微波处理和溶胶凝胶法共同改性废胶粉及其与天然橡胶复合材料性能的研究

采用微波处理打断废胶粉(WRP)的三维网状结构用来提高WRP在有机溶剂中的溶胀性,然后采用溶胶凝胶法,将微波改性后的WRP浸入正硅酸乙酯中,通过水解反应和缩合反应,在WRP表面原位生成SiO2网络,从而制得改性废胶粉(MWRP).将制得MWRP与天然橡胶(NR)共混,制备了NR/MWRP复合材料,研究了NR/MWRP复合材料的性能.通过热重分析仪、差示扫描量热仪和力学分析表明微波处理最佳时间是20 s.由于微波处理提高了NR与WRP的相容性,原位生成的SiO2粒子起到了补强作用,所以所制备的NR/MWRP复合材料拥有较好的力学性能;随着Si69的加入,抑制了SiO2粒子聚集,提高了SiO2粒子的分散性,从而进一步提高复合材料的力学性能并降低复合材料的Payne效应;在进行频率扫描时,硫化胶的储存模量随频率的增大而增大;硫化胶的温度扫描结果表明,随着温度的升高,复合材料中SiO2粒子聚集程度加剧并且复合材料出现老化的现象.为了提高复合材料的耐老化性能,N,N-间苯撑双马来酰亚胺(BMI)作为一种防老剂加入复合材料中,BMI利用Diels-Aider反应补偿橡胶在老化过程中所损失的交联键并提高NR与WRP的界面相容性,从而提高复合材料的耐老化性能.     

Styrenated phenol modified nanosilica for improved thermo-oxidative and mechanical properties of natural rubber

The present work aims to prepare thermal and oxidation resistant Natural Rubber (NR) composites using antioxidant-modified nanosilica (MNS). The thermo-oxidative aging performance of the composites was evaluated by the variations in mechanical properties after aging at 100 °C for 24 h. The performance was further monitored through Scanning Electron Microscopy, Fourier Transform Infrared spectroscopy, Thermogravimetric Analysis, and Dynamic Mechanical Analysis. NR nanocomposite with 1–7.5 phr nanosilica (NS) and 3 phr MNS were prepared and its rheological properties were studied. A comparative study of the theoretical models yielded that modified Guth-Gold equation predicted Young's modulus better than other models. Thermal stability of natural rubber MNS composite was improved by 10 °C with pre-eminent mechanical properties like tensile strength and heat build-up. A linear relationship of compression set with modulus of all composites were also established. Equilibrium swelling test revealed improved crosslink density in NR MNS composite. The strong interaction between antioxidant and nanosilica enabled low migration of antioxidant in NR MNS composite. Hence its protective function after aging showed more effective than NR NS composites. These versatile functional properties of NR MNS composite suggest its potential application in electrical, electronic and high performance rubber products.     

Influence of different curing systems on the physico-mechanical properties and stability of SBR and NR rubbers

The physical properties of radiation, sulfur and peroxide-cured styrene–butadiene rubber (SBR) and natural rubber (NR) were compared. The dependence of the mechanical properties of the radiation-vulcanized SBR and NR on the coagent concentration and radiation dose was studied. The effect of thermal aging on the mechanical properties of the different rubber formulations was discussed. The radiation-cured formulations of SBR have superior mechanical properties and thermal stability compared with those of the chemically vulcanized compounds. Whereas, the radiation-cured formulations of NR have similar mechanical properties but superior thermal stability (based on the % change in E after thermal aging), when compared with those of the sulfur-vulcanized compounds and slightly better than those of the peroxide-vulcanized compounds.     

Effect of nanocrystalline cellulose on the curing characteristics and aging resistance properties of carbon black reinforced natural rubber

This work focused on the effect of nanocrystalline cellulose (NCC) on the curing characteristics, aging resistance and thermal stability of natural rubber (NR) reinforced with carbon black (CB). Sharing the same fillers loading of 45 parts per hundred rubber (phr), NR/NCC/CB composites with different NCC/CB ratios (i.e. 0/45, 5/40, 10/35, 15/30, 20/25 phr) were prepared and analyzed. Resorcinol and hexamethylene tetramine (RH), acting as the modifier in NR/NCC interface, was also discussed for its influence. The result showed that an relatively higher ratio of NCC/CB led to a lower torque, a shorter cure time (T ₉₀), a slightly longer scorch time (T ₁₀) and a bigger vulcanization rate constant (K). This tendency suggested that the existence of NCC accelerated the vulcanization process. Additionally, modified by RH, NR/NCC/CB compounds exhibited a short T ₁₀ and a elevated torque. And a moderate RH content would lower the E _a of vulcanization. A 10 phr substitute of CB by NCC can help to improve aging resistance in terms of mechanical properties. In a high temperature aging condition, composites with 10 phr NCC also performed the highest storage modulus (G′) among composites tested. A moderate NCC content contributed to the best retention of G′ after high temperature aging, so did the incorporation of RH. With the partial replacement of CB by NCC, the temperature of 5% weight-lose had a slight drop and the apparent crosslink density showed a decrease. Thanks to the interaction of RH with both NR and NCC, composites showed an improvement in apparent crosslink density after modified by RH.     

Surface Modification of Rice Husk Ash by Ethanol-assisted Milling to Reinforce the Properties of Natural Rubber/Butadiene Rubber Composites

Rice husk ash(RHA), obtained by pyrolysis of rice husks, can be used as a potential reinforcing filler for rubber composites. In this work, ball milling in ethanol(ethanol-assisted milling) was used to hydroxylate the surface of RHA, promoting the graft modification of bis-(γ-triethoxysilylpropyl)-tetrasulfide(Si69). The obtained modified RHA(RHA-EM-Si69) was filled into the natural rubber/butadiene rubber(NR/BR) composites, and the filler-rubber interactions were enhanced. In consequence, RHA-EM-Si69 filled NR/BR composites showed overall improvement in the mechanical properties compared with RHA filled NR/BR composites. The tear strength increased from 13.37 kN/m to 34.71 kN/m, and the tensile strength increased from 1.84 MPa to 7.75 MPa. Carbon black(N774) was also used for comparison under the same conditions. This method provides a potential for promoting the value of RHA in rubber industry.     

Potential use of NR and wood/NR composites as thermal neutron shielding materials

This work investigated thermal neutron shielding, cure characteristics and mechanical properties of natural rubber (NR) and wood/NR composites with addition of either boron oxide (B₂O₃) or boric acid (H₃BO₃) for potential use as flexible shielding materials. The results showed that increase in the B₂O₃ or H₃BO₃ content from 0 to 80 phr and 0–50 phr in 10-phr increments, respectively, could improve thermal neutron shielding properties but reduced overall tensile properties, while the addition of 20-phr wood particles in wood/NR composites improved surface hardness and dimensional stability. Furthermore, the values of the Half Value Layer (HVL), which represent the required thickness of material to attenuate half of the incoming neutrons, were evaluated at a content of 80-phr B₂O₃ by varying thickness of both NR and wood/NR composites from 2.5 mm to 20.0 mm in 2.5-mm increments. The results indicated that the HVL values were approximately the same at 3.5 mm. Hence, the overall properties investigated in this work suggested great potential of these composites to be used as effective thermal neutron shielding materials.     

The effects of a silane coupling agent on curing characteristics and mechanical properties of bamboo fibre filled natural rubber composites

The effects of a silane coupling agent on curing characteristics and mechanical properties of bamboo fibre filled natural rubber composites were studied. Scorch time, t₂ and cure time, t₉₀ of the composites decrease with increasing filler loading and with the presence of a silane coupling agent, Si69. Mooney viscosity also increases with increasing filler loading but at a similar filler loading shows lower value with the presence of Si69. The mechanical properties of composites viz tensile strength, tear strength, hardness and tensile modulus were also improved with the addition of Si69.     

Preparation of nanoalumina/EPDM composites with good performance in thermal conductivity and mechanical properties

In this paper, nanoalumina (Al₂O₃) highly filled ethylene propylene diene monomer (EPDM) composites are prepared, and the mechanical (static and dynamic) properties and thermal conductivity are investigated systemically through various characterization methods. Furthermore, influences of in situ modification (mixing operation assisted by silane at high temperature for a certain time) with the silane‐coupling agent bis‐(3‐triethoxy silylpropyl)‐tetrasulfide (Si69) and stearic acid (SA) pretreatment on the nano‐Al₂O₃ filled composites are as well investigated. The results indicate that nano‐Al₂O₃ particles can not only perform well in reinforcing EPDM, but also improve the thermal conductivity significantly. Assisted by in situ modification with Si69, the mechanical properties (especially dynamic mechanical properties) of the nano‐Al₂O₃ filled composites are improved obviously, without influencing the thermal conductivity. By comparing to the traditional reinforcing fillers, such as carbon black (grade N330) and silica, in situ modified nano‐Al₂O₃ filled composites exhibit excellent performance in mechanical (static and dynamic) properties as well as better thermal conductivity, especially lower compression heat build‐up and better fatigue resistance. In general, our work indicates that nano‐Al₂O₃, as the novel thermal conductive reinforcing filler, is suitable to prepare rubber products serving in dynamic conditions, with the longer expected service life. Copyright © 2010 John Wiley & Sons, Ltd.     

The synthesis of novel Schiff base antioxidants to promote anti-thermal aging properties of natural rubber

There is of great interest in promotion of anti-thermal aging properties of natural rubber (NR) to improve the applicability. In this study, two novel Schiff base antioxidants (SBAOs) for NR were synthesized utilizing 4-aminodiphenylamine with 3,5-Di-tert-butyl-2-hydroxybenzaldehyde or cinnamic aldehyde in an ethanol medium. IR, ¹³C-NMR, and ¹H-NMR confirmed the structures of SBAOs. Addition of SBAOs improved the rheometric properties, mechanical properties and thermal oxidative stability of NR vulcanizates. Introduction of SBAOs in NR increased the apparent activation energy of thermal oxidative degradation according to Kissinger and FWO methods. Anti-thermal aging performance of SBAOs for NR is related to the structures. The C=N double bonds in SBAOs improve the electron density of Ar–OH and/or Ar–NH–Ar structures, benefiting the release of active hydrogen. The active hydrogen could capture free radicals initiated during the thermal oxidative aging process. The lone pair electrons on nitrogen atom are also beneficial to delay or terminate free radical reaction. NR with SBAOs showed high mechanical properties of the tensile strength, tensile stress at 100% elongation and Shore A hardness compared to commercial BHT and 4010 during aging 96 h. It indicates potential applications of SBAOs as efficient antioxidants for NR.     

Effects of Sericite Modified by Macromolecular Dispersant on the Thermal,Mechanical and Electrical Properties of the NR/SBR Composites

A new hydrosoluble macromolecular dispersant and modifier, poly(ethylene glycol)-maleic anhydride-acrylic acid (PEG-MA-AA) terpolymer was synthesized via ring-opening reaction and free radical polymerization. The chemical structure of the PEG-MA-AA terpolymer was confirmed by Fourier transform infrared (FTIR) spectra and nuclear magnetic resonance spectroscopy (NMR), and its average molecular weight was determined by gel permeation chromatography (GPC). Modified sericite (MSE) was synthesized from sericite (SE) by the surface modification with PEG-MA-AA. The NR/SBR/MSE composites were prepared via the blending of the modified sericite and NR/SBR rubber. The thermal, mechanical and electrical properties of the composites were investigated by TGA, tensile test machine and high-insulation resistance meter. The results showed that the thermal stability and the mechanical and electrical insulation properties of NR/SBR/MSE composites were improved significantly. SEM also revealed that modified sericite possessed good dispersibility.     

Impacts of filler covalent and non‐covalent modification on the network structure and mechanical properties of carbon–silica dual phase filler/natural rubber

The carbon–silica dual phase filler (CSDPF) was modified by bis (3‐triethoxy‐silylpropyl) tetrasulphane (Si69) and 1‐allyl‐3‐methyl‐imidazolium chloride (AMI), respectively. The natural rubber (NR) vulcanizates filled with modified CSDPF were fabricated through mechanical mixing followed by a high‐temperature cure process. The impacts of filler surface modification on the curing characters, crosslinked junctions, network structure, and mechanical properties of NR vulcanizates were investigated. The results showed that the Si69 interacted with CSDPF through covalent bond, while the interaction between AMI and CSDPF was hydrogen bond. Both modifications increased the cure rate of CSDPF/NR compounds as well as the crosslinked degree, compared with those of pristine CSDPF/NR compound. The modifications improved the dispersion of CSDPF in NR matrix. The covalent modification by Si69 caused a limited movement of NR chains in the CSDPF surface, which contributed to a greater tensile modulus of Si69‐modified CSDPF/NR. However, the higher content of mono‐sulfidic crosslink and the poorer content of strain‐induced crystallization in the NR matrix led to a slight increase of tensile strength and tear strength of Si69‐modified CSDPF/NR, compared with those of CSDPF/NR. The tensile modulus of AMI‐modified CSDPF/NR had a lower value due to a faster polymer chain motion on the CSDPF surface. However, the tensile and tear strength of AMI‐modified CSDPF/NR increased significantly because of the increase of mono‐sulfidic crosslink, strain‐induced crystallization, and the existed hydrogen bond between CSDPF and NR. Copyright © 2015 John Wiley & Sons, Ltd.     

Rubber products prepared from silica modified by radiation-induced admicellar polymerization

Unmodified silica, silica modified with Si69, silica modified by thermal admicellar polymerization and silica modified by radiation-induced admicellar polymerization were applied as rubber reinforcement. Mechanical properties of these different rubber formulae were subsequently tested. The results revealed that the mechanical properties of rubber reinforced with silica modified by admicellar polymerization were superior to those reinforced with unmodified silica or silica modified with Si69. As for the silica modified by admicellar polymerization, cetyltrimethyl ammonium bromide (CTAB) proved to be the most effective surfactant, compared to dodecyltrimethyl ammonium bromide (DTAB) and tetradecyltrimethyl ammonium bromide (TTAB).     

Smart modification of inorganic fibers and flammability mechanical and radiation shielding properties of their rubber composites

Facile and smart method for the modification of inorganic fibers has been developed. The polyaniline was synthesized on basalt fiber surface presenting an organic polymer shell to the inorganic fibers. The modified basalt fibers were dispersed in rubber-producing well-dispersed rubber composites. Various mass loadings of modified basalt fibers were dispersed and optimized. The effect of radiation on the properties of developed rubber composites was investigated by exposure to different gamma radiation doses. The flammability, thermal and mechanical properties were studied. The flammability of developed composites was improved achieving 62 and 16% reduction in the peak heat release rate compared to blank rubber and unmodified basalt fiber-based rubber composite, respectively. This is in addition to significant reduction in emission of CO and CO₂ gases by 65 and 58%, respectively. Also, the tensile strength property was enhanced by 38 and 53% compared to blank and unmodified basalt composite, respectively. The role of polyaniline layer on inorganic fiber surface and their effect on the properties of the produced composites was studied. The organic polymer shell achieved good compatibility and interfacial adhesion of basalt fibers with rubber matrix and radiation protection effect for the developed composites.     

Influence of polyfurfuryl alcohol (PFA) loading on the properties of Nafion composite membranes

Composite membranes based on Nafion (N115) loaded with furfuryl alcohol (FA) were prepared by in situ acid-catalyzed polymerization technique, with the aim to improve the ionic conductivity of Nafion membranes. The functionalization, thermal stability, electrical properties and mechanical strength of N115-PFA composites was analyzed by means of Fourier transform infrared (FT-IR) attenuated total reflection (ATR) spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), thermogravimetric analysis (TGA), electrical impedance spectroscopy, dynamic vapor sorption (DVS) and dynamic mechanical analyser (DMA). The FA loading in the resultant composites had a positive correlation with the water uptake (W_u), water vapor uptake (W_vu), ionic conductivity and thermo-mechanical stability. At low polyfurfuryl alcohol (PFA) loading, these membranes displayed higher W_u and improved ionic and electrical properties. Further, the thermo-mechanical stability also gradually increased with the PFA loading. All the composites showed a well-defined glass transition temperature in DMA, which shifted to higher temperature with repeated PFA loading. Overall, the results indicate that the developed composite membrane are promising for low temperature polymer electrolyte membrane (PEM) fuel cells.     

Reinforcement of compatibilized NR/NBR blends by fly ash particles and precipitated silica

Effects of precipitated silica (PSi) and silica from fly ash (FA) particles (FASi) on the cure and mechanical properties before and after thermal and oil aging of natural rubber (NR) and acrylonitrile–butadiene rubber (NBR) blends with and without chloroprene rubber (CR) or epoxidized NR (ENR) as a compatibilizer have been reported in this paper. The experimental results suggested that the scorch and cure times decreased with the addition of silica and the compound viscosity increased on increasing the silica content. The mechanical properties for PSi filled NR/NBR vulcanizates were greater than those for FASi filled NR/NBR vulcanizates in all cases. The PSi could be used for reinforcing the NR/NBR vulcanizates while the silica from FA was regarded as a semi‐reinforcing and/or extending filler. The incorporation of CR or ENR enhanced the mechanical properties of the NR/NBR vulcanizates, the ENR being more effective and compatible with the blend. The mechanical properties of the NR/NBR vulcanizates were improved by post‐curing effect from thermal aging but deteriorated by the oil aging. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and properties of natural rubber composites reinforced with pretreated carbon nanotubes

In order to achieve dramatic improvements in the performance of rubber materials, the development of carbon nanotube (CNT)‐reinforced rubber composites was attempted. The CNT/natural rubber (NR) nanocomposite was prepared through solvent mixing on the basis of pretreatment of CNTs. Thermal properties, vulcanization characteristics, and physical and mechanical properties of the CNT/NR nanocomposites were characterized in contrast to the carbon black (CB)/NR composite. Through the addition of the CNTs treated using acid bath followed by ball milling with HRH (hydrated silica, resorcinol, and hexamethylene tetramine) bonding systems, the crystallization melting peak in differential scanning calorimetry (DSC) curves of NR weakened and the curing rate of NR slightly decreased. Meanwhile, the over‐curing reversion of CNT/NR nanocomposites was alleviated. The dispersion of the treated CNTs in the rubber matrix and interfacial bonding between them were rather good. The mechanical properties of the CNT‐reinforced NR showed a considerable increase compared to the neat NR and traditional CB/NR composite. At the same time, the CNT/NR nanocomposites exhibited better rebound resilience and dynamic compression properties. The storage modulus of the CNT/NR nanocomposites greatly exceeds that of neat NR and CB/NR composites under all temperature regions. The thermal stability of NR was also obviously improved with the addition of the treated CNTs. Copyright © 2008 John Wiley & Sons, Ltd.     

Fabrication of high thermal stable cured novolac/Cloisite 30B nanocomposites by chemical modification of resin structure

Cloisite 30B as a modified kind of nanoclay was utilized for the formation of 3D network based on novolac resin with high thermal stable properties. Two types of phenolic resins including neat novolac (NR) and modified novolac resin were used to create a compatible matrix with nanoclay. For this purpose, NR modified with (3‐chloropropyl)triethoxysilane (CPTES) to form SiNR. For improvement of thermal behaviors, Cloisite 30B was dispersed in matrix via ultrasonic waves and cured with hexamethylenetetramine (HMTA) to form 3D network. X‐ray diffraction (XRD) analysis was used to measure the d‐spacing in intercalated systems and results indicated the optimum amount of clay for appropriate thermal properties. Investigation of the thermal properties of the samples by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that the presence of Cloisite 30B in matrix resulted in much higher thermal stability and char yield with respect to modification of novolac resin originated from formation of 3D Si–O–Si network. Also, cured modified resin and its nanocomposites showed much higher thermal stability than cured NR and its nanocomposites. Such nanocomposite materials with high thermal stability have potential applications in advanced fields such electronic, industrial molds, coatings, adhesives, and aerospace composites.     

The effect of grass fiber filler on curing characteristics and mechanical properties of natural rubber

Natural rubber is reinforced with a novel type of grass fiber (Cyperus Tegetum Rox b). The effects of fiber loading of different mesh sizes on curing characteristics and mechanical properties of grass fiber filled natural rubber composite are studied. Since 400 mesh grass fiber loaded natural rubber composite shows superior mechanical properties, therefore the effect of silane coupling agent was studied for this particular composite. Here composites were prepared by using water leached grass fiber. Optimum cure time increases with the increase in fiber loading but the change in scorch time is less. The same trend of increase in optimum cure time is observed in the presence of Si69. But the value is higher compared to that of rubber composite without Si69. With increase in the fiber loading, modulus and hardness of the composite increases but tensile strength decreases. The mechanical properties of the composite, namely moduli at 200 and 300% elongation and hardness increase in the presence of Si69 but tensile strength is less compared to that of the composite without Si69. Elongation at break is not much affected due to the presence of Si69. Copyright © 2004 John Wiley & Sons, Ltd.     

Characterization of effects of thermal-oxidative aging on styrene-butadiene rubber/silica composites with vitamin C-lanthanum complex

A novel rubber antioxidant, vitamin C-lanthanum complex, was prepared and applied in styrene-butadiene rubber (SBR)/silica composites. The anti-aging behavior of SBR/silica composites with vitamin C-lanthanum complex was systematically investigated by mechanical property retention after aging, oxidation induction time, exothermic enthalpies of thermal oxidation, and thermo-oxidative degradation kinetics. The highlight of this work lies in the fact that several thermal analysis techniques were successfully applied to fully evaluate the thermal-oxidative aging of SBR/silica composites and the vitamin C-lanthanum complex was found to endow SBR/silica composites with better protection against aging than commercial antioxidants, which may be beneficial for better characterization of rubber aging and fruitful for the preparation of highly aging-resistant rubber composites, respectively.     

磺化石墨烯/天然橡胶复合材料的性能研究

以磺化石墨烯为填料,将其填充到天然胶乳中,混合均匀后共沉淀,采用传统橡胶加工方法制备了天然橡胶复合材料。对磺化石墨烯的结构和形貌进行了表征,测定了硫化胶的力学性能、耐磨性能、透气性能和导热性能。研究结果表明:磺化石墨烯表面含有丰富的活性官能团,为少层片状结构,硫化胶的力学性能、耐磨性得到了提高,而透气性和导热性有所下降。当石墨烯添加量为2.0%(wt)时,复合材料的拉伸强度最大为27.06MPa;磨耗体积仅为0.08cm~3;导热系数最小为0.42W/(m·K);透气量最低,为1.98×10~(-4)cm~3/(m~2·d·Pa)。