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At least 397 records · Page 22

Treatment of Magnesium-Thorium Alloy Used in Military Defence Equipment by Separation of Thorium and/or Thermal Oxidation - 17009

Magnesium-alloys doped with thorium (Th, 3% by weight and with a total activity content in the alloy of 120 Bq/g) to improve mechanical properties has been used in, among other applications, military equipment such as in the jet-engines in military aircraft. The material cannot, due to the presence of the radioactive Th, be handled as an ordinary scrap metal. It needs to be treated to render a more stable waste form prior to final disposal in which the amount of disposed metallic magnesium is limited due to the pyrophoric properties of such type of materials. By thermally treating the material it is possible to transform the alloy into oxide form (MgO and ThO{sub 2}) which is a much more stable form than metallic. This itself enables a form suitable for final disposal of the material. The oxidation step does however lead to an increase in volume and is therefore not an optimal treatment method. It is possible to treat the metal oxide powder in order to get a better volume reduction such as by super compaction but a better result can be obtained by separating the Th from the alloy, leaving a much smaller volume for final disposal. One way of separating the Th from the metal is by dissolution of metallic material in acid followed by directed precipitation of Th as Th-oxalate. Several parameters such as the choice of acid, metal concentration in the acid solution, pH prior to precipitation and amount of added oxalic acid have been investigated. Another method to separate Th from Mg is to perform a selective dissolution of MgO from an MgO/ThO{sub 2} mixture with HNO{sub 3} leaving only ThO{sub 2} as a residue. These tests had to be preceded with an oxidation of the alloy. The tests show that it is possible to separate Th from the metal alloy by either dissolution followed by precipitation or selective dissolution of MgO from an MgO/ThO{sub 2} mixture. This leads to very effective volume reduction of the waste. For the direct dissolution and precipitation tests typically > 95% of the magnesium can be found in the acid solution while 99.5 % of the Th is found as a solid in the filters. For the oxide dissolution tests typically 98% of the Th can be separated from the bulk material, leaving the acid solution possible to free release and dispose of in the same way as for the previous method. (authors)

36 MATERIALS SCIENCE↗

Photoluminescent properties and Judd–Ofelt analysis of novel Na0.5Sr0.25NbO3: Eu3+ red phosphor with high quantum efficiency

Highlights: • The Na{sub 0.5}Sr{sub 0.25}NbO{sub 3}: Eu{sup 3+} phosphor with high quantum efficiency has been successfully synthesized by using a molten salt synthesis method. • The effect of the crystal field surrounding the Eu{sup 3+} ions on the luminescent performance was analyzed by the Judd–Ofelt theory. • Photoluminescent properties of Na{sub 0.5}Sr{sub 0.25}NbO{sub 3}: Eu{sup 3+} phosphor were investigated for the first time. - Abstract: We report on a novel Na{sub 0.5}Sr{sub 0.25}NbO{sub 3}: Eu{sup 3+} phosphor fabricated by a molten salt synthesis method with the potential application in white light-emitting diodes (WLEDs) as a red phosphor. The crystal structure, morphology, emission/excitation spectra, as well as decay curves were characterized with X-ray diffraction, Scanning Electron Microscope and photoluminescence spectrometer, respectively. Concentration quenching occurred when the concentration of Eu{sup 3+} was beyond 5 mol% due to the dipole-dipole interaction by nonradiative energy transfer. Besides, the effect of the crystal field surrounding the Eu{sup 3+} ions on the luminescent performance under 396 nm and 466 nm excitions has been investigated by the Judd–Ofelt theory. The result indicated that the quantum efficiency of the phosphor was 62.65% excited by 466 nm, which was superior to 41.43% excited by 396 nm. The optimal sample’s CIE coordinates were (0.6471, 0.3504) with the color purity of 97%, showing a potential application in (WLEDs) illumination field.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of grafting density on the two-dimensional assembly of nanoparticles

Employing grazing-incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that films composed of polyethylene glycol (PEG)-grafted silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs), as well as their binary mixtures, form highly stable hexagonal structures at the vapor–liquid interface. These nanoparticles exhibit remarkable stability under varying environmental conditions, including changes in pH, mixing concentration, and PEG chain length. Short-chain PEG grafting produces dense, well-ordered films, while longer chains produce more complex, less dense quasi-bilayer structures. AuNPs exhibit higher grafting densities than AgNPs, leading to more ordered in-plane arrangements. In binary mixtures, AuNPs dominate the population at the surface, while AgNPs integrate into the system, expanding the lattice without forming a distinct binary superstructure. In conclusion, these results offer valuable insights into the structural behavior of PEG-grafted nanoparticles and provide a foundation for optimizing binary nanoparticle assemblies for advanced nanotechnology applications.

36 MATERIALS SCIENCE↗

Synthesis of Nd3BSi2O10 using a LiCl-flux method

This paper details synthesis methods that were used to fabricate phase-pure Nd3BSi2O10 using a LiCl-flux method. In this study, a variety of conditions were evaluated to find the optimal processing parameters for maximizing the Nd3BSi2O10 yield including the mass ratio of LiCl to target mass of Nd3BSi2O10 including 1:3, 1:2, 1:1, 2:1, and 6:1 as well as the soak temperature (i.e., 700, 800, or 900°C) at the 1:1 ratio. It was found that the optimal ratio of LiCl:Nd3BSi2O10 was 1:1 and the optimal heat-treatment temperature was 900°C. Product made from the 1:1 material synthesized at 900°C was recovered and fired at temperatures of 925–1350°C. After 4-h firings at temperatures of 925–1100°C, the Nd3BSi2O10 phase purity was found to be 100% with powder X-ray diffraction, but started to decompose at the longer firing times at 1100°C and higher temperatures (1350°C) at the 4-h dwell time. The durability of the Nd3BSi2O10 product was examined in flow-through conditions at pH 5.6 and 7.7 and 90°C. The release rate of Nd from the material at pH 5.6 was calculated to be 1.6×10-3 g m-2 d-1 and was determined to have a maximum release rate of Nd at pH 7.7 of 5.6×10-3 g m-2 d-1. These release rates are roughly three orders of magnitude lower than what is typically measured from glass waste forms.

Kroll, Jared O.↗

UniKP: a unified framework for the prediction of enzyme kinetic parameters

Prediction of enzyme kinetic parameters is essential for designing and optimizing enzymes for various biotechnological and industrial applications, but the limited performance of current prediction tools on diverse tasks hinders their practical applications. Here, we introduce UniKP, a unified framework based on pretrained language models for the prediction of enzyme kinetic parameters, including enzyme turnover number (k cat ), Michaelis constant (K m ), and catalytic efficiency (k cat / K m ), from protein sequences and substrate structures. A two-layer framework derived from UniKP (EF-UniKP) has also been proposed to allow robust k cat prediction in considering environmental factors, including pH and temperature. In addition, four representative re-weighting methods are systematically explored to successfully reduce the prediction error in high-value prediction tasks. We have demonstrated the application of UniKP and EF-UniKP in several enzyme discovery and directed evolution tasks, leading to the identification of new enzymes and enzyme mutants with higher activity. UniKP is a valuable tool for deciphering the mechanisms of enzyme kinetics and enables novel insights into enzyme engineering and their industrial applications.

59 BASIC BIOLOGICAL SCIENCES↗

An Advanced TALSPEAK Concept for Separating Minor Actinides. Part 1. Process Optimization and Flowsheet Development

A system is being developed to separate trivalent actinides from lanthanide fission product elements that uses 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester to extract the lanthanide ions into an organic phase, while the actinide ions are held in the citrate-buffered aqueous phase by complexation to N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA). Earlier investigations of this system using a 2-cm centrifugal contactor revealed that the relatively slow extraction of Sm3+, Eu3+, and Gd3+ resulted in low separation factors from Am3+. In the work reported here, adjustments to the aqueous phase chemistry were made to improve the extraction rates. The results suggest that increasing the concentration of the citric acid buffer from 0.2 to 0.6 mol/L, and lowering the pH from 3.1 to 2.6, significantly improved lanthanide extraction rates resulting in an actinide/lanthanide separation system suitable for deployment in centrifugal contactors. Experiments performed to evaluate whether the lanthanide extraction rates can be improved by replacing aqueous HEDTA with nitrilotriacetic acid (NTA) exhibited promising results. However, NTA exhibited an unsatisfactorily high distribution value for Am3+ under the extraction conditions examined.

actinide extraction↗

U(VI) binding onto electrospun polymers functionalized with phosphonate surfactants

We previously observed that phosphonate functionalized electrospun nanofibers can uptake U(VI), making them promising materials for sensing and water treatment applications. Here, we investigate the optimal fabrication of these materials and their mechanism of U(VI) binding under the influence of environmentally relevant ions (e.g., Ca 2+ and CO 3 2- ). We found that U(VI) uptake was greatest on polyacrylonitrile (PAN) functionalized with longer-chain phosphonate surfactants (e.g., hexa- and octadecyl phosphonate; HDPA and ODPA, respectively), which were better retained in the nanofiber after surface segregation. Subsequent uptake experiments to better understand specific solid-liquid interfacial interactions were carried out using 5 mg of HDPA-functionalized PAN mats with 10 μM U at pH 6.8 in four systems with different combinations of solutions containing 5 mM calcium (Ca 2+ ) and 5 mM bicarbonate (HCO 3 -). U uptake was similar in control solutions containing no Ca 2+ and HCO 3 - (resulting in 19 ± 3% U uptake), and in those containing only 5 mM Ca2+ (resulting in 20 ± 3% U uptake). A decrease in U uptake (10 ± 4% U uptake) was observed in experiments with HCO 3 -, indicating that UO 2 -CO 3 complexes may increase uranium solubility. Results from shell-by-shell EXAFS fitting, aqueous extractions, and surface-enhanced Raman scattering (SERS) indicate that U is bound to phosphonate as a monodentate inner sphere surface complex to one of the hydroxyls in the phosphonate functional groups. New knowledge derived from this study on material fabrication and solid-liquid interfacial interactions will help to advance technologies for use in the in-situ detection and treatment of U in water.

42 ENGINEERING↗

Quarterly Soil Core and Root Analyses from the Missouri Ozarks AmeriFlux (MOFLUX) Site, Ashland, Missouri, 2017-2023

This dataset contains quarterly soil core measurements from the Missouri Ozarks AmeriFlux (MOFLUX) site located at the University of Missouri’s Thomas H. Baskett Wildlife Research and Education Area near Ashland, Missouri. These data will be used to parameterize an ensemble of MOFLUX-optimized soil carbon-nitrogen models, used to simulate carbon (C) and nitrogen (N) cycling responses to future hydroclimatic scenarios and the trajectory of soil C stocks with concomitant forest decline. Beginning in 2017, eight soil cores were collected approximately quarterly near plot 1 of the southeast transect, near the automated soil respiration flux chambers, from 0–15 cm depth. Data are currently available through 2023 (2017-06-14 to 2023-11-13); additional observations will be appended to this dataset as they become available. Cores were analyzed for gravimetric moisture content, pH, total carbon and nitrogen, texture, microbial biomass carbon and nitrogen, and extractable dissolved organic carbon and nitrogen. This dataset contains one data file in comma separate (*.csv) format. Additional metadata are provided: one data dictionary and a file-level metadata file in comma separate (*.csv) format and a user guide in PDF (*.pdf) format.

54 ENVIRONMENTAL SCIENCES↗

Quantification of the Impact of Acidified Brine on Fracture-Matrix Transport in a Naturally Fractured Shale Using in Situ Imaging and Modeling

Understanding flow, transport, chemical reactions, and hydromechanical processes in fractured geologic materials is key for optimizing a range of subsurface processes including carbon dioxide and hydrogen storage, unconventional energy resource extraction, and geothermal energy recovery. Flow and transport processes in naturally fractured shale rocks have been challenging to characterize due to experimental complexity and the multiscale nature of quantifying continuum scale descriptions of mass exchange between micrometer-scale fractures and nanometer-scale pores. In this study, we use positron emission tomography (PET) to image the transport of a conservative tracer in a naturally fractured Wolfcamp shale core before and after the core was exposed to low pH brine conditions. Image-based experimental observations are interpreted by fitting an analytical transport model to fracture-containing voxels in the core. Results of this analysis indicate subtle increases in matrix diffusivity and a slightly more uniform fracture velocity distribution following exposure to low pH conditions. These observations are compared with a multicomponent one-dimensional reactive transport model that indicates the capacity for a 10% increase in porosity at the fracture-matrix interface as a result of the low pH brine exposure. This porosity change is the result of the dissolution of carbonate minerals in the shale matrix to low pH conditions. Further, this image-based workflow represents a new approach for quantifying spatially resolved fracture-matrix transport processes and provides a foundation for future work to better understand the role of coupled transport, reaction, and mechanical processes in naturally fractured rocks.

58 GEOSCIENCES↗

Distinct Mechanisms and Hydricities of Cp*Ir-Based CO 2 Hydrogenation Catalysts in Basic Water

Transition metal-catalyzed reversible hydrogenation of CO 2 to formate in aqueous solutions under ambient conditions is an attractive environmentally friendly strategy for the storage and transportation of H 2 in a liquid chemical form. Here, mechanistic details for the CO 2 hydrogenation by a series of pentamethylcyclopentadienyl iridium(III) (Cp*Ir) complexes with picolinamidate ligands are investigated through density functional theory and kinetic isotope effects (KIEs) calculations. Additionally, adopting a speciation approach at a pH of 8.2, CO 2 hydrogenation mechanisms of 37 distinct protonation states and conformers of Cp*Ir type complexes are investigated. This imposes a challenging test for the computational modeling in terms of providing a consistent correlation with experimental kinetics and KIE studies of multiple catalysts instead of a single complex. Overall, H 2 heterolysis to generate an iridium hydride intermediate was demonstrated to be the rate determining step, which proceeds via distinct pathways depending on the stereoelectronic properties of the ligand. A peculiar iridium dihydride route was also uncovered, which could be optimized to accelerate the H 2 heterolysis. We have further computed the thermodynamic and kinetic hydricities of 74 complexes with [Cp*Ir(L)(H)] q ( q = -1, 0, 1 depending on the ligand charge by deprotonation or protonation events) general formula. Hydricity values do not show any noticeable correlation with the thermodynamics (Δ G ) of [Cp*Ir(L)(HCO 2 – )] formation but exhibit linear correlation with the kinetics (Δ G ‡ ) of electrophilic CO 2 attack to iridium hydride species, especially when the charges and local structural effects of the metal hydrides are considered. Insights gained in this study on (i) the factors determining the preferred pathway for the rate-limiting H 2 heterolysis step, (ii) the correlation between thermodynamic hydricity and the kinetics of CO 2 insertion to iridium hydride species, and (iii) mechanistic analysis via combination of free energy profiles and KIE studies for a series of iridium catalysts will provide guidelines for the design of next-generation catalysts for the reversible H 2 storage through CO 2 utilization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microencapsulation of Corrosion Indicators for Smart Coatings

A multifunctional smart coating for the autonomous detection, indication, and control of corrosion is been developed based on microencapsulation technology. This paper summarizes the development, optimization, and testing of microcapsules specifically designed for early detection and indication of corrosion when incorporated into a smart coating. Results from experiments designed to test the ability of the microcapsules to detect and indicate corrosion, when blended into several paint systems, show that these experimental coatings generate a color change, indicative of spot specific corrosion events, that can be observed with the naked eye within hours rather than the hundreds of hours or months typical of the standard accelerated corrosion test protocols.. Key words: smart coating, corrosion detection, microencapsulation, microcapsule, pH-sensitive microcapsule, corrosion indicator, corrosion sensing paint

Li, Wenyan↗

Sustainable network design for multi-purpose pellet processing depots under biomass supply uncertainty

This work develops a two-stage stochastic mixed-integer programming model to manage multi- purpose pellet processing depots under feedstock supply uncertainty. The proposed optimization model would help to minimize cost and to mitigate emissions from the supply chain network. We consider three alternative Biomass Processing and Densi cation Depot (BPDD) technologies; namely, conventional pellet processing, high moisture pellet processing, and ammonia ber expansion. These three technologies pre-process/pre-treat and densify different types of biomass into more highly densi ed intermediate products for different markets in order to improve movability and overall supply network performance in terms of costs and emissions. A hybrid decomposition algorithm was developed that combines sample average approximation with an enhanced Progressive Hedging (PH) algorithm to solve this challenging NP -hard problem. Some heuristics such as Rolling Horizon (RH) heuristic, variable xing technique were later applied to further enhance the PH algorithm. Mississippi and Alabama were selected as a testing ground and ArcGIS was employed to visualize and validate the modeling results. The results of the analysis reveal promising insights that could lead to recommendations to help decision makers achieve a more cost-effective environmentally-friendly supply chain network.

09 BIOMASS FUELS↗

Pulse Electrodeposition for Carbonate-Rich Deposits from Seawater

Seawater electrodeposition is gaining renewed interest in the context of sustainable development, both to build climate-resilient coastal infrastructure and for ocean-based decarbonization applications. Most of the applications benefit from CaCO 3 -rich deposits, but constant-voltage electrodeposition results in a mixture of CaCO 3 and Mg(OH) 2 , especially at higher voltages where precipitation rates are more desirable. The use of pulse voltages can help control interfacial pH that dictates the precipitation reactions. Here, we explore the use of pulse electrodeposition as a function of pulse frequency and duty cycle to control deposit composition. The most CaCO 3 -rich deposits were obtained under 10 Hz frequency and 10% duty cycle conditions for the voltage window investigated (-0.8 V to -1.2 V vs. SCE). While pulsing the voltage increases the amount of CaCO 3 deposited, the energy required per gram of CaCO 3 is significantly higher (14.5×) when compared to the base case of applying a constant voltage of -0.8 V vs. SCE. Further optimization of pulse conditions, electrode materials, and system configuration could lead to finding parameters that result in exclusively carbonate deposits without compromising precipitation rates, which may prove to be more useful for corrosion protection, coastal infrastructure, and other applications in sustainable development.

54 ENVIRONMENTAL SCIENCES↗

High Performance Flow Battery with Inexpensive Inorganic Reactants: DAYS Program (Final Technical Report)

RTRC’s DAYS projects focused on new flow battery (FB) chemistries for long duration energy storage: one that pairs aqueous polysulfide and manganese active materials in strongly alkaline electrolytes (S/Mn); another explores ligand-modified metal (LMM) chemistries in moderate pH electrolyte conditions. The S/Mn chemistry met durability targets by running for over 500 cycles and 1000 hours. Combined with this durability, power densities of up to 60 mW/cm2 at 80% round-trip efficiency, and exceptionally low-cost S and Mn active materials, the S/Mn FB offers a pathway to meeting the <5¢/kW-hr levelized cost of storage (LCOS) target first proposed by the DAYS Program and accepted by the DOE Energy Storage Grand Challenge. The LMM chemistry made impressive progress as well, including durability tests that retained performance over 600 hours of cycling. Cell optimization allowed this chemistry to operate as high as 500 mW/cm2 at 80% round-trip efficiency, nearly 10x the power density of S/Mn and comparable to the power density achieved in RTRC’s flow battery stacks using acidic vanadium battery solutions. This enabled the LMM chemistry to also offer a pathway to the <5¢/kW-hr LCOS DAYS and DOE targets. The promising results from the LMM chemistry have led to a recent DOE AMO award to advance the technology to a 5 kW, 20 kW-hr prototype.

25 ENERGY STORAGE↗

Wheat production in controlled environments

Conditions are optimized for maximum yield and quality of wheat to be used in a controlled environment life support system (CELSS) in a Lunar or Martian base or a spacecraft. With yields of 23 to 57 g/sq m/d of edible biomass, a minimum size for a CELSS would be between 12 and 30 sq m per person, utilizing about 600 W/sq m of electrical energy for artificial light. Temperature, irradiance, photoperiod, carbon dioxide levels, humidity, and wind velocity are controlled in growth chambers. Nutrient solutions (adjusted for wheat) are supplied to the roots via a recirculating system that controls pH by adding HNO3 and controlling the NO3/NH4 ratio in solution. A rock-wool plant support allows direct seeding and densities up to 10,000 plants sq m. Densities up to 2000 plants/sq m appear to increase seed yield. Biomass production increases almost linearily with increasing irradiance from 400 to 1700 micromol/sq m/s of photosynthetic photon flux, but the efficiency of light utilization decreases over this range. Photoperiod and temperature both have a profound influence on floral initiation, spikelet formation, stem elongation, and fertilization.

Salisbury, Frank B.↗

Removal of phosphorus using biochar derived from Fenton sludge: Mechanism and performance insights

Abstract A phosphorus removal biochar adsorbent was prepared from Fenton sludge. The adsorption process was optimized, and its phosphorus adsorption mechanism was discussed. It was found that the phosphorus adsorption performance of biochar prepared from single Fenton sludge (FBC‐400) was better than that of co‐pyrolysis of Fenton sludge and bamboo powder. The optimum condition was that Fenton sludge pyrolyzed at 400°C (FBC‐400). FBC‐400 had a larger specific surface area than that prepared by co‐pyrolysis with bamboo powder. And the high content of iron element could provide a higher surface charge of the biochar, thereby increasing the electrostatic adsorption of phosphorus onto FBC‐400. The phosphorus adsorption was highly pH dependent by FBC‐400, which can enhance electrostatic adsorption and increase adsorption capacity in acidic conditions. The effect of coexisting anion on adsorption performance was mainly affected by CO 3 2− , reducing the adsorption capacity by at least 49%, whereas other anions had no obvious interference. The adsorption process of FBC‐400 accorded with the pseudo‐second‐order kinetic model and the Langmuir model, which indicated that the adsorption process was monolayer adsorption and mainly chemical adsorption, and the maximum saturated phosphorus adsorption capacity was 8.77 mg g −1 . The mechanisms for phosphorus adsorption were electrostatic adsorption and inner‐sphere complexing. 1 M NaOH was used for desorption, and the adsorption capacity remained at 81% in the fifth cycle. Practitioner Points The Fenton sludge biochar usage as an adsorbent could be a win‐win strategy to convert waste biomass to valuable ‐ product. The adsorption process accorded with the Langmuir model, the maximum phosphorus adsorption capacity was 8.77 mg/g at 25°C. The adsorption mechanisms were electrostatic adsorption and inner‐sphere complexing. 1M NaOH was used for desorption, and the adsorption capacity remained at 81% in the fifth cycle.

Liu, Yanfang↗

The Validity Chlorophyll-a Estimation by Sun Induced Fluorescence in Estuarine Waters: An Analysis of Long-term (2003-2011) Water Quality Data from Tampa Bay, Florida (USA)

Satellite observation of phytoplankton concentration or chlorophyll-a is an important characteristic, critically integral to monitoring coastal water quality. However, the optical properties of estuarine and coastal waters are highly variable and complex and pose a great challenge for accurate analysis. Constituents such as suspended solids and dissolved organic matter and the overlapping and uncorrelated absorptions in the blue region of the spectrum renders the blue-green ratio algorithms for estimating chlorophyll-a inaccurate. Measurement of sun-induced chlorophyll fluorescence, on the other hand, which utilizes the near infrared portion of the electromagnetic spectrum, may provide a better estimate of phytoplankton concentrations. While modelling and laboratory studies have illustrated both the utility and limitations of satellite baseline algorithms based on the sun induced chlorophyll fluorescence signal, few have examined the empirical validity of these algorithms using a comprehensive long term in situ data set. In an unprecedented analysis of a long term (2003-2011) in situ monitoring data from Tampa Bay, Florida (USA), we assess the validity of the FLH product from the Moderate Resolution Imaging Spectrometer (MODIS) against chlorophyll ]a and a suite of water quality parameters taken in a variety of conditions throughout a large optically complex estuarine system. A systematic analysis of sampling sites throughout the bay is undertaken to understand how the relationship between FLH and in situ chlorophyll-a responds to varying conditions within the estuary including water depth, distance from shore and structures and eight water quality parameters. From the 39 station for which data was derived, 22 stations showed significant correlations when the FLH product was matched with in situ chlorophyll-alpha data. The correlations (r2) for individual stations within Tampa Bay ranged between 0.67 (n=28, pless than 0.01) and-0.457 (n=12, p=.016), indicating that for some areas within the Bay, FLH can be a good predictor of chlorophyll-alpha concentration and hence a useful tool for the analysis of water quality. Overall, the results show a 106% increase in the validity of chlorophyll -a concentration estimates using FLH over the standard the blue-green OC3M algorithm. This analysis also illustrates that the correlations between FLH and in situ chlorophyll -a measurements increases with increasing water depth and distance of the monitoring sites from both the shore and structures. However, due to confounding factors related to the complexity of the estuarine system, a linear improvement in the FLH to chlorophyll ]a relationship was not clearly noted with increasing depth and distance from shore alone. Correlations of FLH with turbidity, nutrients (total nitrogen and total phosphorous) biological oxygen demand, salinity, sea surface temperature correlated positively with FLH concentrations, while dissolved oxygen and pH showed negative correlations. Principle component analyses are employed to further describe the relationships between the multivariate water quality parameters and the FLH product. The majority of sites with higher and very significant correlations (pless than 0.01) also showed high correlation values for nutrients, turbidity and biological oxygen demand. These sites were on average in greater than seven meters of water and over five kilometers from shore. A thorough understanding of the relationship between the MODIS FLH product and in situ water quality parameters will enhance our understanding of the accuracy MODIS fs global FLH algorithm and assist in optimizing its calibration for use in monitoring the quality of estuarine and coastal waters worldwide.

Moreno-Madrinan, Max Jacobo↗

Origins of wear-induced tungsten corrosion defects in semiconductor manufacturing during tungsten chemical mechanical polishing

During chemical mechanical polishing (CMP) process optimization, a unique corrosion defect was identified in the tungsten (W) contact plugs, which were investigated to develop practical solutions to improve CMP mass productivity. The corrosion defect occurred in the absence of external incident energy and was observed to occur only at the W plugs connected to the P + /n-well close to the wafer edge. To examine the root cause of the corrosion, a series of experiments was carried out at each W CMP step, using in-line defect inspection. Additional experiments were conducted using on-line inductively coupled plasma mass spectrometry (ICP-MS) to understand pH- and potential-dependent electrochemical dissolution behaviors of W. Experimentally, W corrosion was confirmed to be exacerbated if the surface oxide of the W plugs is removed by the deionized water (DIW) rinsing step under wafer pressurization, then exposed to DIW and alkaline cleaning solution. Although the DIW rinsing step is commonly performed to clean polishing pads right after the main polishing, a small amount of applied pressure (0.5 psi) without slurry supply can lead to corrosion defects. Finally, this wear-induced corrosion of the W plugs can be prevented by removing the applied pressure during the post DIW rinsing step of W CMP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗