Determination of bound rubber composition of filled SBR/BR blend compounds by analysis of the unbound rubber composition and bound rubber content

Analytical method for determination of the bound rubber composition of a filled SBR/BR blend compound was developed using measurement of the bound rubber content and microstructural analysis of the unbound rubber composition. Various filled SBR/BR blend compounds with different blend ratios were prepared using SBRs with different microstructures. This method included measurement of the bound rubber content, extraction of the unbound rubber, microstructural analysis of the unbound rubber composition, and process for determination of the bound rubber composition. Composition of the unbound rubber was analyzed using liquid proton nuclear magnetic resonance spectroscopy (H-NMR) and transmission Fourier transform infrared spectroscopy (FTIR). It was found that the analytical results using H-NMR had less experimental errors than those using transmission-FTIR. The raw SBR/BR blends were also analyzed in order to evaluate level of the experimental errors. Average SBR/BR ratios of the unbound rubbers were obtained using the 1,2- and 1,4-unit contents determined by the H-NMR analysis. The bound rubber compositions were obtained using the bound rubber contents and the average unbound rubber compositions. It was found that most of the bound rubbers had higher SBR ratios than the formulation value.     

Electrical properties of carbon black in an SBR–wax matrix

The resistivity and dielectric constant for carbon black (5–12 vol-%) in a nonconducting matrix have been measured over the range 20–90°C and dc to 2–10⁵ Hz. Styrene–butadiene rubber dissolved in tetracosane (22 parts SBR to about 70 parts wax) constituted the matrix. Wide variations in resistivity and dielectric constant with temperature and/or frequency were observed. A theory is presented to explain the experimental observations. It correctly predicts the qualitative features of the experimental results but its predictions are not quantitatively accurate.     

反式丁戊橡胶改性航空轮胎侧胶的结构与性能

采用反式-1,4-丁二烯-异戊二烯共聚橡胶（简称反式丁戊橡胶,TBIR）改性航空轮胎侧胶[天然橡胶（NR）/顺丁橡胶（BR）（质量比80/20）],研究了NR/BR/TBIR混炼胶的结晶行为、力学性能、硫化特性及硫化胶的物理机械性能、动态力学性能和填料分散性.结果表明,相比NR/BR并用胶,结晶性TBIR的并用赋予NR/BR/TBIR混炼胶较高的格林强度和杨氏模量.NR/BR/TBIR混炼胶工艺正硫化时间延长,交联密度提高.TBIR用量范围内,NR/BR/TBIR硫化胶300%定伸应力提高7%,耐屈挠疲劳性能提高35%~50%,滚动阻力降低.m（NR）/m（BR）/m（TBIR）为80/10/10硫化胶具有更好的综合力学性能及耐热氧老化性能.随着硫化时间的延长,NR/BR/TBIR（80/10/10）硫化胶较NR/BR（80/20）硫化胶100%定伸应力提高18%以上,NR/BR体系的耐屈挠疲劳性降低近60%,而NR/BR/TBIR（80/10/10）体系仍能保持原来的50%;反映滚动阻力的60℃损耗因子降低8%~14%,反映抗湿滑性的0℃损耗因子保持不变.填料分散度得到改善,填料聚集体尺寸降低.NR/BR/TBIR（80/10/10）硫化胶具有更好的耐长时间硫化的特性.     

Electron beam crosslinked gels—Preparation,characterization and their effect on the mechanical,dynamic mechanical and rheological properties of rubbers

Electron beam (EB) crosslinked natural rubber (NR) gels were prepared by curing NR latex with EB irradiation over a range of doses from 2.5 to 20 kGy using butyl acrylate as sensitizer. The NR gels were systematically characterized by solvent swelling, dynamic light scattering, mechanical and dynamic mechanical properties. These gels were introduced in virgin NR and styrene butadiene rubber (SBR) matrices at 2, 4, 8 and 16 phr concentration. Addition of the gels improved the mechanical and dynamic mechanical properties of NR and SBR considerably. For example, 16 phr of 20 kGy EB-irradiated gel-filled NR showed a tensile strength of 3.53 MPa compared to 1.85 MPa of virgin NR. Introduction of gels in NR shifted the glass transition temperature to a higher temperature. A similar effect was observed in the case of NR gel-filled SBR systems. Morphology of the gel-filled systems was studied with atomic force microscopy. The NR gels also improved the processability of the virgin rubbers greatly. Both the shear viscosity and the die swell values of EB-irradiated gel-filled NR and SBR were lower than their virgin counterparts as investigated by capillary rheometer.     

Influence of different curing systems on the physico-mechanical properties and stability of SBR and NR rubbers

The physical properties of radiation, sulfur and peroxide-cured styrene–butadiene rubber (SBR) and natural rubber (NR) were compared. The dependence of the mechanical properties of the radiation-vulcanized SBR and NR on the coagent concentration and radiation dose was studied. The effect of thermal aging on the mechanical properties of the different rubber formulations was discussed. The radiation-cured formulations of SBR have superior mechanical properties and thermal stability compared with those of the chemically vulcanized compounds. Whereas, the radiation-cured formulations of NR have similar mechanical properties but superior thermal stability (based on the % change in E after thermal aging), when compared with those of the sulfur-vulcanized compounds and slightly better than those of the peroxide-vulcanized compounds.     

A SAXS and swelling study of cured natural rubber/styrene–butadiene rubber blends

A small‐angle X‐ray scattering (SAXS) and swelling study of natural rubber and styrene–butadiene rubber blends (NR/SBR) is presented. To this aim, specimens of NR and SBR and blends with 75/25, 50/50, and 25/75 NR/SBR ratios (in phr) were prepared at a cure temperature of 433 K and the optimum cure time (t₁₀₀). This time was obtained from rheometer torque curves. The system of cure used in the samples was sulfur/n‐t‐butyl‐2‐benzothiazole sulfenamide. From swelling tests of the cured samples, information about the molecular weight of the network chain between chemical crosslinks was obtained. For all cured compounds, in the Lorentz plots built from SAXS scattering curves, a maximum of the scattering vector q around 0.14 Å^?1 was observed. However, the q position shows a linear‐like shift toward lower values when the SBR content in the SBR/NR blend increases. In pure NR or SBR the q values show a different tendency. The results obtained are discussed in terms of the existence of different levels of vulcanization for each single phase forming the blend and the existence of a third level of vulcanization located in the interfacial NR/SBR layer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2320–2327, 2009     

Radiation Vulcanization of Nitrile Butadiene Rubber/Butadiene Rubber Blends

Blends of nitrile butadiene rubber (NBR) with butadiene rubber (BR) with varying ratios have been prepared. Vulcanization of prepared blends has been induced by ionizing radiation of gamma rays with varying dose up to 250 kGy. Physical properties, namely soluble fraction and swelling number have been followed up using toluene as a solvent. Mechanical properties, namely tensile strength, tensile modulus at 100% elongation and elongation at break have been followed up as a function of irradiation dose, as well as blend composition. Thermal stability of blends was studied by TGA. The result indicated that the addition of NBR has improved the properties of NBR/BR blends. Also, NBR/BR blend is thermally stable than BR alone.     

Evaluation of the polymer-solvent interaction parameter χ for the system cured styrene butadiene rubber and toluene

One of the most popular cured rubbers used in industrial applications is styrene butadiene rubber (SBR) and frequently its network structure is studied by means of swelling techniques in solvent. Normally, toluene is used as solvent in this test. In order to estimate the crosslink density from the equilibrium volume fraction of rubber in the swollen state, the correct evaluation of the Flory-Huggins interaction parameter χ is necessary. This work covers the swelling behavior of cured SBR in toluene. The rubber was vulcanized with different amounts sulfur and accelerator at 433 K in order to obtain several network structures and crosslink densities. Network characterisations of the compounds were made by swelling measurements in the frame of the Flory-Rehner relationship using the molecular weight of the network chain between chemical crosslinks obtained previously by mechanical tests. A relationship between χ and v_r, the polymer volume fraction at equilibrium (maximum) degree of swelling, was established for the cured SBR/toluene system. It was found that χ is not a constant but depends on the crosslink density in the sample. The types of crosslinks in these samples where estimated applying this function to the swelling behavior of the compounds previously treated with the thiol probe method.     

Viscoelastic effects in cutting of elastomers by a sharp object

The cutting behavior of elastomers by a sharp object was investigated using various elastomers such as acrylonitrile–butadiene rubber (NBR), styrene–butadiene rubber (SBR), and natural rubber (NR). The effects of crosslinking density, cutting rate, and temperature on the cutting energy of elastomers were investigated. The cutting behavior of swollen elastomers was also investigated. It was found that the cutting energy increased as the molecular weight between crosslinks increased. It was also found that the cutting energies of various elastomers did not yield a single line. Moreover, even in the threshold condition of cutting process, the cutting energy was much higher than the threshold fracture energy. These results suggest that the cutting behavior cannot be explained by only a C C bond rupture process, but it includes other energy dissipation processes. The curves for cutting energies obtained at different cutting rates and temperatures were well superimposed on a single master curve when they were shifted using the WLF (Williams, Landel, and Ferry) equation. Therefore, it is supposed that the cutting of elastomers by a sharp object includes viscoelastic energy dissipation process and is the viscoelastic behavior. It was also found that the variation of cutting energy over a considerable range of effective rates was smaller than that of the tear energy. It is attributed to the fact that the change of the crack tip diameter, i.e., roughening or reduction, was restricted by the diameter of razor blade. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1283–1291, 1998     

Morphology and mechanical and viscoelastic properties of natural rubber and styrene butadiene rubber latex blends

The morphology and mechanical and viscoelastic properties of a series of blends of natural rubber (NR) and styrene butadiene rubber (SBR) latex blends were studied in the uncrosslinked and crosslinked state. The morphology of the NR/SBR blends was analyzed using a scanning electron microscope. The morphology of the blends indicated a two phase structure in which SBR is dispersed as domains in the continuous NR matrix when its content is less than 50%. A cocontinuous morphology was obtained at a 50/50 NR/SBR ratio and phase inversion was seen beyond 50% SBR when NR formed the dispersed phase. The mechanical properties of the blends were studied with special reference to the effect of the blend ratio, surface active agents, vulcanizing system, and time for prevulcanization. As the NR content and time of prevulcanization increased, the mechanical properties such as the tensile strength, modulus, elongation at break, and hardness increased. This was due to the increased degree of crosslinking that leads to the strengthening of the 3‐dimensional network. In most cases the tear strength values increased as the prevulcanization time increased. The mechanical data were compared with theoretical predictions. The effects of the blend ratio and prevulcanization on the dynamic mechanical properties of the blends were investigated at different temperatures and frequencies. All the blends showed two distinct glass‐transition temperatures, indicating that the system is immiscible. It was also found that the glass‐transition temperatures of vulcanized blends are higher than those of unvulcanized blends. The time–temperature superposition and Cole–Cole analysis were made to understand the phase behavior of the blends. The tensile and tear fracture surfaces were examined by a scanning electron microscope to gain an insight into the failure mechanism. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2189–2211, 2000     

Preliminary study on analysis and removal of wax from a Carrara marble statue

Abstract

This preliminary study has mainly focused on the wax identification by nuclear magnetic resonance (NMR) and removal. Wax is used for many purposes in the field of art as protective coatings on wooden, stone or metal objects. From the comparison of the spectra H NMR and in particular with the correspondence of the resonance peaks of the samples taken from the statue and beeswax and paraffin, we can conclude that the wax applied on the statue surface is beeswax. From our data, it can be concluded that, to remove the beeswax, from any stone support, the more effective solvent is the mixture of cyclohexane/ethyl acetate. The removal percentages ranged from 19 to 99%. Lower percentages of removal have been observed in the case of yellow marble, probably because of its high porosity. We can affirm that, this solvent mixture can be employed in real art objects using cotton swabs to remove protective wax.     

Surface Modification of Rice Husk Ash by Ethanol-assisted Milling to Reinforce the Properties of Natural Rubber/Butadiene Rubber Composites

Rice husk ash(RHA), obtained by pyrolysis of rice husks, can be used as a potential reinforcing filler for rubber composites. In this work, ball milling in ethanol(ethanol-assisted milling) was used to hydroxylate the surface of RHA, promoting the graft modification of bis-(γ-triethoxysilylpropyl)-tetrasulfide(Si69). The obtained modified RHA(RHA-EM-Si69) was filled into the natural rubber/butadiene rubber(NR/BR) composites, and the filler-rubber interactions were enhanced. In consequence, RHA-EM-Si69 filled NR/BR composites showed overall improvement in the mechanical properties compared with RHA filled NR/BR composites. The tear strength increased from 13.37 kN/m to 34.71 kN/m, and the tensile strength increased from 1.84 MPa to 7.75 MPa. Carbon black(N774) was also used for comparison under the same conditions. This method provides a potential for promoting the value of RHA in rubber industry.     

润滑油对轮胎主要成分催化裂解行为的影响

本文研究了润滑油对轮胎的重要组成原料:天然橡胶、聚丁二烯橡胶和丁苯橡胶催化裂解行为的影响.研究发现润滑油的加入明显增强了催化剂ZSM-5对聚丁二烯橡胶的催化裂解作用:液体收率从69.0％提高到83.4％,残渣收率从17.0％降至3.2％;润滑油的加入也提高了丁苯橡胶催化裂解的反应速率,液体产物中的轻油组分由67.5％增...     

Separation of organic mixtures by pervaporation using crosslinked rubber membranes

Natural rubber (NR) and poly(styrene-co-butadiene) rubber (SBR) has been crosslinked with sulfur and accelerator with three different doses of varied accelerator to sulfur ratios to obtain three crosslinked membranes from each of these two rubbers (NR-1, NR-2 and NR-3 and SBR-1, SBR-2 and SBR-3). These six rubber membranes were used for pervaporative separation of toluene–methanol mixture up to 10 wt% of toluene in feed. It has been found that with increase in accelerator to sulfur ratio from membrane-3 to membrane-1, the vulcanization system shifts from conventional to efficient system resulting in higher degree of crosslink density and permeation selectivity. All of these membranes showed reasonably good range of flux (45.26 gm/m² h for NR-3 to 12.0 gm/m² h for SBR-1) and separation factor (162 for SBR-1 to 35.12 for NR-3) for 0.55 wt% of toluene in feed. Among these membranes NR-1 and SBR-1 with highest crosslink density showed maximum separation factor for toluene along with good flux. It has also been found that for comparable crosslink density SBR membranes showed better separation factor than NR membranes.     

Maleic-anhydride grafted EPM as compatibilising agent in NR/BR/EPDM blends

Incorporation of approximately 30 phr Ethylene-Propylene-Diene rubber (EPDM) into natural rubber (NR)/butadiene rubber (BR) is a means to achieve non-staining ozone resistance for tire sidewall applications. However, due to incompatibility of the elastomers and heterogeneous filler distribution in each of the rubber phases, the mechanical properties deteriorate. In the present work, maleic-anhydride modified EPM (MAH-EPM) is added as a compatibilising agent between NR/BR and EPDM. The addition of 5 phr of MAH-EPM results in significantly improved tensile and tear strength when compared to a straight NR/BR/EPDM blend. These improvements can mainly be attributed to a compatibilising effect of MAH-EPM, resulting in a more homogeneous phase distribution, but in particular a much better homogeneous carbon black distribution over the different rubber phases. In addition, ionic crosslinks are introduced into the blends by interaction of MAH-EPM with zinc oxide.     

Filler‐polymer interactions of styrene and butadiene units in silica‐filled styrene–butadiene rubber compounds

Styrene–butadiene rubber (SBR) is a copolymer of styrene and butadiene, and the butadiene unit is composed of cis‐1,4‐, trans‐1,4‐, and 1,2‐components. Filler‐polymer interactions of each component of SBR in silica‐filled SBR compounds were examined by microstructure analysis of the bound and unbound rubbers. The composition ratio of butadiene and styrene units (butadiene/styrene) of the bound rubber was higher than that of the compounded rubber. Of the butadiene units, the 1,2‐component of the bound rubber was more abundant than the cis‐1,4‐ and trans‐1,4‐components. The filler‐polymer interaction of the butadiene unit with silica was stronger than that of the styrene unit, and the interaction of the 1,2‐component was stronger as compared with the others. The butadiene–styrene ratio of the bound rubber of the compounds containing the silane coupling agent was lower than for the compounds without the silane. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 577–584, 2004     

FTIR spectra and mechanical strength analysis of some selected rubber derivatives

Rubber materials have wide range of commercial applications such as, infant diapers, famine hygiene products, drug delivery devices and incontinency products such as rubber tubes, tyres, etc. In the present work, studies on mechanical properties of some selected rubber materials viz., natural rubber (NR), styrene butadiene rubber (SBR), nitrile butadiene rubber (NBR) and ethylene propylene diene monomer (EPDM) have been carried out in three states viz., raw, vulcanized and reinforced. To enhance the quality of rubber elastomers, an attempt is made to prepare new elastomers called polyblends. In the present study an attempt is made to blend NR with NBR and with EPDM. We here report, a novel approach for the evaluation of various physico-mechanical properties such as mechanical strength, tensile strength, elongation and hardness. The method is simple, direct and fast and involves infrared spectral measurements for the evaluation of these properties. With the applications of modern infrared spectroscopy, the mechanical strength of these rubber materials have been analyzed by calculating the internal standards among the methyl and methylene group vibrational frequencies obtained from FTIR spectroscopy. Also the tensile strength measurements carried out by universal testing machine. The results pertaining physico-mechanical properties of the rubber derivatives undertaken in the present study obtained by IR-based method are in good agreement with data resulted from the standard methods.     

A study of the ozonolysis of butadiene rubber in the presence of ethanol

The reaction of ozone with butadiene rubber (BR) having the microstructure: 90% 1,4-cis and 10% 1,4-trans and 1,2-cis, was investigated in pure chloroform and ethanol/chloroform mixture, respectively. Gel permeation chromatography was used to follow the molecular weight change of ozonolysed BR, and FT-IR and ¹H NMR were used to characterize the type and relative content of functional groups of ozonolysis products. It was found out that although the final ozonolysis products had almost the same functional groups whether ethanol was added or not, the addition of ethanol could efficiently prevent the cross-linking of ozonolysed BR.     

线性低密度聚乙烯/橡胶共混体系的相容性研究

本文用FTIR-ATR方法考察了线性低密度聚乙烯与天然橡胶(NR)及丁苯橡胶(SBR)两个共混体系,发现NR的835cm~(-1)和SBR的964cm~(-1)两个吸收峰因与聚乙烯共混而增高变窄,说明聚乙烯的非晶链段和橡胶分子之间存在一定程度的相互作用。     

Morphology dependence of crystallization of natural rubber in blends

Crystallization of natural rubber (NR) was investigated in different morphology for NR/styrene butadiene rubber (SBR) blend and NR/polystyrene-(b)-polyisoprene (SI)/polystyrene (PS) blend. A purified NR (PC-TE) was prepared from pale crape via transesterification. In the blends, PC-TE formed various morphologies; that is, matrix phase, island phase and continuous phase with a nano-scale, respectively, in dependence upon the ratio of the rubbers. The crystallization rate of the blends was also significantly associated with the morphology of the rubbers.