐 𝑁𝐴
where:
𝜌 = 𝑑𝑒𝑛𝑠𝑖𝑡𝑦
𝑛 = 𝑛𝑜. 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠
𝐴 = 𝑎𝑡𝑜𝑚𝑖𝑐/𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑤𝑒𝑖𝑔ℎ𝑡
𝑉𝑐 = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝑁𝐴 = 𝐴𝑣𝑜𝑔𝑎𝑑𝑟𝑜′ 𝑠 𝑛𝑢𝑚𝑏𝑒𝑟
Example:
1. Polonium crystallizes in a simple cubic pattern with a unit cell length of 3.36
angstrom (Å). Estimate the density of Po in g/cm3. (1 Å = 1x10-8 cm)

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Basis: 1 unit cell

Given:
n = 1 atom; a = 3.36x10-8 cm; A = 209 g/mol
Solution:
𝑛𝐴
𝜌=
𝑉𝑐 𝑁𝐴
𝑔
(1 𝑎𝑡𝑜𝑚) (209 )
𝜌= 𝑚𝑜𝑙
𝑎𝑡𝑜𝑚𝑠
(3.36𝑥10−8 𝑐𝑚)3 (6.022𝑥1023 )
𝑚𝑜𝑙
𝝆 = 𝟗. 𝟏𝟓 𝒈/𝒄𝒎𝟑
2. Aluminum has a face-centered cubic unit cell, that is, an atom at each corner
of the unit cell and an atom at the center of each face. The Al-Al distance (2r)
is 0.2863 nm. Calculate the density of aluminum in g/mL. The mass of
aluminum atom is 26.98 amu.

Basis: 1 unit cell

Given:
n = 4 atoms; A = 26.98 g/mol; 2r = 0.2863 nm = 0.2863x10-7 cm
Solution:
(4𝑟)2 = 𝑎2 + 𝑎2
16𝑟 2 = 2𝑎2
𝑎2 = 8𝑟 2

𝑎 = 2√2 𝑟
𝑛𝐴
𝜌=
𝑉𝑐 𝑁𝐴
(4 𝑎𝑡𝑜𝑚𝑠)(26.98 𝑔/𝑚𝑜𝑙)
𝜌= 3 𝑎𝑡𝑜𝑚𝑠
[√2(0.2863𝑥10−7 𝑐𝑚)] (6.022𝑥1023 )
𝑚𝑜𝑙
𝒈
𝝆 = 𝟐. 𝟕 = 𝟐. 𝟕 𝒈/𝒎𝑳
𝒄𝒎𝟑

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Self-Help: You can also refer to the sources below to help you
further understand the lesson.

Hermann, K. (2017). Crystallography and surface structure : An introduction for

surface scientists and nanoscientists. Retrieved from
https://search.proquest.com/docview/2131386643/9651CF2002EF494EPQ/4?
accountid=31259. Chapter 2 Bulk Crystals: Three-Dimensional Lattices pp 7-
90

Let’s Check

Exercises:
1. Molybdenum forms body-centered cubic crystals and at 20 oC the density is
10.3 g/mL. Calculate the distance between the centers of the nearest
molybdenum atoms.
2. An element crystallizes in a body-centered cubic lattice. The edge of the unit
cell is 0.286 nm, and the density of the crystal is 7.92 g/cm 3. Calculate the
atomic weight of the element.
3. Austenite form of iron has FCC crystal lattice structure, whereas its alpha form
has BCC crystal lattice structure. Assuming closest packed arrangement of iron
atoms, what will be the ratio of density of Austenite to that of alpha iron?
4. Sodium crystallizes in the body-centered cubic structure with a=0.424 nm.
Calculate the theoretical density of Na in kg/m3.
5. Find the distance (in nm) between the body-centered atom and one corner atom
in Na, given a=0.424 nm.

Let’s Analyze

Activity 1. Compare and contrast the 7 crystal system.

Activity 2. Compare and contrast the 3 Bravais lattice of the cubic crystal
system.

In a Nutshell

Activity 1. Illustrate the: (a) simple cubic, body-centered, and face-centered cubic of
the cubic crystal system; and (b) hexagonal crystal system.
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Activity 2. How is learning crystal structure relevant in the study of engineering?

Keywords Index

Amorphous Crystal lattice Face- Space lattice Coordination

centered number
cubic
Hexagonal
close-packed
Atomic Cystalline Interfacial Unit cell Face-
Packing angles centered
Factor cubic
Body-centered Crystallographic Lattice Void space Simple cubic
cubic axes parameters
Bravais lattice Density Primitives

References
Atkins, P., & de Paula, J. (2006). Atkins’ Physical Chemistry 8th ed. Oxford University
Press. Chapter 20: Materials 2: The Solid State
Callister, W. (2002). Materials Science and Engineering (6th ed.). San Francisco,
CA: John Wiley and Sons.
Ellis, Arthur B.; et al. (1995). Teaching General Chemistry: A Materials Science
Companion (3rd ed.). Washington, DC: American Chemical Society.
Hermann, K. (2017). Crystallography and surface structure : An introduction for
surface scientists and nanoscientists. Retrieved from
https://search.proquest.com/docview/2131386643/9651CF2002EF494EPQ/4?
accountid=31259. Chapter 2 Bulk Crystals: Three-Dimensional Lattices pp 7-
90
Moore, Lesley E.; Smart, Elaine A. (2005). Solid State Chemistry: An
Introduction (3rd ed.). Boca Raton, Florida: Taylor & Francis, CRC.
Schaffer; Saxena; Antolovich; Sanders; Warner (1999). The Science and Design of
Engineering Materials (2nd ed.). New York, NY: WCB/McGraw-Hill.

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