ENGINEERING MATERIALS

LESSON 1 – MOLECULAR STRUCTURE

OBJECTIVE OF LESSON

When you have successfully completed this lesson, you shou be able to:
• Recognize the structures of metals, polymers and ceramic materials.
• Assess the mechanical and physical properties of engineering materials
• Understand the relationships between the structure of a material and its properties.
• Select materials for specific engineering applications.

CONTENTS

1. Structure of the Atom

Nuclear Charge
Molecule
Sub Atomic Particles
Periodic Table

2. Electrostatic Force

3. Types of Bonds
Van der Waals
Covalent
Ionic
Metallic

4. CRYSTAL STRUCTURES
Body Centre Cubic
Face Centre Cubic
Hexagonal Close Packed
Carbon

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1. ATOMIC STRUCTURES

All substances are made up from atoms. A substance made from only one type of atom is called an
element. There are 92 different elements occurring naturally. The smallest and simplest element is
the hydrogen atom and the largest is uranium.

A molecule is a bonding of two or more atoms which may be of the

same element or of different elements. For example, one molecule of
water is made from two atoms of oxygen and one atom of hydrogen and
has the chemical symbol H2O.

The simplest model for atoms is to represent them as small spheres. This is very simplistic and we
know that an atom is much more complicated. The common model used to represent an atom is that
of a nucleus orbited by small particles called electrons. The orbit is very large compared to the size
of the nucleus. Electrons orbit the nucleus at various distances and form shells.

The nucleus is made up of two sub atomic particles called protons and neutrons that clump together.
These are large compared to the electrons. The protons carry a positive charge of electricity while the
electrons carry a negative charge of electricity (-1.6 x 10-19 Coulomb). The neutrons only affect the
mass of the atom and have no electric charge. Protons and neutrons have similar mass and size.
Electrons have a negligible mass. The mass of an atom is the mass of the nucleus. The atomic mass
is equal to the number of protons plus the number of neutrons. The atomic number Z is equal to the
number of protons. In the lighter elements the number of protons and neutrons are the same but as the
atomic number increases the number of neutrons increasingly exceeds the number of protons.

Positively and negatively charged particles are pulled together by a force of attraction and so the force
between the electrons and protons keep the electrons in orbit. The total positive charge of the nucleus
is always equal to the total negative charge of the electrons.

Electrons orbit the nucleus in shells of different sizes. There are a

maximum number of electrons that can exist in a given shell. The
first shell can contain a maximum of two electrons so if the nucleus
has one proton (Z = 1) there is only one electron and we have the
Hydrogen atom. If the nucleus has two protons (Z = 2), we must have
two electrons and this gives us Helium.

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As the number of protons and hence the charge of the nucleus increases another shell is formed with
anything from 1 to 8 electrons. After this the 3rd shell is formed with up to 18 electrons.
A rule for the maximum number of electrons in any given shell is 2n2 where n is the shell number.
Hence in the first shell it is 2, in the 2nd it is 8, in the third it is 18 and so on. However, it is more
complex than this due to sub shells and you would need to study quantum physics in order to
understand it.
The outer shell is the one that determines the chemical (bonding) properties of the element and it is
called the valence shell. Each atom with equal numbers of electrons and protons is an element. If they
are unequal it is an isotope (see next section). The elements are arranged into a periodic table, part of
which is shown next. The atomic number is the position in the table.

You should now refer to the complete periodic table (preferably by following the interactive link
http://www.ptable.com/). The position in the table is governed by the atomic number. The first line
of the table shows the possible combinations with only one shell (usually called orbital) and so
contains only two elements. The first is Hydrogen with one electron in the first shell and so is
incomplete. The second is Helium with two electrons in the first shell and so it is complete. This line
is not classed as any group of materials and stands on its own.

If the charge in the nucleus is increased to three, we must have 3 protons and this takes us to the next
line or orbital. This contains all the possible eight arrangements with a complete inner shell. Lithium
has a nucleus with 3 protons and 4 neutrons so has an atomic mass of approximately 7 and 3 electrons
to balance the protons. Next is Beryllium with one more charge having 4 protons and 5 neutrons and
so it has an atomic mass of approximately 9. This continues until we have Neon with a complete outer
shell of 8 electrons and a nucleus of 4 protons and 4 neutrons.

The number of protons and neutrons are not always equal so the atomic mass is not always double
the number of protons. For example, Sodium (Z=11) has 11 protons, 12 Neutrons and 11 electrons so
the atomic mass should be 23. In fact, it is 22.989. The atomic mass is not normally an exact number
but very close. Sodium is the first on the 3rd orbital and we might think this line of the table would
contain 18 possible combinations but there are only 8. At the end of this line we have Argon with 18
Protons, 22 Neutrons and 18 electrons with 8 in the outer shell (not 18 the maximum possible).

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If we examine the fourth row or orbital the last one is Krypton with 36 Protons, and 48 Neutrons and
36 electrons. To have 36 electrons it completely fills the third shell with 18 and has 8 in the fourth.

The table proceeds in this way up to the largest atom and the rules governing the structure are
complex and not explained further here.

All elements at the end of each row are noble gasses which will not chemically react with anything.
All others have the ability to combine with other elements to form new molecules. All elements at
the left end are alkaline metals. The elements can be grouped to show they have similar properties
and this is shown in the periodic table.

ISOTOPES

The number of neutron and protons in the core of an atom are usually equal and the mass
number is approximately twice the atomic number. However, there are many instances
where the nucleus contains more or less neutrons giving a slightly different atomic mass. For
example, carbon has 6 electrons so it should have 6 protons and 6 neutrons giving an atomic
mass of 12. It is found that it can also exist with 7 or 8 neutrons giving atomic masses of 13
and 14. These are called isotopes. Naturally occurring materials may have various amounts
of isotopes and the average molecular mass is usually given in the periodic table (e.g.
12.0107 for carbon). You can find many examples by exploring the periodic table.
It is interactive and gives other data as well.

ENERGY BANDS

The energy of an electron relative to the centre of the atom is the sum of the kinetic energy as it orbits
and the potential energy represented by its distance from the centre. The quantum theory supposes
that the total energy can only change in discrete steps so it follows that electrons can only orbit in
shells of fixed radii. This accounts for the various shells that make up the outer layers of an atom.

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 COMPLETE LIST OF THE ELEMENTS

Atomic Symbol Element Atomic Symbol Element Atomic Symbol Element

Number Number No.
(Z) . (Z) (Z)
1 H Hydrogen 36 Kr Krypton 71 Lu Lutecium
2 He Helium 37 Rb Rubidium 72 Hf Hafnium
3 Li Lithium 38 Sr Strontium 73 Ta Tantalum
4 Be Beryllium 39 Yt Yttrium 74 W Tungsten
5 B Boron 40 Zr Zirconium 75 Re Rhenium
6 C Carbon 41 Cb Niobium 76 Os Osmium
7 N Nitrogen 42 Mo Molybdenum 77 Ir Iridium

8 O Oxygen 43 Tc Technetium 78 Pt Platinum

9 F Fluorine 44 Ru Ruthenium 79 Au Gold
10 Ne Neon 45 Rh Rhodium 80 Hg Mercury
11 Na Sodium 46 Pd Palladium 81 TI Thallium
12 Mg Magnesiu 47 Ag Silver 82 Pb Lead
m
13 Al Aluminium 48 Cd Cadmium 83 Bi Bismuth
14 Si Silicon 49 In Indium 84 Po Polonium
15 P Phosphoru 50 Sn Tin 85 At Astatine
s
16 S Sulphur 51 Sb Antimony 86 Rn Radon
17 Cl Chlorine 52 Te Tellurium 87 Fr Francium
18 A Argon 53 I Iodine 88 Ra Radium
19 K Potassium 54 Xe Xenon 89 Ac Actinium
20 Ca Calcium 55 Cs Cesium 90 Th Thorium
21 Sc Scandium 56 Ba Barium 91 Pa Protactinium

22 Ti Titanium 57 La Lanthanum 92 U Uranium

23 V Vanadium 58 Ce Cerium 93 Np Neptunium
24 Cr Chromium 59 Pr Praseodymium 94 Pu Plutonium

25 Mn Manganese 60 Nd Neodymium 95 Am Americium

26 Fe Iron 61 Pm Promethium 96 Cm Curium
27 Co Cobalt 62 Sa Samarium 97 Bk Berkelium
28 Ni Nickel 63 Eu Europium 98 Cf Californium

29 Cu Copper 64 Gd Gadolinium 99 Es Einsteinium

30 Zn Zinc 65 Tn Terbium 100 Fm Fermium

31 Ga Gallium 66 Dy Dysprosium 101 Md Mendelevium

32 Ge Germaniu 67 Ho Holmium 102 No Nobelium

m
33 As Arsenic 68 Er Erbium 103 Lw Lawrencium

34 Se Selenium 69 Tm Thulium
35 Br Bromine 70 Yb Ytterbium

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2. ELECTRO STATIC FORCES

If a material contains a lot of electrons (e.g. copper), the electrons can be induced to break orbit and
flow through the material to form an electric current. If
we succeed in making electrons leave a material so that
it is deficient in electrons, it becomes positively charged.
Similarly, if we make a material obtain extra electrons, it
becomes negatively charged. This is the basis of static
electricity. Similarly charged bodies repel and oppositely
charged bodies attract. Static electricity is simply an
excess or surplus of electrons. Try rubbing an inflated
balloon against your shirt or jersey and observe how it
sticks to you.

The electroscope is an instrument that demonstrates the

repulsive force between charges. When a charged object
such as a glass rod is brought near to the conductor, the
two sheets of foil being similarly charged will fly apart.
Go to these web sites for a demonstration
http://www.shep.net/resources/curricular/physics/P30/Unit2/electroscope.html
http://www.glenbrook.k12.il.us/gbssci/Phys/mmedia/estatics/esn.html

3. BONDS

VAN der WAALS BONDING DISPERSION FORCES

This is a weak bond between molecules that are normally neutral. It comes about because the electron
movement in an individual molecule makes the electric charge vary with time at any given point in
the molecule. This means at any instant in time the molecule is polarised and forms a dipole.

We might think of the molecule as more positively charged at

one end than the other.

If another molecule comes close the uneven charge in the first

tends to attract or repel the electrons in the other and they
become synchronized. Even though the polarity is continually
moving around as the electrons orbit the nucleus, the molecules
will always attract each other.

In a gas these forces are very weak but when the substance is cooled the molecules come closer
together and the Van der Waals force makes the gas condense.

All other things being equal, bigger molecules have higher boiling points than small ones and have
more electrons. Consequently, the bond is larger and so the bigger molecules are "stickier". This
explains the property of liquids and gasses called VISCOSITY.

You will find more on this subject at the following web sites.

http://antoine.frostburg.edu/chem/senese/101/liquids/faq/h-bonding-vs-london-forces.shtml
http://www.chemguide.co.uk/atoms/bonding/vdw.html

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COVALENT BOND

The electrons in the outer shell of an atom are called the valence electrons. When this is incomplete,
it exhibits a force of attraction for electrons on surrounding atoms. This is called the electronegative
force. The reasons for this force are not explained here. The electronegative force is strong in metals
but not in non-metals.

When two atoms with similar electronegative forces come together, they often share an electron. For
example, hydrogen will attract another hydrogen atom to form a molecule consisting of two atoms
that share a common electron in order to be stable. This molecule has a symbol H2 to indicate there
are two atoms. Helium, on the other hand, is stable and will happily exist as one atom. The same thing
happens with oxygen that normally exists as O2 and Nitrogen N2 and so on.

THE HYDROGEN MOLECULE H2

When atoms are joined by sharing one or more electrons to form a molecule, we call it a covalent
bond.

The Methane Molecule CH4 is formed by this method as shown. The carbon atom has four electrons
in the outer shell but would be more stable with eight. The hydrogen atom has one electron but would
be more stable with two. If each hydrogen atom shares its electron with the carbon both are stable.

You will find more information at these web sites

http://en.wikipedia.org/wiki/covalent_bond

http://www.accessexcellence.org/RC/VL/GG/cov_IonicBs.html

This form of bonding is more likely in non-metals because the electronegative force is smaller and
it is easier to share an electron that steal one as happens in ionic bonding described next.

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ELECTROVALENT OR IONIC BONDING

When the electronegative force is large, a molecule may

attract an electron from a neighboring atom without sharing
it. The atom with an extra electron (or more) becomes
negatively charged and forms a negative ION. The atom
that loses an electron becomes positively charged and
forms a positive ION.

For example, when a metal and non-metal come together, the non-metal having a weak
electronegative force might give up its electron to the metal which has strong electronegative force.
The metal becomes negatively charged and the non-metal positively charged. Ions attract each other
like a pair of magnets and bond together. This is called electrovalent or ionic bonding.

For example, consider Lithium and Fluorine. The lithium gives up the one electron in its outer shell
to the fluorine and becomes a positively ion.

The addition of one electron to fluorine completes its outer shell and it becomes a negative ion. The
nucleus has a positive charge of 9 while the electrons total a negative charge of 10.

The lithium is now missing an entire outer shell and has a nucleus with a positive charge of 3 and
electrons with a negative charge of 2. The two nuclei have a difference of 9 – 3 = 6 charges and so
the two elements are pulled together.

For each case such as this, the two elements join together in a pattern that satisfies the condition
produced and in this case the fluorine atom must be surrounded by six lithium atoms and the lithium
atom by six fluorine atoms. When they solidify, a fixed pattern or lattice forms that satisfies this
condition and a crystal is formed. The 3D lattice is illustrated in the diagram and shows every atom
is surrounded by six of the other type.

This is the crystal lattice of lithium fluoride.

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METALLIC BOND

Another way of bonding occurs between the atoms of a metal. As the metal solidifies, the nucleus of
each atom (being positive and unbalanced) all repels each other and consequently form a pattern
(crystal). The nucleus is held in position by a swarm of electrons acting like glue between them. This
is called the metallic bond. This theory explains why metals are good conductors of electricity as the
cloud of electrons may be made to flow along a conductor when an electro motive force is applied.

4. TYPES OF CRYSTALLINE STRUCTURES

There are seven types of crystals based on the shape of the basic lattice. These are called triclinic,
monoclinic, orthorhombic, tetragonal, cubic, rhombohedra and hexagonal. Here are some of the
structures found in crystalline metals. Sometimes the same material may exist in different crystalline
forms and this is called POLYMORPHISM. The different forms are called ALLOTROPES and iron
is one example with two allotropes called  iron and  iron.

This a good web site to visit for an explanation of crystals.

http://www.ami.ac.uk/courses/topics/0131_mb/index.html

BODY CENTRE CUBIC (BCC)

The atoms arrange themselves with one at each corner and one right in the
middle of the cubic space. This is the structure produced for solid
chromium,  Iron and others.

FACE CENTRE CUBIC (FCC)

The atoms arrange themselves with one at each corner and one at the centre
of each face. This is the structure of  iron, aluminium, copper, gold and
nickel.

HEXAGONAL CLOSED PACK (HCP)

Visualize the structure as an extruded hexagon with an atom at every corner

plus three packed into the middle as shown. This is the structure of
Magnesium and Zinc.

In these crystalline structures, each corner atom forms part of another

structure and so the pattern is repeated throughout the crystal.

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CARBON

Carbon deserves a special mention. It exhibits some metallic properties (reasonable conductor) and
in diamond form is the hardest known material. In fibre form it makes a very strong material used in
composites. Used with iron it has a dramatic effect on the mechanical properties.

Carbon can form 2 different types of crystals, diamond and

graphite. A third type called ball carbon has been found but
does not appear to form naturally. Carbon has an atomic
number of 6 and a mass of 12. There are 6 electrons so there
must be four electrons missing from the second shell. This
means there are four bonds or valences to be used up when it
joins with other atoms.

In the diamond form each atom forms a covalent bond with four other atoms to form
a tetrahedral structure. The atom in the middle is surrounded by four others. This
pattern is also repeated for every atom at the corner. The bonding is equally strong
in all directions and this makes the strongest hardest material known.

In the graphite form, only 3 bonds are formed with free electrons so the
graphite forms into slippery layers loosely held together by the electrons.
This makes it suitable for dry lubrication and also enables it to conduct
electricity.

SELF ASSESSMENT EXERCISE No. 1

Research the main uses of diamonds for engineering and manufacturing applications and list
them.

Conduct further research and define the following. (e.g.

http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/Lecture1/Lec1.html#anchor2 )

i. Lattice
Motif
Crystal Structure
Unit Cell
Coordination Number

Describe the similarities and differences of ionic, covalent, metallic and Van der Waals
bonding.

Give examples of common materials exhibiting each of the bonding forces in Q2.

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