“As engineers we are primarily concerned with the properties of

materials at the macrostructural level, but inorder to understand these

properties, and modify them to our advantage, we need an
understanding of the structure of materials at the atomic level through
bonding forces, molecules and molecular arrangement” – Peter
Domone, Senior Lecturer in Concrete Technology, University
College London
So what????
Elements – Oh My Sweet Lord!!!
• Elements are materials too. This fact is often overlooked!
Grand scheme/bigger picture
@ Room Temperature
@ 1000 C – III A to VA Melted. Alkali metals (IA) - Vaporized
@ 2000 C - Alkali earth metals in molten. Transition metals begun to melt.
@ 3500 C – Carbon still holding on…….
First Ionization/Ionization Potential (IE)
 The energy required to remove the most weakly bound (usually outermost)
electron from an isolated gaseous atom (eV)

Z is the effective nuclear charge; n is the principal quantum number

Electron Affinity (EA)
 The reverse process of ionization. It is the energy change associated
with an isolated gaseous atom accepting one electron

EA can be positive or negative. Conditions and examples?

Electronegativity
 The (IE) and (EA) are characteristics of isolated atoms
 It says very little about how two atoms interact with each other
 It would be nice to have an independent measure of the attraction an
atom has for electrons in a bond formed with another atom –
Electronegativity!
Mulliken scale
Classification scheme for the various types of materials
Design of New Materials Through A “Critical
Thinking” Approach

 What exactly is “Critical Thinking”?

 Which other professions practice “Critical Thinking?

Doctors, Lawyers and etc,.

 What is it there for us in MSNT?

An example of a critical thinking scheme for the design of a new material
 Thus the objective of Materials Chemistry is to provide an overview of the
various types of materials, with a focus on synthetic methodologies and
relationships between the structure of a materials and its overall properties

 The broadly defined discipline of materials chemistry is focused on

understanding the relationships between the arrangement of atoms, ions, or
molecules comprising a material, and its overall bulk structural/physical
properties. By this designation, common disciplines such as polymer, solid-
state, and surface chemistry would all be placed within the scope of
materials chemistry.

This broad field consists of studying the structures/properties of existing

materials, synthesizing and characterizing new materials, and using
advanced computational techniques to predict structures and properties of
materials that have not yet been realized.
 Brain Teasers
 Are complex liquids such as crude oil or detergents considered
materials?

 Science is rapidly becoming an interdisciplinary field. Describe the

origin of chemistry disciplines(inorganic, organic, physical), to their
current status including multidisciplinary programs?

When a new technology is introduced, the consumer price is

astronomical. What are the factors that govern when and how much
this price will be lowered? Cite specific examples
Materials Selection and Design Problems
Cartridge brass is an alloy of two metals: 70 wt% copper and 30 wt%
zinc. Discuss the nature of the bonds between copper and zn in this
alloy
In the manufacture of a light bulb, the bulb is evacuated of air and
then filled with argon gas. What is the purpose of this?
A certain application requires a material that is electrically
nonconductive, extremely stiff, and lightweight. Which classes of
materials would you search for this selection? (b) Explain your answer
from a bonding point of view.
 Primary Bonds/Strong Bonds
 Why does bonding even occur?

Direct interaction of electrons between two or more atoms, either

through transfer or as a result of sharing

Four general categories

Ionic/Heteropolar
Covalent/Homopolar
Polar covalent
Metallic
 Ionic bond
Between highly electropositive and electronegative

When electrons are transferred from the more electropositive atom to

the more electronegative atom

Usually results when the electronegativity difference between two

atoms in a diatomic molecule is greater than about 2.0

Both atoms tend to be satisfied

Examples of substances with different types of interatomic bonding
 Covalent bonding
 Electrons are shared between two atoms (H-H)

The binding electron has the equal probability of being found around
either hydrogen atom

Electronegativity typically less than 0.4

Electronegativity between 0.4-2.0 leads to “polar covalent bond”
neither truly ionic or covalent (HF)
 Metallic bonding
Solid metals are visualized as consisting of positive-ion cores(atoms
without their valence electrons)

Valence electrons dispersed in the form of an electron cloud

The valence electrons “loosely” bound – “free electrons”

GRAPHITE

The outer valence electrons of the atoms are shared by many

surrounding atoms, and so, metallic bonding is non-directional
Secondary Bonding/van der Waals Bonds
Fluctuating Dipoles (Ne, Ar, Kr, Xe and Rn)
Permanent Dipoles (Methane, Water etc)
Hydrogen bonding a special case of permanent dipole-dipole
 Mixed Bonding
Ionic-Covalent Mixed Bonding (GaAs, ZnSe)

Metallic-Covalent Mixed Bonding

 Transition metals - high melting points
C, Si, Ge, Sn, Pb

Metallic-Ionic Mixed Bonding

 Significant difference in electronegativity
 Intermetallic compounds (NaZn13)
 Intermolecular Forces and Bonding
How do bonds form in the first place?

What is it that causes a sodium ion and a chloride ion to form a

compound, and what is it that prevents the nuclei from fusing together
to form on element?
Lennard-Jones Potential
 Potential Energy Concept and Analysis

• To calculate binding energies

• Physical Properties: This is in reflection to how tightly atoms are

bound. This further leads to Melting Point, Elastic Modulus, Thermal
Expansion and etc.
Lennard-Jones Potential
Existence of He2 and H2

H2
Depth of Well and Melting Temperature Tm
Crystal Packing and Potential Energy Well
Non-crystalline/Random Packing
 Crystalline/Dense/Ordered Packing

Conclusions: Materials with high ordered packing have good density, and hence good strength. This is because
they sit in the lowest part of the potential well
 Partial Ionic Character
• HF; HCl; HBr
• Though there is significant sharing of the electrons, some charge
distribution exists that results in a polar or partial ionic character to
the bond. The percent ionic character of the bond can again be
related to the electronegativities of the individual atoms:

• % ionic character = 100{1− exp[−0.25(χA − χB)2]}

• What is the percent ionic character of H–F?

Also known as chemical affinity, the attractive energy between atoms is what causes
them to approach each other. This attraction is due to the electrostatic force between
the nucleus and electron clouds of the separate atoms. It should make sense to you
that the attractive energy (UA) is inversely proportional to the separation distance, r;
that is, the further the atoms are apart, the weaker the attraction:

UA = − a/rm (1.9)
where a is a constant that we will describe in more detail in a moment, and m is a
constant with a value of 1 for ions and 6 for molecules. Notice that there is a negative
sign in eqn 1.9. By convention, we will refer to the attractive energy as a “negative
energy.”

Once the atoms begin to approach each other, they can only come so close together
due to the impenetrability of matter. The result is a repulsive energy, which we assign a
positive value, again, by convention. The primary constituents of this repulsive energy
are nucleus–nucleus and electron–electron repulsions. As with the attractive energy,
the repulsive energy is inversely proportional to the separation distance; the closer the
atoms are, the more they repel each other:
UR = b/rn (1.10)
where b and n are constants. The value of n, called the repulsion exponent, depends
on the outer core configuration of the atom. Values of the repulsion exponent are given
in Table 1.6.
….continuation
Properties of substances are dependent on
1. Packing type
2. Nearest neighbor bonds
3. Resulting crystal structure

Al/FCC Mg/HCP
 Mechanical Properties
Materials deformation (elongate, compress, twist) or break as a function of
applied load, time, temperature and other conditions
Hooke’s law σ = Eε; E (Modulus of elasticity or Young’s Modulus)
Stress (σ) and Strain (ε)
E actually tells us about stiffness. Higher E means higher stiffness of the
material or corresponding bonds
 At atomic level macroscopic elastic strain is perceived as small changes in
the interatomic spacing, and the stretching of interatomic bonds
This implies the magnitude of E is a measure of the resistance to separation
of adjacent atoms (interatomic bonding forces)
Ceramics, Metals and Polymers
 Yield Strength

The level of stress above which a material begins to show permanent

deformation
Atomistic/bonding perspective = breaking of bonds = no return =
reorganization of bonds
Low yield strength = inability to regain initial state = low elastic
modulus = low bonding energy = shallow PE well
 High MP Low MP
High TE
Low TE

Deep well