不同处理条件对前驱体转变成ZrW2O8的影响

利用分析纯氯氧化锆(ZrOCl_2·8H_2O)、钨酸(H_2WO_4)、氨水(NH_3·H_2O)作为原材料制备了ZrW_2O_8前驱体。通过对前驱体XRD，SEM和TG-DSC分析，研究了不同处理条件对前驱体转变成立方晶系ZrW_2O_8过程的影响。前驱体在1 100℃分别加热1，2h和5 h后的产物为单斜晶系WO_3和ZrO_2。在1 150℃分别加热0.5，1 h和1.5 h后产物为ZrW_2O_8和WO_3。Zr／w摩尔比为1∶2.5，1∶2.2和1∶2的前驱体，在1150℃保温1.5 h后产物为ZrW_2O_8和WO_3，但相同处理条件下，Zr／W摩尔比为1∶1.8和1∶1.5时，其产物为ZrW_2O_8和ZrO_2。研究结果表明：Zr／w摩尔比为1∶1.8的ZrW_2O_8前驱体，经1 150℃保温1.5 h，所合成的ZrW_2O_8粉末的X射线衍射峰为较好的单一峰。     

流延法制备高致密固态电解质LATP的研究

采用溶胶凝胶法合成了超细固态电解质Li1.3Al0.3Ti1.7(PO4)3(LATP)前驱体粉体,通过配制浆料和流延工艺制备了加工性能良好的LATP素坯体。利用差示扫描量热分析了LATP前驱体的热分解过程,采用X射线衍射、扫描电镜、交流阻抗法对不同烧结工艺条件下LATP玻璃-陶瓷片的结构、形貌和电导率进行分析表征。结果表明,采用溶胶凝胶法制备的LATP前驱体粉体的平均粒径为200 nm,且分布均匀。纳米级的粒径尺寸使得LATP前驱体粉末在烧结过程中具有更好的反应活性,结晶温度比固相烧结法制备的LATP下降了150℃,烧结性能好。通过优化烧结工艺,制备的LATP玻璃陶瓷体的相对密度高达99%,室温电导率为2.19×10-4S·cm-1。     

H6P2Mo9W9O62/Cu3(BTC)2的制备及催化合成缩醛(酮)

采用浸渍法制得H_6P_2Mo_9W_9O_(62)/Cu_3(BTC)_2,利用傅里叶变换红外光谱仪(FT-IR)、X射线衍射仪(XRD)、热重分析仪(TG)以及扫描电镜(SEM)表征其组成、结构、热稳定性以及形貌。以H_6P_2Mo_9W_9O_(62)/Cu_3(BTC)_2为催化剂,环己酮和乙二醇合成缩酮的反应为探针,探究出较佳反应条件:环己酮用量为0.2 mol,n(环己酮)∶n(乙二醇)=1∶1.3,催化剂用量占反应物总质量的0.3%,反应时间为60 min,带水剂用量为6 mL。在此条件下,环己酮乙二醇缩酮收率可达83.7%。且以上条件下催化合成苯甲醛乙二醇缩醛、丁酮乙二醇缩酮、丁酮1,2-丙二醇缩酮、苯甲醛1,2-丙二醇缩醛和环己酮1,2-丙二醇缩酮的收率分别为70.1%,66.0%,62.1%,66.3%和75.8%。与分子筛MCM-48负载硅钨酸、活性炭负载对甲苯磺酸和铝交联蒙脱土催化剂相比,H_6P_2Mo_9W_9O_(62)/Cu_3(BTC)_2是一种催化性能较好的催化剂。     

固体氧化物燃料电池电解质材料La_2Mo_(2-x)Mn_xO_(9-δ)的制备与性能研究

以硝酸镧、钼酸铵、硫酸锰为原料,以柠檬酸为络合剂,采用溶胶-凝胶法合成了可作为中温固体氧化物燃料电池(SOFCs)使用的电解质材料La_2Mo_(2-x)Mn_xO_(9-δ)(x=0、0.05、0.10、0.15、0.20),通过红外光谱(FTIR)、热分析(TGDSC)、X射线衍射(XRD)、扫描电子显微镜(SEM)、交流阻抗(AC)测试等手段对样品进行了表征。研究表明,干凝胶经700℃煅烧2 h后得到了纯相的高烧结活性的La_2Mo_(2-x)Mn_xO_(9-δ)(x=0、0.05、0.10、0.15、0.20)粉体,其在950℃烧结2h即可获得相对密度大于97%的烧结体。电化学性能研究表明Mn掺杂可以有效的提高La_2Mo_2O_9电解质材料的电导率,其中La_2Mo_(1.9)Mn_(0.1)O_(8.9)在800℃时电导率高达0.028 S/cm。     

柠檬酸盐络合物前驱体法制备TiN粉体

以一水合柠檬酸为络合剂,钛酸四丁酯为钛源,采用溶胶-凝胶法制备了柠檬酸盐络合物前驱体,然后在氮气气氛中对前驱体进行热处理制备TiN粉体,研究了反应温度(800～1300℃)、原料配比(n(钛酸四丁酯):n(柠檬酸)分别为3:1、2:1、1.7:1)对碳热还原氮化反应制备TiN粉体的影响.结果表明:前驱体干凝胶为柠檬酸钛...     

AM_2O_8(A=Zr,Hf;M=Mo,W)氧化物粉体的低温 液相合成及其结构控制(英文)

立方AM2O8氧化物(A=Zr,Hf:M=Mo,W)是最有希望的一类负热膨胀材料.为开发这类材料,期望获得高质量AM2O8粉体,而传统固相合成法不能达到这一目的.低温液相合成法是一种有望合成高质量AM2O8氧化物粉体的途径.本文介绍了1998年以来低温液相合成AM2O8粉体的研究进展,首先,概述了AM2O7(OH)2·2H2O脱水的合成工艺,其后讨论了用于制备醇盐或羧酸盐前驱体的凝胶技术.着重讨论了材料结构控制问题, 并提出了进一步研究方向.     

碳热还原法合成硼化锆粉体影响因素探究

以氧化锆(ZrO2)、硼酸(H3 BO3)和碳(C)粉为原料,研究了不同碳粉(活性炭、石墨)与前驱体粒度、温度及保温时间对碳热还原法制备硼化锆(ZrB2)粉体的影响.通过X射线衍射(XRD)分析合成粉体物相,扫描电镜(SEM)观察合成粉体形貌,并通过化学方法分析了合成粉体中的C、O含量.结果表明:以活性炭为碳源合成的粉体形貌呈条棒状,以石墨为碳源合成的粉体形貌呈规则的块状;合成粉体的粒度随前驱体粒度减小而减小,形貌由规则的块状逐渐转变为圆滑的不规则形貌,合成ZrB2粉体最小平均粒度约为1.69μm,产物中C含量随前驱体粒度减小而减少,O含量随前驱体粒度减小而增加,氧含量最低为0.54wt％;碳热还原法合成ZrB2粉体在1500℃下是可行的,但直到1900℃碳热还原反应合成ZrB2才进行完全;碳热还原反应合成ZrB2粉体最佳的反应条件为1900℃保温30 min.     

Li_4Ti_5O_(12)/Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3复合负极材料的制备及性能

采用溶胶-凝胶法合成了Li_4Ti_5O_(12)/Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3复合负极材料,通过X射线衍射、扫描电子显微镜、恒电流充放电、循环伏安和电化学阻抗研究复合材料的结构、形貌及电化学性能。结果表明:溶胶-凝胶法能合成纯相Li_4Ti_5O_(12)/Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3复合负极材料颗粒均匀。与纯相Li_4Ti_5O_(12)相比,引入Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3的Li_4Ti_5O_(12)复合负极材料具有更低的锂离子嵌入/脱出阻抗,Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3质量分数为1%、2%、3%、4%、5%的Li4Ti5O12复合负极材料首次放电容量比纯相Li_4Ti_5O_(12)分别提高了6.2%、11.8%、15.5%、8.0%和2.0%。充放电循环20次后,Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3质量分数为3%的Li_4Ti_5O_(12)复合负极材料循环性能最好,平均每次循环容量衰减率为0.022%。     

新型结构多钼酸铵的制备

在酸性溶液中,钼酸根阴离子聚合而形成钼的同多酸根阴离子。钼同多酸的研究已有较长历史,据目前所知,从水溶液或非水溶液中离析出已知结构的主要钼同多酸根阴离子有[Mo_2O_7]~(2-)、[Mo_5O_(17)H]~(3-)、[Mo_6O_(19)]~(2-)、[Mo_7O_(24))~(6-)、[Mo_8O_(26)]~(4-)、[Mo_(18)O_(34)]~(8-)、[Mo_(36)O_(112)(H_2O)_(16)]~(8-)等。钼同多酸根阴离子结构中,除[Mo_2O_7]~(2-)及[Mo_5O_(17)H]~(3-)中含有一个或数个MoO_4四面体外,基本单元都是MoO_6八面体,这些MoO_6八面体通过角、棱或面相联而构成各种同多酸根阴离子。     

Bi1.5ZnNb1.5O7纳米粉体的水热合成与表征

以分析纯的Bi(NO_3)_3·5H_2O,ZnO和Nb_2O_5为初始原料,KOH为矿化剂,采用水热法合成立方焦绿石结构的Bi_(1.5)ZnNb_(1.5)O_7纳米粉体。通过XRD分析其物相组成,TEM分析其形貌和尺寸,Scherrer公式计算其晶粒的大小。结果表明,在KOH浓度为1.8mol/L,温度为180～220℃反应6～48h,可以合成立方焦绿石结构的Bi_(1.5)ZnNb_(1.5)O_7纳米粉体,粉体颗粒尺寸约30～50nm,形貌呈较为规则的颗粒状。合成温度和反应时间对合成粉体的物相和粒径都有一定的影响,并讨论了水热法合成Bi_(1.5)ZnNb_(1.5)O_7纳米粉体的机理。     

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.