Synthesis,microstructures, and corrosion behaviors of multi-components rare-earth silicates

Multi-components and equimolar rare earth monosilicates, (Y_1/3Dy_1/3Er_1/3)₂SiO₅, (Y_1/3Dy_1/3Lu_1/3)₂SiO₅, (Y_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅ and (Yb_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅, were prepared by solid-state reactions and the following hot-pressing. Dense microstructures with uniform elemental distributions were obtained for all samples. These investigated multi-components monosilicates exhibit low thermal conductivities and similar coefficients of thermal expansion with SiC. Moreover, they exhibit high corrosion resistances in 1400 °C water vapor, especially, four-components (Y_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅ and (Yb_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅ experienced almost invariable weights after small weight losses during the initial 0.5 h. All those results indicate that multi-components rare earth monosilicates are promising candidates of environmental barrier coatings for SiC/SiC composites.     

蒸压建材生产过程中钢渣安定性处理与活性化利用

钢渣安定性处理过程常常造成胶凝活性的损失。为此，本文利用改性助剂消除钢渣水化过程中产生的氢氧化物并生成胶凝产物，在蒸压建材的生产过程中实现钢渣安定性处理和游离氧化物的活性化利用，并避免单独处置钢渣造成的活性物质损失。研究表明，8%秸秆灰和3%磷酸二氢铵作为复合助剂制备的尾矿-钢渣蒸压试块体积稳定，抗压强度达24.0MPa。通过对蒸压样品游离氧化物消解率、化学结合水量及热重、XRD分析，得出钢渣安定性处理与活性化利用机制：硅质材料与钢渣中f-CaO水化生成的Ca(OH)₂结合迅速生成对体系力学强度有益的水化硅酸钙，避免因大量Ca(OH)₂积累造成体积膨胀；磷酸盐中的NH₄⁺、H₂PO₄^-与f-MgO结合生成磷酸铵镁及其他低溶度积复盐类矿物，进而消除因f-MgO水化生成Mg(OH)₂造成体积膨胀的隐患。试样在180℃蒸压4h后，f-CaO及f-MgO消解率分别可达86.28%、89.73%。本文将为利用钢渣大比例取代水泥和石灰生产蒸压建筑材料提供理论基础，对于提高钢渣利用率、减少碳排放具有重要价值。     

Multi-Functional Black Bioactive Glasses Prepared via Containerless Melting Process for Tumor Therapy and Tissue Regeneration

Tissue regeneration in complex lesions such as the site of tumors, bacterial infection, and sites lacking blood vessels, has been a huge challenge. Therefore, developing bioactive implantable materials with multi-functional properties such as tumor destruction, bacteria growth inhibition, and angiogenesis promotion is of great significance. In this study, black CaO-SiO₂-TiO₂ (CST) glasses are prepared through the containerless melting approach, by which heterogeneous nucleation can be avoided and thereby glass formation becomes possible via fast quenching. This approach enables the formation of trivalent titanium (Ti³⁺) without using a reducing atmosphere or reducing agents. The black CST glasses are found in this study to possess a strong ability to inhibit bacteria and tumors by their excellent photothermal and photocatalytic effects. Strikingly, these glasses also promote the formation of blood vessels and accelerate the healing of chronic wounds by the synergistic effects of the photothermal effect and Si ions. Thus, this glass system can be a promising multi-functional material for tissue regeneration in complex lesions.     

Ytterbium (III) oxide reinforced novel TeO2–B2O3–V2O5 glass system: Synthesis and optical,structural, physical and thermal properties

Different samples of xTeO₂.(25-y)B₂O₃.zV₂O₅.yYb₂O₃ (or TBVY) new glass material were synthesized by the classical melt-quenching method. Structural, optical, physical, and thermal analyses of the synthesized glasses were performed in addition to Monte Carlo simulation to test radiation shielding properties. The results showed that increasing ratios of Yb₂O₃ (y = 0.0, 0.5, 1.0, and 1.5 mol%) produced monotonic density values of the synthesized glasses ranging from 4.70058 g cm^?3 to 5.01038 g cm^?3. XRD and FTIR analyses were used to confirm the glass structure of all samples. Optical transmittance and absorption parameters varied almost monotonically with increasing ratios of Yb₂O₃ indicating the ability to predict and control these properties using Yb₂O₃ additive. Furthermore, simulated radiation interaction parameters, such as attenuation coefficients and half-value layer, exhibited well-behaved dependence on the concentration ratio of the Yb₂O₃ additive. This approach to glass material synthesis demonstrate the useful synergetic effect of combining structural, optical, and radiation characteristics.     

Highly disordered ionic distribution in α-dicalcium silicate for structure relaxation

Dicalcium silicate, which is found in steelmaking slag for dephosphorization, exists as the hexagonal α phase at high temperatures. The α-dicalcium silicate forms a solid solution with tricalcium phosphate in the entire composition range, although the reason for high solubility of phosphorus remains unclear in view of the crystal structure. It has previously been reported that the crystal structure of α-dicalcium silicate consists of a symmetric arrangement of Ca²⁺ ions and SiO₄⁴⁻ tetrahedra, although other polymorphs exhibit asymmetric arrangements. However, because the occupation probability of each atomic site in the α polymorph is not limited to unity, it has not been qualified how these ions are exactly arranged. In this study, the ionic distribution in the α polymorph of dicalcium silicate was evaluated by first-principles calculation based on density functional theory (DFT), as well as by molecular dynamics (MD) simulation with a polarizable ion model optimized by DFT calculation. The results indicated that the completely symmetric ionic arrangement, as reported for the α phase, is the most unstable. Electronic-state calculation and MD simulation indicated that a highly disordered ionic arrangement spontaneously forms in the α-phase crystal for structure relaxation when held at high temperatures, or when phosphorus is incorporated.     

Effect of heat treatment on the roughness and mechanical properties of dental lithium disilicate glass-ceramics

In dental clinics, it is common to perform small fitting adjustments in dentures using a micro-grinding tool after testing them in the patient's mouth. This procedure increases local roughness and can lead to formation of microcracks on the prosthesis surface. This study aimed to investigate the benefits of a post-finishing heat treatment to surface roughness and crack healing and its effect on the flexural strength of lithium disilicate (LD) dental glass-ceramics. Commercially available lithium metasilicate, Li₂SiO₃, samples were heat treated at 840 °C for 7 min to induce the phase transformation into LD, Li₂Si₂O₅. The LD samples were characterized by X-ray Diffraction, Scanning Electron Microscopy, Vickers hardness, Young’s modulus, and fracture toughness. One of the surfaces of the LD samples was sanded aiming to simulate the denture fitting adjustments performed in the dentist’s laboratory, generating a rough surface, Group 1. Half of the LD samples had their biaxial flexural strength evaluated by the piston-on-three-ball test (P–3B) and the other half were submitted to a second short-term heat treatment (840 °C - 5 min), Group 2, and later assessed by the P–3B. Roughness parameters in both groups were measured by 3D optical profilometry. After the crystallization heat treatment, formation of elongated LD crystals, Li₂Si₂O₅, 35% amorphous phase, and residual Li₃PO₄ was observed. In addition, the following mechanical property values were obtained: Vickers hardness = 5.8 ± 0.1 GPa, fracture toughness = 2.2 ± 0.1 MPa m^1/2, and Young’s modulus = 100.3 ± 0.3 GPa. The samples in Group 1 showed bending strength of 206 ± 30 MPa and the following roughness parameters: Ra = 0.45 ± 0.16 μm, Rz = 22.7 ± 6.7 μm, and PV = 27.7 ± 7.1 μm. In the samples in Group 2, the Ra, Rz and PV roughness parameters were 0.31 ± 0.12 μm, 5.2 ± 2.5 μm, and 9.2 ± 4.7 μm, respectively. With this decrease in roughness, the bending strength increased by 62%, with a mean value of 331 ± 59 MPa. In the need for machine finishing of LD-based glass-ceramic dental prostheses, the use of a second short-term heat treatment at 840 °C for 5 min generates considerable gains in bending strength, increasing the lifecycle of the prosthesis as a result of reduced surface roughness caused by softening of the remaining amorphous phase in the glass-ceramic. These conditions can be adapted to each chemical and crystallographic composition of the glass-ceramic under study.     

熔融制样-能量色散X射线荧光光谱仪分析硅酸盐中32 种组分

为充分发挥小型实验室设备的功能,实验采用熔融制样,使用台式能量色散X射线荧光光谱仪(10W, Rh靶)定量分析了硅酸盐样品中的Na₂O、MgO、Al₂O₃、SiO₂、P₂O₅、SO₃、Cl、K₂O、CaO、TiO₂、V、Cr、MnO、Fe₂O₃、Co、Ni、Cu、Zn、Ga、Rb、Sr、Y、Zr、Nb、As、Ba、La、Ce、Th、U、Hf、Pb等32种主、次、痕量组分。对3种不同的解谱方法进行比较,确定Na、Mg、Al、Si、P、As、Ce、Cr、Cu、Ga、La、Nb、Ni、Pb、Th、U、V、Y选择感兴趣区解谱,其余元素用高斯或经改进的高斯函数的最小二乘法拟合解谱。选用有代表性的多个硅酸盐类样品,比较了理论检出限及10次重复测定计算3倍标准偏差得出的检出限,发现以3倍标准偏差作为检出限再取它们的平均值则更具代表性和使用意义。各组分的检出限为0.2~1740μg/g。精密度试验表明,各组分测定结果的相对标准偏差(RSD)为0.12%~10.5%(Na为轻元素,由于含量低,小能谱测定的精密度稍差);对两个土壤标准样品进行正确度验证,测定值与标准值一致。     

Pump laser induced photodarkening in ZrO2-doped Yb:Y2O3 laser ceramics

5 at.% Yb:Y₂O₃ transparent ceramics were fabricated using vacuum sintering plus HIP. The ceramics doped with 1 at.% ZrO₂ as the sintering additive were densified at 1700 °C in vacuum followed by HIPing at 1775 °C, while those without sintering additives were densified at 1520 °C in vacuum followed by HIPing at 1450 °C. After sintering, both ceramics had relatively high in-line transmittance. However, during laser experiments, the ZrO₂-doped Yb:Y₂O₃ (Zr-YbY) ceramics were photodarkened when irradiated by 940 nm pump light. The discoloration might be attributed to the formation of Zr³⁺ color centers during lasing. In contrast, no photodarkening effect was detected in the pure Yb:Y₂O₃ ceramics without sintering additives (P-YbY). The P-YbY ceramics exhibited much higher lasing efficiency (17%) than the Zr-YbY ceramics (9%). To our best knowledge, it is the first time that the photodarkening effect was detected in rare-earth doped sesquioxide laser ceramics.     

Oxidation behavior of ytterbium silicide

Si-rich ytterbium silicide was fabricated by through an arc-melting technique for applying use as a bond coat material in an environmental barrier coating system. Evaluation of its potential was accomplished through oxidation tests in dry air and an inert atmosphere. The experimental results showed that the changes in weight and morphologies of ytterbium silicide observed after the tests depended on the oxygen partial pressure. Extensive oxidation and weight gain occurred after oxidation in air. In order to apply this material for hot structures, improvement of the oxidation resistance is needed.     

Nucleation and crystallization of Ba2Si3O8 spherulites in a barium aluminum silicate glass,and mechanical properties of the obtained glass-ceramics

The effect of spherulitic crystallization on the elastic moduli and fracture toughness of a barium aluminum silicate glass was investigated. The crystallization process results in Ba₂Si₃O₈ phase and is initiated from Ba rich nuclei. Nucleation is optimal in the 690-720 °C interval. Young’s modulus is increased by 12.5% when the glass-ceramic conversion is nearly complete. Nevertheless, as the size and the volume fraction of crystals are increased, some microcracking shows up upon cooling from the crystallization temperature. An optimal improvement of the fracture toughness (SEPB method) by 27 % is observed for a 49 % volume fraction of 5 to 10 μm large spherulites.