Refractory Aggregates Research Articles

Effect of Al2O3 nano/micro powder ratio on microstructures and properties of microporous MgO-MgAl2O4 refractory aggregates

In this work, the microporous MgO-MgAl2O4 refractory aggregates were prepared by in-situ decomposition synthesis method. The effect of Al2O3 nano/micro powder ratio on the microstructures and properties was studied under the premise that the fixed total content of Al2O3 was 15 wt%. The results demonstrated that the aggregates were composed of microporous MgO microparticles with nano pores as well as MgAl2O4 grains located among them. The ratio not only influenced the volume expansion through changing the lattice constant of in-situ MgAl2O4, but also affected the formation of two different positions of MgAl2O4 bonds, thereby influencing the microstructures and properties. When the ratio was 4:6, the combined effect of the shrinkage of MgO microparticles and the expansion of in-situ MgAl2O4 grains promoted the formation of the bonds between MgAl2O4 grains and MgO microparticles, as well as among the MgAl2O4 grains, which resulted in the best comprehensive properties of the microporous MgO-MgAl2O4 refractory aggregates, characterized by micro-nano pores, an apparent porosity of 26 %, a flexural strength of 23.2 MPa, a flexure strength after thermal shock of 20.4 MPa and a low thermal conductivity of 2.99 W/(m·K) at 800 °C.

Fabrication of low conductivity and high strength MgO-MgAl2O4 aggregates with sub-micron pore structure

Lightweight MgO-MgAl2O4 refractory aggregates were fabricated by using fine MgO and spherical Al(OH)3 powders as starting materials. The evolutions of microstructure and pores and their effects on the properties of the specimens were investigated. During heating process, MgO crystallites diffused into the formed Al2O3 pseudomorph, producing sub-micron intra-particle pores in both MgAl2O4 cores and MgO matrix. Besides, larger inter-particle pores between the MgAl2O4 cores and MgO matrix were occurred, attributing to the Kirkendall effect resulting from in-situ spinalization. As MgO content increased from 50 wt% to 80 wt%, due to reduction of the number of the porous MgAl2O4 cores, the inter-particle pores caused by Kirkendall effect decreased sharply in both number and size, while no obvious changes occurred in the intra-particle pores as the porous MgO matrix amount increased simultaneously. The decrease of large inter-particle pores caused obvious improvement in strength but slight increase in thermal conductivity. With a further increase of MgO to 90 wt%, as the number of the porous MgAl2O4 cores reduced further and the MgO matrix densification improved obviously, intra-particle pores and thermal insulation performance reduced significantly. The specimen with 80 wt% MgO showed the best performance, with a median pore diameter of 0.26 μm, apparent porosity of 36.0 %, flexural strength of 23.9 MPa, and thermal conductivity of 2.1 W/(m·K) at 500 °C.

From Mg(OH)2 to lightweight closed-pore MgO refractory aggregates: The role of NiO additive

MgO refractory aggregates with high closed porosity were prepared using light-burned MgO and Mg(OH)2 with adding NiO additive. The evolutions of microstructure and pores and their effects on the properties were investigated. The introduction of NiO effectively enhanced growth of MgO grains and transformation of large open pores into small closed ones, attributing to the lattice distortion caused by MgxNi1-xO solid solution formation. Due to the occurrence of more closed pores and lattice distortion, thermal insulation performance was improved significantly. Moreover, the formed circular closed pores and MgxNi1-xO could absorb thermal stress, lower thermal expansion coefficient and induce crack deflection, thus effectively enhancing thermal shock resistance. The specimen with 4.0 wt% NiO showed the best performance, with a median pore diameter of 5.69 μm, closed/apparent porosity of 9.4 %/3.6 %, thermal conductivity of 9.9 W/(m·K) (500 °C), flexural strength of 68.5 MPa, and residual flexural strength of 10.8 MPa after thermal shock.

Effect of TiO2 addition on microstructures and properties of MgO–CaO refractory aggregates

Effect of TiO2 addition on microstructures and properties of MgO–CaO refractory aggregates

Influence of porosity on the Umov effect in silicate and organic refractory aggregates

This study investigates the influence of porosity on the Umov effect, a phenomenon observed in the scattering of light from celestial objects. The Umov effect describes an inverse relationship between the degree of linear polarization and the object’s reflectance (geometric albedo). To study the dependence of porosity on the Umov effect, a wide range of porosity (i.e., from 0.64 to 0.99) is considered. Four types of aggregates, ballistic cluster–cluster aggregate (BCCA), ballistic particle cluster aggregate (BPCA) or ballistic agglomeration (BA), ballistic agglomeration with one migration (BAM1), and ballistic agglomeration with two migrations (BAM2) each having porosity 0.99, 0.87, 0.74, and 0.64 are considered in this study. The multi-sphere T-matrix code is utilized to calculate the linear polarization and geometric albedo (A) considering silicate and organic refractory compositions for monodisperse aggregates. The results are reported for six different wavelengths, ranging from near-ultraviolet to the visible spectrum. When the polarization maximum (Pmax) is plotted against the geometric albedo (A) on a logarithmic scale, an inverse relation is observed. This relation exhibits non-linear changes, fitted by a second-degree polynomial equation, as the porosity changes from 0.64 to 0.99. This finding constitutes one of the interesting results of our study. In addition, the study explores the effect of porosity (P) on the ratio between log(Pmax) and log(A), showing a non-linear relationship. A comparison is drawn between the results obtained from organic refractory compositions and amorphous silicate compositions, emphasizing the importance of porosity and wavelength in regulating the Umov effect. In addition, the research investigates how mixing affects the results at different wavelengths, assuming the aggregates are blends of organic refractory and amorphous silicate compositions. The computations have also been performed for polydisperse aggregates (considering BCCA, BA, BAM1, and BAM2 structures) at a wavelength of 0.45 μm for silicate compositions, which also showed a non-linear dependence as observed in the case of monodisperse aggregates.

Advanced Solid Geopolymer Formulations for Refractory Applications.

Cement, as a construction material, has low thermal resistance, inherent fire resistance, and is incombustible up to a certain degree. However, the loss of its mechanical performance and spalling are its primary issues, and it thus cannot retain its performance in refractory applications. The present study explores the performance of geopolymer formulations that have excellent fire resistance properties for potential refractory applications. This study is unique, as it investigates advanced solid geopolymer formulations that need only water to activate and bind. Various solid geopolymer formulations with fly ash as a precursor; potassium hydroxide and potassium silicate as activators; and mullite and alumina as refractory aggregates were studied for their compressive strength at up to 1100 °C and compared with their two-part conventional liquid alkaline geopolymer counterparts. Advanced solid geopolymer formulations with mullite and alumina as refractory aggregates had mechanical strength values of 84 MPa and 64 MPa post-1100 °C exposure and were further exposed to ten thermal cycles of 1100 °C to study their fatigue resistance and post-exposure compressive strengths. The geopolymer sample with mullite as a refractory aggregate yielded 115.2 MPa compressive strength after the fourth cycle of exposure. This sample was also studied for its temperature distribution upon direct flame exposure. All the geopolymer formulations displayed a drop in compressive strength at 600 °C due to viscous sintering and then a rise in strength at 1100 °C due to phase transformation. X-ray diffraction studies revealed that the formation of crystalline phases such as leucite, sanidine, and annite were responsible for the superior strengths at 1100 °C for the alumina- and mullite-based geopolymer formulations.

Microstructure and properties of microporous MgO–Al2O3 refractory aggregates from Mg(OH)2 and Al(OH)3

AbstractIn this work, microporous MgO–Al2O3 refractory aggregates were prepared with Mg(OH)2 and Al(OH)3 via the in situ decomposition synthesis method. The effect of Al(OH)3 addition on the microstructure and properties of microporous MgO–Al2O3 refractory aggregates was investigated with scanning electron microscope and mercury intrusion porosimetry. The results indicated that the improved green density of the samples and the reaction sintering accelerated the mass transport rate with adding Al(OH)3 from 0 to 4.0 wt%. Besides, a small amount of Al3+ diffused into porous MgO particles, accelerating the merging and growth of nanopores in the porous MgO particles. The intra‐particle pore size and the densification degree of microparticles were increased, and thus the strength of the samples was improved. Due to the formation of Kirkendall voids by interdiffusion of Mg2+ and Al3+, the inter‐particle pore size increased. Adding Al(OH)3 from 4.0 to 17.6 wt%, the Kirkendall voids weakened the mass transport rate and improved the inter‐particle pore size. The merging and growth of nanopores in the MgO particles were limited, resulting in the reduced intra‐particle pore size and increased intra‐particle pore number. The densification degree of microparticles was reduced, and thus the strength of the samples decreased. At the Al(OH)3 addition of 4.0 wt%, microporous MgO–Al2O3 refractory aggregates had the best comprehensive properties, a bulk density of 2.48 g/cm3, an apparent porosity of 29.4%, a median pore size of 1.6 μm with 42.2 vol% nanopores and the thermal conductivity of 4.0 W/(m K).

A novel low thermal conductivity refractory aggregate for high-temperature applications: Lightweight microporous alumina-rich spinel (Mg0.4Al2.4O4)

This study aimed to develop lightweight refractory aggregates with high closed porosity and low thermal conductivity. We report the preparation of a series of lightweight microporous alumina-rich spinel (Mg0.4Al2.4O4) aggregates with low open porosity, high closed porosity, small intragranular pore size, and low thermal conductivity. The sintering activity of the nano-zirconia sol increased the grain boundary migration rate under the action of surface tension during sintering; therefore, the pores were closed before they were eliminated. Simultaneously, Zr4+ replaced Mg2+ and Al3+, which increased the number of cation vacancies in the crystal and accelerated the ion migration, resulting in a faster formation of Mg0.4Al2.4O4. When 0.75 wt% nano-zirconia sol was added, it increased the diffusion rate of ions and the migration rate of grain boundary, which improved the sintering reactivity. The pores were mainly small-sized intragranular pores (median size: 1.89 μm), which reduced the thermal conductivity (2.5 W•m−1K−1 at 1000 °C).

Effect of refractory aggregate shape on the porosity of A356 alloy castings in lost foam casting

Effect of refractory aggregate shape on the porosity of A356 alloy castings in lost foam casting

Eco-friendly design of complex refractory aggregates as alternatives to the magnesia-chromite ones

Besides the good performance of electrofused magnesia-chromite aggregate (EMCA) in ceramic refractories, the generation of toxic Cr+6 after working conditions is driving its urgent replacement. Aiming at optimizing the search towards eco-friendly options, this work applied multiple electron-microscope-based techniques to assess its key microstructural features. BSE/EDS imaging coupled with thermodynamic calculations (CALPHAD) indicated that these aggregates were comprised of a periclase matrix where spinel precipitates (d50≈15μm) were embedded, inducing microcracking due to the thermal expansion mismatch. EBSD technique highlighted its pattern, revealing a good fit with {110} planes, which agrees with the Zener-Stroh crack mechanism. Designing concepts of compositionally complex ceramics were applied to find eco-friendly EMCA alternatives. From the 154 simulated systems, the four most promising ones were experimentally produced and characterized. Although kinetics aspects must be addressed, Cr-free EMCA-inspired microstructures were obtained, highlighting that this design approach can be used to support the development of novel raw materials.

Microstructures and properties of novel lightweight refractory aggregates with microporous MgO@MgAl2O4 core-shell structures

Microstructures and properties of novel lightweight refractory aggregates with microporous MgO@MgAl2O4 core-shell structures

Effect of raw material composition on microstructures and properties of microporous MgO–Mg(Al, Fe)2O4 refractory aggregates

Microporous MgO–Mg(Al, Fe)2O4 refractory aggregates were prepared by the in-situ decomposition synthesis method using the magnesite, Al(OH)3 and Fe2O3 as raw materials. The effect of raw material composition (theoretical Mg(Al, Fe)2O4 contents were 0–55 wt %) on their microstructure and strengths was investigated. When the theoretical Mg(Al, Fe)2O4 contents were relatively low (0–5.5 wt %), the number of neck connections between the particles in the microporous MgO–Mg(Al, Fe)2O4 refractory aggregates was small. As the theoretical Mg(Al, Fe)2O4 contents increased to be 11–22 wt %, the number of neck connections increased and the compressive strengths were enhanced. When the theoretical Mg(Al, Fe)2O4 contents increased to be excessive (33–55 wt %), the inter-particle pore size further increased due to the increase of volume expansion caused by the formation of more spinel, resulting in a decrease of compressive strength. Overall, when the theoretical Mg(Al, Fe)2O4 contents were 11–22 wt %, the microporous MgO–Mg(Al, Fe)2O4 refractory aggregates showed the excellent performances with the median pore sizes of 17.37–25.46 μm, the apparent porosities of 23.4–28.1%, the bulk densities of 2.57–2.79 g/cm3 as well as the compressive strengths of 41.2–75.8 MPa.

Morphology characterization for refractory aggregates

Although refractory aggregates are indispensable components of ordinary refractory ceramics, systematic studies on their morphology and impact on the performance of ordinary refractory ceramics are lacking. This paper aims to address this gap by providing an overview of the morphological parameters and methods commonly used in civil engineering to characterize aggregates on different scales, namely, form, angularity, and texture. Moreover, this paper is expected to help refractory researchers better understand the morphology of refractory aggregates for the deliberate design of ordinary refractory ceramics.

Microstructural evolution during H2 corrosion of Al2O3–SiO2 based refractory aggregates

Hydrogen-based direct reducing iron production (H-DRI) has caused more and more attention in metallurgical industry owing to the near-zero carbon emission. However, the strong reducibility of H2 at elevated temperature can possibly cause serious corrosion to the lining refractories of furnaces. In this study, four types of Al2O3–SiO2 based aggregates (brown corundum, bauxite, mullite and quartz) with various SiO2/Al2O3 mass ratios were utilized for the H2 corrosion test at 1673 K with a soaking time of 8 h. Based on the analysis of weight-loss ratios, phase-composition variation and reduction thermodynamics, the microstructure evolution during H2 corrosion was investigated in detail. The results indicates that the SiO2 impurity of brown corundum was partly reduced by H2 which led to the formation of rod-like or flaky intergranular grains. For bauxite, a porous structure was produced by the accumulation of rod-like or elongated grains owing to the significant reduction of intergranular silicon compounds. Nevertheless, due to the high sintering activity between the Al2O3 products from the reduction of mullite, a high densification structure was realized to effectively prevent the further H2 penetration, hence, mullite inversely obtained the better H2 corrosion resistance than bauxite in spite of its higher S/A ratio. The accumulation of SiO and H2O gases due to the high reduction rate of SiO2 led to the formation of a great deal of SiO2 fiber on the surface of quartz aggregates. The [O] provided by the phase-transformation from α-quartz to cristobalite could be partially captured by the H2 for the reduction, which caused the deterioration of corrosion. With this study, we aim to provide theoretical assistance for the refractory selection applied in hydrogen metallurgy.

Effects of sintering temperature on the properties and the pore evolution of microporous MgAl2O4 aggregates

It is of great significance to develop new types of refractories by replacing the traditional refractory aggregate with a porous refractory aggregate, which enables long-lived operation of high-temperature industries and low carbon emissions. In this study, microporous MgAl2O4 aggregates containing sub-micron pores were successfully prepared from magnesite and boehmite using an in-situ decomposition pore-forming method. The effects of sintering temperature on the phase compositions, sintering properties, and microstructure of aggregates were reported for the first time. The resulting aggregates sintered at 1500 °C showed superior comprehensive performance with a median equivalent pore diameter of 10.75 μm, corresponding to a bulk density and closed porosity of 2.27 g cm−3 and 8.7%, respectively. Meanwhile, several sub-micron pores were observed in microporous MgAl2O4 aggregates, which contributed to a lower thermal conductivity of 1.932 W m−1 k−1 at 500 °C and a higher compressive strength of 40.8 MPa. In addition, the formation mechanism of sub-micron pores was proposed, and the effects of pore structure on the thermal conductivity and compressive strength were discussed.

Microstructure and strength of microporous MgO refractory aggregates with nano-sized pores

ABSTRACT In this work, microporous MgO refractory aggregates with nano-sized pores were prepared by in situ decomposition method using Mg(OH)2 as raw material. The effects of firing temperatures (1600–1700°C) and compacting pressures (100–200 MPa) on the microstructures and properties of microporous MgO refractory aggregates were thoroughly studied. The results showed that the microporous MgO refractory aggregates contained two types of pore structures, which were intra-particle pores with pore sizes of 180.0–230.0 nm formed by in situ decomposition of Mg(OH)2 and inter-particle pores with pore sizes of 1.5–3.0 μm derived from particle packing between Mg(OH)2 pseudomorph particles, respectively. Besides, the firing temperatures had a great influence on the intra-particle pore size and microcrystallite size. And the compacting pressures not only influenced the intra-particle pore size via packing behaviors but also affected the inner firing behaviors of the pseudomorph particles due to the increase in H2O vapor pressure. Overall, at a compacting pressure of 150 MPa and firing temperature of 1650°C, the sample had the best comprehensive performance with a bulk density of 1.92 g/cm3, a compressive strength of 11.9 MPa, an apparent porosity of 45.0%, a relative aggregate tube strength of 25.2% and a median pore size of 262.3 nm.

Ceramic shell waste valorization: A new approach to increase the sustainability of the precision casting industry from a circular economy perspective

The problem of waste generation has grown because of the need to extract natural resources, obtain materials, and consume energy to meet current societal needs. Many studies have been conducted worldwide in favor of technological solutions for the valorization of industrial waste (IW) but few discussed relevant data for effective recovery. In this study, a case study of ceramic shell waste (CSW) was performed using, for the first time, a waste valorization system based on the classification, potentiality, quantity/viability, and applicability criteria (CPQvA) in a specific region (Brazil). CPQvA is a multicriteria decision-making system that acts as a guide to help managers and researchers connect the potential of IW with the feasibility of its application in a product or another process. Using the proposed systematic criteria, it was possible to demonstrate similarities and differences in waste applications. Thirteen possible products made from CSW were analyzed based on all the parameters of CPQvA. Ceramic filters and refractory aggregates were the most viable products. Creating public policies that encourage the use of waste as a raw material could make the precision casting industry process cleaner and the economy more circular.

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.

Microstructures and properties of microporous mullite‐corundum aggregates for lightweight refractories

AbstractFive microporous mullite‐corundum refractory aggregates were prepared from Al(OH)3 and kaolinite gangue through in situ decomposition synthesis technique. The effects of the sintering temperature (1400–1600°C) and the particle sizes of raw materials (20.6–94.5 μm) on the microstructures and strengths of the aggregates were investigated through X‐ray diffractometer, scanning electron microscopy, and energy‐dispersive spectrometer etc., to find out the technological conditions to be controlled in industrial production. The higher sintering temperature promoted the reaction between Al(OH)3 and kaolinite gangue, leading to the development of primary‐mullite as well as the generation of secondary‐mullite, which promoted the formation of the neck and improved the strength. Meanwhile, the dense mullite layers were formed continuously on the surface of Al(OH)3 pseudomorphs, making the micropores inside the pseudomorphs become closed pores, which increased the closed porosity of the aggregates. The reduction of the particle sizes of raw materials changed the particle packing behavior, accelerated the rearrangement of the Al(OH)3 pseudomorph particles during the process of reactive sintering, and then reduced the closed porosity. To realize the industrial production of microporous mullite‐corundum refractory aggregate with high strength (103 MPa) and high closed porosity (16.1%), the sintering temperature should be at about 1600°C, and the median diameter of raw materials should be at 94.5 μm.

REINFORCEMENT BONDING PERFORMANCE IN REFRACTORY CASTABLES UNDER ELEVATED TEMPERATURES

Refractory castables, representing a mixture of a refractory aggregate, calcium aluminate cement, ultra-fine particles, and deflocculants, have been created in the mid of past century ’80s for the metallurgy and petrochemical industries. The designed castable binder shows an excellent ability to preserve the material’s mechanical strength in the 600 °C to 1000 °C temperature range. Besides, the micro-scaled silica/alumina activation process increases the strength and sinterability temperature of the castables regarding traditional alternatives. However, a relatively high price (ten times the ordinary concrete cost) limits the structural application of these advanced materials. Therefore, the studies considered reinforcement aspects of these materials are rare. This investigation focuses on the bond performance of ordinary and stainless steel reinforcement in refractory castables. It is a part of the research project on developing structural concrete fire protection systems, employing refractory castables as a protective shell. This experimental program operates a conventional refractory concrete with a 50 MPa target compressive strength and 25wt% of aluminate cement. In addition, the alternative mixture was modified with a 2.5wt% microsilica, doubling the material strength. The pull-out tests of ribbed and smooth bars demonstrate the importance of the ribs’ mechanical interlock, ensuring reinforcement bonding with the refractory material. Moreover, the ordinary reinforcement demonstrates the bonding ability with refractory castables containing microsilica up to the 1000°C temperature, making the proposed fireprotecting system development possible.