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At least 487 records · Page 27

Effect of Pb content and solution concentration of Pb{sub x}TiO{sub 3} seed layer on (100)-texture and ferroelectric/dielectric behavior of PZT (52/48) thin films

The effect of Pb content and solution concentration of lead titanate (Pb{sub x}TiO{sub 3}) seed layer on the texture and electric properties of Pb{sub 1.1}(Zr{sub 0.52},Ti{sub 0.48})O{sub 3} (PZT) thin films was investigated. A variety of seed layers (y Pb{sub x}TiO{sub 3}) with varying solution concentration (y = 0.02, 0.05, 0.1, and 0.2 M) and Pb content (x = 1.0, 1.05, 1.1, and 1.2) was deposited on Pt/TiO{sub 2}/SiO{sub 2}/Si substrates using chemical-solution deposition method. PZT films were then deposited on these seed layers using the same process. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy investigations of the seed layers confirm change in crystal structure with variation in the solution properties. XRD studies of PZT films deposited on seed layers demonstrate that the seed layer helps in enhancing (100)-texture and suppressing (111)-texture. It was observed that PZT films prepared on seed layers with lower solution concentrations results in highly (100)-textured films, which further helps to improve the electric properties. The polarization and dielectric constant of the PZT films were seen to increase while the coercive field decreased with increase in (100)-texture. Irrespective of the seed layer solution concentration, higher Pb content in the seed layer deteriorates the PZT film properties. Ninety-five percent to ninety-six percent (100)-texture was obtained from thin PZT films deposited on seed layers of 0.02 M solution concentration with 1.05 and 1.10 Pb contents, which is higher than the values reported for thick PZT films. Optimization of both Pb content and solution concentration of the seed layer is a promising route to achieve highly (100)-textured PZT films with improved electric properties.

36 MATERIALS SCIENCE↗

Operando Measurements of Electrolyte Li-ion Concentration during fast charging with FTIR/ATR

The ability to charge a Li-ion battery at high charging rates is critical for electric vehicle adoption; however, further study of ion transport is required to develop electrolytes suitable for fast charge. Fourier transform infrared spectroscopy (FTIR) used with attenuated total reflection (ATR) enables operando measurements of liquid electrolytes. This research focused on solvation shifting of solvent infrared absorption bands in the presence of lithium ions. Lithium-shifted infrared absorption bands and non-shifted bands of ethyl methyl carbonate (EMC) and ethylene carbonate (EC) were compared to infer ion concentration changes during cycling. Lithium concentrations were calibrated using EC/EMC/LiPF 6 electrolytes with known lithium concentrations. A Li-ion half-cell with a graphite anode and EC/EMC/LiPF 6 electrolyte was observed with FTIR/ATR. The results showed that the magnitude of lithium concentration changes increased with increasing C-rate. During a galvanostatic intermittent titration technique (GITT) test, changes in lithium concentration could be observed. During intercalation, a lithium depletion occurred when a negative current was applied, and a lithium surplus occurred during deintercalation when a positive current was applied. The capability of observing lithium concentration has significant implications for the utility of operando studies and the potential to link lithium movement to battery performance.

25 ENERGY STORAGE↗

Comparing Theoretical Salt Concentration Profiles in a Polymer Electrolyte with Experimental Measurements using Operando Raman Spectroscopy

Concentrated solution theory has furthered our understanding of ion transport in electrolytes. This theory can be used to predict salt concentration profiles under an applied current if the transport properties of the electrolyte (conductivity ( κ ), restricted diffusion coefficient ( D ), and the cation transference number with respect to the solvent velocity ( t + 0 )), and the thermodynamic factor ( T f ) are known. In this work, we provide the first study comparing the predicted salt concentration profiles with measurements based on operando Raman spectroscopy. Concentration polarization is asymmetrical; the increase in salt concentration near the positive electrode is a factor of two greater than the decrease in salt concentration near the negative electrode. We find qualitative agreement between theory and experiment. Further work is needed to resolve the quantitative differences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantitative Imaging and In Situ Concentration Measurements of Quantum Dot Nanomaterials in Variably Saturated Porous Media

Knowledge of the fate and transport of nanoparticles in the subsurface environment is limited, as techniques to monitor and visualize the transport and distribution of nanoparticles in porous media and measure their in situ concentrations are lacking. To address these issues, we have developed a light transmission and fluorescence method to visualize and measure in situ concentrations of quantum dot (QD) nanoparticles in variably saturated environments. Calibration cells filled with sand as porous medium and various known water saturation levels and QD concentrations were prepared. By measuring the intensity of the light transmitted through porous media exposed to fluorescent light and by measuring the hue of the light emitted by the QDs under UV light exposure, we obtained simultaneously in situ measurements of water saturation and QD nanoparticle concentrations with high spatial and temporal resolutions. Water saturation was directly proportional to the light intensity. A linear relationship was observed between hue-intensity ratio values and QD concentrations for constant water saturation levels. The advantages and limitations of the light transmission and fluorescence method as well as its implications for visualizing and measuring in situ concentrations of QDs nanoparticles in the subsurface environment are discussed.

36 MATERIALS SCIENCE↗

Charged Species Concentration in Combusting Mixtures Using Equilibrium Chemistry

Ionization in flames is of interest in the design and development of modern combustion devices. The identity and concentration of various charged species in reacting mixtures can play an important role in the diagnostics and control of such devices. Simplified chemistry computations that provide good estimates of ionic species in complex flow-fields can be used to model turbulent reacting flows in various combustion devices, greatly reducing the required computational resources for design and development studies. A critical assessment of the use of the equilibrium chemistry method to compute charged species concentration in combusting mixtures under various temperatures, pressures, and thermal disequilibrium conditions is presented. The use of equilibrium chemistry to compute charged species concentrations in propane-air mixtures performed by Calcote and King has been extended. A more accurate computational methodology that includes the effect of negative ions, chemi-ions (H 3 O + and CHO + ), and thermal nonequilibrium was investigated to evaluate the suitability of equilibrium computations for estimating charged species concentrations in reacting mixtures. The results show that equilibrium computations which include the effects of H 3 O + and elevated electron temperatures can indeed explain the levels of ion concentrations observed in laboratory flame experiments under lean and near-stoichiometric conditions. Furthermore, under engine-like conditions at higher temperatures and pressures, equilibrium computations can be used to obtain useful estimates of charged species concentrations in modern combustion devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Indications of a Decrease in the Depth of Deep Convective Cores with Increasing Aerosol Concentration during the CACTI Campaign

Abstract An aerosol indirect effect on deep convective cores (DCCs), by which increasing aerosol concentration increases cloud-top height via enhanced latent heating and updraft velocity, has been proposed in many studies. However, the magnitude of this effect remains uncertain due to aerosol measurement limitations, modulation of the effect by meteorological conditions, and difficulties untangling meteorological and aerosol effects on DCCs. The Cloud, Aerosol, and Complex Terrain Interactions (CACTI) campaign in 2018–19 produced concentrated aerosol and cloud observations in a location with frequent DCCs, providing an opportunity to examine the proposed aerosol indirect effect on DCC depth in a rigorous and robust manner. For periods throughout the campaign with well-mixed boundary layers, we analyze relationships that exist between aerosol variables (condensation nuclei concentration > 10 nm, 0.4% cloud condensation nuclei concentration, 55–1000-nm aerosol concentration, and aerosol optical depth) and meteorological variables [level of neutral buoyancy (LNB), convective available potential energy, midlevel relative humidity, and deep-layer vertical wind shear] with the maximum radar-echo-top height and cloud-top temperature (CTT) of DCCs. Meteorological variables such as LNB and deep-layer shear are strongly correlated with DCC depth. LNB is also highly correlated with three of the aerosol variables. After accounting for meteorological correlations, increasing values of the aerosol variables [with the exception of one formulation of aerosol optical depth (AOD)] are generally correlated at a statistically significant level with a warmer CTT of DCCs. Therefore, for the study region and period considered, increasing aerosol concentration is mostly associated with a decrease in DCC depth.

54 ENVIRONMENTAL SCIENCES↗

Fundamental and practical limits of planar tracking solar concentrators

Planar microtracking provides an alternate paradigm for solar concentration that offers the possibility of realizing high-efficiency embedded concentrating photovoltaic systems in the form factor of standard photovoltaic panels. Here, we investigate the thermodynamic limit of planar tracking optical concentrators and establish that they can, in principal, achieve the sine limit of their orientationally-tracked counterparts provided that the receiver translates a minimum distance set by the field of view half-angle. We develop a phase space methodology to optimize practical planar tracking concentrators and apply it to the design of a two surface, catadioptric system that operates with > 90% optical efficiency over a 140° field of view at geometric gains exceeding 1000×. These results provide a reference point for subsequent developments in the field and indicate that planar microtracking can achieve the high optical concentration ratio required in commercial concentrating photovoltaic systems.

47 OTHER INSTRUMENTATION↗

DECONTAMINATION FACTORS AND FILTRATION FLUX IMPACT TO ARP AT REDUCED MST CONCENTRATION

Tank Farm and Closure Engineering is evaluating changes to the Actinide Removal Process facility operations to decrease the MST concentration from 0.4 g/L to 0.2 g/L and the contact time from 12 hours to between 6 and 8 hours. For this evaluation, SRNL reviewed previous datasets investigating the performance of MST at 0.2 g/L in salt solutions ranging from 4.5 to 7.5 M in sodium concentration. In general, reducing the MST concentration from 0.4 to 0.2 g/L and increasing the ionic strength from 4.5 to 7.5 M in sodium concentration will decrease the measured decontamination factors for plutonium, neptunium, uranium and strontium. The decontamination factors as well as single standard deviation values for each sorbate are reported. These values are applicable within the sorbate and sodium concentrations used in the experimental measurements. Decreasing the MST concentration in the ARP from 0.4 g/L to 0.2 g/L will produce an increase in the filter flux, and could lead to longer operating times between filter cleaning. The increase in flux is a function of a number of operating parameters, and is difficult to quantify. However, it is estimated that the reduction in MST could result in a reduction of filtration time of up to 20%.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The Concentration of Depleted Uranium (DU) and Beryllium (Be) in Soil and Air on Illeginni Island at Kwajalein Atoll after an AHW Flight Test

An Advanced Hypersonic Weapon (AHW) flight test vehicle impacted on the tarmac surrounding the helipad on Illeginni Island. The exposed soil in the berm created by the impact was analyzed for both U and Be. The U concentration in the berm soil is the average concentration for U as observed in the coral soil in the Marshall Islands and other atolls around the world (about 1.9 µg g -­1 ). The Be concentration in the soil was less than O.003 µg g -­1 . The mean concentration of U in 14 samples collected around the tarmac at 1 meter distance from the tarmac is 22 µg g -1 that is far below the US EPA guidance for U in residential soil of 230 µg g -­1 . Similarly, the mean Be concentration in the 14 samples is 2.1 µg g -­1 that again is far below the USEPA guidance of 160 µg g -­1 for residential soil. The concentration of both U and Be in air are many orders of magnitude below the USEPA guidance for the general public.

42 ENGINEERING↗

Gamma Detector Response/Soil Concentration Correlation Study at the AAR Manufacturing, Inc. Site, Livonia, Michigan

At the NRC's request, ORAU conducted surveys of the AAR Manufacturing site during the period of September 25 through September 27, 2012. The survey activities included walkover surveys and sampling activities. Once the survey team was onsite, the NRC personnel decided to forgo survey activities in the New Addition and the pickling area. Areas of the planned study boundary were inaccessible due to overgrowth/large pieces of concrete covering the soil surface; therefore, the study boundary was redefined. Gamma walkover scans of the site boundary and front yard identified multiple areas of elevated gamma radiation. As a result, two judgmental samples were collected. Sample results were above thorium background levels The answer to the PSQ relating to the relationship between thorium concentration in soil and NaI instrument response is Yes. NaI instrument response can be used as a predictor of Th-232 concentration in the 0 to 1 m layer. An R2 value of 0.79 was determined for the surface soil relationship, thus satisfying the DQOs. Moreover, the regression was cross-checked by comparing the predicted Th-232 soil core concentration to the average Th-232 concentration (Section 5.3.2). Based on the cross-check, the regression equation provides a reasonable estimate for the Th-232 concentration at the judgmental locations. Consideration must be given when applying this equation to other soil areas of the site. If the contamination was heterogeneously distributed, and not distributed in a discrete layer as it was in the study area, then using the regression equation to predict Th-232 concentration would not be applicable.

54 ENVIRONMENTAL SCIENCES↗

Plant-Scale Concentration Column Designs for SHINE Target Solution

Argonne is assisting Morgridge Institute for Research (MIR) in their efforts to develop SHINE, an accelerator-driven process that will utilize a uranyl-sulfate solution for the production of fission product Mo-99. An integral part of the process is the development of a column for the separation and recovery of Mo-99 followed by a concentration column to reduce the product volume from 15–25 L to less than 1 L. Argonne has collected data from batch studies and breakthrough column experiments to utilize the VERSE (Versatile Reaction Separation) simulation program (Purdue University) to design plant-scale product concentration processes. Plant-scale columns for 2, 4, and 6 hr loading times were designed for separation of Mo-99 from 130 g-U/L uranyl-sulfate solution. The Mo-99 product solution volumes from the recovery of Mo-99 from 260 L of uranyl sulfate are 23.5, 17.6, and 14.5 L for the 2, 4, and 6 hr loadings, respectively; the resulting Mo concentration in 0.1-M NaOH is 2.34 × 10 -2 , 3.13 × 10 -2 , and 3.81 × 10 -2 mM, respectively. The resulting product can be acidified to pH 2 using nitric acid and passed through a concentration column to reduce volume to less than 1 L. Concentration column designs have been generated for each of the three process scenarios (2, 4, and 6 hr). The plant-scale concentration column designs assume loading temperature of 80°C.

Stepinski, Dominique C.↗

Maximum Concentration Values Review for Use in NUCON Vapor Abatement Unit Testing

Exponent has recommended that “high inlet spike” concentrations be verified for accuracy regarding their representation of the maximum measured headspace concentrations for tanks at Hanford. Exponent further recommended that “high inlet spike” concentrations of chemicals of potential concern (COPCs) be inclusive of surrogate COPCs. In the initial analysis (Rev. A Test Plan), only analytical results from the Site-Wide Industrial Hygiene Database (SWIHD) were used. The reason for this initial decision was a concern about Washington River Protection Solutions (WRPS) taking responsibility for results that were not produced during their contract tenure. As a result of Exponent’s comments, WRPS verified the “high inlet spike” values for accuracy against the data for single-shell tanks in all the historical databases, not only SWIHD. Measurements made prior to interim waste stabilization or waste retrieval were not considered in the verification of maximum measured concentrations as they are not representative of current tank farm conditions. Data for surrogate COPCs were also considered in determining the “high inlet spike” concentrations. Table S.1 shows the newly evaluated concentrations (COPC and surrogate). The original and revised test conditions are also shown with changes indicated by red text.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Recovery of Mo in LEU-Modified Cintichem Process at Elevated Mo Concentrations

Argonne National Laboratory with support from DOE’s National Nuclear Security Administration Office of Material Management & Minimization (M 3 ) is helping SHINE Medical Technologies in developing domestic production of Mo-99. SHINE is planning to produce Mo-99 by fission of low enriched uranium-235 (LEU) in a subcritical aqueous solution using accelerator-based neutron generation. SHINE’s subcritical system can contain ~250L of LEU solution that is processed through a recovery titania-based column to recover Mo, while the remaining LEU solution can be available for another irradiation. The Mo-containing solution is then fed into another titania-based concentration column to further concentrate the solution to allow for the final purification step using the LEU modified Cintichem (LMC) process. The LMC process is a relatively small-scale process that was designed to work with 50mL volumes. By concentrating the Mo solution that feeds into the LMC process from ~250L to ~50mL, the actual chemical concentration of Mo becomes important. It is estimated that up to ~15mM Mo concentration could be present in the LMC feed. Since the LMC process was originally proposed for purification of Mo after dissolution of irradiated U solid targets, the chemical concentration of Mo was not a concern, due to presence of only trace amounts of Mo.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Calculation of Glycolate Concentration Factors Across the 242-25H (3H) Evaporator System

Two models were developed to predict glycolate concentration factors across the 242-25H (3H) Evaporator system. The first model, identified as the Unrestricted Evaporation Model, was designed to evaluate concentration of typical 3H feed material to relatively high densities in order to calculate the concentration factor of glycolate in a given feed stream. This model may be used to understand the potential of glycolate to concentrate from a generic feed material through the 3H system. The second model, identified as the Holistic Evaporation Model, was designed to evaluate the evaporation of dilute, glycolate-containing Defense Waste Processing Facility (DWPF) waste with the requirement that high silicon concentrations typical of recycle material require dilution to adhere to current technical safety requirements. This model may be used to understand the potential of glycolate from DWPF recycle material to concentrate as a result of feeding through the 3H system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating a Semi-Quantitative, Spectrophotometric Method for the Rapid Determination of Total Rare Earth Element Concentrations in Citrate Leaching Solutions

Quick, reliable methods to measure the rare earth elements (REEs) in process streams are needed to support real-time parameterization and monitoring for a burgeoning number of REE extraction schemes. Such methods would ideally be fast, reproducible, and field-deployable. This study evaluates the feasibility of using a chromogenic indicator, arsenazo(III) (hereafter abbreviated as Arsz(III)) to detect the concentration of REEs in complex citrate leaching solutions using a spectrophotometer. Arsz(III) forms a chromogenic complex with the lanthanide elements that produces a blue/purple color detectable in the visible light range. Matrices of solutions containing varied concentrations of calcium, iron, and lanthanum were scanned in the presence of an Arsz(III) indicator to generate a modeled relationship that could be used to back calculate REE concentrations. While relatively quick (scan times on the order of seconds), the results indicated that the calcium and iron concentrations of typical mining solutions overwhelm the signal of the REEs, to the extent that sensitivity of the method is no less than 50 µM REEs. These results demonstrate the difficulties of accurately measuring trace metals in complex solutions, although the method may still hold utility for processes with significantly lower calcium and iron concentrations or REE concentrations much greater than 50 µM.

36 MATERIALS SCIENCE↗

Retrieved Number Concentration of Cloud Condensation Nuclei (RNCCN) Profile Value-Added Product Report

The cloud condensation nuclei (CCN) concentration at cloud base is the most relevant measure of the aerosol that influences droplet formation in clouds. Since the CCN concentration depends on supersaturation, a more general measure of the CCN concentration is the CCN spectrum (values at multiple supersaturations). The CCN spectrum is now measured at the surface at several U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility observatories and by the ARM Mobile Facility (AMF) but is not measured at the cloud base. Rather than rely on expensive aircraft measurements for all studies of aerosol effects on clouds, a way to project CCN observations made at the surface to cloud base is needed. Remote sensing of aerosol extinction provides information about the vertical profile of the aerosol but cannot be directly related to the CCN concentration because the aerosol extinction is strongly influenced by humidification, particularly near cloud base. Ghan and Collins (2004) and Ghan et al. (2006) propose a method to remove the influence of humidification from the extinction profiles and tie the “dry extinction” retrieval to the surface CCN concentration, thus estimating the CCN profile. This methodology has been implemented as ARM’s Retrieved Number Concentration of CCN (RNCCN) Profile Value-Added Product (VAP).

54 ENVIRONMENTAL SCIENCES↗

Production of Germanium and Gallium Concentrates for Industrial Processes

A conceptual design of a process to produce germanium and gallium metal from mixed rare earth concentrates (consisting of oxides or carbonates) (MREC) produced from lignite carbon-ore was developed. The design was based on past work associated with the recovery of Ge from carbon-ore ash, modeling of the behavior of Ge and Ga in pyrometallurgical processes, and laboratory testing of the potential recovery of Ge and Ga from MREC. A teaming plan was developed that encompasses the entire supply chain that consisted of the Ge and Ga-rich carbon-ore resource, MREC pilot scale concentrate producer, MREC processing facility to produce Ge/Ga concentrates, refining of Ge and Ga concentrates to produce high purity metals (99.999+ purity), and Ge/Ga end users. A research plan was developed to transition the Ge and Ga separation from MREC, concentrating, and refining technology from a conceptual design to commercial scale. A technical and economic assessment of the conceptual design indicated that MREC derived from the UND process can produce 90 to 99% pure Ge and Ga concentrates at >20% lower costs.

01 COAL, LIGNITE, AND PEAT↗

Photonic Luminescent Solar Concentrator Design for High Efficiency, Low Cost Multijunction Photovoltaics

Despite the extraordinary advances in solar cell efficiency in laboratory settings, the deployment of solar cells continues to be limited to low efficiency (<25%) silicon cells because of cost. In this work, we take advantage of the extraordinary optical properties afforded by nanophotonic structures to create a photonic luminescent solar concentrator for an InGaP-Si multijunction concentrator cell. Finite difference time domain (FDTD) simulations demonstrated a concentrator that could effectively capture, downconvert, and guide concentrated light to an InGaP subcell while still transmitting longer wavelengths to a Si subcell. We fabricated the photonic luminescent solar concentrator, which was comprised of CdSe/CdS quantum dots embedded within alternating layers of Si 3 N 4 and SiO 2 , and experimentally verified the optical performance, showing a 40% increase in light guiding and a significant reduction in reabsorption losses in the plane of the luminescent concentrator as compared to traditional designs. Finally, we utilized modified detailed balance calculations that accounted for cell and optical losses and showed >30% efficiencies are possible with this design, demonstrating the potential to meet the demands for high efficiency, inexpensive solar modules.

Eisler, Carissa N.↗