INTRODUCTION TO PLASTIC INDUSTRY

BY

GROUP 2

12BB001813

12BB001814

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1.0 INTRODUCTION TO PLASTIC INDUSTRY

It is very difficult to realize how important plastics have become to our everyday lives.

We always seem to have known these materials, and we tend to take it for granted that

they occur every day and all around us, for example in our clothing, the pen that we

write with, the chair that we sit on or the wrapping of the food that we eat. Look around

you; how much plastic do you see?

Fig1: plastic products

So it is sometimes hard to believe that plastics have only been commonly available for

about the last one hundred years. Yet in this time the impact that they have made

upon the quality of our lives and on the products that we have access to has been

enormous. Plastics give us the possibility of manufacturing well-designed, beautiful

products from the very many different types of plastics materials that are commonly

available today. Within manufacturing technology there is a very high degree of

technological understanding of plastics and a range of sophisticated technological

processes that enable us to make them and shape them in numerous ways.
1.1 The terminology of plastics.

If you are going to understand plastics, you are going to have to learn a lot of new

terms. Some of these terms are not particularly easy to pronounce but you will learn

them with practice. Try saying ‘oxybenzylmethyleneglycolanhydryde’. Perhaps it is

easier to call this plastic by its other name, which is Bakelite. Where possible you must

try to learn the correct terminology when talking about plastics. The word plastic itself

comes from the Greek word plasticos, which means to be able to be shaped or molded

by heat. As we will see, shaping plastics by using heat is a basic part of nearly all plastics

manufacturing processes

1.2 The early history of polymers.

The three-part classification of polymers that we have just looked at gives us an insight

into the history of their use. Naturally occurring plastic materials can be found in the

forms of animal bones, horns, tortoise shells, the fossilized resin from pine trees

(amber), the albumen in egg, the sap from various tropical trees, and the wax from

bees, and many of these natural polymers are still in use today. Casein, derived from

milk, is still used to manufacture buttons. Bitumen is still used in surfacing roads and

shellac, which was used for early gramophone records, is still used in the production

of wood varnish. Shellac, which is produced by the lac beetle, was used by early
Chinese cultures as a varnish and as such is still in use. In the nineteenth century it

was mixed with fillers and molded into brush backs, mirrors and picture frames.

Fig.2.A shellac picture frame, known as a union case, made about 1860.

Papier mache, which because of its moldable properties can be considered a

plastic, was patented in 1772. Gutta Percha, which, like latex, is extracted from tropical

trees, was used to make a wide range of household items and also to insulate the first

submarine telegraph cable between Dover and Calais. It is still used in the

manufacture of some types of golf balls.

In 1838 Charles Goodyear heated latex rubber with Sulphur to make a durable

and elastic material. He found that the more Sulphur that he added the harder the

material became and he termed his new invention ‘vulcanite’. This was the first time

that a natural polymer had been deliberately modified and so was the first of the semi

synthetic materials. One of the uses found for it was to make match stick holders. It is

still used today, molded into pipe stems, and mouthpieces for musical instruments.
 Fig.3: A vulcanite matchbox, known as a vesta case, made about 1880.

Bois Durci, which is made of cellulose in the form of finely ground wood

blended with albumen from cows’ blood, was patented in France in 1855. It was

compression molded in a heated mold and often used to make ornate plaques that

were inlaid into furniture.

In the nineteenth century manufacturing meant huge increases in the mass

production of goods. A rapid increase in population, a general improvement in the

standard of living and the growth of towns and cities brought with them an increased

desire for material goods, especially as status objects. As traditional crafts were

superseded by mechanization (making things by machines instead of by hand) and the

volume of production increased, new materials were needed to replace expensive

natural materials like horn and ivory.

In 1862 a material called Parkensine was exhibited at the Great International

Exhibition in London. It caused a lot of interest as a plastic material that could be used

to make high quality products. It could be repetitiously molded, in colors, and with a
finely detailed surface. Its inventor, Alexander Parkes, had made it by dissolving

cellulose in the forms of wood flour and cotton waste in nitric acid, thereby making

cellulose nitrate. In 1866 Parkes set up a manufacturing company, but he could not

control the quality of the product due to its brittleness and was forced into bankruptcy.

Cellulose nitrate was first adopted commercially in America in 1869 where the Hyatt

brothers made a much more moldable version of it by mixing the cellulose nitrate with

camphor. Cellulose nitrate was given the trade name of ‘celluloid’ and as ivory was in

short supply at the time one of its first uses was

the manufacture of billiard balls. However, it was soon discovered that celluloid made

from cellulose nitrate was explosive, and when you banged the billiard balls together

they sometimes blew up! Celluloid made from cellulose acetate was developed to

overcome this problem, and this is still used today in the manufacture of table tennis

balls. Very large quantities of celluloid products were made for the American and

European markets and the material became the first of the mass-produced plastics.

Fig.4: A celluloid dressing table set made about 1910

 In 1907 a Belgium chemist living in America called Leo Baekeland, developed

the first truly synthetic plastic called phenol formaldehyde, much better known under

the trade name of ‘Bakelite’. Bakelite was used initially in electrical goods but soon

began to appear in other consumer products. Since it was brittle it was strengthened

by adding wood dust to it, which is why much early Bakelite is brown in color. This

process of adding other materials to plastics, (called fillers), to give them strength is an

important part of plastics technology today. Bakelite was an enormously popular

material for domestic products as it was relatively cheap and easy to manufacture and

gave a consistently high quality product. Many Bakelite products were made that still

survive today.

Fig 5: A Bakelite thermos flask.

The early developments in polymer technology occurred without any real knowledge

of the molecular theory of polymers. The idea that the structure of polymers in nature

might give an understanding of plastics was put forward by Emil Fischer, who in 1901

discovered that natural polymers were built up of linked chains of molecules. It was
not until 1922 that the chemist Herman Staudinger, proposed that not only were these

chains far longer than first thought, but they were composed of giant molecules

containing more than a thousand atoms. He christened them ‘macromolecules’, but

his theory was not proved until 1938 when the first plastic was created with a

predictable form. This was the first synthetic fiber, nylon. As metal replaced wood in

many consumer products, plastics were developed as an even cheaper alternative. The

cost of casting metal increased sharply after World War II, while plastic could be

formed relatively cheaply. For this reason, plastics gradually replaced many things that

were originally made in metal, particularly casings for products. In the 1930s,

Bakelite's easily moldable properties were ideal for designers looking for new

materials for cheap domestic products. They wanted a material that could be mass-

produced cheaply, yet still produce stylish products. Now luxury items such as

jewellery, which had previously been made from ivory, could reach the mass market

made of celluloid.
1.3 Plastics timeline.

1980 During this decade ICI and Bayer launch PEEK, PES and PPS as the new

engineering thermoplastics, Costs are enormous but specialist applications make a

lasting market even after ICI retreats from the plastics market.

1982 First artificial heart made mainly of polyurethane implanted in a human.

1983 The slim Swatch watch launched, its case of ABS (acrylonitrile butadiene

styrene) and strap of PVC (polyvinyl chloride). Authentic Ltd., British firm renowned

for its sharp, modern designs in various plastics for domestic use, founded.

1988 Triangular recycling symbols identifying different types of plastics introduced.

1990 First biodegradable plastics launched by ICI

1993 Alessi designs its first all plastic product: the Gino Zucchino sugar pourer

designed by Guido Venturini.

1994 Smart car with lightweight flexible integrally colored polycarbonate panels

introduced.

1998 Amorphous free standing Zanussi Oz fridge, with insulation and outer-skins

made in one process from polyurethane foam, launched.

2000 Issues relating to sustainability and the creation of plastics from renewable

sources start gathering momentum.

2005 Nasa explores the advantages of a polythene-based material, RXF1, for the

space-ship that will send man to Mars.

2007 Tate Britain‘s Christmas tree decorated with plastic Airfix planes.

1.4 Raw materials for plastic industry

Most modern plastics are derived from natural materials such as oil, coal and natural

gas with crude oil remaining the most important raw material for their production.

The starting point for the production process is the distillation, in petrochemical

refineries, of the raw material into fractions (different parts). The heavy fractions give

us lubrication oils and the heavy oils used for heating fuels. The lighter fractions give

us gas, petrol, paraffin and naphtha. The chemical building blocks for making plastics

come mainly from naphtha.

Fig.6 : Distillation from crude oil.

The start of making plastics is to subject naptha to a cracking process in which complex

organic chemical compounds are separated into smaller molecules, dependent on

their molecular weight. These smaller molecules include ethylene, propylene, butene

and other hydrocarbons. The compounds produced through the cracking process are

then further refined to produce the base plastic materials.

Fig 7: Cracking naptha.

2.0 Classification and Properties of plastics

There are several ways of classification of polymers based on some special

considerations. The following are some of the common classifications of polymers:

2.1 Based on source (derivation)

Under this type of classification, there are three sub categories.

2.1.1 Natural polymers

These polymers are found in plants and animals. Examples are proteins, cellulose,

starch, some resins and rubber.

2.1.2 Semi-synthetic polymers

Cellulose derivatives as cellulose acetate (rayon) and cellulose nitrate, etc. are the

usual examples of this sub category.

2.1.3 Synthetic polymers

A variety of synthetic polymers as plastic (polythene), synthetic fibres (nylon 6,6) and

synthetic rubbers (Buna - S) are examples of manmade polymers extensively used in

daily life as well as in industry.

2.2 Based on Processability

A large number of polymer applications in different fields depend ontheir unique

mechanical properties like tensile strength, elasticity, toughness, etc. These

mechanical properties are governed by intermolecular forces, e.g., van der Waals

forces and hydrogen bonds, present in the polymer. These forces also bind the
polymer chains. Under this category, the polymers are classified into the following two

sub groups.

2.2.1 Thermoplastics polymers

The material that softens when heated above the glass transition temperature or

melting temperature and becomes hard after cooling is called thermoplastics.

Thermoplastics can be reversibly melted by heating and solidified by cooling in limited

number of cycles without affecting the mechanical properties. On increasing the

number of recycling of thermoplastics may result in color degradation, thereby

affecting their appearance and properties. In the molten state, they are liquids, and in

the mushy state they are glassy or partially crystalline. The molecules are joined end-

to-end into a series of long chains, each chain being independent of the other. Above

the melting temperature, all crystalline structure disappears and the long chain

becomes randomly scattered.

The molecular structure of thermoplastic (figure 1) has an influence on the chemical

resistance and resistance against environmental effects like UV radiation. The

properties may also vary from optical transparency to opaque, depending on the

molecular structure. The important properties of the thermoplastics are high strength

and toughness, better hardness, chemical resistance, durability, self-lubrication,

transparency and water proofing. With the application of heat, thermoplastic softens

and it can be molded into desired shapes. Some thermoplastics can be joined with the
application of heat and pressure. There are several techniques available for the joining

of thermoplastics such as mechanical fastening, fusion bonding, hot gas welding,

solvent bonding, ultrasonic welding, induction welding, and dielectric welding. The

different types of thermoplastic are: Acrylonitrile Butadiene Styrene (ABS), Acetals,

Acrylics, Cellulosics, Fluorocarbons, Polyamides, Polycarbonates, Polyethylene (PE),

Polypropylenes (PP), Polystyrenes, Polyetheretherketone, Polyvinyl Chloride (PVC),

Liquid Crystal Polymers (LCP), Polyphenylene Sulphide (PPS) and Vinyls.

Fig 8 Molecular structure of thermoplastics

2.2.1.1 Applications

Thermoplastics can be used to manufacture the dashboards and car trims, toys,

phones, handles, electrical products, bearings, gears, rope, hinges and catches, glass

frames, cables, hoses, sheet, and windows, etc.

2.2.2 Thermosets

The property of material becoming permanently hard and rigid after cooling when

heated above the melting temperature is called thermosets. The solidification process

of plastics is known as curing. The transformation from the liquid state to the solid
state is irreversible process, further heating of thermosets results only in the chemical

decomposition. It means that the thermosets can’t be recycled. During curing, the

small molecules are chemically linked together to form complex inter-connected

network structures (figure 2). This cross-linking prevents the slippage of individual

chains. Therefore, the mechanical properties (tensile strength, compressive strength,

and hardness) are not temperature dependent, as compared to thermoplastics. Hence,

thermosets are generally stronger than the thermoplastics.

Fig 9 :Molecular structure of thermosets

The joining of thermosets by thermal processes like ultrasonic welding, laser welding,

and gas welding is not possible, but mechanical fastening and adhesive bonding may

be used for low strength applications. The different types of thermosets are Alkyds,

Allylics, Amine, Bakelite, Epoxy, Phenolic (PF), Polyester, Silicone, Polyurethane

(PUR), and Vinyl Ester.

2.2.2.1 Applications

Thermosets are commonly used for high temperature applications. Some of the

common products are electrical equipments, motor brush holders, printed circuit
boards, circuit breakers, encapsulation, kitchen utensils, handles and knobs, and

spectacle lenses.

2.3 Processing Techniques for Plastics

Plastic materials are synthetic and semi-synthetic organic solids and it can be easily

processed. The processing stages of plastics may be heating, forming and cooling in

continuous or repeated cycles. The processing of plastic product depends on the

shape of the final product and types of plastic material (thermoplastics or thermosets)

being used. The complex plastic product can be produced in a single operation. The

processing of plastic may be automated and suitable for mass production.

Thermoplastics can be processed by heating up to the glass transition temperature and

formed into the desired shape with the application of pressure, for examples,

thermoforming, compression molding, and blown film extrusion.

The processing of thermosets can be completed in two steps; first it can be melted and

then poured into the mold to make a desired shape, for examples, casting, extrusion,

and injection molding.

2.4 Structure of Plastics

The basic structure of plastics depends upon its molecular chains formulated during

chemical reaction (figure 3). A single repeating unit in a molecular chain is called

monomers. There are two different types of chemical reactions which take place

during processing i.e. poly-addition and poly-condensation. In poly-addition, the

monomers bond to each other without the loss of any other atoms, for example

alkene. In case of poly-condensation, the two different monomers combine to form a

single molecule with the loss of atoms, for example: formation of polyester lost

hydrogen molecules.

On the basis of structure, plastics can be classified into four categories i.e. linear

structure, branched structure, cross-linked structure, and network structure.

Figure 10: Structure of plastics

2.4.1 Linear Structure:

The monomers are linked together to form linear chains (figure 4). The van der waals

interaction takes place between the linear chains. Some common examples are nylon,

high density polyethylene, polyvinyl chloride, polyester.

 Figure 11: Linear structure

2.4.2 Branched Structure:

The monomers are joined to form long chains with branches of different lengths

(figure 5). For examples: low density polyethylene, glycogen and starch.

Figure 12: Branched structure

2.4.3 Cross-linked Structure:

The monomers are combined together to form cross-linked chains (figure 6). Chains

are connected by covalent bonds. For example: rubber, bakelite.

Figure 13: Cross-linked structure

2.4.4 Network Structure:

The monomers are joined together to form a large three dimensional network, for

example: epoxy, phenol formaldehyde.

Figure 14: Network structure

Isomers are molecules that have the same molecular formula, but have a different

arrangement of the atoms in space. Isomers may be in two form i.e. stereoisomers

and geometrical isomers.

Further, geometrical isomers can be divided into the trans and cis isomer

depending upon atoms in space, for example: 1, 2 dichloroethene (figure 8). Two

chlorine atoms are joined on opposite side of the double bond is called trans isomer.

If the chlorine atoms are joined on the same side is called cis isomer.

Trans Cis

Figure 15: 1, 2 dichloroethene

The monomers are organic carbon based molecules. Covalent bonds hold the atoms

in the molecules together and secondary bonds hold groups of chains together. For

example, polyethylene is made from ethylene monomers (figure 9). The two mers

are joined together with the application of heat, pressure and catalyst which is called

polymerization to form polyethylene chains.

Figure 16: Polymerization of polyethlene

The polyethylene chains are elongated thousands times greater than its crystalline

structures when stretched. The mechanical properties of plastics depend upon the

number of carbon atom present into the polymeric chain. Some of the common

plastic monomers and their properties are shown in table 2 and 3.

3.0 Chemical and mechanical properties of plastic monomers

Table 1: Chemical properties of plastic monomers

S/N Type of plastic Chemical properties

1 Polyethylene Excellent chemical resistance,

Stable electrical properties,

Soft waxy surface,

Low melting point,

Good transparency.

2 Polyvinyl Hard, rigid (flexible when plasticized),

Chloride Good chemical resistance,

Long term stability,

Good weathering ability,

Stable electrical properties,

3 Polystyrene Clear to opaque

Glassy surface,

Rigid,

Hard Brittle,

High clarity.

4 Polypropylene Excellent chemical resistance

High melting point Hard, but flexible

Waxy surface

Translucent

Strong
 Table 2: Chemical formula of plastic monomers

Polyethylene (PE) Polyvinyl

chloride

(PVC)

Polypropylene (PP) Polystyrene (PS)

Polytetrafluoroethylene Polymethyl

(PTFE) methacrylate

(PMMA)

3.1 Mechanical Properties of Plastics

The mechanical properties of the plastics are given below:

3.1.1 Hardness

Plastics are not very hard, their hardness being comparable to that of brass and

aluminum. Generally, thermosets are harder than thermoplastics. The temperature of

the material substantially affects its properties. The hardness of commonly used

plastics is in the range of 5- 50 BHN.

3.1.2 Stress-Strain Behavior

When the plastic is subjected to uni-axial load, it deforms

permanently and ultimately fails as shown in figure 10. Tensile strengths of plastics

may be in the range of 10 to 100 MPa. The modulus of elasticity for plastic is in the

range of 10 MPa to 4000 MPa. Tensile strength decreases with increasing

temperature. Some of the plastics are brittle in nature. The mechanical properties of

the plastics depend upon the strain rate, temperature, and environmental conditions.

Figure 17: Stress- strain behavior of plastic

3.1.3 Creep

The molecular weight of the polymer affects its creep behavior. As the molecular

weight of the polymer increases, it becomes more creep resistant. When a plastic is
subjected to a constant load, it deforms continuously. The plastic will continue to

deform slowly with long time or until fails. The creep depends on several factors such

as: types of plastic, load applied, temperature and time.

3.1.4 Fatigue Behavior Fatigue failure of thermosets is brittle in nature, but in case of

thermoplastic failure occurs due to initiation of crack propagation. The flexural fatigue

strength of plastics may be in the range of 105 - 107 numbers of cycle to failure at

room temperature (20°C).

4.0 Differences in properties of polymers

4.1 Based on derivation

Table 3: difference in properties based on derivation

S/N Natural polymer Synthetic polymer

1 can be found in living creatures they are man-made, usually by scientists or

and plants engineers.

2 examples include; silk, protein, Examples include; Polyethylene, polyvinyl

cotton, linen, wool and DNA chloride, nylon, rubber, Polystyrene, etc.

used in the

3 pharmaceutical industry as a Used In the production of bags, pipes,

diluent/binder in tablets, drug electrical switches, Telephone parts, Cooker

formulations, Wound handles, etc.

Dressings, etc.
4.2 Based on processability

Table 4: difference in properties based on processability

S/N THERMOPLASTICS THERMOSETTING

1 Formed by addition Polymerization Formed by condensation Polymerization

2 Long chain linear polymers Three dimensional network

structure joined by strong covalent

bonds

3 Soften on heating and stiffen on Do not soften on heating

cooling

4 Can be remolded Cannot be remolded

5 Usually soft, weak & less brittle Usually hard, strong & more brittle

6 Can be reclaimed from wastes Cannot be reclaimed from wastes

7 Soluble in organic solvents Insoluble in organic solvents

5.0 Additives for plastic manufacture and function

Polymers are initially produced as powders, granules or laces (like straws). However,

they are seldom used in their pure form but are changed by adding other materials to

give them their special properties. For example, they may need to be resistant to

sunlight, or very flexible or cheap. By using different types of additive the properties

of the base polymer may be modified in very many different ways so that the range of

use of the base polymer is extended. Some of the possible additives are:

5.1 Blowing agents

Many plastics products are cellular in structure. If you look at them closely they look

like a chocolate Aero bar. These expanded or foamed products can be made from

base polymers by the addition of what are known as 'blowing agents'. This is done in

the molding process by adding a filler, which foams throughout the hot polymer filling

it with bubbles. A good example of this is expanded polystyrene.

5.1.1 Colorants (dyes and pigment)

Plastics can be colored by using either dyes or pigments. Dyes give transparent colors

and pigments give opaque ones. A very wide range of colors can be obtained from

clear to opaque black with a naturally clear material such as acrylic.

5.1.2 Fillers

The term ‘filler’ is a name given to a range of materials that are added to polymers in

order to modify their properties. They may also be added to a base polymer to lower

the manufacturing cost of a product made from it. A good example of this is one of

the first examples of the use of fillers, adding wood flour to phenol formaldehyde.

5.1.3 Protective agents (reinforcements)

Many plastics are degraded by heat and light, especially from the ultra violet light in

sunlight. You may have seen evidence of this by plastics being ‘bleached’ by the sun.

Adding protective agents will stop this. A special form of polyvinyl chloride is called

UPVC, which is used in the manufacture of drainpipes so that the pipes do not

degrade in the sunshine.

5.1.4 Impact modifiers

Some plastics are designed to have great impact strength; the ABS used in the

manufacture of car bumpers for example. Impact modifiers are polymers that when

added to other polymers improve the impact resistance of a product. Impact

modifiers, based on acrylic polymers, are used in conjunction with PVC in order to

get clear rigid bottles with good impact strength.

5.1.5 Lubricants

These additives are widely used to help plastics flow in molds. They are usually waxy

materials that act by reducing the stickiness of the plastic on the mold surface.
5.1.6 Plasticizers.

Plasticizers, such as dioctylphthalate are added to polymers in order to make the

resulting materials more flexible. They make plastics more plastic. Plasticizers can

change unplasticized polyvinyl chloride (UPVC) from a hard, rigid material suitable

for drainpipes into a soft, flexible material suitable for upholstery.

5.2 Plastics Processing

Because of the properties of polymers, it is possible to mold them and change their

shape using a number of different repetitious manufacturing processes. The most

important of these are extrusion, injection molding, blow molding, vacuum forming,

extrusion blow molding, rotational molding, calendaring, foaming and compression

molding.

5.2.1 Extrusion molding

Extrusion is a process that can be compared to squeezing toothpaste out of a tube.

Thermoplastic granules are forced through a heated barrel and the fused polymer is

then squeezed through a die that is the profile of the extruded component.
 Fig 18: Extrusion molding

The extrusion is cooled by water or air as it leaves the die and is finally cut to the

required length. The shape of the die can be varied from a simple hole with a centrally

supported core to produce tubes such as pipes, to very complex sections for curtain

tracks or hollow window frames.

5.2.2 Blow molding

Blow molding is a simple process where compressed air is introduced underneath a

warmed sheet of thermoplastic material forcing the material into a mold cavity, or

allowing it to expand freely into the shape of a hemisphere. It is a good way of forming

large domes, which when made out of clear acrylic sheet is often used in shop displays.
 Fig.19. Blow molding

5.2.3 Vacuum forming

This is a very common manufacturing process used, for example, to make a range of

plastics packaging. Think of the boxes sandwiches come in, or the inner in a chocolate

box, or your acrylic bath. It is really the opposite of blow molding. Instead of the

warmed plastic sheet being forced into a mold by air pressure, in vacuum forming the

air is drawn out from under the softened plastic sheet, so it is forced over or into a

mold by atmospheric pressure. Vacuum forming is a very common and effective way

of producing complex shapes in thermoplastic sheeting.

Fig 20: Vacuum forming

5.2.4 Extrusion blow molding

This is a combination of extrusion and blow molding and is often used where the

article to be made has a narrow neck, such as a bottle. The plastic material is first

extruded as a tube shape into an open die. The die is then closed to seal the ends of

the tube and air is blown in forcing the plastic tube to take up the shape of the die

cavity. As the material is extruded first and then blow molded, the process is known

as extrusion blow molding.

Fig 21: Extrusion blow molding

5.2.5 Injection Molding.

This process is one of the most common of all plastics manufacturing processes. The

polymer, in granule form, is heated until fused and forced into a closed mold. Because

of the viscous (thick, syrupy) nature of the fused polymer, very high pressures are
needed to make it flow, which means that the machine and mold have to be very

strong to withstand the forces involved.

Fig 22: Injection molding.

A typical industrial injection molding machine uses a screw to force the granules along

a heated barrel, and when the granules become fused the screw is used as a plunger

to force the polymer into the mold. The molds are usually made from high-grade steel

to withstand the forces involved and must also be highly polished to produce a very

good finish on the product, as any scratches will show up in the molded plastic surface.

Because of the ability of the plastic to show even the smallest of marks very fine detail
can be cut into the surface of the mold, for example in the form of trade marks,

lettering or textures.

5.2.6 Rotational Molding

Rotational molding is used to produce hollow thermoplastic products such as drums,

storage tanks and litterbins. A carefully calculated amount of plastic is placed in a

closed mold that is heated in an oven and rotated slowly around both a vertical and

horizontal axes. The plastic material fuses and sticks to the hot mold surface, building

up the required thickness. The mold is then gradually cooled by air or water while still

rotating. The mold is opened, the finished product removed and the mold reloaded

and closed for the next cycle. The time it takes to make one of the product is known

as the product’s cycle time.

Fig 23: Rotational molding.

5.2.7 Foaming.

Plastic foams used in packaging and the upholstery industry can be produced by using

blowing agents that are mixed with the base polymer. When heated these agents
release gas which form bubbles in the plastic. Another method is to inject compressed

nitrogen gas into molten plastics during the molding process. A third method is to

freeze a gas within the plastics granules which then expands due in the heat of the

molding process.

5.2.8 Calendering

Calendering is used to produce plastic sheeting and products such as floor tiles, coated

fabrics and coverings for car interiors. Fused thermoplastic is extruded on to heated

rotating rollers that squeeze the material into a continuous sheet or film. The film is

cooled by jets of air or water, before being cut to suitable lengths or loaded onto rolls.

Fig 24: Calendering

5.2.9 Compression molding

Compression molding is one of the oldest manufacturing technologies associated with

plastics and was used in 1854, for example, by Samuel Peck to make picture frames
from shellac mixed with wood flour. The process is almost always used with

thermosetting plastics. A carefully weighed amount of thermosetting polymer is placed

into a preheated lower mold cavity. The mold is then closed by the placing of the

upper half and subjected to further heat, and pressure provided by a press, often of

several hundred tons’ capacity. The pressure and heat causes polymerization and the

flow of the plasticized material within the mold.

Fig 25: Compression molding

Raw thermoplastic materials containing fillers may be compressed whilst cold into

small blocks of predetermined weight called preforms. Using preforms in

compression molds saves having to weigh out powdered material each time the mold

is filled and decreases the cycle time, as the preforms may be preheated. A

development of compression molding is transfer molding. In this process the

thermosetting polymer is first loaded into a heating chamber above the mold cavity
and allowed to polymerize. It is then squeezed through channels into the mold cavity

by the action of a powerful press. Transfer molding is used when complex moldings

are required and the polymer needs to flow quickly around the mold cavity.

Many plastic articles have metal parts included within them during the molding

process. These metal parts are called inserts, and may, for example, be in the form of

captive nuts used in conjunction with bolts to hold other parts of the final product

assembly. The inserts are placed in recesses in the lower mold either by hand or by

using loading jigs before the polymer is introduced into the mold. Compression and

transfer molding are manufacturing techniques that lend themselves to the inclusion

of molded inserts. When inserts are used the technique is often termed insert

molding.

6.0 Polymerization mechanisms

There are two broad types of polymerization reactions, i.e., the addition or

chain growth polymerization and condensation or step growth polymerization.

6.1 Addition (chain growth) polymerization

In this type of polymerization, the molecules of the same monomer or

different monomers add together on a large scale to form a polymer. The monomers

used are unsaturated compounds, e.g., alkenes, alkadienes and their derivatives. This

mode of polymerization leading to an increase in chain length or chain growth can

take place through the formation of either free radicals or ionic species. However, the
free radical governed addition or chain growth polymerization is the most common

mode. A variety of alkenes or dienes and their derivatives are polymerized in the

presence of a free radical generating initiator (catalyst) like benzoyl peroxide, acetyl

peroxide, tert-butyl peroxide, etc. For example, the polymerization of ethene to

polythene consists of heating or exposing to light a mixture of ethene with a small

amount of benzoyl peroxide initiator. The process starts with the addition of phenyl

free radical formed by the peroxide to the ethene double bond thus generating a new

and larger free radical. This step is called chain initiating step. As this radical reacts

with another molecule of ethene, another bigger sized radical is formed. The

repetition of this sequence with new and bigger radicals carries the reaction forward

and the step is termed as chain propagating step. Ultimately, at some stage the product

radical thus formed reacts with another radical to form the polymerized product. This

step is called the chain terminating step.

6.2 Condensation (step growth) polymerization

This type of polymerization generally involves a repetitive condensation

reaction between two bi-functional monomers. These poly-condensation reactions

may result in the loss of some simple molecules as water, alcohol, etc., and lead to the

formation of high molecular mass condensation polymers. In these reactions, the

product of each step is again a bi-functional species and the sequence of condensation

goes on. Since, each step produces a distinct functionalized species and is independent
 of each other, this process is also called as step growth polymerization. The formation
of terylene or Dacron by the interaction of ethylene glycol and terephthalic acid is an
example of this type of polymerization.
Table 5: Difference between addition and condensation reaction
s/n chain or addition polymerization
(e.g. Free Radical)
1 propagation: only monomers react to the “active
site” at the end of the chain; termination: two
chains can react (that’s very rare)
2 monomer exists throughout the reaction; its
concentration decreases steadily with time (as it is
incorporated in polymers)
3 polymer forms throughout the duration of the
reaction
4 polymer forms throughout the reaction and its
molecular weight does not depend on time;
5 the reaction mixture contains primarily monomer
and polymer, and very small amounts (10-8 parts)
of growing chains; the monomer
step-growth polymerization
(e.g. poly-condensation)
any molecule present (monomer, oligomer,
polymer) can react with any other molecule
(monomer, oligomer, polymer)
monomer exists throughout the reaction;
large quantities of
monomers are consumed early in the
reaction (to form oligomers that can react
with each-other)
polymer forms at the very end of the
reaction, by long oligomers reacting with
each-other
Long reaction times have high degrees of
conversion but do not affect the molecular
weight long reaction times are essential for
the synthesis of long (high molecular
weight) polymers (there are many other
factors that are also essential as well
(stoichiometry, contaminations, etc)
population decreases and the polymer
population increases with reaction time
“high” molecular species (oligomers of any
length) exist throughout the reaction, with
the length distribution broadening and
shifting to higher D.P. (Mw) with reaction
time
7.0 Polymerization methods/processes

7.1 Suspension polymerization

Suspension polymerization is used for the commercial manufacture of many

important polymers including poly (vinyl chloride), poly (methyl methacrylate),

expandable polystyrene, styrene–acrylonitrile copolymers and a variety of ion

exchange resins. In suspension polymerization, drops of a monomer-containing phase

are dispersed in a continuous liquid phase and polymer is produced inside the drops.

In many cases, the monomer contains no diluent and the chemical reactions that occur

inside the drops are very similar to those that are found in bulk polymerization.

Advantages of suspension Polymerization

I. Low viscosity due to the suspension

II. Easy heat removal due to the high heat capacity of water

III. Polymerization yields finely divided, stable latexes and dispersions to be used

directly in coatings, paints, and adhesives.

Disadvantages of suspension Polymerization

I. Cannot be used for polymers whose glass transition

II. Temperature is less than the polymerization temperature, or else aggregation

will occur.

III. Must separate and purify polymer, or accept contaminated product.

7.2 Solution polymerization

Reaction mixture contains solvent, initiator, and monomer, this type of process

is also used in the production of polystyrene.

Advantages of Solution Polymerization

I. Very useful for polymers used as solutions (e.g. lacquers, paints)

II. Better heat control

Disadvantages of Solution Polymerization

I. Polymer product contains solvent impurities

II. Yield is significantly lower than in bulk

III. Potential toxicity, flammability and environmental pollution (VOC) of solvents

IV. Polymerization is Expensive due to additional solvent costs

7.3 Emulsion polymerization

Emulsion polymerization is used in the production of a wide range of specialty

polymers including adhesives, paints, binders for nonwoven fabrics, additives for

paper, textiles and construction materials, impact modifiers for plastic matrices,

diagnostic tests, and drug-delivery systems. The development of this industry has been

due to both the possibility of producing polymers with unique properties and the

environmental concerns and governmental regulations to substitute solvent-based

systems by waterborne products. This type of reaction is similar to suspension

polymerization except that the initiator is soluble in the aqueous phase rather than in

the monomer droplets (the monomer is hydrophobic, and the initiator is hydrophilic).

An emulsifying agent is also needed.

7.4 Bulk

Reaction is carried out in the absence of solvent, diluent, or other materials.

Example of Bulk Polymerization free radical (addition) polymerization of ethylene

(narrow tubular reactors are used to facilitate heat removal). This type of process is

also used in the production of nylons.

Advantages of Bulk Polymerization

I. High yield which depends on reactor volume,

II. Very high purity product formed

III. Adaptable to copolymerization with other

IV. compatible co-monomers (vinyls)

Disadvantage of Bulk Polymerization

I. Viscosity increases as conversion increases, making heat removal and

processing more difficult.

8.0 Polymerization products

8.1 Addition polymerization

Generally, thermoplastics are formed by addition polymerization Polyethylene,

teflon, orlon, polyvinyl chloride, are thermoplastics formed by addition

polymerization. They are used in the production of bags, toys, pipes, toys.

Fig 26 Polypropylene Fig 27 polyethylene Fig 28 (PVC) Fig 29 polystyrene

8.2 Condensation polymerization

Thermosetting plastics are formed by condensation polymerization.

Polyamides, Bakelite, Polyesters, Polyurethanes, are thermosets formed by

condensation polymerization. They are used in the production of nylon, Electric

switches, Telephone parts, Cooker handles, Rigid and flexible foams,

Bakelite polyesters polyurethanes

References

1. Asua, J. M. (2002), Program Polymer Science 27, 1283–1346.

2. Barrett, K. E. J. (1975), Dispersion Polymerization in Organic Media; Wiley:

London.

3. Biesenberger, J. Α., Tadmor, Z., (1966), Polymer Eng. Sci. 6, 299.

4. Candau, F. (1997), Principles and Applications. In Polymeric Dispersions;

Asua, J. M., Ed.; Kluwer Academic: Dordrecht.

5. Coen, E. M.; Lyons, R. A.; Gilbert, R. G. (1996), Macromolecules, 29, 5128–

5135.

6. Duerksen, J. H., Hamielec, A. E., J (1968), Polymer Sci. Pt. C 25, 155-166

7. Krishna Venkataswamy, Rajesh Varma and Walter Ripple, (2007), online

technical article Over molding of thermoplastic elastomers: engineered

solutions for consumer product differentiation Division, GLS Corporation,

833, Ridgeview Drive, McHenry.

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&Gardner Publications, Inc. Munich.