超细BaTiO3制备技术研究

超细ＢａＴｉＯ＿３制备技术研究顾达，顾燕芳，郑柏存，胡黎明（华东理工大学技术化学物理研究所，上海２００２３７）ＢａＴｉＯ＿３是电子陶瓷中使用最广的原料之一。影响电子陶瓷ＢａＴｉＯ＿３粉末质量的主要因素是组分的Ｂａ／Ｔｉ比，颗粒的大小、形貌及晶型￣［１...     

BaTiO3纳米晶的合成与表征

以硬脂酸、硬脂酸钡和钛酸丁酯为原料合成了ＢａＴｉＯ３纳米晶，粒度为１０～２０ｎｍ，烧成温度为６５０℃，低于传统的合成温度。用红外光谱、差热分析、热重分析和Ｘ射线衍射对合成过程进行了研究，用透射电镜考察纳米晶的粒度和形貌。用发射光谱和Ｘ射线荧光光谱对样品纯度进行了分析。结果表明，此法合成的纳米晶ＢａＴｉＯ３纯度高、粒度小且较均匀，在常温下属立方钙钛矿型。     

硝酸根离子介质中偏钛酸钡的水热合成

以硝酸和钛酸四丁酯为原料，在２４０℃的碱液中成功地制备了四方相ＢａＴｉＯ３运用ＸＲＤ、ＤＳＣ和ＩＲ等技术碱度、硝酸根离子、钛源活性、填充度等因素对ＢａＴｉＯ３形成、粒度和物相的作用，ＫＯＨ最适宜浓度为１．０ｍｏｌ／Ｌ，碱液中ＢａＴｉＯ３是ＢａＯ－ＴｉＯ２体系中最稳定的物相，硝酸根离子参与了ＢａＴｉＯ３晶体的成核和生长，钛源的高活性和高填充度有利于四方ＢａＴｉＯ３的形成。     

掺杂Ag纳米BaTiO3抑菌剂的制备及其性能

掺杂Ag纳米BaTiO3抑菌剂的制备及其性能;溶胶-凝胶;掺杂Ａｇ;ＢａＴｉＯ３;抑菌性能     

化学沉淀法制备纳米BaTiO3粉体

钛酸钡是一种非常重要的ＡＢＯ３结构的化合物，它具有相当高的介电常数，良好的铁电、压电和绝缘性能，广泛地应用于体积小容量大的微型电容器和温度补偿元件等方面［１］，是一种非常重要的电子陶瓷材料。因而对纳米ＢａＴｉＯ３粉体的制备研究具有重要的意义，但传统方...     

BaZrxTi1-xO3·yLa2O3固溶体的合成、结构与性能

以１００℃以下用软化学合成方法制备了系列ＢａＺｒｘＴｉ１－ｘＯ３．ｙＬａ２Ｏ３固溶体纳米粉末，ＸＲＤ物相分析有ｄ－间隔－组成图证明，产品为完全互溶取代固溶体。从ＴＥＭ谱图观察，粒子为均匀球形，平均粒径６０ｎｍ。通过制陶实验对系列固溶体的介电特性进行了测试，结果表明，采用化学掺杂方法在ＢａＴｉＯ３中掺入适量锆和镧后，样品的室温介电常数可提高２０倍。     

Y掺杂Ba0.90 Sr0.08 Ca0.02 TiO3固溶体纳米晶粒尺寸对其晶体结构的影响

随着电子陶瓷材料向精细、微型、多功能化的方向发展，陶瓷用的粉体晶粒尺寸对物性影响的研究显得越来越重要。钡系钙钛矿结构铁电材料是应用极为广泛的电子陶瓷材料，其铁电性与晶粒尺寸密切相关，尤其是达到纳米级时，可使材料性质发生奇异变化。迄今人们仅对纯ＢａＴｉＯ３超微细粒子的晶粒尺寸对铁电相变的影响进行了研究［１～３］，对稀土钇掺杂Ｂａ（１－ｘ－ｙ）ＳｒｘＣａｙＴｉＯ３固溶体纳米晶的相关研究报道尚少，而铁电尺寸效应对这类电子功能材料的研究、开发起着关键作用。因此，开展这方面的研究具有重要的学术价值和实际意…     

均分散胶体的研究──Ⅷ．草酸钛酰钡均分散颗粒的制备、组成及应用

本文提出了制备草酸钛酰钡均分散颗粒的优选条件．对此条件下制备的均分散颗粒进行了化学分析、ＴＧＡ、ＩＲ分析并确定了其化学组成．将此种颗粒灼烧成氧化物后，基本上可保留原形貌．用ＢａＯ·ＴｉＯ２均分微颗粒与Ｙ２Ｏ３均分散颗粒烧制成ＢａＴｉＯ３均分散陶瓷，以达到控制陶瓷超微结构均匀的目的．     

纳米钙钛矿型氧化物LaF1—yAlyO3—λ制备及催化性能

采用溶胶－胶方法制备了Ｂ－位掺杂的纳米钙钛矿型复合氧化物ＬａＦｅ１－ｙＡｌｙＯ３－λ，并对其催化甲烷完全氧化进行了研究，发现纳米氧化物（ｙ＝０．１）可以大幅度降低反应温度，其比活性和表面Ｏ晶／Ｏ吸较大，晶的种可能有利于甲烷的完全氧化。     

立方Gd2O3∶Eu纳米晶及光谱性质

用透射电镜拍摄球形ＣＧｄ２Ｏ３∶Ｅｕ纳米晶,并研究了室温下它的激发和发射光谱。结果表明,９００℃制备的体材料和相应的纳米晶相比,其激发光谱存在明显差异。前者以基质激发带为主导,电荷转移带（ＣＴＢ）很弱,而后者以ＣＴＢ为主。在绝缘体稀土氧化物中,可以忽略纳米效应对Ｅｕ３＋离子的４ｆ４ｆ能级跃迁的激发和发射光谱峰位的影响     

Mechanism and kinetics for the initial steps of pyrolysis and combustion of 1,6-dicyclopropane-2,4-hexyne from ReaxFF reactive dynamics

We report the kinetic analysis and mechanism for the initial steps of pyrolysis and combustion of a new fuel material, 1,6-dicyclopropane-2,4-hexyne, that has enormous heats of pyrolysis and combustion, making it a potential high-energy fuel or fuel additive. These studies employ the ReaxFF force field for reactive dynamics (RD) simulations of both pyrolysis and combustion processes for both unimolecular and multimolecular systems. We find that both pyrolysis and combustion initiate from unimolecular reactions, with entropy-driven reactions being most important in both processes. Pyrolysis initiates with extrusion of an ethylene molecule from the fuel molecule and is followed quickly by isomerization of the fuel molecule, which induces additional radicals that accelerate the pyrolysis process. In the combustion process, we find three distinct mechanisms for the O(2) attack on the fuel molecule: (1) attack on the cyclopropane, ring expanding to form the cyclic peroxide which then decomposes; (2) attack onto the central single bond of the diyne which then fissions to form two C(5)H(5)O radicals; (3) attack on the alkyne-cyclopropane moiety to form a seven-membered ring peroxide which then decomposes. Each of these unimolecular combustion processes releases energy that induces additional radicals to accelerate the combustion process. Here oxygen has major effects both as the radical acceptor and as the radical producer. We extract both the effective activation energy and the effective pre-exponential factor by kinetic analysis of pyrolysis and combustion from these ReaxFF simulations. The low value of the derived effective activation energy (26.18 kcal/mol for pyrolysis and 16.40 kcal/mol for combustion) reveals the high activity of this fuel molecule.     

逐级酸处理对锡盟褐煤的结构及热解特性的影响

为了探讨高硫褐煤提质利用中酸洗处理对煤质特性的影响,以内蒙古锡盟褐煤为研究对象,依次用HF、HNO₃和HCl的酸溶液进行预处理,对原煤及其酸处理样品进行了傅里叶变换红外光谱的煤结构表征、程序升温差热-热重实验的煤热解特性研究及其反应过程的动力学分析。结果表明,HF处理对煤样的结构影响不大,HNO₃的处理明显改变了HF处理后煤样中有机质的结构,HCl处理又使HNO₃处理引起的煤样中脂肪基团CH₃的吸收峰强度变化减弱;逐级酸处理对锡盟褐煤的热解特性存在一定的影响,HF和HNO₃处理对褐煤的热解反应性具有促进作用,HCl处理对其热解反应性的影响不大。动力学分析显示,不同过程酸预处理对褐煤热解过程的影响不能单独采用热解过程的总包反应活化能进行描述,热解活化能不仅与指前因子存在着补偿效应,也与热解阶段的失重量存在一定的关联。     

Characterization of Fast Pyrolysis Bio-oils Produced from Pretreated Pine Wood

The pretreatment of biomass prior to the fast pyrolysis process has been shown to alter the structure and chemical composition of biomass feed stocks leading to a change in the mechanism of biomass thermal decomposition. Pretreatment of feed stocks prior to fast pyrolysis provides an opportunity to produce bio-oils with varied chemical composition and physical properties. This provides the potential to vary bio-oil chemical and physical properties for specific applications. To determine the influence of biomass pretreatments on bio-oil produced during fast pyrolysis, we applied six chemical pretreatments: dilute phosphoric acid, dilute sulfuric acid, sodium hydroxide, calcium hydroxide, ammonium hydroxide, and hydrogen peroxide. Bio-oils were produced from untreated and pretreated 10-year old pine wood feed stocks in an auger reactor at 450 °C. The bio-oils’ physical properties of pH, water content, acid value, density, viscosity, and heating value were measured. Mean molecular weights and polydispersity were determined by gel permeation chromatography. Chemical characteristics of the bio-oils were determined by gas chromatography–mass spectrometry and Fourier transform infrared techniques. Results showed that the physical and chemical characteristics of the bio-oils produced from pretreated pine wood feed stocks were influenced by the biomass pretreatments applied. These physical and chemical changes are compared and discussed in detail in the paper.     

热解压力对生物质焦结构及气化反应性能的影响

利用加压固定床反应器、吸附仪、X射线衍射仪、元素分析仪、电感耦合等离子原子发射光谱仪等考察了热解压力对生物质半焦(以下简称半焦)产率、物化结构、元素组成的影响规律。同时,利用热天平对不同热解压力下所制半焦的气化行为进行了考察。结果表明,随热解压力升高,半焦产率增大,当压力升至1.0 MPa后,半焦产率基本不变;半焦中C元素含量随热解压力的升高而增加,而H元素含量和BET比表面积则减小;此外,随热解压力升高,玉米秸秆焦和锯末焦的石墨化程度增强,而稻壳焦的石墨化程度则基本不受热解压力影响。气化反应的研究表明,玉米秸秆焦及锯末焦的平均气化反应速率随热解压力的提高而减小,而稻壳焦的平均气化反应速率基本不受热解压力的影响。热解压力对半焦BET比表面积及碳微晶结构的影响规律与气化反应速率变化规律的对比研究表明,热解压力引起半焦微晶结构的变化是造成热解压力对半焦气化反应速率影响的主要原因。     

Gas-phase detection of HSOH: synthesis by flash vacuum pyrolysis of di-tert-butyl sulfoxide and rotational-torsional spectrum

Gas-phase oxadisulfane (HSOH), the missing link between the well-known molecules hydrogen peroxide (HOOH) and disulfane (HSSH), was synthesized by flash vacuum pyrolysis of di-tert-butyl sulfoxide. Using mass spectrometry, the pyrolysis conditions have been optimized towards formation of HSOH. Microwave spectroscopic investigation of the pyrolysis products allowed-assisted by high-level quantum-chemical calculations--the first measurement of the rotational-torsional spectrum of HSOH. In total, we have measured approximately 600 lines of the rotational-torsional spectrum in the frequency range from 64 GHz to 1.9 THz and assigned some 470 of these to the rotational-torsional spectrum of HSOH in its ground torsional state. Some 120 out of the 600 lines arise from the isotopomer H(34)SOH. The HSOH molecule displays strong c-type and somewhat weaker b-type transitions, indicating a nonplanar skew chain structure, similar to the analogous molecules HOOH and HSSH. The rotational constants (MHz) of the main isotopomer (A=202 069, B=15 282, C=14 840), determined by applying a least-squares analysis to the presently available data set, are in excellent agreement with those predicted by quantum-chemical calculations (A=202 136, B=15 279, C=14 840). Our theoretical treatment also derived the following barrier heights against internal rotation in HSOH (when in the cis and trans configurations) to be V(cis) approximately equal to 2216 cm(-1) and V(trans) approximately equal to 1579 cm(-1). The internal rotational motion results in detectable torsional splittings that are dependent on the angular momentum quantum numbers J and K(a).     

含油污泥与配合煤共热解煤焦的微观结构与气化反应特性

以含油污泥与配合煤为原料在850-1150℃热解制得焦样,采用N_2吸附-脱附和X射线衍射(XRD)分析煤焦孔隙结构及碳微晶结构,并运用热重分析(TGA)考察热解温度和含油污泥添加量对煤焦气化反应活性的影响。结果表明,提高热解温度和添加含油污泥能促进煤焦形成更加丰富的孔隙结构,强化煤焦-CO_2气化反应接触并抑制煤焦石墨化进程,从而提高煤焦气化反应活性;然而,热解温度过高或添加油泥量过多则会致使煤焦结构致密或孔隙堵塞,气化反应活性反而降低。     

FLASHCHAIN模型应用于汪清油页岩热解研究

采用~(13)C-NMR技术表征出汪清三个矿区油页岩的碳原子化学结构,并获得碳骨架结构的12个重要参数。利用热重和傅里叶红外联用技术(TG-FTIR)得出了在50℃/min升温速率和热解终温600℃下油页岩热解时轻质气体的生成规律。采用基于燃料化学结构的FLASHCHAIN模型对热解产物的析出进行了模拟,并与实验结果相比较。结果表明,FLASHCHAIN模型用来模拟汪清油页岩热解时,在520℃之前有较好的效果,当温度高于520℃时,由于二次热解反应及页岩中矿物质分解对热解过程的影响,导致模型的预测值与实验值存在一定的误差,且随着温度的升高两者之间的误差也随之加大。     

Thermal Decomposition and Crystallization of Aqueous Sol-Gel Derived Zirconium Acetate Gels: Effects of the Precursor Solution pH

Crystalline zirconia has previously been formed by desiccation and pyrolysis of a pH 3.4 zirconium acetate precursor solution. In this study, amorphous gels were formed by desiccation of zirconium acetate precursor solutions at pH 0.9 to 3.4 obtained by adding hydrochloric acid and at pH 8.0 by adding ammonium hydroxide to the available pH 3.4 precursor solution. The concentrations of the uncomplexed zirconium ion and the 1 : 1 and 1 : 2 zirconium acetate complexes varied with pH. Decomposition of the amorphous gel and its structure evolution to form crystalline zirconia by pyrolysis were studied. Several decomposition and structure transition temperatures occurring in the pyrolysis and the polymorph distribution in the pyrolysis products were dependent on the pH of the precursor solution. These variations of structure evolution with pH were also related to the relative concentrations of specific zirconium complexes in the precursor solutions. Removal of carbon by pyrolysis was improved by adding hydrochloric acid or ammonium hydroxide to the pH 3.4 precursor solution.     

Determination of kerogen type by using DSC and TG analysis

The rate of pyrolysis and oxidation of 8 different samples of oil shale kerogen concentrate (KC) were investigated using DSC analysis. Recently performed thermogravimetric studies (TG and DTG) with the same samples of KC indicated that the activation energy of the pyrolysis of specific KCs increases with increasing paraffinic structure in the KC. An opposite effect, i.e. a decrease of the activation energy with an increase of paraffinic structure was determined in the case of KC oxidation. In this study, using the standard ASTM E-698 method based on the determined temperature at which the maximum heat effect could be observed (exo in the case of oxidation and endo in the case of pyrolysis), an activation energy for the pyrolysis, as well as for the oxidation process was determined and also successfully correlated with the content of paraffinic structure of KC. Thus, the higher content of paraffinic structure in KCs indicates that higher values of the activation energy could be determined either in the case of pyrolysis or oxidation followed by DSC analysis.     

Control of the Composition and Structure of Silicon Oxycarbide and Oxynitride Glasses Derived from Polysiloxane Precursors

The reactions involved in the preparation of silicon oxycarbide and oxynitride glasses by pyrolysis of polysiloxane precursors respectively under argon and ammonia are reviewed. The influence of the composition and structure of the precursor and of these pyrolysis reactions on the pyrolysis yield, the composition, and the structure of the glass is discussed. The free-carbon content of the glass depends on the substituents in the precursor and on the nature of the pyrolysis atmosphere. The composition of the oxynitride or the oxycarbide phase depends on the O/Si ratio of the precursor. The structure of these phases is not directly related to the structure of the precursors, but rather depends on their composition and on the pyrolysis temperature.