w = ΣniMi 2 / Σ niMi

5.8 POLYDISPERSITY INDEX (PDI)

The ratio of weigth average molecular weight w to number average molecular weight n is
known as polydispersity index or distribution ratio.

Polydispersity index = w / n

For polydispersed system, w > n

For monodispersed system w = n

 If a polymer contains molecules of same molecular weight, such system is

known as monodispersed system. But it is unreal condition. Such possibility is available
only in simple chemical compounds like water, alcohol etc.,
 If a polymer contains molecules of different molecular weight, it is polydispersed
system. The deviation of ratio from the unity is taken as a measure of polydispersity of
the polymer sample. For all synthetic polymers, PDI is higher than 1.
 Higher values of the ratio indicate greater polydispersity. It means all the molecules of
the polymers will not have identical molecular weight.

5.9 COMPOUNDING OF PLASTICS (OR) MOULDING CONSTITUENTS

Compounding is the process of incorporating additives, modifiers into polymers for achieving
uniformity on a scale appropriate to the quality of the articles subsequently made from the
compound. It is the first step in most plastic fabrication. Each compounding ingredient will
contribute towards final properties of the product. Plastics are compounded to enhance features
like:

 Mechanical/Physical and Thermal Properties

 Opticals (color/visuals)
 Functional properties
 Reduced cost

5.9.1 INGREDIENTS PLAYING KEY ROLE IN PLASTIC COMPOUNDING ARE:

1. Fibers: increase strength and stiffness
2. Plasticizers: for flexibility
3. Lubricants: to increase moulding property
4. Antioxidants: for high temperature stability
5. UV stabilizers: for resistance to sunlight
6. Fillers: for economy
7. Flame retardants and smoke suppressants
8. Conductive fibers: for electrical properties
9. Color concentrates: for colored plastics
10. Polymer alloys & blends: for performance plastics

Moulding constituents and their functions

S. No Compounding Examples Functions

ingredients

1. Resin It forms the major part It is the binder material

which holds the constituents
together
2. Stabilizers For transparent polymers: They are thermal stabilizers
stearates of lead, cadmium or added to improve the
barium. For opaque polymers: stability of the polymer
Red lead or lead monoxide

3. Accelerators or Hydrogen peroxide, benzoyl Added to accelerate the

Catalysts peroxide and metals like lead, process of polymerization
copper and oxides like zinc oxide reaction during moulding
process
4. Lubricants Waxes, oils and soap It gives a shiny appearance
to the polymer material and
to take out the material
easily from the mould
5. Fillers or Fillers used to increase hardness They are inert materials
extenders are: mica, carborundum, quartz. added to plastics to increase
Asbestos powder is a filler used bulkiness and thereby
to improve thermal and corrosion reduce the cost of production
resistance
6. Plasticizers Vegetable oils, camphor, organic They are added to increase
phosphates softness and flexibility of the
product. It neutralizes the
intermolecular forces present
in the material, thereby the
movement of the molecular
layer will become possible.
7. Pigments Titanium dioxide – white color They will provide the desired
Carbon black – black color color to the product.
Prussian blue – Blue
 Chromium oxide – green
Ferrous oxide – red
Lead chromate -- yellow
8. Antioxidants Phenylparanaphthylamine They protect the polymer
against oxidative
degradation

5.10 MOULDING OF PLASTICS INTO ARTICLES

Moulding is the process of manufacture or fabrication of raw plastic material, whether it is

thermoplastic or thermosetting resin, into a definite shape by using a rigid frame or model.

Polymer Processing

There are five basic processes to form polymer products or parts. These include; injection
moulding, compression moulding, transfer moulding, blow moulding, and extrusion moulding.

The type of moulding method is selected based on the type of resin used. For thermoplastic
resins, compression moulding or transfer moulding methods are used. For thermosetting resins,
injection moulding or extrusion moulding methods are used.

5.10.1 COMPRESSION MOULDING

It is a method of moulding in which a specific quantity of raw, un-polymerised plastic is placed
into a preheated mould which is closed under pressure compressing the molten plastic into the
cavity to produce the desired shape of the plastic material. Pressure is applied to force the
material into contact with all mould areas with continuous application of heat and pressure until
the moulding material is cured. The process employs thermosetting resins in a partially cured
stage, either in the form of granules, putty-like masses, or preforms. It is a high-volume, high-
pressure method.

This type of moulding is the first method to be used to form plastics. The steps involved in this
moulding method are:

1. Pre-formed blanks, powders or pellets are placed in the bottom section of a heated mold
or die.
2. The other half of the mould is lowered and the pressure is applied.
3. The material softens under heat and pressure, flowing to fill the mould. Excess is
squeezed from the mould. For a thermosetting plastic, cross-linking occurs in the mould.
4. The mould is opened and the polymer product is removed.

For thermoplastics, the mould is cooled before removal so the part will not lose its shape.
Thermosetting plastic may be ejected while they are hot and after curing is complete.

Compression moulding was first developed to manufacture composite parts for metal
replacement applications. This method is typically used to make larger flat or moderately curved
parts. This method of moulding is greatly used in manufacturing automotive parts such as
hoods, fenders, scoops, spoilers, as well as smaller more intricate parts.
Compression-molding is suitable for ultra-large basic shape production in sizes beyond the
capacity of extrusion techniques. Materials that are typically manufactured through compression
molding include: Polyester fiberglass resin systems (SMC/BMC), Torlon, Vespel, Poly(p-
phenylene sulfide) (PPS), and many grades of PEEK

Advantages of compression molding :

 It is a method suitable for moulding complex, high-strength fiberglass reinforcements.
 Advanced composite thermoplastics can also be moulded with unidirectional tapes,
woven fabrics, randomly oriented fiber mat or chopped strand.
 Compression moulding has the ability to mould large, fairly intricate parts
 It is one of the lowest cost moulding methods compared to other methods such
as transfer molding and injection molding
 It wastes relatively little material, giving it an advantage when working with expensive
compounds
 There is a small investment for presses and moulds
 Low cost production for samples and pilot production
Limitations :

 It is difficult to mould complex articles with undercuts or small holes

 It has fair tolerances
 Flash can be a problem
Disadvantages:
 It provides poor product consistency and difficulty in controlling flashing.
 It is not suitable for some types of parts
 Fewer knit lines are produced and a smaller amount of fiber-length degradation is
noticeable when compared to injection molding.
 Figure 5.1 Compression moulding

Applications

Components produced by compression moulding are generally electrical components and

fittings as thermosets are good electrical insulators e.g. electrical switches and sockets.

The process is also used for panels, housings, container caps, dishes and automotive parts.

5.10.2 INJECTION MOULDING

Injection molding consists of high pressure injection of the raw material into a mould which
shapes the polymer into the desired shape. Injection molding can be performed with a host of
materials, including metals, glasses, elastomers, confections, and most commonly
thermoplastic and thermosetting polymers.

Material such as polymer granules is fed into a feed hopper, mixed and heated to a molten state
and then injected at high pressure into a prefabricated mould cavity where it cools and hardens
to the configuration of the cavity. The moulds are made from metals like steel or aluminum.
Injection molding is widely used for manufacturing a variety of parts, from the smallest
components to a big one.

The injection moulding process requires strict control of the mould temperature, speed and
pressure of injection, condition of the molten plastic and dwelling/cooling times to ensure high
quality products. It is necessary to have a sufficient clamping force proportional to the projected
area of the mould to prevent creation of excess flash.
The process uses thermoplastics, such as polycarbonate (PC), polyethylene (PE), polystyrene
(PS), polypropylene (PP) and acrylonitrile-butadiene-styrene (ABS).

Injection blow moulding is used for the fabrication of small hollow components which more
intricacies. Injection moulding allows the final component design to be highly complex. Holes,
inserts, threads, bosses, minor undercuts and use of colour are all possible.

Different types of injection molding processes

Although most injection moulding processes are covered by the conventional process described
above, there are other several important molding methods. They are:
 Die casting
 Metal injection moulding
 Thin-wall injection moulding
 Injection moulding of liquid silicone rubber.

Advantages

 Injection moulding is capable of high production rates of 1–50 components/min and the
process becomes highly economical at medium to high production volumes.
 Costs are reduced through good material utilisation: sprues, risers and scraps are all
recyclable. The finishing process is minimal and has low economic impact.
 It has the shortest cure time
 It does not require preforms
 Precise volumes of the raw material can be injected into the mould
 There is high homogeneity of cross linking throughout the product
 There is minimal wastage of the raw material
 Automatisation of the production is possible
 Figure 5.2 Injection moulding

Disadvantages

 A significant capital investment is necessary for injection moulding due to high

equipment and tooling costs.
 Fabrication of complex die cavities usually made from hardened tool steel, will result in
longer lead times.
 The flexibility of the process is limited by its dedicated dies, high cost of tool change over
and machine set up times. However the process lends itself to full automation and the
use of robotics is common for loading and unloading of machines.

Applications

Injection moulding is the most common manufacturing technique for plastic components. It is
capable of producing high precision, complex components with an excellent surface finish which
makes it ideal for production of automotive and aerospace components as well as electrical
parts and housings e.g. computer enclosures and mobile phone cases. Other applications are
fittings, tool handles, crates and containers.

5.10.3 EXTRUSION MOULDING

Extrusion moulding is similar to injection moulding except that a long continuous shape is
produced. In extrusion moulding, a preheated polymer, placed in a feed hopper, is injected
through an orifice with a particular cross section (the die), and a continuous shape is formed
with a uniform cross section similar to that of the orifice.

This process makes parts of constant cross section like pipes and rods. Molten polymer goes
through a die to produce a final shape which involves four steps:
 1. Pellets of the polymer are mixed with coloring and additives
2. The material is heated to its proper plasticity
3. The material is forced through a die
4. The material is cooled

Shapes that can result from extrusion include T-sections, U-sections, square sections, I-
sections, L-sections and circular sections.
One of the most famous products of extrusion moulding is the optical fiber cable.

Although thermosets can be extruded and cross-linked by heating the extrudate, thermoplastics
are commonly extruded and solidified by cooling. The products that are produced by extrusion
moulding method are film, sheet, tubing, pipes, insulation, and home siding. In each case the
profile is determined by the die geometry, and solidification is by cooling.

Most plastic grocery bags and similar items are made by the continuous extrusion of tubing.

The process uses thermoplastics, such as: polyvinyl chloride (PVC), polyethylene (PE) and
polypropylene (PP).

Figure 5.3 Extrusion moulding

Advantages

 The process has extremely high production volumes as continuous lengths are produced
at 60m/min and 5m/min for tube profiles and sheet/rod profiles respectively.
 Multiple holes in the die increase the production rate but to allow smooth running the
extrusion is operated below its maximum speed capability.
 It is economical to run production for 1000kg of profile extrusion and 5000kg for sheet
extrusions and costs are dramatically increased with a high output range.
 Cutting a continuous section to length is the only time there is waste material produced
and the only major finishing cost which is relatively inexpensive.
  The final component design always has a uniform cross section which can be highly
complex.
 Open or closed profiles are possible and solid forms can include re-entrant angles.
 Holes, inserts and grooves are possible but require secondary operations when they are
not parallel to the axis of extrusion. Part consolidation features should be integrated into
the design for increased ease of assembly.

Limitations

 Components made by the process are prone to shrinkage and distortion so that the
accurate control of uniformity and cooling rate is important to reach accurate
dimensions.
 The extruded product may increase in size as it leaves the die and may be compensated
by decreasing extrusion rate or the melt temperature.
 One problem that affects the output and quality of extrusion is the possibility of trapped
gases in the extrusion screw which is particularly common when using powdered raw
materials.

Disadvantages

 The process has high equipment costs as materials that give off toxic or volatile gases
during extrusion demand air extraction or a washing plant.
 Lead times are usually within weeks depending on die complexity.
 The process flexibility is limited to the dedicated tooling but with short set-up and
changeover times.

Applications

Continuous extrusion produces components have complex profiles such as rods, bar, tubing
and sheets, pipes, guttering, window sills, insulation on wires, cling-film and tyre reinforcement.

5.11 CONDUCTING POLYMERS

Conductive polymers are polyconjugated organic polymers that conduct electricity because of
their conjugated π-bonds. Such compounds can have either metallic conductivity or can
be semiconductors. The biggest advantage of conductive polymers is their processability,
mainly by dispersion. Conductive polymers are generally not thermoplastics, i.e., they are not
thermoformable. But, like insulating polymers, they are organic materials. They can offer high
electrical conductivity but do not show similar mechanical properties to other commercially
available polymers. The electrical properties can be fine-tuned using the methods of organic
synthesis and by advanced dispersion techniques.

Some examples of conducting polymers are given in the table

S.No Conducting Structure Conductivity

 Polymer (S/cm)

1. Polyacetylene
103 - 1.7x105

2. Polyphenylene
vinylene
3 – 5x103

3. Polyaniline
(X = NH/N) 30 - 200
Polyphenelene
sulfide (X = S)

4. Polypyrrole
(X = NH) , 102 – 7.5x103
Polythiophene
(X = S)