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。     

工艺参数对镁铝尖晶石保温材料物相与性能的影响

以α-Al2O3微粉、电熔镁砂和ρ-Al2O3为原料,采用泡沫胶凝法制备了体积密度0.9～1.1 g/cm3镁铝尖晶石保温材料,考察了ρ-Al2O3、电熔镁砂加入量、烧成温度和保温时间对镁铝尖晶石保温材料物相与性能的影响.研究结果表明,随着ρ-Al2O3加入量增加试样常温耐压强度与烧成线变化率增大,物相组成均为“刚玉+镁铝尖晶石”;增加MgO加入量试样先收缩后膨胀,加入量为20wt％时常温耐压强度达最大值,物相组成由“刚玉+镁铝尖晶石”变为“镁铝尖晶石”再变为“镁铝尖晶石+方镁石”;提高烧成温度能明显促进试样烧结,延长保温时间可提高试样常温耐压强度.     

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     

基质组成对铝镁质浇注料性能的影响

研究了电熔刚玉、电熔镁砂、镁铝尖晶石等细粉的配比变化对铝镁质浇注料性能的影响。结果表明 ,基质中同时引入一定量的刚玉、镁砂及合成镁铝尖晶石 ,有利于提高浇注料的综合性能 ;当基质中MgO与Al2 O3之比处于尖晶石理论组成附近时 ,材料的综合性能表现较好 ;由镁砂和刚玉粉反应生成的原位尖晶石 ,比加入的预合成尖晶石对提高浇注料性能更能产生积极的影响 ,但原位尖晶石的生成量过大时会导致材料的综合性能下降。     

MgO—Al2O3系浇注料的设计

以相关知识和实践经验为依据，探讨了ＭｇＯ－Ａｌ２Ｏ３系中铝镁质（含刚玉－尖晶石质和矾土熟料－尖晶石质）浇注料的基质料的设计和结合剂的合理选择问题。     

利用无害化铝灰合成耐火原料研究

以无害化铝灰为主要原料,通过与轻烧镁砂混合,在1 650℃下高温反应合成镁铝尖晶石。与滑石和硅石粉混合,在1 380℃下高温反应合成堇青石。借助X射线衍射仪及扫描电子显微镜研究了其物相组成和显微结构,并将合成的尖晶石用于制备刚玉尖晶石浇注料,研究了其抗渣性。研究结果表明,无害化铝灰可以制得纯净的镁铝尖晶石和堇青石。铝灰基镁铝尖晶石致密性高,其体积密度为3.07 kg/L,气孔率为1%,将其应用在刚玉-尖晶石浇注料中,表现出优异的抗渣侵蚀和渗透能力,其原因与铝灰基尖晶石的高活性有关。合成的铝灰基堇青石的体积密度为1.97 kg/L,气孔率为19%,其致密性优于滑石-黏土-氧化铝系堇青石。     

精炼铝炉用刚玉-镁铝尖晶石复合材料的制备与性能

用白刚玉、镁铝尖晶石、电熔镁砂和α-Al2O3微粉,在1 650 ℃烧结3h制备了刚玉-镁铝尖晶石复合材料.按照GBT29971982致密定形耐火制品气孔率和体积密度试验方法和静态坩埚法,并结合X射线衍射、扫描电镜和能谱分析研究了不同组成刚玉-镁铝尖晶石复合材料的常温物理性能、显微结构以及将其应用于精炼铝熔融炉用耐火材料时对高纯度铝的影响.结果表明:在1 650 ℃保温3 h的条件下,试样烧结致密,基质中有镁铝尖晶石生成;所制备的试样中,当α-Al2O3微粉与电熔镁砂的质量比为2∶1时,试样具有较好的室温物理性能,并且对高品质铝液的污染很小.     

镁质耐火材料的最新发展

本文介绍了国外镁质耐火材料,如镁碳砖、镁钙砖、镁钙碳砖、镁锆砖、镁铝尖晶石砖、镁铬砖、镁质涂料和镁碳质、镁铝质、镁锆质浇注料的生产、性能及其使用效果。     

用废弃含碳耐火材料合成方镁石-镁铝尖晶石复相材料

以废弃镁碳砖与废弃滑板为原料,分别按照n(MgO)/n(Al2O3)=1,2,3,4比例进行制样,通过1300℃、1400℃、1500℃保温2h对试样进行煅烧.用X射线衍射仪、扫描电镜及X' Pert plus软件对热处理后试样的组成和结构进行表征.结果发现:以废弃镁碳砖与废弃滑板可以合成出方镁石-尖晶石复相材料,随着废弃镁碳砖引入量增加;试样体积密度降低,显气孔率增加,结构组成中方镁石逐渐增加.煅烧温度的增加促进方镁石与刚玉相形成镁铝尖晶石相.当n(MgO)/n(Al2O3)=3,煅烧温度1500℃时,经煅烧后形成方镁石-尖晶石复相结构中结晶相方镁石含量达到33％,镁铝尖晶石59％,方镁石-尖晶石相间由结晶度较差的玻璃相粘结.     

固溶反应对MA-Al2O3材料结构和性能的影响

以电熔镁铝尖晶石为主要原料并加入少量烧结刚玉细粉部分替代尖晶石细粉,或以白刚玉为主要原料并加入少量电熔镁铝尖晶石细粉替代白刚玉细粉,制备了两组MA-Al₂O₃材料。研究刚玉与镁铝尖晶石之间的固溶反应对材料性能及显微结构的影响。结果表明：1)在两组材料中均发生了固溶反应,使得镁铝尖晶石的富铝程度增大,镁铝尖晶石中的氧化铝含量(w)由约76%增加到80%以上,从而加强了试样骨料与基质的结合,减少结构缺陷,改善了材料的高温性能;2)在以镁铝尖晶石为主要原料的MA-Al₂O₃材料中,加入烧结刚玉可使其常温耐压强度增大,改善其高温抗蠕变性和抗热震性;3)在以白刚玉为主要原料的MA-Al₂O₃材料中,加入镁铝尖晶石细粉,其常温耐压强度、高温抗蠕变性和高温抗折强度均有大幅度提高。     

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。     

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.     

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。     

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.     

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.     

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.     

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.     

Evaluation of fracture behavior of lightweight magnesia-based refractories via wedge splitting test along with acoustic emission detection

The effect of spinel powder on the fracture behavior and mechanical properties of lightweight magnesia-based refractories containing microporous magnesia aggregates with high apparent porosity (37.4%) were investigated by the wedge splitting test (WST) with the digital image correlation and acoustic emission. With the addition of spinel powder, lightweight magnesia spinel refractories showed a higher cold compressive strength compared with lightweight pure magnesia refractories. From the WST, the addition of spinel powder increased the specific fracture energy and characteristic length of lightweight magnesia spinel refractories, which improved the crack propagation resistance. The increased tortuosity of main crack and a higher ratio of crack propagation along the aggregates/matrix interface were main reasons for reducing the brittleness of lightweight magnesia spinel refractories. Besides, acoustic emission (AE) signal activity indicated that the propagation of pregenerated micro-cracks by the thermal mismatch and the development of fracture progress zone were primary ways to consume energy in lightweight magnesia spinel refractories. The reduced proportion of crack propagation within aggregates was also detected by the peak frequency of AE signals in lightweight magnesia spinel refractories. For microporous magnesia aggregates with high apparent porosity (37.4%), lightweight magnesia spinel refractories also showed reduced brittleness fracture behavior than lightweight pure magnesia refractories.     

Microstructural effects on the sliding wear of transparent magnesium-aluminate spinel

Grain size effects have been investigated in the lubricated sliding wear of three transparent magnesium aluminate (MgAl₂O₄) spinel materials with different grains sizes identified as: Nano, Fine, and Coarse. Only Fine spinel shows classical wear behavior, which is characterized by initial mild wear followed by a sharp transition to severe fracture-controlled wear. Worn surfaces of Fine spinel show extensive grain pullout, consistent with intergranular mode of fracture found in that spinel. Nano and Coarse spinels both show gradual transition from mild wear to severe wear, and both have significantly lower overall wear rates compared to Fine spinel. Worn surfaces in both Nano and Coarse spinels show transgranular fracture and material removal, which is reminiscent of lateral-crack induced chipping. The transgranular fracture mode in Nano spinel can be attributed to stronger grain boundaries in that spinel, which could be due to the Y₂O₃ sintering additive used for grain refinement. Whilst the large scale of the grains in Coarse spinel could be responsible for the transgranular fracture observed in that spinel.     

冷却方式对尖晶石型红外辐射陶瓷结晶的影响

在红外陶瓷制备过程中,不同的冷却方式对红外陶瓷的结晶有一定的影响,进而影响到陶瓷的红外辐射率。采用XRD法研究了Fe、Mn、Co、Cu、Ni尖晶石型红外辐射陶瓷在制备过程中的冷却方式对尖晶石结晶的影响。含锰的尖晶石根据含锰量的高低可采用水中淬冷或在空气中急冷的方式,不能采用自然冷却的方式;高锰含量的配方必须采用水中淬冷的冷却方式;锰含量较低时,可采用空气中急冷的方式。为保证尖晶石晶体的结晶良好,镍尖晶石用在空气中冷却的方式最好。本实验采用的3种冷却方式对钴尖晶石都不太适用,使降温速率比自然冷却稍快些,但比空气中急冷稍慢些,可望有更好的效果。铜尖晶石可采用空气中急冷的方式,既能保证尖晶石的充分结晶,又能使反型铜尖晶石结构变为混合型结构,有利于红外辐射率的提高。