聚乙二醇-介孔二氧化硅复合材料的合成及表征

利用共混法合成了聚乙二醇-介孔二氧化硅有机-无机复合材料.采用XRD、N_2吸附-脱附、SEM、TEM、红外光谱(FTIR)、DSC-TG等对聚乙二醇-介孔二氧化硅复合材料进行了表征.结果表明,聚乙二醇-介孔二氧化硅仍保持了原来的介孔结构,可以均匀地分散到介孔二氧化硅的基质中.PEG是靠氢键吸附在纳米HMS颗粒表面,两者并没有发生化学反应生成新的化合物.所合成的聚合物具有比较好的耐温性能, HMS提高了聚合物的耐热性.     

α-NaYF4：Yb，Er／SBA-15主客体复合材料的制备及其上转换性能的研究

本文以介孔二氧化硅材料SBA-15为硬模板,通过纳米浇铸法与水热法,制备介孔二氧化硅与α-NaYF4：Yb3Er的主客体功能复合材料α-NaYF4：Yb,Er／SBA-15。利用广角x射线衍射（WideangleXRD）,扫描电子显微镜（SEM）,并结合小角X射线衍射（SmallangleXRD）,N2吸附（N2adsorption measurement）等手段,证实α-NaYF4：Yb,Er有效地负载到介孔SBA-15的孔道内部,较好保持了其介观结构。上转换性能测试表明,在980nm激光的激发下,该材料的绿光发光强度大幅度提高。在文中,我们对该现象进行了分析,并提出其可能的机理。     

聚甲基丙烯酸/SBA-15复合物的制备

采用超声波分散技术,通过原位合成法将pH敏感的功能单体甲基丙烯酸(MAA)引入到介孔二氧化硅SBA-15的孔道内聚合,制备了pH敏感SBA-15/聚甲基丙烯酸(PMAA)纳米复合材料,对材料的结构和性能进行了测试。结果表明,介孔分子筛SBA-15/PMAA复合材料有较好的光学性能、热性能。聚合反应的发生并没有破坏SBA-15的有序介孔结构,显示出pH敏感性,有望在药物缓释领域得到应用。     

胺功能化介孔二氧化硅捕集CO2的研究进展

胺功能化介孔二氧化硅因其高选择性、高吸附容量、快速的吸附动力学、良好的再生性能和循环稳定性受到广泛关注,在二氧化碳捕集技术中具有优良的应用前景。本文比较了胺改性的M41S、SBA-n、KIT-n、介孔二氧化硅泡沫、介孔二氧化硅纳米球和六方介孔二氧化硅的吸附性能,总结了MCM-41和SBA-15的结构特点。介绍了胺化合物的负载方式——湿法浸渍、化学接枝和原位聚合的胺负载原理。分析了硅源、载体内部性质、气体选择性和不同添加剂对胺功能化介孔二氧化硅材料吸附二氧化碳能力的影响。最后,点明了吸附剂未来的发展目标,对胺功能化介孔二氧化硅材料的研究方向进行了展望。指出未来可关注介孔二氧化硅微观结构和温度对胺与二氧化碳相互作用的影响,增强胺功能化介孔二氧化硅的稳定性,推进其在实际环境下的应用。     

复合材料的结构与性能

分别采用水玻璃（SS）和正硅酸乙酯（TEOS）自组装制备了两种大孔径的虫状介孔二氧化硅（SiO₂）MSU-J-SS以及MSU-J-TEOS；分别制备了介孔SiO₂含量为2wt %--10wt %的橡胶态及玻璃态的环氧树脂介孔复合材料；对介孔SiO₂的物理结构及环氧树脂介孔复合材料的力学性能和微观结构进行了研究。结果表明：硅源及合成条件将影响介孔SiO₂的物理结构，相对于MSU-J-TEOS，MSU-J-SS表现出更好的结构规整性，较大的平均孔径，较小的比表面积、孔容及壁厚；相对于纯环氧树脂，橡胶态和玻璃态环氧树脂介孔复合材料的拉伸强度、拉伸模量均提高，并且由平均孔径较大的MSU-J-SS制备的介孔复合材料的断裂延伸率没有降低，体现出增韧的效果；相对于MSU-J-TEOS，MSU-J-SS在环氧树脂中的分散更为均匀，其拉伸试样表现出相对韧性的断口形貌。     

介孔氧化铝的合成及应用

通过对介孔氧化硅合成工艺的优化与修正可以用来制备介孔氧化铝分子筛。在合成介孔分子筛的前驱物中掺杂其他金属元素而将其引入骨架或将活性组分负载到介孔分子筛的基体上,可以实现对介孔分子筛表面进行表面修饰与改性,以调变分子筛表面的酸催化性能。本文综述了介孔氧化铝合成、改性研究的历史与现状,及在酸催化过程中的应用。     

纳米介孔碳与纳米介孔二氧化硅的复配体系作为润滑油添加剂的摩擦学性能

用均匀设计法将纳米介孔碳与纳米介孔二氧化硅进行复配,利用四球摩擦试验机对复配剂摩擦学性能进行测试。发现复配体系能较好地改善润滑油的抗磨减摩性能;复配体系中纳米介孔碳和介孔二氧化硅均能发挥各自优势,分别改善润滑油的极压性能和减摩性能。     

排球表面用高耐磨低迁移的聚氨酯塑料的制备与性能研究

以硅烷偶联剂KH-550对介孔二氧化硅(MSiO_2)表面进行改性,制备了改性介孔二氧化硅(mMSiO_2),考察了在复合聚氨酯树脂中MSiO_2表面改性对材料性能的影响。结果发现:加入MSiO_2后,复合材料拉伸强度明显提高,断裂伸长率明显降低,而替换为mMSiO_2后复合材料强度进一步提高。加入MSiO_2后复合材料挥发性有机化合物(VOC)散发性能得到优化,并且未改性MSiO_2对复合材料苯系物吸附效果较优,mMSiO_2则对醛酮吸附效果明显。加入MSiO_2后复合材料耐磨性能得到明显提升,并且mMSiO_2效果更好。当MSiO_2和mMSiO_2分别为5份时,VOC综合散发性能最优,Taber磨耗值为0.42 g。     

介孔二氧化硅氨基改性及其CO_2吸附性能的研究进展

综述了介孔二氧化硅氨基改性及其CO2吸附性能的研究进展,主要介绍了MCM-41、SBA-15氨基改性的研究情况。同时对浸渍法和嫁接法在介孔二氧化硅氨基改性过程中的优缺点进行了讨论。最后,提出了介孔二氧化硅氨基改性在CO2吸附方面的研究方向。     

介孔SiO_2的有机化修饰及其对环氧树脂拉伸性能的影响

利用正硅酸乙酯(TEOS)及γ-氨基丙基三甲氧基硅烷(APTMS)共缩聚合成了蠕虫状的介孔二氧化硅(Si O2);研究了有机化修饰对介孔Si O2结构的影响;采用熔融共混法制备了环氧树脂/介孔Si O2复合材料,并研究了复合材料的拉伸性能。结果表明,APTMS的引入使介孔Si O2的有序性变差,孔径、孔容及比表面积减小,当介孔Si O2中APTMS的含量达到20%时,介孔结构消失;当介孔Si O2的用量为2%～10%时,环氧树脂/介孔Si O2复合材料的拉伸强度和断裂韧性提高较为显著,但断裂伸长率变化不大。     

Solution‐blown SPEEK/POSS nanofiber–nafion hybrid composite membranes for direct methanol fuel cells

This study aims to develop novel hybrid composite membranes (NHMs) by impregnating Nafion solution into the porous sulfonated poly(ether ether ketone)/polyhedral oligomeric silsesquioxanes (SPEEK/POSS) nanofibers (NFs). The composite membrane was prepared by solution blowing of a mixture of SPEEK/POSS solution. The characteristics of the SPEEK/POSS NFs and the NHMs, including morphology, thermal stability, and performance of membrane as PEMs, were investigated. The performance of NHMs was compared with that of Nafion117 and SPEEK/Nafion composite membranes. Results showed that the introduction of POSS improved the proton conductivity, water swelling, and methanol permeability of membranes. A maximum proton conductivity of 0.163 S cm^?1 was obtained when the POSS content was 6 wt % at 80°C, which was higher than that of Nafion117 and SPEEK/Nafion. NHMs could be used as proton exchange membranes (PEMs) for fuel cell applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42843.     

Solution blown sulfonated poly(ether sulfone)/poly(ether sulfone) nanofiber‐Nafion composite membranes for proton exchange membrane fuel cells

A composite membrane of sulfonated poly(ether sulfone) (SPES)/poly(ether sulfone) (PES) nanofiber (NF) mat impregnated with Nafion was prepared and evaluated for its potential use as a proton conductor for proton exchange membrane (PEM) fuel cells. The supporting composite nanofibrous mat was prepared by solution blowing of a mixture of SPES/PES solution. The characteristics of the SPES/PES NF and the composite membrane, such as morphology, thermal stability, and performance of membrane as PEMs, were investigated. The performance of composite membranes was compared with that of Nafion117. The introduction of solution blown NFs to composite membranes modestly improved proton conductivity, water swelling, and methanol permeability. Therefore, composite membrane containing SPES/PES NFs can be considered as a novel PEM for fuel cell applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42572.     

Synthesis of organic-inorganic composite membrane by sol-gel process

Silica was succesfully incorporated into cation exchange polymer membranes, CL-25T and Nafion 417, utilizing sol-gel process. As dipping time increased, increase in silica uptake in membrane was observed. In Nafion 417 membrane, no relationship was found between the silica uptake and the change in ion exchange capacity. But CL-25T which has larger pores than Nafion 417 shows proportional decrease in ion exchange capacity with increasing silica uptake. It suggests that the pore structure of membrane and the size control of silica sol are important to modify the structure of composite membranes. In CL-25T membranes modified by silica, the transport rate of IPA (isopropyl alcohol) increased with increasing OH^- concentration on the pore surface.     

Esterification in a structured catalytic reactor with counter-current water removal

In this research the liquid phase esterification of hexanoic acid and 1-octanol was studied. Very high activities were obtained for zeolite BEA and Nafion/silica composite with 13% of Nafion. The advantage of water removal in this system was demonstrated. In a closed system an equilibrium conversion of 35% was reached, while in a system with water removal all the reactants were converted in a shorter period. The initial reaction rate decreases when increasing the initial water concentration, following a Langmuir–Hinshelwood type of rate expression. An active zeolite coated structured monolithic reactor configuration was prepared. Enhancement by the counter-current water stripping of the performance of the structured catalysts was demonstrated.     

Fabrication and characterization of a novel Nafion-PTFE composite hollow fiber membrane

Nafion has been widely used in electrochemistry, but there are only a few reports on its application in other fields, such as, gas separation, even though it exhibits good performance. The primary reason for that is the high cost of Nafion and making a composite membrane with a thin Nafion layer is a potential solution to solve this problem. In this study, a novel Nafion-PTFE composite hollow fiber membrane, which had a thin (~5 μm) and detect-free Nafion layer on PTFE surface, without Nafion filling substrate pores was developed, differing from the reported ones in which Nafion resin was required to impregnate into porous PTFE membrane as thorough as possible to ensure the ion conductivity and operation stability. The surface morphology, crystallite, solubility in ethanol/water mixture, and water uptake of membranes were systemically investigated. The gas permeance tests were also conducted. The permeances of different gasses of prepared composite membranes were significantly enhanced compared with the commercial membranes due to the decrease of Nafion thicknesses, while the selectivity remained the same, verifying the detect-free structure of Nafion layer on PTFE substrate. This study provided a good reference for the preparation and application of low-cost Nafion composite membranes.     

Modification of Nafion membranes with ternary composite materials for direct methanol fuel cells

Composite membranes for direct methanol fuel cells (DMFCs) were prepared by using Nafion115 membrane modification with polyvinyl alcohol (PVA), polyimide (PI) and 8-trimethoxysilylpropyl glycerin ether-1,3,6-pyrenetrisulfonic acid (TSPS). The performance of the composite membranes was evaluated in terms of water sorption, dimensional stability, thermal stability, proton conductivity, methanol permeability and cell performance. The proton conductivity was slightly decreased by 1-3% compared with Nafion115, which still kept the high proton conduction of Nafion115. The methanol permeability of Nafion/PI-PVA-TSPS composite membranes was remarkably reduced by 35-55% compared with Nafion115. The power density of DMFCs with Nafion/PI-PVA-TSPS composite membranes reached to 100 mW/cm², exceeding that with Nafion115 (68m W/cm²).     

Molecular dynamics simulations of Krytox-Silica-Nafion composite for high temperature fuel cell electrolyte membranes

A five percent by weight of carboxylic acid terminated perfluoropolyether hybrid with silica (Krytox-Silica) in Nafion composite polymer was used in the modification of a polymer electrolyte fuel cell membrane in order to improve its efficiency at high operating temperatures. Molecular dynamics (MD) simulations were carried out in order to understand the microscopic properties of two systems, Krytox-Silica in Nafion and pure Nafion. A model of five percent Krytox-Silica in a Nafion composite polymer consisting of 15 Nafion side chains, 15 hydronium ions and one of Krytox-Silica was used. In another system, pure Nafion was modeled without Krytox-Silica. Models with various amounts of water molecules and temperatures were simulated to study the water content and temperature effects. The results were in good agreement with the experiments and could be used to describe the application of Krytox-Silica-Nafion composite at high temperatures. The effect of the amount of water molecules on the diffusion coefficient or proton conductivity showed more deviations between 5% wt of Krytox-Silica-Nafion composite and pure Nafion system at lower water content (or higher temperature) than at high water content (or low temperature). According to the diffusion coefficient results, the percentage of water molecules at each temperature corresponded to the known experimental trend. Silica, as the water absorbent in the hybrid polymer membrane, did not have a strong interaction with water molecules or H₃O⁺ ions; thus the proton conductivities will not be highly affected by adding Krytox-Silica to the Nafion.     

Nafion/PTFE Composite Membranes for Fuel Cell Applications

The composite membranes were prepared by impregnation of porous poly(tetrafluoroethylene) membranes with a 5 wt% Nafion solution. Scanning electron microscope micrographs of composite membranes show the surface and cross section of poly(tetrafluoroethylene) membranes were covered and filled with Nafion resin. Comparison of physical properties and fuel cell performance of composite membranes with those of Nafion membranes (DuPont Co) is presented. The composite membrane has better thermal stability and gas barrier property but worse ionic conductivity than Nafion membrane. Though the composite membrane has a lower conductivity than Nafion membrane, however, owing to the thinner thickness of composite membrane (in thickness of 20±5µm) than Nafion-115 (in thickness of 125µm) and Nafion-117 (in thickness of 175µm) membranes, the composite membrane has a shorter H⁺ ion transporting pathway and thus a higher conductance (conductance = conductivity/membrane thickness) than Nafion-115 and Nafion-117 membranes. Thus the composite membrane has a better fuel cell performance than Nafion-117 and Nafion-115 membranes. In this report, we show that our composite membrane has a fuel cell performance similar to Nafion-112 membrane (in thickness of 50µm).     

The study of PTFE/Nafion/Silicate membranes operating at low relative humidity and elevated temperature

The performance and stability of PTFE/Nafion/Silicate composite membranes (PNS membrane) were studied at low and medium operating temperatures with different humidity, and compared with the Nafion112 membrane at the same conditions. The PNS membrane was prepared by impregnation of PTFE/Nafion composite membrane via sol-gel process with TEOS (tetraethoxysilane). When operated cell at low temperature of 60 °C with 100% R.H. humidified H₂/O₂ gases, the PNS membrane performs better than Nafion112, with 1.0, and 0.4 W/cm², respectively. When operated cell at 60 °C with 37% R.H. humidified gases, the discharge stability of PNS membrane is stable than that of Nafion112, this is due to that silicate could hold more water in the PNS membrane at low relative humidity. While the inlet of cell gases temperature keeps at 80 °C, the cell temperature varied 90, 100, and 110 °C, with 20 psig back pressure, their relative humidities were 67, 48 and 33%, respectively. The stability of discharge current remains constant except in the case of cell temperature being as high as 110 °C. It is believed that silicate could hold water except in the case of cell temperature at 110 °C, which is resulted as the membrane dehydration. On the other hand, the Nafion112 cannot operate at low humidity with cell temperature higher than 80 °C owing to membrane dehydration. The silica modified PTFE/Nafion membrane shows the improving cell performance at lower relative humidity due to adsorbed water inside the membrane and catalyst layer.     

PWA/silica doped sulfonated poly(ether sulfone) composite membranes for direct methanol fuel cells

A novel sulfonated poly(ether sulfone) (SPES)/phosphotungstic acid (PWA)/silica composite membranes for direct methanol fuel cells (DMFCs) application were prepared. The structure and performance of the obtained membranes were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), water uptake, proton conductivity, and methanol permeability. Compared to a pure SPES membrane, PWA and SiO₂ doped membranes had a higher thermal stability and glass transition temperature (T_g) as revealed by TGA‐FTIR and DSC. The morphology of the composite membranes indicated that SiO₂ and PWA were uniformly distributed throughout the SPES matrix. Proper PWA and silica loadings in the composite membranes showed high proton conductivity and sufficient methanol permeability. The selectivity (the ratio of proton conductivity to methanol permeability) of the SPES‐P‐S 15% composite membrane was almost five times than that of Nafion 112 membrane. This excellent selectivity of SPES/PWA/silica composite membranes indicate a potential feasibility as a promising electrolyte for DMFC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011