Part of book chapter added but for

complete discussion follow Notes as

discussed on various points in Class 3152
Dinesh Pathak
CHAPTER

In this introductory chapter, we briefly discuss the nature of Materials Science

and Engineering. After defining or explaining what Materials Science and
Engineering is, we classify engineering materials according to their nature and
the various categories of applications. Then we discuss the different levels of the
internal structure of materials. Finally, we emphasize the importance of the
structure–property relationships in materials, outlining the general approach of
the ensuing chapters.

1.1 Materials Science and Engineering

The phrase ‘Materials Science and Engineering’ needs some elucidation for the
beginner. The word ‘materials’ here does not refer to all matter in the Universe.
If this were so, it would include all the physical sciences and the life sciences—
from astronomy to zoology! By including the word ‘inanimate’ in the definition,
we can exclude the life sciences from our purview. Further, we can restrict the
definition only to matter useful to mankind. Even here, the range is too broad for
the purposes of the engineer. For example, we can list a large number of things
useful to man, such as food, medicines, explosives, chemicals, water, steel,
plastics and concrete, only some of which qualify as engineering materials. We
then have to be more specific and define materials as that part of inanimate
matter, which is useful to the engineer in the practice of his profession. In the
currently understood sense of the term, materials refer only to solid materials,
even though it is possible to quote a number of examples of liquid and gaseous
materials such as sulphuric acid and steam, which are useful to the engineer.
The word ‘science’ in the phrase refers to the physical sciences, in particular
to chemistry and physics. As we confine ourselves mainly to solids in materials
science, the subject is related to solid state chemistry and solid state physics.
The word ‘engineering’ indicates that the engineering usefulness of the matter
under study is always kept in mind, irrespective of whether the basic laws of
science can be applied rigorously or not. Where the basic laws cannot be
applied, the materials engineer does not give up what is important to him from a
practical point of view. He uses the best possible approximation, develops
1
Part of book chapter added but for complete
discussion follow Notes as discussed on
various points in Class 3152
Dinesh Pathak
CHAPTER

Materials can be broadly classified as crystalline and noncrystalline solids. In a

crystal, the arrangement of atoms is in a periodically repeating pattern, whereas
no such regularity of arrangement is found in a noncrystalline material. A
crystalline solid can be either a single crystal, where the entire solid consists of
only one crystal, or an aggregate of many crystals separated by well-defined
boundaries. In the latter form, the solid is said to be polycrystalline.
In this chapter, we introduce the elementary concepts of crystal geometry.
We first discuss the geometry of arranging points in regular patterns in space. A
crystal can be generated starting from such patterns. We then introduce the
conventions associated with representing directions and planes in crystals. We
describe in some detail the experimental method of determining simple crystal
structures using the x-ray diffraction technique.

Units
SI units
Quantity Other units
Unit Symbol
Lattice parameter a
Atomic diameter
nanometre nm Å
Interplanar spacing d
Wavelength of radiation
Camera radius R millimetre mm inch
Bragg angle radian rad °(degree)

Note: Lengths of atomic dimensions can be expressed in units of nanometre. However,

another submultiple of the metre, the angstrom unit (Å), is still used extensively, even
though it is not a preferred submultiple. We will continue to use the angstrom unit, as it
is convenient and as the conversion to metre is straightforward. Likewise, we will
continue to use °(degree) for angle.

23
24 Crystal Geometry and Structure Determination

GEOMETRY OF CRYSTALS

3.1 The Space Lattices

Before discussing the periodic patterns of atomic arrangements in crystals, we

need to look into arrangements of points in space in periodically repeating
patterns. This leads us to the concept of a space lattice. A space lattice provides
the framework with reference to which a crystal structure can be described.
A space lattice is defined as an infinite array of points in three dimensions
in which every point has surroundings identical to that of every other point in
the array. As an example, for ease of representation on paper, consider a two-
dimensional square array of points shown in Fig. 3.1. By repeated translation of

5
1
5 2
1
1
2
1

a
Fig. 3.1 A two-dimensional square array of points gives a square lattice. Two
ways of choosing a unit cell are illustrated.

the two vectors a and b on the plane of the paper, we can generate the square
array. The magnitudes of a and b are equal and can be taken to be unity. The
angle between them is 90°; a and b are called the fundamental translation
vectors that generate the square array. To ignore end effects near the boundary,
we will assume that the array can be extended infinitely. If we locate ourselves
at any point in the array and look out in a particular direction that lies on the
plane of the paper, the scenery is the same, irrespective of where we are.
Consider the immediate surroundings of a point in the array. If we look due
north or due east from this point, we see another point at a distance of 1 unit.
Along northeast, we see the nearest point at a distance of 2 units and along
north-northeast, the nearest point is at a distance of 5 units. As this is true of
every point in the array, the array satisfies the definition given above and can be
called a two-dimensional square lattice.
 The Space Lattices 25

Example 3.1 Draw a two-dimensional pentagonal lattice.

Solution A regular pentagon has an interior angle of 108°. As 360° is not
an integral multiple of 108°, pentagons cannot be made to meet at a point bearing
a constant angle to one another. Hence, a pentagonal lattice is not possible. On the
other hand, a square or a hexagonal two-dimensional lattice is possible.

A space lattice can be defined by referring to a unit cell. The unit cell is the
smallest unit which, when repeated in space indefinitely, will generate the space
lattice. In the above example of the square lattice, the unit cell is the square
obtained by joining four neigbouring lattice points, as shown in Fig. 3.1. Since
every corner of this square is common to four unit cells meeting at that corner,
the effective number of lattice points in the unit cell is only one. Alternatively,
the unit cell can be visualized with one lattice point at the centre of the square
and with none at the corners (see Fig. 3.1).
A three-dimensional space lattice is generated by repeated translation of three
noncoplanar vectors, a, b and c. It so turns out that there are only 14
distinguishable ways of arranging points in three-dimensional space such that each
arrangement conforms to the definition of a space lattice. These 14 space lattices
are known as Bravais lattices, named after their originator. They belong to seven
crystal systems and are listed in Table 3.1 according to the crystal system.
The cubic system is defined by three mutually perpendicular translation
vectors a, b, and c, which are equal in magnitude. The angle between b and c is
, the angle between c and a is , and that between a and b is . This notation
about angles is general and should be consistently followed. As shown in
Table 3.1, there are three space lattices in the cubic crystal system: the simple
cubic, the body centred cubic, and the face centred cubic space lattices.

Example 3.2 Derive the effective number of lattice points in the unit cell of
the three cubic space lattices.

Solution The unit cell in all these three cases is the cube. The corners of
a cube are common to eight adjacent cubes. The faces are common to two
adjacent cubes. The body centre is not shared by any other cube. So, the
effectiveness of a corner lattice point is 1/8, that of a face centred lattice point is
1/2 and that of the body centre is 1.
Referring to Table 3.1, we can write:

Effective number of lattice

Space lattice Abbreviation
points in unit cell
Simple cubic SC 1
Body centred cubic BCC 2
Face centred cubic FCC 4
Part of book chapter added but for complete
discussion follow Notes as discussed on
various points in Class 3152
26 Crystal Geometry and Structure Determination

Dinesh Pathak TABLE 3.1

The Bravais Lattices

Crystal system Space lattice Unit cell

I. Cubic (1) Simple (Lattice
a=b=c points at the eight
= = = 90° corners of the
unit cell)
c
(2) Body centred
(Points at the eight
corners and at the
a body centre)
(3) Face centred
b
(Points at the eight
corners and at the
six face centres)
II. Tetragonal
a=b c
= = = 90° (4) Simple (Points at
c
the eight corners of
the unit cell)

(5) Body centred

(Points at the eight
a
corners and at the
b body centre)
III. Orthorhombic
a b c
= = = 90° (6) Simple (Points at
the eight corners of
the unit cell)
(7) End centred (Also
called side centred
c
or base centred)
(Points at the eight
corners and at two
face centres opposite
to each other)
a (8) Body centred (Points
at the eight corners and
b at the body centre)
(9) Face centred
(Points at the eight
corners and at the
six face centres)
 The Space Lattices 27

The Bravais Lattices

Crystal system Space lattice Unit cell

IV. Rhombohedral
a=b=c
= = 90° (10) Simple (Points at
c the eight corners of
the unit cell)
b

a
V. Hexagonal
a=b c
= = 90°
= 120° (11) Simple [(i) Points at the
c eight corners of the unit cell
outlined by thick lines
or
(ii) Points at the
twelve corners of the
a
hexagonal prism and
at the centres of the
b two hexagonal faces]
VI. Monoclinic (12) Simple (Points at
a b c the eight corners of
= = 90° the unit cell)
c (13) End centred
(Points at the eight
corners and at two
face centres opposite
to each other)
a

b
VII. Triclinic
a b c (14) Simple (Points at
90° the eight corners
c of the unit cell)

a
b
28 Crystal Geometry and Structure Determination

Crystals have inherent symmetry. A cubic crystal is said to have a four-fold rotation
symmetry about an axis passing through the centres of two opposite faces of the unit
cube. During each complete rotation about this axis, the crystal passes through identical
positions in space four times. The rotational, translational and reflection symmetry
operations constitute the symmetry elements of a crystal. The crystal systems in Table
3.1 are arranged in order of decreasing symmetry, the cube being the most symmetric
and the triclinic system being the least symmetric. The details of symmetry elements of a
crystal are given in books on crystallography and will not be covered here.
After the cubic system, the next less symmetric crystal system is the
tetragonal system. It is defined by three mutually perpendicular vectors, only
two of which are equal in magnitude. There are two space lattices here.

Effective number of lattice

Space lattice Abbreviation
points in unit cell
Simple tetragonal ST 1
Body centred tetragonal BCT 2

It is interesting to note that there is no face centred tetragonal space lattice. Any
array of lattice points that can be represented by an FCT cell can equally well be
described by a BCT cell, as illustrated in Fig. 3.2. When there are two such
alternatives of the same crystal system available to describe the same array of
lattice points, the unit cell which has the smaller number of lattice points is
chosen for the Bravais list.

c
c

a
a a a

Fig. 3.2 An array of lattice points that fit in an FCT unit cell should be
represented by a BCT cell (outlined by thick lines inside two adjacent FCT cells).
[For clarity, the face centred atoms on the front and back faces are omitted.]

An orthorhombic cell is defined by three unequal but mutually

perpendicular translation vectors. There are four orthorhombic space lattices.

Effective number of lattice

Space lattice Abbreviation
points in unit cell
Simple orthorhombic SO 1
End centred orthorhombic ECO 2
Body centred orthorhombic BCO 2
Face centred orthorhombic FCO 4
 Space Lattices and Crystal Structures 29

As a final example, let us examine the unit cell of the hexagonal system. In
order that the hexagonal symmetry becomes evident, we can take the unit cell to
be a regular hexagonal prism, see Table 3.1. The effective number of lattice
points in this unit cell is 3. For generating the entire space lattice by translation
of the unit cell, a smaller cell with only one lattice point is used, refer Table 3.1.

Example 3.3 List the lattice (unit cell) parameters required to specify fully
the unit of each crystal system.

Solution
Crystal system To be specified Total number
axes angles of parameters
Cubic a — 1
Tetragonal a, c — 2
Orthorhombic a, b, c — 3
Rhombohedral a 2
Hexagonal a, c — 2
Monoclinic a, b, c 4
Triclinic a, b, c , , 6

3.2 Space Lattices and Crystal Structures

A space lattice is combined with a basis to generate a crystal structure.

Space lattice + Basis Crystal structure
In many elemental crystals, the basis is simple and consists of one atom per
lattice point. In such cases, the crystal is generated by just positioning one atom
of the element at each lattice point. For example, the crystal structures of
chromium and copper are generated as:
BCC space lattice + 1 Cr atom per lattice point BCC crystal of Cr
FCC space lattice + 1 Cu atom per lattice point FCC crystal of Cu
These crystals are called monoatomic crystals, to denote the fact that the basis is
one atom per lattice point. This adjective is often omitted. A BCC crystal means
a monoatomic BCC crystal, unless otherwise stated.
Figure 3.3 shows unit cells of monoatomic cubic crystals. The atoms are
visualized to be hard balls and are shown such that any two nearest neighbours
touch each other. This is consistent with the definition that the diameter of an
atom in an elemental crystal is the closest distance of approach between two
atoms. In the simple cubic unit cell, this distance is the cube edge. In the BCC
cell, it is half of the body diagonal. In the FCC cell, it is half of the face
diagonal. If a is the lattice parameter (cube edge), we can write:
30 Crystal Geometry and Structure Determination

(a) (b)

(c)
Fig. 3.3 Unit cells of monoatomic crystals of (a) simple cubic (SC),
(b) body centred cubic (BCC), and (c) face centred cubic (FCC) structure.

Crystal Number of nearest Closest distance of approach

(monoatomic) neighbours or atomic diameter
SC 6 a
BCC 8 a 3/2
FCC 12 a/ 2

The student should check the number of nearest neighbours listed above for each
case.
In principle, an infinite number of crystal structures can be generated by
combining different bases and different lattice parameters with the same space
lattice. In Fig. 3.4, three different bases are combined with the simple cubic
lattice. In Fig. 3.4a, the crystal is monoatomic, with just one atom at each lattice
point. For clarity, neighbouring atoms are shown separately. Figure 3.4b
illustrates a molecular crystal, with a diatomic molecule at each lattice point.
The centre of the larger atom of the molecule coincides with a lattice point,
while the smaller atom is not at a lattice point. In molecular crystals, the basis is
fully defined by giving the number and types of atoms, the internuclear distance
of separation between neighbours in the molecule and the orientation of the
molecule in relation to the unit cell. In Fig. 3.4c, the corner atoms of the cube
are of one type, but the atom at the body centre is of a different type. The basis
is two atoms, the larger one in this case at a lattice point and the smaller one
positioned half-way along the body diagonal, at the body centre, which is not a
 Crystal Directions and Planes 31

(a) (b)

(c)

Fig. 3.4 Three different crystal structures referred to the same simple cubic
lattice. [For clarity, neighbouring atoms or molecules are shown separated.]

lattice point. In the crystal, of course, the unit cell can be shifted such that the
body centre becomes a lattice point and the body corners are no longer lattice
points. This crystal should not be confused with the monoatomic BCC crystal,
where the body corner and the body centre atoms are of the same type.
The number of crystal structures known to exist runs into thousands. This
indicates that there can be more complex bases than those we have considered
above. For example, one crystal form of manganese has the structure referred to
the BCC space lattice, with 29 atoms grouped together at each lattice point. In
protein structures, the number of atoms in the basis may be as high as 10 000!
Obviously, the description of such bases would include a number of complex
details.

3.3 Crystal Directions and Planes

It is necessary to use some convention to specify directions and planes in a
crystal. For this purpose, the system devised by Miller known as Miller indices
is widely used. In Fig. 3.5, the vector r, passing through the origin o to a lattice
point, can be expressed in terms of the fundamental translation vectors a, b and
c, which form the crystal axes, as
r = rl a + r2 b + r3 c (3.1)
32 Crystal Geometry and Structure Determination

where r1, r2 and r3 are integers. The c-axis is not shown in the figure as r is
assumed to lie on the ab plane. The components of r along the three axes are:
r1 = 2, r2 = 3 and r3 = 0. Then the crystal direction denoted by r is written as
[230] in the Miller notation, with square brackets enclosing the indices.

2 r

b 1 2
o a
Fig. 3.5 The Miller indices of the crystal direction denoted by vector r
are [230].

If there is a negative component along a crystal axis such as –2, it is written

as 2 and read as bar 2. A family of directions is obtained by all possible
combinations of the indices, both positive and negative. The family [230], [203],
[20 3], [302], [320], etc., is represented by 230 , where the angular brackets
denote the entire family. Such a convention of representing a family is very
convenient for cubic crystals.

Example 3.4 Find the family of crystal directions represented by cube edges,
face diagonals and body diagonals of the unit cube. Give the number of
members in each family.

Solution
Direction Miller indices Number in the family
Cube edge 100 6
Face diagonal 110 12
Body diagonal 111 8

It is left as an exercise to the student to write down the Miller indices of each
member of the three families.

The magnitude of the vector r gives the magnitude of that crystal direction.
The crystal directions [230], [460] and [1 1½ 0] all have the same direction, but
different magnitudes. Since Miller indices for directions are usually specified as
the smallest possible integers, the differences in magnitude for the above three
directions are indicated using the following convention:
[230], 2 [230] and 1/2 [230]
 Crystal Directions and Planes 33

The Miller indices of a crystal plane are determined as follows. Referring to the
plane shown in Fig. 3.6:
c

2 b

1 5
4
3
2
1 a
0 1 2 3 4
Fig. 3.6 A crystal plane making intercepts 2, 3 and 1 on the crystal axes a, b
and c. Its Miller indices are (326).

Step 1 Find the intercepts of the plane along the axes

a, b and c (the intercepts are measured as 2 3 1
multiples of the fundamental vectors)
1 1
Step 2 Take reciprocals of the intercepts # 1
2 3
Step 3 Convert into smallest integers in the same ratio 3 2 6
Step 4 Enclose in parentheses (326)
The factor that results in converting the reciprocals to integers may be indicated
outside the brackets, but it is usually omitted. The family of planes with
members (236), (263), (3 62), (326), (6 3 2); etc., is denoted by {326}, the
curly brackets { } standing for the family.

Example 3.5 Find the Miller indices of the direction r and the plane
indicated by unit normal s in Fig. 3.7.

c
3

b
s 4
2 3
2
1
1
r
a
–2 –1 1 2 3

Fig. 3.7 A crystal direction r and a crystal plane denoted by unit normal s.

#
The reciprocal procedure avoids the intercept of for a plane parallel to an axis, by
making it 0.
34 Crystal Geometry and Structure Determination

Solution The direction r does not pass through the origin in the figure.
As the choice of origin is arbitrary, shift the origin so that r passes through it or,
alternatively, draw a vector parallel to r and passing through the origin. Then the
Miller indices are found to be [ 1 10].
The plane s passes through the origin. Draw a parallel plane that makes the
smallest integral intercepts on the coordinate axes. The intercepts for the parallel
plane drawn in Fig. 3.7 are 3, 2 and , so that the Miller indices are given by
(230).

Example 3.6 Draw a (110) and a (1 11) plane inside a cubic unit cell.
Determine the Miller indices of the direction that is common to both these
planes.

Solution In Fig. 3.8, the plane (110) is sketched using the origin O.
Shifting the origin to the opposite corner of the bottom face, the plane (1 11) is
sketched. The direction common to the two planes [110] is also shown.

(110)
c

(1 11)

[110]
O a

Fig. 3.8 (110) and (1 11) planes in a cubic unit cell, with the common direction
[110] .

Some useful conventions and results of the Miller notation are as follows:
(i) Unknown Miller indices are denoted by symbols h, k and l. For
example, for an unknown family of directions, we write hkl .
(ii) When the integers used in the Miller indices contain more than one
digit, the indices must be separated by commas for clarity, e.g.
(3, 10, 15).
(iii) The crystal directions of a family are not necessarily parallel to one
another. Similarly, not all members of a family of planes are parallel to
one another.
 Crystal Directions and Planes 35

(iv) By changing the signs of all the indices of a crystal direction, we

obtain the anti-parallel or opposite direction. By changing the signs of
all the indices of a plane, we obtain a plane located at the same
distance on the other side of the origin.
(v) In cubic crystals, a crystal plane and a crystal direction normal to it
have the same indices, e.g., [11 1] (11 1) .
As a review, some common directions and planes in cubic crystals are
illustrated below:

c c

b b

a a
[010] [011]

c c

a a
[1 1 1] [112]

c c

b b

a a
(001) (110)

c c

b
a a
(1 11) (112)
36 Crystal Geometry and Structure Determination

The interplanar spacing between adjacent planes of Miller indices (hkl), dhkl,
is defined as the spacing between the first such plane and a parallel plane
passing through the origin. For example, the interplanar spacing of (100) planes
in cubic crystals is equal to the lattice parameter a. In x-ray studies, it becomes
necessary to make a distinction between parallel sets of planes such as (100) and
(200). For this purpose, the first (200) plane is taken to make an intercept of
1/2 along the a-axis, 1/2 being the reciprocal of the corresponding index. Hence,
the interplanar spacing for (200) planes is only half of that for (100) planes. In
cubic crystals, the following relationship gives the interplanar spacing as a
function of the Miller indices and the lattice parameter:
a
d{hkl} = (3.2)
2
h k 2 l2
The interplanar spacing is the same for all members of a family of planes, as the
indices are squared and summed in the denominator of Eq. (3.2).
Even though three noncoplanar vectors are sufficient to describe a plane or a
direction in any crystal, a four-digit notation, hkil, called the Miller-Bravais indices, is
used for hexagonal crystals. The use of such a notation enables crystallographically
equivalent planes or directions in a hexagonal crystal to be denoted by the same set of
indices. Three of the axes a1, a2 and a3 are coplanar and lie on the basal plane of the
hexagonal prism (see the unit cell in Table 3.1), with a 120° angle between them. The
fourth axis is the c axis perpendicular to the basal plane.
The determination of the Miller-Bravais indices is illustrated in Fig. 3.9 for the two
examples given below. The indices of a prismatic plane (one of the vertical faces of the
hexagonal prism) is of the type (10 10). It makes an intercept of 1 along at a1, is
parallel to a2 axis, makes an intercept of –1 along a3 axis and is again parallel to the
c-axis. Note that, in this notation, h + k = –i. This equality always holds good for the
Miller-Bravais indices. The indices of a direction that lies along one of the three axes
(parallel to a side of the hexagon) is of the type [2 1 10]. In the example given, the
direction is parallel to the a1 axis and is resolved into components along a2 and a3. Each
of these components being –1, the value of the first index corresponding to the a1 axis
can be obtained as – (–1 –1) = 2 from the condition that h + k = –i. This yields [2 1 10].

a2 –a3

Trace of (10 10)

–a1 a1

[2 1 10]

a3 –a2
Fig. 3.9 Plan view of the hexagonal unit cell showing the plane (1010) and the
direction [2110] in the Miller-Bravais notation.
 The Bragg Law of X-ray Diffraction 37

STRUCTURE DETERMINATION BY X-RAY DIFFRACTION

It is well known that, for visible electromagnetic radiation to be diffracted, the
spacing between lines in a two-dimensional grating must be of the same order as
the wavelength range for light (3900–7800 Å). The same principle holds good
for diffraction by the three-dimensional grating of the periodic array of atoms in
crystals. The typical interatomic spacing in crystals is 2–3 Å. So, the wavelength
of the radiation used for crystal diffraction should be in the same range. X-rays
have wavelengths in this range and are, therefore, diffracted by crystals. This
property is widely used for the study of crystal structures.

3.4 The Bragg Law of X-ray Diffraction

When electrons moving at high speeds are directed to a metal target, a small
percentage of their kinetic energy is converted into x-rays. The x-rays emitted by
the target consist of a continuous range of wavelengths, called white radiation,
by analogy with white light consisting of a range of wavelengths. The minimum
wavelength in the continuous spectrum is inversely proportional to the applied
voltage which accelerates the electrons towards the target. If the applied voltage
is sufficiently high, in addition to the white radiation, a characteristic radiation
of a specific wavelength and high intensity is also emitted by the target. The
radiation emitted by a molybdenum target at 35 kV includes both types of
radiation as illustrated in Fig. 3.10. In spectroscopic notation, the characteristic

6
Relative intensity

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

Wavelength, Å
Fig. 3.10 The spectrum of x-rays emitted from a molybdenum target at
35 kV.
38 Crystal Geometry and Structure Determination

radiations are named K , K , L , etc. K radiation has a high intensity and is

commonly used in diffraction studies. The wavelengths of this radiation for
typical target metals are given in Table 3.2.

TABLE 3.2
Wavelengths of K Radiation for Typical Target Metals

Target metal Mo Cu Co Fe Cr
K wavelength, Å 0.71 1.54 1.79 1.94 2.29
nm 0.071 0.154 0.179 0.194 0.229

A beam of x-rays directed at a crystal interacts with the electrons of the

atoms in the crystal. The electrons oscillate under the impact and become a new
source of electromagnetic radiation. The waves emitted by the electrons have the
same frequency as the incident x-rays. The emission is in all directions. As there
are millions of atoms in a crystal, the emission in a particular direction is the
combined effect of the oscillations of electrons of all the atoms. The emissions
will be in phase and reinforce one another only in certain specific directions,
which depend on the direction of the incident x-rays, their wavelength as well as
the spacing between atoms in the crystal. In other directions, there is destructive
interference of the emissions from different sources. The easiest way to visualize
the diffraction effects produced by the three-dimensional grating provided by the
crystal is to consider the Bragg law.
In Fig. 3.11, a set of parallel planes in a crystal is shown. A beam of x-rays
of wavelength is directed towards the crystal at an angle to the atomic

180 – 2

Plane 1
d

Plane 2
ds
in

Plane 3

Fig. 3.11 Illustration of the Bragg law.

planes. In Bragg law, the interaction described above between x-rays and the
electrons of the atoms is visualized as a process of reflection of x-rays by the
atomic planes. This is an equivalent description of the diffraction effects
produced by a three-dimensional grating. The atomic planes are considered to be
 The Bragg Law of X-ray Diffraction 39

semi-transparent, that is, they allow a part of the x-rays to pass through and
reflect the other part, the incident angle (called the Bragg angle) being equal
to the reflected angle. Referring to Fig. 3.11, there is a path difference between
rays reflected from plane 1 and the adjacent plane 2 in the crystal. The two
reflected rays will reinforce each other, only when this path difference is equal
to an integral multiple of the wavelength. If d is the interplanar spacing, the path
difference is twice the distance d sin , as indicated in Fig. 3.11. The Bragg
condition for reflection can therefore be written as
n = 2d sin (3.3)
where n is an integer and is the wavelength of the x-rays used. A first order
reflection is obtained, if n = l; a second order reflection occurs if n = 2, and so
on.
As sin has a maximum value of 1, for a typical value of interplanar
spacing of 2 Å, Eq. (3.3) gives the upper limit of for obtaining a first order
reflection as 4 Å. There will be no reflection if is greater than 4 Å. can be
reduced indefinitely, obtaining reflections from other sets of planes that have
spacing less than 2 Å as well as an increasing number of higher order
reflections. A very small wavelength of the order of 0.1 Å is not necessarily an
advantage as it tends to produce other effects such as knocking off electrons
from the atoms of the crystal and getting absorbed in the process. The
wavelengths of the K radiation given in Table 3.2 for typical target metals lie in
the right range.
The Bragg equation can be used for determining the lattice parameters of
cubic crystals. Let us first consider the value that n should be assigned. A second
order reflection from (100) planes should satisfy the following Bragg condition:
2 = 2d100 sin
or
= d100 sin (3.4)
Similarly, a first order reflection from (200) planes should satisfy the following
condition:
= 2d200 sin (3.5)
We have earlier noted that the interplanar spacing of (100) planes is twice that
for (200) planes. So, Eqs. (3.4) and (3.5) are identical. For any incident beam of
x-rays, the Bragg angle would be the same, as the two sets of planes in
question are parallel. As Eqs. (3.4) and (3.5) are identical, the two reflections
will superimpose on each other and cannot be distinguished. By a similar
argument, it can be shown that the third order reflection from (100) planes will
superimpose on the first order reflection from (300) planes. In view of such
superimposition, there is no need to consider the variations in n separately;
instead, we take n to be unity for all reflections from parallel sets of planes such
as (100), (200), (300), (400), etc. In a crystal, it may turn out, for example, that
there is no (200) plane with atoms on it. Then, what is designated as a (200)
reflection actually refers to the second order reflection from (100) planes.
40 Crystal Geometry and Structure Determination

Example 3.7 A diffraction pattern of a cubic crystal of lattice parameter

a = 3.16 Å is obtained with a monochromatic x-ray beam of wavelength 1.54 Å.
The first four lines on this pattern were observed to have the following values:
Line (in degrees)
1 20.3
2 29.2
3 36.7
4 43.6
Determine the interplanar spacing and the Miller indices of the reflecting planes.

Solution Using the Bragg equation, we can write the interplanar spacing
d = /(2 sin ). n is assumed to be 1, as higher order reflections superpose on
the lower order ones for parallel sets of planes. The d values can now be
determined. Since d = a / h 2 k 2 l 2 for cubic crystals, h2 + k2 + l2 can also
be determined. The results are tabulated below:

Line dhkl, Å (h2 + k2 + l2 ) = a2/d2 hkl

1 2.220 2 110
2 1.579 4 200
3 1.288 6 211
4 1.116 8 220

Starting from the lowest index plane, we notice that there are no reflections
corresponding to (h2 + k2 + l2) = 1, 3 and 5. There is no plane which has
(h2 + k2 + l2) = 7. Corresponding to (h2 + k2 + l2) = 2, 4, 6 and 8, there are
reflections from {110}, {200}, {211} and {220} planes, respectively.

In diffraction studies, in order to increase the probability that crystals with the right
orientation for Bragg reflection are available, one of the following procedures is adopted:
(i) A monochromatic x-ray beam of a specific wavelength is combined with numerous
possible values so that reflection occurs at the right combination that satisfies
the Bragg law. This is done by placing thousands of crystals of random orientation
in the path of the beam. The crystals are usually in powder form.
(ii) A single crystal is held stationary in the path of the beam so that is kept
constant. A white radiation is then directed at the crystal so that numerous values
of the wavelength are available, and again the right combination will lead to the
diffraction condition. This method is called the Laue technique.
(iii) A single crystal is held in the beam of a monochromatic radiation and is rotated
such that at some position of the crystal, the diffraction condition is satisfied. This
method is known as the rotating crystal method. Even though this is not the most
widely used method, it provides greater certainty in identification, as well as more
accurate measurement of the intensities of the reflected beam.
 The Powder Method 41

3.5 The Powder Method

The powder method is a widely used experimental technique for the routine
determination of crystal structures. It is highly suitable for identification and for
determination of the structures of crystals of high symmetry. Here, a
monochromatic x-ray beam, usually of K radiation, is incident on thousands of
randomly oriented crystals in powder form. The powder camera, called the
Debye-Scherrer camera, consists of a cylindrical cassette, with a strip of
photographic film positioned around the circular periphery of the cassette. The
powder specimen is placed at the centre of the cassette in a capillary tube or
pasted on a thin wire. The tube, the wire and the paste material must be of some
nondiffracting substance such as glass or glue. The x-ray beam enters through a
small hole, passes through the powder specimen and the unused part of the beam
leaves through a hole at the opposite end. The geometry of the powder method
is illustrated in Fig. 3.12.

Film

Exit beam
4

Incident beam

Specimen
(a)

S
R
(b)

Fig. 3.12 The geometry of the powder method.

Consider a set of parallel crystal planes making an angle with the incident
direction. When this angle satisfies the Bragg equation, there is reflection. By
virtue of the large number of randomly oriented crystals in the powder, there are
a number of possible orientations of this set of planes in space for the same
angle with the incident direction. So the reflected radiation is not just a pencil
beam like the incident one; instead, it lies on the surface of a cone whose apex
is at the point of contact of the incident radiation with the specimen. Also, the
interplanar spacing d being the same for all members of a family of crystal
42 Crystal Geometry and Structure Determination

planes, they all reflect at the same Bragg angle , all reflections from a family
lying on the same cone. After taking n = 1 in the Bragg equation, there are still
a number of combinations of d and that would satisfy the Bragg law. For each
combination of d and , one cone of reflection must result and, therefore, many
cones of reflection are emitted by the powder specimen. If the reflected cones
were recorded on a flat film placed normal to the exit beam, they will be in the
form of concentric circles. In the powder camera, however, only a part of each
reflected cone is recorded by the film strip positioned at the periphery of the
cylindrical cassette. The recorded lines from any cone are a pair of arcs that
form part of the circle of intersection. When the film strip is taken out of the
cassette and spread out, it looks like Fig. 3.12b.
Note that the angle between a reflected line lying on the surface of the cone
and the exit beam is 2 . Therefore, the angle included at the apex of the cone is
twice this value, 4 , Fig. 3.12a. When the Bragg angle is 45°, the cone opens out
into a circle and reflection at this angle will make a straight line intersection
with the film strip at the midpoint between the incident and the exit points in
Fig. 3.12b. When the Bragg angle is greater than 45°, back reflection is obtained,
that is, the reflected cones are directed towards the incident beam. Bragg angles
up to the maximum value of 90° can be recorded by the film of the powder
camera, which is not possible on a flat film placed in front of the exit beam.
The exposure in a powder camera must be sufficiently long to give reflected
lines of good intensity. The exposure time is usually a few hours. After the film
is exposed and developed, it is indexed to determine the crystal structure. It is
easily seen that the first arc on either side of the exit point corresponds to the
smallest angle of reflection. The pairs of arcs beyond this pair have larger Bragg
angles and are from planes of smaller spacings, recall that d = /(2 sin ). The
distance between any two corresponding arcs on the spread out film is termed S,
Fig. 3.12b. S is related to the radius of the powder camera R:
S = 4R (3.6)
where is the Bragg angle expressed in radians. For easy conversion of the
distance S measured in mm to Bragg angle in degrees, the camera radius is often
chosen to be 57.3 mm, as 1 rad = 57.3°.
In the powder method, the intensity of the reflected beam can also be
recorded in a diffractometer, which uses a counter in place of the film to
measure intensities. The counter moves along the periphery of the cylinder and
records the reflected intensities against 2 . Peaks in the diffractometer recording
(Fig. 3.13) correspond to positions where the Bragg condition is satisfied.

3.6 Structure Determination

The determination of a complex crystal structure is often time consuming,
requiring a lot of patience and ingenuity. A step-by-step procedure is followed in
such cases, first determining the macroscopic symmetry of the crystal, then the
space lattice and its dimensions, and finally the atomic arrangement within the
unit cell. Measurement of the density of the crystal and the chemical
composition also assist the process of structure determination.
 Structure Determination 43

3
Intensity (arbitrary units)

40 80 120 160
2 , degrees
Fig. 3.13 The tracing from a diffractometer.

In simple crystals of high symmetry, the space lattice and its dimensions can
be determined relatively easily. If the crystal is monoatomic, the space lattice
together with the lattice parameters is a complete description of the crystal
structure. If, on the other hand, the basis is two or more atoms per lattice point,
the number and distribution of atoms within the unit cell can be determined only
from quantitative measurements of the reflected intensities. For such
measurements, the recording from a diffractometer is more useful than the
pattern obtained from a powder camera.
The procedure for determining the structure of monoatomic cubic crystals is
outlined below. Combining Eq. (3.2) for the interplanar spacing d with the Bragg
equation, we obtain
2
sin2 = (h2 + k2 + l2) (3.7)
4a2
n is assumed to be 1 for reasons already outlined. -values can be determined
from a powder pattern using Eq. (3.6). Since monochromatic radiation is used in
the powder technique, the value of is known. Then, the unknowns in Eq. (3.7)
are the Miller indices of the reflecting planes that correspond to the measured
angles of reflection. For a given cubic lattice, it is possible to list all
combinations of h, k and l and arrange (h2 + k2 + l2) in increasing order which
will also be the increasing order of values, as seen from Eq. (3.7). The sin2
values will be in the same ratio as (h2 + k2 + l2), if the assumed and actual
lattices coincide.
44 Crystal Geometry and Structure Determination

The distinction between lattices of the cubic system is possible by using the
fact that not all combinations of (h2 + k2 + l2) lead to reflection for a given lattice.
Consider, for example, the first order reflection from the (100) planes of a BCC
crystal. These planes are the faces of the unit cube and contain the ‘corner’ atoms
of the cube, see Fig. 3.14. The path difference between reflected beams from two
adjacent (100) planes is one full wavelength and, therefore, the reflected beams
are in phase. The midway parallel plane between these two (100) planes contains
the body centred atoms. It is easily seen that the reflection from this midplane will
be out of phase by exactly half of a wavelength with the (100) reflections, see
Fig. 3.14. As the effective number of body centred atoms is equal to the effective
number of corner atoms in a BCC crystal, the intensity of the reflected beams

Fig. 3.14 The (100) reflection is absent for a BCC crystal, as reflection from the
corner atoms is exactly cancelled out by that from body centred atoms.

from atoms at these two locations will be exactly equal. The phase difference /2
then results in a net zero reflected intensity. (Note that the terms, body centred
atoms and body corner atoms, are defined only in a relative sense and are
interchangeable.) There is thus no first order reflection from (l00) planes in a BCC
crystal. A second order reflection from (100) planes is possible, but this will
superimpose on the first order reflection from (200) planes.
By following a similar reasoning, it is possible to derive extinction rules for
different cubic crystals, as given in Table 3.3.

TABLE 3.3
Extinction Rules for Cubic Crystals

Crystal Reflections are allowed

SC for all values of (h2 + k2 + l2)
BCC for even values of (h + k + l)
FCC when h, k and l are all odd or all even
DC when h, k and l are all odd, or when all are even,
(h + k + l) should be divisible by four
 Summary 45

In the above, zero is taken as an even number. The diamond cubic (DC) crystal
is based on the FCC space lattice, with a basis of two atoms per lattice point.
The DC structure is discussed in Chap. 5.
From the extinction rules, we can derive the ratio of (h2 + k2 + l2) values for
allowed reflections from different crystals:
SC 1 : 2 : 3 : 4: 5 : 6 : 8
BCC 1 : 2 : 3:4:5: 6:7
FCC 3 : 4 : 8 : 11 : 12
DC 3 : 8 : 11 : 16
A simple comparison of the observed ratios of sin2 values with the above is
then sufficient to identify the crystal structure.

Example 3.8 From a powder camera of diameter 114.6 mm, using an x-ray
beam of wavelength 1.54 Å, the following S values in mm are obtained for a
material:
86, 100, 148, 180, 188, 232, and 272
Determine the structure and the lattice parameter of the material.

Solution As the camera radius R = 57.3 mm, the Bragg angles in

degrees at which reflections are observed are equal to S/4:
21.5, 25, 37, 45, 47, 58 and 68.
The sin2 values are in the ratio
0.1346 : 0.1788 : 0.3620 : 0.5003 : 0.5352 : 0.7195 : 0.8596
Within experimental error, these values can be expressed in the ratio of integral
numbers
3 : 4 : 8 : 11 : 12 : 16 : 19
From the extinction rules, we note that the structure is FCC. The lattice
parameter calculated from the highest Bragg angle is 3.62 Å. By referring to
table on back inside cover, we note that the material is likely to be copper.

1. A space lattice is an infinite array of points, all with identical

surroundings.
2. A crystal structure is obtained by combining a space lattice with a basis.
The basis must give the number of atoms per lattice point, their types,
mutual orientations and distances of separation.
46 Summary/Problems

3. Space lattices are limited to fourteen, but known crystal structures run into
thousands.
4. Crystal directions and crystal planes are denoted by the Miller indices. A
family of crystal directions or planes includes all possible combinations of
the indices, both positive and negative.
5. The Bragg law gives the condition for diffraction by a crystal.
6. The powder method is the commonly used x-ray diffraction technique.
7. From the positions of lines in a powder pattern and from the extinction
rules for different cubic crystals, the space lattice and its dimensions can
be determined.

3.1 Draw two adjacent FCC unit cells and join the top and bottom face centres
of each cell. Also join these four face centres to the nearest common
corners.
(i) What is the unit cell outlined by this procedure?
(ii) Is it in the Bravais list?
(iii) If so, the FCC cell with a higher symmetry must be a special case of
the outlined cell. Explain.
3.2 There is no end-centred tetragonal lattice in the Bravais list, but there is an
end-centred orthorhombic lattice. Explain why this is so.
3.3 Draw a:
(i) (111) plane in a triclinic lattice;
(ii) (120) plane in a tetragonal lattice;
(iii) [11 1] direction in an orthorhombic lattice; and
(iv) [211] direction in a cubic lattice.
3.4 Draw a (111) plane and a (222) plane in the unit cell of a cubic lattice
with lattice parameter a. Determine their distances from a parallel plane
through the origin.
Answer: a / 3 and a /(2 3) .
3.5 Find the Miller indices of a plane that makes an intercept of 1 on the
a-axis and 2 on the b-axis and is parallel to the c-axis.
Answer: (210).
3.6 Determine the Miller indices of a plane that makes an intercept of 2 Å,
3 Å and 4 Å on the coordinate axes of an orthorhombic crystal with
a : b : c = 4 : 3 : 2.
Answer: (421).
 Problems 47

3.7 Find the Miller indices of a plane that makes intercepts on a, b and c axes
equal to 3 Å, 4 Å and 3 Å in a tetragonal crystal with the c/a ratio of 1.5.
Answer: (436).
3.8 Draw a (11 1) plane in the unit cell of a cubic crystal. Show all the 110
directions that lie on this plane, giving the Miller indices of each one of
them.
Answer: [110], [0 1 1], [101] and the three opposite directions [1 10],
[011], [10 1].
3.9. Sketch a (110) plane in the unit cell of a cubic crystal. Show all the 111
directions that lie on this plane, giving the Miller indices of each one of
them.
Answer: [1 11], [111] and [11 1], [1 1 1].

3.10 What are the Miller indices of the line of intersection of a (1 11) and a
(1 1 1) plane in a cubic crystal? Determine the answer both geometrically
and analytically.
Answer: [1 10] or [110] .
3.11 Calculate the atomic density (number of atoms per unit area) in (111),
(110) and (100) planes of copper (FCC) with the lattice parameter of
3.61 Å. Can you pack atoms more closely than in (111) plane?
Answer: 1.77 1019, 1.08 1019 and 1.53 1019 atoms m–2.
3.12 Calculate the number of atoms per unit area of (111), (110) and (100)
planes of a BCC crystal. The answer may be derived as a function of the
lattice parameter a.
Answer: 1/(a2 3) , 2 /a 2 and 1/a2.
3.13 Express the edge, face diagonal and body diagonal of the unit cell in terms
of the atomic radius r for SC, BCC and FCC crystals.
3.14 The distance between (111) planes in a face centred cubic crystal is 2 Å.
Determine the lattice parameter and the atomic diameter.
Answer: 2 3 Å, 6 Å.
3.15 A BCC crystal is used to measure the wavelength of some x-rays. The
Bragg angle for reflection from (110) planes is 20.2°. What is the
wavelength? The lattice parameter of the crystal is 3.15 Å.
Answer: 1.54 Å.
3.16 X-rays with a wavelength of 1.54 Å are used to calculate the spacing of
(200) planes in aluminium. The Bragg angle for this reflection is 22.4°.
What is the size of the unit cell of the aluminium crystal?
Check your answer with table on back inside cover.
3.17 Determine the structure of the crystal in Example 3.7.
Answer: BCC.
48 Problems

3.18 Using a diffractometer and a radiation of wavelength 1.54 Å, only one

reflection from an FCC material is observed when 2 is 121°. What are the
indices of this reflection? What is the interplanar spacing? Show that the
next higher index reflection cannot occur.
Answer: {111}, 0.885 Å.
3.19 The first three lines from the powder pattern of a cubic crystal have the
following S values: 24.95, 40.9 and 48.05 mm. The camera radius is
57.3 mm. Molybdenum K radiation of wavelength 0.71 Å is used.
Determine the structure and the lattice parameter of the material.
Answer: DC, 5.66 Å.
3.20 The Bragg angle corresponding to a reflection for which (h2 + k2 + l2) = 8
is found to be 14.35°. Determine the lattice parameter of the crystal.
X-rays of wavelength 0.71 Å are used. If there are two other reflections
with smaller Bragg angles, what is the crystal structure?
Answer: 4.05 Å, FCC.
3.21 Aluminium (FCC) has a lattice parameter of 4.05 Å. When a monochro-
matic radiation of 1.79 Å is used in a powder camera, what would be the
first four S values? The camera diameter is 114.6 mm.
Answer: 90.1, 105.0, 154.7, and 188.4 mm.
3.22 The first reflection using copper K radiation from a sample of copper
powder (FCC) has an S value of 86.7 mm. Compute the camera radius.
Answer: 57.3 mm.
3.23 Copper and nickel (both FCC) dissolve in each other in all proportions at
room temperature in the solid state. From a sample of Cu–Ni alloy of
unknown composition, a powder pattern is obtained using monochromatic
radiation of wavelength 1.54 Å. The spread-out film showed that, for the
first reflection, S = 88.4 mm. The distance between inlet and outlet points
of the x-ray beam was 180 mm. Estimate the percentage of copper in the
alloy, assuming a linear variation of lattice parameter with composition.
Answer: 28 atomic %.
3.24 The diffractometer tracing shown in Fig. 3.13 is of silicon (DC). Index the
reflecting planes corresponding to each peak.
3.25 Name the space lattices, which have four lattice parameters.
3.26 In an orthorhombic unit cell, a : b : c = 1 : 2 : 3. The magnitude of a is
2 Å. What are the intercepts in Å of a plane of Miller indices (230)?
Answer: 1 Å, 1.33 Å, .
3.27 In cubic crystals, {110} and {112} planes have a common <111> type of
direction. Within a cubic unit cell, sketch one plane of each type such that
a member of the above family of directions is common to both the planes.
Indicate in your sketch the Miller indices of the two planes and the line of
intersection.
3.28 Explain why there is no end-centred cubic space lattice.
 Problems/Multiple Choice Questions 49

3.29 Explain with a neat sketch why a (100) reflection is not possible from an
FCC crystal.
3.30 A Debye-Scherrer pattern is obtained from an FCC crystal with
a = 3.61 Å. X-rays of wavelength equal to 1.54 Å are used. Determine the
Miller indices of the planes with the lowest and the highest Bragg angles
in this pattern.
Answer: {111} and {420}.
3.31 Only two reflections are observed on the powder pattern of a cubic crystal
at Bragg angles of 34.06° and 65.51°. Chromium K radiation is used.
Determine the crystal structure (if possible) and the lattice parameter.
Show that the third and higher reflections cannot occur.
Answer: DC, 3.56 Å.
3.32 The entry point and the exit point of x-rays on a powder pattern taken
from a cubic material could not be distinguished. Assuming one of the
points to be the exit point, the following S values were obtained: 311.95,
319.10 and 335.05 mm. The camera radius is 57.3 mm. Molybdenum K
radiation was used. Determine the structure and the lattice parameter of the
material.
Answer: DC, 5.66 Å.
3.33 The first two reflections as seen in the powder photograph of a cubic
material have S values of 90.1 and 154.7 mm, respectively. As the film
between these two reflections was torn, it was not clear whether an
additional line was present between the two observed lines. Determine, if
possible, the crystal structure and the lattice parameter. The third and the
fourth reflections as seen in the torn film have S values of 188.4 and
199.8 mm. The camera radius is 57.3 mm. Cobalt K radiation was used.
Answer: FCC, 4.05 Å.
3.34 In the damaged powder film of a cubic material, the locations of only the
first two pairs of lines could be accurately measured. They had S values of
24.95 and 40.9 mm. The camera radius is 57.3 mm. Molybdenum K
radiation was used. If possible, determine the crystal structure and the
lattice parameter of the material. The third pair of lines in the damaged
film was estimated to have an S value of about 49 mm. Determine whether
this confirms your conclusion or not.
Answer: DC, 5.66 Å.

1. The space lattices with two lattice parameters belong to the crystal systems
A. tetragonal B. rhombohedral C. hexagonal D. triclinic
50 Multiple Choice Questions

2. The number of lattice points in the rhombohedral unit cell is

A. 8 B. 4 C. 2 D. 1
3. There is no end-centred orthorhombic lattice
A. as it violates the definition of a space lattice
B. as it can be represented by a simple orthorhombic unit cell
C. as it can be represented by a simple monoclinic unit cell
D. the question is wrong
4. The effective number of lattice points in the unit cell of end-centred
monoclinic lattice is
A. 1 B. 2 C. 4
D. can’t be found unless the angle is given
5. There is no end-centred cubic space lattice, because
A. it can be represented by the simple cubic lattice
B. it can be represented by the simple orthorhombic lattice
C. it violates the cubic symmetry
D. none of these
6. The unit cell with three lattice parameters is
A. tetragonal B. orthorhombic C. monoclinic D. triclinic
7. A unit cell has a = 5 Å, b = 8 Å, c = 3 Å, = 90°, = 65° and = 54°.
The space lattice for this unit cell is
A. orthorhombic B. monoclinic C. rhombohedral D. triclinic
8. The number of Bravais space lattices with two lattice points are
A. 2 B. 3 C. 4 D. 5
9. The tetragon has
A. 4 faces B. 12 edges C. 6 corners D. 8 edges
10. The minimum number of ions in the unit cell of an ionic crystal with FCC
space lattice is
A. 4 B. 8 C. 12 D. 16
11. The atomic diameter of an FCC crystal (lattice parameters is a) is
A. a 2 /2 B. a 2 /4 C. a 3/4 D. a/2
12. If the radius of an atom in a simple cubic crystal is r, the body diagonal of
the unit cell is
A. r 3 B. 2r 3 C. 4r / 3 D. 3r/4

13. The number of unit cells in 1 m3 of FCC nickel (rNi = 1.243 Å) is

A. 2.3 1028 B. 4.2 1028 C. 6.5 1028 D. 18.4 1028
14. The acute angle between [101] and [101] directions in a tetragonal crystal
with c/a = 1.5 is
A. 90° B. 67.38° C. 56.30° D. 33.69°
 Multiple Choice Questions 51

15. The angle between [111] and [112] directions in a cubic crystal is
A. 0° B. 45° C. 90° D. 180°
16. The number of members in the family <123> in a cubic crystal are
A. 8 B. 12 C. 24 D. 48
17. The (1 11) plane is parallel to
A. (111) B. (11 1) C. (1 11) D. (11 1)
18. The Miller indices of a plane in an orthorhombic unit cell (a : b : c =
1 : 2 : 3) making intercepts of 3, 2, 1 Å on a, b, c, axes are
A. (931) B. (139) C. (321) D. (123)
19. The four non-parallel body diagonals of a cube have Miller indices
A. [111], [111], [1 11], [11 1] B. [111], [1 1 1], [1 11], [11 1]
C. [1 1 1], [1 1 1], [11 1], [1 11] D. [1 11], [11 1], [1 11], [111]

20. The Miller indices of the line of intersection of a (1 11) and a (1 10)
plane are
A. [1 10] B. [110] C. [1 10] D. [1 11]
21. If the interplanar spacing obtained from the second reflection of a DC
crystal is 1.81 Å, the lattice parameter is
A. 0.905 Å B. 2.56 Å C. 3.62 Å D. 5.12 Å
22. The first S value on the powder pattern of an FCC crystal (a = 4.05 Å)
taken with a camera of radius 57.3 mm using cobalt K radiation of
1.79 Å is
A. 45 mm B. 51 mm C. 72.8 mm D. 90.0 mm.
23. The second order reflection from (200) planes coincides with the first
order reflection from
A. (100) B. (200) C. (400) D. none of these
24. The interplanar spacing of the first reflecting plane (lowest ) in an FCC
crystal
A. a 3 B. a/ 3 C. a / 2 D. a
25. The first reflection from polonium powder (SC) occurs at Bragg angle of
28.7°. The fourth reflection is at Bragg angle
A. 57.4° B. 114.8° C. 73.8° D. none of these
26. If the first reflection from a BCC crystal has a Bragg angle of 22.2°, the
second reflection will have a of
A. 32.3° B. 25.9° C. 38.1° D. 44.4°
27. No reflection will be observed from a DC crystal (a = 3 Å) if the
wavelength of x-rays is greater than
A. 3.0 Å B. 3.25 Å C. 3.37 Å D. 3.46 Å
52 Source for Experimental Data/Suggestions for Further Reading

28. If the first reflection from a FCC crystal has a Bragg angle of 21.5°, the
second reflection will have an angle of
A. 18.5° B. 25° C. 31.2° D. 36.8°
29. The first three reflecting planes of silicon (DC) are
A. 111, 200, 220 B. 110, 200, 211
C. 111, 220, 311 D. 100, 110, 111
30. Using X-rays of 2.29 Å, the first two reflections have Bragg angles of
34.06° and 65.51°. The Bragg angle for the third reflection is
A. 68.1° B. 75.9° C. 89.9° D. reflection absent
31. The Miller indices of the fifth reflection in an FCC crystal is
A. 331 B. 222 C. 311 D. 400

Answers

1. A, B, C 2. D 3. D 4. B 5. C
6. B 7. D 8. D 9. B 10. B
11. A 12. B 13. A 14. B 15. C
16. D 17. B 18. B 19. A, C 20. B, C
21. D 22. D 23. C 24. B 25. C
26. A 27. D 28. B 29. C 30. D
31. B

Source for Experimental Data

P. Villars and L.D. Calvert, Pearson’s Handbook of Crystallographic Data for

Intermetallic Phases, Vols. 1–3, American Society for Metals, Metals Park, Ohio
(1985).

Suggestions for Further Reading

B.D. Cullity, Elements of X-ray Diffraction, Addison Wesley, Reading, Mass.

(1978).
C. Hammond, The Basics of Crystallography and Diffraction, Oxford University
Press, Oxford (2001).
CHAPTER

The rigidity of a solid arises from the fact that the atoms in the solid are held
together by interatomic bonds. The spatial arrangement of atoms in a solid is
strongly influenced by the nature of these bonds, which in turn is influenced by
the electronic structure of the atoms. The topic of chemical bonding is usually
covered in the first course on general chemistry. Here, we shall briefly review
the structure of the atom in relation to the periodic table and then the chemical
bonding, as relevant to our discussion in the later chapters. The general variation
of properties with bonding character is discussed at the end of the chapter.

Units
SI units
Quantity Other units
Unit Symbol
Frequency of radiation per second s–1 —
or or
hertz Hz
Momentum kilogram metre kg m s–1 —
per second
Electron energy level joule J eV (electron
volt), erg
Ionization potential kilojoule per kJ mol–1 eV/atom,
Electron affinity mole kcal/mole
Bond energy
Bond length nanometre nm Å
Dipole moment coulomb metre Cm debye

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