Novel phenomenon of quasi-volcanic corrosion on the alumina refractory-slag-air interface

A novel phenomenon of quasi-volcanic corrosion at refractory – slag – air interface under simulated normal smelting conditions was discovered when alumina refractory came in contact with CaO-Al₂O₃-SiO₂ slags and soaked at 1600°C. Based on thermodynamic and microstructure analysis, the mechanism of quasi-volcanic corrosion was revealed and the effect of CaO/SiO₂ mass ratio (C/S ratio) on corrosion was discussed. The results indicate that a two-stage intensified convection led to the severe upwelling corrosion of the refractory at the triple-phase interface. Furthermore, the critical intensity of the corrosive convection at the first stage on the formation of “slag volcano” was determined. This can serve as guidance for prolonging the service life of alumina refractory.     

High-temperature flexural strength of SiC ceramics prepared by additive manufacturing

Silicon carbide (SiC) ceramics, as a kind of candidate material for aero-engine, its high-temperature performance is a critical factor to determine its applicability. This investigation focuses on studying the high-temperature properties of SiC ceramics fabricated by using additive manufacturing technology. In this paper, SiC ceramics were prepared by combining selective laser sintering (SLS) with precursor infiltration and pyrolysis (PIP) technique. The microstructure, phase evolution, and failure mechanism after high-temperature tests were explored. SiC ceramic samples tested at room temperature (RT), 800°C, 1200°C, 1400°C, and 1600°C demonstrated bending strengths of 220.0, 226.1, 234.9, 215.5, and 203.7 MPa, respectively. The RT strength of this material can be maintained at 1400°C, but it decreased at 1600°C. The strength retention at 1400°C and 1600°C were 98% and 92%, respectively. The results indicate that the mechanical properties of SiC ceramics prepared using this method have excellent stability. As the temperature increases, the bending strength of the specimens increased slightly and reached the peak value at 1200°C, and dropped to 203.7 MPa at 1600°C. Such an evolution could be mainly due to the crack healing, and the softening of the glassy phase.     

Corrosion resistance and anti-reaction mechanism of Al2O3-based refractory ceramic under weak static magnetic field

A slag resistance experiment of the Al₂O₃-based refractory ceramic with CaO–Al₂O₃–SiO₂ slag at 1600°C under a milli-Tesla static magnetic field was conducted. The magnetic flux density effect on the corrosion at the two- and three-phase interfaces of the Al₂O₃-based refractory ceramic, excluding the ‘electromagnetic damping’, was studied. The slag resistance of the Al₂O₃-based refractory was enhanced and quasi-volcanic corrosion at the three-phase interface was eliminated gradually with an increase in the magnetic flux density. A hypothesis and mechanism for the inhibition effect of the static magnetic field based on the free radical pair reaction model was proposed.     

The role of carbon in microstructure evolution of SiBCO ceramics

The composition of polymer derived ceramics could be readily tuned through controlling the structure and element content of the polymer precursors, and investigation on the effect of the element on microstructure evolution is important to the design of advanced ceramics. In this article, the effect of carbon content in SiBCO polymer precursors was systematically investigated. The polymer network and thermal stability of polymer precursors and the carbon content of pyrolyzed SiBCO ceramic could be readily tuned by controlling the DVB amount used. Carbon contributed to the formation of graphitic carbon in SiBC_xO ceramics and inhibited the growth of β–SiC and SiO₂ crystals at 1600 °C, but lead to an increase in the graphitic carbon phase at 1800 °C.     

High-temperature oxidation behavior and oxidation mechanism of C/SiBCN composites in static air

On account of the excellent oxidation resistance of precursor-derived SiBCN ceramics, carbon-fiber-reinforced SiBCN (C/SiBCN) composites are increasingly being used in high-temperature aerospace applications. However, very few studies have investigated the high-temperature oxidation behavior of C/SiBCN composites for their application to high-heat engines. Herein, C/SiBCN composites prepared by precursor infiltration and pyrolysis were tested in static air up to an oxidation temperature of 1700 °C. The composites’ structural evolution after oxidation and their potential oxidation mechanisms were investigated in detail. The carbon fibers were preferentially oxidized at temperatures in the range of 1200–1500 °C and completely oxidized at 1500 °C. The oxidation of the fibers at 1500 °C resulted in the formation of abundant oxygen channels and consequently a high oxide scale growth rate of 5–7 μm² h⁻¹ and a large mass loss of 54.6 wt%. At elevated temperatures in the range of 1600–1700 °C, a dense SiO₂ oxide layer was formed by the sacrificial oxidation of the SiBCN matrix. The oxidation rate of the composites was therefore controlled by the diffusion rate of oxygen through the protective SiO₂ oxide layer and the weight loss of the composites decreased to 28.6% after oxidation at 1600 °C for 60 min. The structural integrity of the composites was maintained after long-term oxidation at 1600 °C.     

Fabrication of transparent Tb3Al5O12 ceramics by hot isostatic pressing sintering

Tb₃Al₅O₁₂ (TAG) transparent ceramics were prepared by a reactive sintering method using presintering in a muffle furnace combined with hot isostatic pressing (HIP) sintering. The dilatometric, differential scanning calorimetry‐thermogravimetric (DSC‐TG) curves and optical quality were investigated. The microstructure evolution of the TAG ceramic samples was clarified. Two successive transformations were found to generate a TAG phase, as observed in the dilatometric and DSC‐TG curves and XRD patterns of TAG ceramics sintered at different temperature. The changes in average grain size and densification suggest that a 1600°C presintering temperature is suitable for HIP. The optical transmittance of the obtained 0.4 wt% TEOS:TAG transparent ceramics, which were fabricated by a new two‐step sintering of presintering at 1600°C in a muffle furnace followed by HIP at 1650°C, can reach above 80% in the visible (vis) and near‐infrared (NIR) regions. Its transmittance was very close to the theoretical limit. To the best of our knowledge, this is the first time that TAG transparent ceramics with ideal optical quality were obtained without vacuum sintering.     

3D printing of dense structural ceramic microcomponents with low cost: Tailoring the sintering kinetics and the microstructure evolution

In this study, we have successfully developed a unique 3D printing approach based on mask-image-projection stereolithography (MIP-SL) to fabricate structural ceramics microcomponents with low cost and high efficiency. Ultra-dense submicron crystalline ceramics without fierce grain growth could be obtained via tailoring the sintering kinetics. The ZrO₂ ceramic microcomponents reached the highest relative density (RD) of 99.7% with the average grain size of 0.52 μm upon sintering at 1550°C while the Al₂O₃ ceramic microcomponents reached its highest RD of 98.31% with the average grain size of 2.6 μm upon sintering at 1600°C. Oxide ceramics microcomponents of fully flexible design can be produced easily without visible defects via the method developed in this study, which demonstrates significant potential in the applications of microelectromechanical systems, micro-optical electronics systems and micro-opto-electro-mechanical systems. The method developed in this study has addressed the problem successfully by healing the interlayer interface defects in densification process via the sintering kinetic window and microstructure evolution. The current work provides a promising opportunity to fabricate structural ceramic microcomponents with complex shape, high precision, and high surface smoothness.     

Fabrication and microstructure development of Yb:YAG transparent ceramics from co-precipitated powders without additives

Sintering additives are generally considered to be important for improving densification in fabrication of transparent ceramics. However, the sintering aids as impurities doped in the laser materials would decrease the laser output power and produce additional heat during laser operation. In this work, Yb:YAG ceramics were vacuum-sintered without additives at different temperatures for various soaking time through using ball-milled powders synthesized by co-precipitation route. The densification behavior and grain growth kinetics of Yb:YAG ceramics were systematically investigated through densification curves and microstructural characterizations. It was determined that the densification in the 1500°C-1600°C temperature range was controlled by a grain-boundary diffusion. It is revealed that the volume diffusion is the main mechanism controlling the grain growth between 1600°C and 1750°C. Although SiO₂ additives can promote densification during low-temperature sintering, the optical transmittance of Yb:YAG ceramic with no additives, sintered at 1800°C for 15 hours, reaches a maximum of 83.4% at 1064 nm, very close to the measured transmittance value of Yb:YAG single crystal. The optical attenuation loss was measured at 1064 nm in Yb:YAG transparent ceramic, to be 0.0035 cm⁻¹, a value close to that observed for single crystals.     

High-temperature properties and interface evolution of C/SiBCN composites prepared by precursor infiltration and pyrolysis

C/SiBCN composites with a density of 1.64 g/cm³ were prepared via precursor infiltration and pyrolysis and the bending strength and modulus at room temperature was 305 MPa and 53.5 GPa. The precursor derived SiBCN ceramics showed good thermal stability at 1600 °C and the SiC and Si₃N₄ crystals appeared above 1700 °C. The bending strength of the composites was 180 MPa after heat treatment at 1500 °C, and maintained at 40 MPa-50 MPa after heat treatment for 2 h at 1600 °C–1900 °C. In C/SiBCN composites, SiBCN matrix could retain amorphous up to 1500 °C and SiC grains appeared at 1600 °C but without Si₃N₄. The reason for no detection of Si₃N₄ was that the carbon fiber reacted with Si₃N₄ to form an interface layer (composed of SiC and unreacted C) and a polycrystalline transition layer (composed of B and C elements), leading to the degradation of the mechanical properties.     

The Role of Infiltration Temperature in the Reaction Bonding of Boron Carbide by Silicon Infiltration

The present paper is concerned on the effect of infiltration temperature on the components, microstructure, and mechanical properties of reaction‐bonded boron carbide (RBBC) ceramics. RBBC ceramics were fabricated by reactive infiltration of molten silicon (Si) into porous preforms containing boron carbide (B₄C) and free carbon. It has been found that infiltration temperatures have significant influence on the infiltration reactions involved and therefore the evolution of different phases formed in the RBBC ceramics. An increase in grain size of boron carbide particles through the coalescence of neighboring grains was observed at certain infiltration temperatures. The morphology of silicon carbide (SiC) phases developed from discontinuous and cloud‐like SiC to continuous and integrated SiC zones with the increase of infiltration temperatures. With increasing temperatures up to 1600°C, the hardness, flexural strength, and fracture toughness all increased. When the temperatures exceeded 1600°C, while the hardness and flexural strength decreased, the fracture toughness continued to increase.     

Rapid Grain Growth in 3Y‐TZP Nanoceramics by Pressure‐Assisted and Pressure‐Less SPS

Pressure‐less spark plasma sintering (SPS) is a new approach during which rapid densification of ceramic nanopowder green bodies is accompanied by rapid grain growth. Although the origin of this phenomenon has not yet been fully understood significant, difference in grain growth between pressure‐less and pressure‐assisted SPS was expected. In this work 3Y‐TZP nanopowder with average particle size of 12 nm was consolidated using two‐step approach: (1) at an intermediate temperature (600°C to 1000°C) SPS warm pressing followed by (2) high temperature (1400°C to 1600°C) pressure‐less SPS. The standard one step pressure‐assisted SPS experiments were quoted as references. Rapid grain growth was observed during both pressure‐less and standard SPS. The samples prepared by both approaches at the same sintering temperature (1400°C–1600°C) achieved identical grain size and grain size distribution, if large pores were eliminated in early stage by SPS warm pressing. The electric current, electromagnetic field, and mechanical pressure is proven to have a negligible direct influence on grain growth in 3Y‐TZP ceramics at temperatures above 1000°C under standard SPS conditions.     

Preparation and properties of porous alumina with inter-locked platelets structure

Porous alumina ceramics with alumina platelets was prepared by vapor-solid reaction sintering of AlOF mesophase gas by the reaction of HF and Al₂O₃. The effect of heating treatment temperatures on porosity, the formation of inter-locked platelets structure and compressive strength of porous alumina ceramics was determined by Archimedes' method, XRD, SEM and compressive tests. The results indicated that after heating at temperatures from 1300 °C to 1600 °C, the porosity of alumina ceramics decreased from 61.6% to 48.4%. Increasing the heating treatment temperature was beneficial to form inter-locked structure between alumina platelets. The maximum compressive strength of porous ceramics with porosity of 48.4% can reach 29.8 MPa heated at 1600 °C; this strength was attributed to the strong bonding between the alumina platelets.     

Polymer-derived SiOC ceramics: A potential catalyst support controlled by the sintering temperature and carbon content

A series of silicon oxycarbide ceramics with varying carbon content from ca. 10 wt% to ca. 40 wt% were prepared by thermal pyrolysis of four commercially available polysiloxanes and subsequent spark plasma sintering (SPS) at 1200 °C, 1400 °C, and 1600 °C. The results showed that the high carbon content led to a porous microstructure, and for SiOC with ca. 40 wt% carbon content, its porosity and specific surface area at 1600 °C reached 34% and 262 m²/g, respectively. The electrochemical behavior of materials was evaluated. It was shown that SiOC has a certain degree of electrocatalytic activity, and the sample with 10 wt% carbon content obtained at 1200 °C exhibited an overpotential of 450 mV vs. RHE at 10 mA·cm⁻² in acid medium. Finally, it was analyzed that the electrochemical behavior of SiOC is closely related to the phase composition and microstructure of the resulting ceramics.     

Medium-temperature sintering efficiency of ZrB2 ceramics using polymer-derived SiBCN as a sintering aid

Polymer-derived SiBCN, with superior thermal stability and amorphous activity, was introduced into ZrB₂ powders. This sintering aid highly improved the sintering efficiency of ZrB₂ ceramics at medium temperature (1000-1600°C), which showed a different service temperature range from that of traditional crystal additives. The microstructure and densification behavior of ZrB₂–SiBCN samples were mainly studied. The polymer structural evolution including construction, rearrangement, and crystallization of the amorphous SiBCN network, made a large contribution to the densification of ZrB₂ ceramics. The carbothermal reduction of pyrolysis carbon with oxide impurities could not only decrease the oxygen content, but also develop the activity of chemical bonds in SiBCN network. Diffusions and reactions at the interface also benefited the microstructure and consolidation of ZrB₂–SiBCN ceramics.     

Oxidation and microstructure of SiCf/SiC composites in moist air up to 1600°C by X-ray tomographic characterization

SiC_f/SiC composites that possess PyC or BN interface layers were fabricated and then oxidized in moist air at 1000, 1200, 1400, and 1600°C. High-resolution CT was used for capturing 3D images and quantifying the SiC phase, mesophase, and voids. The oxidation behavior and microstructural evolution of SiC_f/SiC with PyC or BN interface are discussed in this study. The microstructure of the SiC_f/SiC with a PyC layer was seriously damaged in moist air at high temperature, whereas the BN interface layer enhanced the oxidation resistance of the SiC_f/SiC. These results are also confirmed by using XRD, oxidation mass gain, tensile testing, and SEM measurements. The results of the oxidation behavior and microstructural evolution for SiC_f/SiC oxidized in dry air are also compared with the results of this study. Comparing the SiC_f/SiC with a PyC interface layer, the composite with a BN interface layer oxidized in moist air exhibits a high void growth rate and a low SiO₂ grain growth rate from 1000 to 1600°C. This work will provide guidance for predicting the service life of SiC_f/SiC for multiscale damage rate models of materials at a local scale and will also provide guidance on the life service design of SiC_f/SiC materials.     

Polymer‐Derived SiC/B4C/C Nanocomposites: Structural Evolution and Crystallization Behavior

Structural evolution and crystallization behavior between 600°C and 1450°C during the preparation of bulk SiC/B₄C/C nanocomposites by the pyrolysis of CB‐PSA preceramic were investigated. The CB‐PSA preceramic converts into carbon‐rich Si–B–C ceramics up to 800°C. Structural evolution and crystallization of Si–B–C materials could be controlled by adjusting the pyrolytic temperature. The Si–B–C ceramics are amorphous between 800°C and 1000°C. Phase separation and crystallization begin at 1100°C. The crystallization of β‐SiC takes place at 1100°C and B₄C nanocrystallites generate at 1300°C. The sizes of β‐SiC and B₄C nanocrystals increase with the pyrolytic temperature rising. In addition, the boron‐doping effect on structural evolution was studied by comparing the crystallization and graphitization behavior of Si–B–C ceramics and the corresponding Si–C materials. Boron is helpful for the growth of β‐SiC nanocrystals and the graphitization, but harmful for the nucleation of β‐SiC crystallites.     

Ultra-high strength medium-entropy (Ti,Zr,Ta)C ceramics at 1800°C by consolidating a core-shell structured powder

We report for the first time the synthesis of a core-shell structured composite powder with a core of Zr(Ti,Ta)C and a shell of Ti,Ta(Zr)C at 1700°C and investigate the formation mechanism for the core-shell structure. The medium-entropy (Ti,Zr,Ta)C ceramics with fine grains (1.1 ± 0.4 μm) and relative density of 94.8% was prepared by hot-pressing at 2100°C. The flexural strength of (Ti,Zr,Ta)C at 1000°C (493 ± 21 MPa) was close to the room temperature (511 ± 52 MPa). As the temperature increased from 1600°C to 1800°C, the flexural strength was increased significantly, with an ultra-high flexural strength of 725 ± 32 MPa at 1800°C. The existence of the core-shell structure in the powder suppressed the grain growth due to the sluggish diffusion effect. The ultra-high strength of (Ti,Zr,Ta)C ceramics was attributed to its fine microstructures, high fracture toughness, and the reinforced the grain boundary strength.     

Elevated Temperature Strength Enhancement of ZrB2–30 vol% SiC Ceramics by Postsintering Thermal Annealing

The mechanical properties of dense, hot‐pressed ZrB₂–30 vol% SiC ceramics were characterized from room temperature up to 1600°C in air. Specimens were tested as hot‐pressed or after hot‐pressing followed by heat treatment at 1400°C, 1500°C, 1600°C, or 1800°C for 10 h. Annealing at 1400°C resulted in the largest increases in flexure strengths at the highest test temperatures, with strengths of 470 MPa at 1400°C, 385 MPa at 1500°C, and 425 MPa at 1600°C, corresponding to increases of 7%, 8%, and 12% compared to as hot‐pressed ZrB₂–SiC tested at the same temperatures. Thermal treatment at 1500°C resulted in the largest increase in elastic modulus, with values of 270 GPa at 1400°C, 240 GPa at 1500°C, and 120 GPa at 1600°C, which were increases of 6%, 12%, and 18% compared to as hot‐pressed ZrB₂–SiC. Neither ZrB₂ grain size nor SiC cluster size changed for these heat‐treatment temperatures. Microstructural analysis suggested additional phases may have formed during heat treatment and/or dislocation density may have changed. This study demonstrated that thermal annealing may be a useful method for improving the elevated temperature mechanical properties of ZrB₂‐based ceramics.     

Strength of Zirconium Diboride to 2300°C

The strength of zirconium diboride (ZrB₂) ceramics was measured up to 2300°C, which are the first reported measurements above 1500°C since 1970. ZrB₂ ceramics were prepared from commercially available powder by hot pressing. A mechanical testing apparatus capable of testing material in the ultra‐high temperature regime with atmosphere control was built, evaluated, and used. Four‐point bend strength was measured as a function of temperature up to 1600°C in air and between 1500°C and 2300°C in argon. Strength between room temperature and 1200°C was ~390 MPa, decreasing to a minimum of ~170 MPa between 1400°C and 1500°C, with strength increasing to ~220 MPa between 1600°C and 2300°C.     

Preparation and properties of porous alumina ceramics with oriented cylindrical pores produced by an extrusion method

Porous alumina ceramics with unidirectionally-oriented pores were prepared by extrusion. Carbon fibers of 14 μm diameter and 600 μm length to be used as the pore-forming agent were kneaded with alumina, binder and dispersing agent. The resulting paste was extruded, dried at 110 °C, degreased at 1000 °C and fired at 1600 °C for 2 h. SEM showed a microstructure of dispersed highly oriented pores in a dense alumina matrix. The pore area in the cross section was 25.3% with about 1700 pores/mm². The pore size distribution of the fired body measured by Hg porosimetry showed a sharp peak corresponding to the diameter of the burnt-out carbon fibers. The resulting porous alumina ceramics with 38% total porosity showed a fracture strength of 171 MPa and a Young's modulus of 132 GPa. This strength is significantly higher than the reported value for other porous alumina ceramics even though the present pore size is much larger.