Scanning electron microscopy studies on tensile failure of thermoplastic elastomers from polypropylene-natural rubber blends

The tensile properties of thermoplastic polypropylene [pp]-natural rubber [NR]blends have been evaluated with special reference to the effect of blend ratios and dynamic cross-linking of the elastomer phase. The effects of silica filler and silane coupling agent on the tensile properties of the 30:70 PP:NR blend have also been studied. Analysis of the stress-strain curves and scanning electron microscopic examination of the tensile fracture surfaces of the blends have been used to correlate the test results on tensile properties.     

Characterization of dispersion state of filler and polymer-filler interactions in rubber-carbon black composites

The physical properties of carbon black-filled rubbers are affected mainly by the distribution of filler, carbon black properties and polymer-filler interactions. A number of experimental methods and approaches for characterization of the dispersion state of filler in rubber-carbon black composites and an investigation of polymer-filler interactions are reviewed. The dispersion state characterization, electrical conductivity measurements, bound rubber evaluations, mechanical properties measurements, carbon black surface properties study, small angle X-ray scattering (SAXS) and nuclear magnetic resonance (NMR) spectroscopy are among the most important ones.     

Master curve of filler localization in rubber blends at an equilibrium state

In this study, the phase-specific localization of filler in NBR/NR blends was characterized by means of the selective extraction method and wetting concept. A strong dependence of silica localization on the filler loading was found. A model based on thermodynamic data was proposed for a quantitative prediction of filler localization in rubber blends. The filler localization can be described by a master curve demonstrating a characteristic behavior in dependence on the filler surface tension data of blend components and filler. The effect of filler loading on the silica localization is sufficiently explained by this model by taking into consideration the deactivation of the silanol groups on the silica surface by adsorbed curing additives. Using the master curve, the surface tension of filler affected by curing additives and silane addition can be estimated that may be useful for evaluation and comparison of the effect of different coupling agents. Surface tension values of different fillers were estimated by means of the master curve and they lie in the same order compared to those reported in literature. A potential transfer of filler within a rubber blend can be also quantitatively predicted.     

Oberflächenenergetische Charakterisierung

Surface Energetic Characterization of Nanoscale Fillers and Elastomers Almost any technically used rubber material is filled with particles in nanometer size, by which the properties of the material can be specific controlled. In modern car tires the used fillers have crucial influence on driving security (wet grip and ice grip), on fuel consumption (rolling resistance) and on the cost‐effectiveness (life time of the tire) [1].The first fillers used in rubber application were carbon blacks; actually in passenger car tires mostly surface modified silica is applied. The implementation of novel filler systems like organophilic modified layered silicates (organo‐clays) or carbon nanotubes is subject of intense research [2,3]. Surface energy and –polarity of the filler surface is a crucial, but often underestimated determining factor. All surface properties of rubber and filler have to be well balanced to get the nanoscale filler particles finely dispersed in the rubber matrix and also to obtain a good adhesion between polymer and filler surface.     

可分散性纳米二氧化硅增强硅橡胶

采用表面经过硅烷偶联剂原位修饰的纳米二氧化硅增强硅橡胶。通过扫描电子显微镜和Payne 效应考察了纳米二氧化硅在硅橡胶中的分散特性; 用DSC 分析了复合体系的低温结晶行为; 考察了填料对硅橡胶力学性能的影响。结果表明, 由于修饰后纳米颗粒表面非极性有机基团的存在和表面能的降低, 无须加入分散剂, 纳米颗粒就能在硅橡胶中有较好的分散; 在各自最优添加量时, DNS-3 链状纳米二氧化硅增强的硅橡胶相对于气相法二氧化硅增强的硅橡胶在拉伸强度、撕裂强度及断裂伸长率上有显著提高; DNS-2 纳米二氧化硅增强性能与气相法二氧化硅的相当, 但前者混炼胶黏度较小, 有较好的加工性。      

Effect of silane coupling agent on vulcanization,network structure,polymer-filler interaction,physical properties and failure mode of mica-filled styrene-butadiene rubber

Physical properties of composites from mica and styrene-butadiene rubber (SBR) have been studied with special reference to the effect of silane coupling agent (A-174) in the compound. Tensile and tear properties increase with the addition of mica. The increase of tensile properties in more pronounced in the case of silane-treated mica. Silane treatment also raises the volume fraction of rubber in solvent-swollen rubber vulcanizate. Attempts have been made to correlate the changes in properties with the network structure of rubber. In order to understand the mechanism of failure, tensile fracture surfaces have been examined by scanning electron microscopy (SEM). The fractographs have been correlated with the strength and type of failure of these composites. The observed values of viscosity (rheometric) correspond to the calculated values from existing theory based on the hydrodynamic model of dispersed particles in a fluid medium.     

改性白炭黑/天然橡胶复合材料的制备及性能

采用双-[γ-(三乙氧基硅)丙基]四硫化物(Si69)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、乙基三甲氧基硅烷(11-100)对白炭黑进行表面改性,并制备改性白炭黑/天然橡胶复合材料。利用红外光谱(FT-IR)、热重分析(TG)、扫描电镜、橡胶加工分析仪等测试手段对改性白炭黑及改性SiO_2/NR复合材料的结构与性能进行了表征,并研究其硫化性能及力学性能。结果表明,经FT-IR、TG分析,3种硅烷偶联剂已成功接枝到白炭黑表面;改性SiO_2/NR复合材料相对于未改性SiO_2/NR,焦烧时间变长,正硫化时间缩短,结合胶含量增大;改性SiO_2/NR与未改性SiO_2/NR相比其定伸应力、撕裂强度明显提高,但断裂伸长率有所减小;改性白炭黑在天然橡胶基体中的分散性明显提高,其中Si69-SiO_2在天然橡胶基体中的分散性最好;Si69-SiO_2/NR复合材料的滚动阻力与生热最低;改性后的SiO_2/NR复合材料的拉伸断面粗糙程度增加。     

Microstructural studies of the interactions in SB rubber and mesoporous silica mixtures

Precipitated silicas have been utilized successfully as rubber reinforcing fillers instead of carbon black. The development of new mesoporous silicas with properties different than the precipitated silicas, specially their high BET surface areas and their organized pore structures with pore sizes between 1.5–10 nm, make them potential materials in rubber reinforcing. The knowledge of the interactions between rubber and its filler at a fundamental level is important to understand the physical and mechanical properties of a filled rubber system. This paper presents a comparative microstructural analysis of the interactions of the styrene butadiene rubber (SBR) with mesoporous silica and with Ultrasil VN3 silica, made on mixtures prepared in a rheometer at 150 °C and their toluene extracted residues. Solid state nuclear magnetic resonance, Fourier transform infrared (FTIR), thermogravimetry (TGA), scanning electron microscopy (SEM) and nitrogen adsorption isotherms, show a relation between the strength of the interaction and the particle size and pore structure characteristics of the mesoporous materials. Such a material prepared under certain specific conditions shows better interaction with the rubber than Ultrasil VN3 silica. Electronic Publication     

Novel precipitated silicas: an active filler of synthetic rubber

Highly dispersed silicas have been obtained at a semi-technical scale by precipitation from sodium metasilicate solutions using appropriately diluted solutions of ammonium hydrogencarbonate or ammonium chloride. The difference, as compared to the generally applied technology of silica precipitation using acids or their anhydrides, has been the involvement of the precipitation reaction in alkaline media. Attempts have been made at changing the silica surface character from hydrophilic to more hydrophobic, using a modifier from the group of silane coupling agents. The alkoxysilanes modifiers contained groups with chemical affinity towards functional groups of butadiene–styrene rubber. Modification of silica surface using silane coupling agents has been found to improve the reinforcement of vulcanizates, by increasing the tensile and tear strength in particular.     

Effect of the temperature on surface modification of silica and properties of modified silica filled rubber composites

The modified silica at different temperature (MSaDT) with bis(3-triethoxysilylpropyl)tetrasulfide (TESPT), and MSaDT filled solution styrene butadiene rubber (SSBR) composites were prepared to investigate the effect of temperature on surface modification of silica. The results showed that TESPT was successfully bonded on the surface of silica by chemical bonds. The grafting degree (K) of MSaDT of 50 °C was 62.2% and higher than that at the other temperatures. The thermal weight loss and the size distribution of MSaDT showed that the silanol of TESPT hydrolysates reacted with the surface hydroxyl groups of silica, decreasing the average size and agglomeration of modified silica. For 50 °C modified silica/SSBR composite, the static mechanical properties and rubber–filler interaction of the composite were better than those of the others. As far as dynamic mechanical properties are concerned, the 50 °C modified silica/SSBR composite owned a best combination of low rolling resistance and high wet skid resistance.     

废胶粉的表面处理及在天然橡胶中的应用

采用硅烷偶联剂KH550对废胶粉进行表面处理,并将处理后的废胶粉与天然橡胶复合制备WRP/NR复合材料。借助L16(45)正交试验及单因素试验,探讨了废胶粉目数、废胶粉用量、硅烷偶联剂KH550用量对复合材料力学性能的影响;对处理后的废胶粉表面和橡胶拉伸试样断裂面进行了扫描电镜(SEM)观察;并通过热重分析研究了天然橡胶和复合材料的热降解性能。结果表明:当废胶粉目数为80目,废胶粉用量为10%,硅烷偶联剂KH550用量为1.5%时,复合材料的力学性能最优,拉伸强度为27.89MPa。SEM结果表明废胶粉表面粗糙度增大,比表面积增大,与NR基体的相容性得到了提高。而热重分析表明改性废胶粉的加入对天然橡胶的热稳定性能影响不大。     

The role of interfacial interactions on the glass-transition and viscoelastic properties of silica/polystyrene nanocomposite

Filler surface properties and polymer-filler interactions have dominate influence on viscoelastic behavior of polymeric matrix composites. When the filler-filler spacing is on the order of the polymeric matrix molecular size, fillers may agglomerate through direct short-range interactions, also by overlapping of interfacial layers of neighboring fillers. In this work the effect of interfacial layer on the viscoelastic properties of silica/polystyrene composite was investigated.The Si/Ps nanocomposites were prepared by solution mixing method, and dynamic rheometry was employed to determine the viscoelastic behavior in the melt state. Experimental results show that, addition of silica nanoparticles to polystyrene matrix would increase the glass-transition temperature of polymer. This increasing will be accelerated by presence of nanoparticles with more filler-polymer adhesion energy, because of more interfacial layer volume fraction. It is helpful in evaluating the volume fraction and equivalent thickness of interfacial layer in polymer nanocomposites. Likewise it is shown that, the dynamic moduli of nanocomposite is enhanced associated with the increase in the glass-transition temperature. This study implies that the main source of increment in both dynamic modulus and glass-transition temperature of polymer nanocomposites is the presence of the immobilized interfacial layer and the secondary filler network.     

Characterization of filled rubbers using small-angle X-ray scattering

It is demonstrated how small-angle X-ray scattering (SAXS) can be used to characterize the structure of fillers such as carbon black and silica both before and after their incorporation into natural rubber. It is found that SAXS has significant advantages over conventional techniques such as gas adsorption or electron microscopy in determining both the size and distribution of sizes of the filler particles. The results are shown to be in good agreement with those obtained using conventional techniques. In addition it is demonstrated that SAXS can be used to characterize the filler particlesin situ enabling the volume fraction, particle size and particle surface area to be determined for a filled rubber and factors such as aggregation to be examined.     

In situ SALS and volume variation measurements during deformation of treated silica filled SBR

Original in situ measurements of volume variation and small angle light scattering (SALS) are performed on silica filled Styrene Butadiene Rubber (SBR) during tensile tests. The influence of the silica treatment on the mechanisms involved is explored with sample carefully characterised and with the same filler dispersion. Two different types of silane are used as treatment, an alkoxy silane (so called covering agent) and a coupling agent which enables covalent bonds between the silica and the polymer matrix. It is shown that the coupling agent delays void formation in the samples and leads at intermediary strain to the reorganisation of the filler structure while the covering agent eases the void formation which also occurs without silica surface treatment.     

超细粉碎表面改性透辉石增强橡胶材料

采用硬脂酸、铝酸酯和硅烷偶联剂3种改性剂分别对超细透辉石粉体进行表面改性,通过接触角和活化指数评价表面改性效果,同时以硬度、扯断强度、扯断伸长率、定伸强度、扯断永久变形和抗老化性能为量化指标分析了改性透辉石粉体取代炭黑作为橡胶填料的力学性能。结果表明,硅烷偶联剂对超细透辉石粉体的改性效果好,并且对橡胶有较好的补强效果,这是因为活化改性增强了透辉石填料与聚合物基体的结合强度,因此能全部或部分代替炭黑等常规橡胶填料,从而降低橡胶生产成本。     

石墨烯硅橡胶复合材料的性能研究

本文采用复配的石墨烯、碳纳米管和氧化铝为导热填料制备了具有导热功能的有机硅复合材料。研究了石墨烯、碳纳米管和氧化铝的复配比例对复合材料体积电阻率、导热系数、拉伸强度等性能的影响;同时,以Gr-C-4#样品为基础配方,采用硅烷偶联剂Si-G-1分别对石墨烯、碳纳米管及氧化铝进行改性,并用改性后的填料配制石墨烯硅橡胶复合材料Gr-C-Si-1#,对比样品Gr-C-4^#与Gr-C-Si-1^#的性能差异,分析了改性复配填料对复合材料性能的影响。采用石墨烯硅橡胶复合材料对电缆终端进行了封装,对封装好的电缆终端开展了100、150、200A电流下的温升实验,未出现局部过热,并测定水浸泡前后的电缆终端电阻,封装后的电缆终端电阻未出现明显上升,实验结果表明本材料可以在电缆终端或中间连接处进行灌封,可对封铅连接处的良好的保护作用,工程应用意义重大。     

Modified zinc silicate — an active rubber filler

Physico-chemical properties have been characterized for zinc silicates obtained in various conditions in reaction of sodium metasilicate solution with water soluble zinc salt (zinc sulphate or chloride). Attempts have been made to apply the precipitated zinc silicates in rubber mixtures based on butadiene-styrene rubber. Appropriate tests have been conducted. Also, a possibility has been tested of eliminating zinc oxide (an activator in the vulcanization process) from the rubber mixture. Studies have been presented on the modification of zinc silicate surface with silane and titanate coupling agents. The extent of surface modification has been estimated measuring heats of surface immersion and determining chemisorbed carbon on the surface which has originated from coupling agents. The effect of modifying zinc silicate surface has been evaluated by strength tests performed on vulcanizates filled with the modified silicates.     

研磨溶液对改性石墨矿表面性质及微观结构的影响

使用行星式球磨机对石墨矿粉(G)进行湿法球磨改性,以硅烷偶联剂Si-69为改性剂,考察了球磨溶液对石墨矿粉微观结构和表面性质的影响,然后将改性石墨矿粉填充到丁苯橡胶中,考察了改性石墨/丁苯胶复合材料的力学性能及微观结构.结果表明,球磨溶液不同,改性石墨矿粉的微观结构和表面性质有所不同.以异丙醇为球磨溶液的改性石墨矿粉(...     

Effect of silica particles modified by in-situ and ex-situ methods on the reinforcement of silicone rubber

In-situ and ex-situ methods were applied to modify silica particles in order to investigate their effects on the reinforcement of silicone rubber. Surface area and pore analyzer, laser particle size analyzer, Fourier-transform infrared spectroscopy (FTIR), contact-angle instrument, and transmission electron microscope (TEM) were utilized to investigate the structure and properties of the modified silica particles. Dynamic mechanical thermal analyzer (DMTA) was employed to characterize the vulcanizing behavior and mechanical properties of the composites. Thermogravimetric analysis (TGA) was performed to test the thermal stability of the composites. FTIR and contact angle analysis indicated that silica particles were successfully modified by these two methods. The BET surface area and TEM results reflected that in-situ modification was more beneficial to preparing silica particles with irregular shape and higher BET surface area in comparison with ex-situ modification. The DMTA and TGA data revealed that compared with ex-situ modification, the in-situ modification produced positive influence on the reinforcement of silicone rubber.     

接枝改性白炭黑对溶聚丁苯橡胶裂纹生长行为的影响

白炭黑是一种重要的橡胶填料,通过硅烷偶联剂改性,制备了不同接枝率白炭黑填充的溶聚丁苯橡胶。研究表明,接枝改性后白炭黑在橡胶基体中的分散得到改善,增强效果提升,裂纹生长速率随接枝率显著降低。进一步在动态载荷下对橡胶裂纹尖端进行正面观察其韧带生成、生长以及断裂的情况,发现随接枝率的提高,裂纹尖端韧带分布呈均匀化和细化的趋势。基于开裂形态与断裂面分析揭示了改性白炭黑填充溶聚丁苯橡胶抗裂纹生长能力提高的原因。