Thermoplastics:

A thermoplastic, or thermo softening plastic, is a plastic material, a polymer that becomes pliable
or moldable above a specific temperature and solidifies upon cooling.

Most thermoplastics have a high molecular weight. The polymer chains associate
through intermolecular forces, which weaken rapidly with increased temperature, yielding a
viscous liquid. Thus, thermoplastics may be reshaped by heating and are typically used to
produce parts by various polymer processing techniques such as injection molding, compression
molding, calendaring, and extrusion. Thermoplastics differ from thermosetting polymers, which
form irreversible chemical bonds during the curing process. Thermosets do not melt when
heated: they decompose and do not reform upon cooling.

Above its glass transition temperature and below its melting point, the physical properties of a
thermoplastic change drastically without an associated phase change. Some thermoplastics do
not fully crystallize below the glass transition temperature, retaining some or all of their
amorphous characteristics. Amorphous and semi-amorphous plastics are used when high optical
clarity is necessary, as light is scattered strongly by crystallites larger than its wavelength.
Amorphous and semi-amorphous plastics are less resistant to chemical attack and environmental
stress cracking because they lack a crystalline structure.

Brittleness can be decreased with the addition of plasticizers, which increases the mobility of
amorphous chain segments to effectively lower the glass transition temperature. Modification of
the polymer through copolymerization or through the addition of non-reactive side
chains to monomers before polymerization can also lower it. Before these techniques were
employed, plastic automobile parts would often crack when exposed to cold temperatures. These
are linear or slightly branched long chain molecules capable of repeatedly softening on heating
and hardening on cooling.

Thermosetting Plastics:

A thermoset, also called a thermosetting plastic, is a plastic that is irreversibly cured from a soft
solid or viscous liquid, pre polymer or resin. The process of curing changes the resin into an
infusible, insoluble polymer network, and is induced by the action of heat or
suitable radiation often under high pressure, or by mixing with a catalyst.
Thermoset resins are usually malleable or liquid prior to curing, and are often designed to
be molded into their final shape, or used as adhesives. Others are solids like that of the molding
compound used in semiconductors and integrated circuits. Once hardened a thermoset resin
cannot be reheated and melted to be shaped differently.

Thermosetting polymers may be contrasted with thermoplastic polymers, which are commonly
produced in pellets, and shaped into their final product form by melting and pressing or injection
molding.

Curing a thermosetting resin transforms it into a plastic, or elastomer (rubber) by cross

linking or chain extension through the formation of covalent bonds between individual chains of
the polymer. Crosslink density varies depending on the monomer or pre polymer mix, and the
mechanism of cross linking.

Acrylic resins, polyesters and vinyl esters with unsaturated sites at the ends or on the backbone
are generally linked by co polymerization with unsaturated monomer diluents, with cure initiated
by free radicals generated from ionizing radiation or by the photolytic or thermal decomposition
of a radical initiator – the intensity of cross linking is influenced by the degree of backbone
unsaturation in the pre polymer.

Epoxy functional resins can be homo-polymerized with anionic or cationic catalysts and heat, or
co polymerized through nucleophilic addition reactions with multifunctional cross linking agents
which are also known as curing agents or hardeners. As reaction proceeds, larger and larger
molecules are formed and highly branched cross linked structures develop, the rate of cure being
influenced by the physical form and functionality of epoxy resins and curing agents – elevated
temperature post curing induces secondary cross linking of backbone hydroxyl functionality
which condense to form ether bonds;

Polyurethanes form when iso cyanate resins and pre polymers are combined with low- or high-
molecular weight polyols, with strict stochiometric ratios being essential to control nucleophilic
addition polymerization – the degree of cross linking and resulting physical type (elastomer or
plastic) is adjusted from the molecular weight and functionality of iso cyanate resins, pre
polymers, and the exact combinations of diols, triols and polyols selected, with the rate of
reaction being strongly influenced by catalysts and inhibitors; polyureas form virtually
instantaneously when iso cyanate resins are combined with long-chain amine functional
polyether or polyester resins and short-chain diamine extenders – the amine-isocyanate
nucleophilic addition reaction does not require catalysts. Polyureas also form when isocyanate
resins come into contact with moisture.

Phenolic, amino and furan resins all cure by poly condensation involving the release of water and
heat, with cure initiation and polymerization exotherm control influenced by curing temperature,
catalyst selection/loading and processing method/pressure – the degree of pre-polymerisation and
level of residual hydroxyl methyl content in the resins determine the crosslink density.

Thermoset plastic polymers characterized by rigid, three-dimensional structures and high

molecular weight, stay out of shape when deformed and undergo permanent or plastic
deformation under load, and normally decompose before melting. Thermoset elastomers, which
are soft and springy or rubbery and can be deformed and revert to their original shape on loading
release, also decompose before melting. Conventional thermoset plastics or elastomers therefore
cannot be melted and re-shaped after they are cured which implies that thermosets cannot be
recycled for the same purpose, except as filler material. There are developments however
involving thermoset epoxy resins which on controlled and contained heating form crosslinked
networks that can be repeatedly reshaped like silica glass by reversible covalent bond exchange
reactions on reheating above the glass transition temperature. There are also thermoset
polyurethanes shown to have transient properties and which can thus be reprocessed or recycled.

Thermosetting polymer mixtures based on thermosetting resin monomers and pre-polymers can
be formulated and applied and processed in a variety of ways to create distinctive cured
properties that cannot be achieved with thermoplastic polymers or inorganic materials.

Application process uses and methods for thermosets include protective coating, seamless
flooring, civil engineering construction grouts for jointing and injection, mortars, foundry
sands, adhesives, sealants, castings, potting, electrical insulation, encapsulation, 3D printing,
solid foams, wet lay-up laminating, pultrusion, gelcoats, filament winding, pre-pregs, and
molding. Specific methods of molding thermosets are:

 Reactive injection moulding (used for objects such as milk bottle crates)
 Extrusion molding (used for making pipes, threads of fabric and insulation for electrical
cables)
 Compression molding (used to shape SMC and BMC thermosetting plastics)

 Spin casting (used for producing fishing lures and jigs, gaming miniatures, figurines,
emblems as well as production and replacement parts)

Reinforcement:

Reinforcement usually adds rigidity and greatly impedes crack propagation. Thin fibres can have
very high strength, and provided they are mechanically well attached to the matrix they can
greatly improve the composite's overall properties.

Fibre-reinforced composite materials can be divided into two main categories normally referred
to as short fibre-reinforced materials and continuous fibre-reinforced materials. Continuous
reinforced materials will often constitute a layered or laminated structure. The woven and
continuous fibre styles are typically available in a variety of forms, being pre-impregnated with
the given matrix (resin), dry, unidirectional tapes of various widths, plain weave, harness satins,
braided, and stitched.

The short and long fibres are typically employed in compression moulding and sheet moulding
operations. These come in the form of flakes, chips, and random mate (which can also be made
from a continuous fibre laid in random fashion until the desired thickness of the ply / laminate is
achieved).

Common fibres used for reinforcement include glass fibres, carbon fibres, cellulose (wood/paper
fibre and straw) and high strength polymers for example aramid. Silicon carbide fibres are used
for some high temperature applications.

FILLERS: Fillers are defined as materials that are added to a polymer formulation to lower the
compound cost or to improve properties . Such materials can be in the form of solid, liquid or
gas. By the appropriate selection of these materials, not only the economics but also the other
properties such as processing and mechanical behavior can be improved. Although these fillers
retain their inherent characteristics, very significant differences are often seen, depending on the
molecular weight, compounding technique, and the presence of other additives in the
formulation. Therefore, once the basic property requirements are established, the optimum filler
type and the loading level for cost and performance balance must be determined [1,8,9].
The addition of fillers also requires a balance of formulation for optimum processing properties.
Therefore, before making a final decision on a filled compound, it is critical to establish the
following:

1. Optimum loading level for property and benefit.

2. Optimum formulation for processing and production output.

3. Economics of filled formulation.

1.2 CLASSIFICATION OF FILLERS

Fillers have been classified in many different ways, ranging from their shapes to specific
characteristics. Broadly, fillers can be classified into two categories, which are as follows:

1.2.1 CLASSIFICATION BASED ON PERFORMANCE

Extenders:

The extender fillers primarily occupy space and are mainly used to lower the formulation
cost.

Properties of extender fillers:

In general, ideal extender filler should

· Be spherical to permit retention of anisotropic properties.

· Have an appropriate particle size distribution for particle packing.

· cause no chemical reactivity with the polymer or the additives

· Have low specific gravity.

· Have desirable refractive index and colour.

· Be low in cost.

Functional fillers:
Functional fillers on the other hand have a definite and required function in the formulation apart
from lowering the formulation cost.

However, some of the extender fillers when reduced to a finer particle size and/or surface treated
would perform as functional filler. Fillers that are functional in one polymer may be merely
extenders in another polymer. Such factors seriously complicate the task of establishing sharp
boundary lines between extenders and functional fillers in terms of their generic composition;
however, on the performance basis they can be separated.

1.2.2 CLASSIFICATION BASED ON TYPE

Particulate fillers:

Particulate fillers are divided into two types, inert fillers and reinforcing fillers. The term inert
filler is something of a misnomer as many properties may be affected by incorporation of such
filler. For normal uses, such fillers should be quite insoluble in any liquids that the polymer
compound is liable to come into contact. Each type of filler may differ in the following ways:
· Average particle size and size distribution.
· Particle shape and porosity.
· Chemical nature of the surface.
· Impurities such as grit and metal ions.

The common observation is that the finer the particle sizes the higher the values of the tensile
strength, modulus and hardness. Coarser particles will tend to give less strong compounds than
the virgin material (i.e. material without the filler), but if the particle size is fine there is an
enhancement of the mechanical properties and the phenomenon is called as reinforcement.

Impurities in the fillers can have serious effects on the polymer compound. Coarse particles lead
to points of weakness in soft polymers and will therefore fail under stresses below that which
might be expected. In general, the phenomenon of reinforcement appears to depend on three
factors:
· An extensity factor – the total amount of surface area of filler per unit volume in
contact with the polymer.
 · An intensity factor – the specific activity of the filler – polymer interface causing
chemical and/or physical bonding.
· Geometrical factors such as structure and porosity of the particles.

Rubbery fillers:

Rubbery fillers are often incorporated into rigid thermoplastics to improve their toughness. The
increase in toughness of the material leads to significant increase in the fracture resistance of the
material.

Fibrous fillers:

Fibrous fillers have been long used in plastic materials. Fibrous fillers are often embedded in the
laminar form. The fibers have higher modulus than the resins in which they are embedded so that
when the composite of resin plus the fiber is strained in the plane of the fibrous layer the bulk of
the stress is taken up by the fiber. As a result of this, both the strength and the modulus are
enhanced when compared to the unfilled resin

Additives, fillers, and reinforcements:

Additives, fillers, and reinforcements are used to change and improve the physical and
mechanical properties of plastics. In general, reinforcing fibers increase the mechanical
properties of polymer composites while particular fillers of various types increase the modulus.

TABLE 1. Effects of additives, fillers, and reinforcements on polymer properties

Additive / Filler / Common materials Effects on polymer properties
Reinforcement
Reinforcing fibers Baron, carbon, fibrous Increases tensile strength.
minerals, glass, Kevlar Increases flexural modulus.
Increases heat-deflection
temperature (HDT).

Conductive fillers Aluminum powders, carbon
fiber, graphite
Coupling agents Silanes, titanates
Flame retardants Chlorine, bromine,
phosphorous, metallic salts
Extender fillers Calcium carbonate, silica,
clay
Plasticizers Monomeric liquids, low-
molecular-weight materials
Colorants (pigments Metal oxides, chromates,
and dyes) carbon blacks
Blowing agents Gas, azo compounds,
hydrazine derivatives
Resists shrinkage and warpage.
Improves electrical and thermal
conductivity.
Improves interface bonding between
polymer matrix and the fibers.
Reduces the occurrence and spread
of combustion.
Reduces material cost.
Improves melt flow properties.
Enhances flexibility.
Provides colorfastness.
Protects from thermal and UV
degradation (with carbon blacks).
Generates a cellular form to obtain a
low-density material.

Modifying polymer properties

Electrical properties can be affected by many fillers. For example, by adding conductive fillers,
an electromagnetic shielding property can be built into plastics, which are normally poor
electrical conductors. Anti-static agents can be used to attract moisture, reducing the build-up of
static charge.

Coupling agents are added to improve the bonding of the plastic matrix and the reinforcing
fibers. Different fillers are used to lower the cost of materials. Other additives include flame
retardants to reduce the likelihood of combustion, lubricants to reduce the viscosity of the molten
plastic, plasticizers to increase the flexibility of the materials, and colorants to provide
colorfastness.

Low-aspect fillers

Fillers modify the properties and molding of the compound to which they are added. If the fillers
are characterized with a low aspect ratio between the longest and the shortest dimensions, the
basic properties will be less changed from those of the unfilled polymer. Fillers benefit plastics
parts in the following ways:
 Shrinkage will be less.
 Thermal resistance may be improved.

 Strength, especially compressive strength, will be improved.

 Impact resistance will often be lower than for the unfilled polymer.

 Solvent resistance will often be improved.

High-aspect fillers: fibers: When the aspect ratio between the longest and the shortest
dimension of the filler is large, for example, greater than 25, the filler can be characterized as a
fiber. Fiber reinforcements will significantly affect the properties of the compounds to which
they are added.

Fibers impact strength: Assuming good bonding between the fiber and the polymer matrix, the
strength in the fiber direction will be significantly increased. If many fibers are oriented in the
same direction, large differences will be noted between the modulus in the orientation direction
and in the direction perpendicular to the orientation. The latter will be very close to that for the
unfilled polymer.

Fibers affect shrinkage: The fibers will also have a significant effect on the shrinkage
properties of the compound: shrinkage in the orientation direction will be much less than the
shrinkage in the cross direction.

Importance of predicting fiber orientation: Because the fiber orientation varies with the
flow direction, in the thickness direction, and at weld line locations, it is important to be able to
predict these orientations, in order to predict the properties of the molded article.

PLASTICIZERS
Plasticizers (UK: plasticisers) or dispersants are additives that increase the plasticity or
decrease the viscosity of a material. These are the substances which are added in order to alter
their physical properties. These are either liquids with low volatility or may be even solids. They
decrease the attraction between polymer chains to make them more flexible. Over the last 60
years more than 30,000 different substances have been evaluated for their plasticizing properties.
Of these, only a small number – approximately 50 – are today in commercial use. The dominant
applications are for plastics, especially polyvinyl chloride (PVC). The properties of other
materials are also improved when blended with plasticizers including concrete, clays, and related
products.

Plasticizers for plastics are additives, most commonly phthalate esters in PVC applications.
Almost 90% of plasticizers are used in PVC, giving this material improved flexibility and
durability. The majority is used in films and cables. It was commonly thought that plasticizers
work by embedding themselves between the chains of polymers, spacing them apart (increasing
the "free volume"), and thus significantly lowering the glass transition temperature for the plastic
and making it softer; however it was later shown that the free volume explanation could not
account for all of the effects of plasticization. For plastics such as PVC, the more plasticizer
added, the lower their cold flex temperature will be. Plastic items containing plasticizers exhibit
improved flexibility and durability. Plasticizers can become available for exposure due to
migration and abrasion of the plastic since they are not bound to the polymer matrix. The "new
car smell" is often attributed to plasticizers or their degradation products. However, multiple
studies on the makeup of the smell do not find phthalates in appreciable amounts, likely due to
their extremely low volatility and vapor pressure.

Plasticizers make it possible to achieve improved compound processing characteristics, while

also providing flexibility in the end-use product. Ester plasticizers are selected based upon cost-
performance evaluation. The rubber compounder must evaluate ester plasticizers for
compatibility, processibility, permanence and other performance properties.
The wide variety of ester chemistries that are in production
include sebacates, adipates, terephthalates, dibenzoates, gluterates, phthalates, azelates, and other
specialty blends. This broad product line provides an array of performance benefits required for
the many elastomer applications such as tubing and hose products, flooring, wall-coverings, seals
and gaskets, belts, wire and cable, and print rolls. Low to high polarity esters provide utility in a
wide range of elastomers including nitrile, polychloroprene, EPDM, chlorinated polyethylene,
and epichlorohydrin. Plasticizer-elastomer interaction is governed by many factors such
as solubility parameter, molecular weight, and chemical structure. Compatibility and
performance attributes are key factors in developing a rubber formulation for a particular
application. Plasticizers also function as softeners, extenders, and lubricants, and play a
significant role in rubber manufacturing.
Plasticizers or water reducers, and superplasticizers or high range water reducers, are
chemical admixtures that can be added to concrete mixtures to improve workability. Unless the
mix is "starved" of water, the strength of concrete is inversely proportional to the amount of
water added or water-cement (w/c) ratio. In order to produce stronger concrete, less water is
added (without "starving" the mix), which makes the concrete mixture less workable and
difficult to mix, necessitating the use of plasticizers, water reducers, superplasticizers, or
dispersants.

Mechanism of Plasticizers
As plasticizers usually possess relatively long alkyl chains, they have the effect of screening the
polymer chains from each other, thereby preventing them from reforming the chain-chain
interactions which give the unplasticized polymer its rigidity.

Classification of Plasticizers:

Depending on their properties plasticizers

1. Polyols
 Glycerol
 Propylene glycol
 Poly Ethylene Glycol 200-6000 grades

2. Organic esters
 Triacetin
 Diethyl phthalate (DEP)
 Dibutyl phthalate (DEB)
 Tributyl citrate (TBC)
3. Oils/Glycerides
 Castor oil
 Fractionated coconut oil
 Acetylated monoglycerides

On the basis of water solubility

1. Water Soluble
 PEG
 TEC
 Triacetin
2. Water insoluble
 DEP
 DBS
 DBP
 ATEC (Acetyl Triethyl Citrate)

Water soluble plasticizers make solutions whereas the insoluble plasticizer is emulsified into
dispersions. With insoluble plasticizers, their dispersion is described as a 3 phase systems
containing water phase, polymer phase and plasticizer emulsified droplets. The rate and the
extend of plasticizers uptake by the colloidal polymers was explained by conducting the effect of
type and concentrations of plasticizers on Aquacoat and the plasticized films so formed were
characterized by HPLC. It showed that the water soluble plasticizers like triacetin were in higher
concentrations in the aqueous phase due to higher concentrations in the aqueous phase due to
higher solubility in aqueous phase. Whereas the water insoluble plasticizers i.e. DBS partitioned
about 90% or more into the polymer phase. And the rest form was present as emulsified droplets.

Under such conditions when the plasticized droplet containing coating dispersions are sprayed
onto the tablets they generate rough, brittle and uneven films which potentially alter mechanical
properties and release profile of drug from the coated dosage forms. The rate of uptake of
plasticizers by the polymers is as function of plasticizing time. But in case of water soluble
plasticizers like triacetin or TEC uptake is not affected by the agitation time or mixing time.
But for water insoluble plasticizers like DBS incomplete plasticizing is observed even after long
plasticization time for ethyl cellulose latex.

Master Batch and Compounding:

Master batch (MB) is a solid or liquid additive for plastic used for coloring plastics (color master
batch) or imparting other properties to plastics (additive master batch). Master batch is a
concentrated mixture of pigments and/or additives encapsulated during a heat process into a
carrier resin which is then cooled and cut into a granular shape. Master batch allows the
processor to color raw polymer economically during the plastics manufacturing process.

The alternatives to using master batches are buying a fully compounded material (which may be
more expensive and less open to e.g. color variability of the product), or compounding from raw
materials on site (which is prone to issues with achieving full dispersion of the colorants and
additives, and prone to preparing more material than what is used for the production run). In
comparison with pure pigments, master batches require more storage space and their lead
times are longer. Another disadvantage is additional exposure of heat ("heat history") to both the
carrier and the additive; this may be important e.g. for marginally thermally stable pigments.

As master batches are already premixed compositions, their use alleviates the issues with the
additive or colorant clumping or insufficient dispersion. The concentration of the additive in the
master batch is much higher than in the end-use polymer, but the additive is already properly
dispersed in the host resin. In a way their use is similar to uses of ferroalloys for adding alloying
elements to steels.

The use of master batches allows the factory to keep stock of fewer grades of the polymer, and to
buy cheaper natural polymer in bulk.

The master batches can be fairly highly concentrated (in comparison with the target
composition), with high "let-down ratios"; e.g. one 25 kg bag can be used for a tonne of natural
polymer. The relatively dilute nature of master batches (in comparison with the raw additives)
allows higher accuracy in dosing small amounts of expensive components. The compact nature
of the grains of solid master batches eliminates problems with dust, otherwise inherent for fine-
grained solid additives. Solid master batches are also solvent-free, therefore they tend to have
longer shelf life as the solvent won't evaporate over time. The master batch usually contains 40-
65% of the additive, but the range can be as wide as 15-80% in extreme cases.

The carrier material of the master batch can be based on a wax (universal carrier) or on a specific
polymer, identical or compatible with the natural polymer used (polymer-specific).
E.g. EVA or LDPE can be used as carriers for polyolefins and nylon, polystyrene can be used
for ABS, SAN, and sometimes polycarbonates. When a carrier different than the base plastic is
used, the carrier material may modify the resulting plastic's properties; where this could be
important, the carrier resin has to be specified. The usual ratio of master batch to the base resin is
1 to 5 percent. Several master batches (color and various additives) can be used together. [1] The
carrier can also double as a plasticizer (common for liquid master batches) or a processing aid.

The machines are usually fed with premixed granules of the host polymer and the master batch.
The final mixing then gets done in the screw and extrusion part of the machine. This is
sometimes prone to adverse effects, e.g. separation of the master batch and the base material in
the machine's hopper. The master batch can be also added directly to the machine's screw, as a
free-flowing solid or in case of a liquid master batch by e.g. a peristaltic pump. Such use of
liquid master batches allows highly accurate dosing and quick change of color between machine
runs. Master batches can be used in most processes, except rotational molding and Plastisol and
other liquid resin systems.
Applications:
Ultraviolet Light Resistance
Flame Retardant
Anti-Fouling
Anti-Static
Lubrication
Anti-Slip
Corrosion Inhibitors for Metals Packaged In Plastic
Anti-Microbials
Anti-Oxidants
Extrusion Aids
Phosphorescence
A fiber-reinforced composite (FRC) is a composite building material that consists of three
components: (i) the fibers as the discontinuous or dispersed phase, (ii) the matrix as the
continuous phase, and (iii) the fine interphase region, also known as the interface. This is a type
of advanced composite group, which makes use of rice husk, rice hull, and plastic as ingredients.
This technology involves a method of refining, blending, and compounding natural fibers from
cellulosic waste streams to form a high-strength fiber composite material in a polymer matrix.
The designated waste or base raw materials used in this instance are those of waste
thermoplastics and various categories of cellulosic waste including rice husk and saw dust.

FRC is high-performance fiber composite achieved and made possible by cross-linking cellulosic
fiber molecules with resins in the FRC material matrix through a proprietary molecular re-
engineering process, yielding a product of exceptional structural properties.

Through this feat of molecular re-engineering selected physical and structural properties of wood
are successfully cloned and vested in the FRC product, in addition to other critical attributes to
yield performance properties superior to contemporary wood.

This material, unlike other composites, can be recycled up to 20 times, allowing scrap FRC to be
reused again and again.

The failure mechanisms in FRC materials include delamination, intralaminar matrix cracking,
longitudinal matrix splitting, fiber/matrix debonding, fiber pull-out, and fiber fracture.

Factors affecting the design of Fiber reinforced composites:

Relative fibre matrix stiffness: The fibres considered should be significantly stiffer than the
matrix and the low modulus of the fibres imparts more energy absorption while high modulus of
the fibres imparts the strength and stiffness

Volume of the fibres: when the volume fraction is very low (<1%) it can be used in the slabs
and pavement that have large exposed surface leading to shrinkage cracking. When the volume
% is moderate i.e, in between 1 to 2% it can be used in construction method and high volume
fraction of >2% is used in making high performance FRC

Aspect ratio of the fibre: It is defined as the length of the fibre to its diameter ratio. More the
aspect ratio more will be the stiffness, strength and toughness of the material.
Orientation of the fibre: it is observed that the fibres aligned parallel to applied load offers
more tensile strength and toughness than the randomly arranged or perpendicular fibres.

Workability and compaction: The amount of useful internal work necessary to produce full
compaction. Internal work is the energy required to overcome the internal friction between the
individual particles in the composite.

Size of coarse aggregate: The largest maximum size utilized to develop the composite is
around <20mm to get the optimum properties of strength, durability, shrinkage etc..

Mixing: Mixing of FRC needs careful precautions to avoid Balling effect () and segregation.
Increase in aspect ratio, size of coarse aggregate and volume fraction will increase the level of
difficulties in the mixing.