Properties of Polymers

M.Sc. (Polymer Science)

Semester-I

Faculty-Manish Kumar
 Unit: 5

2
Additives for Plastics
 Introduction
 Fillers
 Plasticizers and Softeners
 Lubricants and Flow-Promoters
 Anti-ageing-antioxidants
 UV and Related materials additives
 Flame Retarders
 Blowing Agents
 Photodegradation
 Crosslinking Agents
 Sealants
 Introduction
3  Any substance that is added generally in small concentration to resins in order to alter the
properties either to facilitate processing or to change the physical, chemical or electrical
properties of end products

 Bulk properties of a polymer can often be modified considerably by the incorporation of additives. In
rubber technology with the help of additives, wide variety of differing products can be produced
such as tyres, battery boxes, latex foam upholstery, elastic bands and erasers

Salient features of Additives

 Efficient in their function

 Stable under processing and service conditions
 Should not bleed or bloom
 Non-toxic and not impart taste or odour
 Should be cheap
 Should not adversely affect the properties of the polymer

 Additives may be divided into four groups, solids, rubbers, liquids and gases. Later one of these
being used for making cellular polymers
 Additives Can……
4
Change the properties of plastic materials
 Enlarge the field of application drastically
 Protect your plastic against alteration and degradation
 Help to meet the recycling requirements
 Extend the lifetime of product
 Differentiate with others
5 Classification of Additives

Plastic Additives

Additives to modify plastics Additives achieve their effect

Properties by physical means by chemical reactions

Plasticizers Heat stabilizers

Lubricants Antioxidants
Impact modifiers UV absorbers
Fillers Flame Retardants, etc
Pigments, etc
  Bleeding of an additive into an adjacent material occurs when the additive has a degree of solubility
6 in the polymer into which it is incorporated and also in the adjacent material, which could be liquid
or solid. Such bleeding could colour or otherwise contaminate the adjacent material. Bleeding is
much more extensive from polymers which are above their Tg (and melting point Tm , if crystalline)
than from polymers below this temperature

 Blooming is also associated with solubility and occurs when an additive has totally dissolved in the
polymer at processing temperature but is only partially soluble at ambient temperature. As a result
some of the additive is come out of solution on cooling and some of this may collect on the surface
of the polymer mass
*Blooming will not occur either if the additive is totally insoluble at processing
temperature or if it is totally soluble at room temperature
 (1) Fillers

7  Many type of fillers can be added to polymer material to extend the range of physical properties, to
reduce the cost of the compound, to modify the processing properties (e.g., to achieve a reduction in
die swell), and to influence the chemical resistance of the compound

 In addition, fillers can pigment a compound, impart conductivity to it, and influence its aging
characteristics

 A reinforcing filler can be defined as a filler that improves modulus, tensile strength, and tear and
abrasion resistance. However, this improvement of properties is not continuous: when the volume
percentage of filler further increases, the point at which there is insufficient rubber to bind the filler
together eventually will be reached. A noticeable decrease in strength would have become apparent
well before this point

 Fillers can also be classed as semi-reinforcing or diluent

 For a each chemical type of filler, a number of grades are generally available and depends on:

(1) Average particle size and size distribution (2) Particle shape and porosity
(3) Chemical nature of the surface (4) Impurities such as grits and metal ions
 The effect of a particulate filler on a polymer depends on the following factors:
8 1. The surface area of the filler particles. The surface area of a filler particle is directly related to the particle
size; the lower the particle size, the higher the surface area. SAF, a highly reinforcing carbon black, has a
particle size of 11–19 nm and a surface area of 125–155 m2/g, whereas with SRF black, which is
semireinforcing, the values are 61–100 nm and 17–33 m2/g. Coarse inorganic fillers may have surface areas
of around 1 m2/g.

2. The chemical nature of the particle surface. The chemical nature of the particle can vary among different
fillers. On the surface of carbon blacks there are chemically active sites that have a profound effect on the
reinforcement obtained. If the carbon black is exposed to temperatures of 1600–3000°C, these active sites
are destroyed, and reinforcement is lost. Thus both total surface area and surface activity of a filler are
important requirements for the development of reinforcement
Reinforcing effect of several white fillers can be increased by the use of silane coupling agents, which
react with chemical groups on the filler surface

3. Geometrical characteristics. If carbon black is examined under an electron microscope, it is seen that the
primary particles are fused into larger aggregates. The size, shape, and number of voids in this “aggregate”
determine the “structure” of the carbon black, and this structure can influence the physical, and processing
properties obtained
Whereas the primary particles of carbon black are generally spherical, the shapes of inorganic or
mineral filler particles exhibit much greater variation. The anisometry of the filler particle is an important
characteristic, affecting the viscosity and modulus of the resultant polymer composite
  Porosity of the filler particle is another factor that influences the properties obtained. Silicas are generally more
9 porous than carbon black, and thus silica fillers give higher viscosity compounds at equal volume loadings. In
carbon blacks, increasing porosity can decrease the electrical resistivity obtained

 General effects of the surface area and geometric factors of a filler are summarized are as follows
 (1) Clays
10  White clay based fillers are a useful compounding ingredient in rubber. They can be divided into “hard” and “soft”;
the hard clays can be classed as semireinforcing fillers, their smaller particle size giving a greater effect on modulus
than the “soft” types
 Calcination, or removal of combined water from the clay, can modify the properties imparted to the rubber, the
effect on electrical properties being particularly noticeable
 Chemical treatments of the clay by amines or, more important these days, silane coupling agents, can result in
improved reinforcement
(2) Carbon Blacks: produced by the oil furnace process and wide variety are available. At equal volume loadings the
tensile, tear, hardness, modulus, abrasion resistance, and heat buildup properties of a compound decrease as one moves
down the table, whereas flexibility, resilience, elongation at break, and processibility improve

(3) Silica and Silicates: Reinforcing white fillers that can be produced by two processes: precipitation from solution
and combustion methods (fumed silica). As the latter method yields a very fine particle size (ca. 10 nm; surface area ca.
190 m2/g), produces very high viscosity, stiff compounds, it is not as widely used as the precipitated type. The
precipitation process yields a filler with a particle size of 10–40 nm (surface area ca. 150 m2/g), and this type of
process is the more commonly used
Both aluminum and calcium silicates can be produced by the precipitation process; they are classed as
semi-reinforcing white fillers. The calcium silicates, with surface areas of ca. 80 m2/g, are slightly more reinforcing
than the aluminum types
 (4) Calcium Carbonate: Ground calcium carbonate, whiting, has a coarse particle size (0.5–30 m) and is used
11 only as a diluent filler because of its low cost
Precipitated calcium carbonate has a smaller particle size (> 0.1 m), which gives improved properties compared
to the use of whiting. Stearate coated grades, which give improved dispersability, are of superior grade

(5) Rubbery materials (fillers) are often incorporated into rigid amorphous thermoplastics to improve their
toughness. Examples: polybutadiene in polystyrene, butadiene-acrylonitrile rubbers in PVC and ethylene-
propylene rubbers in polypropylene

(6) Fibrous fillers have been long used in plastics materials. Wood flour, cotton flock, macerated fabric,
macerated paper and short lengths of synthetic organic fibres such as nylon can improve the impact strength
and often the rigidity and toughness of moulding compositions
Inorganic fibres such as asbestos and glass fibre are also used in moulding compositions, both
thermoplastic and thermosetting, where heat resistance and strength respectively are required
 (2) Plasticizers and Softeners
12
A plasticizer may be defined as a substance which when incorporated into a polymeric material improves:
o Flexibility and Processability
o Alters temperature depends properties such as softening point low temperature flexibility
o Significantly effects tensile strength, elongation at break and impact properties

Plasticizer Requirement
o The plasticizer achieve these effects by reducing the physical intermolecular forces between polymer
chains, thereby increasing chain mobility which results in softening
o Chemically, plasticizers are generally high boiling, non-volatile solvents, usually ester type organic
compounds, polar and with a relatively high molecular weight
o The degree of polarity in a plasticizer depends to some extent on the attractive forces between the
polymer chains
 Types of Plasticizer
13
(i) Primary Plasticizer (ii) Secondary Plasticizer

Primary Plasticizer:
It should have a sufficient level of compatibility with the polymer for use as sole plasticizer at all
addition levels giving a useful modifying effect and should not exude from plasticized material. For
example DOP (Di octyl phthalate)

Secondary Plasticizer:
 Secondary plasticizer have lower gelation capacity and limited compatibility with the polymer and are
normally only used in mixture with a primary plasticizer
 They enhance the plasticizing performance of primary plasticizers
 When these are used as a cheap partial replacement for a primary plasticizer to reduce cost that are
called extenders e.g. chlorinated paraffin, hydrocarbons
 Note: The plastizer may be primary or secondary depending on the substrates such as mineral oils are
primary for Poly (diene)s but secondary for PVC
 Mechanism of Plasticizer Action
14
(1) Lubricity Theory (2) Gel Theory (3) Mechanistic Theory

(4) Free Volume Theory (5) Solvation Theory (6) Thermodynamic Theory

(7) Polarity Theory

Gel Theory

 The theory assumes the formation of an internal three dimensional honeycomb structure
or gel.
 Plasticizer molecules becomes attached to a given active group only to be replaced by
another
 Considers the rigidity in an unplasticized resinous mass to be caused by an internal three
dimensional honey comb structure or gel formed by loose attachments between the resin
macromolecules which occurs at intervals along the molecular chains
 The action of plasticizer on a resin with many points of attachment along the polymer chains is breakage of the
attachment and masking of the centers of force which holds the polymer chains together by selectively solvating
15 the polymer at these points.
 This results in a dynamic equilibrium, when a certain fraction of the force centre of the polymer chain are marked
by the plasticizer under a given condition i.e. concentration, temperature and pressure.

Lubricity Theory

 This theory views the resistance to deformation as arising from intermolecular friction. According to this theory
the plasticizer acts as a lubricant to facilitate movement of the resin macromolecules over each other, thus
reducing the internal resistance to deformation
 Plasticizer act as lubricant in exhibiting non-bonding forces with the polymer
 Lubricants lower intermolecular forces thereby causing partial plasticizing
 It decreases melt viscosity and facilitate processing
 The resistance of a resin to deform is due to inter molecular friction
 The plasticizer acts as a lubricant to facilitate the movement of macromolecules over each other and provides
internal lubricity
 Thus, these lubricants both internal and external do not allow the resin to melt
 Functions of Plasticizer
 Plasticize polymer
16  Decrease modulus of elasticity and tensile strength at break
 Increase extensibility and elongation at break
 Improves flexibility
 Improves reversed bending strength
 Improves toughness and impact strength
 Lower glass transition temperature
 Extend applicability of polymer to lower temperature
 Improves adhesion to various substrates
 Improve lubricity properties and reduce friction
 Improve gloss and appearance of surface
 Reduce electro statically chargeability
 Act as internal lubricant
 Reduce adhesion to melt surfaces
 Lower processing temperature
 Reduce melt viscosity
 Lower film forming temperature (in adhesion and lattices)
 Improve wetting and dispersion and pigment and filler
 Choice of Plasticizer
17
Selection of plasticizer is done on basis of following:
 Volume cost analysis
 Compatibility
 Processing characteristics
 Thermal, electrical and mechanical properties
 Resistance to water, chemicals, weathering, dirt and microorganism
 Toxicity
 Effect on rheological properties
 Softeners
18 In the rubber industry hydrocarbon oils are often used to reduce the softness and facilitate the processing of
hydrocarbon rubbers. These appear to have a small interaction with the polymer but spacing effects
predominate. Such materials are generally referred to as softeners

The general reasons for adding softeners are as follows:

1. To improve the processing properties
2. To modify the final compound properties (hardness and flexibility)
3. To alter the cost of the compound by allowing further increases in the filler level while maintaining a certain
hardness
4. To reduce power consumption during processing

Petroleum Oils: All petroleum oils are a mixture of paraffinic, naphthenic, and aromatic hydrocarbons, and the
precise composition of the oil determines its compatibility with a rubber

 Paraffinic oils are more compatible with EPDM and butyl rubber, while the more polar aromatic oils are
compatible with the polar rubbers, polychloroprene, nitrile, and chlorosulfonated polyethylene. Most types
of oil are compatible with natural, polybutadiene, and SBR rubbers

 Refinery oils and chlorinated waxes are widely used in PVC for this purpose with the prime aim of reducing
cost although the chlorinated waxes may also be of use as flame retardants
 (3) Coupling agents
19
Coupling agents are the compounds that form a chemical bond between two nonsimilar species to
enhance the interfacial bonding between fibers or particles with the matrix polymer

It is generally observed that the polar end attaches itself to the filler particle whilst the aliphatic
hydrocarbon end is compatible with the rubbery matrix

These chemicals usually modify the surface functionality of filler effectively to aid easy bonding with the
polymer chains. The selection of a suitable coupling agent depends upon the functional properties of
the filler–matrix pairs and the objectives of modification.

Example: (1) Titanate-treated inorganic fillers can be advantageously used in polymer composites as
they induce higher dispersion and interfacial bonding. Titanate treated fillers are hydrophobic,
organophilic (affinity towards organic materials), and organo-functional due to which usually they add
toughness to the polymer matrix. In one such study, where titanate coupling agent (LICA 01)-treated
Fly Ash was incorporated in polybutadiene rubber, tensile strength was increased by 50%
 (2) Silane coupling agents with epoxy or amino functional groups were used to couple glass fibre to
epoxide resins and, with phenolics. Coupling agents with mercaptan groups were used in conjunction with
diene rubbers. A number of silanes are also introduced for use with thermoplastics
20

Examples of Silane Coupling Agents

 (4) Antioxidants
21
 Antioxidants retards oxidation and thus retard the resulting ageing of the polymer
 Antioxidant used for stabilizing oxidative degradation
 Antioxidant as added as early possible in the life cycle of the polymer (before drying stage of the
polymers)
 Examples: Amines, phenolics, phosphites, thioesters, etc

Effect of Oxidation on Polymer Properties

• Oxidation occurs in the polymer during
- Manufacturing
- Storage
- Processing
- End use

• Plastics are sensitive to oxidation

• Stability against oxidation arise from

- Chemical structure of polymers
- Difference in the manufacturing process
- Morphology (crystalline, orientation)
- Commercial; polymer contains catalyst residue and functional groups which
sensitize oxidation
 Oxidation of Polymers
22
• Reaction of organic compounds with molecular oxygen is called auto-oxidation
(oxidative degradation) because these reactions are proceeds automatically

• During auto-oxidation of polymers there are mainly four types of reaction:

 Initiation reaction generating the free radicals
 The propagation reaction
 Chain branching reaction yielding oxidation products
 Termination reactions elimination the free radicals from system

Initiation and Propagation

 Generation of free radicals through heat, radiations, mechanical stress, catalyst residue
REACTION
Initiation
 Propagation
23
 Reaction of an oxygen molecules with free radicals corresponding peroxy radicals
e.g. Alkyl radicals (P∙) transform rapidly to peroxy radicals (POO∙) in presence of oxygen

Propagation and Chain Branching

 Peroxy radicals (POO∙) abstract hydrogen from the neighboring polymeric segment and
forms hydro peroxide (POOH) and a new free radical site.

Chain branching reaction involves decomposition of hydro peroxides through

 Monomolecular decomposition (a)
 Psudeo-monomolecular reaction (b)
 Bimolecular reaction (c)
 Propagation and Chain Branching
24

 Peroxy radicals (POO∙) abstract hydrogen from the neighboring polymeric segment and
forms hydro peroxide (POOH) and a new free radical site.

Chain branching reaction involves decomposition of hydro peroxides through

 Monomolecular decomposition (a)
 Psudeo-monomolecular reaction (b)
 Bimolecular reaction (c)
 Propagation and Chain Branching
25
Reaction

The decomposition of hyderoperoxides efficiently catalyzed by various metal ions. (e.g.

Fe2+/Fe3+, Mn2+, Co2+/Co3+, Cu2+/Cu3+)

The catalytic process-

 Auto-oxidation of Styrene Polymers
26

 Oxidation of PS forms volatile products like phenol, benzaldehyde and acetophenone

 Thermal oxidation of PS leads to physical change through intermolecular hydrogen

abstraction

 Chain scissions of PS attribution by decomposition of tertiary alkoxy radicals

 Presence of oxygen in PS decrease molecular weight during processing

Reaction
 Methods of oxidation stabilization
27
 Structural modification of the polymer (e.g. co-polymerization with vinyl group containing
antioxidant)

 Capping of the end groups

 Physical stabilization by orientation of the polymer (stretching)

 Addition of stabilizing additives

Classification of Antioxidant
 Antioxidants are chemical entities, which retard oxidation and thus retard aging of the
polymer

 Effective at concentration of a fraction of one percent.

 Possible to use more than one antioxidant that give synergistic effect more than 200%.

 Antioxidant are of two types based on the function and mechanism:

 Primary antioxidant (chain termination) – Radical Scavengers
 Secondary antioxidant (hydroperoxide decomposing)
28 Classification of Antioxidant
 Antioxidants are chemical entities, which retard oxidation and thus retard aging of the
polymer

 Effective at concentration of a fraction of one percent.

 Possible to use more than one antioxidant that give synergistic effect more than 200%.

 Antioxidant are of two types based on the function and mechanism:

 Primary antioxidant (chain termination) – Radical Scavengers
 Secondary antioxidant (hydroperoxide decomposing)
 Primary Antioxidant
29
They act rapidly and termed as ‘Radical scavengers’
E.g. Sterically hindered phenolics and secondary aromatic amines

Hindered Phenolics:
 They are high molecular weight and sensitive to thermal and oxidative degardtion due to
formation of free radicals and peroxides

 They protect against degradation at high processing temperature and highly efficient, low in
volatility and non-staining with wide toxicological clearance and are effective at a very low
dosage (0.01-0.1%)
 Secondary Antioxidant
30
 They reacts with hydroperoxide to produce non-radical products and are therefore,
ofetn termed as ‘hydroperoxide decomposers’

 They differ from phenols and amines and on decomposed by reaction with
hydroperoxide, rather than containing it

 They are particularly useful in synergistic combination with primary antioxidant

 There are two mechanism of antioxidant

1. Stabilization of chain breaking antioxidant

a. Chain Breaking Donor Mechanism (CB-D)
b. Chain Breaking Accepter Mechanism (CB-A)

2. Stabilization by preventive antioxidant

 Antioxidants
Oxidation of hydrocarbons, including hydrocarbon polymers, takes the form of a free-radical chain
31 reaction. As a result of mechanical shearing, exposure of ultraviolet radiation, attack by metal
ions such as those of copper and manganese as well as other possible mechanisms, a hydrocarbon
molecule breaks down into two radicals

Such hydrocarbon radicals (R*) rapidly combine with oxygen to form a peroxide radical

Such a radical will then react with a hydrocarbon by the following propagation reaction

Whilst the R* radical again reacts as in equation (7.2) the hydroperoxide may decompose by the
following mechanisms
 Reactions (7.2), (7.3) and (7.4) form a series of chain reactions, with reaction (7.3) the rate-determining
stage. The chain reaction terminates by the reactions
32

It will be seen that reactions (7.5b) and (7.5c) if they occur more than once per hydrocarbon molecule
(radical) will lead to chain extension and, if on average more than twice, to cross-linking
It is also possible that reactions may occur which cause decomposition of the peroxide radicals by
reactions of schematic form

If an antioxidant is to function it must interrupt the above reaction sequence. It is usual to recognise
two types of antioxidant:
(1) Preventive antioxidants which prevent the formation of radicals by reactions (7.1) and (7.3)
(2) Chain-breaking antioxidants which interrupt the propagation cycle by reacting with the radicals R* and
RO2*, introducing new termination reactions

 In addition, other additives may exist which react with R* and RO2*,introducing new propagation
reactions which lead to a slower chain reaction. Such materials would be referred to as oxidation
retarders
 Oxidation retarders of general structure AH, which may function in the following ways
33

Reaction (7.7) is largely pro-oxidant; reactions (7.8a) and (7.8b) are propagation reactions and
reactions (7.9a) and (7.9b) termination reactions. For chain breaking, reactions (7.8a), (7.9a) and
(7.9b) should be preferred. In cases where reaction (7.8a) is preferred to reaction (7.3) and when
(7.8b) is rate determining it is possible for the material to be an effective oxidation retarder
 Main types of chain-breaking antioxidants

34
 (5) Flame Retardant
35
A flame retardants is a chemical compound which adapts polymers to applications where
fire safety is a consideration

Why It Is Used ?
 Thermoplastics are hydrocarbons sometimes contains O(PC), N(Nylon), Halogen(PVC) etc
 These are easily combustible in the presence of oxygen & fire
 Fire retardants prevent the thermoplastic material from fire

Basic Requirements of Flame Retardants

 Provide durable flame retarding effect by adding small quantity of additive

 It should be cheap

 It should be no means cause corrosion of the processing equipment

 It should not be affect the mechanical & physical property of the base resin

 It should be non-toxic

 It should not be decompose at processing temperature

 It should not volatilize

 Flame retardants may be divided into two classes, reactive components and additives.

36 Reactives are used primarily with thermosetting plastics and are special intermediates which are inserted
into the polymer structure during cross-linking. Used largely with polyesters, epoxides and polyurethanes,
such materials are usually either highly halogenated or are phosphorus compounds

Bulk of flame retardants are of the additive type

Flame retardants appear to function by one or more of four mechanisms:

(1) They chemically interfere with the flame propagation mechanism
(2) They may produce large volumes of incombustible gases which dilute the air supply
(3) They may react, decompose or change state endothermically, thus absorbing heat
(4) They may form an impervious fire-resistant coating preventing access of oxygen to the polymer

Examples: (1) Most important class of fire retardants are the phosphates. Tritolyl phosphate and trixylyl phosphate are
widely used plasticisers which more or less maintain the fire-retarding characteristics of PVC

(2) Better results are obtained using halophosphates such as tri(chloroethyl) phosphate, particularly when used in
conjunction with antimony oxide, triphenyl stibine or antimony oxychloride

(3) Antimony trioxide, other oxides include titanium dioxide, zinc oxide and molybdenic oxide
 Classification of Flame Retardants
37
(1) BASED ON MECHANISM OF ACTION

(a) Causing char formation in pyrolysis zone:

E.g. Cellulose + phosporus compound (F.R.). Dehydration (flame) Unsaturated compound Crosslinking char

(b) F.R. that decompose to give –

# Product which cools the pyrolysis zone

flame Alumina decomposes to give water vapour

e.g. Polymer + Alumina
which cool the pyrolysis zone
# Non flammable gases
e.g. Polymer + sodium bicarbonate flame CO2 cut the supply of O2

(c) Retarding combustion process in vapour phase-

It is possible by tracking free radicals
 (2) BASED ON COMPOSITION
 Chlorine Containing
38 e.g. Tetrachlorobisphenol-A --- Used for PC.
e.g. Chlorinated styrene --- Used as a comonomer for styrene & ABS
e.g. Hexachloroendomethylene tetrahydrophalic acid --- Used for unsaturated polyester
e.g. Hexachlorocyclopentadiene --- Used for polyolephine

Advantage - Favourable price

Disadvantage - (1) Low thermal stability
(2) Applicable for thermoplastic below 200 oC

 BROMINE CONTAINING
e.g. Dibromopentaerythrital --- Used for Linear Polyester & Polyurethanes
e.g. Hexabromocyclododecane --- Used for Polyolefins
e.g. Octabromodiphenyl --- Used for Linear Polyester & ABS
e.g. Hexabromobenzene --- Used for Polyamides
e.g. Tetrabromobisphenol-A --- Used for PC. & Epoxy resin

Advantage – (1) On weight basis it is twice effective as

Chlorine containing
(2) Because of smaller quantities it hardly
influence the mechanical properties

Disadvantages – (1) Reduces the U.V. stability

(2) Higher price than organic chlorine compound
  PHOSPHOROPUS CONTAINING
39 e.g. Quaternary phosphonium compound --- Used for ABS &Polyolefins.
e.g. Read Phosphorus & Alkali salts of Phosphoric acids --- Used for Polyamides

 BORON CONTAINING
e.g. Borax & Boric acid --- These forms a glassy layer which protects the flammable plastic from flame
& oxygen

Applications of Flame Retardants

 Electrical - Flame retarded styrenic polymers --- used for cabinet of T.V. & phono devices

 Transportation – Flame retarded polyamides --- used for Aircraft & Ship construction

 Building – Flame retarded Polyolefins

 Furniture – Flame retarded Polyolefins High Impact Polystyrene (HIPS) & Acrylonitrile Butadiene Styrene
(ABS)
 (6) Colorants
40  There are basically four methods used for colouring polymers

 These are surface coating ( e.g. painting), surface dyeing, introduction of colour-forming groups into the
polymer molecules and mass colouration

 Surface coating involves extra processing and can substantially increase the cost of the product

 Surface dyeing can be of limited use with some polar polymers such as the nylons where only a small quantity
of material is required to be coloured

 Introduction of chromophoric groups is an inflexible and expensive method. Therefore, for most applications of
rubbers and plastics the mass colouration approach is favoured

 Colorants are sometimes divided into two classes, insoluble colorants (pigments) and soluble colorants
(dyestuffs). Many colorants have a low but finite solubility. In some cases, low solubility leads to blooming,
therefore, high molecular weight colorants are used

 Pigments that are organic in nature are hard to disperse and tend to form agglomerates (clumps of pigment
particles). These agglomerates can cause spots and specks in the final product

 Inorganic pigments like: Metal oxides and sulphides, carbon black, etc. get more easily dispersed in the resin.
Amongst the inorganic pigments titanium dioxide is the most widely used pigment in the plastics industry

 Major performance properties of pigments in plastics are decided by their weatherability or aging, light
fastness, warping or nucleation and transparency
 Types of Organic Pigments Suitable for Plastics
41 Organic pigments refer to a wide range of chemical families and cover a wide spectrum of properties. They
are mainly used for applications needing high tinting strength and brilliant shades while inorganic pigments
are mainly useful where high opacity is needed.

We can distinguish three main categories of organic pigments:

 Polycyclic
 Azo (Mono- and Di-)
 Metal complexes

Requirement for colorants

 When colorants are added before polymerisation they should not interfere with the polymerisation
reaction nor should they be affected by the presence of other polymerisation additives
 (7) Blowing Agents
42 Many polymers are used in a cellular form in which the polymer matrix is filled with gas-filled cells which may or
may not be intercommunicating. Over the years many methods have been used. The most important methods are
the following:-

(1) Incorporation of a chemical compound which decomposes at some stage of the processing operation to yield volatile
reaction products. These are known as chemical blowing agents

(2) Incorporation of low boiling liquids which volatilise during processing. Such volatile blowing agents are important with
polystyrene and polyurethanes

(3) Diffusion of gases into the polymer under pressure with subsequent expansion of the composition at elevated
temperatures after decompression. Such a process can be employed with a wide variety of polymers.

(4) Incorporation of powdered solid carbon dioxide which volatilises at elevated temperatures. This process has been used
with PVC pastes.

(5) Chemical reactions of polymer intermediate during polymerisation and/or cross-linking. This is important with
polyurethanes.

(6) Mechanical whipping of polymers in a liquid form and subsequent ‘setting’ in the whipped state. The manufacture of
latex rubber foam is the best-known example of this approach.

(7) Incorporation of hollow or expandable spheres of resin or of glass (microballoons).

(8) Leaching out of soluble additives.

 In addition to the requirements common to all additives there are some special requirements. These include:

43 (1) The need for gases to be evolved within a narrow but clearly defined temperature range and in a controlled
and reproducible manner

(2) The decomposition temperature should be suitable for the polymer. For example, a decomposition
temperature for a blowing agent system for PVC should not be above the maximum possible processing
temperature

(3) Gases evolved should not corrode processing equipment

 Chemical Blowing Agents used in commercial use

44
 (8) Cross-linking Agents
 In order to produce thermoset plastics or vulcanised rubbers the process of crosslinking has to occur. Before cross-
45 linking, the polymer may be substantially or completely linear but contain active sites for cross-linking

 Such a situation occurs with natural rubber and other diene polymers where the double bond and adjacent alpha-
methylene groups provide cross-linking sites

 Term cross-linking agents is a very general one and covers:-

(a) Molecules which bridge two polymer molecules during crosslinking

(b) molecules which initiate a cross-linking reaction
(c) those which are purely catalytic in their action
(d) those which attack the main polymer chain to generate active sites

Figure: (a) Bridging agents (b) Cross-linking initiators (c) Catalytic cross-linking agents (d) Active site generators
 Examples:
46
 First type includes vulcanising agents, such as sulphur, selenium and sulphur monochloride, for diene
rubbers; formaldehyde for phenolics; diisocyanates for reaction with hydrogen atoms in polyesters and
polyethers; and polyamines in fluoroelastomers and epoxide resins

 Most well-known cross-linking initiators are peroxides, which initiate a double-bond polymerisation type of
cross-linking in unsaturated polyesters

 Catalytic agents include acids for phenolic resins and amino-plastics and certain amines in epoxides
 (9) Photodegradants
47  Cellulose films are biodegradable, i.e. they are readily attacked by bacteria, films and packaging from
synthetic polymers are normally attacked at a very low rate. This has led to work carried out to find methods
of rendering such polymers accessible to biodegradation

 General approach is to incorporate into the polymer (either into the polymer chain or as a simple additive) a
component which is an ultraviolet light absorber. However, instead of dissipating the absorbed energy as
heat it is used to generate highly reactive chemical intermediates which destroy the polymer

 Iron dithiocarbamate is one such photo-activator

 Once the photo-activator has reduced the molecular weight down to about 9000 the polymer becomes
biodegradable

 Some commercial success has been achieved using starch as a biodegradable filler in low-density
polyethylene

 Introduction of auto-oxidisable oil additives that make the polymer sensitive to traces of transition metals
in soils and garbage, film may be produced which is significantly more biodegradable than that from LDPE
itself

 Rate of degradation depend on the type and amount of photodegradant present and degree of outdoor exposure
and also on the thickness of the plastics article, the amount of pigment, other additives present and furthermore, the
type of polymer used
 (10) Sealants
Sealant is a substance used to block the passage of fluids through openings in materials, a type of
48 mechanical seal. In building construction sealant is sometimes synonymous with caulk (especially if acrylic
latex or polyurethane based) and also serve the purposes of blocking dust, sound and heat transmission.
Sealants may be weak or strong, flexible or rigid, permanent or temporary. Sealants are not adhesives but
some have adhesive qualities and are called adhesive-sealants or structural sealants

OR

Caulk is defined as any substance placed inside a joint for the purpose of creating a harrier &
prevent passage of air, heat, or water through that joint. The chief distinction between a sealant and caulk
is the response to joint movement. Because all building materials expand or contract according to
environmental temperatures.an ideal sealant material must he capable of withstanding this type of
phenomenon
Sealant is defined as a substance not only fulfilling the requirements of a caulk but also a material
capable of being extended and compressed without losing its sealing effectiveness

General Formulation: A sealant might typically consist of a formulation containing

the following:
(1) Polymer: Provides elastomeric and adhesive properties
(2) Plasticizer: Improves sealant flexibility and extrudability and reduces cost
(3) Filler Material: Provides reinforcing and lowers cost
(4) Additive: Used to improve and enhance specific aspects of sealant such as weatherability, adhesion, package
stability, and cure rate (the period of time it takes for a sealant to harden,or "set")
49 Types of Sealants:

(a) Low-Performance Sealants: It generally show little or no chemical curing after application; rather cure’
takes place by solvent or water evaporation. These sealants, although inexpensive, have little flexibility
and tend to crack when subjected to moderate joint movement

(b) Medium-Performance Sealants: Solvents based acrylics and butyl sealants are the two most
commonly used sealing compounds. Butyl sealants are relatively low in price and adhere to wide variety
of substrate. The chief drawbacks of solvent-based butyls are joint shrinkage (due to solvent loss) and
sealant stringiness during application

(c) Medium-Performance Sealants: High-performance sealants used are polysulfides, polyurethanes, and
silicones. All three of these sealants are chemically curing (cure takes place via chemical reaction after
extrusion from the cartridge), have little or no shrinkage, and possess excellent joint movement
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Aerospace sealants
(a) Firewall Sealants – a two-component, firewall sealant intended for use as a coating, sealant or filleting material in
the construction, repair and maintenance of aircraft and is especially useful where fire resistance, exposure to
phosphate ester fluids, and/or exposure to extreme temperatures, -65 °F (-54 °C) to 400 °F (204 °C) are major
considerations

(b) Fuel Tank Sealants – High-temperature fuel resistant sealant intended for use on integral fuel tanks with excellent
resistance to other fluids such as water, alcohols, synthetic oils and petroleum-based hydraulic fluids.

(c) Access Door Sealants – Access door sealant intended for use on integral fuel tanks and pressurized cabins with
low adhesion characteristics and excellent resistance to other fluids such as water, alcohols, synthetic oils and
petroleum based hydraulic fluids

(d) Windshield Sealant – demonstrated to be a useful sealant in a variety of applications where quick setting is desired,
for example, windshield sealants, repair caulks, adhesives, etc
Finished