Plastics (Polymers)

Why Design with Plastics?

 Corrosion resistance
 Low electrical and thermal conductivity, insulator
 Easily formed into complex shapes, can be formed, casted and joined.
 Wide choice of appearance, colors and transparencies

Disadvantages of using Plastics

 Low strength
 Low useful temperature range (up to 600 0F)
 Less dimensional stability over period of time (creep effect)
 Aging effect, hardens and become brittle over time
 Sensitive to environment, moisture and chemicals
 Poor machinability

Polymers

The earliest synthetic polymer was developed in 1906, called Bakelite.

The development of modern plastics started in 1920s using raw material extracted from coal and
petroleum products (Ethylene). Ethylene is called a building block.

Polymers are long-chain molecules and are formed by polymerization process, linking and cross
linking a particular building block (monomer äßæþ$íæ, a unit cell).

The term polymer means many units repeated many times in a chainlike structure.

Most monomers are organic materials, atoms are joined in covalent bonds & Ionic (electron-sharing)
with other atoms such as oxygen, nitrogen, hydrogen, sulfur, chlorine,….

The structure of polymers

Popular Plastics

 Polyethylene
 Acetyl (Delrin)
 ABS
 Polycarbonates
 Nylons

Type properties Application

Polyethylene (LDPE (low Good chemical and electrical Bottles, garbage cans,
density) and HDPE (high properties, strength depends housewares, bumpers, toys,
density) on composition luggage
Acetyl (Delrin) Good strength, good stiffness, Mechanical components;
good resistance to heat, gears, bearings, valves,
moisture, abrasion and rollers, bushings, housings
chemicals
ABS (Acrylonitrile Butadiene Dimensionally stable, good Automotive components,
Styrene) strength, impact and helmets, tool handles,
toughness properties, good appliances, boat hulls,
resistance to abrasion and luggage, decorative panels
chemicals
Polycarbonates Very versatile and has Optical lenses, food
dimensional stability, good processing equipment’s,
mechanical and electrical electrical components and
properties, high resistance to insulators, medical
impact and chemicals equipment’s, windshields,
signs, machine components
Nylons Good mechanical and Mechanical components;
abrasion resistance property, gears, bearings, rollers,
self-lubricating, resistant to bushings, fasteners, guides,
most chemicals but it absorbs zippers, surgical equipment’s.
water, increase in dimension
is undesirable

Classification of polymers
There are two major classifications of polymers

 Thermoplastics.
 Thermosetting Plastics (thermosets)

Thermo & thermosetting plastics

Thermoplastics and thermosetting polymers are types of plastic that undergo different production
processes and yield a variety of properties depending on the constituent materials and production
method. The terms thermoplastic and thermoset stand for how a material is or can be processed
under a changed temperature.

The main physical difference is how they respond to high temperatures. When heated to their
melting point, thermoplastics soften into a liquid form. Therefore, the curing process is reversible,
which means that they can be remolded and recycled. On the other hand, thermoset polymers form
a cross-linked structure during the curing process, preventing them from being melted and
remolded.
As an analogy, think of thermosets like concrete, once they have set, they can never go back to the
liquid form (irreversible process). While thermoplastics are like water, it can transition between ice
and water with the application or removal of heat (reversible process).

Thermoplastics
As the temperature is raised above the melting point, the secondary bonds weaken, making it easier
to form the plastic into any desired shape. When polymer is cooled, it returns to its original strength
and hardness. The process is reversible. Polymers that show this behavior are known as
thermoplastics.

This allows for additional processing of the same material, even after being prepared as a solid.
Processes such as extrusion, thermoforming, and injection moulding rely on such resin behavior.
Some common thermoplastic materials include polyethylene (PE), polycarbonate (PC), and polyvinyl
chloride (PVC).

However, like any other material, thermoplastics have their limitations. If subjected to extremely
high temperatures, the material may unwantedly soften, deform, and lose some of its physical
properties.

Applications of Thermoplastics
Design requirement Applications Plastics
strength Valves, gears, cams, pistons, nylon, acetal (delrin),
fan blades, etc. polycarbonate, phenolic
Functional and decorative knobs, handles, cases, ABS, acrylic, polyethylene,
moldings, pipe fittings, etc. phenolic, polypropylene,
polystyrene
Functional and Transparent lens, goggles, signs, food acrylic, polycarbonate,
processing equipment, etc. polystyrene, polysulfone
Hollow shapes and housings pumps, helmets, power tools, ABS, polyethylene, phenolic,
cases, etc. polypropylene, polystyrene,
polycarbonate

Thermosetting Plastics (thermosets)

Thermosetting plastics are cured into permanent shape. Cannot be re-melted to the flowable state
that existed before curing, continued heating for a long time leads to degradation or decomposition.
This curing (cross-linked) reaction is irreversible. Thermosets generally have better mechanical,
thermal and chemical properties. They also have better electrical resistance and dimensional
stability than do thermoplastics.

thermoplastics Properties Applications

Epoxies good dimensional stability, excellent electrical components
mechanical and electrical requiring strength, tools and
properties, good resistance to heat dies, fiber reinforced epoxies
and chemicals are used in structural
components, tanks, pressure
vessels, rocket motor casing
Phenolics good dimensional stability, rigid, laminated panels, handles,
high resistance to heat, water, knobs, electrical components;
electricity, and chemicals connectors, insulators
Polyesters good mechanical, electrical, and boats, luggage, swimming
(thermosetting, chemical properties, good pools, automotive bodies,
reinforced with glass resistance to heat and chemicals chairs
 fibers)
Silicones excellent electrical properties over a electrical components
wide range of temperature and requiring strength at high
humidity, good heat and chemical temp., waterproof materials,
properties heat seals

When it is placed in a mould and heated, the thermoset solidifies into the specified shape, but this
solidification process includes the formation of certain bonds, called crosslinks, that hold the
molecules in place and change the basic nature of the material, preventing it from melting.

As a result, a thermoset, as opposed to a thermoplastic, cannot return to its initial phase, rendering
the process irreversible. Thermosets, upon heating, become set, fixed in a specific form. During
overheating, thermosets tend to degrade without entering a fluid phase. Processes such as
compression moulding, resin transfer moulding, pultrusion, hand lay-up, and filament winding
depend on thermosetting polymer behavior. Some common thermosets include epoxy, polyimide,
and phenolic, many of which are significant in composites

What is crosslinking (curing)?

Thermosets and thermoplastics differ in various ways in terms of their behavior, but all those
diverging properties result from an underlying, fundamental difference in their chemical structure.
This underlying difference can be noticed in how thermoset resins, throughout the length of their
polymer chain, have particular spots that can be chemically activated to be part in chemical bonding
reactions with neighboring polymer molecules. Since all thermosets carry such chemically reactive
spots, it is often the case that all kinds of thermosets have the tendency to connect to one another.
Such a process of forming chemical links across different thermosetting molecules is called
crosslinking (or curing). Upon curing, formed crosslinks not only confine the polymer molecules from
moving, but also the atoms inside those molecules are impeded to a greater degree than
intermolecular attractions.

Another way of observing the behavioral difference between thermosets and thermoplastics is via
their molecular weight. As we compare both polymer types, thermosets stand out in how their
molecular weight drastically increases upon curing. Thermoplastics are known to have higher
molecular weight values than uncured thermosets. However, when crosslinking occurs between two
thermosets, a polymer network is formed of molecular weight almost double the weight when the
two were separate. As the number of linked molecules increase, the molecular weight continues to
rise, exceeding that of thermoplastics. This drastic increase in molecular weight causes major
changes in material properties, such as an increased melting point. With a continuous increase in
molecular weight due to crosslinking, the melting point can rise and reach a point that exceeds the
decomposition point. In that case, a thermoset polymer would have a very high molecular weight
that it would decompose before it can melt, which defines why thermoset processing is irreversible.

Linear polymers
A sequential structure resulting in thermoplastics like nylon, acrylic, polyethylene. A linear polymer
may contain some branched and cross-linked chains resulting in change in properties.

Branched polymers

Side branch chains are attached to the main chain which interferes with the relative movement of
the molecular chains. This results in an increase in strength, deformation resistance and stress
cracking resistance. Lower density than linear chain polymers.

Cross-linked polymers

Three-dimensional structure, adjacent chains are linked by covalent bonds. Polymers with cross-
linked chains are called thermosetting plastics (thermosets), epoxy and Silicones.

Cross-linking is responsible for providing hardness, strength, brittleness and better dimensional
stability.

Network polymers

A three-dimensional network of three or more covalent bonds. Thermoplastic polymers that have
been already formed could be cross-linked to obtain higher strength. Polymers are exposed to high-
energy radiation.

Properties of thermoplastics vs thermosets

Thermoplastics generally provide high-strength, flexibility and are resistant to shrinkage, depending
on the type of resin (the polymer in melted liquid form). They are versatile materials that can be
used for anything from plastic carrier bags to high-stress bearings and precision mechanical parts.
Thermosets generally yield higher chemical and heat resistance, as well as a stronger structure that
does not deform easily.

Here is a list showing the difference between thermoplastics and thermosets in terms of features
and properties. Notice the effect of crosslinking as an underlying factor in diverging those materials
from one another.

Thermoplastics vs thermosets
Feature/Property Thermoplastics Thermosets

Molecular structure Linear polymer: weak Network polymers: high level

molecular bonds in a straight- of crosslinking with strong
chain formation chemical molecular bonds
Melting point Melting point lower than the Melting point higher than the
degradation temperature degradation temperature

Mechanical Flexible and elastic. High Inelastic and brittle. Strong

resistance to impact (10x more and rigid. Strength comes from
than thermosets). Strength crosslinking.
comes from crystallinity
Polymerisation Addition polymerisation: Polycondensation
repolymerised during polymerisation: polymerised
manufacture (before during processing
processing)
Microstructure Comprised of hard crystalline Comprised of thermosetting
and elastic amorphous regions resin and reinforcing fibre in
in its solid state its solid state
Size Size is expressed by molecular Size is expressed by crosslink
weight density
Recyclability Recyclable and reusable by the Non-recyclable
application of heat and/or
pressure
Chemical resistance Highly chemical resistant Heat and chemical resistant
Crack repair Cracks can be repaired easily Difficult to repair cracks

Process thermal aspect Melting thermoplastics is Crosslinking thermosets is

endothermic exothermic
Service temperature Lower continuous use Higher CUT than
temperature (CUT) than thermoplastics
thermosets
Solubility Can dissolve in organic Do not dissolve in organic
solvents solvents

Polymer’s Structures.
Bonding – monomers are linked together by covalent bonds, forming a polymer chain (primary
bonds). The polymer chains are held together by secondary bonds. The strength of polymers comes
in part from the length of polymer chains. The longer the chain, the stronger the polymer. More
energy is needed to overcome the secondary bonds.
Additives in Plastics
 Additives are added to polymers in order to obtain or improve certain properties such as
strength, stiffness, color, resistance to weather and flammability.
 Plasticizers are added to obtain flexibility and softness, most common use of plasticizers are
in PVC
 Ultraviolet radiation (sunlight) and oxygen cause polymers to become stiff and brittle, they
weaken and break the primary bonds. A typical treatment is to add carbon black (soot) to
the polymer, it absorbs radiation. Antioxidants are also added to protect against
degradation.
 Fillers such as fine saw dust, silica flour, calcium carbide are added to reduce the cost and to
increase harness, strength, toughness, dimensional stability,…..
 Colorants are added to obtain a variety of colors. Colorants are either organic (dye) or
inorganic (pigments). Pigments provide greater resistance to temperature and sunlight.
 Flame retardants such as chlorine, phosphorus and bromine, are added to reduce polymer
flammability. Teflon does not burn and nylon and vinyl chloride are self-extinguishing.
 Lubricants such as mineral oil and waxes are added to reduce friction.

Types of thermoplastics and their applications.

Thermoplastic Properties and applications
Polyamide (nylon) Tough and relatively hard material used for power tool casings,
curtain rails, bearings, gear components and clothes

Polymethyl Methacrylate Stiff, durable and hard plastic that polishes to a sheen, used for
(PMMA, acrylic) signage, aircraft fuselage, windows, bathroom sinks and
bathtubs
Polyvinyl Chloride (PVC) Tough and durable material that is commonly used for pipes,
flooring, cabinets, toys and general household and industrial
fittings
Polypropylene Light, yet hard material that scratches fairly easily, with
excellent chemical resistance, used for medical and laboratory
equipment, string, rope and kitchen utensils

Polystyrene (PS) Light, stiff, hard, brittle, waterproof material used mainly for
rigid packaging

Polytetrafluoroethylene (PTFE, Very strong and flexible material used for non-stick cooking
Teflon) utensils, machine components, gears and gaskets

Low-density Polythene (LDPE) Tough, relatively soft, chemical resistant material used for
packaging, toys, plastic bags and film wrap

High-density Polythene (HDPE) Stiff, hard, chemical resistant material used for plastic bottles
and casing for household goods
Types of thermosetting polymers and their applications.
Thermoset Properties and applications

Epoxy resin Hard material that is brittle without extra reinforcement. Used
for adhesives and bonding of materials

Melamine formaldehyde Hard, stiff and strong, with decent chemical and water
resistance, used for work surface laminates, tableware and
electrical insulation
Polyester resin Hard, stiff and brittle when unlaminated. Used for
encapsulation, bonding and casting

Urea formaldehyde Hard, stiff, strong and brittle used primarily in electrical devices
due to its good electrical insulation properties

Polyurethane Hard, strong and durable material used in paint, insulating

foam, shoes, car parts, adhesives and sealants

Phenol formaldehyde resin Strong, heat and electrical-resistant material used in electrical
(PF) items, sockets and plugs, car parts, cookware and precision-
made industrial parts