additives
DESCRIPTION
chemicalTRANSCRIPT
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WELCOME
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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
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ADDITIVESAny 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
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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
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CLASSIFICATION
Assist Processing • Processing Stabilizer• Lubricants - External• Lubricants - Internal
Modify Bulk Mechanical Properties
• Plasticizer• Reinforcing filler• Toughening Agents
Reduce Cost • Fillers• Diluents & extenders
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CLASSIFICATIONSurface Properties Modifier
• Antistatic • Anti Slip• Anti wear• Anti block• Adhesion Promoters
Optical Properties Modifier
• Nucleating Agents• Colorants
Anti-Ageing • UV Absorbers• Fungicides
Others • Blowing Agents• Flame Retarders
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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.
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Processing Stabilizers
• Primary Stabilizers – Antioxidants
• Secondary Stabilizers – Peroxide decomposes
• Chelating Agents – Metal deactivators
• Special Stabilizers (Heat Stabilizers) – for halogenated polymers
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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%)
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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
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Secondary Stabilizer – Peroxide decomposes
• How it works?– Peroxides are reduced to alcohols & are
deactivated.
• EX:– Sulphur & Phosphorus Compounds such as
Sulphides, thioethers, tertiary phosphites & phosphorates.
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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
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Heat Stabilizers
• Prevent Degradation
• Absorb & Neutralize HCl gas evolved
• Prevent Oxidation reactions
• Prevent Discolouration
• Displace active substituents with stable substituents
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Heat Stabilizers• Lead
– Tri Basic Lead Sulphate (TBLS)– Dibasic Lead Sulphate (DBLS)– Basic Lead Carbonate– Dibasic Lead Phosphite
• Organo-tin– Dibutyltin meleates– Dibutyltin bis mercaptides
• Cadmium / Barium /Zinc– Cadmium/Barium laurates– Cadmium/Barium/Zinc Complexes
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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
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Lubricants or Flow PromotersFunctions :-• 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
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Lubricants or Flow Promoters
• External Lubricants
• Internal Lubricants
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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.
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External Lubricants• Metal Soaps
– Metal Stearates– Zinc Stearates– Calcium Stearates– Magnesium Stearates
• Hydrocarbon waxes
• Stearic Acid & its calcium, lead, Ba, Cd Salt, Hydro carbon & Esters
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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.
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Internal Lubricants
• Amine Waxes
• Ester Derivatives
• Glyceryl mono stearate
• Long chain esters
• Fatty Acids & Amides
• Ethylene bi stear amide
• Zinc Stearates
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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.
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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.
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Effect of Plasticizers
• Easy melt
• Improve flexibility
• Increase Softness and Flexibility.
• Improve Process ability.
• Alters Softening point, Tensile Strength, Elongation at break & Impact.
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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.
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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– Epoxidised oil.
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Extenders
• 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.e.g.
– Chlorinated paraffin wax, – oil extracts.
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Selection of Plasticizers
Solvating power Efficiency Compatibility Flame retardant Toxicity Low Temp. Performance Cost
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FILLERS
It is used to modify mechanical properties & to reduce the cost.
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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.– Increase in HDT.– Reduction of raw material cost.– For e.g. Calcium Carbonate,Red mud
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Fillers
Purpose Filler
Bulk Wood Flour
Saw dust
Wood pulp
Sisal / jute
Purified cellulose
Mica / Rock
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Fillers
Purpose Filler
Hardeners Inorganic Pigments
Mineral Powders
Metallic Oxides
Powder Metals
Graphite
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Fillers
Purpose Filler
Chemical Resistance Glass Fibres & Fabrics
Synthetic Fibres & Fabrics
Graphite
Metallic Oxides
Thermal Insulation Asbestos
Ceramic Oxides
Silica
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Fillers
Purpose Filler
Appearance Colour Pigments
Dyestuffs
Carbon Flakes
Powder Metals
Phosphorescent Minerals
Woven Fabrics
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Fillers
Purpose Filler
Reinforcement Glass fibres
Asbestos Fibbers
Cellulose Fibbers
Cotton Fibbers
Papers
Synthetic Fibbers
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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.
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Fibrous Fillers & ReinforcementGlass 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.
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Coupling Agents
These are used to increase the adhesion between polymer & filler, fiber by covalent bonds.
Ex: Methacrylato-chromo chloride used for glass fibres & Polyester resin
Organosilanes are used for PVC , ABS and PA
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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)
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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
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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.
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Antistatic Agents
• EX:– Amines– Quaternary ammonium compounds, – Phosphates, – Esters, – Polyethylene glycol esters
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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
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Slip & Anti block Agents
• 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
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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
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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
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Optical Brighteners
• It makes a mask over the yellowness formed during processing.
• Optical Brighteners are organic substance which absorb UV radation
e.g. – Benzosulphonic & Sulphonamides
derivatives.– Vinylene bisbenzoxazoles.– 4-alkyl-7-dialkyl amino coumarins.
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Colorants
• Produces varieties of coloured polymers
• Also improves
– Mechanical Strength
– Specific Gravity
– Clarity
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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)
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Colorants
• Pigments (In-Soluble in Polymers)– Inorganic– Organic
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ColorantsInorganic 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
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Selection of Colorants
• Heat Stability
• Disperse ability
• Light fastness
• Chemical Inertness
• Opacity or transparency
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Anti-Ageing Additives
• Deterioration by Atmospheric – Radiation
– Temperature
– Oxygen
– Water
– Micro-Oranisms
– Gases etc
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Ultraviolet Light Absorbers• Detected by
– Loss in Tensile Properties– Discolouration– Brittleness
• EX:– Black in any form : Carbon Black, Black dye, Black paints– Benzophenones – for PE, Polyesters– Benzotriazoles – for PS, Polyesters
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Impact Modifier• To enhance the impact properties of
certain brittle polymers so as to use in the field.
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
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Flame Retardants
• Plastics + Fire –free radical formation combines with Oxygen – CO – CO2
• Application : Automobile, Aerospace, Electrical,Transportation,Building,Furniture, TV cabinet
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Flame Retardants• Prevent Combustion by
– Insulate– Creating endothermic cooling reaction– Coating the product
• EX: - Aluminium trihydrate ( Nylon)– Antimony trioxides (ABS)– Chlorinated Paraffin– Zinc borate– Halogen Compounds– Phosphorous acid esters ( PA,POM,FRP)– Nitrogen Compounds
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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.
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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
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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.
• EX:– Ammonium bi carbonates– Sodium bi carbonates– Azo Di carbonamide– Azo bis formamide– N-nitrogen Compound– Sulfonyl Hydrazides
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Master Batches,Additives & Reinforced Compounds
Material Supplier
Master Batches S.C.J. plastics Ltd. New Delhi
www.scjindia.com
Master Batches & Reinforced Compounds
Aalekh Polymers (P) Ltd.
8/30, Kirti Nagar New Delhi =15
Ph. No. 25195193
Polymer additives Fine organics Bombay 022-25116900-02
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THANK YOU