Effects of different additives on properties of magnesium aluminate Spinel–Periclase castable

Bauxite- and alumina-based spinels were employed as refractory aggregates, and sintered magnesia fine powder, calcium aluminate cement, microsilica, and activated α-Al₂O₃ were utilized as matrices. The effects of alumina powder, analytically pure zinc oxide, and analytically pure zirconia on the properties of magnesium aluminate spinel–periclase castables were studied. The results demonstrated that the addition of the three additives promoted the sintering of magnesium aluminate spinel–periclase castables. Simultaneously, the three additives significantly improved the high-temperature properties of the samples. The thermal shock resistance of the alumina powder sample increased by 200%, that of the pristine zinc oxide sample by 75%, and that of the zirconia sample by 125%. The additives effectively improved the thermal shock resistance of the magnesium aluminate spinel–periclase castable. In addition, the slag resistance depths of the samples with alumina powder and zirconia were 41% lower than that of the sample without additives, which significantly improved the slag resistance of the magnesium aluminate spinel–periclase castable.     

Enhancement of reaction-sintering of alumina-excess magnesium aluminate spinel in presence of titania

Alumina-excess magnesium aluminate spinel finds use in different high temperature applications including steel ladles. Alumina-excess spinel was prepared by solid oxide reaction using magnesia (MgO=10?wt%) and calcined alumina (Al₂O₃ = 90?wt%), in the sintering temperature range of 1500–1700?°C. The role of titania on the densification, spinelisation, evolution of microstructure and phase assemblage was investigated in this MgO-Al₂O₃ system. Titania addition increased the rate of densification 20x compared to undoped composition at 1500?°C under dynamic heating condition. However, under static firing, the beneficial effect of titania on densification could only be discerned at lower temperatures. The microstructure of titania doped sintered alumina-excess spinel compacts contain magnesium aluminium titanate phase in the grain boundary of corundum and spinel grains. The beneficial effect of titania on densification is attributed to magnesium aluminium titanate phase (Mg_xAl_2(1-x)Ti_(1+x)O₅) development and also by incorporation of Ti⁴⁺ into the spinel structure.     

Mechanism of in-situ formation of spinel and its effect on the mechanical properties of Al2O3–C refractories

This work looked at the in-situ formation mechanism of magnesia alumina spinel in Al₂O₃–C refractories with magnesia addition at different firing temperatures. A comprehensive study on the mechanical properties of Al₂O₃–C refractories was performed in comparison to traditional analogs. The magnesia alumina spinel was in-situ formed at the firing temperature of 1150 °C in Al₂O₃–C refractories. With the increase of the firing temperature, the Al₂O₃ phase was gradually dissolved in spinel phase to form aluminum rich spinel phase, resulting in a decrease in its lattice constant due to the defects formation. The formed spinel phase was homogenously distributed and bonded well with corundum, improving the interfacial bond, load transferring capacity and crack propagation resistance. The formation of spinel phase also enhanced the sintering of the alumina matrix owing to the solid solution of alumina in the spinel. Therefore, the mechanical properties such as cold modulus of rupture and hot modulus of rupture in Al₂O₃–C refractories achieved a substantial enhancement compared with traditional refractories.     

Densification and properties of magnesia-rich magnesium-aluminate spinel derived from natural and synthetic raw materials

Magnesia rich magnesium aluminate spinel (MgO: Al₂O₃=2:1) was developed by reaction sintering of Indian natural magnesite of Salem region as well as from synthetic caustic magnesia with calcined alumina. Dilatometric study of the green compacts was carried out to evaluate the spinelisation and sintering behaviour of both the samples. Green samples were heat treated between 1400 to 1600 °C and characterised in terms of densification behaviour, high temperature flexural strength, microstructure and phase development. Spinel and periclase are the major phases in both the samples, where as forsterite is found only in the sample developed from Indian magnesite due to presence of silica as impurities.     

TiO2加入量对固相烧结合成镁铝尖晶石致密化行为的影响

以低品位菱镁矿和工业α氧化铝微粉为主要原料固相烧结合成镁铝尖晶石,探讨TiO2添加剂对合成镁铝尖晶石致密化行为的影响.用X射线衍射(XRD),扫描电镜(SEM)及相关分析软件对烧后试样的相组成和显微结构进行研究,以揭示镁铝尖晶石烧结致密化的过程机理.研究结果表明:添加剂TiO2与形成镁铝尖晶石的置换固溶作用是促进固相合成镁铝尖晶石烧结致密化的重要机理,阳离子空位的产生以及镁铝尖晶石的晶格缺陷,高温下有利于镁铝尖晶石的晶体发育和长大,在空间位阻效应的作用下,达到排除气孔使试样致密化的目的;随着TiO2加入量的增多,镁铝尖晶石的致密化程度也逐渐升高,能够有效的改善制品的烧结性能和显微结构.     

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.     

Effects of different particle size of spinel and Y2O3 additive of the periclase-spinel refractory on the sintering densification and corrosion resistance to copper smelting slag

In order to analyze the sintering densification and copper smelting slag corrosion resistance of periclase-spinel refractories, the periclase-spinel refractories were prepared with fused magnesia, magnesia-rich spinel, industrial alumina, and yttrium oxide as the main raw materials. The different particle sizes of spinel in material and with or without Y₂O₃ additive were studied. The study demonstrated that: (1) The different particle sizes of spinel in periclase-spinel refractories can result in different effects. Adding particle spinel to the refractory can improve the strength and corrosion resistance of the periclase-spinel refractories. The addition of spinel and magnesia powders in the matrix resulted in cracks due to the great difference of coefficient of thermal expansion between magnesia and spinel. The reduction in bulk density and strength of the material decreased slag penetration resistance because of its poor sintering properties. While adding the alumina in the matrix can further fill the crack and prevent slag penetration by the volume expansion of in-situ reaction to form spinel. (2) The periclase-spinel refractories can be reacted with Cu slag to form a Mg₂FeO₄ insulating layer as the iron ion becomes oxidized. Adding Y₂O₃ in periclase-spinel refractories can result in grain boundary phase reconstruction, which can promote sintering densification, improve the slag physical infiltration resistance, and improve the chemical corrosion resistance of materials.     

Sintering of magnesium hydroxide obtained from magnesium chloride solutions

Conclusions We studied two batches of magnesium hydroxide obtained by precipitating out (using dolomite milk) from magnesium chloride solution formed when processing potassium ores.The effect of the compaction pressure, the firing temperature, and prior heat treatment on the sintering process of magnesium hydroxide was investigated.The experimental samples of magnesium hydroxide exhibit high sinterability and facilitate the production of periclase powders (powder bodies) having a porosity of 6.8–9.9% at a firing temperature of 1600°C. The degree of sintering of magnesium hydroxide increases with increasing compaction pressure and firing temperature. Prior heat treatment of the material at 800–1000°C intensifies the sintering process with simultaneous reduction of shrinkage.The studies conducted on the specimens prepared from a fired briquette established that the periclase (magnesite) powder obtained from magnesium hydroxide is suitable for the production of magnesia refractories.A. V. Kushchenko and G. G. Eliseeva (UkrNIIO) participated in this investigation.Translated from Ogneupory, No. 2, pp. 7–10, February, 1988.     

Role of different rare earth oxides on the reaction sintering of magnesium aluminate spinel

Role of three rare earth oxides, viz., La₂O₃, CeO₂ and Yb₂O₃ on reaction sintering of magnesium aluminate spinel having molar ratio of MgO:Al₂O₃?=?1:2 from its solid oxide precursors was investigated in static and dynamic heating conditions. Effect of these additives (3?wt%) on densification behavior, phase assemblage and microstructure development were studied in the temperatures of 1500–1700?°C. Yb₂O₃ enhanced the sintering of spinel, while La₂O₃ and CeO₂ negatively impacted the sintering of magnesium aluminate spinel which can be discerned from the shrinkage curve of TMA as well as from static firing regime. This is ascribed to the formation of secondary phases in La₂O₃ and CeO₂ containing samples which have different crystalline structures to that of spinel. This anisotropy due to different crystallinity hindered the pore shrinkage and pore removal and thereby retarded the densification. Whereas, the cubic structure of the secondary phase formed in Yb₂O₃ containing sample which is isotropic with the crystalline orientation of the parental spinel phase assisted the densification.     

The effects of in situ formation of Y3Al5O12 on property improvement of magnesium aluminate spinel refractories

Magnesium aluminate spinel is widely used in cement rotary kilns, in the iron and steel industries, as well as in glass melting furnaces due to its excellent performance and chemical stability at both room temperature and elevated temperatures. In spite of these advantages, there are some practical problems during production of magnesium aluminate spinel refractories due to their poor sinterability: poor mechanical properties and poor creep resistance. These issues can cause problems during service. This study improved the sinterability of spinel refractories and in turn improved mechanical properties while decreasing the creep rate. This was done by forming a second low creep rate phase of yttrium aluminum garnet in the matrix structure. The addition of Y₂O₃ and reactive Al₂O₃ accelerated the densification process and increased the cold strength. There was a significant increase in the hot modulus of rupture due to the formation of YAG or the solid solution with spinel.     

不同添加剂对镁质浇注料性能的影响

以电熔镁砂和高纯镁砂为主要原料制备了镁质浇注料,研究了不同添加剂对镁质浇注料性能的影响。研究结果表明,5种添加剂中,加入氧化铝微粉的镁质浇注料经1 100℃和1 500℃烧后的体积密度最大,浇注料基质中形成的方镁石/镁铝尖晶石复相结构有利于提高试样的抗热震性。加入氧化铬、铝铬渣和焦宝石的镁质浇注料,其抗热震性均高于未加入添加剂的镁质浇注料的该项性能。     

Formation and Densification Behavior of MgAl2O4 Spinel: The Influence of Processing Parameters

Different types of dense stoichiometric and nonstoichiometric magnesium aluminate (MgAl₂O₄) spinel (MAS) ceramics were prepared following a conventional double-stage firing process using different commercially available alumina and magnesia raw materials. Stoichiometric, magnesia-rich, and alumina-rich spinels were sintered at 1500°–1800°C for 1–2.5 h. The influence of the different processing parameters (average particle size, degree of spinel phase, green density, mass of the powder compact, sintering temperature, holding time at the peak temperature, and starting composition) on the densification behavior of MAS was assessed by measuring the bulk density, apparent porosity, and water absorption capacity, and microstructural observations. Most of the MAS compositions tested exhibited excellent sintering properties.     

Fabrication of periclase and magnesium aluminate spinel refractory from washed residue of secondary aluminum dross

A novel method for fabricating the periclase and magnesium aluminate spinel refractory from the secondary aluminum dross was proposed in the present work by adding magnesium oxide. The fabrication mechanism of the refractory was analyzed by thermogravimetric and differential thermal analysis, scanning electron microscopy, and X-ray Diffraction. The effects of MgO addition and sintering temperature on the mechanical properties and density of refractories were studied. The results showed that with the increase of sintering temperature, the purity, crystallinity, and densification of the refractory were significantly improved, and the porosity of the refractory was decreased. As an obvious second phase in the refractory, periclase can strengthen the grain–grain bonding and inhibit the grain boundary movement. With the increase of MgO addition, due to the significant reduction of porosity, the improvement of grain size uniformity and the absence of microcracks, the flexural strength and the impact toughness were significantly improved. When the MgO addition was 50 wt% at the sintering temperature of 1600 °C, the density and porosity of the refractory were 2.92 g/cm³ and 18.2%, while the flexural strength and impact toughness can reach 270 MPa and 3.7 MPa m^1/2, respectively.     

La2O3对镁铝尖晶石透明陶瓷致密化及其性能的影响

镁铝尖晶石透明陶瓷兼具了良好的光学和力学性能,在军、民两用领域有着广泛的实际和潜在应用前景。由于其致密化速率低,在烧结过程中往往需要引入烧结助剂。稀土倍半氧化物熔点高,高温不易挥发,近些年被证实可以促进镁铝尖晶石陶瓷的致密化,但其促烧机理尚不明确。本文以高纯商业化镁铝尖晶石粉体为原料,La₂O₃为烧结助剂,采用无压预烧结合热等静压烧结,制备镁铝尖晶石透明陶瓷,通过XRD、SEM、紫外-可见分光光度计、万能试验机等测试手段对其致密化过程及其力学和光学性能进行表征和分析,研究了La₂O₃对镁铝尖晶石透明陶瓷致密化过程的影响规律和作用机制。结果表明,La₂O₃通过与尖晶石反应或固溶产生晶格畸变,增加缺陷浓度,从而起到促进致密化的作用,一定程度上降低了预烧温度和热等静压温度。对于190 MPa、1 500 ℃热等静压烧结3 h的样品,La₂O₃掺杂可以显著提高紫外区域的透过率;同时,La偏析到晶粒表面,抑制了尖晶石晶粒的生长,从而提高了样品的力学强度。掺杂0.05%(质量分数)La₂O₃样品较未掺的样品,400 nm处透过率从63%提高到81%,弯曲强度从263.7 MPa提高至319.0 MPa,断裂韧性从1.69 MPa·m^1/2提高至1.82 MPa·m^1/2。     

Room temperature mechanical properties of high alumina refractory castables with spinel, periclase and dolomite additions

The mechanical properties of refractory castables at room temperature are critical parameters for selecting suitable operating conditions for the structural design of refractory components. In this work, high alumina refractory castables based on the alumina-rich zone of the Al₂O₃–MgO–CaO ternary phase equilibrium diagram were prepared by adding synthetic spinel, periclase and dolomite via three processing routes. Bending strength studies at room temperature under several thermal treatments and the analysis of the elastic modulus of the refractories and their matrices point to two different mechanical behaviours. From room temperature to 1000 °C the refractory castables present a pronounced non-linear stress–strain behaviour both in the uniaxial tensile and compressive modes, as a result of damage to the microcrack network. Above 1000 °C the refractory castables begin to sinter owing to a transitory liquid phase, the crystallization of calcium aluminate cement phases (such as CA₂ and CA₆, for example) and the self-forming spinel phase (refractory castables with periclase or dolomite additions). At higher firing temperatures the sintering process leads a strengthening of the mechanical properties.     

Promoting spinel formation and growth for preparation of refractory materials from ferronickel slag

The study provides a method for improving the quality of the refractory material prepared from ferronickel slag by promoting the spinel formation and growth in the slag which was sintered with sintered magnesia and chromium oxide in a broad sintering temperature range from 1200°C to 1500°C. According to the thermodynamic analysis, except for forsterite due to the addition of sintered magnesia, a number of high-melting point spinel phases can also be formed in the presence of chromium oxide and this trend becomes more apparent with increasing sintering temperature, along with declined presence of low-melting point clinopyroxene, mainly enstatite. This expectation was verified by conversion of a part of the original phase of ferronickel slag, olivine, to two main spinel phases, including magnesium aluminate spinel and donathite which was produced by the replacement of nontoxic Cr³⁺ ions with Fe³⁺ ions in the octahedral vacancies of magnesium chromate spinel. The formation and growth of these spinel phases were promoted by elevating temperature from 1200°C to 1500°C, which accelerated the transition of initially generated enstatite to a glassy phase, in favor of densification. The formation and growth of spinel during sintering contributed to high refractoriness and compressive strength of the resulting refractory materials     

高纯镁砂及氧化镁陶瓷研究进展

高纯镁砂是重要的耐高温材料,氧化镁陶瓷则广泛应用于透光材料领域,对两种材料的生产工艺开展研究具有重要理论和实际意义。本文系统地综述了利用菱镁矿、卤水生产高纯氧化镁及镁砂的各种技术,以及氧化镁陶瓷的烧结方法和烧结助剂对烧结过程的影响;介绍了菱镁矿制备高纯镁砂,卤水沉淀法、卤水直接热解法制备高纯氧化镁,以及电熔法制备高纯镁砂等技术。指出了每种生产技术的优缺点及今后的研究与发展方向。介绍了常压烧结、热压烧结、热等静压烧结、放电等离子烧结、微波烧结和真空烧结等氧化镁陶瓷烧结技术及其进展,总结了烧结助剂对烧结过程的影响及其机理,指出氧化镁陶瓷未来的研究关键主要在于对粉体合成技术、致密化烧结技术及烧结助剂的研究。     

添加剂和烧成温度对钛酸铝的合成与烧结性能的影响

研究了添加剂MgO和SiO2 以及烧成温度对钛酸铝的合成及烧结性能的影响。结果表明 ,烧成温度的升高促进了钛酸铝的合成与烧结 ;MgO的引入极大地促进了钛酸铝的合成 ,而对于SiO2 来说 ,这种促进作用在高温下才明显 ;MgO和SiO2 在钛酸铝中均有一定的固溶度 ,超过此固溶极限将有新相 (尖晶石或莫来石 )产生 ,从而导致烧结性能随MgO和SiO2 添加量的变化呈现复杂的变化规律     

Crystallization of sublimation products in periclase refractories in high-temperature processes

Conclusions During the melting, firing, and service of magnesia refractories crystallization occurs in the sublimation products in the form of thin-walled tubes, fine films, dendrites, needles and threads of periclase, periclase-forsterite, and spinel compositions. The presence of carbon in these newly formed compounds indicates development mainly in a reducing atmosphere.Translated from Ogneupory, No. 5, pp. 39–42, May, 1982.     

Effect of composition,quantity, and synthesis temperature of spinels,and some properties of periclase — Spinel compositions

Conclusions The incorporation of spinel (5–10%) into the composition of the solid solution leads to periclase grain growth and to its sintering. Excess spinel in combinations with periclase over this quantity prevents recrystallization sintering of the specimens.A reduction in the synthesis temperature of most the spinels from 1750 to 1450°C contributes the sintering of the compositions under investigation, and improves their technical properties.In the periclase—spinel compositions the maximum influence on the grain growth and the properties of the specimens is exerted by the temperature conditions used for synthesizing the high-alumina spinels, while the conditions used to obtain the highly chromic spinels, and especially the magnesiochromite, have little or no effect on the technical properties of the fired product.With an increase in the spinel phase concentration from 5 to 30%, and also when there is a change in its composition in the direction from magnesia-alumina spinel to magnesiochromite, such factors as strength, porosity, and spalling are impaired.In the MgO-Mg(Al_1–X, Cr_X)₂O₄ system it is possible to obtain strong, dense, and simultaneously spalling-resistant refractories by using small additions of alumina spinel, synthesized at low temperatures ensuring the completion of the spinel-forming reaction.Translated from Ogneupory, No. 3, pp. 53–57, March, 1971.