草酸铵沉淀法制备纳米氧化钕研究

以硝酸钕、草酸铵为原料,六偏磷酸钠为分散剂,采用沉淀法制备纳米氧化钕前驱体,将前驱体在空气中焙烧制备纳米氧化钕粉体。研究了反应温度、物料浓度等因素对粉体的影响,用激光粒度仪测得样品的粒度分布,用X射线衍射和扫描电镜对样品进行表征。实验表明,在最佳条件下可以制得平均粒径为100 nm的片状氧化钕粉体。     

微波水热合成ZrO2-8%Y2O3纳米粉体

以Zr（OH）4和Y（OH）3的共沉淀为前驱体,在碱性介质中用微波水热法合成摩尔分数为8％的氧化钇稳定氧化锆（yttria stabilized cubic zirconia,YSZ）纳米粉体。通过X射线粉末衍射仪、透射电镜和等离子发射光谱等表征粉体的性能。研究了微波水热法的反应温度、时间和前驱物浓度对反应产物形貌、粒度等的影响。获得了制备具有纳米立方相结构的YSZ粉体的最佳工艺参数：粉体粒度为5～10nm,产物纯度为99％。结果表明：温度为200℃时,产物粒径较小且均匀。微波水热制备YSZ的最佳反应时间为20～40min。前驱物中Zr^4＋的最佳浓度为0.2mol／l。增大碱性介质KOH的浓度对产物的晶型和粒度影响不大。     

溶胶-胶水热合成法制备纳米CoAl2O4粉体

以仲丁醇铝和硝酸钴为原料,用溶胶-凝胶水热合成法制备了纳米CoAl2O4粉体,探讨了水热合成中前驱体的制备工艺条件,并用X射线衍射和扫描电镜等手段分析了水热系统中反应温度、反应时间对纳米CoAl2O4粉体的形成以及形貌的影响.结果表明:前驱体在250℃的水热系统中反应24 h,能制备出较纯净、结晶完整、粒度均匀、粒径小、尖晶石结构的纳米CoAl2O4粉体,其平均粒度约为50～60nm.     

超细氧化钇合成与表征

以硝酸钇为原料,氨水、碳酸铵、酒石酸铵为沉淀剂,聚乙二醇、十二烷基苯磺酸钠、十六烷基三甲基溴化铵为表面活性剂,在水溶液中制备氧化钇前驱体,在空气中焙烧制备氧化钇粉体;用X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(IR)对样品进行表征,用激光粒度仪分析样品的晶粒团聚度.结果表明,使用氨水、碳酸铵、酒酸铵为沉淀剂所得前驱体在673 K焙烧2 h,均获得立方晶相氧化钇粉体,一级晶粒直径分别为13,40,63 nm;用小分子有机醇回流处理氧化钇前驱体(氢氧化钇),团聚体粒径为58.8 nm,焙烧后的氧化钇团聚体粒径为423 nm,说明有机醇回流处理阻止了粒子团聚.     

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.     

球形氧化钇粒度测试条件优化

详细研究了激光粒度分析法测量氧化钇粉体粒径的条件。结果表明,分散剂的种类及用量、氧化钇粉体用量、超声波功率和超声时间等对粉体平均粒径的测量结果有较大的影响。对于纳米级或亚微米级氧化钇粉体的粒度测量,适宜的条件:用p H为8.0的氢氧化钠水溶液配制质量浓度为1.0 g/L的多聚磷酸钠溶液作为分散介质,氧化钇用量100 mg/L,超声波功率为300 W,超声时间为10 min,测试折射率为1.65。     

预混火焰中喷雾热分解制备纳米氧化钇

以硝酸钇的水溶液为前驱体,在甲烷和空气的预混火焰中喷雾热分解制备得到了结晶度高、具有较大比表面积的纳米氧化钇粉体。考察了反应过程中形成火焰的混合气体流量比以及雾化气体流量对生成的氧化钇晶型和比表面积的影响。研究表明,随着混合气体流量比的增加,得到的氧化钇粉体的比表面积在为0.48附近出现了一个最大值32 m2/g;雾化气体流量对氧化钇粉体的比表面积的影响不大,不同雾化气流量下制备得到的氧化钇粉体的比表面积为30~33 m2/g。     

球形纳米氧化钇的制备与表征

以尿素为沉淀剂,硝酸钇为钇源,十六烷基三甲基溴化铵为分散剂,采用均相沉淀法制备球形纳米氧化钇粉体,研究了反应物浓度比、表面活性剂用量、反应时间、搅拌转速、反应温度对氧化钇形貌及粒径的影响。通过激光粒度分析、X射线衍射（XRD）分析、扫描电镜（SEM）分析、傅里叶红外光谱（FTIR）分析等手段对样品进行表征。结果表明,反应物浓度比、反应时间、搅拌转速、反应温度会影响粉体的尺寸,适量CTAB的加入可显著降低氧化钇的粒径;在最佳工艺条件下,可制得粒径大小为110~130 nm的球形氧化钇粉体。     

用聚合物前驱体法低温合成铌酸锂纳米粉体

用聚合物前驱体法,以柠檬酸为配位剂．乙二醇为酯化剂．水为溶剂合成纳米铌酸锂（LiNbO3）粉体。研究发现：当柠檬酸和金属离子的摩尔比（下同）为3：1,柠檬酸和乙二醇的为1：2时,可形成稳定的Li-Nb前驱体溶液和凝胶。用差热-热重分析研究凝胶前驱体的热分解历程。用X射线衍射分析和红外光谱分析研究凝胶前驱体及其不同温度下煅烧所得粉体的相组成和结构。结果表明：Li-Nb凝胶前驱体在加热过程中分解形成LizCO3相．Li2CO3与Nb2O3发生固相反应生成LiNbO3。凝胶前驱体经800℃煅烧2h可以制备纯钙钛矿型的纳米LiNbO3粉体。     

室温固相反应制备超细前驱体及其分散性的研究

研究以结晶氯化铝和碳酸氢铵为原料，采用室温固相反应制备尺寸均一、颗粒细小分散的包含有少量纳米晶γ-AIOOH的碱式碳酸铝钱前驱体。用XRD、Zeta电位及粒度分析仪表征，研究了起声分散、聚乙二醇聚合度及其加入量和pH值等对制备起细前驱体的影响。结果表明：在起声分散及酸性条件下，PEG为不同分子量匹配得到的前驱体．在水中的分散和稳定性最好，并制备出比表面高达66.32m^2／g（1100℃煅烧）的纳米α-Al2O3粉体。     

Ammonium complex of niobium as a precursor for the preparation of Nb2O5/Al2O3 catalysts

Ammonium oxalate complex of niobium was investigated as an aqueous precursor for the preparation of x% Nb₂O₅/Al₂O₃ (x=5, 10, 20 and 30 wt.%) samples. Catalysts with the same Nb₂O₅ contents were also prepared from the traditional niobium oxalate/oxalic acid aqueous solution. The catalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), temperature-programmed reduction (TPR), infrared spectroscopy of chemisorbed pyridine and X-ray photoelectron spectroscopy (XPS). A comparison with the preparation method using the niobium oxalate salt was performed. The results showed that the niobium precursor influence the species growing leading to phases with different reducibility. The XPS revealed the presence of multilayers of niobium oxide on the Nb₂O₅/Al₂O₃ samples prepared by using niobium ammonium oxalate complex, while the ones obtained from niobium oxalate led to Nb₂O₅ particles islands. The addition of niobium oxide decreased the fraction of Lewis acid sites and increased the fraction of Brønsted acid sites, independent of the precursor salt. However, the creation of BAS was more pronounced on the Nb₂O₅/Al₂O₃ samples prepared from niobium oxalate.     

Y2O3-CeO2-doped ZrO2 ceramics from coprecipitated oxalate precursors

Y₂O₃-CeO₂-doped ZrO₂ ceramics were prepared from coprecipitated oxalate precursor material. The thermal decomposition behaviour of the oxalates was studied to find proper conditions for conversion to the oxides. The properties of the calcined oxide powders were measured and sintering conditions to prepare ceramic specimen were investigated. The mechanical properties of the sintered bodies are reported and their relations to composition and sintering conditions will be discussed.     

Hot isostatic pressing of SiC/Si3N4 composite with rare earth oxide additions

SiC/Si₃N₄ composites with rare earth oxide additions have been prepared by glass encapsulated hot isostatic pressing at 1850 °C and 200 MPa pressure. Mechanical properties and microstructures of the sintered samples have been studied. It is shown that different molar ratios of La₂O₃ to Y₂O₃ and the total amount of La₂O₃ and Y₂O₃ additions can affect the mechanical properties significantly. With 3 wt% La₂O₃ + Y₂O₃ additions, lower La₂O₃/Y₂O₃ molar ratio exhibits higher bending strength and median fracture toughness, but relatively lower Vickers hardness. For addition of 6 wt% La₂O₃ + Y₂O₃, the higher bending strength, Vickers hardness and fracture toughness correspond to a certain La₂O₃/Y₂O₃ molar ratio of 1.5, 1.0 and 0.5, respectively. SEM observation shows that the SiC matrix composite with fine grain size and homogeneous microstructure can be obtained.     

Partial oxidation of ethane to synthesis gas over Co-loaded catalysts

Attention has been increasingly paid to the partial oxidation of lower alkanes to synthesis gas, due to its intrinsic energy saving process. We studied the partial oxidation of ethane (POE) on Co loaded on various supports. The POE performance varied as follows: Y₂O₃, CeO₂, ZrO₂, La₂O₃  SiO₂, Al₂O₃, TiO₂ > MgO. Comparing Y₂O₃ and CeO₂, the carbon deposition during the POE was negligible on CeO₂ and therefore CeO₂ was the most preferable support. By changing space velocity and O₂ partial pressure, reaction mechanism of POE was studied and it was revealed that two-step mechanism was prevailing; combustion of ethane to H₂O and CO₂ and subsequent reforming of ethane with H₂O and CO₂ to synthesis gas. Co/CeO₂ catalyst exhibited high and stable catalytic activity for 10 h; high ethane conversion of 18% (maximum ethane conversion 20% at O₂/C₂H₆ = 0.2) with H₂ and CO selectivities of 93 and 84%, respectively.     

超重力液相沉淀法制备纳米铁酸钴

针对磁力搅拌器制备纳米材料时存在粒径分布宽、分散不均匀的问题,采用撞击流-旋转填料床结合化学共沉淀法,以Fe（NO₃）₃·9H₂O、Co（NO₃）₂·6H₂O、NaOH为原料制备CoFe₂O₄纳米颗粒。研究了转速、液体流量、NaOH浓度以及晶化时间对CoFe₂O₄纳米颗粒粒径的影响;并与磁力搅拌器制备的CoFe₂O₄纳米颗粒在磁性能方面进行了对比。采用X射线衍射仪（XRD）、傅里叶红外光谱仪（FTIR）、透射电镜（TEM）、纳米粒度仪及振动样品磁强计（VSM）对产物的粒径形貌及磁性能进行表征。结果表明：CoFe₂O₄纳米颗粒的粒径随转速、液体流量和NaOH浓度的增加而减小,但随晶化时间的增加而增大。最佳工艺条件为：转速900r/min,液体流量60L/h,NaOH浓度3mol/L,晶化时间6h。此条件下制备的CoFe₂O₄纳米颗粒的粒径约为20nm,饱和磁化强度为75.43emu/g,较磁力搅拌器提高40%。     

均匀设计在微乳液法制备纳米氧化铝中的应用

对多因素的复杂实验体系,均匀设计法能在不降低交互作用敏感性分析的前提下,可通过较少的实验次数获得可靠的数学模型,高效优化出最佳工艺条件。本文采用优化组合的U₁₂₊（6^6）均匀设计试验方案,考察了微乳液法制备纳米氧化铝前体的工艺条件,获得了氧化铝粉体的粒径与铝盐浓度、沉淀剂浓度、反应温度、表面活性剂与助表面活性剂的体积比、油相与表面活性剂的体积比5个关键因素之间的数学模型。利用该数学模型优化出的最佳制备工艺条件,制备出了氧化铝前体,该前体经1180℃焙烧,转晶为α-Al₂O₃粉体。α-Al₂O₃的一次粒子形状为棒状,一次粒子的Scherrer粒径为30nm左右,二次粒子的粒径D₅₀为760nm。     

Carbon reduction reaction in the Y2O3–SiO2 glass system at high temperature

In order to assess the role of carbon with respect to the grain boundary chemistry of Si₃N₄-based ceramics model experiments were performed. Y₂O₃–SiO₂ glass systems with various amount of carbon (from 1 to 30 wt.%) were prepared by high-temperature treatment in a graphite furnace. High carbon activity of the furnace atmosphere was observed. EDX analysis proved the formation of SiC by the carbothermal reduction of SiO₂ either in the melt or in the solid state. The melting temperature of the Y₂O₃–SiO₂ system is strongly dependent on the amount of reduced SiO₂. XRD analysis of the products documented the presence of Y₂Si₂O₇, Y₂SiO₅ and Y₂O₃ crystalline phases in that order with an increasing amount of free C in the starting mixture. The reduction of Y₂O₃ was not confirmed.     

Preparation of porous aluminium oxide (Al2O3) hollow fibre membranes by a combined phase-inversion and sintering method

Al₂O₃ hollow fibre membranes were prepared by a combined phase-inversion and sintering method. An organic binder solution (dope) containing suspended aluminium oxide (Al₂O₃) powders, either in mono size or a distributed size, is spun to a hollow fibre precursor, which is then sintered at elevated temperatures. In spinning the hollow fibre precursor, polyethersulfone (PESf), N-methyl-2-pyrrolidone (NMP) and polyvinyl pyrrolidone (PVP) were used as a polymer binder, a solvent and an additive, respectively. The Al₂O₃ hollow fibre membranes prepared were characterized using a scanning electron microscope (SEM) and gas permeation techniques. Effects of Al₂O₃ particle size and size distribution, the sintering temperature and Al₂O₃/PESf ratio on the structure and performance of the resulting membranes were studied extensively. The prepared Al₂O₃ hollow fibre membranes retains its asymmetric structure (mainly resulted from the phase inversion technique) even after the sintering process. Preparation of the Al₂O₃ hollow fibre membrane with a high mechanical strength and moderate permeation characteristics is feasible if the Al₂O₃ powders with a distributed particle size in the spinning (dope) solution is employed.     

废弃CRT荧光粉中稀土的提取工艺与技术

以废弃CRT荧光粉为原料,在前期稀盐酸预处理工艺的基础上,通过进一步深入研究,开发出从废弃CRT荧光粉中提取稀土的完整工艺路线。结果表明:稀酸预处理后,盐酸酸浸剩余荧光粉固体的最佳浓度为5 mol·L^-1,最佳反应温度为80℃;酸浸后稀土浸出液净化除杂的pH控制为5.5,DDTC最佳用量比为6:1;稀土净化液经草酸沉淀后煅烧的最佳温度为900℃。从废弃CRT荧光粉中提取到稀土产物Y₂O₃和Eu₂O₃的总含量为99.2%,其晶粒由若干片状晶体密实堆积成多面体结构,晶粒之间相互嵌入,呈镶嵌式接触。     

Polysilazane derived micro/nano Si3N4/SiC composites

The pyrolised polysilazanes poly(hydridomethyl)silazane NCP 200 and poly(urea)silazane CERASET derived Si–C–N amorphous powders were used for preparation of micro/nano Si₃N₄/SiC composites by hot pressing. Y₂O₃–Al₂O₃ and Y₂O₃–Yb₂O₃ were used, as sintering aids. The resulting ceramic composites of all compositions were dense and polycrystalline with fine microstructure of average grain size <1 μm of both Si₃N₄ and SiC phases. The fine SiC nano-inclusions were identified within the Si₃N₄ micrograins. Phase composition of both composites consist of , β modifications of Si₃N₄ and SiC. High weight loss was observed during the hot pressing cycle, 12 and 19 wt.% for NCP 200 and CERASET precursors, respectively. The fracture toughness of both nanocomposites (NCP 2000 and CERASET derived) was not different. Indentation method measured values are from 5 to 6 MPa m^1/2, with respect to the sintering additive system. Fracture toughness is slightly sensitive to the SiC content of the nanocomposite. Hardness increases with the content of SiC in the nanocomposite. The highest hardness was achieved for pyrolysed CERASET precursor with 2 wt.% Y₂O₃ and 6 wt.% Yb₂O₃, HV 23 GPa. This is a consequence of the highest SiC content as well as the chemical composition of additives.