IJOER-FEB-2018-6

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Effect of different sulfur content in Natural Rubber mixtures on their thermo-mechanical and surface properties

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International Journal of Engineering Research Science IJOER ISSN: 2395-6992 Vol-4 Issue-2 February- 2018 Page | 28 Effect of different sulfur content in Natural Rubber mixtures on their thermo-mechanical and surface properties Kinga Tamási 1 Mariann Szabóné Kollár 2 Department of Ceramic and Polymer Engineering University of Miskolc Hungary Abstract— In this study a field experiment was conducted to find out the effect of different levels of sulfur on natural rubbers mixtures. Vulcanization is a chemical process for converting natural rubber or related polymers into more durable materials by heating them with sulfur other equivalent curatives with accelerators. These additives modify the polymer by forming cross-links bridges between individual polymer chains. Vulcanized materials are less sticky and have superior mechanical properties. The results indicated that the application of sulfur -as a vulcanasing agent-had significant effect on mechanical Shore A hardness test thermal DSC calorimetry and surface-optical properties SEM microscopy of mixtures. Keywords— vulcanization sulfur natural rubber additives cross-links. I. INTRODUCTION By far the most common vulcanizing methods depend on sulfur. Sulfur by itself is a slow vulcanizing agent and does not vulcanize synthetic polyolefins. Even with natural rubber large amounts of sulfur as well as high temperatures and long heating periods are necessary and one obtains to an unsatisfactory crosslinking efficiency with unsatisfactory strength and aging properties. Only with vulcanization accelerators can the quality corresponding to todays level of technology be achieved. The multiplicity of vulcanization effects demanded cannot be achieved with one universal substance a large number of diverse additives comprising the "cure package" are necessary. The combined cure package in a typical rubber compound consists of sulfur together with an assortment of compounds that modify the kinetics of crosslinking and stabilize the final product. In this study the following sulfur quantities were used per samples: S1380 g S276 g S31140 g S41520 g S519 g at pressure 220 bar and temperature 145°C and t10 minutes. II. THEORETICAL APPROACH OF VULCANISATION WITH SULFUR Vulcanization is a chemical process that converts natural rubber elastomers into cross-linked polymers. The most common vulcanization agent is sulfur. It forms bridges between individual polymer molecules when heated with rubber. Often a catalyst and initiator is added to accelerate the vulcanization process. The cross-linked elastomers have much improved mechanical properties. In fact unvulcanized rubber has poor mechanical properties and is not very durable. The cross-linking process is rather complicated and involves a sequence of reactions. A free-radical mechanisms was originally assumed which has been described in great detail by Paul J. Flory 1953 and others 1. However all evidence points to an ionic mechanism because neither radicals could be detected nor do free-radical inhibitors and retarders effect sulfur vulcanization whereas organic acids bases as well as solvents of high dielectric constant accelerate sulfur cure 2. A possible reaction mechanism for polyisoprene natural rubber is shown below. The process starts with the formation of a persulfonium ion I by reaction of an isoprene unit with a polarized sulfur molecule or with a sulfur cation. The persulfonium ion reacts than with another isoprene unit by allylic hydrogen abstraction to produce a polymeric allylic carbocation II. In a third step a sulfur molecule cyclic S8 combines with the allylic cation to produce another sulfonium ion IV which releases monomeric sulfur. The polymeric sulfonium ion then undergoes crosslinking by anionic addition to a polymeric double bond to create a new carbocation V which then either reacts with another sulfur molecule or it abstracts hydrogen from another isoprene unit to create a new polymeric cation II. In a third step a sulfur molecule cyclic S8 combines with the allylic cation to produce another sulfonium ion IV which releases monomeric sulfur. The polymeric sulfonium ion then undergoes crosslinking by anionic addition to a polymeric double bond to create a new carbocation V which then either reacts with another sulfur molecule or it abstracts a hydrogen from another isoprene unit to create a new polymeric cation II.

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International Journal of Engineering Research Science IJOER ISSN: 2395-6992 Vol-4 Issue-2 February- 2018 Page | 29 FIG.1. A POSSIBLE REACTION MECHANISM FOR POLYISOPRENE WITH SULPHUR The polysulfide crosslinks formed by these reactions may contain four to six sulfur atoms at low temperatures whereas at higher reaction temperatures shorter sulfur bridges are formed. Vulcanization of rubber by sulfur alone is extremely slow and can take several hours at elevated temperatures 140°C or more. This is problematic because long exposure to temperature and oxygen leads to oxidative degradation which in turn results in poor mechanical properties. It is also not very economical. To minimize rubber degradation and to speed-up the vulcanization process accelerators are usually employed. Vulcanization of rubber by sulfur alone is an extremely slow process and can take several hours at elevated temperature 140°C or more. This is problematic because long exposure to temperature and oxygen leads to oxidative degradation which in turn results in poor mechanical properties 3. It is also not very economical. To minimize rubber degradation and to speed-up the vulcanization process accelerators are usually employed. An accelerator is defined as a compound that increases the speed of vulcanization and that enables vulcanization to proceed at lower temperature and with greater efficiency. Accelerator also decreases the amount of sulfur needed to cross-link the polydiene which improves the aging properties of the vulcanized rubber. Some of the accelerators also function as sulfur donors and thus allow vulcanization to proceed at lower sulfur content. The accelerators can be further classified as primary and secondary accelerators. The primary accelerators are typically used at 0.5 to 1.5 phr. The vulcanization speed of these systems can range from slow to ultra fast depending on composition and type of accelerator. Common primary accelerators include thiazoles and sulfenamides whereas thioureas and dicarbamates can function as both primary and secondary accelerators. Very fast are thioureas and dicarbamates see table below and semi-fast are thiazoles whereas aldehydeamines and guanidines are rather slow. Some other curatives such as sulfenamides are fast curatives and cause a delay in the onset of vulcanization which is often desired in rubber processing because it increases the scorch time. Both the cross-link density and the cure speed depend on the type and dosage of accelerator or in other words the number of sulfur atoms in the sulfur bridges their average number per polymer and the reaction rate depend on the type and composition of the sulfur cure system. Many of the sulfur-based vulcanization systems require activators. For example dithiocarbamate and thiazole accelerators are activated with zinc oxide and stearic acid which also increase the speed of vulcanization.

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International Journal of Engineering Research Science IJOER ISSN: 2395-6992 Vol-4 Issue-2 February- 2018 Page | 30 TABLE 1 ACCELERATORS SYSTEM 4 Compound Chemical Structure Side Groups R Guanidine Moderate R Phenyl Toluoyl R Alkyl Dithiocarbamate Very fast R Phenyl Toluoyl R Alkyl Thiuram Very fast R Alkyl 2-Mercaptobenzothiazole Moderate Zinc-2-mercaptobenzothiazole Very Fast Thiourea Very fast R Alkyl Phenyl Benzothiazole Sulfenamide Fast - Delayed Cure R H Alkyl R Phenyl Isopropylxanthate Ultra Fast Me n+ Zn 2+ Na + An important factor in the vulcanization process is the cure temperature which also affects the crosslink density and structure. To minimize thermal and oxidative degradation vulcanization should be done at the lowest possible temperature. However to increase productivity higher cure temperatures are often chosen. In our study we used the follow vulvanisation’s system: sulfur with ZnO stearic acid and bis 2-benzothiazole disulfide MBTS. III. APPLIED MATERIALS AND METHODS 3.1 Natural Rubber NR Natural Rubber is an elastic substance obtained from the latex sap of trees especially those trees which belong to the general Hevea Brasiliensis. Technically speaking natural rubber is an elastomer or an elastic hydrocarbon polymer. Natural rubber is one of the types of rubber that also include vulcanized rubber which is finished into a variety of rubber products. Natural rubber is also known by the names of India rubber gum elastic and caoutchouc 4.

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International Journal of Engineering Research Science IJOER ISSN: 2395-6992 Vol-4 Issue-2 February- 2018 Page | 31 The raw material from which natural rubber is made comes from the sap of rubber trees. The rubber plants are tapped for collecting the rubber latex. For this an incision is made into the bark of the rubber tree and the latex sap is collected in cups. After collecting the latex sap the raw natural rubber is refined to convert it into a usable rubber. Initially an acid was added to the latex which used to make the sap set like a jelly. The latex jelly thus obtained was then flattened and rolled into rubber sheets and hung out to dry. In the year 1839 Charles Goodyear invented a more sophisticated way of making rubber stronger and more elastic. This was the process of rubber vulcanising. The unprocessed natural rubber is sticky deforms easily when warm and is brittle when cold. In such a state it cannot be used to make products having a good level of elasticity. Vulcanization prevents the polymer chains from moving independently. As a result when stress is applied the vulcanized rubber deforms but upon release of the stress the product reverts to its original shape. FIG.2. CHEMICAL STRUCTURE OF NATURAL RUBBER cis-14-polyisprene AND GUTTA PERCHA trans-14- polyisoprene 5 3.2 Vulcanisation’s system 3.2.1 Sulfur The cross-linking reaction between sulfur and rubber occurs mainly at the carbon-carbon double bonds CC in large excess of sulfur. Often accelerators are added to speed up the vulcanization and to reduce the amount of free sulfur which has a detrimental effect on the properties of the cured rubber. 3.2.2 Bis 2-benzothiazole disulfide MBTS The most widely used primary vulcanization accelerators are thiazoles. They form sulfur bridges between individual polymer molecules when heated with rubber. Often an initiator is added to accelerate the vulcanization process. This process is rather complicated and involves a sequence of reactions. A possible reaction mechanism for 2-2’-Dithiobis benzothiazole MBTS accelerated sulfur vulcanization of rubber is shown below. In the absence of an initiator MBTS reacts with a sulfur molecule cyclic S8 to form a polysulfide sulfurating agent which then reacts with a rubber unit to form a crosslink precursor and a 2 - mercapto-benzothiazole molecule MBT. Two of these MBT molecules react to form MBTS again whereas the sulfurated rubber decomposes into a rubber-polysulfide and MBT radical. Assuming a radical mechanism 6 MBT polysulfide radicals combine to form new sufurating agents and/or they react with rubber to form more rubber crosslink precursors whereas the polymeric persulfenyl radicals either combine or react with other rubber molecule to form sulfur bridges i.e. cross-linked rubber Figure 3.. Thiazoles are only medium fast curatives. To increase their cure speed they are usually combined with small amounts of basic accelerators such as diphenyl guanidine DPG or diorthotolyl guanidine DOTG. These accelerators not only increase the cure speed but also improve scorch delay and crosslink density and thus improve the mechanical performance of the rubber. Furthermore activators such as ZnO / stearic acid are usually added which further increase the efficiency of sulfur based cure systems and produce flat cure with improved reversion resistance. The activity of an accelerator depends on three major factors: the basicity of the amine the strength of the sulfur-nitrogen bonds and the concentration of MBTS. The greater the basicity of the amine the shorter is the scorch delay and the faster is the cure rate. Sterically hindered amines secondary amines usually improve scorch safety and result in slower cure. The same is true for more stabilized S-N bonds.

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International Journal of Engineering Research Science IJOER ISSN: 2395-6992 Vol-4 Issue-2 February- 2018 Page | 32 The activity of thiazoles and sulfenamides and other accelerators in vulcanization systems also depends on the type of rubber and the vulcanization condition that is accelerators can have very different reactivities in different rubber systems and can lead to different crosslink densities 3. FIG.3.MECHANISM OF MBTS AND Zn CATALYSTS 3.3 Activators for sulfur vulcanization 3.3.1 Stearic acid and ZnO Typical rubber vulcanization systems consist of rubber sulfur accelerator metal oxide and fatty acid where the last two ingredients represent the activator. They are important rubber processing additives that not only activate cure but also improve the efficiency of sulfur based cure systems. In fact almost all organic accelerators require the addition of an organic activator to achieve the desired cure and end-use properties. The most common activator is zinc fatty acid ester which is often formed in-situ by reaction of fatty acid with zinc oxide. The most common fatty acids include stearic lauric palmitic oleic and naphthenic acid. The fatty acid solubilizes the zinc and forms the actual catalyst 6. The ZnO can also act as a filler or white colorant in rubber products whereas the fatty acid improves filler incorporation and dispersion by wetting the oxide particles and reducing interfacial tension wetting agent. The addition of activators in combination with secondary alkaline accelerators also allows for a more controlled onset of cure. The mechanism of zinc catalyzed sulfur vulcanization is very complex and is often not fully understood 7. The main catalyst is zinc whereas the fatty acid functions as a solubilizing agent for the zinc which forms a complex with sulfur in the accelerator-polysulfide or is covalently bonded to sulfur atoms in the accelerator molecules as shown below. Both the solubility and reactivity increases if the zinc coordinates with an amine or amide for example with sulfenamide. The chelated amines increase the nucleophilicity of the sulfur in the polysulfide complex and thereby increase the reaction rate of precursor formation. The exact position where zinc complexes in the accelerator complex is often unknown 8. Three possible structures of a Zn – polythio-bisbenzothiazole complex are shown below. The position of the zinc in the accelerator complex affects both the reaction path and the product distribution:

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International Journal of Engineering Research Science IJOER ISSN: 2395-6992 Vol-4 Issue-2 February- 2018 Page | 33 FIG.4. THE ZN-ACCELERATOR COMPLEX 8 The accelerator complex plays an important role in both the insertion of sulfur atoms into the complex and in the formation of initial polysulfidic crosslinks. 2 As it is the case with other catalysts remarkable small quantities of solubilized zinc are needed to initiate and speed up the vulcanization process. In the case 2-2’-dithiobisbenzothiazole MBTS the zinc is assumed to complex with the nitrogen atom of a benzothiazole ring 8 as shown below. FIG.5. THE COMPLEX WITH THE NITROGEN ATOM OF A BENZOTHIAZOLE RING 8

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International Journal of Engineering Research Science IJOER ISSN: 2395-6992 Vol-4 Issue-2 February- 2018 Page | 34 The zinc catalyst lowers the energy of dissociation of the sulfur bonds and allows for faster insertion of sulfur molecules cyclic S8 into the polysulfide sulfurating agent which then reacts with rubber to form a crosslink precursor and 2-mercapto- benzothiazole MBT. The later reacts with another MBT molecule in the presence of zinc to form another MBTS-zinc complex. Assuming a radical mechanism 8 the cross-link precursor cleaves homolytically into a rubber-polysulfide and polysulfidic benzothiazole radical. The later reacts with rubber to form a new cross-link precursor whereas the polymeric persulfenyl radicals either combine or react with other rubber molecules to form sulfur bridges. The crosslinks that are formed initially are predominantly polysulfides. During post cure or service life these polysulfidic crosslinks can degrade desulfurate to more stable mono or disulfidic crosslinks which changes the original rubber properties markedly and/or the polysulfidic crosslinks degrade to elastically ineffective cyclic sulfides or pendant groups. The reaction rate of these post-vulcanization reactions is higher for longer sulfur bridges since the S-S bonds are weaker when the crosslinks are longer. 3.4 Carbon black Carbon blacks are mainly used as reinforcing fillers in tire and other rubber products. The reinforcement effect is influenced by the interaction between the elastomer molecules between the carbon black particles themselves and between the carbon black particles and elastomer matrix also. For elastomer reinforcement the primary particle size specific BET surface area a surface activity of the carbon black types are important as well as their carbon black structure. In addition the degree of carbon black dispersion achieved and the carbon black loading used in the elastomer composite play a role. The type of carbon black can significantly influence the properties of the resulting rubber compounds. This explains the existence of many different standardized industrial carbon black grades being used in rubber compounds for the body and tread of tires. Carbon blacks are expected to continue to dominate the rubber market for the foreseeable future but they are coming under considerable pressure from precipitated silica in some important tire applications. This is because the silica offers lower rolling resistance properties and hence improved fuel economy and lower emissions. This trend is expected to continue to grow. 3.5 Sunflower oil Plasticizers make it possible to achieve improved compound processing characteristics while also providing flexibility in the end-use product. Ester plasticizers are selected based upon cost-performance evaluation. The rubber compounder must evaluate ester plasticizers for compatibility processibility permanence and other performance properties. They are in production include sebacates adipates terephthalates dibenzoates gluterates phthalates azelates and other specialty blends. This broad product line provides an array of performance benefits required for the many elastomer applications such as tubing and hose products flooring wall-coverings seals and gaskets belts wire and cable and print rolls. Plasticizer- elastomer interaction is governed by many factors such as solubility parameter molecular weight and chemical structure. Compatibility and performance attributes are key factors in developing a rubber formulation for a particular application. Sunflower oil is a monounsaturated MUFA/polyunsaturated PUFA mixture of mostly oleic acid omega-9-linoleic acid omega-6 group of oils. The oil content of the seed ranges from 22 to 36 average 28: the kernel contains 45–55 oil. The expressed oil is of light amber color with a mild and pleasant flavor refined oil is pale yellow. Refining losses are low and the oil has good keeping qualities with light tendency for flavor reversion. The oil contains appreciable quantities of vitamin E sterols squalene and other aliphatic hydrocarbons 9 10. TABLE 2 COMPOSITIONS OF MASTER BATCH FORMULATIONS Material Weight g Sample 1. Sample 2. Sample 3. Sample 4. Sample 5. NR 15200 15200 15200 15200 15200 Stearic acid 455 455 455 455 455 Carbon black 7600 7600 7600 7600 7600 ZnO 760 760 760 760 760 MBTS 091 182 274 365 456 Sulphur 380 760 1140 1520 1900 Sunflower oil 3000 3000 3000 3000 3000

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International Journal of Engineering Research Science IJOER ISSN: 2395-6992 Vol-4 Issue-2 February- 2018 Page | 35 The parameters of mixing procedure were the follow: the vulcanisation’s temperature at 145°C pressure at 220 bar during 10 minutes. The amount of sulfur and MBTS were increased proportionally show Table 2.. Base mixtures of NR carbon black antioxidant zinc oxide and stearic acid were prepared in a Banbury internal mixer with a rotor speed of 65 rpm. Curatives were added on an open two-roll mill in a second stage mixing. The base mixes were then crossblended using a masterbatching technique to ensure uniform dispersion of the ingredients and to minimise between-mix variations. The termo-mechanical and optical properties of the mixtures were examined by a Short A hardness tests DSC differential scanning calorimetry and a SEM scanning electron microscope instruments. The next chapter contains the results of them. IV. RESULTS AND CONCLUSION The Shore A hardness test of the rubber samples containing different Sulphur showed was a significant difference between Sample 1 and Sample 5. Fig. 6.. The results demonstrate the influence of sulphur and MBTS during the different stages of the vulcanization. With sulfur present the crosslinked product distribution is influenced as well. FIGURE 6. a. THE MINIMAL AND b. MAXIMAL VALUES OF SHORE A HARDNESS TEST FIGURE 7. THE AVERAGE VALUES OF SHORE A HARDNESS TEST NR-based master batches even when similarly compounded exhibit different cure behavior and cure properties depending on the cure system used the duration and temperature of cure. The results of DSC tests show that the difference between the samples Fig.8.. DSC differential scanning calorimetry is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. Both the sample and reference are maintained at nearly the same temperature throughout the experiment. Differential scanning calorimetry can be used to measure a number of characteristic properties of a sample. Using this technique it is possible to observe fusion and crystallization events as well as glass transition temperatures Tg. DSC can also be used to study oxidation as well as other chemical reactions. In this case we checked the process of vulcanization. Generally the temperature program for a DSC analysis is designed such that the sample holder temperature increases linearly as a function of time from +60°C to +180°C. The cross-linking of polymer molecules that occurs in the curing process is exothermic resulting in a positive peak in the DSC curve that usually appears soon after the glass transition. The reference

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International Journal of Engineering Research Science IJOER ISSN: 2395-6992 Vol-4 Issue-2 February- 2018 Page | 36 sample should have a well-defined heat capacity over the range of temperatures to be scanned. We collected the results below. TABLE 3 THE RESULTS OF DSC MEASUREMENTS Sample ID Color of curve Glass-transition temperature °C Heat capacityJ/g Sample 1. purple 11674 -189 Sample 2. red 11615 -101 Sample 3. green 12052 -141 Sample 4. claret 11903 -110 Sample 5. orange 11543 -128 FIGURE 8. THE DSC CURVES OF THE SAMPLES The aim of the SEM investigation was the examination of blending of raw caoutchouc and rubber mixtures base polymer with additives in 50x and 1000x magnification. It is evident that besides the surface impurities Sample 3. and Sample 5. generated a lot of sulfur aggregation from the vulcanising agent used based on the recipe. FIGURE 9. THE SEM RESULTS OF a. SAMPLE 1. b. SAMPLE 3. AND c. SAMPLE 5. IN 50x MAGNIFICATION

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International Journal of Engineering Research Science IJOER ISSN: 2395-6992 Vol-4 Issue-2 February- 2018 Page | 37 FIGURE 10. THE SEM RESULTS OF a. SAMPLE 1. b. SAMPLE 3. AND c. SAMPLE 5. IN 1000X MAGNIFICATION ACKNOWLEDGEMENTS I owe thanks to my supervisor Gabriella Zsoldos for her support and “Supported by the Únkp-2017-3. New National Excellence Program of the Ministry of Human Capacities”. REFERENCES 1 P. J. Flory „Principles of Polymer Chemistry” 1st ed. Cornell University 1953 pp. 454-464. 2 A. Oae Organic Chemistry of Sulfur Plenum Press New York 1977. 3 A.M. Joseph B. George K.N. Madhusoosaban and R. Alex „Rubber Science”2015 pp. 28 82-121. 4 A.K. Bohwmick H.L. Stephens “Handbook of Elastomers” 2rd ed.. NY Basel: Marcel-Dekker Inc. 2001 pp.3-7. 5 J. D. Robert M. C. Caserio “Basic Principles of Organic Chemistry” 2rd ed. W. A. Benjamin Inc Menlo Park CA. ISBN 0-8053- 8329-8 6 P.J. Nieuwenhuizen A.W. Ehlers J.W. Hofstraat S.R. Janse M.W.F. Nielen J. Reedijk and E.-J. Baerends „Chem. Eur. Journal.1988 Vol. 4 No. 9 pp. 1816-1821 7 P. Ghosh S. Katare P. Patkar J.M. Caruthers V. Venkatasubramanian and K.A. Walker “Rubber Chem. Technol.”2003 Vol. 76 No. 3 592-693 8 A. Y. Coran in The Science and Technology of Rubber 2005 Ch.7 - Vulcanization pp. 321-366. 9 "Sunflower oil production in 2014 Crops processed/Regions/Production quantity pick list". United Nations Food and Agriculture Organization Statistics Division FAOSTAT. 2017.

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