Structure and Properties of

Materials
Introduction

A group of materials normally

obtained by joining organic
(Hydrocarbons) molecules into
giant molecular chain or
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 Inorganic such as Silicon rubber

▪ as Teflon is similar in structure to polyethylene except that all

the hydrogen is replaced with fluorine

▪ Cellulose (found in wood, cabbages, cotton, and linen) is

composed of long chains of sugar rings.

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Polymers Classification
Polymers

Natural Synthetic
Functional
Structural Fibers Plastics
DNA
Nylon Polyester
RNA
Acrylic Bakelite
Proteins
Fibers Gel Polyester PVC
Cellulose Gelatin
Silk Rubbers
Wool

Rubber
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Definitions
Mer –
The repeating unit in a polymer chain
Monomer –
A single mer unit (n=1)
Polymer –
Many mer-units along a chain (n=103 or
more)
Degree of Polymerization –
The average number of mer-units in a
chain.

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 Common

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Polymers

6
Polymers Structures Representation
Three ways to
represent the
structure of
polyethylene
(a) a solid three-
dimensional model
(b) a three
dimensional
“space” model
(c) a simple two-
dimensional model
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Bonding Forces in polymers
• Intramolecular forces (forces between
atoms in one chain): generally covalent
bonds strong bonding;
• Inter-chain forces (forces between two
chains): Van der Waals forces weak
• Entanglements (physical)
In the crystalline state the van der Waals bonds are
very important.
In the rubbery amorphous state the entanglements
are very important.
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General Properties of Polymers
Soft / Ductile - Malleable

Translucency
Low thermal stability
Poor conductor of heat and electricity
(With exception of PPV, etc.)
Lightweight (But high
molecular weight)
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 Polymers
All the repeating
units along a chain
Homopolymer are of the same
type
Chains that are
composed of two or
Copolymers more different repeat
units

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Copolymers A and B are randomly vary in chain

A and B alternate in polymer chain

Chains of B grafted on to A backbone

Large blocks of A alternate with large blocks of B

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 Here are a few to think about:
• Homopolymers are stiffer.
• Homopolymers have higher room temperature
impact strength.
• Homopolymers have higher tensile strength.
• Homopolymers have a slightly higher operation
temperature.
• Homopolymers are slightly harder and more
slippery.
• Copolymers have better dimensional stability.
• Copolymers are more resistant to chemicals.
• Copolymers are less porous when extruded.

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 Molecular Weight
When we talk about molecular weight in terms
of polymers, we are really talking about the
length of the individual chains

The polymerization process is subject to

variation so there is no single chain length,
there is actually a wide range of lengths, so
when we discuss molecular weight, we really
mean the average molecular weight of the
polymer

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 Molecular Weight

20 + 16 + 10
Average molecular weight = M monomer = 15.3M monomer
3
This is what called :
Number average molecular weight
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Degree of Polymerization
Degree of Polymerization “DP” is:

Molecular .weight .of . polymer

DP =
Molecular .weight .of .repeat .unit
It represents the average number of repeat unit in a chain
or
the average length of a linear polymer

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Example: DP of PS = 700

Does every PS chain in a given sample

contain exactly 700 repeat units

No. on average, each PS is 700 repeat

units in length

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Molecular Weight
What is the MW of PS if DP = 700
MWpolymer = DP x MWmer

MWpolymer = 700 x 104 g/mol = 72,800 g/mol

What is the DP of PS if MW = 200,000 g/mol

DP = MWpolymer / MWmer

DP = (200,000 g/mol) / (104 g/mol) = 1923

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Mw at room temperature:
Polymers with short chains ( Mw on the order
of 100 g/mol) will exist as liquid (= viscous
state).
Those with Mw of approx. 1000 g/mol are
waxy solids.
The solid polymers have Mw ranging
between 10,000 and several million g/mol.
For Ethylene:
❑ 10-20 ethylene's – greases or
oils
❑ 200-300 waxes
❑ 20,000 + polyethylene
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The effect of Molecular Weight
Increasing the molecular weight of the material increases many of
the properties of the material by increasing the entanglement of the
molecules
▪ Increases the chemical resistance - to a point. It takes more
damage to the main chains of the molecules before it will affect
the strength of the material;
▪ Increases the ductility, how far the material can stretch before
rupturing; (the higher degree of entanglement allows the
material to be pulled further before the chains break)
▪ Increases the impact resistance of the material. The higher
degree of entanglement means that in order to rupture, more
polymer bonds need to be broken, this means that the polymer
can absorb more energy before failing;
▪ Increases the weather resistance of the material. As in chemical
resistance, the chains are longer, so they can withstand more
damage before the mechanical properties will start to diminish.
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Molecular Shape (Twisting and Entanglement)

The random coils and molecular

entanglements are responsible for
the large elastic extension
displayed by the rubber materials.

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 Molecular Structure
Structure

Linear Branched Cross

linked

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Effect of Molecular Structure, HDPE vs. LDPE

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 Cross-Linking
It is used to refer to the "linking of polymer chains

• Polymers with a high enough degree of cross-linking

have "memory." When the polymer is stretched, the
cross-links prevent the individual chains from
sliding past each other
The chains may straighten out, but once the stress is
removed they return to their original position and the
object returns to its original shape.

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 Cross-Linking
One example of cross-linking is
vulcanization. In vulcanization, a
series of cross-links are
introduced into an elastomer to
give it strength. This technique
is commonly used to strengthen
rubber
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Do not forget Rubber
Rubbers are materials that display
elastomeric properties. This means they
can be stretched and will spring back
when the stress is removed, just a coiled
spring will.
The molecules slide past each other on
deformation, but the cross links prevent
permanent flow and the molecules spring
back to their original position upon
removal of the stress. The presence of the
cross links means that it is difficult if not
impossible to melt a rubber.
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 Vulcanization Process
The crosslinking process in
elastomers is called
vulcanization, which is
achieved by a nonreversible
chemical reaction,
ordinarily carried out at an
elevated temperature. By
the process of vulcanization,
crosslinks are formed Process of vulcanization
between the polymer chains of rubber by applying
so the chains can no longer heat and Pressure in a
move independently. mold over a period of
time
Polymer codes and Recycling
Remember that:
Polymers are usually long chain organic macro-
molecules with covalent bonds

Each molecule is formed from a large number

of unitary molecules known as monomer. For
this reason, the polymers can be bent and
stretched easily

In certain polymers some of the molecules cross

link with each other thereby increasing the
strength across the molecules.
Density Cost
Thermoplastic – Thermoplastic – Less
Lightweight, very expensive and easier to
close to the weight of process;
water; Thermoset – Need more
Thermoset – skill and produce more
Limited in some scrap which cannot be
applications due to reprocessed.
their higher weight.
Coloration
Thermoplastic – Easily colorable
and color is maintained;
Thermoset – Limited options and
colors tend to fade or discolor over
time
The amorphous nature of polymers
is analogous to a plateful of
spaghetti --- loose and randomly
coiled.

While the crystalline state is more

like the uncooked spaghetti in the
box --- the chains are all tightly
bundled and ordered in the same
direction.

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 Degree of crystallinity (D %) and densities of
crystalline (ρc) and amorphous (ρa) polymers in g/cm3

Polymer D ρc ρa
Nylon (PA66 and PA6) 35–45 1.24 1.08
Polyoxymethylene (POM) 70–80 1.54 1.28
Polyethylene terephthalate (PET) 30–40 1.50 1.33
Polybutylene terephthalate (PBT) 40–50 – –
Polytetrafluoroethylene (PTFE) 60–80 2.35 2.00
Isotactic polypropylene 70–80 0.95 0.85
Atactic polypropylene ~0 – –
High-density polyethylene 70–80 1.0 0.85
Low-density
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Effect of Crystallinity
Higher
More
resistance to
strength
dissolution
More
crystallinity
Resistance to
Higher
softening by
density
heating
34
Amorphous vs. Crystalline
Amorphous Crystalline
• Soften over a wide • Distinct and sharp
range of temperatures melting point
• Lower specific gravity • Higher specific
• Lower tensile strength gravity due to better
and tensile modulus packing
• Higher ductility and • Higher tensile
impact strength strength and tensile
• Lower creep resistance modulus
• Lower ductility and
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 Property Crystalline Solids Amorphous Solids
Shape Definite characteristic Irregular shape
geometrical shape
Melting point Melt at a sharp and Gradually soften over a range of
characteristic temperature temperature
Cleavage When cut with a sharp edged When cut with a sharp edged tool,
property tool, they split into two pieces they cut into two pieces with
and the newly generated irregular surfaces
surfaces are plain and smooth
Heat of fusion They have a definite and They do not have a definite and
characteristic heat of fusion characteristic heat of fusion.
Anisotropy Anisotropic in nature. Isotropic in nature. Mechanical
Mechanical strength, electrical strength, electrical & optical
& properties changes with properties are same in all
direction direction.
Nature True solids Pseudo solids or super cooled
liquids
Order in Long range order Only short range order
arrangement of
constituent
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particles
Degree of Crystallinity

M crystalline
%Crystallinity = x100%
M total
 cVc c
= x100% = f c x100%
 tVt t
Mt = Mc + Ma
Vc Va
  tVt =  cVc +  aVa   t =  c +  a
Vt Vt
  t =  c fc +  a fa =  c fc +  a ( 1 − fc ) = fc ( c −  a ) +  a
t − a
 fc =
c − a
c ( t − a )
 %Crystallinity = x100%
t ( c − a )
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 c ( t − a )
%Crystallinity = x100%
t ( c − a )
Where:
ρt = Density of specimen in question
ρa = Density of totally amorphous
ρc = Density of totally crystalline
fc = Volume fraction of crystalline component
fa = Volume fraction of amorphous component
38
 If the thermoplastic material has a high concentration
of polymers with amorphous structures, the material
will have a
▪ poor resistance to loads
▪ an excellent elasticity
On the contrary, if the thermoplastic material has a
high concentration of polymers with a crystalline
structure, the material will be
▪ very strong and even stronger than thermoset
materials,
▪ with a little elasticity that provides the
characteristic fragility of these materials.
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 Summery:
Factors Influencing Properties Polymers
• Molecular Structures
– Linear, branched, crosslinked or network polymers.
• Molecular Weight
– Melting / softening temperatures increase with molecular weight (up to
~ 100,000 g/mol);
– At room temperature, short chain polymers (molar weight ~ 100 g/mol)
are liquids or gases, intermediate length polymers (~ 1000 g/mol) are
waxy solids, solid polymers have molecular weights of 104 - 107 g/mol.
• Crystallinity
- Linear polymers more easily form crystals because the molecules can
orient themselves readily;
- Degree of Crystallinity ranges from 5 - 95% → - The higher %
Crystallinity higher strength.
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 All the energy you add to a crystalline polymer
at its melting point goes into melting, and none
of it goes into raising the temperature. This heat
is called the latent heat of melting. (The word
latent means hidden.)

While in amorphous polymers all energy goes

to change from glassy state (hard and brittle
solid) to rubbery state (soft and flexible state)
But the temperature doesn't go up at the same
rate above the Tg as below it. Because the
glass transition involves change in heat
capacity, but it doesn't involve a latent heat
Glass Transition Temperature
Glass transition temperature is the temperature at which
the mechanical properties of the polymer changes from
elastic/plastic behavior to brittle behavior due to a
reduction in motion of large segments of molecular
chains with decreasing temperature

Natural rubber has a glass transition temperature of 200k

while that of PET is 338K. The molecular weight of rubber is
68.12 g/mol and that of PET is 102.2 g/mol. A polymer with a
high molecular weight is more densely packed than a
polymer with a low molecular weight. In a more densely
pack polymer, the chains have less freedom to move and
requires a higher energy (or higher temperature) for. Since
PET is more densely packed it reaches its glass transition
temperature higher than rubber.
Glass Transition Temperature
Even crystalline polymers will have a some
amorphous portion. This portion usually
makes up 40-70% of the polymer sample.
This is why the same sample of a polymer
can have both a glass transition
temperature and a melting temperature.
But you should know that the amorphous
portion undergoes the glass transition only,
and the crystalline portion undergoes
melting only.
 Glass Transition Temperature
1. Breakdown of Van Der Waals Forces
2. Onset of large scale molecular motions
3. Important in amorphous polymers
4. Upper service temperature

Tg in Semicrystalline Polymers
1. May show where “brittle” behavior begins
2. Not a predictor of service temperature
3. Crystals maintain high E + σY
The Glass Transition Temperature

Tm Melting
temperature
associated with
crystalline zones

Tg Glass
transition
temperature
associated with
amorphous zones
Tg can be defined as the transitional temperature at which
polymer segments begin to flow from the frozen state (with raise
in temperature), or start freezing (with drop in temperature).
The stiffness of a polymer chain increases with the length of its
segment.
Factors affecting Tg
❑ Tg is directly proportional to the molecular weight of the
polymer.
❑ Greater the degree of cross-linking, higher the Tg
❑ Polymers with strong intermolecular forces of attraction
have greater Tg
❑ Side groups, especially benzene and aromatic groups
attached to main chain increases Tg
❑ A small amount of branching tends to lower Tg; on the
other hand, a high density of branches reduces chain
mobility and elevates the glass transition temperature.
❑ Some amorphous polymers are cross-linked, which has
been observed to elevate Tg; with a high density of
crosslinks, molecular motion is virtually disallowed
Additives Function
to improve tensile and compression strengths,
Filler abrasion resistance, toughness, dimensional
and thermal stability and other properties.
to improve the flexibility, ductility, and toughness
Plasticizers and produces reductions in hardness and stiffness.
to reduce the glass transition temperature Tg
Stabilizers are antioxidants and UV protectants

interfering with the combustion process through

the gas phase, or
Flame
Retardants by initiating a chemical reaction that causes a
cooling of the combustion region and a
termination of burning
Dyes or pigments impart a specific color to a
Colorants
polymer
 In your text book:

You are asked to study the following:

from page 590 to 603

Assignment about the degree of

polymerization and degree of crystallinity