Estimated immiscibility isotherms of the Li2O-Al2O3-SiO2 system

Using the immiscibility temperature estimation method, recently developed by the present author and Tomozawa, immiscibility isotherms of the Li₂O-Al₂O₃-SiO₂ system were estimated. High reliability of the estimated immiscibility isotherms was confirmed by observing the morphologies of phase-separated glasses, and also by comparing the estimated and observed immiscibility temperatures at several compositions. The determined immiscibility isotherms revealed that, in the Li₂O-Al₂O₃-SiO₂ system, only composition regions near the Li₂O-SiO₂ and Al₂O₃-SiO₂ binary edges are phase-separable. In composition regions where base glasses for commercial glass-ceramics are located, the immiscibility temperatures were much lower than the glass transition temperatures, implying that no phase separation actually occurs. Accordingly the phase separation in practical glasses for producing glass-ceramics may be attributed to increased immiscibility resulting from various additives.     

Phase separation in Li2O-SiO2 glasses with additions of V2O5, MnO2 and Cr2O3

A number of lithium silicate glasses, inside and just outside the miscibility gap, containing low percentages of V₂O₅, MnO₂ and Cr₂O₃ were examined by electron microscopy techniques. Upon heat treatment in the range 450 to 550° C these glasses exhibited phase separation preceding extensive crystallization. The Li₂O contents (mol%) of the base glass compositions were: 26 (C-I), 30 (C-II), 34 (C-III) and 37 (C-IV). The V₂O₅ and MnO₂ additions were 1 mol% and the Cr₂O₃ addition was 0.1 mol%. Globular or sectorized domains were obtained for compositions C-I to C-III containing V₂O₅, for formulations C-II to C-IV containing Cr₂O₃ and for glass C-I containing MnO₂. In nearly every case a much finer liquid-phase separation of droplet type was also detected. The results indicate that V₂O₅ and MnO₂ widen the Li₂O-SiO₂ miscibility gap and that the Cr₂O₃ may cause fine-scale crystallization.     

Crystallization behavior of amorphous solid solutions and phase sepration in the Cr2O3-Fe2O3 system

Fine particles of the amorphous Cr₂O₃-Fe₂O₂ solid solutions were prepared by dehydration of coprecipitated hydroxides and their crystallization behavior was studied by differential thermal analysis and X-ray diffraction. The peak temperature for crystallization attained a maximum at a composition near Fe₂O₃ content of about 60 mol % and the activation energy for crystallization attained a minimum at a composition near Fe₂O₃ content of about 50 mol % in this quasibinary system. Phase separation occurred in a range of Fe₂O₃ content from about 35 to 80 mol % in the corundum-type solid solutions heat treated at 600 °C for 2 h. Crystallization behavior was discussed briefly related with phase separation and diffusion in fine particles.     

Study of Al2O3 effect on structural change and phase separation in Na2O-B2O3-SiO2 glass by NMR

The effect of Al₂O₃ on the structure change and the phase separation in Na₂O-B₂O₃-SiO₂ glass was investigated using ¹¹B nuclear magnetic resonance (NMR), ²⁹Si MAS NMR, and ²⁷Al MAS NMR together with infrared absorption spectroscopy and field emission scanning electron microscopy (FE-SEM). The results show that the structure change from the introduction of Al₂O₃ contributes greatly to the inhibition of phase separation. First, the introduction of Al₂O₃ imparts an ionic character to the boron-oxygen network, resulting in the formation of B-O-Al-O-Si bonds and thus increases the compatibility of the silicon network with the boron-oxygen network. Second, the addition of Al₂O₃ causes the sodium ion to transfer from the boron-oxygen network to AlO₄ tetradedra, changing a number of four-coordinated borons into three-coordinated borons. As the bond energy of the four-coordinated boron is weaker than that of the three-coordinated boron, the -B-O-Si- bond with the four-coordinated boron in Na₂O-B₂O₃-SiO₂ glasses is easily broken and results in severe phase separation during heat treatment. However, the -B-O-Al- bond with the three-coordinated boron formed in Na₂O-B₂O₃-SiO₂-Al₂O₃ glasses is difficult to be broken due to the high bond energy. In addition, the silicon network in Na₂O-B₂O₃-SiO₂-Al₂O₃ glasses is also strengthened by the addition of Al₂O₃, which prevents [BO] groups from further aggregation. As a result, the tendency of the glass towards phase separation is greatly suppressed in the Na₂O-B₂O₃-SiO₂-Al₂O₃ system.     

Rare-gas mobility in some anisotropic ceramic oxides: Al2O3, Cr2O3, Fe2O3, TiO2, U3O8

The mobility of the inert gases xenon or radon in five anisotropic oxides (hexagonal corundum Al₂O₃, Cr₂O₃, Fe₂O₃, tetragonal rutile TiO₂, and orthorhombic U₃O₈) was studied. The gases were introduced by ion bombardment. The oxides were in the form of powders, sinters, or single crystals. Normal volume diffusion was found at low gas concentration, the activation energies in kilocalories per mole being 85 for Al₂O₃, 73±5 for Cr₂O₃, 68±5 for Fe₂O₃, 78±5 for TiO₂, and 85±8 for U₃O₈, and the pre-exponential termsD ₀ falling into the ideal range of about 3×10^–1±1 cm²/sec. Structural radiation damage, the annealing of which coincided with gas release at low temperatures, and, in some cases, retardation of the gas release were found at higher gas concentrations. Some evidence is presented that grain boundaries, pre-existing vacancy clusters, and dislocation loops may act as trapping sites for gas atoms (or bubbles) and may be stabilised after trapping of the gas.     

Effect of phase separation on the fracture toughness of SiO2-B2O3-Na2O glass

Fracture toughness of glass is usually poor, due to the absence of grain boundaries and discontinuities. The compositions of the glass studied are in the phase separated region of SiO₂-B₂O₃-Na₂O system. The interface between the glass in glass separation enhances the fracture toughness. The increase in the connectivity of phase separated regions causes increase of fracture toughness from 0.98 through 1.43 to 1. 54 MPam1/2.     

Glass formation and immiscibility in the TeO2-B2O3-Fe2O3-MnO system

The glass formation in the quaternary TeO₂-B₂O₃-MnO-Fe₂O₃ system and in its ternary systems was investigated. A range of liquid immiscible phases, located near to the binary TeO₂-B₂O₃ and B₂O₃-MnO systems was established. Using transmission electron microscopy, a trend to metastable liquid-phase separation in the single-phase glasses, located near to the boundary of immiscibility was observed. With an increase in the Fe₂O₃ and MnO content still in the process of cooling of the melts, it was possible for a fine glassy crystalline structure to be formed in them. It was shown that by changing the upper limit of the melting temperature and the cooling rate, the glassy crystalline structure and the Fe₃O₄ content could be modified.     

Structural studies of some V2O5-P2O5-B2O3-Fe2O3 glass systems

X-ray diffraction and infrared measurements were performed on vanadium borophosphate glass containing different amounts of iron ranging from 0–7.5 mol % and heat treated at 300 °C for various times. The structure and phase separation could be determined for each glass composition. V₂O₅ was the main precipitated phase in all heat-treated samples, and its amount was dependent on the heat-treatment time and Fe₂O₃ content. Also FeP was detected in samples heat treated for 24 h. The infrared measurements showed the presence of both V⁴⁺ and V⁵⁺. The symmetry of V₂O ₇ ⁴⁻ and VO ₄ ³⁻ groups was found to increase with increasing Fe₂O₃ content. It was also found that some PO₄ changed to BO₃, forming a non-bridging oxygen.     

Surface tension of PbO-B2O3 and Bi2O3-B2O3 glass melts

The surface tensions of xPbO-(100?x) B₂O₃ (x = 30–80 mol%) and xBi₂O₃-(100?x) B₂O₃ (x = 0–100 mol%) melts were measured using the ring method over the temperature range 973 to 1373 K. The compositional and temperature dependences of surface tension were investigated. Addition of PbO and Bi₂O₃ to B₂O₃ increased the surface tensions of their respective PbO-B₂O₃ and Bi₂O₃-B₂O₃ melts. The surface tension showed a maximum at 60 mol% PbO in the PbO-B₂O₃ melts and at 70–80 mol% Bi₂O₃ in the Bi₂O₃-B₂O₃ melts. The temperature coefficient of surface tension was examined on the basis of its relationship to the structure, and it was suggested that the temperature coefficient of surface tension decreases with an increasing content of four-coordinated boron.     

Subsolidus,high temperature phase relations in the systems Al2O3-Cr2O3-ZrO2, MgO-Cr2O3-ZrO2 and MgO-Al2O3-ZrO2

In the temperature range 1600 to 1900° C, the system A₂O₃-Cr₂O₃-ZrO₂ is characterized by the coexistence of ZrO₂ (unstablilized) and an (Al, Cr)₂O₃ solid solution series. In the systems MgO-Cr₂O₃-ZrO₂ and MgO-Al₂O₃-ZrO₂ a nearly stoichiometric spinel coexists with both stabilized and unstabilized ZrO₂. At temperatures above 1600°C a new ternary Mg-Al-Zr oxide becomes stable in the MgO-rich part of the MgO-Al₂O₃-ZrO₂ system.     

Magnetic and luminescent properties of Fe3O4@Y2O3:Eu3+ nanocomposites

The multifunctional Fe₃O₄@Y₂O₃:Eu³⁺ nanocomposites were prepared by a facile solvothermal method with Fe₃O₄ nanoparticles as the core and europium-doped yttrium oxide (Y₂O₃:Eu³⁺) as the shell. It is shown that Fe₃O₄@Y₂O₃:Eu³⁺ nanocomposites have a strong photoluminescence and special saturation magnetization Ms of 6.1 emu/g at room temperature. The effects of the magnetic field on the luminescence intensities of the nanocomposites are being discussed. The multifunctional nanocomposites with magnetic resonance response and fluorescence probe properties may be useful in biomedical applications, such as cell separation and bioimaging.     

Immiscibility in the TeO2-B2O3 system

Experimental investigations have been carried out to study the phase separation process in the TeO₂-B₂O₃ system. It was found that the phase diagram is of a eutectic-like type (monotectic invariant reaction), with a wide region of stable and metastable phase separation. During the cooling of the melts two phases are obtained. One has a high TeO₂ content and is a transparent glass. The other, richer in B₂O₃, is opaque and in structure constitutes a complicated microheterogeneous system.     

Phase equilibrium relations in the V2O3-La2O3 system

Phase equilibrium relations in the V₂O₃-La₂O₃ system were investigated by X-ray powder diffraction and metallographic techniques. Binary mixtures, prepared from high-purity V₂O₃ and La₂O₃ powders, were equilibrated at 1600° C and then arc-melted under a partial pressure of argon. The specimens were heat-treated at various predetermined temperatures for prolonged periods and the phases present were identified by reflected-light microscopy and X-ray powder diffraction. The system consists of only one binary compound LaVO₃. A eutectic between V₂O₃ and LaVO₃ was established at 1750° C and 19 mol % La₂O₃ and also between LaVO₃ and La₂O₃ at 1765° C and 75 moi % La₂O₃. No appreciable solid solubility was detected in the system.     

Structural and microstructural transitions during phase separation and crystallization of Al2O3-SiO2-P2O5-Y2O3 glass

A highly refractory glass in the system Al₂O₃-SiO₂-P₂O₅-Y₂O₃ has been designed and produced such that, upon heating, an essentially fully crystalline glass—ceramic evolves containing mullite (nominally 3Al₂O₃·2SiO₂) and xenotime (YPO₄) as the final principal phases. Phase separation in this glass occurred during cooling from the melt and continued during annealing. XPS of the Al 2p, P 2p and the Y 3d electrons revealed that the average chemical environment of each of these elements is measurably different in the annealed glass and in the completely crystallized material. This indicates that the compositions of the separated glass phases are very different from those of the crystal phases which form from them. Additional rearrangement of the glass structure was observed at 1173 K. Extensive formation of mullite was initially detected at 1223 K and was followed by the crystallization of xenotime and the transient compounds of Y₄Al₂O₉, Y₂Si₂O₇, AlPO₄ and YP₅O₁₄. The optimum crystal nucleation and crystallization temperatures of 1173 and 1473 K, respectively, were determined from DTA, XRD, SEM and TEM studies.     

Plasma spraying of Al2O3 and Al2O3Y2O3

A microstructural study has been carried out of plasma-sprayed Al₂O₃ and mixed and sintered Al₂O₃Y₂O₃. In order to ascertain the degree of metastability achieved by plasma spraying, these results are compared with a similar experiment utilizing a CO₂ laser for melting and the hammer-and-anvil technique for quenching of the same materials. X-ray diffraction methods were used to determine the obtained phases and crystal structures. In addition, transmission electron microscopy was used to confirm the phases present and to study their morpology. The porosity was studied with both mercury intrusion porosimetry and small angle neutron scattering. The addition of Y₂O₃ is shown to decrease the porosity from 15% to 7.5%. Adhesion is likewise related to the addition of Y₂O₃ and it is seen that adhesion of the mixture is measurably improved over that of pure Al₂O₃. The implication of these results is discussed.     

Some physical properties of V2O5-Fe2O3 and V2O5-Fe2O3-Li2O systems

Various methods have been used to study the physical properties of the V₂O₅-Fe₂O₃ and V₂O₅-Fe₂O₃-Li₂O systems, including X-ray, electron microscope, Mössbauer effect, NMR and thermogravimetric measurements. The iron ions are approximately equally distributed in substitutional and interstitial sites in the V₂O₅ lattice. The maximum number of iron ions dissolved in the V₂O₅ matrix corresponds to 4 mol % Fe₂O₃. In all the samples a quantity of Fe₂O₃ which has not been included in lattice is observed. The V₂O₅-Fe₂O₃ and V₂O₅-Fe₂O₃-Li₂O systems are formed from solid solutions mixed with very small Fe₂O₃ particles. The analysis of the charge compensation of iron ions suggests that V₂O₅ is a quasi-amorphous semiconductor. Irradiation of V₂O₅-based samples with an electron beam induces the V₂O₅ platelets to convert to the VO _x phase.     

Microstructure and mechanical properties of Al2O3-Cr2O3-ZrO2 composites

Al₂O₃ is a popular ceramic and has been used widely in many applications and studied in many aspects. On the other hand, zirconia-toughened alumina (ZTA) is a desirable material for engineering ceramics because of its high hardness, high wear resistance and high toughness. In the present research, Al₂O₃-Cr₂O₃-ZrO₂ composites were produced by hot-pressing in order to harden the Al₂O₃ matrix in ZTA. Its microstructure and mechanical properties were studied by SEM, ESCA, XRD, Vickers hardness and bending strength test. It was found that addition of ZrO₂ inhibited the grain growth of Al₂O₃-Cr₂O₃ and the grain growth of ZrO₂ proceeded with increasing amounts of ZrO₂ in the Al₂O₃-Cr₂O₃-Zr₂ composite. The formation of solid solution Al₂O₃-Cr₂O₃ was also confirmed by XRD, and monoclinic ZrO₂ increased on addition of Cr₂O₃. Maximum hardness was at Al₂O₃-10wt% Cr₂O₃ with 10 vol% ZrO₂ and a stress-induced transformation was confirmed on the fracture surface of the specimen after the bending test.     

Surface,grain-boundary and interfacial energies in Al2O3 and Al2O3-Sn,Al2O3-Co systems

Using the multiphase equilibrium method for the measurement of contact angles, the surface and grain-boundary energies of polycrystalline Al₂O₃ in the temperature range of 1473 to 1923 K were determined. Linear temperature functions were obtained by extrapolation for both quantities between absolute zero and the melting point of Al₂O₃. The temperature dependence of the surface and grain boundary energies can be expressed as $$\gamma _{{\rm A}l_2 O_3 } = 2.559 - 0.784 \times 10^{ - 3} T(J m^{ - 2} )$$ and $$\gamma _{{\rm A}l_2 O_3 - Al_2 O_3 = } 1.913 - 0.611 \times 10^{ - 3} T(J m^{ - 2} )$$ respectively. The interfacial energies of Al₂O₃ in contact with the molten metals tin and cobalt revealed a linear dependence on temperature.     

Solid state reactions in the Fe2O3-CaCO3-In2O3 system

The kinetics of solid-state reactions of powdered reactants were investigated by X-ray and by differential thermogravimetry in a magnetic field. Measurements revealed mutual diffusion of the Fe³⁺ and In³⁺ ions in the Fe₂O₃-In₂O₃ system heat treated for 3 h at 700 to 1400° C. Diffusion of indium into the Fe₂O₃ lattice caused a shift of the Curie temperature of the antiferromagnetic iron oxide towards lower temperatures. Only Caln₂O₄ was found between CaCO₃ and In₂O₃ up to 1400° C. Also, in the Fe₂O₃-CaCO₃-In₂O₃in system, the reaction started with the mutual diffusion of iron and indium and the forming of CaFe₂O₄. End-products were the magnetic -Ca₄Fe₁₄O₂₅ and CaFe₄O₇, and the non-magnetic CaFe₅O₇, depending on the In³⁺ concentration. Indium stabilized the magnetic calcium-iron oxide structures, shifting their Curie temperatures towards lower values.     

In situ fabrication of α-Fe2O3/CaFe2O4 p-n heterojunction with enhanced VOCs photodegradation activity

α-Fe₂O₃/CaFe₂O₄ p-n heterojunctions were prepared via a simple in-situ hydrolysis process as highly efficient VOCs degradation photocatalyst, wherein no additional conditions such as high pressure, high temperature and surfactants were required. The structures and morphologies of the as-prepared samples were analyzed by XRD, SEM and TEM. The results revealed that α-Fe₂O₃/CaFe₂O₄ p-n heterojunctions exhibited superior photocatalytic activity of VOCs degradation compared to pure CaFe₂O₄ and α-Fe₂O₃ in both steady model and flow bed model. It can degrade more than 82% of acetaldehyde within 180?min in steady mode and 65% in flow mode under visible light irradiation. The prominent VOCs remove property could be attributed to the strong interfacial contact caused by the in-situ fabrication process and the promoted charge carrier separation efficiency due to the constructing of α-Fe₂O₃/CaFe₂O₄ p-n heterojunction. It provides some new insights into the design and fabrication of advanced photocatalytic materials with p-n heterojunction for high efficiency in VOCs photodegradation.