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At least 451 records · Page 25

Efficient electrocatalytic valorization of chlorinated organic water pollutant to ethylene

Electrochemistry can provide an efficient and sustainable way to treat environmental waters polluted by chlorinated organic compounds. However, the electrochemical valorization of 1,2-dichloroethane (DCA) is currently challenged by the lack of a catalyst that can selectively convert DCA in aqueous solutions into ethylene. Here, in this work, we report a catalyst comprising cobalt phthalocyanine molecules assembled on multiwalled carbon nanotubes that can electrochemically decompose aqueous DCA with high current and energy efficiencies. Ethylene is produced at high rates with unprecedented ~100% Faradaic efficiency across wide electrode potential and reactant concentration ranges. Kinetic studies and density functional theory calculations reveal that the rate-determining step is the first C–Cl bond breaking, which does not involve protons—a key mechanistic feature that enables cobalt phthalocyanine/carbon nanotube to efficiently catalyse DCA dechlorination and suppress the hydrogen evolution reaction. The nanotubular structure of the catalyst enables us to shape it into a flow-through electrified membrane, which we have used to demonstrate >95% DCA removal from simulated water samples with environmentally relevant DCA and electrolyte concentrations.

Choi, Chungseok↗

An introduction to Spent Nuclear Fuel decay heat for Light Water Reactors: a review from the NEA WPNCS

This paper summarized the efforts performed to understand decay heat estimation from existing spent nuclear fuel (SNF), under the auspices of the Working Party on Nuclear Criticality Safety (WPNCS) of the OECD Nuclear Energy Agency. Needs for precise estimations are related to safety, cost, and optimization of SNF handling, storage, and repository. The physical origins of decay heat (a more correct denomination would be decay power) are then introduced, to identify its main contributors (fission products and actinides) and time-dependent evolution. Due to limited absolute prediction capabilities, experimental information is crucial; measurement facilities and methods are then presented, highlighting both their relevance and our need for maintaining the unique current full-scale facility and developing new ones. The third part of this report is dedicated to the computational aspect of the decay heat estimation: calculation methods, codes, and validation. Different approaches and implementations currently exist for these three aspects, directly impacting our capabilities to predict decay heat and to inform decision-makers. Finally, recommendations from the expert community are proposed, potentially guiding future experimental and computational developments. One of the most important outcomes of this work is the consensus among participants on the need to reduce biases and uncertainties for the estimated SNF decay heat. If it is agreed that uncertainties (being one standard deviation) are on average small (less than a few percent), they still substantially impact various applications when one needs to consider up to three standard deviations, thus covering more than 95% of cases. The second main finding is the need of new decay heat measurements and validation for cases corresponding to more modern fuel characteristics: higher initial enrichment, higher average burnup, as well as shorter and longer cooling time. Similar needs exist for fuel types without public experimental data, such as MOX, VVER, or CANDU fuels. A third outcome is related to SNF assemblies for which no direct validation can be performed, representing the vast majority of cases (due to the large number of SNF assemblies currently stored, or too short or too long cooling periods of interest). A few solutions are possible, depending on the application. For the final repository, systematic measurements of quantities related to decay heat can be performed, such as neutron or gamma emission. This would provide indications of the SNF decay heat at the time of encapsulation. For other applications (short- or long-term cooling), the community would benefit from applying consistent and accepted recommendations on calculation methods, for both decay heat and uncertainties. This would improve the understanding of the results and make comparisons easier.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Identifying and characterizing ultracool dwarfs ejected from post-encounter disintegrating systems

ABSTRACT Disintegrating multiple systems have been previously discovered from kinematic studies of the Hipparcos catalogue. They are presumably the result of dynamical encounters taking place in the Galactic disc between single/multiple systems. In this paper, we aim to expand the search for such systems, to study their properties, as well as to characterize possible low-mass ejecta (i.e. brown dwarfs and planets). We have assembled a list of 15 candidate systems using astrometry from the Tycho-Gaia astrometric solution (later upgraded with Gaia DR3), and here we present the discovery and follow-up of five of them. We have obtained DECam imaging for all five systems and by combining near-infrared photometry and proper motion, we searched for ultracool ejected components. We find that the system consisting of TYC 7731-1951-1, TYC 7731-2128 AB, and TYC 7731-1995-1ABC?, contains one very promising ultracool dwarf candidate. Using additional data from the literature, we have found that three out of five disintegrating system candidates are likely to be true disintegrating systems.

Astronomy & Astrophysics↗

A Multi-Scale Computational Platform for Predictive Modeling of Corrosion in Al-Steel Joints (Final Report)

The research team proposed to develop innovative multi-scale models to predict corrosion and the resulting mechanical performances in aluminum-steel joints. The methods of joining considered are resistance spot welding, self-piercing riveting, and rivet-welding, all suitable for mass production applications. The multi-scale models integrate high throughput first-principle calculations based on density functional theory (DFT), high throughput calculation of phase diagrams (CALPHAD) modeling, and finite element method (FEM) simulations. These models are to be validated through laboratory experiments. Furthermore, the models are available as open source so as to enable scientists and engineers in the community to adapt and contribute to the development and application. The approaches rely on the research team’s extensive experience on the prediction of properties of individual phases at finite temperatures and variable compositions through DFT calculations, and our broad expertise on dissimilar material joining and their corrosion. The proposed computational framework enables high throughput computations for improved predictions of corrosion and the associated mechanical performance in dissimilar material joints, resulting in significant reduction in computational time needed by the current state-of-the-art methods. With the participation of researchers from three universities, an auto manufacturer, two manufacturing technology/equipment suppliers, and a software developer/vendor, the interdisciplinary research team applies the technical development on both phase-based modeling and laboratory experiments into the automobile body joining processes for validation and technology demonstration. The global cost of corrosion was estimated at about 3.4% of the global GDP in 2013. By using available corrosion control practices, it is estimated a saving between 15-35% of the cost of corrosion. In the U.S., more than $276 billion is spent repairing corrosion damage. Prediction of the corrosion and its impact on performance of the dissimilar material joints is critical for reducing the massive number of the current corrosion-based recalls for automobiles. Thus, the project goal is to develop models to enable predictive maintenance and end-of-life planning of multi-metal joints with risk of corrosion under different conditions such as exposure to high temperatures in summer and salt solutions in winter, quantified through its pH. An academia-industry consortium led by the University of Michigan and including Pennsylvania State University, University of Illinois Urbana-Champaign, University of Georgia, General Motors Company, Livermore Software Technology Corporation, and Optimal Process Technologies, LLC. created multi-scale models for prediction of corrosion in aluminum-steel joint structures such of them used in vehicle subassemblies – chassis and transmission systems. Starting from the first principle calculations, the team developed mathematical and data-driven models to predict the metallic components, which are formed during joining of two metals, for example aluminum and steel - a lightweight multilateral system which is currently used in more than 60% car bodies. These models were used for simulating chemical reactions that are happening when the joining metallic components are exposed to high temperatures and different pH values. The team was able to predict how the corrosion installs on the metallic components and how they lead to a sudden failure of components in cars. Newly developed machine learning algorithms combining Science, Technology, Engineering and Math disciplines, advanced finite element simulation and experimental validations have been integrated in a platform for prediction of the corrosion evolution and prediction the failure of joints under mechanical loadings and fatigue. Moreover, based on machine learning and inverse analysis, the team proposed solutions for designing new metallic alloys less susceptible to corrosion when joining multi-material assembles. An average of 4% error compared with experiments was achieved for the most common joints that are used in vehicle subassemblies.

36 MATERIALS SCIENCE↗

Using Al 3+ to Tailor Graphene Oxide Nanochannels: Impact on Membrane Stability and Permeability

Graphene oxide (GO) membranes, which form from the lamination of GO sheets, attract much attention due to their unique nanochannels. There is much interest in controlling the nanochannel structures and improving the aqueous stability of GO membranes so they can be effectively used in separation and filtration applications. This study employed a simple yet effective method of introducing trivalent aluminum cations to a GO sheet solution through the oxidation of aluminum foil, which modifies the nanochannels in the self-assembled GO membrane by increasing the inter-sheet distance while decreasing intra-sheet spacing. The Al 3+ modification resulted in an increase in membrane stability in water, methanol, ethanol, and propanol, yet decreased membrane permeability to water and propanol. These changes were attributed to strong interactions between Al 3+ and the membrane oxygenated functional groups, which resulted in an increase in membrane hydrophobicity and a decrease in the intra-sheet spacing as supported by surface tension, contact angle, atomic force microscopy, and X-ray photoelectron spectroscopy measurements. Our approach for forming Al 3+ modified GO membranes provides a method for improving the aqueous stability and tailoring the permeation selectivity of GO membranes, which have the potential to be implemented in vapor separation and fuel purification applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The LEMMA concept - A new manipulator

The LEMMA is a proposed conceptual design of a remote teleoperator manipulator arm with 6 degrees of freedom, exclusive of the end-effector. The bevel gear arrangement in 4 of the 6 degrees of freedom, together with the concentric-tubular arm configuration, requires a unique and novel drive mechanism. This differential drive assembly, housed in the shoulder, is a self-compensating device and simplifies the matrix solution for the resolved motion rate control system needed to guide the arm in its performances. The article will describe the need for the 6 degrees of freedom as established by the work envelope, the functioning of the differential shoulder drive, the arm and joint configuration, and the anticipated degree of accuracy.

Kersten, L.↗

Substructure program for analysis of helicopter vibrations

A substructure vibration analysis which was developed as a design tool for predicting helicopter vibrations is described. The substructure assembly method and the composition of the transformation matrix are analyzed. The procedure for obtaining solutions to the equations of motion is illustrated for the steady-state forced response solution mode, and rotor hub load excitation and impedance are analyzed. Calculation of the mass, damping, and stiffness matrices, as well as the forcing function vectors of physical components resident in the base program code, are discussed in detail. Refinement of the model is achieved by exercising modules which interface with the external program to represent rotor induced variable inflow and fuselage induced variable inflow at the rotor. The calculation of various flow fields is discussed, and base program applications are detailed.

Sopher, R.↗

Turbine-Driven Pipe-Cleaning Brush

Simple pipe-cleaning device includes small turbine wheel axially connected, by standoff, to circular brush. Turbine wheel turns on hub bearing attached to end of upstream cable. Turbine-and-brush assembly inserted in pipe with cable trailing upstream and brush facing downstream. Water or cleaning solution pumped through pipe. Cable held at upstream end, so it holds turbine and brush in pipe at location to be cleaned. Flow in pipe turns turbine, which turns wheel, producing desired cleaning action. In addition to brushing action, device provides even mixing of cleaning solution in pipe.

Werlink, Rudy J.↗

NASA's Ares I and Ares V Launch Vehicles -- Effective Space Operations Through Efficient Ground Operations

The United States (U.S.) plans to return to the Moon by 2020, with the development of a new human-rated space transportation system to replace the Space Shuttle, which is due for retirement in 2010 after it completes its missions of building the International Space Station and servicing the Hubble Space Telescope. Powering the future of space-based scientific exploration will be the Ares I Crew Launch Vehicle, which will transport the Orion Crew Exploration Vehicle to orbit where it will rendezvous with the Lunar Lander. which will be delivered by the Ares V Cargo Launch Vehicle. This new transportation infrastructure, developed by the National Aeronautics and Space Administration (NASA), will allow astronauts to leave low-Earth orbit for extended lunar exploration and preparation for the first footprint on Mars. All space-based operations begin and are controlled from Earth. NASA's philosophy is to deliver safe, reliable, and cost-effective solutions to sustain a multi-billion-dollar program across several decades. Leveraging 50 years of lessons learned, NASA is partnering with private industry, while building on proven hardware experience. This paper will discuss how the Engineering Directorate at NASA's Marshall Space Flight Center is working with the Ares Projects Office to streamline ground operations concepts and reduce costs. Currently, NASA's budget is around $17 billion, which is less than 1 percent of the U.S. Federal budget. Of this amount, NASA invests approximately $4.5 billion each year in Space Shuttle operations, regardless of whether the spacecraft is flying or not. The affordability requirement is for the Ares I to reduce this expense by 50 percent, in order to allow NASA to invest more in space-based scientific operations. Focusing on this metric, the Engineering Directorate provides several solutions-oriented approaches, including Lean/Six Sigma practices and streamlined hardware testing and integration, such as assembling major hardware elements before shipping to the Kennedy Space Center for launch operations. This paper provides top-level details for several cost saving initiatives, including both process and product improvements that will result in space transportation systems that are designed with operations efficiencies in mind. The Engineering Directorate provides both the intellectual capital embodied in an experienced workforce and unique facilities in which to validate the information technology tools that allow a nationwide team to collaboratively connect across miles that separate them and the engineering disciplines that integrate various piece parts into a whole system. As NASA transforms ground-based operations, it also is transitioning its workforce from an era of intense hands-on labor to a new one of mechanized conveniences and robust hardware with simpler interfaces. Ensuring that space exploration is on sound footing requires that operations efficiencies be designed into the transportation system and implemented in the development stage. Applying experience gained through decades of ground and space op'erations, while using value-added processes and modern business and engineering tools, is the philosophy upon which a new era of exploration will be built to solve some of the most pressing exploration challenges today -- namely, safety, reliability, and affordability.

Dumbacher, Daniel L.↗

Silicon/Carbon Nanotube Photocathode for Splitting Water

A proof-of-concept device is being developed for hydrogen gas production based on water-splitting redox reactions facilitated by cobalt tetra-aryl porphyrins (Co[TArP]) catalysts stacked on carbon nanotubes (CNTs) that are grown on n-doped silicon substrates. The operational principle of the proposed device is based on conversion of photoelectron energy from sunlight into chemical energy, which at a later point, can be turned into electrical and mechanical power. The proposed device will consist of a degenerately n-doped silicon substrate with Si posts covering the surface of a 4-in. (approximately equal to 10cm) wafer. The substrate will absorb radiation, and electrons will move radially out of Si to CNT. Si posts are designed such that the diameters are small enough to allow considerable numbers of electrons to transport across to the CNT layer. CNTs will be grown on top of Si using conformal catalyst (Fe/Ni) deposition over a thin alumina barrier layer. Both metallic and semiconducting CNT will be used in this investigation, thus allowing for additional charge generation from CNT in the IR region. Si post top surfaces will be masked from catalyst deposition so as to prevent CNT growth on the top surface. A typical unit cell will then consist of a Si post covered with CNT, providing enhanced surface area for the catalyst. The device will then be dipped into a solution of Co[TArP] to enable coating of CNT with Co(P). The Si/CNT/Co [TArP] assembly then will provide electrons for water splitting and hydrogen gas production. A potential of 1.23 V is needed to split water, and near ideal band gap is approximately 1.4 eV. The combination of doped Si/CNT/Co [TArP] will enable this redox reaction to be more efficient.

Amashukeli, Xenia↗

Fabrication of a Composite Tow-Steered Structure for Air-Launch Vehicle Applications

Generation Orbit (GO) is developing the GO Launcher-1 (GO-1), a single stage liquid rocket that is launched from a Gulfstream III carrier aircraft platform. The vehicle is designed as the next generation platform for hypersonic flight testing and suborbital microgravity research. To reduce mass and increase payload, GO partnered with NASA Langley Research Center to design, analyze, optimize, and fabricate a tow-steered manufacturing development unit of a cylindrical section of a liquid oxygen tank. The fabrication process of using the ISAAC (Integrated Structural Assembly of Advanced Composites) system is described. The structural design challenges and the concept design solutions are also presented to provide the context for the fabrication process. The in-situ nondestructive evaluation supporting the effort is also described.

Grenoble, Ray↗

Impact of Irradiation and Decay Time on Chemical Speciation in Uranyl Sulfate Solution

A pH-1, 200-g U/L, highly enriched uranyl sulfate solution was neutron-irradiated using an accelerator-driven neutron source (the Universal Neutron Irradiator, UNI) to fission U-235 under conditions similar to those used by SHINE to produce Mo-99 in a subcritical assembly. We completed a series of five uranyl sulfate irradiations to assess the impact of irradiation and decay time on uranium precipitation and iodine speciation in solution. The duration of each irradiation was increased in order, with the shortest irradiation taking 2.9 hours and the longest, 64.5 hours. A total of 9.5E16 U-235 nuclei were fissioned in all irradiations, and a maximum fission power density of 0.26 W/mL was reached in the final irradiation. We observed no evidence of uranyl peroxide or other precipitates, demonstrating that the addition of Fe 2+ to a final Fe concentration of 200 ppm in the target solution was successful at preventing precipitation under representative irradiation conditions. Nonvolatile I - was found to be the dominant (>70%) iodine species in solution, both immediately after irradiation and after days to weeks of decay time.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Effects of Convective Transport of Solute and Impurities on Defect-Causing Kinetics Instabilities

For in-situ studies of the formation and evolution of step patterns during the growth of protein crystals, we have designed and assembled an experimental setup based on Michelson interferometry with the surface of the growing protein crystal as one of the reflective surfaces. The crystallization part of the device allows optical monitoring of a face of a crystal growing at temperature stable within 0.05 C in a developed solution flow of controlled direction and speed. The reference arm of the interferometer contains a liquid-crystal element that allows controlled shifts of the phase of the interferograms. We employ an image processing algorithm which combines five images with a pi/2 phase difference between each pair of images. The images are transferred to a computer by a camera capable of capturing 6-8 frames per second. The device allows data collection data regarding growth over a relatively large area (approximately .3 sq. mm) in-situ and in real time during growth. The estimated dept resolution of the phase shifting interferometry is about 100 A. The lateral resolution, depending on the zoom ratio, varies between 0.3 and 0.6 micrometers. We have now collected quantitative results on the onset, initial stages and development of instabilities in moving step trains on vicinal crystal surfaces at varying supersaturation, position on the facet, crystal size and temperature with the proteins ferritin, apoferritin and thaumatin. Comparisons with theory, especially with the AFM results on the molecular level processes, see below, allow tests of the rational for the effects of convective flows and, as a particular case, the lack thereof, on step bunching.

Vekilov, Peter G.↗

Self-assembly of aramid amphiphiles into ultra-stable nanoribbons and aligned nanoribbon threads

Small molecule self-assembly is an established route for producing high surface area nanostructures with readily customizable chemistries and precise molecular organization. However, these structures are fragile, exhibiting molecular exchange, migration, and rearrangement - among other dynamic instabilities - and ultimately disassociate upon drying. Here we show a small molecule platform, the aramid amphiphile (AA), that overcomes these dynamic instabilities by incorporating a Kevlar-inspired domain into the molecular structure. Strong, anisotropic interactions between AAs suppress molecular exchange and elicit spontaneous self-assembly in water to form nanoribbons with lengths of up to 20 microns. The nanoribbons have a Young’s modulus of 1.7 GPa and tensile strength of 1.9 GPa. Here, we exploit this stability to extend small molecule self-assembly to hierarchically ordered macroscopic materials outside of solvated environments. Through an aqueous shear alignment process, we organize AA nanoribbons into arbitrarily long flexible threads that support 200 times their weight when dried. Tensile tests of the threads provide a benchmark for Young’s moduli (between ~400 and 600 MPa) and extensibilities (between ~0.6 and 1.1%) that depend on the counterion chemistry in solution. This bottom-up approach to macroscopic materials could benefit solid-state applications, historically inaccessible by self-assembled nanomaterials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Physical phenomena and the microgravity response

The living biological cell is not a sack of Newtonian fluid containing systems of chemical reactions at equilibrium. It is a kinetically driven system, not a thermodynamically driven system. While the cell as a whole might be considered isothermal, at the scale of individual macromolecular events there is heat generated, and presumably sharp thermal gradients exist at the submicron level. Basic physical phenomena to be considered when exploring the cell's response to inertial acceleration include particle sedimentation, solutal convection, motility electrokinetics, cytoskeletal work, and hydrostatic pressure. Protein crystal growth experiments, for example, illustrate the profound effects of convection currents on macromolecular assembly. Reaction kinetics in the cell vary all the way from diffusion-limited to life-time limited. Transport processes vary from free diffusion, to facilitated and active transmembrane transport, to contractile-protein-driven motility, to crystalline immobilization. At least four physical states of matter exist in the cell: aqueous, non-aqueous, immiscible-aqueous, and solid. Levels of order vary from crystalline to free solution. The relative volumes of these states profoundly influence the cell's response to inertial acceleration. Such subcellular phenomena as stretch-receptor activation, microtubule re-assembly, synaptic junction formation, chemotactic receptor activation, and statolith sedimentation were studied recently with respect to both their basic mechanisms and their responsiveness to inertial acceleration. From such studies a widespread role of cytoskeletal organization is becoming apparent.

Todd, Paul↗

Self-Assembling Metabolon Enables the Cell Free Conversion of Glycerol to 1,3-Propanediol

Cell free biocatalysis is showing promise as a replacement or complement to conventional microbial biocatalysts due to the potential for achieving high yields, titers, and productivities. However, there exist several challenges that need to be addressed before its broader industrial adoption is achieved. New paradigms and innovative solutions are needed to overcome these challenges. In this study we demonstrate high levels of glycerol conversion to 1,3-propanediol using a self-assembling metabolic pathway leveraging the arraying strategy (protein scaffolds) used by thermophilic cellulolytic bacteria to assemble their biomass degrading enzymes. These synthetic metabolons were capable of producing 1,3-PDO at a yield more than 95% at lower glycerol concentration and close to 70% at higher concentrations at a higher productivity rate than the equivalent microbial strain. One of the benefits of our approach is the fact that no enzyme purification is required, and that the assembly of the complex is accomplished in vivo before immobilization, while product formation is conducted in vitro. We also report the recovery of enzymatic activity upon fusion enzymes binding to these protein scaffolds, which could have broader applications when assembling arrayed protein complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating the X2 initial core zero power physics tests with Serpent-Ants

The validation of the Ants nodal neutronics code for VVER applications is started by modelling the zero power physics tests for the initial core of the Khmelnitsky 2 nuclear power plant as described in the X2 benchmark using the Serpent-Ants two step neutronics calculation chain. The Ants prediction compare favorably against an earlier continuous energy Monte-Carlo reference solution as well as the measured data, except for discrepancies in the SCRAM worth between predicted and measured values. Similar discrepancies have been previously reported for VVER-1000 reactors, and the Ants predicted SCRAM worths match well with the Serpent results. Additionally, the assembly power distribution and axial power distribution predicted by Ants for the critical HZP state of the reactor are also compared to a reference Serpent solution with very good results. Lastly, an investigation into the effects of the few-group structure used in the nodal calculations and the use or lack of leakage correction for group constants on the results shows that the best accuracy is reached with seven or eight energy groups without leakage correction, although a reasonable accuracy can also be obtained with two or three energy groups using fundamental mode leakage correction. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗