ADDITIVES

Polymers unsuitable for processing in pure unmodified form e.g. Polyolefins Oxidative degradation due to heat and pressure during processing PVC - Degradation at processing temperature ADDITIVES Any Substance that is added generally in small concentration to resins in order to : Alter their properties Facilitate processing Change the physical, chemical or electrical properties of end products. Reduce the cost

Requirements of Additives Effectiveness in their function Stable under processing conditions Stable under service conditions Economic Compatibility with Polymer Matrix At molecular level Neither Volatile nor extrude to the surface Neither bleed nor bloom Must have low vapour pressure at high temperature Non Hazardous, non impart taste & odour

CLASSIFICATION Assist Processing Processing Stabilizer Lubricants - External Lubricants - Internal

Modify Bulk Mechanical Properties

Plasticizer Reinforcing filler Toughening Agents Fillers Diluents & extenders

Reduce Cost

Surface Properties Modifier

Antistatic Anti Slip Anti wear Anti block Adhesion Promoters Nucleating Agents Colorants

Optical Properties Modifier

Anti-Ageing

UV Absorbers Fungicides

Others

Blowing Agents Flame Retarders

Processing Stabilizers Prevent degradation which is caused by Heat Oxygen

What Happens ?

Oxygen combines with Polymer under high temp to form carbonyl compounds which leads to yellow & brown discolouration.

Primary Stabilizers Antioxidants Secondary Stabilizers Peroxide decomposes Chelating Agents Metal deactivators Special Stabilizers (Heat Stabilizers) for halogenated polymers

Antioxidants (Primary Stabilizer) They inhibit or retard the oxidative degradation of materials at normal or elevated temperature during processing, storage or service due to Heat Light Chemical Induction

How it works? It interrupt the chain reaction by combining with the free radicals forming a non reactive products

(Amount : 0.1 0.5%)

Effect of Oxidation Loss in Tensile Properties Discolouration i.e. yellowing, Increase in Brittleness Melt Flow Instability Change in appearance. Hardness increases. Loss of Gloss. loss of transparency. Cracking. Hindered Phenols or Aromatic Amines

Secondary Stabilizer Peroxide decomposes How it works? EX: Sulphur & Phosphorus Compounds such as Sulphides, thioethers, tertiary phosphites & phosphorates. Peroxides are reduced to alcohols & are deactivated.

Chelating Agents Metal Deactivators Prevent degradation by metal ions (impurities in polymers ziegler-natta redox initiators, fillers, pigments etc.) EX: Organic Phosphines & Phosphites Higher Nitrogenated compounds Melamine, diamine etc

Heat Stabilizers Prevent Degradation Absorb & Neutralize HCl gas evolved Prevent Oxidation reactions Prevent Discolouration Displace active substituents with stable substituents

Lead o o o o Tri Basic Lead Sulphate (TBLS) Dibasic Lead Sulphate (DBLS) Basic Lead Carbonate Dibasic Lead Phosphite

Organo-tin o o Dibutyltin meleates Dibutyltin bis mercaptides

Cadmium / Barium /Zinc o Cadmium/Barium laurates

Cadmium/Barium/Zinc Complexes

Synergistic Stabilizer Systems The term Synergism is used to describe the combined effect of two or more stabilizers, which is greater than the sum of the effects of the individual stabilizers used in isolation.

Effect (A+B) > Effect A + Effect B Lubricants or Flow Promoters Functions : To reduce friction between the material and the processing equipment. ( Adhesive forces) To reduce heat & wear between two surfaces either between the polymer molecules (Cohesive forces) or between the polymeric material and the equipment. Reduces thermal degradation of the polymer. Modifies flow characteristics. Homogenous the polymer melt with other polymer additives. To prevent the plastic from sticking to the mould surface during processing

Lubricants or Flow Promoters External Lubricants

Prevent friction between polymer melt & metal surface Prevent sticking to the metal parts They are usually high molecular compounds and have non-polar groups. They have low compatibility with the polymer but have high affinity for the metal surface. During processing they form a thin film between polymer melt & metal surface. They improve surface finish & gloss. They help to reduce melt viscosity and give a high output rate. Metal Soaps

o o o o

Metal Stearates Zinc Stearates Calcium Stearates Magnesium Stearates

Hydrocarbon waxes Stearic Acid & its calcium, lead, Ba, Cd Salt, Hydro carbon & Esters

Internal Lubricants Promotes Flow by reducing cohesive forces between molecular interfaces within the resin

They are usually low molecular weight compounds, having polar groups. They function by reducing intra-molecular friction before and during the melt formation of the polymer by promoting flow and reducing melt viscosity of the polymeric mass. They also enhance polymer properties like heat stability, impact strength, colour & clarity. Amine Waxes Ester Derivatives Glyceryl mono stearate Long chain esters Fatty Acids & Amides Ethylene bi stear amide Zinc Stearates

Selection of Lubricants Metal Soaps Low Compatibility with polymer, so used as external lubricants Long Chain Fatty Acids Used as Internal Lubricants for polar polymers.

Long Chain di-alkyl esters Medium compatibility, so act as external & internal lubricants. High Molecular weight paraffin wax low compatibility with polar polymer, so used as external lubricants.

Plasticizers or softeners Improve process ability by reducing Tg These are high boiling non-volatile solvents Polar with a high Mol. Wt. ester type organic compounds. Reduce internal friction between polymer chain. Effect of Plasticizers Easy melt Improve flexibility Increase Softness and Flexibility. Improve Process ability. Alters Softening point, Tensile Strength, Elongation at break & Impact.

Types of Plasticizers Primary These are highly compatible with PVC and can be used alone. e.g. Phthalates Di-Octyl Phthalate (DOP), Di Iso Octyl Phthalate (DIOP) Phosphates Tricresyl Phosphate (TCP), Sebacates, Adipates.

Types of Plasticizers Secondary These are less compatible with resin & and are usually employed together with primary plasticizers. e.g. Di Octyl Sebacate (DOS) Adipic Acid Polyesters

 Extenders e.g.

Epoxidised oil.

These are not used alone as plasticizers. They are limited compatibility with polymer. In conjunction with true plasticizers it enhance the efficiency of plasticizers. Low Cost. It replaces the plasticizers without any adverse effect on polymer.

Chlorinated paraffin wax, oil extracts.

Selection of Plasticizers Solvating power Efficiency Compatibility Flame retardant Toxicity Low Temp. Performance Cost

FILLERS It is used to modify mechanical properties & to reduce the cost.

Effect of Fillers The use of inert fillers can influence the polymer properties in the following ways : Increase in density. Increase in modulus of elasticity. Lower shrinkage. Increase in hardness.

 FILLERS Purpose Bulk

Increase in HDT. Reduction of raw material cost. For e.g. Calcium Carbonate,Red mud

Filler Wood Flour Saw dust Wood pulp Sisal / jute Purified cellulose Mica / Rock

Purpose Hardeners

Filler Inorganic Pigments Mineral Powders Metallic Oxides Powder Metals Graphite

Purpose

Filler

Chemical Resistance

Glass Fibres & Fabrics Synthetic Fibres & Fabrics Graphite Metallic Oxides

Thermal Insulation

Asbestos Ceramic Oxides Silica

Purpose Appearance

Filler Colour Pigments Dyestuffs Carbon Flakes Powder Metals Phosphorescent Minerals Woven Fabrics

Purpose Appearance

Filler Colour Pigments Dyestuffs Carbon Flakes Powder Metals

Phosphorescent Minerals Woven Fabrics

Fibrous Fillers & Reinforcement Reinforcing fillers are those which enhance the mechanical properties like : Tensile Strength Modulus Hardness of a polymer compound.

The product become stiffer and stronger than the base polymer. Fibrous Fillers & Reinforcement Glass Fibres Increase (Tensile, Compressive,Flexural ) Strength ,Increase rigidity, creep resistance hardness and decrease thermal expansion co-efficient, elongation at break. Minerals such as talc, calcuim carbonate, mica increases the compound rigidity, improve the temperature resistance and reduces shrinkage & warpage. Coupling Agents These are used to increase the adhesion between polymer & filler, fiber by covalent bonds.

Antistatic Agents Static charge may built up simply by friction with the ambient air Most plastics have low surface conductivity Static charge is not discharged fast enough

Troublesome effects like: Heavy contamination of plastics parts Shock as charge flows ( floor covering ,

door handles) Antistatic Agents Chemicals added to plastics to reduce built up of electrostatic charges on the surface of materials

Accumulations can occur during processing and at various handling points Static charges are dissipated by increasing the surface conductivity

Antistatic Agents Prevent electrostatic charges mostly seen in PE, PP, PS, Nylons, Polyesters, Urathenes, Cellulosics, Acrylics & Acrylonitriles Because of insulation properties electrical charge may get deposited on the surface of the plastics produced during processing. This may cause severe damage to the products & equipments. It may cause accumulation of dust. The accumulation of static charge can be minimized by the use of antistatic agents. EX: Amines Quaternary ammonium compounds, Phosphates, Esters, Polyethylene glycol esters

Slip & Anti block Agents Slip : Reduces coefficient of friction- They are high molecular weight fatty alcohols Amount (0.05 0.2% ) e.g. For film of 25 micron 0.01% of Oleamide Anti block Agents : Prevent adhesion between the film surface Amount (0.05 0.2%)

e.g. Calcium Carbonate in PVC film Metal Salts Fatty Acids Natural & Synthetic Waxy Materials

Selection of Slip & Anti block Agents Must not spoil optical properties. Must not interface with the adhesion ink to film. Must not prevent the sealing of film. Must be colour less Must be odour less Must be non toxic

Nucleating Agents Aiding transmission of white light in Plastics Forms large nos. of nuclei & reduces the size of spherulites. e.g. Sodium, Potassium, Lithium benzoates. Inorganic Powders Clays, Silica Flour

Optical Brighteners It makes a mask over the yellowness formed during processing. Optical Brighteners are organic substance which absorb UV radation e.g. Colorants Produces varieties of coloured polymers Benzosulphonic & Sulphonamides derivatives. Vinylene bisbenzoxazoles. 4-alkyl-7-dialkyl amino coumarins.

Also improves Mechanical Strength Specific Gravity Clarity

Colorants Dyes (Soluble in Polymers) Impart brilliant transparent colour to clear plastics Inorganic & Organic AZOS (,180 2000C) for brightness and clarity Anthraquinone (AQ) Good heat transparent weathearibility (Auto tube light)

Pigments (In-Soluble in Polymers) Inorganic Organic

Colorants

Inorganic Pigments : Titanium dioxide - White Cadmium sulphide - Yellow orange Lead chromate - Yellow orange Chromium oxide - Green

Organic Pigments : Benzidese Yellow orange Copper phthalocyanine -Blue Chlorinated copper phthalocyanine Aniline black - BLack

Selection of Colorants Heat Stability

Disperse ability Light fastness Chemical Inertness Opacity or transparency

Anti-Ageing Additives Deterioration by Atmospheric Radiation Temperature Oxygen Water Micro-Oranisms Gases etc

Ultraviolet Light Absorbers Detected by Loss in Tensile Properties Discolouration Brittleness

Impact Modifier e.g. Chlorinated polyethylene ,EVA are used for PVC. SBR is used for polystyrene material. EPDM is used for PP ( Bumpers) Acrylic rubbers for Poyamides To enhance the impact properties of certain brittle polymers so as to use in the field.

Flame Retardants Plastics + Fire free radical formation combines with Oxygen CO CO2

Application : Automobile, Aerospace, Electrical,Transportation,Building,Furniture, TV cabinet Flame Retardants Prevent Combustion by Insulate Creating endothermic cooling reaction Coating the product

Blowing Agents Blowing agents are also known as foaming agents. Upon heating liberate Gas Are used to produce porous polymers i.e. cellular/foam plastics.

Blowing Agents Physical Blowing agents: Nitrogen & CO2 inert gas- Low cost, No solid residue Trichlorofluromethane PU foam Pentane and Heptane - PS foam Chemical Blowing agents: High temp, Azo Dicarbonamide decompose on heating to produe free radicals and N2 gas EX: Ammonium bi carbonates Sodium bi carbonates Azo Di carbonamide Azo bis formamide N-nitrogen Compound Sulfonyl Hydrazides