Organic-inorganic nanocomposite polymer electrolyte membranes for fuel cell applications

Organic-inorganic nanocomposite polymer electrolyte membrane (PEM) contains nano-sized inorganic building blocks in organic polymer by molecular level of hybridization. This architecture has opened the possibility to combine in a single solid both the attractive properties of a mechanically and thermally stable inorganic backbone and the specific chemical reactivity, dielectric, ductility, flexibility, and processability of the organic polymer. The state-of-the-art of polymer electrolyte membrane fuel cell technology is based on perfluoro sulfonic acid membranes, which have some key issues and shortcomings such as: water management, CO poisoning, hydrogen reformate and fuel crossover. Organic-inorganic nanocomposite PEM show excellent potential for solving these problems and have attracted a lot of attention during the last ten years. Disparate characteristics (e.g., solubility and thermal stability) of the two components, provide potential barriers towards convenient membrane preparation strategies, but recent research demonstrates relatively simple processes for developing highly efficient nanocomposite PEMs. Objectives for the development of organic-inorganic nanocomposite PEM reported in the literature include several modifications: (1) improving the self-humidification of the membrane; (2) reducing the electro-osmotic drag and fuel crossover; (3) improving the mechanical and thermal strengths without deteriorating proton conductivity; (4) enhancing the proton conductivity by introducing solid inorganic proton conductors; and (5) achieving slow drying PEMs with high water retention capability. Research carried out during the last decade on this topic can be divided into four categories: (i) doping inorganic proton conductors in PEMs; (ii) nanocomposites by sol-gel method; (iii) covalently bonded inorganic segments with organic polymer chains; and (iv) acid-base PEM nanocomposites. The purpose here is to summarize the state-of-the-art in the development of organic-inorganic nanocomposite PEMs for fuel cell applications.     

二甲基二乙氧基硅烷对TEOS凝胶化过程的影响

以TEOS溶胶凝胶过程的动态激光光散射研究为基础,在过程的不同阶段加入二官能团有机硅单体DDS。用SEM分析产物的不同形貌。结果表明,DDS的加入对TEOS凝胶化过程产生了较大的影响,所得相分离产物随着DDS加入时间的不同呈现出一定的规律。这种规律的出现与动态激光光散射的研究结果达到了统一,从宏观上进一步体现了TEOS溶胶凝胶过程的特征,对在活性二氧化硅表面键接复合其它单体的研究必将起着重要的指导作用。     

印山越国王陵墓坑边坡化学加固试验研究

以印山越国王陵墓坑边坡加固为背景,通过试验比较几种化学材料的加固效果。在室内试验中,经过正硅酸乙酯加固的岩石试块效果相对较好:其外观状态改变最小,而单轴抗压强度和耐水性能有所提高,此外正硅酸乙酯的渗透性能也优于其他材料。在现场试验中,采用注射、滴注和喷淋等方式进行加固试验,结果表明正硅酸乙酯加固效果符合设计要求,可以作为墓坑边坡加固的化学材料之一。目前墓坑边坡加固已经完成,岩石表层强度有所增加,而碎石崩塌现象明显减小。     

Silicon oxide synthesized using an atmospheric pressure microplasma jet from a tetraethoxysilane and oxygen mixture

Local deposition of SiO_x was studied using an atmospheric pressure very-high-frequency (VHF) inductive coupling microplasma jet (AP-MPJ) from a tetraethoxysilane ((Si(OC₂H₅)₄), TEOS) and oxygen mixture. The SiO_x obtained showed the dielectric constant of 3.8 with a low leakage current of the order of ∼ 10^− 6 A ·cm^− 2 up to 8 MV ·cm^− 1. Bottom-gated sputtered-ZnO thin-film transistors with a AP-MPJ SiO_x as a gated dielectric layer exhibited a relatively high field-effect mobility of 24 cm² V^− 1 s^− 1, a threshold voltage of 14 V and an on/off current ratio of ∼ 10⁴, a performance comparable to that of thermal silicon dioxide. The TFT performance was also obtained for the top-gated ZnO-TFTs with a field-effect mobility of 1.4 cm² ·V^− 1 s^− 1, a threshold voltage of − 1.9 V, and an on/off current ratio of ∼ 10³.     

硫化物基荧光粉的表面包覆及性能研究

以硫化物为基质的荧光粉长期暴露于湿气中会缓慢发生化学反应从而降低发光特性、限制其应用。本文以正硅酸乙酯(TEOS)作为硅包膜剂,采用溶胶-凝胶法对CaS:Eu,Sm荧光粉进行表面包膜处理,获得了包覆氧化硅膜层的荧光粉。由于CaS:Eu,Sm发光粉体对酸或碱极其敏感,采用水解、包膜两步进行的工艺,先预制正硅酸乙酯的水解包膜液,再进行粉体表面包覆,并对水解工艺条件进行了讨论。对样品进行能谱分析,结果表明样品表面被包膜元素Si、O占据。包膜前、后样品浸水悬浮液的pH值曲线表明包膜后发光粉的耐水性得到较大改善,包膜后样品的上转换发光光谱峰形和峰值位置保持不变。     

丙烯酸酯低皂乳液与有机硅杂化反应研究

采用种子乳液聚合,以聚乙烯醇、壬基酚聚氧乙烯醚作为低皂乳化剂,合成了苯乙烯/丙烯酸丁酯/乙酸乙烯酯/丙烯酸-2-乙基己酯四元共聚乳液,再与硅溶胶、正硅酸乙酯(TEOS)进行杂化反应,制得有机硅丙烯酸酯杂化乳液。用红外光谱对产物进行结构分析,证明PVA、硅溶胶均与TEOS发生水解缩聚反应,使得反应产物的性能有较大提高。实验还考察了PVA浓度、硅溶胶与TEOS配比对样品性能的影响。     

以TEOS为硅源的聚硅硫酸铁制备与除藻性能

采用正硅酸乙酯（TEOS）代替传统的硅酸钠制备活性硅酸,将活性硅酸与聚合硫酸铁反应合成聚硅硫酸铁混凝剂,并研究了相关机理。由于正硅酸乙酯水解很缓慢,容易控制,可以得到重现性好的产物,有利于进行除藻性能的研究。通过正交实验等研究获得了聚硅硫酸铁的优化合成条件,即铁硅摩尔比为1．0,反应温度为50℃和反应时间为60min。论文还研究了优化条件下合成的聚硅硫酸铁混凝剂除藻性能,得到除藻优化条件,即原水的pH值为11．0、预氧化剂的投加量为0．70mg／L,聚硅硫酸铁的投加量为24．1mg／L。     

溶胶-凝胶法制备中孔炭材料及其表征

以正硅酸乙酯为无机模板硅源，蔗糖为炭前驱物，采用溶胶-凝胶法制得了比表面积达1073．36m^2／g，孔径分布集中，平均孔径为2．75nm的中孔炭材料，并采用FT—IR、N2吸附、TG—DTA和XRD等分析手段对其进行了表征。     

Synthesis and characterization of hybrid membranes using poly(vinyl alcohol) and tetraethylorthosilicate for the pervaporation separation of water–isopropanol mixtures

Hybrid membranes were prepared using poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS) via hydrolysis and cocondensation reaction for the pervaporation separation of water‐isopropanol mixtures. The resulting membranes were characterized by Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, and differential scanning calorimetry. The glass transition temperature of these membranes varied from 100 to 120°C with increasing TEOS content. Effects of crosslinking density and feed compositions on the pervaporation performances of the membranes were studied. The membrane containing 1.5:1 mass ratio of TEOS to PVA gave the highest separation selectivity of 900 at 30°C for 10 mass % of water in the feed mixture. It was found that the separation selectivity and permeation flux data are strongly dependent on the water composition of the feed and operating temperature. However, the membrane with the highest crosslinking density showed unusual pervaporation properties. The overall activation energy values were calculated using the Arrhenius‐type equation. The activation energy values for the permeation and diffusion varied from 49.18 to 64.96 and 55.13 to 67.31 kJ/mol, respectively. Pervaporation data have also been explained on the basis of thermodynamic quantities. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1304–1315, 2004     

溶胶-凝胶法制备SiO2杂化有机硅树脂及其耐热性能研究

无机基有机复合光功能材料是材料学界和光学界的研究热点。为了解决传统无机凝胶材料的机械加工性能差,光损耗大等问题,将有机基团引入到无机凝胶基质中,不但可以较好地优化基质的结构,还可在很大程度上改善材料的性能。以一甲基三甲氧基硅烷（MTMS）和正硅酸乙酯（TEOS）为原料,甲醇为溶剂,盐酸为催化剂,通过溶胶-凝胶法制备出分子级复合的SiO2杂化有机硅树脂。分析了SiO2杂化有机硅树脂的合成机理,借助傅立叶变换红外光谱表征其结构,TG和马弗炉灼烧实验研究SiO2杂化有基硅树脂的耐热性能,结果表明SiO2杂化有机硅树脂500～600℃的失重只有3％,具有良好的耐热性,并探讨了耐热机理。