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At least 37 records · Page 2

Physical and optical properties of the International Simple Glass

Abstract Radioactive waste immobilization is a means to limit the release of radionuclides from various waste streams into the environment over a timescale of hundreds to many thousands of years. Incorporation of radionuclide-containing wastes into borosilicate glass during vitrification is one potential route to accomplish such immobilization. To facilitate comparisons and assessments of reproducibility across experiments and laboratories, a six-component borosilicate glass (Si, B, Na, Al, Ca, Zr) known as the International Simple Glass (ISG) was developed by international consensus as a compromise between simplicity and similarity to waste glasses. Focusing on a single glass composition with a multi-pronged approach utilizing state-of-the-art, multi-scale experimental and theoretical tools provides a common database that can be used to assess relative importance of mechanisms and models. Here we present physical property data (both published and previously unpublished) on a single batch of ISG, which was cast into individual ingots that were distributed to the collaborators. Properties from the atomic scale to the macroscale, including composition and elemental impurities, phase purity, density, thermal properties, mechanical properties, optical and vibrational properties, and the results of molecular dynamics simulations are presented. In addition, information on the surface composition and morphology after polishing is included. Although the existing literature on the alteration of ISG is not extensively reviewed here, the results of well-controlled static alteration experiments are presented here as a point of reference for other performance investigations.

36 MATERIALS SCIENCE↗

Tuning optical properties of transparent conducting barium stannate by dimensional reduction

We report calculations of the electronic structure and optical properties of doped n-type perovskite BaSnO 3 and layered perovskites. While doped BaSnO 3 retains its transparency for energies below the valence to conduction band onset, the doped layered compounds exhibit below band edge optical conductivity due to transitions from the lowest conduction band. This gives absorption in the visible for Ba 2 SnO 4 . It is important to minimize this phase in transparent conducting oxide (TCO) films. Ba 3 Sn 2 O 7 and Ba 4 Sn 3 O 10 have strong transitions only in the red and infrared, respectively. Thus, there may be opportunities for using these as wavelength filtering TCO.

36 MATERIALS SCIENCE↗

MAX-Phase Partial Optical Properties

The optical and electrical properties of MAX-phase materials have been thoroughly studied in the past. We present here a new technique to determine and study the partial contributions to the optical properties. Following the same methodology as the decomposition of the density of states to the partial density of states, we have decomposed the optical properties into the partial optical properties. Using this technique the differences of elemental and layer resolved optical properties are displayed for both the 211 and 312 phase of TiSiC and TiAlC MAX-phase materials.

Weigand, Alysse↗

Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga 2 O 3 nanocrystalline films

An approach is presented to design refractory-metal incorporated Ga2O3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga2O3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga2O3), higher Mo-content results in amorphization. Chemically-induced band gap variability (Eg~1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality and performance of Ga-Mo-O films is possible by tuning the Mo-content.

Environmental Molecular Sciences Laboratory↗

Understanding the optical properties of ambient sub- and supermicron particulate matter: results from the CARES 2010 field study in northern California

Abstract. Measurements of the optical properties (absorption, scattering and extinction) of PM1, PM2.5 and PM10 made at two sites around Sacramento, CA, during the June 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES) are reported. These observations are used to establish relationships between various intensive optical properties and to derive information about the dependence of the optical properties on photochemical aging and sources. Supermicron particles contributed substantially to the total light scattering at both sites, about 50 % on average. A strong, linear relationship is observed between the scattering Ångström exponent for PM10 and the fraction of the scattering that is contributed by submicron particles (fsca, PM1) at both sites and with similar slopes and intercepts (for a given pair of wavelengths), suggesting that the derived relationship may be generally applicable for understanding variations in particle size distributions from remote sensing measurements. At the more urban T0 site, the fsca, PM1 increased with photochemical age, whereas at the downwind, more rural T1 site the fsca, PM1 decreased slightly with photochemical age. This difference in behavior reflects differences in transport, local production and local emission of supermicron particles between the sites. Light absorption is dominated by submicron particles, but there is some absorption by supermicron particles ( ∼ 15 % of the total). The supermicron absorption derives from a combination of black carbon that has penetrated into the supermicron mode and from dust, and there is a clear increase in the mass absorption coefficient of just the supermicron particles with increasing average particle size. The mass scattering coefficient (MSC) for the supermicron particles was directly observed to vary inversely with the average particle size, demonstrating that MSC cannot always be treated as a constant in estimating mass concentrations from scattering measurements, or vice versa. The total particle backscatter fraction exhibited some dependence upon the relative abundance of sub- versus supermicron particles; however this was modulated by variations in the median size of particles within a given size range; variations in the submicron size distribution had a particularly large influence on the observed backscatter efficiency and an approximate method to account for this variability is introduced. The relationship between the absorption and scattering Ångström exponents is examined and used to update a previously suggested particle classification scheme. Differences in composition led to differences in the sensitivity of PM2.5 to heating in a thermodenuder to the average particle size, with more extensive evaporation (observed as a larger decrease in the PM2.5 extinction coefficient) corresponding to smaller particles; i.e., submicron particles were generally more susceptible to heating than the supermicron particles. The influence of heating on the particle hygroscopicity varied with the effective particle size, with larger changes observed when the PM2.5 distribution was dominated by smaller particles.

54 ENVIRONMENTAL SCIENCES↗

Tuning magnetic and optical properties through strain in epitaxial LaCrO 3 thin films

We report on the effect of epitaxial strain on magnetic and optical properties of perovskite LaCrO 3 (LCO) single crystal thin films. Epitaxial LCO thin films are grown by pulsed laser deposition on proper choice of substrates to impose different strain states. A combined experimental and theoretical approach is used to demonstrate the direct correlation between lattice-strain and functional properties. The magnetization results show that the lattice anisotropy plays a critical role in controlling the magnetic behavior of LCO films. The strain induced tetragonality in the film lattice strongly affects the optical transitions and charge transfer gap in LCO. This study opens possibilities to tailor the functional properties of LCO and related materials by strain engineering in epitaxial growth.

36 MATERIALS SCIENCE↗

Ionic and Optical Properties of Methylammonium Lead Iodide Perovskite across the Tetragonal–Cubic Structural Phase Transition

Abstract Practical hybrid perovskite solar cells (PSCs) must endure temperatures above the tetragonal–cubic structural phase transition of methylammonium lead iodide (MAPbI 3 ). However, the ionic and optical properties of MAPbI 3 in such a temperature range, and particularly, dramatic changes in these properties resulting from a structural phase transition, are not well studied. Herein, we report a striking contrast at approximately 45 °C in the ionic/electrical properties of MAPbI 3 owing to a change of the ion activation energy from 0.7 to 0.5 eV, whereas the optical properties exhibit no particular transition except for the steady increase of the bandgap with temperature. These observations can be explained by the “continuous” nature of perovskite phase transition. We speculate that the critical temperature at which the ionic/electrical properties change, although related to crystal symmetry variation, is not necessarily the same temperature as when tetragonal–cubic structural phase transition occurs.

Hoque, Md Nadim Ferdous↗

Electronic, transport, and optical properties of bulk and mono-layer PdSe 2

In this study, the electronic and optical properties of bulk and monolayer PdSe 2 are investigated using firstprinciples calculations. Using the modified Becke-Johnson potential, we find semiconductor behavior for both bulk and monolayer PdSe 2 with indirect gap values of 0.03 eV for bulk and 1.43 eV for monolayer, respectively. Our sheet optical conductivity results support this observation and show similar anisotropic feature in the 2D plane. We further study the thermoelectric properties of the 2D PdSe 2 using Blotzmann transport model and find interestingly high Seebeck coefficients (>200 μV/K) for both p- and n-type up to high doping level (–2 x 10 13 cm 2 ) with an anisotropic character in an electrical conductivity suggesting better thermoelectric performance along y direction in the plane.V

36 MATERIALS SCIENCE↗

Electronic structure and optical properties of α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} solid-solution thin films

We have examined the effect of V doping on the electronic and optical properties of epitaxial hematite (α-Fe{sub 2}O{sub 3}) thin films, by employing several characterization techniques and computational modeling. The conductivity of α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} (0 ≤ x ≤ ∼0.5) is enhanced by several orders of magnitude as x is increased, as evidenced by electrical resistivity measurements and x-ray photoelectron spectroscopy core-level and valence-band spectra. Optical absorption shows a reduction in the direct band gap by as much as 0.64 eV for x = 0.53 (E{sub g} = 1.46 eV) relative to that of α-Fe{sub 2}O{sub 3} (E{sub g} = 2.10 eV). Detailed understanding of the character of the optical transitions in the alloys is achieved using first-principles calculations of the ground and excited states. These calculations reveal that V doping results in occupied V 3d orbitals hybridized with Fe orbitals and located at approximately mid-gap in α-Fe{sub 2}O{sub 3}. The lowest energy transitions involve charge transfer from occupied V 3d to unoccupied Fe 3d* orbitals. With a low band gap and high conductivity, α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} is a promising material for photovoltaic and photoelectrochemical applications.

36 MATERIALS SCIENCE↗

Autogenic synthesis of SnO{sub 2} materials and their structural, electrochemical, and optical properties

During autogenic reactions, organometallic precursors are decomposed above their critical temperature within an enclosed chamber at high temperatures and pressures. It has recently been established that such reactions can be used to synthesize carbon-coated metal oxide and metal phosphate nanoparticles. These materials are of interest as electrodes for lithium-ion batteries. In this paper, we report the autogenic fabrication of a carbon-coated SnO{sub 2} product and a carbon-free SnO{sub 2} product after removal of the carbon coating by combustion. The major objectives of the study were to monitor any beneficial effects that carbon-coated electrodes containing a lithium alloying element such as Sn might have in improving the electrical connectivity between electrode particles, which expand and contract significantly on lithiation and delithiation, and their utility in lithium cells. Specifically, we report the compositional, structural and morphological properties, and electrochemical behavior of carbon-coated SnO{sub 2} electrodes. Given the importance of the optical properties of SnO{sub 2}, we also describe the effects of the carbon coating on the optical absorbance and photoluminescence of autogenically-prepared SnO{sub 2} materials. - Graphical abstract: One-step, solvent-free autogenic reactions yield nanosized SnO{sub 2} nanoparticles, uniformly coated and interconnected by 2-4 nm carbon layers, with improved electrochemical performance. Highlights: Black-Right-Pointing-Pointer Distinctive autogenic process synthesized SnO{sub 2} nanoparticles coated with 2-4 nm carbon layers. Black-Right-Pointing-Pointer Carbon coating improved capacity retention and cycling stability of SnO{sub 2} nanoparticles. Black-Right-Pointing-Pointer Carbon coating quenched photoluminescence of SnO{sub 2} component in SnO{sub 2}-C composite. Black-Right-Pointing-Pointer Autogenic approach is extremely versatile, holds promise for designing new nanoarchitectures.

36 MATERIALS SCIENCE↗

Thermal lens study of thermo-optical properties and concentration quenching of Er{sup 3+}-doped lead pyrophosphate-based glasses

In this work, we have used the thermal lens technique combined with conventional spectroscopy to characterize the thermo-optical properties of Er{sup 3+}-doped lead pyrophosphate-based glasses. More precisely, we have investigated and quantified experimentally the fluorescence quantum efficiencies of the Er{sup 3+} levels, and we describe the role of concentration quenching effects. The fluorescence quantum efficiency of the {sup 4}I{sub 13/2} level is very high when compared to other phosphate glasses, while that of the green-coupled levels is very small. Other important photonic materials parameters, such as the thermal diffusivity and temperature coefficient of the optical path length change, were obtained and compared with those of other glass systems. The cumulative results obtained here for the Er-doped lead pyrophosphate glass show that this material is a good candidate for photonic applications with a characteristic Er{sup 3+} infrared emission around 1550 nm.

36 MATERIALS SCIENCE↗

Aerosols from anthropogenic and biogenic sources and their interactions – modeling aerosol formation, optical properties, and impacts over the central Amazon basin

The Green Ocean Amazon experiment – GoAmazon 2014–2015 – explored the interactions between natural biogenic forest emissions from central Amazonia and urban air pollution from Manaus. Previous GoAmazon 2014–2015 studies showed that nitrogen oxide (NO x = NO + NO 2 ) and sulfur oxide (SO x ) emissions from Manaus strongly interact with biogenic volatile organic compounds (BVOCs), affecting secondary organic aerosol (SOA) formation. In previous studies, ground-based and aircraft measurements provided evidence of SOA formation and strong changes in aerosol composition and properties. Aerosol optical properties also evolve, and their impacts on the Amazonian ecosystem can be significant. As particles age, some processes, such as SOA production, black carbon (BC) deposition, particle growth and the BC lensing effect change the aerosol optical properties, affecting the solar radiation flux at the surface. This study analyzes data and models SOA formation using the Weather Research and Forecasting with Chemistry (WRF-Chem) model to assess the spatial variability in aerosol optical properties as the Manaus plumes interact with the natural atmosphere. The following aerosol optical properties are investigated: single scattering albedo (SSA), asymmetry parameter (g aer ), absorption Ångström exponent (AAE) and scattering Ångström exponent (SAE). These simulations were validated using ground-based measurements at three experimental sites, namely the Amazon Tall Tower Observatory – ATTO (T0a), downtown Manaus (T1), Tiwa Hotel (T2) and Manacapuru (T3), as well as the U.S. Department of Energy (DOE) Gulfstream 1 (G-1) aircraft flights. WRF-Chem simulations were performed over 7 d during March 2014. Results show a mean biogenic SOA (BSOA) mass enrichment of 512 % at the T1 site, 450 % in regions downwind of Manaus, such as the T3 site, and 850 % in areas north of the T3 site in simulations with anthropogenic emissions. The SOA formation is rather fast, with about 80 % of the SOA mass produced in 3–4 h. Comparing the plume from simulations with and without anthropogenic emissions, SSA shows a downwind reduction of approximately 10 %, 11 % and 6 % at the T1, T2 and T3 sites, respectively. Other regions, such as those further downwind of the T3 site, are also affected. The g aer values increased from 0.62 to 0.74 at the T1 site and from 0.67 to 0.72 at the T3 site when anthropogenic emissions are active. During the Manaus plume-aging process, a plume tracking analysis shows an increase in SSA from 0.91 close to Manaus to 0.98 160 km downwind of Manaus as a result of SOA production and BC deposition.

54 ENVIRONMENTAL SCIENCES↗

The CU 2-D-MAX-DOAS instrument – Part 2: Raman scattering probability measurements and retrieval of aerosol optical properties

Abstract. The multiannual global mean of aerosol optical depth at 550 nm (AOD550) over land is ∼ 0.19, and that over oceans is ∼ 0.13. About 45 % of the Earth surface shows AOD550 smaller than 0.1. There is a need for measurement techniques that are optimized to measure aerosol optical properties under low AOD conditions. We present an inherently calibrated retrieval (i.e., no need for radiance calibration) to simultaneously measure AOD and the aerosol phase function parameter, g, based on measurements of azimuth distributions of the Raman scattering probability (RSP), the near-absolute rotational Raman scattering (RRS) intensity. We employ radiative transfer model simulations to show that for solar azimuth RSP measurements at solar elevation and solar zenith angle (SZA) smaller than 80°, RSP is insensitive to the vertical distribution of aerosols and maximally sensitive to changes in AOD and g under near-molecular scattering conditions. The University of Colorado two-dimensional Multi-AXis Differential Optical Absorption Spectroscopy (CU 2-D-MAX-DOAS) instrument was deployed as part of the Two Column Aerosol Project (TCAP) at Cape Cod, MA, during the summer of 2012 to measure direct sun spectra and RSP from scattered light spectra at solar relative azimuth angles (SRAAs) between 5 and 170°. During two case study days with (1) high aerosol load (17 July, 0.3 < AOD430 < 0.6) and (2) near-molecular scattering conditions (22 July, AOD430 < 0.13) we compare RSP-based retrievals of AOD430 and g with data from a co-located CIMEL sun photometer, Multi-Filter Rotating Shadowband Radiometer (MFRSR), and an airborne High Spectral Resolution Lidar (HSRL-2). The average difference (relative to DOAS) for AOD430 is +0.012 ± 0.023 (CIMEL), −0.012 ± 0.024 (MFRSR), −0.011 ± 0.014 (HSRL-2), and +0.023 ± 0.013 (CIMELAOD − MFRSRAOD) and yields the following expressions for correlations between different instruments: DOASAOD = −(0.019 ± 0.006) + (1.03 ± 0.02) × CIMELAOD (R2 = 0.98), DOASAOD = −(0.006 ± 0.005) + (1.08 ± 0.02) × MFRSRAOD (R2 = 0.98), and CIMELAOD = (0.013 ± 0.004) + (1.05 ± 0.01) × MFRSRAOD (R2 = 0.99). The average g measured by DOAS on both days was 0.66 ± 0.03, with a difference of 0.014 ± 0.05 compared to CIMEL. Active steps to minimize the error in the RSP help to reduce the uncertainty in retrievals of AOD and g. As AOD decreases and SZA increases, the RSP signal-to-noise ratio increases. At AOD430 ∼ 0.4 and 0.10 the absolute AOD errors are ∼ 0.014 and 0.003 at 70° SZA and 0.02 and 0.004 at 35° SZA. Inherently calibrated, precise AOD and g measurements are useful to better characterize the aerosol direct effect in urban polluted and remote pristine environments.

54 ENVIRONMENTAL SCIENCES↗