Effect of alkali and alkaline earth oxides on crystallization of Li2O-Al2O3-SiO2 glasses

The effect of alkali and alkaline earth oxides on the crystallization of lithia-alumina-silica glasses has been studied. Crystallization behaviour of glasses has been investigated using DTA and XRD techniques. The principal crystallization phases are identified asβ-spodumene solid solution and lithium metasilicate. The crystallization temperature of glasses decreases with increase in the values of the ionic field strength of the alkali and alkaline earth cations. Addition of these oxides at lower concentrations has no significant effect on the crystalline phases.     

Preparation and crystallization of ultrafine Li2O-Al2O3-SiO2 powders

Ultrafine powders of Li₂O-Al₂O₃-SiO₂ (LAS) glass-ceramic were prepared by the sol-gel process using tetraethoxysilane, titanium butoxide, lithium, magnesium, aluminium (and zinc) inorganic salts as starting materials. The effect of pH on the sol-gel transition and particle sizes of the Li₂O-Al₂O₃-SiO₂ system was studied. The nucleation and crystallization process of LAS powders were also investigated by differential thermal analysis and X-ray diffraction. The results show that a surface nucleation process occurs for ultrafine LAS powders. The LAS glass-ceramics fabricated from ultrafine LAS powders have a low thermal expansion coefficient, <10×10^–7 °C.     

Thermal expansion of Li2O-ZnO-Al2O3-SiO2 glasses and corresponding glass-ceramics

The thermal expansion behaviour of some glasses and glass-ceramics within the system Li₂ZnSiO₄-LiAlSi₂O₆ is described. The effect of TiO₂ and ZrO₂ additions is also evaluated. The expansion coefficient () of the glasses increases with an increase of the Li₂ZnSiO₄ component in the glass composition. TiO₂ and ZrO₂ were found to decrease the thermal expansion of the glasses investigated. The dilatometric transition and softening points of the glasses showed the reverse behaviour. The thermal expansion of the glass-ceramics exhibited a wide range, depending upon the type and relative proportions of the crystalline phases present. The values of the glasses ranged between 73.6 and 97.4×10^–7C^–1 in the temperature range 20–450C and those for the crystalline products ranged from 36.1 and 102.6 × 10^–7 in the temperature range 20–450C.     

Radial GRIN glasses in Li2O-Na2O-Al2O3-TiO2-SiO2 systems

A series of GRIN glass rods have been developed in Li2O-Na2O-Al2O3-TiO2-SiO2 systems. Negative radial refractive index profiles were generated by exchanging Na+ for Li+ ions in these glass rods. It has been observed that TiO2 plays a vital role in increase in the profile depth and maximum change in the refractive index because of its ambivalent nature. Change in the refractive index can be further increased by increasing the concentration of exchanging cation in the base glass.     

Dielectric behaviour of glasses and glass ceramics in the system BaO-PbO-TiO2-B2O3-SiO2

Glasses with varying molar ratios of PbO/BaO in the system BaO-PbO-TiO₂-B₂O₃-SiO₂ were prepared keeping (BaO + PbO)/TiO₂ ratio equal to one. The glasses were ceramized by two-stage heat treatment. X-ray diffraction indicates that PbTiO₃ crystallizes in lead-rich glasses while BaTiO₃ precipitates in barium-rich compositions. Solid solution (Ba, Pb)TiO₃ does not seem to crystallize over the entire range of compositions. Simultaneous presence of PbO and BaO in the initial glass composition reduces the yield of ferroelectric phase. Dielectric properties have been interpreted in terms of microstructural features.     

Electrical properties of Li2O-La2O3-SiO2 electrode glasses after Ta2O5 doping and Ta implantation

Electrical conductivities, , of the Li₂O-La₂O₃-SiO₂ glasses were investigated as functions of Ta₂O₅ doping and Ta ion-implantation. A linear relationship between logarithm and the inverse of the sample temperature, T, was found in 2 to 4 mol% Ta₂O5 doped Li₂O-La₂O₃-SiO₂ glasses. The conductivity increases as Ta₂O₅ content increases at sample temperatures above 100°C. Fluences of 50 keV Ta ions per cm² from 5 × 10¹⁶ to 2 × 10¹⁷ were implanted into 0% and 2% Ta₂O₅ containing Li₂O-La₂O₃-SiO₂ glass samples. The activation energy of the conductivity was deduced from the relation between log and 1/T. It was found in implanted samples that the conductivity increased, but the activation energy and T _k–100 decreased, where T _k–100 is the sample temperature when the conductivity reaches 100 × 10^–1 S/cm. However, the Ta₂O₅ containing implanted samples show higher conductivities, lower activation energies and lower T _k–100. X-ray photoelectron spectroscopy (XPS) was used to study the structural modification introduced by implantation. Bridging oxygen (BO) and non-bridging oxygen (NBO), were observed in all samples. The changes in relative concentrations of BO and NBO before and after implantation clearly indicate the structure modification which results in the increase of the conductivity. It was clearly demonstrated in this study that both doping Ta₂O₅ and implanting Ta ions enhance the conductivity of Li₂O-La₂O₃-SiO₂ electrode glasses.     

The crystallisation of glasses based on eutectic compositions in the system Li2O-Al2O3-SiO2

Structural transformations have been studied in glasses related in composition to the binary eutectic between lithium metasilicate and -spodumene. Crystallisation processes and changes in microstructure during the controlled heating of the glasses have been followed using X-ray diffraction, electron microscopy, high temperature microscopy, thermal analysis and electron spin resonance spectroscopy.The influence exerted by titanium dioxide on the phase relationships, crystal growth rates and micromorphology of the polycrystalline products of heat-treatment has been investigated and the findings used as a basis for proposals on the rôle of TiO₂ during nucleation and crystal growth.     

Ce3+掺杂Li2O-MgO-Al2O3-SiO2玻璃的结构与荧光猝灭现象

采用熔融淬冷法制备了不同浓度Ce³⁺离子掺杂的20Li₂O-5MgO-20Al₂O₃-55SiO₂玻璃闪烁材料。采用X射线衍射(XRD)、高分辨透射电镜(HRTEM)技术、密度检测等方法研究了玻璃的微观结构随Ce³⁺离子掺杂浓度的变化规律, 采用荧光分光技术检测了玻璃的紫外光致激发光谱(PLE)、发射光谱(PE)。研究结果表明: 在不对称的晶体场作用下, Ce³⁺离子5d能级被劈裂为5个组分; 随着玻璃基质内Ce³⁺离子掺杂浓度增大, 玻璃的非晶化程度加深; 5d能级的劈裂宽度随之增大, 由此导致激发带向低能量端展宽、发射光谱明显红移; Ce³⁺离子的荧光发射强度随Ce³⁺离子掺杂浓度先升高、后降低, 浓度猝灭过程成为其荧光发射效率降低的主要原因。     

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.     

Mössbauer study of crystallization of glasses in the system K2O-Na2O-CaO-MgO-Al2O3-SiO2

Mössbauer spectroscopy has been used to study several glasses and glass ceramics based on the system K₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂ with additions of Fe₂O₃, Fe₃O₄ and P₂O₅. The change of co-ordination and proportion of Fe²⁺ and Fe³⁺ occurring during the transformation from glass to glass ceramic was studied. By means of the nuclear magnetic hyperfine splitting effect Fe₃O₄ was found in glass ceramics with more than 2% of P₂O₅. The amount of Fe₃O₄ formed was found to increase with P₂O₅ addition, but Fe₃O₄ was not identified in the glass with no P₂O₅ addition.     

Characterization of B2O3-SiO2 glasses prepared via sol-gel

B₂O₃-SiO₂ glasses were prepared by the sol-gel method from boron and silicon alkoxides. The gels were densified by several heat-treatments at temperatures above 800° C. The gel-glass transition was studied with the data obtained from differential thermal analysis, dilatometry and thermal evolution of density. The structural features of the glassy materials prepared were analysed by means of infrared (IR) and near-infrared (NIR) spectroscopy. The IR spectra indicated the existence of mixed Si-O-B bonds, preferential located at the outside of the material particles. The NIR spectra, recorded from gels heat-treated at low temperatures, demonstrated the existence of a great number of OH^– groups varying in nature, as well as their evolution and their positional changes on the silica particle surface as a function of the heat-treatment.     

The crystallisation of glasses based on the eutectic compositions in the system Li2O-Al2O3-SiO2

A study has been made of the crystallisation of glasses based on the eutectic between lithium metasilicate and-eucryptite and of the rÔle of TiO₂ in promoting fine-grained crystallisation. The hypothesis advanced in part 1 of this work is extended to a semi-quantitative measure of the effect of TiO₂.Characteristics of two metastable phases are described in an appendix.     

亚微米Li2O-Al2O3-SiO2微晶玻璃制备

本文利用DTA、XRD和SEM对Li2O-Al2O3-SiO2(以下简称LAS)微晶玻璃核化晶化热处理制度及氟离子在该玻璃体系中的作用进行研究.通过分析得出:含氟LAS玻璃核化温度和晶化温度分别为620℃和710℃,比相同组份的不含氟Li2O-Al2O3-SiO2玻璃核化、晶化温度分别降低了40℃和160℃左右;引入氟离子明显降低LAS玻璃析晶温度,系统的活化能降低约54kJ/mol,当含氟LAS玻璃的核化时间为1h、晶化时间为4hrs,平均微晶颗粒尺寸在50nm左右.     

Crystallization behaviour of β-spodumene in the calcination of Li2O-Al2O3-SiO2-ZrO2 gels

This work was carried out in order to prepare precursor powders with a spodumene composition (Li₂O·Al₂O₃·4SiO₂, LAS) and to investigate their crystallization behaviours during calcination. A fine β-spodumene type amorphous powder was obtained through sol-gel techniques using LiOCH₃, Al(OC₂H₅)₃, Si(OC₂H₅)₄ and Zr(OC₂H₅)₄ as the starting metal alkoxides. The process included well controlled hydrolysis polycondensation of the raw alkoxides. Differential thermal analysis (DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron diffraction (ED) analyses were utilized to study the crystallization behaviour of the gels. The activation energy of β-spodumene crystallization was 192 kJ mol⁻¹ for LAS gels with 4 wt% ZrO₂, being much smaller than those of LAS gel without ZrO₂, 382 kJmol⁻¹. For calcination at 800–1200°C, the crystallized phases comprised a major phase of β-spodumene and a minor phase of zirconia (ZrO₂).     

晶核剂对Li2 O-Al2 O3-SiO2系统微晶玻璃结构和性能的影响

通过传统熔体冷却法制得了以P2O5和TiO2为晶核剂的Li2O-Al2O3-SiO2系统基础玻璃,并经过热处理制得了微晶玻璃.利用红外光谱分析、X射线衍射分析和扫描电子显微镜等对晶化试样的物相和显微结构进行了研究,着重探索了不同晶核剂对玻璃析晶、微晶玻璃结构、微晶玻璃力学和热学性能的影响.结果表明:TiO2更有利于玻璃析晶,但以P2O5为晶核剂的微晶玻璃具有更好的力学和热学性能.     

Li2O-B2O3-SiO2玻璃相对BaAl2Si2O8结构及微波介电性能的影响

采用固相工艺制备BaAl₂Si₂O₈-xwt%Li₂O-B₂O₃-SiO₂(x=0, 0.1, 0.3, 0.5, 1.0, 2.0)陶瓷。探究不同含量的Li₂O-B₂O₃-SiO₂(LBS)玻璃相对BaAl₂Si₂O₈(BAS)陶瓷的烧结温度、结构及微波介电性能的影响。结果表明: LBS玻璃相可明显降低BAS陶瓷的烧结温度, 并促进BAS陶瓷晶粒长大和晶体结构由六方相转变为单斜相。当x=0.1时, 六方相即可全部转变为单斜相, 在0.1≤x≤2.0范围内, BAS陶瓷晶体结构均为单斜相。添加0.3wt%的LBS玻璃相可促进BAS样品密度、介电常数和品质因数增大, 谐振频率温度系数绝对值减小。在x=0.3, 烧结温度为1275 ℃时, 可获得具有较好品质因数的单斜钡长石, 其介电性能: ε_r=6.74, Q×f=34570 GHz, τ_f= -15.97×10 ^-6/℃。