Effect of norbornyl modified soybean oil on CB‐filled chloroprene rubber

Carbon black (CB)‐filled chloroprene rubber (CR) compounds and vulcanizates containing naphthenic oil (NO), soybean oil (SO), and two different levels of norbornyl modified soybean oil (MSO) were prepared and investigated. The MSO was prepared through the reaction of SO and dicyclopentadiene (DCPD) at different ratios. Various properties including gel fraction, crosslink density, bound rubber fraction, curing behavior, thermal, mechanical, and aging properties of CB‐filled CR containing different oils were compared. It was observed that the addition of SO and MSO could benefit the dispersion of the filler, lower the glass transition temperature, and increase the thermal stability of the CB‐filled CR/MSO compounds and vulcanizates, and also slightly decrease the crosslink density of the CB‐filled CR/MSO vulcanizates compared to that of the CR/NO vulcanizate. With the increase of the modification level of the MSO, the curing time of the CB‐filled CR/MSO compounds was found to be decreased, the tensile property, tear strength, abrasion resistance, and aging resistance of the CB‐filled CR/MSO vulcanizates were improved compared with those of the CB‐filled CR/NO vulcanizate. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43809.     

Improvement of properties of silica‐filled styrene–butadiene rubber compounds using acrylonitrile–butadiene rubber

Since silica has strong filler–filler interactions and adsorbs polar materials, a silica‐filled rubber compound has a poor dispersion of the filler and poor cure characteristics. Improvement of the properties of silica‐filled styrene–butadiene rubber (SBR) compounds was studied using acrylonitrile–butadiene rubber (NBR). Viscosities and bound rubber contents of the compounds became lower by adding NBR to the compound. Cure characteristics of the compounds were improved by adding NBR. Physical properties such as modulus, tensile strength, heat buildup, abrasion, and crack resistance were also improved by adding NBR. Both wet traction and rolling resistance of the vulcanizates containing NBR were better than were those of the vulcanizate without NBR. The NBR effects in the silica‐filled SBR compounds were compared with the carbon black‐filled compounds. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1127–1133, 2001     

A comparative study of aging characteristics and thermal stability of oil palm ash,silica, and carbon black filled natural rubber vulcanizates

Filler‐filled natural rubber (NR) vulcanizates were prepared by conventional laboratory‐sized two roll mills and cured using sulfuric system. The effect of thermal aging on physical properties and thermogravimetric analysis (TGA) of oil palm ash (OPA) and commercial fillers (i.e., silica vulkasil C and carbon black N330)‐filled NR vulcanizates at respective optimum loading and equal loading were studied. Before aging, the OPA‐filled vulcanizates showed comparable optimum strength as carbon black‐filled vulcanizates. The hardening of aged filler‐filled NR vulcanizates happened after aging, thereby tensile strength and elongation at break reduced while the modulus increased. Fifty phr carbon black‐filled vulcanizates showed better retention in tensile properties as compared to silica (10 phr) and OPA (1 phr). This was attributed to the addition of different filler loading and this finding was further explained when equal loading of filler‐filled vulcanizates was studied. Fourier transform infra‐red analysis showed chemical structure had changed and tensile fractured surface exhibited smooth appearance due to the deterioration in tensile properties after aging. TGA also denoted the thermal stability was depending on the amount of filler loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4474–4481, 2013     

Nanostructured fly ash–styrene butadiene rubber hybrid nanocomposites

Hybrid nanocomposites of styrene butadiene rubber (SBR) with nanostructured fly‐ash (NFA) were prepared in the laboratory by melt blending technique in an internal mixer. Curatives were added on a laboratory two‐roll mill. Curing characteristics as well as physico‐mechanical properties of the composites were evaluated. A comparison on SBR composites filled with fresh fly‐ash (FFA); carbon black (CB) and precipitated silica (PS) has been reported. In general, SBR‐NFA composites exhibit higher state of cure and higher strength properties as compared with HAF black‐filled and fresh fly‐ash‐filled SBR composites at equivalent loadings. This may be attributed to the higher reinforcing ability of NFA. This fact has also been supported by the swelling studies and Kraus' plot. Tear strength and abrasion resistance of the SBR‐NFA composites were superior to FFA‐filled and precipitated silica‐filled vulcanizates, but were inferior to carbon black‐ filled SBR vulcanizates. The SBR‐NFA composites showed lower hardness as compared with both the carbon black‐filled and silica‐filled composites. Transmission electron microscopy and scanning probe microscopy studies revealed that the NFA particles are well dispersed in the SBR matrix. These results were further supported by fracture surface analysis under the SEM, which revealed the role of NFA in the prevention of fracture propagation. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Influence of 1,2‐unit contents on retraction behaviors of SBR vulcanizates

Styrene‐butadiene rubber (SBR) has four different repeat units of styrene, cis‐1,4‐, trans‐1,4‐, and 1,2‐uints. Influence of the 1,2‐unit content on the retraction behaviors of SBR vulcanizates reinforced with silica or carbon black was studied. The retraction behaviors were compared in terms of the filler systems and the microstructures of SBR. The silica‐filled vulcanizates containing a coupling agent showed nearly the same retraction behaviors as the carbon black‐filled ones, but the silica‐filled vulcanizates without a coupling agent were recovered slower than the carbon black‐filled ones. The vulcanizates with lower 1,2‐unit content started to recover at lower temperature than that with higher 1,2‐unit content. The recovery rate increased with increase of the 1,2‐unit content of SBR. The experimental results were explained with the polymer‐filler interactions, filler dispersion, glass transition temperature, and modulus. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4707–4711, 2006     

Study on the properties of ethylene‐vinyl acetate rubber vulcanizate filled with superfluous magnesium hydroxide/methacrylic acid

Ethylene‐vinyl acetate rubber (EVM) vulcanizates cured by dicumyl peroxide (DCP) with excellent mechanical properties were obtained by adding superfluous magnesium hydroxides (MH)/methacrylic acid (MAA). Different factors such as the DCP content and MH content were investigated to reveal their effects on the properties of the MH/MAA‐filled EVM vulcanizates. The formulation of DCP of 2 phr, MH of 60 phr, and MAA of 5 phr is recommended for the EVM vulcanizates with excellent mechanical properties. The stress relaxation and stress softening behavior of MH/MAA‐filled EVM vulcanizates were studied. The stress relaxation and stress softening became faster and more obvious with increasing MH content. The hot air aging resistance of EVM vulcanizates filled with different fillers such as silica and high abrasion furnace were compared, and the MH/MAA‐filled EVM vulcanizates had the best aging resistance at 40‐phr filler content. The MH/MAA‐filled EVM vulcanizates had excellent flame retardancy due to the high MH content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synergistic effect of carbon black and carbon–silica dual phase filler in natural rubber matrix

In this article, the synergistic effects of carbon black (CB) and modified carbon–silica dual phase filler (MCSDPF) on the properties of natural rubber (NR) were investigated. MCSDPF was prepared by modifying carbon–silica dual phase filler (CSDPF) with bis(3‐triethoxysilylpropyl)tetrasulphane (Si‐69). Fourier transform infrared spectroscopy and thermogravimetric analyzer analyses revealed that Si‐69 was successfully grafted to CSDPF. NR‐based compounds containing various combinations of MCSDPF and CB were prepared through a mechanical mixing. Investigations of mechanical properties, ageing resistance, abrasion resistance, dynamic mechanical properties, and morphology of tear fractured surface of MCSDPF/CB/NR vulcanizates were conducted. Our study shows that adding MCSDPF led to significant improvement in the tear resistance, fatigue life, and elongation at break of MCSDPF/CB/NR vulcanizates. Optimum stoichiometric combination of MCSDPF and CB inside the NR matrix was derived (ratio of MCSDPF and CB in wt% = 15/50), which showed synergistic effects of MCSDPF upon CB that was ultimately reflected in their tensile strength, wet skid resistance, and rolling resistance. POLYM. COMPOS., 35:1466–1472, 2014. © 2013 Society of Plastics Engineers     

莫来石与沉淀法白炭黑填充丁苯橡胶复合材料的性能比较

在双辊开炼机中将未处理或用质量分数为3%的硅烷偶联剂A-189处理的莫来石粉体加入到丁苯橡胶(SBR)中制成复合材料.研究莫来石的加入量对SBR性能的影响,并与沉淀法白炭黑填充的SBR的性能进行了比较.结果表明,莫来石粉体对SBR表现出半增强特性;与沉淀法白炭黑填充的SBR相比,SBR/莫来石复合材料表现出良好的硫化特...     

Effect of silanized silica nanofiller on tack and green strength of selected filled rubbers

BACKGROUND: Tack and green strength of filled and gum (unfilled) natural rubber (NR), poly(styrene‐co‐butadiene) rubber (SBR), polybutadiene rubber (BR) and (SBR‐BR) blend with different loadings of reinforcement agent, silanized silica nanofiller (Coupsil 8113), were studied and the results compared and discussed. RESULTS: It was found that silica was fully dispersed in rubber matrix after 13 min of mixing. In addition, with some exceptions for NR and (SBR‐BR) blend, filler loading decreased the tack strength of the studied filled rubbers. Green strength and Mooney viscosity increased with filler loading for all studied filled rubbers but with different rates and amounts. The optimum filler loadings for NR and (SBR‐BR) filled blend were 30 and 10 phr, respectively. Tacks of NR filled rubbers were much higher than those of synthetic filled rubbers. CONCLUSION: It was concluded that filler loading alters substantially the tack and green strength of the rubbers under investigation. Copyright © 2009 Society of Chemical Industry     

Fly ash particles and precipitated silica as fillers in rubbers. I. Untreated fillers in natural rubber and styrene–butadiene rubber compounds

In this study, we investigated the effects of untreated precipitated silica (PSi) and fly ash silica (FASi) as fillers on the properties of natural rubber (NR) and styrene–butadiene rubber (SBR) compounds. The cure characteristics and the final properties of the NR and SBR compounds were considered separately and comparatively with regard to the effect of the loading of the fillers, which ranged from 0 to 80 phr. In the NR system, the cure time and minimum and maximum torques of the NR compounds progressively increased at PSi loadings of 30–75 phr. A relatively low cure time and low viscosity of the NR compounds were achieved throughout the FASi loadings used. The vulcanizate properties of the FASi‐filled vulcanizates appeared to be very similar to those of the PSi‐filled vulcanizates at silica contents of 0–30 phr. Above these concentrations, the properties of the PSi‐filled vulcanizates improved, whereas those of the FASi‐filled compounds remained the same. In the SBR system, the changing trends of all of the properties of the filled SBR vulcanizates were very similar to those of the filled NR vulcanizates, except for the tensile and tear strengths. For a given rubber matrix and silica content, the discrepancies in the results between PSi and FASi were associated with filler–filler interactions, filler particle size, and the amount of nonrubber in the vulcanizates. With the effect of the FASi particles on the mechanical properties of the NR and SBR vulcanizates considered, we recommend fly ash particles as a filler in NR at silica concentrations of 0–30 phr but not in SBR systems, except when improvement in the tensile and tear properties is required. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2119–2130, 2004     

Preparation and properties of silica/styrene butadiene rubber masterbatches by latex co‐coagulating technology

Silica/styrene butadiene rubber (SBR) masterbatches were prepared by co‐coagulating SBR latex and silica aqueous suspension. The X‐ray diffraction patterns and scanning electron microscopy were employed to characterize the microstructure of the composite. The content and utilization of silica of silica/SBR masterbatches were also investigated. The highest content of silica was achieved when amount of silica is 50 g. Then the cure characteristics, swelling ratio, thermal stability, and mechanical properties of vulcanizates prepared from the masterbatches were compared with those prepared by a conventional direct mixing method. The results revealed that higher maximum torque, shorter cure time, and better swelling resistance of silica/SBR masterbatches were obtained than conventional silica filled composites. The mechanical properties of silica/SBR masterbatches exhibited greater tensile strength and hardness compared to the corresponding conventional mixes. Additionally, the silica/SBR masterbatches vulcanizates exhibited better abrasion resistance, rolling resistance and heat build‐up to those of the conventional composite. POLYM. COMPOS., 35:1212–1219, 2014. © 2013 Society of Plastics Engineers     

稀土BR／SBR共混胶的性能

研究了４种共混比的ＬｎＢＲ／ＳＢＲ共混生胶、混炼胶及硫化胶的性能，并与ＮｉＢＲ／ＳＢＲ共混胶进行了对比。结果表明，共混生胶的ＭＬ均低于ＬｎＢＲ及ＳＢＲ；当ＬｎＢＲ／ＳＢＲ共混混炼胶的ＭＬ、剪切应力、出口膨胀及硫化速度均低于ＮｉＢＲ／ＳＢＲ共混胶，挤出物外观优于后者；共混硫化胶的拉伸强度、热空气老化、拉伸疲劳、湿滑、耐磨等性能均明显优于后者，生热和透气率高于后者。     

甲基丙烯酸对氢氧化铝填充丁苯橡胶性能的影响

将甲基丙烯酸（MAA）用作Al(OH）3填充丁苯橡胶（SBR）复合材料的添加剂，结果表明，在高填充Al(OH）3的SBR中加入MAA可以较大幅度地提高其过氧化物硫化胶的力学性能。当Al(OH）3用量为150份（质量份，下同）时，随着MAA用量增加，SBR硫化胶的邵尔A型硬度和定伸应力逐渐增大，拉伸强度和撕裂强度有较大幅度的提高，当MAA用量为20份时，随着Al(OH）3用量增加，SBR硫化胶的邵尔A型硬度、定伸应力和撕裂强度逐渐增大，拉伸强度在Al(OH）3填充量为25份时最大，大量填充Al(OH）3的SBR硫化胶的阻燃性能较好，氧指数受MAA用量的影响较小，该SBR硫化胶亦具有良好的热空气老化性能。     

BIMS/filler interactions. I. Effects of filler structure

Polymer/filler interactions have been found to affect the performance of tire tread, sidewall, innerliner, or carcass and other industrial rubber products that are all based on filled elastomers. Identification of types of various polymer/filler interactions and ranking of their impacts have been elusive. Isobutylene-based polymers have relatively saturated structures and contain very low concentrations of functional group. Examples are BIMS (a brominated isobutylene/p-methylstyrene copolymer) containing p-bromomethylstyrene and p-methylstyrene; bromobutyl rubber containing  Br and olefin; chlorobutyl rubber containing  Cl and olefin; and butyl rubber containing olefin. On the other hand, high diene rubbers, such as polybutadiene rubber, polyisoprene rubber, and styrene/butadiene rubber, have unsaturated backbones and high olefin contents. Hence, different types and extents of interaction with reinforcing fillers, such as carbon black (CB) or silica, are expected in these two classes of elastomer. This work employs bound rubber (solvent extraction), viscoelasticity, stress–strain measurements, and solid state NMR to identify, differentiate, and scale polymer/filler interactions in unvulcanized BIMS/CB, BIMS/silica, SBR/CB, and SBR/silica composites, where SBR denotes a styrene/butadiene rubber. Four different types of CB and one type of silica have been studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4943–4956, 2006     

Improvement of properties of silica‐filled natural rubber compounds using polychloroprene

Because silica has strong filler–filler interactions, a silica‐filled rubber compound is characterized by a poor dispersion of the filler. Properties of silica‐filled natural rubber (NR) compounds were improved using polychloroprene (chloroprene rubber [CR]). The bound rubber content of the compound increases and the filler dispersion is also improved by adding CR to the compound. Physical properties such as modulus, tensile strength, abrasion, and crack resistance are improved by adding CR. Elongation at break of the vulcanizates containing CR is longer than that of the vulcanizate without CR, although crosslink density of the former is higher than that of the latter. The improved physical properties are attributed to the good dispersion of silica by adding CR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2609–2616, 2002     

Abrasion Property of Epoxidized Natural Rubber

The abrasion resistance of two grades of epoxidized natural rubber (ENR 25 and ENR 50) and one grade of styrene-butadiene rubber (SBR) were studied using an Akron abrasion tester. An accelerated sulfur vulcanization system with 2-mercaptobenzothiazole (MBT) as the accelerator is used throughout the study. Carbon black (N 330), precipitated silica, and calcium carbonate were chosen as the fillers. The range of sulfur and filler loadings was from 1 to 5 phr and 10 to 50 phr, respectively. Mixing was done on a two-roll mill. Results obtained show that for all the rubbers studied, the volume loss due to abrasion decreases with increasing sulfur loading and passes through a minimum at about 3 phr of sulfur. This observation is attributed to the changes of cross-link types from monosulfidic to polysulfidic crosslink as sulfur concentration is increased. However, further sulfur loading would cause a “tight” cure, thus increasing the abrasion loss. For sulfur loading less than 3 phr, ENR 25 indicates the highest abrasion loss, followed by SBR and ENR 50. For the filled stock, minimum loss is observed at about 35–40 phr of filler. Reinforcing filler such as carbon black exhibits better abrasion resistance than calcium carbonate, a nonreinforcing filler. The abrasion loss increases at higher filler loading due to the dilution effect of fillers. Ozone plays an important role in the abrasion property of unsaturated rubbers, as reflected by the higher abrasion loss in the presence of ozone.     

Preparation and properties of styrene‐butadiene rubber nanocomposites blended with carbon black‐graphene hybrid filler

Graphene has become an attractive reinforcing filler for rubber materials, but its dispersion in rubber is still a big challenge. In this work, a novel carbon black‐reduced graphene (CB‐RG) hybrid filler was fabricated and blended with styrene‐butadiene rubber (SBR) via simple two‐roll mill mixing. The prepared CB‐RG hybrids had a microstructure with small CB agglomerates adsorbed onto graphene surfaces. CB acted as a barrier preventing the RG sheets from restacking even after drying. Homogeneous dispersion of graphene sheets in SBR matrix was observed by the mechanical mixing method based on the application of the CB‐RG hybrid fillers. Dynamic mechanical analysis showed that Tg of the SBR/CB‐RG blend was higher than that of the SBR/CB blend indicating strong interfacial interactions between RG and SBR due to the high surface area of graphene and the π‐π interaction between SBR and graphene. The tensile properties of SBR/CB‐RG composites improved significantly and the volume resistivity decreased compared with the SBR/CB blends. The thermal stability of SBR composites filled with CB and CB‐RG showed slight difference. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41309.     

Effects of different interphases on the mechanical properties of cured silanized silica‐filled styrene–butadiene/polybutadiene rubber blends for use in passenger car tire treads

Polybutadiene (BR) and styrene–butadiene (SBR) rubbers containing the same loading of precipitated silica nanofiller were prepared. The silica surfaces were pretreated with bis(3‐triethoxysilylpropyl) tetrasulfide to chemically bond the silica to the rubber. The rubber compounds were mixed together for different times and at different temperatures to produce SBR/BR blends. The mass fraction and composition values of the interphases in the blends were subsequently determined with modulated‐temperature differential scanning calorimetry. These properties changed substantially as a function of mixing temperature and mixing time. The hardness, tensile strength, elongation at break, stored energy density at break, tear strength, modulus, abrasion resistance, heat buildup, and loss tangent of the cured blends were measured over a wide range of test conditions. Elongation at break, stored energy density at break, tearing energy, and abrasion resistance benefited from increases in the mass fraction of the interphase. The remaining properties were influenced mainly by the filler loading and mixing time of the two rubber compounds. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fly‐ash particles and precipitated silica as fillers in rubbers. II. Effects of silica content and Si69‐treatment in natural rubber/styrene–butadiene rubber vulcanizates

This article explored the possibility of using silica from fly‐ash particles as reinforcement in natural rubber/styrene–butadiene rubber (NR/SBR) vulcanizates. For a given silica content, the NR : SBR blend ratio of 1 : 1 (or 50 : 50 phr) exhibited the optimum mechanical properties for fly‐ash filled NR/SBR blend system. When using untreated silica from fly‐ash, the cure time and mechanical properties of the NR/SBR vulcanizates decreased with increasing silica content. The improvement of the mechanical properties was achieved by addition of Si69, the recommended dosage being 2.0 wt % of silica content. The optimum tensile strength of the silica filled NR/SBR vulcanizates was peaked at 10–20 phr silica contents. Most mechanical properties increased with thermal ageing. The addition of silica from fly‐ash in the NR/SBR vulcanizates was found to improve the elastic behavior, including compression set and resilience, as compared with that of commercial precipitated silica. Taking mechanical properties into account, the recommended dosage for the silica (FASi) content was 20 phr. For more effective reinforcement, the silica from fly‐ash particles had to be chemically treated with 2.0 wt % Si69. It was convincing that silica from fly‐ash particles could be used to replace commercial silica as reinforcement in NR/SBR vulcanizates for cost‐saving and environment benefits. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Comparing the dynamic behaviour of several rubbers filled with silanized silica nanofiller

BACKGROUND: The effect of the same amount of precipitated silica nanofiller on the curing and dynamic properties of different rubbers, including natural rubber (NR) without and with the addition of elemental sulfur (NR with S), synthetic polyisoprene (IR), polybutadiene (BR) and poly(styrene‐co‐butadiene) copolymer (SBR), was investigated. The silica surfaces were pre‐treated with bis(3‐triethoxysilylpropyl)tetrasulfane (TESPT) to chemically bond the silica to the rubber. The rubbers were primarily cured by using sulfur in TESPT with the addition of optimum accelerator (TBBS) and activator (ZnO), which helped to form sulfur chemical bonds between the rubber and filler. RESULTS: Cure properties, Mooney viscosity, glass transition temperature, bound rubber and crosslink density along with dynamic properties of the filled rubbers, including tan δ, loss modulus (G″) and storage modulus (G′), were measured as a function of double oscillation amplitude (DSA) from 15 to 1000 µm, temperature from ?130 to 100 °C and frequency from 1 to 100 Hz. The results with emphasis on potential for tyre tread applications are discussed. It emerged that SBR along with BR filled rubbers had the highest rolling resistance while IR filled rubber had the least. Moreover, it was found that SBR filled rubber had the best skid resistance and BR filled rubber the worst. CONCLUSION: Interestingly, the variation of G′ with DSA showed a complicated behaviour for different filled rubbers. It emerged that in some DSA ranges the Payne effect was observed, and in the remaining ranges increments of G′ with DSA were seen. Because the bound rubber of most of the filled rubbers was more than 92%, there should be another predominant mechanism in the systems studied rather than simply de‐agglomeration or filler network breakdown, which is proposed by the Payne model. In addition, the nanoscale of the filler may be effective for this behaviour. Copyright © 2008 Society of Chemical Industry