Y—La—Si—O—N系统氧氮玻璃形成与性能

本研究利用溶胶－凝胶技术制备Ｙ－Ｌａ－Ｓｉ－Ｏ－Ｎ氧氮玻璃配合料，在１大气压Ｎ２气氛中１６００℃左右温度熔制，制备出表观呈灰黑色透明的Ｙ－Ｌａ－Ｓｉ－Ｏ－Ｎ系统氧氮玻璃。实验结果表明氧氮玻璃含氮量为６．７－１０．９ａｔ％；显微硬度Ｈｖ为３．５－６．４７ＧＰａ；断裂韧性为０．６４－１．３８ＭＰａｍ＾１／２，Ｔｇ在１０００℃以上，膨胀系数为１．０５×１０＾－６℃＾－１．     

Glass Formation and Properties in the System Calcia-Gallia-Silica

The glass-formation region of the calcia-gallia-silica system was determined. The glasses within this region were measured to have a density of 3 to 4 g/cm³, a refractive index of 1.6 to 1.73, an Abbe number between 35 and 58, a thermal expansion coefficient of 6.5 × 10⁻⁷/°C to 11.5 × 10⁻⁷/°C, softening temperatures between 730° and 790°C, and a Vickers microhardness of 5.2 to 7.3 GPa. Crystalline phases were identified along the glass-formation boundary. Infrared transmission spectra were used to explain glass structures and their effect on glass properties. The results suggest that the role of calcia in the glass structure is similar to that for calcia in calcium aluminosilicate glasses.     

Physical Properties and Structure of Silica-Alumina-Europium Oxide Glasses

SiO₂–Al₂O3–Eu₂O₃ glasses were prepared for the composition 50siO₂·(50 – x )Al₂O_3·xEu₂O₃, and their density, sound velocity, and elastic modulus were measured. The chemical shift of the AIK a band emission spectra and the isomer shift of ¹⁵¹Eu by Mössbauer effect were obtained to determine the coordination states of Al³⁺ and Eu³⁺ ions in these glasses. It was found that the coordination number of Eu³⁺ ions was 12 and that the average coordination number of A1³⁺ ions was almost 5 in these glasses. By introducing Eu₂O₃, the packing of constituent ions was strongly enhanced and the elastic modulus increased in this system. The compositional dependence of the molar volume and elastic modulus were explained by these states of high coordination number for Eu³⁺ and low coordination number for Al³⁺ ions compared with those in the corresponding M₂O₃ crystals.     

Durability of Fluoride Glasses in Water

The durability of eight fluoride glasses was tested in liquid water from 25° to 75°C. The studies were done by first growing a corrosion layer and then examining structure and chemistry in cross section with an optical microscope and an electron microprobe. In this way the details of the corrosion behavior could be directly determined. The results indicate that the corrosion process proceeds by a moving boundary, whose penetration rate is diffusion limited.     

Local Structure of Alkaline-Earth Boroaluminate Crystals and Glasses: II, 11B and 27Al MAS NMR Spectroscopy of Alkaline-Earth Boroaluminate Glasses

¹¹B and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra of alkaline-earth boroaluminate glasses show that the structure of these glasses are far more complicated than previously thought. The relative concentrations of 3- and 4-coordinated boron vary as found by previous investigators using continuous-wave NMR methods, but the ²⁷Al NMR spectra indicate the presence of Al in 4-, 5-, and 6-fold coordination, in contrast to previous assignments. Analysis of the data based on local charge balance considerations provides a qualitative model that correctly predicts compositional variations of the NMR peak intensities and ²⁷Al chemical shifts for a wide range of boroaluminate glass compositions.     

Rare-Earth Aluminogermanate Glasses

The present study is a comparison of the properties of rare-earth aluminogermanate and rare-earth aluminosilicate glasses. Several properties have been measured, including density, transformation temperature, softening point, thermal expansion, Vickers hardness, magnetic susceptibility, Verdet constant, and IR transmission. The property data are discussed in relationship to the structure of these glasses and the field strength of the rare-earth ions. The Vickers hardness numbers of the glasses are discussed using a unique theory of hardness which involves the relationship between hardness and atom/ion packing in material structures.     

Formation of Ce-Si-O-N Glasses

The glass-forming region in the Ce-Si-O-N system was investigated. A large region of clear-glass formation was observed. The Ce:Si ratio of the clear-glass-forming region was consistent with that of the intergranular glassy phases in Ce-doped Si₂N₂O.     

抗水化型氧化钙的水化过程

用X-射线衍射仪对含Al2O3的氧化钙熟料在不同条件下放置过程中水化产物进行了鉴定;用电子探针分析了Al2O3等在CaO基体中的分布。结果进一步证实了这种熟料抗水化的原因在于其极低的显气孔率和发育良好的CaO晶粒自身水化活性的降低，C3A分布在CaO晶粒周围也起到了保护CaO晶粒免于水化的作用。     

Physical Properties of Chalcogenide and Chalcohalide Glasses

The physical properties of glasses in the Ge₃₀As₁₀Se_{(60— x )}Te _x system with x = 25, 28, 30, and 35 at.% Te, the Ge₃₀As₁₀Se₃₀Te_{(30— y )}I _y system with y = 5, 10, 20, and 30 at.% I, the Ge₃₀As₁₀Se₃₅Te_{(25— z )}I _z system with z = 2, 6, 10, and 20 at.% I, and the [Ge₃₀As₁₀Se₃₀Te₃₀]_{(100— w )}I _w system with w = 0, 5, 10, and 20 at.% I have been investigated. The changes in the glass transition temperature, density, coefficient of thermal expansion, hardness, and viscosity are attributed to the delocalized metallic bonding character of Te in the substitution of Te for Se in the Ge-As-Se-Te glass system and the network-terminating role of iodine in the substitution of I for Te in the Ge-As-Se-Te-I glass system, respectively.     

Properties of Yttria-Aluminoborate Glasses

In the Y₂O₃–Al₂O₃–B₂O₃ system, homogeneous glasses were obtained from compositions containing from 50 to 65 mol% B₂O₃. The density, refractive index, and thermal expansion increase as Y₂O₃ replaces either B₂O₃ or Al₂O₃. These glasses have a dilatometric softening temperature above 665°, and below 300°C their dc electrical resistivity exceeds that of fused silica. The infrared absorption spectra indicate that BO₃, BO₄, and AlO₄, groups are present in these glasses.     

29Si MAS-NMR Study of the Short-Range Order in Lithium Borosilicate Glasses

²⁹Si MAS-NMR measurements have been made on a series of lithium borosilicate glasses of general composition R Li₂O.B₂O₃· K SiO₂. At low alkali contents ( R < 1), the ²⁹Si resonance envelope is broadened and indicates a distribution of Si sites. As R increases above 1, the FWHM of the ²⁹Si resonance narrows considerably to that representative of a single chemical site. Simultaneously, the average chemical shift of the resonance shifts upfield in agreement with the trends found in the binary lithium silicate glass system. Using the chemical shifts for the individual Q species in the binary system it was found that very good agreement between the chemical shifts of the binary glasses and the ternary glasses examined here could be achieved if a model of proportional sharing of the added oxygen (from lithia) between silicate and borate units was used. In contrast to the ¹¹B NMR studies of these same glasses, the ²⁹Si NMR data are quantitatively best-fit if it is assumed that the proportional sharing of the oxygen from the added lithia begins at R = 0. Models of sharing developed from the ¹¹B NMR studies of these glasses, where proportional sharing above a certain fixed (independent of K ) or variable (dependent on K ) minimum R ₀, have been reexamined and were quantitatively shown through residual analysis to give consistently poorer fits to our data. At present the reasons for the discrepancy between the two sets of NMR data are unknown.     

125Te, 27Al, and 71Ga NMR Study of M2O3–TeO2 (M = Al and Ga) Glasses

The structures of M₂O₃–TeO₂ (M = Al and Ga) glasses have been investigated by means of ¹²⁵Te, ²⁷Al, and ⁷¹Ga NMR spectroscopies. The structural units of respective cations in M₂O₃–TeO₂ glasses were quantitatively analyzed. The fractions of TeO₄ trigonal bipyramid, AlO₆ and GaO₆ octahedra decreased and those of TeO₃ trigonal pyramid, AlO₄, AlO₅, and GaO₄ polyhedra increased with increasing M₂O₃ content. Based on the local structures around Te, Al, and Ga atoms, the structure models of M₂O₃–TeO₂ glasses were proposed.     

Structure and Properties of Long-Wavelength-Transmitting Halide Glasses

The lower halides of zinc, namely, ZnCl₂, ZnBr₂, and ZnI₂, may act as network formers in glasses that also contain modifying alkali halides such as KCI, KBr, KI, NaI, or CsI. Compositions which contain only Br⁻ or I⁻ anions are of particular interest because of their extended infrared transmission, which includes the ∼10-μm region, in addition to full visible transparency. A series of modified zinc halide glasses were prepared and characterized by differential scanning calorimetry, middle and far Fourier transform infrared spectroscopy, and polarized Raman spectroscopy. T _g values were characteristically low, around 40°C. Bulk glass infrared transmission up to 15 to 20 μm was recorded. The most probable glass structures are discussed and compared to oxide glass models. An attenuation of  0.001 dB/km has been projected as a possible intrinsic minimum for optical fibers operating near ∼6 μm.     

Corrosion of Borosilicate Glasses Subjected to Aggressive Test Conditions: Structural Investigations

Sodium borosilicate (NBS) and barium sodium borosilicate (BBS) glasses, used for immobilization of high‐level nuclear waste with compositions (SiO₂)_0.477(B₂O₃)_0.239(Na₂O)_0.170(TiO₂)_0.023(CaO)_0.068(Al₂O₃)_0.023 and (SiO₂)_0.482(B₂O₃)_0.244(Na₂O)_0.220(BaO)_0.054 were subjected leaching experiments under hydrothermal conditions in an autoclave at 200°C for different time durations. Morphological and structural transformations associated with leaching, have been monitored with techniques like XRD, SEM, solid‐state nuclear magnetic resonance. XRD and SEM along with NMR studies have confirmed that, upon leaching, formation of an aluminosilicate phase, Zeolite‐P (Na₆Al₆Si₁₀O₃₂·12H₂O), occurs with NBS glass. BBS glass upon subjecting to the same conditions leads to formation of multiple amorphous phases having Q⁴ (silica rich phase) and Q³ structural units of Silicon along with structurally modified residual glass. Upon leaching BO₃ structural units preferentially get released from BBS glass. Comparison of results with international simple glass confirmed that, for the latter, mass loss rates are one order of magnitude lower.     

玻璃中金属纳米颗粒的制备方法及研究进展

含金属纳米颗粒的玻璃材料具有优越的非线性光学特性,在开发具有特定光功能的光学元器件领域有广泛的应用前景。在玻璃材料中制备金属纳米颗粒、研究金属纳米颗粒的形成机制与行为,是目前光学与材料学领域的一大研究前沿。本文较为详尽地介绍了目前在玻璃中制备金属纳米颗粒的方法及研究进展,包括热处理法、离子注入法、光热诱导法等,对光热诱导法巨大的研究价值和应用前景作了较为详细的阐述。     

Local Structure of xAl2O3· (1 −x)NaPO3 Glasses: An NMR and XPS Study

A series of x Al₂O₃· (1 − x )NaPO₃ glasses (0 ≤ x ≤ 0.275) were prepared and characterized by magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and by X-ray photoelectron spectroscopy (XPS). ²⁷AI MAS NMR spectra reveal that: at low alumina contents ( x < 0.125), Al is in dominantly octahedrally coordinated Al(OP)₆ structural environments; in glasses with x > 0.125, Al(OP)₄ environments are increasingly favored; and at x = 0.275, most Al is tetrahedrally coordinated. 5-coordinated Al environments also appear to be present. Variations in the ³¹P MAS NMR spectra are consistent with bonding between neighboring P and Al polyhedra. Quantitative changes in the oxygen bonding, determined from the O 1 s spectra obtained by XPS, also reflect these structural changes. The effects of alumina content on the relative concentration of nonbridging oxygen (PO⁻) are quantitatively described by a simple structural model derived from the MAS NMR data. The thermal expansion coefficients and glass transition temperatures are shown to be sensitive to these structural changes.     

Properties and Structure of Lead Halosilicate Glasses

The glass transformation temperature, thermal expansion coefficient, dc electrical conductivity, and IR transmission have been measured for four series of lead halosilicate glasses of the general composition (65– x )PbO· x PbX₂·35 SiO₂ (X=F, Cl, Br, I). Although results of these and other measurements suggest that the halide ions play similar structural roles in the glass, there appear to be significant differences in physical property behavior between glasses containing F⁻ anions and those containing the other three halide anions. These results are explained by a proposed model incorporating both bridging and nonbridging halide species.     

Glass Formation and Polyamorphism in Rare-Earth Oxide–Aluminum Oxide Compositions

We report formation of single- and two-phase glasses from rare-earth oxide–alumina materials. Liquids with the Y₃Al₅O₁₂ and Er₃Al₅O₁₂ compositions underwent a liquid–liquid phase transition which resulted in glasses with a cloudy appearance due to spheroids of one glass in a matrix of a second glass. The two glasses were isocompositional within the limits of experimental error. Clear, brilliant, single-phase glasses were obtained from La₃Al₅O₁₂, ErLaYAl₅O₁₂, and compositions containing ≥5 mol% La₂O₃ substituted for the other rare-earth oxides. Formation of two glasses is attributed to nucleation and growth of the second liquid at a temperature below the equilibrium liquid–liquid transition temperature. Addition of lanthanum depresses the phase transition temperature below the glass transition temperature and the liquid–liquid phase transition is not observed. The results are discussed in the context of first-order liquid–liquid phase transitions (polyamorphism) and formation of single-phase glass from liquids that contain a high proportion of 4-coordinate aluminum ions.     

Formation and Properties of Calcium Aluminosilicate Glasses

The glass-forming region for calcium aluminosilicate glasses has been determined. A number of properties of these glasses (thermal expansion coefficient, glass transformation and dilatometric softening temperature, and refractive index) have been studied. The results of these measurements suggeq that the structures of these glasses may not as closely resemble those of alkali aluminosilicate glasses as is commonly assumed. Evidence is presented which suggests that the binary calcium aluminate glasses may be phase separated.     

Elastic Properties of Alkali Phosphomolybdate Glasses

Ultrasonic velocities at 10 MHz have been measured in two series of lithium, sodium, and potassium phosphomolybdate glasses with two fixed P₂O₅ concentrations. Elastic moduli, Poisson's ratio, and Debye temperature have been calculated. The composition dependence of most of the properties of lithium glasses exhibits a trend opposite to that of potassium glasses. Properties of sodium glasses lie between the other two alkali systems. Alkali oxide modification is suggested to be accompanied by ring reformation in lithium and sodium glasses. Ring size effects have been shown to account for all of the composition dependence.