Synergic effect of N‐benzylimine aminothioformamide secondary accelerator during sulfur vulcanization of a styrene‐butadiene‐natural rubber blend

In this study we reported synergic activity of a novel secondary accelerator N‐Benzylimine aminothioformamide (BIAT) along with tetramethylthiuram disulfide (TMTD) in improving cure and mechanical properties of gum and filled mixes of Styrene‐Butadiene Rubber (SBR). The feasibility of application of BIAT in sulfur vulcanization of an ideal blend of SBR and natural rubber (NR) has also been investigated. The mechanical properties like t ensile strength, tear resistance, hardness, compression set, and abrasion loss were measured. Swelling values were also determined as a measure of crosslink densities of the vulcanizates. The binary accelerator system BIAT‐TMTD was found very effective in improving cure properties of the mixes of pure SBR and a 50/50 blend of SBR and NR.There was also found simultaneous improvement in mechanical properties of vulcanizates of both pure and blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Nano ZnO as cure activator and reinforcing filler in natural rubber

Zinc oxide (ZnO) nanoparticles of size 20–90 nm and surface area 9.56 m²/g were synthesized from ZnCl₂ and Chitosan and characterized by X‐ray diffraction, high resolution transmission electron microscopy (HRTEM), and scanning electron microscopy (SEM). Natural rubber (NR) vulcanizates containing nano ZnO was prepared by mill mixing and characterized by SEM, energy dispersive X‐ray analysis (EDAX), and HRTEM. Cure characteristics, free volume studies, bound rubber, crosslink density, and dynamic mechanical properties were evaluated and compared with that of NR vulcanizate containing conventional micro ZnO. Considering the cure characteristics, it was found that NR vulcanizate with 0.5 phr (parts per 100 g rubber) of nano ZnO showed low values of optimum cure time (t₉₀) and very high cure rate index compared with 5 phr of conventional micro ZnO. The study shows that micro ZnO can be successfully replaced with nano ZnO for accelerated sulfur vulcanization process in NR, and preparation of vulcanizate containing nano ZnO with better properties as that of micro ZnO. The optimum dosage of nano ZnO as a cure activator in NR vulcanization was found to be 0.5 phr compared with conventional grade micro ZnO. This will lead to substantial cost reduction in the manufacture of rubber products and alleviate environmental pollution due to excess ZnO in rubber compounds. POLYM. ENG. SCI., 2013 © 2013 Society of Plastics Engineers     

Nanomodified fillers in chloroprene‐rubber‐compatibilized natural rubber/acrylonitrile–butadiene rubber blends

Because of the structural dissimilarity, natural rubber (NR) and acrylonitrile–butadiene rubber (NBR) are immiscible, and compatibilizers are used during their blending. Neoprene or chloroprene rubber (CR) has a polar chlorine part and a nonpolar hydrocarbon part. Also, it has many advantageous properties, such as oil resistance, toughness, a dynamic flex life, and adhesion capacity. Hence, it is not less scientific to use CR as a compatibilizer in the blending of NBR with NR. Because many fewer studies on the use of neoprene as a compatibilizer in NR–NBR blend preparation are available, efforts were made to prepare 20:80 NR–NBR blends with CR with the aim of studying the effect of poly(ethylene oxide) (PEO)‐coated nano calcium silicate along with nano N‐benzylimine aminothioformamide and stearic acid coated nano zinc oxide in the sulfur vulcanization of the blends. The optimum dosage of the compatibilizer was derived by the determination of the tensile properties, tear resistance, abrasion resistance, compressions set, and swelling values. The tensile strength, tear resistance, and abrasion resistance of the gum vulcanizates of the blend were improved by the compatibilizing action of CR up to 5 parts per hundred parts of rubber (phr). In the case of the filled vulcanizates, the tear resistance, 300% modulus, hardness, and abrasion resistance increased with increasing dosage of nano calcium silicate. The elongation at break percentage decreased as expected when there was an increase in the modulus. Scanning electron microscopy was used to study the phase morphology of the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of surface‐modified zinc oxide as cure activator on the properties of a rubber compound based on NR/SBR

Zinc oxide (ZnO) and nano‐zinc oxide (nZnO) were surface modified by polyethylene glycol (PEG) and poly propylene glycol (PPG). Modification of particles were controlled by transmission electron microscopy, Brunauer, Emmett, Teller specific surface area measurement, infrared (IR) spectroscopy, and differential scanning calorimetry. IR spectra were shown that the interactions between surface modifiers and particles are hydrogen bonding. Modified particles were applied as an activator in vulcanization of natural rubber/styrene butadiene rubber (NR/SBR) blend. Dispersion of modified particles in rubber matrix was investigated by scanning electron microscopy and shown good results. Blend properties were improved by using modified particles. These improvements were due to the better hydrophobicity of modified particles, which were more compatible with nonpolar rubber matrix and caused better participation in curing process. Modification by PEG and PPG were shown better compound properties for ZnO and nZnO, respectively. Application of ZnO‐modified particles were presented better compound properties in comparison with nZnO‐modified particles. It has confirmed more effective mixing of ZnO‐modified particles in rubber matrix by using ordinary mixers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of zinc‐oxide‐free natural rubber nanocomposites using nanostructured magnesium oxide as cure activator

The effect of sol–gel synthesized magnesium oxide (MgO) nanoparticles as cure activator is studied for the first time in the vulcanization of natural rubber (NR) and compared with conventional zinc oxide (ZnO) in terms of cure, mechanical, and thermal properties. The NR vulcanizate with 1 phr (Parts per hundred parts of rubber) nano MgO shows an excellent improvement in the curing characteristics and the value of cure rate index is about 400% greater for NR vulcanizate containing 1 phr nano MgO in comparison to the NR vulcanizate with 5 phr conventional ZnO. Both mechanical and thermal properties of NR vulcanizate are found to be satisfactory in the presence of 1 phr nano MgO as cure activator in comparison to conventional NR vulcanizate. This study shows that only 1 phr nano MgO can successfully replace 5 phr conventional ZnO with better resulting properties in the sulfur vulcanization of NR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42705.     

Effect of nano zinc oxide on the cure characteristics and mechanical properties of the silica‐filled natural rubber/butadiene rubber compounds

With the increasing interest in environmental and health issues, legal restrictions, such as European Union (EU) End of Life Vehicle Directives, were strengthened. This led us to incorporate nano zinc oxide (nano‐ZnO), with particle sizes of 30–40 nm and specific surface areas of 25.0–50.0 m²/g, instead of conventional ZnO into natural rubber (NR)/butadiene rubber (BR) compounds to decrease the content of zinc in the formulation. In the unfilled system, only a 20 wt % nano‐ZnO content, compared to conventional zinc oxide content, showed the cure characteristics and mechanical properties of the same level. This was because the increase in the specific surface area of the nano‐ZnO led to an increase in the degree of crosslinking. The effect of nano‐ZnO on the cure characteristics and mechanical properties was more pronounced in the silica‐filled system than in the unfilled system. This was mainly because of the dispersing agent used in the silica‐filled system, which also improved the dispersion of nano‐ZnO. The silica‐filled NR/BR compounds containing 0.3–3.0 phr of nano‐ZnO showed improved curing characteristics and mechanical properties, such as optimum cure time, 100 and 300% modulus, tensile strength, and tear strength compared to the compound with 5 phr of conventional ZnO. The optimum amounts of nano‐ZnO and stearic acid were only 1.0 and 0.1 phr, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Studies on sulfur vulcanization of natural rubber accelerated combinedly with 2-mercaptobenzothiazole and diphenylguanidine both in presence and absence of dicumyl peroxide

Sulfuration of natural rubber (NR) by the binary accelerator 2-mercaptobenzothiazole (MBT) and diphenylguanidine (DPG) both in presence and in absence of ZnO and stearic acid with or without dicumylperoxide (DCP) was studied in detail. It was observed that the rate of decomposition of DCP in presence of both MBT and DPG is quite similar to that with MBT alone. The reduction of crosslinking depends also on MBT only. Through DPG has no influence on the decomposition rate, it reacts with MBT during the vulcanization process and suppresses the retardation caused by MBT on the DCP vulcanization. In accordance with the initial additiveness of crosslinking in systems containing DCP, the free sulfur decrease, and the rapidity of crosslink formation the vulcanization process of MBT-DPG-S-NR systems was interpreted in terms of a polar mechanism induced by the complex MSH₂NR′R″. In mixtures containing DCP together with sulfur, MBT, DPG, ZnO, and stearic acid, the initial stage of crosslinking is additive as indicated by a mixed reaction as well as by a methyl iodide treatment of the vulcanizates. Comparison with single accelerators shows a pronounced synergistic effect. This is because of the enhanced activity of the MBT-ZnO-stearic acid complex due to DPG which also induces polar sulfuration of NR by forming the active complex MSH₂NR′R″. In presence of ZnO and stearic acid, DCP cannot increase the net crosslink density but suppresses the reversion so much pronounced in its absence.     

各向同性与各向异性天然橡胶磁流变弹性体的导热性能及磁流变性能（英文）

采用羰基铁粉粒子填充天然橡胶磁流变弹性体(MRE),研究了各向同性与各向异性MRE的磁流变性能及导热性能。结果表明,各向异性MRE的热扩散系数和导热系数比各向同性MRE分别提高了30. 1%和41. 9%。同时,随着应变的增大,MRE的相对磁流变效应呈下降趋势,而在相同应变下,各向异性MRE的储能模量以及相对磁流变效应均高于各向同性MRE。     

Kinetics of accelerated vulcanization. Sulfur vulcanization accelerated with 2-mercaptobenzothiazole and its zinc salt in presence of zinc oxide and zinc oxide and stearic acid

Sulfur vulcanization of natural rubber (NR) and styrene-butadiene rubber (SBR) accelerated with 2-mercaptobenzothiazole and zinc oxide with or without stearic acid has been studied and the results compared with those obtained by replacing the thiazole with its zinc salt. The order of the rate of vulcanization as measured from free sulfur decrease or crosslink formation is observed to be unity with respect to time and less than one with respect to accelerator concentration. In absence of stearic acid, the zinc salt is much less efficient than the thiazole in promoting vulcanization, and the efficiency of the latter shows a noticeable improvement over what is attained in absence of zinc oxide. Addition of stearic acid not only raises the efficiency of both the systems to the same level but also leads to a faster rate of vulcanization, a much higher degree of crosslinking, avoidance of reversion, and production of vulcanizates with considerably improved mechanical properties. The formation of zinc sulfide also reveals interesting variation. Attempts have been made to interprete these results in terms of complex formation between zinc salt of thiazole and zinc stearate.     

Transport and electrical properties of natural rubber/nitrile rubber blend composites reinforced with multiwalled carbon nanotube and modified nano zinc oxide

As a surface modified zinc oxide, stearic acid‐coated nano zinc oxide (ZOS) has been prepared by sol‐gel method and was used along with N‐benzylimine aminothioformamide‐N‐cyclohexyl benzthiazyl sulfonamide binary accelerator system, multiwalled carbon nanotube (MWCNT) and sulfur for vulcanizing 20/80 natural rubber/nitrile rubber (NR/NBR) blend. Different formulations have been prepared by using 1–7 phr of MWCNT. Solvent transport and electrical properties of the rubber compounds have been investigated. The equilibrium solvent uptake (Q_∞) decreased with increase in concentration of the filler due to the decrease in the free volume and the increase in tortuousity. The conductivities of the vulcanizates increased with increase in the dosage of MWCNT from 1 phr in NBCNT₁ to 7 phr in NBCNT₄ indicating the formation of percolating network of MWCNTs in the NBR/NR matrix. POLYM. COMPOS., 35:956–963, 2014. © 2013 Society of Plastics Engineers     

Influence of zinc oxide during different stages of sulfur vulcanization. Elucidated by model compound studies

The addition of zinc oxide (ZnO) as an activator for the sulfur vulcanization of rubbers enhances the vulcanization efficiency and vulcanizate properties and reduces the vulcanization time. The first part of this article deals with the reduction and optimization of the amount of ZnO. Two different rubbers, solution‐styrene‐butadiene rubber and ethylene–propylene–diene rubber, have been selected for this study. The results demonstrate that the curing and physical properties can be retained when the level of ZnO (Red Seal) is reduced to 1 or 2 phr, respectively. Of particular interest is nano‐ZnO, characterized by a nanoscale particle distribution. The cure characteristics indicate that with nano‐ZnO, a reduction of zinc by a factor of 10 can be obtained. In the second part, model compound vulcanization is introduced to investigate the effects of ZnO during the different stages of vulcanization. Experiments are described with two models, squalene and 2,3‐dimethyl‐2‐butene, both with benzothiazolesulfenamide‐accelerated vulcanization systems. The results demonstrate the influence of ZnO during the different stages of the vulcanization. With ZnO present, a marked decrease can be observed in the sulfur concentration during an early stage of vulcanization, along with a slight delay in the disappearance of the crosslink precursor. The crosslinked product distribution is influenced as well. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1388–1404, 2005     

Morphology and properties of NR/EPDM rubber blends filled with small amounts of titania nanoparticles

This article describes the results of an investigation on the influence of titania nanoparticles on the morphology and properties of vulcanized natural rubber (NR)/ethylene‐propylene‐diene monomer (EPDM) blends. The samples were prepared through roll‐milling and melt‐pressing and diphenyl guianidine was used as vulcanization accelerator. The transmission electron microscopy (TEM) and X‐ray diffraction (XRD) results show that the titania particles are concentrated in the NR phase, and that the presence of titania in EPDM seems to initiate the formation of crystals in the rubber phase. From the dynamic mechanical analysis (DMA) and tensile testing results it is clear that the presence of titania particles inhibited the vulcanization process in both the investigated rubbers, and that the mechanical properties of the nanocomposites were influenced by the interaction between the nanoparticles and the rubber, the reduced vulcanization of the two rubber phases, and the development of crystallinity in EPDM. The thermogravimetric (TGA) results show improved thermal stability of EPDM, and of the EPDM phase in the blend, for the samples containing titania nanoparticles. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

双金属稀土促进剂对丁苯橡胶/天然橡胶胎面胶的影响

通过配位反应制备得到双金属硫化促进剂二乙基二硫代氨基甲酸锌镧配合物(ZnLaDC),在不添加传统活化体系氧化锌(ZnO)/硬脂酸(SA)的情况下,考察了ZnLaDC用量对丁苯橡胶(SBR)/天然橡胶(NR)胎面胶复合材料硫化特性及物理机械性能的影响,并与传统硫化体系二乙基二硫代氨基甲酸锌(ZnDC)/ZnO/SA制备的硫化胶性能进行了对比。结果表明,随着ZnLaDC用量的增加,SBR/NR胎面胶复合材料的硫化特性、压缩疲劳生热性能及耐磨性得到有效提高,当ZnLaDC用量为5份时,复合材料的综合性能最佳。与传统硫化体系ZnDC/ZnO/SA制备的硫化胶相比,采用ZnLaDC制备的硫化胶具有更优异的静态力学性能及耐切割性。     

空气弹簧橡胶气囊外层胶配方优化设计

对空气弹簧橡胶气囊外层胶配方进行优化设计.优化配方为:CR70,NR30,炭黑N550 50,氧化镁/氧化锌9.3,硬脂酸0.8,均匀树脂5,防老剂OD/A/DAPD 9,增塑剂 DOS 10,硫黄/HVA-2/秋兰姆类促进剂/次磺酰胺类促进剂2.7,其他5.7.优化配方胶料耐老化性能优异,各项性能符合空气弹簧橡胶气囊...     

Low‐temperature synthesis of nano‐to‐submicron size organo‐zinc oxide and its effect on properties of polybutadiene rubber

Nano‐to‐submicron sized particles of zinc oxide (ZnO) were synthesized by low temperature hydrolysis method. Organo‐ZnO was also synthesized by the aforementioned method in presence of polyethylene glycol (PEG‐2000). The synthesized ZnO particles were characterized by infra‐red spectroscopy, X‐ray diffraction, BET surface area, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). FTIR showed that PEG was present on the ZnO surface. Organo‐ZnO exhibited floral‐shape morphology consisting of concentric nanorods. The average diameter of the nanorods was ～ 250 nm as evident from SEM. TEM showed that the nanorods were made of ～ 50 nm sized small particles. UV‐absorbance property of ZnO was unaltered even after organic coating. Curing, physico‐mechanical and thermal properties of polybutadiene rubber compounded with organo‐ZnO were compared with those of standard commercial rubber grade ZnO and nano‐ZnO prepared by high and low temperature methods. The cure‐characteristics were studied with the help of moving die rheometer as well as differential scanning calorimetry (DSC). Crosslink‐density measurement along the DSC vulcanization exotherm showed better cure efficiency of organo‐ZnO. Organo‐ZnO containing compound exhibited better mechanical and thermal properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Role of geopolymer as a cure activator in sulfur vulcanization of epoxidized natural rubber

Geopolymer (GP) was synthesized and used as activators in sulfur vulcanization of epoxidized natural rubber (ENR). Influences of GP on cure characteristics, crosslink density, mechanical, thermal, and morphological properties were investigated and compared to the conventional rubber formulation with ZnO activator. The ZnO is a hazardous chemical for the environment and has proclaimed that its application in rubber technology should be reduced and controlled. It was found that the GP-activated ENR compounds showed significantly higher vulcanization rate than cases with the conventional ZnO compound. This was indicated by the GP activated compounds having shorter scorch time, cure times, and lower activation energy but higher cure rate index (CRI). Also, the GP activated ENR compounded with stearic acid exhibited the highest conversion. This matches well the highest torque difference and crosslink density, observed by temperature scanning stress relaxation (TSSR) and swelling measurements. Furthermore, the GP-activated vulcanizate had better thermal stability than the ZnO-activated ENR material. In addition, the GP-activated ENR vulcanizate with stearic acid exhibited high 100% moduli, tensile strength, and hardness. This proves that GP has a high potential for use as activators in sulfur vulcanization of rubber compounds, as an alternative to the conventional ZnO. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48624.     

Novel method for preparation of carboxylated nitrile rubber–natural rubber blends using bis(diisopropyl)thiophosphoryl polysulfides

Bis(diisopropyl)thiophosphoryl trisulfide (DIPTRI) and bis(diisopropyl)thiophosphoryl tetrasulfide (DIPTET) are successfully used as a novel coupling agent and accelerator, respectively, to covulcanize an elastomer blend comprising polar carboxylated nitrile rubber (XNBR) and nonpolar natural rubber (NR). These compounds are capable of forming a chemical link between these dissimilar rubbers to produce a technologically compatible blend as judged by a swelling experiment. The blend vulcanizates thus produced exhibit enhanced physical properties that can further be improved by adopting the two‐stage vulcanization technique and also by judicious selection of the NR:XNBR ratio. The blend morphology assessed by scanning electron microcroscopy micrographs accounts for significant improvement in the physical properties of the blend vulcanizates, particularly in two‐stage vulcanization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1725–1736, 2001     

纳米氧化锌在NR/BR并用胶及SBR胶料中的应用

研究纳米氧化锌替代普通氧化锌在天然橡胶(NR)/顺丁橡胶(BR)并用胶以及丁苯橡胶(SBR)胶料中的应用。结果表明,纳米氧化锌减量10%代替普通氧化锌,NR/BR并用胶及SBR胶料的加工性能和物理性能基本不变,质量减小,成本降低。     

纳米氧化锌/二氧化硅杂化体的制备及其对天然橡胶复合材料性能的影响

采用3-氰基丙基三乙氧基硅烷（CTOS）对二氧化硅（SiO₂）进行了氰基化改性,并采用热溶剂法将纳米ZnO沉积于氰基官能化SiO₂（SiO₂-CN）表面,制备出纳米氧化锌/二氧化硅杂化体（ZnO@SiO₂）,并使用X射线衍射仪、傅里叶变换红外光谱仪、扫描电镜等对杂化结构进行表征。将ZnO@SiO₂作为填料添加入天然橡胶中制备复合材料（NR/ZnO@SiO₂）,然后对ZnO@SiO₂与橡胶的界面关系进行了分析,并研究了ZnO@SiO₂对橡胶复合材料的硫化特性、力学性能的影响。结果表明,纳米ZnO成功沉积在SiO₂-CN表面,并且NR/ZnO@SiO₂复合材料表现出优异的机械性能和硫化特性。与天然橡胶相比,仅添加5份杂化体的NR/ZnO@SiO₂复合材料的拉伸强度、100%定伸及300%定伸强度分别增加了150.2%、86.2%和65.5%,并且正硫化时间缩短了38.5%。     

Effects of modified silica on the co-vulcanization kinetics and mechanical performances of natural rubber/styrene–butadiene rubber blends

Rubber blends are widely used for combining the advantages of each rubber component. However, to date, how to determine and distinguish the vulcanization kinetics for each single rubber phase in rubber blends during the co-vulcanization process is still a challenge. Herein, high-resolution pyrolysis gas chromatography–mass spectrometry (HR PyGC-MS) was employed for the first time to investigate the vulcanization kinetics of natural rubber (NR) and styrene–butadiene rubber (SBR) in NR/SBR blends filled with modified silica (SiO₂). The reaction rates of crosslinking of each rubber phase in NR/SBR were calculated, which showed that the crosslinking rates of NR were much lower than those of SBR phase in the unfilled blends and blends filled with unmodified and silane modified silica. Interestingly, the vulcanization rates of NR and SBR phase were approximately same in the vulcanization accelerator modified silica filled blends, showing better co-vulcanization. In addition, the vulcanization accelerator modified silica was uniformly dispersed and endowed rubber blends with higher mechanical strength compared to the untreated silica. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48838.