MME 211
Crystallography and Structure of Materials
MD. MUKTADIR BILLAH, Ph.D. (USA)
Assistant Professor
MME, BUET
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."
Amorphous versus
Crystalline Structure
• 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.
• An amorphous substance is isotropic, i.e., it
exhibits the same physical and chemical
properties when tested in any direction.
Amorphous • Crystal has many properties that are
directional.
versus • The basic feature of all crystals is the
regularity of their atomic arrangement.
Crystalline • The first notable feature of the regularity of
crystal structures is the periodicity of their
Structure patterns.
• In addition to periodicity, most crystal
structures possess the property of symmetry.
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.
• 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.
Lattice
• 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.
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
Cubic Crystal System: Van der Waals Surface
cP, tP & oP Crystal System (Pearson symbol)
cP, tP & oP Crystal System (Pearson symbol)
CLOSE PACK STACKING
CLOSE PACK STACKING
CLOSE PACK STACKING
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: 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
ORTHORHOMBIC : P, I, F, C
LATTICE POSITION:CENTER OF FACE
CENTER POSITIONS: A AND B
ANGLE BETWEEN PLANES/DIRECTIONS
INTERPLANAR SPACING
INTERPLANAR SPACING
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).
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
• 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
