CHAPTER 1

Structure of Matter
Introduction:
All materials are built up from atoms and molecules, so it is not really
surprising that there is a close relationship between the atomic basis of a material and
its properties. Therefore, if we are to understand the properties of materials we need to
have an understanding of the way atoms can combine to make solids.
Generally, the physical, mechanical and chemical properties of any material
depend mainly on:
1- Atomic structure.
2- Inter-atomic bonding.
3- Arrangement of atoms in space.

I. Atomic Structure
The atom is the basic unit of the internal structure of any material
Atom consists of:
1- Central positive nucleus [positively charged protons and uncharged neutrons].
2- Negatively charged particles [electrons] revolving around the nucleus in definite
orbits (state of energy levels or shells).

N.B;
1. Electrical state of atom: Neutral.
2. Atomic number: Number of electrons.
3. Valence electrons: Electrons in the outermost shell, which determines the
chemical reactivity of the element.
4. The Atomic weight: Protons + Neutrons

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II. Inter-atomic Bonding:
Atoms achieve a stable state by having eight electrons in their outer shell (as in
inter gases). This can be obtained by:
a) Receiving extra electrons to complete the outer shell electrons (and the atom
becomes negative ion).
b) Releasing electrons so that the outer shell has eight electrons (and the atom
becomes positive ion).
c) Sharing of electrons so that the outer shells of two or more atoms are complete.
The formation of bonds, therefore, involves only the outer most valence electrons.
In solids, atoms are held together by either primary or secondary bonds.
1. Primary Bonds:
There are three types of primary bonds: Ionic, covalent and metallic bonds.
a) Ionic Bonds:
- It indicates electron transfer,
then the attraction of positive
and negative ions.
- The classic example is sodium chloride (Na+ C1-), because the sodium atom
contains one valence electron in its outer shell and the chlorine atom has seven
electrons in its outer shell, the transfer of the sodium valence electron to the
chlorine atom results in the stable compound Na+ Cl-.
- In dentistry, ionic bonding exists in some dental materials, such as gypsum and
phosphate cements.

Characteristics of ionic solids:

1- Heat resistant.
2- High strength and hardness.
3- Insoluble in organic solvents.
4- Easily dissolved in ionized solvents such as water, acids and alkalis, and
dissociate into their constituent ions in solutions which in their turn can conduct
an electric current.

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b) Covalent Bonds:
- "It is sharing of electrons". In many chemical compounds, two valence
electrons are shared by adjacent atoms.
- The hydrogen molecule, H2, is an example of covalent bonding. The single
valence electron in each hydrogen atom is shared with that of the other
combining atom, and the valence shells become stable.
- Covalent bonding occurs in many organic compounds, such as hydrocarbons
(CH4) and acrylic resin.
Characteristics of covalent bonds:
1) Water insoluble, but can be
dissolved in organic solvents.
2) Very strong and hard.
3) Insulators and can with stand high temperature.
4) Directional: Since the electrons will spend most of their time in the region,
where the orbits over lap.

c) Metallic Bonds:
- "It is the attraction between +ve cores and free electrons or electron cloud".
- It occurs in metals, because they easily give up the electrons in their valence
shells giving positives cores. The electrons move freely through the metal from
atom to atom and form electron cloud.
- There is attraction between free electrons and the positive charged cores.

Metallic bond

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Characteristics of the Metallic Bonds:
The free mobility of electrons contributes to the following properties of metals:
1- High thermal and electrical conductivity.
2- High strength and hardness.
3- Opacity due to absorption of light by free electrons.
4- Lustrous Free electrons reemit light.
5- Metals are malleable They can be hammered into thin sheets without
breaking.
6- Metals are ductile They can be drawn into thin wires.
N.B.:
 Sometimes more than one type of bond can exist in a material. An example is
CaSO4 (It has ionic and covalent bonds).
O
Ca++ [O-S- | O ]-
|
O

 Distinction should be made between atomic solids (e.g. diamond) and

molecular solids (e.g. polymers) where the covalently bonded molecules are
held by Vander Waal forces which control the mechanical properties.

II. Secondary Bonds (Van Der Waal Forces):

These forces are physical, weak, less heat resistant and arise from the polarization of
molecules i.e. formation of electrical dipoles.
A- Fluctuating Dipole:
- Instantaneous location of more electrons on one side of the nucleus than the
other results in asymmetry in their electron distribution.
- Very weak bonds can develop between atoms because these atoms attain a
dipole character. This leads to weak attractive forces between the fluctuating
dipoles in adjoining atoms.

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 Fluctuating Dipole

B- Permanent Dipole:
- The hydrogen bond is an important example. In H2O there is a covalent bond
because oxygen and hydrogen atoms share electrons.
- However, the electrons around oxygen nucleus are more than those around the
hydrogen nucleus and as a result the hydrogen portion of the water molecule is
positive in relation to the oxygen portion.
- Therefore "attraction will take place between the positive hydrogen portion of
one water molecule and the negative oxygen portion of another water
molecule".

Characteristics of secondary bonds:

A solid whose molecules are bonded together by Vander Wall forces has:
1. Low strength and hardness.
2. Low thermal resistance.

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  Inter-atomic Distance
Spacing of solid atoms is influenced by two factors:
- Forces of attraction resulting from different types of bonding.
- Forces of repulsion occur between the electrons of neighboring atoms. These
forces increase rapidly with decreasing inter-atomic distance.
When two atoms are spaced such that these forces (repulsive & attraction) are equal
and opposite, the atoms are in their equilibrium position.
The sum of these attraction and repulsion forces provides the basis for bonding energy
and equilibrium interatomic distance.
Factors Affecting Inter-atomic Distance:
1. Number of adjacent atoms: more adjacent atoms, there is less attraction to any
specific neighboring atom, and the inter-atomic distance is increased.
2. Effect of temperature: increase temperature will increase the amplitude of atomic
or molecular vibration, causing increase in the inter-atomic spacing.
3. Type of the bond: The more the number of electrons shared, the stronger is the
bond and the less the inter-atomic distance; e.g. covalent bonding.
4. External force application: Application of an external force to a solid can
displace atoms from equilibrium position and change the I.A.D., e.g. tensile stress
will increase it.
III. Arrangement of atoms in space:
Properties of materials depend on the arrangement of their atoms.
Solids can be classified according to:
i) Type of bond between the atoms
a. Atomic solid b .Molecular solids
Atomic solids Molecular solids
Primary bond exists Primary bond exists between the
between the atoms and the atoms, while secondary bond exists
molecules of the solids between the molecules of the solids

High strength and hardness Low strength and hardness

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ii) Arrangement of atoms
a. Crystalline solids. b. Amorphous solids.
a) Crystalline Solids:
Solid dental materials are termed crystalline when their atoms are regularly
arranged in a space lattice.
A space lattice is the regular arrangement of atoms in the space so that every
atom is situated similarly to every other atom.
Types of space lattices:
There are about 14 different types of space lattice but only few are of dental
interest. The simplest way to study these types is to consider a unit cell which is the
smallest repeating unit in the space lattice.

Unit cells are classified according to:

a) The length of their axes (a,b,c).
b) The interfacial angles (,,).

1) The Cubic System:

- The length of the axes a,b,c are equal.
- The interfacial angles =  =  = 90°
a. Simple cubic system: (S.C)
The number of atoms per unit cell in S.C. structure=
8 atoms at each corner x 1/8 = 1atom.
b. Body Centered Cubic (B.C.C.): As in iron below 910ºC
The number of atoms per unit cell in B.C.C. structure=
8 atoms at each corner x 1/8 + one atom in the center = 2atoms.
c. Face Centered Cubic (F.C.C.):
As in gold, silver, copper, palladium and platinum.
The unit cell is a cube with an atom at each corner and one in the center of each
of the six faces, but none of the center of the cube.
Therefore the number of atoms in F.C.C. = (8X 1/8) + (6X 1/2) = 4 atoms.

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Atomic Packing Factors:
Atomic packing factor= volume of atoms inside the unit cell
volume of unit cell
Materials having higher atomic packing factor usually have higher stability, higher
densities and higher strength properties
b) Amorphous Solids:
Amorphous means without shape. Gases and liquids are amorphous substances.
Some solids like glass and some polymers are amorphous because of the random
arrangement of their atoms, yet their atoms may form a short localized range of order
lattice with a considerable number of disordered units in between.

Crystalline solids Amorphous solids

1) Have definite melting 1) No definite melting temperature
temperature. (gradually soften on heating and
gradually harden on cooling).
2) Have regular unit cell 2) No regular unit cell but may have a
with repetition. short range of regularity but no
repetition.
3) Low internal energy. 3) Higher internal energy.

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Polymorphism:
Polymorphic materials are these that can exist with more than one crystal structure by
changing the surrounding physical condition. The polymorphic forms have the same
chemical reactions but different physical properties, eg. Silica.
Silica (SiO2)
It is an important example for polymorphism in dentistry. It exist in nature in four
different allotropic forms, which are; Quartz, Tridymite, Cryslobalite and Fused
quartz.
Each form have different physical properties but all are chemically SiO 2.

With the application of heat to silica, two types of transformations can take place:

Reconstructive Transformation Displacive Transformation

-Break down of atomic bonding -No breakdown of atomic bonding

followed by reconstruction of new only displacement of atoms giving the
space lattice. same space lattice but with larger
volume.
- No expansion - accompanied by expansion
-Slow transformation. -Rapid transformation.
-Needs high temperature. -Needs low temperature.

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Crystal imperfections:

The calculated theoretical strength of crystalline materials was found to be much

higher than the actual strength, this is because their nature is not perfect i.e. they
contain defects or imperfections
Types of Crystalline Imperfections:
a. Point defects

Vacancy Impurity

b. Line defects
Dislocation: It is a displacement of a row of atoms from their normal position in
the lattice.
c. Plane defects: grain boundaries in metals.
 Correlation between atomic structure and materials properties:

1. Density is controlled by atomic weight, atomic radius, and the atomic packing
factor.

2. Melting and boiling temperatures can be correlated with the strength of the
bond.

3. Thermal expansions of materials with comparable atomic packing factors vary

inversely with their melting temperature.

4. Hardness: Generally, materials with weaker bonds have a decreased hardness

and low melting point.

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5. Electrical and thermal conductivity are very dependent on the nature of the
atomic bonds [ionic/covalent/metallic].

6. Strength can be primarily governed by the type of bond, although the

arrangement of atoms controls the deformation and resistance to stresses.

7. Crystalline structures and amorphous structures. (As mentioned before).

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