溶胶-凝胶法制备V2O5微晶及其合成活化能研究

以NH4VO3和CO( NH2)2等为起始原料,采用溶胶-凝胶法制备了V2O5微晶.研究了煅烧温度对产物物相和显微结构的影响,以及反应的合成活化能.采用X射线衍射、扫描电镜等手段对产物进行了表征.结果表明,后处理温度为500℃可得到V2O5微晶,当反应温度超过600℃时,V2O5微晶表现出(001)晶面的取向生长特征.通过差热分析,计算得到其合成活化能为95.81 kJ/mol.     

溶胶-凝胶法制备CuAlO2粉末及其光电性能研究

采用柠檬酸络合的无机盐溶胶-凝胶法,结合自蔓延燃烧制备出铜铁矿结构的CuAlO2粉末。用DSC-TGA、X射线衍射仪、扫描电子显微镜等分析方法对CuAlO2的形成过程、物相结构、微观形貌等进行了研究。结果表明:形成CuAlO2相的温度在1092℃左右,在1100℃烧结2 h可以得到铜铁矿结构CuAlO2纳米粉末,其粒径分布在50～200 nm之间。制备的样品为p型半导体,CuAlO2片的电阻率为45.5Ω.cm;光学带隙增大,其值约为3.75 eV。     

煅烧温度对络合溶胶-凝胶法制备ZnGa2O4微晶形貌及光催化性能的影响

采用EDTA络合溶胶-凝胶法制备了尖晶石结构的ZnGa2O4微晶.通过XRD、SEM等分析方法对ZnGa2O4微晶进行了测试和表征.研究了不同煅烧温度对其物相组成、显微结构及光催化性能的影响.结果表明,以乙酸锌和氧化镓为反应原料,以乙二胺四乙酸为络合剂,在650～800℃能合成单一物相的ZnGa2O4微晶.在700℃时可以成功制备八面体形的ZnGa2O4微晶,在800℃时可以合成棒状的ZnGa2O4微晶;随着温度从650～800℃逐渐升高,其对罗丹明B的光催化降解性能逐渐提高.     

非水解和水解溶胶-凝胶法制备TiO2薄膜的对比研究

分别采用非水解和水解溶胶-凝胶法制备TiO2薄膜,利用FTIR、TG-DSC和XRD等手段研究了薄膜形成过程中的溶胶-凝胶转变过程和相变化过程,并探讨了非水解和水解溶胶-凝胶法的微观反应机制.研究表明:非水解溶胶-凝胶法与水解溶胶-凝胶法制备TiO2薄膜的微观反应机制不同,水解溶胶-凝胶法是钛酸丁酯的Ti-O键合(TiOR)断裂形成水解产物Ti-OH,再经失水缩聚或是失醇缩聚反应形成Ti-O-Ti键合.而非水解溶胶-凝胶法是在不生成Ti-OH的情况下,利用Ti-Cl与Ti-OR通过亲核反应直接缩聚反应产生Ti-O-Ti键合.非水解溶胶-凝胶法制备的TiO2薄膜开始出现金红石相的温度为750℃,明显高于水解溶胶-凝胶法制备的TiO2薄膜.     

溶胶凝胶法制备CuAlO2多晶及其性能研究

本文采用溶胶凝胶(Sol-gel)法在1200℃下制备出CuAlO2多晶.使用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、光致发光(PL)以及红外(IR)光谱分别对其物相、化学状态、微观形貌和光学性能进行了表征.XRD测试结果表明所得粉体确为铜铁矿结构的CuAlO2多晶.XPS测得Cu的价态为+1价,从而表明样品中含有Cu空位缺陷.SEM显示晶粒尺寸约为1～3 μm,与从XRD中计算的结果相吻合.通过PL测试,观测到紫外近带发射峰和Cu空位缺陷发射峰,并对CuAlO2显p型导电性的原因进行了阐释.IR光谱测试表明CuAlO2多晶对红外光具有较高的透过率.     

冷冻干燥辅助溶胶凝胶法合成Li1.2Ni0.2Mn0.6O2正极材料及电化学性能改善研究

采用冷冻干燥辅助溶胶凝胶法合成富锂锰基Li1.2 Ni0.2Mn0.6O2正极材料,并将其结构、形貌以及电化学性能与传统溶胶凝胶法合成的材料进行比较.X射线衍射(XRD)结果表明,通过冷冻干燥辅助溶胶凝胶法合成的Li1.2Ni0.2Mn0.6O2粉末阳离子混排程度更低,冷冻干燥工艺的参与可以改善晶体结构.扫描电镜(SEM)照片分析表明,与溶胶凝胶样品相比较,冷冻干燥辅助溶胶凝胶法合成样品的颗粒团聚程度较低.电化学性能测试结果表明,冷冻干燥辅助溶胶凝胶法合成的材料具有更好的倍率性能和循环性能.除此之外,电化学交流阻抗测试(EIS)结果表明,冷冻干燥辅助溶胶凝胶法合成的Li1.2Ni0.2Mn0.6O2电荷转移电阻低于溶胶凝胶法制备的材料,增强了反应动力学.     

水热温度对溶胶-凝胶-水热法合成锆钛酸钡钙纳米粉体的影响

针对传统固相反应或溶胶-凝胶制备锆钛酸钡钙(BCZT)粉体时易引入杂质、导致成分偏析和煅烧温度过高等问题,首次采用了溶胶-凝胶-水热法合成BCZT纳米粉体,重点研究了水热温度对合成粉体结构和形貌的影响.结果表明,在80～180℃的温度范围内,成功合成出物相较纯的BCZT纳米粉体,而且随着水热合成温度的升高,其结晶性提高,颗粒尺寸变大.基于XRD、FTIR、SEM、EDS、TEM和XPS的测试结果,确定了适宜的水热合成温度为180℃,远低于传统固相反应或溶胶-凝胶方法的制备温度.在此温度下,获得的BCZT粉体的平均粒径约为70 nm,粉体结晶性良好,成分和粒度均匀,化学计量比准确,并在室温下呈现出三方相与四方相共存的准同型相界(MPB)结构.     

凝胶燃烧法合成Ca2 SiO4:Eu2+微晶及其发光性质的研究

利用凝胶燃烧法合成了可用于白光LED的Ca2 SiO4:Eu2+微晶,并研究了其发光性质.以(C2H5O)4Si作为硅源,克服了传统的燃烧法无法将硅引入的困难,合成了纯相Ca2 SiO4基质.与高温固相法相比,凝胶燃烧法制备的Ca2 SiO4:Eu2+微晶呈现峰值为501nm的绿色宽带发光,其发射光谱没有变化,可以被350～400 nm的UVLED管芯有效激发,但生成物分散性好,初始制备温度较低(500℃左右),颗粒平均尺寸小于1 μm.     

NiTiO3纳米晶的溶胶-凝胶制备工艺研究

以无机镍盐和钛酸四丁酯为起始原料,采用溶胶-凝胶法制备了NiTiO3纳米晶.采用X射线衍射(XRD)、综合热分析仪(DSC/TG)以及透射电镜(TEM)对制备的纳米晶进行了测试和表征.研究了不同镍源、后处理温度对钛酸镍纳米晶相组成以及显微结构的影响.结果表明:以硝酸镍为起始原料更易获得单一物相的NiTiO3纳米晶;以硝酸镍为原料,乙醇为溶剂,n(柠檬酸):n(Ni2++Ti4+)=1:1,后处理温度为700 ℃为制备NiTiO3纳米晶的最佳工艺条件.由谢乐公式推算得出NiTiO3晶粒生长符合Brook关系式,计算得到晶粒生长活化能为Ea=43.07 kJ/mol.     

Fe2O3掺杂对MgO-Al2O3-SiO2系玻璃析晶和性能的影响

采用高温熔融法和两步法微晶热处理制备了MgO-Al2O3-SiO2系堇青石微晶玻璃和铁尖晶石微晶玻璃.利用DSC分析、X射线衍射、FTIR和扫描电子显微镜等手段研究了Fe2O3对玻璃的析晶性能、显微结构和物理性能的影响.结果表明,Fe2 O3的加入可有效降低析晶活化能,促进晶体的析出.当Fe2O3含量达到7.44;时,主晶相由堇青石变为铁尖晶石.Fe2O3掺杂使样品的介电常数由3.2增大至5.8、热膨胀系数由1.941× 10-7增大至7.74×10-6、维氏硬度由7.131GPa增大至11.655 GPa,同时介电损耗由0.05降低至0.015.     

Characteristic crystal growth from amorphous WO3 film by vacuum heating

Selective growth of WO₂, W and WO_3−x crystals from amorphous WO₃ film by vacuum heating at 400–900°C was clarified. The grown WO_3−x crystals were incommensurate structure based on crystallographic share structure. The growth process of WO₂ crystal in the amorphous film was directly observed at high temperature in the electron microscope. The growth front of the WO₂ crystal consumes WO₃ microcrystallites with various orientations. The growth speed of the WO₂ depended on WO₃ microcrystallites orientation. The origin of the wavy growth front of WO₂ was due to an orientation dependence of the WO₃ microcrystallites.     

On the surface mechanism of crystal melting

A crystal melting mechanism is proposed. The melting is caused by enhanced thermal expansion of the lattice on the surface and around structure defects. For the microcrystallites formed this way an approximate calculation of parameters is made. The microcrystallites surface area per mole is shown to be thousands of m², the radius within 1.5 to 10 nm, the gaps between microcrystallites — by 30 percent more than the lattice interatomic distance. The mean thermal linear expansion coefficients determined on the crystal surface are roughly ten times as much as the bulk values.     

To the Unified Model of Condensed State

The problem of unified model of condensed state can be solved by using solid-like model of liquids. A liquid arises when in a heated crystal a universal process of microcrack formation takes place that leads to originating a great number of very small crystals: microcrystallites. In the paper the two basic notions: the effective temperature of crystal surfaces and the internal thermal stresses in crystals are discussed. These notions make possible the microcrystallite model of liquids and the unified model of condensed state. Thus, the microcracks, resulted from thermal stresses, below the melting point lead only to decreased strength of crystals but above melting point the microcracks are spread all over the crystal bulk and cause splitting of the crystal into microcrystallites that are moving freely, in short, making up a liquid. The simple relations for these processes are given. In the end of the paper the identical features of the condensed states, solid and liquid, has been considered.     

The Slow Precipitation of Sparingly-soluble Metal Salt Powders from Aqueous Solution: Mathematical Relations for the Kinetics of the Crystal Growth Processes in Different Types of Precipitation

The following types of slow precipitation, of sparingly-soluble metal salts from aqueous solution, have been analysed: precipitations without an induction period – (i) with very few microcrystallites or seeds, (ii) with microcrystallites and first/second order surface or diffusion rate-controlled growth, (iii) with very many microcrystallites; precipitations with significant induction periods – (i) with very few microcrystallites or seeds, (ii) with microcrystallites and first/second order surface or diffusion rate-controlled growth, (iii) with very many microcrystallites. Generally, in the early stages of precipitation, growth rates depend on the rate of addition of metal salt ions to the system and on the rate constant for crystal growth; in this stage, rates increase from low values to optimum values: in the later stages of precipitation, the metal salt ions are used up as rapidly as they are added to the system and growth rates then depend only on the rate of addition and on the number of microcrystallites or seeds; in this range, rates gradually decrease to low values. Mathematical relations, for the variation of crystal size with precipitation time at different stages of growth, have been derived for each of the above types of precipitation.     

High-temperature lasing in ZnO microcrystallites

High-temperature studies of the luminescence and lasing spectra parameters of the main UV bands (spontaneous luminescence and lines of stimulated-emission mode structure) and the recombination band of electron-hole plasma in zinc oxide microcrystallites have been performed. ZnO microcrystallites of tetrapod morphology, characterized by type-II lasing (microlasers), have been chosen as objects of study [1]. The temperature behavior of a number of key parameters related to specific features of microlasing is investigated.     

The Microcrystallite Model of Liquids for Noble Gases and Other Non-Metals

Some main parameters of the microcrystallite model of liquids had been estimated for liquid noble gases and other non-metals by earlier proposed method. The obtained data are in good accordance with the results for liquid metals. Thus, the radii and, especially, the relative distances between the microcrystallites in liquid non-metals are similar to those for liquid metals. This confirms a universal feature of the proposed microcrystallite model.     

Texture and surface analysis of thin-film GaAs on glass formed by pulsed-laser deposition

Thin-film GaAs on glass was formed by ablating n-type GaAs with nano-second pulses at 532 nm. The deposition was done in the most straightforward way without heating the substrate. The texture of films has been investigated with X-ray measurements, spatially resolved micro-Raman spectroscopy, and atomic force microscopy. The results reveal that the film texture is of multi-phase nature consisting of randomly oriented GaAs microcrystallites, amorphous parts, and (1 1 1) zincblende migrations in the nano-regime.     

Colloidal sol/gel processing of ultra-low expansion TiO2/SiO2 glasses

A series of titania-silica glasses with 0–9% TiO₂ were fabricated using a sol/gel process. The sol was prepared by dispersing colloidal silica fume in an aqueous solution of titania which was synthesized through the acid-catalyzed hydrolysis of titanium isopropoxide. The sols gelled in 2–4 days, and then were dried for 6–8 days. The dry gels were sintered at 1450–1500°C to produce clear, dense, microstructure-free glasses. The gels underwent a total shrinkage of 50% to yield glass rods about 50 mm long and 5 mm in diameter, or glass discs about 4 cm in diameter and 5 mm thick. The drying step was most critical in the production of crack-free specimens.

In the gel, the transmission electron microscope (TEM) revealed the presence of 1–5 nm rutile microcrystallites uniformly distributed within a network of colloidal silica particles. After sintering to 1450–1500°C, though, a dense, transparent, microstructure-free glass was created. Fourier transform infrared spectroscopy (FTIR) verified the formation of an amorphous solid-solution of titania and silica after sintering.

The thermal expansion of the glasses was measured using a differential dilatometer. The average linear coefficients of thermal expansion (CTE @ 25–675°C) varied between +5 × 10⁻⁷ and −0.2 × 10⁻⁷°C⁻¹ in the range 0 to 9% TiO₂. The glass with 7.2% TiO₂ exhibited a zero thermal expansion coefficient at 150–210°C. The hysteresis in CTE on heating and cooling was of the order of 0.01–0.02 ppm.     

The rapid precipitation of magnesium hydroxide from aqueous solutions: Analysis of nucleation and crystal growth kinetics,final nucleus numbers and primary crystal sizes

The studies of the rapid precipitation of magnesium hydroxide, from aqueous solutions of different concentrations by sodium, calcium and ammonium hydroxides, are analysed. The kinetics of nucleation and microcrystallite formation during the induction periods and the kinetics of crystal growth (onto the microcrystallites) to the final primary crystals are examined; the high final nucleus numbers and the sub-microscopic sizes of the final primary crystals are discussed according to Nielsen's theories.