1.

3 Structure of Materials
Atomic Arrangements: (Short-Range
The applications shown below, and Order - 1 to 10 Å ). Ions in silica (SiO2)
the accompanying figures (Figures 1.1 glass exhibit only a short-range order in
through 1.6) illustrate how important the which Si+4 and O2- ions are arranged in a
different levels of structure are to particular way (each Si+4 is bonded with 4
materials behavior. The applications O2- ions in a tetrahedral coordination, with
illustrated are broken out by their levels each O2- ion being shared by two
of structure and their length scales (the tetrahedra). This order, however, is not
approximate characteristic length that is maintained over long distances, thus
important for a given application). making silica glass amorphous.
Amorphous glasses based on silica and
certain other oxides form the basis for the
Levels of Structure: entire fiber-optic communications
Atomic Structure - (~ 10-10 m or 1 Å ) - industry.
Example is Diamond. Diamond is based
on carbon-carbon (C- C) covalent bonds.
Materials with this type of bonding are
expected to be relatively hard. Thin films
of diamond are used for providing a wear-
resistant edge in cutting tools.
Figure 1.3 Optical fibers based on a form
of silica that is amorphous.

Nanostructure: (10-9to 10-7m) - Nano-

sized particles (~5–10 nm) of iron oxide
are used in ferrofluids or liquid magnets.
An application of these liquid magnets is
Figure 1.1 Diamond-coated cutting tools
as a cooling (heat transfer) medium for 1
to 100 nm) loudspeakers.
Atomic Arrangements: (Long-Range
Order -10 nm to cm). Lead-zirconium-
titanate [Pb (ZrxTi1x) O3] or PZT is an
example. When ions in this material are
arranged such that, they exhibit
tetragonal and/or rhombohedral crystal
structures, the material is piezoelectric
(i.e., it develops a voltage when subjected
to pressure or stress). PZT ceramics are Figure 1.4 - Ferrofluid
used widely for many applications
including gas igniters, ultrasound
Microstructure: (~10-7 to 10-4 m). The
generation, and vibration control.
mechanical strength of many metals and
alloys depends very strongly on the grain
size. The grains and grain boundaries in
this accompanying micrograph of steel
are part of the microstructural features of
this crystalline material. In general, at
room temperature, a finer grain size leads
to higher strength. Many important
Figure 1.2 - Piezoelectric PZT-based gas properties of materials are sensitive to
igniters. When the piezoelectric material the microstructure.
is stressed (by applying a pressure), a
voltage develops, and a spark is created
between the electrodes.
 grams of the Avogadro constant NA of
atoms. The quantity NA = 6.022 X
1023 atoms/ mol is the number of atoms or
molecules in a mole. Therefore, the
atomic mass has units of g/mol. An
alternative unit for atomic mass is
Figure 1.5 Micrograph of stainless-steel the atomic mass unit, or amu, which is
showing grains and grain boundaries 1/12 the mass of carbon 12 (i.e., the
carbon atom with twelve nucleons—six
protons and six neutrons).
Macrostructure: (~>10-4m, ~
>100,000 nm or 100 um). Relatively thick As an example, one mole of iron contains
coatings, such as paints on automobiles 6.022 X 10 23 atoms and has a mass of
and other applications, are used not only 55.847 g, or 55.847 amu. Calculations
for aesthetics, but to provide corrosion including a material’s atomic mass and
resistance. the Avogadro constant are helpful to
understanding more about the structure
of a material.

Example 1: Calculating the Number of

Atoms in Silver
Calculate the number of atoms in 100 g of
Figure 1.6 Several organic and inorganic silver (Ag).
coatings protect the car from corrosion
and provide a pleasing appearance. SOLUTION
The number of atoms can be calculated
from the atomic mass and the Avogadro
1.4 Structure of an Atom constant. From the Periodic Table of
elements, click here, the atomic mass, or
An atom is composed of a nucleus weight, of silver is 107.868 g mol.
surrounded by electrons. The nucleus
contains neutrons and positively charged The number of atoms is
protons and carries a net positive charge.
Number of Ag atoms =
The negatively charged electrons are held
to the nucleus by an electrostatic (100 g) (6.022 x 1023 atoms/mol
attraction. The electrical charge q carried
107.868 g/mol
by each electron and proton is 1.60 X 10 -19
coulomb (C). Image of an atom, click here = 5.58 X 1023 Ag atoms
The atomic number of an element
is equal to the number of protons in each
Example 2: Iron-Platinum
atom. Thus, an iron atom, which contains
Nanoparticles for Information Storage
26 protons, has an atomic number of 26.
The atom is electrically neutral because Scientists are considering using
the number of protons and electrons are nanoparticles of such magnetic materials
equal. as iron-platinum (Fe-Pt) as a medium for
ultra-high density data storage. Arrays of
Most of the mass of the atom is
such particles potentially can lead to
contained within the nucleus. The mass of
storage of trillions of bits of data per
each proton and neutron is 1.67 X 10-24 g,
square inch—a capacity that will be 10 to
but the mass of each electron is only 9.11
100 times higher than any other devices
X 10-28 g.
such as computer hard disks. If these
The atomic mass M, which is equal scientists considered iron (Fe) particles
to the total mass of the average number of are 3 nm in diameter, what will be the
protons and neutrons in the atom in number of atoms in one such particle?
atomic mass units, is also the mass in
SOLUTION
 You will learn in a later chapter on quantum number l, the magnetic
magnetic materials that such particles quantum number ml, and the spin
used in recording media tend to be quantum number ms
acicular (needle like). For now, let us
assume the magnetic particles are
spherical in shape. The principal quantum number reflects
GIVEN the grouping of electrons into sets of
energy levels known as shells. Azimuthal
The radius of a particle is 1.5 nm.
quantum numbers describe the energy
Volume of each iron magnetic levels within each shell and reflect a
nanoparticle = further grouping of similar energy levels,
usually called orbitals. The magnetic
(4/3) Π (1.5x107 cm)3 = 1.4137 X 10-20 cm3
quantum number specifies the orbitals
Density of iron = 7.8 g/cm3 associated with a particular azimuthal
Atomic mass of iron = 55.847 g /mol. quantum number within each shell.
Finally, the spin quantum number (ms) is
Mass of each iron nanoparticle = assigned values of +1/ 2 and -1/ 2, which
7.8 g/cm3 x 1.4137 X 10-20 cm3 reflect the two possible values of “spin” of
an electron.
= 1.1027 X 10-19 g
According to the Pauli Exclusion
ANSWER
Principle, within each atom, no two
One mole or 55.847 g of Fe contains 6.022 electrons may have the same four
x 1023 atoms, therefore, the number of quantum numbers, and thus, each
atoms in one Fe nanoparticle will be electron is designated by a unique set of
1189. four quantum numbers. The number of
possible energy levels is determined by
1.5 The Electronic Structure of
the first three quantum numbers.
the Atom
The principal quantum number n is
Electrons occupy discrete energy assigned integer values 1, 2, 3, 4, 5, . . .
levels within the atom. Each electron that refer to the quantum shell to which
possesses a particular energy with no the electron belongs. A quantum shell is a
more than two electrons in each atom set of fixed energy levels to which
having the same energy. This also implies electrons belong. Quantum shells are also
that there is a discrete energy difference assigned a letter; the shell for n =1 is
between any two energy levels. Since designated K, for n = 2 is L, for n = 3 is M,
each element possesses a different set of and so on. These designations were
these energy levels, the differences carried over from the nomenclature used
between them also are unique. Both the in optical spectroscopy, a set of
energy levels and the differences between techniques that predates the
them are known with great precision for understanding of quantized electronic
every element, forming the basis for many levels.
types of spectroscopies. Using a
spectroscopic method, the identity of The number of energy levels in each
elements in a sample may be determined. quantum shell is determined by the
azimuthal quantum number l and the
magnetic quantum number ml. The
Quantum Numbers. azimuthal quantum numbers are assigned
l = 0, 1, 2, . . ., n - 1. For example, when n =
The energy level to which each 2, there are two azimuthal quantum
electron belongs is identified by four numbers, l = 0 and l = 1. When n = 3, there
quantum numbers. The four quantum are three azimuthal quantum numbers, l =
numbers are the principal quantum 0, l = 1, and l = 2. The azimuthal quantum
number n, the azimuthal or secondary
numbers are designated by lowercase
letters; one speaks, for instance, of the d
orbitals: 1.5.1 Deviations from
s for l = 0 d for l = 2
Expected Electronic
Structures
p for l = 1 f for l = 3
The energy levels of the quantum shells
do not fill in strict numerical order. The
The number of values for the magnetic Aufbau Principle is a graphical device that
quantum number ml gives the number of predicts deviations from the expected
energy levels, or orbitals, for each ordering of the energy levels. To use the
azimuthal quantum number. The total Aufbau Principle, write the possible
number of magnetic quantum numbers combinations of the principal quantum
for each l is 2l + 1. The values for ml are number and azimuthal quantum number
given by whole numbers between -l and for each quantum shell. The combinations
+l. For example, if l = 2, there are 2(2) + 1 for each quantum shell should be written
= 5 magnetic quantum numbers with on a single line. As the principal quantum
values -2, -1, 0, +1, and +2. The number increases by one, the number of
combination of l and ml specifies a combinations within each shell increases
particular orbital in a shell. by one (i.e., each row is one entry longer
than the prior row). Draw arrows through
No more than two electrons with
the rows on a diagonal from the upper
opposing electronic spins (ms = +1/2 and
right to the lower left as shown in Figure
- 1/2) may be present in each orbital.
1.7.
By carefully considering the
Figure 1.7 The Aufbau Principle. By
possible numerical values for n, l, and ml,
following the arrows, the order in which
the range of possible quantum numbers
the energy levels of each quantum level
may be determined. For instance, in the K
are filled is predicted: 1s, 2s, 2p, 3s, 3p,
shell (that is, n = 1), there is just a single s
etc.
orbital (as the only allowable value of l is
0 and ml is 0 ). As a result, a K shell may For example, according to the Aufbau
contain no more than two electrons. As Principle, the electronic structure of iron,
another example, consider an M shell. In atomic number 26, is
this case, n = 3, so l takes values of 0, 1,
1s2 2s2 2p6 3s2 3p6 4s2 3d6
and 2, (there are s, p, and d orbitals
present). The values of ml reflect that Conventionally, the principal quantum
there is a single s orbital (ml = 0, a single numbers are arranged from lowest to
value), three p orbitals (ml = -1, 0, +1, or highest when writing the electronic
three values), and five d orbitals (ml = - 2, structure. Thus, the electronic structure
-1, 0, +1, +2, or five discrete values). of iron is written
1s2 2s2 2p6 3s2 3p6 3d6 4s2

The shorthand notation frequently The unfilled 3d level (there are five d
used to denote the electronic structure of orbitals, so in shorthand d1, d2, . . ., d10
an atom combines the numerical value of are possible) causes the magnetic
the principal quantum number, the behavior of iron.
lowercase letter notation for the
azimuthal quantum number, and a
superscript showing the number of Note that not all elements follow the
electrons in each type of orbital. The Aufbau principle. A few, such as copper,
shorthand notation for neon, which has are exceptions. According to the Aufbau
an atomic number of ten, is 1s2 2s2 Principle, copper should have the
2p6 electronic structure 1s2 2s2 2p6 3s2 3p6
3d9 4s2, but copper has the electronic
structure
1s2 2s2 2p6 3s2 3p6 3d10 4s1
Generally, electrons will occupy
each orbital of a given energy level singly
before the orbitals are doubly occupied.
For example, nitrogen has the electronic
structure 1s2 2s2 2p3
Each of the three p orbitals in the L shell
contains one electron rather than one Figure 1.8 - Electronegativity values for
orbital containing two electrons, one some elements with low
containing one electron, and one electronegativity (i.e., < 2.0) are
containing zero electrons. sometimes described as electropositive.

1.5.2 Valence electrons

1.6 The Classification of
The valence of an atom is the number
of electrons in an atom that participate in Engineering Materials using
bonding or chemical reactions. Usually, the Periodic Table
the valence is the number of electrons in
The periodic table contains valuable
the outer s and p energy levels. The
information about specific elements and
valence of an atom is related to the ability
can also help identify trends in atomic
of the atom to enter into chemical
size, melting point, chemical reactivity,
combination with other elements.
and other properties. The periodic table is
Examples of the valence are
constructed in accordance with the
Mg: 1s2 2s2 2p6 3s2 valence = 2 electronic structure of the elements.
Al: 1s2 2s2 2p6 3s2 3p1 valence = 3 Not all elements in the periodic table are
naturally occurring. Rows in the periodic
Si: 1s2 2s2 2p6 3s2 3p2 valence = 4
table correspond to quantum shells, or
principal quantum numbers. Columns
Electronegativity describes the typically refer to the number of electrons
tendency of an atom to gain an electron. in the outermost s and p energy levels
Atoms with almost completely-filled and correspond to the most common
outer energy levels—such as chlorine— valence. In engineering, we are mostly
are strongly electronegative and readily concerned with metals and alloys,
accept electrons. Atoms with nearly ceramics, polymers (plastics),
empty outer levels—such as sodium— semiconductors, and composite materials.
readily give up electrons and have low
electronegativity. High atomic number
Metals and Alloys. Metals and alloys
elements also have low electronegativity
include steels, aluminum, magnesium,
because the outer electrons are at a
zinc, cast iron, titanium, copper, and
greater distance from the positive
nickel. An alloy is a metal that contains
nucleus, so that they are not as strongly
additions of one or more metals or non-
attracted to the atom.
metals. In general, metals have good
electrical and thermal conductivity.
Metals and alloys have relatively high
strength, high stiffness, ductility or
formability, and shock resistance. They
are particularly useful for structural or
load-bearing applications. Although pure electrical and thermal insulators although
metals are occasionally used, alloys there are exceptions such as the
provide improvement in a particular semiconducting polymers. Although they
desirable property or permit better have lower strength, polymers have a
combinations of properties. very good strength-to-weight ratio. They
are typically not suitable for use at high
temperatures. Many polymers have very
Ceramics. Ceramics can be defined as good resistance to corrosive chemicals.
inorganic crystalline materials typically Polymers have thousands of applications
based on combinations of many elements ranging from bulletproof vests, compact
appearing in Groups 1 through 5B, and disks (CDs), ropes, and liquid crystal
such elements as oxygen, carbon, and displays (LCDs) to clothes and coffee
nitrogen). Beach sand and rocks are cups. Thermoplastic polymers, in which
examples of naturally occurring ceramics. the long molecular chains are not rigidly
Advanced ceramics are materials made by connected, have good ductility and
refining naturally occurring ceramics and formability. Polymers are used in many
other special processes. Advanced applications, including electronic devices.
ceramics are used in substrates that
house computer chips, sensors and
actuators, capacitors, wireless Semiconductors. Silicon, germanium,
communications, spark plugs, inductors, and gallium arsenide-based
and electrical insulation. Some ceramics semiconductors such as those used in
are used as barrier coatings to protect computers and electronics are part of a
metallic substrates in turbine engines. broader class of materials known as
Ceramics are also used in such consumer electronic materials. The electrical
products as paints, plastics, and tires, and conductivity of semiconducting materials
for industrial applications such as the is between that of ceramic insulators and
tiles for the space shuttle, a catalyst metallic conductors. Semiconductors have
support, and the oxygen sensors used in enabled the information age. In some
cars. Traditional ceramics are used to semiconductors, the level of conductivity
make bricks, tableware, toilets, bathroom can be controlled to enable electronic
sinks, refractories (heat-resistant devices such as transistors, diodes, etc.,
material), and abrasives. In general, due that are used to build integrated circuits.
to the presence of porosity (small holes), In many applications, we need large
ceramics do not conduct heat well; they single crystals of semiconductors. These
must be heated to very high temperatures are grown from molten materials. Often,
before melting. Ceramics are strong and thin films of semiconducting materials are
hard, but also very brittle. We normally also made using specialized processes.
prepare fine powders of ceramics and
convert these into different shapes. New
processing techniques make ceramics Many technologically important
sufficiently resistant to fracture that they semiconductors appear in Group 4B (e.g.,
can be used in load-bearing applications, silicon (Si), diamond (C), germanium
such as impellers in turbine engines. (Ge)). Semiconductors also can be
Ceramics have exceptional strength under combinations of elements from Groups 2B
compression. Can you believe that an and 6B (e.g., cadmium selenide (CdSe),
entire fire truck can be supported using based on cadmium (Cd) from Group 2 and
four ceramic coffee cups? selenium (Se) based on Group 6). These
are known as II–VI (two-six)
semiconductors. Similarly, gallium
Polymers. Polymers are plastics that are arsenide (GaAs) is a III–V (three-five)
primarily based on carbon, which appears semiconductor based on gallium (Ga)
in Group 4B). Polymers typically are good from Group 3B and arsenic (As) from
Group 5B. Many transition elements (e.g., material with a very large bandgap (i.e., it
titanium (Ti), vanadium (V), iron (Fe), is not a very effective conductor of
nickel (Ni), cobalt (Co), etc.) are electricity). This is consistent with the
particularly useful for magnetic and fact that carbon (in diamond form) has
optical materials due to their electronic the highest melting point among Group
configurations that allow multiple 4B elements, which suggests the
valences. interatomic forces are strong .

Composite Materials The main idea in As we move down the column, the
developing composites is to blend the bandgap decreases (the bandgaps of Si
properties of different materials. These and Ge are 1.11 and 0.67 eV,
are formed from two or more materials, respectively). Moving farther down, one
producing properties not found in any form of tin is a semiconductor. Another
single material. Concrete, plywood, and form of tin is metallic. If we look at Group
fiberglass are examples of composite 1A, we see that lithium is highly
materials. Fiberglass is made by electropositive (i.e., an element whose
dispersing glass fibers in a polymer atoms want to participate in chemical
matrix. The glass fibers make the polymer interactions by donating electrons and
stiffer, without significantly increasing its are therefore highly reactive). Likewise, if
density. With composites, we can produce we move down Column 1A, we can see
lightweight, strong, ductile, temperature- that the chemical reactivity of elements
resistant materials or we can produce decreases. Thus, the periodic table gives
hard, yet shock-resistant, cutting tools us useful information about formulas,
that would otherwise shatter. Advanced atomic numbers, and atomic masses of
aircraft and aerospace vehicles rely elements. It also helps us in predicting or
heavily on composites such as carbon rationalizing trends in properties of
fiber-reinforced polymers. Sports elements and compounds.
equipment such as bicycles, golf clubs,
tennis rackets, and the like also make use
of different kinds of composite materials 1.6.2 Atomic Properties and
that are light and stiff.
Periodic Table Trends
Periodic trends are specific patterns that
1.6.1 Periodic Properties are present in the periodic table that
illustrate different aspects of a certain
The periodic table contains a element, including its size and its
wealth of useful information (e.g., atomic electronic properties. Major periodic
mass, atomic number of different trends include electronegativity,
elements, etc.). It also points to trends in ionization energy, electron affinity,
atomic size, melting points, and chemical atomic radius, melting point, and metallic
reactivity. For example, carbon (in its character. Periodic trends, arising from
diamond form) has the highest melting the arrangement of the periodic table,
point (3550°C). Melting points of the provide chemists with an invaluable tool
elements below carbon decrease (i.e., to quickly predict an element's
silicon (Si) (1410°C), germanium (Ge) properties. These trends exist because of
(937°C), tin (Sn) (232°C), and lead (Pb) the similar atomic structure of the
(327°C). Note that the melting elements within their respective group
temperature of Pb is higher than that of families or periods, and because of the
Sn. The periodic table indicates trends periodic nature of the elements.
and not exact variations in properties.
We can discern trends in other properties
from the periodic table. Diamond is a Atomic Radius Trends
The size of atoms is important when
trying to explain the behavior of atoms or
Electronegativity Trends
compounds. One of the ways we can
express the size of atoms is with the Electronegativity can be understood as a
atomic radius. This data helps us chemical property describing an atom's
understand why some molecules fit ability to attract and bind with electrons.
together and why other molecules have Electronegativity measures an atom's
parts that get too crowded under certain tendency to attract and form bonds with
conditions. The atomic radius is one-half electrons. This property exists due to the
the distance between the nuclei of two electronic configuration of atoms. Most
atoms. Atomic size gradually decreases atoms follow the octet rule (having the
from left to right across a period of valence, or outer, shell comprise of 8
elements. This is because, within a period electrons). Because elements on the left
or family of elements, all electrons are side of the periodic table have less than a
added to the same shell. However, at the half-full valence shell, the energy required
same time, protons are being added to the to gain electrons is significantly higher
nucleus, making it more positively compared with the energy required to
charged. The effect of increasing proton lose electrons. As a result, the elements
number is greater than that of the on the left side of the periodic table
increasing electron number; therefore, generally lose electrons when forming
there is a greater nuclear attraction. This bonds. Conversely, elements on the right
means that the nucleus attracts the side of the periodic table are more
electrons more strongly, pulling the energy-efficient in gaining electrons to
atom's shell closer to the nucleus. The create a complete valence shell of 8
valence electrons are held closer towards electrons. The nature of electronegativity
the nucleus of the atom. As a result, the is effectively described thus: the more
atomic radius decreases. inclined an atom is to gain electrons, the
more likely that atom will pull electrons
toward itself.
Down a group, atomic radius increases.
The valence electrons occupy higher
levels due to the increasing quantum From left to right across a period of
number (n). As a result, the valence elements, electronegativity increases. If
electrons are further away from the the valence shell of an atom is less than
nucleus as ‘n’ increases. Electron half full, it requires less energy to lose an
shielding prevents these outer electrons electron than to gain one. Conversely, if
from being attracted to the nucleus; thus, the valence shell is more than half full, it
they are loosely held, and the resulting is easier to pull an electron into the
atomic radius is large. valence shell than to donate one.
From top to bottom down a group,
electronegativity decreases. This is
Atomic radius decreases from left to right
because atomic number increases down a
within a period. This is caused by the
group, and thus there is an increased
increase in the number of protons and
distance between the valence electrons
electrons across a period. One proton has
and nucleus, or a greater atomic radius.
a greater effect than one electron; thus,
electrons are pulled towards the nucleus,
resulting in a smaller radius. Ionization Energy Trends
Atomic radius increases from top to Ionization energy is the energy required
bottom within a group. This is caused by to remove an electron from a neutral
electron shielding or principal quantum atom in its gaseous phase. Conceptually,
number, n. ionization energy is the opposite of
electronegativity. The lower this energy occurs when an electron is added to a
is, the more readily the atom becomes a neutral gas atom. The more negative the
cation. Therefore, the higher this energy electron affinity value, the higher an
is, the more unlikely it is the atom atom's affinity for electrons.
becomes a cation. Generally, elements on
Electron affinity increases from left to
the right side of the periodic table have a
right within a period. This is caused by
higher ionization energy because their
the decrease in atomic radius.
valence shell is nearly filled. Elements on
the left side of the periodic table have low Electron affinity decreases from top to
ionization energies because of their bottom within a group. This is caused by
willingness to lose electrons and become the increase in atomic radius.
cations. Thus, ionization energy increases
from left to right on the periodic table.
1.7 Atomic Bonding
Another factor that affects ionization There are four important mechanisms by
energy is electron shielding. Electron which atoms are bonded in engineered
shielding describes the ability of an materials.
atom's inner electrons to shield its
positively charged nucleus from its These are:
valence electrons. When moving to the  metallic bonds.
right of a period, the number of electrons  covalent bonds.
increases and the strength of shielding  ionic bonds; and
increases. As a result, it is easier for  van der Waals bonds.
valence shell electrons to ionize, and thus
the ionization energy decreases down a The first three types of bonds are
group. Electron shielding is also known as relatively strong and are known as
screening. primary bonds (relatively strong bonds
between adjacent atoms resulting from
the transfer or sharing of outer orbital
The ionization energy of the elements electrons). The van der Waals bonds are
within a period generally increases from secondary bonds and originate from a
left to right. This is due to valence shell different mechanism and are relatively
stability. weaker.

The ionization energy of the elements

within a group generally decreases from The Metallic Bond
top to bottom. This is due to electron
shielding. The metallic elements have
electropositive atoms that donate their
The noble gases possess very high valence electrons to form a “sea” of
ionization energies because of their full electrons surrounding the atoms.
valence shells as indicated in the graph.
Note that helium has the highest
ionization energy of all the elements.

Electron Affinity Trends

As the name suggests, electron affinity is
the ability of an atom to accept an
electron. Unlike electronegativity, Figure 1.10 - Metallic bonding
electron affinity is a quantitative
measurement of the energy change that
Aluminum, for example, gives up its three atom, which has a valence of four, obtains
valence electrons, leaving behind a core eight electrons in its outer energy shell by
consisting of the nucleus and inner sharing its valence electrons with four
electrons. Since three negatively charged surrounding silicon atoms, as in Figure
electrons are missing from this core, it 1.11
has a positive charge of three. The valence
electrons move freely within the electron
sea and become associated with several
atom cores. The positively charged ion
cores are held together by mutual
attraction to the electrons, thus producing
a strong metallic bond. Because their Figure 1.11 - The center silicon atom
valence electrons are not fixed in any one shares an electron with each of the four
position, most pure metals are good surrounding silicon atoms creating a
electrical conductors of electricity at covalent bond with each.
relatively low temperatures (~T < 300 K). Each instance of sharing represents
Under the influence of an applied voltage, one covalent bond; thus, each silicon atom
the valence electrons move, causing a is bonded to four neighboring atoms by
current to flow if the circuit is complete. four covalent bonds. In order for the
Metals show good ductility since the covalent bonds to be formed, the silicon
metallic bonds are non-directional. There atoms must be arranged so the bonds
are other important reasons related to have a fixed directional
microstructure that can explain why relationship with one another. A
metals exhibit lower strengths and higher directional relationship is formed when
ductility than what we may anticipate the bonds between atoms in a covalently
bonded material form specific angles,
from their bonding.
depending on the material.
Covalent bonds are very strong. As a
result, covalently bonded materials are
very strong and hard. For example,
Ductility refers to the ability of diamond (C), silicon carbide (SiC), silicon
materials to be stretched or bent nitride (Si3N4), and boron nitride (BN) all
permanently without breaking. In have covalent bonds. These materials also
general, the melting points of metals are exhibit very high melting points, which
relatively high. means they could be useful for high-
temperature applications. On the other
hand, the high temperature needed for
From an optical properties processing presents a challenge. The
viewpoint, metals make good reflectors of materials bonded in this manner typically
visible radiation. Owing to their have limited ductility because the bonds
electropositive character many metals tend to be directional. The electrical
such as iron tend to undergo corrosion or conductivity of many covalently bonded
materials (i.e., silicon, diamond, and many
oxidation. Many pure metals are good
ceramics) is not high since the valence
conductors of heat and are effectively
electrons are locked in bonds between
used in many heat transfer applications. atoms and are not readily available for
conduction. With some of these materials
such as Si, we can get useful and
1.7.1 Covalent Bond controlled levels of electrical conductivity
by deliberately introducing small levels of
Materials with covalent bonding are other elements known as dopants.
characterized by bonds that are formed
by sharing of valence electrons among
two or more atoms. For example, a silicon
1.7.2 The Ionic Bond
 When more than one type of atom is
present in a material, one atom may
donate its valence electrons to a different
atom, filling the outer energy shell of the
second atom. Both atoms now have filled
(or emptied) outer energy levels, but both
have acquired an electrical charge and
behave as ions. The atom that contributes
the electrons is left with a net positive
charge and is called a cation, while the
atom that accepts the electrons acquires a
net negative charge and is called
an anion. The oppositely charged ions are Figure 1.13 - An induced electrical dipole
then attracted to one another and
produce the ionic bond. For example, the In some molecules, the dipole moment
attraction between sodium and chloride does not have to be induced—it exists by
ions (Figure 1.12) produces sodium virtue of the direction of bonds and the
chloride (NaCl), or table salt. nature of atoms. These molecules are
known as polarized molecules. An
example of such a molecule that has a
permanently built-in dipole moment is
water (Figure 1.14 (Links to an external
site.)).

Figure 1.12 - Ionic bonding between

sodium and chlorine atoms.

1.7.3 Van der Waals Bonding

The origin of van der Waals forces Figure 1.14 – Dipole-dipole
between atoms and molecules is quantum interaction between water molecules
mechanical in nature and a meaningful
Molecules or atoms in which there
discussion is beyond the scope of this
is either an induced or permanent dipole
book. We present here a simplified
moment attract each other. The resulting
picture. If two electrical charges +q and -
force is known as the van der Waals force.
q are separated by a distance d, the dipole
Van der Waals forces between atoms and
moment is defined as q x d. Atoms are
molecules have their origin in
electrically neutral. Also, the centers of
interactions between dipoles that are
the positive charge (nucleus) and
induced or in some cases interactions
negative charge (electron cloud) coincide.
between permanent dipoles that are
Therefore, a neutral atom has no dipole
present in certain polar molecules. What
moment. When a neutral atom is exposed
is unique about these forces is they are present
to an internal or external electric field, the in every material.
atom may become polarized (i.e., the
centers of positive and negative charges
separate). This creates or induces a dipole
moment (Figure 1.13). 1.8 Types of Van der Waals
Interactions
There are three types of van der
Waals interactions, namely London
forces, Keesom forces, and Debye
forces. If the interactions are between represent one of the polarized regions.
two dipoles that are induced in atoms or Thus, hydrogen bonding is essentially a
molecules, we refer to them as London Keesom force and is a type of van der
forces ( Figure 1.15 ). Example is a Waals force.
helium atom.
Note that Van der Waals bonds
are secondary bonds, but the atoms
within the molecule or group of atoms are
joined by strong covalent or ionic bonds.
Heating water to the boiling point breaks
the Van der Waals bonds and changes
water to steam, but much higher
temperatures are required to break the
covalent bonds joining oxygen and
hydrogen atoms. Although termed
“secondary,” based on the bond energies,
Figure 1.15 London forces, a type of Van Van der Waals forces play a very
der Waals interaction important role in many areas of
engineering. Van der Waals forces
When an induced dipole (that is, a dipole between atoms and molecules play a vital
that is induced in what is otherwise a role in determining the surface tension
non-polar atom or molecule) interacts and boiling points of liquids. In materials
with a molecule that has a permanent science and engineering, the surface
dipole moment, we refer to this tension of liquids and the surface energy
interaction as a Debye interaction. An of solids come into play in different
example of Debye interaction would be situations. For example, when we want to
forces between water molecules and process ceramic or metal powders into
those of O2 molecule. dense solid parts, the powders often have
to be dispersed in water or organic
liquids. Whether we can achieve this
dispersion effectively depends upon the
surface tension of the liquid and the
surface energy of the solid material.
Surface tension of liquids also assumes
importance when we are dealing with
processing of molten metals and alloys
(e.g., casting) and glasses.
Van der Waals bonds can dramatically
Figure 1.16 A Debye interaction (van der change the properties of certain
Waals force) of O2 molecule and water. materials. For example, graphite and
If the interactions are between molecules diamond have very different mechanical
that are permanently polarized (e.g., properties. In many plastic materials,
water molecules attracting other water molecules contain polar parts or side
molecules or other polar molecules), we groups (e.g., cotton or cellulose, PVC,
refer to these as Keesom interactions Teflon). Van der Waals forces provide an
(electrostatic interaction). The extra binding force between the chains of
attraction between the positively charged these polymers. (Figure 1.17)
regions of one water molecule and the
negatively charged regions of a second
water molecule provides an attractive
bond between the two water molecules as
in Figure 1.14.
The bonding between molecules that have
a permanent dipole moment, known as
the Keesom force, is often referred to as
a hydrogen bond, where hydrogen atoms
Figure 1.17 (a) In polyvinyl chloride Figure 1.18 Atoms or ions are
(PVC), the chlorine atoms attached to the separated by an equilibrium spacing that
polymer chain have a negative charge and corresponds to the minimum interatomic
the hydrogen atoms are positively energy for a pair of atoms or ions
charged. The chains are weakly bonded
The minimum energy in Figure 1.18
by van der Waals bonds. This additional
is the binding energy, or the energy
bonding makes PVC stiffer. (b) When a
required to create or break the bond.
force
Consequently, materials having a high
is applied to the polymer, the van der
binding energy also have a high strength
Waals bonds are broken, and the chains
and a high melting temperature. Ionically
slide past one another.
bonded materials have a particularly
large binding energy because of the large
difference in electronegativities between
1.9 Binding energy and the ions. Metals have lower binding
energies because the electronegativities
Interatomic Spacing of the atoms are similar.
Interatomic Spacing is the Table 1.1 Binding energies for the four
equilibrium distance between atoms is bonding mechanisms
caused by a balance between repulsive
and attractive forces. In the metallic bond, Binding
for example, the attraction between the Bond Energy
electrons and the ion cores is balanced by (kcal/mol)
the repulsion between ion cores. Ionic 150-370
Equilibrium separation occurs when the
total interatomic energy (IAE) of the pair covalent 125-300
of atoms is at a minimum, or when no net metallic 25-200
force is acting to either attract or repel Van der Waals <10
the atoms (Figure 1.18). The inter-
atomic spacing in a solid metal
is approximately equal to the atomic
diameter, or twice the atomic radius r. We 1.10 Modulus of Elasticity, Yield Strength
cannot use this approach for ionically and Coefficient of Thermal Expansion
bonded materials, however, since the Other properties can be related to the
spacing is the sum of the two different force-distance and energy-distance
ionic radii. expressions in Figure 1.19 . For example,
the modulus of elasticity of a material
(the slope of the stress-strain curve in the
elastic region, also known as Young’s
modulus) is related to the slope of the
force-distance curve ( Figure 1.18). A
steep slope, which correlates with a
higher binding energy and a higher
melting point, means that a greater force
is required to stretch the bond; thus, the deep interatomic energy (IAE) trough
material has a high modulus of elasticity. caused by strong atomic bonding is
characteristic of the material (Figure
1.20), the atoms separate to a lesser
degree and have a low, linear coefficient
of thermal expansion. Materials with a
low coefficient of thermal expansion
maintain their dimensions more closely
when the temperature changes.
Materials that have very low
expansion are useful in many applications
where the components are expected to
repeatedly undergo relatively rapid
heating and cooling. For example,
cordierite ceramics (used as catalyst
support in catalytic converters in cars),
ultra-low expansion (ULE) glasses, Vision
Figure 1.19 The force-distance curve for
ware™, and other glass-ceramics
two materials. The slope gives the
developed by Corning, have very low
Young's Modulus or Modulus of elasticity.
thermal expansion coefficients.
An interesting point that needs to
be made is that not all properties of
engineered materials are microstructure
sensitive. Modulus of elasticity is one such
property. If we have two aluminum
samples that have essentially the same
chemical composition but different grain
size, we expect that the modulus of
elasticity of these samples will be about
the same; however, yield strengths, the
level of stress at which the material
begins to permanently deform, of these Figure 1.20 The interatomic energy (IAE)
samples will be quite different. The yield —separation curve for two atoms.
strength, therefore, is a microstructure Materials that display a steep curve with a
sensitive property. Compared to other deep trough have low linear coefficients
mechanical properties such as yield of thermal expansion.
strength and tensile strength; the
modulus of elasticity does not depend
strongly on the microstructure. The 1.11 The Many Forms of
modulus of elasticity can be linked
directly to the stiffness of bonds between Carbon
atoms. Thus, the modulus of elasticity
Relationships Between Arrangements
depends primarily on the atoms that
of atoms and Materials Properties
make up the material.
Carbon is one of the most abundant
Another property that can be
elements on earth. Carbon is an essential
linked to the binding energy or
component of all living organisms, and it
interatomic force distance curves is the
has enormous technological significance
coefficient of thermal expansion (CTE).
with a wide range of applications.
The CTE, often denoted as αα, is the
fractional change in linear dimension of a For example, carbon dating is a
material per degree of temperature. The process by which scientists measure the
CTE is related to the strength of the amount of a radioactive isotope of carbon
atomic bonds. For the atoms to move that is present in fossils to determine
from their equilibrium separation, energy their age, and now some of the most
must be supplied to the material. If a very cutting-edge technologies exploit one of
the world’s strongest materials: carbon One of the allotropes of carbon above all
nanotubes. And of course, a small amount others is the diamond. The figure shows
of carbon (e.g., 0.5 wt %) converts iron that for diamond each sphere is an atom,
into steel. and each line represents covalent bonds
between carbon atoms. It shows that
Pure carbon exists as
each carbon atom is bonded to four other
several allotropes, meaning that pure
carbon atoms. These bonds are covalent,
carbon exists in different forms (or has
meaning
different arrangements of its atoms)
that each carbon atom shares each one of
depending on the temperature and
its outermost electrons with an adjacent
pressure. Two allotropes of carbon are
carbon
very familiar to us: diamond and graphite,
atom, so each atom has a full outermost
while two other forms of carbon have
quantum shell. The predominantly
been discovered much more recently:
covalent bonding in diamond profoundly
buckminsterfullerene also known as
influences its macroscopic properties.
“buckyballs” and carbon nanotubes.
Diamond is one of the highest melting-
The allotropes of carbon all have the point materials known with a melting
same composition—they are pure carbon temperature of 3550°C (6420°F). This is
— and yet they display dramatically due to the strong covalent bonding
different materials properties. The key to between atoms. Diamond also has one of
understanding these differences is to the highest known thermal
understand how the atoms are arranged conductivities. The high thermal
in each allotrope. conductivity of diamond is due to the
rigidity of its covalently bonded
Carbon has an atomic number of structure. On the other hand, diamond is
six, meaning it has six protons. Thus, a an electrical insulator. All of the valence
neutral carbon atom has six electrons. electrons of each carbon atom are shared
Two of these electrons occupy the with the neighboring atoms, leaving no
innermost quantum shell (completely free electrons to conduct electricity.
filling it), and four electrons occupy the Diamond is one of the hardest substances
quantum shell with the principal known, which is why it is often used in
quantum number n = 2. Each carbon atom cutting tools in industrial applications.
has four valence electrons and can share
electrons with up to four different atoms. Graphite, like pure diamond,
Thus, carbon atoms can combine with contains only carbon atoms, but we know
other elements as well as with other from the experience of writing with
carbon atoms. This allows carbon to form graphite pencils that the properties of
many different compounds of varying graphite are significantly different from
structure as well as several allotropes of that of diamond. In graphite, the carbon
pure carbon. atoms are arranged in layers. In each
layer, the carbon atoms
are arranged in a hexagonal pattern, as
shown in Figure 1.21. Recall that in
diamond, each carbon atom is covalently
bonded to four others, but in each
graphite layer, each carbon atom is
bonded covalently to only three others.
There is a fourth bond between the
layers, but this is a much weaker van der
Waals bond. Like diamond, graphite has a
high melting point. To heat a solid to the
point at which it becomes a liquid, the
spacing between atoms must be
Figure 1.21 The three allotropes of increased. In graphite, it is not difficult to
carbon separate the individual layers, because
the bonds between the layers are weak
(in
fact, this is what you do when you write directions to produce nanotubes with
with a graphite pencil—layers are different configurations, as shown in
separated and left behind on your paper), Figure 1.22. Carbon nanotubes may be
but each carbon atom has three strong single-walled or multi-walled. Multi-
bonds in the layer that cause the graphite walled carbon nanotubes consist of
to have a high melting point. Graphite has multiple concentric nanotubes. Carbon
a lower density than diamond because of nanotubes are typically 1 to 25 nm in
its layer structure—the atoms are not diameter and are on the order of microns
packed as closely together. Unlike long. Carbon nanotubes with different
diamond, graphite is electrically configurations display different materials
conductive. This is because the fourth properties. For example, the electrical
electron of each carbon atom, which is not properties of nanotubes depend on the
covalently bonded in the plane, is helicity and diameter of the nanotubes.
available to conduct electricity. Carbon nanotubes are currently being
used as reinforcement to strengthen and
Buckminsterfullerene, an allotrope
stiffen polymers and as tips for atomic
of carbon, was discovered in 1985. Each
force microscopes. Carbon nanotubes
molecule of buckminsterfullerene or
also are being considered as possible
“buckyball” contains sixty carbon atoms
conductors of electricity in advanced
and is known as C60. A buckyball can be
nanoelectronics devices.
envisioned by considering a two-
dimensional pattern of twelve regular
pentagons and twenty regular hexagons
arranged as in Figure 1.21. If this pattern
is folded into a three-dimensional
Atomic and Ionic
structure by wrapping the center row into Arrangements
a circle and folding each end over to form
end caps, then the polygons fit together This chapter will examine the
perfectly— like a soccer ball! This is a influence of atomic and ionic
highly symmetrical structure with sixty arrangements on the properties of
corners, and if a carbon atom is placed at engineered materials. We will
each corner, then this is a model for the concentrate on “perfect” arrangements of
C60 molecule. Buckyballs can enclose atoms or ions in crystalline solids. The
other atoms within them, appear to be concepts discussed in this chapter will
quite strong, and have interesting prepare us for understanding
magnetic and superconductive how deviations from these perfect
properties. arrangements in crystalline materials
create what are described as atomic level
defects. The term defect in this context
refers to a lack of perfection in atomic or
ionic order of crystals and not to any flaw
or quality of an engineered material.
Short-Range Order vs Long-Range
Order
In different states of matter, we can
find four types of atomic or ionic
arrangements (Figure 2.1 ).

Figure 1.22 Single walled carbon

nanotubes
Carbon nanotubes, a fourth
allotrope of carbon, can be envisioned as
sheets of graphite rolled into tubes with
hemispherical fullerene caps on the ends.
A single sheet of graphite, known as
graphene, can be rolled in different
 Figure 2.2 Si-O tetrahedron in silicate
glass.
In contrast, in quartz or other forms of
crystalline silica, the (SiO4)4- tetrahedra
are indeed connected in different periodic
arrangements.
Figure 2.1 Levels of atomic arrangements
Long-Range Order (LRO)
in materials.
Most metals and alloys,
semiconductors, ceramics, and some
polymers have a crystalline structure in
No Order and Short-Range which the atoms or ions display long-
Order range order (LRO); the special atomic
arrangement extends over much larger
No Order length scales ~ 7100 nm. The atoms or
In monoatomic gases, such as argon ions in these materials form a regular
(Ar) or plasma created in a fluorescent repetitive, grid-like pattern, in three
tube light, atoms or ions have no orderly dimensions. We refer to these materials
arrangement. as crystalline materials.

Short-Range Order (SRO) If a crystalline material consists of

only one large crystal, we refer to it as a
A material displays short-range single crystal. A polycrystal line material
order (SRO) if the special arrangement of is composed of many small crystals with
the atoms extends only to the atom’s varying orientations in space. These
nearest neighbors. Each water molecule smaller crystals are known as grains.
in steam has short-range order due to the Many crystalline materials we deal with
covalent bonds between the hydrogen in engineering applications are
and oxygen atoms; that is, each oxygen polycrystalline (e.g., steels used in
atom is joined to two hydrogen atoms, construction, aluminum alloys for
forming an angle of 104.5° between the aircrafts, etc.).
bonds. There is no long-range order,
however, because the water molecules in
steam have no special arrangement with
respect to each other’s position.
Amorphous Materials
A similar situation exists in Any material that exhibits only a
materials known as inorganic glasses. short-range order of atoms or ions is an
The tetrahedral structure in silica amorphous material; that is, a non-
satisfies the requirement that four oxygen crystalline one. In general, most materials
ions be bonded to each silicon ion. In a want to form periodic arrangements since
glass, individual tetrahedral units are this configuration maximizes the
joined together in a random manner. thermodynamic stability of the material.
These tetrahedra may share corners, Amorphous materials tend to form when,
edges, or faces. Thus, beyond the basic for one reason or other, the kinetics of the
unit of a (SiO4)4- tetrahedron, there is no process by which the material was made
periodicity in their arrangement. did not allow for the formation of periodic
arrangements.
 Glasses, which typically form in Bravais lattices are three-
ceramic and polymer systems, are good dimensional arrangements of lattice
examples of amorphous materials. points named after Auguste Bravais
Similarly, certain types of polymeric or (1811–1863) who was an early French
colloidal gels, or gel-like materials, are crystallographer. The fourteen Bravais
also considered amorphous. Amorphous lattices are shown in Figure 2.4. A lattice
is infinite in extent, so a single unit cell is
materials often offer a unique blend of
shown for each lattice.
properties since the atoms or ions are not
assembled into their “regular” and
periodic arrangements.

Lattice, Basis and Unit Cell

A lattice is a collection of points,
called lattice points, which are arranged
in a periodic pattern so that the
surroundings of each point in the lattice
are identical. A lattice is a purely
mathematical construct and is infinite in
extent. A lattice may be one-, two-, or
three-dimensional. In one dimension,
there is only one possible lattice: It is a
line of points with the points separated Figure 2.4 The fourteen Bravais
from each other by an equal distance, as lattices
shown in Figure 2.3
The fourteen Bravais lattices are
grouped into seven crystal systems. The
seven crystal systems are known as cubic,
tetragonal, orthorhombic, rhombohedral
(also known as trigonal), hexagonal,
monoclinic, and triclinic. Note that for the
cubic crystal system, we have simple
cubic (SC), face-centered cubic (FCC), and
body-centered cubic (BCC) Bravais
lattices. Note that although we have only
fourteen Bravais lattices, we can have an
infinite number of bases. Hundreds of
Figure 2.3 Lattice and Basis different crystal structures are observed
A group of one or more atoms in nature or can be synthesized. Many
located in a particular way with respect to different materials can have the same
each other and associated with each crystal structure. For example, copper
lattice point is known as and nickel have the face-centered cubic
the basis or motif. The basis must crystal structure for which only one atom
contain at least one atom, but it may is associated with each lattice point. In
contain many atoms of one or more more complicated structures, particularly
types. We obtain a crystal structure by polymer, ceramic, and biological
placing the atoms of the basis on every materials, several atoms may be
lattice point (i.e., crystal structure = associated with each lattice point (i.e., the
lattice + basis), as shown in Figure 2.3. basis is greater than one), forming very
complex unit cells.

Bravais Lattices
Classification of Materials
 Materials science and engineering titanium, copper, and nickel. An alloy is a
(MSE) is an interdisciplinary field of metal that contains additions of one or
science and engineering more metals or non-metals. In general,
those studies and manipulates the metals have good electrical and thermal
composition and structure of materials conductivity. Metals and alloys have
across length scales to control materials relatively high strength, high stiffness,
properties through synthesis and ductility or formability, and shock
processing. resistance. They are particularly useful
for structural or load-bearing
The term composition means the
applications. Although pure metals are
chemical make-up of a material. The
occasionally used, alloys provide
term structure means a description of
improvement in a particular desirable
the arrangement of atoms, as seen at
property or permit better combinations
different levels of detail. The structure at
of properties.
a microscopic level is known as the
microstructure. Many properties of
materials depend strongly on the
Metals and alloys have good
structure, even if the composition of the
strength, good ductility, and good
material remains the same. Therefore, the
formability. Metals have good electrical
structure-property or microstructure
and thermal conductivity. Metals and
property relationships in materials are
alloys play an indispensable role in many
extremely important.
applications such as automotive,
In materials science, the emphasis is buildings, bridges, aerospace, and the like.
on the underlying relationships between
the synthesis and processing, structure,
and properties of materials. Our
knowledge of atomic structure provides
Ceramics and Glasses
us understanding on how this affects the Ceramics can be defined as inorganic
properties, behavior, and resulting crystalline materials. Beach sand and
applications of engineering materials. In rocks are examples of naturally occurring
materials engineering, the focus is on how ceramics.
to translate or transform materials into
useful devices or structures. Advanced ceramics are used in
substrates that house computer chips,
Materials are classified as metals and
sensors and actuators, capacitors,
alloys, ceramics, glasses and glass-
ceramics, composites, polymers, and wireless communications, spark plugs,
semiconductors. (Figure 3.1) inductors, and electrical insulation. Some
ceramics are used as barrier coatings to
protect metallic substrates in turbine
engines. In general, due to the presence of
porosity (small holes), ceramics do not
conduct heat well; they must be heated to
very high temperatures before melting.
Ceramics are strong and hard, but also
very brittle. Modern ceramics form the
underpinnings of many microelectronic
Figure 3.1 Classification of Materials. and photonic technologies.
Materials in each of these groups possess
different structures and properties.
Glasses and Glass-Ceramics
Glass is an amorphous material,
Metals and Alloys often, but not always, derived from a
molten liquid. The fiber optics industry is
Metals and alloys include steels,
aluminum, magnesium, zinc, cast iron, founded on optical fibers based on high
purity silica glass. Glasses are also used in different materials. These are formed
houses, cars, computer and television from two or more materials, producing
screens, and hundreds of other properties not found in any single
applications. Glasses can be thermally material. Concrete, plywood, and
treated (tempered) to make them fiberglass are examples of composite
stronger. Glass-ceramics are formed by materials. Fiberglass is made by
annealing glasses to nucleate small dispersing glass fibers in a polymer
crystals that improve resistance to matrix.
fracture and thermal shock.
The glass fibers make the polymer
stiffer, without significantly increasing its
density. With composites, we can
Polymers and Semi- produce lightweight, strong, ductile,
Conductors temperature-resistant materials or we
can produce hard, yet shock-resistant,
Polymers are typically organic cutting tools that would otherwise
materials. They are produced using a shatter. Advanced aircraft and aerospace
process known as polymerization. vehicles rely heavily on composites such
Polymeric materials include rubber as carbon fiber-reinforced polymers as
(elastomers) and many types of shown in Figure 3.1. Sports equipment
adhesives. Polymers typically are good such as bicycles, golf clubs, tennis rackets,
electrical and thermal insulators although and the like also make use of different
there are exceptions such as the kinds of composite materials that are light
semiconducting polymers. Many and stiff.
polymers have very good resistance to
corrosive chemicals.
Polymers have thousands of
applications ranging from bulletproof
vests, compact disks (CDs), ropes, and
liquid crystal displays (LCDs) to clothes
and coffee cups. Thermoplastic polymers,
in which the long molecular chains are Figure 3.2 An image of carbon fiber-
not rigidly connected, have good ductility reinforced polymers
and formability; thermosetting polymers
are stronger but more brittle because the
molecular chains are tightly linked
Energy
Because energy takes many forms,
Semiconductors only some of which can be seen or felt, it
Silicon, germanium, and gallium is defined by its effect on matter. For
arsenide-based semiconductors such as example, microwave ovens produce
those used in computers and electronics energy to cook food, but we cannot see
are part of a broader class of materials that energy. In contrast, we can see the
known as electronic materials. The energy produced by a light bulb when we
electrical conductivity of semiconducting switch on a lamp. In this section, we
materials is between that of ceramic describe the forms of energy and discuss
insulators and metallic conductors. the relationship between energy, heat,
and work.
Energy can be defined as the
Composite Materials capacity to supply heat or do work. One
type of work (w) is the process of causing
The main idea in developing
matter to move against an opposing force.
composites is to blend the properties of
Like matter, energy comes in different
types. One scheme classifies energy into
two types: potential energy, the energy an
object has because of its relative position,
composition, or condition, and kinetic
energy, the energy that an object
possesses because of its motion. A
battery has potential energy because the Figure 4.1 (a) The molecules in a
chemicals within it can produce sample of hot water move more rapidly
electricity that can do work. than (b) those in a sample of cold water.

Energy can be converted from one Click on this interactive simulation (Links
form into another, but all of the energy to an external site.) to view the effects of
temperature on molecular motion.
present before a change occurs always
exists in some form after the change is
completed. This observation is expressed Heat
in the law of conservation of energy:
during a chemical or physical change, Heat (q) is the transfer of thermal
energy can be neither created nor energy between two bodies at different
temperatures. Heat flow (a redundant
destroyed, although it can be changed in
term, but one commonly used) increases
form. (This is also one version of the first
the thermal energy of one body and
law of thermodynamics) decreases the thermal energy of the
other.
Suppose we initially have a high
Thermal Energy, temperature (and high thermal energy)
Temperature, Heat substance (H) and a low temperature
(and low thermal energy) substance (L).
Thermal energy is kinetic energy The atoms and molecules in H have a
associated with the random motion of higher average KE than those in L. If we
atoms and molecules. Temperature is a place substance H in contact with
quantitative measure of “hot” or “cold.” substance L, the thermal energy will flow
When the atoms and molecules in an spontaneously from substance H to
object are moving or vibrating quickly, substance L. The temperature of
they have a higher average kinetic energy substance H will decrease, as will the
(KE), and we say that the object is “hot.” average KE of its molecules; the
When the atoms and molecules are temperature of substance L will increase,
moving slowly, they have lower average along with the average KE of its
KE, and we say that the object is “cold” molecules. Heat flow will continue until
(Figure 4.1). If no chemical reaction or the two substances are at the same
phase change (such as melting or temperature (Figure 4.2 ).
vaporizing) occurs, increasing the amount
of thermal energy in a sample of matter
will cause its temperature to increase.
And, if no chemical reaction or phase
change (such as condensation or freezing)
occurs, decreasing the amount of thermal Figure 4.2 (a) Substances H and L are
energy in a sample of matter will cause its initially at different temperatures, and
temperature to decrease. their atoms have different average kinetic
energies. (b) When they contact each
other, collisions between the molecules
result in the transfer of kinetic (thermal)
energy from the hotter to the cooler
matter. (c) The two objects reach
“thermal equilibrium” when both
substances are at the same temperature
and their molecules have the same Heat capacity is determined by both
average kinetic energy. the type and amount of substance that
absorbs or releases heat. It is therefore an
extensive property—its value is
Energy Units proportional to the amount of the
substance.
Matter undergoing chemical
reactions and physical changes can The specific heat capacity (c) of a
release or absorb heat. A change that substance, commonly called its “specific
releases heat is called an exothermic heat,” is the quantity of heat required to
process. A reaction or change that raise the temperature of 1 gram of a
absorbs heat is an endothermic process. substance by 1 degree Celsius (or 1
kelvin):
Historically, energy was measured
in units of calories (cal). A calorie is the c= q / mΔT
amount of energy required to raise one
gram of water by 1 degree centigrade.
Specific heat capacity depends only
However, this quantity depends on the
on the kind of substance absorbing or
atmospheric pressure and the starting
releasing heat. It is an intensive property
temperature of the water. The ease of
—the type, but not the amount, of the
measurement of energy changes in
substance is all that matters.
calories has meant that the calorie is still
frequently used. The Calorie (with a The molar heat capacity, also an
capital C), or large calorie, commonly intensive property, is the heat capacity
used in quantifying food energy content, per mole of a particular substance and
is a kilocalorie. has units of J/mol °C.

The SI unit of heat, work, and Energy Calculations

energy is the joule. A joule (J) is defined as
the amount of energy used when a force Sample Problem
of 1 newton moves an object 1 meter. It is Measuring Heat
named in honor of the English physicist
A flask containing 8.0 × 102 g of water is
James Prescott Joule. One joule is
heated, and the temperature of the water
equivalent to 1 kg m2/s2, which is also
increases from 21 °C to 85 °C. How much
called 1 newton–meter. A kilojoule (kJ) is
heat did the water absorb?
1000 joules. To standardize its definition,
1 calorie has been set to equal 4.184 Solution
joules.
To answer this question, consider these
factors:

Specific Heat the specific heat of the substance being

heated (in this case, water)
We now introduce two concepts
the amount of substance being heated (in
useful in describing heat flow and
this case, 8.0 × 102 g)
temperature change. The heat capacity
(C) of a body of matter is the quantity of the magnitude of the temperature change
heat (q) it absorbs or releases when it (in this case, from 21 °C to 85 °C).
experiences a temperature change (ΔT) of
The specific heat of water is 4.184
1 degree Celsius (or equivalently, 1
J/g °C, so to heat 1 g of water by 1 °C
kelvin):
requires 4.184 J. We note that since 4.184
C= q/ ΔT J is required to heat 1 g of water by 1 °C,
we will need 800 times as much to heat
8.0 × 102 g of water by 1 °C. Finally, we
observe that since 4.184 J are required to
heat 1 g of water by 1 °C, we will need 64
times as much to heat it by 64 °C (that is,
from 21 °C to 85 °C).
Using the equation from the
previous page, the value of q = 210,000 J
Because the temperature increased, the Figure 4.3 In a calorimetric
water absorbed heat and q is positive. determination, either (a) an exothermic
process occurs and heat, q, is negative,
indicating that thermal energy is
transferred from the system to its
Calorimetry surroundings, or (b) an endothermic
process occurs and heat, q, is positive,
One technique we can use to indicating that thermal energy is
measure the amount of heat involved in a transferred from the surroundings to the
chemical or physical process is known system.
as calorimetry. Calorimetry is used to
measure amounts of heat transferred to Fuels
or from a substance. To do so, the heat is
exchanged with a calibrated object According to the law of conservation
(calorimeter). The temperature change of energy, energy can never actually be
measured by the calorimeter is used to “consumed”; it can only be changed from
derive the amount of heat transferred by one form to another. What is consumed
the process under study. The on a huge scale, however, are resources
measurement of heat transfer using this that can be readily converted to a form of
approach requires the definition of energy that is useful for doing work.
a system (the substance or substances energy that is not used to perform work is
undergoing the chemical or physical either stored as potential energy for
change) and its surroundings (all other
future use or transferred to the
matter, including components of the
surroundings as heat.
measurement apparatus, that serve to
either provide heat to the system or
absorb heat from the system).
Primary fuels or primary energy
A calorimeter is a device used to sources are dense sources of primary
measure the amount of heat involved in a energy found as natural resources.
chemical or physical process. For Primary fuels are fuels that are found in
example, when an exothermic reaction
nature and can be extracted, captured,
occurs in solution in a calorimeter, the
cleaned, or graded without any sort of
heat produced by the reaction is absorbed
by the solution, which increases its energy conversion or transformation
temperature. When an endothermic process. This means that all processing
reaction occurs, the heat required is and collecting of the fuel is done before
absorbed from the thermal energy of the the fuel is converted into heat or
solution, which decreases its temperature mechanical work. These primary fuels
(Figure 4.4). The temperature change, tend to be non-renewable, and some of
along with the specific heat and mass of the most commonly known primary fuels
the solution, can then be used to calculate are fossil fuels. Energy harvested from
the amount of heat involved in either primary fuels tends to make up most of a
case. country's total primary energy supply.

Most of the primary fuels used

currently are non-renewable. However,
one major renewable primary fuel is from
biomass sources. Other examples of
primary fuel include coal, crude oil, Particles in Nuclear
bitumen and natural gas. Reactions
Many entities can be involved in
Nuclear Reactions as nuclear reactions. The most common are
protons, neutrons, alpha particles, beta
Source of Energy particles, positrons, and gamma rays, as
shown in Table 4.2. Protons and neutrons
After the discovery of radioactivity, are the constituents of atomic
the field of nuclear chemistry was created nuclei. Alpha particles also represented
and developed rapidly during the early by the symbol α are high-energy helium
twentieth century. Series of new nuclei. Beta particles, β, are high-energy
discoveries in the 1930s and 1940s, along electrons, and gamma rays are photons of
with World War II, combined to usher in very high-energy electromagnetic
the Nuclear Age in the mid-twentieth radiation. Positrons are positively
century. Scientists learned how to create charged electrons (“anti-electrons”). The
new substances, and certain isotopes of subscripts and superscripts are necessary
certain elements were found to possess for balancing nuclear equations but are
usually optional in other circumstances.
the capacity to produce unprecedented
amounts of energy, with the potential to
cause tremendous damage during war, as
well as produce enormous amounts of
power for society’s needs during peace.

The process of converting very light

nuclei into heavier nuclei is also
accompanied by the conversion of mass
Figure 4.4 Some species encountered in
into large amounts of energy, a process
nuclear reactions, this table summarizes
called fusion. The principal source of the names, symbols, representations, and
energy in the sun is a net fusion reaction descriptions of the most common ones.
in which four hydrogen nuclei fuse and
produce one helium nucleus and two
positrons.
Balancing Nuclear Reactions
A balanced chemical reaction
Many heavier elements with smaller equation reflects the fact that during a
binding energies per nucleon can chemical reaction, bonds break and form,
decompose into more stable elements and atoms are rearranged, but the total
that have intermediate mass numbers and numbers of atoms of each element are
larger binding energies per nucleon. This conserved and do not change. A balanced
decomposition is called fission, the nuclear reaction equation indicates that
breaking of a large nucleus into smaller there is a rearrangement during a nuclear
pieces. The breaking is rather random reaction, but of nucleons (subatomic
with the formation of a large number of particles within the atoms’ nuclei) rather
different products. Fission usually does than atoms. Nuclear reactions also follow
not occur naturally but is induced by conservation laws, and they are balanced
bombardment with neutrons. A in two ways:
tremendous amount of energy is
produced by the fission of heavy 1. The sum of the mass numbers of the
elements. reactants equals the sum of the mass
numbers of the products.
2. The sum of the charges of the reactants When it comes to redox reactions, it
equals the sum of the charges of the is important to understand what it means
products. for a metal to be “oxidized” or “reduced”.
An easy way to do this is to remember the
If the atomic number and the mass
phrase “OIL RIG”.
number of all but one of the particles in a
nuclear reaction are known, we can
identify the particle by balancing the
OIL = Oxidization is Loss (of e-)
reaction.

RIG = Reduction is Gain (of e-)

Redox Reactions
Electrochemistry deals with
chemical reactions that produce
electricity and the changes associated
Voltaic Cells
with the passage of electrical current In redox reactions, electrons are
through matter. The reactions involve transferred from one species to another.
electron transfer, and so they are If the reaction is spontaneous, energy is
oxidation-reduction (or redox) reactions. released, which can then be used to do
Many metals may be purified or useful work. To harness this energy, the
electroplated using electrochemical reaction must be split into two separate
methods. Devices such as automobiles, half reactions: the oxidation and
smartphones, electronic tablets, watches, reduction reactions. The reactions are put
pacemakers, and many others use into two different containers and a wire is
batteries for power. Batteries use used to drive the electrons from one side
to the other. In doing so, a Voltaic/
chemical reactions that produce
Galvanic Cell is created.
electricity spontaneously and that can be
converted into useful work. All When a redox reaction takes place,
electrochemical systems involve the electrons are transferred from one
transfer of electrons in a reacting system. species to the other. If the reaction is
In many systems, the reactions occur in a spontaneous, energy is released, which
region known as the cell, where the can be used to do work. Consider the
reaction of a solid copper (Cu(s)) in a silver
transfer of electrons occurs at electrodes.
nitrate solution (AgNO3(s)). ( Figure 4.5 )

A redox reaction is one that entails

changes in oxidation number (or
oxidation state) for one or more of the
elements involved. The oxidation number
of an element in a compound is
essentially an assessment of how the
electronic environment of its atoms is
different in comparison to atoms of the
pure element. By this description, the
oxidation number of an atom in an
element is equal to zero. For an atom in a Figure 4.5
compound, the oxidation number is equal
This reaction releases energy. When
to the charge the atom would have in the
the copper electrode solid is placed
compound if the compound were ionic.
directly into a silver nitrate solution,
The sum of oxidation numbers for all however, the energy is lost as heat and
atoms in a molecule is equal to the charge cannot be used to do work. In order to
on the molecule. harness this energy and use it do useful
work, we must split the reaction into two (1) Primary cells: In these cells, the
separate half reactions; The oxidation and electrode reactions cannot be reversed by
reduction reactions. A wire connects the an external electric energy source. In
two reactions and allows electrons to these cells, reactions occur only once and
flow from one side to the other. In doing after use they become dead. Therefore,
so, we have created a Voltaic/ Galvanic they are not chargeable. Some common
Cell. example are, dry cell, mercury cell,
Daniell cell and alkaline dry cell
(2) Secondary cells: in these cells, the
reaction can be reversed by running a
current into the cell with a battery
charger to recharge it, regenerating the
chemical reactants. Primary cells are
made in a range of standard sizes to
power small household appliances such
as flashlights and portable radios.

Figure 4.6 A Voltaic Cell.

A Voltaic Cell (also known as a Figure 4. 7 A variety of standard sizes of
Galvanic Cell) is an electrochemical cell primary cells. From left: 4.5V multicell
that uses spontaneous redox reactions to battery, D, C, AA, AAA, AAAA, A23, 9V
generate electricity. It consists of two multicell
separate half-cells. The salt bridge is a battery, (top) LR44, (bottom) CR2032
vital component of any voltaic cell. It is a
tube filled with an electrolyte solution A common secondary cell is the
such as KNO3(s) or KCl(s). The purpose of Lead-acid battery. This can be commonly
the salt bridge is to keep the solutions found as car batteries. They are used for
electrically neutral and allow the free their high voltage, low costs, reliability
flow of ions from one cell to another. and long lifetime. Lead-acid batteries are
Without the salt bridge, positive and used in an automotive to start an engine
negative charges will build up around the and operate the car's electrical
electrodes causing the reaction to stop. accessories when the engine is not
running. The alternator, once the car is
running, recharges the battery.

Commercial Voltaic
Cells
One of the main uses of galvanic
cells is the generation of portable
electrical energy. These cells are also
popularly known as batteries. The term
battery is generally used for two or more
Galvanic cells connected in series. Thus,
a battery is an arrangement of
electrochemical cells used as an energy
source. The basis of an electrochemical
cell is an oxidation – reduction reaction.
Types of commercial cells: There are
mainly two types of commercial cells,