COVENANT UNIVERSITY

COLLEGE OF SCIENCE AND TECHNOLOGY

DEPARTMENT OF CHEMISTRY

COURSE TITLE: Polymer Technology

COURSE CODE: CHM423 UNIT: 2
SESSION: 2019/2020 LOCATION: Hall 112
LECTURER: A. A. Akinsiku (PhD)

STUDIES OF THERMOPLASTICS RESINS

Thermoplastic resins (TP) are polymer compounds that become soft or fluid when heated,
and then return to its original state when cooled. TP can be remoulded into any shape before
they cool down to a solid. They exist in semi-crystalline or amorphous form, and can also be
recycled. Thermoplastic resins are most commonly unreinforced, meaning, the resin is
formed into shapes and have no reinforcement providing strength.

Thermoplastics are also referring to linear polymers, whose molecules are synthesised in the
shape of long threads; they soften upon heating and harden upon cooling reversibly. In the
melted state, they are rubber-like liquids, and in the hard state they are glassy and brittle, e.g.
Perspex or partially crystalline, e.g. nylon.

Thermoplastics are recyclable and are used frequently today to create objects such as foam
cups, polyethylene squeeze bottles, acrylic lenses and safety helmets. Their unique properties
set them apart from thermosets and elastomers. Molecules of thermoplastics do not cross-
link on heating, thus, can be maintained in a softened state while being made to flow under
pressure into a new shape.

Examples of thermoplastic resins used today, and products manufactured with them include:

1) PET (Polyethylene terephthalate) - Water and soda bottles

2) Polypropylene - Packaging containers
3) Polycarbonate - Safety glass lenses
4) PBT (Polybutylene terephthalate) - Children's Toys
5) Vinyl - Window frames
6) Polyethene - Grocery bags
7) PVC (Polyvinyl chloride) - Piping
8) PEI (Polyetherimide) - Airplane armrests
9) Nylon - Footwear

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Recycling of Different Plastics

Recycling is a viable alternative to all other means of dealing with consumer plastic waste; it
is a cost-effective means of dealing with consumer plastic waste.

Major Plastic Resins and their Uses

Resin Code Resin Name Common Uses Examples of Recycled Products

Polyethylene Soft drink bottles, Liquid soap bottles, strapping,

Terephthalate peanut butter jars, fibrefill for winter coats,
1 (PET or PETE) salad dressing surfboards, paintbrushes, fuzz
bottles, mouth wash on tennis balls, soft drink
jars bottles, film

High-Density Milk, water, and Soft drink-based cups, flower

Polyethylene juice containers, pots, drain pipes, signs,
2 (HDPE) grocery bags, toys, stadium seats, trash cans,
liquid detergent recycling bins, traffic barrier
bottles cones, golf bag liners, toys

Polyvinyl Chloride Clear food Floor mats, pipes, hoses, mud

or Vinyl packaging, shampoo flaps
3 (PVC-V) bottles

Low-density Bread bags, frozen Garbage can liners, grocery

Polyethylene (LDPE) food bags, grocery bags, multi-purpose bags
4 bags

Polypropylene Ketchup bottles, Manhole steps, paint buckets,

(PP) yoghurt containers, videocassette storage cases,
5 margarine, tubs, ice scrapers, fast food trays,
medicine bottles lawn mower wheels,
automobile battery parts.

Polystyrene Videocassette cases, License plate holders, golf

(PS) compact disk jackets, course and septic tank
coffee cups, cutlery, drainage systems, desktop
6 cafeteria trays, accessories, hanging files, food
grocery store meat service trays, flower pots,
trays, fast-food trash cans
sandwich container

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Polyethylene

Polyethylene comes in many different well-known grades, depending on their density as

influenced by the degree of micro-structural crystallinity. Low-density polyethylene (LPDE) is
flexible and strong, used for the less expensive end of the commodity market such as bowls,
buckets and bottles. It burns only slowly and softens at approximately 50oC, and, therefore
resist boiling water; usually, it is optically translucent. High-density polyethylene (HDPE) is
used where more rigidity is required. It softens at approximately 800C. Optically, it is less clear
than LDPE. Therefore, several other grades of polyethylene.

Polyolefins

Polyethylene is made from the polymerization of ethylene (or ethene) monomer.

Polyethylene chemical formula is (C2H4)n.

Their repeat structures of polyethylene are shown below:

There are two types of polyethylene:

a) Low-density polyethylene (LDPE):
• This resin contains branches or comonomer components, because of disruptions in
chain regularity,
• LDPE has a much lower crystallinity than high-density polyethylene (HDPE) and hence,
a lower density.
• One consequence of this lower density is a lower modulus, which means LDPE is often
selected as a matrix for composites. One exception is polyethylene fibre reinforced
polyethylene.
• Since LDPE has a lower melting point than the ultra-high molecular weight
polyethylene, it is used to make polyethylene fibres (~140 oC), it is possible to
consolidate LDPE without melting the fibres.

b) High-density polyethylene (HDPE)

• HDPE is highly crystalline and nonpolar; it is quite inert.
• It absorbs very little water, not easily attacked by most acids, bases or solvents.
• They are used in containers, such as milk bottles.
• Since HDPE is relatively inert, it is difficult to achieve excellent interfacial adhesion in
composites.

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 • Often maleic anhydride grafted polyethylene is added to HDPE to improve interfacial
adhesion to the reinforcing fibres.

Properties of Polyethylene

• flexible pipe
• used for pressurized water systems - sprinkler.
• not usable for hot water

Polypropylene

polypropylene is similar to PEs but more versatile and sturdier. Some grades only soften at as
high as 140oC. Therefore, suitable as stream hospital ware, not affected by environmental
stress, cracking and it exhibits outstanding resistance to fatigue on flexing. Polyolefins (a
generic name for the aliphatic polymers such as PEs and PPs) offer a range of plastics of
increasing softening point, rigidity, gloss and chemical resistance. Therefore, it is not used for
more applications usually associated with LDPE, mainly because of flexibility requirements
and depending on market circumstance cost may become a factor.

It is non-polar; hence, it absorbs very little water. Due to its glass transition temperature
below room temperature.

Properties

• lightweight
• temperature up to 180oF (82oC)
• highly resistant to acids, bases and many solvents
• usable in laboratory plumbing
• It exhibits good impact strength.
• Because of these properties, polypropylene used 90% of the time in glass material
thermoplastic

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Polyvinylchloride (PVC)

PVC is one of the few plastics to which plasticisers is added; thus, exists as rigid as a flexible
market. Unplasticised (UPVC) is a hard, somewhat brittle (not soluble ketones, esters and
chlorinated hydrocarbons). Furthermore, it is one of the very few polymers with reasonable
inherent resistance to catching/spreading of flame. It offers insulation and softens at about
80-1000C.

Properties
• PVC is inexpensive and readily extended with low-cost fillers; it is the sold more than
any other polymer.
• PVC has tensile and flexural properties similar to many of the styrene family. Unless
filled, it is inherently hard.
• When PVC degrades, at too high a temperature, hydrochloric acid is released.
• Due to the presence of chlorine, PVC has a comparatively high density; it is non-
flammable and environmentally durable.
• PVC is used in numerous outdoor applications, such as gutters, siding and shutters on
homes.
• Since the glass transition temperature of PVC is 85oC, it is not suitable for hot water
pipe.
• strong and rigid
• resistant to a variety of acids and bases
• susceptible to attack by some solvents and chlorinated hydrocarbons
• maximum usable temperature 140oF (60oC)
• usable for water, gas and drainage systems
• not useable in hot water systems

PVDF - Polyvinylidene Fluoride

• strong and very tough material

• resistant to abrasion, acids, bases, solvents and much more
• usable to 280oF (138oC)
• usable in laboratory plumbing

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There are many aspects and properties to consider when choosing a thermoplastic resin for
a product:
Flexibility

• Transparent vs Opaque
• Impact Strength
• Chemical Resistance
• Fatigue Resistance

Polystyrene (PS)

PS readily identified by the metallic noise when dropped onto a hard surface, PS is colourless,
transparent, hard and brittle, softens at 85-950C. Resistant to aliphatic hydrocarbons, but is
soluble in aromatics like benzene. Like ordinary PS, it is not expensive. The lightweight PS
(structural foam PS of expanded PS-EPS is an excellent heat insulator, but since PS dissolves
in aromatics solvents as display/insulation panel. It should only be painted with emulsion
paints.

Properties
Polystyrene has many attractive properties for consideration as a composite matrix:
• It has a low density, modest Tg, high modulus, and virtually no water absorption.
• However, it is brittle and sensitive to solvent attack.
• Butadiene is added to improve its toughness.
• Acrylonitrile is added to improve its chemical resistance.
• Maleic anhydride is incorporated as a comonomer to achieve higher temperature
performance.
Styrenics
• Unlike the polyolefins, the styrene family consists primarily of amorphous polymers
due to irregularities in their repeat structures.
• Consequently, the styrene family relies on having glass transition temperatures above
room temperature to be structurally useful.
• All the styrene has densities higher than the polyolefins and most cost more.
• In general, the strengths and moduli of the styrene exceed the polyolefins.
• Their heat deflection temperatures are close to their glass transition temperatures.

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Polyamides/nylons
These are extensively used in textile and engineering, e.g. as self-lubricating bearings
(especially as food packaging, where the presence of lubricating oil might lead to
contamination). Some nylons offer an excellent barrier to gas permeation used as a film for
packaging cheese slices etc. Although demonstrating brilliant chemical resistance, it is
susceptible to high water absorption.

H H O O
N (CH2 ) N + C (CH ) C
6 2 4
H Hexamethylene H HO HO
diamine Adipic acid
(This polymer is known as H H O O
nylon 66 because of the six
carbon atoms in both the N (CH2 ) C (CH2 )4
N
hexamethylene diamine 6 C + H2 O
and the adipic acid.) H Hexamethylene adipamide
(Nylon 66) HO water

Properties of polyamides (Nylons)

• Nylon is a thermoplastic that resists abrasion and is self-lubricating, often it is used to
make ropes, fishing line and zippers.
• Acrylics are used to make goggles, windows and lenses because of their impact
strength and transparency.
• Polyethylene is very strong and tends to resist impact, and so it is used to make buckets
and toys.

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 • Most nylons are crystalline and have relatively low melt viscosities.
• The primary nylons in use, nylon 6 and nylon 66, are quite similar.
• Nylon 66 has slightly higher transition temperatures compared to nylon 6.
• Both types have excellent strength, stiffness and toughness. They are self-lubricating
and exhibit good abrasion resistance.
• Both nylon 6 and 66 have excellent chemical resistance. However, they are sensitive
to strong acids.
• They absorb significant quantities of water. The absorption of water leads to lower
strength and modulus and higher impact strength. Nylon expands due to the
absorption of water.

Polyethylene terephthalate, PET

• Is the lowest cost, highest volume polyester produced, even compared to
thermosetting polyesters.
• Used in textile applications and for bottles for carbonated beverages.
• The melt viscosity of PET is low compared to most polypropylenes;
• Based on its relatively low cost it is often considered as an alternative to
polypropylene composites when higher service temperatures are needed.
• Compared to polypropylene PET provides a stiffer, stronger matrix.

Properties of Thermoplastics

Plastic materials and thermal effects

Thermoplastics may be divided into two groups, amorphous and semi crystalline, each with
its own set of properties. Amorphous thermoplastics have no order beyond that on the level
of the repeat units, which make up the long-chain macromolecule. The linear chains often
exist in random positions and orientations in the bulk polymer and are separated by a
distance proportional to their dynamic state, which is governed by temperature.

For every amorphous thermoplastic homopolymer (one exhibiting no crystallinity), there

exists a narrow temperature region in which it changes from a viscous or rubbery condition
at temperatures above this region, to a hard and relatively brittle one (sometimes called
glassy) below it). This temperature region is called the glass transition temperature Tg (Fig. 1)
and is usually obtained from a volume versus temperature plot of observations taken on
cooling (McCrum et al., 1988). Since the movement of whole polymer chain segments is a

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necessary prerequisite of welding, amorphous thermoplastics need to be above Tg before
welding can take place.

Fig. 1: A typical graph of specific volume versus temperature for an amorphous

thermoplastic (from Wise, 1999).

Semi crystalline thermoplastics are composed of crystalline regions and amorphous regions.
For flow to occur in these polymers, their temperature must be above the crystalline melting
point Tm, as shown in Fig. 2, which is the temperature at which all of the crystalline regions
have disappeared.

Semi crystalline thermoplastics will generally have a Tg associated with the amorphous
regions and Tm associated with the crystalline regions, with Tm > Tg. Viscous flow will generally
only occur above Tm.

Fig. 2: A typical graph of specific volume versus temperature for a semi-crystalline

thermoplastic (from Wise, 1999).

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Thermal welding of thermoplastics relies on the temperature at the interface being above Tg
for amorphous thermoplastics or above Tm for semi-crystalline thermoplastics. Above Tm or
Tg, there is increased chain mobility of the thermoplastic in the region of the weld. It is this
increased mobility of the chains, which allows them to diffuse across the joint interface and
entangle with chains on the other side of the interface.

Mechanical properties of polymers

Tensile Yield Strength: Maximum engineering stress in psi (or Pa) at which permanent non-
elastic deformation of the thermoplastic material begins.

Yield Point: First point where the specimen yields and specimen's cross-sectional area begins
to contract significantly, or where the strain can increase without an increase in the stress.

Ultimate tensile strength: Maximum stress the thermoplastic material can withstand before
failing, whichever occurs at the higher stress level.

Tensile Modulus: Also known as Young's Modulus is the ratio of stress to strain within the
elastic region of the stress-strain curve before the yield point.

The Glass Transition Temperature (Tg)

Tg is the temperature, or range of temperatures, over which the polymer exhibits a marked
change in several physical properties, most notably specific volume, thermal coefficient of
expansion, specific heat capacity, and refractive index.

Below the Tg, there may be small local rotations (e.g. rotation around the C-C bond to a side-
chain methyl group). Still, the polymer chains themselves are frozen into fixed positions
(albeit not in a regular crystalline array), and the polymer is hard brittle glass.

Above the glass transition temperature, the thermal energy is sufficient to allow rotations and
limited translations of large segments of the polymer chain. On the macroscopic scale, the
polymer has the dimensional constancy of a solid, but on the molecular level, the chain
segments exhibit liquid-like properties.

The mechanical properties of polymers are also sensitive to temperature changes. Fig. 3
illustrates the difference in modulus with respect to temperature for an amorphous
thermoplastic. Below its glass transition temperature (Tg), the modulus is relatively constant.
As the temperature increases above Tg, the modulus drops roughly three orders of magnitude
to 0.28 GPa (0.4 ksi) and the polymer becomes rubbery. If the molecular weight of the
polymer is high, the polymer becomes a viscoelastic fluid about 100°C above its glass
transition temperature. At this temperature, the polymer can be processed as a melt.

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Fig. 3: Modulus versus temperature for an amorphous thermoplastic

A crystalline thermoplastic has a modulus similar to an amorphous thermoplastic if both are

below their Tg. As shown in Fig. 3, above Tg a crystalline polymer, has an intermediate modulus
depending on the degree of crystallinity present. Crystallinity disappears during melting,
leading to a rapid drop in modulus as the polymer becomes a viscoelastic fluid.

In comparing crystalline polymers and thermosetting polymers, a similar trend is observed

above Tg. For thermosets, the modulus above Tg is dependent on the crosslink density.
However, crosslink is permanent covalent bonds which cannot be "melted" like polymer
crystals. From this perspective, crystalline polymers have thermally reversible crosslinks
which enable them to processed. When polymers are reinforced, the modulus is raised. The
transition temperatures, Tg and Tm, are not changed significantly. Fig. 4 is the relationship
between Module and temperature for crystalline thermoplastics.

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Fig. 4: Module versus temperature for crystalline thermoplastics

Bibliography
1. Materials, Design and Manufacturing for Lightweight Vehicles, 2010
2. Jones, in Handbook of Laser Welding Technologies, 2013
3. Billmeyer, F. Textbook of Polymer Science, 2nd ed., John Wiley and Sons, Inc.,
NY (1971).
4. Braun, D, Simple Methods for Identification of Plastics, Macmillan Publishing
Co. Inc., NY (1982).
5. Handbook of Chemistry and Physics, 65th ed., CRC Press, Inc., Boca Raton, FL
(1985).

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