Studies on Bi-Sr-Ca-Cu-O glasses and superconducting glass ceramics

Bi-Sr-Ca-Cu-O glasses and glass ceramics of various compositions were synthesised. The glass transition temperature varies from 396 to 422°C depending on the glass composition. The bulk glass ceramics of 4334, 4336, 2223 and 4246 compositions show superconductivity when the corresponding glass samples were heat-treated in air at 820°C for 3, 9, 12 and 24 h respectively. X-ray diffraction studies show that the superconducting phase present in all these compositions is Bi₂Sr₂Ca₁Cu₂O _x . The 4334 glass ceramic is almost a single-phase material with a preferred orientation such that thec axis is normal to the sample surface. The 2223 glass ceramic has a higherT _c (onset) than the other three compositions indicating the presence of highT _c phase (110K) also. ESR studies on the glass samples indicate the existence of Cu²⁺. The effect of heat treatment on ESR shows that the intensity of resonance decreases with increase in heat-treatment duration. This effect is more pronounced for the 4334 and 2223 compositions. The advantages of synthesizing superconducting materials by glass route are discussed in view of practical applications.     

玻璃与陶瓷高温超导体制取工艺的进展

简略介绍以玻璃与陶瓷为基体的高温超导材料的各种制取工艺。     

热压铸玻璃陶瓷的研制和生物学评价

制备了SiO2-Al2O3-K2O-Na2O系可压铸玻璃陶瓷,采用X射线和SEM等方法对材料的结构和物理性能进行了测试和分析。结果表明材料的主晶相为白榴石．抗压强度为420MPa,抗弯强度为102MPa,具有与牙釉质相近的性能,是一种理想的口腔修复材料;生物学实验显示,这种材料有良好的生物相容性,具有开发的价值和前景。     

以钙云母为主相的可切削微晶玻璃的显微结构和性能

研究根据提高云母层结合强度的构想,研制以钙云母为主相可切削微晶玻璃,以钙云母和氧化锆为主相的微晶玻璃,具有棒状,长径比大,相互交错的晶粒,强度184MPa,断裂韧性2.17MPa.m^1/2,比目前临床用VITA提高了一倍,切削性能优良,材料的断裂和加工断口主要是云母层间的解理断裂和准解理断裂,故切削面光滑,易于保证加工的精度。同时说明提高云母层间结合强度是此类材料增强的本质所在。     

含钙铁氧体磁性生物活性玻璃陶瓷热种子的制备与表征

本工作将钙铁氧体与溶胶-凝胶法制得的生物活性玻璃陶瓷复合,制备了含钙铁氧体磁性生物活性玻璃陶瓷磁热种子。对所制得材料的物相组成、磁性、体外生物活性、磁生热能力及磁热对肿瘤细胞的杀伤效应、组织相容性进行了表征。结果表明,材料主晶相为CaSiO₃、Ca₅(PO₄)₃F和CaFe₂O₄。充磁约8×10⁵ A·m-1时,材料饱和磁化强度约5 A·m²·kg-1,矫顽力约2×10⁴ A·m-1。暴露在342 kHz、1×10³ A/m的交变磁场下,0.1 g材料20 min内即能实现升温约40 ℃。在浸泡入模拟体液中14 d后,材料表面能形成不连续的含有碳酸根生物的活性层。MTT细胞增殖实验显示材料无细胞毒性,MG63细胞能在材料上粘附和生长。将材料与VX2细胞在交变磁场下复合培养20 min,材料周围出现明显的死亡细胞圈。兔肌肉植入实验显示材料组织相容性良好。     

退火工艺对SiO2-Al2 O3-MgO-F系玻璃陶瓷分相和析晶的影响

以SiO2、Al2O3、MgO和AlF3为主要原料,采用高温熔融法,在一定温度下将原料熔化,然后将熔体浇铸到预热的模具中,经不同退火工艺得到基础玻璃。将此玻璃快速加热到析晶温度,进行相同的析晶处理,得到玻璃陶瓷样品。应用TEM、SEM和XRD等技术,系统研究了退火工艺对SiO2-Al2O3-MgO-F系玻璃陶瓷分相和析晶的影响。结果表明：随着退火温度的提高,玻璃的结构逐渐得到松弛,促进了Mg^2 和F^-离子的扩散,玻璃内分相程度逐渐增大,其分相形貌由液滴状→连通状→团簇状过渡;玻璃的分相程度对高温析晶时晶体的析出形态也有一定影响,与低温退火的玻璃相比较,高温退火时析出的云母晶体更加均匀;随着退火时间的延长,析出的晶体变得越来越细小,晶体间的交错度和晶体的均匀程度逐渐增大。     

Structure and luminescence properties of Eu/Tb codoped oxyfluoride glass ceramics containing Sr2GdF7 nanocrystals

Eu/Tb codoped transparent oxyfluoride borosilicate glass ceramics containing Sr₂GdF₇ nanocrystals were fabricated under a reductive atmosphere and the conversion of Eu³⁺ ions to Eu²⁺ ions was observed. The Sr₂GdF₇ nanocrystals with an average size of 32 nm were homogeneously precipitated in the oxyfluoride borosilicate glass matrix, which could be evidenced by X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) spectroscopy. The enhancement of photoluminescence emission intensity, reduction of the relative emission intensities between ⁵D₀ → ⁷F₂ and ⁵D₀ → ⁷F₁, and long fluorescence lifetimes of Eu²⁺, Eu³⁺, and Tb³⁺ ions revealed that more rare earth ions were partitioned into the low phonon energy environment Sr₂GdF₇ nanocrystals. Under ultraviolet excitation, pure and bright white light emission was obtained in the oxyfluoride borosilicate glass ceramic, which may be a potential blue, green and red-emitting phosphor for white LEDs.     

原子吸收法测定钠钙玻璃中常量元素的方法改进

传统原子吸收法测定钠钙玻璃中各元素的标准溶液的配制方法既繁琐且不容易消除干扰。通过实验,我们根据标准钠钙玻璃和样品基体元素相近来消除干扰,改进了配制标准溶液的方法,使标准溶液配制简单易行。     

Porous hydroxyapatite and biphasic calcium phosphate ceramics promote ectopic osteoblast differentiation from mesenchymal stem cells

Abstract

Because calcium phosphate (Ca–P) ceramics have been used as bone substitutes, it is necessary to investigate what effects the ceramics have on osteoblast maturation. We prepared three types of Ca–P ceramics with different Ca–P ratios, i.e. hydroxyapatite (HA), beta-tricalcium phosphate (β-TCP), and biphasic calcium phosphate (BCP) ceramics with dense-smooth and porous structures. Comprehensive gene expression microarray analysis of mouse osteoblast-like cells cultured on these ceramics revealed that porous Ca–P ceramics considerably affected the gene expression profiles, having a higher potential for osteoblast maturation. In the in vivo study that followed, porous Ca–P ceramics were implanted into rat skeletal muscle. Sixteen weeks after the implantation, more alkaline-phosphatase-positive cells were observed in the pores of hydroxyapatite and BCP, and the expression of the osteocalcin gene (an osteoblast-specific marker) in tissue grown in pores was also higher in hydroxyapatite and BCP than in β-TCP. In the pores of any Ca–P ceramics, 16 weeks after the implantation, we detected the expressions of marker genes of the early differentiation stage of chondrocytes and the complete differentiation stage of adipocytes, which originate from mesenchymal stem cells, as well as osteoblasts. These marker gene expressions were not observed in the muscle tissue surrounding the implanted Ca–P ceramics. These observations indicate that porous hydroxyapatite and BCP had a greater potential for promoting the differentiation of mesenchymal stem cells into osteoblasts than β-TCP.     

Preparation and characterization of magnesium-aluminium-silicate glass ceramics

Synthesis of machinable quality magnesium aluminium silicate (MgO-Al₂O₃-SiO₂) for fabrication of insulators/spacers usable in high voltage applications under high vacuum conditions has been carried out following two different routes i.e. (i) sintering route, and (ii) glass route. A three-stage heating schedule involving calcination, nucleation and crystallization, has been evolved for the preparation of magnesium aluminium silicate (MAS) glass ceramic with MgF₂ as a nucleating agent. The effect of sintering temperature on the density of compacted material was studied. Microstructure and machinability of samples obtained from both routes were investigated. They were also characterized for microhardness. Initial studies on material obtained by glass route reveal that these samples are superior to those obtained from sintered route in respect of their high voltage breakdown strength and outgassing behaviour. Outgassing rate of 10⁻⁹ Torr l·s⁻¹ cm⁻² and breakdown strength of 160 kV/cm were obtained. Different types of spacers, lugs, nuts and bolts have been prepared by direct machining of the indigenously developed glass ceramic.     

Studies of radiation defects in cerium,europium and terbium activated oxyfluoride glasses and glass ceramics

Terbium, cerium and europium activated oxyfluoride glasses and glass ceramics have been studied by thermally stimulated luminescence (TSL) and optical absorption techniques after the X-ray irradiation. A creation of colour centres in oxyfluoride glass matrix and TSL peaks depending on the activator type were observed. LaF₃ and rare earth activators were analysed by SEM–EDS.     

Crystallisation effects on rare earth dopants in oxyfluoride glass ceramics

Transparent oxyfluoride glass-ceramic materials are of significant interest for the production of new optoelectronic devices. In this paper we report measurements of the detailed spectroscopy of rare earth dopants in both an oxyfluoride transparent glass ceramic and its glass precursor. We show that several spectroscopically different sites exist for the rare earth even in the glass precursor material, where a significant amount of the rare earth is already coordinated with fluorine. In the glass-ceramic material, these glassy fluorine-coordinated sites are replaced with crystalline sites, but a significant fraction of the rare earth ions are still within the glass phase. The fraction of rare earth ion that is incorporated into the crystalline phase is estimated from the rare earth spectroscopy, and the role of the rare earth coordination in the precursor glass is discussed.     

Crystallization and optical properties of a transparent mullite glass ceramic

Transparent mullite - based glass ceramics in the system SiO₂-Al₂O₃-B₂O₃-ZnO-K₂O were prepared. The activation energy of crystallization, the Avrami constants and the mechanism of crystallization of mullite were determined by the Matusita method through differential thermal analysis. X-ray diffraction and scanning electron microscopy methods were also used to determine the type and morphology of the precipitated crystalline phase. In addition, the degree of crystallinity was determined by the internal standard method. The results showed that bulk crystallization was the main mechanism for crystallization of the glasses. Optical absorption and photoluminescence properties of the obtained transparent glass-ceramics and their initial glasses were also studied. The glass-ceramics exhibited two emissions at 680 and 700 nm.     

BaFe12O19／Al2O3—SiO2—K2O微晶玻璃陶瓷的柠檬酸Sol—Gel合成及其微波性能的研究

采用柠檬酸sol-gel工艺合成了BaFe12O19/Al2O3-SiO2-K2O微晶玻璃陶瓷，并对其介电常数及其磁导率在1MHz～6GHz下的变化规律进行了研究。结果表明，BaFe12O19/Al2O3-SiO2-K2O微晶玻璃陶瓷的合成与体系中Fe/Ba、烧结温度密切相关；其介电常数、磁导率基本都随测试频率的增加而下降；介电损耗值最大可达到0.30，磁损耗值较小。     

Preparation and photoluminescence properties of fluorosilicate glass ceramics containing CeOF: Dy nanocrystals

The Ce³⁺ and Dy³⁺ co-doped oxyfluoride glasses and glass ceramics containing CeOF or CeF₃ nanocrystals have been prepared in the reducing atmosphere. The crystallinity increased significantly with the Ce³⁺ concentration, while the crystal size of nanocrystals is mainly influenced by the annealing temperatures. The glasses and glass ceramics emitted white light, deriving from a combination of the Ce³⁺ blue and the Dy³⁺ yellow light. The emission intensity and CIE chromaticity coordinates of the Ce³⁺ and Dy³⁺ co-doped glasses can be tuned by adjusting the ratio of Ce³⁺/Dy³⁺ concentration or the annealing temperature.     

Temperature dependence of luminescence behavior in Er/Yb co-doped transparent phosphate glass ceramics

The effect of temperature on the luminescence intensity of up-conversion and near infrared in Er³⁺/Yb³⁺ co-doped phosphate glass ceramics has been investigated. Efficient green and red up-conversion luminescence and strong infrared fluorescence at 1.54 μm wavelength are observed under excitation of 975 nm. The fluorescence intensity is changing at different temperature and the results are explained with the level transitions in Er³⁺/Yb³⁺ co-doped system. Meanwhile, the lifetime of Er³⁺:⁴I_13/2 level corresponding to different operating temperature and pump power is also discussed, and the experimental results are fitted using multiphonon relaxation theory.     

Powder synthesis and properties of LiTaO3 ceramics

The LiTaO₃ powders with sub micrometer grade grain size have been synthesized successfully using a molten salt method. Lithium tantalate began to form at 400 °C reaction temperature and transformed to pure phase without residual reactants when it was processed at 500 °C for 4 h in static air. The undoped LiTaO₃ ceramics with a Curie temperature about 663 °C were obtained by pressureless sintering at 1300 °C for 3 h. The relative dielectric constant (ɛ_r) increases from 50 to 375 at temperature ranging from 30 to 663 °C and then decreases quickly as the temperature increases above 663 °C. The ceramics shows a relative dielectric constant of 49.4, a dielectric loss factor (tan δ) of 0.007, a coercive field (Ec) of 28.66 kV/cm and a remnant polarization (Pr) of 32.48 μC/cm² at room temperature.     

赤泥-粉煤灰微晶玻璃晶化行为研究

综合利用赤泥和粉煤灰两种废渣制备高附加值的微晶玻璃材料,两种废渣总吃渣量能够达到90wt%以上,降低了生产成本.对不同核化温度、晶化温度对微晶玻璃显微组织的影响进行了研究.结果表明:最佳核化温度由基础玻璃的DTA曲线的吸热峰确定,大约697℃;最佳的晶化温度略高于DTA析晶峰的温度,大约为950℃.     

NixFe3-xO4包覆空心玻璃微球的铁氧体化学镀制备及性能

采用铁氧体化学镀技术,在空心玻璃微球表面包覆了一层NixFe3-xO4膜,并采用X-射线衍射仪,扫描电子显微镜和电子能谱对其进行了表征.空心玻璃微球表面薄膜的厚度约为0.5微米,具有非晶结构.反应物的比例以及制备条件能够影响所制备铁氧体薄膜中镍和铁的比例.振动样品磁强计研究结果表明退火后样品显示铁磁特性.     

氧化铋对微晶玻璃的相转变和性能的影响

为研究Bi2O3在堇青石基微晶玻璃烧结中的作用及其添加量对微晶玻璃的相转变和性能的影响,采用烧结法制备了不同Bi2O3含量的微晶玻璃,并对其进行了X射线衍射分析、显微分析和性能测试.结果表明:Bi2O3的加入降低了堇青石的u相向a相转变的温度,并有效促进微晶玻璃的烧结致密化;烧结样品的介电常数和抗折强度均随着Bi2O3加入量的增加而增加,且与密度变化规律相似;当Bi2O3添加量(质量分数)达5%时样品的介质损耗因子最低(＜10-3);微晶玻璃烧结样品的热膨胀系数基本符合线性规律.