Introduction to polymer

product processing and

engineering
Prof. Shushil Kumar
Department of chemical engineering
Indian Institute of Technology Roorkee
What is Polymer processing?

Polymer processing

Polymer granules Finished products

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nance/
Product quality
• Design
• Materials
• Processing technique
Selection of material
• Material should meet design and in service requirements.
• Mechanical properties (Hardness, strength)
• Chemical properties (corrosion, toxicity, stability)
• Physical properties (melting point, density)
• Manufacturing properties (Machinability)
• Service life
• Recycling and waste disposable
• Cost and availability
Selection of processing technologies
• Properties of the raw material (melting point, hardness)
• Size and shape of the final product
• Production volume
• Quality requirement of the final product
• In service requirement of the final product
Properties of polymer
Types of polymer
Classification by structure and processibility
• Linear (polyethylene, polyvinylalcohol,
polyvinylchloride etc.)
• Branched (low-density polyethylene (LDPE))
• Cross-linked (vulcanization of rubber,
thermosetting plastics)

Source: Polymer process engineering by Richard G. Griskey

Polymer classification by type of
processibilty
Thermoplastic Thermosets
Use melt in liquids shaping stage Use lower molecular weight or rubbery polymers
at shaping stage

Harden by freezing the melt Harden by chemical reaction, often cross-linking

Liquid-solid reversible Irreversible

Linear, branched Highly cross-linked
Ceiling service temperature Often can withstand high temperatures

e.g. Polyethylen, polystyrenes, e.g.  epoxy, silicone, polyurethane and phenolic

polyvinylcholoride
Polymer structure and behaviour: Effect of
temperature
Temperature can and do influence the behaviour of polymers
Five regions of viscoelastic behavious
Glassy
1. Glassy
2. Leathery/Glass transition region Leathery

3. Rubbery
Rubbery
4. Rubbery flow Rubbery flow

5. Liquid flow Liquid flow

Finally decompose!
Source: Polymer process engineering by Richard G. Griskey
Polymers and additive
• Alter the properties of the material e.g harder, flexible, cheaper, fire
retardant
• Increases stability of the material during processing and/or in service
Fillers (reinforcing and non-reinforcing)
Added to a polymer formulation to reduce the costs and improve the
properties (e.g. to touphen polymers).
• They occupy space and replace the expensive resin with less
expensive compounds without modifying other characteristics.
• It can be either solid, liquid or gas.
• The properties a filler offers are largely determined by its own
physical and chemical characteristics.
• Eg. alumina trihydrate, kaolin clay, calcium carbonate, talc, Carbon
black and silica
Fillers (reinforcing and non-reinforcing)
• Calcium carbonate is one of the most widely utilized minerals
additives in several PVC applications. Ground calcium carbonates
(GCC) are used mainly as fillers, while precipitated calcium
carbonates (PCC) are multi-functional additives that can function as
reinforcing fillers, processing aids and impact modifiers.
• Carbon black is added to rubbers to toughen that
Increases abrasion resistance (e.g in tyres, conveyer belts)
Plasticizers
Plasticizers are relatively non-volatile organic substances (mainly liquids) incorporated
into a plastic or elastomer to improve the polymer's:

• Flexibility
• Extensibility and,
• Processability
•
Plasticizers increase the flow and thermoplasticity of a polymer by decreasing the
viscosity of the polymer melt, the glass transition temperature (Tg), the melting
temperature (Tm) and the elastic modulus of the finished product without altering
the fundamental chemical character of the plasticized material.
Plasticizers
• Plasticizers are among the most widely used additives in the plastic industry.
They are also usually cheaper than other additives used in polymer processing.

Plasticizers are most often used in PVC, the third largest polymer by volume after
PP and PE. In turn, PVC is used in a wide range of products. Examples include:

Unplasticized PVC (or rigid PVC) is used in applications such as pipes, siding, and
window profiles.
• Plasticized PVC (or flexible PVC) finds applications in automotive interior trim,
cables, PVC films, flooring, roofing and wall coverings, etc.
• E.g. Doctyl phthalate (DOP), tricresyl phosphate (TCP)
Chemical additives
• Used to bring changes in the properties
• Polymer chains are chemically bonded to one another along their
length
• Properties is controlled by controlling the additive amounts
• E.g. vulcanization of rubbers (increases strength and stiffness, and
reduceses creep)
Antioxidants
• Protect against atmospheric oxidation during processing as well as
during service life
• Many poymers have sites which are susceptible to attack by oxygen
• E.g tertiary hydrogen atom in polypropylene
* *

• Antioxidants chemically interfere to prevent oxidative attack

Antioxidants
• Heat stabilizers: prevents degradation at high processing
temperatures. E.g preventing depolymirization at higher temperature
• PVC readily degades and darkens when heated, realising hydrogen
chloride
• Antiozonants: prevent attack by ozone (found in air). E.g. unsaturated
double bonds in rubber molecules can be attacked by ozone leading
to surface cracks
UV Stabilizers
• UV stabilizers absorb the UV radiation preferentially, and remit the
energy harmlessly at a lower wavelength
• UV radiation generally attack at the reactive site formed during
oxidative reaction
• Therefore, typically used in conjunction with antioxidants
Antistatic agents
• Prevents buildup of undesired static charges either during processing
or during in service
• Static charges can produce sparks and therefore can be dangerous
where flammable solvents are in use
Processing lubricants
• Internal lubricants: lubricates the polymer granules and other
additives during processing, allows easier and cooler melting with a
reduced risk of thermal degradation
• External lubricants: Lubricates the polymer mix against the processing
machinery. This allows correct degree of friction for the process to
work without causing local hot spot and degradation.
Colorants
• Chemical compounds used to color polymer.
• Come in a form of dyes and pigments.
• The type of a colorant is chosen based on the type of a polymeric
resin, that needs to be colored
• Dyes are usually used with polycarbonates, polystyrene and acrylic
polymers. Pigments are better suited for use with polyolefins.
Colorants
• The colorant must satisfy various constraints,
• Chemically compatible with the base resin,
• Suitable match with a color standard
• Chemically stable: able to survive the stresses and processing
temperature during fabrication as well as during service.
• Should provide desired effect to the final product e.g. being pearlescent,
metallic, fluorescent, phosphorescent, thermochromic or photochromic etc.
• Suitable for type of application e.g. general purpose, food contact
item, toy, package
Flame retardants
• Prevent ignition & flame spread, prolong escape time

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Mechanisms for flame retardance in polymers

• Vapor Phase Inhibition

During combustion, flame retardant additives react with the burning polymer in the vapor phase
disrupting, at a molecular level, the production of free radicals and shuts down the combustion
process. This mechanism is commonly used with halogenated flame retardant systems.
• Solid Phase Char-Formation
Char-forming flame retardant additives react to form a carbonaceous layer on the material’s
surface. This layer insulates the polymer, slowing pyrolysis, and creates a barrier that hinders the
release of additional gases to fuel combustion. This method is commonly deployed by non-
halogen systems using phosphorous and nitrogen chemistries.
• Quench & Cool
Hydrated minerals make up a class of halogen-free flame retardant systems commonly used for
extruded applications like wire and cable. These systems use an endothermic reaction in the
presence of fire to release water molecules that cool the polymer and dilute the combustion
process.

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flame-retardant-systems-work-in-plastics/#:~:text=Some%20po
Polymer mixes
Polymer is generally mixed with various additives during its processing
into final product

Two types of mixing processes

1. Extensive or distributive or blending mixing
2. Intensive or compounding or dispersive mixing
Extensive/Distributive mixing
• Essentially, stirring together the ingredients to obtain a well
distributed formulation
• Often this is blending of a number of solids e.g. polypropylene pwder,
colorant, antioxidant etc.
• Individual powders remain separate entity, and can be separated in
principle ( difficult in practice)
Intensive/Dispersive mixing
• Involves the more Intimate dispersion of the additives into the matrix
of the polymer
Often requires
• A physical change in the componnets
• High shear forces to bring about the change
• Polymer to be in the molten or rubbery state during mixing
Distinction between distributive and
dispersive mixing

Source: Polymer processing by D.H Morton-Jones

Chapman and Hall
When to use blending?
In most cases, a well distributed and a well dispersed formulation will
be desired.
• When the fabricating process to follow offers some compounding
action. E.g. pigments may be added prior to extrusion or injection
moulding to give a coloured product
• Thermosetting powders are often blends of powdered resin and
fillers which disperse upon fusion of the resin during moulding
• As a pre step to a separate compounding process
When to use compounding?
• When accurate distribution and dispersion of ingredients is required
• When fabricating process offers little or insufficient compounding
action
• When large amounts of modifying ingredients (e.g. fillers, plasticizers,
other polymers etc. ) are being used
Mixing and compounding equipment
• Tumbler

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Ribbon blender
• Chamber is stationary while ribbon rotates
• Tumbling action by constantly scooping the material from the outside
to the centre
• Can be heat traced for heating

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High speed mixer
• A more sophisticated and rapid machine for blending
• Forms a circulating vortex of powder
• Heat is generated due to friction (up to temperature 150-200oC)
• Widely used for PVC dry blends, drying, incorporating pigments,
antioxidants etc. in preblend powder

Source: Polymer processing by D.H Morton-Jones

Chapman and Hall
Z-blade mixer
• Used for dough like blends e.g. dough moulding compound (DMC)
• DMC is a blend of syrupy unsaturated polyester resin and fillers
• Two Z-shaped blades counter-rorate to distribute the solid fillers into
the liquid base
Dip mixer
• Used for low viscosity liquid blends
• Strirer is dipped into the mix placed in a “change can”
Compounding-rubbers
• Requires high shear processes and powerfull machinery
• Two-roll mill: a pair of rollers with axes horizontally disposed to one
another, giving a vertical ‘nip’ in between them
• Polymer matrix and additives are subjected to high shear in the nip as
the rolls rotate in opposite direction

Source: Polymer processing by D.H Morton-Jones

Chapman and Hall
https://en.wikipedia.org/wiki/Two_roll_rubber_mill
• Mixes well along the machine direction but poorly along the rolls
• Good at intensive or dispersive mixing but poor at extensive and
distributive mixing (produces well dispersed but poorly distributed mix)
• Quality depends upon processor person
• Feeding is done through the nip
• Often the rolls are preheated
• One of the rolls, generally hotter and faster, forms the band of the
polymer mix
• The nip can be adjusted by moving the rolls
Internal mixer
• Banbury mixer
• Two counter rotating rotors within a chamber
• Each rotor has two or four blades which mix by smearing the material
against the chamber wall
• A weighted ram keeps the mix in place inside the chamber
• Unifromity of mix is achieved by a swirling action due to speed
differential of the rotors
• video
• Possible end points for Banbury mixing
Compounding - thermoplastics
• Typically additives such as antioxidants, UV stabilizers, colorants,
lubricants are required in standardized and much smaller amount
• Compounding is typically done by polymer manufacturer
• Processor selects a suitable grade of polymer (in form of granules or
nib) for his purpose and simply process it
• Sometimes extruder is sufficient to achieve desired mixing
Forces in mixing
• Shear stress in mixer breaks down agglomerates of additive particles
• Consider two spherical additive particles, radii r1 and r2