Compositional characterization of cottonseed soapstocks

Cottonseed soapstock samples, collected during the 1993–1994 crushing season from oilseed extraction mills throughout the United States Cotton Belt, were analyzed by chemical and chromatographic methods. Volatiles averaged 48.7±10.6% (mean±SD,n=39). On a dry basis, the samples averaged 33.3±7.3% fatty acids, 26.3±6.9% phospholipids, 8.4±6.4% triglycerides, and 7.5±3.0% gossypol. The analytical techniques accounted for 93.3±8.6% of the dry soapstock matter. The AOCS method for total fatty acids in soapstock yielded values in agreement with the chromatographic and phosphorus analyses. In contrast, the AOCS method for neutral oil in soapstock gave values that were significantly higher than those obtained by chromatography. The amount of nonlipid material in the samples correlated with the phosphorus content. Total gossypol and nitrogen levels were also related.     

Graft polymerization of vinyl acetate onto silica

The free‐radical graft polymerization of vinyl acetate onto nonporous silica particles was studied experimentally. The grafting procedure consisted of surface activation with vinyltrimethoxysilane, followed by free‐radical graft polymerization of vinyl acetate in ethyl acetate with 2,2′‐azobis(2,4‐dimethylpentanenitrile) initiator. Initial monomer concentration was varied from 10 to 40% by volume and the reaction was spanned from 50 to 70°C. The resulting grafted polymer, which was stable over a wide range of pH levels, consisted of polymer chains that are terminally and covalently bonded to the silica substrate. The experimental polymerization rate order, with respect to monomer concentration, ranged from 1.61 to 2.00, consistent with the kinetic order for the high polymerization regime. The corresponding rate order for polymer grafting varied from 1.24 to 1.43. The polymer graft yield increased with both initial monomer concentration and reaction temperature, and the polymer‐grafted surface became more hydrophobic with increasing polymer graft yield. The present study suggests that a denser grafted polymer phase of shorter chains was created upon increasing temperature. On the other hand, both polymer chain length and polymer graft density increased with initial monomer concentration. Atomic force microscopy–determined topology of the polymer‐grafted surface revealed a distribution of surface clusters and surface elevations consistent with the expected broad molecular‐weight distribution for free‐radical polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 300–310, 2003     

An adaptive hybrid time‐stepping scheme for highly non‐linear strongly coupled problems

This paper deals with the design and implementation of an adaptive hybrid scheme for the solution of highly non‐linear, strongly coupled problems. The term ‘hybrid’ refers to a composite time stepping scheme where a controller decides whether a monolithic scheme or a fractional step (splitting) scheme is appropriate for a given time step. The criteria are based on accuracy and efficiency. The key contribution of this paper is the development of a framework for incorporating error criteria for stepsize selection and a mechanism for choosing from splitting or monolithic possibilities. The resulting framework is applied to silylation, a highly non‐linear, strongly coupled problem of solvent diffusion and reaction in deforming polymers. Numerical examples show the efficacy of our new hybrid scheme on both two‐ and three‐dimensional silylation simulations in the context of microlithography. Copyright © 2005 John Wiley & Sons, Ltd.     

反胶束法原位合成P25-MPTMS-CdS及光化学性能研究

本文将反胶束法制备的CdS晶体键合在经γ 巯丙基三甲氧基硅(MPTMS)修饰的P25粒子的表面.产物P25 MPTMS CdS复合粒子的紫外 可见吸收和粒子形貌分别用漫反射光谱仪和透射电镜进行了表征.同时也进行了光催化降解甲基橙溶液的实验,发现P25 MPTMS CdS在紫外和可见光下区域都具备较高的光催化活性.经过18h的可见光照后(λ>400nm),紫外 可见光谱表明,P25 MPTMS CdS粒子具备较好的光稳定性.     

改性硅藻土负载Keggin型杂多酸催化剂的制备及其催化性能

用盐酸与3-氨丙基三乙氧基硅烷对硅藻土进行改性,将改性后硅藻土负载Keggin型H5PMo10V2O40杂多酸(PMo V),制得负载型催化剂。采用FTIR,XRD,BET等方法对负载型催化剂进行表征。以正丁醇与乙酸合成乙酸正丁酯的反应为探针反应,考察了负载型催化剂的制备条件和用量对其性能的影响,并进行了催化剂的重复性实验。表征结果显示,PMo V负载在硅藻土表面上,PMo V仍保持Keggin型结构;负载型催化剂的最佳制备条件为:硅藻土焙烧温度500℃,用2.5 mol/L的盐酸酸化,PMo V负载量35%(w)(占硅藻土的质量)。在乙酸用量0.10 mol、正丁醇用量0.05 mol、反应温度120℃、反应时间150 min、催化剂用量1.0 g的条件下,乙酸正丁酯的收率为90.7%,重复使用5次后乙酸正丁酯的收率仍为81.2%,催化剂可重复使用。     

改性木质素/PBAT复合包装膜的研究

目的 将硅烷化木质素（SAL）与聚己二酸/对苯二甲酸丁二酯（PBAT）共混制备包装性能更为优良的SAL/PBAT复合包装膜,使其在包装领域应用更广。方法 通过对木质素进行硅烷化改性,以咪唑作为中间体,将叔丁基二甲基氯硅烷（TBDMSCl）接枝到木质素的羟基上制备SAL,并将SAL与PBAT进行熔融共混吹塑成膜,探讨其对包装膜的力学和阻隔等性能的影响。结果 与纯PBAT膜相比,SAL/PBAT复合包装膜拉伸强度提高了31.0%,断裂伸长率降低了37.4%,弹性模量提高了529.7%,氧气透过率降低了39.4%,水蒸气透过率降低了42.4%。结论 改性木质素与PBAT复合能够产生协同效应,可以有效改善SAL/PBAT复合包装膜的力学和阻隔性能。     

化学液相沉积法改性ZSM-5沸石上的甲苯择形歧化反应 Ⅰ沉积条件的影响

以硅氧烷为改性剂,采用化学液相沉积法制备了系列改性HZSM-5催化剂,用X射线衍射(XRD)、低温N2物理吸附及程序升温氨脱附(NH3-TPD)表征了催化剂的物化性质,并在高压微型反应装置上考察了改性催化剂在甲苯歧化反应中的催化性能,详细考察了催化剂制备过程中沉积量、沉积时间和沉积次数对甲苯转化率和对二甲苯选择性的影响。结果表明,催化剂颗粒的内外层SiO2沉积不均匀,形成了蛋壳型的催化剂;SiO2主要沉积在ZSM-5晶粒的外表面,而内部结构和酸性影响不显著。改性催化剂可大幅度提高甲苯歧化的对位选择性;沉积时间对选择性影响不大,多次沉积、增加沉积剂量可提高对位选择性,且存在一个最佳沉积量。     

A new route for preparation of sodium-silicate-based hydrophobic silica aerogels via ambient-pressure drying

An in-depth investigation into the synthesis of hydrophobic silica aerogels prepared by the surface derivatization of wet gels followed by subsequent drying at ambient pressure is reported. The following sol–gel parameters were examined for their effect on the physical properties of the derived aerogels: number of gel washings with water, percentage of hexane or methanol in silylating mixture, molar ratio of tartaric acid: Na₂SiO₃, gel aging period, weight% of silica, trimethylchlorosilane (TMCS) percentage, and silylation period. These parameters were varied from 1 to 4, 0 to 100%, 0.27 to 1.2, 0 to 4 h, 1.5 to 8 wt.%, 20 to 40% and 6 to 24 h, respectively. The properties of hydrophobic silica aerogels synthesized by this new route were investigated in terms of bulk density, percentage volume shrinkage, percentage porosity, thermal conductivity and contact angle with water, and by Fourier transform infrared spectroscopy (FTIR). The as-prepared hydrophobic silica aerogels exhibited high temperature stability (up to approximately 435 °C) as measured by thermogravimetric/differential thermal analysis (TGA-DTA). The optimal sol-gel parameters were found to be a molar ratio of Na₂SiO₃:H₂O : tartaric acid : TMCS of 1 : 146.67 : 0.86 : 9.46, an aging period of 3 h, four washings with water in 24 h and the use of a 50% hexane- or methanol-based silylating mixture. Aerogels prepared with these optimal parameters were found to exhibit 50% optical transparency in the visible range, 84 kg m⁻³ density, 0.090 W mK⁻¹ thermal conductivity, 95% porosity and a contact angle of 146° with water.     

Phase‐inversion applications beyond membrane formation. I. Lithography films

Polymeric films cast from a polymer solution can develop a bulk porosity, if the conditions are favorable for phase inversion (PI), a physical chemical process based on fluid–fluid demixing of which there are two known major variants: wet and dry PI. As the formation of polymeric coatings often involves a polymeric solution or gel precursor, dry or wet PI phenomena may affect the structure formation of the final solvent‐free coating. In this article we identify the situations under which lithographic films can develop a PI structure and focus on solid polymer layers undergoing postcasting wet processing. Examples are provided from the wet processing of a fractionated epoxy novolac resin currently used in lithographic patterning. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2145–2157, 2000     

Acid/Base Properties of Fumed Silica Fillers Used in Silicone Elastomers

Inverse gas chromatography (IGC) and photoacoustic infrared spectroscopy (PAS) were used to investigate the effects of thermal history and silane treatment on the surface energetics of various fumed silica fillers. The specific interaction parameter, I_sp, was a factor of 2.3 (THF probe) lower for a silane treated fumed silica (Degussa R972) relative to an untreated filler (Degussa A200), thus confirming the deactivating effects of silane treatment. Heat treatment of raw fumed silica (Cabot HS-5) at 150°C and 650°C decreased I_sp (THF probe) from 15.3 kJ/mol to 10.5 kJ/mol. This decrease was attributed to the loss of bound water and surface silanols. The dispersive interactions increased with heat treatment as a result of the formation of higher electron density sites such as strained Si-O-Si bonds. Silazane-treated fillers were prepared using heat treated and hydrated feedstocks. I_sp values were a factor of 2-30 lower, depending upon the probe, for silazane-treated fillers made from heat treated feedstock. The dispersive interactions increased from 27.2 mJ/m² to 57.8 mJ/m² as a result of using heat treated feedstock, thus suggesting some of the strained Si-O-Si bonds formed upon drying remained intact even after silazane treatment.