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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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28 records · Page 2

Disulfonated Poly(arylene ether sulfone) Random Copolymers Containing Hierarchical Iptycene Units for Proton Exchange Membranes

Two series of disulfonated iptycene-based poly(arylene ether sulfone) random copolymers, i.e., TRP-BP (triptycene-based) and PENT-BP (pentiptycene-based), were synthesized via condensation polymerization from disulfonated monomer and comonomers to prepare proton exchange membranes (PEMs) for potential applications in electrochemical devices such as fuel cell. To investigate the effect of iptycene units on membrane performance, these copolymers were systematically varied in composition (i.e., iptycene content) and the degree of sulfonation (i.e., 30–50%), which were characterized comprehensively in terms of water uptake, swelling ratio, oxidative stability, thermal and mechanical properties, and proton conductivity at various temperatures. Comparing to copolymers without iptycene units, TRP-BP and PENT-BP ionomers showed greatly enhanced thermal and oxidative stabilities due to strong intra- and inter-molecular supramolecular interactions induced by hierarchical iptycene units. In addition, the introduction of iptycene units in general provides PEMs with exceptional dimensional stability of low volume swelling ratio at high water uptakes, which is ascribed to the supramolecularly interlocked structure as well as high fractional free volume of iptycene-based polymers. It is demonstrated that the combination of high proton conductivity and good membrane dimension stability is the result of the synergistic effects of multiple factors including free volume (iptycene content), sulfonation degree, hydrophobicity, and swelling behavior (supramolecular interactions).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure of a monolayer of molecular rotors on aqueous subphase from grazing-incidence X-ray diffraction

In situ grazing-incidence X-ray scattering shows here that a monolayer of artificial rod-shaped dipolar molecular rotors produced on the surface of an aqueous subphase in a Langmuir trough has a structure conducive to a 2D ferroelectric phase. The axes of the rotors stand an average of 0.83 nm apart in a triangular grid, perpendicular to the surface within experimental error. They carry 2,3-dichlorophenylene rotators near rod centers, between two decks of interlocked triptycenes installed axially on the rotor axle. The analysis is based first on simultaneous fitting of observed Bragg rods and second on fitting the reflectivity curve with only three adjustable parameters and the calculated rotor electron density, which also revealed the presence of about seven molecules of water near each rotator. Dependent on preparation conditions, a minor and variable amount of a different crystal phase may also be present in the monolayer.

36 MATERIALS SCIENCE↗

Implications of styrenic triblock copolymer gel mechanics on midblock bridging fraction

Triblock copolymer gels have garnered considerable scientific interest over the past few decades and are used in a variety of applications including consumer cushioning, pressure-sensitive adhesives, and ballistics gels. While many of their applications rely upon understanding mechanical properties, mechanical studies of block copolymer gels are relatively disjointed with each focusing on specific copolymers, which inherently have a fixed molecular weight and composition. Here, the present study examines the quasistatic mechanical response of styrenic triblock copolymer gels composed of seven unique triblock copolymers at various concentrations. Resultant stress-extension data is fitted with the slip-tube network (STN) theory that describes gel mechanics based upon crosslinked network (G c ) and chain entanglement (G e ) modulus contributions. Collectively, modulus contributions imply that midblock bridging is independent of copolymer identity (i.e., molecular weight and block fraction) and dependent on triblock copolymer concentration via F b ∝ φ ABA 0.91±0.39 over the concentration range examined (φ ABA = 0.05–0.39). Gels composed of a complementary diblock-triblock copolymer pair were subsequently analyzed to explore the influence of interlocking loop-loop and loop-bridge pairs within the effective midblock bridging population. These results point to the presence of a physically significant quantity of interlocked loops, but quantitative analysis was inconclusive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extragalactic Magnetism with SOFIA (Legacy Program). I. The Magnetic Field in the Multiphase Interstellar Medium of M51*

The recent availability of high-resolution far-infrared (FIR) polarization observations of galaxies using HAWC+/SOFIA has facilitated studies of extragalactic magnetic fields in the cold and dense molecular disks. We investigate whether any significant structural differences are detectable in the kiloparsec-scale magnetic field of the grand design face-on spiral galaxy M51 when traced within the diffuse (radio) and the dense and cold (FIR) interstellar medium (ISM). Our analysis reveals a complex scenario where radio and FIR polarization observations do not necessarily trace the same magnetic field structure. We find that the magnetic field in the arms is wrapped tighter at 154 μm than at 3 and 6 cm; statistically significant lower values for the magnetic pitch angle are measured at FIR in the outskirts (R ≥ 7 kpc) of the galaxy. This difference is not detected in the interarm region. We find strong correlations of the polarization fraction and total intensity at FIR and radio with the gas column density and 12CO(1–0) velocity dispersion. We conclude that the arms show a relative increase of small-scale turbulent B-fields at regions with increasing column density and dispersion velocities of the molecular gas. No correlations are found with H i neutral gas. The star formation rate shows a clear correlation with the radio polarized intensity, which is not found in FIR, pointing to a small-scale dynamo-driven B-field amplification scenario. This work shows that multiwavelength polarization observations are key to disentangling the interlocked relation between star formation, magnetic fields, and gas kinematics in the multiphase ISM.

Spiral galaxies↗

Allosteric control of olefin isomerization kinetics via remote metal binding and its mechanochemical analysis

Abstract Allosteric control of reaction thermodynamics is well understood, but the mechanisms by which changes in local geometries of receptor sites lower activation reaction barriers in electronically uncoupled, remote reaction moieties remain relatively unexplored. Here we report a molecular scaffold in which the rate of thermal E-to-Z isomerization of an alkene increases by a factor of as much as 10 4 in response to fast binding of a metal ion to a remote receptor site. A mechanochemical model of the olefin coupled to a compressive harmonic spring reproduces the observed acceleration quantitatively, adding the studied isomerization to the very few reactions demonstrated to be sensitive to extrinsic compressive force. The work validates experimentally the generalization of mechanochemical kinetics to compressive loads and demonstrates that the formalism of force-coupled reactivity offers a productive framework for the quantitative analysis of the molecular basis of allosteric control of reaction kinetics. Important differences in the effects of compressive vs. tensile force on the kinetic stabilities of molecules are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Self-Assembly of Monodisperse Graphene Nanoribbons: Access to Submicron Architectures with Long-Range Order and Uniform Orientation

Fabricating organic semiconducting materials into large-scale well-organized architectures is critical for building high performance molecular electronics. While graphene nanoribbons (GNRs) hold enormous promise for various device applications, their assembly into a well-structured monolayer or multilayer architecture poses a substantial challenge. Here we report the preparation of length-defined monodisperse GNRs via the integrated iterative binomial synthesis (IIBS) strategy and their self-assembly into submicron-architectures with long-range order, uniform orientation as well as regular layers. Further, the use of short alkyl side chains benefits forming stable multi-layers through interlocking structures. By changing the length and backbone shapes of these monodisperse GNRs, various three-dimensional assemblies including multilayer stripes, monolayer stripes, and nanowires, can be achieved, leading to different photophysical properties and band gaps. The discovery of these intriguing self-assembly behaviors of length-defined GNRs is expected to open the door for various future applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Snapshots of Ce 70 Toroid Assembly from Solids and Solution

Crystallization at the solid–liquid interface is difficult to spectroscopically observe and therefore challenging to understand and ultimately control at the molecular level. The Ce70-torroid formulated [Ce IV 70 (OH) 36 (O) 64 (SO 4 ) 60 (H 2 O) 10 ] 4– , part of a larger emerging family of M IV 70 -materials (M = Zr, U, Ce), presents such an opportunity. We elucidated assembly mechanisms by the X-ray scattering (small-angle scattering and total scattering) of solutions and solids as well as crystallizing and identifying fragments of Ce 70 by single-crystal X-ray diffraction. Fragments show evidence for templated growth (Ce 5 , [Ce 5 (O) 3 (SO 4 ) 12 ] 10- ) and modular assembly from hexamer (Ce 6 ) building units (Ce 13 , [Ce 13 (OH) 6 (O) 12 (SO 4 ) 14 (H 2 O) 14 ] 6– and Ce 62 , [Ce 62 (OH) 30 (O) 58 (SO 4 ) 58 ] 14- ). Ce 62 , an almost complete ring, precipitates instantaneously in the presence of ammonium cations as two torqued arcs that interlock by hydrogen boding through NH 4 + , a structural motif not observed before in inorganic systems. The room temperature rapid assemblies of both Ce 70 and Ce 62 , respectively, by the addition of Li + and NH 4 + , along with ion-exchange and redox behavior, invite exploitation of this emerging material family in environmental and energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design, Synthesis and Characterization of Triptycene-Containing Macromolecules with Hierarchically Controlled Architectures as Functional Membrane Materials for Energy Applications

This DOE CAREER award supported the Guo research group at the University of Notre Dame in its efforts to develop hierarchically functional polymer membrane materials based on iptycene unit to enable energy-efficient molecular separations and fast ion transport in polymeric membranes. To do this, the Guo group engaged in three major research objectives, each exploiting a unique molecular motif offered by iptycene units: (1) developing glassy microporous polymers with exquisitely tailored free volume microporosity for ultra-fast and selective gas transport; (2) developing robust PEO-rich multicomponent polymers via supramolecular reinforcement for CO 2 -selective membranes; and (3) developing ion-containing, nanophase separated multiblock copolymers with suppressed water swelling and fast proton transport for hydrogen fuel cells. Through the research in this project, the iptycene strategy has established a new paradigm of macromolecular design for harnessing free volume microporosity and specific structure motifs to facilitate fast and selective molecular and ion transport in polymers. The results from this project not only provide new fundamental knowledge to the membrane community and broader materials community, but also bridge the technical gaps via providing robust high performance polymer materials for a wide range of applications that impact energy and environmental sustainability. This technical report summarizes the major accomplishments of the study of these innovative polymer membrane materials in this project. For example, introducing triptycene unit into polybenzoxazole structures led to superior size sieving properties, which, along with their ultrahigh gas permeability, placed these polymers among the best gas separation membranes ever reported; the study of PEO-based model network structures demonstrated for the first time that crosslink inhomogeneity (i.e., uneven distribution of crosslink sites)–an previously unexplored structure parameter, plays a significant role in regulating gas transport, ushering in a completely new dimension in the design of crosslinked polymers with broad applicability; exploiting the unique supramolecular interlocking and chain threading interactions and the internal free volume offered by iptycene units addressed the grand challenge of excessive water swelling encountered by conventional ion-containing polymers while allowing nanophase separated membrane morphologies enabling fast ion transport. The new polymer membrane materials and the new macromolecular design strategies developed from this project hold great potential for a much wider applicability beyond gas separations and polyelectrolyte membranes.

36 MATERIALS SCIENCE↗

An extreme-halophile archaebacterium possesses the interlock type of prephenate dehydratase characteristic of the Gram-positive eubacteria

The focal point of phenylalanine biosynthesis is a dehydratase reaction which in different organisms may be prephenate dehydratase, arogenate dehydratase, or cyclohexadienyl dehydratase. Gram-positive, Gram-negative, and cyanobacterial divisions of the eubacterial kingdom exhibit different dehydratase patterns. A new extreme-halophile isolate, which grows on defined medium and is tentatively designated as Halobacterium vallismortis CH-1, possesses the interlock type of prephenate dehydratase present in Gram-positive bacteria. In addition to the conventional sensitivity to feedback inhibition by L-phenylalanine, the phenomenon of metabolic interlock was exemplified by the sensitivity of prephenate dehydratase to allosteric effects produced by extra-pathway (remote) effectors. Thus, L-tryptophan inhibited activity while L-tyrosine, L-methionine, L-leucine and L-isoleucine activated the enzyme. L-Isoleucine and L-phenylalanine were effective at micromolar levels; other effectors operated at mM levels. A regulatory mutant selected for resistance to growth inhibition caused by beta-2-thienylalanine possessed an altered prephenate dehydratase in which a phenomenon of disproportionately low activity at low enzyme concentration was abolished. Inhibition by L-tryptophan was also lost, and activation by allosteric activators was diminished. Not only was sensitivity to feedback inhibition by L-phenylalanine lost, but the mutant enzyme was now activated by this amino acid (a mutation type previously observed in Bacillus subtilis). It remains to be seen whether this type of prephenate dehydratase will prove to be characteristic of all archaebacteria or of some archaebacterial subgroup cluster.

NASA Discipline Number 52-30↗

Diagnostics: Chapter 8 of the special issue: on the path to tokamak burning plasma operation

This chapter presents the activity conducted by the ITPA topical group (TG) on Diagnostics over about the last 15 years. Following a general introduction of the ITER Diagnostics led by their measurement roles, the document is organized in several subchapters detailing the design support, research and development activity conducted by each of the specialist working groups (WGs) of the TG. Please note that the magnetic diagnostics were supported at the TG without a specific WG. Their status is included in the general introduction. In the following some highlights of the subchapter’s contents are provided. Recent advances in ITER first wall (FW) diagnostics for the measurements of plasma-metallic wall interaction in support of the ITER research plan are reported. An InfraRed imaging Video Bolometer for ITER has been developed and tested on several tokamaks to measure the radiated power loss. A laser-induced breakdown spectroscopy (LIBS) technique which utilizes a pulsed laser beam to ablate locally by forming a crater, will measure local tritium inventory in the FW material. Real-time Residual Gas Analyzers will measure the neutral gas composition in a divertor port and an equatorial port during plasma operation. Due to the full metallic FW environment, the plasma-wall interaction in ITER will face several challenges such as the compromised radiated power and divertor heat flux measurements by reflection. Ray tracing and analysis codes have been developed to eliminate and correct the effects of reflection in the measurements. The characteristics of the reflecting surfaces depending on the roughness and angle of the incidence have been measured by dedicated experiments, and the results were applied to the reflection elimination. For the measurement of the metallic impurity radiation induced by eroded metallic atoms, a vacuum ultraviolet spectrometer has been developed and tested. An extensive thermonuclear diagnostic suite will be required to support the operation of ITER and the planned experimental program for future burning plasma experiments. Due to the harsh environmental conditions, the implementation of diagnostic systems in ITER is a major challenge. These conditions include high levels of neutron and gamma fluxes, neutron heating, particle bombardment. Therefore, the selection and design of diagnostic systems must take into account a number of phenomena previously unseen in diagnostic design. For this reason, the measurement of neutrons and confined or lost fast ions, with particular emphasis on alpha particles, is critical to ITER. The diagnostics associated with these measurements will be important for future plasma-burning experiments at ITER. The high neutron emission and very large plasma size in ITER make neutron diagnostics the main diagnostic method used to measure plasma parameters such as fusion power, fusion power density, ion temperature, energy of fast ions and their spatial distributions in the plasma core. Active spectroscopy techniques are methods where a neutral particle beam is injected into the plasma and information on plasma parameters is extracted from the measurement of line emission resulting from the beam-plasma interaction, either by plasma ions or by beam atoms. Spatial localization is achieved by crossing the beamline and multiple observation lines. The ITER plasma will be a high temperature, moderately dense, fully ionized collisional plasma. The plasma facing surfaces are principally metallic being fashioned from beryllium or tungsten but many other elements, arising from either structural or from operational needs, may enter this plasma. The energy range of the emitted photons range from meV (infra-red) to multi keV (x-rays) and originate from all areas of the plasma volume. The primary role of passive emission diagnostics is to identify what is in the plasma from spectral signatures. Extracting quantitative information from these measurements such as impurity content, ion temperature, rotation, degree of detachment and radiated power depends on calibrated instruments, a physics model of the atomic and molecular processes and plasma transport and an analysis workflow that takes into account environmental effects such as reflections. The particular needs for ITER have prompted a multi-machine, many-year effort to address all these aspects and this chapter reviews the work on diagnostic design, experiments and new analysis techniques. An overview of the laser diagnostics to be implemented on ITER is also provided in this paper. This includes descriptions of the Thomson scattering in the core, edge and divertor regions, polarimetry and interferometry diagnostics used for measuring plasma density and also measurements of helium density in the divertor using Laser Induced Flourescence. Techniques which can allow improvements on current measurements are also addressed in particular expanding poloidal polarimetry measurements to measure field fluctuations and proposed use of dispersion interferometery which has a number of advantages over existing methods. This paper identifies particular areas where further research and testing on existing tokamaks is useful even at this advanced stage to inform the design of diagnostics for ITER. Outstanding areas of concern for the implementation of laser diagnostics, in particular with a view to reliable operation are identified. An overview of the latest developments of microwave diagnostic systems and techniques is given. The primary focus is the contributions for ITER—the next step burning plasma experiment—which is supplemented by describing recent progress of techniques applicable for fusion experiments beyond ITER. The contributions are intentionally kept concise, and are being supplemented by a rich list of references for further studies. Radiation induced effects are receiving continuous and well-deserved attention of the ITER diagnostic community and they are in many cases one of the primary design drivers of the ITER diagnostic systems. The paper summarizes recent progress in this area focusing primarily on the ITER diagnostics but in some cases provides also outlook for the possible solutions for even more demanding radiation environment of fusion reactors beyond ITER. Despite advancements in the area of modeling and simulation of various radiation induced effects, experimental testing in a nuclear environment as close as possible to the target one is still seen as unavoidable for proper qualification of particular diagnostic functional elements. Recent advancement within three diagnostic areas: optical diagnostics, magnetics and bolometers is covered. Encouraging results on qualification of silica glass vacuum window assemblies are presented. In the area of magnetic sensors, progress of irradiation tests performed on ITER in-vessel LTCC inductive sensors is presented with outlook for novel technological approaches to inductive sensors utilizing thick printing and photolithography technologies being highlighted. Summary of advancements in the area of steady state magnetic field sensors based on Hall effect is given. New results of neutron irradiation test of the ITER borosilicate glass inserts for vacuum electrical feedthroughs are summarized finding negligible swelling at target level of neutron fluence. Off-line irradiation tests of fiber optic current sensors for plasma current measurement demonstrated that both for gamma doses up to 5 MGy and a total neutron fluence up to 10 15 cm −2 , radiation induced changes are still compatible with required measurement accuracy on ITER. The ITER bolometers are given as an example how considering radiation effects may influence the diagnostic design. Finally, outlook for future main R&D directions is outlined. All optical and laser-based diagnostics in ITER will be using mirrors to guide plasma radiation toward detectors, cameras and sensors. In the hostile plasma, radiation and particle environment the optical characteristics of diagnostic mirrors will degrade directly affecting the entire performance of involved diagnostic systems. An assessment of factors affecting mirror performance is provided. Among the prime adverse factors are deposition of plasma impurities, sputtering of mirror surface and steam ingress in the vicinity of mirrors. Within the International Tokamak Physics Activity with active support by ITER central team and domestic agencies, the structured research and development (R&D) program on mitigation of risks for diagnostic mirrors is underway. Within this program the mirror material development, the passive mitigation of mirror degradation by using diagnostic ducts and shutters along with an active mirror recovery program comprising the in-situ mirror cleaning and calibration is underway. Recent developments in diagnostic mirror R&D are described in this Chapter along with an example of their implementation of R&D solutions in ITER Infrared Thermography diagnostic. An assessment of still open engineering and physics questions, considerations on mirror risks during an early phase of ITER operation are given along with an overview of diagnostic mirror evolution in the late ITER operation stage toward the demonstration fusion power plant. Several crucial areas of diagnostic R&D outlined in ITER Research Plan are addressed. The basic control groups in a fusion reactor can be broken-down in five categories: (1) plasma position, magnetic configuration, and plasma current control, (2) profile control and confinement optimization, (3) MHD control and suppression, (4) edge dissipation control, radiation and plasma exhaust control and (5) break-down optimization. These categories are coupled via the physics (a control action in one domain will affect the other domains) and via shared actuators (e.g. ECRH for impurity accumulation avoidance, current density distribution control and MHD suppression). Consequently, a supervisory control system should determine the priority of the various control tasks, their couplings, and the interfaces with the safety and interlock system. For the systematic development of the various controllers taking the complexity of the plasma and the control system into account, a model-based approach is required. A short historical overview is given of the developments in systems and control theory and control engineering with special emphasis on those developments that are most relevant for Nuclear Fusion research and operation. An overview is given of the state of the field of fusion plasma control for the control categories. It will be shown how synthetic diagnostics are being developed in ITER and how they are used in diagnostic design and design validation and how they can be in model-based controller synthesis using relatively simple models. In modern control methods, multiple diagnostics are used to constrain relatively simple models. The constrained models provide an estimate for the state. This opens the route to state controllers, such as model predictive control. A major challenge in nuclear fusion research is the coherent combination of data from heterogeneous diagnostics and modeling codes for machine control and safety as well as physics studies. Measured data from different diagnostics often provide information about the same subset of physical parameters. Additionally, information provided by some diagnostics might be needed for the analysis of other diagnostics. A joint analysis of complementary and redundant data allows, e.g. to improve the reliability of parameter estimation, to increase the spatial and temporal resolution of profiles, to obtain synergistic effects, to consider diagnostics interdependencies and to find and resolve data inconsistencies. Physics-based modeling and parameter relationships provide additional information improving the treatment of ill-posed inversion problems. A coherent combination of all kind of available information within a probabilistic framework allows for improved data analysis results. The concept of integrated data analysis (IDA) in the framework of Bayesian probability theory is outlined and contrasted with conventional data analysis. Components of the probabilistic approach are summarized and specific ingredients beneficial for data analysis at fusion devices are discussed.

ITER↗