BatStateU - The National Engineering University

CHAPTER 3
The Chemistry of
ENGINEERING MATERIALS

Rhoda Pangan-Montalbo
 TOPICS
A. SOLIDS
B. METALS
C. POLYMERS
D. NANOMATERIALS
 TOPICS - C
• Properties and structures
• Common Polymeric materials
• Thermoplastic and Thermosets
POLYMERS
 INTRODUCTION

POLYMERS
• Molecular compound that can be distinguished by a high molar mass ranging
from thousands and even millions of mass; repeated chemical units joined
together, like beads on a string. Chemists also call them macro-molecules.
• Polymers may be natural, such as starch, cellulose and DNA, or synthetic, such
as nylon or polyethylene.
• Monomers: simple repeating units that are used for synthesizing polymers
• Homopolymer: polymer made up of only one type of monomer, ex.
Polyethylene, polytetrafluoroethylene (Teflon) and polyvinyl chloride.
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 PROPERTIES & CHARACTERIZATION

POLYMER MOLECULES
• Gigantic molecules, macromolecules
• The backbone of each of a carbon-chain polymer is a string of carbon atoms
and within each molecule, the atoms are bound together by covalent
interatomic bonds.
NATURAL POLYMER
• cellulose, starch, other
complex carbohydrates,
natural rubber, and
DNA.

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SYNTHETIC POLYMER
• crude oil is the starting material for
many synthetic polymers in plastics,
pharmaceuticals, fabrics, and other
carbon-based products.
• Examples are nylon, polyethylene,
polyester, Teflon, and epoxy

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HOMOPOLYMER
• polymer made up of only one
type of monomer
• Polyethylene,
polytetrafuoroethylene (Teflon)
and polyvinyl chloride.

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 POLYETHYLENE

• Ethylene (C2H4) is a gas at ambient temperature and pressure. Under

appropriate conditions, ethylene gas will react and it will transform to
polyethylene (PE) which is a solid polymeric material.
• Ethylene is a stable molecule with two carbon atoms connected by a
double bond. Polyethylene is made by the reaction of multiple
ethylene molecules in the presence of catalyst.
 POLYETHYLENE - process
begins when an active center is
formed by the reaction between an
initiator or catalyst species (R·) and
the ethylene monomer

polymer chain forms by the

sequential addition of
After the addition of many monomer units to this
ethylene monomer units, the actively growing chain
final result is the molecule
polyethylene molecule:
polyethylene chain structure or
POLYETHYLENE - process

For polyethylene, (a) a schematic representation of

repeat unit and chain structures, and (b) a
perspective of the molecule, indicating the zigzag
backbone structure

(Callister & Rethwisch, 2014)

 Polytetrafluoroethylene (PTFE)

PTFE - trade name Teflon; belongs to a family of

polymers called the fluorocarbons
 Polyvinyl Chloride (PVC)

• Vinyl chloride 𝐂𝐇𝟐 = 𝐂𝐇𝐂𝐥 monomer is a slight

variant of ethylene in which one of the four H atoms
is replaced with a Cl atom; polymerization leads to
polyvinyl chloride
 Polymer: General Form

• where the R represents either an atom [i.e., H or Cl,

for polyethylene or poly(vinyl chloride),
respectively] or an organic group such as CH3,
C2H5, and C6H5 (methyl, ethyl, and phenyl)
COPOLYMERS
• composed of two repeat units
• It is possible that there are different sequencing
arrangements along the polymer chains which
depends on the polymerization process and the
relative fractions of these repeat unit types.
• Synthetic rubbers are usually copolymers.

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COPOLYMERS

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POLYMERIZATION
• it is chemical reaction in which two or more
than two molecules of one or more than one
substance combine to form a molecule of high
molecular weight.
STRUCTURE
• Linear polymers are those in which the repeat
• units are joined together end to end in single

LINEAR chains.
• These long chains are flexible where each circle
represents a unit.
• There may be extensive van der Waals and
hydrogen bonding between the chains.
• Some of the common polymers that form with
• linear structures are polyethylene, poly(vinyl
• chloride), polystyrene, poly(methyl
methacrylate), nylon, and the fluorocarbons.
 STRUCTURE

• The chain packing efficiency is reduced with

BRANCHED the formation of side branches, which results
in a lowering of the polymer density.
• For example, high-density polyethylene (HDPE)
is primarily a linear polymer, whereas low-
density polyethylene (LDPE) contains short-
chain branches.
• Straight long chain with different side chains
• Molecules are irregularly packed having low
density, tensile strength
 STRUCTURE

• Adjacent linear chains are joined one to

another at various positions by covalent bonds.

CROSSLINKED • The process of crosslinking is achieved either

during synthesis or by a nonreversible
chemical reaction.
• Often, this crosslinking is accomplished by
additive atoms or molecules that are covalently
bonded to the chains. Many of the rubber
elastic materials are crosslinked.
• Two linear chains are joined together by covalent
bonds having three dimensions
• Hard, rigid and brittle due to network structure
 STRUCTURE

• multifunctional monomers forming three or

NETWORK more active covalent bonds make three-

dimensional networks.
• A polymer that is highly crosslinked may also
classified as a network polymer.
• These materials have distinctive mechanical
and thermal properties; the epoxies,
polyurethanes, and phenol-formaldehyde
belong to this group.
Common polymeric materials

Presently, there are more than 60,000

synthetic polymers known, with this,
six types of polymers account for
roughly 75% of those used in both
Europe and the United States.

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Common polymeric materials
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DEGREE of POLYMERIZATION
• Number of monomer or repeating unit(n) in the
polymer chain
• Degree of polymerization (DP) is used to
calculate the average molecular weight of
polymer.
THERMOSETS AND THERMOPLASTICS
Think of thermoplastics as butter – butter can be melted and
cooled multiple times to form various shapes. Thermoset is
similar to bread in that once the final state is achieved, any
additional heat would lead to charring.

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THERMOSETS AND THERMOPLASTICS
Molecular structure has a great effect on how
polymers react to mechanical forces at elevated
temperatures. One classification for these materials is
according to behavior with rising temperature.
Thermoplastics and thermosets are the two
subdivisions.
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THERMOSETS AND THERMOPLASTICS
Molecular structure has a great effect on how
polymers react to mechanical forces at elevated
temperatures. One classification for these materials is
according to behavior with rising temperature.
Thermoplastics and thermosets are the two
subdivisions.
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THERMOPLASTICS
• soften upon heating and later liquefy, then it hardens when
cooled This process is reversible and can be repeated. As the
temperature is increased, secondary bonding forces of the
molecules are decreased so that the relative movement of
adjacent chains is facilitated when a stress is applied.
Exposure of a molten thermoplastic polymer to a very high
temperature results to an irreversible degradation.
• Examples of common thermoplastic polymers are PE, PS,
PETE and PVC

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THERMOSETS
• network polymers
• they do not soften upon heating and they become permanently hard during their
formation.
• During heat treatment, the bonds fasten the chains together to resist the vibrational
and rotational chain motions at high temperatures. Therefore, the materials do not
soften when heated. Excessive heating temperatures will cause severance of these
crosslink bonds and polymer degradation. As compared to thermoplastics, these
thermoset polymers are generally harder and stronger and have better dimensional
stability. Examples of these thermosets (crosslinked and network polymers) are
vulcanized rubbers, epoxies, phenolics, and some polyester resins.

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POLYMER CRYSTALLINITY
• Polymer crystallinity is the packing of molecular
chains to produce an ordered atomic array.
• In crystalline state, the atomic arrangement in
polymer materials are more complex as compared
to metals because in polymers it involves molecules
instead of just atoms or ions.
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