MME 211

CRYSTALLOGRAPHY AND STRUCTURE OF MATERIALS

MD. MUKTADIR BILLAH, Ph.D. (USA)

Associate Professor
MME, BUET
LATTICE AND MOTIF
Introduction
• Motion of atoms in solids is restricted to small
vibrations about a mean position.
• As temperature is raised, atoms in a solid
become increasingly more mobile until orderly
array in the solid disintegrates and it becomes
a liquid.
• Gas is a state in which atoms have gained so
much freedom of motion that they no longer
bother to stick together at all.
Introduction
• When temperature is lowered sufficiently, a
liquid freezes and a solid results.
• When liquid cools, two types of solids can form.
• If liquid cools sufficiently slowly, atoms can
assume an orderly arrangement and a crystal
results.
• If temperature is dropped abruptly, arresting
motion of the atoms before they can reorganize
themselves, then a mixed-up structure called a
glass or an amorphous solid may result.
Amorphous versus Crystalline Structure
• A crystal may be defined as a solid composed of atoms arranged in a
pattern periodic in three dimensions.
• Crystals differ in a fundamental way from gases and liquids because
atomic arrangements in the latter do not possess the essential
requirement of periodicity.
• Not all solids are crystalline, however; some are amorphous, like glass,
and do not have any regular interior arrangement of atoms.
• There is, in fact, no essential difference between an amorphous solid and
a liquid, and the former is often referred to as an "undercooled liquid."
 An amorphous substance is isotropic, i.e., it exhibits
the same physical and chemical properties when tested
in any direction.
Crystal has many properties that are directional.
Amorphous
versus The basic feature of all crystals is the regularity of their
atomic arrangement.
Crystalline
Structure The first notable feature of the regularity of crystal
structures is the periodicity of their patterns.

In addition to periodicity, most crystal structures

possess the property of symmetry.
Lattice
• Crystal structure means regular
arrangement of atoms or molecules.
“Regular” implies existence of
something that repeats itself,
“arrangement” implies presence of
a pattern.
• It is convenient to ignore actual
atoms composing the crystal and
their periodic arrangement in space,
and to think instead of a set of
imaginary points which has a fixed
relation in space to the atoms of the
crystal and which may be regarded
as a sort of framework or skeleton
on which the actual crystal is built.
Lattice
• Imagine space to be divided by three
sets of planes, the planes in each set
being parallel and equally spaced.
• This division of space will produce a
set of cells each identical in size,
shape, and orientation to its
neighbors.
• Each cell is a parallelepiped, since its
opposite faces are parallel, and each
face is a parallelogram.
• The space-dividing planes will intersect
each other in a set of lines, and these
lines in turn intersect in the set of
points referred to above.
Lattice
• A set of points so formed has an important
property: it constitutes a point lattice,
which is defined as an array of points in
space so arranged that each point has
identical surroundings.
• By "identical surroundings" we mean that
the lattice of points, when viewed in a
particular direction from one lattice point,
would have the same appearance when
viewed in the same direction from any
other lattice point.
Motif • In a crystal, points of the lattice must be
occupied by atoms, ions, or molecules.
Because the points are all identical, the
collections of objects occupying them must
also be identical. The drawing consists of a
motif which is repeated by translating it
from one point, chosen as the origin, to
other points arranged in a 2-D pattern.
• The set of points constitutes a net in two
dimensions (2-D) and a lattice in three
dimensions (3-D). The motif represents the
decoration of that net or lattice. In the
same way, a crystal structure can be
described as a 3-D lattice, decorated with
atoms or molecules.
Unit Cell • Since all the cells of the lattice shown are
identical, we may choose any one as a unit
cell.
• The size and shape of the unit cell can in
turn be described by the three vectors a, b,
and c drawn from one corner of the cell
taken as origin.
• These vectors define the cell and are called
the crystallographic axes of the cell.
• They may also be described in terms of
their lengths (a, b, c) and the angles
between them (α, β, γ).
• These lengths and angles are the lattice
constants or lattice parameters of the unit
cell.
Lattice
Lattice
Lattice
PATTERN
PATTERN
PATTERN
PATTERN
PATTERN
CRYSTAL SYSTEMS
The Four 2-D
Crystal Systems
• If we take arbitrary values for all
three parameters, then we end up
with oblique net {a, b, γ}.
• When γ = 90◦, the unit cell of a net
becomes a rectangle {a, b, γ = 90◦}.
• When a = b and γ = 90◦, the unit cell
of a net becomes a square {a, a, γ =
90◦}.
• When a = b and γ = 60◦, the unit cell
of a net becomes a hexagonal {a, b,
γ = 60◦}.
The Four 2-D
Crystal Systems
• If we take arbitrary values for all
three parameters, then we end up
with oblique net {a, b, γ}.
• When γ = 90◦, the unit cell of a net
becomes a rectangle {a, b, γ = 90◦}.
• When a = b and γ = 90◦, the unit cell
of a net becomes a square {a, a, γ =
90◦}.
• When a = b and γ = 60◦, the unit cell
of a net becomes a hexagonal {a, b,
γ = 60◦}.
THE SEVEN
3-D
CRYSTAL
SYSTEMS
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
TRICLINIC/
ANORTHIC
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
MONOCLINIC
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
HEXAGONAL
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
RHOMBOHEDRAL/
TRIGONAL
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
ORTHORHOMBIC
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
TETRAGONAL
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
CUBIC
SYMMETRY
ELEMENTS
SYMMETRY
ELEMENTS
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System: Van der Waals Surface
cP, tP & oP Crystal System (Pearson symbol)
cP, tP & oP Crystal System (Pearson symbol)
The Five 2-D Bravais Nets
The Fourteen 3-D Bravais Nets
The Fourteen 3-D Bravais Nets
The Fourteen 3-D Bravais Nets
Simple Cubic Crystal
SC
BCC
FCC
CRYSTALLOGRAPHIC
CALCULATIONS
 Atomic Packing Factor
• The filling factor of a crystal structure is defined as the fraction of the total crystal
volume filled with atoms considered hard spheres.
• Sometimes instead of filling factor the expressions “atomic packing factor” or
“packing fraction” are used.
• The filling factor gives us an idea how close “the atoms are packed” in the crystal
structure.
• In conclusion, the filling factor together with the coordination number give us an idea
about the degree of filling the crystal volume with atoms, and, at the same time, tells us
how close the atoms in a crystal are packed.
Atomic Packing Factor

SC
Atomic Packing Factor

BCC SC
Atomic Packing Factor

BCC FCC SC
1st Nearest Neighbor: 6, Distance: a
2nd Nearest Neighbor: 12, Distance: a√
3rd Nearest Neighbor: 8, Distance: a√

SC
1st Nearest Neighbor: 8, Distance: a√ /2
2nd Nearest Neighbor: 6, Distance: a

BCC
1st Nearest Neighbor: 8, Distance: a√ /2
2nd Nearest Neighbor: 6, Distance: a

BCC
1st Nearest Neighbor: 12, Distance: a√ /2
2nd Nearest Neighbor: 6, Distance: a

FCC
1st Nearest Neighbor: 12, Distance: a√ /2
2nd Nearest Neighbor: 6, Distance: a

FCC
 NN = 8 & NNN = 6

BCC
 NN = 12 & NNN = 6

FCC
LINEAR DENSITY : SC
LINEAR DENSITY : BCC
LINEAR DENSITY : FCC
Planar Density : SC (100) Plane
Planar Density : SC (110) Plane
Planar Density : SC (111) Plane
Planar Density : BCC (100) Plane
Planar Density : BCC (110) Plane
Planar Density : BCC (111) Plane
Planar Density : FCC (100) Plane
Planar Density : FCC (110) Plane
Planar Density : FCC (111) Plane
POINTS, DIRECTIONS
AND PLANES
Points, Directions and Planes
• Miller indices are used to specify directions and planes.
• These directions and planes could be in lattices or in crystals.
• Indices of crystallographic points, directions, and planes are given in
terms of the lattice constants of the unit cell.
• For points and directions, consider the indices to be coefficients of the
lattice constants.
• Only need to invert the indices for planes.
• It is essential to label axes, lattice constants, and identifying information
for directions (vector arrowhead) and planes (axes intercepts) in order
to receive full credit.
Points

• Labeling points in a unit cell follows the same procedure for listing points
in any Cartesian coordinate system.
• The indices used to refer to points are q, r, and s.
• They are listed without commas, parentheses, or brackets.
• Consider point P, in Figure.
• If you were standing at the origin of the unit cell, you could travel q · a in
the x-direction, r · y in the y-direction, and s · c in the z-direction to get to
point P.
• Thus, we point P corresponds to the q r s point coordinates.
Points
To find q, r, and s when you are shown a drawing with a point:
• Start with your pencil at the origin.
• Count the number lattice constants you must move in the x-, y-, and z-
directions to reach the point.
• Write the point as q, r, s without parentheses, or brackets.
• Do not convert the coordinates to reduced integers. The point in the
BCC structure is not the same as the 1 1 1 point.
Points
Points
Directions
To draw a direction given the [u v w] indices:
• Choose a point for the origin of your vector.
• Simple directions are easy to draw using the 0 0 0 crystallographic point
as the origin.
• For more complicated directions, it is more convenient to translate
(add or subtract) or scale (multiply or divide) the indices of the direction.
• If you translate your origin to the point 0 0 1 for example, the tail of
your direction vector will be at this point.
• 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.
• Draw and label a point.
• Draw a line from your chosen origin to the point you just drew.
• Add an arrowhead at the point.
Directions

• It is extremely important when drawing directions that you label the

point that lies at the end of your direction vector.
• It is also highly preferred that you shift the origin and scale of the
direction vector so that it is contained inside the unit cell.
• If you shifted the origin, a way to check that you drew your direction
properly is to subtract the point coordinates of the arrowhead from those
of its tail.
• The resulting indices should be [u v w].
Directions
To write the [u v w] indices given a drawing of a direction:
• Place your pencil at the tail of the given vector.
• 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.
• If necessary, multiply by a common number to make the indices integers.
• Rewrite the indices and enclose them in square brackets [u v w].
Family of Directions

• Directions having similar

indices are equivalent, e.g.,
faces of the cube [1 0 0], [0 1
0] and [0 0 1].
• This is termed as a family of
planes and denoted as <1 0
0> which includes all the [1 0
0] combinations including
negative indices.
Directions
Directions
Directions
Directions
Planes
To draw a plane given the (h k l) indices:
• Find the reciprocal of (h k l). If one or more of the indices is zero, consider the
reciprocal to be infinity. The values , and 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 (2 2 1) plane, the
reciprocals would be, 1
• For all non-zero indices, draw a point on the x-axis at , a point on the y-axis
at , and a point on the z-axis at .
• Connect the dots.
Planes
To list the (h k l) indices given a drawing of a plane:
• Check to see if the plane goes through the origin. 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. This new plane is equivalent to the first.
• 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.
• Take the reciprocal of these intercepts. 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, (2 2 0) instead of
(1 1 0) - for use in x-ray diffraction questions.
• Enclose the indices in parentheses without commas (h k l). It is extremely
important when drawing planes that you label where the plane intersects the
axes.
Planes
Planes
 • Planes having similar indices are equivalent, e.g. faces of the cube
(1 0 0), (0 1 0) and (0 0 1). This is termed as a family of planes and
denoted as {1 0 0} which includes all the (1 0 0) combinations
including negative indices.
• Thus, planes of {1 0 0} are (1 0 0), (0 1 0), (0 0 1), (1 0 0), (0 1 0)
and (0 0 1).
• So, multiplicity factor for {1 0 0} is 6.
Family of • Multiplicity factor for {1 1 0} is 12 and the planes are (1 1 0), (1 0
1), (0 1 1), (1 1 0), (1 0 1), (0 1 1), (1 1 0), (1 0 1), (0 1 1), (1 1 0), (1
Planes/ 0 1) and (0 1 1).
Multiplicity • Multiplicity factor for {1 1 1} is 8 and the planes are (1 1 1), (1 1 1),
(1 1 1), (1 1 1), (1 1 1), (1 1 1), (1 1 1) and (1 1 1).
Factor
{100} and {110} Planes
Planes

Planes
Planes

Planes
HCP UNIT CELL
 HCP UNIT CELL: c/a Ratio
• A sketch of one third of an hcp unit cell (true unit cell) is
shown here. Consider the tetrahedron labeled as ,
which is reconstructed here.
• The atom at point is midway between the top and bottom
faces of the unit cell that is = . And, since atoms at
points , and touch one another, so,

• Here, is the atomic radius. Furthermore, from triangle ,

• Now, we can determine the length by consideration of

triangle , which is an equilateral triangle:
 HCP UNIT CELL: c/a Ratio

• A sketch of one third of an hcp unit cell (true unit cell) is

shown here. Consider the tetrahedron labeled as ,
which is reconstructed here.
• Substituting this value for in the expression yields,
 HCP UNIT CELL: APF
• let’s demonstrate that the APF for hcp is 0.74. Again, the APF
is the ratio of the total sphere volume to the unit cell
volume . For hcp, there are the equivalent of six spheres per
unit cell, and thus,

• Now, the unit cell volume is the product of the base area
times the cell height, c. The base area can be calculated as
follows. The following figure shows an hcp unit cell and the
basal plane. The base area is equal to six times the area of the
equilateral triangle .

• The area of equilateral triangle,

 HCP UNIT CELL: APF
• Thus, the area of the basal plane

• Further, as can be seen from the figure of the basal plane,

• Therefore, the base area

• The unit cell volume can now be calculated as:

 HCP: DIRECTIONS
• It is convenient to use a four- axis (Miller-Bravais) coordinate
system: a1, a2, a3 axes lay in one basal plain and located at 120°
to each other, while the z axis is perpendicular to the basal
plane.
• Same rules determine in this case four indices [u v s w]: by
convention the first three pertain to projections in a1, a2 and z
axes.
• [ ] - [" # $ %] Conversion system:
HCP: DIRECTIONS
HCP: DIRECTIONS
HCP: PLANES
HCP: PLANES
HCP: PLANES
HCP: PLANES
HCP: PLANES
HCP: PLANES
INTERSTITIAL SITES
INTERSTITIAL SITES: TETRAHEDRAL
INTERSTITIAL SITES: OCTAHEDRAL
EFFECT OF RADIUS RATIO: STABILITY
 EFFECT OF RADIUS RATIO ON CN
NUMBER

There are unfortunately several challenges with using this idea to predict crystal structures:

• Atoms in crystals are not really ions - there is a varying degree of covalency depending
electronegativity differences.
• Bond distances (and therefore ionic radii) depend on bond strength and coordination
number.
• Ionic radii depend on oxidation state (higher charge => smaller cation size, larger anion size).
RADIUS RATIO: <0.155

Radius ratio: 0.10

Radius ratio: 0.155

 RADIUS RATIO: 0.155

Radius ratio: 0.10

Radius ratio: 1.0 Radius ratio: 0.155

RADIUS RATIO: 0.155

Radius ratio: 0.155

 RADIUS RATIO: 0.225

Radius ratio: 0.155

Radius ratio: 1.0 Radius ratio: 0.225

RADIUS RATIO: 0.225

Radius ratio: 0.225

 RADIUS RATIO: 0.414

Radius ratio: 0.225

Radius ratio: 1.0 Radius ratio: 0.414

RADIUS RATIO: 0.414
Sin 45o = (r+ + r-)/2r-
or 2 Sin 45o r- = (r+ + r-)
or r+ = (2 Sin 45o - 1) r-
or r+ /r- = 0.414

Radius ratio: 0.414

 RADIUS RATIO: 0.732

Radius ratio: 0.414

Radius ratio: 1.0 Radius ratio: 0.732

RADIUS RATIO: 0.732

Radius ratio: 0.732

 FCC: OCTAHEDRAL VOID

½ 0 0 and equivalent ½½½

positions
• 4 atoms/unit cell
• 4 octahedral sites/unit cell
• 1 octahedral sites/atom
 FCC: OCTAHEDRAL VOID

½ 0 0 and equivalent ½½½

positions
• 4 atoms/unit cell
• 4 octahedral sites/unit cell
• 1 octahedral sites/atom
FCC: TETRAHEDRAL VOID

¼ ¼ ¼ and equivalent
positions
• 4 atoms/unit cell
• 8 tetrahedral sites/unit cell
• 2 tetrahedral sites/atom
FCC: TETRAHEDRAL VOID

¼ ¼ ¼ and equivalent
positions
• 4 atoms/unit cell
• 8 tetrahedral sites/unit cell
• 2 tetrahedral sites/atom
 BCC: OCTAHEDRAL VOID

½ 0 0 and equivalent ½ ½ 0 and equivalent

positions positions
• 2 atoms/unit cell
• 6 octahedral sites/unit cell
• 3 octahedral sites/atom
 BCC: OCTAHEDRAL VOID

½ 0 0 and equivalent ½ ½ 0 and equivalent

positions positions
• 2 atoms/unit cell
• 6 octahedral sites/unit cell
• 3 octahedral sites/atom
BCC: TETRAHEDRAL VOID

½ ¼ 0 and equivalent
positions
• 2 atoms/unit cell
• 12 tetrahedral sites/unit cell
• 6 tetrahedral sites/atom
BCC: TETRAHEDRAL VOID

½ ¼ 0 and equivalent
positions
• 2 atoms/unit cell
• 12 tetrahedral sites/unit cell
• 6 tetrahedral sites/atom
 PLANES AND
DIRECTIONS:
RELATIONSHIP
ANGLE BETWEEN PLANES/DIRECTIONS
INTERPLANAR SPACING
INTERPLANAR SPACING
STEREOGRAPHIC
PROJECTION
Stereographic Projection
 Stereographic Projection
• Angular relationship among crystal faces, crystal edges, zones and
crystallographic symmetry elements cannot be accurately displayed by
perspective drawings.
• If they are stated precisely in mathematical terms, they are often difficult to
comprehend and to manipulate.
• But frequently we are more interested in these angular relationships than in
any other aspect of the crystal.
• Therefore, we need a kind of drawing on which the angles between planes
can be accurately measured.
• Which will permit graphical solution of problems involving such angles.
• The stereographic projection permits the mapping of crystallographic planes
and directions in two dimensions in a convenient and straightforward
manner.
• The real value of the method is attained when it is possible to visualise
crystallographic features directly in terms of their stereographic projections.
 Reference Sphere
• The nature of stereographic projection of a crystal is easily understood if the
crystal is assumed to be very small and to be located exactly at the center of
a sphere.
• Crystal planes within the crystal can be represented by:
(i) A set of plane normal radiating from some one point within the crystal.
• This is because the orientation of any plane in a crystal can also be
represented by the inclination of the normal to that plane relative to some
reference plane.
• If a reference sphere is now described about this point, the plane normal will
intersect the surface of the sphere in a set of points called poles.
• Array of poles on the sphere, forming a pole figure, represents the
orientation of the crystal planes without, of course, indicating the size and
shape of the crystal planes.
Pole Figure
Pole Figure: {110} & {111}
 Reference Sphere
(ii) By the trace, the extended plane makes in the surface of the sphere.
• The trace ABCDA represents the plane whose pole is P1.
• Crystal is assumed to be so small that all planes pass through center of the
sphere.
• Trace ABCDA is a great circle (a circle of maximum diameter) on the sphere.
• A plane not passing through the center will intersect the sphere in a small
circle.
• The angle α between two planes is evidently equal to the angle between
their great circles or to the angle between their normal.
• This angle, in degrees, can also be measured on the surface of the sphere
along the great circle KLMNK connecting poles P1 and P2 of the two planes,
if this circle is divided into 360 equal parts.
• The measurement of an angle has thus been transferred from the planes
themselves to the surface of the reference sphere.
Angle Between Planes
 Stereographic Projection
• In practice it is usually more convenient to measure angles on a flat sheet of
paper rather than on the surface of a sphere.
• The stereographic projection is one of the methods by which the sphere may
be mapped without distorting the angular relations between the planes or
the poles.
• The stereographic projection is made by placing a plane of projection normal
to the end of any chosen diameter of the sphere and using the other end of
that diameter as the point of projection.
• Here the projection plane is normal to the diameter AB, and the projection is
made from the point B.
• If the sphere is transparent, the markings on the surface of the sphere will be
projected as shadows on the plane of projection.
• The pattern made by the shadows is a stereographic projection.
Stereographic Projection
 Stereographic Projection
• Point P′ is the stereographic projection of pole P.
• This is obtained by drawing line BP producing it until it meets projection plane.
• Alternately stated, the stereographic projection of the pole P is the shadow
cast by P on the projection plane when a light source is placed at B.
• The observer views the projection from the side opposite the light source.
• Distance of projection plane from the sphere is immaterial; a change in
distance merely changes magnification and does not alter geometrical relation.
• The plane NESW is normal to AB and passes through the center C.
• It cuts the sphere in half and its trace in the sphere is a great circle.
• This great circle projects to form basic circle N′E′S′W′ on projection, all poles
on left-hand hemisphere will project within the basic circle shown in figure.
 Stereographic Projection
• Poles on the right-hand hemisphere will project outside this basic circle, and
those near B will have projections lying at very large distances from the center.
• If we wish to plot such poles, we move the point of projection to A and the
projection plane to B and distinguish the new set of points so formed by minus
signs, the previous set (projected from B) being marked with plus signs.
• It is possible to represent the whole sphere within the basic circle if the two
projections are superimposed.
• The one for the left-hand hemisphere constructed with the light source at B
and the other for the right-hand hemisphere with the light source at A and the
screen on the right (at B).
• The movement of the projection plane along AB or its extension merely alters
the magnification; we usually make it tangent to the sphere.
• But we can also make it pass through the center of the sphere, for example, in
which case the basic circle becomes identical with the great circle NESW.
Stereographic Projection
 Stereographic Projection
• A lattice plane in a crystal is several steps removed from its stereographic
projection.
• It may be worth-while at this stage to summaries these steps:
(i) The plane C is represented by its normal CP.
(ii) The normal CP is represented by its pole P (its intersection with the reference
sphere).
(iii) The pole P is represented by its stereographic projection P′.
• A student should have enough familiarity with the stereographic projection, to
be able mentally to omit these intermediate steps and refer to the projected
point P′ as the pole of the plane C or, even more directly, as the plane C itself.
Stereographic Projection
 Projection of Great and Small Circles
• A great circle projects within the basic circle as an arc of a circle.
• Great circles that pass through the points A and B will project as straight
lines through the center of the projection.
• Great circle AWBE will project to form a straight-line W′E′.
• Great circle and its projection are in fact lines of intersection of a plane
with the sphere and projection plane, respectively.
• If the great circle is graduated in degrees, its projection will be a scale of
stereographically projected degree points.
• Will be useful for reading angular distances on the projection.
 Projection of Great and Small Circles
• A small circle inscribed about a point such as P that lies on the great
circle AWBE will cut the great circle at two points, each of which is φo
from P.
• The point P will project to P′.
• Point P′ will not be in the center of the area of this projected circle but
will lie on the line W′E′ at a point located at an equal number of
projected degrees (φo in this case) from all points of the projected circle.
• The center of the projected circle is at C.
• If the radius of the small circle is increased, it finally becomes a great
circle.
Projection of Great and Small Circles
Properties of Stereographic Projection
• Angular truth is conserved, i. e., angle between lines on the surface of a
sphere is equal to the angle between the projections of these two lines.
• Circles on the surface of the sphere projects as circles on the plane of
projection (circles project as circles).
• This is true for both great circles and small circles.
• Centers of the small circles on the sphere do not project to the center of
the area of the projected circles but will be displaced radially.
• Great circles on the sphere appear on the projections as circles cutting
the basic circle at two diametrically opposite points.
• Great circle lying in a plane perpendicular to the projection plane
becomes a diameter on the projection.
 Projection for a Cubic Lattice
• Stereographic projection is a two-dimensional drawing of three-
dimensional data.
• Geometry of all crystallographic planes and directions is accordingly
reduced by one dimension.
• Planes are plotted as great circle lines; directions are plotted as points.
• Normal to plane completely describes the orientation of a plane.
• Stereographic projection of each plane can be represented either by a
great circle or by a point showing the directions in space that is normal to
the plane.
Projection for a Cubic Lattice
Directions that Lie in a Plane
Planes of a Zone
Planes of a Zone
 Wolf Net
• The device most useful in solving problems
involving the stereographic projection is the Wulff
net.
• It is the projection of a sphere ruled with parallels
of latitude and longitude lines on a plane parallel to
the north-south axis of the sphere.
• On a Wulff net all meridians (the longitude lines)
are great circles connecting the north and south
poles of the net.
• The equator is also a great circle.
• All other latitude lines on a Wulff net are small
circles extending from side to side.
 Wolf Net
• These nets are available in various sizes, one of 18-cm diameter giving
an accuracy of about one degree, which is satisfactory for most
problems; to obtain greater precision, either a larger net or
mathematical calculation must be used.
• In solving problems with the Wulff net, it is customary to cover it with
a piece of tracing paper.
• A common pin is then driven through the paper and into the exact
center of the net so that it is free to rotate with respect to the net.
• The paper thus mounted serves as the work sheet on which
crystallographic data are plotted with the basic circle of the same
diameter as that of the Wulff net.
Wolf Net
 Measurement of Angle
• Poles Lie on a Great Circle: The angle
between two crystal planes can be measured
on the surface of the sphere along the great
circle connecting the poles of the two planes.
• This measurement can also be carried out on
the stereographic projection if, and only if,
the projected poles lie on a great circle.
• For example, the angle between the planes A
and B or C and D can be measured directly,
simply by counting the number of degrees
separating them along the great circle on
which they lie.
• The angle C-D equals the angle E-F.
 Measurement of Angle
• Poles Not on a Great Circle: If the two poles
do not lie on a great circle, then the
projection is rotated relative to the Wulff net
until they do lie on a great circle, where the
desired angle measurement can then be
made.
 Measurement of Angle
• Intersection of Great Circles: A plane may also be represented by its
trace in the reference sphere.
• This trace becomes a great circle in the stereographic projection.
• Every point on this great circle is 90o from the pole of the plane.
• Therefore, the great circle may be found by rotating the projection
until the pole falls on the equator of the underlying Wulff net and
tracing that meridian which cuts the equator 90o from the pole.
• If this is done for two poles, the angle between the corresponding
planes may be found from the angle of intersection of the two great
circles corresponding to these poles.
• This method of angle measurement is not, however, very accurate.
Measurement of Angle
Standard Projection of Crystals
Representation of Symmetry on the
Stereographic Projection
XRD
 Determination of Crystal Structure
• The most common method of structure determination uses the
technique of x-ray diffraction.
• Before the discovery of x-rays, crystallographers and mineralogists
had accumulated a vast knowledge about crystals by measurement
of interfacial angles, chemical compositions and physical properties.
• The phenomenon of diffraction was well understood, and it was
known that diffraction occurred whenever wave motion encountered
a set of regularly spaced scattering objects, provided that the
wavelengths of the waves were of the same order of magnitudes as
the repeat distance between the scattering centers.
INTERACTION OF X-RAYS WITH ATOMS
AND LATTICE STRUCTURE
• When a beam of x-rays encounters an electron, the electric field of
the beam sets it into a vibrating or oscillatory motion.
• Thus, the electron becomes a source of a new set of electromagnetic
waves.
• Since the frequency of oscillation of the electron will be the same as
that of the incident beam, the emitted radiations also have the same
frequency as the incident beam.
• The process is thus referred to as ‘Coherent Scattering’.
• The electron therefore receives a part of the incident energy and
radiates it in all directions.
INTERACTION OF X-RAYS WITH ATOMS
AND LATTICE STRUCTURE
• When an x-ray beam encounters an atom, the interaction is limited
to the extra nuclear electrons and the nucleus does not take part in
this interaction.
• Each electron in the atom now becomes a source of x-rays.
• Although the electrons in the atom are in constant motion around
the nucleus of the atom, to a fair degree of approximation it may be
assumed tat all the electrons scatter from the center of the atom.
• Thus, the atom becomes a point source of x-rays radiating x-rays of
the same frequency in all directions.
• Since there exists Z number of electrons in an atom of atomic
number Z, the intensity scattered by the atom is larger than that
scattered by a single electron.
INTERACTION OF X-RAYS WITH ATOMS
AND LATTICE STRUCTURE
• When atoms spaced at regular intervals are irradiated by a beam of
x-rays, each atom in the array starts scattering the beam, and all the
scattered beams have the same wavelength.
• Depending on the phase difference or the path difference, the wave
originating from different atoms take part in constructive or
destructive interference, leading respectively to addition or
annihilation of intensities of the individual waves.
• In an actual crystal the beam would be reflected from a large number
of parallel planes in the crystal and constructive interference can
occur only under highly restricted conditions.
BRAGG’S LAW FOR DIFFRACTION
BRAGG’S LAW FOR DIFFRACTION
• Let’s determine the criteria for maximum reinforcement of x-rays
reflected from atoms on a number of equally spaced parallel planes
such as exist in crystals.
• This reinforcement occurs when all the diffracted waves are in phase
with one another.
• For this purpose, let us consider each plane of atoms in a crystal as a
semi-transparent mirror; that is each plane reflects a part of the x-ray
beam and also permits part of it to pass through.
• When x-rays strike a crystal, the beam is reflected not only from the
atoms at the surface layers but also from atoms underneath the
surface to a considerable depth.
• In the actual case, the beam would be reflected not from two lattice
planes but from a large number of parallel planes.
BRAGG’S LAW FOR DIFFRACTION
BRAGG’S LAW FOR DIFFRACTION
BRAGG’S LAW FOR DIFFRACTION
BRAGG’S LAW FOR DIFFRACTION
BRAGG’S LAW FOR DIFFRACTION
BRAGG’S LAW FOR DIFFRACTION
DIFFRACTION PATTERN
 Order of Reflection
• The value of ‘n’ in this equation is called the order of reflection,
which may be any positive integer (n = 1, 2, 3).
• It means that for a given value of wavelength and plane spacing ‘d’
there may be several angles θ1, θ2, etc., at which diffraction may
occur, consistent with the fact that sin θ should not exceed unity.
• In a first order reflection, the scattered beam for adjacent planes
such as planes I and II, would differ in path by one wavelength
• Those from alternate planes such as planes I and III, would differ by
two wavelengths etc.
Order of Reflection
 Order of Reflection
• Only a very slight shift in the angle θ away from any of these eleven
values causes destructive interference and cancellation of the
reflected beams.
• If one chooses two crystals with widely different atom spacing, even
then planes with the same ‘d’ spacing in the two crystals will diffract
in the same directions.
• Although the x-rays are reflected by atoms, it would appear as
though x-rays are being reflected by the planes.
• In fact, it is conventional to use the term ‘reflecting planes’ and
‘reflected beams’ even if it actually means ‘diffracting planes’ and
‘diffracted beams’.
 Order of Reflection
• Angle between diffracted beam and transmitted beam is 2θ and is
called the ‘diffraction angle’, which is the one measured in the
experiments.
• Since sin θ can not exceed unity, diffraction takes place for ‘d’ values
which satisfy the relation (nλ/2d) less than unity. i.e., nλ must be less
than 2d for diffraction to occur.
• In other words, the wavelength used must be less than twice the
largest value of the interplanar spacing within the crystal.
• Ultraviolet rays with wavelength 500Å could not possibly be
diffracted by a crystal.
• If the wavelength is too small, the values will be too small to be
conveniently measured.
FORBIDDEN REFLECTIONS
FORBIDDEN REFLECTIONS
EXPERIMENTAL DIFFRACTION METHODS
THE POWDER METHOD
THE POWDER METHOD
THE POWDER METHOD
THE POWDER METHOD
THE POWDER METHOD
THE POWDER METHOD
RECIPROCAL LATTICE
 RECIPROCAL LATTICE
• The Bragg law is a very powerful tool and is all that is needed for an
understanding of a great many applications of x-ray diffraction.
• However, it is useful under certain conditions to transform a Bravais lattice to
what is known as a reciprocal lattice.
• For example, the Bragg law is totally unable to explain the diffraction effects
involving diffuse scattering at non-Bragg angles, and these effects demand a
more general theory of diffraction for their explanation.
• The reciprocal-lattice theory of diffraction, being general, is applicable to all
diffraction phenomena from the simplest to the most intricate.
• The reciprocal lattice is best formulated in terms of vectors.
 VECTOR MULTIPLICATION
• The scalar product of two vectors may be
a.b = ab cos α regarded as the product of the length of one
vector and the projection of the other upon
the first.
• If one of the vectors, say a, is a unit vector (a
vector of unit length), then a.b gives
immediately the length of the projection of b
on a.
• The scalar product of sums or differences of
vectors is formed simply by term-by-term

• multiplication:
VECTOR MULTIPLICATION
• The vector product (or cross product) of two
vectors a and b, written a × b, is a vector c at
right angles to the plane of a and b, and equal
in magnitude to the product of the absolute
values of the two vectors and the sine of the
angle α between them, or

• The magnitude of c is simply the area of the

parallelogram constructed on a and b.
• The direction of c is that in which a right-hand
screw would move if rotated in such a way as
to bring a into b.
• It follows from this that the direction of the
vector product c is reversed if the order of
multiplication is reversed, or that
 RECIPROCAL LATTICE
• Corresponding to any crystal lattice.
• So called because many of its properties are reciprocal to those of the crystal lattice.
• Let the crystal lattice have a unit cell defined by the vectors a1, a2 and a3 m these vectors will
be the edges of a unit cell and will have lengths a1, a2 and a3 respectively.
• The corresponding reciprocal lattice has a unit cell defined by the vectors b1, b2 and b3.

• V is the volume of the crystal unit cell.

• A vector to any corner in this lattice is:
 RECIPROCAL LATTICE
• This way of defining the vectors b1, b2, b3 in terms of the vectors a1, a2, a3
gives the reciprocal lattice.
• Consider the general triclinic unit cell, reciprocal-lattice axis b3 is normal to
the plane of a1 and a2. Its length is given by:
 RECIPROCAL LATTICE
• By extension, similar relations are found for all the planes of the
crystal lattice.
• Since OP, the projection of a3 on b3, is equal to the height of the cell,
which in turn is simply the spacing d of the (001) planes of the crystal
lattice.
• Similarly, we find that the reciprocal lattice axes b1 and b2 are normal
to the (100) and (010) planes, respectively, of the crystal lattice, and
are equal in length to the reciprocals of the spacing of these planes.
• The whole reciprocal lattice is built up by repeated translations of the
unit cell by the vectors b1, b2, b3.
 RECIPROCAL LATTICE

• This produces an array of points each of which is labeled with its

coordinates in terms of the basic vectors.
• Thus, the point at the end of the b1 vector is labeled 100, that at
the end of the b2 vector 010, etc.
• It is thus seen that there is a one-to-one correspondence between
points in the reciprocal
• space and planes in the Bravais lattice.
• For each Bravais lattice there is a corresponding reciprocal lattice.
 RECIPROCAL LATTICE
• This extended reciprocal lattice has the following properties:
• (1) A vector Hhkl drawn from the origin of the reciprocal lattice to any
point in it having coordinates hkl is perpendicular to the plane in the
crystal lattice whose Miller indices are hkl.
• This vector is given in terms of its coordinates by the expression:

• (2) The length of the vector Hhkl is equal to the reciprocal of the
spacing d of the (hkl) planes, or:
 RECIPROCAL LATTICE
• The reciprocal lattice is drawn from any convenient origin, not necessarily
that of the crystal lattice, and to any convenient scale of reciprocal
angstroms.
• The Equations take on a very simple form for any crystal whose unit cell is
based on mutually perpendicular vectors, i.e., cubic, tetragonal, or
orthorhombic.
• For such crystals, b1, b2 and b3 are parallel, respectively, to a1, a2 and a3, while
b1, b2 and b3 are simply the reciprocals of a1, a2 and a3.
RECIPROCAL LATTICE
RECIPROCAL LATTICE
RECIPROCAL LATTICE
 Problem
• Example 7.1: Show that reciprocal lattice vector Hhkl is normal to the
plane (hkl).
• Let ABC be part of the plane nearest the origin in the set (hkl).
• Then, from the definition of Miller indices, the vectors from the origin
to the points A, B and C are a1/h, a2/k and a3/l, respectively.
 Problem
• Consider the vector AB, that is, a vector drawn from A to B, lying in
the plane (hkl).

• Since this product is zero, H must be normal to AB.

• Similarly, it may be shown that H is normal to AC.
• Since H is normal to two vectors in the plane (hkl), it is normal to the
plane itself.
 Problem
• Example 7.2: Show that the reciprocal lattice vector Hhkl is the
reciprocal of spacing of the hkl planes, dhkl.
• To prove the reciprocal relation between H and d, let n be a unit
vector in the direction of H, i.e., normal to (hkl).
SYMMETRY
Lattice: Symmetry
Lattice: Symmetry
Operations of the first kind: Pure translations
• A pure translation is characterized by a translation vector t.
• In crystals, a translation vector is limited to the lattice
vectors and, if present, the lattice centering vectors.
• We will see later that certain fractions of lattice translation
vectors may also be allowed.
Operations of the first kind: Pure rotations
• A pure rotation is characterized by a rotation axis and a rotation
angle that is chosen to be positive for a counterclockwise
rotation.
• The rotation axis can be described by a direction vector [uvw],
or by the equation of the line that represents the rotation axis.
• It is customary to write the rotation angle as a fraction of 2π,
i.e., α = 2π/n.
• The number n is the order of the rotation, and we say that a
rotation is n-fold if its angle is given by 2π/n.
Operations of the first kind: Pure rotations
• There are two basic types of rotational symmetry
operations.
• Proper rotations move an object, but do not change the
handedness of the object.
• Improper rotations include a proper rotation as well as a
component that inverts the handedness of the object.
Operations of the first kind: Pure rotations
• 1-Fold Rotation: A 1(C1)-fold rotation operation implies either a 0° rotation or a
360° rotation and is referred to as the identity operation.
• 2-Fold Rotation: A 2-fold (C2) rotation operation moves the object by (360/2) ° =
180 °. The symbol used to designate a 2-fold axis is a solid oval.
• 3-Fold Rotation: A 3-fold (C3) rotation operation moves the object by (360/3) ° =
120 °. The symbol used to designate a 3-fold axis is a solid equilateral triangle.
• 4-Fold Rotation: A 4-fold (C4) rotation operation moves the object by (360/4) ° =
90 °. The symbol used to designate a 4-fold axis is a solid square.
• 6-Fold Rotation: A 6-fold (C6) rotation operation moves the object by (360/6) ° =
60 °. The symbol used to designate a 6-fold axis is a solid hexagon.
Operations of the first kind: Pure rotations
Operations of the first kind: Pure rotations
Operations of the first kind: Pure rotations
Operations of the second kind: Pure
reflection: Mirror symmetry
Operations of the second kind: Pure
reflection: Mirror symmetry
Operations of the second kind: Inversions
Combination of mirrors and translations:
Glide
Combination of rotations with the inversion
center
Combination of rotations and mirrors
Combination of rotations and translations
Combination of rotations and translations
IMPERFECTIONS IN
SOLIDS
Vacancies and Self-interstitials
Vacancies
Frenkel and Schottky Defect
Dislocations - Linear Defects

Edge Dislocations
Dislocations - Linear Defects
Dislocations - Linear Defects

Edge Dislocations
Dislocations - Linear Defects

Edge Dislocations
Dislocations - Linear Defects

Screw Dislocations
Dislocations - Linear Defects

Screw Dislocations
Dislocations - Linear Defects

Screw Dislocations
Interfacial Defects: External Surfaces

Grain Boundaries
Interfacial Defects: External Surfaces

Grain Boundaries
Interfacial Defects: External Surfaces

Grain Boundaries
VOID
ORTHORHOMBIC : P, I, F, C
LATTICE POSITION:CENTER OF FACE
CENTER POSITIONS: A AND B