Structure and crystallization behaviour of Li2O-Fe2O3-SiO2 glasses

Iron-containing lithium disilicate glasses, other silicate and borate glasses, and crystallized lithium disilicate glasses have been studied by Raman spectroscopy, luminescence spectroscopy and X-ray diffraction. In the as-quenched glasses the presence of iron leads to a strong Raman band at 950 cm^–1 and to a broad Raman scattering continuum below 500cm^–1. There is also an emission due to trivalent iron at about 14000cm^–1 Lithium metasilicate has been identified in all crystallized glasses with more than 1% Fe₂O₃. It was possible to crystallize some of the glasses by irradiating them with intense blue laser light, and Raman spectra of various stages of photocrystallization have been obtained. By comparing the Raman spectra of the crystallized glasses with those of as-quenched glasses it is deduced that the trivalent iron has its own distinct local environment in the glass.     

Sintering of Si3N4 in the presence of additives from Y2O3-SiO2-Al2O3 system

The sintering process of Si₃N₄ in the presence of a liquid phase from the Y₂O₃-SiO₂-Al₂O₃ system was investigated. The starting composition of liquid phase was varied according to data in the phase diagram of the Y₂O₃-SiO₂-Al₂O₃ system, in order to lower the temperature of liquid formation because it might exhibit an influence on the sintering behaviour of Si₃N₄. Densification as well as phase analysis were followed as a function of composition and the amount of liquid phase, both in the sintered and in hot pressed samples.     

Glass formation and crystallization of barium ferrite in the Na2O-BaO-Fe2O3-SiO2 system

Amorphous ribbons of approximate composition 0.13Na₂O-0.30BaO-0.30Fe₂O₃-0.27SiO₂ were successfully fabricated using roller-quenching, after melting at 1400C. Devitrification of the amorphous phase by annealing at 710C for 2 h formed a uniform distribution of barium ferrite (BaFe₁₂O₁₉) particles with a mean diameter of 55.88 nm. Other crystalline phases formed on heat treatment were BaFe₂O₄ and Na₂Ba₂Si₂O₇. Devitrified ribbons showed a saturation magnetization (M _S) of 24.41 emu g^–1 and a coercivity (H _C) of 3.06 kOe.     

B2O3-Al2O3-SiO2透明玻璃陶瓷研究

玻璃陶瓷属于一类多晶陶瓷材料.通过调整玻璃基质和晶相组成可以制备出具有良好的力学、热学、电学和光学性能的玻璃陶瓷材料.采用传统的熔融和退火技术制备出含B2O3-Al2O3-SiO2-Li2O-K2O组分的硼铝硅玻璃,并通过成核和长晶工艺最终制备出透明玻璃陶瓷.配合料在铂金坩埚中于1450℃下熔融2h,然后经两步热处理制度控制晶核的生成和晶粒的长大.采用差热分析技术确定成核和长晶温度.采用X射线衍射技术对不同热处理制度下的玻璃陶瓷样品进行分析,以确定最佳成核和长晶条件.采用扫描电子显微镜分析玻璃陶瓷形态,晶粒尺寸及其在残余玻璃相中的分布.采用UV-Vis-Nir分光光度计测定玻璃陶瓷样品的透过率.     

超重力熔铸Y2O3-Al2O3-SiO2玻璃的晶化行为研究

研究了以超重力熔铸方法制备的Y₂O₃-Al₂O₃-SiO₂玻璃的晶化行为, 并结合相图分析了热处理条件对晶化过程的影响规律。实验结果表明, Y₂O₃-Al₂O₃-SiO₂玻璃的晶化行为与热处理温度和SiO₂含量密切相关。当热处理温度为1050℃时, 晶化后样品的相组成沿超重力场方向呈现出梯度分布, 自上而下分别为Al₆Si₂O₁₃玻璃陶瓷、纯玻璃相、χ-Al₂O₃玻璃陶瓷。当退火温度为1100℃时, 析出晶相主要为Y₃Al₅O₁₂及Y₂Si₂O₇; 退火温度为1200℃时主要析出Y₃Al₅O₁₂。因此, 以超重力熔铸法制备YAS玻璃结合后续热处理的工艺, 提供了一种快速制备YAS基微晶玻璃的新方法。     

B2O3-Al2O3-SiO2系微晶玻璃析晶动力学研究

采用差示扫描量热（DSC）分析法对B2O3-Al2O3-SiO2系统微晶玻璃的析晶动力学参数进行了测定，研究了该系统微晶玻璃的析晶动力学。结果表明：随着B2O3/SiO2比的降低，该系统玻璃的析晶活化能E呈先升高后降低的变化趋势，当B2O3/SiO2比为11：5时，析晶活化能最小，Emin=375．4kJ／mol，晶化指数n则先减小后增大，但均〉4，表明该系统玻璃可整体析晶。     

超重力辅助燃烧合成Y2O3-Al2O3-SiO2玻璃/Y3Al5O12陶瓷梯度复合材料

以超重力场辅助燃烧合成技术制备了呈梯度分布的Y2O3-Al2O3-SiO2透明玻璃/Y3Al5O12陶瓷梯度复合材料.结果表明,梯度布置两种组分的原料既可防止下层熔体的喷溅,又能提高上层玻璃的透过率.该梯度材料沿超重力方向依次为YAS透明玻璃层、YAS-YAG玻璃陶瓷层和YAG陶瓷层.     

An investigation of phase stability in the Y2O3-Al2O3 system

The stability of the three known phases in the Y₂O₃-Al₂O₃ pseudo-binary system has been investigated. YAlO₃ (YAP) and Y₄Al₂O₉ (YAM) decompose at elevated temperatures, the products of the reaction being the third compound Y₃Al₅O₁₂ (YAG) and an unknown phase (designated X). The decomposition is most evident in powders but can also be initiated on the surface of bulk single crystals. X-ray diffraction studies have been performed in an attempt to identify the structure and composition of the unknown phase. The thermal decomposition has been found to be surface controlled and an optical and scanning electron microscope study of the associated morphological changes in YAlO₃ indicates that the reaction involves localized surface melting, probably with the loss of oxygen which effectively moves the composition off the binary join.     

The crystallization of Gd2 3 -Al2O3 glasses

Glasses of Gd₂O₃ · x Al₂O₃ compositions where x represents 5/3, 4 and 6, were prepared using a rapid quenching apparatus and a laser beam. The crystallization process of the glasses was studied by means of differential thermal analysis (DTA), X-ray diffraction analysis and electron microscopy. The crystallizations of Gd₂O₃ · 5/3Al₂O₃, Gd₂O₃ · 4Al₂O₃ and Gd₂O₃ · 6Al₂O₃ are complex and exhibit one, two and three exothermic peaks in DTA measurement with increasing Al₂O₃ concentration, respectively. The crystallization process of Gd₂O₃ · 5/3Al₂O₃ glass involved the direct formation of the gadolinium aluminium garnet, 3Gd₂O₃ · 5l_{2 3} (GdAG), which is not obtained by the ordinary solid phase reaction. After crystallization of Gd₂O₃ · 4Al₂O₃ and Gd₂O₃ · l_{2 3} glass, both phases become a mixture of Gd₂O₃ · Al₂O₃ (perovskite type) and -Al₂O₃.     

Fabrication of hollow glass microspheres in the Na2O-B2O3-SiO2 system from metal alkoxides

Hollow glass microspheres (HGS) for laser fusion targets were fabricated in the system Na₂O-B₂O₃-SiO₂ from NaOCH₃, B(OCH₃)₃ and Si(OC₂H₅)₄. Gel powders prepared from metal alkoxides and urea liberate H₂O, CO₂ and NH₃ gases, evolution of which takes place completely at about 500° C. The precursor of HGS is formed by the encapsulation of these gas components in the glass layer formed at the surface of the powder. HGS are produced from the gel powders having both a melting temperature lower than about 1000° C and a viscosity at that temperature lower than 10⁵ P. In the Na₂O-B₂O₃-SiO₂ system, the compositions from which HGS are produced are those containing 55–75 wt% SiO₂ and 0–20 wt% B₂O₃. HGS ranging from 100–500m diameter and 0.5–7.0m wall thickness are obtained by change of urea content.     

Toughened glass-ceramics in the ZrO2-Al2O3-SiO2 system prepared by the sol-gel process

Monolithic glass-ceramics containing Al₂O₃ or TiO₂ were prepared in the ZrO₂-SiO₂ system by the sol-gel process from metal alkoxides. Tetragonal ZrO₂ was precipitated by heat treatment at 900–1200 °C and its crystal growth was increased by adding TiO₂ or Al₂O₃. Further heating at higher temperature resulted in the precipitation of zircon and monoclinic ZrO₂ which was transformed from tetragonal ZrO₂. The addition of Al₂O₃ had less effect on both the tetragonal-to-monoclinic ZrO₂ transformation and the precipitation of zircon. The fracture toughness increased as the size of tetragonal ZrO₂ particles increased and then decreased with the appearance of monoclinic ZrO₂ or zircon. The fracture toughness of the glass-ceramics was measured in the glass-forming regions of the ZrO₂-Al₂O₃-SiO₂ system. The fracture toughness was sensitively dependent on both Al₂O₃ and ZrO₂ content, of which the highest value achieved was 9 MPa m^1/2 for the 50ZrO₂·10Al₂O₃·40SiO₂ composition.     

Sm3+:ZnO-B2O3-Al2O3-SiO2系透明玻璃陶瓷的制备和表征

采用熔融和晶化技术合成出含ZnAl2O4微晶的Sm3+:ZnO-B2O3-Al2O3-SiO2(ZBAS)玻璃陶瓷材料,并通过DSC、XRD、SEM和UV-Vis-Nir分光光度计和傅里叶变换荧光光谱仪等对样品进行了表征.结果表明,玻璃陶瓷主晶相为ZnAl2O4,晶相粒径为30nm;可见光透过率为最高可达70％,近红外透过率为70％～85％.该玻璃陶瓷能够受激发射出红光,且发光强度高于同组分的玻璃.     

Na_2O-CaO-Al_2O_3-SiO_2-H_2O系水化物凝胶对Cs~+的吸附机理

在35℃恒温水化反应90d条件下,制备了Na2O-CaO-Al2O3-SiO2-H2O系水化物凝胶,探讨了水化物凝胶的化学组成对Cs+吸附性能的影响;讨论了水化物凝胶对Cs+的吸附热力学行为。结果表明,当化学组成为n(CaO+Na2O)/n(SiO2+Al2O3)=0.66,n(Al2O3)/n(SiO2)=0.3时,凝胶对Cs+的3d吸附量可达10.6936mg/g;温度越低,吸附量越大,凝胶对Cs+的吸附近似服从Freudlich、Langmuir和D-R吸附等温式,反应为放热反应,且以离子交换吸附为主;吉布斯自由能和吸附熵为均为负值,反应能自发进行。吸附动力学符合Lagergren假二级速率方程模型。     

Sinterability of Y2O3-Al2O3 particulate stainless steel matrix composites

P/M 316L austenitic stainless steel has been reinforced with yttria and alumina particles. In order to improve the sintering behaviour of these composite materials, chromium diboride and boron nitride were added. The sinterability of the different materials has been characterised through dilatometry and sintering curves (sintered density vs. sintering temperature). A metallographic study by SEM coupled with microprobe has also been performed. Composites materials present a good densification. Chromium diboride and boron nitride react with the matrix in different manners, but they both greatly improve the sinterability of reinforced materials. The optimum sintering temperature for these composites materials is 1250 °C.     

Transparency of LiTaO3-SiO2-Al2O3 glass-ceramics in relation to their microstructure

The glasses with various compositions in the LiTaO₃-SiO₂-Al₂O₃ system were heated from room temperature to temperatures ranging from 750° to 1050° C at a rate of 5° C min^–1. From the glasses in the LiTaO₃-SiO₂ system no transparent glass-ceramic was obtained even when their LiTaO₃/SiO₂ mole ratios were as high as 2.33. The diameter and number of the LiTaO₃ crystal grains precipitated in the glasses were 5–15 m and 10⁸–10¹⁰ grains cm^–3, respectively. On the contrary, transparent glass-ceramics were obtained from the glasses containing Al₂O₃; their compositions covered a fairly large area in the LiTaO₃-SiO₂ -Al₂O₃ system, which encompasses the compositions with the LiTaO₃/SiO₂+AlO_1.5 mole ratio as low as 0.25. The diameter and number of the LiTaO₃ crystal grains precipitated in the transparent glass-ceramics were as small as 10–20 nm and as many as 10¹⁶–10¹⁸ grains cm^–3, respectively. High nucleation rates of the LiTaO₃ crystals in the Al₂O₃-containing glasses were interpreted in terms of structural inflexibility induced in the glass-network by the addition of Al₂O₃ to the LiTaO₃-SiO₂ system.     

Sintering and crystallization of a glass powder in the MgO-Al2O3-SiO2-ZrO2 system

The sintering and crystallization behaviour was studied of a glass powder in the MgO-Al₂O₃-SiO₂-ZrO₂ system in which the main crystal phases to form are clino-enstatite (MgSiO₃) and cubic zirconia (c-ZrO₂). During isothermal, atmospheric sintering of the glass powder, a fine dispersion of c-ZrO₂ particles, 50–100 nm diameter, was observed to form, but this did not appear to inhibit the sintering process. Nucleation of the main crystal phase, clino-enstatite, occurred both within the original glass powder particles and at the former particle surfaces, but the rate of crystallization was greater at the former particle surfaces. The c-ZrO₂ precipitates are thought to act as nucleation sites for the crystallization of the clino-enstatite. Relative densities of up to 98% were attainable during sintering, and were reached at a stage where a significant degree of crystal phase development had already taken place, proving that completion of sintering prior to the commencement of crystallization is not always a pre-requisite for the attainment of high final densities. In the material studied, the large volume contraction ( 11%) on crystallization and the possible release of dissolved gases led to a decrease in relative density as crystallization proceeded. The relative density after complete crystallization was found to be 94%±1%, irrespective of the temperature and duration of the initial sintering stage of heat-treatment, and it appeared that most of the residual porosity was a result of the volume contraction on crystallization rather than poor densification during sintering.