逆уCeO2/CuχCo1-χOδ催化剂的制备 及其CO催化氧化性能

以Cu(NO_3)_2·3H_2O、Co(NO_3)_2·6H_2O、Ce(NO_3)_3·6H_2O和(NH_4)_2CO_3为原料,采用共沉淀法-浸渍法结合的制备方式,制得逆负载型уCe O_2/Cu_χCo_(1–χ)O_δ催化剂(у=0、5%、15%、25%;χ=0～1.0;δ=1.0～1.4)。通过XRD、BET、H_2-TPR、XPS考察了Cu O和Co_3O_4质量比[m(Cu O)∶m(Co_3O_4)]、表面Ce O_2负载量(у)(以Cu_χCo_(1–χ)O_δ质量为基准,下同)对逆负载уCe O_2/Cu_χCo_(1–χ)O_δ催化剂催化氧化CO性能的影响。结果表明,15%Ce O_2/Cu_(0.2)Co_(0.8)O_δ[m(Cu O)∶m(Co_3O_4)=0.2∶0.8]催化剂催化性能最佳。常压下,当反应温度为75℃时,CO转化率可达100%。由于15%Ce O_2/Cu_(0.2)Co_(0.8)O_δ比表面积较大,两相界面较多,进而使得Ce O_2与Cu—O—Co固溶体相互作用较强,表面存在较多的氧空穴、Cu~+和Co~(3+),催化剂还原温度较低,催化活性较好。     

纳米CeO_2制备的工艺研究

以Ce(NO_3)_3·6H_2O为铈源,(NH_4)_2CO_3·H_2O为沉淀剂,采用燃剂燃烧法制备前驱体Ce_2(CO_3)_3·H_2O,前驱体经热处理合成纳米CeO_2。结果表明,CeO_2的最佳制备条件是500℃下焙烧40min。     

溶胶-凝胶法低温制备Ce_(0.8)Sm_(0.2)O_(2-α)及其复合电解质的中温燃料电池性能

以三氧化二钐、浓硝酸、硝酸铈铵、柠檬酸为原料,采用溶胶-凝胶法低温(900℃)制备Ce_(0.8)Sm_(0.2)O_(2-α)(SDC),低于通常高温烧结温度(1400℃),并与(Li/K)_2CO_3共熔体进行复合。采用DSC-TGA确定制备Ce_(0.8)Sm_(0.2)O_(2-α)的烧结温度。XRD结果表明,(Li/K)_2CO_3与Ce_(0.8)Sm_(0.2)O_(2-α)复合后没有发生化学反应。SEM图像表明,SDC粒径均匀一致,(Li/K)_2CO_3作为SDC颗粒黏结剂均匀覆盖SDC颗粒表面。采用电化学工作站研究了复合电解质在400~600℃下干燥氮气气氛中的电导率。结果表明,温度为600℃时,复合电解质在干燥氮气气氛中的电导率达到最大值3.3×10~(-2)S/cm,高于单一二氧化铈材料在相同条件下的电导率。氧分压与电导率关系曲线表明,复合电解质具有良好的氧离子导电性。H_2/O_2燃料电池性能测试表明复合电解质Ce_(0.8)Sm_(0.2)O_(2-α)-(Li/K)_2CO_3(SDC-SG-LK)在600℃开路条件下的电解质阻抗、极化阻抗分别为3.13W·cm~2、0.81W·cm~2,最大输出功率密度为130m W/cm~2。     

镁铝钡三元水滑石的制备及吸附性能

以Al(NO_3)_3·9H_2O、Mg(NO_3)_2·6H_2O、Ba(NO_3)_2为原料,用共沉淀法制备了Mg/Al/Ba-三元水滑石,经过傅里叶红外光谱和比表面及孔径分析法进行表征。考察了该水滑石对重金属铬离子(Ⅲ)的吸附行为及干扰离子影响,优化了浓度、时间、温度、酸度(pH)等因素对Mg/Al/Ba-三元水滑石吸附性能的影响。结果表明,在最佳浓度13mg/mL、时间150min、温度30℃、pH=6时吸附容量最大达到400mg/g。     

稀土复合催化剂的制备及催化湿式氧化性能

以550℃焙烧的拟薄水铝石为载体,Fe(NO_3)_2·9H_2O和Ce(NO_3)_2·6H_2O为前驱体,通过等体积浸渍法制备负载型Fe_xCe_(1-x)/γ-Al_2O_3(x=0,0.5,1)复合催化剂,通过SEM、TEM表征Fe/γ-Al_2O_3、Ce/γ-Al_2O_3及Fe_(0.5)Ce_(0.5)/γ-Al_2O_3催化剂,并考察Fe_(0.5)Ce_(0.5)/γ-Al_2O_3复合型催化剂分别在160、180、200和220℃反应温度条件下陶瓷印花废水的降解性能。结果表明:Ce改性后的Fe_(0.5)Ce_(0.5)/γ-Al_2O_3催化剂表面颗粒分布均匀,颗粒大小约为30 nm,在200℃反应温度条件下陶瓷印花废水的脱色率高达99.1%,色度为70倍,达到《污水综合排放标准》(GB8978-1996)中染料类废水的二级排放标准。     

水热法制备In_2O_3晶体及其形貌研究

以In(NO_3)_3·5H_2O原料,通过水热法一步制备了In_2O_3晶体。通过XRD、SEM等手段对所制备样品的物相、粒度和形貌进行了表征。研究结果表明,通过此方法所制备的样品为高纯相的In_2O_3晶体,并具有由纳米粒子堆积组装成的类球型形貌,粒径为200nm左右,大小均匀。在此基础上,研究了In(NO_3)_3·5H_2O用量对所制备样品形貌的影响。结果表明,增加In(NO_3)_3·5H_2O用量会使粒子堆积更加致密。此外,通过研究结果对In2O3类球体的形成机理进行了初步探讨。     

镁合金表面Ce-Mn和Ce-Mo复合转化膜性能的研究

对镁合金表面Ce-Mn和Ce-Mo复合转化膜的性能进行了研究。镁合金Ce-Mo复合转化的最佳配方为:Ce(NO3)39g/L,Na_2MoO_4 4g/L,C_6H_5Na_3O_7·2H_2O 2g/L,温度25℃,时间10min。镁合金Ce-Mn复合转化的最佳配方为:Ce(NO_3)_3 5g/L,KMnO_4 2g/L,NH_4HF_2 0.1g/L,Na_2B_4O_7·10H_2O 0.2g/L,温度25℃,时间2min。最优配方下得到的镁合金复合转化膜平整、结晶细致。Ce-Mo复合转化膜的相组成为Mg、MoO_2、MoO_3、CeO_2和Ce2O_3;Ce-Mn复合转化膜的相组成为Mg、MgO、MnO_2、CeO_2和Ce_2O_3。两种复合转化膜的耐蚀性均比单系转化膜的耐蚀性好,其中Ce-Mo复合转化膜的耐蚀性最好。     

基于Dawson型H_6P_2Mo_(18)O_(62)杂化材料[Ni(2,2'-bipy)_3]_3(P_2Mo_(18)O_(62))的制备及其吸附性能研究

以H_6P_2Mo_(18)O_(62)、[Ni(2,2'-bipy)_3]Cl_2·5.5H_2O为原料,通过化学共沉淀法制备[Ni(2,2'-bipy)_3]_3(P_2Mo_(18)O_(62))复合材料,采用FT-IR、SEM、TG、BET等手段进行表征,并研究其对亚甲基蓝(MB)溶液的吸附性能。探讨了pH、初始浓度、温度等条件对MB溶液吸附效果的影响。结果表明,将H_6P_2Mo_(18)O_(62)与[Ni(2,2'-bipy)_3]Cl_2·5.5H_2O进行复合形成复合物[Ni(2,2'-bipy)_3]_3(P_2Mo_(18)O_(62))后,可有效克服其水溶性,大大提高了其液相吸附能力,且温度对其吸附性能影响不大。从实验结果可知,复合物对MB溶液的吸附分别符合Langmuir等温吸附模型和拟二级动力学模型。热力学参数ΔG~00、ΔH~00和ΔS~00,表明该吸附剂对亚甲基蓝的吸附是自发且放热的,且对其他阳离子染料罗丹明B也有较好的吸附效果。     

pH值对钼酸铋及其光催化性能的影响研究

在可溶性淀粉作为模板剂的情况下,以(NH_4)_6Mo_7O_(24)·4H_2O 和Bi(NO_3)_3·5H_2O为原料,以NH_3·H_2O作为酸碱剂调节溶液的pH值,用水热法合成了Bi_2MoO_6固体光催化剂,采用测试手段对Bi_2MoO_6光催化剂进行了结构和性能表征,并用合成的Bi_2MoO_6固体光催化剂来降解罗丹明B溶液,研究其光催化性能。     

一例基于[BiW_9O_(33)]~(9-)建筑单元的稀土多钨铋酸盐的合成、晶体结构和性质

本文在水溶液中以Na_(12)[Bi_2W_(22)O_(74)(OH)_2]·44H_2O、Na_9[Bi W_9O_(33)]·16H_2O、Ce Cl_3和Na_2CO_3为原料合成了一例基于[Bi W_9O_(33)]~(9-)建筑单元的稀土多钨铋盐Na_(22)[(Bi W_9O_(33))_4(WO_3){Bi_6(μ_3-O)_4(μ_2-OH)_3}(Ce_3(H_2O)_6CO_3)]·85H_2O。并对其进行了红外、元素分析和热重分析。     

Effects of calcination condition on expansion property of MgO-type expansive agent used in cement-based materials

Previous research indicated that the expansion property of MgO-type expansive agent (MEA) depended strongly on the calcining conditions, i.e. kiln temperature and residence time. However, the intrinsic effect of calcination condition on the expansion property of MEA has not been clearly demonstrated. In the present work, the effects of calcination condition on the microstructure, hydration activity, and expansion property of MEA have been investigated, and their correlations are also studied. Results indicate that the microstructure of MEA is the intrinsic factor that controlling its expansion property, which is influenced by the calcination condition. MEA produced under higher temperature and longer residence time has less interior pores, larger crystal size of MgO, and smaller specific surface area, thus resulting in lower hydration activity and slower expansion at early age, but larger “ultimate” expansion at late age. While, a new expansion model of MEA is proposed to explain these results.     

Material and environmental parameter effects on the leaching of cement pastes: Experiments and modelling

Results already published on the leaching of cement pastes have shown that the kinetics depends sensitively on the material and environment. However and because of the variability of the tested materials and leaching protocols, it is difficult to compare these data and quantify the effect of each parameter. In this paper, a large experimental database on the leaching kinetics of cement pastes is built. Four parameters are investigated: type of cement (portland cement, silica fume cement, slag cement, ternary cement with slag and fly ash); water-to-cement ratio (0.5; 0.4; 0.25), temperature (26 °C; 72 °C; 85 °C) and chemical composition of the leaching solution (pure water, mineralised water, ammonium nitrate solution). Firstly, the database is used to calculate the leaching kinetics of the cementitious materials. Secondly, a simplified model predicting the one-dimensional leaching kinetics for other water-to-cement ratios and temperature up to 85 °C is presented.     

Toughening of polypropylene with styrene/ethylene‐butylene/styrene triblock copolymer: Effects of reactive and nonreactive compatibilization

The effects of the compatibilization on the toughening of polypropylene (PP) by melt blending with styrene/ethylene‐butylene/styrene triblock copolymer (SEBS) in a twin‐screw extruder were investigated. The compatibilizers used were an SEBS functionalized with maleic anhydride, a PP functionalized with acrylic acid, and a bifunctional compound, p‐phenylenediamine (PPD). The effects of the compatibilization were evaluated through the mechanical properties and by the determination of the phase morphology of the blends by scanning electron microscopy. Reactive compatibilized blends show up to a 30‐fold increase in impact strength compared to neat PP, which was likely to have been due to the reaction of the bifunctional compound (PPD) with the acid acrylic and maleic anhydride groups, which rendered both morphological and mechanical stability to these blends. The addition of the PPD to the blends significantly changed their phase morphologies, leading to larger dispersed particles' average diameters, probably due to the morphological stabilization at the initial processing steps during extrusion, with the occurrence of the chemical reactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1081–1094, 2003     

Photocatalytic degradation of air pollutants — From modeling to large scale application

Indoor as well as outdoor air quality and their limiting values remain a major problem to our present-day society.This paper addresses the modeling of the decomposition process of nitrogen monoxide (NO) on reactive concrete surfaces under the controlled exposition of a UV source. Within this model the external mass transfer of the pollutant and the internal molecule diffusion-reaction were considered. A first-order kinetics equation is derived with respect to the NO concentration and a site-competitive adsorption between NO/NO₂ and water molecules, resulting in a dependence of the reaction kinetics on the relative humidity. Using the proposed model, a reaction rate constant k and an adsorption equilibrium constant K_d can be derived which describe an active paving stone accurately. Experimental results from a self-developed photoreactor with continuous flow mode were used to validate the proposed kinetic expression. Furthermore, the effect of variations in process conditions such as irradiance and relative humidity on the two constants k and K_d is investigated. All modeling work provides a sound foundation for the translation of this process to real outside conditions. In this regard an upcoming project in a Dutch city is described in brief.     

(SrZrO_3)_(10)(SrTiO_3)_(90)缓冲层对PZT结晶及性能的影响

采用Sol-gel法制备了PbZr0.52Ti0.48O3 (PZT)薄膜,并研究了(SrZrO3)10(SrTiO3)90((SZO)10(STO)90)缓冲层对PZT薄膜结晶和性能的影响.X射线衍射(XRD)结果表明:(SZO)10(STO)90缓冲层对PZT薄膜结晶有取向诱导作用,由(SZO)10(STO)90诱导的PZT薄膜有很强的(111)择优取向,缓冲层将PZT薄膜的取向度α由45.0%提高到了90.1%以上;PZT的(111)择优取向提高了薄膜的电性能,使剩余极化强度Pr从26.8 μC/cm2增大到38.8 μC/cm2.     

硫氰酸锰及其相关衍生物的合成及化学表征

合成了金属有机配合物非线性光学晶体硫氰酸汞锰，及其相关衍生物，二二甲亚砜合硫氰酸汞锰，乙二醇一甲醚合硫氰酸汞锰，二水合二N，N－二甲基乙酰胺合硫氰酸汞锰，二水合二N－甲基－α－吡咯烷酮合硫氰酸汞锰。采用元素分析，红外光谱以及紫外－可见－近红外透央求我谱分析对其进行了化学表征。     

Design and processing of ZnO doped tricalcium phosphate based materials: Influence of β/α polymorph phase assemblage on microstructural evolution

Tricalcium phosphate (TCP) based biomaterials are excellent candidates in hard tissue engineering due to their similarity to the natural bone composition and outstanding properties. The presence of additives such as (Mg²⁺, Zn ²⁺, F⁻, CO₃²⁻ and/or SiO₄⁻) in solid solution in the structure of TCP, affects the stability of its different polymorphs and therefore the properties of TCP based biomaterials. It is known that the incorporation of zinc in TCP in the non-toxic level stimulates bone growth and its mineralization, hence its interest. Nevertheless its effect on phase assemblage and microstructure evolution has not been clearly established. The main purpose of this study was to synthesize TCP and zinc doped monophasic/biphasic α/β-TCP dense biomaterials, by solid-state sintering process, with different ZnO contents and controlled phase proportions and microstructure on the final material. The effect of ZnO content and sintering temperature on phase assemblage, densification and microstructural evolution has been investigated.     

Optimizing multiple qualities in as‐spun polypropylene yarn by neural networks and genetic algorithms

This investigation considers a quantitative procedure for determining the values of critical process parameters in melt spinning to optimize the qualities of denier, tenacity, breaking elongation, and denier variance in as‐spun polypropylene yarn. An orthogonal array in the Taguchi method defines the minimum set of parameter‐level combinations that are experimentally tested. The significant process parameters, namely the third extruder barrel temperature, spinning temperature, metering pump speed, and take‐up velocity, are identified on the basis of the analysis of variance and F test. After a confirmation experiment is conducted to ensure the reproducibility of the experimental results, the back‐propagation neural network establishes a continuous system linking 10 process parameters and four qualities. The technique for order preference by similarity to an ideal solution can be used to obtain a performance measure for assessing multiple qualities. The genetic algorithm attempts to find parameter values for optimizing the quality performance, including the denier, tenacity, breaking elongation, and denier variance. Finally, the experimental results demonstrate that the smallest denier, largest tenacity, smallest breaking elongation, and second smallest denier variance of as‐spun polypropylene yarn can be achieved with the proposed approach in melt spinning. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2532–2541, 2006     

Selective plasma‐induced grafting of polystyrene onto polyolefin blends

Plasma pretreatment has been used to generate reactive radicals and oxygenated groups on polymer surfaces for graft polymerization. The polymer substrates studied were composed of a polypropylene–polyethylene (PP–PE) copolymer, which was predominantly PP, and also contained blended ethylene–propylene rubber (EPR) as either about 15 or about 60 mol %. A pure PP substrate was also studied for comparison. The grafted polymer was polystyrene (PS). Raman microspectroscopic 2‐dimensional mapping was used to elucidate the role of crystallinity and EPR in the plasma treatment and graft polymerization process. It was found that the plasma pretreatment favored the EPR component of the substrate and the graft yield was related to the EPR content. Crystallinity seemed to have a much less significant effect on the grafting reaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1643–1652, 2003     

Porosity and specific surface area of Roman cement pastes

Mercury porosimetry, water vapour and nitrogen adsorption were used to follow the hydration of Roman cements — belite cements calcined at low temperature. Generally, unimodal distribution of pore sizes was observed, with the threshold pore width decreasing considerably with increasing curing time. An open porous structure with the threshold pore diameter between 0.2 and 0.8 μm and the specific surface area not exceeding 20 m²/g was produced at early ages when quick growth of the C–A–H phases is observed. The surface area reached up to 120 m²/g and the threshold pore width shifted to around 0.02 μm when the subsequent formation of C–S–H gel filled the larger pores. Both mercury porosimetry and water vapour adsorption were found to be capable of following the progress of hydration of the Roman cements with high reliability at least for a comparative evaluation of historic Roman cement mortars and repair materials used in restoration projects.