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Chapter

Structure of Crystalline Solids

Intended Learning Outcomes

After studying this chapter, you should be able to do the following:

1. Illustrate the different structures of crystalline solids.
2. Describe the difference in atomic/molecular structure between crystalline and noncrystalline
materials.
3. Draw unit cells for face-centered cubic, body- centered cubic, and hexagonal close-packed
crystal structures.
4. Derive the relationships between unit cell edge length and atomic radius for face-centered
cubic and body-centered cubic crystal structures.
5. Compute the densities for metals having face- centered cubic and body-centered cubic crystal
structures given their unit cell dimensions.
6. Distinguish between single crystals and polycrystalline materials.
7. Define isotropy and anisotropy with respect to material properties.

This chapter primarily presents the various types of atomic bonding, which are determined by the
electron structures of the individual atoms. The present discussion is devoted to the next level of the
structure of materials, specifically, to some of the arrangements that may be assumed by atoms in the
solid state. Within this framework, concepts of crystallinity and noncrystallinity are introduced. For
crystalline solids, the notion of crystal structure is presented, specified in terms of a unit cell. The three
common crystal structures found in metals are then detailed, along with the scheme by which
crystallographic points, directions, and planes are expressed. Single crystals, polycrystalline materials,
and noncrystalline materials are considered. Another section of this chapter briefly describes how
crystal structures are determined experimentally using x-ray diffraction techniques.

FUNDAMENTAL CONCEPTS
Crystalline material - is one in which the atoms are situated in a repeating or periodic array over
large atomic distances—that is, long-range order exists, such that upon solidification, the atoms
will position themselves in a repetitive three-dimensional pattern, in which each atom is bonded
to its nearest neighbor atoms.

Non-crystalline/Amorphous Material -do not crystallize and the long-range atomic order is
absent.

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2.1 CRYSTALS STRUCTURE

Crystal structure - Some of the properties of crystalline solids depend on the crystal structure of
the material, the manner in which atoms, ions, or molecules are spatially arranged.
Atomic hard-sphere model - where spheres representing nearest-neighbor atoms touch one
another.
Lattice - lattice means a three-dimensional array of points coinciding with atom positions (or
sphere centers).

Figure 2.1. 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.
[Figure (c) adapted from W. G. Moffatt, G. W. Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. I, Structure, p.
51. Copyright © 1964 by John Wiley & Sons, New York.]

UNIT CELLS

- small groups of atoms form a repetitive pattern.

- are parallelepipeds or prisms having three sets of parallel faces; one is drawn within the
aggregate of spheres which in this case happens to be a cube.
- is the basic structural unit or building block of the crystal structure and defines the crystal
structure by virtue of its geometry and the atom positions within.

METALLIC CRYSTAL STRUCTURES

The atomic bonding in this group of materials is metallic and thus nondirectional in nature.
Consequently, there are minimal restrictions as to the number and position of nearest-neighbor
atoms; this leads to relatively large numbers of nearest neighbors and dense atomic packings for
most metallic crystal structures.

Three relatively simple crystal structures are found for most of the common metals:

1. face-centered cubic,
2. body centered cubic, and
3. hexagonal close-packed.

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The Face-Centered Cubic Crystal Structure

The crystal structure found for many metals has a unit cell of cubic geometry, with atoms
located at each of the corners and the centers of all the cube faces. It is aptly called the face-
centered cubic (FCC) crystal structure. Some of the familiar metals having this crystal structure
are copper, aluminum, silver, and gold.
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

Table 2.1
Atomic Radii and Crystal Structures for 16 Metals

Crystal Atomic Crystal Atomic

Metal Metal
Structurea Radiusb (nm) Structure Radius (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. bA nanometer (nm) equals
a

10-9 m; to convert from nanometers to angstrom units (Å), multiply the nanometer value by 10.

The number of atoms per unit cell, N, can be computed using the following formula:
𝑁𝑓 𝑁𝑐
𝑁 = 𝑁𝑖 + +
2 8
Where:
Ni = the number of interior atoms
Nf = the number of face atoms
Nc = the number of corner atoms

Ex. for the FCC crystal structure, there are eight corner atoms (Nc= 8), six face atoms (Nf = 6),
and no interior atoms (Ni = 0).

Thus,
6 8
𝑁 =0+ + =𝟒
2 8

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

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Two other important characteristics of a crystal structure are the coordination number and the
atomic packing factor (APF).

For metals, each atom has the same number of nearest-neighbor or touching atoms, which is the
coordination number. For face-centered cubics, the coordination number is 12. This may be
confirmed by examination of Figure 2.1a; the front face atom has four corner nearest-neighbor
atoms surrounding it, four face atoms that are in contact from behind, and four other equivalent
face atoms residing in the next unit cell to the front (not shown).

Atomic packing factor (APF) = 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—that is,

APF = volume of atoms in a unit cell

Total unit cell volume

For the FCC structure, the atomic packing factor is 0.74, which is the maximum packing possible
for spheres all having the same diameter.

The Body-Centered Cubic Crystal Structure

Another common metallic crystal structure also has a cubic unit cell with atoms located at
all eight corners and a single atom at the cube center. This is called a body-centered cubic
(BCC) crystal structure.

Figure 2.2 For the body-centered cubic crystal structure, (a) a hard-sphere unit cell representation, (b) a
reduced sphere unit cell, and (c) an aggregate of many atoms.
[Figure (c) from W. G. Moffatt, G. W. Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. I, Structure,
p. 51. Copyright © 1964 by John Wiley & Sons, New York.]

Center and corner atoms touch one another along cube diagonals, and unit cell length a
and atomic radius R are related through

𝟒𝑹
a=
√𝟑
Each BCC unit cell has eight corner atoms and a single center atom, which is wholly contained
within its cell; therefore, the number of atoms per BCC unit cell is 2.

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The coordination number for the BCC crystal structure is 8; each center atom has as nearest
neighbors its eight corner atoms. Because the coordination number is less for BCC than for FCC,
the atomic packing factor is also lower for BCC—0.68 versus 0.74.

It is also possible to have a unit cell that consists of atoms situated only at the corners of a cube.
This is called the simple cubic (SC) crystal structure; hard-sphere and reduced-sphere models
are shown, respectively, in Figures 2.3a and 2.3b. None of the metallic elements have this crystal
structure because of its relatively low atomic packing factor. The only simple-cubic element is
polonium, which is considered to be a metalloid (or semi-metal).

Figure 2.3 For the simple cubic crystal structure, (a) a hard-sphere unit cell, and (b) a reduced-sphere unit
cell.

The Hexagonal Close-Packed Crystal Structure

Not all metals have unit cells with cubic symmetry; the final common metallic crystal
structure to be discussed has a unit cell that is hexagonal. Figure 2.4a shows a reduced sphere
unit cell for this structure, which is termed hexagonal close-packed (HCP); an assemblage of
several HCP unit cells is presented in Figure 2.4b.

Figure 2.4 For 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.
[Figure (b) from W. G. Moffatt, G. W. Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. I, Structure,
p. 51. Copyright © 1964 by John Wiley & Sons, New York.]

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The top and bottom faces of the unit cell consist of six atoms that form regular hexagons and
surround a single atom in the center. Another plane that provides three additional atoms to the
unit cell is situated between the top and bottom planes. The atoms in this midplane have as
nearest neighbors atoms in both of the adjacent two planes.

In order to compute the number of atoms per unit cell for the HCP crystal structure,

𝑁𝑓 𝑁𝑐
𝑁 = 𝑁𝑖 + +
2 6

That is, one-sixth of each corner atom is assigned to a unit cell (instead of 8 as with the cubic
structure). Because for HCP there are 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, the value of N for HCP is found to be 6. Thus, 6 atoms are assigned
to each unit cell.

Example Problem 2.1

Determination of FCC Unit Cell Volume

Calculate the volume of an FCC unit cell in terms of the atomic radius R.

Solution
In the FCC unit cell illustrated, the atoms touch one another
across a face-diagonal, the length of which is 4R. Because the
unit cell is a cube, its volume is a3, where a is the cell edge
length. From the right triangle on the face, a2 + a2 = (4R)2

or, solving for a, a = 2R√𝟐

The FCC unit cell volume VC may be computed from

VC = a3 = (2R√2)3 = 16R3√2

DENSITY COMPUTATIONS

A knowledge of the crystal structure of a metallic solid permits computation of its

theoretical density ρ through the relationship:

𝒏𝑨
ρ=
𝑽𝒄 𝑵𝒂
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)

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Example Problem 2.2

Computation of the Atomic Packing Factor for FCC

Show that the atomic packing factor for the FCC crystal structure is 0.74.

Solution
The APF is defined as the fraction of solid sphere volume in a unit cell, or
APF = volume of atoms in a unit cell = Vs
Total unit cell volume Vc

Both the total atom and unit cell volumes may be calculated in terms of the atomic radius R. The
4
volume for a sphere is πR3, and because there are four atoms per FCC unit cell, the total FCC
3
atom (or sphere) volume is
4 𝟏𝟔
Vs = (4) πR3 = πR3
3 𝟑

From Example Problem 2.1, the total unit cell volume is

VC = 16R3√2
Therefore, the atomic packing factor is

APF = Vs = 16/3 πR3

Vc 16R3√2
= 0.74

Example Problem 2.3

Theoretical Density Computation for Copper

Copper has an atomic radius of 0.128 nm, an FCC crystal structure, and an atomic weight of 63.5
g/mol. Compute its theoretical density, and compare the answer with its measured density.

Solution
Because the crystal structure is FCC, n, the number of atoms per unit cell, is 4. Furthermore, the
atomic weight ACu is given as 63.5 g/mol. The unit cell volume VC for FCC was determined in
Example Problem 2.1 as 16R3√2, where R, the atomic radius, is 0.128 nm.
Substitution for the various parameters into Equation for density yields
𝒏𝑨 𝒏𝑨𝑪𝒖
ρ= =
𝑽𝒄 𝑵𝒂 16R3√2 𝑵𝒂

= (4 atoms/unit cell)(63.5 g/mol)

[16√2(1.28 x10-8 cm)3/unit cell](6.022 x 1023 atoms/mol)

= 8.89 g/cm3

The literature value for the density of copper is 8.94 g/cm 3, which is in very close agreement
with the foregoing result.

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Polymorphism and Allotropy

Polymorphism - when metals and nonmetals have more than one crystal structure
Allotropy - when more than one crystal structure is found in elemental solids
Crystal structure depends on temperature and external pressure

CRYSTAL SYSTEMS

There are seven different possible combinations of a, b, and c and a, b, and g, each of
which represents a distinct crystal system. These seven crystal systems are cubic, tetragonal,
hexagonal, orthorhombic, rhombohedral, monoclinic, and triclinic. The lattice parameter
relationships and unit cell sketches for each are represented in Table 2.1. The cubic system, for
which a = b = c and α = β = γ = 90o, has the greatest degree of symmetry. The least symmetry is
displayed by the triclinic system, because a = b = c and α ≠ β ≠ γ.

It is important to note that many of the principles and concepts addressed in previous
discussions in this chapter also apply to crystalline ceramic and polymeric systems. For example,
crystal structures are most often described in terms of unit cells, which are normally more complex
than those for FCC, BCC, and HCP. In addition, for these other systems, we are often interested
in determining atomic packing factors and densities. Furthermore, according to unit cell geometry,
crystal structures of these other material types are grouped within the seven crystal systems.

Figure 2.5 A unit cell with x, y, and z coordinate axes, showing axial lengths (a, b, and c) and interaxial
angles (α, β and γ).

Crystallography is the science of measuring the crystal structure of a crystal. One widely used
crystallography technique is X-ray diffraction

When dealing with crystalline materials, it often becomes necessary to specify a particular point
within a unit cell, a crystallographic direction or some crystallographic plane of atoms.

For some crystal systems - namely hexagonal, rhombohedral, monoclinic, and triclinic - the three
axes are not mutually perpendicular, as in the familiar Cartesian coordinate scheme.

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Table 2.2 Lattice Parameter Relationships and Figures Showing Unit Cell Geometries for the
Seven Crystal Systems

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POINTS COORDINATES

Sometimes it is necessary to specify a lattice position within a unit cell. This is possible
using three point coordinate indices: q, r, and s. These indices are fractional multiples of a, b, and
c unit cell edge lengths—that is, q is some fractional length of a along the x axis, r is some
fractional length of b along the y axis, and similarly for s; or
qa = lattice position referenced to the x axis
rb = lattice position referenced to the y axis
sc = lattice position referenced to the z axis

To illustrate, consider the unit cell in Figure 3.6, the x-y-z coordinate system with its origin
located at a unit cell corner, and the lattice site located at point P. Note how the location of P is
related to the products of its q, r, and s coordinate indices and the unit cell edge lengths.

Figure 2.6 The manner in which the q, r, and s coordinates at point P within the unit cell are determined.
The q coordinate (which is a fraction) corresponds to the distance qa along the x axis, where a is the unit
cell edge length. The respective r and s coordinates for the y and z axes are determined similarly.

CRYSTALLOGRAPHIC DIRECTIONS

A crystallographic direction is defined as a line directed between two points, or a vector.

The following steps are used to determine the three directional indices:
1. A right-handed x-y-z coordinate system is first constructed. As a matter of convenience, its
origin may be located at a unit cell corner.
2. The coordinates of two points that lie on the direction vector (referenced to the coordinate
system) are determined—for example, for the vector tail, point 1: x1, y1, and z1; whereas for the
vector head, point 2: x2, y2, and z2.
3. Tail point coordinates are subtracted from head point components - that is, x2 - x1, y2 - y1, and
z2 - z1.
4. These coordinate differences are then normalized in terms of (i.e., divided by) their respective
a, b, and c lattice parameters—that is,
x2 - x1 y2 - y1 z2 - z1
a b c
which yields a set of three numbers.

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5. If necessary, these three numbers are multiplied or divided by a common factor to reduce them
to the smallest integer values.
6. The three resulting indices, not separated by commas, are enclosed in square brackets, thus:
[uvw]. The u, v, and w integers correspond to the normalized coordinate differences referenced
to the x, y, and z axes, respectively.

In summary, the u, v, and w indices may be determined using the following equations:
u = n { x2 - x1} v = n {y2 - y1} w =n {z2 - z1}
a b c
In these expressions, n is the factor that may be required to reduce u, v, and w to integers. For
each of the three axes, there are both positive and negative coordinates. Thus, negative indices
are also possible, which are represented by a bar over the appropriate index. For example, the
[111] direction has a component in the -y direction. Also, changing the signs of all indices
produces an antiparallel direction; that is, [111] is directly opposite to [111]. If more than one
direction (or plane) is to be specified for a particular crystal structure, it is imperative for
maintaining consistency that a positive– negative convention, once established, not be changed.
The [100], [110], and [111] directions are common ones; they are drawn in the unit cell shown in
Figure 2.7.

Figure 2.7 The [100], [110], and [111] directions within a unit cell.

CRYSTALLOGRAPHIC PLANES

In all but hexagonal crystal system, crystallographic planes are specified by three (3) Miller
indices (Ml).
Procedures employed in determination of the h, k, and l index numbers:
1. If the plane passes through the selected origin, either another parallel plane must be
constructed within the unit cell by an appropriate translation, or a new origin must be established
at the corner of another unit cell.
2. At this point the crystallographic plane either intersects or parallels each of the three axes; the
length of the planar intercept for each axis is determined in terms of the lattice parameters.
3. The reciprocals of these numbers are taken. A plane that parallels an axis may be considered
to have an infinite intercept, and, therefore, a zero index.
4. If necessary, these three numbers are changed to the set of smallest integers by multiplication
or division by a common factor.
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5. Finally, the integer indices, not separated by commas, are enclosed within parentheses: (hkl).

Example Problem 2.4

Determination of Directional Indices

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An intercept on the negative side of the origin is indicated by a bar or minus sign positioned
over the appropriate index. Furthermore, reversing the directions of all indices specifies another
plane parallel to, on the opposite side of, and equidistant from the origin. Several low-index planes
are represented in Figure 2.8.

Figure 2.8. Representations of a series each of the (a) (001), (b) (110), and (c) (111) crystallographic planes.

One interesting and unique characteristic of cubic crystals is that planes and directions
having the same indices are perpendicular to one another; however, for other crystal systems
there are no simple geometrical relationships between planes and directions having the same
indices.

Example 2.5
Determination of Planar (Miller) Indices
Determine the Miller indices for the plane shown in the accompanying sketch (a).

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ATOMIC ARRANGEMENTS

The atomic arrangement for a crystallographic plane, which is often of interest, depends
on the crystal structure. The (110) atomic planes for FCC and BCC crystal structures. Reduced-
sphere unit cells are also included. Note that the atomic packing is different for each case. The
circles represent atoms lying in the crystallographic planes as would be obtained from a slice
taken through the centers of the full-size hard spheres.
A “family” of planes contains all planes that are crystallographically equivalent— that is,
having the same atomic packing; a family is designated by indices enclosed in braces—such as
{100}. For example, in cubic crystals, the (111), (1 1 1), (111), (1 1 1), (111), (1 1 1), (111), and
(111) planes all belong to the {111} family. crystal structures, the {100} family contains only the
(100), (100), (010), and (010) planes because the (001) and (001) planes are not
crystallographically equivalent. Also, in the cubic system only, planes having the same indices,
irrespective of order and sign, are equivalent. For example, both (123) and (312) belong to the
{123} family.

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Hexagonal Crystals

For crystals having hexagonal symmetry, it is desirable that equivalent planes have the same
indices; as with directions, this is accomplished by the Miller–Bravais system. This convention
leads to the four-index (hkil) scheme, which is favored in most instances because it more clearly
identifies the orientation of a plane in a hexagonal crystal. There is some redundancy in that i is
determined by the sum of h and k through i = -(h + k)
Otherwise, the three h, k, and l indices are identical for both indexing systems. We determine
these indices in a manner analogous to that used for other crystal systems as described
previously—that is, taking normalized reciprocals of axial intercepts.

This concludes our discussion on crystallographic points, directions, and planes. A review and
summary of these topics is found in Table 2.3.

Table 2.3 Summary of Equations Used to Determine Crystallographic Point, Direction,

and Planar Indices

LINEAR AND PLANAR DENSITIES

Directional equivalency is related to linear density in the sense that, for a particular material,
equivalent directions have identical linear densities. The corresponding parameter for
crystallographic planes is planar density, and planes having the same planar density values are
also equivalent.

Linear density (LD) is defined as the number of atoms per unit length whose centers lie on the
direction vector for a specific crystallographic direction; that is,

LD = number of atoms centered on direction vector

length of direction vector

The units of linear density are reciprocal length (e.g., nm-1, m-1).

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In an analogous manner, planar density (PD) is taken as the number of atoms per unit area that
are centered on a particular crystallographic plane, or

PD = number of atoms centered on a plane

area of plane

The units for planar density are reciprocal area (e.g., nm-2, m-2).

CLOSED-PACKED CRYSTAL STRUCTURES

You may remember from the discussion on metallic crystal structures that both face-
centered cubic and hexagonal close-packed crystal structures have atomic packing factors of
0.74, which is the most efficient packing of equal-size spheres or atoms. In addition to unit cell
representations, these two crystal structures may be described in terms of close-packed planes
of atoms (i.e., planes having a maximum atom or sphere-packing density). Both crystal structures
may be generated by the stacking of these close-packed planes on top of one another; the
difference between the two structures lies in the stacking sequence.

Let the centers of all the atoms in one close-packed plane be labeled A. Associated with this plane
are two sets of equivalent triangular depressions formed by three adjacent atoms, into which the
next close-packed plane of atoms may rest. Those having the triangle vertex pointing up are
arbitrarily designated as B positions, whereas the remaining depressions are those with the down
vertices, which are marked C in Figure 2.9a. A second close-packed plane may be positioned
with the centers of its atoms over either B or C sites; at this point, both are equivalent. Suppose
that the B positions are arbitrarily chosen; the stacking sequence is termed AB, which is illustrated
in Figure 2.9b.

Figure 2.9 (a) A portion of a close-packed plane of atoms; A, B, and C positions are indicated. (b) The AB
stacking sequence for close-packed atomic planes.
(Adapted from W. G. Moffatt, G. W. Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. I, Structure,
p. 50. Copyright © 1964 by John Wiley & Sons, New York.)

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2.2. CRYSTALLINE AND NON CRYSTALLINE MATERIALS

SINGLE CRYSTALS

For a crystalline solid, when the periodic and repeated arrangement of atoms is perfect or
extends throughout the entirety of the specimen without interruption, the result is a single crystal.
All unit cells interlock in the same way and have the same orientation. Single crystals exist in
nature, but they can also be produced artificially. They are ordinarily difficult to grow because the
environment must be carefully controlled. If the extremities of a single crystal are permitted to
grow without any external constraint, the crystal assumes a regular geometric shape having flat
faces, as with some of the gemstones; the shape is indicative of the crystal structure. A garnet
single crystal is shown in Figure 2.10. Within the past few years, single crystals have become
extremely important in many modern technologies, in particular electronic microcircuits, which
employ single crystals of silicon and other semiconductors.

Figure 2.10 A garnet single crystal that was found in Tongbei, Fujian Province, China.
(Photograph courtesy of Irocks.com, Megan Foreman photo.)

POLYCRYSTALLINE MATERIALS
Most crystalline solids are composed of a collection of many small crystals or grains; such
materials are termed polycrystalline. Various stages in the solidification of a polycrystalline
specimen are represented schematically in Figure 2.11. Initially, small crystals or nuclei form at
various positions.

These have random crystallographic orientations, as indicated by the square grids. The
small grains grow by the successive addition from the surrounding liquid of atoms to the structure
of each. The extremities of adjacent grains impinge on one another as the solidification process
approaches completion. As indicated in Figure 2.11, the crystallographic orientation varies from
grain to grain. Also, there exists some atomic mismatch within the region
where two grains meet; this area, called a grain boundary.

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Figure 2.11 Schematic diagrams of the various stages in the solidification of a polycrystalline material; the
square grids depict unit cells. (a) Small crystallite nuclei. (b) Growth of the crystallites; the obstruction of
some grains that are adjacent to one another is also shown. (c) Upon completion of solidification, grains
having irregular shapes have formed. (d) The grain structure as it would appear under the microscope; dark
lines are the grain boundaries.
(Adapted from W. Rosenhain, An Introduction to the Study of Physical Metallurgy, 2nd edition, Constable & Company
Ltd., London, 1915.)

Reference: Materials Science and Engineering: An Introduction, 10th Edition by William D. Callister Jr and
David G. Rethwisch

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