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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 ? .
Cracking. loss of transparency. Loss of Gloss.e. Hindered Phenols or Aromatic Amines . 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. Hardness increases. Increase in Brittleness Melt Flow Instability Change in appearance. yellowing. 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.1 – 0.5%) Effect of Oxidation – – – – – – – – – – Loss in Tensile Properties Discolouration i.– • • • • Oxygen combines with Polymer under high temp to form carbonyl compounds which leads to yellow & brown discolouration.
Chelating Agents – Metal Deactivators • • Prevent degradation by metal ions (impurities in polymers – ziegler-natta redox initiators. tertiary phosphites & phosphorates. fillers. Peroxides are reduced to alcohols & are deactivated.Secondary Stabilizer – Peroxide decomposes • How it works? – • EX: – Sulphur & Phosphorus Compounds such as Sulphides.) EX: – – Organic Phosphines & Phosphites Higher Nitrogenated compounds – Melamine. pigments etc. 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 . thioethers.
During processing they form a thin film between polymer melt & metal surface.o 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. Modifies flow characteristics. • • • • Reduces thermal degradation of the polymer. 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. 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. Homogenous the polymer melt with other polymer additives. Metal Soaps . They improve surface finish & gloss. They have low compatibility with the polymer but have high affinity for the metal surface. They help to reduce melt viscosity and give a high output rate.
Cd Salt. lead. 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. 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. impact strength. . colour & clarity. having polar groups. They also enhance polymer properties like heat stability. Hydro carbon & Esters • Internal Lubricants Promotes Flow by reducing cohesive forces between molecular interfaces within the resin They are usually low molecular weight compounds.o o o o Metal Stearates Zinc Stearates Calcium Stearates Magnesium Stearates Hydrocarbon waxes Stearic Acid & its calcium. so used as external lubricants Long Chain Fatty Acids – Used as Internal Lubricants for polar polymers. Ba.
e. – – – – Phthalates – Di-Octyl Phthalate (DOP). Wt. e. Elongation at break & Impact. so act as external & internal lubricants. so used as external lubricants.g. High Molecular weight paraffin wax – low compatibility with polar polymer. Effect of Plasticizers Easy melt Improve flexibility Increase Softness and Flexibility. Types of Plasticizers • • Primary – These are highly compatible with PVC and can be used alone. Types of Plasticizers • • Secondary – These are less compatible with resin & and are usually employed together with primary plasticizers.g. Alters Softening point. ester type organic compounds. Adipates. Improve Process ability. Tensile Strength. Di Iso Octyl Phthalate (DIOP) Phosphates – Tricresyl Phosphate (TCP). Reduce internal friction between polymer chain.• • Long Chain di-alkyl esters – Medium compatibility. Plasticizers or softeners • • • • • • • • • • Improve process ability by reducing Tg These are high boiling non-volatile solvents Polar with a high Mol. – – Di Octyl Sebacate (DOS) Adipic Acid Polyesters . Sebacates.
It replaces the plasticizers without any adverse effect on polymer. Increase in modulus of elasticity. – – Epoxidised oil. Low Cost. Chlorinated paraffin wax. Lower shrinkage. oil extracts.– Extenders • • • • • e. In conjunction with true plasticizers it enhance the efficiency of plasticizers. . Increase in hardness. Effect of Fillers • The use of inert fillers can influence the polymer properties in the following ways :– – – – Increase in density. They are limited compatibility with polymer. Selection of Plasticizers Solvating power Efficiency Compatibility Flame retardant Toxicity Low Temp.g. Performance Cost FILLERS • It is used to modify mechanical properties & to reduce the cost. These are not used alone as plasticizers.
Reduction of raw material cost.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 .g.– – – FILLERS Purpose Bulk Increase in HDT. Calcium Carbonate. For e.
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 .
calcuim carbonate. mica – increases the compound rigidity. Compressive. Minerals such as talc. The product become stiffer and stronger than the base polymer. 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 . Fibrous Fillers & Reinforcement Glass Fibres – Increase (Tensile. elongation at break.Flexural ) Strength . creep resistance hardness and decrease thermal expansion co-efficient. Coupling Agents • These are used to increase the adhesion between polymer & filler.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. fiber by covalent bonds. improve the temperature resistance and reduces shrinkage & warpage. .Increase rigidity.
It may cause accumulation of dust.g. For film of 25 micron 0.01% of Oleamide • Anti block Agents : Prevent adhesion between the film surface Amount (0. Polyethylene glycol esters Slip & Anti block Agents • Slip : Reduces coefficient of friction. Esters. Acrylics & Acrylonitriles Because of insulation properties electrical charge may get deposited on the surface of the plastics produced during processing. Cellulosics. PP. Phosphates. Nylons. Urathenes.05 – 0.2%) . EX: Amines Quaternary ammonium compounds. The accumulation of static charge can be minimized by the use of antistatic agents.2% ) e. This may cause severe damage to the products & equipments.They are high molecular weight fatty alcohols Amount (0. PS.05 – 0. Polyesters.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.
4-alkyl-7-dialkyl amino coumarins. Inorganic Powders – Clays. e. Optical Brighteners are organic substance which absorb UV radation e. Must be colour less Must be odour less Must be non toxic Nucleating Agents • • Aiding transmission of white light in Plastics Forms large nos. Potassium. – – Sodium. – – – Colorants • Produces varieties of coloured polymers Benzosulphonic & Sulphonamides derivatives. Must not interface with the adhesion ink to film. Vinylene bisbenzoxazoles. Silica Flour Optical Brighteners • • It makes a mask over the yellowness formed during processing. of nuclei & reduces the size of spherulites.e.g.g.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 prevent the sealing of film. Lithium benzoates.
Yellow orange Lead chromate .White Cadmium sulphide .Yellow orange Chromium oxide .Green Organic Pigments : • • • • Benzidese – Yellow orange Copper phthalocyanine -Blue Chlorinated copper phthalocyanine Aniline black .BLack Selection of Colorants • Heat Stability .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 .• Also improves – – – Mechanical Strength Specific Gravity Clarity Colorants Dyes (Soluble in Polymers) » » » » » Impart brilliant transparent colour to clear plastics Inorganic & Organic AZOS (.
g. – – – – Chlorinated polyethylene . SBR is used for polystyrene material. Flame Retardants • Plastics + Fire –free radical formation combines with Oxygen – CO – CO2 .• • • • 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. 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.EVA are used for PVC.
No solid residue Trichlorofluromethane – PU foam Pentane and Heptane .Low cost. 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. Electrical. Blowing Agents Physical Blowing agents: Nitrogen & CO2 inert gas. 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 . cellular/foam plastics.• • • Application : Automobile.Building.Furniture. Aerospace.e.PS foam Chemical Blowing agents: High temp. Upon heating liberate Gas Are used to produce porous polymers i.Transportation.