Subsolidus structure of the CaO−Al2O3−SiO2−P2O5 system

Geometric and topological characteristics of the CaO?Al₂O₃?SiO₂?P₂O₅ system and estimates of liquidus surfaces and solidus boundaries of interest for manufacturing refractory and heat-resistant materials are presented. The presence of phosphate compounds with various structures and the possibility of their formation in the synthesis process make it possible to predict a wide spectrum of important technological properties in the synthesized compositions and a wide range of products of the refractory industry based on them.     

Influence of TiO2 on the densification behaviour of Yb2O3

The effect of temperature and heating rate on the densification of ytterbia (Yb₂O₃), with and without titania (TiO₂) doping was investigated. It is shown that up to a certain doping level, titania doping enhances the densification behaviour of ytterbia. The effect of titania doping on crystal structure confirms that titania is substitutionally incorporated in ytterbia up to the solubility limit, which corresponds well with the densification results. The increased densification rate of titania-doped ytterbia is attributed to the formation of cation vacancy and lattice distortion. Using constant heating rate experiments, the activation energy for densification has been calculated and it is shown that in the intermediate density range (60 % to 85 %), the activation energy is independent of the density. Titania doping increases the activation energy for densification.     

粉末-烧结法制备CaO-P2O5-TiO2-Na2O系微晶玻璃

用粉末-烧结法制备了钙磷酸盐微晶玻璃,通过DTA,XRD,SEM测试探讨了材料的制备过程、相组成及显微结构.玻璃粉末在烧结的同时进行晶化,热处理后得到了主晶相为β-Ca3(PO4)2和β-Ca2P2O7的微晶玻璃,随着烧结温度的提高,β-Ca2P2O7的含量先减小后增大,950℃烧结的微晶玻璃中β-Ca2P2O7的含量最大.实验结果表明,用粉末-烧结法可制得具有生物活性晶相的钙磷酸盐微晶玻璃.     

Synthesis of glass–ceramics in the CaO–MgO–SiO2 system with B2O3, P2O5, Na2O and CaF2 additives

Glass–ceramics based on the CaO–MgO–SiO₂ system with limited amount of additives (B₂O₃, P₂O₅, Na₂O and CaF₂) were prepared. All the investigated compositions were melted at 1400 °C for 1 h and quenched in air or water to obtain transparent bulk or frit glass, respectively. Raman spectroscopy revealed that the main constituents of the glass network are the silicates Q¹ and Q² units. Scanning electron microscopy (SEM) analysis confirmed liquid–liquid phase separation and that the glasses are prone to surface crystallization. Glass–ceramics were produced via sintering and crystallization of glass-powder compacts made of milled glass-frit (mean particle size 11–15 μm). Densification started at 620–625 °C and was almost complete at 700 °C. Crystallization occurred at temperatures >700 °C. Highly dense and crystalline materials, predominantly composed of diopisde and wollastonite together with small amounts of akermanite and residual glassy phase, were obtained after heat treatment at 750 °C and 800 °C. The glass–ceramics prepared at 800 °C exhibited bending strength of 116–141 MPa, Vickers microhardness of 4.53–4.65 GPa and thermal expansion coefficient (100–500 °C) of 9.4–10.8 × 10⁻⁶ K⁻¹.     

Al2O3-SiC-C耐火材料抗CaO-SiO2-K2O渣侵蚀性能研究

研究了Al2O3-SiC-C耐火材料的抗CaO-SiO2-K2O渣侵蚀性能,以及添加Cr2O3对Al2O3-SiC-C材料抗渣侵蚀性能的影响.研究结果表明CaO-SiO2-K2O熔渣对Al2O3-SiC-C材料具有明显的侵蚀作用;在Al2O3-SiC-C材料中添加适量的Cr2O3可以有效地抑制CaO-SiO2-K2O熔渣向耐火材料内部的渗透,降低耐火材料的侵蚀速度.     

CaO—SiO2—P2O5—H2O系统材料中磷的分光光度法测定

将采用溶胶－凝胶法合成的ＣａＯ－ＳｉＯ２－Ｐ２Ｏ５－Ｈ２Ｏ系统材料在５￣１０℃、１＋１的ＨＮＯ３介质中分解。于１．０ｍｏｌ／Ｌ的ＨＮＯ３介质中,正磷酸根和钼酸铵及钒酸铵形成Ｐ：Ｍｏ：ｖ＝１：１：１１的黄色三元杂多酸。在４２０ｎｍ波长处测量三元杂多酸的吸光度,求出未知试样中ＰＯ４＾３－的含量。聚磷酸根的含量则在１ｍｏｌ／Ｌ的ＨＮＯ３介质中于沸水中浴中水解后同法测总ＰＯ４＾３－,用差减法求出。工作曲线     

Effect of boron oxide on the microstructure of mullite-based glass-ceramic glazes for floor-tiles in the CaO–MgO–Al2O3–SiO2 system

The effect of increasing replacement of Al₂O₃ by B₂O₃ in a parent glass on the sintering and further crystallization of mullite was investigated. The composition of the parent glass was chosen in the mullite primary phase field of the CaO–MgO–Al₂O₃–SiO₂ quaternary system. Glass powder pellets were heated under standard (10 °C/min and 2 h of hold time) and fast heatings (25 °C/min and 5 min of hold time) at different temperatures from 700 to 1190 °C. Sintering of B₂O₃-containing glasses took place in the range between 850 and 1050 °C. X-ray diffraction results showed that mullite formed as unique crystalline phase for glasses containing amounts of B₂O₃ larger than 6 wt%. For lower amounts of boron oxide cordierite was formed as secondary crystalline phase. Quantitative determination of mullite by Rietveld analysis indicated that the higher amount of mullite present in the glass-ceramic fast heated at 1160 °C was 19.5 wt% for the glass containing 9 wt% of B₂O₃. The final microstructure of the glass-ceramic glazes showed the presence of well shaped, long acicular mullite crystals dispersed within the residual glassy phase. Results of glass-ceramic glazes when applied as slurry and under industrial heating conditions pointed out promising mechanical properties.     

Effect of different valence forms of iron on the properties of glasses in the SiO2 - Al2O3 - Fe x O y - CaO - MgO system

The effect of different valence forms of iron on the physicomechanical and crystallization properties of glasses in the SiO₂ - Al₂O₃ - Fe _x O _y - CaO - MgO system is described. It is established that the properties of the glasses improve with an increase in the fraction of bivalent iron. A mechanism of crystallization in the glasses is suggested and the effect of the redox synthesis medium on the process of devitrification of iron-containing glasses is substantiated.Translated from Steklo i Keramika, No. 9, pp. 3 – 5, September, 1996.     

Transparent glass and glass-ceramic in the binary system NaPO3-Ta2O5

Transparent and homogeneous tantalum phosphate glasses were prepared in the binary system (100-x)NaPO₃-xTa₂O₅ with x varying from 10 to 50 mol%. Thermal, structural, and optical properties, as well as crystallization mechanisms, were investigated by thermal analysis, X-ray diffraction, Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopies, optical absorption, transmission electron microscopy in terms of Ta₂O₅ content. FTIR and Raman results support the tantalum insertion in the phosphate chains with [TaO₆] polyhedra cross-linking the phosphate units. At higher Ta₂O₅ content, [TaO₆] clusters are formed and connected to the phosphate network by P-O-Ta bonds. This structural evolution is in good agreement with the thermal features measured by differential scanning calorimetry (DSC) with a strong increase of the T_g temperatures up to 920°C, high thermal stability against crystallization for low Ta₂O₅ content and increasing of crystallization tendency for the most Ta-concentrated samples. Besides, due to the progressive insertion of [TaO₆] units, the precipitation of Na₂Ta₈O₂₁ perovskite-like phase was identified in the sample with 50 mol% of Ta₂O₅. The optimal heat treatment conditions were identified using DSC measurements and a transparent glass-ceramic from 50NaPO₃ to 50Ta₂O₅ composition was prepared. The obtaines glass-ceramic has great potential for optical applications, such as host for rare-earth ions, nonlinear optical materials, and ferroelectric domain.     

用磷酸二氢钙制磷酸二氢钾的磷收率研究

采用单因素实验和二次回归正交实验设计,对磷酸二氢钙与硫酸钾生产磷酸二氢钾反应过程中反应温度、反应时间、硫酸钾与磷酸二氢钙摩尔比以及液固比诸因素对五氧化二磷收率的影响进行了研究,最终得到适宜的工艺条件为:反应温度50℃,反应时间120min,反应液固比4:1,硫酸钾与磷酸二氢钙摩尔比(K2O:P2O5)1.1:1,所得P2O5收率超过70%.     

A glass in the CaO/MgO/Al2O3/SiO2 System for the rapid laser sealing of alumina

In the field of microelectronics housings made of corundum or sapphire are used, because they resist high mechanical stresses and can be used in extreme environments. For joining these components, sealing materials are necessary, which have a thermal expansion coefficient adapted to corundum or sapphire (8.2×10 ⁻⁶K⁻¹) and resist high temperature. This can be achieved by glass, which is crystallized during the joining process. However, the temperatures in conventional joining processes are not suitable for the encapsulation of temperature “sensitive components”. During a laser joining process only the joining zone is heated up for a short period of time and the components were not destroyed. For this process glasses from the system CaO/MgO/Al₂O₃/SiO₂ were chosen and analyzed with respect to their sintering and crystallization behavior. The glasses could be sintered and crystallized by using the laser joining process. The crystallized glasses have a thermal expansion coefficient between 8.1×10 ⁻⁶ K⁻¹ and 9.3×10⁻⁶ K⁻¹ and hence, show a good match for joining of corundum and sapphire.     

Effects of Nb2O5 and Gd2O3 doping on boron volatility and activity between glass seals and lanthanum-containing cathode

In planar Solid Oxide Fuel Cells (SOFCs), the boron species volatilize from glass seals, and react with lanthanum-containing cathodes (i.e., La_0.6Sr_0.4Co_0.2Fe_0.8O_3 − δ, LSCF) to form LaBO₃ under cathodic polarization, which decomposes the perovskite structure and consequently decreases the electrochemical activity of cathode. In this study, Nb₂O₅ and Gd₂O₃ are added to an aluminoborosilicate glass to reduce the boron volatility from glass and the reaction between sealing glass and LSCF cathode. Both Nb₂O₅ and Gd₂O₃ doping increases the network connectivity, but Nb₂O₅ doping enhances the [BO₃] → [BO₄] transition and reduces the boron volatility from glass seals, thus effectively suppressing the deposition and poisoning of boron contaminants on the LSCF cathode. However, an obvious degradation of the electrocatalytic activity of LSCF occurs in the presence of Gd₂O₃-doped glass. The relationship between glass structure and glass/cathode interaction has been established to provide useful information for designing stable sealing materials for SOFC applications.     

液相沉淀Al2O3-SiO2-P2O5-CaF2系玻璃粉体的性能表征

选取几种分别含有Al3+,SiO32-,P3O105-,Ca2+,F-的无机盐作为初始反应物,采用液相沉淀法合成了Al2O3-SiO2-P2O5-CaF2系纳米玻璃态粉体,在400～900℃温度范围内对粉体进行热处理,借助TEM,EDAX,XRD,IR,DSC等分析手段表征了粉体的形貌、化学组成、结晶状态、玻璃结构及析晶特性.结果表明,该液相沉淀粉体由含有Al,Si,Ca,P,O,F元素的中空近球状纳米粒子组成,粒径约在30～70 nm范围内,呈典型的非晶态特性.当热处理温度达到600℃时,晶相CaF2优先析出,随温度的升高,Al2SiO5,Ca2SiO4,Ca3(PO4)2等晶相相继析出.其主体结构为[SiO4],[AlO4],[PO4]四面体以共用角顶氧原子的相连形式而构成空间网络结构.     

Crystallization of glass of the system K2O(Na2O)Al2O3SiO2

In a whiteware composition, the glassy phase derives from the molten feldspar in which a portion of quartz, clay and other crystalline constituents are dissolved. This glass is the major and continuous phase in the whiteware body and is the potential source of the crystalline phase, viz. mullite. Synthetic glass has been prepared by melting mixtures of feldspar and quartz comparable to whiteware-glass in composition. Glasses were also synthesized by melting mixtures of feldspar, quartz and mineralizers. All of these glasses were heat-treated and their mullite contents were estimated by X-ray analysis supported by TEM & SEM study. Among thirtyone (31) different mineralizers tried, only thirteen (13) are found to be effective mullite is builders. The cation of the mineralizer helps replacement of the Al³⁺ ion from the glass which subsequently diffuses through the residual SiO₂ and mullite is formed. The replacement reaction and hence the degree of mullitization is dependent on factors, e.g. charge, radius, field strength of the cation as well as on the cation-oxygen bond strength. This last appears as the most predominant factor for mullitization.     

The effects of SiO2 and K2O on glass forming ability and structure of CaOTiO2P2O5 glass system

The effects of SiO₂ and K₂O were investigated on the glass forming ability (GFA) and structural characteristics of CaOTiO₂P₂O₅ system. Differential thermal analyzer (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR and ³¹P magic angle spinning NMR methods were applied for characterizations of the system.Unwanted crystallization in the initial three components base glass composition was observed by adding SiO₂ and crystalline phases such as TiP₂O₇, rutile (TiO₂) and cristobalite (SiO₂) were formed in it.The results showed that K₂O prevents crystallization of glasses and promotes the formation of glass. FT-IR and X-ray diffraction showed that the addition of K₂O caused the formation of phosphate–silicate network as POSi, and formation of isolated droplet phases (rich of Si and P) separated from the phosphate matrix.The optimum amounts of SiO₂ and K₂O in phosphate structure were respectively 6 and 2 wt.%, 0 in accordance with glass forming ability (GFA) parameters. Despite addition of SiO₂ along with K₂O; the ³¹P MAS NMR and infrared spectrums of glasses show that no Q² sites were in the phosphate network. The Q¹ and the pyrophosphate groups was the predominant structural unit in these glasses.     

新型镁钙铝浇注料的脱磷作用研究

将等质量而磷含量不同的铁粉分别置于以高铝水泥为结合剂浇注成型的镁钙铝质坩埚内 ,并将坩埚埋入石墨粉中经 1 6 0 0℃保温 2h ,冷却后测定金属样中和坩埚衬表层的磷含量 ,发现金属样中磷含量显著下降而坩埚衬中磷含量增多 ,表明该浇注料有脱磷作用。采用SEM和EDAX方法探讨了浇注料脱磷机理和过程。其脱磷作用是由于镁钙砂中游离态的氧化钙能逐步吸收转化磷杂质为磷硅酸钙的固溶体存在于浇注料中     

Thermal and crystallization behavior of SiO2-PbF2 glass system in the presence of ErF3 and Al2O3

Oxyfluoride glass-ceramics have been introduced as one of the best bulk hosts for upconversion process of rare-earth ions. However, less attention to the technological topics in the process of glass crystallization has hindered the development of them in industrial scale applications. In this research, SiO₂–PbF₂ glasses were investigated to clarify the ambiguous role of rare-earth ions and alumina content in the microstructure and crystallization behavior. Results indicated that Er³⁺ addition caused a liquid-liquid phase separation via nucleation and growth mechanism, which led to single phase crystallization of β-PbF₂:Er³⁺ solid solution. Moreover, Er³⁺ had a significant effect on the crystallite size, size distribution, and PbF₂ crystallization temperature. On the other hand, increasing Al₂O₃ content enhanced the transparency and thermal stability of glass samples, whereas it reduced the amount of fluorine loss and increased the dissolution of Er³⁺ in fluoride crystalline structure. These results address some of the most controversial issues about crystallization behavior of rare-earth-doped oxyfluoride glasses.     

Determination of the SiO2 Activity in Melts of the CaO–Al2O3–SiO2 System by High-Temperature Mass Spectrometry

This paper reports on the results of systematic investigations into the thermodynamic properties of melts lying along the joins with constant SiO₂ contents of 0.5 and 0.6 mole fractions in the CaO–Al₂O₃–SiO₂ system at mole fraction ratios CaO : Al₂O₃ varying from 0.25 to 4.0. The activities of SiO₂ in melts of this system at a temperature of 1905 ± 10 K are determined by high-temperature mass spectrometry. It is found that, in the concentration range studied, the activity of SiO₂ remains constant at SiO₂ contents of 0.5 and 0.6 mole fractions.