Effect of fillers on natural rubber/high styrene rubber blends with nano silica: Morphology and wear

The blends of high styrene rubber (HSR) and natural rubber (NR) with nano silica were prepared using a blending technique in presence of different types of carbon black. The effect of filler on morphological and wear characteristics was studied. ISAF (Intermediate Super Abrasion Furnace) type of carbon black have showed a significant effect on optimum cure time, cure rate index and mechanical properties by reacting at the interface between HSR and NR matrix. All the samples show only one melting peak on the DSC curve; this is attributed to the same backbone structure of the matrix and the carbon black reinforcement. The samples containing 30 wt.% of HSR with ISAF type of carbon black has shown maximum heat buildup, lower swelling and lower compression set value. Blends containing ISAF type of carbon black with 30 wt.% of HSR showed high abrasion resistant properties against Du-Pont abrader, DIN abrader and different mining rock surfaces and also is found to be the toughest rubber against all types of rock. Coal is main abrader against the rubber under this study.     

Effect of fillers and nitrile blended PVC on natural rubber/high styrene rubber with nanosilica blends: Morphology and wear

The blends of high styrene rubber (HSR) and natural rubber (NR) with nitrile blended PVC (NVC) and nanosilica are prepared by using a blending technique in presence of different types of carbon black. The effect of filler on morphological and wear characteristics is studied. ISAF type of carbon black have showed a significant effect on optimum cure time, cure rate index and mechanical properties by reacting at the interface between NVC, HSR and NR matrix. All the samples show only one melting peak on the DSC curve; this is attributed to the same backbone structure of the matrix and the carbon black reinforcement. The samples containing 20 wt.% of NVC with ISAF N234 type of carbon black has shown maximum heat buildup and lower compression set value. Blends containing ISAF type of carbon black with 20 wt.% of NVC shows high abrasion resistant properties against Du-Pont abrader, DIN abrader and different mining rock surfaces and also is found to be the toughest rubber against all types of rock. Coal is identified the main abrader against the rubber blends under this study.     

Effect of epoxidized natural rubber–organoclay nanocomposites on NR/high styrene rubber blends with fillers

Epoxidized natural rubber (ENR) and organoclay nanocomposites (Cloisite 20A) were prepared by solution mixing in this study. The obtained nanocomposites were incorporated in natural rubber (NR) and high styrene rubber (HSR) blends in presence of ISAF and SRF types of carbon black as reinforcing fillers. Morphology, curing characteristics, mechanical and thermal properties and wear characteristics of the nanocomposites against standard abrader and different mining rock surfaces were analyzed. The morphology of the ENR/nanoclay showed a highly intercalated structure. The nanocomposites containing SRF N774 type of carbon black has showed increase in cross-link density, maximum torque and cure rate index compared to ISAF N231 type of carbon black. The overall mechanical properties and thermal stability was higher for the nanocomposites containing SRF type of carbon blacks. The compounds containing EC in NR–HSR have higher barrier properties compared to without EC. EC with SRF N774 carbon black has showed minimum compression set value due to the increased formation of effective network chains due to higher reinforcing efficiency of the nanoclay in the rubber matrix. EC with SRF N774 type of carbon black showed high abrasion resistance property against Du-Pont abrader, DIN abrader and rock–rubber experimental study and also it has been found to be the toughest rubber compound against all types of rock under the present study. Concrete has been identified as the major abrader against the blends than other rock types.     

超声分散制备天然橡胶/丁苯橡胶/炭黑/碳纳米管纳米复合材料

通过超声分散制备了分散均匀的碳纳米管(CNTs)/天然橡胶母料,利用母料制备了天然橡胶(NR)/丁苯橡胶(SBR)/炭黑(CB)/碳纳米管复合材料。通过比较常规搅拌、双辊混炼和超声分散三种方法对碳纳米管的分散及对复合材料性能的影响,表明超声分散能实现碳纳米管在基体中均匀分散,CNTs和CB的协同作用提高了复合材料的力学性能,当CB/CNTs之比为37/3时力学性能最高,与未加CNTs增强的体系相比,拉伸强度提高了6.4%。当CNTs含量为7phr,与未加CNTs的体系相比,压缩模量提高了20%。     

Effects of particle size and structure of carbon blacks on the abrasion of filled elastomer compounds

The effects of the particle size and structure of various carbon blacks on friction and abrasion behavior of filled natural rubber (NR), styrene–butadiene rubber (SBR) and polybutadiene (BR) compounds were investigated using a modified blade abrader. The effect of particle size and structure on abrasion resistance should be considered for the optimum design of desired wear properties. Characteristic parameters were introduced from the particle size and the structure of carbon blacks, with a linear relationship between the Young’s modulus and these characteristic parameters. The frictional coefficient depended not only on the particle size, but also on the structure of carbon black. The rates of abrasion were decreased with increasing surface area and developing structure of carbon blacks. Abrasion rates of the compounds were found to be proportional to a power n of the applied frictional work input. It was also observed that BR compounds caused much slower wear than NR and SBR compounds. The worn surfaces of the rubber compounds filled with carbon black having smaller particle size and a more developed structure showed narrower spaced ridges and better abrasion resistance. It means that smaller particle size and better structure development of carbon black resulted in improved abrasion resistance.     

Barrier properties of natural rubber/ethylene vinyl acetate/carbon black composites

Composites based on natural rubber (NR), ethylene vinyl acetate (EVA) and carbon black were prepared. Three types of carbon black viz.; semireinforcing furnace (SRF), high-abrasion furnace (HAF) and intermediate superabrasion furnace (ISAF) were used for reinforcement. The barrier properties of these filled samples were examined in an atmosphere of petrol, kerosene and diesel. Blends loaded with ISAF exhibited the lowest liquid uptake which has been attributed to the higher filler reinforcement and crosslink density of the matrix. Among the three vulcanising systems used, viz.; sulphur (S), dicumyl peroxide (DCP) and mixed (S+DCP), DCP crosslinked samples exhibited high barrier properties to the probe molecules. Diesel showed the lowest interaction with the composites compared to petrol and kerosene. The sorption data were used to estimate the enthalpy, entropy and free energy of the transport process.     

天然橡胶与其环氧化物并用胶基复合材料的黏弹阻尼性能

为改善天然橡胶（NR）的阻尼性能,在密炼机中以质量比20：80混合不同环氧度环氧化天然橡胶（ENR）与天然橡胶制备ENR-NR并用橡胶基体,在橡胶基体的混炼与开炼过程加入其他填充组分（硫磺、促进剂2,2'-二硫代二苯并噻唑（DM）、促进剂N-环己基-2-苯并噻唑次磺酰胺（CZ）、ZnO、硬脂酸、炭黑）得到了宽温域阻尼ENR-NR基复合材料。采用橡胶加工分析仪和动态力学热分析仪,研究了ENR-NR混炼胶和硫化胶的动态力学和阻尼性能。结果表明：NR环氧化增强了分子链局部刚性,改善了胶体与填料的黏结性,但ENR吸附较多炭黑后不易均匀分散于连续相NR中。因此,ENR-NR并用混炼胶的黏度和储能模量随ENR环氧度增大而增加;在NR中加入ENR可改善硫化胶的弹性和阻尼性能。ENR-NR并用胶的有效阻尼温度范围拓宽到较高温度,环氧度为25的ENR与NR并用后,有效阻尼温度范围为-57~1℃,明显宽于NR的-57~-20℃,但高环氧度并用胶则出现阻尼失效区。加入少量ENR对NR的硬度、模量和断裂伸长率影响不大。     

Studies on microcellular soles based on natural rubber/polyethylene blends

Microcellular (MC) soles based on NR/polyethylene blends were developed as possible replacements for the conventional NR/HSR soles. The mechanical properties of the soles suggest that 80/20 NR/LDPE blends can be used for light weight good quality soles. 80/20 blends of NR/HDPE are also found to be promising base materials for good quality soles. A part of HSR in a NR/HSR blend was replaced by LDPE and the effect of replacement on the mechanical properties was evaluated. It is found that 70/15/15 NR/HSR/LDPE and 60/20/20 NR/HSR/LDPE based MC soles show better mechanical properties than NR/LDPE based MC soles.     

Modified phosphate pigments as high performance reinforcing materials for rubber vulcanizates

This study is focusing on the synthesis of novel modified micronized phosphate pigments as reinforcing materials for the vulcanizates of styrene-butadiene rubber (SBR), natural rubber (NR) and their blends. The metal phenyl phosphate pigments were prepared via co-precipitation process from the reaction of equimolar ratios of the disodium phenyl phosphate solution and the water soluble salts of the investigated metals. The white prepared phosphate pigments were introduced in the rubber formulations to replace carbon black the highly common and commercial reinforcing material in rubber vulcanizates. The rheometric characteristics, physico-mechanical properties in addition to the accelerated aging properties of the rubber vulcanizates were investigated, discussed and interpreted in the light of previous studies. The results showed that, phenyl phosphate pigments exercised a great effect on the rheological characteristics (scorch time, cure time…etc.), and achieved high performance and pronounced mechanical properties. The stress and strain at yield and at rupture of the loaded rubber with modified phosphates are better than that loaded with carbon black and Hisil e.g. tensile strength data were (20.0–23.4), 18.01 MPa and 15.05 for rubber blend vulcanizates loaded with 30 phr of modified phosphate pigments, carbon black and Hisil, respectively.     

环保型水切割胶粉对天然橡胶力学性能和动态性能的影响

采用环保型水切割胶粉及力化学改性胶粉（MRP）与天然橡胶（NR）复合制备胶粉-NR复合胶,并探讨了胶粉用量对复合胶力学性能和动态性能的影响。通过红外和热失重分析确定了胶粉的主要成分为NR和丁苯橡胶（SBR）,且改性后胶粉大分子链结构未发生明显变化。通过橡胶加工分析仪研究了胶粉用量及改性对复合胶加工性能的影响。采用炭黑分散仪研究并观察了胶粉在NR中的分散情况。结果表明,胶粉改性后与NR的相容性提高,二者界面结合力增大,MRP-NR复合胶加工性能改善。炭黑分散结果表明,胶粉用量越多,其分散性越差,改性后胶粉的分散性提高,MRP-NR复合胶的力学性能最优,拉伸强度为27.9 MPa。     

多壁碳纳米管填充丁苯橡胶复合材料的研究

采用浓硝酸(HNO3)氧化处理后的多壁碳纳米管(MWNTs)与丁苯橡胶(SBR)及其他配合剂在开炼机上进行混炼加工制备MWNTs／橡胶复合材料，并与炭黑补强橡胶体系进行对比，进而研究了MWNTs／橡胶复合材料的物理性能，并初步探讨了该材料微观结构与性能之间的关系。结果表明：随着MWNTs质量百分含量的增加，橡胶复合材料的力学性能也随之增高；MWNTs／橡胶复合材料的抗撕裂强度(25．9kN／m)、硬度(58)、磨耗(0．22mL/1．61km)性能较炭黑／橡胶体系要好。由MWNTs补强的橡胶对开发具有低滚动滞后性和抗疲劳损失的轮胎胎面胶将有很大的实用潜力。     

Development of expanded graphite filled natural rubber vulcanizates in presence and absence of carbon black: Mechanical,thermal and morphological properties

As nanosized expanded graphite (EG) reveals a similar layered structure like organoclay and also it has a high expansion ratio so rubber chains can easily be intercalated into the gallery space. To improve the dispersion of EG in the rubber matrices, primarily the surface modification of the expanded graphite have been done and then the modified expanded graphite (MEG)/polar compatibilizer [epoxidized natural rubber (ENR)] master batch have been prepared by solution mixing method in the laboratory. After that the MEG/ENR master batch have been mixed with bulk natural rubber (NR) in presence and absence of carbon black (CB) in a laboratory scale open two roll mixing mill. Wide angle X-ray diffraction (WAXD) and high resolution transmission electron microscopic (HR-TEM) analysis of the nanocomposites revealed that MEG was intercalated and as well as delaminated in the NR matrix. Scanning electron microscope (SEM) images of the nanocomposites showed very rough surface than the pure NR matrix. In presence of expanded graphite the crack paths are channelized and coincide in one point suggesting the effect of plate like expanded graphite to acts as a barrier. We have got improved mechanical, thermal and dynamic mechanical properties for the MEG and MEG/CB loaded NR compounds compared to EG and EG/CB loaded NR compounds.     

低压缩永久变形导电炭黑/硅橡胶复合材料的制备与性能

为获得一种低压缩、永久变形及高回弹的导电屏蔽硅橡胶密封材料,以经偶联剂表面处理的炭黑作补强剂及导电填料,乙烯基硅橡胶生胶作基料,制备出一种导电炭黑/硅橡胶复合材料。研究了不同炭黑含量的导电炭黑/硅橡胶复合材料的力学性能、弹性、分散性以及电性能,采用SEM观察了炭黑在硅橡胶基体中的分布形貌,分析了导电炭黑/硅橡胶复合材料的导电机制及屏蔽机制。结果表明:随着炭黑含量的增加,导电炭黑/硅橡胶复合材料的Shore A硬度由31增至70;拉伸强度先由3.31 MPa增至5.28 MPa,而后趋于稳定;拉断伸长率先由198%增至297%,然后再减小至210%;恒定压缩永久变形量先减小后增大,瞬间回弹率逐渐减小;由于"炭黑簇"的形成及导电通路的完善,导电炭黑/硅橡胶复合材料的导电性能及屏蔽效能增强。     

Effect of multi-wall carbon nanotubes on the mechanical properties of natural rubber

Multi-walled carbon nanotubes (MWNTs) were used to prepare natural rubber (NR) nanocomposites. Our first effort to achieve nanostructures in MWNTs/NR nanocomposites were formed by incorporating carbonnanotubes in a polymer solution and subsequently evaporating the solvent. Using this technique, nanotubess can be dispersed homogeneously in the NR matrix in an attempt to increase the mechanical properties of these nanocomposites. The properties of the nanocomposites such as tensile strength, tensile modulus, tear strength, elongation at break and hardness were studied. Mechanical test results show an increase in the initial modulus for up to 12 times in relation to pure NR. In addition to mechanical testing, the dispersion state of the MWNTs into NR was studied by transmission electron microscopy (TEM) in order to understand the morphology of the resulting system. According to the present study, application of the physical and mechanical properties of carbon nanotubes to NR can result in rubber products which have improved mechanical, physical and chemical properties, compared with existing rubber products reinforced with carbon black or silicone.     

Microscopic studies on the mechanisms of wear of NR,SBR and HNBR vulcanizates under different conditions

Microscopic investigations, undertaken to understand the mechanism of wear of natural rubber (NR), styrene-butadiene rubber (SBR) and hydrogenated nitrile rubber (HNBR) vulcanizates abraded against hard rock, a knurled aluminium disc and a silicone carbide abrader under different conditions, are reported. The wear of NR and SBR vulcanizates against hard rock at low normal load (6 kPa) takes place by a fatigue wear mechanism and it switches over to frictional wear at high normal load (above 18 kPa). In HNBR vulcanizates the wear takes place by an abrasive wear mechanism. Ridges are observed on worn surface of swollen N R and SBR vulcanizates at low normal load, but at higher normal load the wear takes place by catastrophic fracture and extensive plough marks along the direction of abrasion are observed. The wear of NR and SBR vulcanizates proceeds by frictional wear, even at elevated temperatures. In HNBR vulcanizates, the mechanism changes from abrasive wear at 25C to frictional wear above 50C. Above 50C, ridges are observed and the spacing between adjacent ridges increases with rise of temperature.     

表面接枝防老剂的白炭黑在天然橡胶中的应用

为了提高白炭黑与橡胶的相容性,同时防止防老剂的挥发,采用γ-缩水甘油醚氧丙基三甲氧基硅烷与对氨基二苯胺(PPDA)的反应物对白炭黑进行表面改性,得到表面接枝防老剂的白炭黑。将改性白炭黑应用于天然橡胶(NR)中考察其增强与防老性能,并与炭黑/NR、未改性白炭黑/NR和Si69改性白炭黑/NR复合材料相比较(均添加防老剂4020)。结果表明,改性白炭黑/NR复合材料的焦烧时间延长,硫化时间缩短,白炭黑在橡胶中的分散性提高,同时具备更出色的力学性能。随着表面接枝防老剂含量的增加,改性白炭黑/NR复合材料的拉伸强度和撕裂强度比未改性白炭黑和Si69改性白炭黑/NR均有大幅提高。当接枝的PPDA含量达到5.27%(与白炭黑的质量比)时,其拉伸强度比未改性白炭黑/NR提高了90%,比Si69改性白炭黑/NR提高了73%,并接近炭黑/NR; 其撕裂强度是未改性白炭黑/NR的5倍,Si69改性白炭黑/NR的2.5倍,炭黑/NR的2倍。另外,表面接枝防老剂的白炭黑/NR复合材料具有优异的抗热氧、抗臭氧和湿热老化性能;其抗臭氧老化性能优于添加通用防老剂4020的对比复合材料。     

稻壳源白炭黑/炭黑并用对天然橡胶协同补强作用研究

通过扫描电镜观察了稻壳源白炭黑(RHS)在天然橡胶(NR)交联体系中的分散,显示RHS作为刚性补强粒子微观呈纳米尺度均匀分布,这是补强作用的基础。依据非平衡态分子动力学原理,探究了RHS纳米粒子与炭黑(CB)对NR的协同补强作用机理。通过研究双相填料(RHS/CB)对NR协同补强作用,不同的RHS/CB比例对协同补强作用影响较大,适宜的用量比不仅提高物理力学性能,同时改善动态力学性能。     

Synergy in carbon black-filled natural rubber nanocomposites. Part I: Mechanical,dynamic mechanical properties,and morphology

Synergistic effect of carbon black (CB) in presence of nanofillers (nanoclay and nanofiber) on mechanical and dynamic mechanical properties was discussed in light of electrostatic interactions and the concomitant microstructural developments, in Part I of this series. These interactions enhanced filler dispersion and ensured efficient stress transfer from the matrix resulting in improvement in properties, undiminished even by continual increase in CB loading. In this part, the micromechanical processes that influence wear behavior have been addressed conjointly with dynamic mechanical properties. Tribological characteristics were studied by sliding rubber wheel samples against a steel blade, in a specially designed abrader, in both transient and steady state conditions. Wear loss was reduced in the dual filler nanocomposites by 33% (over the CB microcomposite) in less stringent and 75% under severe wear conditions. These CB filled nanocomposites also illustrated lowering of coefficient of friction and temperature build-up. This was attributed to efficient heat dissipation due to the formation of a unique microstructural architecture by the participating fillers and also an adhering transfer film on the abraders’ counterface. From viscoelastic measurements, the CB filled nanocomposites were also found to lie in the high performance window of good wet skid and low rolling resistance.     

Synergy in carbon black filled natural rubber nanocomposites. Part II: Abrasion and viscoelasticity in tire like applications

Synergistic effect of carbon black (CB) in presence of nanofillers (nanoclay and nanofiber) on mechanical and dynamic mechanical properties was discussed in light of electrostatic interactions and the concomitant microstructural developments, in Part I of this series. These interactions enhanced filler dispersion and ensured efficient stress transfer from the matrix resulting in improvement in properties, undiminished even by continual increase in CB loading. In this part, the micromechanical processes that influence wear behavior have been addressed conjointly with dynamic mechanical properties. Tribological characteristics were studied by sliding rubber wheel samples against a steel blade, in a specially designed abrader, in both transient and steady state conditions. Wear loss was reduced in the dual filler nanocomposites by 33% (over the CB microcomposite) in less stringent and 75% under severe wear conditions. These CB filled nanocomposites also illustrated lowering of coefficient of friction and temperature build-up. This was attributed to efficient heat dissipation due to the formation of a unique microstructural architecture by the participating fillers and also an adhering transfer film on the abraders’ counterface. From viscoelastic measurements, the CB filled nanocomposites were also found to lie in the high performance window of good wet skid and low rolling resistance.     

Effects of virgin Ethylene–Propylene–Diene–Monomer and its preheating time on the properties of natural rubber/recycled Ethylene–Propylene–Diene–Monomer blends

Blending of natural rubber/recycled Ethylene–Propylene–Diene–Monomer (NR/R-EPDM) blends was carried out. A fixed amount of carbon black and virgin Ethylene–Propylene–Diene–Monomer (EPDM) were also introduced into the blends. Applications of two different processing methods were carried out to improve the cure compatibility, crosslink distribution, and hence mechanical properties of the blends. Simple processing method was done by mixing the entire additives and rubbers on a laboratory-sized two-roll-mill at ambient temperature. Whereas, reactive processing method was conducted by mixing virgin EPDM, recycled EPDM and other compounding ingredients using an internal mixer, the compound was later preheated according to designated time before blending with natural rubber and carbon black. Results revealed that the enhancement of the physical and mechanical properties was significantly achieved towards preheating time of EPDM/R-EPDM blends. The improved properties in the blends suggested that the reactive processing method had led to more homogeneous blends due to a better crosslink distribution and more homogeneous carbon black distribution.