Eutectic structure evolution of Al2O3-ZrO2-Y2O3 system for potential hybrid solar cell application

Abstract

Ternary Al₂O₃-ZrO₂-Y₂O₃ samples with a eutectic composition were prepared by slow cooling. The microstructural evolution was observed with X-ray diffraction (XRD), scanning electron microscopy (SEM).

The SEM observation of the ternary samples agreed with the XRD with a completion of crystallisation by slow cooling. The target materials commonly have ‘cantaloupe skin’ microstructures as shown in the previous studies by Han et al. The nanocomposite may have experienced different cooling rates with two different microstructures, near the surface having experienced optimal conditions for the eutectic reaction during their cooling and thus formed the eutectic microstructure, near the centre having experienced a slower cooling rate. The crystallised eutectic ternary Al₂O₃-ZrO₂-Y₂O₃ system had three different phases with a 3Y₂O₃-5Al₂O₃ (yttrium-aluminium garnet phase), an alumina phase formed by the eutectic reaction, and a solid solution of ZrO₂ and Y₂O₃.     

Phase equilibrium studies in V2O5-Fe2O3 and V2O5-TiO2 systems

V₂O₅-Fe₂O₃ and V₂O₅-TiO₂ systems represent two important chemical systems with various applications, including energy, catalysts, and high-performance materials. In the present study, high-temperature phase equilibrium experiments were conducted at the temperature range of 670–1000°C in air. Electron probe X-ray micro-analyzer (EPMA) was used to analyze the microstructure and composition of the phases presented in quenched samples. Systematic experiments demonstrated that V₂O₅-containing systems should not be quenched by water-based quenching media. Phase diagrams in both systems were constructed, and the eutectic and peritectic points of the systems were confirmed and compared with previous studies. The present study improved the previous results and could be used as the base for thermodynamic modelings and further applications of the two systems.     

Effect of Concentration and Temperature on the Surface Morphology of Gd2O3 Nanocrystallites in Silica

Gd(NO₃)₃.6H₂O and TEOS were used as precursors and obtained Gd₂O₃:SiO₂ ceramic powder having different concentration of Gd₂O₃ as 2.2, 2.8, 3.4, and 4.0 wt % using solgel process. The powdered samples were annealed at 500°C and 900°C temperatures and characterized by XRD, FTIR, SEM, and TEM. In X‐ray diffraction, cubic phase of Gadolinium oxide is reported only for the annealed samples having higher concentration (3.4 & 4.0 wt %) of Gd₂O₃. SEM and TEM results further confirm that the surface morphology of the microstructures depend on the temperature and concentration.     

The structural and electrical comparison of Y2O3 and Ti-doped Y2O3 dielectrics

A Ti-doped Y₂O₃(Y₂Ti₂O₅) dielectric on polycrystalline silicon followed by rapid thermal annealing results in improved characteristics including a higher effective dielectric constant, higher breakdown electric field, lower electron trapping rate, and larger charge-to-breakdown when compared with Y₂O₃. The performance of high-k Y₂O₃ and Y₂Ti₂O₅ dielectrics were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), capacitance-voltage, and current density-voltage. Incorporating Ti into the Y₂O₃ dielectric imparts improvements in the structural and electrical performance of the material. The Y₂Ti₂O₅ dielectric with 800 °C annealing treatment has the best performance among all the samples tested.     

Changes in Ba Phases in BaO/Al2O3 upon Thermal Aging and H2O Treatment

The effects of thermal aging and H₂O treatment on the physicochemical properties of BaO/Al₂O₃ (the NO_x storage component in the lean NO_x trap systems) were investigated by means of X-ray diffraction (XRD), BET, TEM/EDX and NO₂ TPD. Thermal aging at 1000 °C for 10 h converted dispersed BaO/BaCO₃ on Al₂O₃ into low surface area crystalline BaAl₂O₄. TEM/EDX and XRD analysis showed that H₂O treatment at room temperature facilitated a dissolution/reprecipitation process, resulting in the formation of a highly crystalline BaCO₃ phase segregated from the Al₂O₃ support. Crystalline BaCO₃ was formed from conversion of both BaAl₂O₄ and a dispersed BaO/BaCO₃ phase, initially present on the Al₂O₃ support material after calcinations at 1000 and 500 °C, respectively. Such a phase change proceeded rapidly for dispersed BaO/BaCO₃/Al₂O₃ samples calcined at relatively low temperatures with large BaCO₃ crystallites observed in XRD within 10 min after contacting the sample with water. Significantly, we also find that the change in barium phase occurs even at room temperature in an ambient atmosphere by contact of the sample with moisture in the air, although the rate is relatively slow. These phenomena imply that special care to prevent the water contact must be taken during catalyst synthesis/storage, and during realistic operation of Pt/BaO/Al₂O₃ NO_x trap catalysts since both processes involve potential exposure of the material to CO₂ and liquid and/or vapor H₂O. Based on the results, a model that describes the behavior of Ba-containing species upon thermal aging and H₂O treatment is proposed.     

Photoluminescence properties of Eu3+-doped stalk-like Al2O3 via a hydrothermal route followed by heat treatment

ABSTRACT

Uniform Al₂O₃:Eu³⁺ samples were successfully fabricated via a hydrothermal method and subsequent thermal decomposition of Eu³⁺-doped precursors. The sample characterisations were carried out by means of X-ray diffraction (XRD), scanning electron microscope (SEM) and photoluminescence spectra. XRD results revealed Eu³⁺-doped samples were a pure γ-Al₂O₃ phase after being calcined at 1173?K. SEM results showed that these Eu³⁺-doped Al₂O₃ samples were stalk-like, with an average length of 1.5?μm. Upon excitation at 394?nm, the orange–red emission bands, having wavelengths longer than 580?nm, were to be from ⁵D₀→⁷F_J (J?=?1, 2) transitions. The asymmetry ratio of (⁵D₀→⁷F₂)/(⁵D₀→⁷F₁) intensity is about 0.54, 2.76, 3.29, 2.86, 3.36, 3.13 for Eu³⁺ concentrations of 0.1, 0.4, 0.7, 1.0, 1.5 and 2.0?mol-%, respectively. The optimal doping concentration of Eu³⁺ ions in Al₂O₃ is 1.5?mol-%. According to Dexter's theory, the critical distance between Eu³⁺ ions for energy transfer was determined to be 14?Å.     

Thermochemistry of BaSm2O4 and thermodynamic assessment of the BaO–Sm2O3 system

The BaO–Sm₂O₃ system is of interest for the optimization of synthesis of electroceramics. The only systematic experimental study of phase equilibria in the system was performed more than 40 years ago. The reported experimental values of the enthalpy of formation of BaSm₂O₄ are in conflict, and the reported compound Ba₃Sm₄O₉ has never been confirmed. In this work we synthesized BaSm₂O₄ by solid‐state reaction and determined its heat capacity, enthalpy of formation, and phase transitions by differential scanning calorimetry, high‐temperature oxide melt solution calorimetry and ultra‐high‐temperature differential thermal analysis, respectively. We confirmed the existence of Ba₃Sm₄O₉ and its apparent stability from 1873 to 2273 K by X‐ray diffraction on quenched laser‐melted samples but were not able to obtain single‐phase material for calorimetric measurements. The CALPHAD method was used to assess phase equilibria in the BaO–Sm₂O₃ system, using both available literature data and our new measurements. A self‐consistent thermodynamic database and the calculated phase diagram of the BaO–Sm₂O₃ system are provided. This work can be used to model and thus to understand the relationships among composition, temperature, and microstructure for multicomponent systems with BaO and Sm₂O₃.     

Statistical Optimization of the Biodiesel Production Process Using a Magnetic Core‐Mesoporous Shell KOH/Fe3O4@γ‐Al2O3 Nanocatalyst

A magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was synthesized using the Fe₃O₄@γ‐Al₂O₃ core‐shell structure as support and KOH as active component. The prepared samples were characterized by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), energy‐dispersive X‐ray spectroscopy (EDS), Fourier transform infrared (FTIR), Brunauer‐Emmett‐Teller (BET), and vibrating sample magnetometry (VSM) techniques. Transesterification of canola oil to methyl esters (biodiesel) in the presence of the magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was investigated. Response surface methodology (RSM) based on the Box‐Behnken design (BBD) was employed to optimize the influence of important operating variables on the yield of biodiesel. A biodiesel yield of 97.4 % was achieved under optimum reaction conditions. There was an excellent agreement between experimental and predicted results.     

Synthesis of Nanofiber‐like Mesoporous γ‐Al2O3 toward Its Adsorption Efficiency for Congo Red

Nanofiber‐like mesoporous γ‐Al₂O₃ was synthesized using freshly prepared boehmite sol in the presence of triblock copolymer, P123 following evaporation‐induced self‐assembly (EISA) process followed by calcinations at 400°C–1000°C. The samples were characterized by thermogravimetry (TG), differential thermal analysis (DTA), X‐ray diffraction (XRD), N₂ adsorption–desorption, and transmission electron microscopy (TEM). The adsorption efficiency of the samples with Congo red (CR) was studied by UV – vis spectroscopy. XRD results showed boehmite phase in the as‐prepared sample while γ‐Al₂O₃ phase obtained at 400°C was stable up to 900°C, a little transformation of θ‐Al₂O₃ resulted at 1000°C. The Brunauer‐Emmett‐Teller surface area of the 400°C‐treated sample was found to be 175.5 m²g ^{? 1}. The TEM micrograph showed nanofiber‐like morphology of γ‐Al₂O_3. The 400°C‐treated sample showed about 100% CR adsorption within 60 min.     

Phase relations of CaO-Al2O3-Sc2O3 ternary system

We investigated the isothermal section of the CaO-Al₂O₃-Sc₂O₃ ternary system at 1773 and 1873 K for 24 hours in Ar, and quenched in water to determine the operative phase equilibrate. The composition of the phases in equilibrium was determined by electron probe microanalysis. The isothermal section phase diagram of two temperature points (1773 and 1873 K) is obtained. The 1773 K isothermal section consists of one liquid compound (L), six binary compounds (CaO+L, Ca₂Sc₆Al₆O₂₀+L C₃A+L, CaO.Sc₂O₃+L, CA+L, Ca₂Sc₆Al₆O₂₀+Sc₂O₃) and seven ternary compounds (Ca₂Sc₆Al₆O₂₀+Sc₂O₃+CA₆, Ca₂Sc₆Al₆O₂₀+Sc₂O₃+L, Ca₂Sc₆Al₆O₂₀+CA+L, Ca₂Sc₆Al₆O₂₀+CA₂+CA, Ca₂Sc₆Al₆O₂₀+CA₂+CA₆, CaO.Sc₂O₃+L+Sc₂O₃, C₃A+CaO+L). At 1873 K, we found one liquid compound (L), five binary compounds (CaO+L, Ca₂Sc₆Al₆O₂₀+L, CaO.Sc₂O₃+L, CA+L, Ca₂Sc₆Al₆O₂₀+Sc₂O₃₎ and six ternary compounds (Ca₂Sc₆Al₆O₂₀+Sc₂O₃+CA₆, Ca₂Sc₆Al₆O₂₀+Sc₂O₃+L, Ca₂Sc₆Al₆O₂₀+CA+L, Ca₂Sc₆Al₆O₂₀+CA₂+CA, Ca₂Sc₆Al₆O₂₀+CA₂+CA₆, CaO.Sc₂O₃+L+Sc₂O₃) to exist at the isothermal section. The experimental information obtained in the present work not only is essential for the thermodynamic assessment of the CaO-Al₂O₃-Sc₂O₃ ternary system, but also is important for further investigation on separation of rare earths from metallurgical slags and rare-earth recovery.     

Crystallization kinetics of La2O3–Al2O3–B2O3 glass–ceramic composites

One glass formulation (L2 glass) with the composition of La₂O₃, Al₂O₃ and B₂O₃ in a molar ratio of 10:10:80 was selected to cofire with Al₂O₃ filler. The composites underwent a two-stage crystalline evolution in the temperature range of 800 to 975 °C. The crystallization kinetics of LaBO₃ grains and the transformation to LaAl₂B₃O₉ phase were investigated by DTA, XRD, SEM/EDS, and TEM. The results showed that the Al₂O₃ filler plays an important role as the heterogeneous sites of LaBO₃ nuclei, and as reactant for the formation of flaky LaAl₂B₃O₉ crystals. The apparent activation energy of LaBO₃-phase formation in L2 glass was 534 kJ/mol and reduced to 466 kJ/mol by the addition of Al₂O₃. The detail transformation reactions, kinetics, and the crystalline orientation relationship between those phases are reported.     

Electrical characterisation of Pb2Bi3SmTi5O18 ceramic using impedance spectroscopy

Abstract

Polycrystalline sample of Pb₂Bi₃SmTi₅O₁₈, a member of tungsten–bronze (TB) family, was prepared using a high temperature solid state reaction technique. X-ray diffraction (XRD) analysis indicated the formation of a single phase orthorhombic structure. AC impedance plots were used as a tool to analyse the electrical behaviour of the sample as a function of frequency at different temperatures. The ac impedance studies revealed the presence of grain boundary effect, from 350°C onward. Complex impedance analysis indicated non-Debye type dielectric relaxation. The Nyquist plot showed the negative temperature coefficient of resistance (NTCR) character of Pb₂Bi₃SmTi₅O₁₈. AC conductivity data were used to evaluate the density of states at Fermi level and activation energy of the compound.     

Long-sized rods of Al2O3–SiC–TiB2 ceramic composite material obtained by SHS-extrusion: Microstructure,X-ray analysis and properties

Long-sized rods of Al₂O₃–SiC–TiB₂ ceramic composite material were obtained by SHS-extrusion. The material was synthesized by self-propagating high-temperature synthesis (SHS) followed by high-temperature shear deformation. Ceramic samples app up to 465 mm in length and 5 mm in diameter were obtained. According to the results of XRD and SEM the obtained rods have a composite structure. The matrix is Al₂O₃ with distributed titanium diboride and silicon carbide particles. A uniform phase distribution was observed along the entire length of the rod. The microhardness of the matrix was 25–26 GPa, that of the dispersion-strengthening phases - 32–34 GPa. Heat resistance tests showed that during heat treatment at T = 1000 °C for 21 h, the sample specific weight gain and its real rate were 8.3 g/m² and 1 g/(m²∙h), respectively. The density, hardness and electrical resistivity of the samples obtained in this work were 3.27 g/cm³, 19.5 GPa, 3.1∙10⁻⁵ Ohm∙m, respectively.     

Synthesis and characterization of polyimide‐γ‐Fe2O3 nanocomposites

Novel polyimide‐γ‐Fe₂O₃ hybrid nanocomposite films (PI/γ‐Fe₂O₃) has been developed from the poly(amic acid) salt of oxydianiline with different weight percentages (5, 10, 15 wt %) of γ‐Fe₂O₃ using tetrahydrofuran (THF) and N,N‐dimethylacetamide (DMAc) as aprotic solvents. The prepared polyimide‐γ‐Fe₂O₃ nanocomposite films were characterized for their structure, morphology, and thermal behavior employing Fourier transform infrared spectroscopy (FTIR), scanning electron micrograph (SEM), transmission electron micrograph (TEM), X‐ray diffraction (XRD), ¹³C‐NMR, and thermal analysis (TGA/DSC) techniques. These studies showed the homogenous dispersion of γ‐Fe₂O₃ in the polyimide matrix with an increase in the thermal stability of the composite films on γ‐Fe₂O₃ loadings. Magnetization measurements (magnetic hysteresis traces) have shown very high values of coercive force indicating their possible use in memory devices and in other related applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 834–840, 2007     

Influence of the Fuel Used in the Microwave Synthesis of Cr2O3

The synthesis and physico-chemical characterization of chromium oxide (Cr₂O₃) is reported. Samples were prepared by a novel microwave technique using two different fuels, i.e., tetraformaltrisazzine (TFTA) and urea. The physical characterization of the synthesized chromium oxides was achieved using XRD, IR, Raman, BET surface area and pore size distribution (PSD) techniques. The XRD and IR and Raman spectroscopy studies reveal that crystalline Cr₂O₃ is the only phase formed. The XRD, surface area and particle size analysis reveal that the samples prepared using TFTA as the fuel possess a larger surface area, smaller crystalline size, smaller particle size and larger pore diameter. Both samples were calcined at 600°C for 6 h so that they could be used for the catalytic oxidation of LPG. Catalytic runs on the Cr₂O₃ samples revealed that the two samples possess different activity and selectivity. The Cr₂O₃ sample prepared by using TFTA as the fuel gave rise to more dehydrogenation and cracking compared to the sample prepared by using urea as the fuel, which gave more combustion products.     

High-performance Al2O3 ceramics prepared by DCC-HVCI via microwave heating

A novel and rapid fabrication method for Al₂O₃ ceramics by the DCC-HVCI method via microwave heating was proposed. Effects of microwave heating temperature on coagulation time, micromorphology, as well as performance of the green body and ceramic sample were studied. As the microwave heating temperature rises, the coagulation time gradually reduced and compressive strength of green sample decreased while relative density and flexural strength of ceramics rose at the beginning and then dropped. The 50 vol.% Al₂O₃ suspension was coagulated and demolded after treating at 60°C for 800 s by microwave heating. The compressive strength of green samples reached 1.12 ± 0.13 MPa. The relative density of Al₂O₃ ceramic samples reached 99.39%. And the flexural strength of Al₂O₃ ceramics reached 334.55 ± 26.41 MPa. The Weibull modulus of Al₂O₃ ceramics reached 19. In contrast with the ceramic samples heated through water bath, the ceramic samples treated through microwave possessed uniform microstructures. Microwave heating could reduce the coagulation time by 77%. Meanwhile, it could significantly raise the compressive strength of green bodies by 65%. Additionally, it could increase the flexural strength of ceramics by 30%.     

Microwave-assisted synthesis of nanosized α-Al2O3

Nanosized alumina powder was prepared from a mixture of aluminium nitrate and carbon black through microwave heating (2.45 GHz and 900 W) for different times. The products were characterized by powder X-ray diffraction. The results showed that γ-Al₂O₃ was the main phase for powder samples heated for 4 and 6 min. When heating was extended to 8 min, weak peaks of α-Al₂O₃ also appeared. For heating times longer than 10 min, α-Al₂O₃ was the only crystalline phase present. The resultant particles were observed by SEM and TEM methods. The average particle size was found to be 96 nm. The surface area of powder was 48 m²/g after 15 min heating.     

Investigation on the phase stability of cubic perovskite BaCo0.7Fe0.2Nb0.1O3-δ oxygen-permeable membrane

The phase stability of the cubic perovskite-type oxide BaCo_0.7Fe_0.2Nb_0.1O_3?δ (BCFNO) has been examined by means of X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). And, the timescale on the second phases has been established by using the TOPAS 4.2. Compared with Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCFO), for samples annealed at T?=?1023?K for t?=?64 d, the rhombohedral and hexagonal phases formed on the surface of cubic perovskite BCFNO surface simultaneously and the amount of them is smaller. As for the rhombohedral phase, it comes out firstly along the grain boundary, and whose amount in equilibrium is about 5％. In contrast to the rhombohedral phase, the hexagonal phase is more likely to form at lower temperature which lead to the microcracks. In brief, obtaining the eligible phase stability is crucial for the industrial application of the oxygen permeation membrane.     

In situ reaction synthesis of Al2O3–SiC nanostructure using different carbon sources

Abstract

The formation of Al₂O₃–SiC nanostructure was studied using three different carbon sources (charcoal activated, graphite and carbon black) mixed with colloidal silica and aluminium nitrate. All mixtures were heated at 1500°C for duration of 30, 45 and 60 min. The results showed that Al₂O₃–SiC powders with an average diameter of ～220 nm and almost equiaxial geometry with aspect ratio of 1–1·2 could only be synthesised from the mixture containing carbon black (30 wt-%) at low heating time (30 min). It was found that the intensity of SiC peaks was the highest in samples containing graphite which was attributed to the higher initial density of this sample.     

Mechanism-based tuning of room-temperature ferromagnetism in Mn-doped β-Ga2O3 by annealing atmosphere

Mn-doped β-Ga₂O₃ (GMO) films with room-temperature ferromagnetism (RTFM) are synthesized by polymer-assisted deposition, and the effects of annealing atmosphere (air or pure O₂ gas) on their structures and physical properties are investigated. The characterizations show that the concentrations of vacancy defects and Mn dopants in various valence states and lattice constants of the samples are all modulated by the annealing atmosphere. Notably, the samples annealed in air (GMO–air) exhibit a saturation magnetization as strong as 170% times that of the samples annealed in pure O₂ gas (GMO–O₂), which can be quantitatively explained by oxygen vacancy (V_O)-controlled ferromagnetism due to bound magnetic polarons established between delocalized hydrogenic electrons of V_Os and local magnetic moments of Mn²⁺, Mn³⁺, and Mn⁴⁺ ions in the samples. Our results provide insights into mechanism-based tuning of RTFM in Ga₂O₃ and may be useful for design, fabrication, and application of related spintronic materials.