1

Why Additives?

• Additives are added to the polymers to facilitate

processing without degradation or decomposition
and also to cater to the requirements of specific
application.
• Polymer additives or compounding ingredients
may be solids, liquids or even rubbery materials.
 Desirable properties of an additive
They should be
i) Stable under the processing conditions and also under the
conditions of their applications
ii) Efficient, i.e., a small quantity should do the required job
iii) Compatible so that no migration of them takes place under
the processing or the service conditions, i.e. they should be
non-bleeding and non-blooming
iv) Non-toxic and not impart any taste and odour to the
polymer and should not negatively affect the inherent
properties of the polymer
v) Cheap
 Fillers
There are two objectives of adding fillers to a polymer
i) Improvement of physical properties
ii) Making the material cost less.

• Fillers may be organic, inorganic, mineral, natural or synthetic in

nature.

• They may be particulate, rubbery, resinous or fibrous.

• Fillers may be reactive or non-reactive type.

• Synthetic fillers are more commonly used in thermosetting resins such

as the phenolics, the ureas and the melamines.

• Sometimes a rubbery filler may be added to a synthetic polymer, while

very often synthetic fillers are added to rubbers.
 Reinforcing agents

• These are added to improve the mechanical properties of the

polymer.
• A reinforcing agent may perform dual role of a filler and of a
reinforcing agent.
Eg: Saw dust or wood shavings added to PF-resins

The saw dust increases the volume, thus lowering the cost,
while it gives mechanical strength to the polymer which in its pure
form is rather brittle and lacking any strength of its own.

Examples:
• α – cellulose fillers cum reinforcing agent is added to UF resins
• Glass fibers of different lengths are added to unsaturated polyester
resins (Thermosets)
• Rubber + carbon black
 Reinforcing agents…

• In order to improve the adhesion

between the organic polymer and
the inorganic fillers or
reinforcements, coupling agents are
sometimes used.

• Coupling agents have organic and

inorganic structures combined in
them. Hence, they link the polymer
and the filler or the reinforcement
by covalent bonds.
 Plasticisers and softners

• Plasticisers are stable organic compounds which

usually have low volatility. They are added to a
polymer to bring about changes in its physical
properties.

• Certain non-volatile additives which are relatively

poor solvents are sometimes added with the
plasticisers. These liquids are called softeners.
 Plasticisers and softners…
• External Plasticisers: Plasticisers may
simply exist physically, mixed with the
polymer system and bring about the
modification by acting as spacers
between the polymer molecules. The
method of incorporating them in the
polymers is called external
plasticisation.
• Internal Plasticisers:Plasticiser
molecules go into the chemical
structures of the polymer molecules and
bring about the modification by
becoming a part of the system. The
method of incorporating them in the
polymers is called internal
plasticisation.
 Blowing Agents
•These are additives to produce cellular polymers.
• The blowing agent may be a solid, a liquid or a gas.
• Whatever in state, the agent must, at the manufacturing temperature, turn to
a gaseous form to pervade the mass of the polymer.
•When the gas bubbles through the polymerizing substance or the molten
polymer, it gives a cellular structure to the material.

Eg:
i) Azo-dicarbonamide (for PVC and Polyolefins) which decomposes at 190-230 ◦C
giving off N2, CO and CO2 gases
ii) Az0-bis-isobutyronitrile (for PVC) which decomposes rapidly at 95-98 ◦C giving N2
gas.

Eg: Sodium bicarbonate for fried delicacies (at the

domestic level). Yeast or sodium bicarbonate in
contact with water liberated CO2 which makes the
material fluffy and porous
 Cross-linking Agents
• For polymers such as rubbers, the elastic property
needs to be controlled and the mass changed to
thermoset plastic. For this vulcanisation (cross linking
process) is done.

• Cross linking agents are those molecules which

bridge two polymer molecules
(or)
Which initiate a cross linking reaction
(or)
Those that are catalytic in their action
(or) those which attack the main polymer chain to
generate active sites for cross linking to take place
 Colourants

• Added to have aesthetic appeal, to give a means of

identification, to improve visibility or for imitating the
appearance of a natural, conventional article.

• Four methods to impart colours to polymers

i) Coating the surface
ii) Dyeing the surface
iii) Incorporation of materials which would provide
chromophoric groups in the polymer
iv) Adding the colouring matter in ‘mass colouration’
method
 Colourants…

• Colourants fall into two groups – dyes and pigments

• Dyes promote colour by dissolving in the polymer while

pigments do so by dispersing throughout the mass of the
polymer

• Dyed plastics hold their colours much better against

fadding than pigmented plastics.

• Dyes are more heat sensitive while pigments are very

light sensitive
 UV-degratants

• These are to facilitate disposal of the polymers after they

have been used

•When UV-light is absorbed, the usual process of

neutralizing the effect as to dissipate the energy.

•Plastics in which UV-absorbers are used are given some

agents called photodegradants

•But in this case, the heat generates a highly reactive

chemical intermediate which destroys the polymer.
 Additive Function Examples
Filler Increase bulk density Calcium carbonate, talc,
limestone
Plasticizer Improve processability, reduce Phthalate esters,
product brittleness phosphate esters
Antioxidant Prevent polymer oxidation Phenols, aromatic amines
Colorant Provide desired part application Oil-soluble dyes, organic
color pigments
Flame retardant Reduce polymer flammability Antimony trioxide
Stabilizer Stabilize polymer against heat or Carbon black,
UV light hydroxybenzophenone
Reinforcement Improve strength E-glass, S-glass, carbon,
Kevlar fibers
 Mixing
Mixing in polymer processing addresses two tasks

• Addition of various ingredients (additives)

• Production of polymer blends and alloys

Additives used to alter the

properties of the matrix
polymer such as impact
strength, flexural modulus,
modulus of elasticity,
foaming ability and cost are Additives are also used to
called modifying additives prevent polymer degradation
and they are called protective
additives
 Mixing

The other important task of mixing is the blending of

other polymer with the given polymer to obtain a desired
improvement in the given polymer
Eg: Blending of rubber with polystyrene (PS) produces a
very fine dispersion of rubber particles in the PS matrix
called high impact PS (HIPS), with great improvement in
energy absorbing characteristics.
 Mixing
There are differences between mixing requirement for the
additives and the blending of polymers.

Blending of polymers usually involves

large concentration (weight %) of the
additive phase, various degrees of
compatibility between the various phases,
small density differences and the
hydrodynamics prevailing in the mixing Where as in polymer additive
environment. systems the following characteristics
prevails:
low concentrations, large density
differences and solid liquid
distribution and dispersion of
agglomerates into particles that
cannot be divided any further
 Mixing…
In general in Polymer processing we are concerned with
mixing in three types of systems
1)Liquid - Liquid
2)Solid - solid
3) liquid -solid
Each with different mechanisms and kinetics of mixing

In liquid - liquid case mixing is Solid- solid mixing involves

concerned with either low blending of either two polymers
viscosity monomers or high or resins or an additive and a
viscosity polymer melts. polymer

Liquid - solid mixing involves blending of liquid additives and

solid polymers (not melted) or solid additives (below their
melting point) and melted polymer s.
 Description of Mixing
The term mixing refers to operations that
have a tendency to reduce non uniformities
or gradients in concentration, temperature,
size of a dispersed phase or other
properties of materials.

Mixing is one of the most widespread unit

operations. Might be a process in itself
(eg: polymerization processes) or might be
a part of a more extended sequence of
processes (eg: polymer processing)
 Types of Mixing

Two basic types of mixing are

Extensive mixing (also called distributive,
convective, repetitive, simple mixing , blending)
Intensive mixing (also called compounding,
dispersive, dispersing mixing )

In study of mixing of two components, the two components are

designed as either major or minor components by the level of
their total concentration
 Types of Mixing…
Extensive mixing refers to processes that
reduce the non-uniformity of the
distribution of the minor into the major
component without disturbing the initial
scale of the minor component

Intensive mixing refers to processes that

break down the liquid dispersed phase or
the initial particle agglomerates and they
decrease the ultimate particle of the
dispersion
 Mixing…

The important factors that determine the relative strengths

of the mixing mechanisms

•The geometry of the mixing equipment,

•Physical parameters such as viscosity, density, interfacial
tension, elasticity and attractive forces for solids,
• Operation conditions such as temperature, speed of rotating
parts, flowing velocity and residence time
As a consequence, this relative strength affects the efficiency
of mixing and the quality of the product.
 Mixing…

• In almost all cases, both good distribution and

dispersion are required
• In some cases only distributive mixing can be
tolerated if the next step offers dispersive
characteristics
• Dispersive mixing is used when a finely dispersed
mixture is required and when the next step does not
offer any dispersion characteristics
 Mixing…
The distinction between good and poor dispersion and distribution
 Compounding
The process by which ingredients are
intimately melt - mixed together into a
nearly a homogeneous mass as possible is
known as compounding

• Because of the nature of both the resin and the other

ingredients, compounding requires a wide range of mixes -
dry powders, slurries, pastes etc., and a corresponding range
of mixing operations

• The use of heat, either internally generated by shear or

externally applied, is needed to obtain compound uniformity.
In some cases to avoid excess heating of polymer, proper
cooling system is arranged to supplement heat transfer.
 Compounding…

The major types of plastic compounding

equipment in current use are
 Intensive dry mixers
 Two roll mills
 Single screw extruders / twin screw
extruders
Compounder- Extruder

The simplest and basic machine for intensive mixing is the two roll mill.
 Two Roll Mill Compounding…

The two roll mill is comprised of a pair of

rollers with axes horizontally disposed to
one another giving a vertical ‘nip’ between
them.

Rolls rotate in opposite

directions. Material leaving the
nip adheres to either roll if rolls
rotate at equal speed.
Two Roll Mill… Compounding…

• The polymer matrix and additives are subjected to high shear

in the nip as the rolls rotate in opposite directions.
• The rolls may rotate at the same speed or sometimes with a
speed ratio between them which may variously be 1/1.1 to
1/1.4.
• The resultant mix is an intimate one, below the resolution of
the eye.
• Two roll mills do this well in the machine direction but poorly
across (i.e. along the rolls). Thus we can say that this machine
is good at intensive or dispersive mixing but poor at extensive
or distributive mixing; it produces a well dispersed but poorly
distributed mix, unless the processor takes steps to correct
matters.
Two Roll Mill… Compounding…
How to achieve good distribution in Two Roll mill

When a two roll mill is used for mixing, the technique is

to pass the appropriate loading of matrix material,
usually raw polymer, through the nip a few times until it
warms up, softens and forms a smooth band round one
of the rolls.
Often the rolls are preheated, by steam or electrically
heated oil, the temperature required depends on the
individual polymer properties. Which roll forms the
band depends on the polymer and the conditions, but in
general it is the hotter, faster roll.
Two Roll Mill… Compounding…
How to achieve good distribution in Two Roll mill…
The bearings of the rolls are held in movable bushes, which can be usually
adjusting the nip gap. The nip is adjusted, once the band is formed rounded
preferred roll, to give a small ‘bank’ of polymer rolling along the top of the nip.
As soon as this condition is achieved, the additives can be introduced. This is
done by distributing them manually along the length of the nip. The mill
immediately begins to incorporate them into the material on the mill, as ‘band’
and ‘bank’ material interchange in the rolling bank.
This process is assisted manually by cutting the band with a knife from the one
edge to two thirds to three quarters of its width, so that a flap of it is formed
which can be folded to the other side. This allows rapid exchange of bank and
band material and also improves lateral distribution of the batch.
By cutting and folding many times, from both sides good distribution and
dispersion are achieved. The entire batch can be removed from the mill by
cutting across the full width and pulling off the batch as a continuous sheet. If
the batch size is too large for this to be convenient, it can be removed by cutting
suitably sized sheets until the whole batch is off.
Two Roll Mill… Compounding…
Two roll mill mixing started in rubber
processing. Mills of many different sizes exist
for various functions. The biggest production
machines have 84'' rolls other standard sizes
being 60’’, 48'' and 36''. Smaller mills are used
in pilot - scale and laboratory work, where 18'',
12'' and 6’’ are common sizes.

As might be expected from the description of

the process, mixing on the two roll mill is time
consuming - 2 h for a 200 kg mix on a 84'' wide
mill and it depends for its success on
considerable skill on the part of the mill
operator. It is no longer in use as a primary
production process, although still widely used
for laboratory scale work, and sometimes for
one-off trial batches.
Two Roll Mill… Compounding…
The mill is still widely used as the receiver of material mixed in
internal mixers.
In this roll it is important

• As a refiner of the mix

• As a cooler - the internal mixer produces large masses of hot
mix which often require cooling, especially rubber compounds.
• As a convenient way of turning the large chunks into easily
handled sheets.
• For the addition of sensitive ingredients, for example
vulcanizing additives for rubbers.
 बुद्धिहीन तनु जाननके, सुमिरौं पवन कुिार ।
बल बद्धु िद्धवद्या दे हु िोहहिं, हरहु कलेश द्धवकार ॥
Buddhi-Hiina Tanu Jaanike, Sumirau Pavan Kumaar |
Bala Buddhi-Vidyaa Dehu Mohi, Harahu Kalesha Vikaar ||
Meaning:
Considering Myself as Ignorant, I Meditate on You, O Pavan Kumar (Hanuman). Bestow on me
Strength, Wisdom and Knowledge, and Remove my Afflictions and Blemishes.

Hanuman on how to speak!

Clarity in content, No negative words should be used. There should not be any mistakes in the
sentences. No grammatical errors in the sentences

Body language must be perfect. There should not be any ill feelings expressed on face, eyes,
forehead and eye brows. Proper Body language is the sign of effective communication.

One should not speak, which is not related to the subject

There should not be any ambiguity in communication

Clarity in communication must be always given top priority.

There should not be many pauses

Communication must appeal to heart and mind.

One must speak in middle octave

Words must be mesmerizing to the listeners. Even the hardest enemy must become silent with
folded hands.

Anybody, who can practice like Hanuman can achieve success in any of his or her chosen field.