一种合成ZnO压敏电阻陶瓷主料的新方法

以Zn(NO3)2为原料,采用NaOH为沉淀剂,制备氧化锌压敏电阻陶瓷主料ZnO。结果显示制备的ZnO均为纳米级,并通过调节控制酸碱度pH值、反应温度、反应溶液的浓度等,探索了实验的最佳条件。为今后采用共沉淀法制备氧化锌压敏电阻陶瓷复合粉体奠定了扎实的基础。     

不同方法合成掺杂ZnO粉体制备ZnO压敏电阻

分别采用低温固相化学法和共沉淀法合成掺杂ZnO粉体,并用这两种粉体在不同温度下烧结制备了ZnO压敏电阻。借助XRD、SEM、TEM、BET等检测手段对粉体产物的性能进行了表征,采用XRD、SEM等手段对ZnO压敏陶瓷的物相、结构进行了分析,并对两种方法制备的粉体及压敏电阻的性能进行了比较研究。结果表明:采用低温固相化学法合成的粉体平均粒径为23.95 nm,用其制备ZnO压敏电阻的最佳烧结温度是1 080℃,其电位梯度为791.64 V/mm,非线性系数是24.36;采用共沉淀法合成的粉体平均粒径为188 nm,用其制备ZnO压敏电阻的最佳烧结温度是1 130℃,其电位梯度为330.99 V/mm、非线性系数是19.70,低温固相化学法制备的ZnO压敏电阻性能优于共沉淀法制备的ZnO压敏电阻。     

共沉淀法制备纳米羟基磷灰石

以硝酸钙、磷酸混合水溶液为前驱体,以氨水为沉淀剂,采用共沉淀法制备纳米羟基磷灰石。探讨了加料方式、加料速度、Ca-P溶液初始浓度、陈化温度、陈化时间以及反应pH值等工艺条件对纳米羟基磷灰石的结晶粒度与分散性的影响。结果表明,采用将氨水加入Ca-P溶液、快速加料的方式,在Ca2+浓度为1.0mol.L-1、陈化温度为60℃、陈化时间为12h、反应pH值为10的条件下可高效制备分散性较好的短棒状纳米羟基磷灰石粉体。     

纳米氢氧化镁粉体制备研究

以六水氯化镁为原料,利用氨水和氢氧化钠混合溶液为沉淀剂,采用直接沉淀法制备纳米氢氧化镁。其最佳反应条件为温度60℃,反应时间90 min,氯化镁浓度0.5 mol/L,体积比为1∶1乙醇和水为混合溶剂,表面活性剂聚乙二醇-400用量为六水氯化镁质量的3%,烘干温度为80℃。实验得到粒径分布窄、分散性好的氢氧化镁粉体,对纳米氢氧化镁的工业化生产有重要意义。     

化学共沉淀法制备纳米四氧化三铁粉体

采用化学共沉淀法制备纳米Fe3O4粉体,并用聚乙二醇表面活性剂进行表面改性,在铁离子浓度比Fe2＋：Fe3＋=1：2时,对制备工艺影响因素进行了讨论。通过实验得到的最佳工艺条件为：控制温度介于40～60℃,最佳的pH取值为9,聚乙二醇的适宜用量取5～10 mL。采用TEM观测制备的纳米Fe3O4颗粒的形貌及其大小,得到的纳米Fe3O4颗粒粒径为20～50 nm之间。     

FTO薄膜表面激光诱导制备ZnO纳米结构

采用磁控溅射法在FTO(掺氟二氧化锡)玻璃基底表面沉积金属Zn层,再将其置于双氧水溶液中,通过纳秒脉冲激光对其表面进行辐照处理来实现ZnO纳米结构的制备。研究了激光能量密度和扫描速率对ZnO纳米结构的形成和得到的ZnO纳米结构复合FTO(Zn O/FTO)薄膜表面形貌和光电性能的影响。结果表明,当Zn层厚度为200 nm时,可保证FTO薄膜表面既出现完整的Zn O纳米结构,又仅有少量Zn剩余。当激光能量密度为0.80 J/cm2,扫描速率为15 mm/s时,FTO薄膜表面制备出了均匀一致性最好的ZnO纳米结构,此时ZnO/FTO薄膜有最佳的光电性能,其在400～800 nm波段的平均透光率为70.18%,平均反射率为7.10%,方块电阻为9.23Ω。     

纳米SiO2的制备及其原位改性

以天然优质粉石英自制的Na2O·3.1SiO2为原料、硅烷偶联剂KH-560、KH-570为改性剂、HCl为沉淀剂、聚乙二醇为表面活性剂,采用化学沉淀法制备了分散性好的改性纳米SiO2粉体.研究了硅烷偶联剂KH-560、KH-570对溶液中生成的二氧化硅粒子表面原位改性的影响及机理,优化了制备改性纳米SiO2粉体的工艺条件.利用扫描电镜(SEM)、红外光谱(FTIR)、热分析仪及粘度计对制备的产物进行了表征.结果表明硅烷偶联剂KH-560、KH-570都是有效的改性剂.     

ZnO异质复合对纳米TiO2晶型转变和晶粒生长的影响

以TiCl4,ZnSO4溶液为原料,采用液相沉淀法制备了不同ZnO/TiO2摩尔比的纳米复合粉体.对合成的纳米复合晶的相变、晶粒生长过程以及紫外-可见光吸收性能进行了研究.结果表明:纳米TiO2经ZnO复合后,其晶型转变和晶粒生长均受到抑制.当ZnO为30%(摩尔分数)时,且采用氨水滴入TiCl4和ZnSO4溶液中的沉淀方式制备的ZnO/TiO2纳米复合晶的晶型转变和晶粒生长最缓慢.紫外-可见光吸收测试表明:800℃煅烧的ZnO/TiO2复合粉体的吸收强度比纯TiO2的高;900～1 050℃煅烧的复合粉体,虽然紫外区的吸收强度有所下降,但其光吸收带边比纯TiO2纳米晶的有显著红移.     

高压ZnO压敏电阻陶瓷材料研究进展

综述了高压氧化锌压敏电阻的导电原理及制备工艺,从超细粉体的制备、稀土添加剂、烧结工艺等方面重点分析了目前该材料的制备方法。并指出高压氧化锌压敏电阻材料今后应从以下几方面进行重点研究:①加强大电流区的失效模式与显微结构之间的相关理论研究;②稳定纳米ZnO粉体,特别是掺杂如Bi_2O_3等其他成分纳米复合粉末的制备研究;③复合稀土氧化物对氧化锌电阻片的微观和电学性能的影响研究,对掺杂量的控制及作用机理将是未来研究的重点;④开发和优化如微波烧结等新的烧结工艺。     

室温固相合成掺杂ZnO纳米粉体制备ZnO压敏电阻

以金属离子盐和草酸为原料,采用室温固相化学反应合成掺杂ZnO前驱物,根据DSC-TG分析结果,将其在450℃热分解2 h,得到掺杂ZnO粉体,并用此粉体制备了片式ZnO压敏电阻。借助XRD、TEM、BET等检测手段对粉体产物的物相、形貌、粒度等进行了表征。研究了烧结温度对ZnO压敏电阻电性能的影响。结果表明,所制备的粉体为平均粒径24 nm左右、颗粒呈球状、分散性好的纤锌矿结构掺杂ZnO。在1 080℃烧结时,ZnO压敏电阻的综合电性能达到最佳,电位梯度为791.64 V/mm,非线性系数为24.36,漏电流为43μA。     

Fabrication of an Electrically-Resistive,Varistor-Polymer Composite

This study focuses on the fabrication and electrical characterization of a polymer composite based on nano-sized varistor powder. The polymer composite was fabricated by the melt-blending method. The developed nano-composite was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FeSEM), and energy-dispersive X-ray spectroscopy (EDAX). The XRD pattern revealed the crystallinity of the composite. The XRD study also showed the presence of secondary phases due to the substitution of zinc by other cations, such as bismuth and manganese. The TEM picture of the sample revealed the distribution of the spherical, nano-sized, filler particles throughout the matrix, which were in the 10–50 nm range with an average of approximately 11 nm. The presence of a bismuth-rich phase and a ZnO matrix phase in the ZnO-based varistor powder was confirmed by FeSEM images and EDX spectra. From the current-voltage curves, the non-linear coefficient of the varistor polymer composite with 70 wt% of nano filler was 3.57, and its electrical resistivity after the onset point was 861 KΩ. The non-linear coefficient was 1.11 in the sample with 100 wt% polymer content. Thus, it was concluded that the composites established a better electrical non-linearity at higher filler amounts due to the nano-metric structure and closer particle linkages.     

表面活性剂对纳米氧化锌粉体分散性的影响

以硝酸锌、碳酸氢铵为原料,通过沉淀反应制备ZnO超细粉体。考察了制备过程中不同种类、添加量的表面活性剂(DBS、PEG、Tw-80)对ZnO粉体平均粒径的影响。试验结果表明:在沉淀过程中添加表面活性剂可抑制前驱体碱式碳酸锌的长大和团聚,制备出的ZnO粒径小,粒径分布范围窄,且Tw-80的分散效果优于DBS和PEG。     

Microstructural and compositional aspects of ZnO-based varistor ceramics prepared by direct mixing of the constituent phases and high-energy milling

ZnO-based varistor samples were prepared by the direct mixing of the constituent phases (DMCP) and sintering at 1100 °C for 2 h. The influence of the starting powder mixture's composition – the amounts of the pre-reacted varistor compounds and their composition – and its preparation, either with or without mechano-chemical activation (MCA), on the microstructure, phase composition and electrical characteristics of the varistor samples was studied. It showed that MCA improved the density and microstructural homogeneity of the varistor samples. MCA strongly affected the grain growth: it enhanced the nucleation of inversion boundaries (IBs) in the ZnO grains and the IBs-induced grain-growth mechanism resulted in uniform grain growth and hence a microstructure with smaller ZnO grains and a narrower grain size distribution. The final phase composition of the samples prepared by the DMCP method mainly depended on the presence of varistor dopants that can prevent the formation of the pyrochlore phase, especially Cr₂O₃, while MCA can affect it mostly by providing a homogeneous distribution of those dopants. The DMCP varistor samples prepared with MCA had much better current–voltage characteristics than the samples of the same composition prepared from unactivated powders.     

氨水沉淀法制备纳米粉氢氧化锌和氧化锌

在水—乙醇介质中用氨水沉淀法制备出了纳米Zn(OH)_2和ZnO材料,讨论了介质组成对沉淀产物ZnO微粉的粒径范围及形貌的影响,并研究出由Zn(OH)_2分解为纳米ZnO的最佳干燥脱水条件为200℃、2h。表明本方法不需高温处理就可得到颗粒均匀且分布窄的ZnO纳米材料,粒径可达17～6nm。     

锌灰制备碱式碳酸锌和超细氧化锌及表征

室温下采用氨浸出锌灰制得碱式碳酸锌,再经煅烧制得超细氧化锌。研究了在合成碱式碳酸锌过程中表面活性剂对碱式碳酸锌和氧化锌颗粒尺寸与形貌的影响。结果表明,聚乙二醇（PEG20000）和聚乙烯吡咯烷酮（PVP-K30）这两种表面活性剂对颗粒的分散效果最好,制得的碱式碳酸锌颗粒为无定形片状且分散均匀,平均粒径为1 μm,煅烧后的氧化锌颗粒为六方晶系纤锌矿结构,粒径约为0.7 μm。添加PVP-K30比添加PEG20000的碱式碳酸锌热分解温度高。添加PEG和PVP的碱式碳酸锌反应活化能分别为139.9 kJ/mol和146.8 kJ/mol。     

卤水-烧碱直接沉淀法制备纳米氢氧化镁的研究

以苦卤水、烧碱为原料,采用直接沉淀法在表面活性剂的辅助下制备出纳米氢氧化镁粉体。实验研究了反应温度、反应物物质的量比、表面活性剂、不同干燥方式和滴加方式等对所得粉体粒度的影响,通过X射线衍射仪（XRD）和扫描电子显微镜（SEM）对粉体进行表征,用差热-热重分析仪（TG-DTA）分析了产物的热稳定性,并用激光粒度测试仪测试了产物的粒度大小及其分布情况。实验表明：在合适的反应温度及物质的量比下,用PEG200作为表面活性剂、正丁醇共沸蒸馏干燥制得的粉体为流动性较好且厚度约为10 nm的片状纳米氢氧化镁粉体。     

表面活性剂在制备超细石英粉体中的应用

选择了三种不同的表面活性剂硅酸钠、十二烷基磺酸钠、聚丙烯酰胺,通过控制表面活性剂的加入量和石英粉体悬浮液的pH,利用搅拌磨制备出超细石英粉体.比较了不同条件下石英粉体的粒度和分散度的变化规律,并分析了产生的原因.     

草酸沉淀法制备超细氧化镧粉体研究

以工业生产萃取、分离及提纯过的稀土氯化镧溶液为原料,一定条件下制备出D₅₀小于10 μm的超细氧化镧粉体,研究了制备过程中焙烧温度、分散剂种类、溶液pH对氧化镧粉体粒径分布的影响。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。结果表明,焙烧温度为750 ℃、焙烧时间为2 h、加入质量分数为1%的分散剂PEG2000,在酸性反应条件下可制备出粒度均匀,分散性好的超细氧化镧粉体。     

Plasma dynamic synthesis of composite ZnO-Bi2O3 material with a core-shell structure for varistor ceramics

Zinc oxide has been studied for many years and found many applications in different areas, including the power engineering, where the ZnO-based ceramics could be used as a varistor. However, there is a necessity to add different oxides to ZnO to make a uniform ceramics structure with well enough nonlinear characteristics. In this regard, the uniform distribution of additives in the structure of a composite based on ZnO becomes an urgent task to prepare the high-quality ceramics. This work shows the possibility to obtain the composite powdered material with the uniformly distributed Bi₂O₃ addition in the ZnO crystallites by a plasma dynamic method. The features of this method and flowing reactions allow forming the ZnO-Bi₂O₃ particles with the core-shell structure. The spark plasma sintering of the ZnO-Bi₂O₃ composite material with such particles structure provides the production of varistor ceramics characterized by a fine-grained ZnO structure (average grain size is about 1?µm) with uniformly filled intergranular spaces by Bi₂O₃. The comparison of voltage-current characteristics with the ceramics made of ball-milled commercial powders showed the prospects of using as-prepared ZnO-Bi₂O₃ composite with core-shell structure.