«fs, ¢3 egppicsscio fn TOPIC: SILICONE RUBBERS GVHD: TS. Cao Xuan Vist Student: NGO TRAN DANG QUANG-2114506 LE BUC ANH - 2012589 HCMUT April 2024CONTENTS 1. Introduction 2»Formation History 3.Silicone Market 4.General properties of Silicones 5.Manufacture of Silicones 6. Classify 7.Processing Methods 8.Vulcanization mechanism and processing method 9. ApplicationsIntroduction licones are synthetic polymers with a silicon-oxygen backbone similar to that in silicon dioxide (silica), but with organic groups attached to the silicon atoms by C-Si bonds. The silicone chain exposes organic groups to the outside, Thus, despite having a very polar chain, the physical properties of silicones are similar to those of The Si-O bond energy is much larger than the C-C bond energy and this enables the -Si-O-framework of the silicone to give the polymers thermal stability, as in silica, and so y they can be used where comparable organic materials would melt or decompose. 1Introduction To distinguish between different silicones, systematic names are used, based on the monomer. The simplest silicon is silane, SiH4 which belongs to the homologous series of silanes. Silanes correspond to the alkanes Whose simplest member is methane, CH4. y 4 A y Tee Lee H 4 i ae A A The presence of the oxygen atoms in the silicone chain is indicated by using the systematic name, siloxane, so termed as it contains a silicon atom, an oxygen atom and it is saturated as in an alkane. y 2Introduction if the groups attached to the siloxane chain are phenyl groups, the resulting silicone is called poly(diphenylsiloxane) and has these repeating units along the chain. vv ry Ue] A O AIntroduction T widely used silicones are those which have methyl groups along the backbone. Properties such as solubility in organic solvents, water-repellence and flexibility can be altered by substituting other organic groups yeimethyl groups. ‘example, silicones with phenyl groups are more flexible polymers than those with methyl groups. y are also better lubricants and are superior solvents for organic compounds. he structure of the repeating units of silicones can be represented as: d Wy R A ACIT 4 vv R represents organic groups attached to the silicone backbone, for example: A y y CH—- fe HE—=CHHe gractacrs methyl phenyl ethenyl trifluoropropy A AA AIn 1771, people synthesized the first covalent substance of silicone, SIF4. yy. Morrison produced metallic silicon by reducing SiO2 using carbon in an electric arc furnace. 7 s yo y Kipping is considered the father of organosilicon chemistry. He used Grignard agents to create compounds with the general formula R4-xSiCIx. 4 In 1930, Corning Glass made the first efforts to find uses for silicon compounds. A + In 1940, Rochow discovered a direct synthesis of methylchlorosilane by passing methyl chloride gas. through a solid mixture of silicon and copper at high temperature (250-3000C). y 6ea eee ae Ser KER 9 Supreme SiconesGeneral properties of silicones High binding energy The siloxane bonds (-Si- O-Si-) that form the backbone of silicone (dimethyl polysiloxane) are highly stable. At 433 k)/mol, their binding energy is higher than that of carbon bonds (C-C), at 355 kJ/mol. Thus, compared to common organic polymers, silicone rubbers have higher heat resistance and chemical Stability, and provide better electrical insulation. ¢ Heat resistance « Flame retardancy ¢ Chemical stability © Good weatherability * Radiation resistance * Electrical properties 8Intermolecular force is low, and coil formation capacity is Silicone molecules are helical and intermolecular force is low, resulting in high elasticity, high compressibility, and excellent resistance to cold temperatures. Furthermore, the methyl groups located ‘on the outside the coil structure can rotate freely. This characteristic gives silicone its distinctive interfacial properties, including water repellency and good releasability. © Water repellency * Cold resistance ¢ Releasability * Good compression characteristicGeneral properties of silicones ‘Comparison of properties of various rubbers using natural rubber as a reference vv oe Vv ¥ y rons y (Chemical resistance (Cold resistance y 10Heat and cold resistance ‘Operating life of silicone rubber in high-temperature conditions (Orage et as tinea whi orion a beak 172 ol ae) set 160180 200 220240260 Temperature (0) oer any et pn sent ter a ac ‘omanpon se ners eryapet dhe ae Silicone rubber withstands high and low temperatures far better than organic rubbers. Silicone rubber can be used indefinitely at 150°C with almost no change in its properties. It withstands use even at 21 10,000 hours or more, and some products can withstand heat of 350 short periods. Silicone rubbers are thus suitable as a material for components used in high temperature environments. 4 Silicone rubber also has excellent resistance to cold temperatures. embrittlement point of typical organic rubbers is between -20° and compared to -60° to -70°C for silicone rubbers. Even at tem Which organic rubbers turn brittle, silicone rubber remains el products withstand extremely low temperatures of -100°C and Some itWeatherability Results of long-term outdoor exposure testing of various rubbers \condtons | _Time uti surface cracks are first apparent (years) | Tim ot sunght expasure nt elongation s 1/2 at of he nial ae (ears) ber type Panama Rock sland Panama ‘Rock sland 1 [styrene butadiene 2-35 Over 10 years 4 10 ee 05-1 | = 7 | o i croropene = [ = 85 [over to years 7 sitcone (meta vy) ‘ver toyears | _Over 10 years Over tOyears | Over t0years to decine to 75% 4 sitcone (methyiobenyt) = [ = Over 10years | ——_Over tOyears ‘i = I = os | 4 ttyene propylene = | = 10 [lover 8 years to decine to 75% uorie 0 0 (ver 10 years to dein to 90% Silicone rubbers have exceptional weatherability. Ozone created by corona discharge rapidly deteriorates most organic rubbers, but has almost no effect on silicone rubber. In addition, silicone rubber can be exposed to wind, rain and UV rays for long periods with j ¥irtually no change in its physical properties. 12Eee Riche le} ‘Steam resistance of silicone rubber (%owing steam 21064 NPs) (Change intensie strength ‘Change in elongabon ——1—1— KES KET6HT KE-951 ° 1 ° 0 1 a a ee) ar a ae) 0 0 2% 0 0 0 o Tie (days) Time (¢ays) Time (days) ‘lonatin at break (*%) See. = “a Tensile strength (MPa) Sticone rubber can be immersed in water (cold water, warm water, boling water) for log periods with water absorption of about 186 snd wth Virtually no effect on mechanical strength or electrical properties. Typically, under ordinary pressure, contact with steam causes almost: no deterioration of silicone rubbers. With pressurized steam, however, the effects increase as steam pressure increases. High pressure steam at smperatures over 150°C causes breakdown of the siloxane polymer and a decline in the properties of the rubber. This effect can be ameliorated by adjusting the slicone rubber formula, selecting a proper curing agent, and/or post-curing. There are numerous products available with, improved resistance to steam and hot water 13. LX Valet Bo) Temperature range and various oils applicable to various rubbers “i nme i hh i ato ec ts ls, solvents, and other chemicals Silicone rubber has outstanding resistance to oll at high temperatures. Among common organic rubbers, nitrile rubber and chloroprene rubber have somewhat higher oll resistance at temperatures below 100°C, but at higher temperatures silicone rubber is superior. Silicone rubber also has excellent resistance to solvents and chemicals. It is essentially unaffected by polar compounds (aniline, alcohol, etc.) or dilute acids or bases, wi the increase in volume due to swelling in the range of only 10% 15%. Silicone rubber does swell in non - polar organic cnt. bezene, toluene and gasoline; but unlike most organi ru does not decompose or dissilve, and will return to er state when the solvent it removed. Silicone rubber Is, a adversely affected by strong acids and bases, so it sh used where it will come in contact with such chemicals 14Moisture and steam resistance Ol and chemical resistance of common methyl vny silicone rubber fmm nat ‘rage reper amen “Can | Harespons [Weigh % | Voume | Tiegh [gabon 7S a 10s 168 10 Compression set Creep properties of rubbers* (temp. tad When using rubber materials for gaskets that will be under compression in heated conditions, 120 the abilty of these materials to recover Natural rubber compression deformation is. a 100 a tenaeraion, The compressa oa bee rubber is consistent over a wide temperature = croroprena range, from -60° to +250°C. Although the 3 Styrene aaa compression set of typical organic rubbers & 0 ee relatively low around room. temperatu increases significantly as temperatures 40 SIlicone rubbers generally require. post Post-curing and selection of a proper curing Furor agent are_ particularly som en using slicone rubber to make for lige rubber 10 700 7,000 Time (hour) which low compression set is desired. 20Tear strength and tensile strengt! Temperature dependency of rubber strength Tew sera Tense sea The tear strength of slcone rubber is generally around 9.8 KNim. There ‘re high-strength avalable with strength between 29.4 kam and 49, sc tush Vv 2 andjor judicious of filers and cross ‘These products, ar for -. ‘arg reverse and items — wher ‘strength is required. “ent strangt (MPa) Tear svengh Crescent ees (Ne) s atl a Cr ee) Temperature (*) Temperate 0) ‘eT seng osteo aber a oem terpeateesfeorat o oe bee uscone ter marta seg betes bon rere sh al hwo early ade pices one ah 21Bir Uae arta RE CLC} Comparison of the tear strength of silicone rubbers (temp.: 23°C) za & — Tear strength test crescent piece) En 3 E a e953 2 | Keast 3 aa 3 4 5 : g z 22Gas permeability ‘Compared to organic rubber or plastic films, thin films of silicone rubber have better gas and vapor permeability, have selectivity. One application for silicone rubber being investigated is as a gas and water separation and th name in oxygen enrichment systems. y y wy ‘Comparison of gas permeability with natural ubber=100 for reference (25°C) = aaa A | pau meee m4 a at m8 as pee = ‘an [em | a0 [ano [ar te Baha ewe «ps 5 ‘ ‘a ro) oil [EN wai |v nel ewe | nT = a al sa ais ma | ome es] a ce 6 =| eit [er alt ast | io a ea ape = enn 60888 cia 7 i — Piva 2 f +: z = ei i ¢ 2 2 1 = a 4 & A.Water vapor permeability of plastic films Material Water vapor permeability* Silicone rubber 15.5-51.8 A PVA 0.04-40.0 Ethylcellulose 21.5 “ Polyethylene 0.05-4.85 Seal aaa Polytetratluoroethylene (PTFE) 2.94 Polycarbonate 1.0 Nylon 0.32-0.63 24Transparency and coloring properties Most organic rubbers are black due to their carbon content. In contrast, it is possible to make highly transparent silicone rubber because the fine silica it contains does not spoil the natural transparency of silicone. Shin-Etsu has developed high-transparency high-strength silicone rubbers that are used for tubing and molded items in the food industry. Its high transparency makes silicone rubbereasy to colorwith pigments, so manufacturers can produce colorful molded items. 25ECE ene ie Ula Common silicone rubber (dimethyl silicone rubber) really has no bet ter tadiation resistance than other organic rubbers. Methylphenyl silicone rubber, which features phenyl groups added to the polymer molecules, resists radiation and is used in the manufacturing of the cables and connectors used in nuclear power plants. Silicone rubber with added phenyl groups has the same fine heat resistance, electrical insulating properties, flame retardancy and chemical resistance intrinsic to other silicone rubbers. 26ECE eee Ula At high temperatures, although q 2 natural rubber and other organic y i rubbers show a decline in - performance due to thermal 4 “| degradation, — silicone —_rubbr resists radiation even at ae temperatures of 200°C-300°C A Pre REE 1 : : ‘ i enone 27—— SE aa hn in at 28Al eye Uae letolgs) The loss modulus (tan (1) of silicone rubber is generally low, making it ill-suited for use as ition insulator. Products with enhanced vibration absorption performance, however, a vibration consistently over a wide temperature range, from -50°C to +100°C. Lace moss (an) Tepentue (0) e tard « 2. tony oan Sn ‘neue we yr ee pe ‘nee enon a A y \ A 29Releasability and N * Silicone rubber is chemically inert with good release properties, so it does not corrode other materials. Silicone rubber is thus used for the fixingrollers, printing rollersand sheets of photocopiers, and for lost-wax casting. Living tissues are affected by contact with silicone rubber to a lesser degree than by exposure to other organic polymers. Silicone rubber is physiologically inert, and is thus used for baby bottle nipples and stoppers in medical applications. In addition, it is pleasant to the touch with a high-grade feel, making it ideal for leisure items such as swimming caps and goggles. 30Manufacture of TT jilicones are manufactured from pure silicon which has been obtained by reduction of silicon dioxide (silica) in the form of sand with carbon at 7” temperatures: SiO(s) + 2C(s) —> Si(s) + 2CO(g) a) synthesis of chlorosilanes b) hydrolysis of chlorosilanes C) condensation polymerization y 31 A production of silicones from silicon takes place in three stages: aManufacture of TT (a) Synthesis of chlorosilanes Silicon is first converted into chlorosilanes, e.g. RSiCI3, R2SiCI2 and R3SiCl, where R is an organic group. When chloromethane is passed through heated silicon at about 550 K under slight pressure and in the presence of a copper catalyst (often copper itself but other copper-containing materials can be used, for example, brass or copper(II) chloride) a volatile mixture of chlorosilanes distils over. For example: Si(s) + 2CH3Cl(g)—* (CHs)2SiCl,(g) 32Manufacture of silicones The mixture of liquids produced contains these three compounds: Hs gts qs Me Vv 7 y y cl—si—Cl cl—si—Cl CI—Si—CH3 | | | dl cl CH; CH3 CHSiCls (CH3)SiCl (CHs)3SiCI A Careful distillation of the liquid mixture of chlorosilanes produces A fractions of each chlorosilane. Dimethyldichlorosilane is the main product y (ca 70-90%, the amount depending on the conditions used). 33Manufacture of silicones (b) Hydrolysis of chlorosilanes “Waktorsiane is hydrolyzed to a molecule with two hydroxyl groups: v i i CFG +2140 —e HOON + ae y i k product is a disilanol. The suffix -ol in a silanol is to show that the molecule contains at lea: ‘one hydroxyl group attached to a silicon atom and the simplest example is dimethyldisilanol: e A l Gerad CH y dimethyldisilanol 34Manufacture of silicones The hydroxyl groups of silanols react spontaneously to form a siloxane: vy v If R is a methyl group, the polymer is a poly(dimethylsiloxane). Poly(dimethylsiloxanes) are produced with n = 20-50, which is not long enough to produce useful silicones. ese relatively short polymers are known as oligomers. Cyclic polymers, for example Wissrscy, are also produced and then separated out. >. b> GH cry \ ~ ¥ Ho“ / wo ft ons a o° 35Manufacture of silicones he oligomers are washed and dried. The hydrochloric acid produced when the chlorosilanes are hydrolyzed a y recycled and reacts with methanol to regenerate chloromethane: d Y Gama) AS AManufacture of silicones (c) Condensation polymerization ‘Gre oligomers condense rapidly in the presence of an acid catalyst to form long chain polymers: Hy Hy re & a 7 y y The value of (m+n) is usually between 2000 and 4000. The production of lor chains is favoured if the water is removed, for example by working under vacuum. y 37Manufacture of silicones (i) Cross-linking is often effected by first synthesizing silanes with a functional group, in place of a roup, that will react further. For example, a silane containing an ethenyl (vinyl) group s_ethenylmethyldichlorosilane, can be added to, for example, dimethyldichlorosilane, er with ethenyl groups in the chain, the chains are also able to undergo free radi ‘an reactions, in a similar way to the free radical polymerization of chloroethene ‘int chloride). This leads to cross-linking between the polymer chains. As with this polymerization, addition reactions are initiated by radicals supplied on decomposition of an organic peroxide (for ple, dicumy! peroxide): R—O:—O—R —> 2RO° Hg where R = ©- i an CH; . fkFofjsexample, the windows of the capsules are made of reinforced glass (using polyvinyl butyral, PVB_as the laminate) which is anchored to the metal frame with a silicone resin. This resin is prepared in situ from two components one of which isa silicone with alkoxy groups which provide the cross-linking needed to form the resin. The result is that the capsule can withstand winds of 280 km h-1 . These systems are also being used in buildings which are considered to be vulnerable to terrorist attacks, the glass, resistant to bomb blasts and bullets, will keep in place because of the very strong bonding to the metal frames. 39Manufacture of silicones (ii) Cross-linking can also be achieved by using siloxanes with ethenyl (vinyl) groups and other siloxanes containing Si-H groups, with a platinum compound as catalyst: Vv fone * es =~ aaa V hs, bu 8 A (il) A further Way of producing cross-linking is to have an ethanoyl group in the silane. When these silicones are exposed to the air, the moisture reacts with the functional group, yielding a cross-linked silicone. An organometallic tin compoun ee the reaction. These systems are often used as sealants and can be used in the home. The other product form én joic acid which can be recognized by its vinegary smell. If some methyltrichlorosilane is added to the reactant, say dimethyldichlorosilane, the three chlorine ato hydrolyzed, thus producing a three dimensional network. CHLSiCl, + 3H,0 —» HO-Si—OH + sHCL on all four methods, the physical properties of the silicone can be modified by varying the proportions of the reactants, Which controls the extent of cross-linking and hence how rubbery is the product. 40Rauition Aiton ‘Addition Condensation) — (‘Condensation Pecataly Pecatalysed Preatalysed) —{ Sm-catalysed Sn-catalysed Fig 4: Curing method Networking at room temperature, single component. Networking at room temperature, two components ligh temperature curing, solid silicone rubber, high density rubber y ~~ LR: Liquid rubber, liquid silicone rubber (also cured at high temperature) 41RIV (Room temperature ulcanisation) 10-40 shore A‘One-part room-temperature-vulcanizing (RTV-1) silicones are ready- to-use systems consisting of polysiloxane, a curing agent, fillers and additives. Immediately after application, the material starts crossiinking on contact with moisture in the air. Byproducts are ‘eleased during curing. Crosslinking starts with the formation of ‘askin on the rubber surface and gradually progresses into the compound. Depending on the nature of the crosslinker, small ‘amounts of acetic acid, amine or neutral byproducts, such as alcohol, are released during vulcanization. RTV-1 silicones are ideal for sealing, bonding and coating applications innearly all industries, such as: 43naa ‘Two-part room-temperature-vulcanizing silicones (RTV-2) are \ pourable, spreadable or kneadable formulations that vulcanize after mixing, produces one of three physically different product types: solid elastomers, gels and flexible foams. There are two different types of erossiinking reactions: by condensation or by addition. ‘Condensation curing requires an organotin catalyst and always Feleases byproducts. Addition curing requires a platinum catalyst and does not generate any byproduct. ' Ci T~ ‘Special RTV-2 silicone rubber grades can be flash vulcanized using UV light. The vulcanization time can be controlled by adjusting the UV Intensity and exposure time. Like RTV-1 silicones, RTV-2 formulations are ideal for almost al ‘sealing, bonding and coating applications, where they are used for the sy i| "IRTV ‘Technology cua fue RTV-1, one-component Room Temperature Vucanizing, is based | RTV-2, two-component Room Temperature Vulanizing, are silicone cn paly-condensation reaction. This type of silcone rubber is __| rubber formulations made by associating a base to curing Definition ‘made with an OH terminated sllcone polymer, crosslinker and a | elements. The curing is achieved by crosslinking, initiated by catalyst. Te latter being in most ofthe case an organic tin mixing the two components and occurs by condensation, using an compound, ‘organictin or, by addition reaction witha platinum catalyst. The Shore A hardness can be modulated from 18 to 60. RTV2 is avalable ina vscosty hardness range varying from soft to General information medium, usually from 15 to 40 Shore A RTVel features convenient characteristics such as easy RRTV2 features several advantageous characteristics, Induding ease application, soft curing conditions, good adhesion, weather and | of application and processing, light viscosity and good flowability, Typical properties | heat resistance. low shrinkage, no deformation, customizable hardness, resistance Vulcanization (curing) (Curing Mechanism (Polycondensation) re-mxed compounds for specific processes and in-vacuum or N2 to high and low temperatures, acd and alkali, thus generating highly durable products, ‘Curing Mechanism (Polyaddition) ‘Curing Mechanism (Polycondensation) Raw materials mixed for specific processes and equipment, and Processability protection, subsequently elspensed by toos, wth defined then cured moisture evacuation and curing times. ‘pplication/final | RTV-115 used in construction Industal sealing and Bonding, | RTV-2)s used In tote coating, mold mating, release coating, 3D products sets, healthcare products, coatings etc or adative printing, cock instruments, potting of engine ectronics and gasketing 45MAYA Cam eee Coral eV ola) N | 2 LRorLSRHCR (Heat Cured Rubbe: Heat Cuted Rubber elastomers are also known as High Temperature Valeanizing silicone rubber (HTV). They are made from reactive silicone ‘gums, in other words, straight chains, with very high molecular weight maefortolécules containing various reactive groups. The most frequently —~ used gums are either partly phenylated or perfluorinated vinylated gums. Various raw materials are added to give additional properties to the HCR 21g; fred oF precipitated silicas with high specific surface area to improve ~ mechanical properties, heat stabilizers and various other additives such as plasticizers or anti-structuring agents. Cross-linking occurs using organic peroxides in polycondensation systems or platinum catalysts in \ ~ polyaddition systems. Heat-ering slicone rubber is used in a diverse range of applications across II all kinds of industries:LR or LSR (Liq Ligh Sticone Rubber (LSR) isa two-component system, where long polysiloxane chains are reinforced with specially treated silica. Component. ‘A contains a platinum catalyst and Component B con irogensiloxane as a cross-linker and an alcohol inhibitor. meer differentiator between liquid scone rubber (LSR) and high con: rubber (HCR) is the “flowable” or “liquid” nature of LSR. 15, While HCR can use ether a peroxide or a platinum curing ;, LSR uses only additive curing with platinum. Due to the mosetting nature of the material, liquid siicone rubber injection molding requires special treatment, such as intensive distributive mixing, ‘hile maintaining the material at a low temperature before it is pushed into the heated cavity and vulcanized. — Ax > GHTV Addition cure Peroxide cure Addition cure Cure System Process Addition | Manual Party automation none Alittle None By-product Cure rate Fast Very fast Law material Liquid Solid Material loss Little Many Large volume article & Difficult Deliicate articles production sss Cycle time Long Small quantities production | Not suitable Suitable 49delet methods HTV grades are processed by conventional methods, such as extrusion, injection, transfer and compression molding, and by calendering Veo Process ‘Solid Siicone Ruboor guid Sitcone Rubber Exivsion x Coemuten x ‘Comerossen mortng x ‘Yanster molding x ‘nection motsing x x caienserng Low pressure ting x owwscosty grades) y 50Extrusion isa continuous manufacturing process in which silicone rubber is forced through a die and then vulcanized. The extrudate its shape. The necessary pressure is via a conveying screw, in which the material is nized, compressed and vented main challenge for manufacturers using this technique is to se the right grade of silicone rubber with the adapted catalyst system that will perform best in their specific ‘mechanical and temperature and speed-controlled processes and will enable the final products to meet specifications, criteria and comply with regulatory standards. ided products include: Tubing Profiles “Cables es ‘Schematic diagram of an extruder fitted with a crosshead de -Round cords y 51Ceryiil oles ‘Compression molding processes are used for a wide range of HR is cured in molds by heat and pressure. For this , the silcone rubber remains flexible and then placed in a ‘mold and closed using a sealed clasping system, with Movable (00) ‘applied to force the material to fil the entire cavity. The a ‘and pressure are maintained unti the slicone has cured. + Slicone rubber E Compression and injection molding are similar in that they fil a Fred potions: y preformed cavity, but they are different in that compression ‘mold hal ‘molds are prefilled directly with the charge, while in injection the charge Is injected into a previously fully closed cavity. Ejector: main advantages of compression molding processing include: ‘Schematic diagram of compression molding) fi Lower tooling costs Very little waste of material providing ~Cost effective, especially for large parts Useful for some very large parts that cannot be made with extrusion molding Designing aesthetically creative parts, y -Used in several industries, including keypads for computers, kitchenware, electrical parts and some medical and dental devices. 52Compression and Transfer Molding “Transfer molding is similar to compression molding in several ways: It uses HCRS, pressed from an auxiliary chamber (known as a Pot) into a closed pressurized mold system that incorporates a heated container above the mold where the slicone rubber is larged using 2 piston-powered gate and runner system that can move relatively hard materials into the mold before heating. ne rubber transfer molding process is ideal for manufacturing high precision silicone molded parts as well as ‘overmolding’ r materials, thus enabling the molding of complex geometries. The combination of HCR and the transfer molding process leads uality, manufactured parts that offer design flexibility and shorter production cycles. nsfer molding differs from compression in that the mold is fully enclosed and not in two parts. For this reason, it also differs injection molding in that requires higher pressure to fil the mold. This also allows transfer molding to accept added fibers or ‘on its outer layers, to produce customized reinforced parts. A in advantages of transfer molding ene ing include: ~\ uced tooling costs tome Infor, accurate and more consistent parts = a ~ ‘compared to compression molding due to the a — pass ‘one-piece mold and high dimensional tolerance - - coon “Efficient and agile capacity for accepting ee = different reinforcement fibers pre-positioned fat” _— oa TTT in the mold, including glass, carbon and cons fue anaes ate ‘aramid, as well as natural plant fibers. ‘Transfer molding process 53Tal tsrertted amc tel ia) Injectionsmolding is the most popular and efficient process for mass- [producing products that must meet strict demands for consistently high quality. It is characterized by high dimensional accuracy, produces high- quality parts without the need for secondary finishing, and allows much shorter production cycles than other processes. The disadvantages are higher mold and machine costs, though these are offset by the high productivity. Injection molding is ideal for small to medium-sized parts and large production runs, such as -Nipples for baby bottles Gasket rings 54Due to the thermosetting nature of the material, LSR injection molding requires special treatment, such as intensive distributive yy" maintaining the material ata low temperature before it 's pushed into the heated cavity and vulcanized. jection, like its HR counterpart, is used for creating molded end-products in cavities. The LSR process uses unheated id oF viscous material that is pumped by an injection nozzle into the mold cavity. The raw material is simply funneled into the sed heated cavity using pressure, instantly filing the cavity. y ‘The main advantages of LSR injection molding include: -Short and accurate molding cycles -High volume production -Efficient and economical processing Versatility for making a wide range of general-purpose products: -Fast curing and excellent mold release hae asd LLSR (Liquid Silicone Rubber) injection molding process: aaa “tT 55High Consistency Rubber (HCR) injection mold ‘amount of HCR is injected directly from a cylinder through a screw mechanism and a nozzle Into a closed heated mold, through a ‘material fills and packs the cavities of the mold to form the part. ¥ ‘main advantages of HCR injection molding include: y Short and accurate molding cycles f SF unit costs: Low waste of material Possibility of mixed molding with other materials (Ex: plastics or metals) Consistent production in terms of finished products “Superior precision and fling for complex parts compared to, compression or transfer molding. HCR injection molding process y 56Textile Coating / Calenderi (Calenideting is a mechanical process that involves compressing and calender: Z calender: smoothing @ material in a continuous manner by moving a sheet Coating weight: over Coating weight: over through pairs of heated rolls. These double or multiple hard steel rol $00 g/m* 500 g/m? known as calenders. They are adjusted for pressure to Solid rubber a predetermined and uniform thickness, surface finish and re for silicone rubber which can be shiny, matte, smooth, (OF embossed, etc. he raw material, typically HR, which determines the mechanical properties ofthe finished product, is previously heat softened or , ‘extruded and then forced through the aligned cylindrical rolls. The ‘calendering process presses the uncured silicone preform into a inuous silicone sheet. The silicone can then be pressed onto rious substrates such as release film liners or combined with a fariety of fabrics, glass, plastic, etc. “The main advantages of calendering processing include: Schematic diagram of calendering -High-volume, continuous processing of quality products -Standalone sheets (unsupported) delivered in protective liners or products in combination with other materials, including Organic oF artical fabrics (Polyamide, viscose, polyesters, etc), glass, plastics, etc. Almost endless applications, from liners for construction, home products, clothing, upholstery, food contact products, industrial p conveyor belts, autoclavable products for medical applications etc 57HTV Addition cure Cure System Addition Peroxide cure Manual Addition cure Party automation By-product none Very fast Large volume article & Pe a Deliicate articles production cae Cycle time Short Not suitable Small quantities production Alittle Long None Solid Many Difficult Suitable 58VULCANIZATION MECHANISM AND PROCESSING METHOD Quartz ( the sand) | vy ee cc Silicon vy : T fn spam y y silica — d v HTV LR RTV-1 RTV-2 y 59RUBBER CURING (VULCANIZATION) OF SILICONE om oy ta wa-0- = Ob a soe Fy nH sae Mer 3 a ¢. et ¢ oo coffe + pe + fap * ? a anil Poymer chain end Curng agent Peter cain enc ane Pt Catalytic oo es tefol Bote Radical Condensation y Fig 1: Curing method 601 t ° heap ets whororf _ : ; sien mace ! 9 ° a--n eden Leeds staat a ~o eGo es -When adding the Platinum catalyst, the Si-H groups ofthe 1 ‘ ' ' agent react withthe vinyl groups of the polymer to form a three- | 2 $ mn ° dimensional network. | me nt “Production of HTV, RTV-2 and LSR f & Z ig 2: Pt catalytic mechanism in the curing process osRUBBER CURING (VULCANIZATION) OF SILICONE ERE Cee eee ee af 4 y fh | y Figures Reaction mechanism of the condensation curing process of RTV-1 or RTV-2 systems 62ROOR ——> 2R0e The initiator used is an organic initiator. At high temperatures, substances decompose into free radicals. Free radicals react with polymer chains to form three-dimensional network with high elasticity. -Production of HTV 7 “Table 4 Perorides used in curing slid silicone rubber HIV For moulding Dosage ‘Reacts with (Ch) Dicumyl prone as 98% crystals o Hon CO, 07% 68%) | _ vinyl peste (Co) 25. bs-bupiperony}2 Saimetybesans a 4% iw ATV aber | 12% ‘slaps Fer exirsion Dosae ‘eats with (B 2.4coodbenzoyperonde, 0% in icone ‘ing and ety soaps 7 63 y.., 2: Radical mechanism in the curing processROH + ROH -During condensation curing, the terminal hydroxy groups of the polymer react with the curing agent siloxane, releasing A volatile compounds such as alcohols, acetic acid, and amines. “Production of RTV-1 & RTV-2. y 64 ‘Table 26 Summary of general purpose mould making condensation and addition curing materials (bold letters highlight the most important properties of each material) wesw Yo | atte] me | = [ees (ELASTOSIL®) (mPas) | (Shore A) (N/mm?) (%) (N/mm) (%) ‘M1470 Kneadable 10° 50 45 230 >10 02 ‘M2471 ‘Spreadable 250,000 35 45 170 >7 04 M4400, Pourable, soft 25,000 23 25 250 >3 ‘M4440 Pourable, hard | 25,000 7 20 200 23 M4503 Pourable, soft 40,000 2s 50 ‘350 >20 M4514 Pourable, soft 25,000 25 45 450 >25 'M4600A/B Addition | Pourable, soft 15,000 20 70 800 >20 'M4601A/B Addition | Pourable, soft 15,000 28 65 700 > 'M4642A/B Addition | Pourable, hard | 15,000 a” 70 ‘550 >30 Pa ba ‘i PeA. INHIBITORS: Reduces catalyst activity reases product retention time in the mold for convenient processing mmon catalytic inhibitor + Unsaturated organic compounds + Acetylene dicarboxy salt + Acetylenenic alcohol ‘+ Fumarate and maleate salts B. STABILIZERS: Mainly to optimize heat and environmental resistance. ‘Some commonly used stabilizers: metal complexes, metal salts of inorganic acids... a 4 PLASTICIZER A A. ‘Added to increase the catalytic properties and adhesion of the product. ‘+ Usually MDxM liquid POMS resins D. ADHESION ‘= Use when you need to increase adhesion on difficult-to-stick surfaces such as glass, metal or plastic ‘+ People often use adhesion enhancing agents such as y-aminopropyltrimethoxysilane, y glycidoxypropyltrimethoxysilane ‘+ Some other additives include iron oxides and rare earth oxides y increase heat resistance, platinum to increase fire resistance, pigments... 67E, FILLER rs not only reduces the price of the product but also helps enhance certain properties of silicone rubber products. llers ne rubber are divided into two main types: F. rcement filer R’ LER of inert fillers is to help reduce the cost per unit of product. In addition, they also have a number of other effects such stability, creating color or increasing electrical conductivity of the product. Products. of inert fillers include powdered calcium carbonate, clay, silicate and aluminate salts, titanium oxides, aluminum oxides, = Oxide pigments: increases heat resistance and oxidation resistance temperature environments black: increases electrical conductivity and creates color 1003 powder, clay, silicate salts,. . REINFORCEMENT FILLER ‘+ Reinforcing filers are used to increase the physical and mechanical properties of silicone rubber products such as strength, abrasion resistance... + The most common type of reinforcing filer for scone rubber sslica filer, used in many forms such as slica fume, precip dehydrated silica gel, silica mulch and finely ground natural silica. * Reinforcing fillers ‘Smoked/Precipitated silica hydrated silica gel. 68* Detrosters + Hot air brushes APPLICATION: Consumer electronics Heat resistance, cold resistance, electrical insulation Heat resistance, weatherability, 00d coloring properties, * Microwave oven window gaskets ~~ Heat resistance * Microwave oven drive belts -- Low compression set 69APPLICATIONS Office automation equipment ‘Keypads of calculators, -_Conductivit, electrical insulation, computer keyboards flex fatigue resistance : Conductivity, tame rtardancy, oo tharmal conductivity ‘* Photocopier (PPC) rollers:APPLICATION: Automobiles Oil resistance, heat resistance, cold resistance, flex fatigue resistance + Spark plug boots Oil resistance, heat resistance + Waterproof connectors Heat resistance, oil resistance Heat resistance, cold resistance, + low compression set, steam resistance + Diaphragms, O-rings + Hoses ‘Turbo chargers Heat resistance, ol resistance + Intercooler hoses flex fatigue resistanceElectrical wiring + Lead wires of mators and home electronic goods + Heatar wires of rice cookers, otc. + Refrigerator defroster wires Electrical insulation, heat resistance, * Ignition wires Tes cold rostered sara earch TOKAI flame retardancy 72APPLICATIO! Machinery = Low frequency therapy devices -.. Conductivity * Lost-wax casting Heat resistance, non-adhesiveness * Solar hoses Chemical resistance, weatherability ‘* Hot stamping rollers Heat resistance, low compression set * Vibration insulation rubber Vibration absorption CaAPPLICATIO! Food * Gaskets for pressure cookers, Steam resistance, chemical resistance, electronic rice cookers and kets “” low compression set * Milking machines Transparency, high tear strength * Nipples Transparency, physiological inertness * Food container gaskets Low compression setLeisure 2 seeuns Goggles ‘Transparency, high tear strength, = Mouthpieces opera ens Ste B congls ace physiological inertness % a}Um 1 Silicones. (n.d.). http://www.essentialchemicalindustry.org/polymers/silicones. html 2, Materials science for a better future. (n.d.). https://www.dowcorning.com/content/publishedlit/01-3077.pdf 3 ie kj thu&t co khi Cao su Trinh Phat. (2019, August 29). Cao su Silicone la gi? - Cao su Trinh Phat. Cao Su Trinh vat. Phi /Jcaosutrinhphat.com/cao-su-silicone-la-gi/ se: Silicone la gi? (n.d.). &Copy; 2014 - caosu.net.vn. https://caosu.net. n/hoi-dap-trong-nganh-cao-su/cao-su-silicone-a~ 2. php 5, Wikipedia contributors. (2024, April 1). Silicone rubber. Wikipedia. https://en.wikipedia.org/wiki/Slicone_rubber 6. Mazurek, P., Vudayaairi, S., & Skov, A. L. (2019). How to tailor flexible silicone elastomers with mechanical integrity: a tutorial review. Chemical Society Reviews, 48(6), 1448-1464. httpsi//doi.org/10.1039/c8cs00963e bout silicone rubber ~ properties, applications and uses. (2023, September 18). https://www.thomasnet.com/articles/plastics- ‘fabout-siicone-rubber/ A 8, The Ecltors of Encyclopaedia Britannica. (2024, February 22). Silicone | Definition, Composition, Properties, Uses, & Facts Encyclopedia Britannica. https:// www.britannica.com/science/siliconeyref17197 ‘9, Room-Temperature-Vulcanizing Silicone rubber (RTV-1/RTV-2). (nud.). Wacker Chemie AG. https:// www. wacker.com/ems/ Lus/products/product-groups/silicone-rubber/room-temperature-silicone-rubber. html 10. Céc nha cung cp, nha san xuét, nha may silicone lut héa nhiét 46 phong cia Trung Quéc - Gié bén buén - YIRUN. (n.d). https: /vn.xysiliconeink.com/silicone-ink/silicone-compounds/room-temperature-vulcanized-slicone-rtv.html 11. Unknow. (2022, September 30), Silicone elastomers (RApra review Reports). dokumen.tips. https://dokumen.tips/documents/silicone- ‘elastomers-rapra-review-reports.html?page=72.