Grain Growth Kinetics in Liquid-Phase-Sintered Zinc Oxide–Barium Oxide Ceramics

Grain growth of ZnO in the presence of a liquid phase of the ZnO–BaO system has been studied for temperatures from 1300° to 1400°C. The specimens were treated in boiling water and the grains were separated by dissolving the matrix phase in an ultrasonic bath. As a consequence three-dimensional grain size measurements were possible. Microstructural examination shows some grain coalescence with a wide range of neck size ratios and corresponding dihedral angles, however, most grains are isolated. Lognormal grain size distributions show similar shapes, indicating that the growth mechanism is invariant over this time and temperature. All regressions between G ⁿ and time for n = 2 and 3 proved statistically significant. The rate constants calculated with the growth exponent set to n = 3 are on the same order of magnitude as in metallic systems. The apparent activation energy for growth is estimated between 355 and 458 kJ/mol.     

Grain Growth of Zinc Oxide During the Sintering of Zinc Oxide—Antimony Oxide Ceramics

Grain growth in a high-purity ZnO with systematic additions of Sb₂O₃ from 0.29 to 2.38 wt% was studied for sintering in air from 1106° to 1400°C. The results are discussed and compared with previous studies of pure ZnO and ZnO with Bi₂O₃ additions in terms of the kinetic grain growth expression: Gⁿ – Gⁿ ₀= K ₀ t exp(— Q/RT ). Additions of Sb₂O₃ inhibited the grain growth of ZnO and increased the grain growth exponent ( n -value) to 6 from 3 for pure ZnO and 5 for the ZnO—Bi₂O₃ ceramic. The apparent activation energy for the grain growth of ZnO also increased to about 600 kJ/mol from 220 kJ/mol for pure ZnO and 150 kJ/mol for the ZnO—Bi₂O₃ ceramics. Both the grain growth exponent and the activation energy were independent of the Sb₂O₃ content. Particles of the Zn₇Sb₂O₁₂ spinel were observed on the grain boundaries and at the grain triple point junctions. It was also observed that the Sb₂O₃ additions caused twin formation in each ZnO grain. It is concluded that both the Zn₇Sb₂O₁₂ particles and the twins are responsible for the ZnO grain growth inhibition by Sb₂O₃.     

纳米氧化锌晶体生长宏观动力学研究

采用均匀沉淀法制备了纳米氧化锌晶体,考察了影响纳米氧化锌晶粒大小的因素及晶粒生长特性,利用晶体生长动力学理论得到纳米氧化锌晶体生长动力学方程,激活能E=27.87 kJ/mol,指前因子A=6.31×106 nm6·h-1,并对氧化锌晶粒生长机制进行了初步探讨.     

氧化锌单晶的研究进展

目前生长ZnO的方法有助熔剂法、水热法、气相沉积法和坩埚下降法等等,但生长出的ZnO单晶的尺寸和质量都有待于提高。     

氧化锌纳米线的制备及其应用研究

氧化锌纳米线是一种性能优异的新型功能材料,应用前景广阔。综述了氧化锌纳米线的常用制备方法,如化学气相法、电化学法、溶胶-凝胶法和溶液法,以及近年来新的应用领域和研究前沿。     

Direct Determination of Grain Growth Behavior in Zinc Oxide with Added Barium Oxide

Grain growth behavior in ZnO with 4 to 12 wt% BaCO₃ (3.12 to 9.59 wt% BaO) added was studied by a new method, in which the sintered specimen was treated with boiling water to separate the grains by dissolving the grain-boundary phase. The separated grains were examined with SEM to obtain quasi-three-dimensional information on the grain shape, size, and size distribution. The grains had a rounded shape, and the size distribution was found to be lognormal.     

Admittance—Frequency Response in Zinc Oxide Varistor Ceramics

The lumped parameter/complex plane analysis technique revealed several contributions to the terminal admittance of the ZnO—Bi₂O₃ based varistor grain-boundary ac response. The terminal capacitance has been elucidated via the multiple trapping phenomena, a barrier layer polarization, and a resonance effect in the frequency range 10⁻²≤ f ≤ 10⁹ Hz. The characterization of the trapping relaxation behavior near ∼ 10⁵ Hz (∼ 10⁻⁶ s) provided a better understanding of a previously reported loss-peak. The possible nonuniformity in this trapping activity associated with its conductance term observed via the depression angle of a semicircular relaxation in the complex capacitance ( C *) plane has been postulated.     

Preparation and Electric Properties of Dense Nanocrystalline Zinc Oxide Ceramics

This communication reports on the preparation and electric properties of dense nanocrystalline ZnO ceramics. By spark plasma sintering, nanocrystalline (∼100 nm) ZnO ceramics with a high density of 98.5% were obtained at a very low temperature of 550°C. Electric property measurement revealed a novel conduction nonlinearity in the sample sintered at 500°C. This phenomenon is due to the nanometerization of ZnO crystal and the grain boundary layer with an amorphous interfacial layer.     

纳米氧化锌水溶胶的紫外-可见光特性

利用固 -固相反应制得纳米氧化锌 ,经分散处理后对w(纳米氧化锌 ) =0 0 12 5 %～ 0 2 %的水溶胶在波长为 2 0 0～ 80 0nm的光区进行了透光率和吸光度分析。结果表明 :纳米氧化锌在 4 2 5～ 80 0nm光区有普通氧化锌所不具备的高度透明性 ,平均透过率最大的为 96 9% ,最小的为 5 5 3% ;在 2 0 0～ 4 2 4nm光区有很强的紫外光宽带吸收 ,w(纳米氧化锌 ) =0 0 1%时吸光度最大 ,超过 2 5 ,是同质量普通氧化锌的 13倍。考虑到纳米氧化锌对可见光的透明性和紫外光的遮蔽性 ,其质量分数在 0 0 5 %～ 0 1%较合适。     

Transmission Electron Microscope Study of Antimony-Doped Zinc Oxide Ceramics

A transmission electron microscope investigation of a ZnO powder and low-temperature air-sintered pellets with small additions of Sb₂O₃ was conducted in order to study the thin Sb-rich film on the surfaces of ZnO particles. This film was found to be noncrystalline at temperatures below 700°C, and partially crystalline or completely crystalline above this temperature. An oriented overgrowth of the spinel Zn₇Sb₂O₁₂ was observed on the prismatic planes as well as on the basal planes of ZnO crystallites. It is shown that these coherently overgrown spinel films are responsible for the inhibition of grain growth at high temperatures.     

Mechanical Strength and Microstructure of Zinc Oxide Varistor Ceramics

ZnO-based varistor ceramics were sintered under various conditions to optimize their mechanical strength. For highest strength, the optimum sintering temperature was 1070°C or below. At higher maximum temperature, the strength decreased because of grain coarsening and the increasingly inhomogeneous distribution of secondary phases thereby induced. Fracture typically started from holes associated with hollow or poorly compacted sprayed granules. All series contained the same type of critical flaws, but, depending on the sintering temperature, the fracture toughness changed, which led to different strengths. At sintering temperatures above 1050°C, the density started to decrease slightly because of swelling attributed to the pressure of gas entrapped in closed pores.     

Sintering of Zinc Oxide Doped with Antimony Oxide and Bismuth Oxide

The phase change, densification, and microstructure development of ZnO doped with both Bi₂O₃ and Sb₂O₃ are studied to better understand the sintering behavior of ZnO varistors. The densification behavior is related to the formation of pyrochlore and liquid phases; the densification is retarded by the former and promoted by the latter. The pyrochlore phase, whose composition is Bi_3/2ZnSb_3/2O₇, appears below 700°C. The formation temperature of the liquid phase depends on the Sb/Bi ratio: about 750°C for Sb/Bi < 1 by the eutectic melting in the system ZnO—Bi₂O₃, and about 1000°C for Sb/Bi > 1 by the reaction of the pyrochlore phase with ZnO. Hence, the densification rate is determined virtually by the Sb/Bi ratio and not by the total amount of additives. The microstructure depends on the sintering temperature. Sintering at 1000°C forms intragrain pyrochlore particles in ZnO grains as well as intergranular layers, but the intragrain particles disappear at 1200°C by the increased amount of liquid phase, which enhances the mobility of the solid second phase.     

改性氧化锌晶须对丁腈橡胶性能的影响

分别采用偶联剂(Si—69,NDZ—201,KH—550)对氧化锌晶须进行表面改性,研究了改性氧化锌晶须对丁腈橡胶性能的影响。结果表明:Si—69改性氧化锌晶须补强的NBR橡胶物理机械性能、耐老化性能、耐液体性能等优异,效果较KH—550和NDZ—201的好,用量为4份时硫化胶综合性能较好。     

用含锌烟尘制备活性氧化锌的工艺研究

以含锌烟尘为原料,用酸法制得了活性氧化锌,产品达部颁标准。考察了硫酸浓度、固液比、温度及时间对浸出率的影响。在优惠条件下,实验浸出率可达９８％左右。三段控温添加锌粉除杂以及氨水与碳酸氢铵复配作为沉淀剂是技术关键。     

ZnO对M9O-Al2O3-SiO2微晶玻璃结构与透光性能的影响

研究了MgO-Al2O3-SiO2系统微晶玻璃中ZnO含量对微晶玻璃结构及透光性能的影响.采用差热分析、X射线衍射、场发射扫描电镜、紫外-可见-近红外分光光度计对材料进行测试.结果表明:透明微晶玻璃主晶相为尖晶石晶体:ZnO含量的增加使玻璃析晶程度提高,析出晶体尺寸变小且分布更加均匀;添加2%(质量分数,下同)的ZnO可使晶粒尺寸显著减小,得到透明微晶玻璃样品平均晶粒尺寸为27nm,在可见光区透过率大于85%:当ZnO含量从0%增加到4%时,透明微晶玻璃的紫外吸收极限逐渐向短波方向移动.

Abstract：

The influence of zinc oxide (ZnO) addition on the microstructure and transparent property of MgO-Al2O3-SiO2 glassceramics was investigated by using differential thermal analysis, X-ray diffraction, field emissionenvironment scanning electron microscope and ultraviolet-visible-near infrared scanning spectrophotometer. The results show that cubic spinel is the main crystalline phase in the transparent glass-ceramics.The crystallinity increased, the crystalline grain size decreased and became more uniform with increasing ZnO content. The average grain size was 27 mn, and the transmittance of the glass-ceramic was more than 85% in visible spectra region at ZnO content of 2% (in mass, the same as below). The ultraviolet cut-off wavelength moved to the shorter wave when ZnO content increased from 0% to 4%.     

锌灰制备活性氧化锌工艺的研究

以冶炼厂废锌灰为原料,经硫酸浸取,考察了不同工艺条件对锌的浸出率的影响。实验结果表明:锌灰在50℃下浸取,pH值为1.5时,可使锌灰中锌的溶出率达93.5%。碱式碳酸锌最佳水解温度为40℃,水解时间为2 h,pH值为7.5时,溶液中锌含量为12 g/L,得到96%以上的水解率。     

Grain Growth Control in Sb2O3-Doped Zinc Oxide

Microstructure development in Sb₂O₃-doped ZnO was studied to evaluate the influence of inversion boundaries (IBs) on ZnO grain growth. In general, the addition of Sb₂O₃ is believed to inhibit the ZnO grain growth via the formation of spinels and IBs, but we have shown that even the conditions of exaggerated grain growth can be created in this system. We designed an experiment for diffusional doping of ZnO under slightly increased partial pressure of Sb₂O₃. In the high-concentration regime we observed no spinels, and yet the ZnO grains were small and inhibited in growth, while in the low-concentration regime we found huge grains, several times larger than normal ZnO grains, showing an obvious exaggerated growth. By controlling the number of nuclei with IBs we can design coarse-grained microstructures even with Sb₂O₃ doping, which has far-reaching implications in the production of low-voltage varistor devices.     

低纯度氧化锌制备磷酸锌研究

研究了用低纯度氧化锌(96%)通过复合溶剂净化,同时将氧化锌转化为液相改变传统的固-液相反应为液-液反应制备磷酸锌的新工艺,考察了净化和液-液反应的有关的工艺条件,制备得到高纯度磷酸锌。     

Direct-Write Fabrication of Zinc Oxide Varistors

Zinc oxide (ZnO)-based pastes with tailored rheological properties have been developed for direct-write fabrication of thick-film varistor elements in highly integrated, multifunctional electroceramic devices. Such pastes exhibited pseudoplastic behavior with a low shear apparent viscosity of roughly 1 × 10⁴ Pa·s. Upon aging, the pastes attained printable, steady-state viscosities of approximately 3 × 10² Pa·s at 10 s⁻¹. Square and rectangular elements were patterned on dense alumina substrates and sintered at varying temperatures between 800° and 1250°C. Varistor elements fired at 900°C exhibited nonlinearity coefficients (α= 30) that were equivalent to high-density (>95%) varistors formed by cold isostatic pressing at 100 MPa (15 ksi) of a similar chemically derived powder heat-treated under analogous conditions.     

ZnO纳米片生长过程的研究

本文研究了以碱式硫酸锌为前驱体,三聚磷酸钠为表面改性介质,水热法获得ZnO片状结构的形成机理以及工艺参数对ZnO晶体形貌的影响,运用场发射扫描电镜、透射电镜等手段对所得ZnO粉末进行表征,结果表明:磷酸根可以修饰ZnO晶体的生长形貌,限制沿c轴方向的快速生长,而向二维空间发展形成片状结构.改变三聚磷酸钠的浓度和水热溶液pH值,所得ZnO晶体的形貌发生变化,当三聚磷酸钠的浓度为0.1 mol/L,pH值为9～10时,180℃水热28 h可获得厚度小于50nm0的六角形片状ZnO晶体.