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At least 1,243 records · Page 69

Dopant segregation in YAG single crystal fibers grown by the laser heated pedestal growth technique

In this work, we report self-segregation of dopants in a crystal matrix within a single crystal (SC) fiber. Neodymium and holmium-doped yttrium aluminum garnet (YAG) fibers were grown using the Laser Heated Pedestal Growth (LHPG) technique and cross-sectional dopant concentration was measured using electron-probe micro-analysis. It was observed that the degree of auto-segregation of the rare-earth dopant depended on the difference in ionic size of the dopant ion and the Y 3+ ion in the YAG matrix. While holmium showed little tendency to self-segregate, the concentration of neodymium ions varied as much as 25% across the cross-section of the fiber. Strong correlation between the dopant concentration profile and fiber draw speed was also demonstrated. Since the local refractive index depends on the concentration of dopants, a refractive index profile can be achieved by a dopant profile across the fiber cross-section. Engineered index profiles can be realized by varying growth conditions, dopants, crystal matrix, etc. Such an approach is promising in applications such as the development of monolithic SC fibers with graded-index profiles.

36 MATERIALS SCIENCE↗

Non-destructive characterization of corroded glass surfaces by spectroscopic ellipsometry

Characterization of the alteration layers that form on glass surfaces during corrosion processes provides valuable information on both the mechanisms and rate of glass alteration. In recent years, state-of-the-art materials and surface characterization techniques have been employed to study various aspects of the alteration layers that result from corrosion. In most cases, these techniques are destructive and thus can only be employed at the end of the corrosion experiment. We show that the alteration layers can be investigated by non-destructive spectroscopic ellipsometry (SE), which provides pertinent information on alteration layer thickness, morphology, and, through correlation of the index of refraction, porosity. SE measurements of silicate glass coupons altered in aqueous solutions of pH 3, 5, 7, 9, and 11 at 90 °C for 7 days are compared to cross-sectional secondary electron microscopy images. In most cases, quantitative agreement of the alteration layer thickness is obtained. The fractional porosity calculated from the index of refraction is lower than the porosity calculated from elemental analysis of the aqueous solutions, indicating that the alteration layer has compacted during corrosion or the subsequent supercritical CO 2 drying process. Our results confirm the utility of performing non-destructive SE measurements on corroded glass surfaces.

36 MATERIALS SCIENCE↗

Effect of vanadium oxide addition on thermomechanical behaviors of borosilicate glasses: Toward development of high crack resistant glasses for nuclear waste disposal

The effect of of V2O5 additions (up to 8 mol%) on the physical properties (e.g., density, glass transition temperature and refractive indices) and mechanical behaviors (e.g., hardness, fracture toughness, elastic modulus) of a soda-lime borosilicate glass with a composition of 60.2SiO(2)-16.0B(2)O(3)-12.6Na(2)O-3.8Al(2)O(3)-5.7CaO-1.7ZrO(2) (mol%) have been investigated systematically. It was found that introducing V2O5 decreases the glass transition temperature and hardness while increases the refractive index and crack initiation load. Composition-property relationships, especially on mechanical properties, were examined in order to provide insights for the development of new glass materials with outstanding mechanical properties. The results show that V2O5 can be a glass component for engineering and insuring high crack resistant glasses and glasses with long-term stability. Additionally, elastic properties as a function of temperature were studied using Brillouin light scattering and temperature-independent elastic moduli behaviors were observed.

Lu, Xiaonan↗

The HITRAN2016 molecular spectroscopic database

This paper describes the contents of the 2016 edition of the HITRAN molecular spectroscopic compilation. The new edition replaces the previous HITRAN edition of 2012 and its updates during the intervening years. The HITRAN molecular absorption compilation is comprised of five major components: the traditional line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, infrared absorption cross-sections for molecules not yet amenable to representation in a line-by-line form, collision-induced absorption data, aerosol indices of refraction, and general tables such as partition sums that apply globally to the data. The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additional absorption phenomena, added line-shape formalisms, and validity. Moreover, molecules, isotopologues, and perturbing gases have been added that address the issues of atmospheres beyond the Earth. Of considerable note, experimental IR cross-sections for almost 200 additional significant molecules have been added to the database.

Gordon, I. E.↗

Optical properties and radiative forcing of fractal-like tar ball aggregates from biomass burning

Tar balls are frequently found in slightly aged biomass burning plumes. They are spherical in shape, have diameters between ~100 and 300 nm, are amorphous and composed mostly of oxygen and carbon. Tar balls are light absorbing and considered to be a component of brown carbon. Tar balls have been typically reported and analyzed as individual spheres; however, in a recent study, we reported the presence of significant fractions of fractal-like tar ball aggregates in fire plumes from different geographical locations. Aggregation affects the optical properties of particles; therefore, we use T-Matrix and Lorenz-Mie simulations to explore the effects of aggregation on the tar balls’ optical properties in the 350 – 1150 nm wavelength range. We also evaluate the effects of different index of refraction values available from the literature, different monomer numbers, and monomer sizes, as these are key factors determining the aggregates optical properties. Furthermore, we estimate the direct radiative forcing for low and high surface albedos. The single scattering albedo of aggregates exceed by up to 77% that of individual tar balls. The hemispherical upscatter fraction of tar ball aggregates are more than 100% larger than for individual tar balls in many cases. The top of the atmosphere simple forcing efficiency over dark surfaces shows large variabilities with differences up to ~53% between the tar ball aggregates and individual tar balls. These results demonstrate that aggregation of tar balls can have a significant impact on their optical properties and radiative forcing.

Tar balls, aggregates, brown carbon, biomass burni↗

Light scattering study of highly absorptive, non-fractal, hematite aggregates

In this paper, we present measurements of the scattered light intensity by aerosolized hematite aggregate particles. The measurements were made at a wavelength of 532 nm in the scattering angle range from 0.32° to 157°. Hematite has high values of the real and imaginary parts of the refractive index m = n + iκ = 3 + i0.5 at the studied wavelength. Scanning electron micrographs (SEM) indicated that the particles were aggregates whereas the optical microscope pictures showed that the aerosol had a bimodal distribution with effective mean diameters of roughly 1 and 10 µm. This is consistent with the light scattering results which displayed two Guinier regimes. The aggregates were composed of smaller grains with an approximate size of 200 nm. Ultra Small-Angle X-ray Scattering (USAXS) indicate that the aggregates were uniform and non-fractal. Mie calculations for a sphere equivalent to the aggregate size were compared to the experimentally observed results. The observed results showed an enhanced backscattering, whereas the Mie calculations did not due to the large imaginary part of the refractive index. Hematite aggregates were simulated by assuming they were composed of spherical monomers inside a spherical volume. Then the light scattering was calculated using the T-matrix method for these simulated aggregates. The calculated results show an enhanced backscattering. We present a dimensional analysis to estimate the extent of multiple scattering within the aggregate and find a correlation between the average number of scattering events within the aggregate and the enhancement in the backscattering.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Preparation and characterization of SiO₂:Sm³⁺ nanotube arrays with 1.06 μm laser antireflective property

SiO₂: Sm³⁺ nanotube arrays with excellent antireflective property at 1.06 μm were synthesized by a template-assisted sol–gel process. The molecular structure, morphology and optical properties of the fabricated SiO₂:Sm³⁺ nanotube arrays were investigated by a Fourier transform infrared spectroscope (FTIR), a Scanning electron microscope (SEM), and a spectro-fluorometer, respectively. The experimental results demonstrate that the SiO₂:Sm³⁺ nanotube arrays were formed via the AAO membrane during the sol–gel process. The remarkable antireflective characteristic of about 0.166% at 1.06 μm was attributed to the drastic decrease of effective refraction index which enhances the matching effect between air and substrate. As well as the absorption performance of Sm³⁺ at 1.06 μm which consumes the energies of incident light. - Graphical abstract: Directional aligned SiO₂:Sm³⁺ nanotube arrays were synthesized in AAO template by sol–gel process, and the antiflective performance of arrays is prominent comparing to the blank AAO template. Highlights: • SiO₂:Sm³⁺ nanotube arrays are synthesized by a template-assisted sol–gel process. • SiO₂:Sm³⁺ nanotube arrays have remarkable antireflective properties at 1.06 μm. • The subwavelength structure results in a decrease of effective refraction index. • The absorption performance of Sm³⁺ at 1.06 μm consume the energies of incident light.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First-principles studies of the structural, electronic, and optical properties of a novel thorium compound Rb{sub 2}Th{sub 7}Se{sub 15}

The structural, electronic, and optical properties of a recently synthesized thorium compound Rb{sub 2}Th{sub 7}Se{sub 15} have been calculated in the density functional theory framework for the first time. The calculated direct band gap was 1.471 eV (generalized gradient approximation) and 1.171 eV (local density approximation), with both results being close to the experimental result of 1.83 eV. High covalency/iconicity of the Th–Se/Rb–Se bonds was demonstrated by calculating effective Mulliken charges of all ions. The polarized calculations of the complex dielectric function are presented; dependence of the calculated index of refraction was fitted to the Sellmeyer equation in the wavelength range from 500 to 2500 nm. - Graphical abstract: Calculated band structure of Rb{sub 2}Th{sub 7}Se{sub 15}. - Highlights: • The first theoretical analysis of the Rb{sub 2}Th{sub 7}Se{sub 15} properties is reported. • Structural, electronic and optical properties of Rb{sub 2}Th{sub 7}Se{sub 15} were calculated. • An indirect character of Rb{sub 2}Th{sub 7}Se{sub 15} band gap was confirmed. • Dependence of the refractive index on the wavelength was calculated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The influence of Cd doping on the microstructure and optical properties of nanocrystalline copper ferrite thin films

Highlights: ► The structural and optical properties of Cu{sub 1−x}Cd{sub x}Fe{sub 2}O{sub 4} thin films were studied. ► The micro structural parameters of the films have been determined. ► The room temperature reflectance and transmittance data are analyzed. ► The refractive index and energy gap are determined. ► The single oscillator parameters were calculated. - Abstract: Nanocrystalline thin films of mixed Cu–Cd ferrites, Cu{sub 1−x}Cd{sub x}Fe{sub 2}O{sub 4} (x = 0, 0.2, 0.3, 0.5, 0.7, 0.8, 0.9 and 1), were deposited by electron beam evaporation technique. The films were annealed at 450 °C for 1 h. The effect of Cd doping on the structural and optical properties of the deposited films has been investigated by using X-ray diffraction (XRD) and optical spectrophotometry. XRD patterns of the annealed films show spinal cubic structure. The lattice parameter was found to increase with the increase of cadmium concentration. The crystallite size of the films was found to vary from 8 nm to 30 nm. The optical transition was found to be direct and indirect transitions with energy gaps decrease from 2.466 (x = 0) to 2.00 (x = 1) eV and from 2.148 (x = 0) to 1.824 (x = 1) eV, respectively. The refractive index dispersion of the films was found to increase with Cd content and discussed in terms of the Wemple–DiDomenico single oscillator model.

36 MATERIALS SCIENCE↗

Introducing single-crystal scattering and optical potentials into MCNPX: Predicting neutron emission from a convoluted moderator

Neutron transport simulation codes are an indispensable tool used for the design and construction of modern neutron scattering facilities and instrumentation. It has become increasingly clear that some neutron instrumentation has started to exploit physics that is not well-modelled by the existing codes. Particularly, the transport of neutrons through single crystals and across interfaces in MCNP(X), Geant4 and other codes ignores scattering from oriented crystals and refractive effects, and yet these are essential ingredients for the performance of monochromators and ultra-cold neutron transport respectively (to mention but two examples). In light of these developments, we have extended the MCNPX code to include a single-crystal neutron scattering model and neutron reflection/refraction physics. Furthermore, we have also generated silicon scattering kernels for single crystals of definable orientation with respect to an incoming neutron beam. As a first test of these new tools, we have chosen to model the recently developed convoluted moderator concept, in which a moderating material is interleaved with layers of perfect crystals to provide an exit path for neutrons moderated to energies below the crystal s Bragg cut off at locations deep within the moderator. Studies of simple cylindrical convoluted moderator systems of 100 mm diameter and composed of polyethylene and single crystal silicon were performed with the upgraded MCNPX code and reproduced the magnitude of effects seen in experiments compared to homogeneous moderator systems. Applying different material properties for refraction and reflection, and by replacing the silicon in the models with voids, we show that the emission enhancements seen in recent experiments are primarily caused by the transparency of the silicon/void layers. Finally the convoluted moderator experiments described by Iverson et al. were simulated and we find satisfactory agreement between the measurement and the results of simulations performed using the tools we have developed.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Optical properties of a nanostructured glass-based film using spectroscopic ellipsometry

Nanostructured glass films, which are fabricated using spinodally phase-separated low-alkali glasses, have several interesting and useful characteristics, including being robust, non-wetting and antireflective. Spectroscopic ellipsometry measurements have been performed on one such film and its optical properties were analyzed using a 5-layer structural model of the near-surface region. Since the glass and the film are transparent over the spectral region of the measurement, the Sellmeier model is used to parameterize the dispersion in the refractive index. To simulate the variation of the optical properties of the film over the spot size of the ellipsometer (~ 3 × 5 mm), the Sellmeier amplitude is convoluted using a Gaussian distribution. The transition layers between the ambient and the film and between the film and the substrate are modeled as graded layers, where the refractive index varies as a function of depth. These layers are modeled using a two-component Bruggeman effective medium approximation where the two components are the layer above and the layer below. Lastly, the fraction is continuous through the transition layer and is modelled using the incomplete beta function.

36 MATERIALS SCIENCE↗

Richtmyer–Meshkov instability when a shock is reflected for fluids with arbitrary equation of state

First predicted by Richtmyer in 1960 and experimentally confirmed by Meshkov in 1969, the Richtmyer–Meshkov instability (RMI) is crucial in fields such as physics, astrophysics, inertial confinement fusion and high-energy-density physics. These disciplines often deal with strong shocks moving through condensed materials or high-pressure plasmas that exhibit non-ideal equations of state (EoS), thus requiring theoretical models with realistic fluid EoS for accurate RMI simulations. Approximate formulae for asymptotic growth rates, like those proposed by Richtmyer, are helpful but rely on heuristic prescriptions for compressible materials. These prescriptions can sometimes approximate the RMI growth rate well, but their accuracy remains uncertain without exact solutions, as the fully compressible RMI growth rate is influenced by both vorticity deposited during shock refraction and multiple sonic wave refractions. This study advances previous work by presenting an analytic, fully compressible theory of RMI for reflected shocks with arbitrary EoS. It compares theoretical predictions with heuristic prescriptions using ideal gas, van der Waals gas and three-term constitutive equations for simple metals, the latter being analysed with detailed and simplified ideal-gas-like EoS. We additionally offer an alternative explicit approximate formula for the asymptotic growth rate. The comprehensive model also incorporates the effects of constant-amplitude acoustic waves at the interface, associated with the D'yakov–Kontorovich instability in shocks.

Napieralski, Mario (ORCID:0009000692344901)↗

The Influence of Nonlocal Metal–Dielectric Environments on Physical and Chemical Processes

Plasmonic nanolayers and laminar metallic/dielectric multilayers were originally developed for optical cloaking applications and lensing applications that could potentially image objects whose size was below the diffraction limit. These assemblies were initially formed from gold or silver nanorods grown within an alumina mesh. However, more recently, assemblies with similar properties have also been prepared by sequential thin-layer deposition of alternating layers of gold and magnesium fluoride (MgF 2 ). These metal/dielectric composite materials enable control of the dielectric constant in the directions perpendicular to the layers and balance the real and imaginary dielectric constants of the assembly such that the speed and the amplitude of the waves traveling through the assembly are not attenuated. In this Account, we will also focus on a few of the applications ranging from surface wetting to fluorescence quenching to enhancement of photochemical reactions. First, we will share an introduction to processes used to create these materials, which are combinations of low refractive index metals and transparent higher index materials arranged in a scalable repeating fashion. Two fabrication methods were employed: an electrochemical deposition of Ag nanorods into an anodized alumina matrix which produced materials with an anisotropic negative refractive index material within the plane of the film and lamellar metal/dielectric layers in which the negative index perpendicular to the growth direction. These alternating layers of plasmonic metals and dielectric materials were ultimately chosen to prepare films for further testing, because of their relative ease of fabrication. We will continue with a discussion of a few of the applications of both of these nonlocal dielectric composite materials including more specialized plasmonic, composite, and hyperbolic metamaterials including fluorescence quenching, photochemical reactions, and surface wetting. In each of these applications, the unique response caused by the enhancement of the electric field and the interface between hyperbolic materials and plasmonic materials as they interact photophysically with their near neighbors is presented. In each of the applications, the enhanced electric field extends from the composite substrate layer to interact with its near neighbors and beyond. Furthermore, the presence of this extended interaction can be observed in the form of decreased emission lifetime, enhancement of photochemical reaction rates, and changes in the surface energies measured by contact angle goniometry. In this Account, all of these situations will be addressed. Finally, we will conclude with a summary and vision for the future as well as a discussion of the unique challenges and opportunities available as research active faculty at an HBCU.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dual-Responsive Reversible Plasmonic Behavior of Core–Shell Nanostructures with pH-Sensitive and Electroactive Polymer Shells

In this paper, we report novel dual-responsive plasmonic core–shell anisotropic nanostructures composed of gold nanorod (AuNR) and responsive polyaniline (PANI) shells with plasmonic mode appearance reversibly modulated through orthogonal stimuli (i.e., electrical potential and pH change). In this system, the PANI shells provide AuNR cores with three different refractive index environments depending on stimuli (pH and electrical potential). Therefore, no additional secondary responsive component is necessary to induce the dual-responsive properties of AuNR cores. Furthermore, in this study, dual-responsive properties can be realized for nanostructures fixed on substrates, whereas previously reported dual-responsive plasmonic systems can only be controlled in solution. Here, the highest localized surface plasmonic resonance (LSPR) shift of the AuNR cores can be induced by changing both local pH and applying electric potential. Notably, a significant plasmon band shift by 107 nm is realized with only 8 nm thick PANI shell due to the large refractive index change at the gold–polymer interface. A maximum shift of the longitudinal plasmon mode of 149 nm is obtained by applying a modest electrical potential (below ±1 V), a large shift rarely reported in the literature for metal nanostructures. Moreover, our anisotropic core/shell nanostructures exhibit stable and reversible dual-responsive LSPR behavior over 100 cycles without degradation.

36 MATERIALS SCIENCE↗

Optical Properties of Individual Tar Balls in the Free Troposphere

Tar balls are brown carbonaceous particles, highly viscous, spherical, amorphous, and light absorbing. They are believed to form in biomass burning smoke plumes during transport in the troposphere. Tar balls are believed to have a significant impact on the Earth’s radiative balance, but due to poorly characterized optical properties, this impact is highly uncertain. Here, we investigate the chemical composition and optical properties of individual tar balls transported in the free troposphere to the Climate Observatory “Ottavio Vittori” on Mt. Cimone, Italy (2165 meters above sea level) using multi-modal micro-spectroscopy. Our results show that tar balls contributed 50% of carbonaceous particles by number in the size range from 0.25 to 1.8 µm. Of those tar balls, 16% were inhomogeneously mixed with other constituents. Using electron energy loss spectroscopy, we retrieved the complex refractive index from 200 to 1200 nm for both inhomogeneously and homogeneously mixed tar balls. We found no significant difference in the average refractive index of inhomogeneously and homogenously mixed tar balls (1.40 - 0.03i, and 1.36 - 0.03i at 550 nm, respectively). Furthermore, we estimated the top of the atmosphere radiative forcing using the Santa Barbara DISORT Atmospheric Radiative Transfer model (SBDART) and found that a layer of only tar balls with an optical depth of 0.1 above vegetation would exert a positive radiative forcing ranging from 2.8 Wm-2 (on a clear sky day) to 9.5 Wm-2 (when clouds are below the aerosol layer). In conclusion, understanding the optical properties of tar balls can help reduce uncertainties associated with the contribution of biomass-burning aerosol in current climate models.

54 ENVIRONMENTAL SCIENCES↗

Solvent and Temperature Effects on Photoinduced Proton-Coupled Electron Transfer in the Marcus Inverted Region

Concerted proton-coupled electron transfer (PCET) in the Marcus inverted region was recently demonstrated. Understanding the requirements for such reactivity is fundamentally important and holds promise as a design principle for solar energy conversion systems. Herein, we investigate the solvent polarity and temperature dependence of photoinduced proton-coupled charge separation (CS) and charge recombination (CR) in anthracene–phenol–pyridine triads: 1 (10-(4-hydroxy-3-(4-methylpyridin-2-yl)benzyl)anthracene-9-carbonitrile) and 2 (10-(4-hydroxy-3-(4-methoxypyridin-2-yl)benzyl)anthracene-9-carbonitrile). Both the CS and CR rate constants increased with increasing polarity in acetonitrile:n-butyronitrile mixtures. The kinetics were semi-quantitatively analyzed where changes in dielectric and refractive index, and thus consequently changes in driving force (–ΔG°) and reorganization energy (λ), were accounted for. The results were further validated by fitting the temperature dependence, from 180 to 298 K, in n-butyronitrile. The analyses support previous computational work where transitions to proton vibrational excited states dominate the CR reaction with a distinct activation free energy (ΔG* CR ~ 140 meV). However, the solvent continuum model fails to accurately describe the changes in ΔG° and λ with temperature via changes in dielectric constant and refractive index. Satisfactory modeling was obtained using the results of a molecular solvent model, which predicts that λ decreases with temperature, opposite to that of the continuum model. To further assess the solvent polarity control in the inverted region, the reactions were studied in toluene. Nonpolar solvents decrease both ΔG° CR and λ, slowing CR into the nanosecond time regime for 2 in toluene at 298 K. This demonstrates how PCET in the inverted region may be controlled to potentially use proton-coupled CS states for efficient solar fuel production and photoredox catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Continuous Structural Transition in Glass-Forming Molten Titanate BaTi 2 O 5

The structure of the model titanate glass former BaTi2O5 has been studied over a wide temperature (T) range in the molten, supercooled, and glassy states under conditions of aerodynamic levitation. Both high-energy X-ray diffraction and Ti K-edge X-ray absorption spectroscopy reveal a continuous structural transition involving reduction of the cation-oxygen (and oxygen-cation) average coordination numbers and bond lengths with increasing T. Ti-0 coordination in the moderately supercooled and equilibrium melt follows a linear trend n(Tio) = 5.4(1)- [3.5(7) x 10(-4)]T [K] (1300 <= T <= 1830 K, T-g = 960 K, T-m = 1660 K). Comparison to the melt-quenched glass implies an increase in partial derivative n(Tio)/partial derivative T at lower T, as T-g is approached from above. Both Ba-0 coordination and bond length also decrease at higher T, and the role of Ba addition is to reduce n(Tio) below its value in pure molten TiO2, which is related to the presence of density maxima in molten BaO-TiO2. Density measurements made by imaging of the levitated melt yielded rho(T) = 4.82(55)- 0.0004(3)T in units of K and g cm(-3). While BaTi2O5 glass likely consists of a fully connected Ti-0 network, free of nonbridging oxygen (NBO) [OTi1 and with at least 13(4)% [OTi3] triclusters, the 1835(40) K equilibrium melt contains at least 10(4)% NBO along with 90(4)% bridging oxygen [OTi2]. The results highlight the fact that glasses can be considered as structural analogues of melts only for those melts deeply supercooled into the glass transition region. The results imply possible fictive T dependence of titanate glass structure, suggesting applications as, e.g., laser written waveguides with large refractive indices and refractive index contrasts. The temperature-dependent structure further implies a super-Arrhenian melt viscosity with consequences for glass manufacture, titanate-rich slags produced in iron smelting, TiO2-bearing magmas, and by analogy silicate melts at high pressures, as found in planetary interiors.

36 MATERIALS SCIENCE↗