Pb/Al codoped germano-silicate optical fiber with high non-resonant third-order nonlinearity

A germano-silicate optical fiber codoped with Pb²⁺ and Al³⁺ was developed by modified chemical vapor deposition and solution doping techniques. The non-resonant third-order optical nonlinearity was measured to be 6.9105 × 10⁻²⁰ m²/W by using the continuous-wave self-phase modulation method. The enhanced non-resonant nonlinearity was ascribed to the increasing number of non-bridging oxygens due to the incorporation of the glass modifiers Pb²⁺ and Al³⁺, the large molar refraction from heavy metal ions Pb²⁺, and the enhanced hyper-polarization from PbO doped into the core of the made fiber.     

Viscosity and glass transition temperature of hydrous float glass

Viscosity of water-bearing float glass (0.03-4.87 wt% H₂O) was measured in the temperature range of 573-1523 K and pressure range of 50-500 MPa using a parallel plate viscometer in the high viscosity range and the falling sphere method in the low viscosity range. Melt viscosity depends strongly on temperature and water content, but pressure up to 500 MPa has only minor influence. Consistent with previous studies on aluminosilicate compositions we found that the effect of dissolved water is most pronounced at low water content, but it is still noticeable at high water content. A new model for the calculation of the viscosities as a function of temperature and water content is proposed which describes the experimental data with a standard deviation of 0.22 log units. The depression of the glass transition temperature T_g by dissolved water agrees reasonably well with the prediction by the model of Deubener [J. Deubener, R. Müller, H. Behrens, G. Heide, J. Non-Cryst. Solids 330 (2003) 268]. Using water speciation measured by near-infrared spectroscopy we infer that although the effect of OH groups in reducing T_g is larger than that of H₂O molecules, the difference in the contribution of both species is smaller than predicted by Deubener et al. (2003). Compared to alkalis and alkaline earth elements the effect of protons on glass fragility is small, mainly because of the relatively low concentration of OH groups (max. 1.5 wt% water dissolved as OH) in the glasses.     

Incorporation of silver into soda-lime silicate glass by a classical staining process

Silver was introduced into soda-lime silicate glass by a classical staining process under varying conditions of temperature and time. The spectroscopic features of the stained glasses were investigated by studying absorption, photoluminescence and electron paramagnetic resonance properties. The diffusion parameters (diffusion coefficient and diffusion activation energy) of silver ions were calculated based on elemental analysis data from inductively coupled plasma (ICP) spectrometry, and line scan profiles from energy dispersion X-ray analysis (EDX).     

Coordination and optical attenuation of TiO2-SiO2 glass by electron energy loss spectroscopy

Electron energy loss spectroscopy (EELS) techniques have been applied to investigate both the coordination and optical attenuation of TiO₂-SiO₂ glass. The coordination was determined from the electron energy loss near edge fine structure (ELNES) of Ti L_2,3-edges, and the results show that Ti ions substitute for Si ions in the tetrahedral coordinated sites. The optical attenuation of the glass was obtained from low energy loss of EELS data through Kramers-Kronig analysis, and the results show that Ti-doped silica has an absorption edge near 4.0 eV.     

Crystal/glass phase change in K1−xRbxSb5S8 (x = 0.25, 0.50, 0.75) studied through thermal analysis techniques

K_1−xRb_xSb₅S₈ (x = 0.25, 0.5, 0.75) is a well-defined single-phase system that undergoes a reversible phase-change. We determined the activation energy of glass transition and crystallization, respectively, for the three compositions using the Kissinger and Ozawa-Flynn-Wall equations. The results have shown that for K_0.25Rb_0.75Sb₅S₈ the crystallization mechanism could be interpreted in terms of a single-step reaction. For the other two compositions the glass-to-crystal transformation is a process of increasing mechanistic complexity with time and it involves simultaneously several different nucleation and growth events. The slope of the lines in the Avrami plots was observed to be independent of heating rate for K_0.25Rb_0.75Sb₅S₈ and the mean value of the activation energy was found to be 262 ± 6 kJ/mol. For the other two compositions, the slope varies with the heating rate. In the K_0.25Rb_0.75Sb₅S₈ glasses, bulk nucleation with three-dimensional crystal growth appears to dominate the phase-change process.     

A study of nonlinear optical properties in Bi2O3-WO3-TeO2 glasses

A series of bismuth tungsten tellurite glasses were prepared and their densities, linear refractive indices and transmission spectra were measured. The optical bandgaps E_opt and Urbach energies E_e of glasses were obtained from ultraviolet absorption edges. Both the optical gap (E_opt) and the band tail (E_e) are behaving oppositely. As the value of E_opt decreases with increasing WO₃ content, the degree of disorder increases which causes more defects or localized states resulting in deep localized in the bandgap with the tailing increased. Z-scan technique was carried out to investigate the third-order nonlinear optical properties of Bi₂O₃-WO₃-TeO₂ glasses. The third-order optical nonlinearity increases with decreasing the optical bandgap E_opt, since a increase of WO₃ content can provide the non-bridging oxygen ion content.     

Theory of fluidity of liquids, glass transition, and melting

This is a presentation of a rigorous theory of fluidity of liquids, glass transition and melting of solids in the frame of an asymmetric double well potential model. Potential wells are doubled time to time by the local density fluctuations caused by the thermal longitudinal waves. The average frequency of doubling of potential wells is equal to the frequency of the most energetic waves which obey a law similar to Wein’s displacement law in black body radiation. Based on the equilibrium thermodynamic theory of fluctuations and the displacement law, a law of linear pre-diffusion mean-square displacement of particles in a solid is derived: the mean-square displacement of molecules within their potential wells increases linearly with temperature. It is shown that when this is broken-down (where the mean-square displacement at a certain temperature rapidly changes its slope as a function of temperature) glass devitrifies and crystal melts, and all possible solid-liquid transitions of a substance occur at the same critical mean-square displacement: any solid (not only crystals) transforms into liquid when the mean-square displacement, as a fraction of the average intermolecular distance, acquires a certain universal critical value - the same for different substances. It is proved that molecules in a liquid perform specific Brownian motion. The average jump distance is a function of temperature and it is much smaller than the nearest intermolecular distances. At a certain temperature, shown to be the Kauzmann temperature, the average jump distance of Brownian motion becomes equal to zero: the super-cooled liquid undergoes glass transition. The transition was proven to be a phase transition of the fourth order: the free energy of the system and its first, second and third derivatives are all continuous functions, but its fourth derivative with respect to temperature is discontinuous. Molecular mobility, diffusion and viscosity are obtained as functions of temperature.     

Structure and lattice dynamics of binary lead silicate glasses investigated by infrared spectroscopy

The polar lattices dynamics of seven binary lead silicate glasses have been studied by infrared spectroscopy. The analysis of the reflectivity spectra with a dielectric function model, based on a modified Gaussian profile, allows a quantitative evaluation of the presence of lead cations within different structural sites. From the role of the lead cations versus the degree of polymerization of the silicate network and the comparison with literature results, we may to give a scenario for explaining the observed structural evolution of the glass matrix and more particularly the drastic change occurring around 45% of lead content. Below this threshold, lead cations act only as modifiers of the silicate network. Above, the glass structure is deeply modified; a lead network involving around 10% of the lead content appears in glasses whose composition is just above the threshold and progressively grows at the expense of the silicate network with the increase of lead content. For high lead content, lead cations can act as modifiers of the silicate network or as network formers. Results also show that the analysis of far infrared measurements combined with the knowledge of the UV edge optical response is very promising to characterize the local disorder around cations in glasses.     

Sulfur behavior in silicate glasses and melts: Implications for sulfate incorporation in nuclear waste glasses as a function of alkali cation and V2O5 content

The presence of sulfur in radioactive waste to be incorporated in borosilicate glasses entails difficulties mainly due to the relatively low solubility of sulfates in the vitreous phase. In this work a study is presented on the effects of the ratio R = [Na₂O]/[B₂O₃], the type of sulfate added and the addition of V₂O₅ on the incorporation of sulfates in borosilicate glasses. Glass samples were prepared at the laboratory scale (up to 50-100 g) by melting oxide and sulfate powders under air in Pt/Au crucibles. XRF and ICP/AES chemical analysis, SEM/EDS, microprobe WDS and Raman spectroscopy were employed to characterize the fabricated samples. The main experimental results confirm that the incorporation of sulfates in borosilicate glasses is favored by the network depolymerization, which evolves with the ratio R. The addition of V₂O₅ seems to accelerate the kinetics of sulfur incorporation in the glass and, probably, increase the sulfate solubility by modifying the borate network and fostering the formation of voids of shape and size compatible with the sulfur coordination polyhedron in the glassy network. The kinetics of X₂SO₄ incorporation in the glass seems to be slower when X = Cs.     

Energy transfer between Tm and Er ions in a TeO2-based glass pumped at diode laser wavelength

In this paper we investigate the energy transfer processes in Tm³⁺/Er³⁺ doped telluride glass pumped at the commercial diode laser pump wavelength ∼800 nm. Tailoring the rare-earths content in the glass matrix, seven main energy transfer channels within the doping range considered were identified. A 6-fold enhancement of the Er³⁺ visible frequency upconversion fluorescence at ∼660 nm is observed due to the inclusion of Tm³⁺ ions. This is evidence of the relevant contribution of the route Er₁(⁴I_11/2) + Er₂(⁴I_13/2) → Er₁(⁴I_15/2) + Er₂(⁴F_9/2) to the process. Energy migration among pumped ⁴I_9/2 level reducing the efficiency of the upconversion emission rate (³H_11/2, ⁴S_3/2, and ⁴F_9/2) is observed for Er³⁺ above 1.5 wt%. The rate equations regarding the observed energy transfer routes are determined and a qualitative analysis of the observed processes is reported.     

Improvement of the Tm:H4 level lifetime in silica optical fibers by lowering the local phonon energy

The role of some glass network modifiers on the quantum efficiency of the near-infrared fluorescence from the ³H₄ level of Tm³⁺ ion in silica-based doped fibers is studied. Modifications of the core composition affect the spectroscopic properties of Tm³⁺ ion. Adding 17.4 mol% of AlO_3/2 to the core glass caused an increase of the ³H₄ level lifetime up to 50 μs, 3.6 times higher than in pure silica glass. The quantum efficiency was increased from 2% to approximately 8%. On the opposite, 8 mol% of PO_5/2 in the core glass made the lifetime decrease down to 9 μs. These changes of Tm³⁺ optical properties are assigned to the change of the local phonon energy to which they are submitted by modifiers located in the vicinity of the doping sites. Some qualitative predictions of the maximum achievable quantum efficiency are possible using a simple microscopic model to calculate the non-radiative de-excitation rates.     

Effect of BaO content on the sintering and physical properties of BaO-B2O3-SiO2 glasses

A BaO-B₂O₃-SiO₂ glass system was chosen as a candidate composition for the application to Pb-free low temperature sinterable glass. The effect of BaO content on the crystallization, sintering behavior, and properties of the glasses was examined. Both the glass transition temperature and crystallization temperature decreased as the BaO content increased. Crystallization easily occurred during sintering with a BaO content of more than 50 mol%, which effectively inhibited the over-firing phenomenon. The dielectric characteristics and thermal expansion coefficient of the glasses were examined and the results were explained on the basis of the crystallization and densification of the specimens.     

Texture and surface analysis of thin-film GaAs on glass formed by pulsed-laser deposition

Thin-film GaAs on glass was formed by ablating n-type GaAs with nano-second pulses at 532 nm. The deposition was done in the most straightforward way without heating the substrate. The texture of films has been investigated with X-ray measurements, spatially resolved micro-Raman spectroscopy, and atomic force microscopy. The results reveal that the film texture is of multi-phase nature consisting of randomly oriented GaAs microcrystallites, amorphous parts, and (1 1 1) zincblende migrations in the nano-regime.     

Chemical durability of lead silicate glass in HNO3, HCl and H2SO4 aqueous acid solutions

Acid dissolution of silicate glasses with different lead contents was rigorously investigated. Aqueous solutions containing 0.5, 1, and 2 N HNO₃, HCl and H₂SO₄ were used to measure the durability of the glass probes. Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), Inductively Coupled Plasma (ICP), X-ray Diffraction (XRD) and weight loss analyses were used to evaluate the morphological/compositional changes of the probes, the ash deposit, and the aqueous solutions produced due to the dissolution of the glass specimens. Empirical results showed that any increase in the lead content of the probes deteriorated the durability of the glasses by accelerating the hydrolysis of the silica network. ZrO₂ and TiO₂ additions had inverse effect and improved the chemical durability and the practical life-time of the lead glasses.     

Influence of zirconium on the structure of pristine and leached soda-lime borosilicate glasses: Towards a quantitative approach by O MQMAS NMR

¹⁷O MQMAS NMR was used to characterize the influence of zirconium on the structural organization of soda-lime borosilicate glasses. A new method of quantitative analysis of the ¹⁷O MQMAS spectra is presented, by a direct fit of the two-dimensional MQMAS spectrum which provides the resolution of all the structural groups in glasses containing up to five oxides. Additional data were also obtained from the quantitative deconvolution of the ¹¹B MAS NMR spectra, with the help of the direct fit of MQMAS data as well. Excess of non-bridging oxygen is clearly identified in these glasses. Sixfolded zirconium is preferentially compensated rather than the tetrahedral boron and calcium only partially compensate the tetrahedral boron. Alteration gels arising from glass leaching were probed by oxygen-17 supplied by the alteration solution. Most of the zirconium is inserted in the silicate network forming Si-O-Zr bonds with the same configuration in the glass and in the gel. During leaching, calcium clearly remains in the alteration gel, either near non-bridging oxygen or as a zirconium charge compensator. This quantitative approach applied to ¹⁷O MQMAS spectra demonstrates its potential for investigating the structure of increasingly complex glass and gel compositions.     

Annihilation of E′ center defects in silica glass by hydrogen treatment

It was found, using electron paramagnetic resonance (EPR), that the signal of E′ centers in silica glass totally disappeared following a 1 h heat-treatment at 1000 °C under hydrogen atmosphere. However, by subsequent heat-treatment at the same temperature under a dry nitrogen atmosphere, some of the E′ centers re-appeared.     

Laser-induced crystallization of β′-RE2(MoO4)3 ferroelectrics (RE: Sm, Gd, Dy) in glasses and their surface morphologies

The glasses with the compositions of 21.25RE₂O₃-63.75MoO₃-15B₂O₃ (RE: Sm, Gd, Dy) were prepared and the formation of β′-RE₂(MoO₄)₃ ferroelectrics was confirmed in the crystallized glasses obtained through a conventional crystallization in an electric furnace. The features of the glass structure and crystallization behavior were clarified from measurements of Raman scattering spectra. Continuous-wave Nd:YAG laser with a wavelength of 1064 nm (laser power: 0.6-0.9 W, laser scanning speed: S = 1-16 μm/s) was irradiated to 10.625Sm₂O₃-10.625Gd₂O₃ (or Dy₂O₃)-63.75MoO₃-15B₂O₃ glasses, and the structural modification was induced at the glass surface. At the scanning speed of S = 10 μm/s, crystal lines consisting of β′-Gd_2−xSm_x(MoO₄)₃ or β′-Dy_2−xSm_x(MoO₄)₃ crystals were patterned on the glass surface. It was found that those crystal lines have the surface morphology with periodic bumps. At S = 1 μm/s, it was found that crystal lines consist of the mixture of paraelectric α-Gd_2−xSm_x(MoO₄)₃ and ferroelectric β′-Gd_2−xSm_x(MoO₄)₃ crystals, indicating the phase transformation from the β′ phase to the α phase during laser irradiation. Homogeneous crystal lines with β′-RE₂(MoO₄)₃ ferroelectrics have not been written in this study, but further research is continuing.     

Fabrication and properties of novel low-melting glasses in the ternary system ZnO-Sb2O3-P2O5

Glasses in the ternary system ZnO-Sb₂O₃-P₂O₅ were investigated as potential alternatives to lead based glasses for low temperature applications. The glass-forming region of ZnO-Sb₂O₃-P₂O₅ system has been determined. Structure and properties of the glasses with the composition (60 − x)ZnO-xSb₂O₃-40P₂O₅ were characterized by infrared spectra (IR), differential thermal analysis (DTA) and X-ray diffraction (XRD). The results of IR indicated the role of Sb³⁺ as participant in glass network structure, which was supported by the monotonic and remarkable increase of density (ρ) and molar volume (V_M) with increasing Sb₂O₃ content. Glass transition temperature (T_g) and thermal stability decreased, and coefficient of thermal expansion (α) increased with the substitution of Sb₂O₃ for ZnO in the range of 0-50 mol%. XRD pattern of the heat treated glass containing 30 mol% Sb₂O₃ indicated that the structure of antimony-phosphate becomes dominant. The improved water durability of these glasses is consistent with the replacement of easily hydrated phosphate chains by corrosion resistant P-O-Sb bonds. The glasses containing ?30 mol% Sb₂O₃ possess lower T_g (<400 °C) and better water durability, which could be alternatives to lead based glasses for practical applications with further composition improvement.     

Effect of N2/CH4 flow ratio on microstructure and composition of hydrogenated carbon nitride films prepared by a dual DC-RF plasma system

Hydrogenated carbon nitride (a-CN:H) films were deposited on n-type (1 0 0) silicon substrates making use of direct current radio frequency plasma enhanced chemical vapor deposition (DC-RF-PECVD), using a gas mixture of CH₄ and N₂ as the source gas in range of N₂/CH₄ flow ratio from 1/3 to 3/1 (sccm). The deposition rate, composition and bonding structure of the a-CN:H films were characterized by means of X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectrometry (FTIR). The mechanical properties of the deposited films were evaluated using nano-indentation test. It was found that the parameter for the DC-RF-PECVD process had significant effects on the growth rate, structure and properties of the deposited films. The deposition rate of the films decreased clearly, while the N/C ratio in the films increased with increasing N₂/CH₄ flow ratio. CN radicals were remarkably formed in the deposited films at different N₂/CH₄ flow ratio, and their contents are related to the nitrogen concentrations in the deposited films. Moreover, the hardness and Young’s modulus of the a-CN:H films sharply increased at first with increasing N₂/CH₄ flow ratio, then dramatically decreased with further increase of the N₂/CH₄ flow ratio, and the a-CN:H film deposited at 1/1 had the maximum hardness and Young’s modulus. In addition, the structural transformation from sp³-like to sp²-like carbon-nitrogen network in the deposited films also was revealed.     

Stress-enhanced ion diffusion at the vicinity of a crack tip as evidenced by atomic force microscopy in silicate glasses

The slow advance of a crack in soda-silicate glasses was studied at nanometer scale by in-situ and real-time atomic force microscopy (AFM) in a well-controlled atmosphere. An enhanced diffusion of sodium ions in the stress-gradient field at the sub-micrometric vicinity of the crack tip was revealed through several effects: growth of nodules in AFM height images, changes in the AFM tip-sample energy dissipation. The nodules patterns revealed a dewetting phenomenon evidenced by ‘breath figures’. Complementary chemical micro-analyses were done. These experimental results were explained by a two-step process: (i) a fast migration (typical time: few milliseconds) of sodium ions towards the fracture surfaces as proposed by Langford et al. [J. Mat. Res. 6 (1991) 1358], (ii) a slow backwards diffusion of the cations as evidenced in these AFM experiments (typical time: few minutes). Measurements of the diffusion coefficient of that relaxing process were done at room temperature. Our results strengthen the theoretical concept of a near-surface structural relaxation due to the stress-gradient at the vicinity of the crack tip. The inhomogeneous migration of sodium ions might be a direct experimental evidence of the presence of sodium-rich channels in the silicate structure [A. Meyer et al., Phys. Rev. Let. 93 (2004) 027801].