Contents

Part 1: Material Science

Bonds in Solids
Crystal Geometry
Crystal Structure and Defects
Electron Theory of Metals
Diffusion in Solids

Crystal Geometry,
Structure and Defects
Minta Yuwana
2009

Learning Objectives
1. Describe the difference in atomic/molecular structure
between crystalline and noncrystalline materials.
2. Draw unit cells for face-centered cubic, bodycentered
cubic, and hexagonal close-packed crystal structures.
3. Derive the relationships between unit cell edge length
and atomic radius for face-centered cubic and bodycentered cubic crystal structures.
4. Compute the densities for metals having facecentered
cubic and body-centered cubic crystal structures given
their unit cell dimensions.

Learning Objectives
5. Given three direction index integers, sketch the direction
corresponding to these indices within a unit cell.
6. Specify the Miller indices for a plane that has been
drawn within a unit cell.
7. Describe how face-centered cubic and hexagonal closepacked crystal structures may be generated by the
stacking of close-packed planes of atoms.
8. Distinguish between single crystals and polycrystalline
materials.
9. Define isotropy and anisotropy with respect to material
properties.

Crystal
solids which have a regular periodic
arrangement in their component parties,
bounded by flat faces, orderly arranged in
reference to one another, which converge
at the edges and vertices.

Crystal
A crystal is symmetrical about its certain
elements like points, lines or planes
if crystal rotated about these elements, it is not possible to
distinguish its new position from the original position.

Symmetry is an important characteristic based on

internal structure of crystal.
Symmetry helps one to classify crystals and
describing their behavior.

At temperatures below that of crystallization, the

crystalline state is stable for all solids.

Lattice Points and Space Lattice

The atomic arrangement in crystal is
called the crystal structure.
In perfect crystal, there is a regular
arrangement of atoms.

A simple model of crystal structure,

points representing the centers of ions, atoms
or molecules.
Such points in space are called lattice points.

Lattice Points and Space Lattice

The totality of lattice points forms a crystal
lattice or space lattice.
The space lattice is defined as an array of
imaginary points which are so arranged in
space that each point has identical
surroundings.

Lattice Points and Space Lattice

The periodicity in the arrangement of ions,
atoms or molecules generally varies in different
directions.
If all the atoms, molecules or ions at the lattice
points are identical, the lattice is called a Bravias
lattice.
The space lattice of a crystal is described by
means of a three-dimensional co-ordinate
system
the coordinate axis coincide with any three edges of
the crystal that intersect at one point and do not lie in
a single plane.

Lattice Points and Space Lattice

The space-lattice concept was introduced by
R.J. Hauy
It was postulated that an elementary unit, having all
the properties of the crystal, should exist, or
conversely that a crystal was built up by the
juxtaposition of such elementary units.

Define vectors representing points forming the

vertices of a parallelepiped OABC as
OA OB OC
a space lattice is obtained by translations
parallel to and equal to OA,OB and OC.
The parallelepiped is called the unit cell.

Lattice Points and Space Lattice

Most of metallic crystals have highly symmetrical
structures with closed packed atoms.
Complex lattices are frequently encountered in
metals.
It comprise of several primitive translation lattices
displaced in relation to each other.

The most common types of space lattices are:

Body centered cubic (BCC) lattices,
Face centered cubic (FCC) lattices and
Hexagonal closed packed (HCP) lattices.

Lattice Points and Space Lattice:

Basis

Crystal structure is described in terms of

atoms rather than points.
To obtain a crystal structure, an atom or a
group of atoms must be placed on each
lattice point in a regular fashion.
Such an atom or a group of atoms is
called the basis
this acts as a building unit or a structural unit
for the complete crystal structure.

Lattice Points and Space Lattice:

Basis

A lattice combined with a basis generates

the crystal structure.
Space lattice + Basis Crystal Structure

A lattice is a mathematical concept, the

crystal structure is a physical concept.
The crystal structure is obtained by placing
the basis on each lattice point such that
the centre of the basis coincides with the
lattice point.

Lattice Points and Space Lattice:

Basis

Lattice Points and Space Lattice:

Basis

Note:
the number of atoms in a basis may vary from
one to several thousands,
the number of space lattices possible is only
fourteen
one can obtain a large number of crystal structures
from just fourteen space lattices because of the
different types of basis available.
If the basis consists of a single atom only, a mono
atomic crystal structure is obtained.
Copper is an example of mono atomic face-centered cubic
structures.
Examples of complex bases are found in biological materials.

Unit Cell
The smallest repetitive division of crystal
structure.
The smallest component of the space
lattice.
The basic structural unit or building block
of the crystal structure by virtue of its
geometry and atomic positions within.

Unit Cell
Space lattices of various substances differ
in the size and shape of their unit cells.
The distance from one atom to another
atom measured along one of the axis is
called the space constant.
The unit cell is formed by primitives or
intercepts a, b and c along X, Y and Z
axes respectively.

Unit Cell
A unit cell can be completely described by the three
vectors a, b, and c ( OP, OQ and OR) when the length
of the vectors and the angles between them (, , ) are
specified.
The three angles , and are called interfacial angles.
Taking any lattice point as the origin, all other points on
the lattice, can be obtained by a repeated of the lattice
vectors a, b and c.
These lattice vectors and interfacial angles constitute the
lattice parameter of a unit cell.
If the values of these intercepts and interfacial angles
are known, one can easily determine the form and actual
size of the unit cell.

Primitive Cell
Defined as a geometrical shape which, when
repeated indefinitely in 3-dimensions, will fill all
space and is equivalent of one lattice point, i.e.
the unit cell that contains one lattice point only at
the corners.
Note that in some cases the unit cell may coincide
with the primitive cell, but in general the former differs
from the latter in that it is not restricted to being the
equivalent of one lattice point.

Primitive Cell
The units cells, which contain more than
one lattice point are called non-primitive
cells.
The unit cells may be primitive cells, but all
the primitive cells need not to be unit cells.

Crystal Classes
The atoms or molecules or ions in
crystalline state are arranged in a regular,
repetitive and symmetrical pattern,
but the crystal will have the external
symmetrical shape only, if no restraint is
imposed during crystal growth.

Crystal Classes
Crystals possess symmetry
The symmetry of crystals is investigated
by means of symmetry operations,
as a result of which the crystal coincides
with itself in various positions.

Crystal Classes
The simplest of such operations
(rotation, reflection and translationparallel displacement) are associated
with the elements of symmetry.
The simplest elements of symmetry are
the axis and planes of symmetry.

Crystal Classes
The shape of the crystal is said to be
symmetrical if it possesses one or more
elements of symmetry.
A group of symmetry operations,
consisting commonly of a combination of
rotations, reflections and rotations with
reflection, is called a symmetry class.

Crystal Classes
The elements of symmetry are:
(i) The Symmetry Plane
(ii) The Symmetry Axis
(iii) The Centre of Symmetry

Crystal Classes
(i) The Symmetry Plane:
The shape of the crystal is said to be
symmetrical about a plane if it divides
the shape into two identical halves or
into two halves which are mirror images
of one another.
Note that only in an ideal crystal the faces
are of exactly same size.

Crystal Classes
(ii) The Symmetry Axis:
If the shape can be rotated about an axis so
that the shape occupies the same relative
position in space more than once in a
complete revolution, such an axis is called to
be axis of symmetry.
Such axes may be either 2, 3, 4 or 6 fold. The axis
of symmetry causes the crystal to occupy more
than one congruent position during rotation about
that axis during rotation by 360.

Crystal Classes
(iii) The Centre of Symmetry:
Within a crystal, there is some point about
which crystallographically similar faces are
arranged in parallel and corresponding
positions, e.g., the centre of the cube is a
centre of symmetry.
Note that a tetrahedron has no such centre. A
cube has highly symmetrical shape and contains
many planes and axis of symmetry.

Crystal Classes
The principal axes of a cube are four fold,
i.e. during each complete rotation about the
axis, the crystal passes four through identical
positions.

The body diagonal axes are three fold and

there are six two-fold axes.
The vertical axis of hexagonal prism is a
six-fold axes.

Crystal Classes
A symmetry operation is one that leaves the
crystal and its environment invariant.
Symmetry operations performed
about a point or a line are called point group
symmetry operations
by translations are called space group symmetry
operations.

Note that crystals exhibit both types of

symmetries independently and in compatible
combinations.

Crystal Classes
The different point group symmetry
elements that are exhibited by crystals:
(i) centre of symmetry or inversion centre
(ii) reflection symmetry
(iii) rotation symmetry.

Crystal System
If all the atoms at the lattice points are
identical, the lattice is said to be Bravais
lattice.
There are four systems and five possible
Bravais lattices in two dimensions.

The four crystal systems of two

dimensional space are oblique,
rectangular, square and hexagonal.

Crystal System
The rectangular crystal system has two
Bravais lattices,
rectangular primitive and
rectangular centered.

In all, there are five Bravais lattices.

Crystal System

Crystal System
Based on pure symmetry considerations,
there are only fourteen independent ways
of arranging points in three-dimensional
space,
such that each arrangement is in accordance
or in confirmation with the definition of a
space lattice.

These 14 space lattices with 32 point

groups and 230 space groups are called
Bravais lattices.

Crystal System
Each space lattice can be defined by
reference to a unit cell which, when
repeated in space an infinite number of
times, will generate the entire space
lattice.

Crystal System
To describe basic crystal structures,
the 14 types of unit cells are grouped in seven
different classes of crystal lattices,
i.e. to describe basic crystal structures, seven
different co-ordinate systems of reference axes are
required.

Crystal System
The number of lattice points in unit cell can be
calculated as:
Contribution of lattice point at the corner = th of the
point
Contribution of the lattice point at the face = of the
point
Contribution of the lattice point at the centre = 1 of the
point

Every type of unit cell is characterized by the

number of lattice points (not the atoms) in it.

Crystal System
For example, the number of lattice points
per unit cell for
simple cubic (SC) is 1
body centered cubic (BCC) is 2
Face centered cubic (FCC) is 4

Crystal System
Volume of a unit cell can be calculated with the
help of the relation
Atomic Packing Factor (APF):
defined as the ratio of total volume of atoms in a unit
cell to the total volume of the unit cell.
also called relative density of packing (RDP).

ENERGY AND PACKING

Non dense, random packing

Dense, regular packing

Dense, regular-packed structures tend to have

lower energy.
2

METALLIC CRYSTALS
tend to be densely packed.
have several reasons for dense packing:
-Typically, only one element is present, so all atomic
radii are the same.
-Metallic bonding is not directional.
-Nearest neighbor distances tend to be small in
order to lower bond energy.

have the simplest crystal structures.

Crystal System: Cubic

SIMPLE CUBIC STRUCTURE (SC)

Rare due to poor packing (only Po has this structure)
Close-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

4

Crystal System: Simple Cubic

APF for a simple cubic structure = 0.52

Crystal System: Face Centered Cubic

FACE CENTERED CUBIC STRUCTURE (FCC)

Close packed directions are face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

Coordination # = 12

Adapted from Fig. 3.1(a),

Callister 6e.
(Courtesy P.M. Anderson)

ATOMIC PACKING FACTOR: FCC

APF for a body-centered cubic structure = 0.74

Unit cell c ontains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell

a
Adapted from
Fig. 3.1(a),
Callister 6e.

Crystal System:

Body Centered Cubic (BCC)

BODY CENTERED CUBIC STRUCTURE (BCC)

Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

Coordination # = 8

Adapted from Fig. 3.2,

Callister 6e.

(Courtesy P.M. Anderson)

ATOMIC PACKING FACTOR: BCC

APF for a body-centered cubic structure = 0.68

R
Adapted from
Fig. 3.2,
Callister 6e.

Unit cell c ontains:

1 + 8 x 1/8
= 2 atoms/unit cell

Crystal System: Tetragonal

Crystal System: Hexagonal

Crystal System: Hexagonal

Crystal System: Hexagonal

HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
ABAB... Stacking Sequence

3D Projection

2D Projection
A sites
B sites
A sites

Adapted from Fig. 3.3,

Callister 6e.

Coordination # = 12
APF = 0.74

Crystal System: Hexagonal

Crystal System

Crystal System

Crystal System

Crystal System

Crystallographic Points,
Directions, and Planes
POINT COORDINATES
The position of any point
located within a unit cell
specified in terms of
fractional multiples of the
unit cell edge lengths
(a,b, and c).

POINT COORDINATES

POINT COORDINATES
Solution
From the sketch (a), edge lengths for this unit
cell are:
a = 0.48 nm, b = 0.46 nm, and c = 0.40 nm.
Fractional lengths are: q=1/4, r=1, s=1/2
The location of point:
the x axis (to point N) = *0.48 = 0.12 nm
the y axis (to point O) = 1*0.46 = 0.46 nm
The z axis (to point P) = *0.40 = 0.20 nm

POINT COORDINATES

POINT COORDINATES

CRYSTALLOGRAPHIC DIRECTIONS
Defined as a line between two points, or a
vector.
The steps utilized in the determination of
the three directional indices are:
1. A vector of convenient length is positioned
such that it passes through the origin of the
coordinate system.
Any vector may be translated throughout the
crystal lattice without alteration, if parallelism is
maintained.

CRYSTALLOGRAPHIC DIRECTIONS
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, without commas, are
enclosed in square brackets, thus: [uvw].
The u, v, and w integers correspond to the
reduced projections along the x, y, and z axes,
respectively.

CRYSTALLOGRAPHIC DIRECTIONS

CRYSTALLOGRAPHIC DIRECTIONS

CRYSTALLOGRAPHIC DIRECTIONS:

Hexagonal

A problem arises, some crystallographic

equivalent directions will not have the
same set of indices.
Circumvented by utilizing a four-axis, or
MillerBravais, coordinate system.
The three a1, a2 and a3 axes are all contained
within a single plane (called the basal plane)
and are at 120 angles to one another.
The z axis is perpendicular to this basal
plane.

CRYSTALLOGRAPHIC DIRECTIONS:

Hexagonal

Directional indices will be denoted by four

indices, as [uvtw];
by convention, the first three indices pertain to
projections along the respective a1, a2 and a3
axes in the basal plane.

CRYSTALLOGRAPHIC DIRECTIONS:

Hexagonal

CRYSTALLOGRAPHIC DIRECTIONS:

Hexagonal

CRYSTALLOGRAPHIC DIRECTIONS:

Hexagonal

CRYSTALLOGRAPHIC PLANES
The orientations of planes for a crystal
structure are represented in a similar manner.

The unit cell is the basis, with the threeaxis coordinate system.
Except 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.

CRYSTALLOGRAPHIC PLANES

The procedure to determine the h, k, l :

1. If the plane passes through the selected
origin,

either another parallel plane must be constructed

within the unit cell by an appropriate translation,
or a new origin must be established at the corner
of another unit cell.

CRYSTALLOGRAPHIC PLANES
2. At this point 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.
The reciprocals of a, b, c are taken as the index.
A plane that parallels an axis may be considered
to have an infinite intercept, and, therefore, a
zero index.

CRYSTALLOGRAPHIC PLANES
3. If necessary, these three numbers are
changed to the set of smallest integers by
multiplication or division by a common
factor.
4. Finally, the integer indices, not separated by
commas, are enclosed within parentheses,
thus: (hkl).

CRYSTALLOGRAPHIC PLANES
An intercept on the negative side of the
origin is indicated by a bar or minus sign
positioned over the appropriate index.
Reversing the directions of all indices
specifies another plane parallel to, on the
opposite side of and equidistant from, the
origin.

CRYSTALLOGRAPHIC PLANES
One interesting and unique characteristic
of cubic crystals is
that planes and directions having the same
indices are perpendicular to one another;

For other crystal systems there are no

simple geometrical relationships between
planes and directions having the same
indices.

Atomic Arrangements
The atomic arrangement for a crystallographic
plane, depends on the crystal structure.
The (110) atomic planes for FCC and BCC crystal
structures are represented in the next figures;
reduced-sphere unit cells are also included.
Note that the atomic packing is different for each
case.
The circles represent atoms lying in the
crystallographic planes as would be obtained from a
slice taken through the centers of the full-sized hard
spheres.

Atomic Arrangements
A family of planes contains all those
planes that are crystallographically
equivalentthat is, having the same
atomic packing; and a family is designated
by indices that are enclosed in braces
such as {100}.
For example, in cubic crystals the (111),
(111), (111 ), (111 ), (111 ), (111), (111 ), and
(111 ) planes all belong to the {111} family.

Atomic Arrangements
On the other hand, for tetragonal crystal
structures,
the {100} family would contain only the (100), (100),
(010), and (010)
the (001) and (001) planes are not crystallographically
equivalent.

Also, in the cubic system only, planes having the

same indices, irrespective of order and sign, are
equivalent. For example, both (123) and (312)
belong to the {123} family.

CRYSTALLOGRAPHIC PLANES
Hexagonal Crystals
The MillerBravais system of the fourindex (hkil) scheme is favored.
There is some redundancy in that i is
determined by the sum of h and k through
i = -(h + k)
Otherwise the three h, k, and l indices are
identical for both indexing systems.

CRYSTALLOGRAPHIC PLANES

LINEAR AND PLANAR DENSITIES

Linear density (LD) is defined as the
number of atoms per unit length whose
centers lie on the direction vector for a
specific crystallographic direction:

The units are reciprocal length nm-1, m-1

Linear Density
For example: determine the linear density of the
[110] direction for the FCC crystal structure.
An FCC unit cell (reduced sphere) and the [110]
direction therein are:

Linear Density
Represented in the figure (b) are those five
atoms that lie on the bottom face of this unit
cell; here the [110] direction vector passes
from the center of atom X, through atom Y,
and finally to the center of atom Z.
With regard to the numbers of atoms, it is
necessary to take into account the sharing of
atoms with adjacent unit cells (as discussed in
the atomic packing factor computations).

Linear Density

X
Y
Z

Linear Density
Each of the X and Z corner atoms are also shared
with one other adjacent unit cell along this [110]
direction (i.e., one-half of each of these atoms
belongs to the unit cell being considered), while
atom Y lies entirely within the unit cell.

Thus, there is an equivalence of two atoms

along the [110] direction vector in the unit cell.
The direction vector length is equal to 4R
(Figure b); thus the [110] linear density for
FCC is

Planar Density
Planar density (PD) is taken as the
number of atoms per unit area that are
centered on a particular crystallographic
plane, or

The units for planar density are nm-2, m-2.

Planar Density
For example, consider the section of a
(110) plane within an FCC unit cell.

Planar Density
Although six atoms have centers that lie on
this plane,
only one-quarter of each of atoms A, C,D, and F,
one-half of atoms B and E,
total equivalence of just 2 atoms are on that plane.

The area of this rectangular section is

the length (horizontal dimension) = 4R, the width
(vertical dimension) = 2R2.
Thus, the area of this planar region = 8R22

The planar density is determined as follows:

CLOSE-PACKED CRYSTAL
STRUCTURES
Face-centered cubic and hexagonal closepacked crystal structures have atomic packing
factors of 0.74,
the most efficient packing of equal-sized spheres or
atoms.

In addition to unit cell representations, these two

crystal structures may be described in terms of
close-packed planes of atoms (i.e., planes
having a maximum atom or sphere-packing
density);
a portion of one such plane is illustrated in Figure
3.13a.

CLOSE-PACKED CRYSTAL
STRUCTURES

CLOSE-PACKED CRYSTAL
STRUCTURES
Both crystal structures may be generated by the
stacking of these close-packed planes on top of
one another;
the difference between the two structures lies in the
stacking sequence.

Let the centers of all the atoms in one closepacked plane be labeled A.
Associated with this plane are two sets of equivalent
triangular depressions formed by three adjacent
atoms, into which the next close-packed plane of
atoms B may rest.
The remaining depressions are those with the down
vertices, which are marked C.

CLOSE-PACKED CRYSTAL
STRUCTURES
A second close-packed plane may be
positioned with the centers of its atoms
over either B or C sites; at this point both
are equivalent.
Suppose that the B positions are arbitrarily
chosen; the stacking sequence is termed AB.
The centers of the third plane are situated
over the C sites of the first plane, This yields
an ABCABCABC . . .

CLOSE-PACKED CRYSTAL
STRUCTURES

FCC STACKING SEQUENCE

ABCABC... Stacking Sequence
2D Projection
A
B
B
C
A
B
B
B
A sites
C
C
B sites
B
B
C sites

FCC Unit Cell

20

STRUCTURE OF COMPOUNDS: NaCl

Compounds: Often have similar close-packed structures.
Structure of NaCl
Close-packed directions
--along cube edges.

Click on image to animate

(Courtesy P.M. Anderson)

Click on image to animate

(Courtesy P.M. Anderson)

21

CLOSE-PACKED CRYSTAL
STRUCTURES
The real distinction between FCC and HCP lies
in the position of the third close-packed layer.
For HCP, the centers of this layer are aligned directly
above the original A positions.
This stacking sequence, ABABAB . . . , is repeated
over and over. (the ACACAC . . . is equivalent).
These close-packed planes for HCP are (0001)-type
planes.
The correspondence between this and the unit cell
representation is shown in following figure.

CLOSE-PACKED CRYSTAL
STRUCTURES

IONIC BONDING & STRUCTURE

Charge Neutrality:
--Net charge in the
structure should
be zero.

--General form:

Stable structures:
--maximize the # of nearest oppositely charged neighbors.
Adapted from Fig. 12.1,
Callister 6e.

15

COORDINATION # AND IONIC RADII

Coordination # increases with
Issue: How many anions can you
arrange around a cation?

Adapted from Fig. 12.4,

Callister 6e.

Adapted from Fig. 12.2, Callister

6e.

Adapted from Table 12.2,

Callister 6e.

Adapted from Fig. 12.3, Callister

6e.

16

EX: PREDICTING STRUCTURE OF FeO

On the basis of ionic radii, what crystal structure
would you predict for FeO?

Cation
Al3+
Fe 2+
Fe 3+
Ca 2+
Anion
O 2Cl F-

Answer:
r cation 0.077

r anion
0.140
0.550
based on this ratio,
--coord # = 6
--structure = NaCl

Data from Table 12.3,

Callister 6e.

17

AmXp STRUCTURES
Consider CaF2 :

r cation 0.100

0.8
r anion
0.133

Based on this ratio, coord # = 8 and structure = CsCl.

Result: CsCl structure w/only half the cation sites
occupied.
Only half the cation sites
are occupied since
#Ca2+ ions = 1/2 # F- ions.

Adapted from Fig. 12.5, Callister

6e.

18

DEMO: HEATING AND

COOLING OF AN IRON WIRE
Demonstrates "polymorphism"

The same atoms can

have more than one
crystal structure.

19

Solid Bodies
Solids exist in nature in two principal
forms:
Crystalline:
Single
Poly

non-crystalline (amorphous)

Their properties differ substantially.

Crystalline bodies
Remain solid up to a definite temperature
(melting point) at which they change from
the solid to liquid state.
During cooling, the inverse process of
solidification takes place, again at the
definite solidifying temperature, or point.
In both cases, the temperature remains
constant until the material is completely
melted or respectively solidified.

Crystalline bodies
Characterized by an ordered arrangement
of their ions, atoms or molecules.
The properties of crystals depend on
the electronic structure of atoms
the nature of their interactions in the crystal,
the spatial arrangement of their ions, atoms or
molecules,
the composition, size and shape of crystals.

Crystalline bodies
may be either in the form of
single crystal (grain) or
an aggregate of many crystals usually
known as polycrystalline separated by
well-defined grain boundaries.

Crystalline bodies
Polycrystalline material is stronger than
ordinary one
Tiny crystals (grains) have different
orientations with respect to each other and
grain boundaries obstruct the movement of
dislocations.

Polycrystalline material are called isotropic

exhibit same properties in every plane and
direction

Single crystal is called anisotropic.

Amorphous Bodies
Amorphous substances have no crystalline
structure in the condensed state
ordinary glass, sulphur, selenium, glycerin and most
of the high polymers can exist in the amorphous
state.

Amorphous bodies, when heated, are gradually

softened in a wide temperature range and
become viscous and only then change to the
liquid state.
In cooling, the process takes place in the
opposite direction.

SINGLE VS POLYCRYSTALS
Single Crystals
Data from Table 3.3,
Callister 6e.
(Source of data is R.W.
Hertzberg, Deformation
and Fracture Mechanics
of Engineering
Materials, 3rd ed., John
Wiley and Sons, 1989.)

-Properties vary with

direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:

Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)

-If grains are textured,

anisotropic.

200 mm

Adapted from Fig.

4.12(b), Callister 6e.
(Fig. 4.12(b) is courtesy
of L.C. Smith and C.
Brady, the National
Bureau of Standards,
Washington, DC [now
the National Institute of
Standards and
Technology,
Gaithersburg, MD].)

24

Amorphous Bodies
On repeated heating, long holding at 20-25C or,
in some cases, deformation of an amorphous
body, the instability of the amorphous state may
result in a partial or complete change to the
crystalline state.
Examples of such changes are the turbidity effect
appearing in inorganic glasses on heating or in optical
glasses after a long use, partial crystallization of
molten amber on heating, or additional crystallization
and strengthening of nylon fibers on tension.

MATERIALS AND PACKING

Crystalline materials...
atoms pack in periodic, 3D arrays
typical of: -metals
-many ceramics
-some polymers

crystalline SiO2
Adapted from Fig. 3.18(a),
Callister 6e.

Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline

noncrystalline SiO2
Adapted from Fig. 3.18(b),
Callister 6e.

26

GLASS STRUCTURE
Basic Unit:
4Si0 4 tetrahedron
Si 4+

O2-

Glass is amorphous
Amorphous structure
occurs by adding impurities
(Na+,Mg2+,Ca2+, Al3+)

Impurities:
interfere with formation of
crystalline structure.

Quartz is crystalline
SiO2:

(soda glass)
Adapted from Fig. 12.11,
Callister, 6e.

28

Single crystal
No matter how large, is a single grain.
Regular polyhedrons whose shape
depends upon their chemical composition.
Single crystals of metals of many cubic
centimeters in volume are relatively easy to
prepare in the laboratory.

Single crystal

CRYSTALS AS BUILDING BLOCKS

Some engineering applications require single crystals:
--diamond single
crystals for abrasives

--turbine blades

(Courtesy Martin Deakins,

GE Superabrasives,
Worthington, OH. Used with
permission.)

Fig. 8.30(c), Callister 6e.

(Fig. 8.30(c) courtesy
of Pratt and Whitney).

Crystal properties reveal features

of atomic structure.
--Ex: Certain crystal planes in quartz
fracture more easily than others.
(Courtesy P.M. Anderson)

22

Whiskers
Very thin filaments, hair-like single crystals
of about 13 mm length and perhaps 104
cm diameter.
Produced as dislocations of free crystals
and are without any structural defect.
Far stronger than polycrystals of same
material.

Whiskers
Used as reinforcements in materials to increase
strength by embedding fibers of one material in
a matrix of another.
The properties of fiber or whisker-reinforced
composites can often be tailored for a specific
application.

The increase in diameter of the whiskers

decreases its strength and increases its ductility.
The cost of whiskers and the expensive
fabrication is the major disadvantage of the
method.

Whiskers
Whiskers are the most defect-free crystalline
solids available today.
Whiskers can bear considerably high stresses
both at low and relatively elevated temperatures.
The best-known composite are probably, fiber
glass,
consists of glass-reinforcing fibers in a matrix of either
an epoxy polymer or polyester

Whiskers of SiC, Al2O3, S-Glass, graphite,

boron, iron, silver, copper and tin can be
produced by means of special techniques.

Whiskers
Whiskers of a wide variety of substances,
e.g., mercury, graphite, sodium and
potassium chlorides, copper, iron, and
aluminium oxide, have been grown from
super saturated media.
Whiskers grown in this way are usually a few
micrometers in diameter and up to a few
inches long.
Some are exceptionally strong, both in bend
tests and in tension tests.

Whiskers
In addition to exceptional strength,
whiskers often have unique electrical,
magnetic, or surface properties.
This behavior can be interpreted to mean that
the crystal structure of whiskers is virtually
perfect, particularly with respect to line
defects.
Actually it appears that some whiskers contain line
defects whereas others do not. However, no
general correlation between whisker properties
and whisker structure have been established.

Polycrystalline
Most crystalline solids
made up of millions of grains
each grain constitutes microstructure
commonly said as polycrystalline.

Grain
a tiny single crystals
oriented randomly with respect to each other

POLYCRYSTALS
Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 6e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)

1 mm
Nb-Hf-W plate with an electron beam weld.
Each "grain" is a single crystal.
If crystals are randomly oriented,
overall component properties are not directional.

Crystal sizes typ. range from 1 nm to 2 cm

(i.e., from a few to millions of atomic layers).

23

POLYMORPHISM AND ALLOTROPY

Some metals, as well as nonmetals, may
have more than one crystal structure, a
phenomenon known as polymorphism.
When found in elemental solids, the
condition is often termed allotropy.
The prevailing crystal structure depends
on both the temperature and the external
pressure.

POLYMORPHISM AND ALLOTROPY

One familiar example is found in carbon:
graphite is the stable polymorph at ambient
conditions,
diamond is formed at extremely high pressures.

Pure iron has a

BCC crystal structure at room temperature,
changes to FCC iron at 912C.

Most often a modification of the density and

other physical properties accompanies a
polymorphic transformation.

DENSITY COMPUTATIONS

DENSITY COMPUTATIONS

Characteristics of Selected Elements at 20C

Element
Aluminum
Argon
Barium
Beryllium
Boron
Bromine
Cadmium
Calcium
Carbon
Cesium
Chlorine
Chromium
Cobalt
Copper
Flourine
Gallium
Germanium
Gold
Helium
Hydrogen

Symbol
Al
Ar
Ba
Be
B
Br
Cd
Ca
C
Cs
Cl
Cr
Co
Cu
F
Ga
Ge
Au
He
H

At. Weight
(amu)
26.98
39.95
137.33
9.012
10.81
79.90
112.41
40.08
12.011
132.91
35.45
52.00
58.93
63.55
19.00
69.72
72.59
196.97
4.003
1.008

Density
(g/cm 3 )
2.71
-----3.5
1.85
2.34
-----8.65
1.55
2.25
1.87
-----7.19
8.9
8.94
-----5.90
5.32
19.32
-----------

Atomic radius
(nm)
0.143
-----0.217
0.114
Adapted from
-----Table, "Charac-----teristics of
0.149 Selected
0.197 Elements",
inside front
0.071 cover,
0.265 Callister 6e.
-----0.125
0.125
0.128
-----0.122
0.122
0.144
----------12

DENSITIES OF MATERIAL CLASSES

metals ceramic

s polymer s

Why?
Metals have...
close-packing
(metallic bonding)
large atomic mass

Ceramics have...
less dense packing
(covalent bonding)
often lighter elements

Polymers have...
poor packing
(often amorphous)
lighter elements (C,H,O)

Composites have...
intermediate values

Data from Table B1, Callister 6e.

13

X-RAYS TO CONFIRM CRYSTAL STRUCTURE

Incoming X-rays diffract from crystal planes.

Adapted from Fig. 3.2W,

Callister 6e.

Measurement of:
Critical angles, qc,
for X-rays provide
atomic spacing, d.

25

XRD pattern

SUMMARY
Atoms may assemble into crystalline or
amorphous structures.
We can predict the density of a material,
provided we know the atomic weight, atomic
radius, and crystal geometry (e.g., FCC,
BCC, HCP).
Material properties generally vary with single
crystal orientation (i.e., they are anisotropic),
but properties are generally non-directional
(i.e., they are isotropic) in polycrystals with
randomly oriented grains.
27

 Part 2: Material Properties

Mechanical Properties
Thermal Properties
Electrical and Magnetic Properties
Superconductivity

 Part 3: Material Engineering

Alloy Systems
Phase Diagrams and Phase Transformations
Heat Treatment
Deformation of Materials
Corrosion
Organic Materials:
Polymers and Elastomers
Wood
Composites

Nano structured Materials