Photosensitive Mechanism of Dopant-Free, Ultraviolet-Sensitive Calcium Aluminate Glasses

Calcium aluminate glasses show high sensitivity to ultraviolet radiation without the doping of optically active components. A mechanism is proposed to account for their photosensitivity on the basis of the result that the cause of UV-induced coloring is the emergence of two kinds of paramagnetic centers, an aluminum-oxygen hole center (Al-OHC) and an ozonide (O^-₃). In this model, a peroxy linkage connecting tetrahedrally coordinated Al³⁺s and a physically dissolved O₂ molecule are assumed to be present in the glasses as structural defects. On exposure to UV rays, the peroxy linkage homolvtically dissociates into a pair of A1-OHC's by absorbing UV quanta and one of the two resulting A1-OHC's combines with a nearby O₂ to form an ozonide. Experimental evidences substantiating the mechanism are also reported.     

Properties and Structure of Glasses in the System Ge-S

Distinct glass-forming composition regions were found in the system Ge-S (1) from GeS₂ to GeS₉ and (2) from GeS_1.21 a to GeS_1.5 The properties of these glasses, e.g. ir absorption spectra, thermal expansion, extraction of S₈ molecules with CS₂, Vickers hardness, density, and optical absorption, led to the conclusion that the structures of glasses in the two regions differ. In region (1), the structure is based on a three-dimensional inorganic polymer of polymeric S chains cross-linked with Ge; in region (2), it involves GeS₂ (GeS₄ tetrahedra) and GeS (GeS₆ octahedra) components that can be regarded as network formers and modifiers, respectively.     

Preparation and Properties of Heavy-Metal Fluoride Glasses Containing Ytterbium or Lutetium

Beginning with a 19BaF₂−27ZnF₂−27YbF₃−27ThF₄ (mol%) base glass, compositional modifications were made to improve optical properties and glass-forming ability. Replacement of YbF₃ by LuF₃ removed a strong near-ir electronic absorption band, and small additions of LiF and NaF improved glass quality. The multicomponent BaF₂/ThF₄ glasses had higher refractive indices and lower expansion coefficients than fluorozirconate and fluorohafnate glasses. In the 6 to 10 μm region, these materials exhibit absorption coefficients an order of magnitude lower than those reported for other heavy-metal fluoride glasses.     

Preparation of CdS-doped Glasses from Gels Containing Diethyldithiocarbamatocadmium

CdS-doped SiO₂ glasses were prepared via silica gels containing diethyldithiocarbamatocadmium Cd(S₂CN(C₂H₅)₂)₂. Heat treatment of the gels gave transparent yellow SiO₂glasses doped with hexagonal CdS crystals. In optical absorption and fluorescence spectra, the optical absorption edge and the emission peak clearly exhibited a blue shift, which was attributed to the quantum size effect of the carrier confinement, as the CdS content was decreased. In the fluorescence spectra of the CdS-doped silica glasses, the emission peak was observed only near 500 nm and not observed at longer wavelengths which were known to be present if there were sulfur vacancies.     

Thermochromism in Reduced Phosphate Glasses

Coloring and bleaching of reduced phosphate glasses in the systems K₂O-B₂O_r Al₂O₃-P₂O₅ and K₂O-Al₂O₃-P₂O₅, containing no silver halide, were studied. The as-cast glasses, which are colorless and transparent, become tinged with red when they are reheated at high temperatures for long times. The bleached specimens (PTC-RP glass) are obtained by heating at >600°C, then quenching. The PTC-RP glasses exhibit coloring phenomena by irradiation of light or by heating above 200°C; the colored glasses are again bleached thermally. Coloring of the glasses by heating is described in this paper in terms of phase change within the colloidal phosphorus formed in the glasses. The apparent activation energy for the thermocoloring is estimated to be ∼15×10⁴ J/mol (35 kcal/mol).     

Preparation of Cerium-Activated Silica Glasses: Phosphorus and Aluminum Codoping Effects on Absorption and Fluorescence Properties

Cerium-activated silica (SiO₂) glasses were prepared by plasma torch chemical vapor deposition (CVD). In Ce-doped SiO₂ glasses, most Ce exists as Ce⁴⁺ ions; the remaining small amount of Ce³⁺ ions exhibits a broad fluorescence spectrum with a large Stokes shift, ∼9600 cm^-1, from the excitation spectrum peak of 324 nm. Aluminum and phosphorus codoping considerably increases the Ce³⁺ ratio and shifts the peaks of both spectra to shorter wavelengths. P codoping is the more effective way to achieve this result and in some cases produces an absorption spectrum similar to that of a Ce-doped phosphate glass. These findings are consistent with the solvatiorn shell model for codoping, as previously proposed. To codope P, a soot remelting method was devised to deal with the highly volatile P₂O₅.     

Influence of As2O3 on the Optical Properties of Ultrapure Multicomponent Silicate Glasses and Optical Fibers

To obtain low transmission loss optical fibers from ultrapure multicomponent silicate glasses, it is necessary to add small quantities of As₂O₃ (or Sb₂O₃). In optical fibers prepared from glasses without these agents, a significant increase in loss is observed. To investigate this effect, the influence of As₂O₃ (added to the batch and present in the glass as As₂O₅) on the optical properties of ultrapure silicate glasses was studied. These properties are the Rayleigh scattering loss coefficient, transition metal absorption, and position of the uv absorption edge. This study showed that the increase in loss of As₂O₃-free glass cannot be assigned to any of these contributions and was attributed to absorption by electrons, trapped in relatively shallow traps in the glass network. The As⁵⁺ ions serve as deep traps and therefore remove the additional absorption. The same phenomenon, although much more pronounced, was observed in optical fibers prepared from alkali borosilicate glasses.     

Ultraviolet Absorption of Pentavalent Vanadium in Binary Alkali Borate Classes

The ultraviolet absorption of vanadium(V) in R₂O-B₂O₃ glasses (R represents Li, Na, or K) and in aqueous buffer solutions was investigated. In glasses of variable R₂O:B₂O₃ ratio, a change in the absorption spectra similar to the [VO₄]³- → [VO₃(OH)]^2- change in aqueous solution was observed. It is suggested that vanadium(V) in these glasses may be present as either [VO₄]^3- or [VO₃O_1/2]^2- (O_1/2 indicates a bridging oxygen ion), depending on the basicity of the melt. The critical R₂O concentration, above which this change in vanadium(V) environment occurs with increasing alkalinity, is 24, 26, and ≅30 mol%, for K₂O, Na₂O, and Li₂O, respectively.     

Effects of Doping Trivalent Ions in Bismuth Borate Glasses

Bismuth borate glasses from the system: 40Bi₂O₃–59B₂O₃–1Tv₂O₃ (where Tv=Al, Y, Nd, Sm, and Eu) and three glasses of composition: 40Bi₂O₃–60B₂O₃, 37.5Bi₂O₃–62.5B₂O₃ and 38Bi₂O₃–60B₂O₃–2Al₂O₃ were prepared by melt quenching and characterized by density, UV-visible absorption spectroscopy and differential thermal analysis (DTA) studies. Bismuth borate glasses exhibit a very strong optical absorption band just below their absorption edge. Glasses were devitrified by heat treatment at temperatures above their glass transition temperatures and the crystalline phases produced in them were characterized by Fourier transform infrared (FTIR) absorption spectroscopy and X-ray diffraction (XRD). Bi₃B₅O₁₂ was found to be the most abundant phase in all devitrified samples. DTA studies on glasses and FTIR and XRD analysis on crystallized samples revealed that very small amounts of trivalent ion doping causes significant changes in the devitrification properties of bismuth borate glasses; rare-earth ions promote the formation of metastable BiBO₃–I and BiBO₃–II phases during glass crystallization.     

Determination of OH Extinction Coefficients in R2O-B2O3-SiO2 Glasses (R = Li, Na, K)

Infrared spectra of glasses of the system R₂O-B₂O₃-SiO₂ were investigated. The extinction coefficients of the hydroxyl absorption band ("free OH") were calculated by a method proposed for alkali borate glasses. The results confirmed the applicability of this method to homogeneous and phase-separated alkali borosilicate glasses. The variation of the hydroxyl absorption band position was interpreted according to the structural characteristics of the studied glasses.     

Preparation by a Sol-Gel Process of Borosilicate Glasses Containing Microcrystals of Tellurium and Zinc Telluride

Borosilicate glasses, 5B₂O₃· 95SiO₂ (mol%), containing TeO₂ and ZnO nominally equivalent to 10 wt% Te and ZnTe were prepared by a solgel method from Si(OC₂H₅)₄, B(OCH₃)₃, H₆TeO₆, and Zn(NO₃)₂. A study by electron spectroscopy for chemical analysis (ESCA) showed that glasses heated at high temperature (450°C) in air contained both Te⁶⁺ and Te⁴⁺ ions on the surface layer, but that mainly Te⁴⁺ ions occurred inside the bulk glass. When solgel-derived borosilicate glasses containing the TeO₂ compound were reduced at elevated temperature in a hydrogen atmosphere, Te crystallites ranging in size from 4 to 15 nm were produced at a lower temperature, between 200° and 250°C. The absorption edge moved from the infrared to the visible wavelength region as the particle size decreased to about 4 nm. For glasses containing both TeO₂ and ZnO, ZnTe crystallites formed at high temperature—over 300°C—and existed along with the Te phase.     

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.     

Infrared Spectra and Atomic Arrangement in Fused Boron Oxide and Soda Borate Glasses

The infrared absorption spectra of fused B₂O₃ and of a series of soda borate glasses are presented. These spectra were obtained using vacuum-pressed briquettes of the powdered glass and powdered KBr. The spectrum of fused B₂O₃ shows quite definitely that this glass does not consist of a completely continuous triangularly coordinative network. It is shown that hydrogen bonds play an important part in the atomic arrangement of the glasses of zero or low soda content. The B₂O₃ glass apparently consists of complexes of an approximate unit (B₉O₁₄)- held together by hydrogen bonds. One in nine borons is tetrahedrally coordinated. The glasses of low soda content are similar. The spectra for soda concentrations greater than 15% did not permit the determination of the atomic arrangement with exactitude, but it is shown to be quite different from that found in glasses with 10% Na₂O or less.     

Structure and Properties of Silver Borate Glasses

Clear glasses form in the system Ag₂O-B₂O₃ up to about 35 mol% (65 wt%) Ag₂O. Infrared absorption, thermal expansion, and density data indicated an analogy to the Na₂O-B₂O₃ system. Pentaborate-triborate group pairs appear to be formed on addition of Ag₂O to B₂O₃ up to 20 mol% Ag₂O and diborate groups from 20 to 33 mol% Ag₂O. This interpretation is supported by the comparison of the infrared absorption spectra of quenched and crystallized glasses. One crystallization product, Ag₂O-4B₂O₃, was identified previously. A new compound starts to appear at 28 mol% Ag₂O. The theory that silver is generally present as a network modifier like sodium was substantiated by the comparison of the molar volume of sodium and silver borate glasses. Above 27 mol% Ag₂O some atomic silver is assumed to be present; below 15 mol%, exploratory studies indicate a two-phase structure within an immiscibility gap. A low-temperature internal friction peak in the glasses up to 28 mol% Ag₂O corresponds to the alkali peak in other glasses; a high temperature peak appearing in the 34 mol% Ag₂O glass is associated with the appearance of nonbridging oxygen in the system.     

Compositional Dependence of Absorption and Fluorescence of b3+ in Oxide Glasses

The integrated absorption cross section, the spontaneous emission probability, and the stimulated emission cross section of Yb³⁺ were determined in silicate, phosphate, borate, germanate, aluminate, gallate, and ZBLAN host glasses. The compositional dependence of the stimulated emission cross section of the ²F_5/2→²F_7/2 transition is determined mainly by the integrated absorption cross section in the glasses. A peak stimulated emission cross section above 1 pm², which is the highest value in glasses, was obtained in a gallate glass with a composition of 40K₂O·20Ta₂O₅. 40Ga₂O₃. The factors affecting the integrated absorption cross section are discussed using the Judd-Ofelt parameters of Er³⁺ calculated in previous studies.     

Gamma Irradiation Studies of Some Borate Glasses

The gamma-ray-induced optical absorption in a series of cabal (calcium-boron-aluminum) glasses was studied and is interpreted, wherever possible, in terms of structural concepts. A resolution of the observed absorption spectra showed that three Gaussian-shaped bands were induced with their maxima at about 2.3, 3.5, and 5.0 e.v. (550, 350, and 250 m_μ). The 2.3-e.v. band decreased in intensity with increasing CaO content, reaching a minimum intensity at a composition corresponding to the four-coordination of about 20% of the boron. Further increase in CaO content was associated with an increase in the intensity of this band. The intensity of the 3.5-e.v. band decreased gradually with increased mole per cent of CaO and increased with increased Al₂O₃. The 5.0-e.v. band showed an abrupt increase in intensity which corresponded to the appearance of non-bridging oxygens in the network. Replacing Ca²⁺ by Mg²⁺, Sr²⁺, or Ba²⁺ or replacing Li⁺ by Na⁺ or K⁺ showed that glasses containing large ions of low field strength give less induced absorption than glasses containing small ions of high field strength. A potassium alumina borate glass melted under reducing conditions gave a considerably higher ultraviolet transmission, before irradiation, as compared with the same glass melted under normal conditions. The gamma-induced absorption of these two glasses showed that reducing conditions resulted in a decrease in the intensity of the 2.3- and 3.5-e.v. bands, whereas it caused an increase in the far-ultraviolet-induced absorption. The effect of additions of arsenic, thallium, titanium, germanium, and some rare-earth oxides is discussed.     

Relation of Dissolved Nitrogen to Phototropy of Reduced Silicate Glasses

Soda-silica glasses melted under strong reducing conditions (graphite crucible) contain the precursor of a 570-nm color center. Glasses thus prepared under an N₂ atmosphere are readily colored by exposure to ultraviolet light; the uv-generated color fades rapidly at room temperature, giving phototropic response. However, with glasses melted under N₂-free atmospheres (for example, Ar), this phototropic response is greatly attenuated or absent. The precursor of the 570-nm center evidently results from strong reduction of the glass independent of the covering atmosphere, since X irradiation generates the same characteristic optical absorption in glasses melted under both N₂ and Ar. For compositions melted under N₂, the amount of N dissolved correlates positively with increasing SiO₂ content and phototropic response. The dissolution of N markedly affects the uv absorption of otherwise "clean" glass. An N-free reduced soda-silica glass exhibits essentially the same uv absorption as a similar oxidized glass. However, as N dissolves in the glass, the uv cutoff moves to longer wavelengths. The phototropic response of reduced glasses under long-wavelength uv light is greatly enhanced by incorporation of europium. Again, an N₂ atmosphere during melting yields improved phototropic response. Dissolved N lowers the dissolved H₂O content and increases the concentration of Eu in the lower valence state (Eu²⁺).     

Synthesis and Optical Properties of Rare-Earth–Aluminum Oxide Glasses

Single-phase glasses containing 37.5 mol% Y₂O₃, 7 mol% La₂O₃, and 1 mol% Pr, Ho, Nd, Er, Sm, Tm, Eu, or Yb oxide substituted for part of the Y₂O₃ were synthesized by containerless melting. The spectral transmission and absorption cross sections of the glasses were determined at wavelengths from 360 to 3300 nm. The electronic transitions were broadened compared with results obtained in a crystalline yttrium aluminum garnet (YAG) host. The infrared transmission of the host glass extended to 6000 nm. The optical and physicochemical properties of these glasses are well suited for optical device applications.     

DTA and X-Ray Analysis Study of Nucleation and Crystallization of MgO-Al2O3-SiO2 Glasses Containing ZrO2, TiO2, and CeO2

Crystallization sequences of glasses with compositions in the tridymite primary phase field of the MgO-Al₂O₃-SiO₂ system were studied by DTA, X-ray diffraction, and other techniques. Crystallization was catalyzed by the addition of 7 wt% of either ZrO₂ or TiO₂. Up to 10 wt% CeO₂ was also added to some glasses. Metastable solid solutions with the high-quartz structure exhibiting varying lattice parameters commonly occurred at low temperatures, transforming into a high cordierite at higher temperatures. Depending on the composition and heat treatment, other phases also appeared, e.g. Ce₂Ti₂O₄ (Si₂O₇). The rate of crystallization was markedly dependent on the catalyst. Colloidal precipitation of the catalyst accompanied by bulk crystallization of the glass was observed with ZrO₂, but no crystalline TiO₂ was detected. In the presence of CeO₂, TiO₂ was a more effective catalyst than ZrO₂. Although CeO₂ lowered the melting temperatures of the glass-ceramics, it increased the stability of the glasses and inhibited volume nucleation, causing coarse structures to form on crystallization.