助熔剂法合成α-Al2O3片晶及其多孔陶瓷的制备及表征

实验首先以γ-AlOOH粉体为原料,KCl-Na2SO4复合盐为熔剂,采用助熔剂法合成了α-Al2O3片晶,通过对合成片晶成型烧成,制备具有片状晶体支撑的氧化铝多孔陶瓷材料.并对α-Al2O3片晶形成过程,多孔陶瓷显气孔率、抗折强度、微观结构以及孔径分布进行了研究.研究结果表明,在KCl与Na2SO4复合盐存在情况下,可在900℃条件下合成分散性好,颗粒大小均匀的六方形α-Al2O3片晶,片晶的直径大约在10μm,厚度为0.3～0.5 μm.合成的α-Al2O3片晶具有非常好的烧结活性,在无添加烧结助剂的情况下,1600℃保温2h得到了显气孔率为41.74;,抗折强度为115.34MPa,孔径分布范围窄的氧化铝多孔陶瓷.窄的孔径分布以及优异的机械性能使其成为一种很有前途的膜支撑体和精确过滤材料.     

纳米TiO2对氧化铝质多孔陶瓷膜支撑体烧结过程的影响

采用原位水解法,以钛酸四丁酯为前驱体,研究了纳米TiO2对多孔陶瓷膜支撑体烧结过程的影响.结果表明,以钛酸四丁酯为前驱体,采用原位水解法可以将纳米TiO2与大粒径的氧化铝颗粒均匀混合,起到良好的助烧结作用;预烧温度在一定程度上起到调节纳米TiO2添加量的作用并影响支撑体的各项性能.当预烧温度为1300℃,纳米TiO2添加量为0.4wt;时,支撑体经1650℃煅烧2h后,支撑体内部的细颗粒迁移至粗颗粒颈部而基本消失,一定程度上提高支撑体的抗折强度.随着保温时间延长,支撑体的抗折强度不断提高,孔径逐渐增大.但是,较多量的纳米TiO2存在于支撑体内部,起不到良好的助烧结作用.     

磷酸盐结合法制备Al2O3多孔陶瓷及性能

以煅烧α-Al2O3粉为骨料、磷酸二氢铝为高温烧成粘结剂、石蜡为成型助剂,通过模压成型、干燥、烧结等工序制备了氧化铝多孔陶瓷,研究了烧成温度和磷酸二氢铝含量对氧化铝多孔陶瓷微观形貌、物相组成、线收缩率、孔隙率和弯曲强度的影响,探讨了磷酸盐结合法烧结机理.结果表明:氧化铝多孔陶瓷物相由α-Al2 O3和AlPO4构成,在较低温度下,氧化铝颗粒仅依靠AlPO4的粘结作用而形成多孔陶瓷,氧化铝多孔陶瓷线收缩率和弯曲强度随磷酸二氢铝含量的增加而缓慢增大,孔隙率则缓慢降低;随着烧结温度的提高,AlPO4的存在促进了氧化铝颗粒间的液相烧结,线收缩率和弯曲强度随烧结温度的升高而显著增大,孔隙率也明显降低.     

烧成温度对La0.7Ca0.3CrO3/Al2O3导电陶瓷微滤膜支撑体结构与性能的影响

采用高温固相反应烧结法制备La0.7Ca0.3CrO3(LCC)/Al2O3导电陶瓷微滤膜支撑体.研究了烧成温度对制备的LCC/Al2O3支撑体样品的物相组成、微观结构、烧成收缩、孔隙率和孔径分布、电导率、抗弯强度、渗透通量及耐腐蚀性能等的影响.结果表明,高温烧成过程中LCC与Al2O3发生复杂的固相反应,样品主晶相为菱形结构La07Ca0.3Cr1-xAlxO3,并生成了少量LaAl11O18和CaCr2O4等.烧成温度从1350℃提高到1600℃时,样品的烧结程度、电导率、抗弯强度和耐酸腐蚀性能明显提高,而孔隙率明显减小.样品的平均孔径和纯水渗透通量随烧成温度提高,表现出先增大后减小的变化趋势.在1550℃时保温2h烧成制备的LCC/Al2O3支撑体,具有高的孔隙率(43.4;)和抗弯强度(36.9 MPa),其平均孔径(d50)为1.02 μm、纯水通量为2.24 m3/m2·h·bar、电导率为0.11 S/m,且具有良好的耐腐蚀性能.     

粉体粒度对硅藻土基微孔陶瓷结构和性能的影响

以硅藻土为主要原料,采用固相烧结法,制备了硅藻土基微孔陶瓷,探讨了粉体粒度对其比表面积、烧结样品的孔径及其分布、孔隙率等性能的影响.结合SEM、BET、压汞仪等手段对样品进行了表征.结果表明:在d50=3.57～1.17 μm间,随粉体粒度的减小,粉体比表面积上升,烧结样品的平均孔径及孔隙率下降,其后孔径分布变宽并出现团聚;d50=1.17 μm时,粉体比表面积48.59 m2/g,烧结样品平均孔径157.8 nm,孔隙率39.3;;对孔雀石绿溶液的脱色研究表明,粉体粒度减小,多孔陶瓷的脱色能力增强,反应420 min,d50=1.17 μm粉体烧结样品的脱色率达90.8;.     

冰模板法制备反应结合多孔Si3N4/SiC复相陶瓷

以微米级SiC和Si粉为原料,采用冰模板法和氮化反应烧结法制备了孔道中修饰α-Si3N4、Si2N2O纳米线的β-Si3N4结合多孔SiC复相陶瓷.研究了反应烧结温度、SiC/Si比和固相含量对多孔陶瓷的物相结构、形貌、孔分布和压缩强度的影响.结果表明:多孔陶瓷具有层状定向通孔结构,孔隙率介于50; ～ 70;之间,孔径分布呈现双峰分布特点;当烧结温度达到1350℃以上时,在层状孔道中交织形成α-Si3N4和Si2N2O纳米线的网络结构.反应温度超过1450℃时,通过液态Si的氮化反应原位形成β-Si3N4结合相将SiC颗粒粘结起来;当浆料中Si含量由16wt;增加至33wt;时,多孔陶瓷的开气孔率从69.78;降至62.64;,而压缩强度由2.2 MPa提高到8.73 MPa;随着浆料固相体积含量从25;增加到45;,多孔陶瓷的气孔率从71.81;降至54.85;,同时压缩强度从4.99 MPa提高到24.16 MPa.     

利用无机胶凝材料制备莫来石多孔陶瓷

本文利用无机胶凝材料成功制备了莫来石多孔陶瓷.以硅藻土和ρ-Al2O3为原料,AlF3和MoO3为添加剂,利用ρ-Al2O3遇水硬化的特点,来实现陶瓷浆料的固化成型,再将成型后的陶瓷生坯经高温烧结得到莫来石多孔陶瓷.该方法绿色环保,整个制备过程中无有机物的排放.通过使用XRD、SEM等表征测试手段,研究了烧结温度对莫来石多孔陶瓷的相组成、微观形貌、线收缩率、开孔孔隙率以及抗压强度的影响.实验结果表明,制备的莫来石多孔陶瓷由生长良好的莫来石晶须构成,在1500℃下烧结的莫来石多孔陶瓷孔隙率可达到82.3;.     

La2O3对氧化铝/高岭土复合定向多孔陶瓷性能的影响

以微米级α-Al2O3、陶瓷水体分散剂为主要原料,以La2O3-水洗高岭土为烧结助剂,采用冰模板法制备了一种具有高孔隙率和较高抗压强度的氧化铝/高岭土复合定向多孔陶瓷.研究了不同添加量的La2O3对多孔陶瓷的显气孔率、体积密度、抗压强度和微观形貌的影响.结果表明:添加适量的稀土La2O3能降低多孔陶瓷烧结温度、提高体积密度和抗压强度.通过高能机械球磨法添加La2O3,在1350℃烧结制备的多孔材料样品显气孔率为82;,样品的抗压强度达到10 MPa以上.当La2O3加入量达到3;时,可使多孔陶瓷抗压强度提高到15.2 MPa,较不掺加La2O3提高了约53;.     

双模板法制备分级孔结构SiC陶瓷

以冰晶和聚苯乙烯(PS)微球为模板,微米级SiC粉体为原料,通过双模板法制备了具有三级孔径分布的多孔SiC陶瓷.研究了SiC的固含量和PS微球的大小对多孔SiC陶瓷的微观形貌、孔隙率和压缩强度的影响.研究结果表明:分级孔结构的多孔SiC陶瓷具有冰模板升华后遗留下的对齐排列的大孔、分布于孔壁中的由PS微球热解留下的中孔和颗粒之间堆积形成的小孔.随着SiC固相含量的增加,大孔孔径和孔容降低,但压缩强度增加.当PS微球粒径约为0.90 μm时,中孔孔径分布在0.7～1.5 μm之间;当PS微球粒径约为2.51 μm时,孔径分布较宽,约为1～3 μm.     

多孔氮化硅陶瓷的微观结构、力学性能和气体透气性的研究

本研究中,以石油焦为造孔剂、Y2O3-Al2O3为烧结助剂,通过注浆成型制备出多孔氮化硅陶瓷.研究石油焦的加入量对多孔氮化硅陶瓷微观结构、力学性能及气体透气性的影响.结果表明:多孔氮化硅陶瓷的微孔是由长棒状的β-Si3N4晶粒互相搭接而成,大孔是由石油焦燃烧而成.随着石油焦加入量的增加,气孔率及达西渗透系数(μ)增大,但试样的抗弯强度降低.在起始α-Si3N4粉末中添加10wt;～50wt;石油焦、5wt; Y2O3-3wt;Al2O3 1800℃下保温2h制备出气孔率为37.08;～59.40;、抗弯强度为52.00～154.27 MPa、μ值为(3.04 ～6.87)×10-13m2的多孔氮化硅陶瓷.     

粉体粒径对氧化铝陶瓷膜孔径的影响及控制

将三种不同粒径的α-Al2O3(平均粒径为1μm、3μm、5μm)混合后配置稳定悬浮液,利用颗粒级配理论,建立粉体比例、粉体粒径及其分布和膜层厚度对无机膜孔径及其分布的影响,实现利用粉体粒径分布控制膜层孔径分布,获得多选择的无机膜.研究结果表明,无机微滤膜的孔径取决于粉体的粒径分布,其孔径变化的上下限分别为由最粗和最细粉体所组成陶瓷膜的膜孔径.粉体的混合会在一定程度上扩大无机微滤膜的孔径分布,但有助于减少最大膜孔.膜层的厚度的增加在一定程度上降低无机微滤膜的最大孔和平均孔径.该实验结果有助于实现利用粉体粒径控制无机微滤膜的控制,促使无机微滤膜的孔径的多样化.     

Size dependent photoluminescence of SiC nanocrystals

The paper presents the results of porous SiC study using photoluminescence and scanning electronic microscopy. It is shown that the intensity of defect-related PL bands (2.08, 2.27, 2.44 and 2.63 eV) increases monotonically with the rise of PSiC thickness from 2.1 up to 12.0 μm. These luminescence centers are assigned to surface defects which appear at the PSiC etching process. Photoluminescence intensity stimulation for surface defects is attributed to rise of defect concentrations with increasing of porous layer thickness and to realization of the hot carrier ballistic mechanism at surface defect excitation. Intensity enhancement for exciton-related PL bands (2.79, 2.98 and 3.26 eV ) is attributed to increasing the exciton recombination rate as result of exciton weak confinement in big size SiC NCs of different polytypes (6H–PSiC with inclusions of 15R- and 4H–PSiC).     

Size dependent kinetics of oriented aggregation

Oriented aggregation is an important, nonclassical crystal growth mechanism by which nanocrystals grow, defects are formed, and unique—often symmetry-defying—crystal morphologies can be produced. This growth mechanism involves the irreversible and crystallographically specific self-assembly of primary nanocrystals and results in the formation of new single crystals, twins, and intergrowths. This paper presents data showing that growth by oriented aggregation is consistent with second-order kinetics with respect to the concentration of the primary nanoparticles and demonstrates that the overall rate constant for growth by oriented aggregation increases dramatically with decreasing primary particle size. Results are discussed in the context of DLVO interactions. The experimental results explain the common observation that growth by oriented aggregation slows as a function of continued crystal growth.     

Size Distribution Analysis of Needle-Shaped Crystals

Two methods of measurement of the crystal size distribution of needle-shaped carystals are compared: direct measurement of a number of crystals on a microphotograph, which is rather tedious and time consuming, and the photosedimetric method which is quicker, easy to perform but not so suitable for not isometric crystals. A methods is described that brings results of both of these methods into agreement. The method has been verified on strongly anisometric particles of calcium sulphate.     

Size effect in displacive ferroelectrics

It is ascertained that the size effect in thin ferroelectric films is related to the spatial correlation of ferroelectric polarization, depending on boundary conditions. The influence of the size effect on the permittivity of displacive ferroelectrics is described. It is shown that the size effect manifests itself differently for different orientations of the polarization vector with respect to the boundaries of a ferroelectric layer.     

Size effects in oxide mechanochemistry

A new size effect has been experimentally found: the mechanochemical synthesis of previously mechanically activated powder mixtures of MgO-Al₂O₃ oxides with a block size of about 80 nm leads to the formation of MgAl₂O₄ spinel at room temperature. A model is proposed according to which the mechanism of mechanochemical solid-phase synthesis changes from dislocation transgranular embrittlement to grainboundary sliding, which is accompanied by the generation of dynamic vacancies and low-temperature phase formation via the diffusion-induced migration of grain boundaries.     

Size and morphology controlled synthesis of barium sulfate

In this work submicron barium sulfate (BaSO₄) particles were synthesized successfully by chemical precipitation technique. We focused on the effects of pH and additives on the size and morphology of BaSO₄ crystals. Polyacrylic acid, polyvinyl sulfonic acid and ethylenediaminetetraacetic acid were used as crystal growth modifiers. BaSO₄ crystals were characterized using scanning electron microscopy, X‐ray diffraction, and Fourier transform infrared resonance techniques. The results show that the submicron BaSO₄ particles have been synthesized successfully and the particle size of the barium sulfate was effectively controlled under the experimental conditions. Experimental studies revealed that the additive concentration and pH had great effect on the morphology and size of barium sulfate.     

金刚石织构体及其纳米级亚晶

在冲击合成的金刚石中存在一种织构体组织.织构是由沿[110]cd和[12-10]hd方向排列的金刚石纳米级亚晶组成的.除常见的立方金刚石结构外,还存在一种罕见的六方金刚石结构.它们通常共存在一个金刚石织构体中,形成共生晶体.     

地聚物凝胶转换法制备大尺寸方沸石晶体

本研究采用溶胶-凝胶法合成了成分可控、高纯和高活性的Al2 O3-SiO2粉体.以工业级水玻璃为碱激发剂,将二者按照方沸石理论配比(Na∶ Al∶ Si=1∶1∶2)混合后制备得到Na2 O-Al2O3-4SiO2-8H2O地质聚合物凝胶体;将地质聚合物凝胶体在70℃烘箱中养护一定时间后脱模;研究采用X射线衍射(XRD)、扫描电镜(SEM)和BET等对产物进行了表征,无模板剂的条件下利用240℃水热反应制备了50～ 1200μm不同粒径的方沸石晶体,并初步探讨了大尺寸方沸石晶体的形成机理.     

Kinetics of Overall Phase Transition in Changing Size System

Kinetics of phase transition is studied for the more general case when the size of the system is assumed time dependent. In the three dimensional case typical examples in this respect could be connected with the solution of cosmological problems. In the two dimensional case could be the spreading and crystallization of undercooled water on oil or the experiments concerning phase transition in monolayers in a Lengmuir balance. The time dependence of the degree of overall transformation α(t) is formulated in a generalized form corresponding to above assumption. Explicit solutions are given for a constant rate of expanding (or shrinking) and for a constant acceleration of the size change of the system under the assumption that both nucleation rate I and linear growth rate G are constants. It is demonstrated that the process of phase transition proceeds much faster in a shrinking systems and is impeded in expanding ones. The reason for this effect is that parts of the new phase, formed in the initial parts of the system, are transferred into the diminishing volume (or surface). Thus the concentration of the new phase is mechanically increased.