Effect of FeO Concentration on the Crystallization of High‐Temperature CaO–Al2O3–MgO–FeO Melts

Continuous cooling transformation (CCT) and time–temperature transformation (TTT) diagrams were plotted for CaO–Al₂O₃–MgO–FeO melts, and the morphology of the primary crystals formed was determined with a confocal laser scanning microscope (CLSM). When the CaO/Al₂O₃ ratio is 1.0, the crystallization temperature and incubation time increase with increasing MgO content. The TTT curve at 7.5 mass% MgO has a “C” shape, which facilitates the formation of amorphous phases. However, increasing the FeO content accelerated the crystallization time and lowered the crystallization temperature. The solidified melt with an FeO content of less than 10 mass% was a combination of the C₃MA₂ and C₅A₃ phases; higher FeO content led to the formation of a secondary phase of Ca₂FeAlO₅ and CA following the precipitation of the C₃MA₂ primary phase. In addition, kinetic evaluation of the crystal growth with confocal micrographs indicated that the calculated crystal volume agreed well with the Johnson–Mehl–Avrami sigmoidal curve fit.     

High‐pressure synthesis of a 12CaO·7Al2O3–12SrO·7Al2O3 solid solution

Solid solutions of 12CaO·7Al₂O₃ (C12A7) and 12SrO·7Al₂O₃ (S12A7) crystals were synthesized under high pressure. X‐ray diffraction patterns revealed that the lattice constants of the synthesized samples depend linearly on the compositional ratio of C12A7 and S12A7. Electron‐probe X‐ray microanalyses show that the chemical compositions of the crystals are represented by xC12A7·(1?x)S12A7 (0<x<1). These results indicate that the variation in the lattice constants is originated from a difference in the ionic radii of Ca²⁺ and Sr²⁺ ions. From impedance measurements, it was found that S12A7 has the highest conductivity (~1 × 10^?3 Scm^?1 at 550°C) among the solid solutions in the C12A7–S12A7 system.     

High‐Energy Pollen‐Like Porous Fe2O3/Al Thermite: Synthesis and Properties

A pollen‐like porous Fe₂O₃/Al thermite was prepared by a templated method, with aluminium nanoparticles (Al‐NPs) embedded in the porous channels. The thermite prepared by reduced pressure released the largest exothermic heat during DSC testing period compared with Fe₂O₃/Al thermites prepared by ultrasonic mixing and physical mixing. The exothermic heats in the range of 773 K to 1273 K are 3742.3 J g⁻¹, 2279.0 J g⁻¹, 1981.1 J g⁻¹, and 2621.0 J g⁻¹ for pollen‐like Fe₂O₃/Al by reduced pressure, pollen‐like Fe₂O₃/Al by ultrasonic mixing, pollen‐like Fe₂O₃/Al by physical mixing, and commercial Fe₂O₃/Al by ultrasonic mixing, respectively. The reactivity between Fe₂O₃ and Al‐NPs was efficiently improved, corresponding to its enlarged contact surface area between Al‐NPs and the porous pollen‐like Fe₂O₃, and the reduced pre‐combustion sintering. Furthermore, pollen‐like Fe₂O₃/Al has good compatibility with both RDX and HMX and it is not compatible with Cl‐20 and GAP.     

Thermodynamic Modeling of the HfO2–La2O3–Al2O3 System

Based on phase equilibria, thermodynamic, and crystal structure data, the thermodynamic modeling of HfO₂–La₂O₃–Al₂O₃ system is presented. Liquid phase is described by the modified quasichemical model considering the short‐range ordering in liquid solution. Solid solutions are described by the ionic sublattice model considering respective crystal structure. The model (La³⁺, Hf⁴⁺)₂(Hf⁴⁺, La³⁺)₂(O^2?, Va)₆(O^2?)₁(Va, O^2?)₁ successfully describes the structure defect, homogeneity range, and thermodynamic property of pyrochlore solid solution. A set of optimized model parameters is obtained which reproduces most experimental data well. Isothermal sections, liquidus and solidus projections, and Scheil reaction scheme are constructed.     

Promoted Fe2O3‐Al2O3‐CuO Chromium‐Free Catalysts for High‐Temperature Water‐Gas Shift Reaction

Promoted Fe₂O₃‐Al₂O₃‐CuO (FAC) chromium‐free catalysts were prepared for high‐temperature water‐gas shift reactions and characterized by X‐ray diffraction (XRD), Brunauer‐Emmett‐Teller method (BET), temperature‐programmed reduction (TPR), and transmission electron microscopy (TEM) techniques. The catalytic results revealed that among the investigated promoted catalysts with Ce, La, Zn, Y, and Mn as promoters, the Mn‐promoted sample showed higher activity compared to the other promoted catalysts. Increasing the Mn content improved the surface area and catalytic activity. The FAC catalyst promoted with a high Mn content exhibited maximum activity and relatively high stability in high‐temperature water‐gas shift reaction.     

Coupled Experimental and Thermodynamic Optimization of the Na2O–FeO–Fe2O3–Al2O3 System: Part 1. Phase Diagram Experiments

As part of the complete thermodynamic modeling of the Na₂O–FeO–Fe₂O₃–Al₂O₃ system, the Na₂O–FeO–Fe₂O₃–Al₂O₃ phase diagrams in air (1583 and 1698 K) and at Fe saturation (1573 and 1673 K) were investigated using the quenching method followed by Electron Probe Micro‐Analyzer (EPMA) and X‐ray Diffraction (XRD) phase analysis. General features of the phase diagrams in this system were well revealed for the first time. A complete meta‐oxide solid solution between NaAlO₂ and NaFeO₂ was observed. An extensive solid solution of Na₂(Al,Fe)₁₂O₁₉ Na‐β?‐alumina was found and the existence of a miscibility gap in this solution was confirmed. Several compatibility triangles of three‐phase assemblages were also identified in air and at Fe saturation.     

Effect of Polyacrylic Acid Addition on Rheology of SiC‐Al2O3‐ZrO2(3Y) Mixed Suspensions

A suspension with good rheology and high stability is crucial for slip casting and gelcasting technology. However, a mixed suspension from two or more different powders usually has bad rheology because of the easy agglomeration of mixed powders caused by the attractive force between the powders with heterocharges. We studied the surface modification of the each single‐component powders (SiC, Al₂O₃, ZrO₂(3Y) powders) and the SiC‐Al₂O₃‐ZrO₂(3Y) mixed powders to increase the repulsive force by adjusting the pH value and adding polyacrylic acid (PAA) as dispersant. The PAA addition effects on the SiC‐Al₂O₃‐ZrO₂(3Y) mixture were investigated in terms of zeta potential, pH range for heterocharge region, dispersion of the mixed powders and rheology of the mixed slurry based on the study of each unary suspensions. The results show that before surface modification the SiC‐Al₂O₃‐ZrO₂(3Y) mixed powders were agglomerated severely because they were in the heterocharge region with a broad pH range from 3.5 to 8.25, while after surface modification (pH = 10.5, PAA = 0.8wt%) the heterocharge region was narrowed with a relatively narrower pH range from 2.6 to 3.7. The mixed powders with homocharges were dispersed well because of the great electrostatic repulsive force and steric hindrance offered by PAA and the mixed suspensions had favorable rheology.     

High‐Temperature Aging of Plasma Sprayed Quasi‐Eutectoid LaYbZr2O7‐Part I: Phase Evolution

Phase and microstructure stability is an important issue for the durability and performance of thermal barrier coating (TBC) materials which have to work at high temperature for long time. In this work, we present a meta‐stable structure LaYbZr₂O₇ by air plasma spraying process, which can convert into thermodynamically stable fine‐grained quasi‐eutectoid structure with enhanced thermal insulation properties even under high‐temperature annealing. In this part, we first report on the phase composition and relationship in the LaYbZr₂O₇ coatings. The as‐sprayed LaYbZr₂O₇ coatings initially exhibited a mixture of amorphous phase and a nonequilibrium fluorite phase. Then it underwent a fast crystallization and a quasi‐eutectoid transformation during the first few hours of annealing at 1300°C. The phase constitution quickly reached an equilibrium state consisting of La‐rich pyrochlore phase and Yb₂Zr₂O₇ fluorite phase after 6 h annealing and kept stable ever since. Coherent phase boundaries were observed between the La‐rich pyrochlore and Yb₂Zr₂O₇ fluorite phase, indicating a lower interface energy, a lower ionic diffusion rate, a higher strength and creeping resistance of this material at high temperature, all of which could be particularly advantageous to a TBC material for high‐temperature gas turbine applications.     

Enhanced Electrical Resistivity of Al2O3 Addition Modified Na0.5Bi2.5Nb2O9 High‐Temperature Piezoceramics

Enhanced electrical resistivity about over two orders of magnitude for Na_0.5Bi_2.5Nb₂O₉ (NBNO) high‐temperature piezoceramics potentially used in piezoelectric sensors is achieved by the introduction of highly insulating Al₂O₃ addition. Possible pyrochlore secondary phases of two types of grains: irregular polyhedral and platelike, forming at the grain boundaries, have significant blocking effect on the electric current paths and thus lead to improved electrical resistivity. Al₂O₃‐modified NBNO ceramics show higher d₃₃ values up to 16.5 pC/N than that of pure NBNO ceramics (12.4 pC/N) because higher electric field is applied during poling process owing to enhanced electrical resistivity, whereas the T_c values keep almost constant. A compromise between high T_c, good polarizability and enhanced electrical resistivity has been achieved by suitable addition of Al₂O₃, which would shed light on how to obtain novel Aurivillius phase ferroelectrics for practical applications at high temperature.     

High‐Temperature Phase Relations in the Lu2O3–Ta2O5 System

The compounds formed from the Lu₂O₃–Ta₂O₅ system in the composition range 25–60 mol% Ta₂O₅ were prepared by solid‐state reaction from 1350°C to 2058°C, and the phase transitions were investigated by X‐ray diffraction (XRD). Cubic Lu₃TaO₇, M′‐LuTaO₄, M‐LuTaO₄, O‐Ta₂O₅, and T‐Ta₂O₅ are observed. With the temperature increase, there is an irreversible phase transition from M′ to M‐LuTaO₄ near 1770°C in the composition of 30–52 mol% Ta₂O₅, and another phase transition from T‐Ta₂O₅ to O‐Ta₂O₅ at about 1685°C when the ratio of Ta₂O₅ is >52 and ≤60 mol%. A phase diagram of the Lu₂O₃–Ta₂O₅ system in the range 0–100 mol% Ta₂O₅ was constructed. These results are helpful to explain the phase transition of Lu₂O₃–Ta₂O₅ system and design the preparation technique of LuTaO₄ single crystal or ceramic scintillator, which may be applied in the fields of nuclear medicine and high‐energy physics.     

Equiaxed β–Si3N4 ceramics prepared by rapid reaction‐bonding and post‐sintering using TiO2–Y2O3–Al2O3 additives

Sintered reaction‐bonded Si₃N₄ ceramics with equiaxed microstructure were prepared with TiO₂–Y₂O₃–Al₂O₃ additions by rapid nitridation at 1400°C for 2 hours and subsequent post‐sintering at 1850°C for 2 hours under N₂ pressure of 3 MPa. It was found that α–Si₃N₄, β–Si₃N₄, Si₂N₂O, and TiN phases were formed by rapid nitridation of Si powders with single TiO₂ additives. However, the combination of TiO₂ and Y₂O₃–Al₂O₃ additives led to the formation of 100% β–Si₃N₄ phase from the nitridation of Si powders at such low temperature (1400°C), and the removal of Si₂N₂O phase. As a result, dense β–Si₃N₄ ceramics with equiaxed microstructure were obtained after post‐sintering at high temperature.     

Perfect High‐Temperature Plasticity Realized in Multiwalled Carbon Nanotube‐Concentrated α‐Al2O3 Hybrid

We investigate the high‐temperature compressive deformation behavior of a novel, fully dense and structurally uniform, 20 vol% multiwalled carbon nanotube (MWCNT)–α‐Al₂O₃ matrix hybrid, which has a strong room‐temperature interfacial shear resistance (ISR) and a unique MWCNT‐concentrated grain‐boundary (GB) structure. We realized a perfect plastic deformation at 1400°C and a rather high initial strain rate of 10^?4 s^?1 by a low ~30 MPa flow stress, which is contrary to the strain hardening response of fine‐grain monolithic Al₂O₃. This unique performance in CNT–ceramic system in compression is explained as follows: the concentrated network of individual MWCNTs perfectly withstands the high‐temperature and shear/compressive forces, and strongly preserves the nanostructure of Al₂O₃ matrix by preventing the dynamic grain growth, even during a large ~44% deformation. Furthermore, the presence of large amount of radially soft/elastic, highly energy‐absorbing MWCNTs in the GB and specially multiple junction areas, and a potentially weak 1400°C‐ISR, could greatly facilitate the GB sliding process (despite the hybrid's strong room‐temperature ISR), as evidenced by the formation of some submicrometer‐scale MWCNT aggregates in GB area, the equiaxed grains and dislocation‐free nanostructure of the deformed hybrid. The results presented here could be attractive for the ceramic forming industry and could be regarded as a reference for oxide systems in which, the GB areas are occupied with soft/elastic, highly energy‐absorbing nanostructures.     

YCrO3/Al2O3 Core‐Shell Design: The Effect of the Nanometric Al2O3‐Shell on Dielectric Properties

We report a novel strategy to improve the dielectric properties of the biferroic YCrO₃ ceramic compound through interface conduction control by means of an insulating Al₂O₃ using a core‐shell design. The YCrO₃ particles were covered with several layers of insulating Al₂O₃ using the atomic layer deposition technique to produce the core‐shell structure. TEM images reveal homogeneous and well‐defined Al₂O₃ coatings of ~8, ~60, and ~130 nm thickness. XRD shows the Al₂O₃‐shell to be amorphous. The dielectric characteristics of the sintered nano‐composite were investigated in the 100 Hz–1 MHz frequency range and temperature between 300 and 580 K. As the Al₂O₃‐shell thickness covering the YCrO₃ particles is increased, a decrease of the dielectric permittivity, loss tangent and AC conductivity values was found in the whole range of temperatures and frequencies. Furthermore, the rounded hysteresis loop, typical of conductive ceramic is restored as the insulating Al₂O₃ layer becomes thicker. This behavior is explained because the insulating Al₂O₃‐shell acts as internal barrier layer localizing the surface charges on the sintered grain boundaries. This fact was confirmed by Electron Beam Induced Current technique where a clear contrast at the grain boundaries confirms the charge localization at the YCrO₃/Al₂O₃ interface. These results also reveal that the Al₂O₃‐shell induces another conductive mechanism when the insulating Al₂O₃ layer becomes thicker. Nonetheless, this new strategy is an effective approach to suppress the parasitic conductivity in polycrystalline multiferroic ceramics and increasing thus the multifuncionality.     

Phase Evolution of SiO2–Al2O3–ZnO–CaO–ZrO2–TiO2‐Based Glass with Added Y‐PSZ Particles

Yttria partially stabilized zirconia Y‐PSZ/glass‐ceramic composites were prepared by reaction sintering using powder mixtures of a SiO₂–Al₂O₃–ZnO–CaO–ZrO₂–TiO₂‐based glass and yttria partially stabilized zirconia (Y‐PSZ). The glass crystallized during sintering at temperatures of 1173, 1273, and 1373 K to give a glass‐ceramic matrix for high‐temperature protecting coatings. With the increasing firing time, the added zirconia reacted with the base glass and a glass‐ceramic material with dispersed zircon particles was prepared in situ. Furthermore, the added zirconia changed the crystallization behavior of the base glass, affecting the shape, amount, and distribution of zircon in the microstructure. The bipyramid‐like zircon grains with imbedded residual zirconia particles turned out to have two growth mechanisms: the inward growth and the outward growth, and its rapid growth was mainly dominated by the later one. For comparison, the referenced glass‐ceramic was prepared by sintering using exclusive glass granules and its crystallization behavior at 1173–1373 K was examined as well. Scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDS), transmission electron microscopy (TEM), and X‐ray diffraction (XRD) were used to characterize the crystallization behavior of the base glass and the phase evolution of the Y‐PSZ/glass‐ceramic composites.     

Effects of Bi2Se3 Amount in Thermoelectric Performance of Bi2(TeSe)3 Materials Fabricated by High‐Energy Ball Milling

Amount of Bi₂Se₃ has significant role in controlling thermoelectric properties of n‐type Bi₂(TeSe)₃ material. In this study, effects of Se alloying amount in Bi₂(TeSe)₃ thermoelectric materials fabricated by high‐energy ball milling and spark plasma sintering were studied and compared with other fabrication methods. Amount of Bi₂Se₃ (5%, 10%, 15%, and 20%) did not have any significant effect over fabricated powder size, grains of consolidated bulks, and mechanical properties; however, electrical properties and thermoelectric efficiency were noticeably influenced. Both carrier concentration and carrier mobility decreased with increase in Se amount. In total, 20% Se alloying was effective in improving thermoelectric figure of merit ZT value by almost 40% compared with only 5% Se alloying.     

Microwave Processing for Improved Ionic Conductivity in Li2O–Al2O3–TiO2–P2O5 Glass‐Ceramics

Li_1.4Al_0.4Ti_1.6(PO₄)₃ (LATP) was synthesized using a glass‐ceramics approach through crystallization in a conventional box furnace and a modified microwave furnace. The microstructure of samples that were microwave processed at 1000°C showed a larger average grain size (0.87 μm) when compared with the grain size of conventionally processed samples (0.30 μm) at the same temperature. Microwave processing led to significant enhancement of the conductivity when compared with conventional processing for all crystallization temperatures investigated. The highest total conductivity achieved was of glass microwave processed at 1000°C, with a conductivity of 5.33 × 10^?4 S/cm. This conductivity was five times higher than that of LATP crystallized conventionally at the same temperature.     

New Sintered Li2O–Al2O3–SiO2 Ultra‐Low Expansion Glass‐Ceramic

We developed a new Li₂O–Al₂O₃–SiO₂ (LAS) ultra‐low expansion glass‐ceramic by nonisothermal sintering with concurrent crystallization. The optimum sintering conditions were 30°C/min with a maximum temperature of 1000°C. The best sintered material reached 98% of the theoretical density of the parent glass and has an extremely low linear thermal expansion coefficient (0.02 × 10^?6/°C) in the temperature range of 40°C–500°C, which is even lower than that of the commercial glass‐ceramic Ceran^® that is produced by the traditional ceramization method. The sintered glass‐ceramic presents a four‐point bending strength of 92 ± 15 MPa, which is similar to that of Ceran^® (98 ± 6 MPa), in spite of the 2% porosity. It is white opaque and does not have significant infrared transmission. The maximum use temperature is 600°C. It could thus be used on modern inductively heated cooktops.     

Druck‐ und Bruchverhalten von γ‐Al2O3‐Granulaten

The material behaviour of dominant elastic‐plastic, spherical γ‐Al₂O₃‐granules at compression until primary breakage has been experimentally studied. The influence of particle size and moisture content on the compression behaviour was also investigated. The mechanical properties of the granules can be determined using the recorded force‐displacement curves. Additionally, the specific fracture energy distribution and the distribution of the equivalent impact velocity at fracture can be derived from the force‐displacement curves.     

Metastability in the MgAl2O4–Al2O3 System

Aluminum oxide must take a spinel form (γ‐Al₂O₃) at increased temperatures in order for extensive solid solution to form between MgAl₂O₄ and α‐Al₂O₃. The solvus line between MgAl₂O₄ and Al₂O₃ has been defined at 79.6 wt% Al₂O₃ at 1500°C, 83.0 wt% Al₂O₃ at 1600°C, and 86.5 wt% Al₂O₃ at 1700°C. A metastable region has been defined at temperatures up to 1700°C which could have significant implications for material processing and properties. Additionally, initial processing could have major implications on final chemistry.