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At least 1,387 records · Page 77

Doping of CdTe Using CuCl2 Solution for Highly Efficient Photovoltaic Devices

Here, we report doping of cadmium telluride (CdTe) thin film solar cells using copper (II) chloride (CuCl 2 ) solution in deionized water. The CdTe thin films were immersed in 0.1 mmol CuCl 2 solution in water and annealed in the temperature range of 180-240 degrees C for various time durations. The devices were completed using thermally evaporated gold (Au) and measured under simulated AM1.5G spectrum. The average device efficiency of CuCl 2 treated CdTe devices increased to 13.7 % (best cell reaching 14.0%) with significant improvement on open-circuit voltage (VOC ) as compared with 12.4% (best cell 12.7%) for thermally evaporated Cu doped CdTe devices. For CuCl 2 treated CdTe devices, we found higher photoluminescence (PL) intensity and longer carrier life time at room temperature indicating solution based doping offers better control of Cu doping density as compared with evaporated Cu.

14 SOLAR ENERGY↗

Searching for Suitable Binary Fluid for an Ejector Heat Pump for Domestic Water Heating

Water heating is a major source of energy consumption in the U.S. residential sector. Heat pumps can significantly increase the energy efficiency of water heating. An ejector heat pump (EHP) is a novel, thermally driven heat pump that uses an ejector as a thermocompressor. Choosing suitable working fluids is critical in developing high-performance EHPs. Therefore, this research screens binary fluid pairs (BFPs) for EHPs to produce domestic hot water at a high coefficient of performance (COP). The criteria for screening BFP candidates for EHP water heaters (EHPWHs) are established, and BFP candidates are shortlisted. This study identifies HFE7000, Novec649, HFE7100, HFE7200, and HFE7500 for the primary fluids and RE170, R600a, R600, and R1234ze(Z) for the secondary fluids. The thermodynamic model is employed to investigate the performance of EHPWHs using the shortlisted BFPs under various operating parameters, including the evaporation pressure of the primary working fluid in the high-temperature evaporator and the condensation temperature. In conclusion, the highest heating-cycle COP of 1.328 is achieved by an EHPWH operating with HFE7000/R600 at a condenser temperature of 50 °C and a pressure of 1.69 MPa in the high-temperature evaporator.

42 ENGINEERING↗

Application of templated vapor-liquid-solid growth to heteroepitaxy of InP on Si

Direct growth of III–V semiconductors on Si promises to combine the superior optoelectronic properties of III–Vs with the existing large-scale fabrication capabilities for Si. Vapor-liquid-solid-based growth techniques have previously been used to grow optoelectronic-quality III–Vs in polycrystalline films and various photolithography-defined features. We show that templated vapor-liquid-solid growth can produce epitaxial material when performed on crystalline substrates. In templated vapor-liquid-solid growth, the metal group-III precursor is evaporated along with a capping SiO 2 layer on the crystalline substrate, then melted and converted with exposure to a vapor-phase group-V precursor. We demonstrate homoepitaxial growth of InP on InP wafers using two forms of the SiO x capping layer to confine the liquid metal: evaporated SiO 2 and solgel SiO x , the latter of which is necessary for growth on Si. We then demonstrate heteroepitaxial growth of InP islands on Si substrates from both evaporated and electroplated In metals. The templated vapor-liquid-solid process provides better material utilization and growth rates than common vapor-phase techniques, with similar control and convenience, providing a path toward the large-scale fabrication of integrated optoelectronic components.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Ar + H{sub 2} Plasma Interacting with Lithium-Filled Capillary Porous Structure

Ar + H{sub 2} plasma interacting with liquid lithium was carried out on a one-cathode linear plasma device (SCU-PSI). The lithium sample was covered with capillary porous structure (CPS). It is found that the electron temperature of applied plasma ranged from ~0–1 eV and electron density ranged from 0.1 × 10{sup 20} to 1 × 10{sup 20} m{sup −3}. The experimental results indicate that a reduction in the electron temperature and the lithium evaporation is found as the percentage of H{sub 2} increases When the ratio of argon and hydrogen keeps constant, the electron temperature and lithium evaporation increase with applied input power, respectively. The retention of hydrogen atoms in lithium surface results in reducing the lithium evaporation. The XRD analysis result shows that during plasma radiation no LiH is formed.

74 ATOMIC AND MOLECULAR PHYSICS↗

Hawking radiation as instantons

There have been various interpretations of Hawking radiation proposed based on the perturbative approach, and all have confirmed Hawking’s original finding. One major conceptual challenge of Hawking evaporation is the associated black hole information loss paradox, which remains unresolved. A key factor to the issue is the end-stage of the black hole evaporation. Unfortunately by then the evaporation process becomes non-perturbative. Aspired to provide a tool for the eventual solution to this problem, here we introduce a new interpretation of Hawking radiation as the tunneling of instantons. We study instantons of a massless scalar field in Einstein gravity. We consider a complex-valued instanton that connects an initial pure black hole state to a black hole with a scalar field that represents the Hawking radiation at future null infinity, where its action depends only on the areal entropy difference. By comparing it with several independent approaches to Hawking radiation in the perturbative limit, we conclude that Hawking radiation may indeed be described by a family of instantons. Since the instanton approach can describe non-perturbative processes, we hope that our new interpretation and holistic method may shed lights on the information loss problem.

79 ASTRONOMY AND ASTROPHYSICS↗

Factors Influencing the Stability of Au-Incorporated Metal-Oxide Supported Thin Films for Optical Gas Sensing

There is interest in using Au-nanoparticle incorporated oxide films as functional sensor layers for high-temperature applications in optical-based sensors for measurements in both highly-oxidizing and highly-reducing atmospheres at temperatures approaching 900°C-1000°C because of a relatively high melting temperature combined with the inert nature of Au nanoparticles. This study includes a systematic series of experiments and theoretical calculations targeted at further understanding stability of Au-nanoparticle incorporated TiO 2 films as archetype sensing materials. A combination of thermodynamic modeling and long-term exposure tests were utilized to unambiguously determine that gas stream composition-dependent reactive evaporation of Au (to form predominately Au(g) or AuH(g), depending upon the environment) at the surface of the nanoparticles is the dominant mechanism for mass loss of Au. Primary factors dictating the rate of reactive evaporation, and hence the associated film stability, were determined to be the gas stream temperature and the concentration of H 2 , with the former playing a more significant role over the ranges of temperatures (700°C - 800°C) and H 2 concentrations (1% to 29% H 2 by volume) explored. The mitigation of Au-mass loss through reactive evaporation was also successfully demonstrated by depositing a SiO 2 overlayer on the Au-nanoparticle embedded films to prevent direct Au-nanoparticle/vapor-phase contact.

36 MATERIALS SCIENCE↗

Protective Ceramic Coatings for Solid Oxide Fuel Cell (SOFC) Balance‐of‐Plant Components

Solid oxide fuel cells (SOFCs) have the potential to meet the growing need for electrical power generation if the cost per megawatt can be further reduced. Currently, SOFC stacks are replaced too frequently to be cost competitive. SOFC service life can be extended by preventing chromium‐ (Cr‐) bearing species from evaporating from the interior surfaces of balance of plant (BOP) components and poisoning the cathode to increase the lifetime. We have developed yttria‐stabilized zirconia (YSZ) and aluminum oxide‐ (Al 2 O 3 ‐) modified sol‐gel paints or inks for coating BOP components. 430 stainless steel (430SS) substrates with three surface conditions were coated with the 0.8–1.5 µ m thick YSZ and Al 2 O 3 paints. The coated 430SS samples were tested for thermal cycling resistance, thermal soak, and Cr evaporation. Thermal soak and thermal cycling test results show promise for the YSZ‐coated 430SS substrates. The Cr evaporation test of a coated substrate showed a 51% reduction in Cr generation, when compared with a bare substrate.

36 MATERIALS SCIENCE↗

Study of the impact of pre- and real-time deposition of lithium on plasma performance on NSTX

The efficiency of two lithium (Li) injection methods used on the National Spherical Torus Experiment (NSTX) are compared in terms of the amount of Li used to produce equivalent plasma performance improvements, namely Li evaporation over the divertor plates, prior to the initiation of the discharge, and real-time Li injection directly into the plasma scrape-off layer during the discharge. The measurements show that the real-time method can affect the energy confinement and edge stability of NSTX plasmas in a more efficient way than the Li evaporation method as it requires only a fraction of the amount of Li used by the evaporation method to produce similar improvements.

Lithium↗

The Dual Nature of Entrainment-Mixing Signatures Revealed through Large-Eddy Simulations of a Convection-Cloud Chamber

Abstract Entrainment of subsaturated air into a cloud can influence its optical and microphysical properties in various ways, depending on the droplet evaporation and turbulent mixing time scales. Previous experiments in the Pi convection-cloud chamber have revealed that, given a fixed entrained air property, the mixing of entrained subsaturated air results in complete evaporation of some cloud droplets, with the rest remaining unchanged. This is a signature of inhomogeneous mixing. While comparing the results of entrainment with varying air properties, the mixing signature appears as if the subsaturated air is well mixed with the cloud to evenly reduce the droplets’ size. In other words, taken together, the experiments appear to have the signature of homogeneous mixing. To explore these results in a greater depth, we conduct large-eddy simulations combined with a bin microphysics scheme. Our results reproduce the similar signatures of inhomogeneous and homogeneous mixing, implying that LES can resolve the inhomogeneous mixing when the grid spacing is smaller than the entrained air parcel. Additionally, we observe that increasing the aerosol injection rate enhances the signature of inhomogeneous mixing, while coarser grid spacing diminishes it. Finally, the change in wall fluxes in response to various entrained air properties confirms that the homogeneous signature seen in the analysis of an ensemble of simulations is the result of various equilibrium states. This further strengthens the suggestion that the homogeneous mixing signature found in aircraft observations near the cloud top may result from combining entrainment events of different intensities, possibly caused by various-sized eddies. Significance Statement Large-eddy simulation and size-resolved microphysics can resolve time scales for turbulent mixing and evaporation and, therefore, are well suited for reproducing, extending, and interpreting the entrainment experiment in the Pi convection-cloud chamber. Our simulation results confirm (i) the inhomogeneous mixing signature for an individual entrainment event and (ii) the appearance of homogeneous mixing in an ensemble of entrainment episodes. Furthermore, we demonstrate that the inhomogeneous mixing signature is more pronounced in a polluted cloud, but coarser grid spacing in simulations may compromise the accuracy of this signature. Last, the homogeneous mixing signature results from various equilibrium states established for different entrainment intensities and adjusted wall fluxes, which are challenging to measure experimentally but can be easily analyzed in the simulations.

54 ENVIRONMENTAL SCIENCES↗

The Effect of an Equatorial Continent on the Tropical Rain Belt. Part 1: Annual Mean Changes in the ITCZ

The TRACMIP (Tropical Rain Belts with an Annual Cycle and Continent Model Intercomparison Project) ensemble includes slab-ocean aquaplanet controls and experiments with a highly idealized tropical continent, characterized by modified aquaplanet grid cells with increased evaporative resistance, increased albedo, reduced heat capacity, and no ocean heat transport (zero Q-flux). In the annual mean, an equatorial cold tongue develops west of the continent and induces dry anomalies and a split in the oceanic intertropical convergence zone (ITCZ). Ocean cooling is initiated by advection of cold, dry air from the winter portion of the continent; warm, humid anomalies in the summer portion are restricted to the continent by anomalous surface convergence. The surface energy budget suggests that ocean cooling persists and intensifies because of a positive feedback between a colder surface, drier and colder air, reduced downwelling longwave (LW) flux, and enhanced net surface LW cooling (LW feedback). A feedback between wind, evaporation, and SST (so-called WES feedback) also contributes to the establishment and maintenance of the cold tongue. Simulations with a gray-radiation model and simulations that diverge from protocol (with negligible winter cooling) confirm the importance of moist-radiative feedbacks and of rectification effects on the seasonal cycle. This mechanism coupling the continental and oceanic climate might be relevant to the double ITCZ bias. The key role of the LW feedback suggests that the study of interactions between monsoons and oceanic ITCZs requires full-physics models and a hierarchy of land models that considers evaporative processes alongside heat capacity as a defining characteristic of land.

54 ENVIRONMENTAL SCIENCES↗

The Heavy Rainfall Mechanism Revealed by a Terrain-Resolving 4DVar Data Assimilation System—A Case Study

In this study, a newly developed terrain-resolving four-dimensional variational (4DVar)-based data assimilation system, Immersed Boundary Method_Variational Doppler Radar Analysis System (IBM_VDRAS), is applied to investigate the mechanisms leading to a heavy precipitation event that occurred in Taiwan during the Southwesterly Monsoon Experiment (SoWMEX) conducted in 2008. The multivariate analyses using IBM_VDRAS and surface observations reveal that the warm and moist southwesterly flow from the ocean decelerates after making landfall, forming a surface convergence zone along the coast, which is further strengthened during the passage of a prefrontal rainband. The flow ascends as it advances inland until reaching the mountains, producing persistent precipitation and the enhancement of evaporative cooling as well as a widespread high pressure zone. A very shallow (<0.4 km) layer of offshore flow can be identified over the southwestern plain, which helps to generate a quasi-stationary convergence zone near the coast. Furthermore, sensitivity studies are carried out to quantify the relative importance of the contributions made by topographic blockage, evaporative cooling, and their nonlinear interaction, to the evolution of this type of convective system. The influence of the topography is identified as the dominant factor in modulating the flow structure of the rainfall system. However, it is the nonlinear interaction between terrain and evaporation that determines the distribution of the temperature and pressure fields.

54 ENVIRONMENTAL SCIENCES↗

Development of a two-zone zero-dimensional mixing model for actively fueled prechamber engines

In this numerical work, a zero-dimensional, two-zone mixing model was developed and validated to capture the mixture preparation process of an actively fueled prechamber engine. The model was developed for ethanol-gasoline fuel blends but is applicable to various fuels of interest relevant to prechamber applications. The model was exercised to demonstrate the effects of boundary conditions, fuel composition, and residual content on the mixture stoichiometry predictions. The 0D model showed reasonable agreement in prechamber equivalence ratio predictions with higher fidelity computational fluid dynamics modeling, but the accuracy of model was constrained to the governing assumptions of the injection process. The modeling assumptions surrounding the non-dimensional injection of mass into the prechamber were scrutinized to identify key areas of model improvement. The results indicate heat transfer effects play a crucial role in the evaporation of the fuel within the confined auxiliary chamber, especially when considering fuels with high latent heat of vaporization. Additionally, the presence of fuel films that collect on the prechamber surfaces complicated the modeled evaporative cooling loses as the modeling suggests the films evaporate primarily by means of conduction from the boundary. Furthermore, the developed model serves as a simplified framework to generate calibration maps of prechamber fueling or run real time as an open loop control strategy such that desired prechamber mixture proportions are effectively targeted.

Zero-dimensional↗

Assessing Air Velocity Distribution in Three Sizes of Commercial Broiler Houses During Tunnel Ventilation

Abstract. Convective cooling is a critical management strategy for maintaining an environment that promotes production efficiency, thermal comfort, and animal well-being in commercial broiler houses. Variations in house size, design, and equipment configuration contribute greatly to the air velocity distribution within the facility. This study assessed total airflow, air velocity distribution, and quantified the floor area in three facilities experiencing insufficient air velocity for maintenance of production efficiency, thermal comfort, and animal well-being. Test facility 1 was an 18.3 × 170.7 m solid side-wall broiler house, test facility 2 was a 15.24 × 144.8 m solid side-wall broiler house, and test facility 3 was a 12.19 × 121.9 m curtain side-wall broiler house. Total airflow of each facility, measured with a Fan Assessment and Numeration System, was 512,730, 389,495, and 329,270 m 3 h -1 for test facilities 1, 2, and 3, respectively. Air velocity distribution patterns were characterized in each house with a Scalable Environment Assessment System (SEAS) and spatial statistics. The air velocity distributions within the test facilities were variable, with notable maxima immediately downstream of the tunnel inlets, which serve as a well-defined vena contracta, and local minima near the leading end of the evaporative pads and the exhaust fans. Equipment within the facilities had an impact on the air velocity distribution by creating reduced cross-sectional areas that resulted in localized increases in air velocity. The percentage of total bird-level floor area in each facility experiencing air velocities below 1.5 m s -1 was 14.3%, 20.7%, and 10.0% for test facilities 1, 2, and 3, respectively. The effective design velocity (V ed ) was calculated from total airflow using the measured building cross-sectional area. The V ed measured 2.97, 2.45, and 2.34 m s -1 for test facilities 1, 2, and 3, respectively. Mean cross-sectional air velocity (V cs ) was calculated from SEAS data and normalized using each facility’s V ed to account for differences in building size for comparison. Test facility 1, the largest of the three houses, generated substantially higher V cs /V ed than test facilities 2 and 3. Test facilities 2 and 3 maintained a larger proportion of V cs above V ed than test facility 1. Test facility 1 showed 26.5% of the total house length below V ed , while test facilities 2 and 3 had only 20.8% and 17.5%, respectively, of the total house length below V ed . The lower-velocity regions were due to the length of the evaporative cooling pad inlet and the use of tunnel doors, and the exhaust fan placement on the side-walls in test facility 1 created an additional pronounced low-velocity area. Placement of tunnel ventilation fans on the end-wall of the facility, rather than the side-wall, eliminated the low-velocity region at the exhaust end of the facility. Modifications to current practices for broiler production facility construction and evaporative cooling pad inlet installation would be required to minimize the low-velocity region at the inlet end of these facilities. Consideration of house width and physical arrangement of the air inlets, tunnel fans, and internal equipment are critical for improving the uniformity of air velocity in commercial broiler houses. Keywords: Air velocity, Anemometer, Broiler house, FANS, Tunnel ventilation.

Agriculture↗

AmeriFlux US-GL1 Stannard Rock

This is the AmeriFlux version of the carbon flux data for the site US-GL1 Stannard Rock. Site Description - Stannard Rock is located 39 km from the nearest shore (Keweenaw Peninsula) in Lake Superior, 44 miles NNE of Marquette, Michigan, and 24 miles ESE of Manitou Island. The site is located on the historic Stannard Rock Lighthouse, which was completed in 1882. Eddy covariance instrumentation was installed in 2008 by a network of scientists from both US and Canada, eventually to be called the Great Lakes Evaporation Network (GLEN). The intent of GLEN has been to provide observations of over-lake meteorology and evaporation, improve forecasting of Great Lakes water levels, and support a wide variety of stakeholders, including the National Weather Service (NWS), Environment and Climate Change Canada, National Oceanic and Atmospheric Administration, U.S. Coast Guard, recreational boaters and commercial shipping, emergency management officials, and the Great Lakes research community. The eddy covariance station along with other ancillary meteorological instrumentation is located at an approximate elevation of 39.2 meters above mean lake water level. Meteorological data from the lighthouse are sent to the National Data Buoy Center, where they can be viewed in real-time at http://www.ndbc.noaa.gov/station_page.php?station=stdm4 Uncorrected half-hour fluxes were computed directly on the logger using a 30-minute block averaging period as high-frequency data were not available. The half hour flux measurements downloaded from the datalogger were post-processed with the following filters and corrections. Latent and sensible heat and carbon dioxide fluxes were corrected with 2-D coordinate rotation. Although the primary objective of data collection at Stannard Rock was to quantify the evaporative flux, additional preliminary measurements of the carbon dioxide concentration and flux from the LI-7500 are also included in this dataset but it is advised to use the carbon data with caution. Carbon data reported in this dataset includes turbulent fluxes of CO2 with no storage correction (FC, µmol m-2 s-1) and CO2 density in mole fraction of wet air (CO2), which was originally output on the datalogger as average CO2 density (mg m-2 s-1) and converted into µmol mol-1 using air temperature and pressure in post-processing. Webb, Pearman, and Leuning terms were applied to account for density fluctuations for water vapor and CO2. Sonic path length, high-frequency attenuation and sensor separation were accounted for according to Horst and Massman, and the oxygen absorption correction for the KH2O hygrometer was also applied. Latent and sensible heat fluxes were assumed to be unrealistic above an absolute value of 1000 W m-2 and were removed. Both carbon flux (FC) and carbon dioxide mole fraction in wet air (CO2) and were assumed to be unrealistic above 1000 µmol m-2 s-1 and 1000 µmol mol-1 respectively. Spikes in latent and sensible heat and carbon fluxes and densities (often due to periods of precipitation) were identified by computing the mean and standard deviation over a moving, overlapping window of 336 half-hours (7 days), similar to Shao et al., and were removed when the flux was more than 1.5 standard deviations from the moving window’s mean. While Vickers and Mahrt use a threshold of 3.5 standard deviations from the mean, a conservative value of 1.5 was chosen due to the noisy nature of over-lake data at this particular site. This process was repeated twice for latent and sensible heat, and carbon dioxide fluxes and densities and therefore it is possible that some real, realistic data was filtered out in this process. No detrending was performed. As per AmeriFlux standards, no friction velocity (USTAR, m s-1) filtering was performed.

Spence, Chris↗

AmeriFlux FLUXNET-1F US-GL1 Stannard Rock

This is the AmeriFlux Management Project (AMP) created FLUXNET-1F version of the carbon flux data for the site US-GL1 Stannard Rock. This is the FLUXNET version of the carbon flux data for the site US-GL1 Stannard Rock produced by applying the standard ONEFlux (1F) software. Site Description - Stannard Rock is located 39 km from the nearest shore (Keweenaw Peninsula) in Lake Superior, 44 miles NNE of Marquette, Michigan, and 24 miles ESE of Manitou Island. The site is located on the historic Stannard Rock Lighthouse, which was completed in 1882. Eddy covariance instrumentation was installed in 2008 by a network of scientists from both US and Canada, eventually to be called the Great Lakes Evaporation Network (GLEN). The intent of GLEN has been to provide observations of over-lake meteorology and evaporation, improve forecasting of Great Lakes water levels, and support a wide variety of stakeholders, including the National Weather Service (NWS), Environment and Climate Change Canada, National Oceanic and Atmospheric Administration, U.S. Coast Guard, recreational boaters and commercial shipping, emergency management officials, and the Great Lakes research community. The eddy covariance station along with other ancillary meteorological instrumentation is located at an approximate elevation of 39.2 meters above mean lake water level. Meteorological data from the lighthouse are sent to the National Data Buoy Center, where they can be viewed in real-time at http://www.ndbc.noaa.gov/station_page.php?station=stdm4 Uncorrected half-hour fluxes were computed directly on the logger using a 30-minute block averaging period as high-frequency data were not available. The half hour flux measurements downloaded from the datalogger were post-processed with the following filters and corrections. Latent and sensible heat and carbon dioxide fluxes were corrected with 2-D coordinate rotation. Although the primary objective of data collection at Stannard Rock was to quantify the evaporative flux, additional preliminary measurements of the carbon dioxide concentration and flux from the LI-7500 are also included in this dataset but it is advised to use the carbon data with caution. Carbon data reported in this dataset includes turbulent fluxes of CO2 with no storage correction (FC, µmol m-2 s-1) and CO2 density in mole fraction of wet air (CO2), which was originally output on the datalogger as average CO2 density (mg m-2 s-1) and converted into µmol mol-1 using air temperature and pressure in post-processing. Webb, Pearman, and Leuning terms were applied to account for density fluctuations for water vapor and CO2. Sonic path length, high-frequency attenuation and sensor separation were accounted for according to Horst and Massman, and the oxygen absorption correction for the KH2O hygrometer was also applied. Latent and sensible heat fluxes were assumed to be unrealistic above an absolute value of 1000 W m-2 and were removed. Both carbon flux (FC) and carbon dioxide mole fraction in wet air (CO2) and were assumed to be unrealistic above 1000 µmol m-2 s-1 and 1000 µmol mol-1 respectively. Spikes in latent and sensible heat and carbon fluxes and densities (often due to periods of precipitation) were identified by computing the mean and standard deviation over a moving, overlapping window of 336 half-hours (7 days), similar to Shao et al., and were removed when the flux was more than 1.5 standard deviations from the moving window’s mean. While Vickers and Mahrt use a threshold of 3.5 standard deviations from the mean, a conservative value of 1.5 was chosen due to the noisy nature of over-lake data at this particular site. This process was repeated twice for latent and sensible heat, and carbon dioxide fluxes and densities and therefore it is possible that some real, realistic data was filtered out in this process. No detrending was performed. As per AmeriFlux standards, no friction velocity (USTAR, m s-1) filtering was performed.

Spence, Chris [Environment and Climate Change Cana↗

Sacrificial Protective Coating Materials that can be Regenerated In-Situ to Enable High Performance Membranes

In the pulp and paper industry, weak black liquor concentration is carried out using energy intensive evaporators. Briefly, after wood digestion, water is evaporated to concentrate weak black liquor to the point where the black liquor can be burned in a recovery boiler, which ultimately leads to the recovery of digestion chemicals. Because it is less energy intensive than heat-driven separation, pressure-driven separation of water from black liquor using membranes could reduce the energy usage by 55 trillion Btu yr -1 and carbon dioxide emissions by more than 11 million metric tons CO 2 per year if the first two evaporators are replaced. However, weak black liquor is a hot, corrosive, and highly fouling feed with organic molecules, colloids, and ions that clog membranes within hours of operation. We have shown that membrane-based concentration of weak black liquor is feasible, but only with our antifouling and anti-clogging technology that is based on a sacrificial Bio-inspired Living Skin concept. This concept is based on a conformal coating that is formed at the membrane surface and within the pores. Weak foulant adhesion dramatically decreases membrane fouling while the superhydrophilicity of the coating increases the water permeability. Moreover, the coating can be completely removed during backflushing, which removes foulants that may irreversibly adhere to the coating over long periods of time. The skin shedding completely regenerates the membrane surface and pores, restoring the original flux. This is followed by in-situ recoating, using the existing membrane plumbing and pumps, which essentially creates a brand new membrane surface.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Evaluation of Immobilizing Secondary Waste from a Proposed Treatment Process for Hanford WTP LAW Melter Condensate

The off-gas system in the Low Activity Waste (LAW) vitrification facility at the Hanford Waste Treatment and Immobilization Plant (WTP) will generate an aqueous condensate recycle stream. Two unit operations generate this condensate, a Submerged Bed Scrubber and a Wet Electrostatic Precipitator (LAW SBSWESP condensate). The expected disposition of this stream during baseline operations is to send it to the WTP Pretreatment Facility, where it will be blended with LAW, concentrated by evaporation and recycled to the LAW vitrification facility again. The primary reason to recycle this stream is to immobilize the semivolatile 99 Tc isotope into the glass. During the Direct Feed Low Activity Waste (DFLAW) portion of the mission, the condensate is sent to the Effluent Management Facility (EMF) where it is evaporated then recycled to the LAW facility where the evaporated condensate is combined with the LAW feed from the pretreatment system.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Glycolate Analysis in Tank 22: Developing and Testing Analytical Methods for the Savannah River Site Liquid Waste System

Researchers developed and tested a range of techniques to support a low mg/L Limit of Quantitation (LOQ) of glycolate in radioactive Tank 22 waste solution by Ion Chromatography (IC) and by proton NMR. For the IC method, Dionex OnGuard II cartridges were tested as a means of removing alkali earth and transition metals that can interfere during ion chromatography applications especially when analyzing for low-concentration, chelating analytes. Additionally, concentrations of nitrate in the raw Tank 22 sample (5,000 to 10,000 mg/L) were managed by using reasonable levels of sample dilution. The resulting IC performance quality was enhanced by improving the baseline, increasing sensitivity [Limit of Quantitation (LOQ) of 12 mg/L and Limit of Detection (LOD) of 4.0 mg/L], and resolving analytes into well-defined Gaussian peaks when using the Dionex OnGuard II H⁺ cartridges to remove matrix interferences. High concentrations of nitrate limited the performance of the IC method. To achieve an acceptable baseline, samples with high nitrate content require more dilution, resulting in higher detection limits. Tests on samples with higher concentrations of nitrate (Tank 30 and 32 supernate with approximately 150000 mg/L nitrate) suggested that IC detection limits for glycolate in these samples would be > 500 mg/L. Thus, an LOQ of 12 mg/L is not feasible by this IC method on evaporator feed samples. An alternative method of glycolate analysis, using proton nuclear magnetic resonance (H NMR), was developed by the research team. In initial tests, the H NMR technique provided reasonable quantitation of glycolate in Tank 22 conditions by direct observation of the liquid. The H NMR method may provide improved detection limits for solutions with higher nitrate concentrations. We recommend further development of this analysis for high nitrate LWS samples such as evaporator feed and evaporator drop tank content. A method for pretreatment of samples using crystalline silicotitanate (CST) was developed and tested. The objective of the pretreatment was to facilitate analysis of samples with higher levels of radioactivity. The pretreatment did not influence the glycolate concentration in solution, and the pretreatment is projected to reduce Cs 137 activity in a sample by a factor of 16,200. The double strike CST pretreatment was demonstrated and would allow milliliters of higher activity samples to be transferred from the Shielded Cells and handled in a containment unit for glycolate analysis. The various studies validated IC and H NMR methods for glycolate analysis, defined the range of applicability, and demonstrated key supporting analytical protocols. Based on the results, high quality glycolate analysis of Tank 22 is feasible down to approximately 12 mg/L, with the potential for broader applicability of the methods to other conditions in the Savannah River Site Liquid Waste System (LWS).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗