2022

Materials (1)
lecture 10 – Polymers
Dr. Janusz Bucki, PhD, MSEng, CEng

Wołoska 141, room 308, 02-507 Warszawa

[email protected]

Warsaw, 2022/23

Polymers (plastics)
Polymers: materials made of large molecules
(macromolecules), composed of many repeated
subunits (mers, monomers). For most polymers used
in industry, a mer is a single hydrocarbon molecule,
such as e.g. ethylene (C2H4) - a long-chain molecule
composed of many such mers bonded together is
polyethylene -(C2H4)-n n=100-1000 and more

Polymers besides carbon and hydrogen contain also:

• oxygen (e.g. acrylics)
• nitrogen (nylons)
• fluorine (fluoroplastics)
• silicon (silicones)

Characteristic features:
• low density (lightweight)
• low cost
• low melting point
• higher chemical reactivity than metals and ceramics

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Polymers production

https://committee.iso.org/files/live/sites/t
c61/files/The%20Plastic%20Industry%20B
erlin%20Aug%202016%20-%20Copy.pdf
access: 2019-01-06

https://www.darrinqualman.com/global-plastics-production/ access: 2019-01-06 3

Polymers are huge chain-like molecules in which the atoms forming the backbone chain
are linked by covalent bonds. The chain backbone is usually made from carbon atoms.
Polymers are in formed polymerization process in which the double bonds of monomers
break, allowing them to link others.
Polyethylene – made by the catalytic polymerization of ethylene

Polystyrene – made by polymerization of styrene:

A copolymer is made by the polymerization of two monomers,

adding them randomly (random copolymer) or in an ordered
way (a block polymer).
cyclic compound
The three dimensional
appearance of a short
bit of a polyethylene
molecule 4
Styrene-butadiene rubber (SBR).

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Molecular length and degree of polymerization

Polymerization breaks the double
bonds, activating monomer and
allowing it to link to others, forming
a long chain (macromolecule).
The ends of the chain link to other
macromolecules, or end with
terminator (e.g. OH group)
Properties of polymers depends on
the number of monomer units in a
macromolecule (molecular length)
called as degree of polymerization
(DP).
To create a solids with
useful mechanical
properties the chain
must have at least
500 monomers. For
commercial polymers
DP=103 -105.

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Ethylene, C2H4, is a molecule (square box – carbon atoms, small circles – hydrogen)

Molecular length and degree of polymerization

Probability of a given DP

In all commercial polymers there is

a range of DP, so the average
molecular length is used.

Most polymer properties depend

on : tensile strength,
softening temperature etc. Strength as a
function of DP
< 300 give no strength (short
macromolecules slide apart too
easily). The strength rise with

It is hard to mould polyethylene

with >> 103 Softening
temperature
as a function
of DP
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Polymeric Structures
Most polymers are amorphous, and the long molecules twin around each other

Polymeric Structures
Polymers which can crystallize are almost always only partly crystalline: segments of
molecules form crystallites, but other segments form amorphous structure in between.

(chains
randomly
arranged)

(oriented
chains)

(partly crystalline polymer)

In crystalline region, the chains sometimes are folded backwards and forwards over
one another. The chains could also form spherulites. 8

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Polymeric Structures - Spherulites

Crystalline platelets
often organize
themselves into
spherulites

doi.org/10.1081/MB-120017116 access: 2019-01-06 doi.org/10.1016/j.progpolymsci.2015.11.006 access: 2019-01-06

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Classes of the polymers

1. Thermoplastics - which soften on heating and eventually melt

2. Thermosets or resins – become more rigid on heating.

3. Elastomers or rubbers – in which secondary bonds are melted at

room temperature. Occasional cross-links enable returning them to
original shape when they are unloaded

4. Natural polymers – which provide the mechanical bases of most plants

and animal life (eg. cellulose, lignin, protein)

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Thermoplastic polymers
Thermoplastic polymers - linear polymers their chains are
not cross-linked, so they soften when heated. When their
secondary bonds melt, the polymers flow like a viscous liquid
and can be formed easily.
The molecules in linear polymers have a range of molecular
weights and they pack together in a variety configurations so
they do not have a sharp melting point. Their viscosity falls
over a range of temperature, like inorganic glass.

• Polyethylene (PE) – Tubing, film, bottles, electrical insulation, packaging (Polythene)

• Polypropylene (PP) – As PE but lighter, stiffer. Ropes. Expanded (EPP) – packaging
• Polystyrene (PS) – Cheap molded objects. High-impact polystyrene (HIPS)
toughened with butadiene. PS can be foamed with CO2 to make common packaging.
• Polyvinylchloride (PVC) – Rigid: Water pipes, window frames. Plasticized: electrical
cables insulation, artificial leather, hoses, clothing (colloquial: polyvinyl, vinyl) .
• Polytetrafluoroethylene (PTFE) – good high temperature polymer with very low
friction and adhesion characteristics. Bearings, seals, clothing. (Teflon, Gore-Tex)
• Polyethylene terephthalate (PET) – packaging, textiles (Dacron, Terylene, Mylar)
• Polycarbonate (PC) – Aircraft windows, eyeglasses, CD/DVD/Blu-Ray (Lexan).
• Polymethylmethacrylate (PMMA) – Transparent sheet and moldings, laminated
windscreens (Plexiglas, Acrylite, Lucite, Perspex). 11
• Polyamide (PA) – Textiles, ropes, moldings (Nylon, Kevlar, Trogamid, Zytel).

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Thermosetting polymers
Resin + Hardener  Thermoset polymer

During polymerization the cross-links form so the obtained polymer is usually heavily
cross-linked - its structure is almost always amorphous.
Thermoset polymers are described as network polymers.

Thermosets are a bit stiffer than thermoplastics, but they can not easily be crystalized
or oriented, so there is less scope for changing their properties by processing.

On heating, the additional secondary bonds melt, and the modulus of the polymer
drops: but the cross-links prevent the polymer melting or viscous flow (they soften
but do not melt). Cannot be hot-worked. Further heating decompose the polymer.

Thermosets:
• Epoxies – used as matrix materials for fiber-reinforced polymers and adhesives
• some Polyesters – as above, but cheaper
• Formaldehyde-based polymers – electrical fittings, tableware
• Polyurethanes – fabrics, car parts, shoe soles, often foams (bed mattresses)
• some Polysiloxanes (silicones) – sealants, adhesives, electrical insulation 12

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Elastomers

Elastomers or rubbers are almost-linear polymers with occasional cross-links

in which at room temperature the secondary bonds have already melted. The
cross-links provide the „memory” of the material so that it returns to its original
shape on unloading.

Elastomers:
• Polyisoprene – the main component of the natural rubber
• Polybutadiene – synthetic rubber, car tires
• Polychloroprene – oil-resistant rubber used for seals

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Polymers production

both from:
committee.iso.org/files/live/sites/tc61/files/The%20Plastic%2
0Industry%20Berlin%20Aug%202016%20-%20Copy.pdf 14
access: 2019-01-06

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Glass transition of polymers

In polymers no perfect crystallization (at the characteristic melting point Tm the random
arrangement of the atoms in the liquid changes discontinuously to the ordered one) is not
observed

The melting temperature of the crystalline polymers is blurred by the range of molecular
weights

In polymers which solidify to a glass the melting point disappears completely, but
the glass temperature, Tg can be defined.

Below Tg secondary bonds bind the molecules into an amorphous solid.

Above Tg a polymer becomes first leathery, then rubbery, capable to large elastic
extensions without brittle fracture

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Mechanical behaviour of polymers

Between -20oC and +200oC polymers can

pass through a spectrum of mechanical
states (from brittle-elastic at low
temperature, to viscous at high
temperature).

Their modulus and strength can change

more than 1000 times, so we can not
treat them as having a constant stiffness
and strength for design near ambient
temperature.

The mechanical state of a polymer depends on its molecular weight and on the
temperature. Some polymers (eg. PMMA or epoxies) are brittle at room temperature
(RT), because RT = 0.75 Tg.

Others (eg. polyethylenes) are leathery (RT = 1.0 Tg) or they are elastomers (eg.
polyisoprene) RT = 1.5 Tg.

So a normalized temperature (T/Tg) is often used to describe polimer properties. 16

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Mechanical behaviour of polymers

Elongation of
polymers increase
with the loading time
and temperature.
The deflection is
elastic but the strain
disappear often after
a time. Modulus of
polymers change by a
factor of 1000 as the
temperature is
changed and is time
dependent.

Linear amorphous polymers show five regimes of deformation:

• the glassy regime (large modulus around 3GPa)
• the glass-transition regime (modulus drops steeply from 3GPa to 3MPa
• the rubbery regime (modulus around 3MPa)
• the viscous regime (polymer starts to flow)
• the regime of decomposition (chemical breakdown starts) 17

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Modulus and strength diagrams for polymers

Cross-linking raises and

extends the rubbery plateau,
increasing the rubber-
modulus and suppressing
melting.

Crystallization increases the

modulus too (because the
polymer is more densely
packed) but does not
suppress melting, so
crystalline linear-polymers
(eg. high-density PE) can be
formed by heating and
moulding, just like linear
polymers; cross linked
polymers cannot.

The influence of cross linking on a contour of the modulus diagram for polyisoprene 18

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Properties of polymers

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Properties of polymers

For accurate data you must use the

manufacturers’ data sheets, or
conduct your own tests

The properties of polymers may be

very different depending on the
manufacturer because: doi.org/10.1515/cdbme-2016-0142 access: 2019-01-06

• all polymers contain a spectrum of

molecular lengths, slight changing in
processing change this spectrum
• details of the polymerization change
the extent of molecular branching and
the degree of crystallinity in final
product
• properties can be (and almost always
are) changed by mechanical processing
and by proprietary additives
(plasticizers, fillers, colorants).
Manufacturers rarely disclose their
additives. norner.no/nor/polymer-institutt/polymerisasjon-og-polymerutvikling
20
access: 2019-01-06

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Design with polymers involves taking into account that:

• below glass temperature Tg most polymers have a
modulus around 3GPa but above Tg the modulus
falls dramatically – to 3 MPa or less (linear polymers
become viscous liquid, occasionally cross-linked
polymers become rubbers). The Tg is always not far
from room temperature.

• even if Troom <Tg , Troom is a large fraction of Tg and

under load the secondary bond creep and the
modulus falls. The tables give moduli for loading time
100s at room temperature (20oC). For loading time
1000 hours the modulus can fall to one-third of that
value!
• near Tg most polymers are fairly tough, but can drop steeply as the
temperature is reduced.

• elastic deflections of polymers is much larger than in metals in ceramics.

• the coefficients of thermal expansion of polymers are 10 to 100 times larger

than those for metals. This can lead to problems of thermal stress when
polymers and metals are joined. 21
sites.google.com/site/mse553g6lab7/lab-2-1/results-discussion/ductile-brittle access: 2019-01-06

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Forming and joining of polymers

Thermoplastics are formed by: Thermosets are applied as a fluid mixture of resin
• extrusion and hardener which has to be mixed just before
• injection moulding it is used, and cured almost as soon as applied.
• vacuum forming They are formed and cured usually by compression
• compression moulding moulding.

Rubbers are formed like thermosets by pressing

and heating a mix of elastomer and vulcanizing
agent in a mould

Polymer fibers are produced by forcing molten

polymer or polymer in solution through fine
nozzles.
The formed fibers are twisted into a yarn and
woven into fabric.

Polymers may be expanded into foams by Polymers are joined by:

mixing in chemicals that release CO2 bubbles • gluing / cementting
into a molten polymer or in curing resin, or by • welding
expanding a dissolve gas into bubbles by • friction-welding
reducing the pressure. • various sorts of fasteners
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Degradation of polymers
• Dissolution
(when the polymer is completely soluble)

• Swelling
(partial dissolution process in which there is only limited solubility of the polymer in solvent)

• Bond rupture (breaking of molecular chain bonds)

 radiation effects (x-rays, α,  and -rays, ultraviolet radiation)
(ionization and broken of the covalent bonds)

 chemical reaction effects

(when oxygen, ozone or other substances cause the chain scission as a result of
chemical
 reaction e.g. vulcanized rubber exposed to ozone)

 thermal effects
(scission of molecular chains at elevated temperatures)

 weathering
(combination of several different processes of degradation at outdoor conditions)

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Damaging of the polymers

Polymers are damaged by radiation, particularly by the ultraviolet in sunlight
(an ultraviolet photon break the C_C bond in the polymer backbone, cutting it into
shorter chains). Paints are especially exposed to this sort of radiation damage.

The solution is to add a pigment or filler (like carbon) which absorb radiation.
Car tires contain as much as 30 wt% of carbon to stabilize the polymer against attack
by sunlight.

Oxygen can damage the polymer by creating -O- cross-links between the
polymer chains (it is a sort of unwanted vulcanization).
The cross-links raise Tg and make the polymer brittle. Ozone is especially damaging
because it supplies oxygen in a unusually active form. Sunlight (particularly ultraviolet)
promotes oxidation.
Polymers containing a C=C double bond are particularly vulnerable, because oxygen
links to it to give C-O-C cross-links. That is why rubbers are attacked by oxygen more
than other polymers.

The solution is to avoid polymers containing double-bonds, and stabilize them by

adding fillers (carbon) or pigments.
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Polymers recycling

In the EU, an estimated 41.5% of plastic packaging waste was

recycled in 2018. In seven EU Member States, more than half of
the plastic packaging waste generated was recycled.

https://ec.europa.eu/eurostat/web/products-eurostat-news/-/ddn-20210113-1 accessed 2022.01.15 25

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Polymers recycling

https://ourworldindata.org/plastic-pollution based on data from: https://www2.mst.dk/Udgiv/publications/2018/02/978-87-93614-73-4.pdf accessed 2022.01.15 26

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Polymers recycling
• Simple LDPE bags: Can be directly reused as waste bin bags for climate change, should be reused at least 1 time for
grocery shopping considering all other indicators; finally reuse as waste bin bag.

• PP bags, woven: Reuse for grocery shopping at least 5 times for climate change, at least 45 times considering all
indicators; finally dispose with recyclables, otherwise reuse as waste bin bag if possible, lastly incinerate.

• Biopolymer bags: Can be directly reused as waste bin bags for climate change, should be reused at least 42 times
for grocery shopping considering all other indicators. Finally, reuse as waste bin bag if possible, otherwise
incinerate.

• Unbleached paper bags: Can be directly reused as waste bin bags for climate change, should be reused at least 43
times considering all other indicators. Finally, reuse as waste bin bag if possible, otherwise incinerate.

• Bleached paper bags: Reuse for grocery shopping at least 1 time for climate change, at least 43 times considering
all indicators; reuse as waste bin bag if possible, otherwise incinerate.

• Conventional cotton bags: Reuse for grocery shopping at least 52 times for climate change, at least 7100 times
considering all indicators; reuse as waste bin bag if possible, otherwise incinerate.

https://www2.mst.dk/Udgiv/publications/2018/02/978-87-93614-73-4.pdf accessed 2022.01.15 27

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PE (polyethylene)

Forming: Injection moulding, extrusion

Properties: density 0,915-0,92 g/cm3
Young modulus at tension 200-400 MPa
Elongation at fracture >50 %
Stress at yielding 8-10 MPa
Application:
Packing foils, heat-shrinkable foils , pipes and tubes, cable
coatings etc.

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PP (polypropylene)
Forming :
Injection moulding, extrusion, pressing

Properties : density 0,905-0,915 g/cm3

Young modulus at tension 1300-1800 MPa
Elongation at fracture >50 %
Stress at yielding 25-40 MPa
Application :
Structural elements, melting glues, packing's, roofing tars, etc.

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PS (polystyrene)

Forming :
Injection moulding

Properties : density 1,04-1,05 g/cm3

Young modulus, E 3100-3300 MPa
Elongation at fracture 1,5-3%
Tensile strength 30-55 MPa
Application :
Packages for food, medicines, cosmetics etc.

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PMMA (poly(methyl methacrylate))

Forming : Injection moulding, extrusion

Properties : density 1,17-1,19 g/cm3
Young modulus, E 3100-3300 MPa
Elongation at fracture 2-6%
Yield strength 60-75 MPa
Application :
tubes, optical lenses, casings, covers, optical waveguides, laminated
glasses,wood impregnants

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PET (polyethylene terephthalate )

Forming
Injection moulding

Properties Density (partly crastalline PET) 1,38-1,40 g/cm3

Young modulus, E 2800-3100 MPa
Elongation at fracture >50%
Yield strength 60-80 MPa
Application :
bearings, gears, shafts, couplings, heat insulating foils, bottles etc.

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PC (polycarbonate)

Forming : Injection moulding, extrusion etc.

Properties : density 1,20 g/cm3
Young modulus, E 2300-2400 MPa
Elongation at fracture >50 %
Yield strength 55-65 MPa
Application : Covers of the fluorescent lamps, greenhouses, optical glasses, contact
lenses, compact discs, etc.
Large elements, like cabin bowl of F22 (3,56m length, 1,14m width,
0,7m height, 160kg, 2 3/8” layers laminated)

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ABS (acrylonitrile/butadiene/styrene)

Forming :
Injection moulding, extrusion

Properties : density 1,03-1,07 g/cm3

Young modulus, E 2200-3000 MPa
Elongation at fracture 15-20 %
Yield strength 50-65 MPa
Application :
Heat insulation foils, tubes, tv and telephone casings, car caps, etc.

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PUR (polyurethane)

Insulations of the cables Racing tracks of the wear resistant rolls Profiles and seals

Bed mattres Toothed stripes Shoe sole 35

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