Classification of compounding ingredients 1. Elastomers- natural and synthetic 2. Cross-linking agents 3. Accelerators 4, Activators and retarders 5. Antidegradents (antioxidants and antiozonants) 6. Fillers (reinforcing and Non reinforcing) 7. Processing aids (peptizers, plasticizers, softeners, and extenders) 8. Special purpose materialsElastomers ¢ Natural Rubber- Discussed in Unit1 ¢ Synthetic Rubbers — Will discussed in Unit 2Peptizers Elastomers exhibit higher viscosity because of high molecular weight so it is very difficult to incorporate fillers and other additives to the matrix. Viscosity control is the key challenging parameter for rubber compounding The peptizers are used to increase the efficiency of mastication of rubbers. Peptizers are added to the rubber at the starting of mastication, 0.5 phr or less is used. The main role of peptizers is to accelerate the oxidation rate; they act as an oxidation catalyst and prevent chain recombination. Renacit [V—Zinc salt of pentachlorothiophenol Pepton 44—Activated dithiobisbenzanilideActivators Activators are inorganic and organic chemicals used to activate the action of accelerators. These materials reduce the vulcanization time (cure time) by increasing the rate of vulcanization. Zinc oxide is generally used in combination with a fatty acid (stearic acid) to form an in situ zinc stearate in the rubber matrix. Zinc oxide and steric acid system is the generally used activator system in sulfur cured compounds. The normal dosage of zinc oxide is 2 to5 phr and stearic acid is 1 to 4 phr. The finer the particle size of zinc oxide, the higher is the effectiveness.Fillers * Fillers are defined as materials that are added to a polymer formulation to lower the compounding cost and mechanical improve properties. * Types of fillers — Based on Reinforcement * Reinforcing -impart good mechanical properties to the vulcanizates — (Carbon black-HAF,ISAF, pptd silica) * Non reinforcing -inert fillers are generally used to reduce the cost of the compound. — (GPF, clay, etc)* The reinforcing fillers, when incorporated in rubber matrix during mixing improve — the mechanical properties, such as tensile strength, modulus, abrasion resistance, hardness, and tear resistance. * They are classified as black and non black. * The reinforcement behavior of filler depends on — Particle size of filler (smaller particle size more reinforcing power) — Structure of filler (the higher the structure the higher the reinforcement) — Concentration of fillers (optimum filler loading imparts higher reinforcement) — Physical and chemical nature of filler — Porosity of filler* Carbon black is manufactured by four different process: furnace process, thermal process, channel process, and lamp black process. Nomenclature for carbon blacks Super abrasion furnace Intermediate super abrasion High abrasion fumace Fast extrusion fumace General purpose furnace Semireinforcing furnaceNon-reinforcing fillers ¢ Non-reinforcing fillers are also known as inert filler, generally used for reducing the cost of the compound. Details of nonreinforcing fillers and their specific gravity values Fillers si Fillers China clay Calcium oxide Calcium carbonate 24 Fumed anhydrous silica Calcium oxide (lime) 7 Precipitated amorphous hydrated silica Calcium siticate x Calcium hydroxide China clay (kaolin) 2 Magnesium silicate Magnesium oxide Lead oxide Aluminum hydroxide | 2. Zine oxide Aluminum silicate Titanium dioxide (rutile)Plasticizers * Aplasticizer is a substance that is added to a material to make it softer and more flexible * The plasticizers are classified * Petroleum-based Petroleum oils VGC Aniline point Aromatic Naphthenic Paraffinic 0.95—-1.00 0.85-0.9 0.78—0.82 25-SO°C 55-75°C 100—150°C Ester plasticizers — generally used in NBR and CR — dibuty! phthalate (DBP), dioctylphtalate (DOP), diisooctylphtalate (DIOP), trixylyl phosphate, and dibutylsebacate.Other processing aids * softeners and extenders in rubber compounding Name of processing aid Example Use Factice Vulcanized vegetable oils N-Cyclobexylthiophthalimide (CTP) Pine tar ‘Coumarone-indene resins High styrene resins Phenol formaldehyde resins Whole tyre reclaim Buty! reclaim Controls die swell, improves surface quality and preparation of soft compounds Retards the cure reaction Improves the tackiness of the compounds Tackifiers and plasticisers Good processability and high hardness Tackifiers and reinforcing agent Controls die swell and reduces the costAccelerators * The rate of vulcanization of a rubber compound is controlled by the selection of the accelerator. — The accelerators are classified according to the chemical structure Chemical class Chemical name Thiazole 2-Mercaptobenzothiazole Zine-2-mercaptobenzothiazole Dibenzothiazy! disulfide Guanidines Diphenyl guanidine Di-o-toluylguanidine ‘Sulfenamides: N-cyclohexyl-2-benzothiazolsulfenamide N-tert- butyl-2 benzothiazolsu 'fenamide 2-(4-Morpholinothiobenzothiazole N.N-dicyclohexyl-2-benzothiazylsulfenamide Dithocarbamates | Zine-dimethyl-dithiocarbamate Zine-diethyl-dithiocarbamate Zine dibutyldithiocarbamate Thiuramsulfides | Tetramethyl-thiurammonosulfide Tetrumethyl-thiuramdisulfide Tetraethy!-thiuramdisulfide Xanthates Zine isopropyl xanthates Sodium isopropyl xanthates Zine butyl xanthatesAccelerators based on functional action * According to their functional action the accelerators are classified as primary or secondary. * Primary accelerators show scorch delay (slow to delayed fast) and secondary accelerators are scorchy (fast curing) DPG, DOTG CBS, TBBS, DCBS, MBTS, MBS TMTM, TMTD, TETD ZIX, ZDMC, ZDECAntidegradents Most of the elastomers contain unsaturated hydrocarbons, which makes them subject to attack by both oxygen, ozone, light, and metal ions. Their properties are thus decreased with an increase in the service period. The antidegradant protects rubber compounds against the attack of oxygen and ozone. Typical loading levels are of the order of 1-4 phr. Antidegradants can be classified as — antioxidants = antiozonantsAntioxidants * There are two types of antioxidant used for the rubber compounding * They are amine and phenolic types. * Amine types are staining types and phenolic types are non-staining, used in colored compounds Amine-based antioxidants (staining antioxidants) Dihydroquinolines | 2,2,4-Trimethyl-1,2 dihydroquinoline 6-Ethoxy-2,2,4-trimethyl-1,2 dihydroquinoline Naphtylamines Phenyl-a-naphthylamine Pheny!-8-naphthylamine Phenol-based antioxidants (non staining) Monophenols Styrenated phenol 2,6-Di-t-buty! hydroxyl toluene Bisphenols 2,2'-Methylene-bis-(4-methyl-6-1er7.butylphenol)Antiozonants Amine-based antiozonants (staining) Paraphenylenediamines | N-(1,3-Dimethylbutyl)-’-phenyl-p- phenylenediamine NN -Dipheny!-pphenylenediam ine N-Isopropyl-N -phenyl-p-phenylenediamine Phenol-based antiozonants (nonstaining) Monophenols Styrenated phenol Other class Paraffin waxCuring agents The generally used curing agents are — sulfur, peroxides, and metal oxides. These materials are used to cross-link the rubber matrix These cross-links form different bonds, such as carbon-carbon, carbon-sulfur, and sulfur- sulfur linkages. The bond energy also depends on the type of cross-linking formed in the elastomer matrixSulphur ¢ The sulfur vulcanization was discovered in 1839 by Charles Goodyear. During vulcanization, the rubber molecule becomes cross-linked and a three-dimensional network structure is formed.Different types of sulfur vulcanization system Sulfur Accelerator Types of linkage formed Property improvementSulfur donors (sulfur bearing chemicals) Organic accelerators and similar compounds that release sulfur at vulcanization temperatures can also be used as vulcanization agents. These materials are added in 3-5 phr and form monosulfidic linkages with excellent heat resistance. ‘Sulfur donor Tetramethylthiuram disulfide (TMTD) N-oxydiethylene-N’-oxydiethy lenethiocarbamy Isulfonamide (OTOS) Dipentamethylenethiuramtetrasul fide (DPTT) 2-Morpholinodithiobenzothiazole (MBSS) Dithiomorpholine (DTDM) Caprotactam disulfide (CLD) Alkyl phenol disulfidePeroxides * Organic peroxides are normally used to cross-link saturated and unsaturated rubbers. * The peroxide is decomposed forming a free radical on the polymer chain. * The peroxide radical forms a carbon-carbon linkage with adjacent polymer chains. ~~ CMs Heat | CH, 2 CHa R ah Schematic representation of peroxide curing mechanism The unsaturated polymers such as NR, SBR, NBR, etc. can also be cross- linked with peroxide, but IIR is degraded by peroxideResin curing Phenolic resins are used to cure IIR. This cure system is widely used for the bladders used in curing new tyres, and the curing bags used in the retreading. The low level of unsaturation of IIR requires resin cure activation by halogen-containing materials such as SnClz or halogen-containing elastomers such as neoprene. The resin cured butyl vulcanizates have excellent heat resistanceMetal oxides curing * Polychloroprene rubber (Neoprene) and CSM are vulcanized with metal oxides. * The commonly used metal oxides are zinc oxide, magnesium oxide, lead oxide, etc.Special purpose additives Blowing agents Silane coupling agents Antistatic agents Flame retardantsBlowing agents * These are the materials generally used for the production of cellular/sponge rubber products. — 1. Inorganic blowing agents —release carbon dioxide gas E.g., Sodium bicarbonate, ammonium carbonates, ammonium bicarbonates — 2. Organic blowing agents—release nitrogen gas E.g., Dinitrosopenta methylene tetra amine (DNPT), Azodicarbonamide (ADC), Benzene sulphonylhydrazide (BSH)Silane-coupling agents * Silane coupling agents improve the mechanical properties of silica and silicate containing fillers. * Achemical bond is formed between the filler and the rubber matrix. The generally used silane coupling agents are bis- (3-triethoxysilylpropyl) tetrasulfane and 3-thio- cyanatopropyl triethoxysilane. The incorporation of coupling agents improves the cross-link density and tear properties; it reduces compression set, heat buildup and damping behavior.Antistatic agents ¢ Incertain rubber articles, such as conveyor belts, textile rollers, trolley wheels, andspinning cots, the buildup of static electricity is undesirable. * The generally used antistatic agents are quaternary ammonium salts or ethylene oxide condensateFlame retardants * These materials are added to rubber compounds for reducing their flammability; this is achieved by a mixture of organic and inorganic materials. * The generally used materials are antimony trioxide, chlorinated derivative of paraffin hydrocarbons, zinc borate.Typical Formulation TRUCK TYRE RETREADS NR-BR blend | Light Duty Material UR based sad tev R (RSS-1) 100.0 75.0 soo | iimast-7 0.4 0.1 o1 | 25.0 20.0 Cure 150°C-25min 150°C-25min 150°C-20min