MATERIALS SCIENCE AND ENGINEERING

Chapter 2. Atomic Structure

Prof. Dr. Gültekin GÖLLER

04.11.2020
Objectives Of Chapter 1

 Introduce the field of materials science

and engineering (MSE)

 Provide introduction to the classification

of materials

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Materials Science and Engineering

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Objectives Of Chapter 2

 The goal of this chapter is to describe the underlying physical

concepts related to the structure of matter.

 To examine the relationships between structure of atoms-

bonds-properties of engineering materials.

 To describe the structure of materials at different levels

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Outline

 The Structure of Materials: Technological Relevance

 Discovery of Atom
 The Structure of the Atom
 The Electronic Structure of the Atom
 Quantum Numbers
 Valance, Atomic Stability, Electronegativity
 The Periodic Table
 Atomic Bonding
 Binding Energy and Interatomic Spacing

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The Structure of Materials: Technological Relevance

 Nanotechnology

 micro-electro-mechanical
systems (MEMS), airbag
deployment sensors

 Nanostructures

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Structure of materials
 Atomic structure
 Atomic Arrangements
 Microstructure
 Macrostructure

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Levels of structure

Level of Structure Example of Technologies

Atomic Structure Diamond: Diamond is based on

carbon-carbon (C-C) covalent bonds.

Atomic Arrangements : Lead-zirconium-titanate

(LRO) [Pb(ZrxTi1 x)O3] or PZT:

Atomic Arrangements Ions in silica (SiO2) glass exhibit

(SRO) only a short-range order

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Level of Structure Example of Technologies

Nanostructure Nano-sized particles (5–10 nm) of

iron oxide

Microstructure The mechanical strength of many

metals and alloys depends
very strongly on the grain

Macrostructure Relatively thick coatings, such as

paints on automobiles and other
applications

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Structure of Materials

Atoms and Big Bang Theory

 About 15 billion years ago a tremendous explosion started the
expansion of the universe. This explosion is known as the Big Bang. At
the point of this event all of the matter and energy of space was
contained at one point. As the universe expanded further, and thus
cooled, common particles began to form. These particles are called
baryons and include photons, neutrinos, electrons and quarks would
become the building blocks of matter and life as we know it.
 After about one to three minutes had passed since the creation of the
universe, protons and neutrons began to react with each other to form
deuterium, an isotope of hydrogen. Deuterium, or heavy hydrogen,
soon collected another neutron to form tritium. Rapidly following this
reaction was the addition of another proton which produced a helium
nucleus. Scientists believe that there was one helium nucleus for every
ten protons within the first three minutes of the universe. After further
cooling, these excess protons would be able to capture an electron to
create common hydrogen. Cosmic temperature continued to decline
and the big bang chronology also continued untill 3000K. Heavy
elements formed after formation of the first star.
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Dimensional Comparison of atom and subatomic particle

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Atom Models

• Democritus (B.C. 400’s)

He assumed materials were formed from particles and

named them atom.
According to this assumption;

 When the material cut into pieces finally there will be an

indivisible particle and this particle is an atom.
 All materials formed from same atoms.
 Materials are different from each other because the number
and arrangement of atoms are different.
 Atoms are invisible and indivisible.

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Atom Models

Radioactive atoms can be

• Dalton’s Atom Model saperated into smaller
particles and form to
different atoms have
 The smallest unit of the matter is atom. different chemical
 Atom is indivisible. properties.

 Atom’s shape is like a filled sphere Porous structure

 All matters are made of different kind of atoms.
 The reason of the differences between matters is each matter
formed from different atoms.
 Atoms of a matter are identical.
Atoms of the same kind of elements are
not identical. There are atoms have
different mass (isotope).

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• Thomson’s Atom Model (John Joseph Thomson, 1897)

Discovery of electron
 First model about structure
of atom.

 When high voltage is applied to the tube which have metals named
electrodes in both edges, the electrodes are charged.
 (+) charged electrode  anode
 (-) charged electrode  cathode
 When magnetic and electric field is applied to a cathode beam tube, beams
go to the negative side (cathode) of the tube and he discovered electrones
and cathode beam.
 He calculated doses of electron stray in electric field and charge/mass ratio.
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Atom Models

Robert Millikan Calculation of

electron charge

 Oil spray was produced from brass

atomizer, at the same time electrons
transfred into the oil drops.
 (-) charged oil drops fall onto charged
plates by gravity and he observed that
charge of oil-drops changed.
 He determined that every charge
comprises of scales of smaller charges
and reached the conclusion that this
small charge is the e- charge.
 e- ve (-1) electron charge was
calculated after this experiment.
 Electron mass calculated with Thomson
and Millikan experiments.
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Atom Models

Robert Millikan

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Atom Models

Modified Cathode Beam Tube Experiment (Thomson‘s

Model)
Discovery of proton
 Electrons are break up from atoms by high
voltage so positive ions are formed.
 Positive ions move through negative
electrode (cathode) in an electric field.
 Most of these ions crash into electrons
and form neuter atoms. A few ions reach
the cathode. If the cathode has holes,
positive particles (protons) pass through
these holes.
 Rutherford 1914

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Atom Models

J.J. Thomas
Discovery of Isotope
 He discovered two Ne atoms each has same chemical
properties but different mass, while he was studing on Neon.

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Atom Models

Henry Moseley (1913) Determination of Atomic Number

 He discovered that;
 X-ray wavelength is characteristic of
anode metal,
 The atomic number of elements
correctly.
 Atomic number is equal to number of
positive charges,
 X-ray wavelength depends on atomic
number,
 Atoms of an element may contain same
number of protons while contain
different number of neutrons. (Dalton’s
atom model’s mistake)

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Atom Models

Nuclear Atom – Rutherford and His Team (1912-1913)

 (+) charged subatomic particles are mobilized to gold foil. Most

of these particles pass into the foil.

Determination of Atom’s porous structure

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Nuclear Atom – Rutherford and His Team (1912-1913)

 A few mobilized particles deflected slightly. Almost all particles passed into
foil without straying. The experiment was repeated with lead, cooper and
platinum foils and the results were same.
 If particles crash into electrons, they could break up electrons and stand on.
 Most particles went right through the gold foil but to his amazement a few
particles rebounded almost directly backwards. As a result, the whole mass of
the atom is concentrated in the center of the atom, in small volume, named
nucleus.

Discovery of Nucleus 21
Atom Models

Nuclear Atom – Rutherford and HisTeam (1912-1913)

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Atom Models

James Chadwick (1932)

Discovery of Neutron
Studying on Beryllium.
Electron: JJ.Thomson (1897)
Proton: Rutherford (1914)
Neuter: James Chadwick (1932)

Beryllium was bombarded with alpha particles and spread unknown

beams. Firstly, it was thought that these beams are gamma beams.

It is proved that this beam’s mass was equal to proton’s mass and
uncharged particles.

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Atom Models

James Chadwick (1932)

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Atom Models

Radioactivity

Radioactivity is getting stable of some

instable elements by disintegration
spontaneously and giving off particle or
electromagnetic radiation.

α, β (particle) and γ (beam)

When stable nucleus is bombarded with

accelerated particles, radiation can be
produced.

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Atom Models

Rutherford-Bohr Model of Atom

 Rutherford-Bohr, depicts the atom as a small, positively
charged nucleus surrounded by electrons that travel in circular
orbits around the nucleus—similar in structure to the solar
system, but with electrostatic forces providing attraction, rather
than gravity.
 The simplest example of the Bohr Model is for the hydrogen
atom (n = 1). An electron in the first allowed orbit (closest to the
nucleus) has n=1, an electron in the next allowed orbit further
from the nuclei has n=2, and so on.
 Electrons can only move from one orbital to another allowed
orbital at one time. If an electron drops down from n=2 to n=1
energy is emitted, and if the electron moves up from n=1 to n=2
energy is absorbed.
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Atom Models

Different
Atom Models

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Atomic Structure

To visualize the minuteness of the atom

 Consider that a typical human hair is about 1 million

carbon atoms in width
 A single drop of water contains about 2 sextillion (2×1021)
atoms of oxygen, and twice the number of hydrogen
atoms.
 A single carat diamond with a mass of 2×10−4 kg contains
about 10 sextillion (1022) atoms of carbon.
 If an apple were magnified to the size of the Earth, then
the atoms in the apple would be approximately the size of
the original apple.

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Atomic Structure

Comparison with Atomic Size

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Atomic Structure

 The electron (symbol: e−) is a subatomic particle with a

negative elementary electric charge

 The proton is a subatomic particle with the symbol p or p+ and

a positive electric charge of 1 elementary charge.

 The neutron is a subatomic hadron particle which has the

symbol n or n0, no net electric charge and a mass slightly larger
than that of a proton.

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Atomic Structure

An atom is composed of a nucleus

surrounded by electrons. (-)

 The nucleus contains neutrons and

positively charged protons and carries a
net positive charge
 The negatively charged electrons are
held to the nucleus by an electrostatic
attraction

(+)

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Structure of Atoms

Electrical Charge (C) Mass (g)

Electron 1.60x10-19 9.11X10-28
Proton 1.60x10-19 1.67x10-24
Neutron 0 1.67x10-24 (-) charge

(+) charge

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Atomic Structure

Gold “Au (100)” surface in Scanning Tunnel Microscope

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 THE STRUCTURE OF THE ATOM

 The atomic number of an element is equal to the number

of electrons or protons in each atom.
 The atomic mass of an element is equal to the average
number of protons and neutrons in the atom.
 The Avogadro number of an element is the number of
atoms or molecules in a mole.
 The atomic mass unit of an element is the mass of an atom
expressed as 1/12 the mass of a carbon atom.

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 Atomic Structure

 The nucleus contains neutrons and positively charged

protons and carries a net positive charge.
 The negatively charged electrons are held to the nucleus
by an electrostatic attraction.
 The atomic number of an element is equal to the
number of protons in each atom.
 The atomic mass M, which is equal to the total mass of
the average number of protons and neutrons in the atom
Atomic
in atomic mass units, is also the mass in grams of the structure of
Avogadro constant NA of atoms. He element
 An alternative unit for atomic mass is the atomic mass
unit, or amu, which is 1/12 the mass of carbon 12 (i.e.,
the carbon atom with twelve nucleons—six protons and
six neutrons).

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Atomic Structure

 An atom containing an equal number of protons and

electrons is electrically neutral, otherwise it has a positive
charge if there are fewer electrons (electron deficiency) or
negative charge if there are more electrons (electron
excess).

 A positively or negatively charged atom is known as an ion.

 An atom is classified according to the number of protons

and neutrons in its nucleus: the number of
protons determines the chemical element, and the number
of neutrons determines the isotope of the element

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Example - 1

Calculate the number of atoms in 100 g of silver.

SOLUTION
(100g )(6.0231023 atoms mol )
The number of silver atoms is =
(107.868 g mol )

= 5.58  1023

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Example - 2

Nano-Sized Iron-Platinum Particles For Information

Storage
Scientists are considering using nano-particles of such
magnetic materials as iron-platinum (Fe-Pt) as a medium
for ultrahigh density data storage. Arrays of such
particles potentially can lead to storage of trillions of bits
of data per square inch—a capacity that will be 10 to 100
times higher than any other devices such as computer
hard disks. If these scientists considered iron (Fe)
particles that are 3 nm in diameter, what will be the
number of atoms in one such particle?

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SOLUTION
The radius of a particle is 1.5 nm.
Volume of each iron magnetic nano-particle
= (4/3)(1.5  10-7 cm)3
= 1.4137  10-20 cm3
Density of iron = 7.8 g/cm3. Atomic mass of iron is 56 g/mol.
Mass of each iron nano-particle
= 7.8 g/cm3  1.4137  10-20 cm3
= 1.102  10-19 g.
One mole or 56 g of Fe contains 6.023  1023 atoms, therefore,
the number of atoms in one Fe nano-particle will be 1186.
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Example - 3
Dopant Concentration In Silicon Crystals
Silicon single crystals are used extensively to make computer chips.
Calculate the concentration of silicon atoms in silicon, or the
number of silicon atoms per unit volume of silicon. During the
growth of silicon single crystals it is often desirable to deliberately
introduce atoms of other elements (known as dopants) to control
and change the electrical conductivity and other electrical
properties of silicon. Phosphorus (P) is one such dopant that is
added to make silicon crystals n-type semiconductors. Assume that
the concentration of P atoms required in a silicon crystal is 1017
atoms/cm3. Compare the concentrations of atoms in silicon and
the concentration of P atoms. What is the significance of these
numbers from a technological viewpoint? Assume that density of
silicon is 2.33 g/cm3.
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SOLUTION
Atomic mass of silicon = 28.09 g/mol.
So, 28.09 g of silicon contain 6.023  1023 atoms.
Therefore, 2.33 g of silicon will contain
(2.33  6.023  1023/28.09) atoms = 4.99  1022 atoms. Mass of
one cm3 of Si is 2.33 g.
Therefore, the concentration of silicon atoms in pure silicon is
5  1022 atoms/cm3.

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SOLUTION (Continued)
Significance of comparing dopant and Si atom concentrations: If we
were to add phosphorus (P) into this crystal, such that the
concentration of P is 1017 atoms/cm3, the ratio of concentration of
atoms in silicon to that of P will be
(5  1022)/(1017)= 5  105. This says that only 1 out of 500,000 atoms
of the doped crystal will be that of phosphorus (P). This is equivalent
to one apple in 500,000 oranges. This explains why the single crystals
of silicon must have exceptional purity and at the same time very
small and uniform levels of dopants.

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The Electronic Structure of the Atom

 Electrons occupy discrete energy levels within the atom.

Each electrons possesses a particular energy, with no more
than two electrons in each atom having the same energy.

 This also implies that there is a definite energy difference

between each electron.

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The Electronic Structure of the Atom

Quantum Numbers
 The energy level to which each electron belongs is
determined by four quantum numbers.
 The Principal Quantum Number, n
 Azimuthal Quantum Number, l
 Magnetic Quantum Number, m1
 Spin Quantum Number, s

 The number of possible energy levels is determined

by the first three quantum numbers.

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Quantum Numbers
1. The Principal Quantum Number (n)
 The principal quantum number reflects the grouping of electrons into
sets of energy levels known as shells.

2. Azimuthal Quantum Number (l) and Magnetic Quantum

Number (ml)
 Azimuthal quantum numbers describe the energy levels within each shell
and reflect a further grouping of similar energy levels, usually called orbitals.
The magnetic quantum number specifies the orbitals associated with a
particular azimuthal quantum number within each shell.

3. Pauli Exclusion Principle and Spin Quantum Number (ms)

The spin quantum number (ms) is assigned values of +1/2 and -1/2, which
reflect the two possible values of “spin” of an electron

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Quantum Numbers

1. The principal quantum number (n) is assigned integral values

1, 2, 3, 4, 5, …, that refer to the quantum shell to which electron
belongs.

The atomic structure of

sodium, atomic number 11,
showing the electrons in the
K, L, and M quantum shells

Principle quantum number (n): 1 2 3 4 5 ...

Letters showing theShells: K L M N O ...
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Quantum Numbers

2. The number of energy levels in each quantum shell is

determined by the azimuthal quantum number (l)

l = 0, 1, 2, 3, …., n-1

 If n=2, then there are also two azimuthal quantum numbers,

l = 0 and l = 1.

s for l = 0 d for l = 2
p for l = 1 f for l = 3

Azimuthal quantum number (l) 0 1 2 3 4 ...

Letters showing theShells : s p d f g ...

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Quantum Numbers

3. The magnetic quantum number (ml).

 The magnetic quantum number ml gives the number of

energy levels, or orbitals, for each azimuthal quantum number.
The total number of magnetic quantum numbers for each “l”
is 2l + 1.

 The values for ml are given by whole numbers between –l

and +l.

 For l = 2,
ml = (2)2 + 1 = 5
magnetic quantum numbers with values -2, -1, 0, +1, and +2.

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Quantum Numbers

4. The Pauli exclusion principle specifies that no more

than two electrons, each with opposing electronic spins, may be
present in each orbital.

 The spin quantum number (ms) is assigned

values +1/2 and -1/2 to reflect the different spins.

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The complete set of quantum numbers for each of the 11 electrons in sodium

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The Electronic Structure of the Atom

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52
 Deviation from the Electronic Structure

 Electronic structure increases by increase of atomic number.

While d and f levels start to fill up, electrons are
 For example; atomic number of Fe is 26;

 Expected: 1s2 2s2 2p6 3s23p63d8

 In real: 1s2 2s2 2p6 3s23p63d64s2

 The unfilled area in 3d level gives magnetic characteristic to Fe.

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Valence

 The valence of an atom is related to the ability of the atom to

enter into chemical combination with other elements and is
often determined by the number of electrons in the outermost
combined sp level.

Mg: 1s22s22p6 3s2 valence = 2

Al: 1s22s22p6 3s23p1 valence = 3

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 Atomic Stability

 If an atom has a valence of zero, no electrons enter into

chemical reactions and the element is inert.

Argon
1s22s22p6 3s23p6

Chlorine The reactivity of chlorine is caused by its desire to

1s22s22p6 3s23p5 fill its outer energy level by accepting an electron.

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 Electronegativity
 Describes the tendency of an atom to gain an electron.

 Atoms with almost completely filled outer energy levels,

like chlorine, are strongly electronegative and readily accept
electrons.

 However, atoms with nearly empty outer levels, such as

sodium, readily give up electrons and strongly
electropositive.

1s22s22p6 3s1 Valence electrons electronegativitybonding type

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 © 2003 Brooks/Cole Publishing / Thomson Learning™
The electronegativities of selected elements relative to the position
of the elements in the periodic table

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Example - 4
Comparing Electronegativities
Using the electronic structures, compare the electronegativities of
calcium and bromine.
SOLUTION
The electronic structures, obtained from Appendix C, are:
Ca: 1s22s22p63s23p6 4s2
Br: 1s22s22p63s23p63d10 4s24p5
Calcium has two electrons in its outer 4s orbital and bromine has seven
electrons in its outer 4s4p orbital. Calcium, with an electronegativity of
1.0, tends to give up electrons and has low electronegativity, but
bromine, with an electronegativity of 2.8, tends to accept electrons and
is strongly electronegative. This difference in electronegativity values
suggests that these elements may react readily to form a compound.
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The Periodic Table

 The periodic table contains valuable information about specific

elements and can also help identify trends in atomic size, melting
point, chemical reactivity, and other properties.

 On July 2012, the International Union of Pure and Applied Chemistry

(IUPAC) approved the addition of flerovium and livermorium to the
periodic table of elements.

 Two new elements brings the total number of elements on the

periodic table to 118.

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The Periodic Table
THE PERIODIC TABLE

The IA to VIIA Elements

 The rows in the periodic table correspond to quantum

shells, or principal quantum numbers.

 Li – Ne  contain electrons in the L shell (n=2)

Na – Ar  contain electrons in the M shell (n=3)

 Li, Na and K in column IA have a valence of one

F, Cl and Br in column VIIA have a valence of seven

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The Periodic Table

The IIIB to VIIIB Elements

 In each of these rows, an inner energy level is progressively

filled.
 Sc – Zn  Transition elements and contain valence
electrons in the N shell.

The electronic configuration of the transition elements

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The Periodic Table

The IB to IIB Elements

 Complete inner shells and one or two valence electrons.

 K: 1s22s22p63s23p6 4s1

 Cu: 1s22s22p63s23p6 3d104s1

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The Periodic Table

• Hydrogen
– Hydrogen is all alone in its own group
– Reactive gas
– It caused hinderberg explosion
– Altenative fuel

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The Periodic Table

 Alkali Metals
 The alkali metals, found in group 1 of the
periodic table, are highly reactive metals that
do not occur freely in nature.
 These metals have only one electron in their
outer shell. Therefore, they are ready to lose
that one electron in ionic bonding with other
elements.
 As with all metals, the alkali metals are
malleable, ductile, and are good conductors of
heat and electricity.
 The alkali metals are softer than most other
metals.
 Na, K, Li, Rb, Cs, Fr
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The Periodic Table

 Alkaline Metals
 The alkaline earth elements are metallic
elements found in the second group of the
periodic table.
 All alkaline earth elements have an
oxidation number of +2, making them very
reactive
 Mg, Ca, Ba, Be

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The Periodic Table

 Transition Metals
 The 38 elements in groups 3 through 12 of the
periodic table are called "transition metals."
 As with all metals, the transition elements are
both ductile and malleable, and conduct
electricity and heat.
 Their valence electrons are present in more
than one shell. This is why they often exhibit
several common oxidation states.
 V, Cr, Mn, Fe

66
The Periodic Table

Other metals
The "other metals" elements are located in groups 13, 14, and
15.
While these elements are ductile and malleable, they are not
the same as the transition elements.
These elements, unlike the transition elements, do not exhibit
variable oxidation states, and their valence electrons are only
present in their outer shell. A
ll of these elements are solid, have a relatively high density,
and are opaque.
They have oxidation numbers of +3, ±4, and -3.
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The Periodic Table

Metalloids Non-metals
 Metalloids are the elements  Non-metals are the elements in
found between the boundary groups 14-16 of the periodic table.
that distinguishes metals  Non-metals are not able to conduct
from non-metals. electricity or heat very well.
 Metalloids have properties  As opposed to metals, non-metallic
of both metals and non- elements are very brittle.
metals.
 The non-metals can be gases, such
 Some of the metalloids, such as oxygen and solids, such as
as silicon and germanium, are carbon.
semi-conductors
 The non-metals have no metallic
luster, and do not reflect light.
 They have oxidation numbers of
±4, -3, and -2.

68
The Periodic Table

Noble gases
Halogens The noble gases are found in
The halogens are five non- group 18 of the periodic table.
metallic elements found in group These elements have an
17 of the periodic table. oxidation number of 0.
All halogens have 7 electrons This prevents them from
in their outer shells, giving them forming compounds readily.
an oxidation number of -1.
All noble gases have 8 electrons
in their outer shell, making them
stable.

69
The Periodic Table

Rare Earth
 The 30 rare earth elements are composed of the
lanthanide and actinide series.
 One element of the lanthanide series and most of the
elements in the actinide series are synthetic, that is,
human-made.
 All of the rare earth metals are found in group 3 of the
periodic table, and the 6th and 7th periods.

70
 71
Periodic Table of Elements
© 2003 Brooks/Cole Publishing / Thomson Learning™
Atomic Bonding

There are 4 important mechanisms by which atoms are

bonded in solids. In three of the four mechanisms, bonding
is achieved when the atoms fill their outer s and p levels.

1. Metallic Bond
2. Covalent Bond
3. Ionic Bond
4. Van der Waals Bonding

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Metallic Bonding
 The metallic elements, which have a low valence, give up their
valence electrons to form a “sea” of electrons surrounding the
atoms.
 Metallic bonds are nondirectional.

 Allows metals to be ductile, good

electrical conductors.

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Metallic Bonding

Mechanical Properties of Metallic Bond

Force

 Atoms joined by the metallic bond can shift their relative

positions when the metal is deformed, permitting metals to
have good ductility.

74
Metallic Bonding

When voltage is applied to a metal, the electrons in the electron

sea can easily move and carry a current 75
 Example - 5

Calculate the number of electrons capable of conducting an electrical charge in

ten cubic centimeters of silver.
SOLUTION
The valence of silver is one, and only the valence electrons are expected to
conduct the electrical charge. From Appendix A, we find that the density of silver
is 10.49 g/cm3. The atomic mass of silver is 107.868 g/mol.

Mass of 10 cm3 = (10 cm3)(10.49 g/cm3) = 104.9 g

(104.9 g )(6.0231023 atoms / mol )
Atoms =  5.85 1023
107.868g / mol
Electrons = (5.85  1023 atoms)(1 valence electron/atom)
= 5.85  1023 valence electron/atom per 10 cm3

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Covalent Bonding

 Share e- among two or more atoms.

 Directional
 Strong
 Covalently bonded materials are brittle and behave as electrical insulator.

In silicon, with a valence of four, four covalent bonds must be formed. 77

 78

© 2003 Brooks/Cole Publishing / Thomson Learning™

Covalent Bonds are directional.
Covalent Bonding

Force

Force

 Covalently bonded materials have poor ductility and poor

electrical conductivity.

 For an e- to move and carry a current, the covalent bond must be

broken, requiring high temperature or voltages.
79
Example - 6

Assuming that silica (SiO2) has 100 % covalent bonding, describe

how oxygen and silicon atoms in silica (SiO2) are joined.
SOLUTION
Silicon has a valence of four and shares electrons with four oxygen
atoms, thus giving a total of eight electrons for each silicon atom.
However, oxygen has a valence of six and shares electrons with
two silicon atoms, giving oxygen a total of eight electrons. Figure
2-16 illustrates one of the possible structures. Similar to silicon
(Si), a tetrahedral structure also is produced. We will discuss later
in this chapter how to account for the ionic and covalent nature of
bonding in silica.

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The tetrahedral structure of silica (Si02), which contains covalent
bonds between silicon and oxygen atoms (Example 6)
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Example - 7

A thermistor is a device used to measure temperature by taking

advantage of the change in electrical conductivity when the
temperature changes. Select a material that might serve as a
o
thermistor in the 500 to 1000 C temperature range.

Photograph of a commercially available

thermistor. (Courtesy of Vishay
Intertechnology, Inc.)

82
SOLUTION
The resistance of a thermistor can be made to increase or
decrease with increasing temperature.These are known as
positive temperature coefficient of resistance (PTCR) or negative
temperature coefficient of resistance (NTCR) thermistors,
respectively.The fact that a thermistor changes its resistance in
response to a temperature change is used to control
temperature or switch (turn ‘‘on’’ and ‘‘off ’’) the operation of
an electrical circuit when a particular device (i.e., a refrigerator,
hairdryer, furnace, oven, or reactor) reaches a certain
temperature.

83
SOLUTION (Continued)
Two design requirements must be satisfied. First, a material with a high
melting point must be selected. Second, the electrical conductivity of the
material must show a systematic and reproducible change as a function of
temperature. Covalently bonded materials might be suitable. They often
have high melting temperatures, and, as more covalent bonds are broken
when the temperature increases, increasing numbers of electrons become
available to transfer electrical charge.
The semiconductor silicon is one choice: Silicon melts at 1410oC
and is covalently bonded. A number of ceramic materials also have high
melting points and behave as semiconducting materials. Silicon will have
to be protected against oxidation. We will have to make sure the changes
in conductivity in the temperature range are actually acceptable. Some
thermistors that show a predictable decrease in the resistance with
increasing temperature are made from semiconducting materials.
84
SOLUTION (Continued)
Polymers would not be suitable, even though the major
bonding is covalent, because of their relatively low melting, or
decomposition, temperatures. Many thermistors that can be
used for switching applications make use of barium titanate
(BaTiO3) based formulations. Many useful NTCR materials are
based on Fe3O4-ZnCr2O4, Fe3O4-MgCr2O4, or Mn3O4, doped with
Ni, Co, or Cu.
In almost any design situation, once the technical
performance criteria are met we should always pay attention to
and take into account the cost of raw materials, manufacturing
costs, and other important factors such as the durability. In
some applications, we also need to pay closer attention to the
environmental impact including the ability to recycle materials.

85
Ionic Bonding

 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.
 Oppositely charged ions are attracted to one another and produce the
ionic bond.
 An ionic bond is created between two unlike atoms with different
electronegativities. When sodium donates its valence electron to chlorine,
each becomes an ion; attraction occurs, and the ionic bond is formed
Properties of ionic bonds
 Strong
 Low electrical conductivity
 Brittle
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 © 2003 Brooks/Cole Publishing / Thomson Learning™
 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 then
attracted to one another and produce the
ionic bond.
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Example - 8
Describing the Ionic Bond Between Magnesium and Chlorine
Describe the ionic bonding between magnesium and chlorine.
SOLUTION
The electronic structures and valences are:
Mg: 1s22s22p6 3s2 valence = 2
Cl: 1s22s22p6 3s23p5 valence = 7
Each magnesium atom gives up its two valence electrons,
becoming a Mg2+ ion. Each chlorine atom accepts one
electron, becoming a Cl- ion. To satisfy the ionic bonding, there
must be twice as many chloride ions as magnesium ions
present, and a compound, MgCl2, is formed.
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SOLUTION (Continued)

Solids that exhibit considerable ionic bonding are also often

mechanically strong because of the strength of the bonds.
Electrical conductivity of ionically bonded solids is very limited. A
large fraction of the electrical current is transferred via the
movement of ions. Owing to their size, ions typically do not
move as easily as electrons. However, in many technological
applications we make use of the electrical conduction that can
occur via movement of ions as a result of increased temperature,
chemical potential gradient, or an electrochemical driving force.
Examples of these include, lithium ion batteries that make use of
lithium cobalt oxide, conductive indium tin oxide coatings on
glass for touch sensitive screens for displays, and solid oxide fuel
cells based on compositions based on zirconia (ZrO2).
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When voltage is applied to an ionic material, entire ions must

move to cause a current to flow. Ion movement is slow and the
electrical conductivity is poor (for Example 8)
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Van Der Waals Bonding

 Join molecules or groups of atoms by weak electrostatic attractions.

 Interactions are formed as a result of polarization of molecules or groups

of atoms.

 In water, e- in the oxygen tend to concentrate away from the hydrogen.

The resulting charge difference permits the molecule to be weakly bonded
to other water molecules
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Illustration of London forces, a type of a van der Waals force,
between atoms

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Mixed Bonding

(a) In polyvinyl chloride (PVC),

the chlorine atoms attached to
the polymer chain have a
negative charge and the
hydrogen atoms are positively
charged. The chains are
weakly bonded by van der
Waals bonds.
This additional bonding makes
PVC stiffer, (b) When a force is
applied to the polymer, the
van der Waals bonds are
broken and the chains slide
past one another

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Example - 9
Determine if Silica is Ionically or Covalently Bonded
In a previous example, we used silica (SiO2) as an example of a
covalently bonded material.In reality, silica exhibits ionic and covalent
bonding. What fraction of the bonding is covalent? Give examples of
applications in which silica is used.
SOLUTION
We estimate the electronegativity of silicon to be 1.8 and that of
oxygen to be 3.5. The fraction of the bonding that is covalent is:
Fraction covalent = exp[-0.25(3.5 - 1.8)2] = exp(-0.72) = 0.486
Although the covalent bonding represents only about half of the
bonding, the directional nature of these bonds still plays an important
role in the eventual structure of SiO2.

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SOLUTION (Continued)

Silica has many applications. Silica is used for making glasses and
optical fibers. We add nano-sized particles of silica to tires to
enhance the stiffness of the rubber. High-purity silicon (Si) crystals
are made by reducing silica to silicon.

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Example - 10

Design Strategies for Silica Optical Fibers

Silica is used for making long lengths of optical fibers. Being a
covalently and ionically bonded material, the strength of Si-O
bonds is expected to be high. Other factors such as
susceptibility of silica surfaces to react with water vapor in
atmosphere have a deleterious effect on the strength of silica
fibers. Give n this, what design strategies can you think of such
that silica fibers could still be bent to a considerable degree
without breaking?

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SOLUTION
Based on the mixed ionic and covalent bonding in silica we know
that the Si-O bonds are very strong. We also know that covalent
bonds will be directional and hence we can anticipate silica to
exhibit limited ductility. Therefore, our choices to enhance ductility
of optical fibers are rather limited since the composition is
essentially fixed. Most other glasses are also brittle. We can make
an argument that silica fibers will exhibit better ductility at higher
temperatures. However, we have to use them for making long
lengths of optical fibers (most of which are to be buried
underground or under the sea) and hence keeping them at an
elevated temperature is not a practical option.

97
SOLUTION (Continued)
Therefore, we need to understand, beyond what the
nature of bonding consideration can offer us, why glass fibers
exhibit limited ductility. Is this a property that is intrinsic to the
glass or are there external variables that are causing a change in
the chemistry and structure of the glass? Materials scientists and
engineers have recognized that the lack of ductility in optical
glass fibers is linked to the ability of the silica surface to react
with water vapor in the atmosphere. They have found that water
vapor in the atmosphere reacts with the surface of silica leading
to micro-cracks on the surface. When subjected to stress these
cracks grow rapidly and the fibers break quite easily! They have
also tested silica fibers in a vacuum and found that the levels to
which one can bend fibers are much higher.
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Binding Energy and Interatomic Spacing

Interatomic spacing equilibrium distance between atoms and is

caused by a balance between repulsive and attractive forces.
Binding energy The energy required to separate two atoms from their
equilibrium spacing to an infinite distance apart. The binding energy is
a measure of the strength of the bond between two atoms.
Yield strength The level of stress above which a material permanently
deforms.
Coefficient of thermal expansion (CTE) The fractional change in linear
dimension of a material per degree of temperature. A material with a
low coefficient of thermal expansion tends to retain its dimensions
when the temperature changes.

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 Binding Energy and Interatomic Spacing

Atoms or ions are separated by and

equilibrium spacing that corresponds
to the minimum inter-atomic energy
for a pair of atoms or ions (or when
zero force is acting to repel or attract
the atoms or ions)

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Binding Energy and Interatomic Spacing

Bond Binding Energy (kcal/mol)

Ionic 150-370
Covalent 125-300
Metallic 25-200
Van der Waals < 10

 Materials having a high binding energy also have a high strength

and a high melting temperature.

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The force-distance curve for two materials, showing the relationship

between atomic bonding and the modulus of elasticity, a steep dF / da
slope gives a high modulus
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Learning™

 The inter-atomic energy (IAE)-separation curve for two atoms.

 Materials that display a steep curve with a deep trough have low linear
coefficients of thermal expansion. 103
 Example - 11
NASA’s space shuttles have a long manipulator robot arm, also known as
the Shuttle Remote Manipulator System or SRMS, that permits astronauts
to launch and retrieve satellites. It is also used to view and monitor the
outside of the space shuttle using a mounted video camera. Select a
suitable material for this device.

NASA’s Shuttle Remote

Manipulator System: SRMS
Courtesy of Getty Images)

104
SOLUTION
Let’s look at two of the many material choices.First, the
material should be stiff so that little bending occurs when a
load is applied; this feature helps the operator maneuver
the manipulator arm precisely. Generally, materials with
strong bonding and high melting points also have a high
modulus of elasticity, or stiffness. Second, the material
should be light in weight to permit maximum payloads to be
carried into orbit; a low density is thus desired. It is
estimated that it costs about US $100,000 to take the
weight of a beverage can into space! Thus, the density must
be as low as possible.

105
SOLUTION (Continued)
Good stiffness is obtained from high-melting-point metals (such as
beryllium and tungsten), from ceramics, and from certain fibers
(such as carbon). Tungsten, however, has a very high density, while
ceramics are very brittle. Beryllium, which has a modulus of
elasticity that is greater than that of steel and a density that is less
than that of aluminum, might be an excellent candidate. However,
toxicity of Be and its compounds must be considered. The preferred
material is a composite consisting of carbon fibers embedded in an
epoxy matrix. The carbon fibers have an exceptionally high modulus
of elasticity, while the combination of carbon and epoxy provides a
very low-density material. Other factors such as exposure to low
and high temperatures in space and on earth must also be
considered. The current shuttle robot arm is about 45 feet long, 15
inches in diameter and weighs about 900 pounds. When in space it
can manipulate weights up to 260 tons.
106
Summary

107