Phase transition of nanophase ferroelectric PbTiO3 ultrafine powders

In this paper, ferroelectric PbTiO³ (PT) ultrafine powders with nanosized grains are prepared through sol-gel and hydrolysis-aging process. The lattice constants and grain size are determined by XRD analysis. The phase transition is examined by DSC and Second Harmonic Generation (SHG) measurements. The relation between onset temperature of phase transition and grain size is obtained. Results indicate that the phase transition of nanosized PT powder is broadened. The mechanism of broadened phase transition is discussed.     

CuFe_2O_4光催化剂在模拟太阳光下对大肠杆菌杀灭作用的研究

采用溶胶-凝胶法制备了纳米CuFe2O4光催化剂,并通过TEM,XRD和UV-visDRS对其进行表征,表明样品是由粒径约为80nm的粒子组成,晶体结构均匀,具有良好的可见光吸收性能。以大肠杆菌为研究对象,考察了光催化剂在模拟太阳光照射下的杀菌性能。结果表明:CuFe2O4光催化剂杀菌性能随着焙烧温度的不同而变化,当焙烧温度为700℃时,杀菌效果最佳,光照60m in后,细菌的存活率仅为5.6%,而在相同条件下使用催化剂避光和不用催化剂光照时细菌存活率分别为94.4%和87.4%,说明该催化剂本身无毒性,是一种在可见光下有优良杀菌性能的光催化剂。     

Influence of synthesis process on the AC response of PLZT (8/65/35) ferroelectric ceramics

AC conductivity measurements have been carried out to study the dielectric characteristics of a ferroelectric PLZT (8/65/35). The initial powders were synthesized by two different methods: conventional mixed oxides and a chemical coprecipitation method. In both cases, the final ceramic bodies were obtained by an uniaxial hot-pressing step. The grain and grain boundary responses have been separated and a mixture of ionic-electronic conductivity was evaluated from the Arrhenius dependence. The preparation techniques led to different absolute conductivity values for each contribution (grain, σ_g, or grain boundary, σ_gb). The samples prepared by the mixed oxide method (MO) showed a higher bulk conductivity than those prepared by the coprecipitation method (CP). This result was explained taking into account the different concentration of charge carriers in MO than CP samples, influenced by the PbO content in the grain boundary. The dielectric analyses showed classical ordinary relaxor-dielectrics with a diffuse phase transition, which was markedly larger in the oxide-milled method (MO). The conductive mechanisms and their influence on the dielectric behavior were studied and led to the conclusion that they affect the dielectric permittivity measurements. The dielectric permittivity without the conductivity component showed a phase transition with lower dispersion for both preparation techniques.     

Fe3+掺杂TiO2溶胶的低温制备及其光催化性能

采用溶胶-凝胶法在低温下制备出Fe3+掺杂TiO2(Fe3+/TiO2)溶胶,研究Fe3+掺杂对TiO2催化性能的影响,用TG/DTA技术分析TiO2粉末的热分解过程,用XRD、TEM等表征Fe3+掺杂对TiO2晶型、晶粒尺寸、晶粒形貌的影响,结果表明:Fe3+掺杂会对纳米TiO2晶粒的粒径及晶体形貌产生影响,抑制TiO2晶型由锐钛矿向金红石的转变。将亚甲基蓝作为目标污染物进行光催化降解试验,紫外-可见漫反射吸收光谱分析表明:经适量Fe3+掺杂后的TiO2溶胶光催化活性提高,当硝酸铁与钛酸丁酯的物质的量比为0.20%时,光催化活性最佳。     

聚钛硅氧烷的溶胶-凝胶合成及转变规律研究

以甲基三甲氧基硅烷和钛酸四丁酯为原料、甲醇为溶剂、盐酸为催化剂采用溶胶-凝胶法制备了含有杂原子钛的甲基硅树脂基体，借助傅立叶变换红外光谱研究了其特性。为了全面地了解该体系的溶胶-凝胶转相规律，我们分别做出了加水量为理论水解量30％、40％、50％时体系的转相相图，并将其转换为直角坐标以考察加水量、甲醇用量对相转变的影响a结果表明，选用反应条件为：甲醇用量大于70％、水用量小于40％、反应温度为50℃、盐酸用量为10％时，容易形成含钛量大于50％的溶胶状态的甲基硅树脂。     

Nanoscale potassium niobate crystal structure and phase transition

Nanoscale potassium niobate (KNbO₃) powders of orthorhombic structure were synthesized using the sol-gel method. The heat-treatment temperature of the gels had a pronounced effect on KNbO₃ particle size and morphology. Field emission scanning electron microscopy and transmission electron microscopy were used to determine particle size and morphology. The average KNbO₃ grain size was estimated to be less than 100 nm, and transmission electron microscopy images indicated that KNbO₃ particles had a brick-like morphology. Synchrotron X-ray diffraction was used to identify the room-temperature structures using Rietveld refinement. The ferroelectric orthorhombic phase was retained even for particles smaller than 50 nm. The orthorhombic to tetragonal and tetragonal to cubic phase transitions of nanocrystalline KNbO₃ were investigated using temperature-dependent powder X-ray diffraction. Differential scanning calorimetry was used to examine the temperature dependence of KNbO₃ phase transition. The Curie temperature and phase transition were independent of particle size, and Rietveld analyses showed increasing distortions with decreasing particle size.     

The FRL-FRH phase transition in PZT 95/5 thin film

The PZT 95/5 thin film was prepared on Pt/Ti/ SiO₂Si substrate by sol-gel method. The behavior of F_RL-F_RH phase transition was investigated in the thin film. The change of the remanent spontaneous polarization during the F_RL-F_RH phase transition is 0.6 μc/cm².     

制备方法对尖晶石Li4Ti5O12负极材料的性质影响

采用高温固相法、热聚合法和改良溶胶-凝胶法制备锂离子电池负极材料Li4Ti5O12。通过X-射线衍射、扫描电镜、恒电流充放电及电化学阻抗等技术和手段表征合成产物的结构、形貌及电化学性能。结果表明：溶胶-凝胶法合成的粉末为纯相Li4Ti5O12,而高温固相法和聚合法合成的Li4Ti5O12则存在TiO2杂相。高温固相法合成的Li4Ti5O12粉末晶粒最大,溶胶-凝胶法合成的粉末晶粒最小,分布最为均匀,晶粒尺寸约为80nm。高温固相法、热聚合法和溶胶-凝胶法制备的Li4Ti5O12粉末首次放电容量分别为161.6mAh/g、165.9mAh/g和171.5mAh/g,循环25次后的容量保持率分别为84.7%、87.7%和94.3%,溶胶-凝胶法合成的Li4Ti5O12粉末电化学性能最好。     

A comparative study of the structure,defects, optical,dielectric, and magnetic properties of GdMnO3 multiferroic ceramics synthesized by solid-state reaction and sol-gel methods

In this work, GdMnO₃ ceramics were synthesized by solid state reaction and sol-gel methods, and the structure, defects and optical, dielectric and magnetic properties of the synthesized samples were comparatively investigated. The samples synthesized by different methods show a single phase structure without any detectable impurities. The SEM results suggest that the particle size of the specimen obtained by the solid phase route is on the micron scale, while that of the specimen fabricated by the sol-gel route is on the nanometer scale. Compared with the ceramic fabricated by solid-state reaction technology, the specimen synthesized by sol-gel technique possesses lower oxygen vacancies and Mn²⁺ concentration, and Mn³⁺ concentration. The positron annihilation analyses show that the cation vacancy concentration of the specimen synthesized by the solid phase approach is higher than that of the specimen synthesized via the sol-gel approach. The compound obtained by the solid phase reaction has better dielectric properties than that obtained with the sol-gel method. The magnetic transition temperature and the effective magnetic moment are influenced by the Mn ion valence state in GdMnO₃. The stronger magnetization of the ceramic synthesized via the sol-gel approach is associated with the lower concentration of cation vacancies.     

溶胶-凝胶法制备负载型钨磷酸催化剂

为改善浸渍法制备的负载型钨磷酸催化剂HPWA/SiO2,在有水参与的反应中活性中心Keggin结构钨磷酸(HPWA)的流失,换用溶胶-凝胶法制备了一系列w(HPWA)=11.1%~40%的负载型钨磷酸催化剂HPWA-SiO2。通过红外光谱和紫外漫反射光谱联合表征,证明溶胶-凝胶法制备的HPWA-SiO2催化剂中,钨磷酸依然保持Keggin结构,没有转变为钨硅盐等而失去酸催化功能。在此基础上对溶胶-凝胶法制备的HPWA-SiO2和浸渍法制备的HPWA/SiO2进行了水相中钨磷酸流失率考察,结果表明,溶胶-凝胶法制备的HPWA-SiO2催化剂的流失率基本保持在0.71%~0.84%,而浸渍法制备的HPWA/SiO2催化剂的流失率为2.4%,是前者的3倍多,从而证明溶胶-凝胶法制备的负载型钨磷酸催化剂,能够更好地防止钨磷酸活性中心在水相反应中的流失。     

Effect of rare earth doping on sol-gel derived PZT thin films

We have studied the effect of rare earth dopants (Nd, Gd and Ce) on the phase formation behavior and electrical properties of sol-gel derived Pb_1.05(Zr_0.53Ti_0.47)O₃ thin films. In all these films the perovskite phase is obtained up to 5 at% doping and beyond that pyrochlore phase was found to coexist with the perovskite phase. Ce and Gd doping(1-2 at%) exhibited improved ferroelectric and dielectric properties as compared to the undoped PZT films. Nd doping (2 at%) was found to be effective to increase the retained switchable polarization of undoped PZT from 63% to 84%. The transition temperature of undoped PZT film was found to be reduced with Nd doping. The Nd doped films also exhibited typical relaxor behavior and a diffuse phase transition, characteristic of the relaxor material. Introduction of Nd into the PZT lattice probably introduces disorder in the B site of ABO₃ lattice which causes the observed relaxor behavior     

Pore Structure Control of Silica Gels Based on Phase Separation

In the alkoxy-derived sol-gel system, various macroporous morphologies can be obtained by inducing the phase separation parallel to the sol-gel transition. This principle of macroporous morphology control can be best applied to pure silica and silica-based multicomponent oxide systems. The earlier the phase separation takes place than the sol-gel transition, the larger the characteristic sizes of pores and gel skeletons become. The time resolved light scattering measurements revealed that the morphology formation process exhibits the features of spinodal decomposition and that the final gel morphology is determined by the competitive kinetics between the domain coarsening and the structure freezing by sol-gel transition. The mesopore structure of such macroporous gel skeletons could be easily tailored by the solvent exchange procedures. Silica gels with controlled macropores and mesopores were successfully applied as a material for the continuous rod type column for high performance liquid chromatography.     

Effect of Preparation Conditions on Phase Formation, Densification, and Microstructure Evolution in La-β-Al2O3/Al2O3 Composites

In situ development of La-ß-Al₂O₃(LBA) platelets in alpha-Al₂O₃was studied as a function of the preparation method: a conventional solid-state reaction of commercial Al₂O₃powder and La(NO₃)₃as well as a sol-gel method starting with boehmite and the same La₂O₃precursor. In both cases, homogeneous distribution of the reinforcing phase was achieved, and a noteworthy inhibition of Al₂O₃grain growth resulted. However, samples prepared by solid-state reaction densified more easily than those prepared via sol-gel, but the formation of the LBA phase occurred at a lower temperature in samples prepared by the sol-gel approach. Results on the correlation of the onset of LBA grain growth and densification to microstructure are discussed.     

溶胶-凝胶法合成掺铕硼酸镧钙荧光粉及其表征

首次采用溶胶-凝胶法制备Eu:La<,2>CaB<,10>O<19>,借助XRD、SEM和荧光光谱仪等测试手段对荧光粉进行表征与分析.结果表明,煅烧温度对产物的物相有较大影响,700℃煅烧前驱体12 h便具有单一晶相;800℃煅烧前驱体12 h得到的荧光粉,粒径为100 nm左右;用溶胶-凝胶制备的Eu:La<,2>L...     

预涂钴离子的二氧化钛薄膜制备和性能

采用溶胶-凝胶法在玻璃表面预涂一层Co离子TiO2薄膜.研究了Co离子掺杂对样品相结构、晶粒尺寸和光催化降解亚甲基蓝活性的影响.实验结果表明,钴的掺杂对二氧化钛的相变有很大的抑制作用,并使其光谱响应范围向可见光区拓展.与未掺杂的二氧化钛相比较,经钻掺杂的二氧化钛具有更高的催化性能.     

Fabrication and characterization of composite sol-gel coatings on porous ceramic substrate

Highly porous ceramic materials were coated using a composite sol-gel method. Alumina powder is dispersed in a silica sol-gel solution and then dip-coated on the substrate. The resulting coatings present a composite microstructure in which crystalline alumina grains are linked to each other by an amorphous silica phase. In this work, we show that, by accurately controlling the sol-gel parameters (water, solvent and silica precursor (TEOS) ratio, pH and ageing time of the sol) and also the powder grain size distribution it is possible to obtain crack-free thick films (more than 20 μm in one step). These coatings present good adherence to the substrate, decrease the roughness and also close the surface porosity of the substrate. Coating mechanical properties have been evaluated thanks to micro-indentation measurements and linked to coating structural evolution with the thermal treatment temperature.     

Gd,B共掺杂改性TiO_2纳米颗粒的可见光光催化活性

采用溶胶-凝胶法制备了Gd和B共掺杂的TiO2纳米颗粒,研究了TiO2纳米颗粒在可见光下的光催化活性。应用XRD、TEM和UV-Vis等手段对TiO2纳米颗粒的物相、粒径、形貌及光学性能进行了表征。结果表明,掺杂可以抑制TiO2晶粒增长,阻碍TiO2由锐钛矿相向金红石相的转变。紫外-可见吸收光谱显示,共掺杂纳米颗粒在可见光区吸收有较强提高,共掺杂离子以协同作用拓展TiO2光谱响应,使吸收带产生红移,提高光生载流子的分离效率。光催化降解实验表明,共掺杂TiO2纳米颗粒有很高的可见光光催化活性,以500℃热处理的共掺杂摩尔比为0.005 Gd和0.04 B的TiO2纳米颗粒光催化效果最好,在可见光下对甲基橙的降解率为98.9%。     

Gd,B共掺杂改性TiO2纳米颗粒的可见光光催化活性

采用溶胶-凝胶法制备了Gd和B共掺杂的TiO2纳米颗粒,研究了TiO2纳米颗粒在可见光下的光催化活性。应用XRD、TEM和UV-Vis等手段对TiO2纳米颗粒的物相、粒径、形貌及光学性能进行了表征。结果表明,掺杂可以抑制TiO2晶粒增长,阻碍TiO2由锐钛矿相向金红石相的转变。紫外-可见吸收光谱显示,共掺杂纳米颗粒在可见光区吸收有较强提高,共掺杂离子以协同作用拓展TiO2光谱响应,使吸收带产生红移,提高光生载流子的分离效率。光催化降解实验表明,共掺杂TiO2纳米颗粒有很高的可见光光催化活性,以500℃热处理的共掺杂摩尔比为0.005 Gd和0.04 B的TiO2纳米颗粒光催化效果最好,在可见光下对甲基橙的降解率为98.9%。     

Preparation and Properties of Lead Zirconate Stannate Titanate Sintered by Spark Plasma Sintering

Lanthanum-doped lead zirconate stannate titanate ceramics were successfully compacted to full density by spark plasma sintering (SPS). SPS samples densified at 900° or 950°C exhibit nearly full density and fine grain size (about 300 nm). Compared with samples from conventional sintering (CS), SPS samples show larger permittivity accompanied by a deterioration in dielectric loss and special strain hysteresis loops similar to those of ferroelectric relaxors, with a diffuse AFE–FE phase transition and less field-induced longitudinal strain. The differences in the properties of SPS and CS materials are attributed to the variations of the resultant microstructures, especially the grain size, of the ceramics.     

两种合成方式对制备纳米二氧化钛粉体的影响

以钛酸四丁酯为原料,分别通过溶胶-凝胶法和硬脂酸凝胶法制得TiO2前驱体,在450℃煅烧后分别得到粒径在42.4,9.4 nm的混晶纳米TiO2。运用XRD和TEM等方法对TiO2进行表征,探讨了两种合成方式对纳米TiO2粒径大小及TiO2晶型转变温度的影响。结果表明,以硬脂酸凝胶法合成的纳米TiO2纯度高、粒径小,且晶型转变温度低,这是由于晶粒细化后晶型转变温度降低的缘故。