Unit 6: Manufacturing processes for polymers.

6.1 Types of processes for the manufacturing of polymers.

The increase in the production of items made of polymer materials in recent years
has been great. Currently the volume of polymers and plastics produced exceeds
that of metals. In many applications, polymers have already replaced conventional
materials such as metals, wood, and natural fibers such as cotton and wool.

Polymers are a group of materials composed of long molecules with covalent

bonds, including plastics and rubbers. Polymers have existed naturally since the
origins of life, in forms such as DNA, RNA, proteins, among others.

The use of polymeric materials is associated in its beginnings with names such as:
Thomas Hancock (1820), who invented the process of "masticating" rubber to
fluidize it, and Charles Goodyear (1839), who discovered that the properties of
rubber improved when heated. with sulfur, giving rise to what is known as
vulcanization. The first synthetic polymer marketed was bakelite, a phenol-
fonnaldehyde resin, in 1910.

Many inventions and advances in

polymer science and technology
have occurred since those times.
Currently, there are research
programs in the area of pollin1ers
in almost all universities in
industrialized countries, as well as
in large multinational companies.
This article aims to offer an
overview of a class of polymeric
materials, thermoplastics, their
characteristics, and mainly their
manufacturing processes, and
some variations thereof that have given rise to composite materials, foams and
others.
Polymeric materials:

Many processing techniques for polymers have their counterparts in metal and
ceramic processes. In general, plastics can be processed at much lower
temperatures than metals, eliminating many processing difficulties and allowing
some processes that are not practical for metals.

As mentioned above, a polymer is a material composed of molecules, which have

long sequences of one or more kinds of atoms or groups of atoms, linked together
by primary bonds, generally covalent. Polymers are produced by the
polymerization of the monomers or simple units from which they are formed.
Different polymerization processes have been developed.

Plastics is the conventional name by which polymeric materials are known (they
may include some type of additive) due to their behavior in the fluid state,
particularly in the case of thermoplastics.

In a very general way, polymers can be classified into three groups:

Thermoplastics

Thermosetting

Thermosets

Elastomers

Thermoplastics are composed of linear or branched chains and have the

characteristic of softening with the addition of heat, and are processable in the fluid
state. They can be reprocessed. Examples of thermoplastic materials are:
Polyethylene (PE), Polypropylene (PP), Polystyrene (PS), Polyvinyl chloride (PVC),
etc.
In thermosetting materials, the chains are part of a three-dimensional network, and
are linked by crosslinks. This structure gives them the properties of hardness and
heat resistance that they possess. They are manufactured based on monomeric
resins that are low viscosity liquids. The most used resins are unsaturated
polyester (UP), epoxy and phenolic resins.

Elastomers, which include rubbers, rubbers, and gums, also have a three-
dimensional structure, but the bonds are weaker than in the case of thermosetting
materials, giving rise to the well-known properties of elasticity and tolerance of
large deformations.

The mechanical behavior of elastomers has been modeled quite precisely by the
rubber elasticity theory.

In this theory, the structure of elastomers is modeled as a three-dimensional

network and use is made of thermodynamic considerations and the
incompressibility of these materials when subjected to mechanical deformations, to
propose stress and deformation relationships (Treloar).

Manufacturing of thermoplastics.
Thermoplastics, presented in the previous section, occupy first place in terms of
volume among polymeric materials. The most used are: polyethylene (PE),
polyvinyl chloride (PVC), polystyrene (PS) and polypropylene (PP). In this article,
only manufacturing processes concerning thermoplastics will be discussed. The
technology used to process thermosets and elastomers will be described on
another occasion.

Stages in the manufacturing of thermoplastics .

Every thermoplastic manufacturing process includes the following stages:

plasticization, forming or molding, and cooling1. In Fig. 1 you can see the diagram
that involves these basic operations in the processing of thermoplastics. The
plasticization process occurs when the material is heated.

Heating can be from external sources (conduction, convection, radiation) or

internal sources (dissipation by mechanical or dielectric work). In this stage the
polymer goes from the solid state to the fluid state. Forming or molding requires the
use of molds or dies to produce objects of different shapes.

The last stage, cooling the molded or formed object, is the one that usually takes
the longest due to the low thermal conductivity that thermoplastics have.

Properties of thermoplastics.

Thermoplastics have specific properties that must be taken into account when
designing and implementing a manufacturing process for them, such as:

l. Low thermal conductivity

2. High viscosity (1000-10000 Pa.s)2
3. Visco elasticity

In some cases molding and cooling occur at the same location, for example in
injection molding.
Pa.s means Pascals x seconds and is the SI unit to characterize the viscosity of a
fluid.

Stages in the processing of thermoplastic polymers.

The first is a well-known property in plastic materials, since they have a thermal
conductivity that is much lower than that of metals. For example, polypropylene
(PP) has a thermal conductivity k= 0.17 W/mK at room temperature.

This property is, in the case of thermoplastic processing, what determines long
cooling times in its processing, and consequently long cycle times. Obviously, this
is a disadvantage when high productivity is needed.

The high viscosity in plastic materials in a state of fluidity causes high shear
stresses in processing, which give rise to great thermal dissipation. This can be
used advantageously by reducing the amount of heat that must be added to the
polymer for plasticization, however, it has the drawback of generating high
pressures, and thus the need to use robust machinery for processing.
Since thermoplastics, in the fluid state, behave like non-Newtonian fluids (that is,
they do not follow Newton's law of fluids), their viscosity decreases as the
deformation rate increases.

One of the simplest expressions to represent the behavior of polymeric fluids is the
power or exponential law, which can be expressed as follows:

The low thermal conductivity of polymers is what has determined their use as
insulating materials par excellence, which is the case of polyurethane foam
bubbles.
Viscoelasticity is a typical phenomenon of polymeric materials (although it also
occurs in other materials, for example, metals, pastes, etc.).

The term viscoelasticity refers to the behavior of a material, when it has properties
of a viscous liquid and an elastic solid at the same time. It also implies the
dependence of mechanical properties as a function of time.

Viscoelasticity is a favorable property in processes that require high mechanical

resistance in the liquid or semi-liquid state, such as: fiber stretching, film blowing,
bottle blowing, etc.

This excess resistance of the fluid with respect to a Newtonian liquid, such as
water for example (water cannot be stretched), is due to the elastic component of
the material.

Although viscoelasticity is explained by complicated theories, it serves to explain

extremely practical and everyday issues in plastics processing.

For example, anyone who has worked in plastic extrusion has surely noticed that
the section of the product when it comes out of the die is larger than the section of
the hole in the extrusion die.
This phenomenon known as "die swell" is well known to researchers and plastics
processors, and has been widely reported in the literature.

What happens is that the polymer molecules are oriented in the direction of flow
when passing through the die and due to viscoelastic behavior, they return to their
original position when leaving the die, thus causing swelling. Fig. 2 shows a
diagram of the swelling phenomenon in the case of plastic pipe extrusion.

This type of phenomena related to the flow of plastics in the state of

Fluidity is studied by "rheology", which is the science that deals with the flow (reo
means flow in Greek) of materials.

In plastics processing, determining how the material flows when processed is of

great importance to predict the final properties of the product.

The use of numerical methods, such as finite elements (FEM) and control volumes
(control volume: CV or finite volume: FV), are standard practice when simulating
the flow of non-Newtonian fluids such as plastics in the state of flow.
Fig. 3 (part of a work carried out in the Polymer Engineering division of UMIST,
UK) presents the graph of the velocity vectors of a plastic flow in a channel of
complex geometry. With this type of analysis it is possible to improve the design of
the molds and matrices, and optimize the properties of the process, as well as the
final product.

Other properties such as resistance to thermal degradation, miscibility, surface

tension properties, etc., are also important, to a greater or lesser extent depending
on the process.

Main manufacturing processes with thermoplastics .

Most of the processes are suitable for manufacturing various products from a wide
variety of plastics. Following the logic adopted when treating metal transformation
processes, plastic manufacturing processes are analyzed according to their
temperature in descending order.
Emptying:

The term casting is used to describe the "filling of a mold by gravity."

Consequently, the material must have a viscosity low enough to flow freely. This is
achieved by several means:

1.- Thermoplastics can be encouraged beyond their Tm (hot melt plastics) and
poured into molds.
Heavy weight nylon parts

Extrusion:

This is a continuous process for the manufacture of constant section materials

such as: tubes, profiles, films, plates, etc. The material is forced by a rotating screw
through a specifically shaped opening (die or head) that bears some relationship to
the shape of the product to be obtained.

In conventional extrusion (with plasticization of the material) the material enters the
extruder in the solid state (granules, powder or recycled), then it is plasticized, and
finally it is dosed constantly towards the extrusion die. Depending on the product,
different operations are performed after the preform leaves the die.

Injection molding:
Injection molding is one of the most common processes for manufacturing plastic
items. The material is fed to a machine called an injector, which plasticizes it and
then injects it through the positive displacement of a reciprocating screw, into a
closed cavity called a
mold.
The mold presents the
shape of the article to be
obtained. The plastic
article solidifies in the mold
and is then removed. This
is a manufacturing process
for mass production due to
the high cost of molds.

Blow molding:

Blow molding is a means of producing hollow objects with a single opening smaller
than the largest diameter of the object, such as bottles. This process developed
from the blowing of glass bottles, and in most cases a sealed tube is first
manufactured, on one side, which is then blown into a mold with the shape of the
object to be obtained.

If the tube, also called "parison", is manufactured by extrusion, the process is

called extrusion blowing or extrusion-blowing. If instead of extruding a tube, a
preform is injected in the form of a test tube, and then heated, stretched, and
blown, this process is called injection blowing or injection blowing.
This last process was developed to take advantage of the stretching properties of
thermoplastic polyester (PET or polyethylene terephthalate) and is the
conventional method for manufacturing carbonated soft drink and water bottles.
Calendering:

This process is used when you want to manufacture plastic films and sheets. The
raw material is passed through a combination of hot rollers. Combinations of four
rollers with three material passes are usually used. The greatest application of
calendering is in the production of PVC films and sheets, since the risk of thermal
degradation is considerably reduced compared to that found in the extrusion of
PVC sheets.

Shrinkage effects during cooling, and viscoelastic effects, must be considered

when designing the mold (or the die in the case of extrusion). The dimensions of
this, generally, do not coincide with the dimensions of the final product.

Calendering is also used for the manufacture of elastomer sheets.

Thermo formed:

In the thermoformed a plastic sheet is heated until it softens. By means of external

pressure or vacuum, the sheet is stretched and shaped by adhering it to a mold so
that it takes its shape.
The deformed sheet is then cooled in the mold. Through this process it is possible
to manufacture a large number of hollow shapes, such as panels for automobiles
and airplanes, packaging, among others.
The patterns can be positive or negative. The most used materials in
thermoforming are amorphous polymers since they have a wider softening range
than semicrystalline polymers, although lately more and more semicrystalline
polymers have been used, especially PP.

Composite materials: Reinforced thermoplastics.

In general, polymers have low mechanical strength and low stiffness compared to
metals. The modulus of elasticity of thermoplastics is, in most cases, approx. 2
GPa (100 times less than steel) and mechanical strength values are approx. 5
times less than in metals. To increase the rigidity and resistance of a plastic article,
ingenious construction details are often used, such as ribs, hollow sections, multi-
cavity hollow walls, etc.

Another method of increasing the rigidity and resistance of thermoplastics is by

reinforcing the polymer with particles or fibers, forming a composite material. Most
thermoplastics are fiber reinforced.
Said reinforcement can be continuous or discontinuous. Thermoplastics reinforced
with continuous fibers form laminates with different orientations so that the article
can withstand loads in various directions. Those reinforced with discontinuous
fibers can have aligned fibers or have a random distribution in the orientations of
the fibers. The latter can be processed by conventional methods such as injection
molding, extrusion, blow molding, and thermoforming. The material most used as
reinforcing fiber (95% of the total) is glass fiber, although carbon fibers are also
used in requirements of high rigidity, high resistance to fatigue and low specific
weight, such as, for example: equipment sports (snowshoes, skis), aerospace
industry and competitive automotive industry. However, carbon fibers are much
more expensive than glass fibers.
Another type of reinforced thermoplastics, which has caused a great impact in the
automotive industry, are glass mat reinforced thermoplastics or GMT. These are
produced from a mat composed of fibers, in different orientations (random or
unidirectional orientation), which is hot stamped in a matrix of thermoplastic
material.

An example of GMT in the automotive industry is found in the bumpers of some

Peugcot vehicles, and are composed of a polypropylene (PP) matrix GMT, with a
reinforcement of 20% unidirectional glass fibers and 20'/'o with random
orientations.

Among the most used thermoplastic matrices are: Nylon 6.6, e! polypropylene,
PEEK or poly-ether ether ketone manufactured by ICI, which is a relatively new
polymer with very good mechanical properties and that can be used at high
temperatures, but of high relative cost.

It is used in applications with high requirements, in which the high cost is justified.
As for fibers, the most used are glass fiber, followed by carbon and Kevlar or
aramid fibers, with Kevlar 49 being the most used among the latter.

Reinforcement with particles in thermoplastics is used in cases where, for example,

it is desired to improve impact resistance, as occurs in thermoplastics reinforced
with rubber particles.
Rigidity and low specific weight: cellular polymers-foams.

In the search for optimal solutions in the design with thermoplastics, as mentioned
before, the following criteria can be adopted: a) improve construction forms and b)
the use of reinforcing fibers. Another solution is the use of cellular materials or
foams.

In general, these were created by blowing phenolic and polyurethane

(thermosetting) resins with some gas, so that a hollow structure is obtained, full of
hollow cavities or cells inside. Under the microscope, its structure resembles that of
a honeycomb.

This process also applies to thermoplastic materials, although the density of a

thermoplastic foam is higher than that of a thermosetting foam. The density of a
phenolic or polyurethane foam is in the range of 20-100 kg/m3, while that of a
thermoplastic foam is approx. 700 kg/m3.

The gases used in blowing thermoplastic foams are: N2 and C02, and can be
generated in situ with the decomposition of a blowing agent. The gas remains in
solution in the plastic in a liquid state, while it is processed in an extruder or
injection molding machine.

This article only mentions the thermoplastic matrices used, however, it should be
taken into account that the largest quantity by volume of composite materials is
made with thermosetting matrices such as epoxy and polyester.

When the plastic flow (containing the gas) enters the mold or die, pressure is lost
and the gas expands, causing the solution to fill the cavity.

Thermoplastic foams are known as structural foams and find application in the
following areas: automotive industry (large areas required), when weight reduction
is required and when high rigidity is required without the inclusion of ribs (this
reduces die and mold costs ). On the other hand, thermosetting foams are rather
used as thermal insulators and packaging materials.
The term casting is used to describe the "filling of a mold by gravity."
Consequently, the material must have a viscosity low enough to flow freely. This is
achieved by several means: