二氧化硅填料与硅橡胶在热老化时的作用

本文研究了三种表面性质不同的二氧化硅填料与二甲基硅橡胶在热老化时的作用。使混炼胶和硫化胶分别在甲苯和甲苯-氨中溶胀,测定了结合胶及溶胀度的变化。证明在老化时填料和橡胶之间有数量可观的化学键生成,并且发生氢键向化学键的转化。填料表面经过化学处理或加结构化控制剂,对它和橡胶之间的氢键结合,化学反应均有一定的抑制作用。     

Thermal Oxidative Degradation and Ageing Performance of Silicone Rubber Filled with Attapulgite

The natural attapulgite (NAPT) was disaggregated by high-pressure homogenization technology combined with extrusion process to prepare the attapulgite with disaggregated rod crystal bundles (DAPT) and large specific surface area of 133.7 m²/g. NAPT and DAPT were incorporated into the silicone rubber to obtain the composite NAPT-SR and DAPT-SR by mechanical blending method, respectively. After thermal oxidative ageing at 300 ℃ for 0.5 h, temperature for the 5% weight loss increased greatly from 385 ℃ of the neat silicone rubber to 396℃ - 399 ℃ with addition of NAPT and DAPT. NAPT and DAPT enhanced the interaction between the filler nanoparticles and rubber matrix thus inhibited the nanoparticle agglomeration. The conservation rate of the side methyl group in NAPT-SR and DAPT-SR was greatly improved after ageing. Therefore, the thermal oxidative degradation and ageing performance of the silicone rubber composites was significantly reinforced. Moreover, DAPT could greatly restrain the growth of nanoparticles after ageing. Therefore, DAPT-SR showed the better retention of tensile strength (40.6%), elongation at break (34.9%) and tear strength (30.1%) compared with the corresponding mechanical properties of the neat silicone rubber (10.6%, 7.4%, and 5.0%) after ageing.     

Surface modification of calcium sulfate whisker using thiol-ene click reaction and its application in reinforced silicone rubber

The hemihydrate calcium sulfate whisker (HCSW) was modified by γ-(methacryloxy)propyl trimethoxy silane (KH570) and trimethylolpropane tris(3-mercaptopropionate) via wet modification and thiol-ene click reaction, and then the unmodified and modified HCSW were added into α, ω-dihydroxy polysiloxane (DPS) matrix to prepare silicon rubber composites. After the dual-surface modification, the surface of HCSW was transformed to hydrophobic, the hydration of whisker was obviously improved, and the whisker dispersed more evenly in the polymer. The mechanical properties, dynamic mechanical properties, and the medium resistance of the silicone rubber composite were compared. The tensile test shows that the silicone rubber shows better mechanical properties after adding the modified whiskers, among which HCSW-KH570-SH has the most significant reinforcement effect. Moreover, DPS/HCSW-KH570-SH shows the best medium resistance in toluene, gasoline, and water. The addition of modified whiskers can improve the storage modulus of silicone rubber significantly, while DMA and DSC show that the addition of modified whiskers can reduce the glass transition temperature of silicone rubber. The bound rubber indicates that the interface interaction between HCSW-KH570-SH and silicone rubber is the best.     

Surface modification of magnesium hydroxide particles using silane coupling agent by dry process

In order to improve the dispersion and compatibility of magnesium hydroxide (MH) when added in the polymer matrix as fillers, the surface of MH was modified by dry process using vinyltrimethoxysilane (VTMS), and the interfacial interaction between MH and VTMS was also studied. Scanning electronic microscopy, transmission electron microscopy, and X‐ray powder diffraction analyses showed that the agglomerations of MH particles were effectively relieved, and a thin layer was formed on the surface of modified MH. Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy analyses showed that the VTMS molecules bound strongly to the surface of MH particles and chemical bond (Si―O―Mg) was formed after modification. The effect of surface modification was evaluated by contact angle, the settlement curve, and thermogravimetric analysis. The results showed that the surface of MH particles was transformed from hydrophilic to hydrophobic, with the dispersibility and the compatibility of MH particles significantly improved in the organic phase. Additionally, the thermal stability of the VTMS modified MH particles had improved significantly.     

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.     

质子辐照对有机硅树脂增强甲基硅橡胶的性能损伤及机理

硅橡胶具有优良的电绝缘性以及耐高低温、耐电晕、耐化学腐蚀、耐大气老化、耐臭氧和耐辐射等性能，近年来在航天领域得到了广泛应用．在宇宙空间的带电粒子如质子、电子等的辐照作用下，硅橡胶会发生性能退化，其质损率上升，产生析气现象，从而直接影响航天器的可靠性和寿命．自80年代以来，人们就对不同辐照源及不同粒子注量对硅橡胶材料的影响进行了研究，但直到近几年才将研究热点转向辐照场中硅橡胶的性能退化及微观结构的演变规律，其辐照环境大多集中于γ射线、Si^＋和F^＋离子、He^2＋离子等．对于空间环境下带电粒子辐照对硅橡胶材料的影响，国外由于相应的研究工作保密性强，报道甚少；国内哈尔滨工业大学则对我国自行研制的白炭黑增强空间级甲基硅橡胶质子辐照作用后的性能与微观结构的变化做了较为深入的研究。     

硅橡胶新硫化体系的研究

本文介绍一种硅橡胶新硫化体系,即利用Diels-Alder反应使聚硅氧烷进行交联。所用生胶为含乙烯基的高分子量聚甲基硅氧烷,所用交联剂(硫化剂),即双烯体,系含有环戊二烯基的有机硅化合物。所得弹性体的物理机械性能达到高强度硅橡胶水平。     

The improvement of thermal stability and adhesion of silicone rubber composites modified by phenolic epoxy resin

The phenolic epoxy resin (F51) was siliconized by KH550 and the product was named as FKS. A hydroxyl-terminated polydimethylsiloxane (HTPDMS) which was modified with FKS was prepared. The siliconization reaction ensured a segment of siloxane on the side chain of F51. FT-IR and ¹H-NMR were employed to confirm the chemical structure of FKS. Morphology observations revealed that the enhancement of mechanical properties of the silicone rubber systems can be attributed to good compatibility between FKS and silicone rubber matrix. Thermogravimetric analysis showed that the residual yield at 800?°C of silicone rubber composites increased significantly when compared with that of neat HTPDMS. The mechanical properties demonstrated that tensile strength and elongation at break of silicone rubber system increased distinctly after modification, especially when 30 phr siliconized F51 were added to the silicone rubber. Shear strength was improved gradually with the addition of FKS. These above observations emphasize the vital effect of FKS on the behavior of modified HTPDMS.     

双马来酰亚胺在改进硅橡胶热稳定性中的作用

 双马来酰亚胺能改进硅橡胶在空气或氧气中的热稳定性。热老化试验和热降解动力学分析表明,其机理可能是双马来酰亚胺能优先与氧作用,避免了硅橡胶链上侧甲基被氧化,减轻了交联密度的提高,从而提高了硅橡胶的热稳定性。     

双马来酰亚胺在改进硅橡胶热稳定性中的作用

双马来酰亚胺能改进硅橡胶在空气或氧气中的热稳定性。热老化试验和热降解动力学分析表明,其机理可能是双马来酰亚胺能优先与氧作用,避免了硅橡胶链上侧甲基被氧化,减轻了交联密度的提高,从而提高了硅橡胶的热稳定性。     

3-氨丙基三乙氧基硅烷对聚氨酯/Al-Sm_2O_3复合涂层自然老化性能的影响

通过硅烷偶联剂3-氨丙基三乙氧基硅烷(KH550)改性聚氨酯(PU)/Al-Sm_2O_3复合涂层,从功能特性和力学性能角度系统研究了改性前后涂层自然老化性能的变化规律。结果表明,改性后PU/Al-Sm_2O_3复合涂层的红外发射率对自然老化的稳定性得到明显增强,在同等条件下改性后的涂层发射率要明显低于未改性的涂层发射率。改性后涂层表面的Sm_2O_3颗粒分散更加均匀,对近红外光的吸收强度有所增强,从而使改性后涂层对1.06μm近红外光的反射率要明显低于未改性涂层。改性前后涂层的硬度对自然老化具有良好的稳定性,其硬度可保持在3 H;未改性涂层的附着力和耐冲击强度受自然老化影响明显,但改性后涂层的附着力和耐冲击强度得到明显加强,经自然老化4个月后仍然可保持在1级和50 kg·cm。     

添加稀土氧化物助剂的CeO2-ZrO2固溶体的储氧性及热稳定性研究

大多数工业催化剂都是在稳定的操作条件下进行的,然而汽车尾气净化催化剂却被暴露在大气中,使用条件经常变化,尤其是空燃比(A/F)的变化,直接影响了对氧敏感的三效催化剂的氧化和还原性能[1].CeO2则是一种具有储氧/释氧能力的催化材料,它作为助剂加入三效催化剂中,可在贫况下储存氧(以Ce4+存在)利于NOx的还原,在富况下释放氧(以Ce3+存在),利于HC、CO的氧化,从而提高了催化剂的活性.然而,CeO2 的储氧性通常局限在表面上,当温度超过400℃以上时,其比表面积降低从而引起储氧性能急剧下降,直接影响催化剂的性能和寿命.     

Effect of 200 keV proton irradiation on the properties of methyl silicone rubber

The effects of 200 keV proton irradiation on methyl silicone rubber were studied. The changes in surface morphology, mechanical properties, cross-linking density, glass transition temperature, infrared attenuated total reflection spectrum and mass spectrum indicated that, at lower fluence, the proton irradiation induced cross-linking, resulting in an increase in tensile strength and hardness of the methyl silicone rubber. However, at higher proton fluence, radiation-induced degradation, which decreased the tensile strength and hardness, became dominant. A macromolecular-network destruction model for silicone rubber irradiated with protons was proposed.     

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.     

Investigation of photo‐oxidative effect on morphology and degradation of mechanical and physical properties of nano CaCO3 silicone rubber composites

Photo‐oxidative degradation of treated and untreated nano CaCO₃: silicone rubber composite was studied under accelerated UV irradiation (≥290 nm) at different time intervals. Prolonged exposure to UV leads to a progressive decrease in mechanical and physical properties along with the change in behavior of filler‐matrix interaction. This was due to decrease in cross‐linking density with increase in mobility of rubber chains. Meanwhile, synthesized nano CaCO₃ was modified with stearic acid for uniform dispersion in rubber matrix. The increase in carbonyl (>CO), hydroxyl (? OH), CO₂, and alkene functional groups on the UV exposed surface of treated and untreated nano CaCO₃: silicone rubber composites at different time intervals was studied using Fourier transform infrared (FTIR) spectroscopy. The change in morphological behavior of filler‐matrix interaction after UV exposure was studied using SEM. Overall, the study showed that the treated nano CaCO₃: silicone composites were affected more by UV exposure than untreated nano CaCO₃: silicone composites and pristine composite after UV exposure. This effect was due to peeling of stearic acid from the surface of CaCO₃, which makes the rubber chains slippery and thus separation of filler and rubber chains takes place with initiation of fast‐degradation. Copyright © 2011 John Wiley & Sons, Ltd.     

Development of Natural Rubber-Fibrous Nano Clay Attapulgite Composites: The Effect of Chemical Treatment of Filler on Mechanical and Dynamic Mechanical Properties of Composites

Common nano clay fillers have layered structure. Some nano clays like Attapulgite (AT), Sepiolite have rod like fibrous structure. Compared to layered structured clay fibrous clay AT can undergo better dispersion in polymer matrix leading to better improvement in composite properties. Chemical modifications of AT are done through amine treatment as well as by amine+silane treatment to get chemically modified fillers AAT and SAT respectively. In the present investigation, nano composites are prepared using natural rubber (NR) filled with AT, AAT and SAT. Three different loadings of each filler are used namely 2.5, 5, and 10 phr (parts per hundred of rubber). Mechanical properties like tensile strength, elongation at break increase with the increase in filler loading up to 5 phr there after these properties marginally fall when loading is increased to 10 phr due to problem of filler dispersion at higher loading. However, modulus at 300% elongation and tear strength increases with the increase in filler loading up to 10 phr. Very similar trend can also be observed for composites with chemically modified fillers, AAT and SAT. But the degree of reinforcement is higher in the case of AAT and SAT compared to that of unmodified filler AT for the same filler loading. This difference is mainly due to better polymer-filler interaction and filler dispersion in the case of chemically modified clays AAT and SAT compared to unmodified AT. Tear strength of composites increases remarkably with the addition of AT and which is further enhanced when chemically modified clays AAT and SAT are added. Dynamic-mechanical analyses of different clay composites give idea about the difference in the degree of polymer–filler interaction due to chemical treatment of filler.     

通过氧化改性提高载银活性炭的抗菌性能

使用浓HNO3和浓H2O2对活性炭进行常温氧化改性,用FTIR和N2吸附法对活性炭进行表面分析,用AAS、SEM、XRD研究银在活性炭表面的吸附和分布特征,并研究了载银活性炭的抗茵性能.结果表明,活性炭经浓HNO3常温改性后,比表面积提高,而经浓H2O2常温改性后,比表面积略有下降,但都使活性炭表面含氧基团增加.改性后,活性炭表面增加的含氧基团为[Ag(NH3)2] 的还原吸附提供更多的活性点,使银的吸附量增大5倍多,银颗粒更加密集,大小更加均一.研究表明,载银活性炭具有明显的抗茵作用,其中对金黄色葡萄球菌的杀灭效果优于对大肠杆菌的杀灭效果,氧化改性使载银活性炭抗茵作用显著增强,其中硝酸改性现象更加明显.     

含改性硅微粉硅橡胶阻燃抑烟研究

为进一步提升硅橡胶(SR)的阻燃性能,利用硅烷偶联剂对硅微粉(SF)进行表面改性,以改性后的SF为阻燃剂,制备出SR样品。通过扫描电子显微镜(SEM)对改性前后SF表面形貌进行表征,通过极限氧指数(LOI)、水平垂直测试、锥形量热仪(CCT)、烟密度测试(SDT)等手段研究SR复合材料力学性能、阻燃性能、抑烟性能。研究表明:添加相同质量的SF和改性SF时,含改性SF的SR力学性能明显提升。其中,含21%(wt)改性SF/SR复合材料的力学、阻燃性能综合最佳。与纯SR相比,改性SF/SR复合材料的LOI增加了15%,热释放速率峰值降低86%,火灾增长指数降低了58%,最大烟密度降低43%。     

硅氢加成型室温固化硅橡胶胶粘剂的研究

<正> 我们研制了一种硅氢加成型室温固化硅橡胶,这种橡胶不但有较好的力学性能,而且与各类材料如金属、塑料、陶瓷、玻璃等都有很好的粘结力,是一种具有弹性的胶粘剂。该胶粘剂是利用一种含乙烯基聚硅氧烷、含氢聚硅氧烷以及二氧化硅补强剂在铂催化剂     

聚醚扩链脲增韧环氧树脂体系的冲击性能及其断裂面形态结构

聚醚扩链脲增韧环氧树脂体系的冲击性能及其断裂面形态结构