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At least 847 records · Page 47

The Invigoration of Deep Convective Clouds Over the Atlantic: Aerosol Effect, Meteorology or Retrieval Artifact?

Associations between cloud properties and aerosol loading are frequently observed in products derived from satellite measurements. These observed trends between clouds and aerosol optical depth suggest aerosol modification of cloud dynamics, yet there are uncertainties involved in satellite retrievals that have the potential to lead to incorrect conclusions. Two of the most challenging problems are addressed here: the potential for retrieved aerosol optical depth to be cloud-contaminated, and as a result, artificially correlated with cloud parameters; and the potential for correlations between aerosol and cloud parameters to be erroneously considered to be causal. Here these issues are tackled directly by studying the effects of the aerosol on convective clouds in the tropical Atlantic Ocean using satellite remote sensing, a chemical transport model, and a reanalysis of meteorological fields. Results show that there is a robust positive correlation between cloud fraction or cloud top height and the aerosol optical depth, regardless of whether a stringent filtering of aerosol measurements in the vicinity of clouds is applied, or not. These same positive correlations emerge when replacing the observed aerosol field with that derived from a chemical transport model. Model-reanalysis data is used to address the causality question by providing meteorological context for the satellite observations. A correlation exercise between the full suite of meteorological fields derived from model reanalysis and satellite-derived cloud fields shows that observed cloud top height and cloud fraction correlate best with model pressure updraft velocity and relative humidity. Observed aerosol optical depth does correlate with meteorological parameters but usually different parameters from those that correlate with observed cloud fields. The result is a near-orthogonal influence of aerosol and meteorological fields on cloud top height and cloud fraction. The results strengthen the case that the aerosol does play a role in invigorating convective clouds.

Koren, Ilan↗

Effects of Interface Modification on Mechanical Behavior of Hi-Nicalon Fiber-Reinforced Celsian Matrix Composites

Unidirectional celsian matrix composites having approx. 42 volume percent of uncoated or BN/SiC-coated Hi-Nicalon fibers were tested in three-point bend at room temperature. The uncoated fiber-reinforced composites showed catastrophic failure with strength of 210 +/- 35 MPa and a flat fracture surface. In contrast, composites reinforced with BN/SiC-coated fibers exhibited graceful failure with extensive fiber pullout. Values of first matrix cracking stress and strain were 435 +/- 35 MPa and 0.27 +/- 0.01 %, respectively, with ultimate strength as high as 960 MPa. The elastic Young's modulus of the uncoated and BN/SiC-coated fiber-reinforced composites were measured as 184 q 4 GPa and 165 +/- 5 GPa, respectively. Fiber push-through tests and microscopic examination indicated no chemical reaction at the uncoated or coated fiber-matrix interface. The low strength of the uncoated fiber-reinforced composite is probably due to degradation of the fibers from mechanical surface damage during processing. Because both the coated and uncoated fiber reinforced composites exhibited weak interfaces, the beneficial effect of the BN-SiC dual layer is primarily the protection of fibers from mechanical damage during processing.

Bansal, Narottam P.↗

Improving the Transformation Efficiency of Synechococcus sp. PCC 7002 via Methylome-Guided Premethylation of DNA

Cyanobacteria are promising microbial platforms for a diverse set of biotechnology applications, from living materials to photosynthetic chemical production, but are less well characterized than commonly engineered microbes such as Escherichia coli. This study facilitates genetic engineering in Synechococcus sp. PCC 7002, a fast-growing, halotolerant, and naturally competent strain, by identifying ten native methylation motifs and designing shuttle strains that mimic the native methylation state by expressing a subset of heterologous methyltransferases. DNA methylation in E. coli with as few as two active methyltransferases increased transformation efficiency up to 30-fold across four distinct integration sites in PCC 7002. This work provides an experimental framework to bypass native restriction-modification systems for efficient genome editing and metabolic engineering in nonmodel bacteria.

59 BASIC BIOLOGICAL SCIENCES↗

An investigation of the physical and chemical changes of Pd nanoparticles on carbon supports in response to the release of hydrogen from aqueous formate solutions

Palladium nanoparticles on carbon supports (Pd/C) are effective for catalyzing hydrogen release from aqueous formate solutions but typically suffer from a gradual decrease of activity. This study finds two primary factors influencing activity: (i) the number of available surface Pd sites, and (ii) metal-support interactions which depend on the nature of the C support. We propose that the Pd/C catalyst is structure insensitive and undergoes Ostwald ripening to yield an active ‘conditioned’ catalyst with dispersion plateauing between ca. 15–20 %. Contrary to earlier studies, in-situ XANES experiments show that PdO is not an active catalyst for formate dehydrogenation. Calcination of Pd/C before dehydrogenation increases the catalytic activity which suggests a beneficial, albeit temporary, modification of the metal support interaction. N-containing supports minimize nanoparticle growth and also increase activity through a metal-support interaction. In conclusion, these findings advance our understanding of catalyst evolution and stability in formate dehydrogenation systems.

Formate dehydrogenation↗

Systematic Influence of Electronic Modification of Ligands on the Catalytic Rate of Water Oxidation by a Single-Site Ru-Based Catalyst

Catalytic water oxidation is an important process for the development of clean energy solutions and energy storage. Despite the significant number of reports on active catalysts, systematic control of the catalytic activity remains elusive. In this study, descriptors are explored that can be correlated with catalytic activity. [Ru(tpy)(pic) 2 (H 2 O)](NO 3 ) 2 and [Ru(EtO-tpy)(pic) 2 (H 2 O)](NO 3 ) 2 (where tpy=2,2': 6',2“-terpyridine, EtO-tpy=4'-(ethoxy)-2,':6',2”-terpyridine, pic=4-picoline) are synthesized and characterized by NMR, UV/Vis, EPR, resonance Raman, and X-ray absorption spectroscopy, and electrochemical analysis. Addition of the ethoxy group increases the catalytic activity in chemically driven and photocatalytic water oxidation. Thus, the effect of the electron-donating group known for the [Ru(tpy)(bpy)(H 2 O)] 2+ family is transferable to architectures with a tpy ligand trans to the Ru-oxo unit. Under catalytic conditions, [Ru(EtO-tpy)(pic) 2 (H 2 O)](NO 3 ) 2 displays new spectroscopic signals tentatively assigned to a peroxo intermediate. In conclusion, reaction pathways were analyzed by using DFT calculations. [Ru(EtO-tpy)(pic) 2 (H 2 O)](NO 3 ) 2 is found to be one of the most active catalysts functioning by a water nucleophilic attack mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design issues for a reinforcement-based self-learning fuzzy controller

Fuzzy logic controllers have some often cited advantages over conventional techniques such as PID control: easy implementation, its accommodation to natural language, the ability to cover wider range of operating conditions and others. One major obstacle that hinders its broader application is the lack of a systematic way to develop and modify its rules and as result the creation and modification of fuzzy rules often depends on try-error or pure experimentation. One of the proposed approaches to address this issue is self-learning fuzzy logic controllers (SFLC) that use reinforcement learning techniques to learn the desirability of states and to adjust the consequent part of fuzzy control rules accordingly. Due to the different dynamics of the controlled processes, the performance of self-learning fuzzy controller is highly contingent on the design. The design issue has not received sufficient attention. The issues related to the design of a SFLC for the application to chemical process are discussed and its performance is compared with that of PID and self-tuning fuzzy logic controller.

Yen, John↗

A study of low emissions gas turbine combustions

Analytical studies have been conducted to determine the best methods of reducing NO(x) emissions from proposed civilian supersonic transports. Modifications to the gas turbine engine combustors and the use of additives were both explored. It was found that combustors which operated very fuel rich or lean appear to be able to meet future emissions standards. Ammonia additives were also effective in removing NO(x), but residual ammonia remained a problem. Studies of a novel combustor which reduces emissions and improves performance were initiated. In a related topic, a study was begun on the feasibility of using supersonic aircraft to obtain atmospheric samples. The effects of shock heating and compression on sample integrity were modeled. Certain chemical species, including NO2, HNO3, and ClONO2 were found to undergo changes to their composition after they passed through shock waves at Mach 2. The use of detonation waves to enhance mixing and combustion in supersonic airflows was also investigated. This research is important to the use of airbreathing propulsion to obtain orbital speeds and access to space. Both steady and pulsed detonation waves were shown to improve engine performance.

Adelman, Henry G.↗

Design, development and analysis of large-area industrial silicon solar cells featuring a full area polysilicon based passivating contact on the rear and selective passivating contacts on the front

We present SERIS’ biPoly™ technology platform on large-area (M2), n-type rear-junction silicon solar cells featuring selective poly-Si/SiOx based passivated contacts on the front side and full-area poly-Si/SiOx contacts on the rear. The selective poly-Si ‘fingers’ are formed using an industrial ink-jet masking process followed by wet-chemical etching. The metal contacts are formed by an industrial screen-printing process using high-temperature fire-though metal pastes. We obtain excellent passivation on the front and rear surfaces, resulting in iVoc values between 720 mV and 730 mV on unmetallized solar cells. After high-temperature metallization, we achieve 22% efficiency on solar cells with selective poly-Si fingers on the front. We further develop the model for biPoly™ solar cells and with the help of a detailed loss analysis and simulations, identify the various loss components to identify the device modifications required for efficiency improvements.

36 MATERIALS SCIENCE↗

High temperature thermocouple development program, part A and part B

The problem of extending the useful life of thermocouples intended for in-core and out-of-core thermionic applications in a vacuum environment at temperatures up to 2273 K for periods of time up to 10,000 hours was investigated. Many factors that may influence this useful life were examined, and a basic probe design was developed. With a few modifications, twenty-three thermocouple assemblies were fabricated. Generally the finished thermocouple consisted of solid doped W-3% Re and W-25% Re wires and high purity and high density BeO insulators, and was sheathed in a high purity tantalum tube. In a few probes, stranded thermocouple wires were substituted; commercial grade BeO was used; and in two cases, CVD W-22% Re tubing was used. Each of the components was made of the highest purity materials available; was subjected to special cleaning steps, and was assembled in a class 10,000 clean room. Pertinent physical and chemical properties were determined on each of the components. Special processing techniques were used in the fabrication of the high purity (99.95%), high density (over 95% of theoretical) BeO.

Toenshoff, D. A.↗

Realistic Ion Dynamics through Charge Renormalization in Nonaqueous Electrolytes

While many practically important electrolytes contain lithium ions, interactions of these ions are particularly difficult to probe experimentally because of their small X-ray and neutron scattering cross sections and large neutron absorption cross sections. Molecular dynamics (MD) is a powerful tool for understanding the properties of nonaqueous electrolyte solutions from the atomic level, but the accuracy of this computational method crucially depends on the physics built into the classical force field. In this study, we demonstrate that several force fields for lithium bistriflimide (LiTFSI) in acetonitrile yield a solution structure that is consistent with the neutron scattering experiments, yet these models produce dramatically different ion dynamics in solution. Such glaring discrepancies indicate that inadequate representation of long-range interactions leads to excessive ionic association and ion-pair clustering. We show that reasonable agreement with the experimental observations can be achieved by renormalization of the ion charges using a “titration” method suggested herewith. This simple modification produces realistic concentration dependencies for ionic diffusion and conductivity in <2 M solutions, without loss in quality for simulation of the structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Melt Processing Pretreatment Effects on Enzymatic Depolymerization of Poly(ethylene terephthalate)

Poly(ethylene terephthalate) (PET) is a common thermoplastic material, used in a wide variety of applications (i.e., bottles, fabrics, packaging, electronics, and automotive components). Increasing demand for PET has precipitated a need for improved recycling technology, especially for single-use PET waste. Recently, enzymatic depolymerization has shown promise as an environmentally responsible alternative for PET chemical recycling that yields economically useful products (e.g., terephthalic acid, adipic acid, and ethylene glycol). However, the depolymerization system still suffers from low rates on crystalline PET substrates, and effects of realistic waste streams are not known. In our work, PET waste is pretreated using an ultra-high-speed twin-screw extruder system. PET substrates were modified by various processing pretreatments to allow enzymes better access to depolymerize substrate materials. The effect of varying throughput and mechanical shear on structural properties of the PET waste was analyzed using molecular weight and thermal characterizations. These pretreated samples exhibit modifications in molecular weight, glass transition temperature, crystallinity, and specific surface area. The unpurified leaf-branch compost cutinase enzyme produced from the fed-batch fermentation of Escherichia coli BL21(DE3) was used in enzymatic depolymerization, where a faster reaction was observed as crystallinity was decreased and the specific surface area was increased. The rate of terephthalic acid production was also significantly higher for samples processed at lower mechanical shear with higher throughputs. As a result, this work demonstrates the potential for tailoring pretreatments in pursuit of faster and more energy efficient PET recycling using enzymes, with facile adaptation to the industrial scale for the circular economy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pioneer Jupiter Orbiter/Probe mission. I - Spacecraft system description

This paper discusses the Pioneer Jupiter Orbiter/Probe mission with emphasis on the orbiter spacecraft system. In this mission, the atmosphere of Jupiter will be investigated for physical and chemical structure by a probe which survives entry and transmits data while descending below the 10-bar level. The spacecraft deflects after probe separation to a nonimpacting approach trajectory, acts as a communications relay for data from the descending probe, and propulsively enters an orbit about Jupiter. As an orbiter, it explores the environment of Jupiter for three years, making in situ measurements of the particles and fields of the Jovian magnetosphere together with remote measurements (including images) of Jupiter and the Galilean satellites. The spacecraft system is logically based on the design of Pioneers 10 and 11 with modifications for these different mission requirements: antenna, receiver, and memory for the probe-spacecraft data link; a retropropulsion system for the high velocity-change requirements of orbit insertion; a data system consistent with the requirements of a line-scan imaging system; and an improved complement of radioisotope-thermoelectric-generator power sources to provide adequate power six years after launch.

Lassen, H. A.↗

Highly efficient Pt catalyst on newly designed CeO 2 -ZrO 2 -Al 2 O 3 support for catalytic removal of pollutants from vehicle exhaust

Pt-CeO 2 catalysts have been widely studied for the vehicle emission control. Designing novel CeO 2 based supports with improved physical-chemical properties has become a research hotspot to further promote the catalytic performance and stability of Pt-CeO 2 catalysts. In this work, through utilizing a unique, two-step incipient wetness impregnation (T-IWI) method for ceria-zirconia-alumina (CZA-T) support preparation, a Pt single site catalyst (Pt/CZA-T) with excellent thermal stability was synthesized. Higher oxidation activity and Oxygen storage capacity (OSC) were achieved on activated Pt/CZA-T, comparing to Pt catalysts on regular CeO 2 /Al 2 O 3 (Pt/CA) and one-step prepared CeZrO x /Al 2 O 3 (Pt/CZA). Via the modification of hydrophilic/hydrophobic properties of γ-Al 2 O 3 by this unique T-IWI method, finer Ce 0.9 Zr 0.1 O 2 particles with higher density of surface defects were formed on CZA-T, on which a higher Pt dispersion and stronger Pt-O-Ce interaction were achieved. Upon activation, smaller, well-dispersed Pt clusters on CZA-T were generated. It was concluded that the CO oxidation performance and OSC were highly related to the size of Pt clusters on different supports that we have developed. Finally, more Pt sites located at Pt cluster-CeZrO x interfaces, which were the real active sites, were responsible for the highest OSC function and CO oxidation activity of activated Pt/CZA-T catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Manipulation in Piezoresponse Force Microscopy: Creating Nonequilibrium Phases with Large Electromechanical Response

We discuss how domain walls and topological defects in ferroelectric materials have emerged as a powerful tool for functional electronic devices including memory and logic. Similarly, wall interactions and dynamics underpin a broad range of mesoscale phenomena ranging from giant electromechanical responses to memory effects. Exploring the functionalities of individual domain walls, their interactions, and controlled modifications of the domain structures is crucial for applications and fundamental physical studies. However, the dynamic nature of these features severely limits studies of their local physics since application of local biases or pressures in piezoresponse force microscopy induce wall displacement as a primary response. Here, we introduce an approach for the control and modification of domain structures based on automated experimentation, whereby real-space image-based feedback is used to control the tip bias during ferroelectric switching, allowing for modification routes conditioned on domain states under the tip. This automated experiment approach is demonstrated for the exploration of domain wall dynamics and creation of metastable phases with large electromechanical response.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Global biogeochemical cycles: Studies of interaction and change, some views on the strategy of approach

The global biosphere is an exceedingly complex system. To gain an understanding of its structure and dynamic features, it is necessary to increase knowledge about the detailed processes, but also to develop models of how global interactions take place. Attempts to analyze the detailed physical, chemical and biological processes need, in this context, to be guided by an advancement of understanding of the latter. It is necessary to develop a strategy of data gathering that serves both these purposes simultaneously. climate research during the last decade may serve as a useful example of how to approach this difficult problem in a systematic way. Large programs for data collection may easily become rigid and costly. While realizing the necessity of a systematic and long lasting effort of observing the atmosphere, the oceans, land and life on Earth, such a program must remain flexible enough to permit the modifications and even sometimes improvisations that are necessary to maintain a viable program.

Bolin, B.↗

ASTRO-2 Spacelab Instrument Pointing System mission performance

This paper reports the performance of the Instrument Pointing System (IPS) that flew on the National Aeronautics and Space Administration (NASA) ASTRO-2 Spacelab mission aboard the Space Shuttle Endeavour in March 1995. The IPS provides a stabilizing platform for the ASTRO-2 instrument payload complement that consists of three main experiments (telescopes). The telescopes observe stellar targets in the universe within the ultraviolet portion of the electromagnetic spectrum that must be observed from beyond the earth's atmospheric filtering effects. The three main experiments for observation are the Hopkins Ultraviolet Telescope (HUT), the Ultraviolet Imaging Telescope (UIT), and the Wisconsin Ultraviolet Photo-Polarimetry Experiment (WUPPE). The HUT uses spectroscopy to obtain the structure and chemical makeup of ultraviolet targets. UIT is responsible for wide field photographing to capture the hidden view of the ultraviolet universe. The WUPPE gathers data on the polarization of the ultraviolet electromagnetic energy coming from the astronomical targets. The capability of IPS enables the experiments to 'see' faint celestial objects. A brief explanation of the IPS is given followed by a review of engineering efforts to improve IPS performance over the ASTRO-1 mission. The main focus of improvements was on enhancing the star acquisition capability through improved guide star selection, lab simulations, computer upgrades, data display systems improvements, and software modifications. A star simulator was developed in the lab to enable IPS to be simulated on the ground pre-mission with flight hardware and software in the loop. The paper concludes with results from the ASTRO-2 mission. The number of targets acquired and the IPS pointing accuracy/stability is reported along with recommendations for the future use of the Instrument Pointing System.

Wessling, Francis C., III↗

Evaluation of a New Cloud Droplet Activation Parameterization wtih in Situ Data from CRYSTAL-FACE and CSTRIPE

The accuracy of the 2003 prognostic, physically based aerosol activation parameterization of A. Nenes and J. H. Seinfeld (NS) with modification introduced by C. Fountoukis and A. Nenes in 2005 (modified NS) is evaluated against extensive microphysical data sets collected on board the Center for Interdisciplinary Remotely Piloted Aircraft Studies (CIRPAS) Twin Otter aircraft for cumuliform and stratiform clouds of marine and continental origin. The cumuliform cloud data were collected during NASA's Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE, Key West, Florida, July 2002), while the stratiform cloud data were gathered during Coastal Stratocumulus Imposed Perturbation Experiment (CSTRIPE, Monterey, California, July 2003). In situ data sets of aerosol size distribution, chemical composition, and updraft velocities are used as input for the NS parameterization, and the evaluation is carried out by comparing predicted cloud droplet number concentrations (CDNC) with observations. This is the first known study in which a prognostic cloud droplet activation parameterization has been evaluated against a wide range of observations. On average, predicted droplet concentration in adiabatic regions is within -20% of observations at the base of cumuliform clouds and -30% of observations at different altitudes throughout the stratiform clouds, all within experimental uncertainty. Furthermore, CDNC is well parameterized using either a single mean updraft velocity w or by weighting droplet nucleation rates with a Gaussian probability density function of w. This study suggests that for nonprecipitating warm clouds of variable microphysics, aerosol composition, and size distribution the modified NS parameterization can accurately predict cloud droplet activation and can be successfully implemented for describing the aerosol activation process in global climate models.

Meskhidze, Nicholas↗

Reversible Modification of Rashba States in Topological Insulators at Room Temperature by Edge Functionalization

Quantum materials with novel spin textures from strong spin-orbit coupling (SOC) are essential components for a wide array of proposed spintronic devices. Topological insulators have a necessary strong SOC that imposes a unique spin texture on topological states and Rashba states that arise on the boundary, but there is no established methodology to control the spin texture reversibly. Here, it is demonstrated that functionalizing Bi 2 Se 3 films by altering the step-edge termination directly changes the strength of SOC and thereby modifies the Rashba strength of 1D edge states. Scanning tunneling microscopy/spectroscopy shows that these Rashba edge states arise and subsequently vanish through the Se functionalization and reduction process of the step edges. The observations are corroborated by density functional theory calculations, which show that a subtle chemical change of edge termination fundamentally alters the underlying electronic structure. Importantly, fully reversible and repeatable switching of Rashba edge states across multiple cycles at room temperature is experimentally demonstrated. The results imply Se functionalization as a practical method to control SOC and spin texture of quantum states in topological insulators.

Rashba edge states↗