In situ generation of sulfur using silica as a carrier in the wet mixing of natural rubber latex

Using sodium thiosulfate and hydrochloric acid as the raw materials and a silica aqueous dispersion as the carrier, sulfur is generated in situ by a chemical precipitation method, and an in situ sulfur-silica/natural rubber (in situ S-Silica/NR) composite is prepared. The in situ sulfur is characterized, and its effects on the natural rubber composites' cross-linking density, vulcanization characteristics, mechanical properties, aging properties, dynamic mechanical properties, and Payne effect are studied. The experimental results show that the particle size of in situ sulfur is small, with a maximum of 5 μm, and the cross-linking ability is stronger than commercial sulfur. Due to the strong surface adsorption force of silica, the interfacial bonding strength is enhanced, and the dispersion of the two components in the rubber matrix is improved. Compared with commercial sulfur-silica/natural rubber (S-Silica/NR) composites, the tensile strength is 20.3% higher, the elongation at break is 28.5% higher, and it better retains its aging properties and has a lower rolling resistance. This study provides a theoretical basis for the development of functional rubber vulcanizing agents and the preparation of high-performance rubber composites.     

TENSILE PROPERTY OF EPOXIDIZED NATURAL RUBBER/NATURAL RUBBER BLENDS

The tensile strength and elongation at break of epoxidized natural rubber (ENR) blended with natural rubber (NR) was studied. ENR 25, ENR 50, and one grade of natural rubber (SMR L) were used as the elastomers. The composition of ENR was varied from 0% to 100% rubber. The accelerated sulfur vulcanization system was used throughout the investigation. The tensile property of unaged and aged samples was determined by using the Monsanto tensometer (T10) operating at 50 cm/min. Results show that the tensile strength and elongation at break passes through a maximum at 50% ENR for both ENR25/SMR L and ENR50/SMR L blends. This positive deviation from ideality is attributed to the mutual reinforcement of ENR and NR in the blends as a result of strain-induced crystallization. This synergistic effect is more pronounced in the case of ENR 25 due to the higher crystallinity and availability of more double bonds, which is more compatible to NR compared to ENR 50/NR blends. For the aged samples, a drop in the tensile property associated to the breakdown of the polysulfidic cross-link during aging is observed. A systematic study of the effect of sulfur concentration on the percentage retention of tensile property of the ENR blends after aging reveals that percentage retention decreases with increasing sulfur loading, which, in turn, enhances the formation of the polysulfidic cross-link; thus, more breakdown is observed in the rubber vulcanizate.     

Novel dynamic vulcanization of polyethylene and ozonolysed natural rubber blends: Effect of curing system and blending ratio

Dynamic vulcanization was studied in terms of the change in α‐relaxation temperatures of the LDPE matrix, morphology, and mechanical properties of LDPE/ozonolysed NR blends which were vulcanized at various blend ratios and with different curing systems, i.e., peroxide and sulfur systems. The ozonolysed NR with M _w = 8.30 × 10⁵ g mol⁻¹ and M _n = 2.62 × 10⁵ g mol⁻¹, prepared by the in situ ozonolysis reaction of natural rubber latex, was used in this study. The significant change in the α‐relaxation temperature of LDPE in the LDPE/ozonolysed NR, dynamically vulcanized using the sulfur system, suggested that sulfur vulcanization of the blend gave a higher degree of crosslink density than using peroxide and corresponded with the improved damping property and homogenous phase morphology. However, the peroxide cured blends of LDPE/ozonolyzed NR gave more improvement of tensile strength and elongation at break than the sulfur cured system. Furthermore, the mechanical properties of tensile strength, elongation at break, and damping were improved by increasing the ozonolyzed natural rubber content in both DCP and sulfur cured blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Relationship Among Thermal Ageing Degradation,Dynamic Properties,Cure Systems,and Antioxidants in Natural Rubber Vulcanisates

The present work aims to study the relationship among the thermal ageing stability, dynamic properties, cure systems, and antioxidants in natural rubber (NR) vulcanisates. Thermal degradation behavior of NR vulcanisates has been investigated and correlated to the changes in cross-link density, tensile and dynamic mechanical properties. The results obtained show that thermal ageing properties of NR vulcanisates depend strongly on cross-link density, which changes during thermal oxidative ageing or the so-called postcuring effect. In addition, the increases in ageing temperature and time lead dominantly to the postcuring and linkages scission phenomena in vulcanisates cured with CV and EV systems, respectively. With increasing ageing temperature, the tensile strength shows sharp drop at ageing temperature higher than 70°C and 100°C for the specimens cured with CV and EV systems, respectively. The sharp drop of tensile strength of vulcanisates cured with CV system is attributed to the too high cross-link density, which is caused by the postcuring effect. In the case of the vulcanisates cured with EV system, the linkage scission causes the sharp drop of tensile strength. The addition of amine-based antioxidant appears to improve ageing properties. However, the excessive antioxidant reduces tensile properties via a decrease in cross-link density.     

Devulcanization of Natural Rubber Vulcanizates by Mechanochemical Process

Using a suitable disulfide-based devulcanizing agent, which cleaved the sulfur cross-links in vulcanized rubber at high temperature, devulcanization of gum natural rubber was carried out. High sulfur and medium sulfur, as well as low sulfur–containing rubber vulcanizates were used to study the cleavage of sulfidic bonds. The cure characteristics and mechanical properties of vulcanized natural rubber and revulcanized natural rubber were studied. Thermal properties of the rubber were analyzed by thermogravimetric analysis (TGA), which indicates that the onset degradation temperature further increased on revulcanization with higher amount of disulfide. The properties of the revulcanized natural rubber increased with increasing disulfide concentration, also the mechanical properties of the devulcanized natural rubber were increased by decreasing the sulfur content in the original rubber vulcanizate. From the rheometric study increases in optimum cure time were observed when ground rubber vulcanizates were treated with higher amounts of disulfide. The scanning electronic microscopy (SEM) study suggested the change in failure mechanism as influenced by the type of cross-linking present and the devulcanizing agent used. From infrared (IR) spectroscopy it was observed that the oxidation of the main polymeric chain did not occur at the time of high temperature milling.     

Structure and performance of hydrogenated natural rubber prepared by the latex method

Hydrogenated natural rubber (HNR) with different degrees of hydrogenation was prepared by the latex method. The hydrazine hydrate/hydrogen peroxide/boric acid catalytic system could result in the hydrogenation of natural rubber (NR) under the latex state. The NR without hydrogenation contained around 13% of gel, when the hydrogenation degree reached 66.9%, the gel content was 34.4%. The decomposition temperature of HNR kept on increasing, which was all higher than that of NR and the glass transition temperature increased slightly. The cross-linking density of vulcanised rubber rose along with the increasing degree of hydrogenation, the NR cross-linking density was 0.114 mmol cm^?3, when the hydrogenation degree was 34.6%, 42.7% and 66.9%, the cross-linking density was 0.182, 185 and 221 mmol cm^?3, respectively. This further proved decreasing flexibility of the HNR after hydrogenation and weakening crystallisation of HNR along with increasing degree of hydrogenation.     

Properties of natural rubber/recycled ethylene–propylene–diene rubber blends prepared using various vulcanizing systems

The role of various vulcanizing systems on the curing characteristics, mechanical properties, morphology and dynamic mechanical analysis of natural rubber and recycled ethylene–propylene–diene rubber blends was investigated. Accelerated sulfur-vulcanizing systems (semi-EV and EV), peroxide, and mixed sulfur/peroxide-vulcanizing systems (semi-EV/peroxide and EV/peroxide) were observed and compared. The blends were processed on a two-roll mill, and a fixed amount of carbon black was also incorporated. Amongst the blends, accelerated sulfur-vulcanizing systems exhibited higher torques, state of cure, tensile strength and elongation-at-break, in comparison with the peroxide-vulcanizing system, whereas the tensile modulus, hardness and cross-link density showed lower trend. In the mixed sulfur/peroxide-vulcanizing systems, it showed intermediate behavior to the individual sulfur- or peroxide-vulcanizing systems. This was associated to the interference of peroxide during the cross-linking formation. SEM micrographs of semi-EV-vulcanizing system exhibited more roughness and cracking path indicating that higher energy was required towards the fractured surface. The high cross-link density observed from the swelling study could be verified from the storage modulus (E′) where peroxide vulcanized blends provided a predominant degree of cross-linking followed by semi-EV, semi-EV/peroxide, EV and EV/peroxide-vulcanizing systems, respectively. The glass transition temperature (T _g) depicted at maximum peak of mechanical loss factor (tanδ _max), indicating that semi-EV-vulcanizing system showed highest T _g value. The T _g values can be ordered as semi-EV > peroxide > semi-EV/peroxide > EV > EV/peroxide-vulcanizing systems. The T _g of rubber vulcanizates can be increased due to the restriction of molecular movement such as cross-link density.     

Analysis of variation of molecular parameters of natural rubber during vulcanization in conformational tube model. II. Influence of sulfur/accelerator ratio

A natural rubber (NR) with a conventional sulfur cure system and a ratio of sulfur/accelerator (Ω) equal to 3 was investigated. The network structure of the NR during vulcanization was analyzed using a model of rubber elasticity based on the tube concept, which was applied to the treatment of the stress–strain measurements. The influence of cure time and temperature on the chemical crosslinks density was analyzed. The values were compared with those obtained by means of an equilibrium volume swelling measurement. The differences between samples of NR cured with Ω = 3 and 1.5 were analyzed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2747–2755, 1999     

Spectroscopic and SEM studies of SWNTs: Polymer solutions and films

Raman spectra of SWNTs suspended in aqueous solutions containing fragmented single-stranded DNA (SWNT:DNA), and films obtained from this suspension have been obtained. SEM study of the dried films indicated that the nanotubes tend to aggregate into bundles which results in the enhancement of the Raman intensity of the G⁻ tangential band, and an upshift and broadening of the G⁺ band. The intensity of radial breathing modes of metallic SWNTs is higher in the SWNT:DNA films as compared to that of the SWNT:DNA solution. The Raman spectra of SWNT:PVP and SWNT:agaroza samples exhibit similar changes as the SWNT:DNA samples when films are cast from the corresponding solutions. Both films and the solution forms of SWNT:DNA yield luminescence spectra which indicates the presence of individual tubes or small bundles in the films. The luminescence bands of SWNT:DNA films are relatively wider and is attributed to the interaction of DNA with the nanotube surface in the solid state.     

Change of network structure of natural rubber vulcanizate with thermal aging

The effect of sulfur accelerators during the curing process in natural rubber (NR) was investigated. The samples were prepared by adding the same fraction of various types of accelerators in the compound and all samples were cured at the same temperature but for two different times. Determination of the molecular mass between crosslinks immediately after vulcanization shows the crosslink density in the samples, which differs for different accelerators. After that, the same samples undergo thermal aging and the changes of the crosslink density were studied. During the first period of thermal aging, additional crosslinks were observed and then a period of deterioration of the network structure is following. From the obtained results of the molecular mass between crosslinks as well as from mechanical properties, conclusions can be drawn about the most suitable accelerator for use in certain conditions and applications. To predict the behavior of vulcanizates under various effects as heat and radiation, it is important to know more about the chemical structure of the network. The changes of crosslink density in the investigated samples were followed by equilibrium swelling and by mechanical measurements. IR spectroscopy was used to study the changes of the crosslink bridges.     

Influence of ionic liquid on the polymer–filler coupling and mechanical properties of nano‐silica filled elastomer

The natural rubber (NR) nanocomposites were fabricated by filling ionic liquid (1‐allyl‐3‐methyl‐imidazolium chloride, AMI) modified nano‐silica (nSiO₂) in NR matrix through mechanical mixing and followed by a cure process. Based on the measurements of differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), solid state nuclear magnetic resonance spectroscopy, and Raman spectroscopy, it was proved that AMI could interact with nSiO₂ through hydrogen bonds. With the increase of AMI content, the curing rate of nSiO₂/NR increased. The results of bound rubber and dynamic mechanical properties showed that polymer–filler interaction increased with the modification of nSiO₂. Morphology studies revealed that modification of nSiO₂ resulted in a homogenous dispersion of nSiO₂ in NR matrix. AMI modified nSiO₂ could greatly enhance the tensile strength and tear strength of nSiO₂/NR nanocomposites. Compared to unmodified nSiO₂/NR nanocomposite, the tensile strength of AMI modified nSiO₂/NR nanocomposite increased by 102%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44478.     

Mechanical properties of thermoplastic elastomeric blends of chitosan and natural rubber latex

Thermoplastic chitosan/natural rubber blends (Cs/NR) were prepared from natural rubber latex and chitosan by solution casting technique. The blends were characterized by mechanical analysis (stress–strain) and the mechanical properties were found to vary with chitosan/natural rubber ratios. Experimental values were compared with different theoretical models. Effect of thermal aging on mechanical properties was also investigated. Dicumyl peroxide was used as the crosslinking agent. The effect of crosslinking on mechanical properties of Cs/NR has also been studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of quasi‐nanogel particles on the rheological and mechanical properties of natural rubber: A new insight

The influence of sulfur‐crosslinked, quasi‐nanosized gels on the rheological and mechanical properties of raw natural rubber (NR) was investigated. Latex gels with different crosslink densities were prepared through the variation of the sulfur‐to‐accelerator ratio. These gels were characterized by dynamic light scattering, solvent swelling, and mechanical properties. The gels were mixed with raw NR latex at concentrations of 2, 4, 8, and 16 phr, and their effect on the rheological properties of NR was studied by Monsanto processability tester. The presence of gel in raw NR reduced the apparent shear viscosity and die swell considerably. Initially, the viscosity decreased up to a 8 phr gel loading and then increased with an increase in the gel loading. However, the change in the viscosity was related to the crosslink density of the gels. A new empirical equation relating the viscosity, volume fraction of the gels, and crosslink density was proposed. The die swell of gel‐filled raw NR was at least 10% lower than that of unfilled raw NR and decreased with an increase in the gel loading. The effect of the gels on the die swell properties was explained through the calculation of the principal normal stress difference of gel‐filled NR systems. Scanning electron photomicrographs of the extrudates revealed much better surface smoothness for the gel‐filled virgin rubber systems than for the unfilled rubber. The addition of the gels to raw NR increased the modulus and tensile strength, whereas the elongation at break decreased. The effect of the gels on the dynamic mechanical properties of NR was also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

炭黑/煤矸石/碳纳米管复合填料体系对天然橡胶性能的影响研究*

利用硝酸氧化法对碳纳米管(CNTs)进行纯化,并用环氧天然橡胶(ENR)进行改性处理。结合胶质量分数测定结果表明, ENR用量15%(质量)时效果最佳。采用胶乳凝聚法制备CNTs/天然橡胶(NR)母料。煤矸石粉(CG)经高温煅烧和表面改性处理。 将CNTs/天然橡胶(NR)母料、CG和炭黑(CB)通过机械混炼法与天然橡胶及配合剂混合,制备CB/CG/CNTs/NR复合材料,并对复合材料进行硫化特性及物理机械性能。结果表明： CNTs延迟硫化效应明显;相比炭黑,CG对硫化具有促进作用。硫化特性和甲苯溶胀法测定结果表明,在填料份数相同的条件下,单独由CB填充的NR有最大的交联密度,CNTs对交联密度影响不明显。物理机械性能测试结果表明,当CG：CB：CNTs=17.5:16.5:1(Phr)时,NR硫化胶的300%定伸应力和扯断伸长率明显高于单独由CB填充NR,而拉伸强度与之接近,复合填料样填充NR具有较好的综合性能。扫描电镜测试结果表明,复合填料在NR基体中分布均匀。     

Curing characteristics,mechanical properties and morphology of butyl rubber filled with ground tire rubber (GTR)

The results on testing application of ground tire rubber (GTR), as potential filler for butyl rubber, are presented. The GTR content variation, within the range of 10–90 phr, was studied with respect to the vulcanization process, static mechanical properties (tensile strength, elongation-at-break, hardness and resilience), dynamic mechanical properties and the morphology of the obtained vulcanizates. Butyl rubber was characterized by its low compatibility to other elastomers [i.e., natural rubber and styrene–butadiene rubber (SBR)—the main ingredients of tires] and low degree of unsaturation. To evaluate the impact of these factors on curing characteristics and mechanical properties of butyl rubber vulcanizates filled with GTR, the same compositions of SBR compounds, cured under identical conditions, were used as reference samples. Based on the obtained data, it can be stated that butyl rubber vulcanizates containing 30 phr of GTR as filler revealed the highest tensile strength and elongation-at-break. The microstructural analysis of a sample containing 30 phr of GTR revealed strong interactions between the butyl rubber matrix and GTR. This phenomenon resulted mainly from two factors. First, the cross-link density of the butyl rubber matrix was affected by its competition against GTR for cross-linking agents. Secondly, the migration of carbon black particles from GTR into the butyl rubber matrix had a significant impact on properties of the obtained vulcanizates.     

Surface characterization of cross-linked elastomers by shear modulation force microscopy

Brominated poly(isobutylene-co-4-methylstyrene) (BIMS) is a synthetic terpolymer which can be stoichiometrically cross-linked by N,N′-dicinnamylidene-1,6-hexanediamine (DIAK). The degree of cross-links on bulk samples was determined by measuring the low frequency shear modulus with parallel plate method. The surface modulus of the same samples was measured using a new method, shear modulation force microscopy (SMFM). The moduli of the bulk sample and the surface were found to have the same scaling with the cross-link density, and good agreement with rubber elasticity theory was obtained in both cases. The SMFM was then used to monitor the cross-linking process, as a function of DIAK concentration and curing time, in thin films where standard rheological methods cannot be applied. The results show that in all cases the cross-linking reaction at the surface reaches saturation in less than 10 min as compared to at least 1 h in the bulk samples.     

Conductivity and mechanical properties of well-dispersed single-wall carbon nanotube/polystyrene composite

The morphologies, electrical and mechanical properties and structure of polystyrene (PS) composites with varying concentrations of single-wall carbon nanotubes (SWNT) are analyzed. Using Raman spectroscopy and electron microscopy, we demonstrate that initial thermal annealing of SWNT significantly improves their dispersion in PS. In dielectric measurements, the annealed SWNT/PS composites show higher electrical conductivity and a lower percolation threshold (less than 0.3 wt%) than the raw SWNT/PS composites, which provides further evidence of good dispersion of the annealed SWNT in PS. Raman spectra of composites under tension show good transfer of an applied stress from the polymer matrix to SWNT. However, mechanical moduli of the annealed SWNT/PS composites are only increased slightly. The reason for this discrepancy remains unclear.     

Distribution of carbon black in natural rubber/acrylic rubber blends

Distributions of carbon black in 30/70% (w/w) natural rubber (NR)/acrylic rubber (ACM) blends were investigated as a function of the carbon black content and type using a dynamic mechanical thermal analysis (DMTA) technique. Two different types of carbon black (N220 and N330) were used, and 10–50 phr carbon black was compounded to the rubber blends. From the DMTA thermograms of various blends, the weight fractions of carbon black in the NR and ACM phases were calculated. Carbon black was unevenly distributed in the rubber blend. It preferred to migrate into the NR phase, regardless of the amount of carbon black that was used. By increasing the carbon black content, the weight fraction of carbon black in the NR phase decreased whereas that in the ACM phase increased. A change in the type of carbon black from N220 to N330 significantly decreased the weight fraction of carbon black in the NR phase, but it was not sufficiently strong to affect the tensile properties and hardness of the rubber blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:248–256, 2006     

防老剂MB用量对CM／EVM共混胶性能的影响

研究了共混比为70／30的氯化聚乙烯（CM）／乙烯一醋酸乙烯酯橡胶（EVM）共混胶中不同MB的用量下,共混胶的硫化特性,热空气老化前后共混胶的力学性能、两相交联密度和动态力学性能。研究表明：随着MB用量的增加,共混胶的硫化特性稍有变化;老化前后,1#共混胶的力学性能及交联密度变化率较高,玻璃化转变温度的变化程度较大;老化前后,5#共混胶的力学性能变化率较低,交联密度变化率较低,玻璃化转变温度的变化程度较小。     

Influence of Nanogels on Mechanical, Dynamic Mechanical, and Thermal Properties of Elastomers

Use of sulfur crosslinked nanogels to improve various properties of virgin elastomers was investigated for the first time. Natural rubber (NR) and styrene butadiene rubber (SBR) nanogels were prepared by prevulcanization of the respective rubber lattices. These nanogels were characterized by dynamic light scattering, atomic force microscopy (AFM), solvent swelling, mechanical, and dynamic mechanical property measurements. Intermixing of gel and matrix at various ratios was carried out. Addition of NR gels greatly improved the green strength of SBR, whereas presence of SBR nanogels induced greater thermal stability in NR. For example, addition of 16 phr of NR gel increased the maximum tensile stress value of neat SBR by more than 48%. Noticeable increase in glass transition temperature of the gel filled systems was also observed. Morphology of these gel filled elastomers was studied by a combination of energy dispersive X-ray mapping, transmission electron microscopy, and AFM techniques. Particulate filler composite reinforcement models were used to understand the reinforcement mechanism of these nanogels. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.