Formation of hollow MgO-rich spinel whiskers in low carbon MgO–C refractories with Al additives

MgO–C refractories with different carbon contents have been developed to meet the requirement of steel-making technologies. Actually, the carbon content in the refractories will affect their microstructure. In the present work, the phase compositions and microstructure of low carbon MgO–C refractories (1 wt% graphite) were investigated in comparison with those of 10 wt% and 20 wt% graphite, respectively. The results showed that Al₄C₃ whiskers and MgAl₂O₄ particles formed for all the specimens fired at 1000 °C. With the temperature up to 1400 °C, more MgAl₂O₄ particles were detected in the matrix and AlN whiskers occurred locally for high carbon MgO–C specimens (10 wt% and 20 wt% graphite). However, the hollow MgO-rich spinel whiskers began to form locally at 1200 °C and grew dramatically at 1400 °C in low carbon MgO–C refractories, whose growth mechanism was dominated by the capillary transportation from liquid Al at these temperatures.     

Effect of MgAl2O4 nanoparticles addition on the densification and properties of MgO-CaO refractories

MgAl₂O₄nanoparticles were added to MgO–CaO refractory ceramic composites in the range of 0–8 wt%. Refractory specimens were obtained by sintering at 1650 °C for 3 h in an electric furnace. Refractory specimens were characterized by measurements of bulk density, apparent porosity, hydration resistance, cold crushing strength, crystalline phase formation, and microstructural analysis. Results show that with additions of MgAl₂O₄ nanoparticles the bulk density of the samples increased. But the apparent porosity and cold crushing strength decreased and increased, respectively with addition MgAl₂O₄ nanoparticles up to 6 wt% and for further MgAl₂O₄ nanoparticles, due to the thermal expansion mismatch, the results is reversed. Also, the hydration resistance of the samples was appreciably improved by the addition of MgAl₂O₄ nanoparticles due to its effect on decreasing the amount of free CaO in the refractory composite and promotion of densification by creating a dense microstructure.     

Synthesis and characterization of a MgO-MgAl2O4-ZrO2 composite with a continuous network microstructure

Using analytically pure MgO, analytically pure Al₂O₃ and analytically pure ZrO₂ as raw materials, Mg_4.68Al_2.64Zr_1.68O₁₂ was prepared at 1993 K for 10 h, and then, a MgO-MgAl₂O₄-ZrO₂ composite with a continuous network was successfully obtained by controlling the cooling rate based on the in-situ decomposition reaction of Mg_4.68Al_2.64Zr_1.68O₁₂ at temperatures below 1887 K. The three phases of MgO, MgAl₂O₄ and ZrO₂ are highly dispersed in this continuous network microstructure, with ZrO₂ intertwined by MgO and MgAl₂O₄ and micropores with a size of less than 2 µm. Furthermore, the synthesis mechanism of Mg_4.68Al_2.64Zr_1.68O₁₂ is given as follows: first, MgAl₂O₄ is synthesized using the reaction: MgO(s)+Al₂O₃(s)=MgAl₂O₄(s) at temperatures below 1894 K; and then, Mg_4.68Al_2.64Zr_1.68O₁₂ is further prepared through MgO and ZrO₂ diffusion and dissolution into MgAl₂O₄ at temperatures above 1894 K, for example, at 1923 K or 1993 K in this work.     

Effects of LiF on the microstructure and optical properties of hot-pressed MgAl2O4 ceramics

Transparent magnesium aluminate spinel (MgAl₂O₄) ceramics were fabricated by hot-pressing of the MgO and α-Al₂O₃ powder mixture using LiF as a sintering aid. Effects of the LiF additive on densification, microstructure and optical properties of MgAl₂O₄ ceramics were systematically investigated. It has been found that the addition of LiF can effectively remove the porosity and increase the optical transparency of MgAl₂O₄ ceramics. For the spinel ceramics HP-ed at 1550 °C for 3 h with 1 wt% LiF addition, the average grain size is about 36 µm and the in-line transmittance exceeds 60% at the wavelength of 800 nm.     

Growth of MgAl2O4/MgO eutectic crystals by the micro-pulling-down method and its characterization

MgAl₂O₄/MgO eutectic fibers and rods have been grown successfully by the micro-pulling-down method, and the microstructures and optical characterizations of grown crystals were performed. MgAl₂O₄/MgO eutectic fibers of 0.3–1 mm in diameter and about 500 mm in length, and the rods having 5 mm in diameter with approximately 60 mm in length have been grown with the 6–120 mm/h of growth speed. The eutectic fibers showed homogeneous microstructure in which MgO fiber/whisker aligned to the growth direction in the MgAl₂O₄ (spinel) matrix. The grown crystals looked semitransparence under naked eyes. Optical and orientational characterizations were performed. The second phase of MgO was easily removed by selective etching with hydrochloric acid, and then porous single crystalline bodies were obtained.     

Poly(N-isopropylacrylamide) assisted microwave synthesis of magnesium aluminate spinel oxide for production of highly transparent films by hot compression

Magnesium aluminate spinel oxides have been prepared via poly(N-isopropylacrylamide) assisted microwave technique. The prepared MgAl₂O₄ powders showed a crystalline cubic structure with spinel phase after calcination at 600 °C only. The poly(N-isopropylacrylamide) amount showed a high effect on the crystallite size and the densification behavior of MgAl₂O₄. The increase of the amount of poly(N-isopropylacrylamide) reduced the sintering temperature of MgAl₂O₄ from 1400 °C to 1050 °C. The hot-pressed of MgAl₂O₄ powders in the presence of 3 wt% of poly(N-isopropylacrylamide) exhibited a full density at sintering temperature 1100 °C in 15 min only. The sintered films showed high transparency (81 ± 2%) in the wavelength range 500–1000 nm.     

Microstructure of the directionally solidified ternary eutectic ceramic Al2O3/MgAl2O4/ZrO2

The directionally solidified Al₂O₃/MgAl₂O₄/ZrO₂ ternary eutectic ceramic was prepared via induction heating zone melting. Smooth Al₂O₃/MgAl₂O₄/ZrO₂ eutectic ceramic rods with diameters of 10 mm were successfully obtained. The results demonstrate that the eutectic rods consist of Al₂O₃, MgAl₂O₄ and ZrO₂ phases. In the eutectic microstructure, the MgAl₂O₄ and Al₂O₃ phases form the matrix, the ZrO₂ phase with a fibre or shuttle shape is embedded in the matrix, and a quasi-regular eutectic microstructure formed, presenting a typical in situ composite pattern. During the eutectic growth, the ZrO₂ phase grew on non-faceted phases ahead of the matrix growing on the faceted phase. The hardness and fracture toughness of the eutectic ceramics reached 12 GPa and 6.1 MPa·m ^1/2, respectively, i.e., two times and 1.7 times the values of the pre-sintered ceramic, respectively. In addition, the ZrO₂ phase in the matrix reinforced the matrix, acting as crystal whiskers to reinforce the sintered ceramic.     

Highest UV–vis transparency of MgAl2O4 spinel ceramics prepared by hot pressing with LiF

Reaction sintering of MgO and Al₂O₃ with addition of LiF as sintering additive was used to prepare MgAl₂O₄ spinel ceramic by hot pressing. The process parameter (temperature, pressure, dwell time), the stoichiometric ratio of MgO to Al₂O₃ and the selection of the alumina raw powder are equally important for highest transparency of the spinel ceramic. With this optimization highest transparency of 86% in the visible range at λ = 640 nm together with UV transmission of 62% at 200 nm for spinel ceramic with 4 mm thickness was reached.     

Effect of MgO/La2O3 additives on sintering behavior and microwave dielectric properties of (Sr,Ca)TiO3-(Sm,Nd)AlO3 ceramics

The effect of MgO/La₂O₃ additives on phase composition, microstructures, sintering behavior, and microwave dielectric properties of 0.7(Sr_0.01Ca_0.99)TiO₃−0.3(Sm_0.75Nd_0.25)AlO₃ (7SCT-3SNA) ceramics prepared via conventional solid-state route were systematically investigated. MgO/La₂O₃ as additives showed no obvious influence on the phase composition of the 7SCT-3SNA ceramics and all the samples exhibited pure perovskite structures. The presence of MgO/La₂O₃ additives effectively reduced the sintering temperature of 7SCT-3SNA ceramics due to the formation of a liquid phase at a relatively low temperature during sintering progress. The 0.5 wt% MgO doped 7SCT-3SNA sample with 0.5 wt% of La₂O₃, sintered at 1320 °C for 4 h, was measured to show superior microwave dielectric properties, with an ε_r of 45.57, a Q×f value of 46205 GHz (at 5.5 GHz), and τ_f value of −0.32 ppm/°C, which showed dense and uniform microstructure as well as well-developed grain growth.     

Direct mineralogical composition of a MgO-C refractory material obtained by Rietveld methodology

Magnesia-graphite refractory materials are used in large quantities in the steelmaking process. The chemical characterization of this type of refractories is an arduous task that requires a rigorous set of laboratory tests and analyses. In the present paper, proper characterization of magnesia-graphite refractories has been approached by X-ray powder diffraction combined with Rietveld methodology. The quantitative phase analysis of a MgO-graphite refractory has been 68.3 wt% of MgO, 8.1 wt% of graphite, 13.5 wt% of Al₂O₃, 4.4 wt% of SiC, 0.6 wt% of Si, 1.2 wt% of Al, 1.5 wt% of AlPO₄ and 2.4 wt% of silicone. These results have been checked and validated with those obtained by other analysis procedures used to determine the crystalline and non-crystalline phases present in these materials.     

Wettability between Fe-Al alloy and sintered MgO

In the current study, the wettability between Fe-Al alloy and sintered MgO substrate was investigated. The stable contact angle between the sintered MgO substrate and the liquid iron was approximately 134° at 1550 °C, hardly influenced by Al concentrations of 18 ppm and 370 ppm in the liquid iron. By changing hydrogen partial pressure from 0 vol% to 1 vol%, the oxygen partial pressure decreased. Meanwhile, the contact angle between the MgO substrate and the liquid iron with 370 ppm Al increased with the decrease of oxygen partial pressure. The oxygen partial pressure and contact angle were scarcely affected by increasing hydrogen partial pressure from 1 vol% to 5 vol%. In all cases with 370 ppm Al in the liquid iron, oxide layers were detected on the surface of iron samples. The oxidation of iron could be effectively prevented by increasing the hydrogen partial pressure. The MgO substrate was reduced to Mg vapor in the reducing atmosphere at a high temperature. Then the Mg vapor was dissolved into the iron even before iron melting. Under thermodynamic equilibrium condition, an oxide layer containing two components, i.e. MgO·Al₂O₃ phase and CaO-SiO₂-MgO-Al₂O₃ phase, was generated on the surface of the iron sample. Due to the different wettability between the iron and the two phases, MgO·Al₂O₃ phase was repelled, while the CaO-SiO₂-MgO-Al₂O₃ phase adhered to the inside area.     

Dilatometric sintering study of fine-grained ceramics from ultradispersed admixture composed of Ce0.09Zr0.91O2 and MgO–Al2O3

The experiment was carried out to produce fine-grained ceramics with a grain size of less than 5 μm. Ultradispersed oxide mixture MgO–Al₂O₃ (weight ratio MgO/Al₂O₃ value was 3/97) and solid solution Ce_0.09Zr_0.91O_2?δ were used as initial nanopowders with a crystallite size less than 10 nm. Dilatometric investigation was carried out at the temperature interval 1100–1550 °C using three temperature modes, included various heating and cooling rates and isothermal plots. Initial metal oxide powders were obtained by modified sol–gel technique using N-containing organic compounds for sol stabilization. It was shown that the role of MgO in nanopowdery composition for sintering is to accelerate the sintering due to the formation of the liquid phase with spinel MgAl₆O₁₀. It was determined, that the presence of interim isotherms on the temperature rise curves does not impact the rate and quality of sintering.     

Effect of heat treatment conditions on the growth of MgAl2O4 nanoparticles obtained by sol-gel method

MgAl₂O₄ nanoparticles (NPs) were prepared by sol–gel method using aluminium nitrate, magnesium nitrate and citric acid as starting materials, phenolic formaldehyde resin and carbon black as additives. Growth of MgAl₂O₄ NPs in different heat treatment conditions (temperature, atmosphere, carbon additives and in Al₂O₃-C system) was investigated. MgAl₂O₄ NPs were formed at 600 °C in air atmosphere with serious agglomeration of nanoparticles having diameter of approximate 30 nm. The size of MgAl₂O₄ NPs increased greatly from 40 to 50 nm to several hundreds of nanometres as the temperature was raised from 800 °C to 1400 °C. Partial sintering of NPs was observed upon heating at temperatures higher than 1200 °C in air. In reducing atmosphere, the size of MgAl₂O₄ NPs (about 30–50 nm) changed slightly with increasing temperature. This was attributed to the dispersion of carbon inclusions in the MgAl₂O₄ grain boundaries, inducing a steric hindrance effect and inhibiting the growth of particles. MgAl₂O₄ NPs (30–50 nm) in the Al₂O₃-C system were in-situ formed at high temperatures with the use of dried precursor gels. MgAl₂O₄ NPs can contribute to improving the thermal shock resistance of Al₂O₃-C materials.     

Preparation and thermal shock resistance of cordierite-spodumene composite ceramics for solar heat transmission pipeline

Cordierite-spodumene composite ceramics with 5, 10, 15 wt% spodumene used for solar heat transmission pipeline were in-situ prepared via pressureless sintering from kaolin, talc, γ-Al₂O₃ and spodumene. Effects of spodumene on densification, mechanical properties, thermal shock resistance, phase composition and microstructure of the composite ceramics were investigated. The results showed that spodumene used as flux material decreased the sintering temperature greatly by 40–80 °C, and improved densification and mechanical properties of the composite ceramics. Especially, sample A3 with 10 wt% spodumene additive sintered at 1380 °C exhibited the best bending strength and thermal shock resistance. The bending strengths of A3 before and after 30 thermal shock cycles (wind cooling from 1100 °C to room temperature) were 102.88 MPa and 96.29 MPa, respectively. XRD analysis indicated that the main phases of the samples before 30 thermal shock cycles were α-cordierite, α-quartz and MgAl₂O₄, and plenty of β-spodumene appeared after thermal shock. SEM micrographs illustrated that the submicron β-spodumene grains generated at the grain boundaries after thermal shock improved the thermal shock resistance. It is believed that the cordierite-spodumene composite ceramics can be a promising candidate material for heat transmission pipeline in the solar thermal power generation.     

MgAl2O4 spinel as an effective ceramic bonding in a MgO–CaZrO3 refractory

The influence of MgAl₂O₄ spinel addition as a ceramic bonding in the MgO–CaZrO₃ refractory was established by the evaluation of physical and microstructural characteristics in terms of density, porosity, crystalline phases, phase distribution and morphology. X-ray diffraction analyses and scanning electron microscopy with microanalysis have been used. The mechanical behavior has been evaluated in terms of cold crushing strength at room temperature and modulus of rupture at 25 and 1260 °C. Static and dynamic resistances tested by chemical attack of clinker raw constituents have been carried out at 1450 °C. Results showed that thermo-mechanical properties significantly improved with increasing the content of spinel. Microstructural analysis revealed that spinel phase aided to develop a strong bond between MgO and CaZrO₃ refractory aggregates. Finally, the refractory bodies exhibited a good thermal stability and an excellent chemical resistance against the clinker raw material.     

The effect of Cr2O3 as a nucleating agent in iron-rich glass-ceramics

In this work, the effect of Cr₂O₃ as a nucleating agent, in iron rich glasses has been investigated by means of DTA, XRD and density measurements. By Cr₂O₃ addition, from 0·4 to 1·0 wt%, a lowering of the crystallisation peak temperature resulted in the DTA trace, the maximum effect corresponding to 0·7 wt%. By evaluating the degree of crystallisation of the glass at 0·7 wt% Cr₂O₃, the highest efficiency in the nucleation process also corresponds. The optimum values for the nucleation and crystallisation time and temperature, determined for 0·7 wt% Cr₂O₃ addition, have been 70 min at 630°C and 30  min at 800°C. The crystalline phases formed at different thermal treatment temperatures of the parent glass have been investigated by XRD; the spinel is the only phase after the nucleation; pyroxene is the major phase after the crystallisation. The results of this study have highlighted that a small percentage of Cr₂O₃ strongly affects the spinel formation thereby reducing the time and temperature of the thermal treatment and enhancing the degree of crystallisation of high iron content glasses. ©     

Silver cofirable (Ca0.9, Mg0.1)SiO3 microwave dielectric ceramics with Li2CO3–Bi2O3 additive

The effects of Li₂CO₃–Bi₂O₃ (LB) additive on the microstructure, phase formation, microwave dielectric properties and applicability for low-temperature co-fired ceramics (LTCC) technology of (Ca_0.9Mg_0.1)SiO₃ (CMS) ceramics were investigated. The sintering temperature of the CMS ceramics was reduced from 1290 °C to 890 °C by the addition of LB. Secondary phases SiO₂ and Bi₄(SiO₄)₃ were detected when LB content was less than 9 wt%. Low melting point liquid phases were formed when LB content was 11–14 wt%. The Q_f value initially increased with the addition of LB and attained the maximum value for the 9 wt% LB-doped CMS ceramic. When the LB content exceeded 9 wt%, the Q_f value decreased because of the presence of liquid phase and abnormal growth of grains. ?_r of 6.92, Q_f of 27,600 GHz and τ_f of ?43.6 ppm/°C were obtained for 9 wt% LB-doped CMS ceramics sintered at 890 °C for 2 h. Also the ceramics can be well co-fired with Ag electrode.     

Effect of H3BO3 flux on the morphology and optical properties of Sr2MgAl22O36:Mn4+ red phosphors for agricultural light conversion films

H₃BO₃ was added during the preparation of Sr₂MgAl₂₂O₃₆:Mn⁴⁺ phosphors by a high-temperature solid-state reaction method. The influence of H₃BO₃ flux on the crystal structure, particle morphology and photoluminescence properties of the Sr₂MgAl₂₂O₃₆:Mn⁴⁺ phosphors was investigated by employing X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy, respectively. The results indicate that adding H₃BO₃ flux can improve the luminescence intensity and morphology, and reduce the synthesis temperature of the Sr₂MgAl₂₂O₃₆ phosphor. The formation temperature of pure-phase Sr₂MgAl₂₂O₃₆ was significantly decreased when H₃BO₃ flux as introduced. The excited state lifetime of the Sr₂MgAl₂₂O₃₆:1.2 mol% Mn⁴⁺ phosphor by the addition of 2.0 wt% H₃BO₃ was ~1.02 ms. We demonstrated the potential of these phosphors to enhance sunlight harvesting by agricultural light conversion film testing. We propose that films containing the Sr₂MgAl₂₂O₃₆:1.2 mol% Mn⁴⁺ phosphor can be applied to increase the production of agricultural plants.     

Effect of boron oxide on the microstructure of mullite-based glass-ceramic glazes for floor-tiles in the CaO–MgO–Al2O3–SiO2 system

The effect of increasing replacement of Al₂O₃ by B₂O₃ in a parent glass on the sintering and further crystallization of mullite was investigated. The composition of the parent glass was chosen in the mullite primary phase field of the CaO–MgO–Al₂O₃–SiO₂ quaternary system. Glass powder pellets were heated under standard (10 °C/min and 2 h of hold time) and fast heatings (25 °C/min and 5 min of hold time) at different temperatures from 700 to 1190 °C. Sintering of B₂O₃-containing glasses took place in the range between 850 and 1050 °C. X-ray diffraction results showed that mullite formed as unique crystalline phase for glasses containing amounts of B₂O₃ larger than 6 wt%. For lower amounts of boron oxide cordierite was formed as secondary crystalline phase. Quantitative determination of mullite by Rietveld analysis indicated that the higher amount of mullite present in the glass-ceramic fast heated at 1160 °C was 19.5 wt% for the glass containing 9 wt% of B₂O₃. The final microstructure of the glass-ceramic glazes showed the presence of well shaped, long acicular mullite crystals dispersed within the residual glassy phase. Results of glass-ceramic glazes when applied as slurry and under industrial heating conditions pointed out promising mechanical properties.     

Phase-microstructure-property relationship in high quality factor MgO-Al2O3-SiO2-TiO2-La2O3 glass-ceramics

MgO-Al₂O₃-SiO₂-TiO₂-La₂O₃ glass-ceramics were investigated with respect to the phase compositions and the microstructure as well as the microwave dielectric properties. Indialite, magnesium aluminum titanate (MAT, Mg₄Al₂Ti₉O₂₅), perrierite, and spinel were the main crystal phases in the studied 1.8MgO-1.2Al₂O₃-2.8SiO₂-1.4TiO₂-xLa₂O₃ (x=0.4, 0.3, 0.2) glass-ceramics. Mg₄Al₂Ti₉O₂₅ was detected inside the indialite domain as well as at the boundary while no decomposition product (rutile) is found, proving that Mg₄Al₂Ti₉O₂₅ is fully stabilized. After heat-treatment at 1200 °C, the quality factor (Q×f) of the glass-ceramics increases from 27,500 to 40,000 GHz with decreasing La₂O₃ concentrations. This is caused by the formation of more indialite and MAT. Meanwhile, the temperature coefficient (τ_f) shifts positively from −95 to −65 ppm/°C because of the smaller perrierite concentration. However, τ_f is still too negative due to the absence of rutile that possesses a high positive τ_f. For the 1.3MgO-1.2Al₂O₃-2.8SiO₂-1.4TiO₂-0.2La₂O₃ glass-ceramic with lower MgO molar composition, the peaks assigned to rutile is found and the chemical formula of MAT changes to MgAl₂Ti₃O₁₀ while spinel disappears. MgAl₂Ti₃O₁₀, which distributes mainly at the boundary, decomposes partially, leading to the precipitation of rutile inside the indialite domain. Thus, the τ_f of the glass-ceramic could be adjusted to near 0 ppm/°C with ε_r=9.9 and Q×f=28,600 GHz, which are favorable properties for microwave dielectric applications.