Multicomposition EPSR: toward transferable potentials to model chalcogenide glass structures

The structure of xAs40Se60–(1 – x)As40S60 glasses, where x = 1.000, 0.667, 0.500, 0.333, 0.250, and 0.000, is investigated using a combination of neutron and X-ray diffraction coupled with computational modeling using multicomposition empirical potential structure refinement (MC-EPSR). Traditional EPSR (T-EPSR) produces a set of empirical potentials that drive a structural model of a particular composition to agreement with diffraction experiments. The work presented here establishes the shortcomings in generating such a model for a ternary chalcogenide glass composition. In an enhancement to T-EPSR, MC-EPSR produces a set of pair potentials that generate robust structural models across a range of glass compositions. The structures obtained vary with composition in a much more systematic way than those taken from T-EPSR. For example, the average arsenic–sulfur bonding distances vary between 2.28 and 2.46 Å in T-EPSR but are 2.29 ± 0.02 Å in MC-EPSR. Similarly, the arsenic–selenium bond lengths from T-EPSR vary between 2.28 and 2.43 Å but are consistently 2.40 ± 0.02 Å in the MC-EPSR results. Analysis of these models suggests that the average separation of the chalcogen (S or Se) atoms is the structural origin of the changes in nonlinear refractive index with glass composition

Bifurcated polarization rotation in bismuth-based piezoelectrics

ABO3 perovskite-type solid solutions display a large variety of structural and physical properties, which can be tuned by chemical composition or external parameters such as temperature, pressure, strain, electric, or magnetic fields. Some solid solutions show remarkably enhanced physical properties including colossal magnetoresistance or giant piezoelectricity. It has been recognized that structural distortions, competing on the local level, are key to understanding and tuning these remarkable properties, yet, it remains a challenge to experimentally observe such local structural details. Here, from neutron pair-distribution analysis, a temperature-dependent 3D atomic-level model of the lead-free piezoelectric perovskite Na0.5Bi0.5TiO3 (NBT) is reported. The statistical analysis of this model shows how local distortions compete, how this competition develops with temperature, and, in particular, how different polar displacements of Bi3+ cations coexist as a bifurcated polarization, highlighting the interest of Bi-based materials in the search for new lead-free piezoelectrics

Modelling of multimode selenide-chalcogenide glass fibre based MIR spontaneous emission sources

Chalcogenide glass fibres have been demonstrated as a suitable medium for the realisation of spontaneous emission sources for mid-infrared photonics applications with a particular emphasis on sensor technology. Such sources give a viable alternative to other solutions due to their potentially low cost, high reliability and robustness when pumped using commercially available semiconductor lasers. We present a comprehensive analysis of the properties of selenide-chalcogenide glass fibres applied as spontaneous emission sources. We extract the modelling parameters from measurements using in house fabricated bulk glass and fibre samples. We apply the well-established rate equations approach to determine the level populations, the distribution of the photon intensity within the fibre and the output power levels. We compare the modelling results with experiment

Numerical modelling of Tb3+ doped selenide-chalcogenide multimode fibre based spontaneous emission sources

A model is developed of a terbium (III) ion doped selenide chalcogenide glass fibre source that provides spontaneous emission within the mid-infrared (MIR) wavelength range. Three numerical algorithms are used to calculate the solution and compare their properties

Numerical modeling of lathanide-ion doped fibre lasers operating within mid-infrared wavelength region

We discuss the numerical modelling of lanthanide-ion doped chalcogenide glass fibre lasers for operation in the mid-infrared wavelength region. We extract the modelling parameters from emission and absorption measurements using Judd-Ofelt and McCumber theory. Numerical algorithms are developed based on the experimentally extracted fibre parameters. The simulation results predict lasing with slope efficiency of at least 20 % provided, that the fibre loss can be kept at the level of 1 dB/m or less

Alkali environments in tellurite glasses

Neutron diffraction measurements are reported for five binary alkali tellurite glasses, xM2O · (100 − x)TeO2 (containing 10 and 20 mol% K2O, 10 and 19 mol% Na2O, and 20 mol% 7Li2O), together with 23Na MAS NMR measurements for the sodium containing glasses. Differences between neutron correlation functions are used to extract information about the local environments of lithium and sodium. The Na–O bond length is 2.37(1) Å and the average Na–O coordination number, nNaO, decreases from 5.2(2) for x = 10 mol% Na2O to 4.6(1) for x = 19 mol% Na2O. The average Li–O coordination number, nLiO, is 3.9(1) for the glass with x = 20 mol% Li2O and the Li–O bond length is 2.078(2) Å. As x increases from 10 to 19 mol% Na2O, the 23Na MAS NMR peak moves downfield, confirming an earlier report of a correlation of peak position with sodium coordination number. The close agreement of the maximum in the Te–O bond distribution for sodium and potassium tellurite glasses of the same composition, coupled with the extraction of reasonable alkali coordination numbers using isostoichiometric differences, gives strong evidence that the tellurium environment in alkali tellurites is independent of the size of the modifier cation used

Yttrium doped phosphate-based glasses: structural and degradation analyses

This study investigates the role of yttrium in phosphate-based glasses in the system 45(P 2 O 5)-25(CaO)-(30-x)(Na 2 O)-x(Y 2 O 3) (0≤ x≤ 5) prepared via melt quenching and focuses on their structural characterisation and degradation properties. The structural analyses were performed using a combination of solid-state nuclear magnetic resonance (NMR), Fourier transform infrared spec-troscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). 31 P NMR analysis showed that depolymerisation of the phosphate network occurred which increased with Y 2 O 3 content as metaphosphate units (Q 2) decreased with subsequent increase in pyrophosphate species (Q 1). The NMR results correlated well with structural changes observed via FTIR and XPS analyses. XRD analysis of crys-tallised glass samples revealed the presence of calcium pyrophosphate (Ca 2 P 2 O 7) and sodium metaphosphate (NaPO 3) phases for all the glass formulations explored. Yttrium-containing phases were found for the formulations containing 3 and 5 mol% Y 2 O 3. Degradation analyses performed in Phosphate buffer saline (PBS) and Milli-Q water revealed significantly reduced rates with addition of Y 2 O 3 content. This decrease was attributed to the formation of Y-O-P bonds where the octahedral structure of yt-trium (YO 6) cross-linked phosphate chains, subsequently leading to an increase in chemical durability of the glasses. The ion release studies also showed good correlation with the degradation profiles

Immunization with vaccinia virus induces polyfunctional and phenotypically distinctive CD8+ T cell responses

Vaccinia virus immunization provides lifelong protection against smallpox, but the mechanisms of this exquisite protection are unknown. We used polychromatic flow cytometry to characterize the functional and phenotypic profile of CD8+ T cells induced by vaccinia virus immunization in a comparative vaccine trial of modified vaccinia virus Ankara (MVA) versus Dryvax immunization in which protection was assessed against subsequent Dryvax challenge. Vaccinia virus–specific CD8+ T cells induced by both MVA and Dryvax were highly polyfunctional; they degranulated and produced interferon γ, interleukin 2, macrophage inflammatory protein 1β, and tumor necrosis factor α after antigenic stimulation. Responding CD8+ T cells exhibited an unusual phenotype (CD45RO−CD27intermediate). The unique phenotype and high degree of polyfunctionality induced by vaccinia virus also extended to inserted HIV gene products of recombinant NYVAC. This quality of the CD8+ T cell response may be at least partially responsible for the profound efficacy of these vaccines in protection against smallpox and serves as a benchmark against which other vaccines can be evaluated

Modeling of resonantly pumped mid-infrared Pr3+-doped chalcogenide fiber amplifier with different pumping schemes

We propose a model for resonantly pumped Pr3+-doped chalcogenide fiber amplifiers which includes excited state absorption and the full spectral amplified spontaneous emission spanning from 2 μm to 6 μm. Based on this model, the observed near- and mid-infrared photoluminescence generated from Pr3+-doped chalcogenide fiber is explained. Then the output properties of a 4.1 μm resonantly pumped Pr3+-doped chalcogenide fiber amplifier are simulated in both co- and counter-pumping schemes. Results show that the 4.1 μm counter-pumped fiber amplifier can achieve a power conversion efficiency (PCE) of over 62.8 % for signal wavelengths ranging from 4.5 μm to 5.3 μm. This is, to our best knowledge, the highest simulated PCE for a Pr3+-doped chalcogenide fiber amplifier

Toward a structural model for the aluminum tellurite glass system

Neutron diffraction, 27Al MAS NMR, and 27Al Double Quantum MAS NMR results are presented and analyzed to determine the local environments of the cations in a series of aluminum tellurite glasses. Total scattering results show that, within a maximum Te–O distance of 2.36 Å, tellurium exhibits a mix of [TeO3E] and [TeO4E] environments (E = electron lone-pair), with a linear reduction in the average tellurium–oxygen coordination number as Al2O3 is added to the glass. This is accompanied by a linear decrease in the average aluminum–oxygen coordination number as [AlO4] units form at the expense of [AlO6] units, while the fraction of [AlO5] units remains roughly constant. A consideration of the bonding requirements of the five structural units in the glass, [TeO3E], [TeO4E], [AlO4], [AlO5], and [AlO6], has allowed a direct quantitative relationship between tellurium–oxygen and aluminum–oxygen coordination numbers to be derived for the first time, and this has been successfully extended to the boron tellurite system. Double Quantum 27Al MAS NMR indicates that, in contrast to previous reports, the shortest Al...Al separations are significantly smaller (∼3.2 Å) than expected for a uniform distribution and there is a preference for [AlO6]–[AlO6] and [AlO4]–[AlO4] corner sharing polyhedra. These associations support a new structural model which successfully applies the principle of charge balance to describe the interaction of tellurium and aluminum and identifies and explains the clustering of [AlOn] polyhedra in the glass and their preferred associations. [AlO6] and [TeO4E] units dominate the network in TeO2-rich glasses and [AlO4]− units form to stabilize the [TeO3E]+ units as alumina is added to the glass