Self-assembled natural rubber/silica nanocomposites: Its preparation and characterization

A novel natural rubber/silica (NR/SiO₂) nanocomposite is developed by combining self-assembly and latex-compounding techniques. The results show that the SiO₂ nanoparticles are homogenously distributed throughout NR matrix as nano-clusters with an average size ranged from 60 to 150 nm when the SiO₂ loading is less than 6.5 wt%. At low SiO₂ contents (4.0 wt%), the NR latex (NRL) and SiO₂ particles are assembled as a core-shell structure by employing poly (diallyldimethylammonium chloride) (PDDA) as an inter-medium, and only primary aggregations of SiO₂ are observed. When more SiO₂ is loaded, secondary aggregations of SiO₂ nanoparticles are gradually generated, and the size of SiO₂ cluster dramatically increases. The thermal/thermooxidative resistance and mechanical properties of NR/SiO₂ nanocomposites are compared to the NR host. The nanocomposites, particularly when the SiO₂ nanoparticles are uniformly dispersed, possess significantly enhanced thermal resistance and mechanical properties, which are strongly depended on the morphology of nanocomposites. The NR/SiO₂ has great potential to manufacture medical protective products with high performances.     

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。     

氧化石墨烯/天然橡胶-丁腈橡胶复合材料的制备与性能

为研究氧化石墨烯（GO）对共混橡胶的补强改性作用,首先,通过改进的Hummers方法制备了GO,并通过乳液共混法制备了GO/天然橡胶（NR）-丁腈橡胶（NBR）复合材料;然后,采用SEM、FTIR、XRD、溶胀测试和力学性能测试表征了GO、NR-NBR硫化胶和GO/NR-NBR复合材料的微观形态、结构和力学性能。结果表明:所得GO含有大量的含氧官能团,氧化效果较好;橡胶基体中GO分散均匀,且GO/NR-NBR复合材料的拉伸断面粗糙程度显著增加;GO的填充可以提高复合材料的表观交联密度;GO/NR-NBR复合材料的力学性能随着GO含量的增加而改善,当GO含量为3.0wt%时,GO/NR-NBR复合材料的拉伸强度、100%定伸应力和邵氏A硬度分别提高了53.3%、67.3%和10.5%,断裂伸长率降低了9.6%。      

纳米二氧化硅粒径对橡胶复合材料力学性能的影响

以不同粒径的纳米二氧化硅为填料加到天然橡胶中制备纳米二氧化硅/天然橡胶(NR)复合材料。研究了不同粒径纳米二氧化硅(15,30和80nm)对复合材料的力学性能、应力软化效应、Payne效应、动态热机械性能、压缩生热和损耗因子等基本特性的影响。结果表明,随着纳米二氧化硅粒径的增大,复合材料的抗拉强度变大,应力软化效应增大;同时,复合材料的Payne效应和损耗因子越低,其动态压缩温升越低。Payne效应分析及扫描电镜观察还表明,大粒径纳米二氧化硅在橡胶基体中易于分散均匀,粒子间聚集程度更小,而小粒径的则表现出较明显的团聚现象,粒子在橡胶基体中的分散性对复合材料力学性能有直接影响。     

天然橡胶-氢化丁腈橡胶的共硫化及性能研究

天然橡胶(NR)和氢化丁腈橡胶(HNBR)因不饱和度和极性的差异,存在硫化速度不匹配、填料分散等问题,难以实现两胶的并用。本文通过先制备不同硫黄/促进剂比例的NR和HNBR母炼胶,再将母炼胶并用制备NR/HNBR复合材料,解决了NR和HNBR共硫化的问题。研究了NR/HNBR的相态结构和填料在NR和HNBR两相的分散状态,结合相态结构和填料分散分析了NR/HNBR并用比对复合材料硫化特性、动静态力学性能、耐磨性和压缩温升的影响。结果表明:并用HNBR的复合材料混炼胶的门尼黏度增大,焦烧时间和正硫化时间缩短;随着HNBR含量增加,HNBR相的尺寸增大,硫化胶的硬度及100%和300%定伸应力增加,拉伸强度、撕裂强度、断裂伸长率和拉断永久变形减小,耐磨性和抗湿滑性提高,压缩疲劳温升增大。     

纳米石墨/天然橡胶复合材料的应力软化与动态性能

以不同尺寸的纳米石墨为原料,制备了纳米石墨/天然橡胶(NR)复合材料.研究不同尺寸(30、80、150 nm)的纳米石墨对复合材料的应力软化效应(Mullins效应)、Payne效应、动态生热和损耗因子的影响.结果表明:随着纳米石墨尺寸的增大,纳米填料对纳米石墨/NR复合材料体系的补强作用明显,应力软化效应增大、动态损耗因子增加,但Payne效应降低;纳米石墨/NR复合材料动态损耗因子越大,其动态生热越高;动态生热还与填料粒子网络形成紧密相关.SEM观察及Payne效应分析结果表明:采用不同尺寸的纳米石墨材料填充天然橡胶,大尺寸石墨在橡胶基体中易于分散均匀,片层的聚集程度小,而小尺寸纳米片层表现出较明显的团聚.     

Combination of photocatalytic and antibacterial effects of silver oxide loaded on titania nanotubes

Silver nanoparticles were photodeposited on titania nanotubes and their antibacterial activity was tested. Investigation of the structure and morphology of the nanostructures showed nanometer size silver oxide particles homogeneously distributed on titania nanotubes. Furthermore the modified titania nanotubes were spin-coated as thin films and their antibacterial activity was examined under visible light irradiation and in complete darkness. Although silver oxide loaded titania nanotubes (TiNT-AgO) has a potential for antibacterial activity in both conditions with and without light irradiation, enhanced activity was observed in visible light irradiation condition.     

Organosulfonic acid-functionalized mesoporous composites based on natural rubber and hexagonal mesoporous silica

This study is the first report on synthesis, characterization and catalytic application of propylsulfonic acid-functionalized mesoporous composites based on natural rubber (NR) and hexagonal mesoporous silica (HMS). In comparison with propylsulfonic acid-functionalized HMS (HMS-SO₃H), a series of NR/HMS-SO₃H composites were prepared via an in situ sol–gel process using tetrahydrofuran as the synthesis media. Tetraethylorthosilicate as the silica source, was simultaneously condensed with 3-mercaptopropyltrimethoxysilane in a solution of NR followed by oxidation with hydrogen peroxide to achieve the mesoporous composites containing propylsulfonic acid groups. Fourier-transform infrared spectroscopy and ²⁹Si MAS nuclear magnetic resonance spectroscopy results verified that the silica surfaces of the NR/HMS-SO₃H composites were functionalized with propylsulfonic acid groups and covered with NR molecules. After the incorporation of NR and organo-functional group into HMS, the hexagonal mesostructure remained intact concomitantly with an increased framework wall thickness and unit cell size, as evidenced by the X-ray powder diffraction analysis. Scanning electron microscopy analysis indicated a high interparticle porosity of NR/HMS-SO₃H composites. The textural properties of NR/HMS-SO₃H were affected by the amount of MPTMS loading to a smaller extent than that of HMS-SO₃H. NR/HMS-SO₃H exhibited higher hydrophobicity than HMS-SO₃H, as revealed by H₂O adsorption–desorption measurements. Moreover, the NR/HMS-SO₃H catalysts possessed a superior specific activity to HMS-SO₃H in the esterification of lauric acid with ethanol, resulting in a higher conversion level.     

Aerosol-assisted synthesis of nanoporous silica/titania nanoparticles composites and investigation of their photocatalytic properties

Nanoporous silica/titania nanoparticles composites with relatively large TiO2 content are successfully synthesized by aerosol-assisted co-assembly. By the hybridization of titania with nanoporous silica having high surface area, both the adsorption capability and the reaction rates for the photocatalytic decomposition of methylene blue (MB) are dramatically improved in comparison with unmodified titania nanoparticles without nanoporous silica. Through the quantitative evaluation of the amount of adsorbed and photo-decomposed organic molecule throughout the reaction process, the role of nanoporous silica layers on titania surface is clarified. Rational design of future hybrid photocatalyst with precisely controlled nanostructure will be possible by optimization of our synthetic procedure and careful study of the adsorption and photocatalytic properties.     

Improving properties of modified acrylic sheet via addition of graft natural rubber

The mechanical properties of a modified acrylic sheet prepared by bulk copolymerization of methyl methacrylate (MMA) and styrene (ST) were improved by the addition of a small amount of graft natural rubber (GNR). The graft copolymerization of MMA and ST onto natural rubber latex was carried out by emulsion polymerization using potassium persulfate as an initiator. The properties of the modified acrylic sheet containing GNR with 22.5 wt.% graft copolymer were investigated as a function of GNR content. The results indicated that the impact resistance, tensile strength and elongation at break of the modified acrylic sheet increased with the increase in the amount of GNR in the range of 0.5-4 parts. From the stress-strain behavior, the characteristic of the modified acrylic sheet shifted from brittle to ductile when the amount of GNR was increased. The scanning electron micrographs of the modified acrylic sheets show the relatively smooth fracture surface with relatively few small cracks. This implies that the GNR can be used as an impact modifier for acrylic plastics.     

硅酸盐纳米纤维增强橡胶复合材料的结构与性能

利用天然针状硅酸盐——凹凸棒石(AT)的结构特点, 采用机械共混法并结合原位改性技术制备了一系列硅酸盐纳米纤维/橡胶复合材料, 研究了复合材料的结构与性能, 分析了针状硅酸盐良好增强效果的内在机制。借助硅烷偶联剂的原位改性和混合过程中的机械剪切力, AT微米聚集体被解离成长径比为10~30的纳米纤维分散在橡胶基体中, 纳米复合材料表现出短纤维/橡胶复合材料(SFRC)的应力-应变特性和明显的力学性能各向异性。而且, AT/橡胶纳米复合材料具有优良的高温模量和加工性能。AT的优良的增强效果来源于AT的纳米分散和良好的纤维-橡胶界面结合。      

Silsesquioxane-based hybrid nanocomposites with methacrylate units containing titania and/or silver nanoparticles as antibacterial/antifungal coatings for monumental stones

The present paper reports on the evaluation of two silsesquioxane-based hybrid nanocomposites with methacrylate units containing titania and/or silver nanoparticles aimed as antibacterial coatings for monumental stones. Sol–gel reaction of titanium isopropoxide and/or 3-(trimethoxysilyl)propyl methacrylate, in the presence of silver nitrate and a primary amine surfactant, yielded new types of hybrid nanocomposites with high antibacterial/antifungal efficacy. Different polymer behaviours regarding a frequently used monumental stone originating from Romania were evidenced through Fourier-transform infrared (FTIR) spectroscopy and powder X-ray diffraction (PXRD) technique. Conclusions regarding the stones acid-resistant character and lower influence of salt weathering on its durability, as well as a better protective coating containing titania units were revealed.     

UV modification of tire rubber for use in cementitious composites

The use of recycled rubber as a possible aggregate in concrete is known to result in a reduction of compressive and flexural strength. This paper summarises the results of initial studies on the effect of surface-treating rubber crumb (obtained from discarded tires) with ultraviolet (UV) radiation, with the aim of mitigating such losses. Investigation focussed on changing the surface energy, and therefore the bond strength, between cement and rubber. To identify the most effective UV wavelength for this purpose, a water retention test method was utilized, resulting in the selection of the UV-C wavelength range for treatment. Additionally, specimens containing rubber, treated for different time periods, were subjected to flexural testing. As expected, the addition of untreated crumb rubber resulted in a degradation of flexural strength, however exposure to UV-C generated, at best, values only 6% weaker than those of rubberless specimens, indicating the benefits of the investigated surface treatment.     

环氧化天然橡胶改性石墨烯-炭黑/天然橡胶复合材料的制备及性能

以环氧化天然橡胶(ENR)为界面改性剂,制备了石墨烯-炭黑/天然橡胶-ENR(GR-CB/NR-ENR)复合材料,研究了ENR用量对GR-CB/NR-ENR复合材料的加工性能、力学性能和动态力学性能的影响。结果表明,ENR的加入可以改善GR-CB/NR-ENR复合材料的加工性能及CB粒子在天然橡胶基体中的分散性,增加GR与NR的相容性,增强填料与NR基体间的界面相容性,同时改善GR-CB/NR-ENR硫化胶的动态力学性能、物理性能和耐老化性能。当ENR添加量为6 wt%时,GR-CB/NR-ENR复合材料撕裂强度和拉伸强度最高,硫化胶耐老化性最好。随着ENR含量的增加,GR-CB/NR-ENR复合材料的压缩疲劳温度先升高后降低;随着应变的不断增大,GR-CB/NR-ENR复合材料的储能模量G'不断减小,损耗因子tanδ先增大后减小;动态模量随着应变的增加急剧下降。      

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.     

Novel mesoporous composites based on natural rubber and hexagonal mesoporous silica: Synthesis and characterization

The present study is the first report on the synthesis and characterization of mesoporous composites based on natural rubber (NR) and hexagonal mesoporous silica (HMS). A series of NR/HMS composites were prepared in tetrahydrofuran via an in situ sol–gel process using tetraethylorthosilicate as the silica precursor. The physicochemical properties of the composites were characterized by various techniques. The effects of the gel composition on the structural and textural properties of the NR/HMS composites were investigated. The Fourier-transform infrared spectroscopy (FTIR) and ²⁹Si magic angle spinning nuclear magnetic resonance (²⁹Si MAS NMR) results revealed that the surface silanol groups of NR/HMS composites were covered with NR molecules. The powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) data indicated an expansion of the hexagonal unit cell and channel wall thickness due to the incorporation of NR molecules into the mesoporous structure. NR/HMS composites also possessed nanosized particles (∼79.4 nm) as confirmed by scanning electron microscopy (SEM) and particle size distribution analysis. From N₂ adsorption–desorption measurement, the NR/HMS composites possessed a high BET surface area, large pore volume and narrow pore size distribution. Further, they were enhanced hydrophobicity confirmed by H₂O adsorption–desorption measurement. In addition, the mechanistic pathway of the NR/HMS composite formation was proposed.     

Effect of processing methods on physicochemical properties of titania nanoparticles produced from natural rutile sand

Titania (TiO₂) nanoparticles were produced from natural rutile sand using different approaches such as sol–gel, sonication and spray pyrolysis. The inexpensive titanium sulphate precursor was extracted from rutile sand by employing simple chemical method and used for the production of TiO₂ nanoparticles. Particle size, crystalline structure, surface area, morphology and band gap of the produced nanoparticles are discussed and compared with the different production methods such as sol–gel, sonication and spray pyrolysis. Mean size distribution (d₅₀) of obtained particles is 76 ± 3, 68 ± 3 and 38 ± 3 nm, respectively, for sol–gel, sonication and spray pyrolysis techniques. The band gap (3.168 < 3.215 < 3.240 eV) and surface area (36 < 60 < 103 m² g^?1) of particles are increased with decreasing particle size (76 > 68 > 38 nm), when the process methodology is changed from sol–gel to sonication and sonication to the spray pyrolysis. Among the three methods, spray pyrolysis yields high-surface particles with active semiconductor bandgap energy. The effects of concentration of the precursor, pressure and working temperature are less significant for large-scale production of TiO₂ nanoparticles from natural minerals.     

天然橡胶/羧甲基壳聚糖抗菌复合膜的力学性能研究

采用胶乳共混法制备得到了天然橡胶羧甲基壳聚糖(NR/CCS)复合胶膜,通过NMR交联密度仪、拉力测试机、动态热力学分析仪等对复合材料的性能进行了表征。结果表明,复合胶膜的交联密度略微增大(5.75×10-5mol/cm3),力学性能增强到11.25MPa,并且复合胶膜的弹性模量增大,刚性增强,并通过这些测试证明了NR与CCS分子存在氢键的作用。     

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.     

四针状氧化锌晶须/天然橡胶抗菌医用复合材料的制备

将硬脂酸钠改性四针状氧化锌晶须(Sodium stearate-T-ZnOw)超声分散液引入天然胶乳(NRL)基体中,制备了绿色环保的Sodium stearate-T-ZnOw/橡胶(NR)抗菌医用复合材料.系统研究了Sodium stearate-T-ZnOw/NR复合材料的综合力学性能、抗菌性能和热稳定性能.结果...