Density functional theory and machine learning guided search for RE2Si2O7 with targeted coefficient of thermal expansion

Density functional theory (DFT) calculations and machine learning (ML) methods are used to establish a relationship between the crystal structures of rare-earth (RE) disilicates (RE₂Si₂O₇) and their coefficient of thermal expansion (CTE). The DFT total energy data predict the presence of several energetically competing crystal structures, which is rationalized as one of the reasons for observing polymorphism. An ensemble of support vector regression models is trained to rapidly predict the CTE as a function of RE₂Si₂O₇ crystal chemistry. Experiments subsequently validated the structure and CTE predictions for Sm₂Si₂O₇.     

Role of thermodynamic miscibility gaps in phase selection in sol-gel synthesis of yttrium silicates

Yttrium monosilicate and disilicate are important materials for environmental barrier coatings. The two silicates were synthesized by sol-gel route and their phase selection upon calcination and thermal exposure was studied. First products of crystallization were the monosilicate and yttria. Amorphous silica precipitated out at 1300 °C as apatite phase. During prolonged high temperature treatment, up to 100 h at 1400 °C, the apatite disappeared and the disilicate appeared, only to disappear itself as the system approached equilibrium. Thermodynamic calculations performed using Thermo-Calc software show the presence of a metastable miscibility gaps in the amorphous (liquid) phase field. As a consequence, phase separation in the amorphous phase prior to crystallization is responsible for the formation of yttria-rich and silica-rich phases during crystallization. Multiple phase formation during both, yttrium monosilicate and disilicate synthesis is consistent with the presence of the amorphous phase miscibility gaps around the silicate compositions.     

Luminescent properties of Sr2MgSi2O7 and Ca2MgSi2O7 long lasting phosphors activated by Eu, Dy

Long lasting afterglow phosphors Sr₂MgSi₂O₇:Eu,Dy and Ca₂MgSi₂O₇:Eu,Dy were prepared by solid-state reaction method. It is revealed by the results that both phosphors show two emission peaks that are caused by the different emitting centers Eu²⁺ held in the host lattice. Wavelength shift was observed due to the slight differences in the structure parameters of the two hosts. Investigation on afterglow property shows that Sr₂MgSi₂O₇:Eu,Dy phosphor held a better afterglow property than Ca₂MgSi₂O₇:Eu,Dy phosphor. Thermal simulated luminescence study indicates that the long afterglow is generated by a higher trap concentration formed by the co-doped rare earth ions within the host.     

Improvement of high-temperature oxidation resistance of TiAl-based alloy by sol–gel method

Lithium lanthanoid silicate, a high temperature lithium ion conducting solid electrolyte, synthesized by sol–gel method, has been characterized by TGA/DTA, XRD, FTIR and SEM. Conductivity was found to be 0.847 × 10⁻⁶ Ω⁻¹ cm⁻¹ at 750 °C and activation energy was 0.5 eV.     

Alumina Dissolution into Silicate Slag

Dissolution of commercial white fused and tabular Al₂O₃ grains into a model silicate slag was investigated after 1 h at 1450° and 1600°C. Formation of CA₆ and hercynitic spinel layers was observed at all Al₂O₃/slag interfaces. The spinel layer was not always continuous, and so, compared with the CA₆ layer, it had a less-significant effect on the dissolution process. The CA₆ layer that formed adjacent to the tabular Al₂O₃ was incomplete at both temperatures, so that its dissolution was not a totally indirect process. These incomplete CA₆ and spinel layers meant that slag penetrated into the tabular Al₂O₃ grains, which, thus, were corroded and disintegrated by the penetrating slag. There was evidence of liquid in the CA₆ layer adjacent to the fused Al₂O₃ after 1 h at 1450°C, which also enabled direct dissolution. After 1 h at 1600°C, fused Al₂O₃ revealed a thick (∼60 μm), continuous and unpene-trated CA₆ layer, indicating fully indirect dissolution at this temperature.     

LED用稀土Eu掺杂硅酸盐基荧光粉的研究进展

由于硅酸盐为基体的光转换材料具有原料来源丰富、工艺适应性广泛及晶体结构稳定性较高等特点,目前已成为白光发光二极管(light-emitting diode,LED)用荧光粉的研究重点之一。本文综述了近年来国内外硅酸盐基稀土荧光粉材料的研究进展,对硅酸盐基稀土荧光粉的材料体系、发光机理及发光特性的改进方面进行了分析与探讨。通过比较固相反应法和溶胶-凝胶法两种不同制备方法的优缺点,阐述了不同制备方法对白光LED质量的影响,并对硅酸盐基荧光粉的发展趋势和应用前景作了简要展望。     

Nonlinear dielectric response and positive dielectric tunability in antipolar CaTiSiO5

Dielectric tunability has been extensively investigated in ferroelectric materials, which exhibit a negative tunability of dielectric permittivity in an external electric field. In contrast, positive tunability is rare and has been reported only in a few antiferroelectric materials. We present positive (and negative) tunability in the titanite, CaTiSiO₅. The dielectric property of CaTiSiO₅ was measured up to an extraordinarily high electric field of 40 MV/m. A nonlinear polarization field loop with no hysteresis was obtained. The dielectric permittivity of ε_r ~ 25 increases up to ε_r ~ 40 at 20 MV/m and room temperature. Although titanite has an antipolar structure and is expected to be “antiferroelectric,” its dielectric response in high electric fields up to ~40 MV/m differs from that of conventional antiferroelectrics. We demonstrate that the phase-transition temperature and dielectric tunability could be modulated through the chemical substitution of Ca_1−xLa_xTiSi_1−xAl_xO₅, in which the destabilization of the long-range antipolar order is revealed by transmission electron microscopy analysis. These results indicate that the observed dielectric response to an electric field may originate from the unique features of the antipolar and domain structures in CaTiSiO₅.     

High-temperature Na2SO4 interaction with air plasma sprayed Yb2Si2O7 + Si EBC system: Topcoat behavior

The high-temperature interaction between ~2.5 mg/cm² of Na₂SO₄ and an atmospheric plasma sprayed (APS) Yb₂Si₂O₇ topcoat–Si bond coat system on SiC CMC substrates was studied for times up to 240 h at 1000°C–1316°C in a 0.1% SO₂–O₂ gaseous environment. Yb₂Si₂O₇ reacted with Na₂SO₄ to form Yb₂SiO₅ and an intergranular amorphous Na-silicate phase. Below 1200°C, the reaction was sluggish, needing days to cause morphological changes to the “splat microstructure” associated with APS coatings. The reaction was rapid at 1200°C and above, needing only a few hours for the entire topcoat to transform into a granulated microstructure consisting of Yb₂SiO₅ and Yb₂Si₂O₇ phases. Na₂SO₄ deposits infiltrated the Yb₂Si₂O₇ topcoat and transformed into an amorphous Na-silicate in less than 1 h at all exposure temperatures. Quantitative assessment of the Yb₂SiO₅ area fraction in the topcoat showed a linear decrease over time at 1316°C, attributed to reaction with the SiO₂ thermally grown oxide (TGO) formed on the Si bond coat and rapid transport through the interpenetrating amorphous Na-silicate grain boundary phase. It was predicted that nearly 2 weeks is needed for complete removal of Yb₂SiO₅ from the topcoat at 1316°C for a single applied loading of Na₂SO₄.