MME101 Materials Engineering Fundamentals

Lecture 33-34
A. K. M. Bazlur Rashid Part E: Processing and Applications
Professor, Dept. of Materials and Metallurgical Eng.
Bangladesh Univ. of Eng. and Tech., Dhaka-1000 6 – Polymeric materials

Lecture Outcome (LO)

At the end of this lecture, students should be able to
1. describe the character of different types of polymer molecule structures and determine
number-average and weight average molecular weights for a specific polymer,
2. classify and describe the behaviour and molecular structure and applications of different
polymeric materials,
3. discuss polymer synthesis and degree of polymerisation,
4. make schematic plots and describe different stress-strain behaviour observed for
polymeric materials,
5. Discuss the influence of different factors on mechanical behaviour of polymers,
6. Name and describe different fabrication techniques used for plastic polymers.

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 Part 1
Structure and Classification of Polymers

1. What is a Polymer ?

❑ The suffix mer means “unit.” ❑ Polymerization is the process by which small
molecules consisting of one unit (known as a
❑ Thus, the term polymer means “many units,” monomer) or a few units (known as oligomers)
and in this context, the term mer refers to a are chemically joined to create these giant
unit group of atoms or molecules that defines molecules.
a characteristic arrangement for a polymer.
❑ Usually contain 5 or more monomers, and
❑ Polymers consist of chains of molecules. The some may contain 100s or 1000s of
chains have average molecular weights that monomers in each chain.
range from 10,000 to more than one million
g/mol built by joining many mers through ❑ Most polymers are organic, meaning that they
chemical bonding to form giant molecules are carbon-based; however, polymers can be
known as macromolecules. inorganic (e.g., silicones based on a Si-O
network).
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 Molecular Forces in Polymers

1. Intra-molecular forces ❑ In the crystalline state, the van der

• Forces between atoms in one chain Waals bonds are important.
- generally covalent bonds (strong) ❑ In the rubbery amorphous state,
the entanglements are important.
2. Intermolecular forces
• Forces between two chains
- van der Waals forces (in PE)
and hydrogen bridges (in PS) (stronger)
• Can become very strong as M increases

3. Entanglements (physical)

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2. Polymer Molecules
❑ Most polymers are organic and formed from
hydrocarbon molecules.
❑ They consist of long and flexible chains with a
string of C atoms as a backbone. Each C atom
has four e- that participate in bonds, each H atom
has one bonding e-
❑ C atoms are side-bonded to H or other atoms or
radicals. Double and triple bonds are possible in
both chain and side bonds.

Three ways to represent the structure of polyethylene:

(a) a solid three-dimensional model, (b) a three-dimensional
“space” model, and (c) a simple two-dimensional model.

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 Unsaturated hydrocarbon molecules Saturated hydrocarbon molecules

 contain double and triple bonds  all bonds are single ones
between C atoms
H H H
 sharing of two or three electron pairs | | |

H–C–H H–C–C-H
 more reactive | | |

H H H
H H H–CC–H
| | methane, CH4 ethane, C2H6
C=C acetylene, C2H2
| |

H H
ethylene, C2H4

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❑ Even though the basic makeup of many polymers is

carbon and hydrogen, other elements can also be
involved.
Examples of Some Polymers
❑ Example: H H X=H Polyethylene (PE)
H (polyethylene) N (nylon) X = CH3 Polypropylene (PP)
C C
O (polyester) F (PTFE or Teflon) X = Cl Polyvinylchloride (PVC)
Si (silicone) Cl (PVC) , etc. H X
n X= Polystyrene (PS)

❑ There are also some polymers that, instead of

❑ When all mars are the same, the polymer
having a carbon backbone, have a silicon or
molecule is called homopolymer.
phosphorous backbone.
• These are considered inorganic polymers.
❑ When there are more than one types of
mars, the molecule is called copolymer.
• E.g., polysiloxanes (silicones) and polyphosphazenes.

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 Polymer Molecular Shape

❑ The angle between the singly bonded carbon atoms is 109°

– carbon atoms form a zigzag pattern in a polymer molecule.

r = n

❑ While maintaining the 109° angle between bonds polymer, r = head-toe distance
n = no. of steps
chains can rotate around single C-C bonds (double, triple  = length of step
bonds are very rigid). Random kinks and coils lead to entanglement,
like in the spaghetti structure
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Polymer Molecular Structure

❑ The physical characteristics of polymer material depend not only on
molecular weight and shape, but also on molecular structure.
❑ There are four types of polymer molecule structures.
Linear polymers
Branched polymers
• The repeat units are joined together end
to end in single chains. • Inefficient chain packing
causes reduced density
• Van der Waals and hydrogen bonding
between chains. • Examples: LDPE
• Examples: polyethylene, nylon, HDPE.

Network polymers
Cross-linked polymers • 3D networks made from
• Chains are connected by trifunctional mers.
covalent bonds. • Examples: epoxies,
• Example: rubbers. phenolformaldehyde resin
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 Polymer Crystallinity
❑ Atomic arrangement in polymer crystals is complex. crystalline region

❑ Polymer molecules are often semi-crystallined, with partially

crystalline regions dispersed within amorphous material.
𝜌𝑐 𝜌𝑠 − 𝜌𝑎
% Crystallinity = × 100
𝜌𝑠 𝜎𝑐 − 𝜌𝑎
c = density of perfect crystalline polymer
a = density of completely amorphous polymer
s = density of partially crystalline polymer sample amorphous region

❑ The degree of crystallinity depends on • annealing causes crystalline regions

1. Rate of cooling (faster cooling, less crystallinity) to grow  % crystallinity ↑
2. Type of polymer (simple structure (e.g., PE), more crystallinity) • density, TS, E ↑ with crystallinity
3. Linear polymers form crystals more easily.
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Polymer Molecular weight, MW

❑ The average molecular weight can be obtained by averaging the masses with
the fraction of times they appear (number-average molecular weight) or with
the mass fraction of the molecules (weight-average molecular weight).

Number average: 𝑀𝑛 = ෍ 𝑥𝑖 𝑀𝑖 Mi = the mean mol. wt. of range i

fi = wt. fraction of chains of length i
xi = no. fraction of chains of length i
Weight average: 𝑀𝑤 = ෍ 𝑓𝑖 𝑀𝑖

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 ❑ Final molecular weight (chain length) is controlled by the synthesis process of
polymers, which is known as the polymerization.
❑ Melting / softening temperatures, and tensile strength increase with molecular
weight (up to ~ 100,000 g/mol) of polymers.
❑ At room temperature,
• short chain polymers (molar weight ~ 100 g/mol)  liquids or gases
• intermediate length polymers (~ 1000 g/mol)  waxy solids
• long chain polymers (104 - 107 g/mol)  solid

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Example 1
We have a polyethylene sample containing 4000 chains with molecular weights between 0 and 5000 g/mol,
8000 chains with molecular weights between 5000 and 10,000 g/mol, 7000 chains with molecular weights
between 10,000 and 15,000 g/mol, and 2000 chains with molecular weights between 15,000 and 20,000
g/mol. Determine both the number and weight average molecular weights.

Solution
First, we need to determine the number
fraction xi and weight fraction fi for each of the
four ranges. We can then use the equations
to find the molecular weights.

4000 chains M = 0 - 5000 g/mol

8000 chains M = 5000 - 10,000 g/mol
7000 chains M = 10,000 - 15,000 g/mol
2000 chains M = 15,000 - 20,000 g/mol
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 The Glass Transition Temperature
❑ It is difficult to crystallise polymer. More often they are
amorphous and have properties more like glass.
❑ Tm and Tg temperatures are critical aspects of designing
with semi-crystalline and amorphous polymers
❑ Modulus of elasticity and other properties change at the Tg.

Sample Tg values:
Low density polyethylene (LDPE) -110°C
High density polyethylene (HDPE) -90°C
Polyvinyl chloride +87 °C
Polystyrene +100 °C
Polycarbonate +150 °C specific volume vs. temperature
of different polymers
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3. Classification of Polymers
Thermoplastics (or, Plastics) Thermosetting polymers (or, Resins) Elastomers (or, Rubbers)
• Ductile and reversibly soften when • Do not soften with heating; harden • These are either thermoetting
heated and hardened when cooled. permanently when heated. or lightly cross-linked
thermosets and have
• Secondary bond that binds the • Secondary bond melt but cross links
extensive (more than 200%)
molecules to each other melts so remain and prevent melting and viscous
elastic deformation.
that it flows like viscous fluid and flow, so thermosets cannot be hot worked;
allowing it to be deformed. further heating causes decomposition. • Amorphous and show
• Linear or branched polymers; • Networked polymers with heavily cross- resistance to crystallization.
chains of molecules are not linked to produce a strong 3D structure.
• Example: rubber.
interconnected (cross-linked) to
• Thermosets are harder, more stable
one another.
dimensionally, and more brittle than
• Example: PE, PP, PTFE (teflon), thermoplastics.
PS, PVC, PMMA (prespex), nylon.
• Example: polyester resin, phenolic resins,
epoxies, silicones. 16/44

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 Table 1: Generic thermoplastics.

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Table 2: Generic thermosets.

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 Table 3: Generic elastomers.

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Example 2 Design/Materials Selection for Polymer Components

Design the type of polymer material you might select for the following applications:
(a) a surgeon’s glove, (b) a beverage container, (c) a pulley.

❑ The glove must be capable of stretching a great deal

to slip onto the surgeon’s hand. This requirement describes an elastomer.
❑ A thermoplastic such as polyethylene terephthalate (PET)
will have the necessary formability and ductility needed for this application.
❑ A relatively strong, rigid, hard material is required to prevent wear,
so, a thermosetting polymer might be most appropriate.

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 Part 2
Synthesis and Processing of Polymers

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4. Polymer Synthesis
❑ The synthesis of large molecular weight polymer is called polymerization.
• most of the raw materials for synthetic polymers are derived from coal and petroleum
products, which are low molecular weight polymers.
• low molecular weight monomers are joined over and over.

❑ The degree of polymerization obtained during polymer synthesis can be

determined by dividing the average molecular weight of the polymer by the
molecular weight of the monomer.
❑ Two types of polymerization reactions:
1. Addition (chain reaction) polymerization
2. Condensation (step reaction) polymerization
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 Addition Polymerization
• Process by which polymer chains are built up by attaching monomers
(having unsaturated bonds) units one at a time without creating a byproduct.
• A catalyst reacts with a monomer to produce an active centre
(which has an unpaired electron) which is capable of propagation.

Example: Addition reaction for

producing polyethylene from
ethylene molecules.
Unsaturated double bond in the
monomer is broken to produce
R• + active sites, which then attract
additional repeat units to either
end to produce a chain.
catalyst
active site

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Condensation Polymerization

❑ In condensation polymerization,
a relatively small molecule (such
as water, ethanol, methanol, etc.)
is formed as byproduct because
of the polymerization reaction.

❑ Here, the OCH3 group and a

hydrogen atom are removed from
the monomers, permitting the two
monomers to join and producing
methyl alcohol as a byproduct.
condensation reaction for polyethylene terephthalate (PET),
a common polyester

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 5. Polymer Processing

❑ It is relatively rare for an article to be made from polymer alone.

❑ Most are polymer compounds, consisting of a mixture of polymer and various

additives. These additives are used to modifying physical, mechanical and chemical
properties.

❑ Common additives include:

(a) Fillers
(b) Plasticizers
(c) Stabilizers/Antioxidants
(d) Colourants

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Fillers Plasticizers
• Solid additives used to improve tensile and compressive • Small molecules of non-volatile solvents which occupy
strengths, abrasion resistance, toughness, and thermal positions between polymer chains (increase distance and
stability. interactions between chains).
• Particle sizes range from very small (10 nm) to large • Used to increases flexibility, ductility, and toughness, and to
(mm). reduces hardness and stiffness in brittle polymers e.g., PVC.
• Examples: Wood flour, silica flour, sand, glass, clay, talk, • Almost 90% of plasticizers are used to lower the Tg value of
limestone. the polymer.
• Reduces the cost of product by replacing more • Examples: phthalate ester (in PVC).
expensive polymer.
Stabilisers/Antioxidants
Colourants • Compounds that reduce polymer degradation (in exposure
• Additives used to change product aesthetics. to ultraviolet radiation) through intervention in free radical
• Examples: pigments (soluble colourants), dyestuffs reactions.
(insoluble additives). • Examples: antioxidant, ultraviolet stabilizers, emulsifiers &
surfactants.
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 6. Polymer Forming

❑ Depends on
◼ the type of polymers ◼ temperature
◼ atmospheric stability ◼ geometry of finished product

❑ Forming Processes for Thermoplastics

◼ Extrusion ◼ Blow molding
◼ Injection molding ◼ Thermoforming

❑ Forming Processes for Thermosetting polymers

◼ Calendaring ◼ Spinning
◼ Compression molding ◼ Transfer molding

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schematic of an extruder used for polymer processing

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 One technique by which polymer films (used in the manufacture of garbage bags,
for example) can be produced. The film is extruded in the form of a bag, which is
separated by air pressure until the polymer cools.
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Typical forming processes for thermoplastic: (a) extrusion, (b) blow molding,
(c) injection molding, (d) thermoforming, (e) calendaring, and (f) spinning. 30/44

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 Typical forming processes for thermosetting polymers:
(a) compression molding, and (b) transfer molding.
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7. Polymer Joining

❑ Cementing with a solution of the same polymer in a volatile solvent. The solvent
softens the surface, and the dissolved polymer molecules bond them together.

❑ Monomer-cementing, where surfaces are coated with monomer which polymerise

onto the pre-existing polymer chains, creating a bond.

❑ Use of epoxy additives and various snap fasteners; must be designed to

distribute the fastening load uniformly over a wide area to avoid fracture.

❑ Can be friction-welded, by bringing the rotating parts into contact; frictional heat
melts the surfaces which are held under static load until they re-solidify.

❑ Joining can sometimes be avoided by integral design, in which coupled components

are moulded into a single unit.

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 Part 3
Properties of Polymers

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8. Polymer Properties
❑ Three typically different types of stress–strain
behaviour are found for polymeric materials. brittle
• Curve A illustrates the stress–strain character for a brittle
Stress (MPa)

polymer (aligned, cross linked and networked) which fractures

plastic
while deforming elastically.
• The behaviour for a plastic polymer (semi-crystalline), curve
highly elastic - elastomeric
B, is like that for many metallic materials; the initial deformation
is elastic, which is followed by yielding and a region of plastic
deformation.
• The deformation displayed by elastomers in curve C shows
rubber-like total elasticity (large recoverable strains produced at
low stress levels). Strain
three typical classes of polymer
• Between -20 and +200 °C, polymer can pass through all these
stress-strain characteristic
mechanical states.
• modulus and strength can change by a factor of 1000 or more. 34/44

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 Stress
necking

non-linear elastic
deformation plastic
YIELD deformation TENSILE
STRENGTH STRENGTH

linear elastic
deformation
Strain

Schematic tensile stress–strain curve for a semi-crystalline polymer

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∆𝑡
𝑡0

𝑡0

stage 1 stage 2

(a) (b)
(c)

stages in the elastic deformation of a semi-crystalline polymer

(a) Two adjacent chain-folded lamellae and interlamellar amorphous material before deformation.
(b) Elongation of amorphous tie chains during the first stage of deformation. (c) Increase in lamellar
crystallite thickness (which is reversible) due to bending and stretching of chains in crystallite regions.
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 stage 3 stage 4 stage 5

(a) (b) (c)

stages in the plastic deformation of a semi-crystalline polymer
(a) Two adjacent chain-folded lamellae and interlamellar amorphous material after elastic deformation, (d)
(b) Tilting of lamellar chain folds, (c) Separation of crystalline block segments,
(d) Orientation of block segments and tie chains with the tensile axis in the final plastic deformation stage.
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Temperature and Strain Rate Effect on Stress-Strain Curve

❑ The mechanical characteristics of polymers, for
the most part, are highly sensitive to strain rate,
temperature, and chemical nature of the
environment (the presence of water, oxygen,
organic solvents, etc.).

❑ Mechanical characteristics of polymers

are much more sensitive to temperature changes
near room temperature.
❑ Decreasing Temperature
• increases E
• increases TS
• decreases % EL
❑ Decreasing strain rate causes the same effects as
increasing temperature i.e., the material becomes
effect of temperature on stress-strain behavior of PMMA
softer and more ductile.
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 Factors Controlling Mechanical Properties
of Semi-Crystalline Polymers

1. Temperature
2. Strain rate
3. Structural/processing factors
(a) molecular weight – tensile strength increases with increasing molecular weight
by increased chain entanglements
(b) degree of crystallinity – tensile modulus and strength increases significantly
with degree of crystallinity; materials become brittle
(c) pre-deformation (drawing) – improve mechanical strength and tensile modulus
(analogous to strain hardening in metal)
(d) heat-treatment (annealing) – increase in the percent crystallinity and crystallite size;
increase in tensile modulus and yield strength, and reduction in ductility (opposite to
those experienced in metals)
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9. Polymeric Materials Data

❑ Specifications are not tight as in metals.
• properties of two pieces of 316L stainless steels from two different manufacturers
will not differ much
• but properties of polyethylene made by one manufacturer may be very different
from polyethylene made by another
• this is due to the variations in polymerisation process, which controls (1) molecular
length, (2) molecular branching, and (3) degree of crystallinity in the final product
• all of these can be further changed by a varying degrees of mechanical processing

❑ For all these reasons, data from compilations are approximate.

❑ Fore accurate data, use manufacturers’ data sheet, or conduct your own tests.

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Next Class
Lecture 35
Part E: Processing and Applications
7 – Composite materials

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