High-surface-area mesoporous silica-yttria-zirconia ceramic materials prepared by coprecipitation method ― the role of silicon

A high surface area is one of desired properties for yttria-zirconia (Y₂O₃–ZrO₂) ceramic materials given their catalytic applications. The objective of this study is to develop high-surface-area Y₂O₃–ZrO₂ materials by silicon (Si) modification and investigate the role of Si. Si-modified yttrium-zirconium hydroxides were prepared via a one-step precipitation process and calcined at 800 or 950 °C to form Si-modified Y₂O₃–ZrO₂ (denoted as SiO₂–Y₂O₃–ZrO₂) materials containing 0-20 wt% Si as SiO₂. These hydroxides or materials were characterized by ²⁹Si NMR, XPS, TG-DSC, XRD, UV Raman, TEM, and N₂ physisorption measurements. Si species uniformly distributed in the hydroxides tended to be enriched on the material surface at high temperatures. These Si species dominated by the silicates blocked the migration of Y and Zr atoms, which resisted the crystallite growth of Y₂O₃–ZrO₂ components and reduced their crystallite size. Therefore, the SiO₂–Y₂O₃–ZrO₂ possessed a surface area of 59-112 m²/g after calcination at 950 °C for 9 h, which was significantly higher than that of the Y₂O₃–ZrO₂ (23 m²/g). This study may stimulate ideas for developing high-surface-area crystalline ceramic materials calcined at high temperatures.     

硅酸盐型胶磷矿单一反浮选工艺研究及工业化应用

云南某矿区产的硅酸盐型胶磷矿的SiO_2含量一般在30%以上,堆存数量巨大,使用常规的单一反浮选工艺难以达到要求的精矿指标,但是使用正反浮选工艺或者双反浮选工艺的生产成本又较高,经济效益不理想。从矿石的多元素分析发现,与CaO∶P_2O_5大于1.79的碳酸型磷块岩配矿后使用单反浮选工艺可以获得合格的精矿指标。在此思路上,对两种矿石进行配合比、解离度、磨矿细度和药剂制度的探索研究。当配合比为1∶3,磨矿细度为92%,药剂制度为抑制剂1.5kg/t、调整剂18kg/t、捕收剂3.0kg/t的情况下,最终可以获得P_2O_5品位为28.89%,MgO品位为0.91%,产率62.73%,回收率85.24%的精矿指标。     

Phase equilibria in the system CaO–SiO2–Nb2O5–La2O3 at 1473 K with pO2=10−15.47 atm

Phase equilibria in the CaO–SiO₂–La₂O₃–Nb₂O₅ system are important for the utilization of Nb and Rare Earth resources. In the present work, phase equilibria in the CaO–SiO₂–La₂O₃–Nb₂O₅ system at 1473 K in H₂ (pO₂ = 10^−15.47atm) were studied by the equilibrium experiment. SEM, EDS and XRD analysis were employed to identify the equilibrium phase relations. The isothermal spatial phase diagram of the CaO–SiO₂–La₂O₃–Nb₂O₅ system and the isothermal section of CaO–SiO₂–Nb₂O₅-(5%, 10%) La₂O₃ pseudo-ternary system were constructed. A total of eight equilibrium phase regions were determined, including Liquid + CaNb₂O₆+CaSiO₃+LaNbO₄ region, Liquid + CaNb₂O₆+SiO₂+CaSiO₃ region, Liquid + CaSiO₃+CaNb₂O₆ region, Liquid + CaSiO₃+SiO₂ region, Liquid + CaNb₂O₆+SiO₂ region, Liquid + CaSiO₃ region, Liquid + SiO₂ region and Liquid + CaNb₂O₆ region. Additionally, the influence of pO₂ on equilibrium composition and temperature was also investigated considering its significant effect on phase equilibria in the slag system with variable valence elements. The results indicated that higher external pO₂ can increase the equilibrium O content in a slag system, while higher equilibrium temperature corresponds to higher equilibrium pO₂. Besides, the relationship between phase equilibria shown in the traditional slag system and in the related generalized alloy system was also revealed. The present experimental data can help further study on Nb-bearing and RE-bearing slag systems, and the theoretical conclusions will help the development of thermodynamic models.     

Biomineralization,strength and cytocompatibility improvement of bredigite scaffolds through doping/coating

Coprecipitation-derived, sacrificial polymeric (urethane) foam-fabricated bredigite (Ca₇MgSi₄O₁₆) scaffolds were processed by individual and combined treatments of fluoride doping and poly (lactic-co-glycolic acid) (PLGA) coating and then studied in terms of structure, mechanical strength, bioactivity and cell biocompatibility in vitro. According to scanning electron microscopy and Archimedes porosimetry, the geometrical characteristics of pores for all the scaffolds are in the appropriate range for hard tissue regeneration applications. The apatite-formation ability of the samples immersed in a simulated body fluid is improved by doping for both the bare and coated conditions, based on microscopic and energy-dispersive X-ray spectroscopic analyses. Both the treatments advantageously buffer physiological pH changes imposed due to the fast bioresorption of the ceramic. Also, the biodegradable PLGA coating typically enhances the compressive strength of the scaffolds, which is critical for bone tissue engineering. In accordance with the MTT assay on osteoblast-like cells (MG-63) cultures, both the processes individually enhance the cell viability, while the highest improvement is obtained for the combined application of them. It is finally concluded that fluoride doping and PLGA coating are impressive approaches to improve the bioperformance of bredigite-based scaffolds.     

Effects of adhesive modulus and curing conditions on curing behavior of silicate based ceramic coatings on carbon fiber reinforced resin matrix composites

Sodium silicate based ceramic coatings were prepared on the surface of carbon fiber reinforced epoxy resin matrix composite. The coatings were obtained by curing the mixture of silicate adhesive, SiO₂ or Na₂SiF₆ as curing agent, and YSZ and Al₂O₃ as filler. The effects of adhesive modulus, curing agent, curing temperature and time on curing behavior of the coatings were investigated. The results indicated that the coating obtained from 2.7 modulus of silicate adhesive was dense, cohesiveness, uniform and continuous. As curing agent, SiO₂ could promote curing better than Na₂SiF₆, achieving complete curing of the coating. And the coating containing SiO₂ as curing agent was dense, flat and well adhered to the substrate. The curing behavior of coatings was significantly affected by curing temperature and time. The coatings could be cured completely with the increase of curing temperature. The best curing result was obtained at 100 °C curing temperature. Also the experimental results showed that the characteristics of coatings were improved to a certain extent by prolonging the curing time.     

Phase equilibria in the CaO·SiO2Na2O·SiO2Na2O·Al2O3·6SiO2 system

Equilibrium phase relations in the system CaO·SiO₂Na₂O·SiO₂Na₂O·Al₂O₃·6SiO₂ at 40–80 wt% Na₂O·Al₂O₃·6SiO₂ composition range have been experimentally studied at temperatures between 800 °C and 1200 °C. The liquidus temperature was determined with differential scanning calorimetry. The equilibrated samples were quenched with pressurized nitrogen, and examined with electron probe X-ray microanalysis and X-ray diffraction for identification of microstructure and phase relations. Five primary phase fields, CaO·SiO₂, Na₂O·SiO₂, Na₂O·2CaO·3SiO₂, 2Na₂O·CaO·3SiO₂ and Na₂O·Al₂O₃·6SiO₂ were established. The ternary eutectic point of CaO·SiO₂, Na₂O·2CaO·3SiO₂ and Na₂O·Al₂O₃·6SiO₂ was determined to be at 1030 °C with the composition of 29.0 wt% CaO·SiO₂, 12.0 wt% Na₂O·SiO₂ and 59.0 wt% Na₂O·Al₂O₃·6SiO₂. Peritectic reaction of Na₂O·2CaO·3SiO₂, 2Na₂O·CaO·3SiO₂ and Na₂O·Al₂O₃·6SiO₂ occurred at 930 °C with the composition of 13.0 wt% CaO·SiO₂, 29.0 wt% Na₂O·SiO₂ and 58.0 wt% Na₂O·Al₂O₃·6SiO₂. The liquidus surface projection of the ternary system has been constructed in the composition region important for the bottom ash application.     

浅谈PLS纳米复合材料的结构和阻燃性能

阻燃聚合物／层状无机纳米复合材料的结构控制与阻燃原理作为新一代火灾防治高新技术，是需要重点研究的基础课题。介绍了PLS(Polymer／Lavered Silicate，聚合物／层状硅酸盐)纳米复合材料的研究现状，分析了结构形态、特征及其对性能的影响，探讨了它在阻燃领域的研究方向。     

渗透结晶型液体硬化剂表面处理方法及作用机理研究

阐述了渗透结晶型表面处理剂的作用机理。渗透结晶型表面处理剂渗透进入水泥基内部后,与水泥的水化产物发生反应可以生成新的晶体来填补水泥缝隙,使基体更加密实,研究发现,这是通过与水泥基的化学反应增强机制来实现强化的。本文主要介绍了氟硅酸盐与水泥基材料的作用机理,并初步研究了氟硅酸盐表面硬化的处理方法。     

Weak ferroelectricity and low-permittivity microwave dielectric properties of Ba2Zn(1+x)Si2O(7+x) ceramics

Ba₂Zn_(1+x)Si₂O_(7+x) ceramics were prepared using the conventional solid-state method at 1200 °C for 3 h in air. Apart from the previously reported Ba₂Zn_(1+x)Si₂O_(7+x) (x = 0) with a monoclinic structure (C 2/c), the end-member compositions at x = −1 and 1 exhibit single-phase β-BaSiO₃ with an orthorhombic structure (P2₁2₁2₁) and BaZnSiO₄ with a hexagonal structure (P6₃), and possess a coexistence of weak ferroelectricity and low-permittivity microwave dielectric properties. A reduction in Zn²⁺ content mainly decreases the intensity of the ε_r anomaly peak at lower temperature and increases the ε_r (or frequency) stability against temperature. The Zn²⁺-rich BaZnSiO₄ phase has a τ_f value of −181 ppm/°C, whereas the τ_f value of Zn²⁺-free BaSiO₃ phase decreases to −35.4 ppm/°C. The Zn²⁺ deficiency in Ba₂ZnSi₂O₇ composition could inhibit the presence of BaZnSiO₄ phase and improve the τ_f value, whereas excessive Zn²⁺ cations prompt the formation of the BaZnSiO₄ phase to deteriorate significantly the τ_f value.