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At least 325 records · Page 18

Free-volume characteristics of epoxies

Positron annihilation spectroscopy was used to measure free-volume characteristics of selected epoxies. Fluorene resins, a new family of high-temperature thermosetting resins, were selected as the test medium. Experimental results indicate that the free-volume cell size V sub f varies with the molecular weight between the cross-links M sub c according to an equation of the form V sub f = AM sub c sup B, where A and B are structural constants. In two of the samples, the concentration of bulky fluorene groups was increased in the network backbone by replacement of some of the conventional bisphenol A epoxy resin with fluorene-derived epoxy resin. This resulted in an increase in their glass transition temperature for a given level of cross-linking. It was found that in these samples, the Doppler broadening of the annihilation peak decreases with the increasing fluorene content, presumably due to enhanced damping of the chain motions.

Singh, Jag J.↗

Autonomous Agents: The Origins and Co-Evolution of Reproducing Molecular Systems

The central aim of this award concerned an investigation into, and adequate formulation of, the concept of an "autonomous agent." If we consider a bacterium swimming upstream in a glucose gradient, we are willing to say of the bacterium that it is going to get food. That is, we are willing, and do, describe the bacterium as acting on its own behalf in an environment. All free living cells are, in this sense, autonomous agents. But the bacterium is "just" a set of molecules. We define an autonomous agent as a physical system able to act on its own behalf in an environment, then ask, "What must a physical system be to be an autonomous agent?" The tentative definition for a molecular autonomous agent is that it must be self-reproducing and carry out at least one thermodynamic work cycle. The work carried out in this grant involved, among other features, the development of a detailed model of a molecular autonomous agent, and study of the kinetics of this system. In particular, a molecular autonomous agent must, by the above tentative definition, not only reproduce, but must carry out at least one work cycle. I took, as a simple example of a self-reproducing molecular system, the single-stranded DNA hexamer 3'CCGCGG5' which can line up and ligate its two complementary trimers, 5'CCG3' and 5'CGG3'. But the two ligated trimers constitute the same molecular sequence in the 3' to 5' direction as the initial hexamer, hence this system is autocatalytic. On the other hand the above system is not yet an autonomous agent. At the minimum, autonomous agents, as I have defined them, are a new class of chemical reaction network. At a maximum, they may constitute a proper definition of life itself.

Kauffman, Stuart↗

Open cells exhibit weaker entrainment of free-tropospheric biomass burning aerosol into the south-east Atlantic boundary layer

This work presents synergistic satellite, airborne and surface-based observations of a pocket of open cells (POC) in the remote south-east Atlantic. The observations were obtained over and upwind of Ascension Island during the CLouds and Aerosol Radiative Impacts and Forcing (CLARIFY) and the Layered Smoke Interacting with Clouds (LASIC) field experiments. A novel aspect of this case study is that an extensive free-tropospheric biomass burning aerosol plume that had been transported from the African continent was observed to be in contact with the boundary layer inversion over the POC and the surrounding closed cellular cloud regime. The in situ measurements show marked contrasts in the boundary layer thermodynamic structure, cloud properties, precipitation and aerosol conditions between the open cells and surrounding overcast cloud field. The data demonstrate that the overlying biomass burning aerosol was mixing down into the boundary layer in the stratocumulus cloud downwind of the POC, with elevated carbon monoxide, black carbon mass loadings and accumulation-mode aerosol concentrations measured beneath the trade-wind inversion. The stratocumulus cloud in this region was moderately polluted and exhibited very little precipitation falling below cloud base. A rapid transition to actively precipitating cumulus clouds and detrained stratiform remnants in the form of thin quiescent veil clouds was observed across the boundary into and deep within the POC. The subcloud layer in the POC was much cleaner than that in the stratocumulus region. The clouds in the POC formed within an ultra-clean layer (accumulation-mode aerosol concentrations of approximately a few cm -3 ) in the upper region of the boundary layer, which was likely to have been formed via efficient collision–coalescence and sedimentation processes. Enhanced Aitken-mode aerosol concentrations were also observed intermittently in this ultra-clean layer, suggesting that new particle formation was taking place. Across the boundary layer inversion and immediately above the ultra-clean layer, accumulation-mode aerosol concentrations were ~1000 cm -3 . Importantly, the air mass in the POC showed no evidence of elevated carbon monoxide over and above typical background conditions at this location and time of year. As carbon monoxide is a good tracer for biomass burning aerosol that is not readily removed by cloud processing and precipitation, it demonstrates that the open cellular convection in the POC is not able to entrain large quantities of the free-tropospheric aerosol that was sitting directly on top of the boundary layer inversion. This suggests that the structure of the mesoscale cellular convection may play an important role in regulating the transport of aerosol from the free troposphere down into the marine boundary layer. We then develop a climatology of open cellular cloud conditions in the south-east Atlantic from 19 years of September Moderate Resolution Imaging Spectroradiometer (MODIS) Terra imagery. This shows that the maxima in open cell frequency (> 0.25) occurs far offshore and in a region where subsiding biomass burning aerosol plumes may often come into contact with the underlying boundary layer cloud. If the results from the observational case study applied more broadly, then the apparent low susceptibility of open cells to free-tropospheric intrusions of additional cloud condensation nuclei could have some important consequences for aerosol–cloud interactions in the region.

54 ENVIRONMENTAL SCIENCES↗

First Results from a Nb3Sn-Coated 1.5-Cell 650 MHz SRF Cavity for Cryogen-Free Industrial Accelerators

First Results from a Nb3Sn-Coated 1.5-Cell 650 MHz SRF Cavity for Cryogen-Free Industrial Accelerators ABSTRACT = Fermilab is advancing the development of a compact, high-power electron beam accelerator using superconducting radio frequency (SRF) technology as a non-radioactive alternative to traditional radiological sources. The current design targets continuous-wave (CW) operation at \SI{1.6}{MeV} and \SI{20}{kW}. To ensure suitability for industrial environments, the system is being designed for cryogen-free operation, driving the adoption of a novel Nb$_3$Sn-coated 1.5-cell SRF cavity operating at \SI{650}{MHz}. This contribution reports on the fabrication, surface preparation, and Nb$_3$Sn coating process of the cavity, as well as first results from vertical test stand (VTS) measurements performed in a liquid helium bath. These initial tests mark a key milestone toward demonstrating the viability of conduction-cooled Nb$_3$Sn SRF cavities for industrial-scale deployment.

Tagdulang, N. [Fermilab]↗

Improving the bulk gas transport of Fe-N-C platinum group metal-free nanofiber electrodes via electrospinning for fuel cell applications

To overcome transport limitations associated with thicker platinum group metal-free (PGM-free) electrodes, it's essential to investigate and tailor alternative electrode architectures to maximize the bulk electrode transport properties, whilst not significantly impeding electrocatalyst active site accessibility and electrode proton resistance. In this work, PGM-free nanofiber electrode mats, prepared by electrospinning a mixture of pyrolyzed Fe-N-C catalyst, Nafion ionomer and a carrier polymer Poly Acrylic acid (PAA), were compared to traditionally prepared electrodes. The morphological properties and elemental distribution of the fabricated nanofiber electrodes showed that the exterior surface of the PGM-free nanofibers was conformally covered with a thin ionomer film. Electrochemical diagnostics performed utilizing cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and H 2 -limiting current measurements, revealed an increase in electric double layer capacitance, reduction in electrode proton transport and a significant improvement in bulk-electrode gas transport properties for the nanofiber electrodes, supporting the observed performance increase from electrochemical polarization data obtained in H 2 -O 2 /Air fuel cells. At 100% RH in H2/Air, the power density of the nanofiber electrodes increased ca. 50% vs. the traditionally prepared electrodes (ca. 260 vs 175 mW cm -2 ), which was attributed to a less tortuous molecular diffusion pathway and an associated reduction in the pressure dependent and independent gas transport resistances in the nanofiber electrodes.

25 ENERGY STORAGE↗

Low‐PGM and PGM‐Free Catalysts for Proton Exchange Membrane Fuel Cells: Stability Challenges and Material Solutions

Abstract Fuel cells as an attractive clean energy technology have recently regained popularity in academia, government, and industry. In a mainstream proton exchange membrane (PEM) fuel cell, platinum‐group‐metal (PGM)‐based catalysts account for ≈50% of the projected total cost for large‐scale production. To lower the cost, two materials‐based strategies have been pursued: 1) to decrease PGM catalyst usage (so‐called low‐PGM catalysts), and 2) to develop alternative PGM‐free catalysts. Grand stability challenges exist when PGM catalyst loading is decreased in a membrane electrode assembly (MEA)—the power generation unit of a PEM fuel cell—or when PGM‐free catalysts are integrated into an MEA. More importantly, there is a significant knowledge gap between materials innovation and device integration. For example, high‐performance electrocatalysts usually demonstrate undesired quick degradation in MEAs. This issue significantly limits the development of PEM fuel cells. Herein, recent progress in understanding the degradation of low‐PGM and PGM‐free catalysts in fuel cell MEAs and materials‐based solutions to address these issues are reviewed. The key factors that degrade the MEA performance are highlighted. Innovative, emerging material concepts and development of low‐PGM and PGM‐free catalysts are discussed.

Du, Lei↗

Investigations on gel forming media use in low gravity bioseparations research

Research on gelling media and conditions suitable for the preservation of the spatial configuration of cell suspensions and macromolecular solutions after separation in free fluid during low gravity experiments is presented. The examples studied included free electrophoresis of cells in a cylindrical column and two-phase aqueous polymer separation. Microgravity electrophoresis experiments were simulated by separating model cell types (animal or human) in a vertical density gradient containing low-conductivity buffer, 1.7-6.5 percent Ficoll, 6.8-5.0 percent sucrose, and 1 percent SeaPrep low-melting temperature agarose. Upon cooling, a gel formed in the column and cells could be captured at the forming locations. Two-phase extraction experiments were simulated using two-polymer solutions in which phase separation occurs in normal saline at temperatures compatible with cell viability and in which one or both phases form a gel upon cooling. Suitable polymers included commercial agaroses (1-2 percent), maltodextrin (5-7 percent), and gelatin (5-20 percent).

Todd, Paul↗

Water-Free Proton-Conducting Membranes for Fuel Cells

Poly-4-vinylpyridinebisulfate (P4VPBS) is a polymeric salt that has shown promise as a water-free proton-conducting material (solid electrolyte) suitable for use in membrane/electrode assemblies in fuel cells. Heretofore, proton-conducting membranes in fuel cells have been made from perfluorinated ionomers that cannot conduct protons in the absence of water and, consequently, cannot function at temperatures >100 C. In addition, the stability of perfluorinated ionomers at temperatures >100 C is questionable. However, the performances of fuel cells of the power systems of which they are parts could be improved if operating temperatures could be raised above 140 C. What is needed to make this possible is a solid-electrolyte material, such as P4VPBS, that can be cast into membranes and that both retains proton conductivity and remains stable in the desired higher operating temperature range. A family of solid-electrolyte materials different from P4VPBS was described in Anhydrous Proton-Conducting Membranes for Fuel Cells (NPO-30493), NASA Tech Briefs, Vol. 29, No. 8 (August 2005), page 48. Those materials notably include polymeric quaternized amine salts. If molecules of such a polymeric salt could be endowed with flexible chain structures, it would be possible to overcome the deficiencies of simple organic amine salts that must melt before being able to conduct protons. However, no polymeric quaternized amine salts have yet shown to be useful in this respect. The present solid electrolyte is made by quaternizing the linear polymer poly- 4-vinylpyridine (P4VP) to obtain P4VPBS. It is important to start with P4VP having a molecular weight of 160,000 daltons because P4VPBS made from lower-molecular-weight P4VP yields brittle membranes. In an experimental synthesis, P4VP was dissolved in methanol and then reacted with an excess of sulfuric acid to precipitate P4VPBS. The precipitate was recovered, washed several times with methanol to remove traces of acid, and dried to a white granular solid. In another synthesis, nanoparticles of silica rich with surface hydroxyl groups were added to P4VP in methanol solution, which was then reacted with excess sulfuric acid to precipitate granules of a composite that most probably had the composition (P4VPBS)-SiO2-SiO(HSO4)2. The granular P4VPBS produced in the first-mentioned synthesis was dissolved in water to make a glue-like, turbid solution; the granular P4VPBS/silica composite produced in the second-mentioned synthesis was mixed with water to make a turbid, glue-like suspension. The proportions of polymer salt to water in such preparations can be varied; it was found that approximately equal parts of water and polymer salt yield a solution or suspension amenable to further processing.

Narayanan, Sekharipuram↗

Mesoporous Textured Fe-N-C Electrocatalysts as Highly Efficient Cathodes for Proton Exchange Membrane Fuel Cells

A new platinum group metal (PGM)-free proton exchange membrane fuel cell (PEMFC) cathode catalyst materials, synthesized using the VariPore™ method by Pajarito Powder, LLC, are characterized for their structure and activity. The physico-chemical analysis of the iron-nitrogen-carbon (Fe-N-C) electrocatalysts show mesoporous carbon material effectively doped with iron and nitrogen. The materials have an average pore size of 7-8 nm and high specific surface area. The Fe-N-C catalysts exhibit good oxygen reduction reaction (ORR) activity in 0.5 M H2SO4 electrolyte with high half-wave potential and sustainable electrochemical stability over 10,000 repeated potential cycles with insignificant losses in their activities. As cathode catalysts in a PEMFC, the Fe-N-C materials deliver remarkably good fuel cell performance at low overpotential approaching that of the commercial Pt catalyst. The high ORR electrocatalytic activity of these Fe-N-C catalysts is credited to the synergy between nitrogen-moieties, specifically pyrrolic-N, pyridinic-N, and graphitic-N, and iron in addition to the high mesoporosity that facilitate an effective reaction path in boosting the electrocatalytic activity and stability.

DIRECT ENERGY CONVERSION↗

Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells

Here, the design of cathodic catalysts layer (CCL) consisted of Platinum Group Metal-free (PGM-free) electrocatalysts was done by catalyst coated membrane approach. Three different Fe-Mn-N-C compounds were synthesized with Fe:Mn ratio of 1:1, 2:1 and 2:1 with modified heat treatment profile. The catalysts were characterized by X-ray photoelectron spectroscopy, X-ray powder diffraction, pore and particle size distribution, zeta potential and transmission electron microscopy. Electrocatalysts were integrated into membrane electrode assembly and evaluated by electrochemical methods. Electrochemical impedance spectroscopy in combination with modeling were used for estimation of proton conductivity of CCL and its oxygen diffusivity. It was found that all CCLs possess extremely high proton conductivity, which was demonstrated for the first time for these types of PGM-free catalysts. The observed ORR mechanism was predominantly 4e- due to peroxide/radicals scavenging effect of Mn.

impedance↗

Super Flexible Transparent Conducting Oxide-Free Organic–Inorganic Hybrid Perovskite Solar Cells with 19.01% Efficiency (Active Area=1 cm 2 )

Highly efficient organic-inorganic hybrid perovskite solar cells (OIHP-SCs) are often fabricated on a transparent conducting oxide (TCO) substrate such as indium tin oxide (ITO). However, the presence of TCOs is disadvantageous to the development of flexible OIHP-SCs due to the brittle nature of ITO which is easily breakable during bending. Herein, a flexible TCO-free OIHP-SC is demonstrated by using lithium bis(trifluoromethane)sulfonimide (Li-TFSI) as a codopant for the single-layer graphene transparent conducting electrode and poly(triarylamine) hole-transporting material (HTM) on a flexible polydimethylsiloxane substrate. The optical and electrical properties of the Li-TFSI-doped graphene substrate are measured by controlling the doping amount and the best conditions for charge extraction are established at a doping concentration of 20 mm Li-TFSI, thus optimizing the device photovoltaic performance. As a result, a highest power conversion efficiency of 19.01% is demonstrated by the flexible TCO-free OIHP-SC devices with an active area of 1 cm 2 . In addition, the flexible TCO-free OIHP-SCs exhibit good bending stability after 5000 bending cycles at radii of 6, 4, and 2 mm and excellent light soaking stability under 1 Sun light intensity over 1000 h as opposed to the poor stability when using poly(3,4-ethylenedioxythiophene) polystyrene sulfonate as the HTM.

14 SOLAR ENERGY↗

Durable Mn-Based PGM-Free Catalysts for Polymer Electrolyte Membrane Fuel Cells

This proposed project aims to develop and evaluate novel manganese based, nitrogen-derived, PGM-free electrocatalysts (denoted as Mn-N-C) to fully address the membrane electrolyte assemblies (MEA)’s ionomer degradation issue resulting from iron. Four thrusts will be pursed in this proposed project. First, advanced first-principles computation methods will be employed to accelerate the rational catalyst design and synthesis. Second, an effective hydro-gel method will be used to maximize atomic Mn active sites embedded in carbon matrix. Next, state-of-the art methods in fuel cell companies will be used to fabricate MEAs containing the Mn-N-C catalysts. Finally, industry standards will be rigorously followed to evaluate fuel cell performance and durability of the Mn-N-C catalysts. With successful completion of the project, it is expected that the following outcomes will be achieved. (1) A set of MEAs containing the Mn-N-C catalysts and with active area large than 50 cm 2 for independent testing, (2) testing results demonstrating that the MEAs of Mn-N-C catalysts have mass activity of 0.044 A/cm 2 at 0.9 VIR-free and H 2 /air performance of 0.50 V at 1.0 A/cm 2 ; (3) fundamental understanding of the composition-structure-property relation of the PGM-free Mn- N-C catalysts, and (4) computational data, measurement data, and publications deposited into the database of ElectroCat Consortium.

08 HYDROGEN↗

Reassembly of Peptide Nanofibrils on Live Cell Surfaces Promotes Cell–Cell Interactions

Nature regulates cellular interactions through the cell-surface molecules and plasma membranes. Despite advances in cell-surface engineering with diverse ligands and reactive groups, modulating cell–cell interactions through scaffolds of the cell-binding cues remains a challenging endeavor. Here, we assembled peptide nanofibrils on live cell surfaces to present the ligands that bind to the target cells. Surprisingly, with the same ligands, reducing the thermal stability of the nanofibrils promoted cellular interactions. Characterizations of the system revealed a thermally induced fibril disassembly and reassembly pathway that facilitated the complexation of the fibrils with the cells. Using the nanofibrils of varied stabilities, the cell–cell interaction was promoted to different extents with free-to-bound cell conversion ratios achieved at low (31%), medium (54%), and high (93%) levels. Further, this study expands the toolbox to generate desired cell behaviors for applications in many areas and highlights the merits of thermally less stable nanoassemblies in designing functional materials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Microgravity and clinorotation cause redistribution of free calcium in sweet clover columella cells

In higher plants, calcium redistribution is believed to be crucial for the root to respond to a change in the direction of the gravity vector. To test the effects of clinorotation and microgravity on calcium localization in higher plant roots, sweet clover (Melilotus alba L.) seedlings were germinated and grown for two days on a slow rotating clinostat or in microgravity on the US Space Shuttle flight STS-60. Subsequently, the tissue was treated with a fixative containing antimonate (a calcium precipitating agent) during clinorotation or in microgravity and processed for electron microscopy. In root columella cells of clinorotated plants, antimonate precipitates were localized adjacent to the cell wall in a unilateral manner. Columella cells exposed to microgravity were characterized by precipitates mostly located adjacent to the proximal and lateral cell wall. In all treatments some punctate precipitates were associated with vacuoles, amyloplasts, mitochondria, and euchromatin of the nucleus. A quantitative study revealed a decreased number of precipitates associated with the nucleus and the amyloplasts in columella cells exposed to microgravity as compared to ground controls. These data suggest that roots perceive a change in the gravitational field, as produced by clinorotation or space flights, and respond respectively differently by a redistribution of free calcium.

short duration↗