Short-Range Structure, Thermal and Elastic Properties of Binary and Ternary Tellurite Glasses.

Glasses Al2/3O-TeO2, ZnO-TeO2 and R2/3O-ZnO-TeO2 (R = Al, B) were prepared by melting in Pt crucibles and studied for correlations between structure and thermal as well as mechanical properties, whereby the glass composition is varied to tailor the short-range speciation of tellurite, aluminate, and borate groups. The glass structure was studied by Raman and infrared spectroscopy analyses, and the measured properties include glass-transition temperature (Tg), density (ρ), and ultrasonic longitudinal (VL) and transverse (VT) velocities. In addition, atomic packing density (Cg), elastic moduli, and Poisson's ratio (σ) were evaluated from the measured properties. It was found that Al2/3O leads to cross-linked alumino-tellurite networks by strong Te-O-Al bonds, which cause a profound enhancement in Tg. The influence of ZnO and B2/3O on Tg is relatively smaller due to the weaker cross-linking effects of ZnO4 tetrahedra and of Te···O-B bonds. Short-range bonding characteristics, interatomic bonding energy differences, and atomic packing density were found to have a strong effect on VT and mostly on the VL sound velocity. The combined effects of structure and bonding are nicely expressed in the composition dependence of Poisson's ratio; it exhibits decreasing trends with Al2/3O content in the binary and ternary glasses studied here, but increasing trends with ZnO and B2/3O additions in glasses ZnO-TeO2 and B2/3O-ZnO-TeO2, respectively. The results for Poisson's ratio and atomic packing density for the studied glasses were found to fit nicely in the global σ versus Cg correlation established previously for a range of glasses not including tellurites so far. Finally, the sound velocities and Poisson's ratio of pure TeO2 glass were determined for the first time and found to differ markedly from those in the literature for TeO2 glass melted in alumina crucible; this is because the latter glass is highly doped by Al2O3 leached from the alumina crucible.

Fluoride-sulfophosphate glasses as hosts for broadband optical amplification through transition metal activators.

Unusually stable multi-anion glasses of the fluoride-sulfophosphate type (FPS) are introduced as a new host material for optically active cation species. Despite a notoriously low polymerization grade, anion mixing in this glass system enables facile manufacture of bulk or fiber devices which combine several advantages of fluoride and phosphate glasses while using the stabilizing effect of sulfate additions. Using the example of chromium doping, we demonstrate broad red photoluminescence at 734 nm and inhomogeneous broadening of the R-line at 694 nm, originating from the 4T2 → 4A2 and 2E → 4A2 transitions of Cr3+, respectively. The luminescence mechanism is further analyzed on the basis of the corresponding Tanabe-Sugano diagram. Tailored through chemical composition, internally nucleated precipitation of a nanocrystalline fluoride phase enables switching between high-field and low-field configurations of the Cr3+ ion, resulting in the specific emission properties and setting the path towards FPS-based optical devices.

Transition and post-transition metal ions in borate glasses: Borate ligand speciation, cluster formation, and their effect on glass transition and mechanical properties.

A series of transition and post-transition metal ion (Mn, Cu, Zn, Pb, Bi) binary borate glasses was studied with special consideration of the cations impact on the borate structure, the cations cross-linking capacity, and more generally, structure-property correlations. Infrared (IR) and Raman spectroscopies were used for the structural characterization. These complementary techniques are sensitive to the short-range order as in the differentiation of tetrahedral and trigonal borate units or regarding the number of non-bridging oxygen ions per unit. Moreover, vibrational spectroscopy is also sensitive to the intermediate-range order and to the presence of superstructural units, such as rings and chains, or the combination of rings. In order to clarify band assignments for the various borate entities, examples are given from pure vitreous B2O3 to meta-, pyro-, ortho-, and even overmodified borate glass compositions. For binary metaborate glasses, the impact of the modifier cation on the borate speciation is shown. High field strength cations such as Zn2+ enhance the disproportionation of metaborate to polyborate and pyroborate units. Pb2+ and Bi3+ induce cluster formation, resulting in PbOn- and BiOn-pseudophases. Both lead and bismuth borate glasses show also a tendency to stabilize very large superstructural units in the form of diborate polyanions. Far-IR spectra reflect on the bonding states of modifier cations in glasses. The frequency of the measured cation-site vibration band was used to obtain the average force constant for the metal-oxygen bonding, FM-O. A linear correlation between glass transition temperature (Tg) and FM-O was shown for the metaborate glass series. The mechanical properties of the glasses also correlate with the force constant FM-O, though for cations of similar force constant the fraction of tetrahedral borate units (N4) strongly affects the thermal and mechanical properties. For paramagnetic Cu- and Mn-borate glasses, N4 was determined from the IR spectra after deducing the relative absorption coefficient of boron tetrahedral versus boron trigonal units, α = α4/α3, using NMR literature data of the diamagnetic glasses.

Medium-range topological constraints in binary phosphate glasses.

The theory of temperature-dependent topological constraints has been used to successfully explain the compositional dependence of glass properties for oxide and non-oxide compositions. However, even though the predictions are qualitatively accurate, not all quantitative predictions are as precise. Here, we report on the applications of this theoretical framework to available data for binary phosphate and silver metaphosphate--silver halide glasses. We find that some compositions are overconstrained and some are underconstrained relative to the predicted values. We suggest that the origin of this difference is due to the presence of medium-range constraints such as sterical hindrance which is dependent on packing density and chain length.

Mid-infrared supercontinuum generation in As2S3-silica "nano-spike" step-index waveguide.

Efficient generation of a broad-band mid-infrared supercontinuum spectrum is reported in an arsenic trisulphide waveguide embedded in silica. A chalcogenide "nano-spike", designed to transform the incident light adiabatically into the fundamental mode of a 2-mm-long uniform section 1 µm in diameter, is used to achieve high launch efficiencies. The nano-spike is fully encapsulated in a fused silica cladding, protecting it from the environment. Nano-spikes provide a convenient means of launching light into sub-wavelength scale waveguides. Ultrashort (65 fs, repetition rate 100 MHz) pulses at wavelength 2 µm, delivered from a Tm-doped fiber laser, are launched with an efficiency ~12% into the sub-wavelength chalcogenide waveguide. Soliton fission and dispersive wave generation along the uniform section result in spectral broadening out to almost 4 µm for launched energies of only 18 pJ. The spectrum generated will have immediate uses in metrology and infrared spectroscopy.

Affinity and its derivatives in the glass transition process.

The thermodynamic treatment of the glass transition remains an issue of intense debate. When associated with the formalism of non-equilibrium thermodynamics, the lattice-hole theory of liquids can provide new insight in this direction, as has been shown by Schmelzer and Gutzow [J. Chem. Phys. 125, 184511 (2006)], by Möller et al. [J. Chem. Phys. 125, 094505 (2006)], and more recently by Tropin et al. [J. Non-Cryst. Solids 357, 1291 (2011); ibid. 357, 1303 (2011)]. Here, we employ a similar approach. We include pressure as an additional variable, in order to account for the freezing-in of structural degrees of freedom upon pressure increase. Second, we demonstrate that important terms concerning first order derivatives of the affinity-driving-force with respect to temperature and pressure have been previously neglected. We show that these are of crucial importance in the approach. Macroscopic non-equilibrium thermodynamics is used to enlighten these contributions in the derivation of C(p),κ(T), and α(p). The coefficients are calculated as a function of pressure and temperature following different theoretical protocols, revealing classical aspects of vitrification and structural recovery processes. Finally, we demonstrate that a simple minimalist model such as the lattice-hole theory of liquids, when being associated with rigorous use of macroscopic non-equilibrium thermodynamics, is able to account for the primary features of the glass transition phenomenology. Notwithstanding its simplicity and its limits, this approach can be used as a very pedagogical tool to provide a physical understanding on the underlying thermodynamics which governs the glass transition process.

Supercontinuum generation in chalcogenide-silica step-index fibers.

We explore the use of a highly nonlinear chalcogenide-silica waveguide for supercontinuum generation in the near infrared. The structure was fabricated by a pressure-assisted melt-filling of a silica capillary fiber (1.6 µm bore diameter) with Ga4Ge21Sb10S65 glass. It was designed to have zero group velocity dispersion (for HE11 core mode) at 1550 nm. Pumping a 1 cm length with 60 fs pulses from an erbium-doped fiber laser results in the generation of octave-spanning supercontinuum light for pulse energies of only 60 pJ. Good agreement is obtained between the experimental results and theoretical predictions based on numerical solutions of the generalized nonlinear Schrödinger equation. The pressure-assisted melt-filling approach makes it possible to realize highly nonlinear devices with unusual combinations of materials. For example, we show numerically that a 1 cm long As2S3:silica step-index fiber with a core diameter of 1 µm, pumped by 60 fs pulses at 1550 nm, would generate a broadband supercontinuum out to 4 µm.

Structural heterogeneity and pressure-relaxation in compressed borosilicate glasses by in situ small angle X-ray scattering.

We report on Brillouin and in situ small angle X-ray scattering (SAXS) analyses of topological heterogeneity in compressed sodium borosilicate glasses. SAXS intensity extrapolated to very low angular regimes, I(q = 0), is related to compressibility. From Brillouin scattering and analyses of the elastic properties of the glass, the Landau-Placzek ratio is determined and taken as a direct reflection of the amplitude of frozen-in density fluctuations. It is demonstrated that with increasing fictive pressure, topological (mid- and long-range) homogeneity of the glass increases significantly. Heating and cooling as well as isothermal scans were performed to follow the evolution of density fluctuations upon pressure recovery. For a sample with a fictive pressure p(f) of 470 MPa, complete recovery to p(f) = 0.1 MPa was observed to occur close to the glass transition temperature. The values of fictive and apparent fictive temperature, respectively, as obtained via the intersection method from plots of I(q = 0) vs. temperature were found in good agreement with previous calorimetric analyses. Isothermal scans suggest that mid- and long-range recovery govern macroscopic density relaxation.

Non-Debye normalization of the glass vibrational density of states in mildly densified silicate glasses.

The evolution of the boson peak with densification at medium densification rates (up to 2.3%) in silicate glasses was followed through heat capacity measurements and low frequency Raman scattering. It is shown that the decrease of the boson peak induced by densification does not conform to that expected from a continuous medium; rather it follows a two step behaviour. The comparison of the heat capacity data with the Raman data shows that the light-vibration coupling coefficient is almost unaffected in this densification regime. These results are discussed in relation to the inhomogeneity of the glass elastic network at the nanometre scale.