The Structures of Crystalline Solids

When most liquids are cooled, they eventually freeze and form crystalline solids, solids in which

the atoms, ions, or molecules are arranged in a definite repeating pattern. It is also possible for a

liquid to freeze before its molecules become arranged in an orderly pattern. The resulting

materials are called amorphous solids or non-crystalline solids (or, sometimes, glasses). The

particles of such solids lack an ordered internal structure and are randomly arranged (Figure 1).

Figure 1. The entities of a solid phase may be arranged in a regular, repeating pattern (crystalline
solids) or randomly (amorphous).

Metals and ionic compounds typically form ordered, crystalline solids. Substances that

consist of large molecules, or a mixture of molecules whose movements are more restricted,

often form amorphous solids. For examples, candle waxes are amorphous solids composed of

large hydrocarbon molecules. Some substances, such as boron oxide (shown in Figure 2), can

form either crystalline or amorphous solids, depending on the conditions under which it is

produced. Also, amorphous solids may undergo a transition to the crystalline state under

appropriate conditions.

1
Figure 2. (a) Diboron trioxide, B2O3, is normally found as a white, amorphous solid (a glass),
which has a high degree of disorder in its structure. (b) By careful, extended heating, it can be
converted into a crystalline form of B2O3, which has a very ordered arrangement.

Crystalline solids are generally classified according the nature of the forces that hold its

particles together. These forces are primarily responsible for the physical properties exhibited by

the bulk solids. The following sections provide descriptions of the major types of crystalline

solids: ionic, metallic, covalent network, and molecular.

IONIC SOLIDS

Ionic solids, such as sodium chloride and nickel oxide, are composed of positive and

negative ions that are held together by electrostatic attractions, which can be quite strong (Figure

3). Many ionic crystals also have high melting points. This is due to the very strong attractions

between the ions—in ionic compounds, the attractions between full charges are (much) larger

than those between the partial charges in polar molecular compounds. This will be looked at in

more detail in a later discussion of lattice energies. Although they are hard, they also tend to be

brittle, and they shatter rather than bend. Ionic solids do not conduct electricity; however, they do

conduct when molten or dissolved because their ions are free to move. Many simple compounds

formed by the reaction of a metallic element with a nonmetallic element are ionic.

2
 Figure 3. Sodium chloride is an ionic solid.

METALLIC SOLIDS

Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms

Figure 4. The structure of metallic crystals is often described as a uniform distribution of atomic

nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held

together by a unique force known as metallic bonding that gives rise to many useful and varied

bulk properties. All exhibit high thermal and electrical conductivity, metallic luster, and

malleability. Many are very hard and quite strong. Because of their malleability (the ability to

deform under pressure or hammering), they do not shatter and, therefore, make useful

construction materials. The melting points of the metals vary widely. Mercury is a liquid at room

temperature, and the alkali metals melt below 200 °C. Several post-transition metals also have

low melting points, whereas the transition metals melt at temperatures above 1000 °C. These

differences reflect differences in strengths of metallic bonding among the metals.

3
 Figure 4. Copper is a metallic solid.

MOLECULAR SOLID

Molecular solids, such as ice, sucrose (table sugar), and iodine, as shown in Figure 6, are

composed of neutral molecules. The strengths of the attractive forces between the units present in

different crystals vary widely, as indicated by the melting points of the crystals. Small

symmetrical molecules (nonpolar molecules), such as H2, N2, O2, and F2, have weak attractive

forces and form molecular solids with very low melting points (below −200 °C). Substances

consisting of larger, nonpolar molecules have larger attractive forces and melt at higher

temperatures. Molecular solids composed of molecules with permanent dipole moments (polar

molecules) melt at still higher temperatures. Examples include ice (melting point, 0 °C) and table

sugar (melting point, 185 °C).

4
Figure 6. Carbon dioxide (CO2) consists of small, nonpolar molecules and forms a molecular
solid with a melting point of −78 °C. Iodine (I2) consists of larger, nonpolar molecules and forms a
molecular solid that melts at 114 °C.

PROPERTIES OF SOLIDS

A crystalline solid, like those listed in Table 7, has a precise melting temperature because each

atom or molecule of the same type is held in place with the same forces or energy. Thus, the

attractions between the units that make up the crystal all have the same strength, and all require

the same amount of energy to be broken. The gradual softening of an amorphous material differs

dramatically from the distinct melting of a crystalline solid. This results from the structural

nonequivalence of the molecules in the amorphous solid. Some forces are weaker than others,

and when an amorphous material is heated, the weakest intermolecular attractions break first. As

the temperature is increased further, the stronger attractions are broken. Thus, amorphous

materials soften over a range of temperatures.

Type of Type of Type of Particles Properties Examples Solid

Attractions
hard, brittle, conducts electricity as
ionic ions ionic bonds a liquid but not as a
solid, high to NaCl, Al2O3 very high melting
points
atoms of shiny, malleable, ductile, conducts
metallic Cu, Fe, Ti, metallic electropositive heat and
electricity well, variable bonds Pb, U elements hardness and melting

5
 temperature
Type of Type of
Solid Type of Particles Attractions Properties Examples
atoms of covalent covalent very hard, not
conductive, very
C (diamond),
electronegative network bonds high melting
points SiO2, SiC
elements
molecular variable hardness, variable H2O, CO2, I2,
molecules (or C12H22O11
IMFs brittleness, not conductive, low atoms)
melting points
Table 7. Types of Crystalline Solids and Their Properties

A crystalline material is one in which the atoms are situated in a repeating or periodic

array over large atomic distances; 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.

Metallic Crystals

They tend to be densely packed and have several reasons for dense packing. Typically,

only one element is present, so all atomic radii are the same. Metallic bonding is not directional.

Nearest neighbor distances tend to be small in order to lower bond energy.

Unit Cells

The atomic order in crystalline solids indicates that small groups of atoms form a

repetitive pattern. Thus, in describing crystal structures, it is often convenient to sub- divide the

structure into small repeat entities called unit cells. Unit cells for most crystal structures 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. A unit cell is chosen to represent the symmetry

of the crystal structure, wherein all the atom positions in the crystal may be generated by

translations of the unit cell integral distances along each of its edges. Thus, the unit cell is the

6
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.

Coordination number - the number of nearest neighbor atoms or ions surrounding an atom or

ion Lattice - 3D array of points coinciding with atom positions (center of spheres)

The structure of a crystal can be seen to be composed of a repeated element in three

dimensions. This repeated element is known as the unit cell. It is the building block of the crystal

structure. We define the unit cell in terms of the lattice (set of identical points). In three

dimensions the unit cell is any parallelepiped whose vertices are lattice points, in two dimensions

it is any parallelogram whose vertices are lattice points.

Of course, this definition means that there are an infinite number of possible unit cells. So,

in general, the unit cell is chosen such that it is the smallest unit cell that reflects the symmetry of

the structure. There are two distinct types of unit cell: primitive and non-primitive. Primitive unit

cells contain only one lattice point, which is made up from the lattice points at each of the corners.

Non-primitive unit cells contain additional lattice points, either on a face of the unit cell or within

the unit cell, and so have more than one lattice point per unit cell.

It is often the case that a primitive unit cell will not reflect the symmetry of the crystal

structure. A suitable non-primitive unit cell will be picked in such cases.

7
 It was mentioned above that the (eight) lattice points at the corners of the unit cell

contribute only one lattice point to the cell. This is because the lattice points at the corners are

shared between eight-unit cells. Each corner lattice point therefore is equivalent to 1/8 of a lattice

point per unit cell. Similarly lattice points on the edge of a unit cell are shared among four-unit

cells and are worth 1/4 of a lattice point per unit cell. Lattice points on the face of a unit cell are

shared between two-unit cells and are worth 1/2 of a lattice point per unit cell. Lattice points

contained entirely within the unit cell are worth one lattice point per unit cell.

The most common types of unit cell are the primitive(P) unit cell with one lattice point

per unit cell; the face-centered(F) unit cell with additional lattice points at the center of each

face and four lattice points per unit cell; and the body-centered(I) unit cell with a lattice point in

the middle of the unit cell and two lattice points per unit cell. Other cell types are the C

facecentered unit cell and the rhombohedral unit cell.

Bravais lattice

A lattice is a framework, resembling a three-dimensional, periodic array of points, on

which a crystal is built. The smallest array which can be repeated is the ‘unit cell’. In 1850, M.

A. Bravais showed that identical points can be arranged spatially to produce 14 types of regular

pattern. These

14 space lattices are known as ‘Bravais lattices’

Unit Cells and Lattice Parameters

Crystal structures are made up of repeating units of atoms in well-defined locations in a

lattice. In order to describe these structures, it is useful to define the smallest unit of this structure.

This is called the unit cell. The unit cell is the smallest unit of a crystal structure that can be used

to tile space and make the larger macroscopic structure.

8
 There are many shapes and patterns of unit cells. To describe these shapes, we use lattice

parameters, or variables that describe the orientation of the unit cell. The typical lattice

parameters that are used are the length of each side, which are typically labelled a, b, and c, and

the angles between these sides, which are typically labelled α, β, and γ. In this lesson we are

going to discuss three cubic unit cells in detail. A cubic unit cell is exactly the way it sounds: its

basic outer structure is a cube.

Because a crystalline solid consists of repeating patterns of its components in three

dimensions (a crystal lattice), we can represent the entire crystal by drawing the structure of the

smallest identical units that, when stacked together, form the crystal. This basic repeating unit is

called a unit cell. For example, the unit cell of a sheet of identical postage stamps is a single

stamp, and the unit cell of a stack of bricks is a single brick. In this section, we describe the

arrangements of atoms in various unit cells.

Unit cells are easiest to visualize in two dimensions. In many cases, more than one-unit

cell can be used to represent a given structure, as shown for the Escher drawing in the chapter

opener and for a two-dimensional crystal lattice in Figure 12.2. Usually the smallest unit cell that

completely describes the order is chosen. The only requirement for a valid unit cell is that

repeating it in space must produce the regular lattice. Thus, the unit cell in part (d) in Figure 12.2

is not a valid choice because repeating it in space does not produce the desired lattice (there are

triangular holes). The concept of unit cells is extended to a three-dimensional lattice in the

schematic drawing in Figure 12.3.

9
 Figure 12.2 Unit Cells in Two Dimensions. (a–c) Three two-dimensional lattices illustrate the
possible choices of the unit cell. The unit cells differ in their relative locations or orientations
within the lattice, but they are all valid choices because repeating them in any direction fills the
overall pattern of dots. (d) The triangle is not a valid unit cell because repeating it in space fills
only half of the space in the pattern. (CC BY-NC-SA; anonymous by request)

Figure 12.3 Unit Cells in Three Dimensions. These images show (a) a three-dimensional unit
cell and (b) the resulting regular three-dimensional lattice. (CC BY-NC-SA; anonymous by
request)

The Unit Cell

There are seven fundamentally different kinds of unit cells, which differ in the relative

lengths of the edges and the angles between them (Figure 12.4). Each unit cell has six sides, and

each side is a parallelogram. We 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.

10
 Figure 12.4 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. (CC BY-NCSA;
anonymous by request)

If the cubic unit cell consists of eight component atoms, molecules, or ions located at the

corners of the cube, then it is called simple cubic (part (a) in Figure 12.5). If the unit cell also

contains an identical component in the center of the cube, then it is body-centered cubic (bcc)

(part (b) in Figure 12.5). If there are components in the center of each face in addition to those at

the corners of the cube, then the unit cell is face-centered cubic (fcc) (part (c) in Figure 12.5).

Figure 12.5 The Three Kinds of Cubic Unit Cell.

For the three kinds of cubic unit cells, simple cubic
(a), body-centered cubic (b), and face-centered
cubic (c), there are three representations for each:
a ball-and-stick model, a space-filling cutaway
model that shows the portion of each atom that lies
within the unit cell, and an aggregate of several
unit cells. (CC BY-NC-SA; anonymous by request)

As indicated in Figure 12.5, a solid consists

of a large number of unit cells arrayed in three dimensions. Any intensive property of the bulk

material, such as its density, must therefore also be related to its unit cell. Because density is the

11
mass of substance per unit volume, we can calculate the density of the bulk material from the

density of a single unit cell. To do this, we need to know the size of the unit cell (to obtain its

volume), the molar mass of its components, and the number of components per unit cell. When

we count atoms or ions in a unit cell, however, those lying on a face, an edge, or a corner

contribute to more than one-unit cell, as shown in Figure 12.5. For example, an atom that lies on

a face of a unit cell is shared by two adjacent unit cells and is therefore counted as 12 atom per

unit cell. Similarly, an atom that lies on the edge of a unit cell is shared by four adjacent unit

cells, so it contributes 14 atoms to each. An atom at a corner of a unit cell is shared by all eight

adjacent unit cells and therefore contributes 18 atoms to each. The statement that atoms lying on

an edge or a corner of a unit cell count as 14 or 18 atom per unit cell, respectively, is true for all

unit cells except the hexagonal one, in which three unit cells share each vertical edge and six

share each corner (Figure 12.4), leading to values of 13 and 16 atom per unit cell, respectively,

for atoms in these positions. In contrast, atoms that lie entirely within a unit cell, such as the atom

in the center of a body-centered cubic unit cell, belong to only that one-unit cell.

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.

Simple Cubic Structure

The arrangement of the atoms in a solid that has a simple cubic unit cell was shown in

part (a) in Figure 12.5. 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

12
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. Simple cubic unit cells are, however, common among binary

ionic compounds, where each cation is surrounded by six anions and vice versa.

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

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 12.5, the

bodycentered 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

squareshaped “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 bodycentered cubic structures.

13
Hexagonal Close-Packed and Cubic Close-Packed Structures

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 12.6. 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 12.6. 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 12.6: Close-Packed Layers of Spheres. (a) In this single layer of close-packed spheres,
each sphere is surrounded by six others in a hexagonal arrangement. (b) Placing an atom at a B
position prohibits placing an atom at any of the adjacent C positions and results in all the atoms
in the second layer occupying the B positions. (c) Placing the atoms in the third layer over the
atoms at A positions in the first layer gives the hexagonal close-packed structure. Placing the
third-layer atoms over the C positions gives the cubic close-packed structure. (CC BY-NC-SA;
anonymous by request)
If we place the second layer of spheres at the B positions in part (a) in Figure 12.6, we

obtain the two-layered structure shown in part (b) in Figure 12.6. There are now two alternatives

for placing the first atom of the third layer: we can place it directly over one of the atoms in the

first layer (an A position) or at one of the C positions, corresponding to the positions that we did

not use for the atoms in the first or second layers (part (c) in Figure 12.6). If we choose the first

14
arrangement and repeat the pattern in succeeding layers, the positions of the atoms alternate from

layer to layer in the pattern ABABAB…, resulting in a hexagonal close-packed (hcp) structure

(part (a) in Figure 12.7). If we choose the second arrangement and repeat the pattern indefinitely,

the positions of the atoms alternate as ABCABC…, giving a cubic close-packed (ccp) structure

(part (b) in Figure 12.7). Because the ccp structure contains hexagonally packed layers, it does

not look particularly cubic. As shown in part (b) in Figure 12.7, however, simply rotating the

structure reveals its cubic nature, which is identical to a fcc structure. The hcp and ccp structures

differ only in the way their layers are stacked. Both structures have an overall packing efficiency

of 74%, and in both each atom has 12 nearest neighbors (6 in the same plane plus 3 in each of the

planes immediately above and below).

Figure 12.7 Close-Packed Structures: hcp and ccp.

The illustrations in (a) show an exploded view, a side view, and a top view of the hcp

structure. The simple hexagonal unit cell is outlined in the side and top views. Note the similarity

to the hexagonal unit cell shown in Figure 12.4. The ccp structure in (b) is shown in an exploded

view, a side view, and a rotated view. The rotated view emphasizes the fcc nature of the unit cell

(outlined). The line that connects the atoms in the first and fourth layers of the ccp structure is the

body diagonal of the cube. (CC BY-NC-SA; anonymous by request)

Table 12.1 compares the packing efficiency and the number of nearest neighbors for the

different cubic and close-packed structures; the number of nearest neighbors is called the

15
coordination number. Most metals have hcp, ccp, or bcc structures, although several metals

exhibit both hcp and ccp structures, depending on temperature and pressure.

Table 12.1: Properties of the Common Structures of Metals

Percentage of Space
Structure Coordination Number
Occupied by Atoms
simple cubic 52 6
body-centered cubic 68 8
hexagonal close packed 74 12
cubic close packed (identical
74 12
to face-centered cubic)
Summary

The smallest repeating unit of a crystal lattice is the unit cell. The simple cubic unit cell

contains only eight atoms, molecules, or ions at the corners of a cube. A body-centered cubic

(bcc) unit cell contains one additional component in the center of the cube. A face-centered cubic

(fcc) unit cell contains a component in the center of each face in addition to those at the corners

of the cube. Simple cubic and bcc arrangements fill only 52% and 68% of the available space

with atoms, respectively. The hexagonal close-packed (hcp) structure has an ABABAB…

repeating arrangement, and the cubic close-packed (ccp) structure has an ABCABC… repeating

pattern; the latter is identical to an fcc lattice. The hcp and ccp arrangements fill 74% of the

available space and have a coordination number of 12 for each atom in the lattice, the number of

nearest neighbors.

The simple cubic and bcc lattices have coordination numbers of 6 and 8, respectively.

Metallic Crystal Structures

16
 Simple Cubic Structure

The simple cubic unit cell 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. By convention, the edge of a unit cell always connects

equivalent points. Each of the eight corners of the unit cell therefore

must contain an identical particle. Other particles can be present on

the

edges or faces of the unit cell, or within the body of the unit cell. But the minimum that must be

present for the unit cell to be classified as simple cubic is eight equivalent particles on the eight

corners.

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. For the FCC crystal structure,

each corner atom is shared among eight-unit cells, whereas a face-centered atom belongs to only

two. Therefore, one-eighth of each of the eight corner atoms and one-half of each of the six face

atoms, or a total of four whole atoms,

17
may be assigned to a given unit cell. This is depicted in Figure 3.1a, where only sphere portions

are represented within the confines of the cube. The cell comprises the volume of the cube,

which is generated from the centers of the corner atoms as shown in the figure.

For face-centered cubics, the coordination number is 12.

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

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. Two atoms are associated with each BCC

unit cell: the equivalent of one atom from the eight corners, each of which is shared among

eightunit cells, and the single center atom, which is wholly contained within its cell.

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

FCC, so also is the atomic packing factor for BCC lower—0.68 versus 0.74.

18
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. 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 coordination number and the atomic packing factor for the HCP crystal

structure are the same as for FCC: 12 and 0.74, respectively and since the parameters involved c

and a, the ratio between the two is 1.633

In hexagonal close packing, layers of spheres are packed so that spheres in alternating

layers overlie one another. As in cubic close packing, each sphere is surrounded by 12 other

spheres. Taking a collection of 13 such spheres gives the cluster illustrated above. Connecting

the centers of the external 12 spheres gives Johnson solid known as the triangular

orthobicupola (Steinhaus 1999, pp. 203-205; Wells 1991, p. 237).

Hexagonal close packing must give the same packing density as cubic close packing,

since sliding one sheet of spheres cannot affect the volume they occupy. To verify this, construct

a threedimensional diagram containing a hexagonal unit cell with three layers (Steinhaus 1999,

pp. 203204). Both the top and the bottom contain six -spheres and one hemisphere. The total

number of spheres in these two rows is therefore

19
 (1)

The volume of spheres in the middle row cannot be simply computed using geometry.

However, symmetry requires that the piece of the sphere which is cut off is exactly balanced by

an extra piece on the other side. There are therefore three spheres in the middle layer, for a total

of six, and a total volume

(2) The base of the unit cell is a regular hexagon made

up of six equilateral triangles with side lengths

. The unit cell base area is therefore

(3)

The height is the same as that of two tetrahedra length on a side, so

(4)

giving

(5)

(Conway and Sloane 1993, pp. 7 and 9). Now that the Kepler conjecture has been established,

hexagonal close packing and cubic close packing, both of which have the same packing density

of

20
, are known to be the densest possible packings of equal spheres.

21
ATOMIC PACKING FACTOR EXAMPLE COMPUTATION

22
 DENSITY COMPUTATIONS

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

theoretical density r through the relationship

Where:

n number of atoms associated with each unit cell

A atomic weight

VC volume of the unit cell

23
NA Avogadro’s number 16.022 = 1023 atoms/mol2
SAMPLE PROBLEM (COPPER):

24
TABLES RELATED TO DENSITY

Polymorphism

Polymorphism is the ability of a solid material to exist in more than one form or crystal

structure. We can find this characteristic in any crystalline material such as polymers, mineral,

metal, etc.

25
 The variation of the conditions during the crystallization process is the main reason that is

responsible for the occurrence of the polymorphism in crystalline materials. These variable

conditions are as follows:

• Polarity of solvent

• Presence of impurities

• The level of supersaturation at which the material starts to crystalize

• Temperature

• Changes in stirring conditions Example:

Aluminum Oxide Chromium Oxide Iron (III) Oxide

Allotropy

Allotropy is the existence of two or more different physical forms of a chemical element.

These forms exist in the same physical state, mostly in the solid state. Allotropes contain atoms

of the same chemical element that binds with each other in different ways.

Moreover, these different forms may have different physical properties because they have

different structures and chemical behavior may vary as well. One allotrope may convert into

another when we change some factors such as pressure, light, temperature, etc. allotropes

• Carbon – diamond, graphite, graphene, fullerenes, etc.

• Phosphorous – white phosphorous, red phosphorous, diphosphorous, etc.

• Oxygen – dioxygen, ozone, tetraoxygen, etc.

26
 • Boron – amorphous boron, alpha rhombohedral boron, etc.

• Arsenic – yellow arsenic, grey arsenic, etc.

Diamond Red Phosphorous

Amorphous Boron Yellow Arsenic

From the figure, the different forms of the chemical element may result to different physical

property because they have different structures and chemical behavior. The factors that caused

this change are pressure, light, and temperature.

27
 Polymorphism Vs Allotropy
Polymorphism Allotropy

Definition Polymorphism is the ability of a Allotropy is the existence of two or

solid material to exist in more
than one form or crystal structure more different physical forms of a

chemical element.

Occurrence Polymorphism occurs in chemical Allotropy occurs in chemical

compounds elements

Description of Describes the differences in Describes the differences un atomic

crystal structures of compounds
Structure arrangement of compounds having

the atoms of the same chemical

element

The 7 Crystal Systems

• A method of classifying crystals according to their atomic lattice or structure.

• The atomic lattice is a three-dimensional network of atoms that are arranged in a

symmetrical pattern.

28
 •
The unit cell geometry is completely defined in terms of six parameters: the three edge

lengths a, b, and c, and the three interaxial angles a, b, and y. These are termed the lattice

parameters of a crystal structure.

Cubic

• Has the highest symmetry

• All three axes are of equal length and intersect at right

angles.

Based on a square inner structure.

• a=b=c

• α = β = γ = 90° Example:

Fluorite Pyrite

Hexagonal

• Can be visualized as a prism with hexagons as the bases.

• Three out of the four axes are in one plane, of the same length, and

intersect each other at angles of 60 degrees. The fourth axis is of a

different length and intersects the others at right angles.

• Based on a hexagonal (6-sided) inner structure.

29
 •
• a=b≠c
α = β = 90° and γ = 120°

Example:

Beryl Zincite

Trigonal

• Also known as rhombohedral.

• Axes and angles in this system are similar to the Hexagonal

System.

• In the cross-section of a Trigonal crystal there will be three sides.

• Based on a triangular inner structure.

• a=b=c

• α = β = γ ≠ 90° Example:

30
 •
Ruby Quartz
Calcite Tetragonal Based on a rectangular inner structure.

• Two axes are of equal length and are in the same plane, the

main axis is either longer or shorter, and all three intersect at

right angles.

• a=b≠c

• α = β = γ = 90°

Example:

Rutile Zircon Anatase

Orthorhombic

• Based on a rhombic (diamond-shaped) inner structure.

• Three axes, all of different lengths, are at right angles to each

other.

• a≠b≠c

• α = β = γ = 90°

31
 •

Example:

32
 Topaz Tanzanite Iolite

Monoclinic

• Based on a parallelogram inner structure.

• There are three axes, each of different lengths. Two are at right

angles to each other and the third is inclined.

• a≠b≠c

• α = γ = 90° and β ≠ 90° Example:

Gypsum Muscovite (Mica) Zurite

Triclinic

• Based on a 'triclinic' inner structure, meaning 'three inclined angles’.

• All three axes are of different lengths and inclined towards each other.

• a≠b≠c

• α≠β≠γ

33
Example

Amazonite Rhodonite

Crystallographic Points, Planes, and Directions

• Labeling conventions have been established in which three numbers or indices are used

to designate point locations, directions, and planes.

• The basis for determining index values is the unit cell, with a right-handed coordinate

system consisting of three (x, y, and z) axes.

Point coordinates

• The position of any point (e.g. P) within the unit cell can be defined in terms of

generalized coordinates (e.g. q, r, s) which are fractional multiples of the unit cell edge

length (a, b, c respectively): (q r s).

• Used to know the atomic positions in a cell.

34
Step-by-step guide to get the location of the point

1. Start with your pencil at the origin.

2. Count q · a in the x-direction, r · b in the y-direction, and s · c in the z-direction.

3. Draw and label the point.

Sample Problem:

A.) Location of Point Having Specified Coordinates

For the unit cell shown in the accompanying sketch (a), locate the point having coordinates

¼ 1 ½.

35
 Answer:

B.) Specification of point coordinates

Specify point coordinates for all atom positions for a BCC unit cell.

Answer:

36
Crystallographic Directions

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

• It is a vector connecting the coordinate origin and a specific point of a unit cell.

• Vector defined by three direction indices [u v w].

• The following steps are used to determine the three directional indices:

1. Place your pencil at the tail of the given vector.

2. Count how many lattice constants you must move in the x-, y-, and z-directions to

reach the head of the vector. Write them down. Be mindful of negatives.

3. These three numbers are multiplied or divided by a common factor to reduce them to

the smallest integer values.

4. The three indices, not separated by commas, are enclosed in square brackets, thus:

[uvw]. The u, v, and w integers correspond to the reduced projections along the x, y,

and z axes, respectively.

Sample Problem:

Determination of Directional Indices

37
 1.) Determine the indices for the direction shown in the accompanying figure.

Answer:

2.) Determine the indices for the direction shown in the accompanying figure.

Construction of Specified Crystallographic Directions

Indices of crystallographic points, directions, and planes are given in terms of the lattice

constants of the unit cell. For points and directions, you can consider the indices to be

38
coefficients of the lattice constants It is important to label axes, lattice constants, and identifying

information for directions (vector arrow head) and planes (axes intercepts).

Steps on constructing Crystallographic Directions

1. Choose a point for the origin of your vector. Simple directions, such as those shown in

Figure 2a, are easy to draw using the 000 crystallographic point as the origin.

2. Start with your pencil on your chosen origin. Move your pencil u · a in the x-direction, v

· b in the y-direction, and w · c in the z-direction. If u, v, or w are negative, move in the

negative direction on that axis.

3. Draw and label a point

4. Draw a line from your chosen origin to the point you just drew. Add an arrow head at the

point.

Note: Always remember to

label the point that lies at the

end of your direction vector.

39
Example:

Draw a [1 1 0] direction within a cubic unit cell.

Solution:

First, construct an appropriate unit cell and coordinate axes system. In the accompanying figure

the unit cell is cubic, and the origin of the coordinate system, point O, is located at one of the

cube corners.

Note: For some crystal structures, several nonparallel directions with different indices are

crystallographically equivalent; this means that the spacing of atoms along each direction is the

same.

Hexagonal Crystals

• The hexagonal system has four crystallographic axes consisting of three equal horizontal,

or equilateral axes at 120 degrees to each other, as well as one vertical axis which is

perpendicular to the other three. This vertical axis can be longer or shorter than the

horizontal axes.

40
• A problem arises for crystals having hexagonal symmetry in that some crystallographic

equivalent directions will not have the same set of indices. This is circumvented by

utilizing a four-axis, or Miller Bravais, coordinate system as shown in Figure 3.7.

• The first three indices pertain to projections along the respective a1, a2, and a3 axes in

the basal plane.

41
Determination of Directional Indices for a Hexagonal Unit Cell

• It is essential to label axes, lattice constants, and identifying information for directions (vector

arrowhead) and planes (axes intercepts) just like in a cubic unit cell.

• A difference of cubic and hexagonal unit cell is that there are only three axes in a cubic

unit cell whereas there are four axes found in a hexagonal unit cell.

Example:

Determine the directional indices (four-index system) for the direction shown in the

accompanying figure.

Convert the indices into an index set referenced to the four-axis scheme:

42
Crystallographic Planes

• Any set of parallel and equally spaced planes that may be supposed to pass through the

centers of atoms in crystals. As every plane must pass through atomic centers and no

centers must be situated between planes, the distance between successive planes in a set

depends on their direction in relation to the arrangement of atomic centers.

• Crystallographic planes are specified by three Miller indices as (hkl). Any two planes

parallel to each other are equivalent and have identical indices.

• Those planes that make rational intercepts with crystallographic axes and that may be

noted by their intercept reciprocals, the Miller indices enclosed in parentheses, (hkl).

Such planes may represent crystal faces, cleavage planes, twin planes, lattice points, or

planes of atomic particles in a crystal structure.

43
Steps on constructing Crystallographic Planes:

1. Find the reciprocal of (hkl). If one or more of the indices is zero, consider the reciprocal

to be infinity. The values 1/h , 1/k , and 1/l are the intercepts of the x-, y-, and z-axes,

respectively. If one or more intercept is infinity, this means that the plane will never

intercept that axis (it is parallel to that axis). For the (221) plane shown in Figure 3a, the

reciprocals would be 1/2, 1/2, and 1.

2. For all non-zero indices, draw a point on the x-axis at a/h, a point on the y-axis at b/k, and

a point on the z-axis at c/l.

3. Connect the dots.

Steps on how to list the (h, k , l) indices given in a drawing of a plane:

1. Check to see if the plane goes through the origin, as in Figure 4a. If not, proceed to step

2. If it does, shift the plane 1 lattice constant in an axis such that it no longer passes

through the origin (see Figure 4b). This new plane is equivalent to the first.
44
 2. Find the coefficients by which you would multiply the lattice constants to identify where

the plane intercepts the x-, y-, and z-axes. Be mindful of negative intercepts. If the plane

doesn’t intercept an axis (it is parallel to that axis), call the intercept infinity. Write down

these values.

3. Take the reciprocal of these intercepts. The value of 1 ∞ is zero.

4. If necessary, multiply or divide by a common number to put the indices in the most

reduced integer form. Sometimes you will be asked to leave the indices unreduced - for

example,

(220) instead of (110) - for use in x-ray diffraction questions.

5. Enclose the indices in parentheses without commas (hkl)

Example figures:

Miller Indices

 A group of three numbers that indicates the orientation of a plane or set of parallel planes of

atoms in a crystal. If each atom in the crystal is represented by a point and these points are

45
 connected by lines, the resulting lattice may be divided into a number of identical blocks, or

unit cells.

 Miller indices form a notation system in crystallography for planes in crystal lattices. In

particular, a family of lattice planes is determined by three integers h, k, and l.

 A symbolic vector representation for the orientation of an atomic plane in a crystal lattice

and are defined as the reciprocals of the fractional intercepts which the plane makes with the

crystallographic axes.

 Miller indices are mainly used to specify directions and planes

 The directions and planes could be in lattices or in crystals Notation summary of Miller

indices:

 (h,k,l) represents a point

 Negative numbers/directions are denoted with a bar on top of the number

 [hkl] represents a direction

 <hkl> represents a family of directions

 (hkl) represents a plane

 {hkl} represents a family of planes

HKL definition in Miller indices
 denotes a plane that intercepts the three points a 1/h, a2/k, and a3/l, or some multiple thereof.

That is, the Miller indices are proportional to the inverses of the intercepts of the plane, in

the basis of the lattice vectors.

Steps on how to determine Miller indices in planes:

46
1. Identify the plane intercepts on the x, y and z-axes.

2. Specify intercepts in fractional coordinates.

3. Take the reciprocals of the fractional intercepts.

Principles to remember in determining Miller indices

 If a Miller index is zero, the plane is parallel to that axis.

 The smaller a Miller index, the more nearly parallel the plane is to the axis.

 The larger a Miller index, the more nearly perpendicular a plane is to that axis.

 Multiplying or dividing a Miller index by a constant has no effect on the orientation of the

plane

 Miller indices are almost always small.

Determination of Planar (Miller) Indices

Example 1

Consider the plane in pink, which is one of an infinite number of parallel plane each a consistent

distance (“a”) away from the origin (purple planes)

47
 The plane intersects with the x-axis at point a and runs parallel along the y and z axes 
This

plane can be designated as (1,∞,∞)

48
 Whereas, the yellow plane can be designated as (∞,1,∞)

 The green plane can be designated as (∞,∞,1)

Note: Miller indices are reciprocals of the parameters of each crystal face

Pink Face = (1/1, 1/∞, 1/∞) = (100)

Green Face = (1/∞, 1/∞, 1/1) = (001)

49
Yellow Face = (1/∞, 1/1, 1/∞) = (010)

Example 2

50
 The plane shown in the figure above intersects with two of the crystallographic axes and

these are the x and y axes

 Intercepts: (1,1, ∞)

 (1/1,1/1,1/∞) = 110

Example 3

51
 The plane shown in the figure above intersects with all three crystallographic axes

 Intercepts (1,1,1)

 (1/1,1/1,1/1) = 111

Construction of Specified Crystallographic Plane

Example:

52
Atomic Structure

Atoms are the small building blocks of all existing substances. They are so tiny that we can’t

even observe with our naked eye. Normally, atoms are in the Angstrom range. With the

discovery of subatomic particles, the next question for scientists was to find how they are

arranged in an atom.

Crystal Structure

Crystal structure is how the atoms or molecules are arranged in a crystal. This has a

threedimensional arrangement in space. Normally, in a crystal, there is a repeating arrangement

of certain atoms or molecules. One of the repeating units of a crystal is named as a “unit cell.”

Because of this repeating arrangement, there is a pattern and a long-range order in a crystal. The

crystal structure determined many of its physical and chemical properties such as electronic band

structure, cleavage, transparency, etc. There are seven crystal lattice systems, which are

categorized based on their shape. They are cubic, tetragonal, orthorhombic, hexagonal, trigonal,

triclinic and monoclinic. According to the properties also crystals can be categorized as covalent,

metallic, ionic, and molecular crystals.

53
Atomic Structure Vs Crystal Structure

Atomic structure gives an idea of the shape of an atom and how the subatomic particles are

arranged in an atom. Crystal structure tells about how the atoms or the molecules are arranged in

a crystal solid or a liquid.

Overall atomic structure is common to all the atoms except the number of subatomic

particles. But there are a large number of crystal structure variations.

Hexagonal Crystals

The hexagonal system has four crystallographic axes consisting of three equal horizontal, or

equilateral axes at 120 degrees to each other, as well as one vertical axis which is perpendicular

to the other three. This vertical axis can be longer or shorter than the horizontal axes.

The system has the following forms:

• Prism

• Pinacoid

• Dipyramid

• Ditrigonal Pyramid

• Trigonal Prism

• Ditrigonal Prism.

54
 In crystallography, the hexagonal crystal family is one of the 6 crystal families, which

includes 2 crystal systems (hexagonal and trigonal) and 2 lattice systems (hexagonal and

rhombohedral). The hexagonal crystal family consists of the 12-point groups such that at least

one of their space groups has the hexagonal lattice as underlying lattice and is the union of the

hexagonal crystal system and the trigonal crystal system. There are 52 space groups associated

with it, which are exactly those whose Bravais lattice is either hexagonal or rhombohedral.

Determination of Miller – Bravais System

55
Miller-Bravais System

Miller indices form a notation system in crystallography for planes in crystal (Bravais)

lattices.

In particular, a family of lattice planes is determined by three integers h, k, and ℓ, the

Miller indices. They are written (hkℓ), and denote the family of planes that are orthogonal. The

basis of the reciprocal lattice vectors (note that the plane is not always orthogonal to the linear

combination of direct lattice vectors because the reciprocal lattice vectors need not be mutually

orthogonal).

By convention, negative integers are written with a bar, as in 3 for −3. The integers are usually

written in lowest terms, i.e. their greatest common divisor should be 1. Miller indices are also

used to designate reflections in X-ray crystallography. In this case the integers are not

necessarily in lowest terms, and can be thought of as corresponding to planes spaced such that

the reflections from adjacent planes would have a phase difference of exactly one wavelength

(2π), regardless of whether there are atoms on all these planes or not.

Formula for Miller-Bravais System

h + k = -i
56
Hexagonal Unit Cell
Hexagonal unit cell is single entity of hexagonal crystal system. It means there are a no. of

repetitive hexagonal unit cells inside a hexagonal crystal system.

Linear and Planar Densities

Linear Densities, directional equivalency is related to the atomic linear density in

the sense that equivalent directions have identical linear densities. The direction vector is

positioned so as to pass through atom centers. The fraction of line length intersected

y these atoms is equal to the linear density.

Planar Densities, planar density (PD) is taken as the number of atoms per unit area that

are centered on a particular crystallographic plane.

Close-Packed Crystal Structures

The term "closest packed structures" refers to the most tightly packed or

spaceefficient composition of crystal structures (lattices). Imagine an atom in a crystal

lattice as a sphere. While cubes may easily be stacked to fill up all empty space, unfilled

space will always exist in the packing of spheres. To maximize the efficiency of packing

and minimize the volume of unfilled space, the spheres must be arranged as close as

possible to each other. These arrangements are called closest packed structures.

The packing of spheres can describe the solid structures of crystals. In a crystal

structure, the centers of atoms, ions, or molecules lie on the lattice points. Atoms are

assumed to be spherical to explain the bonding and structures of metallic crystals. These

57
spherical particles can be packed into different arrangements. In closest packed

structures, the arrangement of the spheres is densely packed in order to take up the

greatest amount of space possible.

Hexagonal Closest Packed (HCP)

In a hexagonal closest packed structure, the third layer has the same

arrangement of spheres as the first layer and covers all the tetrahedral holes. Since

the structure repeats itself after every two layers, the stacking for HCP may be

described as "a-b-a-b-a-b." The atoms in a hexagonal closest packed structure

efficiently occupy 74% of space while 26% is empty space.

Cubic Closest Packed (CCP)

The arrangement in a cubic closest packing also efficiently fills up 74% of

space. Similar to hexagonal closest packing, the second layer of spheres is placed

58
on to of half of the depressions of the first layer. The third layer is completely

different than that first two layers and is stacked in the depressions of the second

layer, thus covering all of the octahedral holes. The spheres in the third layer are

not in line with those in layer A, and the structure does not repeat until a fourth

layer is added. The fourth layer is the same as the first layer, so the arrangement

of layers is "a-b-c-a-b-c."

Single Crystals

Single crystal, any solid object in which an orderly three-dimensional

arrangement of the atoms, ions, or molecules is repeated throughout the entire

volume. Certain minerals, such as quartz and the gemstones, often occur as single

crystals; synthetic single crystals, especially silicon and gallium arsenide, are used

59
in solid-state electronic devices such as integrated circuits and light-emitting

diodes (LEDs).

In the preparation of synthetic single crystals, special techniques are

employed to control the deposition of material upon one nucleus (see nucleation),

which often is a small single crystal of the substance obtained from a previous

preparation.

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.

Polycrystalline Materials

Polycrystalline materials are composed of a large number of grains. As

mentioned, the lattice arrangement of atoms within each grain is nearly identical,

but the orientation of the atoms is different for each adjoining grain. The surface

60
 that separates neighboring grains is the grain boundary. Grain boundaries impede

the movement of dislocations and thereby have a strengthening effect.

Most crystalline solids are composed of a collection of many small

crystals or grains; such materials are termed polycrystalline.

Types of Solids

Crystalline Solids

By definition, a crystalline solid, also simply known as a crystal, is a solid material whose

basic constituents such as atoms, ions, and molecules are arranged in a highly ordered and

61
welldefined microscopic structure, known as a crystal lattice. These solids are formed in a

process known as crystallization, wherein, the lattice structure gets extended in all directions.

Macroscopic single crystal structures too are found in nature having the characteristic

crystalline shape, comprising flat faces and characteristic orientations. These include snowflakes,

diamonds, table salt, etc.

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 may also be produced artificially. They are ordinarily difficult to grow, because

the environment must be carefully controlled.

Polycrystalline

Most crystalline solids are composed of a collection of many small crystals or grains;

such materials are termed polycrystalline. 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.

Non-crystalline Solids

Sometimes called Amorphous meaning literally “without form”, the atomic structure of

non-crystalline solids resembles that of the atomic structure of liquids. Amorphous solids are

basically the exact opposite of crystalline solids. While an amorphous solid may display some

62
finite order in terms of the arrangement of its atoms, ions, and molecules, it clearly lacks the

longrange systematic and regular arrangement atomic structure over relatively large atomic

distances that a crystalline solid exhibit.

Examples: Glass, Rubber, Cotton Candy

The arrangement of elements in amorphous solids is mostly random and disorderly.

Because of this, when amorphous solids are cut, they break into uneven pieces. Examples include

window glass, various polymers, rubber, etc.

A single crystal has atoms in a near-perfect periodic arrangement; a polycrystal is

composed of many microscopic crystals (called "crystallites" or "grains"); and an amorphous

solid has no periodic arrangement even microscopically.

63
Anisotropy

Different directions in a crystal have different packing. The physical properties of single

crystals of some substances depend on the crystallographic direction in which measurements are

taken. For example, the elastic modulus, the electrical conductivity, and the index of refraction

may have different values in the [100] and [111] directions. Properties of crystals may be

different along different directions, because atomic periodicities are different. Single crystals are

anisotropic as their properties vary with direction. While not all polycrystalline solids are

anisotropic and are distinguished as anisotropic if their grains are textured.

Modulus of Elasticity Values for Several Metals at Various

Crystallographic Orientations

Modulus of Elasticity (Gpa)

Metal [100] [110] [111]

Aluminum 63.7 72.6 76.1

Copper 66.7 130.3 191.1

Iron 125.0 210.5 272.7

Tungsten 384.6 384.6 384.6

Isotropy

Substances in which measured properties are independent of the direction of

measurement are isotropic. Here Properties of crystals are the same in all directions. No solid

crystals are isotropic, however, some polycrystalline solids are isotropic, depending if its gains

are randomly oriented.

Isotropy vs. Anisotropy

64
 In the images above, the left shows a how the glass, an isotropic amorphous solid,

refracts the line behind it. While the image on the right shows the double refraction, also known

as birefringence, produced by the calcite, an anisotropic crystalline solid.

Crystalline Solids vs. Amorphous Solids

1. Characteristic Geometry - The atoms, ions, and molecules in a crystalline solid are

arranged in such a way that they have a definite shape and structure, known as characteristic

geometry. In amorphous solids, such a characteristic geometry isn’t present.

2. X-ray Diffraction- The elemental components of crystalline solids are arranged in

regular arrays. Hence, when they are exposed to X-rays, each solid produces a unique diffraction

pattern, which can be used for its identification. Different amorphous solids don’t show very

distinctive diffraction patterns, as their elemental components aren’t arranged in regular arrays.

3. Melting Point - Crystalline solids have sharp melting points, that is, they change into

liquids at definite temperatures. Amorphous solids, on the other hand, are thought to be liquids at

all temperatures. This is because, on being heated, they do not abruptly change into liquids, but

instead soften and start flowing in a semisolid form.

65
4. Cooling Characteristics - The graphical representation of the cooling characteristics of

an amorphous solid gives a smooth curve. For that of a crystalline solid, the graphical

representation has two break points along the curve. These break points indicate the beginning

and end of the crystallization process, during which, the temperature remains constant. This

happens because, in the crystallization process, energy is released, which goes on to compensate

for the heat loss.

5. Isotropy and Anisotropy - Amorphous solids display several of the characteristics of a

liquid. Just like in liquids, in amorphous solids, properties such as electrical conductivity,

thermal conductivity, mechanical strength, refractive index, etc., remain the same in all

directions. Hence, they are known as isotropic materials. Crystalline solids, on the other hand,

have these characteristics in varying amounts in different directions. For example, light traveling

through a crystal travels at different speeds in different directions within it. That is why

crystalline solids are known as anisotropic.

6) Cutting - A crystalline solid, when cut using the right cutting tool, cleanly splits into two
parts.

An amorphous solid, on the other hand, give irregular cuts, because of its uneven composition.

Crystalline vs. Amorphous

Crystalline Amorphous

Characteristic Geometry Present Not Present

No distinctive diffraction
X-ray Diffraction Unique diffraction pattern pattern

66
 Change into liquids at Soften and starts flowing in a
Melting Point definite temperatures semisolid form upon heating

Cooling Characteristics
(Graphical Rep.) Two break points Smooth Curve

Isotropy and Anisotropy Anisotropic Isotropic

Cutting Cleanly splits into two parts Gives irregular cuts

Diamonds, Table Salt,

Example Snowflakes Glass, Polymers, Rubber

Amorphous Solid Crystalline Solid

X-Ray

The X-ray was discovered in 1895 by the German physicist Wilhelm Conrad Röntgen. It

is an invisible, high penetrating electromagnetic radiation of much shorter wavelength and higher

frequency than visible light.

67
Diffraction

Diffraction is the spreading of waves around obstacles. It takes place with sound, with

electromagnetic radiation, such as light, X-rays, and gamma rays, and with very small moving

particles such as atoms, neutrons, and electrons, which show wavelike properties. This is wave

phenomenon in which the apparent bending and spreading of waves happen when they meet an

obstruction.

Diffraction Methods
68
 X-Ray Diffraction

This is also called as X-Ray Crystallography. Developed by the physicists William

Lawrence Bragg and William Henry Bragg, X-ray diffraction is used to determine the crystal

structures by interpreting the diffraction patterns formed when X-rays are scattered by electrons

of atoms in crystalline solids. William Lawrence Bragg developed Bragg’s law in 1912-1913,

which connects the observed scattering with reflections from evenly spaced planes within the

crystal. Xrays are sent through a crystal to reveal the pattern in which the molecules and atoms

contained within the crystal are arranged.

William Henry Bragg William Lawrence Bragg

69
70
 Bragg’s Law

W.L. Bragg considered crystals to be made up of parallel planes of atoms. Incident waves

are reflected spectacularly from parallel planes of atoms in the crystal, with each plane is

reflecting on a very small fraction of the radiation, like a lightly silvered mirror. In mirror-like

reflection, the angle of incidence is equal to the angle of reflection. Bragg’s Law shows the

relationship among x-ray wavelength, interatomic spacing, and angle of diffraction for

constructive interference.

̅̅ ̅𝑸̅𝑻̅̅̅
nλ = ̅𝑺𝑸̅+

nλ = 𝒅𝒉𝒌𝒍 𝒔𝒊𝒏θ + 𝒅𝒉𝒌𝒍 𝒔𝒊𝒏θ nλ

= 2 𝒅𝒉𝒌𝒍 𝒔𝒊𝒏θ

The Bragg’s Law is nλ = 2dhklsinθ, wherein n is the order of diffraction and d is the

interplanar spacing. Interplanar spacing is The magnitude of the distance between two adjacent

and parallel planes of atoms is a function of the Miller indices (h,k & l) as well as the lattice

parameter/ the unit cell edge length (a).

71
Application of X-Ray Diffraction

1. Differentiation between crystalline and amorphous materials.

2. Determination of the structure of crystalline materials.

3. Determination of electron distribution within the atoms, and throughout the unit cell

4. Determination of the orientation of single crystals.

5. Determination of the texture of polygrained materials.

6. Measurement of strain and small grain size.

Neutron Diffraction

Neutrons do not interact with electron in the crystal. Neutron diffraction is more useful than

Xrays for determining the crystal structures of solids containing light elements.

Electron Diffraction

Electron diffraction is used in the analysis of crystal structure. Electrons are charged particles
and interact strongly with all atoms. This method requires a beam of very high energy, as well
as the specimen must be thin. The experiment must be carried out in a high vacuum, so it brings
complications and it is expensive to conduct.

X-Ray Diffraction Neutron Diffraction Electron Diffraction

Interact with electron Interact with nuclei Interact with electron

Penetrating Highly Penetrating Less Penetrating

Diffraction Techniques

1. Powder Method - Uses a powdered specimen consisting of many fine and randomly

oriented particles that are exposed to monochromatic x-radiation. This method is useful

for samples that are difficult to obtain in a single crystal form. Used to determine the

value of the lattice parameters accurately, which will define the unit cell for the crystal.

72
2. Laue Method - Mainly used to determine the orientation of large single crystals by

means of a continuous spectrum of X-rays that are reflected from or transmitted through a

fixed crystal.

3. Rotating Crystal Method - The shape and size of the unit cell, as well as the

arrangement of atoms inside the cell can be determined by recording the diffraction

patterns.

73
References:

Callister, W. & Rethwisch, D. (2010). Fundamentals of Material Science & Engineering: an

Integrated Approach (8th ed.). Hoboken, NJ: John Wiley & Sons.

CrystalAge. (2020). The Seven Crystal Systems. Retrieved from

https://www.crystalage.com/crystal_information/seven_crystal_systems/?fbclid=IwAR0A

W1n1sMaPI6CaHI_Rwdh3mL8lRjW2rKLSIpPuIcEJXLtf3foYFd7fRy4

Davis, U. (2018). Close-Packed Structures. Retrieved from https://chem.libretexts.org/

Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modul

es_(Physical_and_Theoretical_Chemistry)/Physical_Properties_of_Matter/States_of_Matte

r/Properties_of_Solids/Crystal_Lattice/Closest_Pack_Structures.

Dawson, O. (2011). Difference Between Atomic Structure and Crystal Structure. Retrieved from

https://www.differencebetween.com/difference-between-atomic-structure-and-

vscrystalstructure/.

Eldek, S. (2013). X-Ray Diffraction in Crystal. Retrieved from

https://www.slideshare.net/Ouniyeh/x-ray-diff-lecture-3
Hudson Institute of Minerology. (2020). Definition of Crystallographic Planes. Retrieved from

https://www.mindat.org/glossary/crystallographic_planes
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