Fluorine in Complex Alumino-Boro-Silicate Glasses: Insight into Chemical Environment and Structure.

Fluorine incorporation into silicate glasses is important for technical fields as diverse as geophysics, extractive metallurgy, reconstructive dentistry, optical devices, and radioactive waste management. In this study, we explored the structural role of fluorine in alkaline alumino-borosilicate glass, with increasing amounts of fluorine up to 25 mol % F while maintaining the glass composition. Glasses were characterized by X-ray diffraction (XRD), 27Al and 19F magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, and electron probe microanalysis. Results showed that essentially all F was retained; however, between 12 and 15 mol % F (∼3.6 and 4.5 wt % F), excess fluorine partitions to CaF2 and then NaF and Na-Al-F crystalline phases. Even prior to crystallization, there exist five distinct F sites, three of which evolve into crystalline phases. The two persistent glassy sites likely involve [4]Al-F-Ca/Na local structures. We propose a general understanding of the expected chemical shift of 19F NMR in systems containing Al, Ca, and Na.

Temperature-Dependent Anisotropic Refractive Index in ß-Ga2O3: Application in Interferometric Thermometers.

An accurate knowledge of the optical properties of ß-Ga2O3 is key to developing the full potential of this oxide for photonics applications. In particular, the dependence of these properties on temperature is still being studied. Optical micro- and nanocavities are promising for a wide range of applications. They can be created within microwires and nanowires via distributed Bragg reflectors (DBR), i.e., periodic patterns of the refractive index in dielectric materials, acting as tunable mirrors. In this work, the effect of temperature on the anisotropic refractive index of ß-Ga2O3n(λ,T) was analyzed with ellipsometry in a bulk crystal, and temperature-dependent dispersion relations were obtained, with them being fitted to Sellmeier formalism in the visible range. Micro-photoluminescence (µ-PL) spectroscopy of microcavities that developed within Cr-doped ß-Ga2O3 nanowires shows the characteristic thermal shift of red-infrared Fabry-Perot optical resonances when excited with different laser powers. The origin of this shift is mainly related to the variation in the temperature of the refractive index. A comparison of these two experimental results was performed by finite-difference time-domain (FDTD) simulations, considering the exact morphology of the wires and the temperature-dependent, anisotropic refractive index. The shifts caused by temperature variations observed by µ-PL are similar, though slightly larger than those obtained with FDTD when implementing the n(λ,T) obtained with ellipsometry. The thermo-optic coefficient was calculated.

Effect of extended defects on photoluminescence of gallium oxide and aluminum gallium oxide epitaxial films.

In this work, a systematic photoluminescence (PL) study on three series of gallium oxide/aluminum gallium oxide films and bulk single crystals is performed including comparing doping, epitaxial substrates, and aluminum concentration. It is observed that blue/green emission intensity strongly correlates with extended structural defects rather than the point defects frequently assumed. Bulk crystals or Si-doped films homoepitaxially grown on (010) ß-Ga2O3 yield an intense dominant UV emission, while samples with extended structural defects, such as gallium oxide films grown on either (-201) ß-Ga2O3 or sapphire, as well as thick aluminum gallium oxide films grown on either (010) ß-Ga2O3 or sapphire, all show a very broad PL spectrum with intense dominant blue/green emission. PL differences between samples and the possible causes of these differences are analyzed. This work expands previous reports that have so far attributed blue and green emissions to point defects and shows that in the case of thin films, extended defects might have a prominent role in emission properties.

Reproduction of melting behavior for vitrified hillforts based on amphibolite, granite, and basalt lithologies.

European Bronze and Iron Age vitrified hillforts have been known since the 1700s, but archaeological interpretations regarding their function and use are still debated. We carried out a series of experiments to constrain conditions that led to the vitrification of the inner wall rocks in the hillfort at Broborg, Sweden. Potential source rocks were collected locally and heat treated in the laboratory, varying maximum temperature, cooling rate, and starting particle size. Crystalline and amorphous phases were quantified using X-ray diffraction both in situ, during heating and cooling, and ex situ, after heating and quenching. Textures, phases, and glass compositions obtained were compared with those for rock samples from the vitrified part of the wall, as well as with equilibrium crystallization calculations. 'Dark glass' and its associated minerals formed from amphibolite or dolerite rocks melted at 1000-1200 °C under reducing atmosphere then slow cooled. 'Clear glass' formed from non-equilibrium partial melting of feldspar in granitoid rocks. This study aids archaeological forensic investigation of vitrified hillforts and interpretation of source rock material by mapping mineralogical changes and glass production under various heating conditions.

Structure and properties of Na5FeSi4O12 crystallized from 5Na2O-Fe2O3-8SiO2 glass.

The phase Na5FeSi4O12 [pentasodium iron(III) silicate] crystallizes readily from the Na2O-Fe2O3-SiO2 glass system in a relatively large compositional range. However, its crystal structure and properties have not been studied in detail since its discovery in 1930. In this work, the Na5FeSi4O12 phase was crystallized from a host glass with 5Na2O·Fe2O3·8SiO2 stoichiometry, and both the glass and the crystal were studied. It was found that the Na5FeSi4O12 phase crystallizes at ∼720 °C from the glass and melts at ∼830 °C when heated at a rate of 10 °C min-1. The crystal structure was solved using single-crystal X-ray diffraction and the refined data are reported for the first time for the Na5FeSi4O12 phase. It exhibits trigonal symmetry, space group R-3c, with a = 21.418 and c = 12.2911 Å. The Na atoms located between adjacent structural channels exhibit positional disorder and splitting which was only refined by using low-temperature data collection (150 K). While ∼7% of the total Fe cations occur as Fe2+ in the glass, four-coordinated Fe3+ constitutes ∼93% of the total Fe cations. However, iron in the crystal, which exhibits a paramagnetic behavior, is solely present as six-coordinated Fe3+. The magnetic and vibrational properties of the glass and crystal are discussed to provide additional insight into the structure.

Compositional Dependence of Solubility/Retention of Molybdenum Oxides in Aluminoborosilicate-Based Model Nuclear Waste Glasses.

Molybdenum oxides are an integral component of the high-level waste streams being generated from the nuclear reactors in several countries. Although borosilicate glass has been chosen as the baseline waste form by most of the countries to immobilize these waste streams, molybdate oxyanions (MoO42-) exhibit very low solubility (∼1 mol %) in these glass matrices. In the past three to four decades, several studies describing the compositional and structural dependence of molybdate anions in borosilicate and aluminoborosilicate glasses have been reported in the literature, providing a basis for our understanding of fundamental science that governs the solubility and retention of these species in the nuclear waste glasses. However, there are still several open questions that need to be answered to gain an in-depth understanding of the mechanisms that control the solubility and retention of these oxyanions in glassy waste forms. This article is focused on finding answers to two such questions: (1) What are the solubility and retention limits of MoO3 in aluminoborosilicate glasses as a function of chemical composition? (2) Why is there a considerable increase in the solubility of MoO3 with incorporation of rare-earth oxides (for example, Nd2O3) in aluminoborosilicate glasses? Accordingly, three different series of aluminoborosilicate glasses (compositional complexity being added in a tiered approach) with varying MoO3 concentrations have been synthesized and characterized for their ability to accommodate molybdate ions in their structure (solubility) and as a glass-ceramic (retention). The contradictory viewpoints (between different research groups) pertaining to the impact of rare-earth cations on the structure of aluminoborosilicate glasses are discussed, and their implications on the solubility of MoO3 in these glasses are evaluated. A novel hypothesis explaining the mechanism governing the solubility of MoO3 in rare-earth containing aluminoborosilicate glasses has been proposed.

Pre-viking Swedish hillfort glass: A prospective long-term alteration analogue for vitrified nuclear waste.

Models for long-term glass alteration are required to satisfy performance predictions of vitrified nuclear waste in various disposal scenarios. Durability parameters are usually extracted from short-term laboratory tests, and sometimes checked with long-term natural experiments on glasses, termed analogues. In this paper, a unique potential ancient glass analogue from Sweden is discussed. The hillfort glass found at Broborg represents a unique case study as a vitrified waste glass analogue to compare to Low Activity Waste glass to be emplaced in near surface conditions at Hanford (USA). Glasses at Broborg have similar and dissimilar compositions to LAW glasses, allowing the testing of long-term alteration of different glass chemistries. In addition, the environmental history of the site is reasonably well documented. Initial investigations on previously collected samples established methodologies for handling and characterizing these artifacts by laboratory methods while preserving their alteration layers and cultural context. Evidence of possible biologically influenced glass alteration, and differential alteration in the 2 types of glass found at the Broborg site is presented.

Chemical Trends in Solid Alkali Pertechnetates.

Insight into the solid-state chemistry of pure technetium-99 (99Tc) oxides is required in the development of a robust immobilization and disposal system for nuclear waste stemming from the radiopharmaceutical industry, from the production of nuclear weapons, and from spent nuclear fuel. However, because of its radiotoxicity and the subsequent requirement of special facilities and handling procedures for research, only a few studies have been completed, many of which are over 20 years old. In this study, we report the synthesis of pure alkali pertechnetates (sodium, potassium, rubidium, and cesium) and analysis of these compounds by Raman spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), solid-state nuclear magnetic resonance (static and magic angle spinning), and neutron diffraction. The structures and spectral signatures of these compounds will aid in refining the understanding of 99Tc incorporation into and release from nuclear waste glasses. NaTcO4 shows aspects of the relatively higher electronegativity of the Na atom, resulting in large distortions of the pertechnetate tetrahedron and deshielding of the 99Tc nucleus relative to the aqueous TcO4-. At the other extreme, the large Cs and Rb atoms interact only weakly with the pertechnetate, have closer to perfect tetrahedral symmetry at the Tc atom, and have very similar vibrational spectra, even though the crystal structure of CsTcO4 is orthorhombic while that of RbTcO4 is tetragonal. Further trends are observed in the cell volume and quadrupolar coupling constant.

Regenerative feedback resonant circuit to detect transient changes in electromagnetic properties of semi-insulating materials.

A prototype regenerative feedback resonant circuit has been developed for measuring the transient spectral response due to perturbations in properties of various electromagnetic materials. The circuit can accommodate a variety of cavity resonators, shown here in the 8 GHz range, with passive quality factors (Qstat) as high as 7000 depending upon material loading. The positive feedback enhanced dynamic quality factors (Qdyn) of resonator∕material combinations in the regenerative circuit are on the order of 10(7)-10(8). The theory, design, and implementation of the circuit is discussed along with real-time monitored example measurements of effects due to photon-induced charge carriers in high-resistivity silicon wafers and magnetic-field induced perturbations of yttrium-iron garnet.

Combined charge carrier transport and photoelectrochemical characterization of BiVO4 single crystals: intrinsic behavior of a complex metal oxide.

Bismuth vanadate (BiVO4) is a promising photoelectrode material for the oxidation of water, but fundamental studies of this material are lacking. To address this, we report electrical and photoelectrochemical (PEC) properties of BiVO4 single crystals (undoped, 0.6% Mo, and 0.3% W:BiVO4) grown using the floating zone technique. We demonstrate that a small polaron hopping conduction mechanism dominates from 250 to 400 K, undergoing a transition to a variable-range hopping mechanism at lower temperatures. An anisotropy ratio of ~3 was observed along the c axis, attributed to the layered structure of BiVO4. Measurements of the ac field Hall effect yielded an electron mobility of ~0.2 cm(2) V(-1) s(-1) for Mo and W:BiVO4 at 300 K. By application of the Gärtner model, a hole diffusion length of ~100 nm was estimated. As a result of low carrier mobility, attempts to measure the dc Hall effect were unsuccessful. Analyses of the Raman spectra showed that Mo and W substituted for V and acted as donor impurities. Mott-Schottky analysis of electrodes with the (001) face exposed yielded a flat band potential of 0.03-0.08 V versus the reversible H2 electrode, while incident photon conversion efficiency tests showed that the dark coloration of the doped single crystals did not result in additional photocurrent. Comparison of these intrinsic properties to those of other metal oxides for PEC applications gives valuable insight into this material as a photoanode.

Magnetic properties of double perovskite La2BMnO6 (B = Ni or Co) nanoparticles.

Double perovskite La2BMnO6 (B = Ni and Co) nanoparticles with average particle size of ~50 nm were synthesized using a facile, environmentally friendly, and scalable molten-salt reaction at 700 °C in air. Their structural and morphological properties were characterized by X-ray diffraction and transmission electron microscopy. Their magnetic properties were evaluated and compared using dc magnetic M-T and M-H, and ac magnetic susceptibility versus frequency, temperature, and field for the first time. The dc magnetization curves show paramagnetic-ferromagnetic transitions at TC∼ 275 and 220 K for La2NiMnO6 (LNMO) and La2CoMnO6 (LCMO) nanoparticles, respectively. ac susceptibility revealed that the LCMO nanoparticles had a single magnetic transition indicative of Co(2+)-O(2-)-Mn(4+) ordering, whereas the LNMO nanoparticles showed more complex magnetic behaviors suggesting a re-entrant spin glass.

Rhenium solubility in borosilicate nuclear waste glass: implications for the processing and immobilization of technetium-99.

The immobilization of technetium-99 ((99)Tc) in a suitable host matrix has proven to be a challenging task for researchers in the nuclear waste community around the world. In this context, the present work reports on the solubility and retention of rhenium, a nonradioactive surrogate for (99)Tc, in a sodium borosilicate glass. Glasses containing target Re concentrations from 0 to 10,000 ppm [by mass, added as KReO(4) (Re(7+))] were synthesized in vacuum-sealed quartz ampules to minimize the loss of Re from volatilization during melting at 1000 °C. The rhenium was found as Re(7+) in all of the glasses as observed by X-ray absorption near-edge structure. The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) using inductively coupled plasma optical emission spectroscopy. At higher rhenium concentrations, additional rhenium was retained in the glasses as crystalline inclusions of alkali perrhenates detected with X-ray diffraction. Since (99)Tc concentrations in a glass waste form are predicted to be <10 ppm (by mass), these Re results implied that the solubility should not be a limiting factor in processing radioactive wastes, assuming Tc as Tc(7+) and similarities between Re(7+) and Tc(7+) behavior in this glass system.

Millimeter-wave dielectric properties of single-crystal ferroelectric and dielectric materials.

Transmittance measurements on various single crystal ferroelectric and dielectric materials, BaTiO(3), SrTiO(3), LiNbO(3), LiTaO(3), (PbMg(1/3)Nb(2/3)O(3))0.73-(PbTiO(3))0.27, LaAlO(3), and Bi(4)Ge(3)O(12), over a broad millimeter-wave (MMW) frequency range have been performed. Frequency dependence of the complex dielectric permittivity has been measured in the MMW region using high-power sources for the first time, using a free-space, quasi-optical MMW spectrometer equipped with high-power backward wave oscillators (BWOs) as sources of coherent radiation, tunable in the range from 30 to 120 and 180 to 260 GHz. These results are compared with MMW permittivity of these materials obtained by other methods as well as to RF, microwave, and optical frequency permittivities for all the materials tested. The effects of both crystallographic orientation and quality of the surface polishing of the crystals have been examined. Uncertainties and possible sources of instrumentation and measurement errors related to the freespace MMW technique are discussed. This work demonstrates that precise MMW permittivity data can be obtained even on relatively small and thin crystals of different surface conditions and orientations using the high-power BWO-based quasioptical approach.

Magnetotransport properties of high quality Co:ZnO and Mn:ZnO single crystal pulsed laser deposition films: pitfalls associated with magnetotransport on high resistivity materials.

The electrical resistivity values for a series of pure and doped (Co, Mn, Al) ZnO epitaxial films grown by pulsed laser deposition were measured with equipment designed for determining the direct current resistivity of high resistance samples. Room-temperature resistances ranging from 7 x 10(1) to 4 x 10(8) Omega/sq were measured on vacuum-reduced cobalt-doped ZnO, (Al,Co) co-doped ZnO, pure cobalt-doped ZnO, Mn-doped ZnO, and undoped ZnO. Using a four-point collinear geometry with gold spring-loaded contacts, resistivities were measured from 295 to 5 K for resistances of < approximately 10(12) Omega/sq. In addition, magnetoresistance and Hall effect were measured as a function of temperature for select samples. Throughout the investigation, samples were also measured on commercially available instrumentation with good agreement. The challenges of transport measurements on high resistivity samples are discussed, along with some offered solutions to those challenges.