改性剂种类对白炭黑补强阻尼硅橡胶性能的影响

以阻尼硅橡胶母胶、气相法白炭黑、改性剂为原料,制成了热硫化阻尼硅橡胶。研究了羟基硅油、六甲基环三硅氮烷、乙烯基三乙氧基硅烷(A-151)、γ-氨丙基三乙氧基硅烷(KH 550)、γ-环氧丙氧基丙基三甲氧基硅烷(KH 560)及其并用对阻尼硅橡胶硫化性能、分散性能、力学性能和黏弹性能的影响。结果表明,硅烷偶联剂类改性剂能显著加快混炼胶的硫化速度、缩短硫化时间;羟基硅油、六甲基环三硅氮烷和KH 560作改性剂时白炭黑的分散效果良好,而采用A 151作改性剂时白炭黑填料网络的Payne效应较明显,但在宽温域(-120~100℃)范围内具有温度稳定性;不同改性剂并用对改善白炭黑分散性没有明显的协同作用;改性剂种类对硫化胶的力学性能影响不大;六甲基环三硅氮烷与KH 560并用时,硅橡胶的阻尼性能最高。     

Tailoring Silica Surface Properties by Plasma Polymerization for Elastomer Applications

The surface properties of reinforcing fillers are a crucial factor for dispersion and filler–polymer interaction in rubber compounds, as they strongly influence the final vulcanized properties of the rubber article. Silica is gaining more and more importance as reinforcing filler for rubbers, as it allows for a reduction of rolling resistance and thus energy losses in tires, compared to the use of carbon black as filler. However, silica and common elastomers differ greatly in polarity and, therefore, are difficult to mix and thus have little interaction. In the present study plasma-coating of silica-filler with acetylene, thiophene and pyrrole is applied, and the surface-treated silicas are blended with S-SBR rubber, in an attempt to enhance the compatibility between the two. The dispersion and reinforcing effects of the modified silicas are investigated and compared with untreated and silanized silica. The relative rankings of the various coatings in reduction of filler–filler interaction, improved dispersion, enhanced polymer–filler interaction, apparent crosslink density and tensile mechanical properties are mutually different. Where the best silica dispersion and largest reduction in filler–filler interaction are obtained with polyacetylene coating and the worst with polythiophene coating, but the tensile properties achieved with the polythiophene coating are far better than all others. Apparently, the sulfur contained in the thiophene-moiety enhances the filler–polymer interaction and contributes to the degree of crosslinking. Unmodified silica performs worst in all aspects, also because its acidic nature harms the preferably alkaline vulcanization process. Silane treatment of silica has a positive effect on reduction of filler–filler interaction and improved dispersion, but has little effect on polymer–filler interaction in the still unvulcanized state. Its tensile properties after vulcanization are comparable with polyacetylene- or polypyrrole-coated silica. This investigation shows that the compatibility and interaction of silica with a polymer can be controlled by tailoring the surface energy of the filler by coating with plasma polymers. An appropriate monomer for the plasma polymerization process allows to improve the cured rubber properties.     

环保型溶聚丁苯橡胶/顺丁橡胶并用胶与白炭黑的相互作用研究

探讨了国产环保型溶聚丁苯橡胶SSBR2564S和端基硅偶联SSBR72612S在半钢子午胎胎面胶中的应用,研究了两种SSBR与BR并用对白炭黑分散性的影响,并进一步考查了各并用体系混炼胶和硫化胶的基本性能。结果表明：BR与白炭黑的相互作用较SSBR要弱,SSBR更利于白炭黑的分散,端基硅偶联SSBR与白炭黑的相互作用更强;BR能有效缩短并用胶的硫化时间,改善SSBR72612S的加工性能;随BR并用量的增加,硫化胶的耐磨性得到明显改善,断裂伸长率、撕裂强度和回弹均有所提升,而300%定伸应力降低。BR能降低SSBR2564S体系的滚动阻力,但使两种SSBR体系的抗湿滑性损失较大。     

白炭黑/天然橡胶复合材料疲劳过程中微观结构与性能演变

本研究采用单轴疲劳机对白炭黑/天然橡胶复合材料样品进行了不同程度的疲劳,并对样品在不同阶段的微观结构和力学性能进行了表征。透射电镜扫描显示在疲劳过程中白炭黑的分散程度以及填料网络出现了先变好后变差的现象。溶胀法测试交联密度显示交联密度也经历了一个先降低后升高再降低的过程,说明复合材料的填料网络和交联网络在疲劳的过程中经历了一个破坏重建再破坏的过程。动态热机械分析仪(DMA)显示在疲劳过程中样品的玻璃化转变温度是先降低后升高。模量-应变曲线显示10万次疲劳后的试样内部填料的分散非常均匀,Payne效应减弱。力学性能测试表明经历了5-10万次的疲劳后,样品的力学性能超过了未疲劳样品。     

硅橡胶补强填料的研究进展

纯硅橡胶的机械强度很低,添加补强填料是提高硅橡胶物理机械性能的主要手段。简要介绍了近年来有关气相法白炭黑、沉淀法白炭黑、短纤维与碳纳米管、纳米碳酸钙在硅橡胶补强中的应用研究概况。     

Experimental tracking of silica dispersion into silicone polymer

This work deals with the experimental tracking of a dispersion of very fine silica particles in PDMS using a new, easily implemented methodology. The dispersion experiments are carried out in an 8-l capacity mixer equipped with a torquemeter. Using a Couette analogy, the torque-rotational speed data can be converted into process viscosity-effective shear rate data. Simultaneously, the Particle Size Distribution (PSD) evolution is followed through Laser Light Scattering measurements on diluted samples. The PSD evolution allowed us to interpret the dispersion process in terms of different mechanisms, such as breaking-up and erosion of aggregates, as well as, in some cases, re-agglomeration (or flocculation) of particles.     

聚硅氧烷消泡剂的失活和再生机理

介绍了聚硅氧烷消泡剂失活和再生的现象,分析了失活过程中消泡剂分散体粒径大小和分布,泡沫体系的表面张力、接触角、硅油铺展层的厚度以及泡沫膜的结构和状态,结果表明：硅油组成的改变、硅油和疏水二氧化硅微粒的分离、消泡剂分散体粒径的变小、铺展油层的消失和白色絮凝物的出现导致消泡剂失活,其中二氧化硅硅粒-硅油的分离和泡沫膜上硅油铺展油层的消失是主要因素。失活的消泡剂中加入硅油,消泡活性可再次恢复,这主要是由于消泡剂分散体粒子中的硅油-二氧化硅硅粒比例达到最佳的状态并在泡沫膜上又形成了新的具有消泡活性的硅油铺展油层。     

填料对双组分缩合型室温硫化硅橡胶性能的影响

考察了多种补强填料和半补强(或增量)填料如硅藻土、碳酸钙和氧化铝等对室温硫化(RTV)硅橡胶的机械性能和介电性能的影响。结果表明,采用经六甲基二硅氮烷处理的气相法白炭黑或沉淀法白炭黑作填料时,RTV硅橡胶多方面的性能都有所提高;采用补强填料和半补强填料并用的RTV硅橡胶的性能优于使用单一补强填料的RTV硅橡胶;随着填料用量的增加,RTV硅橡胶的机械性能、相对介电常数和介质损耗因数都有一定程度的提高,但体积电阻率有所降低。     

聚碳酸酯微粉/气相白炭黑杂化增强硅橡胶

利用磨盘形力化学反应器常温粉碎制备了聚碳酸酯（PC）微粉，在硅橡胶的常规补强体系中，引入PC微粉部分代替白炭黑，实现了对硅橡胶的杂化增强，在一定程度上改善了硅橡胶复合材料的力学性能。考察了PC微粉添加量、粒径以及表面处理白炭黑对硅橡胶复合材料力学性能的影响。结果表明，用PC微粉部分代替白炭黑，可以大幅度提高硅橡胶复合材料的断裂伸长率，从230％提高到最大320％左右，撕裂强度从12．3kN／m提高到最大14．6kN／m，复合材料的硬度显著降低，从78降低至68，白炭黑经硅烷偶联剂处理后，硅橡胶复合材料的硬度减小为63。     

Large strain and toughness enhancement of poly(dimethyl siloxane) composite films filled with electrospun polyacrylonitrile-graft-poly(dimethyl siloxane) fibres and multi-walled carbon nanotubes

Unfilled cross-linked poly(dimethyl siloxane) (PDMS) is a weak material and is generally filled with high levels of particulate fillers such as silica, calcium carbonate and carbon black to improve its mechanical properties. The use of fibrous fillers such as electrospun nanofibres and multi-walled carbon nanotubes as fillers for PDMS has not been widely studied. In this study anew copolymer, polyacrylonitrile-graft-poly(dimethyl siloxane) (PAN-g-PDMS), is used as fibrous filler for PDMS. The graft copolymer is electrospun to produce the fibre filler material. It is shown how the PDMS content of the graft copolymer provides increased compatibility with silicone matrices and excellent dispersion of the fibre fillers throughout a silicone matrix. It is also shown that it is possible to include multi-walled carbon nanotubes in the electrospun fibres which are subsequently dispersed in the PDMS matrix. Fibre mats were used in the non-woven and the aligned forms. The differently prepared fibre composites have significantly different mechanical properties. Conventional composites using fibrous fillers usually show increased strength and stiffness but usually with a resultant loss of strain. In the case of the composites produced in this study there is a dramatic improvement in the extensibility of the non-woven PAN-g-PDMS fibre mat filled silicone films of up to 470%.     

Produkteigenschaften und Verfahrenstechnik

Product properties and process engineering. The properties of solids are determined by their chemical composition, their state of dispersion, and their interfacial forces. They are largely responsible for the behaviour of the products during the manufacturing process and for the desired quality characteristics of the finished product. The aim of this survey is to illustrate the influence of particle size distribution and interfacial forces on product properties. The effects shown can be explained with the aid of a few physical modes. The first part shows how product properties can be adjusted to achieve a particular aim, principally by modifying the particle size. These include product-relevant properties such as filtration properties, miscibility, and potential for dust explosion, as well properties relevant to the (final) product such as colour and taste. As the particle size decreases, the forces acting between the particle become increasingly important. The second part of this article therefore focuses on those product properties which can be influenced by way of changes in the cohesive forces. Production-relevant properties are flow properties, bulk density, agglomeration behaviour; product-relevant properties are tablet stability and redispersibility of foods, dyes, etc. Among the cohesive forces, capillary forces deserve particular attention. The paper concludes with an account of their role in the manufacture and use of solids. The pore structure of an agglomerated solid is determined by capillary forces and the external forces required during the manufacturing process.     

Improvement of properties of silica‐filled natural rubber compounds using polychloroprene

Because silica has strong filler–filler interactions, a silica‐filled rubber compound is characterized by a poor dispersion of the filler. Properties of silica‐filled natural rubber (NR) compounds were improved using polychloroprene (chloroprene rubber [CR]). The bound rubber content of the compound increases and the filler dispersion is also improved by adding CR to the compound. Physical properties such as modulus, tensile strength, abrasion, and crack resistance are improved by adding CR. Elongation at break of the vulcanizates containing CR is longer than that of the vulcanizate without CR, although crosslink density of the former is higher than that of the latter. The improved physical properties are attributed to the good dispersion of silica by adding CR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2609–2616, 2002     

炭黑/白炭黑并用对溶聚丁苯橡胶性能的影响

研究了白炭黑/炭黑并用体系对溶聚丁苯橡胶（SSBR）加工性能、力学性能和动态力学性能的影响,并对填料分散性进行了研究。结果表明,白炭黑和炭黑并用时可提高补强效果,白炭黑/炭黑并用比为30/20时的硫化胶综合力学性能最佳;TEM观察结果表明,填料与SSBR基体的临界界面模糊,填料分散较为均匀,填料网络化程度降低。     

Cardanol grafted natural rubber: A green substitute to natural rubber for enhancing silica filler dispersion

Natural rubber (NR) usage is wide‐spread from pencil erasers to aero tyres. Carbon black and silica are the most common reinforcing fillers in the rubber industries. Carbon black enhances the mechanical properties, while silica reduces the rolling resistance and enhances the wet grip characteristics. However, the dispersion of polar silica fillers in the nonpolar hydrocarbon rubbers like natural rubber is a serious issue to be resolved. In recent years, cardanol, an agricultural by‐product of the cashew industry is already established as a multifunctional additive in the rubber. The present study focuses on dispersion of silica filler in natural rubber grafted with cardanol (CGNR) and determination of its technical properties. The optimum cure time reduces and the cure rate increases for the CGNR vulcanizates as compared to that of the NR vulcanizates at all loadings of silica varying from 30 to 60 phr. The interaction between the phenolic moiety of cardanol and the siloxane as well as silanol functional groups present on the silica surface enhances the rubber–filler interaction which leads to better reinforcement. The crosslink density and bound rubber content are found to be higher for the silica reinforced CGNR vulcanizates. The physico‐mechanical properties of the silica reinforced CGNR vulcanizates are superior to those of the NR vulcanizates. The CGNR vulcanizates show lower compression set and lower abrasion loss. The dynamic‐mechanical properties exhibit less Payne effect for silica reinforced CGNR vulcanizates as compared to the NR vulcanizates. The transmission electron photomicrographs show uniform dispersion of silica filler in the CGNR matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43057.     

Multiscale characterization of filler dispersion and origins of mechanical reinforcement in model nanocomposites

We report on the influence of parameters controlling filler dispersion and mechanical reinforcement in model nanocomposites. We elaborate a series of nanocomposites and present a structural characterization of silica dispersion in polymer matrix for several particle sizes and polymer matrices, at all relevant scales, by coupling Small Angle X-ray Scattering and Transmission Electronic Microscopy. The mechanical properties are investigated in the linear regime by coupling Dynamical Mechanical Analysis and plate/plate rheology. The results show that: (i) for all filler sizes and matrices, a structural transition is observed from non-connected fractal aggregates at low silica concentration to connected network at high particle content. (ii) In the dilute regime, the reinforcement implies a polymer chain contribution with different possible origins: increase of entanglements density for PS and increase of friction coefficient for PMMA. (iii) In the concentrated regime, for a given polymer, the reinforcement amplitude can be tuned by the rigidity of the filler network, which directly depends on the particle–particle interaction.     

In situ generation of the surface‐modified silica nanoparticles within the silicone matrix

In this study, silica nanoparticles were generated and simultaneously modified inside the silicone resin. Intensive dispersion of the filler and prevention of the cure inhibition effect associated with the regular and unmodified silica particles as well as providing the conditions for grafting to the resin chains were targeted in this work. The dimensions of the nanoparticles, surface morphology, and cure property of the composites were investigated by transmission electron microscopy and differential scanning calorimetry and optimized. Surface chemistry of the modified nanoparticles was investigated by Fourier transform infrared spectroscopy and water contact angle measurement. The effect of in situ synthesis/modification of the silica nanoparticles on mechanical characteristics of the obtained nanocomposites were also examined mainly by tensile properties. POLYM. COMPOS., 36:1365–1370, 2015. © 2014 Society of Plastics Engineers     

Effects of silanization temperature and silica type on properties of silica‐filled solution styrene butadiene rubber (SSBR) for passenger car tire tread compounds

Influence of silanization temperature on properties of silica‐filled solution polymerized styrene butadiene rubber was investigated. Two types of silica, i.e., highly dispersible silica (HDSi) and conventional silica (CSi), were compared. Results show that the increased silanization temperature leads to the enhanced rubber–filler interaction, filler dispersion, and cross‐link density giving rise to the improvement in vulcanizate properties such as modulus, heat build‐up (HBU), and dynamic set, as well as tire performance, e.g., wet grip (WG), rolling resistance (RR), and abrasion resistance. Great care, however, must be taken to avoid the scorching phenomenon during the mixing process at too high temperature. Taken as a whole, the balanced properties are found at the silanization temperature of 140°C. Surprisingly, HDSi provides insignificant differences in degree of filler dispersion, WG, and RR, compared to CSi, despite its claimed greater dispersability. Probably, the relatively long mixing time used in this experiment may override the influence of silica type. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43342.     

Phenolic rigid organic filler/isotactic polypropylene composites. I. Preparation

A novel phenolic rigid organic filler (KT) was melt-mixed with an isotactic polypropylene (iPP) to prepare a series of PP/KT composites, with or without maleic anhydride grafted polypropylene (MAPP) as compatilizer. The evolution of filler morphology during melt-mixing and melt-pressure processes was monitored by scanning electron microscope (SEM) and polarized optical microscope (POM). The influences of shear force, pressure time, filler content and MAPP concentration on the final filler dispersion were studied. We found that this rigid organic filler readily melted and dispersed homogenously into the iPP matrix through a fission-fusion process during the melt-mixing process. Thus a balanced dispersion, which was closely related to shear force and MAPP concentration, can be achieved. During the melt-pressure process, parts of the filler particles combined gradually through a coalescence process. However, the incorporation of MAPP can effectively inhibit the tendency to coalesce and refine the filler particles sizes into nanoscale. Thus, a series of PP/KT composites with controllable filler particles size and narrow size distribution can be obtained just by adjusting process conditions and MAPP concentration. In addition, due to the in-situ formation mechanism, the filler phase possessed a typical solid true-spherical shape.     

Application of rice husk ash as fillers in the natural rubber industry

Rice husk ash (RHA) obtained from agricultural waste, by using rice husk as a power source, is mainly composed of silica and carbon black. A two‐stage conventional mixing procedure was used to incorporate rice husk ash into natural rubber. For comparison purposes, two commercial reinforcing fillers, silica and carbon black, were also used. The effect of these fillers on cure characteristics and mechanical properties of natural rubber materials at various loadings, ranging from 0 to 40 phr, was investigated. The results indicated that RHA filler resulted in lower Mooney viscosity and shorter cure time of the natural rubber materials. The incorporation of RHA into natural rubber improved hardness but decreased tensile strength and tear strength. Other properties, such as Young's modulus and abrasion loss, show no significant change. However, RHA is characterized by a better resilience property than that of silica and carbon black. Scanning electron micrographs revealed that the dispersion of RHA filler in the rubber matrix is discontinuous, which in turn generates a weak structure compared with that of carbon black and silica. Overall results indicate that RHA can be used as a cheaper filler for natural rubber materials where improved mechanical properties are not critical. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 34–41, 2005     

Mechanical,dielectric, and thermal properties of polydimethylsiloxane/polysilsesquioxane nanocomposite for sealant application

Polysilsesquioxanes (PS) powder was synthesized from methyltrimethoxysilane and vinyltrimethoxysilane by hydrolytic condensation method in aqueous phase. The prepared PS powder was characterized using Fourier transform infrared spectroscopy, particle size, and polydispersity of the powders was determined using dynamic light scattering technique. Polydimethylsiloxane (PDMS) nanocomposites and the sealant were synthesized using different weight percentage (1–4 wt %) of PS powder and hydrophobic fumed silica. Tensile strength and thermal stability of the nanocomposites showed perceptible enhancement on increasing the filler ratio when compared to pristine PDMS composites. The surface morphology and the extent of filler dispersion were visualized from the scanning electron microscopy images. Dielectric strength of the composites also showed significant improvement on increasing the filler loading. Poly(methyl/vinyl)silsesquioxane (PMVS) (4 wt %) reinforced composites showed a considerable enrichment in properties when compared to other formulations. Adhesive strength of silicone sealant on both the alumina and mild steel substrate was studied by conducting lap shear test. PMVS-loaded nanocomposites exhibited more adhesive strength on both the substrates and hence it can be used as a sealant in electronic assemblies. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47228.