Anisotropic properties of textured h-BN matrix ceramics prepared using 3Y2O3-5Al2O3(-4MgO) as sintering additives

Textured hexagonal boron nitride (h-BN) matrix composite ceramics were prepared by hot pressing using 3Y₂O₃-5Al₂O₃ (mole ratio of 3:5) and 3Y₂O₃-5Al₂O₃-4MgO (mole ratio of 3:5:4) as liquid phase sintering additives, respectively. During the sintering process with liquid phase environments, platelike h-BN grains were rotated to be perpendicular to the sintering pressure, forming the preferred orientation with the c-axis parallel to the sintering pressure. Both h-BN matrix ceramic specimens show significant texture microstructures and anisotropic mechanical and thermal properties. The h-BN matrix ceramics prepared with 3Y₂O₃-5Al₂O₃-4MgO possess higher texture degree and better mechanical properties. While the anisotropy of thermal conductivities of that prepared with 3Y₂O₃-5Al₂O₃ is more significant. The phase compositions and degree of grain orientation are the key factors that affect their anisotropic properties.     

Effect of Y2O3 addition on tribological properties of plasma sprayed Al2O3-13% TiO2 coating

The effect of Y₂O₃ addition on structure, mechanical properties and tribological properties of Al₂O₃-13 wt% TiO₂ coating was investigated. The addition of 20 wt% Y₂O₃ resulted in better densification, stabilization of alpha (α) alumina phase and improvement in fracture toughness of Al₂O₃-13 wt% TiO₂ coating. Abrasive wear tests were performed over a range of loads and sliding speeds. The stabilization of α alumina phase further increased with an increase in severity of wear test conditions, as noted from X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS) analysis of worn coatings. Al₂O₃-13 wt% TiO₂-20 wt% Y₂O₃ coating displayed lower friction coefficient and lower abrasive wear rate than Al₂O₃-13 wt% TiO₂ coating, which was due to synergistic effect of α alumina phase and formation of magneli phase oxide of titanium; Ti₂O₃. Friction energy map was used to rationalize observed wear rates, to identify different regimes of wear and degradation modes of coatings.     

PRELIMINARY STUDY ON PORTIONS OF SYSTEMS Na2O-CaO-AI2O3-Fe2O3 AND Na2O-CaO-Fe2O3-SiO2*

Portions of the quaternary system Na₂O-CaO-Al₂O₃-Fe₂O₃ have been studied by the exploration of (1) the plane CaO-4CaO.Al₂O₃°Fe₂O₃-(Na₂O + 3Al₂O₃) and (2) planes above the base system CaO.5CaO.3Al₂O3–2CaO.Fe₂O₃ which contain successively increasing amounts of Na₂O up to 6%. A portion of the quaternary system Na₂O-CaO-Fe₂O₃-SiO₂ has been studied by the exploration of a plane containing 5% of Na₂O above the base system CaO-2CaO.SiO₂-CaO.Fe₂O₃. In the pseudosystem CaO-4CaO.Al₂O₃.Fe₂O₃-(Na₂O + 3A1₂O₃) the compound Na₂O.-8CaO.3A1₂O₈ was found to exist as a primary phase, and the area in which the plane cuts the Na₂O.8CaO.3A1₂O₃ primary-phase volume was established. Three points on uni-variant curves were located. The iron phase (4CaO.A1₂O₃.Fe₂O₃ solid solution) was observed to exist in a solid-solution series. In the system Na₂O-CaO-5CaO.3Al₂O_3--2CaO.Fe₂O₃ it was found that the compound Na₂O.8CaO.3Al₂O3 appears at an Na₂O concentration of 4.2%. As soda, however, is taken into solid solution by other phases, it was not feasible at this time to determine the invariant point for Na₂O.8CaO.3A1₂O₃, 3CaO.Al₂O₃, 5CaO.3A1₂O₃, and 4CaO.Al₂O₃.-Fe₂O_a solid solution. In the system Na₂O-CaO-2CaO.SiO₂-CaO.Fe₂O₃ no ternary compounds were observed up to the 5% limit of Na₂O employed. A soda-containing phase occurred in solid solution with α-2CaO.SiO₂, which may precipitate on cooling, forming inclusions in the ß-2CaO.SiO₂, or enter into reaction with the glassy phase.     

Understanding the structure,thermal, and optical properties in Al2O3-incorporated La2O3-TiO2-Nb2O5 glasses

Glasses in the 30La₂O₃-40TiO₂-30Nb₂O₅ system are known to have excellent optical properties such as refractive indices over 2.25 and wide transmittance within the visible to mid-infrared (MIR) region. However, titanoniobate glasses also tend to crystallize easily, significantly limiting their applications in optical glasses due to processing challenges. Therefore, the 30La₂O₃-40TiO₂-(30−x) Nb₂O₅-xAl₂O₃ (LTNA) glass system was successfully synthesized using a aerodynamic containerless technique, which improves glass thermal stability and expands the glass-forming region. The effects of Al₂O₃ on the structure, thermal, and optical properties of base composition glasses were investigated by XRD, DSC, NMR, Raman spectroscopy, and optical measurements. DSC results indicated that as the content of Al₂O₃ increased, the thermal stability of the glasses and glass-forming ability increased, as the 30La₂O₃-40TiO₂-25Nb₂O₅-5Al₂O₃ (Nb-Al-5) glass obtained the highest ΔT value (103.5°C). Structural analysis indicates that the proportion of [AlO₄] units increases gradually and participates in the glass network structure to increase connectivity, promoting more oxygen to become bridging oxygen and form [AlO₄] tetrahedral linkages to [TiO₅] and [NbO₆] groups. The refractive index values of amorphous glasses remained above 2.1 upon Al₂O₃ substitution, and a transmittance exceeding 65% in the visible and mid-infrared range. The crystallization activation energies of 30La₂O₃-40TiO₂-30Nb₂O₅ (Nb-Al-0) and Nb-Al-5 glasses were calculated to be 611.7 and 561.4 kJ/mol, and the Avrami parameters are 5.28 and 4.96, respectively. These results are useful to design new optical glass with good thermal stability, high refractive index and low wavelength dispersion for optical applications such as lenses, endoscopes, mini size lasers, and optical couplers.     

Phase equilibrium in binary La2O3-Dy2O3 and ternary CeO2-La2O3-Dy2O3 systems

Cerium oxide doped with oxides of rare earth elements is a multifunctional material, a wide range of uses which is associated with its unique physicochemical properties. Phase diagrams of multicomponent systems are the physicochemical basis for the creation of new materials with improved characteristics.In this work, phase equilibria in ternary CeO₂–La₂O₃–Dy₂O₃ and binary La₂O₃–Dy₂O₃ systems in the whole concentration range were studied. No new phases have been identified in these systems. An isothermal section of the phase diagram of the CeO₂–La₂O₃–Dy₂O₃ system at a temperature of 1500 °С is constructed. No new phases have been detected in the system. It was found that in the studied ternary system solid solutions are formed on the basis of (F) modification of CeO₂ with structure of fluorite type, monoclinic (B), cubic (C) and hexagonal (A) modifications of Ln₂O₃.In the La₂O₃–Dy₂O₃ binary system (1500–1100 °С) three types of solid solutions are formed: based on hexagonal modification A-La₂O₃, monoclinic modification B-Dy₂O₃ and cubic modification C-Dy₂O₃ separated by two-phase fields (A+B) and (B+C), respectively. The boundaries of the regions of homogeneity of solid solutions based on A-La₂O₃ are determined by compositions containing 35–40, 20–25, 15–20 mol% Dy₂O₃ at 1500, 1250, 1100 °C, respectively. From the obtained data it follows that the solubility of Dy₂O₃ in the hexagonal modification of lanthanum oxide is 39 mol% at 1500 °C, 23 mol. % at 1250 °C and 16 mol% at 1100 °C. The limits of existence of solid solutions based on monoclinic B-modification are determined by compositions containing 30–35, 65–60 (1250 °С), 35–40, 55–60 (1100 °С) 40–45, 70–75 (1500 °C) mol% Dy₂O₃.In the studied system, with a decrease in temperature from 1500° to 1100°C, there is a decrease in the solubility of La₂O₃ in the crystal lattice of cubic solid solutions of C-type from 16 to 10 mol%.     

Special features of the formation of an ultradisperse state in ceramic powders of the ZrO2 - Y2O3 - Al2O3 system

The influence of heat and laser treatment during the formation of the ultradisperse structure of composite powders of the ZrO₂ - Y₂O₃ - Al₂O₃ system is investigated. The parameters of short-range order of amorphous powders in the process of heat and laser treatment are determined. The effect of surface modification of ultradisperse powders on the structure formation and phase composition of the ceramics is established.Translated from Ogneupory, No. 11, pp. 12 – 14, November, 1994.     

Bactericidal Effectiveness of O3, O3/H2O2 and O3/TiO2 on Clostridium perfringens

The purpose of this research is to evaluate the bactericidal capacity of different Advanced Oxidation Treatments (AOTs) based on ozone: ozone, ozone/hydrogen peroxide and ozone/titanium dioxide on a wild strain of Clostridium perfringens, a fecal bacterial indicator in drinking water. The dose of ozone consumed ranges from 0.6 mg L^?1 min^?1 to 5.13 mg L^?1 min^?1 depending on the process and on the sample. In the treatments combined with O₃, H₂O₂ dose utilized is 0.04 mM and TiO₂ dose, 1 g L^?1. In order to evaluate the influence of natural organic matter and suspension solids over the disinfection rate, treatments are performed with two types of water – natural water from Ebro River (Zaragoza, Spain) and NaCl solution 0.9%. To achieve 4 log units of inactivation, 3.6 mg O₃ L^?1 is necessary in O₃ treatment, 4.25 mg O₃ L^?1 in O₃/TiO₂ system and 2.7 mg O₃ L^?1 in O₃/H₂O₂ after processing the natural water. In NaCl solution, to get the same inactivation, 0.42 mg O₃ L^?1 is necessary in O₃ treatment, 1.15 mg O₃ L^?1 in O₃/TiO₂ system and 0.06 mg O₃ L^?1 in O₃/H₂O₂ process. Even though the three treatments studied have a high bactericidal activity due to the number of surviving bacteria decreases to non-detectable levels, O₃/H₂O₂ is the most effective system for eliminating C. perfringens cells in a lower contact time, followed by O₃ and finally O₃/TiO₂ system.     

Behaviour of 54.4SiO2-13.7Na2O-1.7K2O-5.0CaO-12.4MgO-0.6Y2O3-11.3Al2O3-0.9B2O3 HT-SOFC glass sealant under oxidising and reducing atmospheres

The behaviour of the promising glass sealant 54.4SiO₂-13.7Na₂O-1.7K₂O-5.0CaO-12.4MgO-0.6Y₂O₃-11.3Al₂O₃-0.9B₂O₃ for solid oxide fuel cells (SOFCs) under SOFC operating conditions was studied. First, the kinetics of the crystallisation processes at the operating temperature (850 °C) was discussed (maximum exposure time of 1000 h), and the effect of crystallisation on the coefficient of thermal expansion (CTE) of the sealant was studied. Furthermore, the degradation processes at the interface of the glass sealant and functional SOFC materials (Crofer 22 APU, YSZ, and NiO(Ni)-YSZ) during exposure to 850 °C in oxidising and reducing atmospheres for 500 h were studied. The tests demonstrated good performance of the sealant studied and possibility of its application in SOFCs.     

Air plasma-sprayed Y2O3 coatings for Al2O3/Al2O3 ceramic matrix composites

Al₂O₃/Al₂O₃ ceramic matrix composites (CMC) are candidate materials for hot-gas leading components of gas turbines. Since Al₂O₃/Al₂O₃ CMC are prone to hot-corrosion in combustion environments, the development of environmental barrier coatings (EBC) is mandatory. Owing to its favorable chemical stability and thermal properties, Y₂O₃ is considered a candidate EBC material for Al₂O₃/Al₂O₃ CMC. Up to 1 mm thick Y₂O₃ coatings were deposited by means of air plasma spraying (APS) on Al₂O₃/Al₂O₃ CMC with a reaction-bonded Al₂O₃ bond-coat (RBAO). APS Y₂O₃ coatings exhibit a good adherence in the as-deposited state as well as upon isothermal annealing up to 1400 °C. Moreover, furnace cyclic testing performed at 1200 °C revealed an excellent durability. This is explained by the formation of a continuous, approximately 1 μm thick reaction zone at the APS Y₂O₃/RBAO interface. The reaction zone between Y₂O₃ and Al₂O₃ comprises three layers of thermodynamically stable yttrium-aluminates exhibiting strong bonding, respectively.     

Effect of NiO on phase formation in fused specimens of the ZrO2 - Al2O3 - NiO - Y2O3 system and properties of ceramics based on it

The effect of NiO on the formation of phases in the ZrO₂ - Al₂O₃ -Y₂O₃ - NiO system in heating of mixtures of the corresponding composition in a solar furnace is investigated. Some physicomechanical characteristics of ceramics based on them are described. Laboratory investigations showed that additions of NiO improve the operational properties of such ceramics strengthened due to the polymorphism of ZrO₂.Translated from Ogneupory, No. 10, pp. 14 – 15, October, 1995.     

Thermodynamic modeling of the K2O-Al2O3 and K2O-MgO-Al2O3 systems with emphasis on β- and βʹʹ-aluminas

A critical evaluation and thermodynamic modeling study including key phase diagram experiments was performed to investigate the K₂O-Al₂O₃ and K₂O-MgO-Al₂O₃ systems. For the first time, potassium β- and β??-alumina solid solutions were described using the Compound Energy Formalism with accurate cation distributions in their sublattices. From the new experimental results, the stability of potassium β??-alumina was assured up to 1600?°C. A large discrepancy reported in the literature, the eutectic temperature between KAlO₂ and β-alumina in the K₂O-Al₂O₃ system, was resolved. A set of self-consistent Gibbs energy functions for all stable phases in the K₂O-MgO-Al₂O₃ system was obtained. As a result, any phase diagram sections and thermodynamic properties of the K₂O-MgO-Al₂O₃ system can be calculated from the optimized Gibbs energy functions. In particular, the cation distribution in the β- and β??-alumina solid solutions is calculated depending on the non-stoichiometry of solution and temperature.     

Comprehensive study on corrosion protection properties of Al2O3, Cr2O3 and Al2O3–Cr2O3 ceramic coatings deposited by plasma spraying on carbon steel

In this study, individual Al₂O₃ and Cr₂O₃ coatings and Cr₂O₃-25, 50, 75 wt% Al₂O₃ composite coatings were applied on carbon steel by atmospheric plasma spraying method. Corrosion experiments were performed on as-sprayed and epoxy resin sealed coatings including potentiodynamic polarization, electrochemical impedance spectroscopy and long-term immersion in 3.5 wt% NaCl solution. Phase composition and microstructure of the coatings were investigated by x-ray diffraction, optical microscopy and scanning electron microscopy, before and after the corrosion experiment. The results showed that the Cr₂O₃ coating exhibited the best corrosion resistance, due to the densest microstructure and highest adhesion strength. The Cr₂O₃-25 wt% Al₂O₃ coating had the highest interconnected porosities and thus had the least corrosion resistance compared to other coatings. In general, the as-sprayed coatings induced a maximum increase of 3.93 times the polarization resistance (R_p) in the polarization experiment and a 3.5 times increase in the charge transfer resistance (R_ct) in the EIS experiment, which was not significant. Stresses caused by increased volume of corrosion products in the coating-substrate interface resulted in the spallation of Cr₂O₃-25, 50 wt% Al₂O₃ coatings from the substrate over long-term of immersion. The adhesion strength of the coatings was a determining criterion for the long-term durability of the coatings. The sealing treatment resulted in a significant increase in R_p and R_ct.     

Dielectric characterization of a novel Bi2O3-Nb2O5-SiO2-Al2O3 glass-ceramic with excellent charge-discharge properties

A newly designed glass-ceramic system consisting of 15Bi₂O₃-15Nb₂O₅-40SiO₂-30Al₂O₃ was successfully prepared, which was followed by its controlled crystallization at different heating temperatures. The effects of crystallization temperature on the microstructure, phase evolution and the energy storage behaviors of the novel material were systematically investigated. A maximum theoretical energy storage density of up to 15.3 J/cm³ was found in the samples heated at 800 °C. The polarization-electric (PE) hysteresis loops of this material exhibited very good linear character and high energy efficiency. In addition, an approximate value of 25 ns for discharged period T has been obtained, which demonstrated that most of the energy stored in dielectric was released over a very short time. The maximum powder density exceeds a high value of 90 MW/cc in a 390 kV/cm electric field. Therefore, the new developed Bi₂O₃-Nb₂O₅-SiO₂-Al₂O₃ glass-ceramic can be used as an alternative, promising high-performance electrostatic capacitor material.     

Temporal stability of oxygen-ion conductivity in 1Nb2O5-10Sc2O3-89ZrO2

A slight Nb₂O₅ co-doping in 11Sc₂O₃-89ZrO₂ was earlier reported to stabilize the high-symmetry cubic phase completely and enhances the conductivity significantly. The present work looked at the temporal stability of conductivity in 1Nb₂O₅-10Sc₂O₃-89ZrO₂ (1Nb10ScSZ) for the electrolyte application in solid oxide fuel cells. In-situ conductivity measurement was done using impedance spectroscopy at 650 °C in the air for 2000 h. A substantial conductivity loss (29%) was observed in the first 1000 h. Following which, conductivity remained relatively stable for the next 1000 h. Impedance analysis showed that the main contribution to the conductivity degradation was from grain conductivity. Phase analysis performed using XRD, TEM and Raman spectroscopy revealed that both the unaged and aged 1Nb10ScSZ samples consisted of metastable t″-phase. However, the extent of tetragonality was found to increase after ageing. The formation of low-symmetry phase was suggested to be the reason for the grain conductivity loss in 1Nb10ScSZ.     

(Sb2O3/Sb2O5)-doped SnO2–Co3O4–Cr2O3 varistors: The Sb2O4 in-situ formation and its influence over the electrical and microstructural properties

The present study aimed to systematically study the transitions and consequential effects of antimony oxide (Sb₂O₃ or Sb₂O₅) additions over the properties of a SnO₂-based varistor system. High energy ball-milling and conventional sintering were used to obtain the samples with the following molar composition: (98.95-X)% SnO₂ - 1% Co₃O₄ - 0.05% Cr₂O₃ - X% Sb₂O₃/Sb₂O₅ where X = 0, 0.05, 0.1, 0.2 and 0.4 mol%. The thermal analysis suggested the in-situ formation of Sb₂O₄ at ~450 °C from Sb₂O₃ or Sb₂O₅ during the sintering of mixed oxides. SEM, XRD, and electrical analysis revealed similar results by using Sb₂O₃ or Sb₂O₅; the addition of 0.05 mol% antimony oxide provides the foremost properties. The transition equations from Sb₂O₃ or Sb₂O₅ to Sb₂O₄ demonstrate equivalency in the amount of Sb₂O₄ formed. That fact, besides the results obtained, were used to discuss a reasonable route for Sb³⁺ and Sb⁵⁺ incorporation within the SnO₂ lattice.     

Influence of boron substitution on the crystallisation behaviour of tetracalcium phosphate phase in the 4.5SiO2-3Al2O3-1.5P2O5-5CaO glass system

This study focuses on the effect of boron substitution on the crystallisation behaviour of an important bioceramic phase, tetracalcium phosphate (TTCP, Ca₄P₂O₉), in the 4.5SiO₂-3Al₂O₃-1.5P₂O₅-5CaO glass system. The influence of phase separation on the crystallisation activation energy as well as the microstructure is systematically analysed. The results indicate that increasing the extent of substitution of B for Al tends to lead to a decrease of the glass-transition temperature (T_g) and crystallisation temperature (T_p). When the substitution amount of B reaches 15 mol%, phase separation is observed. Weak phase separations during glass making can promote the nucleation of crystals due to heterogeneous nucleation with reduced nucleation activation energy. When 50 mol% B is substituted, serious phase separation is observed, with spherical-shaped TTCP phases appearing in the glass. The growth of striped-shaped TTCP crystals is largely suppressed even when a long holding time (1 h) at 900 °C is applied.     

Spontaneous infiltrations of compound systems of Y2O3, Sm2O3, RE2O3, Al2O3 and AIN in SiC ceramics

Silicon carbide ceramics (SiC) are used in different applications in the engineering area due to the excellent properties, mainly in high temperatures. They are usually obtained by liquid-phase sintering enabling to form volatile products and, consequently, defects. The present work aims at studying the obtention of SiC ceramics by spontaneous infiltration using a eutectic composition of the Al₂O₃/Y₂O₃, AlN/Y₂O₃, Al₂O₃/Sm₂O₃, AlN/Sm₂O₃, Al₂O₃/RE₂O₃ and AlN/RE₂O₃ systems. RE₂O₃ is the concentrate of the rare-earth oxide obtained from Xenotime ore. Infiltration tests were carried out in argon atmosphere, graphite crucibles, in several temperatures near the melting point of each system, varying from 2.5 to 60 min. It was observed that Al₂O₃/Y₂O_3, Al₂O₃/Sm₂O₃, AlN/Sm₂O₃ and Al₂O₃/RE₂O₃ systems do not infiltrate appropriately and the AlN/Y₂O₃ and AlN/RE₂O₃ systems infiltrated spontaneously more than 20 mm; however, the first one presented a higher degree of infiltration, approximately 97%.     

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.     

Reactive sintered highly transparent AlON ceramics with Y2O3-MgAl2O4-H3BO3 ternary additive

In this study, highly transparent aluminate oxynitride (AlON) ceramics were prepared via the reactive sintering of Al₂O₃ and AlN powders using a Y₂O₃-MgAl₂O₄-H₃BO₃ ternary sintering additive. The ternary doping process resulted in the efficient preparation of transparent AlON ceramics with small grains and high transmittance as compared to the binary doping (Y₂O₃-MgAl₂O₄) process. The addition of 0.1 wt.% Y₂O₃-0.4 wt.% MgAl₂O₄-0.12 wt.% H₃BO₃ resulted in the formation of a 4-mm-thick AlON ceramic with high transmittance (81% at 600 nm) and low haze (3.46%). This is the best performance in terms of the thickness and transmittance reported for AlON transparent ceramics prepared by the reactive sintering method.