Unit 3 – The Chemistry of e n g i n e e r i n g

materials

Basic Concepts of Crystal Structures

LEARNING OBJECTIVES
• Describe the basic structural unit or building block of the crystal
structure.
• Determine to compute the density of a solid given its unit cell.
• Classify the four types of crystals.
• Describe the characteristics of amorphous solids.

1.0 Crystal Structures

Crystalline and amorphous are the two categories of solids. For example, ice which is
a crystalline solid possesses the following characteristics: has rigid and long-range order
and its atoms, molecules, or ions occupy specific positions. In a crystalline solid, the
arrangement of particles is such that the net attractive intermolecular forces are at their
maximum. The molecular forces responsible for the stability of a crystal can be ionic forces,
covalent bonds, van der Waals forces, hydrogen bonds, or a combination of these forces. For
amorphous solids such as glass, absence of a well-defined arrangement and long-range
molecular order can be observed.
Atoms or ions (described as crystalline structures) are thought of as being solid
spheres having well-defined diameters. This is known as the atomic hard-sphere model in
which spheres representing nearest-neighbor atoms touch one another. Figure 2c showed
an example of the hard-sphere model for the atomic arrangement found in some of the
common element metals. In this specific case all the atoms are identical. Sometimes the word
lattice is used in the context of crystal structures; in this sense lattice means a three-
dimensional array of points coinciding with atom positions or sphere centers.
2.0 UNIT CELLS
A unit cell is the basic structural (repeating) unit of a crystalline solid. Figure 1 shows
a unit cell and its extension in three dimensions. For each sphere, it denotes an atom, ion, or
molecule and it is called a lattice point. In many crystals, the lattice point does not actually
contain such a particle. Rather, there may be several atoms, ions, or molecules identically
arranged about each lattice point. To be simple, we can assume that each lattice point is
occupied by an atom where cases are mostly metals. Table 1 shows the seven types of unit
cells where every crystalline solid can be expressed.

a) b)

Figure 1. (a) unit cell and (b) an extension of unit cell in three dimensions. The black spheres
denote either atoms or molecules (Chang & Goldsby, 2017).

Table 1. The seven types of unit cells. Angle α is defined by edges b and c, angle β by edges a
and c, and angle γ by edges a and b (Chang & Goldsby, 2017).

Unit cells Figure Dimensions and angle

Simple cubic 𝑎=𝑏=𝑐

𝛼 = 𝛽 = 𝛾 = 90°

Tetragonal 𝑎=𝑏≠𝑐
𝛼 = 𝛽 = 𝛾 = 90°

Orthorhombic 𝑎≠𝑏≠𝑐
𝛼 = 𝛽 = 𝛾 = 90°
 Rhombohedral 𝑎=𝑏=𝑐
𝛼 = 𝛽 = 𝛾 ≠ 90°

Monoclinic 𝑎≠𝑏≠𝑐
𝛾 ≠ 𝛼 = 𝛽 = 90°

Tricilinic 𝑎≠𝑏≠𝑐
𝛼 ≠ 𝛽 ≠ 𝛾 ≠ 90°

Hexagonal 𝑎=𝑏≠𝑐
𝛼 ≠ 𝛽 = 90°, 𝛾 = 120°

The Face-Centered Cubic Crystal Structure

A unit cell of cubic geometry is considered to be the crystal structure found for many
metals. The face-centered cubic (FCC) is a crystal structure with atoms located at each of
the corners and the center of all the cube faces. Some familiar metals having this crystal
structure are copper, aluminum, silver, and gold (See Table 2). Figure 2a shows a hard-
sphere model for the FCC unit cell, whereas in Figure 2b the atom centers are represented
by small circles to provide a better perspective on atom positions. The aggregate of atoms in
Figure 2c represents a section of crystal consisting of many FCC unit cells. These spheres or
ion cores touch one another across a face diagonal; the cube edge length a and the atomic
radius R are related through

𝑎 = 2𝑅√2 Equation 1

Table 3 shows the relationship between the edge length (a) and radius (r) of atoms in the
SCC, BCC and FCC cell.
 Example 1. Calculate the volume of an FCC unit cell in terms of the atomic
radius R.

Solution:
V = 𝑎+ 𝑏𝑢𝑡 𝑎 =? 𝑡ℎ𝑒𝑛 𝑠𝑜𝑙𝑣𝑒 𝑓𝑜𝑟 𝑎.

From the figure, solve for a: 𝑎 +𝑎 = (4𝑅)

Therefore, 𝑎 = 2𝑅√2

𝑉& = 𝑎+ = (2𝑅√2)+ = 𝟏𝟔𝑹𝟑√𝟐

Table 2. Atomic Radii and Crystal Structures for 16 Metals (Callister & Rethwisch, 2014).

Metal Crystal Atomic Metal Crystal Atomic

Structure* Radius** Structure* Radius**
(nm) (nm)
Aluminum FCC 0.1431 Molybdenum BCC 0.1363
Cadmium HCP 0.1490 Nickel FCC 0.1246
Chromium BCC 0.1249 Platinum FCC 0.1387
Cobalt HCP 0.1253 Silver FCC 0.1445
Copper FCC 0.1278 Tantalum BCC 0.1430
Gold FCC 0.1442 Titanium (𝛼) HCP 0.1445
Iron (𝛼) BCC 0.1241 Tungsten BCC 0.1371
Lead FCC 0.1750 Zinc HCP 0.1332
*FCC = face-centered cubic; HCP = hexagonal close-packed; BCC=body-centered cubic.
**A nanometer (nm) equals 10-9m; to convert nanometers to angstrom units (Å), multiply the
nanometer value by 10.
 a) b) c)

Figure 2. For the face-centered cubic crystal structure, (a) a hard-sphere unit cell
representation, (b) a reduced- sphere unit cell, and (c) an aggregate of many atoms (Callister
& Rethwisch, 2014).

In determining the number of atoms associated with each unit cell that depends on
an atom’s location, shared with adjacent unit cells may be considered. That is, some fraction
of the atom is assigned to a specific cell. For example, for cubic unit cells, an atom completely
within the interior “belongs” to that unit cell, one at a cell face is shared with one other cell,
and an atom residing at a corner is shared among eight. The number of atoms per unit cell,
N, can be computed using the following formula:
<$
𝑁= 𝑁 + + <& Equation 2
) ! 8

Where Ni = the number of interior atoms; Nf = number of face atoms and Nc = number
of corner atoms

For the FCC crystal structure, there are eight corner atoms, six face atoms and no interior
atoms. Therefore, from Equation 2.
6 8
𝑁 =0+ + = 4
2 8

A total of four whole atoms may be assigned to a given unit cell.

There are two important characteristics of a crystal structure: (a) the coordination
number (for metals) wherein each atom has the same number of nearest-neighbor or
touching atoms; and (b) atomic packing factor (APF) which is the sum of the sphere
volumes of all atoms within a unit cell (assuming the atomic hard-sphere model) divided by
the unit cell volume. For FCCs, the coordination number is 12 as can be seen in Figure 2a.
Front face atoms has four nearest neighboring atoms around it, four face atoms that are link
from behind, and four other equivalent face atoms positioned in the next unit cell to the front
which is not shown.

From the definition of APF, the formula is:

=.2>'? .@ AB? 1A.'C )* 1 >*)A &?22
𝐴𝑃𝐹 =
D.A12 >*)A .@ &?22 =.2>'?
Equation 3
 Example 2. Show that the atomic packing factor for the FCC crystal structure
is 0.74.

Solution:
B
𝐴𝑃𝐹 = =

Volume of a sphere (𝑉C) in terms of the atomic radius R is equal to

$ 𝜋𝑅+, and the number of atoms per FCC unit cell if four. Therefore, the total
FCC atom or sphere volume is

From Example 1, the total unit cell volume is

𝑉& = 16𝑅+√2

Therefore, the atomic packing factor is

𝐴𝑃𝐹 = =

The Body-Centered Cubic Crystal Structure

A body-centered cubic (BCC) is another common metallic crystal structure that also
has a cubic unit cell with atoms located at all eight corners and a single atom at the center of
the cube. Figures 3a and 3b showed the diagrams of BCC unit cells with the atoms
represented by hard-sphere and reduced-sphere models while Figure 3c displayed a
collection of spheres depicting this c rystal structure. Corner atoms and center touch one
another along with the diagonal of the cube, and unit cell length a and atomic radius R are
related by the way of
$E
𝑎=
√+
Equation 4

From Equation 2, the number of atoms per BCC is

<$
𝑁=𝑁 + + <& = 1 + 0 + 8 =2
) ! 8 8
 The BCC crystal structure has 8 coordination number. The atomic packing factor for
BCC 0.68 which is lower than for FCC, since BCC has lesser coordination number.

a) b) c)

Figure 3. Body-centered cubic crystal structure, (a) a hard-sphere unit cell representation,
(a) a reduced-sphere unit cell, and (c) an aggregate of many atoms (Callister & Rethwisch,
2014).

The possibility of a unit cell that consists of atoms placed only at the corners of a cube
do exist and it is called the simple cubic (SC) crystal structure. The illustration is shown in
Figure 4a and 4b. Polonium, a metalloid or a semi-metal is the only simple-cubic element that
has a relatively low atomic packing factor.

a) b)

Figure 4. Simple cubic crystal structure, (a) hard-sphere unit cell, and (b) a reduced-sphere
unit cell (Callister & Rethwisch, 2014).

Table 3. The Relationship Between the edge length (a) and radius (r) of atoms in the SCC,
BCC and FCC cell (Chang & Goldsby, 2017).

Unit cells Figure Relationship

Simple Cubic a= 2r
 Body-centered cubic

b2 = a2 + a2
c2 = a2 + b2 = 3a2
c = √3a = 4r
a = 4r
√3

Face-centered cubic
b = 4r
b2 = a2 + a2
16r2 = 2a2
a = √8r

The Hexagonal Close-Packed Crystal Structure

The final common metallic crystal structure to be discussed is the hexagonal close-
packed (HCP). The top and bottom faces of the unit cell is consist of six atoms that form
regular hexagons and surround a single atom in the center. Between the top and bottom
planes, there is another plane that provides three additional atoms to the unit cell. The atoms
in this midplane have as nearest neighbors atoms in both of the adjacent two planes. Figure
5a shows a reduced-sphere unit cell for HCP structure and Figure 5b presents an assemblage
of several HCP unit cells.
To compute the number of atoms per unit cell for HCP crystal structure, the formula
is shown below: <
𝑁 = 𝑁 + $ + <& Equation 5
) ! 5

One-sixth of each corner atom is designated to a unit cell instead of 8 as with the cubic
structure. This is because, HCP has 6 corner atoms in each of the top and bottom faces for a
total of 12 corner atoms, 2 face center atoms (one from each of the top and bottom faces),
and 3 midplane interior atoms. Using Equation 5, the value of N for HCP can be found.

𝑁 = 3+ ! + (! = 6 (there are 6 atoms assigned to each unit cell)

(! 5
 a) b)

Figure 5. The hexagonal close-packed crystal structure, (a) a reduced-sphere unit cell (a
and c represent the short and long edge lengths, respectively), and (b) an aggregate of
many atoms (Callister & Rethwisch, 2014).

3.0 DENSITY COMPUTATIONS

A theoretical density (𝜌) can be computed with a knowledge of the crystal structure
of a metallic solid through the relationship

!"
𝜌= Equation 6
#!$"

Where n = number of atoms associated with each unit cell

A = atomic weight
VC = volume of the unit cell
NA = Avogadro’s number (6.022 x 1023 atoms/mol)

Example 3. Copper (A=63.5 g/mol) has an atomic radius of 0.128 nm, an FCC
crystal structure, and an atomic weigh of 63.5 g/mol. Compute its theoretical
density, and compare the answer with its measured density.
Solution:

( )

( /( ))( . / )
( . ) / ]( . / )

𝒈
𝒄𝒎𝟑