尖晶石及高铝—尖晶石浇注料的开发应用

探讨了我国镁铝尖晶石及高铝－尖晶石（含刚玉－尖晶石及矾土熟料－尖晶石）浇注料的开发应用,阐述了我国没档尖晶石的技术特征和优点以及矾土熟料－尖晶石浇注料研制开发和成功应用的巨大意义,认为：从兼顾技术上和经济上的可行性考虑,尖晶石及高铝－尖晶石浇注料的开发应用已经是呈现了蓬勃发展的大好局面,在推进尖晶石及高铝－尖晶石浇注料的开发应用上,我国的耐火材料工作者正站在开发应用的前列、发挥着具有开拓意义的主导     

镁砂与电熔合成铁铝尖晶石-刚玉复合材料的反应

以电熔合成铁铝尖晶石-刚玉复合材料和电熔镁砂为原料制备了铁铝尖晶石-镁铝尖晶石复合材料。检测了各烧后试样的线变化率、体积密度和显气孔率,并用XRD、SEM等研究了镁砂与电熔铁铝尖晶石-刚玉复合材料之间的反应,结果未发现有单一的镁铝尖晶石相生成,在高温下,MgO与铁铝尖晶石-刚玉之间存在互扩散,形成镁铝尖晶石和铁铝尖晶石固溶体;随着镁砂细粉加入量的提高,镁铝尖晶石向铁铝尖晶石中的固溶量加大;当电熔铁铝尖晶石-刚玉复合材料以颗粒加入时,发现在某些铁铝尖晶石颗粒周围存在环形裂纹;随着镁砂加入量的提高,试样的显气孔率下降,体积密度增大。     

铁铝尖晶石加入量对镁铁铝尖晶石砖的性能影响

为了研究铁铝尖晶石加入量对镁铁铝尖晶石砖的性能影响,本实验以粒度为3~1 mm、1~0 mm、≤0.088 mm的97高纯镁砂和1~0 mm的电熔铁铝尖晶石为原料,讨论了铁铝尖晶石加入量分别为3%、6%、9%、12%和15%时镁铁铝尖晶石砖的性能,利用XRD分析了试样的物相变化,采用SEM分析了烧后试样的微观结构。结果表明:铁铝尖晶石加入量为6%时,镁铁铝尖晶石砖有较高的体积密度和耐压强度以及较低的显气孔率,铁铝尖晶石加入量越多,镁铁铝尖晶石砖的荷重软化温度越低,铁铝尖晶石加入量3%~6%之间为宜。从显微结构照片中可以看出铁铝尖晶石周围生成的尖晶石环和环形裂纹,这是高温过程中部分铁铝尖晶石与方镁石发生离子交换反应所致,这种结构对镁铁铝尖晶石砖的结构柔韧性起着一定的作用。     

自分散法温烧成镁铝尖晶石制品的研究

采用金属铝粉氧化大量放热的自分散法与ＭｇＯ合成镁铝尖晶石和低温下直接制成高纯镁铝尖晶石制品进行了研究。结果表明：在１４００℃温度下可制成镁铝尖晶石制品。     

关于陶瓷釉用黑色色料在使用过程中需要注意的问题

陶瓷釉用黑色色料从结构上来划分，属于尖晶石系列。由于含有不同的元素，不同的尖晶石可以有不同的颜色，如镁尖晶石在红、蓝、绿、褐或无色之间；锌尖晶石则为暗绿色；铁尖晶石为黑色等等。     

尖晶石种类对刚玉-尖晶石浇注料性能的影响

采用板状刚玉颗粒（6～3、3～1、≤1 mm）及细粉（0.045 mm）、电熔尖晶石颗粒（≤1 mm）及细粉（0.045 mm）、烧结尖晶石颗粒（≤1 mm）及细粉（0.045 mm）、活性尖晶石微粉(d₅₀=1.82μm)、活性α-Al₂O₃微粉(d₅₀=1.68μm)、Secar 71水泥等原料制备了刚玉-尖晶石浇注料。研究了不同种类尖晶石（电熔尖晶石、烧结尖晶石、烧结尖晶石+活性尖晶石）对浇注料性能的影响。结果表明：1)在刚玉-尖晶石浇注料中引入不同的尖晶石对试样经110℃保温24 h烘干后的抗折强度和耐压强度影响不大，但采用电熔尖晶石能降低加水量，提高流动性，得到优良的施工性能；2)采用电熔尖晶石有利于材料的抗渣侵蚀性能，但在抗渣渗透性及抗热震性方面，烧结尖晶石更占优势；3)加入适量的活性尖晶石微粉可以弥补烧结尖晶石的不足，提高浇注料的可施工性能，但对抗热震性会产生一定负面影响。     

不同组成尖晶石对MgO-尖晶石浇注料抗渣性能的影响

采用静态坩埚法和动态回转法研究了不同组成尖晶石对MgO-尖晶石浇注料抗渣性能的影响,并采用扫描电镜和能谱分析测定了渣蚀残样中尖晶石的存在形式和化学组成。结果表明,在基质组成相同的情况下,添加富铝尖晶石的浇注料在加热过程中可生成较多的原位生成尖晶石,原位生成尖晶石吸收渣中FeO3、CaO能力是合成尖晶石的3～5倍,因而该浇注料具有较好的抗渣性能。     

镁铬砖内二次尖晶石的分布与性能

采用计点法，在显微镜下测定了高温烧成镁铬砖内二次尖晶石量。清晰地显示二次尖晶石量受烧成温度及原材料配比的极大影响。     

不同粒度锌铝尖晶石加入量对方镁石-锌铝尖晶石性能的影响

以高纯镁砂(5～0.074、≤0.074 mm)为主要原料，分别以烧结法合成的锌铝尖晶石颗粒(5～0.074 mm)和细粉(≤0.074 mm)取代相应粒度的高纯镁砂，制备了方镁石-锌铝尖晶石试样，分别研究了锌铝尖晶石颗粒(加入质量分数分别为10%、15%和20%)和细粉(加入质量分数分别为5%、10%和15%)的引入量对试样性能的影响，并与市售的铁铝尖晶石砖的性能作对比。结果表明：1)随锌铝尖晶石颗粒引入量的增加，试样的显气孔率增大，体积密度和常温耐压强度降低，抗热震性能稍有提高；2)随锌铝尖晶石细粉引入量的增加，试样的常温物理性能和抗热震性能均有提高；3)当锌铝尖晶石以10%(w)颗粒料或5%～10%(w)细粉料引入时，其抗侵蚀性能均优于目前水泥窑使用铁铝尖晶石砖的。综合来看，锌铝尖晶石以5%(w)细粉形式引入的试样性能最好。     

铁铝尖晶石的合成及应用研究进展

较系统地介绍了铁铝尖晶石的合成机制,并对铁铝尖晶石的合成方法特点进行了对比,同时还对比了以铁铝尖晶石为原料制备的氧化镁-铁铝尖晶石砖与其他水泥回转窑烧成带常用砖的基本性能与特点,指出铁铝尖晶石是一种非常有使用前景的水泥回转窑衬砖用耐火原料。     

化学组成对轻烧镁铝尖晶石结构与性能的影响

相比传统电熔镁铝尖晶石和烧结镁铝尖晶石,轻烧镁铝尖晶石晶格畸变大,反应活性高,所制备的铝镁浇注料抗渣渗透性更好。本文以工业氧化铝和轻烧镁砂细粉为原料,在1 600 ℃下烧结合成Al₂O₃质量分数在68%~76%的富镁尖晶石(68%和70%)、正尖晶石(72%)和富铝尖晶石(76%)试样,研究Al₂O₃含量对尖晶石试样常温物理性能、物相组成、晶体结构参数和显微结构的影响。结果表明:Al₂O₃含量的增加提高了试样的显气孔率;富镁尖晶石试样的物相为尖晶石和少量方镁石,其余试样只有尖晶石相;富铝尖晶石的晶格畸变大于富镁尖晶石和正尖晶石,晶粒尺寸和平均孔径小于富镁尖晶石和正尖晶石。     

Role of Ti and Sn ions in spinel formation and reactive sintering of magnesia-rich ceramics

The solid solubility of magnesia in magnesium aluminate spinel and magnesium aluminate spinel in magnesia does not change with temperature thus not creating bonds or precipitation over periclase grains in a single stage sintering process. In comparison, the precipitated spinels in magnesia-chromia refractories form complex spinel due to inversion in the position of bivalent and trivalent cations within the structure, making them more stable at high temperature than either normal or inverse spinel. Additives form low-temperature compounds that diffuse into the spinel structure and create defects that change the properties of spinel solid solution. In the present study, magnesia and alumina powders along with tetravalent oxide additives were analyzed for their role in reactive densification of spinel in a single stage firing process in order to achieve a better binding system for magnesia-based refractories. These tetravalent oxides on reaction with magnesia form spinel solid solution with MgAl₂O₄ as they have similar crystal structure. The spinel solid solution formed using oxide additives is expected to have higher solubility in magnesia than magnesium aluminate spinel, resulting in improvement of the bonding during sintering through increased in solid solubility at elevated temperatures followed by precipitation of secondary spinel phases, similar to the complex spinel in magnesia-chrome refractories. The formation of spinel during firing remains as a second phase that retards the grain growth of periclase. The changes in unit cell dimensions with temperature and amount of additive were analyzed using Reitveld method and correlated with the densification behaviour at different temperatures.     

Thermodynamics and electronic structure characteristics of MFe2O4 with different spinel structures: A first-principles study

In recent years, spinel ferrites with chemical formula MFe₂O₄, have attracted much attention due to their impressive photocatalytic and electrocatalytic performances, which are significantly influenced by their spinel structures. However, it is still a big challenge to distinguish or predict spinel structures for spinel ferrites. As an attempt to address this issue, this paper presents a first-principles study of the thermodynamics and electronic structures for six spinel ferrites with different spinel structures. The configurational free energy of these spinel ferrites at different inversion degrees is calculated to determine the equilibrium inversion degree for each spinel, which successfully predicts the spinel structure type of these spinel ferrites. The partial density of states is obtained for six spinel ferrites assuming they are normal or inverse spinels. The electronic states close to the Fermi energy of each spinel ferrite are carefully examined, showing that normal spinels have weak interactions between M and Fe states, while strong interactions exist in mixed or inverse spinels. Our results offer an insightful understanding of different spinel structures, and provide a reliable approach to determine the spinel structure of spinel ferrites.     

Characterization of spinel bubbles and preparation and properties of lightweight ceramics

During the selection of materials for anti-lithium ion corrosion, magnesium aluminate spinel has been found to have good corrosion resistance and low cost. During the preparation of light-weight spinel ceramics, it is considered to be kiln body material. In this work, spinel bubbles were prepared using electrofusion injection process. Bulk density, volume density and pressure resistance of spinel bubbles in different particle sizes were counted. Light-weight spinel bubble ceramics with different densities were prepared by using electrofused spinel bubbles as light aggregates and using ρ-Al₂O₃ and caustic burnt magnesia powder as matrix powders. The microstructure of spinel bubbles with different particle sizes and light spinel ceramics was analyzed using scanning electron microscope. Results show that the spinel bubble has complete structure, good sphericity, perfect grain crystallization, and clear edges and corners. Although there are some fine cracks and cavities, grains are tightly bound. Compressive strength and bending strength of light-weight spinel ceramics, whose density were found to lie within the range of 0.99–1.63 g cm^?3, were found to be 5.19–36.33 MPa and 3.48–12.84 MPa, respectively.     

Microstructure and phase evolution of Indian magnesite‐derived MgAl2O4 as a function of stoichiometry and ZrO2 doping

To aid development of cost‐effective sintered spinel as a refractory raw material, this paper presents an extensive analysis of microstructure and complex phase evolution of Al‐rich, Mg‐rich, and stoichiometric spinel aggregates derived from Indian magnesite and calcined alumina. Pore morphology in Al‐rich spinel was transformed upon sintering at 1650°C and corundum laths embedded in porous Al‐rich spinel matrix was formed. Stoichiometric spinel sintered at 1600°C consisted of mostly direct bonded angular equiaxed spinel grains which incorporated the impurities in solid solution. Mg‐rich spinel was composed of spinel grains with reduced angularity along with intergranular amorphous phase, small round monticellite grains, and periclase. EDS line scan revealed impurity‐free joins existed between direct bonded spinel grains. Mg‐rich spinel containing 0.65 wt% ZrO₂ formed cubic ZrO₂‐CaO‐MgO solid solution located along spinel boundaries, which reduced both intergranular amorphous phase and monticellite. This increased SiO₂ and MgO content in spinel solid solution triggering exsolution of metastable cubic forsterite manifested as split spinel peaks in XRD pattern. A 14.7% reduction in slag penetration was exhibited upon doping Mg‐rich spinel with 0.21% ZrO₂. Stoichiometric and Mg‐rich spinels attained 0.35% and 0.54% apparent porosity at 1600°C, which is better than most commercial sintered refractory spinels.     

二氧化锆对低品位菱镁矿制备镁铝尖晶石材料组成结构的影响

以低品位菱镁矿与工业氧化铝为原料制备镁铝尖晶石材料,分析研究二氧化锆对以低品位菱镁矿为原料制备的镁铝尖晶石的组成、结晶度、晶胞参数和微观结构的影响,用XRD和SEM对烧后试样的相组成和显微结构进行研究。利用X’pert plus软件对试样中结晶相的相对结晶度进行计算,并对镁铝尖晶石相的晶胞参数进行分析。结果表明:适量引入二氧化锆有利于以低品位菱镁矿与工业氧化铝为原料制备镁铝尖晶石材料;材料中结晶相的结晶度随二氧化锆加入量的增加呈现出先增加后降低的现象;镁铝尖晶石材料中主晶相镁铝尖晶石的晶胞参数及晶胞体积受到锆离子的置换固溶作用的影响;当二氧化锆加入量为1.2%时,镁铝尖晶石的晶胞参数和晶胞体积最大,结构中镁铝尖晶石形成量最大,而玻璃相形成量最小。因此对于以低品位菱镁矿与工业氧化铝为原料制备的镁铝尖晶石材料,二氧化锆的最佳引入量为1.2%。     

Effect of the particle size distribution of spinel on the mechanical properties and thermal shock performance of MgO–spinel composites

The influence of varying the amounts of spinel with a similar median particle size, but with different distribution, on the mechanical properties and thermal shock performance of MgO–spinel composites was investigated. Mechanical properties of composites decreased significantly with increasing spinel content due to the thermal expansion mismatch. However, γ_WOF values of composites increased markedly, because of a significant change in the fracture mode from transgranular to intergranular fracture. A narrow distributed spinel A (Alcoa MR66) particles resulted in shorter initial crack propagation distances from the spinel particles, but spinel B (Britmag 67) particles with a significantly broader distribution were the origins of longer interlinked cracks. The improved resistance to thermal shock in MgO–spinel composites can therefore be attributed to the microcrack networks developed around the spinel particles, associated with the high values of γ_WOF, and not to an increased K_1c. On the basis of theoretically calculated R values and experimentally found γ_WOF/γ_i ratios, resistance to thermal shock damage would be more strongly favoured with materials containing spinel B particles, rather than spinel A, for which a much larger volume% was required to achieve a similar improvement.     

Reaction Between Nitrogen and Spinel in Chromium

The reaction between nitrogen dissolved in chromium and a dispersion of magnesium aluminate particles in chromium at high temperatures is discussed. The equilibrium state for various nitrogen concentrations in a 94 chromium-6 spinel mixture was investigated between 1200° and 1400°C. Experimental techniques included electron-beam microprobe analysis and mass spectrometry. Partitioning of nitrogen between chromium and spinel was strongly in favor of the spinel. Mass spectrometry indicated coordination of nitrogen with magnesium in the spinel lattice. The spinel-nitrogen reaction is important because it can prevent the embrittling of chromium by nitrogen.     

Synthesis and densification of magnesium aluminate spinel: effect of MgO reactivity

Stoichiometric magnesium aluminate spinel was synthesized by reaction sintering of alumina with caustic and sintered magnesia. The volume expansion of 5–7% during MgAl₂O₄ formation was utilized to identify the starting temperature of spinel formation and densification by high temperature dilatometry. The magnesia reactivity was determined by measurement of crystallite size and specific surface area. Caustic magnesia and sintered magnesia behave differently vis-à-vis phase formation and densification of spinel. Densification of stoichiometric Mag-Al spinel was carried out between 1650 and 1750 °C. Attempts were made to correlate the MgO reactivity with microstructure and densification of spinel.     

Thermal Analysis of Nucleation and Growth of Crystalline Phases in Vitrified Industrial Wastes

Devitrification behavior of vitrified industrial waste (electric arc furnace dust and foundry sand) was examined by differential thermal analysis (DTA), X-ray diffractometry, and scanning electron microscopy (SEM). Crystalline phases identified were primarily solid solutions of spinel and augite. The temperature of maximum nucleation rate for spinel was determined by DTA to be 635°C. Variations in the quench temperature resulted in changes of both grain size and volume fraction of an equixed spinel. The evolution of morphological changes upon heat treatment was examined by SEM. TiO₂ additions were ineffective as spinel nucleating agents, because additions of >5 wt% resulted in decreased spinel formation and the crystallization of titanium-iron and titanium-divalent-metal oxides. Controlling process and heat-treatment temperatures to optimize the amount of the spinel and to achieve a high-grade abrasive product also are discussed.