湿炼法NR/nSiO_2和NR/炭黑复合材料的制备、结构与性能的研究
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摘要
橡胶，尤其汽车轮胎用橡胶必须用补强剂补强，其硫化胶的性能才符合使用要求。炭黑是橡胶最主要、补强效果最好、用量最大的补强剂，其次是白炭黑，但补强效果不如炭黑，应用也不普遍。然而用白炭黑补强橡胶制造的汽车轮胎具有抗湿滑性能好和滚动阻力低的显著优点。目前用白炭黑补强橡胶制备轮胎胎面胶已成为研究热点。
自橡胶工业诞生以来，橡胶加工行业一直以固体橡胶和粉体填料为原料，用机械混炼法即干炼法生产混炼胶。干炼法工艺复杂，设备投资大，劳动强度高，所用补强剂尤其炭黑会造成黑色污染。加工汽车轮胎胶料所用炭黑或白炭黑属纳米粉体，表面能高，用机械湿炼法很难达到纳米级分散，而往往以粒径较大的聚集体分布于橡胶基体中，从而损害其硫化胶的物理机械性能。湿炼法是指以橡胶胶乳和填料浆液为原料，通过液相混合将填料粒子分散于橡胶乳胶粒之间，构成湿炼体系，凝聚共沉后形成橡胶/填料复合材料的技术过程。湿炼法可容易地克服干炼法难以克服的缺点。
本文首先用原位生成-湿炼法制备天然橡胶（NR）/二氧化硅（SiO_2）纳米复合材料。其过程是用NR胶乳与SiO_2的前驱体硅溶胶混合，利用硅溶胶受热生成SiO_2凝胶的性质，对湿炼体系加热，使硅溶胶在NR胶乳中原位生成纳米二氧化硅粒子（nSiO_2），然后凝聚共沉，获得NR/nSiO_2复合材料。系统研究了硅溶胶粒子及nSiO_2粒子表面处理剂的类型及用量，硅溶胶的类型、粒径及浓度，NR胶乳的浓度，硅溶胶转化为nSiO_2凝胶粒子的反应温度与反应时间，凝聚剂的类型及用量，nSiO_2的用量等湿炼条件以及不同硫化配方对原位生成-湿炼法NR/nSiO_2硫化胶物理机械性能的影响，确定了能使硫化胶达到最佳性能的湿炼条件和硫化配方，并与干炼法NR/白炭黑硫化胶进行了系统比较。结果表明，影响硫化胶物理机械性能的关键因素是硅溶胶的类型和表面处理剂的类型，当以中性硅溶胶为SiO_2前驱体和醇醚作表面处理剂时，其硫化胶在SiO_2用量为50~90phr的范围内具有优良的物理机械性能，尤其300%定伸应力、拉伸强度、撕裂强度、耐磨性能、压缩疲劳生热及其永久变形都达到良好水平。用FTIR、DSC和TG、DTG对复合材料及其硫化胶进行了分析，测定了NR/nSiO_2复合材料的结合胶含量及其硫化胶的交联程度。结果表明，在湿炼体系中硅溶胶全部转化为nSiO_2，随着SiO_2用量的增加，复合材料及其硫化胶的Tg变化不明显，起始热分解温度则逐渐提高。用DMA和RPA对硫化胶进行了系统分析。结果表明，随着SiO_2用量的增加，硫化胶的抗湿滑性能有所下降，滚动阻力有所增大，Payne效应即SiO_2网络结构程度增大。SEM分析显示，硅溶胶在NR胶乳中原位生成了平均粒径为50nm的nSiO_2粒子，硫化胶拉伸断面呈“瓣膜”结构，无裸露的nSiO_2聚集体及裂纹存在，表明nSiO_2在NR基体中的良好预分散赋予了其硫化胶以特殊的“瓣膜”结构为特征的基体剪切屈服的补强机理，使硫化胶具有优良的物理机械性能和动态力学性能。
本文还用天然胶乳和二氧化硅纳米分散体（DnSiO_2）为主要原料，以湿炼法成功制备出NR/DnSiO_2复合材料。研究了随着SiO_2用量的增加硫化胶的物理机械性能及微观结构的变化规律，并与SiO_2用量相等的原位生成-湿炼法NR/nSiO_2硫化胶进行了比较。结果表明，湿炼法NR/DnSiO_2硫化胶在SiO_2用量为50~80phr的范围内，300%定伸应力略高，抗湿滑性能较低，滚动阻力较大，Payne效应明显较大，在NR/DnSiO_2复合材料中，SiO_2以粒径为150~210nm的聚集体存在；在SiO_2用量为50phr和60phr时撕裂强度和耐屈挠龟裂性能较优，其他物理机械性能相近，而拉伸断面呈“瓣膜”结构即补强机理为基体剪切屈服，无裸露的nSiO_2粒子存在，故硫化胶的综合性能较好；但在SiO_2用量为70phr和80phr时各项物理机械性能明显降低，拉伸断面无“瓣膜”结构存在，nSiO_2粒子分散不良，存在粒径为23~28μm的nSiO_2聚集体，故其硫化胶的综合性能明显较差。
通过比较分析表明，在SiO_2用量和硫化配方相同的条件下，硫化胶的综合性能以原位生成-湿炼法NR/nSiO_2最好，湿炼法NR/DnSiO_2次之，干炼法NR/白炭黑最差。
本文最后用NR胶乳与炭黑（N234）浆液以湿炼法制备了NR/N234复合材料，研究了随着炭黑用量的增加其硫化胶物理机械性能与结构的变化规律，并与干炼法NR/N234硫化胶进行了系统比较。结果表明，湿炼法NR/N234硫化胶的物理机械性能较好，尤其300%定伸应力、拉伸强度、撕裂强度和回弹值明显较高，而压缩疲劳温升及其永久变形大幅度降低，Payne效应明显较低，抗湿滑性能较好，而滚动阻力则相近。
研究结果表明，SiO_2用量为50~70phr的原位生成-湿炼法NR/nSiO_2、SiO_2用量为50~60phr的湿炼法NR/DnSiO_2和炭黑N234用量为45~55phr的NR/N234三类硫化胶的综合性能符合载重子午线轮胎胎面胶的要求，是优良的载重子午线轮胎胎面用胶料。
Only after the rubbers, especially the rubbers used for preparing car tires, reinforcedwith a reinforcing agent, the performance of the vulcanizates could meet the requirement forapplication. The carbon black is the most important reinforcing agent, and has the bestreinforcement effect to rubber and the maximum consumption. The white carbon black (SiO_2powder) is followed. The reinforcement effect of SiO_2is not better than that of carbon black,and the application of SiO_2was not universal too. But the rubber tire with silica as reinforcingagent had a significant advantage of a high wet skid resistance and low rolling resistance. Thestudy on rubber and silica composites being used to prepare tire tread has become a hot topicat present.
Since the birth of the rubber industry, the solid rubbers and the powder fillers were usedas raw material, and the mechanical refining method, or dry refining method was used topreparing masterbatch stock along with the rubber processing industry. The dry refiningmethod has the shortcomings of complex process, big investment for equipment and highlabor intensity. Reinforcing agents, especially carbon black, could be caused the blackpollution. The carbon black and the silica used to reinforcing rubber were nano-powders withhigh surface energy, so it is difficult to disperse the carbon black or the silica particles torubber matrix with mechanical shearing. The nano-particles often aggregated with severalmicrons in the rubber matrix, causing to damaging the physical and mechanical properties ofvulcanizates. The wet refining method is a novel technology for preparing masterbatch usingthe rubber latex and filler slurry as raw material. The filler particles were dispersed uniformlybetween the rubber latex particles by liquid mixing, and the wet refining system were formed.After coagulation-coprecipitation, the rubber/filler composites were obtained. The wetrefining method could easily overcome the shortcomings which are difficult to be overcomeby dry refining method.
In this article, firstly, the NR/nano-silica composites were prepared by the in situgeneration-wet refining method. Using the character of silica sol easy forming silica gel whenheated, the natural rubber latex (NR) was mixed with silica sol (silica precursor), and then thewet refining system was heated until the silica sol generating in-situ the nano-silica particles (nSiO_2) in the NR latex. The NR/nSiO_2nano-composites were obtained by means ofcoagulation. The effects of wet refining conditions and the different vulcanization recipeswere studied on the physical and mechanical properties of the NR/nSiO_2vulcanizates. Thewet refining conditions were involved the types and the contents of the surface active agentfor the silica sol particles and the nSiO_2particles, the type particle size and concentration ofthe silica sol, the concentration of NR latex, the reaction temperature and reaction time for theconversion of the silica sol into the nSiO_2gel particles, the types and the dosages offlocculant and the nSiO_2contents of the materbatch stock and so on. The optimiumconditions of wet refining and vulcanization recipe were determined with which thevulcanizates obtained had the best physical and mechanical properties. The results obtainedwere compared with the NR/SiO_2vulcanizates based on traditional dry mixing of bale naturalrubber and white carbon black. The results showed that the key factors affecting the physicaland mechanical properties of the vulcanizates were the type of the surface-active agent andthe type of the silica sol. When using the hydroxylether as the surface-active agent and aneutral silica sol as SiO_2precursor, the vulcanizates had excellent physical and mechanicalproperties with the SiO_2contents50~90phr. In particular,300%modulus, tensile strength,tear strength, abrasion resistance, compression fatigue heat and permanent deformation of thevulcanizates achieved a good level. The composites and its vulcanizates were analyzed byFourier transform infrared spectroscopy (FTIR)、differential scanning calorimetry (DSC) andthermal gravimetric analysis (TG、DTG). The bound rubber content of the NR/nSiO_2composites and the cross-linking degree of its vulcanizates were measured. The resultsindicated that silica sol in wet refining system was completely converted into nSiO_2. With theSiO_2contents increasing, the Tg of the composites and its vulcanizates did not changesignificantly and the initial thermal decomposition temperature gradually increased. TheNR/SiO_2vulcanizate was studied using rubber processing analyzer (RPA) and dynamicviscoelastic analysis (DMA). The results showed that, with the SiO_2content increasing, thePayne effect, or the SiO_2network architecture of the vulcanizates increased, the wet skidresistance decreased and rolling resistance increased. The scanning electron microscopy(SEM) analysis showed that, in the NR latex, the silica sol converted in-situ into SiO_2 surfaces of the vulcanizates shown a "valves" structure. This novel structure had not beenreported before. There were no bare nSiO_2aggregates and cracks existing on the tensilefracture surfaces. It was indicated that reinforcement mechanism of the NR/nSiO_2vulcanizates was NR matrix shear yield with the character of the "valve" structure. A goodpre-dispersity of nSiO_2particles in NR matrix and the reinforcement mechanism of matrixshear yield charactered by the special "valves" structure were the main reasons forvulcanizates having excellent physical mechanical properties and dynamic mechanicalproperties.
The NR/DnSiO_2composites and its vulcanizates were successfully prepared by the wetrefining method with natural latex and silica nano-dispersion (DnSiO_2) liquid as the main rawmaterial, under the condition without adding any surface-active agent for nSiO_2particles. Thevariation of mechanical properties and the microstructure of the vulcanizates was studiedwith the SiO_2contents increasing, and compared with the NR/nSiO_2vulcanizates prepared byin situ generation-wet refining method under the condition of the same SiO_2content. Theresults showed that, when the SiO_2contents were varied from50phr to80phr, the NR/DnSiO_2vulcanizates had slightly higher300%modulus, lower rolling resistance, significantly higherpayne effect and the SiO_2existed in the morphology of aggregates with average particle sizeof150~210nm in the NR/DnSiO_2composites, when the SiO_2contents at50phr and60phr, theNR/DnSiO_2vulcanizates had better tear strength, higher flex cracking resistance performance,similar other physical and mechanical properties and the "valve" structure without bare nSiO_2aggregates showed on the tensile fracture surface of the vulcanizates, which meant that thereinforcement mechanism was matrix shear yield, so that the vulcanizates had bettercomprehensive performance. But when the SiO_2contents at70phr and80phr, there was no"valve" structure on the tensile fracture surface of the NR/DnSiO_2vulcanizates in which theSiO_2particles were poorly dispersion and existed in aggregates with particle diameter of23μm~28μm. As a result, the overall performance of the vulcanizates was significantlyreduced.
The comparative analysis above showed that under the same SiO_2contents and samevulcanization recipe. among the three types of vulcanizates, the NR/nSiO_2vulcanizates hadthe best comprehensive performance, followed by the NR/DnSiO_2vulcanizates and the NR/silica vulcanizates, the worst
Finally the NR/N234composites prepared by wet refining method and traditional dryrefining method. The physical and mechanical properties and the structures of the two typesof vulcanizates were investigated. The results showed that compared with the vulcanizates ofthe NR/N234prepared by dry refining method, the NR/N234vulcanizates prepared by wetrefining method had better physical and mechanical properties, in particularly significantlyhigher300%modulus, tensile strength, tear strength and resilience value, and significantlylower compression fatigue temperature rise, compression permanent deformation, andpayne effect, better wet skid resistance and similar the rolling resistance.
The results showed that the comprehensive performance of three types of vulcanizes,involving the NR/nSiO_2vulcanizes prepared by in situ generation-wet refining method withSiO_2content of50~70phr, NR/DnSiO_2vulcanizes prepared by wet refining method with SiO_2contents of50~60phr and the NR/N234vulcanizes prepared by wet refining method withcarbon black N234contents of45~55phr, met the requirements for preparation of the radialtruck tire tread, and were the excellent composites of NR to prepare radial truck tire tread.
自橡胶工业诞生以来，橡胶加工行业一直以固体橡胶和粉体填料为原料，用机械混炼法即干炼法生产混炼胶。干炼法工艺复杂，设备投资大，劳动强度高，所用补强剂尤其炭黑会造成黑色污染。加工汽车轮胎胶料所用炭黑或白炭黑属纳米粉体，表面能高，用机械湿炼法很难达到纳米级分散，而往往以粒径较大的聚集体分布于橡胶基体中，从而损害其硫化胶的物理机械性能。湿炼法是指以橡胶胶乳和填料浆液为原料，通过液相混合将填料粒子分散于橡胶乳胶粒之间，构成湿炼体系，凝聚共沉后形成橡胶/填料复合材料的技术过程。湿炼法可容易地克服干炼法难以克服的缺点。
本文首先用原位生成-湿炼法制备天然橡胶（NR）/二氧化硅（SiO_2）纳米复合材料。其过程是用NR胶乳与SiO_2的前驱体硅溶胶混合，利用硅溶胶受热生成SiO_2凝胶的性质，对湿炼体系加热，使硅溶胶在NR胶乳中原位生成纳米二氧化硅粒子（nSiO_2），然后凝聚共沉，获得NR/nSiO_2复合材料。系统研究了硅溶胶粒子及nSiO_2粒子表面处理剂的类型及用量，硅溶胶的类型、粒径及浓度，NR胶乳的浓度，硅溶胶转化为nSiO_2凝胶粒子的反应温度与反应时间，凝聚剂的类型及用量，nSiO_2的用量等湿炼条件以及不同硫化配方对原位生成-湿炼法NR/nSiO_2硫化胶物理机械性能的影响，确定了能使硫化胶达到最佳性能的湿炼条件和硫化配方，并与干炼法NR/白炭黑硫化胶进行了系统比较。结果表明，影响硫化胶物理机械性能的关键因素是硅溶胶的类型和表面处理剂的类型，当以中性硅溶胶为SiO_2前驱体和醇醚作表面处理剂时，其硫化胶在SiO_2用量为50~90phr的范围内具有优良的物理机械性能，尤其300%定伸应力、拉伸强度、撕裂强度、耐磨性能、压缩疲劳生热及其永久变形都达到良好水平。用FTIR、DSC和TG、DTG对复合材料及其硫化胶进行了分析，测定了NR/nSiO_2复合材料的结合胶含量及其硫化胶的交联程度。结果表明，在湿炼体系中硅溶胶全部转化为nSiO_2，随着SiO_2用量的增加，复合材料及其硫化胶的Tg变化不明显，起始热分解温度则逐渐提高。用DMA和RPA对硫化胶进行了系统分析。结果表明，随着SiO_2用量的增加，硫化胶的抗湿滑性能有所下降，滚动阻力有所增大，Payne效应即SiO_2网络结构程度增大。SEM分析显示，硅溶胶在NR胶乳中原位生成了平均粒径为50nm的nSiO_2粒子，硫化胶拉伸断面呈“瓣膜”结构，无裸露的nSiO_2聚集体及裂纹存在，表明nSiO_2在NR基体中的良好预分散赋予了其硫化胶以特殊的“瓣膜”结构为特征的基体剪切屈服的补强机理，使硫化胶具有优良的物理机械性能和动态力学性能。
本文还用天然胶乳和二氧化硅纳米分散体（DnSiO_2）为主要原料，以湿炼法成功制备出NR/DnSiO_2复合材料。研究了随着SiO_2用量的增加硫化胶的物理机械性能及微观结构的变化规律，并与SiO_2用量相等的原位生成-湿炼法NR/nSiO_2硫化胶进行了比较。结果表明，湿炼法NR/DnSiO_2硫化胶在SiO_2用量为50~80phr的范围内，300%定伸应力略高，抗湿滑性能较低，滚动阻力较大，Payne效应明显较大，在NR/DnSiO_2复合材料中，SiO_2以粒径为150~210nm的聚集体存在；在SiO_2用量为50phr和60phr时撕裂强度和耐屈挠龟裂性能较优，其他物理机械性能相近，而拉伸断面呈“瓣膜”结构即补强机理为基体剪切屈服，无裸露的nSiO_2粒子存在，故硫化胶的综合性能较好；但在SiO_2用量为70phr和80phr时各项物理机械性能明显降低，拉伸断面无“瓣膜”结构存在，nSiO_2粒子分散不良，存在粒径为23~28μm的nSiO_2聚集体，故其硫化胶的综合性能明显较差。
通过比较分析表明，在SiO_2用量和硫化配方相同的条件下，硫化胶的综合性能以原位生成-湿炼法NR/nSiO_2最好，湿炼法NR/DnSiO_2次之，干炼法NR/白炭黑最差。
本文最后用NR胶乳与炭黑（N234）浆液以湿炼法制备了NR/N234复合材料，研究了随着炭黑用量的增加其硫化胶物理机械性能与结构的变化规律，并与干炼法NR/N234硫化胶进行了系统比较。结果表明，湿炼法NR/N234硫化胶的物理机械性能较好，尤其300%定伸应力、拉伸强度、撕裂强度和回弹值明显较高，而压缩疲劳温升及其永久变形大幅度降低，Payne效应明显较低，抗湿滑性能较好，而滚动阻力则相近。
研究结果表明，SiO_2用量为50~70phr的原位生成-湿炼法NR/nSiO_2、SiO_2用量为50~60phr的湿炼法NR/DnSiO_2和炭黑N234用量为45~55phr的NR/N234三类硫化胶的综合性能符合载重子午线轮胎胎面胶的要求，是优良的载重子午线轮胎胎面用胶料。
Only after the rubbers, especially the rubbers used for preparing car tires, reinforcedwith a reinforcing agent, the performance of the vulcanizates could meet the requirement forapplication. The carbon black is the most important reinforcing agent, and has the bestreinforcement effect to rubber and the maximum consumption. The white carbon black (SiO_2powder) is followed. The reinforcement effect of SiO_2is not better than that of carbon black,and the application of SiO_2was not universal too. But the rubber tire with silica as reinforcingagent had a significant advantage of a high wet skid resistance and low rolling resistance. Thestudy on rubber and silica composites being used to prepare tire tread has become a hot topicat present.
Since the birth of the rubber industry, the solid rubbers and the powder fillers were usedas raw material, and the mechanical refining method, or dry refining method was used topreparing masterbatch stock along with the rubber processing industry. The dry refiningmethod has the shortcomings of complex process, big investment for equipment and highlabor intensity. Reinforcing agents, especially carbon black, could be caused the blackpollution. The carbon black and the silica used to reinforcing rubber were nano-powders withhigh surface energy, so it is difficult to disperse the carbon black or the silica particles torubber matrix with mechanical shearing. The nano-particles often aggregated with severalmicrons in the rubber matrix, causing to damaging the physical and mechanical properties ofvulcanizates. The wet refining method is a novel technology for preparing masterbatch usingthe rubber latex and filler slurry as raw material. The filler particles were dispersed uniformlybetween the rubber latex particles by liquid mixing, and the wet refining system were formed.After coagulation-coprecipitation, the rubber/filler composites were obtained. The wetrefining method could easily overcome the shortcomings which are difficult to be overcomeby dry refining method.
In this article, firstly, the NR/nano-silica composites were prepared by the in situgeneration-wet refining method. Using the character of silica sol easy forming silica gel whenheated, the natural rubber latex (NR) was mixed with silica sol (silica precursor), and then thewet refining system was heated until the silica sol generating in-situ the nano-silica particles (nSiO_2) in the NR latex. The NR/nSiO_2nano-composites were obtained by means ofcoagulation. The effects of wet refining conditions and the different vulcanization recipeswere studied on the physical and mechanical properties of the NR/nSiO_2vulcanizates. Thewet refining conditions were involved the types and the contents of the surface active agentfor the silica sol particles and the nSiO_2particles, the type particle size and concentration ofthe silica sol, the concentration of NR latex, the reaction temperature and reaction time for theconversion of the silica sol into the nSiO_2gel particles, the types and the dosages offlocculant and the nSiO_2contents of the materbatch stock and so on. The optimiumconditions of wet refining and vulcanization recipe were determined with which thevulcanizates obtained had the best physical and mechanical properties. The results obtainedwere compared with the NR/SiO_2vulcanizates based on traditional dry mixing of bale naturalrubber and white carbon black. The results showed that the key factors affecting the physicaland mechanical properties of the vulcanizates were the type of the surface-active agent andthe type of the silica sol. When using the hydroxylether as the surface-active agent and aneutral silica sol as SiO_2precursor, the vulcanizates had excellent physical and mechanicalproperties with the SiO_2contents50~90phr. In particular,300%modulus, tensile strength,tear strength, abrasion resistance, compression fatigue heat and permanent deformation of thevulcanizates achieved a good level. The composites and its vulcanizates were analyzed byFourier transform infrared spectroscopy (FTIR)、differential scanning calorimetry (DSC) andthermal gravimetric analysis (TG、DTG). The bound rubber content of the NR/nSiO_2composites and the cross-linking degree of its vulcanizates were measured. The resultsindicated that silica sol in wet refining system was completely converted into nSiO_2. With theSiO_2contents increasing, the Tg of the composites and its vulcanizates did not changesignificantly and the initial thermal decomposition temperature gradually increased. TheNR/SiO_2vulcanizate was studied using rubber processing analyzer (RPA) and dynamicviscoelastic analysis (DMA). The results showed that, with the SiO_2content increasing, thePayne effect, or the SiO_2network architecture of the vulcanizates increased, the wet skidresistance decreased and rolling resistance increased. The scanning electron microscopy(SEM) analysis showed that, in the NR latex, the silica sol converted in-situ into SiO_2 surfaces of the vulcanizates shown a "valves" structure. This novel structure had not beenreported before. There were no bare nSiO_2aggregates and cracks existing on the tensilefracture surfaces. It was indicated that reinforcement mechanism of the NR/nSiO_2vulcanizates was NR matrix shear yield with the character of the "valve" structure. A goodpre-dispersity of nSiO_2particles in NR matrix and the reinforcement mechanism of matrixshear yield charactered by the special "valves" structure were the main reasons forvulcanizates having excellent physical mechanical properties and dynamic mechanicalproperties.
The NR/DnSiO_2composites and its vulcanizates were successfully prepared by the wetrefining method with natural latex and silica nano-dispersion (DnSiO_2) liquid as the main rawmaterial, under the condition without adding any surface-active agent for nSiO_2particles. Thevariation of mechanical properties and the microstructure of the vulcanizates was studiedwith the SiO_2contents increasing, and compared with the NR/nSiO_2vulcanizates prepared byin situ generation-wet refining method under the condition of the same SiO_2content. Theresults showed that, when the SiO_2contents were varied from50phr to80phr, the NR/DnSiO_2vulcanizates had slightly higher300%modulus, lower rolling resistance, significantly higherpayne effect and the SiO_2existed in the morphology of aggregates with average particle sizeof150~210nm in the NR/DnSiO_2composites, when the SiO_2contents at50phr and60phr, theNR/DnSiO_2vulcanizates had better tear strength, higher flex cracking resistance performance,similar other physical and mechanical properties and the "valve" structure without bare nSiO_2aggregates showed on the tensile fracture surface of the vulcanizates, which meant that thereinforcement mechanism was matrix shear yield, so that the vulcanizates had bettercomprehensive performance. But when the SiO_2contents at70phr and80phr, there was no"valve" structure on the tensile fracture surface of the NR/DnSiO_2vulcanizates in which theSiO_2particles were poorly dispersion and existed in aggregates with particle diameter of23μm~28μm. As a result, the overall performance of the vulcanizates was significantlyreduced.
The comparative analysis above showed that under the same SiO_2contents and samevulcanization recipe. among the three types of vulcanizates, the NR/nSiO_2vulcanizates hadthe best comprehensive performance, followed by the NR/DnSiO_2vulcanizates and the NR/silica vulcanizates, the worst
Finally the NR/N234composites prepared by wet refining method and traditional dryrefining method. The physical and mechanical properties and the structures of the two typesof vulcanizates were investigated. The results showed that compared with the vulcanizates ofthe NR/N234prepared by dry refining method, the NR/N234vulcanizates prepared by wetrefining method had better physical and mechanical properties, in particularly significantlyhigher300%modulus, tensile strength, tear strength and resilience value, and significantlylower compression fatigue temperature rise, compression permanent deformation, andpayne effect, better wet skid resistance and similar the rolling resistance.
The results showed that the comprehensive performance of three types of vulcanizes,involving the NR/nSiO_2vulcanizes prepared by in situ generation-wet refining method withSiO_2content of50~70phr, NR/DnSiO_2vulcanizes prepared by wet refining method with SiO_2contents of50~60phr and the NR/N234vulcanizes prepared by wet refining method withcarbon black N234contents of45~55phr, met the requirements for preparation of the radialtruck tire tread, and were the excellent composites of NR to prepare radial truck tire tread.
引文
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