Sanaag University

Chapter two

Structure of materials
Introduction

All matter has physical and chemical properties

 Physical properties: are characteristics that scientists can measure without changing the
composition of the sample under study. Here are many physical properties, and include
color, density, volume (the amount of space occupied by a sample) , mass, boiling point,
and melting point.
 Chemical properties: Describe the characteristic ability of a substance to react to form
new substances; they include its flammability and susceptibility to corrosion. All samples
of a pure substance have the same chemical and physical properties. For example, pure
copper is always a reddish-brown solid (a physical property) and always dissolves in
dilute nitric acid to produce a blue solution and a brown gas (a chemical property).
 Physical properties can be extensive or intensive.
 Extensive properties: depend on the amount of matter in the sample and include mass,
weight, and volume
 Intensive properties: In contrast, do not depend on the amount of the substance; they
include color, melting point, boiling point, electrical conductivity, and physical state at a
given temperature. For example, elemental sulfur is a yellow crystalline solid that does
not conduct electricity and has a melting point of 115.2 °C, no matter what amount is
examined
 Atoms, molecules and Brownian motion

 The modern atomic theory was proposed in 1803 by John Dalton, an English
schoolteacher. He thought of atoms as tiny, indivisible particles, all the atoms of a given
element being exactly alike and different from those of other elements in behavior and
mass. By making simple assumptions he explained the gravimetric (i.e. by weight) laws
of chemical combination but failed to account satisfactorily for the volume relationships
which exist between combining gases. This required the introduction in 1811 by the
Italian scientist, Amedeo Avogadro, of the molecule as the smallest particle of an element
or compound capable of existing independently and consisting of two or more atoms, not
necessarily identical. So, while we could only have atoms of elements, molecules of both
elements and compounds were possible
 At the end of the nineteenth century some scientists felt that evidence, more direct than
that provided by the chemist, was needed to justify the basic assumption that atoms and
molecules exist. In 1827 the Scottish botanist, Robert Brown, discovered that fine pollen
grains suspended in water were in a state of constant movement, describing small,
irregular paths but never stopping. The effect, which has been observed with many kinds
of small particles suspended in both liquids and gases, is called Brownian motion. It is
now considered to be due to the unequal bombardment of the suspended particles by the
molecules of the surrounding medium.
 Very small particles are essential. If the particle is very large compared with the size of a
molecule, the impacts, occurring on every side and irregularly, will cancel out and there
will be no average resultant force on the particle. However, if the particle is small enough
to suffer impacts with only a few hundred molecules at any instant, the chances of these
cancelling out are proportionately less. It is then likely that for a short time most of the
impacts will be in one direction; shortly afterwards the direction will have changed. The
phenomenon can be observed in smoke in a small glass cell which is illuminated strongly
from one side and viewed from above with a low-power
microscope, Fig. below How would the random motion
be affected by:

(i) cooling the air to a low temperature

(ii) using smaller smoke particles

 Avogadro constant: the mole

 Atomic and molecular masses give the masses of atoms and molecules compared with the
mass of another kind of atom. Originally the hydrogen atom was taken as the standard,
with atomic mass 1, since it has the smallest mass. In 1960 it was agreed internationally
to base atomic and molecular masses on the carbon-12 isotope 126𝐶 The atomic mass of
carbon-12 is taken as exactly 12, making that of hydrogen 1.008 and of oxygen 16.00.
Atomic masses are found very accurately using a mass spectrometer.
 From the definition of atomic mass, any number of atoms of carbon will have 12 times
the mass of the same number of atoms of hydrogen; 1 g of hydrogen mill contain the
same number of atoms as 12 g of carbon. In general, the atomic mass of any element.
Expressed in grams, contains the same number of atoms as 12 g of carbon. This number
is, by definition, a constant. It is called the Avogadro constant and is denoted by L. Its
accepted experimental value is 6.02 x 1023
 The number of molecules in the molecular mass in grams of a substance is also the same
for all substances and equal to the Avogadro constant. There are, therefore, 6.02 x 1023
molecules in 2 g of hydrogen (molecular mass 2) and in 18 g of water (molecular mass
18). The Avogadro constant is useful when dealing with other particles besides atoms and
molecules, and a quantity which contains 6.02 x1023 particles is called a mole. We can
have a mole of atoms, a mole of molecules, 3 mole of ions or a mole of electrons; all
contain 6.02x1023 particles
L= 6.02x1025 particles per mole
 Sometimes quantities are expressed in terms of kilogram-moles; the number of particles
per kilogram-mole is 6.02 𝑥1026. The Avogadro constant has been measured in various
ways. In an early method alpha particles emitted by a radioactive source were counted by
allowing those within a small known angle to strike a fluorescent screen. Each particle
produced one scintillation on the screen and if it is assumed that one particle is emitted by
each radioactive atom an approximate value for L can be obtained other methods give
more reliable results; one involves X-ray crystallography.
 Periodic table

o If the elements are arranged in order of increasing atomic mass at certain repeating
interval, elements occur with similar chemical properties
o Sometimes is necessary to place an element of large atomic mass before one of the
slighter atomic mass to preserve the pattern.
o The first eighteen elements of this arrangement is called periodic table.
o The third and the eleventh and elements are alkali metals (Li, and Na)
o The nine and seventeen are halogens (F and Cl)
o The serial number of an element in the table is called its atomic number.

Inter atomic bonds

Inter atomic bonding: The bonding between atoms which holds atoms together to form solids
materials.

The type of chemical bonds formed varies in strength and properties. There are 4 primary types
of chemical bonds which are formed by atoms or molecules to yield compounds. These types of
chemical bonds include:

 Ionic Bonds
 Covalent Bonds
 Hydrogen Bonds
 Polar Bonds
These types of bonds in chemical bonding are formed from the loss, gain, or sharing of electrons
between two atoms/molecules.

Ionic Bonding
Ionic bonding is a type of chemical bonding which involves a transfer of electrons from one
atom or molecule to another. Here, an atom loses an electron which is in turn gained by another
atom. When such an electron transfer takes place, one of the atoms develops a negative charge
and is now called the anion.
The other atom develops a positive charge and is called the cation. The ionic bond gains strength
from the difference in charge between the two atoms, i.e. the greater the charge disparity
between the cation and the anion, the stronger the ionic bond.
What is Ionic Bond?
The bond formed as a result of strong electrostatic forces of attraction between a positively and
negatively charged species is called an electrovalent or ionic bond. The positively and negatively
charged ions are aggregated in an ordered arrangement called the crystal lattice which is
stabilized by the energy called the Lattice enthalpy.
Conditions for the formation of an Ionic Bond

 The low ionization energy of the atom forming the cation.

 High electron gain enthalpy of the atom forming the anion.
 High negative lattice enthalpy of the crystal formed.
Generally, the ionic bond is formed between a metal cation and non-metal anion

Covalent Bonding
A covalent bond indicates the sharing of electrons between atoms. Compounds that contain
carbon (also called organic compounds) commonly exhibit this type of chemical bonding. The
pair of electrons which are shared by the two atoms now extend around the nuclei of atoms,
leading to the creation of a molecule.

Polar Covalent Bonding

Covalent bonds can be either be Polar or Non-Polar in nature. In Polar Covalent chemical
bonding, electrons are shared unequally since the more electronegative atom pulls the electron
pair closer to itself and away from the less electronegative atom. Water is an example of such a
polar molecule.
A difference in charge arises in different areas of the atom due to the uneven spacing of the
electrons between the atoms. One end of the molecule tends to be partially positively charged
and the other end tends to be partially negatively charged.

Hydrogen Bonding
Compared to ionic and covalent bonding, Hydrogen bonding is a weaker form of chemical
bonding. It is a type of polar covalent bonding between oxygen and hydrogen where in the
hydrogen develops a partial positive charge. This implies that the electrons are pulled closer to
the more electronegative oxygen atom.
This creates a tendency for the hydrogen to be attracted towards the negative charges of any
neighboring atom. This type of chemical bonding is called a hydrogen bond and is responsible
for many of the properties exhibited by water.

Solid state

 The matter is made up of very tiny particles and these particles are so small that we
cannot see them with naked eyes.

 Matter can be classified into different categories based on the physical properties
exhibited by them and the states in which they exist; these are called states of matter.
 Following are the basic three states of matter:

 Solid
 Liquid
 Gas
 Apart from the above mentioned three, there are 2 more states of matter which we do not
see in our everyday life. They are Plasma & Bose-einstein condensate.
 During changes of state, temperature does not change it is remains constant, if the
temperature changes change of state does not occur.
Solid
 In solids, particles are tightly or closely packed.
 The gaps between the particles are tiny and hence it is
tough to compress them.
 Solid has a fixed shape and volume.
 Due to its rigid nature, particles in solid can only
vibrate about their mean position and cannot move.
 Force of attraction between particles is adamant.
 The rate of diffusion in solids is very low.
 An example of solids: solid ice, sugar, rock, wood, etc
 Liquid

 in a liquid state of matter, particles are less tightly packed as

compared to solids.
 Liquids take the shape of the container in which they are
kept.
 Liquids are difficult to compress as particles have less space
between them to move.
 Liquids have fixed volume but no fixed shape.
 The rate of diffusion in liquids is higher than that of solids.
 Force of attraction between the particles is weaker than
solids.
 Example of a liquid state of matter: water, milk, blood, coffee, etc

Gas
 In gases, particles are far apart from each other.
 Force of attraction between the particles is negligible,
and they can move freely.
 Gases have neither a fixed volume nor a fixed shape.
 The gaseous state has the highest compressibility as
compared to solids and liquids.
 The rate is diffusion is higher than solids and liquids.
 The kinetic energy of particles is higher than in solids
and liquids.
 An example of gases: air, helium, nitrogen, oxygen, carbon dioxide, etc

Plasma
 Plasma is a not so generally seen form of matter. Plasma consists of particles with
extremely high kinetic energy. Electricity is used to ionize noble gases and make glowing
signs, which is essentially plasma.
 Superheated forms of plasma are what stars are.

Bose-Einstein Condensates

 Discovered in 1995, Bose-Einstein condensates were made with the help of the
advancements in technology.
 Carl Weiman and Eric Cornell cooled a sample of rubidium with the help of magnets and
lasers to within a few degrees of absolute zero.
  At the said temperature, the motion of the molecules becomes negligible. As this brings
down the kinetic energy, the atoms no longer stay separate, but they begin to clump
together. As the atoms join together they form a super-atom.
 Light slows down as it passes through a BEC helping scientists to study more about the
nature of light as a wave and particle.
 BEC’s also show properties of a superfluid which implies, that it flows without friction

Can matter be created?

In addition, the first law of thermodynamics does not state that matter can not be created or
destroyed, but rather that the total amount of energy in a closed system can not be created or
destroyed, although it can be modified from one form to another.

Is matter created or destroyed?

There is a scientific law called the Mass Conservation Law, which Antoine Lavoisier discovered
in 1785. It states in its most compact form: matter is not created or destroyed. The universe’s
total mass and energy is constant.

Is matter-energy?
The mass of these three particles is less than a neutron’s mass, so each of them still gets some
energy. So the same thing is really power and matter. Fully interchangeable. So in a way, all
facets of the same thing are energy, matter, space and time.

Types of Solid States

Based on the arrangement of constituent particles, solids are classified into two-state types:

1. Crystalline Solids
2. Amorphous Solids or glassy

Crystalline Solid State

Crystalline solids are those that have a typical geometry. In such type of solids, there are definite
arrangements of particles (atoms, molecules or ions) throughout the 3-dimensional network of a
crystal in a long-range order. Examples include Sodium Chloride, Quartz, Diamond, etc.
Properties of Crystalline Solids

 Crystalline solids have a sharp melting point and start melting when it reaches a
particular temperature.
 The shape of crystalline solids are definite and having typical arrangements of particles.
 They show cleavage property i.e. when they are cut with the edge of a sharp tool they
split into two pieces and the newly generated surfaces are smooth and plain.
  They have definite heat of fusion (amount of energy needed to melt a given mass of solid
at its melting point).
 Crystalline solids are anisotropic which means their physical properties like electrical
resistance or refractive index show different values when they are measured along with
different directions in the same crystal.
 Crystalline solids are true solids.

Amorphous Solid State

Amorphous solid-state comprises of those solids which have the property of rigidity and
incompressibility but to a certain extent. They do not have a definite geometrical form or long
range of order. Examples include glass, rubber, plastic, etc.
Properties of Amorphous Solids

 Amorphous solids are gradually softened over a range of temperature and they can be
molded into different shapes on heating.
 Amorphous solids are pseudo solids or super cooled liquids which means they have a
tendency to flow very slowly. If you observe that the glass pans which is fixed to
windows of old buildings they are found to be slightly thicker from the bottom than at the
top.
 Amorphous solids have irregular shape i.e. their constituent particles do not have definite
geometry of arrangements.
 When amorphous solids are cut with a sharp edge tool they form pieces with irregular
surfaces.
 Amorphous solids do not have definite heat of fusion due to its irregular arrangement of
the particles.
 Amorphous solids are isotropic in nature which means the value of any physical property
would be same along any direction because of the irregular arrangement of particles.

Amorphous Solids Uses

Amorphous silicon which are one of the best photovoltaic material converts sunlight into
electricity.

Crystal structure
 In any sort of discussion of crystalline materials, it is useful to begin with a discussion of
crystallography.
 Crystallography: the study of the formation, structure, and properties of crystals.
 Crystal structure: is defined as the particular repeating arrangement of atoms
(molecules or ions) throughout a crystal.
 Structure: refers to the internal arrangement of particles and not the external appearance
of the crystal. However, these are not entirely independent since the external appearance
of a crystal is often related to the internal arrangement. For example, crystals of cubic
 rock salt (NaCl) are physically cubic in appearance. Only a few of the possible crystal
structures are of concern with respect to simple inorganic salts and these will be
discussed in detail, however, it is important to understand the nomenclature of
crystallography.
 Crystal lattice: is the symmetrical three-dimensional
structural arrangement of atoms, ions or molecules
(constituent particle) inside a crystalline solid as points.
It can also be defined as the geometrical arrangement of
the atoms, ions or molecules of the crystalline solid as
points in space

Crystallography
Crystallography: is a branch of science that deals with discerning the arrangement and bonding
of atoms in crystalline solids and with the geometric structure of crystal lattices. Classically, the optical
properties of crystals were of value in mineralogy and chemistry for the identification of substances.
Modern crystallography is largely based on the analysis of the diffraction of X-rays by crystals acting
as optical gratings. Using X-ray crystallography, chemists are able to determine the internal structures
and bonding arrangements of minerals and molecules, including the structures of large complex
molecules, such as proteins and DNA..

Description of Crystal Structures

Crystal structures may be described in a number of ways. The most common manner is to refer to the size
and shape of the unit cell and the positions of the atoms (or ions) within the cell. However, this
information is sometimes insufficient to allow for an understanding of the true structure in three
dimensions. Considering in several unit cells, the arrangement of the atoms with respect to each other, the
number of other atoms they in contact with, and the distances to neighboring atoms, often will provide a
better understanding. A number of methods are available to describe extended solid-state structures. The
most applicable with regard to elemental and compound semiconductor, metals and the majority of
insulators is the close packing approach.
Cubic Close Packing

Many crystal structures can be described using the concept of close packing. This concept
requires that the atoms (ions) are arranged so as to have the maximum density. In order to
understand close packing in three dimensions, the most efficient way for equal sized spheres to
be packed in two dimensions must be considered.

The most efficient way for equal sized spheres to be packed in two
dimensions is shown in Figure. in which it can be seen that each sphere
is surrounded by, and is in contact with, six other spheres. It should
be noted that contact with six other spheres the maximum possible is
the spheres are the same size, although lower density packing is possible.
Close packed layers are formed by repetition to an infinite sheet.
Within these close packed layers, three close packed rows are present,
shown by the dashed lines in Figure

The most efficient way for equal sized spheres to be packed in three dimensions is to stack close
packed layers on top of each other to give a close packed structure. There are two simple ways in
which this can be done, resulting in either a hexagonal or cubic close packed structures.

Hexagonal Close Packed

If two close packed layers A and B are placed in contact with each other so
as to maximize the density, then the spheres of layer B will rest in the
hollow (vacancy) between three of the spheres in layer A. This is
demonstrated in Figure on right. Atoms in the second layer, C (shaded
light gray), may occupy one of two possible positions (Figure on right
a or c) but not both together or a mixture of each. If a third layer is
placed on top of layer C such that it exactly covers layer A, subsequent
placement of layers will result in the following sequence, AC…AC… AC
This is known as hexagonal close packing or hcp.

Cubic Close Packed: Face-centered Cubic

Hexagonal system is one of the principal categories of structures to which a given crystalline solid can
be assigned. Components of crystals in this system are located by reference to four axes—three of equal
length set at 120° to one another and a fourth axis perpendicular to the plane of the other three. If
the atoms or atomic groups in the solid are represented by points and the points are connected
by line segments, the resulting lattice will define the edges of an orderly stacking of blocks, or unit cells.
The hexagonal unit cell is distinguished by the presence of a single line, called an axis of 6-fold
symmetry, about which the cell can be rotated by either 60° or 120° without changing its appearance.
 Tetrahedral
 Tetra- denotes four, and -hedral refers to a solid’s face; “tetrahedral
” literally means “having four faces.” When there are four bonds all
on one central atom and no lone electron pairs, this shape is formed.
The bond angles between the electron bonds are 109.5°.
 Methane is an example of a tetrahedral molecule (CH4). The four
equivalent bonds in three dimensions point in four geometrically
equivalent directions, corresponding to the four corners of a
tetrahedron centred on the carbon atom
 Tetrahedral is a molecular shape that occurs when there are four bonds and no lone pairs in
the molecule’s central atom. The atoms bonded to the central atom are located at the four
corners of a tetrahedron, with 109.5° angles between them.

Dislocations in a Crystal Lattice

Extended defects may be created either during crystal

growth or as a consequence of stress in the crystal lattice.

The plastic deformation of crystalline solids does not

occur such that all bonds along a plane are broken and
reformed simultaneously. Instead, the deformation occurs
through a dislocation in the crystal lattice.

The figure shows a schematic representation of a dislocation in a crystal lattice. Two features of
this type of dislocation are the presence of an extra crystal plane, and a large void at the
dislocation core. Impurities tend to segregate to the dislocation core in order to relieve strain
from their presence.