ATOMIC THEORY OF THE STRUCTURE

OF ENGINEERING MATERIALS
(POLYMERS AND CERAMICS)

9th August, 2016

Polymers consist of several structural units(mers) bound together by covalent bonds
e.g Polyethylene –CH2-CH2-CH2-CH2-CH2-

Most polymers being covalently bonded are organic in nature. Most organic materials
are hydrocarbon i.e containing hydrogen and carbon (single, double or tripple covalent
bonded)

Some of the simple hydrocarbons belong to the paraffin family – methane, ethane,
butane, propane etc.

Covalent bonds in each molecule are strong, but only weak hydrogen and van der
waals bonds exist between molecules, and thus this hydrocarbons have relatively low
melting point and boiling point. However, boiling temperature rise with increasing
molecular weight.

Molecules with double and triple bond are termed unsaturated (i.e each carbon atom
is not bonded to the maximum(or four) other atoms; as such it is possible for another
atom or group of atoms to become attached to the original molecules)

Single bonded molecules are saturated; and no new atoms may be joined without the
removal of others that are already bonded.
CLASSIFICATION OF POLYMERS
 CLASSIFICATION BASED ON POLYMERIZATION MECHANISM
 ADDITION; polymers formed by sequential addition of one bifuntional or
polyfuntional monomer to growing polymer chains without the elimination of any
part of the monomer molecule. Involves reaction of unsaturated monomers

Polyethylene (PE

If all the hydrogen atoms in polyethylene are

replaced by flourine, the resulting polymer is
polytetrafluoroethylene(PTFE). TEFLON.

If the 4th hydrogen is replaced with chlorine atom,

the resulting polymer is polyvinyl chloride(PVC).

If the 4th hygrogen is replaced with methyl (CH3)

or benzene, the resulting polymer is Polypropylene
and polystyrene respectively.

Polymer has the same emperical formula as the

monomer but a higher molecular mass.
CONDENSATION;polymer formed from bifuntional or polyfuntional monomers with
the elimination of a small molecular species such as H2O, methanol or NH3 as by-
product.
Types of condensation polymers include polyamides, polyacetals and polyesters.

Polyamides (sometimes called Nylons) are an important class of condensation

polymers that are formed by reaction between amine and acid groups, as in

NH2 –(CH2)6-NH2 + COOH-(CH2)4-COOH = {NH-(CH2)6-NHCO-(CH2)6} + H2O

Hexamethylene Poly(hexamethylene adipamide)

Adipic acid
diamine nylon 66

The carboxylic acids and amines link to form peptide bonds, also known as amide
groups. Proteins are condensation polymers made from amino acid monomers.
Carbohydrates are also condensation polymers made from sugar monomers such as
glucose (i.e. cellulose [1] or glycogen) and galactose.
 CLASSIFICATION BASED ON MOLECULAR STRUCTURE
LINEAR; mer units joined together ene to end (hydrogen and van der waals bonding
between chains) in single chains. E.g PE,PVC,Polystyrene, Nylon & the fluorocarbons.
BRANCHED; side-branch chains are connected to the main chain. Chain packing
efficiency is reduced with formation of side branches, which results in lowering the
density of the polymer.
CROSSLINKED; adjacent linear chains are joined one to another at various positions
by covalent bonds. Many of the rubber elastic materials are crosslinked.
NETWORK; formation of 3-D networks by trifuntional mer units, having three active
covalent bonds. Highly crosslinked polymers maybe classified as network polymer. E.g
epoxies and phenol-formaldehyde.

(a) linear, (b) branched, (c) crosslinked,

(d) network (three-dimensional) molecular
structures. Circles designate individual
mer units.
 CLASSIFICATION BASED ON RESPONSE TO HEAT
THERMOPLASTICS; polymers melt on heating and solidify on cooling. The heating and
cooling cycles can be applied several times without affecting the properties. E.g Most linear
polymers and those having some branched structures with flexible chains
THERMOSETTING;polymers melt only the first time they are heated. During the
initial heating, the polymer is “cured”; therefore, it those not melt on reheating, but
degrades. E.g most crosslinked and network polymers.(Vulcanized rubber, epoxies,
phenolic, polyesters resin).
 GLASS AND CERAMICS
Ceramics are composed of at least two elements. E.g CaF2, MgO, NaCl, Al2O3,SiO2,
Si3N4, ZnS, SiC.

The atomic bonding in these materials ranges from purely ionic to totally covalent;
many ceramic exhibits a combination of these two bonding types.

The crystal structure is influenced by: (1) the magnitude of the electrical charge on
each of the component ions. (2) the relative sizes(ionic radius) of the cations and
anions.

The different crystal structure found in ceramics are

 rock salt structure e.g NaCl, MgO, FeO.
Cesium chloride structure
Zinc blende structure e.g ZnS, ZnTe, SiC.

NOTE: STUDY ALL THIS CRYSTAL STRUCTURES AND NOTE THE DIFFERENCES
IN TERMS ARRANGEMENT AND PROPERTIES..
SUBMIT NEXT CLASS.
 Like crystals, glasses consist of an extended 3-D network, but the network does not
have translational periodicity/symmetry; this makes it difficult to study the structure
of glass.
TYPES OF CERAMIC GLASSES
Slicate glass (soda-lime glass). Based on SiO2-Na2O-CaO. Used as sheet glass, bottles,
tableware.
Lead glass. SiO2-PbO-CaO. Used for lamp tubing, TVs (the bulb), and thermometer
tubing.
Borate glass(borosilicate glass) . SiO2-B2O3-R2O (R is the alkali).
Fused silica :being essentially pure SiO2, it is used for high temperature applications.
Phosphate glass: important because they are semiconducting. Used in the manufacture
of electron multipliers.
Chalcogenide glass: based on As, Se, and Te. These glasses are infrared transparent.
They are nonoxide semiconductor and are used in special electron devices and lenses.
Fluoride glass: halides glasses are based on BeF2, and ZnCl2 and are used in optical
waveguides (OWG) where the cost can be justified.

QUESTION: WHAT IS RESPONSIBLE FOR THE TRANSPARENCY IN GLASS?