The Structure of

Crystalline Solids
 Describe the difference in atomic/molecular structure
between crystalline and non-crystalline materials.
 Draw unit cells FCC, BCC, and HCP crystal structures.
 Derive the r/nships b/n unit cell edge length and
atomic radius for FCC and BCC crystal structures.
 Compute densities for metals having FCC, & BCC
given their unit cell dimensions.
 Etc ….
 Properties of some materials are directly related to their
crystal structures.
 pure and undeformed Mg, having 1 crystal structure, are
much more brittle than pure and undeformed metals
such as gold and silver that have yet another crystal
structure.
 significant property differences exist between
crystalline and noncrystalline materials having the
same composition.
 noncrystalline ceramics and polymers normally are
optically transparent; the same materials in crystalline (or
semicrystalline) form tend to be opaque or, at best,
translucent.
 Solid mtls classified according to the regularity atoms or
ions are arranged with respect to one another.
 A crystalline material:- atoms are situated in a repeating
or periodic array over large atomic distances
 long-range order exists,
 upon solidification, the atoms will position themselves in a
repetitive 3-D pattern
  All metals,
 Many ceramic materials, and
 Certain polymers
form crystalline structures under normal
solidification conditions.

For non-crystalline or amorphous

materials this long-range atomic order is
absent.
 Is the manner in which atoms, ions, or molecules are
spatially arranged.
 Determines some of the properties of crystalline solids
 It vary from relatively simple structures for metals to
complex ones, as in some of the ceramic and polymeric
materials.
 In describing crystalline structures, atoms (or ions) are
thought of as being solid spheres having well-defined
diameters.
 atomic hard sphere model

 the term lattice is also used

in the context of crystal
structures;

“lattice” means a 3-D array

of points coinciding with atom positions (or
sphere centers).
 in describing crystal structures, it is often convenient to
subdivide the structure into small repeat entities called
unit cells.
 Unit cells for most crystal structures are parallelepipeds or
prisms having three sets of parallel faces.
 A unit cell is chosen to represent the symmetry of the
crystal structure.
 the basic structural unit or building block of the crystal
structure
 Atomic bonding in this group of materials is metallic
and thus non-directional in nature.
 this leads to relatively large numbers of nearest
neighbors and dense atomic packing's.
 In addition, for metals each sphere represents an ion
core.
 The three relatively simple crystal structures are found
in common metals:

Face centered cubic, (FCC)

Body-centered cubic, (BCC) and
Hexagonal close-packed (HCP).
(a) a hard sphere unit cell (b) A reduced-sphere unit cell (c)an aggregate of many
representation atoms

 Crystal structure found in many metals has a unit cell of

cubic geometry, with atoms located at each of the
corners and the centers of all the cube faces.
 2.2 STRUCTURE OF
CRYSTALLYNE SOLIDS  For atoms in FCC crystal structure:
2.2.1 INTRODUCTION  Atoms in corners are ⅛ within the cell.
2.2.2 CRYSTAL STRUCTURES
2.2.3 UNIT CELL  Atoms on faces and edges are ½
2.2.4 METALLIC CRYSTAL STRUCTURE within the cell.
[Link] THE FACE-CENTERED CUBIC
CRYSTAL STRUCTURE  A face-centered cubic unit cell contains
a total of 4 atoms: 1 from the corners,
and 3 from the faces.
4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

b) Atoms in faces

a) Atoms in corners
 familiar metals having this crystal structure are
 copper,
 aluminum,
 silver,and gold
 These spheres or ion cores touch one another across a
face diagonal;
 the cube edge length a and the atomic radius R are
related through
 For FCC crystal structure, each corner atom is shared
among 8 unit cells,whereas a face-centered atom belongs
to only two.
 Therefore, 1/8 of each of the eight corner atoms and 1/2 of
each of the six face atoms,or a total of four whole
atoms,may be assigned to a given unit cell.
 Two other important characteristics of a FCC crystal
structure are
 the coordination number and
 the atomic packing factor (APF).
 Coordination number:- number of nearest-neighbor
or touching atoms.
 For FCC, the coordination number is 12.
 E.g. the front face atom has:
 4 corner nearest-neighbor atoms surrounding it,
 4 face atoms that are in contact from behind, and
 4 other equivalent face atoms residing in the next unit
cell to the front
 Has also a cubic unit cell with atoms located at all eight
corners and a single atom at the cube center.

a hard sphere a reduced-sphere an aggregate of many atoms

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

 Chromium
 Iron
 Tungsten are some metals that exhibit BCC
structure.
 Two atoms are associated with each BCC unit cell
 one atom from the eight corners and
 the single center atom
 The coordination number for the BCC crystal structure
is 8
 the atomic packing factor for BCC is 0.68
 Here the unit cell has hexagonal geometry.

(a) a reduced-sphere unit (b) an aggregate of many atoms

cell
 Top and bottom faces consist 6 atoms that form
regular hexagons and surround a single atom in
the center.
 Another plane b/n the top and bottom planes
provides 3 additional atoms

A sites

B sites

A sites

• 3D Projection • 2D Projection
 The equivalent of six atoms is contained in each
unit cell;
 one-sixth of each of the 12 top and bottom face
corner atoms,
 one-half of each of the 2 center face atoms, and
 all 3 mid-plane interior atoms

• Coordination # = 12
• APF = 0.74
If a and c represent the short and long unit cell
dimensions then, the ratio c/a should be 1.633
 Theoretical density for metals can be determined by:
E.g/
 Polymorphism:- a phenomenon in which some
materials (metal or non-metal)may have more than one
crystal structure.
 When found in elemental solids, the condition is often
termed allotropy.
 The crystal structure depends on both the temperature
and the external pressure.
 Example:
 Pure iron has a BCC crystal structure at room temperature,
which changes to FCC iron at 9120C (16740F)
 Is a way of classifying crystal structure into groups based
on unit cell geometry &/or atomic arrangements.
 Unit cell geometry:- an x, y, z coordinate system is
established with its origin at one of the unit cell corners.
 Is defined in terms of 6 parameters:
 the three edge lengths a, b, and c, and
 the three inter-axial angles , β and r.
 Are called lattice parameters of a crystal
structure.
On this bases there are 7 possible combinations of
lattice parameters each of which represents a distinct
crystal system.

A unit cell with x, y, and z coordinate

axes, showing axial lengths (a, b,and c)
and interaxial angles

Cubic system( ):- has

the greatest degree of symmetry, while

Triclinic system( ):- has least

symmetry
 3.8 POINT COORDINATES
Position of any point within a unit cell may be specified
in terms of its coordinates as fractional multiples of the
unit cell edge lengths (i.e., in terms of a, b, and c).

 Consider the unit cell and the point P

We specify the position of P in terms of the generalized
coordinates q, r, and s whr.
q is some fractional length of a along the x axis,
r is some fractional length of b along the y axis,
similarly for s.

 Thus, the position of P is designated using

coordinates q r s with values that are less than or
equal to unity.
 Normal convention, q r s are not separated by any
punctuation mark.
E.g.
E.g.2
 It is a line b/n two points, or a vector.
 Steps to determine the 3 directional indices:
1. A vector of convenient length is positioned such that it
passes through the origin of the coordinate system.
2. The length of the vector projection on each of the three
axes is determined; these are measured in terms of the
unit cell dimensions a, b, and c.
3. These three numbers are multiplied or divided by a
common factor to reduce them to the smallest integer
values.
4. The three indices, not separated by commas, are enclosed
in square brackets, thus:[uvw].
 The [100], [110], and [111]
directions within a unit cell

 Negative indices are also possible, which are

represented by a bar over the appropriate index.
 E.g. the direction would have a component
in –y the direction.
E.G 3
  For some crystal structures, directions with different
indices are actually equivalent;
this means that the spacing of atoms along each
direction is the same.
E.g. in cubic crystals:
The ff. indices are equivalent

 Equivalent directions are grouped together into a

family, which are enclosed in angle brackets,

In addition, directions in cubic crystals having the

same indices without regard to order or sign are
equivalent. E.g [123] and

This is, in general, not true for other crystal systems

 Crystallographic equivalent directions will not have the
same set of indices.
 And we use a four-axis, or Miller–Bravais, coordinate
system to describe:

The 3 axes(a1,a2,a3) are on a

single plane (called the basal
plane)

The z axis is perpendicular

to this basal plane.
 by convention, the first three indices pertain to
projections along the respective a1,a2,a3 axes in the
basal plane.
 And the 4th indices is obtained by the ff. formula:

E,g, the [010] direction becomes

 In all but, the hexagonal crystal system, crystallographic
planes are specified by three Miller indices as (hkl).

 Any two planes parallel to each other are

equivalent and have identical indices.

 Steps to determination of the h, k, and l

index numbers:
1. If the plane passes through the selected origin,
Either another parallel plane must be constructed
within the unit cell by translation, or
 A new origin must be established at the corner of
another unit cell.
2. At this pt. the crystallographic plane either intersects or
parallels each of the three axes;
the length of the planar intercept for each axis is
determined in terms of the lattice parameters a, b, and c.
3. Take reciprocals of these numbers (intercepts).

4. If necessary, change numbers into smallest integers

5. Finally, the integer indices, not separated by commas, are
enclosed within parentheses, thus:(hkl).
 Unique characteristic of cubic crystals is that planes and
directions having the same indices are perpendicular to
one another.

 However, for other crystal systems there are no

simple geometrical relationships between planes
and directions having the same indices.
 Representations of a series a. (001), b. (110),and c.
(111) crystallographic planes.
E.g.
Determine the Miller indices for the plane shown in the
accompanying sketch(a).
The atomic arrangement for a crystallographic
plane, depends on the crystal structure.
The (110) atomic planes for FCC and BCC crystal
structures are represented as:
a) Reduced sphere FCC
unit cell with
(110) plane

(b) Atomic packing of

an FCC (110)
plane
(a)Reduced-sphere BCC unit cell with (b)Atomic packing of a BCC (110)
(110) plane. plane.
 A “family” of planes contains planes that are
crystallographically equivalent.
i.e. having the same atomic packing;
is designated by indices with enclosed in braces.
For example, in cubic crystals:

all belong to the {111} family

Also, in the cubic system only, planes having the

same indices, irrespective of order and sign, are
equivalent.
both( ) and ( ) belong to the {123} family.
 SINGLE CRYSTALS:
when the periodic and repeated arrangement of
atoms is perfect or extends throughout the
entirety of the specimen without interruption.

 All unit cells interlock in the same way and have the same
orientation.

 Single crystals exist in nature and produced artificially under

carefully controlled env’t.
Within the past few years, single crystals have become
extremely important in many modern technologies
in particular electronic microcircuits, which employ
single crystals of silicon and other semiconductors.
  composed of a collection of many small crystals or
grains.
 Various stages in the solidification of a
polycrystalline
Initially, small crystals or nuclei form at various
positions having random crystallographic orientations.
 The small grains grow by the successive addition from the
surrounding liquid of atoms to the structure of each.

The extremities of adjacent grains interrupt on one

another as the solidification process approaches
completion.
  Also, there exists some atomic mismatch within the
region where two grains meet; this area, called a grain
boundary.

The grain structure as it would

Upon completion of appear under the microscope;
solidification, grains having dark lines are the grain
irregular shapes have formed. boundaries.
 The directionality of physical properties of substances.

 For example, the elastic modulus, the electrical

conductivity, and the index of refraction may have
different values in the [100] and [111] directions.
 it is associated with the variance of atomic or ionic
spacing with crystallographic direction.

 The extent and magnitude of anisotropic effects are

a function of symmetry.
 the degree of anisotropy increases with decreasing structural
symmetry
 triclinic structures normally are highly anisotropic.

Where as, Substances in which measured properties are

independent of the direction of measurement are
isotropic.
  lack a systematic and regular arrangement of
atoms over a relatively large atomic distances.

 Sometimes such materials are also called amorphous

 (meaning literally without form),or
 super cooled liquids, in as much as their atomic
structure resembles that of a liquid.
(a) crystalline silicon dioxide (b) non-crystalline silicon dioxide