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.     

Transparent magnesium aluminate spinel: Effect of critical temperature in two-stage spark plasma sintering

The discolouration of magnesium aluminate spinel caused by carbon contamination is a main drawback of fabricating transparent bodies by spark plasma sintering (SPS). In this study, a two-stage heating rate profile was used to produce transparent MgAl₂O₄ without using sintering aids by SPS at 1250°C. The effect of critical temperature (Tc), at which the heating rate is decreased, on transparency and carbon contamination was investigated: higher critical temperature resulted in higher contamination. Non-uniform densification indicated that fast heating results in a hot-zone formation in the centre of sintered pellets; the higher temperature of centre favoured reaction of graphite die with spinel and formation of disordered carbon structures in residual pores.     

Aluminous cements containing magnesium aluminate spinel from Egyptian dolomite

Three mixes of calcium aluminate cements containing MA spinel were prepared using appropriate mixtures of Egyptian dolomite (MgO, 20.16% and CaO, 31.32%) with active alumina (99.50% A)¹. The cement mixes were prepared at 1600°C using the sintering method. The products were finely ground and their chemical and mineralogical compositions were investigated using the appropriate techniques. Also, their physicomechanical and refractory properties had been determined. The results indicated that their mineralogical compositions were refractory MA spinel, in addition to CA and/or CA₂ phases depending on the composition of the starting materials. The prepared cements exhibited a compromise between considerable strength and higher refractoriness. When 10% of such cements were added to refractory grade magnesia aggregate, in the presence of 0.1% Li₂CO₃ as a strength modifier, refractory castable bodies with improved hot-strength and thermal shock resistance had been achieved.     

Effect of segregation on particle size stability and SPS sintering of Li2O-Doped magnesium aluminate spinel

Magnesium aluminate spinel (MAS) was prepared using the simultaneous precipitation method by varying the concentration of Li₂O from 0 to 5 mol%. No residual chlorine from the LiCl precursor was detected in the final powders while Li achieved the target concentration in all samples and contributed to stabilizing nanoparticles smaller than 10 nm. Li segregation to both interfaces (surfaces and grain boundaries) occurred and tended to be more pronounced at the grain boundaries stabilizing this type of interface during processing rather than surfaces. Spark plasma sintering (SPS) was used to consolidate the nanopowders into fully dense nanostructured pellets. The increase in Li content facilitated the sintering process and pore elimination occurred at 850–900 °C, a much lower temperature range as compared to conventional sintering (1650 °C). Samples containing 5 mol% Li sintered at 850 °C exhibited a medium grain size of ?25 nm, microhardness of ?24 GPa and ?50% in-line optical transmission at the 800 nm.     

Effect of Eu2O3 on sintering densification and corrosion resistance of magnesium aluminate spinel

The effect of the doping amount of Eu₂O₃ on the densification behaviour of magnesium aluminate spinel (MAS) and its corrosion resistance to aluminium electrolyte were studied. The relative density, phase composition, micro morphology and hardness of the sintered samples were characterised by Archimedes’ drainage method, X-ray diffractometer, scanning electron microscope and automatic micro Vickers hardness tester. Results showed that the doping of Eu₂O₃ was conducive to the densification of MgAl₂O₄. When the content of Eu₂O₃ was 3 wt.%, the relative density of MAS was the largest (99.32%), the microstructure was more compact and the hardness was the largest (2293.4 kgf/mm²). The MAS sample with 3 wt.% Eu₂O₃ had the best corrosion resistance to aluminium electrolyte, and the corrosion depth was 80.99 μm. It was speculated that the electrolyte may penetrate into the sample through the micropores, and the fluoride salt chemically reacted with MgAl₂O₄ to form Al₂O₃, NaF and MgF₂.     

Direct measurement of interface energies of magnesium aluminate spinel and a brief sintering analysis

Surface and grain boundary energies are key parameters for understanding and controlling microstructural evolution. However, reliable thermodynamic data on interfaces of ceramics are relatively scarce, limiting the realization of their relevance in processes such as sintering and grain growth. In this work, the heat of sintering itself was used to quantify both surface and grain boundary energies in MgAl₂O₄ spinel. Nanoparticles were compacted and heated inside a Differential Scanning Calorimeter (DSC) when densification and grain growth were observed. The evolved heat signal was quantitatively attributed to the respective microstructural evolution in terms of interfacial area change, allowing determination of average surface and grain boundary energies for MgAl₂O₄ as 1.49 J m⁻² and 0.57 J m⁻², respectively. The data was then used to interpret the thermodynamics involved in density and grain growth during isothermal sintering of MgAl₂O₄.     

Sintering and grain growth behaviour of magnesium aluminate spinel: Effect of lithium hydroxide addition

Lithium hydroxide, LiOH, in the amounts ranging from 0.1 to 1.2 wt% has been used as a sintering aid to improve the densification of MgAl₂O₄. The addition of 0.3 wt% LiOH promotes densification and limits grain growth. The activation energy of sintering, calculated using master sintering curve approach, decreases from 790 ± 20 kJ.mol^?1 to 510 ± 20 kJ.mol^?1 with the addition of 0.3 wt% of LiOH. In addition, MgAl₂O₄ was also mixed with 10 wt% of LiOH to amplify the formation of reaction products. High-temperature XRD results showed that secondary phases (MgO and LiAlO₂) are produced above 1040 °C. The secondary phases start to disappear at T > 1200 °C, and MgAl₂O₄ is produced. While adding small amounts of LiOH, up to ca. 0.3 wt%, is beneficial for densification and suppressing grain growth, there exists a critical concentration of Li⁺ that is accounted for by the preferential incorporation of lithium ions into MgAl₂O₄ crystal lattice.     

Preparation of macrospherical magnesia-rich magnesium aluminate spinel catalysts for methanolysis of soybean oil

In order to fully exploit the green characteristics of solid base catalysts they should be fabricated into macrostructured rather than powder form. Magnesia-rich magnesium aluminate spinel (MgO·MgAl₂O₄) framework catalysts with tunable basicity have been prepared by using γ‐Al₂O₃ macrospheres (0.5-1.0 mm in diameter) as a hard template. The process involves in situ growth of magnesium-aluminum layered double hydroxides (MgAl-LDHs) in the channels of the γ‐Al₂O₃ macrospheres by the urea hydrolysis method, followed by calcination, tuning of the basicity through etching of excess aluminum with aqueous alkali and a final calcination step. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), elemental analysis and low temperature N₂ adsorption-desorption studies demonstrate that the composite MgO·MgAl₂O₄ materials are composed of nanosized rod-like particles aggregated into a spherical framework. Catalytic reactivity was investigated by using methanolysis of soybean oil as probe reaction. The MgO·MgAl₂O₄ composite shows a higher biodiesel yield compared to an MgO/MgAl₂O₄/γ‐Al₂O₃ material with the same loading of magnesium prepared by a conventional impregnation method. The enhanced catalytic activity of the former material can be ascribed to its higher basicity, specific surface area, pore volume and pore size.     

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.     

Effect of Yb2O3 and TiO2 on reaction sintering and properties of magnesium aluminate spinel

Magnesium aluminate spinel with an initial MgO: Al₂O₃ molar ratio of 2:1 was prepared from its constituent oxides through a solid-state sintering process at temperatures ranging from 1550 to 1700 °C in a normal air atmosphere. The effect of varying amount (0.25–1.0 wt%) of TiO₂ and Yb₂O₃ on densification, phase assemblage, mechanical, thermo-mechanical properties and microstructure of magnesia-rich spinel were investigated under static heating condition. The addition of TiO₂ and Yb₂O₃ favours the densification of magnesia-rich spinel, which is discernible up to 1650 °C. This beneficial effect may be attributed to the development of the secondary phase and formation of solid solution due to the dissolution of the additive ions in the spinel structure. A marginal increase in the average grain size of the samples along with a narrower grain size distribution occurred with the incorporation of both the additives. Both the additives improved the mechanical properties of the magnesia-rich spinel; however, better room temperature flexural strength was achieved with Yb₂O₃ as compared to TiO₂ addition. For the samples sintered at 1550 °C, 1.0 wt% Yb₂O₃ addition resulted in 30% increase in flexural strength; however, same amount of TiO₂ addition increased the strength by 20%. In case of thermal shock resistance, 1.0 wt% TiO₂ and 0.25 wt% Yb₂O₃ addition demonstrated promising result among all the samples.     

Molten salt synthesis and formation mechanism of magnesium aluminate spinel using different shape Al2O3 as the templets

In order to verify the “Al₂O₃-template-formation” mechanism of magnesium aluminate (MA) spinel proposed previously using Al₂O₃ and MgO micro-powders as raw materials, in this work, MA spinel was synthesized by nanograined, plate-like, and fibrous Al₂O₃ in LiCl molten salt at 1150 °C for 3 h, respectively. The products were characterized by XRD, SEM, TEM, and EDS techniques, and the grain size of the products and raw materials were analyzed. The results showed clearly that the MA spinel was initially nucleated and subsequently developed to octahedral crystal. When the reaction further took place, when using nanograined Al₂O₃, the newly formed MA spinel seeds initially moved and attached to the surface of the large octahedral MA spinel crystal, and they were subsequently engulfed by the large MA spinel crystal, which further grew via layer-by-layer to become micro-sized crystal. Using plate-like or fibrous Al₂O₃ raw material, MgO diffused continuously into the interior of Al₂O₃ to form MA spinel with a gradient growth from surface to depth. These revealed that whatever shape of Al₂O₃ was used, the synthesis of MA spinel was governed by “Al₂O₃-template formation mechanism”, i.e., by the reaction of MgO diffusion into the Al₂O₃ templet in the molten salt.     

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.     

煤熔渣对镁铝尖晶石质耐火材料的侵蚀机制

为了实现水煤浆气化炉炉衬材料的无铬化,研究开发合适的耐火材料代替水煤浆气化炉用高铬砖,以尖晶石骨料及细粉、α-Al_2O_3微粉和轻烧Mg O微粉为原料,于1 600℃保温5 h烧成,制备了φ50 mm×40 mm、内孔为φ25 mm×25 mm的镁铝尖晶石质坩埚试样。采用静态坩埚法,借助XRD、SEM+EDS研究了高温煤熔渣对试样的侵蚀行为。结果表明:1)侵蚀后的镁铝尖晶石材料结构疏松,出现较明显的裂纹,煤熔渣完全渗入试样内部。2)经煤熔渣侵蚀后的镁铝尖晶石材料,物相组成发生变化,除原有的镁铝尖晶石外,还有新物相镁铁铝复合尖晶石相存在。3)煤熔渣对镁铝尖晶石材料的侵蚀机制是物理渗透为主,化学熔蚀为辅。     

Effect of grain size on the static and dynamic mechanical properties of magnesium aluminate spinel (MgAl2O4)

Samples of transparent polycrystalline spinel with average grain size varying from 0.14 to 170 μm were prepared by different sintering approaches. The effect of grain size on the flexural strength, hardness and Hugoniot elastic limit (impact loading) was investigated. It was found that values of hardness divided by three for samples with grain size in the 0.14–15 μm range were almost equal to the dynamic yield strength values, estimated based on the Hugoniot elastic limit. This led to the assumption that the onset of inelastic deformation at the Hugoniot elastic limit was brittle rather than ductile. The observed departure of the dynamic yield strength from the hardness divided by three value for ceramics with grain size >15 μm was associated with either impact-induced shear banding or twinning. The feasibility of such banding/twinning intervention in initiating inelastic deformation in the spinel is supported by the values of apparent Hall-Petch coefficients in the corresponding grain size domains.     

低品位菱镁矿与工业铝灰制备镁铝尖晶石

以低品位菱镁矿与工业铝灰为原料制备镁铝尖晶石材料。分析讨论了不同煅烧温度对工业铝灰材料组成与微观结构的影响,并进一步研究了煅烧温度对制备镁铝尖晶石材料的组成、镁铝尖晶石相晶胞常数及材料微观结构的影响。用X射线衍射（XRD）和扫描电镜（SEM）对煅烧后试样的物相和显微结构进行研究。利用X′ pert plus软件对试样中主晶相的晶格常数进行计算,比较不同温度煅烧试样的相对结晶度。结果表明：随着工业铝灰煅烧温度的升高,材料中主晶相六方晶型的刚玉相晶胞常数呈现各向异性的变化趋势。低品位菱镁矿与工业铝灰经1 400 ℃高温煅烧可以制备出以镁铝尖晶石为主晶相的镁铝尖晶石材料,该温度煅烧的镁铝尖晶石材料晶粒相对均匀、结构相对致密,主晶相镁铝尖晶石相晶格常数最大。     

The effect of synthesis conditions on the physicochemical properties of magnesium aluminate materials

Magnesium aluminate-based materials were prepared by applying different methods: (i) mechanochemical milling of the initial mixture of magnesium and aluminium nitrate powders (in appropriate stoichiometric amounts) followed by heat treatment at temperatures of 650 °C and 850 °C and (ii) melting of the mixture of nitrate precursors at 240 °C followed by thermal treatment at 650 °C, 750 °C and 850 °C. The effect of synthesis method on the structure and morphology of the obtained solids was studied by using various techniques such as: nitrogen adsorption-desorption isotherms, powder XRD, IR spectroscopy and SEM. It was shown that the mechanochemical milling performed before calcination procedure leads to obtaining of nanocrystalline magnesium aluminate spinel phase at lower temperature of 650 °C in comparison with the method using thermal treatment only (at 750 °C). The obtained nanomaterials exhibit mesoporous structure.     

Kinetic analysis of magnesium aluminate spinel formation: Effect of MgO:Al2O3 ratio and titania dopant

The mechanistic pathway of MgO-Al₂O₃ reaction in solid state to form MgAl₂O₄ spinel was investigated to correlate the kinetic parameters with ratio of reactants (MgO:Al₂O₃) and with the presence of a doping agent, TiO₂. The time-temperature-expansion data of oxide compacts was analyzed using several model free analyses and model based (linear and non-linear) kinetic algorithms. These indicated that spinel formation process can be best described by single step with n-dimensional Avrami equation for every MgO:Al₂O₃ ratio, irrespective of titania dopant. The activation energy (E_a) of the process was proportional to % spinel formed in each system and validated with quantitative XRD analysis. The higher value of Avrami coefficient (n) in 90 wt% Al₂O₃ compositions has been explained with geometric considerations of powder packing. Incorporations of 1% TiO₂ in the MgO: Al₂O₃ oxide compact did not markedly affect the reaction model, frequency factor and Activation energy.     

Low-pressure injection molding of magnesium aluminate nanoparticles: Rheological behavior and flexural properties of sintered component

This research aims to investigate the density and flexural strength of nanostructured spinel parts fabricated using the low-pressure injection molding (LPIM) method. For this purpose, firstly, the effect of the amount of binder was tested on the rheology behavior of the feedstocks containing spinel nanopowder for producing ceramic parts using the LPIM method. The rheometric analysis indicated that the feedstocks containing 80 wt% powder and 20 wt% binders showed shear-thinning fluid behavior and were chosen as the optimal low-viscosity feedstocks for the LPIM process. After binder removal from LPIMed part, secondly, the effect of sintering temperature was examined on the relative density and flexural strength of the spinel parts. The results indicated that by increasing sintering temperature from 1550 °C to 1700 °C, the size of pores was reduced and grain size was increased from 2 μm to 6 μm. Furthermore, the flexural strength of the parts sintered at 1700 °C was 10 MPa greater than that of the sample sintered at 1650 °C.     

Low temperature synthesis of nanocrystalline magnesium aluminate spinel by a soft chemical method

A new simple soft chemical method – synthesizing nanocrystalline MgAl₂O₄ spinel powder with oxalic acid as organic template and nitric acid as an oxidizing agent – is described. The method was developed with the objective of obtaining phase pure nanocrystalline MgAl₂O₄ spinel powder with uniform particle size and morphology at a much lower temperature than that used by conventional methods. The synthesized powders were characterized by X-ray diffractometry (XRD), thermogravimetry (TGA), Fourier transform infrared spectroscopy (FTIR), surface area analysis (BET) and field emission scanning electron microscopy (FE-SEM). The average crystallite size of the single phase material was 30 nm. Through this method, porous MgAl₂O₄ powder with a high surface area of 162.2 m²g⁻¹ and 141 m²g⁻¹ was obtained at 600 °C and 700 °C, respectively.     

Microstructural evolution and relevant mechanical properties of Al-rich transparent magnesium aluminate ceramics

A novel phenomenon is found that the grain growth of aluminum-rich magnesium aluminate is suppressed to 5 μm, despite of high-temperature hot-isostatic-press at 1750 °C. For the transparent MgO-nAl₂O₃ (n = 1.2, 1.5, 2.0), the transmittance and strength tended to be enhanced with increasing Al₂O₃ content, having the highest values 80 % at 550 nm and 214.3 MPa for n = 2.0. This is due to the different microstructural evolution depending on the composition. When the excessive Al₂O₃ was small, the inhomogeneous microstructure with bimodal grain size and lots of rod-shaped particles were observed. However, as the Al₂O₃ amount increased, the microstructure became homogeneous with reducing the grain size and the rod-shaped particles. The microstructural and compositional analysis revealed that the rod-shaped particle were generated due to the trace potassium impurity as well as the different cationic diffusion rate, and the suppression of grain growth was induced by the severe Al segregation at the grain-boundaries.