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     

Cesium salt of a heteropolyacid in nanotubular channels and on the external surface of SBA-15 crystals: preparation and performance as acidic catalysts

The Cs-salt of heteropolyacid with stoichiometry Cs_2.5H_0.5PW₁₂O₄₀ (CsHPW) was deposited selectively at the external surface of the SBA-15 silica microcrystals, inside its mesoporous channels and simultaneously at both location modes. The structure, texture and performance of these CsHPW/SBA-15 composites were compared with that of a reference bulk salt of the same composition. Location of CsHPW salt on the external surface of SBA-15 microcrystals leads to disintegration of its agglomerates increasing acidity of the catalytic phase. A novel preparation strategy consisting of grafting the basic Cs-species at the internal pores surface of SBA-15 stabilized the CsHPW phase inside the channels in form of 5–8 nm nanocrystals at 30–70 wt.% loadings. The catalytic tests demonstrated that insertion of the CsHPW catalytic phase inside the nanotubular channels of SBA-15 in combination with location of an additional amount of this phase at the external surface of SBA-15 microcrystals allows to increase the specific activity of this phase in MTBE synthesis, propionylation of anisole and alkylation of catechol with t-butanol by a factor of 1.5–3. This level of specific activity in combination with high total loading of catalytic phase >60 wt.% permit to get composite catalytic materials with catalytic activity higher by a factor of 1.2–1.5 with respect to the bulk CsHPW catalyst and stabilizing the catalytic phase against colloidization in polar media.     

Characterization and Sintering Behavior of Alkoxide-Derived Aluminosilicate Powders

Submicrometer SiO₂-Al₂O₃ powders with compositions of 46.5 to 76.6 wt% Al₂O₃ were prepared by hydrolysis of mixed alkoxides. Phase change, mullite composition, and particle size of powders with heating were analyzed by DTA, XRD, IR, BET, and TEM. As-produced amorphous powders partially transformed to mullite and Al-Si spinel at around 980°C. The compositions of mullite produced at 1400° and 1550°C were richer in Al₂O₃ than the compositions of stable mullite solid solutions predicted from the phase diagram of the SiO₂-Al₂O₃ system. Particle size decreased with increasing Al₂O₃ content. The sintered densities depended upon the amount of SiO₂-rich glassy phase formed during sintering and the green density expressed as a function of particle size.     

Effect of filler network on dynamic viscoelastic properties of uncured polymethylvinylsiloxanes filled with silica and carbon black

Dynamic properties of polymethylvinylsiloxane (PMVS) filled with filler‐blends composed of carbon black (CB) and silica (SiO₂) were investigated using an advanced rheometric expansion system. A variety of weight fraction of CB to SiO₂ were 0/100, 10/90, 30/70, 50/50, 70/30, 90/10, and 100/0, and a bifunctional organsilane, bis(3‐triethoxysilylpropyl)tetrasurfane, was used to facilitate the filler dispersion. The results reveal that the incorporation of CB/SiO₂ filler‐blends into PMVS result in a reduced Payne effect. This effect reaches a minimum when the ratio of CB/SiO₂ approaches 1, and then it began to rebound with the ratio increase. Meanwhile, a characteristic Newtonian viscosity plateau appearing in low frequencies also significantly decreases, depending on the amount of CB or SiO₂ added. On the basis of a simplified Fowke model, we ascribe this phenomenon to the deteriorated filler network, which is predominantly induced by the totally different surface activity between CB and SiO₂. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3477–3482, 2006     

Silica to Silicon: Key Carbothermic Reactions and Kinetics

The primary carbothermic reactions for the reduction of silica to produce silicon were defined and the reaction kinetics were determined. Most possible reactions between silicon oxide and carbon or carbon compounds were studied by a series of thermogravimetric analyses at temperatures up to 2000°C. Four key sequential reactions occur with SiC and SiO as intermediate reactants; two reactions involve SiO₂ and two involve SiO. Reaction rate versus temperature, activation energy, and preexponential factors were determined for each of six reactions involving SiO₂ or SiO. These kinetic studies show that SiO, when combined with either carbon or Sic, reacts in the gaseous state, and the sublimation of SiO is not the rate-limiting reaction for forming silicon.     

掺氟石英玻璃的研究

利用溶胶-凝胶法,以氟化铵(NH_4F)作掺氟源,使氟离子参与水解和聚合反应,经过热处理制成掺氟石英玻璃。在烧结时通入氟里昂(CCl_2F_2)进一步提高玻璃中氟重量含量直至2.50%。研究得出石英玻璃中氟含量与折射率、密度呈线性关系。氟有利于凝胶玻璃成块。用Raman和红外光谱研究掺氟石英玻璃结构,提出了氟进入玻璃网络的结构模型,并认为氟在玻璃中的存在状态为[SiO_3F]。     

丙烯酸酯聚氨酯/SiO2纳米复合涂层结构与形态对其耐刮伤性影响研究

以四乙氧基硅烷(TEOS)作为主要前驱体,通过改变溶胶-凝胶工艺参数制得了结构和形态各异的丙烯酸酯聚氨酯/SiO2纳米复合涂层,利用TEM、SAXS等手段表征涂层的结构与形态,由洗刷前后涂层的失光率来表征耐刮伤性,详细探讨了纳米复合涂层耐刮伤性与SiO2相特征、有机无机相作用力及SiO2质量分数之间的关系。研究表明:丙烯酸酯聚氨酯涂层中引入纳米SiO2相后,耐刮伤性明显提高。有机相与SiO2相之间的作用力是影响涂层耐刮伤性的最重要因素,作用力越强,耐刮伤性越好。网络状纳米SiO2与颗粒状纳米SiO2相比,更有利于耐刮伤性的提高,且网络状纳米SiO2质量分数越大,耐刮伤性越佳,但SiO2相的致密度和尺寸对耐刮伤性影响较小。对于颗粒状胶体SiO2,在15~160 nm范围内,粒径对耐刮伤性没有明显影响;随着胶体SiO2粒子的质量分数增加,耐刮伤性先增大后减小。     

Methanol synthesis over Cu/SiO2 catalysts

The rates of CO and CO/CO₂ hydrogenation at 4.2 MPa and 523 K are reported for a series of Cu/SiO₂ catalysts containing 2 to 88 wt.% Cu. These catalysts were prepared on a variety of silica sources using several different Cu deposition techniques. In CO/CO₂ hydrogenation, the rate of methanol formation is proportional to the exposed Cu surface area of the reduced catalyst precursor, as determined by N₂O frontal chromatography. The observed rate, 4.2×10^–3 mole CH₃OH/Cu site-sec, is within a factor of three of the rates reported by others over Cu/ZnO and Cu/ZnO/Al₂O₃ catalysts under comparable conditions. These results suggest that the ZnO component is only a moderate promoter in methanol synthesis. Hydrogenation of CO over these catalysts also gives methanol with high selectivity, but the synthesis rate is not proportional to the Cu surface area. This implies that another type of site, either alone or in cooperation with Cu, is involved in the synthesis of methanol from CO.     

SiO2/Zn2SnO4/环氧丙烯酸酯涂层的阻燃性能

为了探究复合纳米颗粒对环氧丙烯酸酯（EA）涂层阻燃性能的影响，以十六烷基三甲基溴化铵（CTAB）和正硅酸乙酯（TEOS）为原料合成了介孔二氧化硅纳米颗粒，以ZnCl₂和SnCl₄·5H₂O为原料合成了锡酸锌（Zn₂SnO₄）纳米颗粒，将它们复合制成了介孔二氧化硅/锡酸锌复合纳米颗粒（SiO₂/Zn₂SnO₄），并用X射线粉末衍射仪（XRD）、透射电镜（TEM）对其表征。将所制的纳米颗粒（介孔SiO₂、Zn₂SnO₄、SiO₂/Zn₂SnO₄）与丙烯酸、丙烯酰胺、EA复合，经UV光固化制备出3种涂层（SiO₂/EA、Zn₂SnO₄/EA、SiO₂/Zn₂SnO₄/EA），通过紫外-可见光谱仪、差示扫描量热仪（DSC）及氧指数测定仪等对涂层的透光率、热稳定性、阻燃性能进行测试。结果表明：SiO₂/Zn₂SnO₄/EA涂层的综合性能较佳，当SiO₂/Zn₂SnO₄质量分数为4.85%时，该涂层的热稳定性及阻燃性能最佳，其极限氧指数、燃烧级别、残炭率（500℃下马弗炉煅烧）和硬度分别为31、V-0、17.32 % 及6H。     

PTA尾气吸附系统的优化

针对吸附系统内除湿剂硅胶频繁破碎现象进行优化。在找出硅胶破碎原因的基础上,通过吸附塔直径放大18.3%,引出部分尾气,使床层流速降低。在吸附塔进口管处,安装雾沫分离器;在硅胶前沿填充部分耐水硅胶以减少液态水的冲击。再生蒸汽加热管上加调节阀防止硅胶过分干燥。使A塔硅胶使用了540d,B塔硅胶使用了630d。