Microgravity effects on nonequilibrium melt processing of neodymium titanate: thermophysical properties, atomic structure, glass formation and crystallization.

The relationships between materials processing and structure can vary between terrestrial and reduced gravity environments. As one case study, we compare the nonequilibrium melt processing of a rare-earth titanate, nominally 83TiO2-17Nd2O3, and the structure of its glassy and crystalline products. Density and thermal expansion for the liquid, supercooled liquid, and glass are measured over 300-1850 °C using the Electrostatic Levitation Furnace (ELF) in microgravity, and two replicate density measurements were reproducible to within 0.4%. Cooling rates in ELF are 40-110 °C s-1 lower than those in a terrestrial aerodynamic levitator due to the absence of forced convection. X-ray/neutron total scattering and Raman spectroscopy indicate that glasses processed on Earth and in microgravity exhibit similar atomic structures, with only subtle differences that are consistent with compositional variations of ~2 mol. % Nd2O3. The glass atomic network contains a mixture of corner- and edge-sharing Ti-O polyhedra, and the fraction of edge-sharing arrangements decreases with increasing Nd2O3 content. X-ray tomography and electron microscopy of crystalline products reveal substantial differences in microstructure, grain size, and crystalline phases, which arise from differences in the melt processes.

Laser cooling ytterbium doped silica by 67 K from ambient temperature.

Laser cooling of a 5 cm long, 1 mm diameter ytterbium doped (6.56×1025 ions/m3) silica rod by 67 K from room temperature was achieved. For the pump source, a 100 W level ytterbium fiber amplifier was constructed along with a 1032 nm fiber Bragg grating seed laser. Experiments were done in vacuum and monitored with the non-contact differential luminescence thermometry method. Direct measurements of the absorption spectrum as a function of temperature were made, to avoid any possible ambiguities from site-selectivity and deviations from McCumber theory at low temperature. This allowed direct computation of the cooling efficiency versus temperature at the pump wavelength, permitting an estimated heat lift of 1.42 W/m as the sample cooled from ambient temperature to an absolute temperature of 229 K.

Impact of site-selective spectroscopy on laser cooling parameter characterization.

From laser design to optical refrigeration, experimentally measured fluorescence spectra are often utilized to obtain input parameters for predictive models. However, in materials that exhibit site-selectivity, the fluorescence spectra depend on the excitation wavelength employed to take the measurement. This work explores different conclusions that predictive models reach after inputting such varied spectra. Here, temperature-dependent site-selective spectroscopy is carried out on an ultra-pure Yb, Al co-doped silica rod fabricated by the modified chemical vapor deposition technique. The results are discussed in the context of characterizing ytterbium doped silica for optical refrigeration. Measurements made between 80 K and 280 K at several different excitation wavelengths yield unique values and temperature dependencies of the mean fluorescence wavelength. For the excitation wavelengths studied here, the variation in emission lineshapes ultimately lead to calculated minimum achievable temperatures (MAT) ranging between 151 K and 169 K, with theoretical optimal pumping wavelengths between 1030 nm and 1037 nm. Direct evaluation of the temperature dependence of the fluorescence spectra band area associated with radiative transitions out of the thermally populated 2F5/2 sublevel may be a better approach to identifying the MAT of a glass where site-selective behavior precludes unique conclusions.

Potential of ytterbium doped silica glass for solid-state optical refrigeration to below 200 K.

We report on the optical refrigeration of ytterbium doped silica glass by >40 K starting at room temperature, which represents more than a two-fold improvement over the previous state-of-the-art. A spectroscopic investigation of the steady-state and time-dependent fluorescence was carried out over the temperature range 80 K to 400 K. The calculated minimum achievable temperature for our Yb3+ doped silica sample is ≈150 K, implying the potential for utilizing ytterbium doped silica for solid-state optical refrigeration below temperatures commonly achieved by standard Peltier devices.

Zinc borate glasses: properties, structure and modelling of the composition-dependence of borate speciation.

The short-range order of binary zinc borate glasses, xZnO-(1-x)B2O3, has been quantitatively described as a function of ZnO content over the entire glass forming range for the first time, to the best of our knowledge. Multiple spectroscopic techniques (11B NMR, Raman, infrared) reveal detailed structural information regarding borate speciation and network connectivity, and a new model for quantifying the molar fractions of short-range order units is proposed. A consistent thermal history dependence for the fraction of tetrahedral boron (N4) is well accounted for by the proposed model. The model predicts density within 0.1% of experimental values and N4 to within 1% of NMR values. The intermediate character of four-coordinated zinc in borate glasses of this series is evident by the far infrared profiles and the glass transition temperature behavior, which decreases non-monotonically with increasing ZnO content.

Laser cooling experiments to measure the quantum efficiency of Yb-doped silica fibers.

A detailed investigation into the wavelength-dependent cooling efficiencies of two ultra-pure large core diameter ytterbium-doped silica fibers is carried out by means of the laser-induced thermal modulation spectroscopy (LITMoS) method. From these measurements, an external quantum efficiency of 0.99 is obtained for both fibers. Optimal cooling is seen for pump wavelengths between 1032 and 1035 nm. The crossover wavelength from heating to cooling is identified to be between 1018 and 1021 nm. The fiber with higher Yb3+ ion density exhibits better cooling, seen by the input power normalized temperature differential.

Laser cooling of a Yb doped silica fiber by 18 Kelvin from room temperature.

An ytterbium doped silica optical fiber with a core diameter of 900µm has been cooled by 18.4 K below ambient temperature by pumping with 20 W of 1035 nm light in vacuum. In air, cooling by 3.6 K below ambient was observed with the same 20 W pump. The temperatures were measured with a thermal imaging camera and differential luminescence thermometry. The cooling efficiency is calculated to be 1.2±0.1%. The core of the fiber was codoped with Al3+ for an Al to Yb ratio of 6:1, to allow for a larger Yb concentration and enhanced laser cooling.