MATERIAL SCIENCE SUMMARY NOTES.

A crystalline material is one in which the atoms are situated in a

repeating or periodic array over large atomic distances—that is, long-
range order exists, such that upon solidification, the atoms will
position themselves

CRYSTAL STRUCTURE: Is the manner in which atoms, ions, or

molecules are spatially arranged in a crystal

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. One familiar example is found

in carbon:

graphite is the stable polymorph at ambient conditions, whereas

diamond is formed

at extremely high pressures. Also, pure iron has a BCC crystal

structure at room

temperature, which changes to FCC iron at 912°C (1674°F). Most often

a modification

of the density and other physical properties accompanies a

polymorphic transformation.

CRYSTAL SYSTEM

The unit cell geometry is completely defined in terms of six

parameters: the three edge

lengths a, b, and c, and the three interaxial angles 𝛼, 𝛽, and 𝛾. These

are indicated in
Figure 3.5, and are sometimes termed the lattice parameters of a
crystal structure.

One such scheme is based on the unit cell geometry, that is, the
shapeof the appropriate unit cell parallelepiped without regard to the
atomic positions in

the cell. Within this framework, an x-y-z coordinate system is

established with its origin

at one of the unit cell corners; each of the x, y, and z axes coincides
with one of the

three parallelepiped edges that extend from this corner

These seven crystal systems: are cubic,tetragonal, hexagonal,

orthorhombic, rhombohedral,2 monoclinic, and triclinic. axial lengths
(a, b, and c) and interaxial angles

Crystallographic Points,

Directions, and Planes

When dealing with crystalline materials, it often becomes necessary to

specify a particular

point within a unit cell, a crystallographic direction, or some

crystallographic plane

of atoms. For some crystal systems—namely, hexagonal,

rhombohedral,

monoclinic, and triclinic—the three axes are not mutually

perpendicular, as in the familiar

Cartesian coordinate scheme.

Crystallographic directions

A crystallographic direction is defined as a line directed between two

points, or a vector
The following steps are used to determine the three directional
indices:
1. A right-handed x-y-z coordinate system is first constructed. As a
matter of convenience,
its origin may be located at a unit cell corner.
2. The coordinates of two points that lie on the direction vector
(referenced to
the coordinate system) are determined—for example, for the vector
tail, point
1: x1, y1, and z1; whereas for the vector head, point 2: x2, y2, and z2.5
3. Tail point coordinates are subtracted from head point components—
that is,
x2 − x1, y2 − y1, and z2 − z1.
4. These coordinate differences are then normalized in terms of (i.e.,
divided by)
their respective a, b, and c lattice parameters—that is,
x2 − x1
a
y2 − y1
b
z2 − z1
c
which yields a set of three numbers.
5. If necessary, these three numbers are multiplied or divided by a
common factor
to reduce them to the smallest integer values.
6. The three resulting indices, not separated by commas, are enclosed
in square
brackets, thus: [uvw]. The u, v, and w integers correspond to the
normalized
coordinate differences referenced to the x, y, and z axes, respectively.
In summary, the u, v, and w indices may be determined using the
following equations:
u = n(
x2 − x1
a ) (3.10a)
v = n(
y2 − y1
b ) (3.10b)
w = n(
z2 − z1
c ) (3.10c)
In these expressions, n is the factor that may be required to reduce u,
v, and w to integers.
For each of the three axes, there are both positive and negative
coordinates. Thus,
negative indices are also possible, which are represented by a bar
over the appropriate
index. For example, the [111] direction has a component in the −y
direction. Also,
changing the signs of all indices produces an antiparallel direction;
that is, [111] is
directly opposite to [111]. If more than one direction (or plane) is to be
specified for a
particular crystal structure, it is imperative for maintaining
consistency that a positive–
negative convention, once established, not be changed.
The [100], [110], and [111] directions are common ones; they are
drawn in the unit
cell shown

Atomic Arrangements
The atomic arrangement for a crystallographic plane, which is often of
interest, depends
on the crystal structure

A “family” of planes contains all planes that are crystallographically

equivalent—
that is, having the same atomic packing; a family is designated by
indices enclosed in
braces—such as {100}. For example, in cubic crystals, the (111), (1 1
1), (111), (1 1 1), (111),
(1 11), (111), and (111) planes all belong to the {111} family. However,
for tetragonal
crystal structures, the {100} family contains only the (100), (100),
(010), and (010)
planes because 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. Hexagonal Crystals
For crystals having hexagonal symmetry, it is desirable that equivalent
planes have
the same indices; as with directions, this is accomplished by the
Miller–Bravais system
shown in Figure 3.8a. This convention leads to the four-index (hkil)
scheme, which is
favored in most instances because it more clearly identifies the
orientation of a plane
in a hexagonal crystal. There is some redundancy in that i is
determined by the sum of
h and k through
i = −(h + k) (3.14)
Otherwise, the three h, k, and l indices are identical for both indexing
systems.
We determine these indices in a manner analogous to that used for
other crystal systems
as described previously—that is, taking normalized reciprocals of axial
intercepts,
as described in the following example problem.
Figure 3.13 presents several of the common planes that are found for
crystals having
hexagonal symmetry.
A′
B′
C′
E′
D′
(a)

LINEAR AND PLANAR DENSITIES

Directional equivalency is related to linear density in the sense
that, for a particular material, equivalent directions have identical
linear densities. The
corresponding parameter for crystallographic planes is planar density,
and planes having
the same planar density values are also equivalent.

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

In an analogous manner, planar density (PD) is taken as the number of

atoms per
unit area that are centered on a particular crystallographic plane, or

CLOSE-PACKED CRYSTAL STRUCTURES

You may remember from the discussion on metallic crystal structures

(Section 3.4) that
both face-centered cubic and hexagonal close-packed crystal
structures have atomic
packing factors of 0.74, which is the most efficient packing of equal-
size 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). 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.

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 may rest.
Those having the
triangle vertex pointing up are arbitrarily designated as B positions,
whereas the remaining
depressions are those with the down vertices, which are marked C in
Figure 3.15a

crystallographic planes and directions in terms of directional and

Miller indices; furthermore,
on occasion it is important to ascertain the atomic and ionic
arrangements of particular
crystallographic planes. Also, the crystal structures of a number of
ceramic materials
may be generated by the stacking of close-packed planes of ions

Crystalline and Noncrystalline Materials

SINGLE CRYSTAL

For a crystalline solid, when the periodic and repeated arrangement of

atoms is perfect
or extends throughout the entirety of the specimen without
interruption, the result is
a single crystal. All unit cells interlock in the same way and have the
same orientation.
Single crystals exist in nature, but they can also be produced
artificially. They are ordinarily
difficult to grow because the environment must be carefully controlled.
If the extremities of a single crystal are permitted to grow without any
external
constraint, the crystal assumes a regular geometric shape having flat
faces, as with some
of the gemstones; the shape is indicative of the crystal structure.

POLYCRYSTALLINE MATERIALS

Most crystalline solids are composed of a collection of many small

crystals or grains;
such materials are termed polycrystalline.
crystals or nuclei form at various positions. These have random
crystallographic
orientations, as indicated by the square grids. The small grains grow
by the successive
addition from the surrounding liquid of atoms to the structure of each.
The
extremities of adjacent grains impinge on one another as the
solidification process
approaches completion. As indicated in Figure 3.19, the
crystallographic orientation
varies from grain to grain. Also, there exists some atomic mismatch
within the region
where two grains meet; this area, called a grain boundary,

ANISOTROPY

This directionality of properties is termed anisotropy, and it

is associated with the variance of atomic or ionic spacing with
crystallographic direction.

Substances in which measured properties are independent of the

direction of measurement
are isotropic. The extent and magnitude of anisotropic effects in
crystalline materials
are functions of the symmetry of the crystal structure; the degree of
anisotropy
increases with decreasing structural symmetry—triclinic structures
normally are highly
anisotropic. The modulus of elasticity values at [100], [110], and [111]
orientations for
several metals

X-RAY DIFFRACTION: DETERMINATION

OF CRYSTAL STRUCTURES

The Diffraction Phenomenon

Diffraction occurs when a wave encounters a series of regularly
spaced obstacles that
(1) are capable of scattering the wave, and (2) have spacings that are
comparable in
magnitude to the wavelength. Furthermore, diffraction is a
consequence of specific
phase relationships established between two or more waves that have
been scattered
by the obstacles.

X-Ray Diffraction and Bragg’s Law

X-rays are a form of electromagnetic radiation that have high energies
and short
wavelengths—wavelengths on the order of the atomic spacings for
solids. When a beam
of x-rays impinges on a solid material, a portion of this beam is
scattered in all directions
by the electrons associated with each atom or ion that lies within the
beam’s path.
Let us now examine the necessary conditions for diffraction of x-rays
by a periodic
arrangement of atoms.
Consider the two parallel planes of atoms A–A_ and B–B_ in Figure
3.22, which
have the same h, k, and l Miller indices and are separated by the
interplanar spacing dhkl.
Now assume that a parallel, monochromatic, and coherent (in-phase)
beam of x-rays
of wavelength l is incident on these two planes at an angle u. Two rays
in this beam,
labeled 1 and 2, are scattered by atoms P and Q. Constructive
interference of the scattered
rays 1_ and 2_ occurs also at an angle u to the planes if the path length
difference
between 1–P–1_ and 2–Q–2_ (i.e., SQ + QT) is equal to a whole number,
n, of wavelengths—
that is, the condition for diffraction is
nl = SQ + QT

in such a way that they traverse different paths. The phase

relationship between the
scattered waves, which depends upon the difference in path length, is
important.
One possibility results when this path length difference is an integral
number of
wavelengths. As noted in Figure 3.21a, these scattered waves (now
labeled 1_ and 2_)
are still in phase. They are said to mutually reinforce (or constructively
interfere
with) one another; when amplitudes are added, the wave shown on the
right side of
the figure results. This is a manifestation of diffraction, and we refer to
a diffracted
beam as one composed of a large number of scattered waves that
mutually reinforce
one another.
Other phase relationships are possible between scattered waves that
will not
lead to this mutual reinforcement. The other extreme is that
demonstrated in
Figure 3.21b, in which the path length difference after scattering is
some integral
number of half-wavelengths. The scattered waves are out of phase—
that is, corresponding
amplitudes cancel or annul one another, or destructively interfere (i.e.,
the
resultant wave has zero amplitude), as indicated on the right side of
the figure. Of
course, phase relationships intermediate between these two extremes
exist, resulting
in only partial reinforcement.

NONCRYSTALLINE SOLIDS

It has been mentioned that noncrystalline solids lack a systematic and

regular arrangement
of atoms over relatively large atomic distances. Sometimes such
materials are also
called amorphous (meaning literally “without form”), or supercooled
liquids, inasmuch
as their atomic structure resembles that of a liquid.
An amorphous condition may be illustrated by comparison of the
crystalline and
noncrystalline structures of the ceramic compound silicon dioxide
(SiO2), which may exist
in both states. Figures 3.25a and 3.25b present two-dimensional
schematic diagrams
for both structures of SiO2. Even though each silicon ion bonds to
three oxygen ions
for both states, beyond this, the structure is much more disordered
and irregular for the
noncrystalline structure.
Whether a crystalline or an amorphous solid forms depends on the
ease with which
a random atomic structure in the liquid can transform to an ordered
state during solidification.
Amorphous materials, therefore, are characterized by atomic or
molecular
structures that are relatively complex and become ordered only with
some difficulty. Furthermore, rapidly cooling through the freezing
temperature favors the formation of
a noncrystalline solid, because little time is allowed for the ordering
process.
Metals normally form crystalline solids, but some ceramic materials
are crystalline,
whereas others—the inorganic glasses—are amorphous. Polymers may
be completely
noncrystalline or semicrystalline consisting of varying degrees of
crystallinity. More
about the structure and properties of amorphous ceramics and
polymers is contained in

HISTORY OF MATERIAL SCIENCE

fact, early civilizations have been designated by the level of their

materials
development (Stone Age, Bronze Age, Iron Age).1
The earliest humans had access to only a very limited number of
materials, those that
occur naturally: stone, wood, clay, skins, and so on. With time, they
discovered techniques
for producing materials that had properties superior to those of the
natural ones; these
new materials included pottery and various metals. Furthermore, it
was discovered that the
properties of a material could be altered by heat treatments and by the
addition of other
substances. At this point, materials utilization was totally a selection
process that involved
deciding from a given, rather limited set of materials, the one best
suited for an application
by virtue of its characteristics. It was not until relatively recent times
that scientists came to
understand the relationships between the structural elements of
materials and their properties.
This knowledge, acquired over approximately the past 100 years, has
empowered them
to fashion, to a large degree, the characteristics of materials. Thus,
tens of thousands of different
materials have evolved with rather specialized characteristics that
meet the needs of
our modern and complex society, including metals, plastics, glasses,
and fibers.
The development of many technologies that make our existence so
comfortable
has been intimately associated with the accessibility of suitable
materials. An advancement
in the understanding of a material type is often the forerunner to the
stepwise
progression of a technology. For example, automobiles would not have
been possible
without the availability of inexpensive steel or some other comparable
substitute. In the
contemporary era, sophisticated electronic devices rely on
components that are made
from what are called semiconducting materials.

MATERIAL SCIENCE AND ENGINEERING

We present an example of these processing-structure-properties-

performance principles
in Figure 1.2, a photograph showing three thin disk specimens placed
over some
printed matter. It is obvious that the optical properties (i.e., the light
transmittance) of each
of the three materials are different; the one on the left is transparent
(i.e., virtually all of the

Metals
Metals are composed of one or more metallic elements (e.g., iron,
aluminum, copper,
titanium, gold, nickel), and often also nonmetallic elements (e.g.,
carbon, nitrogen,
oxygen) in relatively small amounts.8 Atoms in metals and their alloys
are arranged in a
very orderly manner (as discussed in Chapter 3) and are relatively
dense in comparison
to the ceramics and polymers (Figure 1.4). With regard to mechanical
characteristics,
these materials are relatively stiff (Figure 1.5) and strong (Figure 1.6),
yet are ductile
(i.e., capable of large amounts of deformation without fracture), and
are resistant to
fracture (Figure 1.7), which accounts for their widespread use in
structural applications.
Metallic materials have large numbers of nonlocalized electrons—that
is, these electrons
are not bound to particular atoms. Many properties of metals are
directly attributable
to these electrons. For example, metals are extremely good
conductors of electricity

Ceramics
Ceramics are compounds between metallic and nonmetallic elements;
they are most frequently
oxides, nitrides, and carbides. For example, common ceramic
materials include
aluminum oxide (or alumina, Al2O3), silicon dioxide (or silica, SiO2),
silicon carbide (SiC),
silicon nitride (Si3N4), and, in addition, what some refer to as the
traditional ceramics—those
composed of clay minerals (e.g., porcelain), as well as cement and
glass. With regard to mechanical
behavior, ceramic materials are relatively stiff and strong—stiffnesses
and strengths
are comparable to those of the metals (Figures 1.5 and 1.6). In
addition, they are typically
very hard. Historically, ceramics have exhibited extreme brittleness
(lack of ductility) and are
highly susceptible to fracture (Figure 1.7). However, newer ceramics
are being engineered
to have improved resistance to fracture; these materials are used for
cookware, cutlery, and even automobile engine parts. Furthermore,
ceramic materials are typically insulative to the
passage of heat and electricity (i.e., have low electrical conductivities,
Figure 1.8) and are
more resistant to high temperatures and harsh environments than are
metals and polymers.
With regard to optical characteristics, ceramics may be transparent,
translucent, or opaque
(Figure 1.2), and some of the oxide ceramics (e.g., Fe3O4) exhibit
magnetic behavior.

Polymers
Polymers include the familiar plastic and rubber materials. Many of
them are organic
compounds that are chemically based on carbon, hydrogen, and other
nonmetallic elements
(i.e., O, N, and Si). Furthermore, they have very large molecular
structures, often
chainlike in nature, that often have a backbone of carbon atoms. Some
common and
familiar polymers are polyethylene (PE), nylon, poly(vinyl chloride)
(PVC), polycarbonate
(PC), polystyrene (PS), and silicone rubber. These materials typically
have low
densities (Figure 1.4), whereas their mechanical characteristics are
generally dissimilar
to those of the metallic and ceramic materials—they are not as stiff or
strong as these
Composites
A composite is composed of two (or more) individual materials that
come from the
categories previously discussed—metals, ceramics, and polymers. The
design goal of a
composite is to achieve a combination of properties that is not
displayed by any single
material and also to incorporate the best characteristics of each of the
component materials.
A large number of composite types are represented by different
combinations
of metals, ceramics, and polymers. Furthermore, some naturally
occurring materials are
composites—for example, wood and bone. However, most of those we
consider in our
discussions are synthetic (or human-made) composites.
One of the most common and familiar composites is fiberglass, in
which small glass
fibers are embedded within a polymeric material (normally an epoxy or
polyester).9 The
glass fibers are relatively strong and stiff (but also brittle), whereas
the polymer is more
flexible. Thus, fiberglass is relatively stiff, strong (Figures 1.5 and 1.6),
and flexible. In
addition, it has a low density (Figure 1.4).
Another technologically important material is the carbon fiber–
reinforced polymer
(CFRP) composite—carbon fibers that are embedded within a polymer.
These materials
are stiffer and stronger than glass fiber–reinforced materials (Figures
1.5 and 1.6) but
more expensive. CFRP composites are used in some aircraft and
aerospace applications,
as well as in high-tech sporting equipment (e.g., bicycles, golf clubs,
tennis rackets, skis/
snowboards) and recently in automobile bumpers. The new Boeing 787
fuselage is primarily
made from such CFRP composites.
Chapter 16 is devoted to a discussion of these interesting composite
materials
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