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At least 181 records · Page 10

High-Current Density Durability of Pt/C and PtCo/C Catalysts at Similar Particle Sizes in PEMFCs

The durability of carbon supported PtCo-alloy based nanoparticle catalysts play a key role in the longevity of proton-exchange membrane fuel cells (PEMFC) in electric vehicle applications. To improve its durability, it is important to understand and mitigate the various factors that cause PtCo-based cathode catalyst layers (CCL) to lose performance over time. These factors include i) electrochemical surface area (ECSA) loss, ii) specific activity loss, iii) H + /O 2 -transport changes and iv) Co 2+ contamination effects. We use a catalyst-specific accelerated stress test (AST) voltage cycling protocol to compare the durability of Pt and PtCo catalysts at similar average nanoparticle size and distribution. Our studies indicate that while Pt and PtCo nanoparticle catalysts suffer from similar magnitudes of electrochemical surface area (ECSA) losses, PtCo catalyst shows a significantly larger cell voltage loss at high current densities upon durability testing. The distinctive factor causing the large cell voltage loss of PtCo catalyst appears to be the secondary effects of the leached Co 2+ cations that contaminate the electrode ionomer. A 1D performance model has been used to quantify the cell voltage losses arising from various factors causing degradation of the membrane electrode assembly (MEA).

08 HYDROGEN↗

Effect of Anion Size on Conductivity and Transference Number of Perfluoroether Electrolytes with Lithium Salts

Mixtures of perfluoropolyethers (PFPE) and lithium salts with fluorinated anions are a new class of electrolytes for lithium batteries. Unlike conventional electrolytes wherein electron-donating oxygen groups interact primarily with the lithium cations, the properties of PFPE-based electrolytes appear to be dependent on interactions between the fluorinated anions and the fluorinated backbones. We study these interactions by examining a family of lithium salts wherein the size of the fluorinated anion is systematically increased: lithium bis(fluorosulfonyl)imide (LiFSI), bis(trifluoromethanesulfonyl)imide (LiTFSI) salts and lithium bis(pentafluoroethanesulfonyl)imide (LiBETI). Two short chain perfluoroethers (PFE), one with three repeat units, C6-DMC, and another with four repeat units, C8-DMC were studied; both systems have dimethyl carbonate end groups.We find that LiFSI provides the highest conductivity in both C6-DMC and C8-DMC. These systems also present the lowest interfacial resistance against lithium metal electrodes. The steady-state transference number (t + ss ) was above 0.6 for all of the electrolytes and was an increasing function of anion size. The product of conductivity and the steady-state transference number, a convenient measure of the efficacy of the electrolytes for lithium battery applications, exhibited a maximum at about 20 wt% salt in all electrolytes. Finally, amongst the systems studied, LiFSI/PFE mixtures were the most efficacious electrolytes.

25 ENERGY STORAGE↗

ActiveBAS: A Low-cost, Scalable Control Solution for Grid-Interactive Small and Medium Sized Commercial Buildings

This project aims to develop and enhance a low-cost, highly scalable control solution for Small and Medium-Sized Commercial Buildings (SMCB), assess the business potential at multiple sites, and perform commercialization efforts. The technology can be applied to any buildings served by multiple units, with the benefits being greatest for open-spaced buildings, such as banks, retail stores, restaurants, and factories. This project aims to develop an affordable control solution for: 1) SMCB grid responsiveness, 2) reduction of GHG by changing unit operations, 3) greater reduction in utility costs, and 4) rapid adoption in the marketplace. The proposed technology will be built on a previously developed and demonstrated MPC solution. The minimal sensor requirement and less need of control expertise are the unique feature of the algorithm that leads to low capital and maintenance costs, and short installation and implementation time. These attributes contribute to low capital and maintenance costs, as well as a short installation and implementation time. However, these advantages come with a trade-off: increased difficulties and unreliability when applying traditional modeling and MPC control approaches due to limited information. This final report describes the modeling approaches developed and tested to overcome these challenges. It begins by outlining the modeling challenge posed by minimal sensor requirements, then delves into the proposed modeling approaches, which primarily involve system identification. Finally, preliminary test results for a simulation case study are presented.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Particle Size gradients in Modeled Vibrated beds of continuously sized powders

Ensuring powder mixture homogeneity is paramount for modern powder processing techniques. A promising recent development in the field of powder processing, resonant acoustic mixing (RAM), proposes to use low-frequency vertical vibration to deliver well-mixed powders without relying on mechanical agitators. However, an undesirable outcome of vibrations applied to granular materials comprised of non-uniform particle sizes is the tendency towards size segregation. In this work, we experimentally ex

Renfroe, Steven Emad [Sandia National Laboratories↗

Comparison of drop size distributions from two droplet sizing systems

A comparison between the Phase Doppler Particle Analyzer and the combined measurements from Particle Measuring Systems' Forward Scattering Spectrometer Probe and the Optical Array Probe was conducted in an icing wind tunnel using NASA Icing Research Tunnel spray nozzles to produce the supercooled water droplet cloud. Clouds having a range of volume median diameters from 10 to greater than 50 microns were used for the instrument comparisons. A volume median diameter was calculated from combining the droplet distributions of the Optical Array Probe and the Forward Scattering Spectrometer Probe. A comparison of the combined volume median diameters and the Phase Doppler Particle Analyzer volume median diameters showed agreement from 10 microns up to 30 microns. Typical drop size distributions from the Phase Doppler Particle Analyzer, the Forward Scattering Spectrometer Probe, and Optical Array Probe are presented for several median volume diameters. A comparison of the distributions illustrates regions of the distributions where there is good agreement and other regions where there are discrepancies between the Phase Doppler Particle Analyzer and the Particle Measuring Systems' droplet size instruments.

Oldenburg, John R.↗

Monte Carlo predictions of DNA fragment-size distributions for large sizes after HZE particle irradiation

DSBs (double-strand breaks) produced by densely ionizing space radiation are not located randomly in the genome: recent data indicate DSB clustering along chromosomes. DSB clustering at large scales, from >100 Mbp down to approximately 2 kbp, is modeled using a Monte-Carlo algorithm. A random-walk model of chromatin is combined with a track model, that predicts the radial distribution of energy from an ion, and the RLC (randomly-located-clusters) formalism, in software called DNAbreak. This model generalizes the random-breakage model, whose broken-stick fragment-size distribution is applicable to low-LET radiation. DSB induction due to track interaction with the DNA volume depends on the radiation quality parameter Q. This dose-independent parameter depends only weakly on LET. Multi-track, high-dose effects depend on the cluster intensity parameter lambda, proportional to fluence as defined by the RLC formalism. After lambda is determined by a numerical experiment, the model reduces to one adjustable parameter Q. The best numerical fits to the experimental data, determining Q, are obtained. The knowledge of lambda and Q allows us to give biophysically based extrapolations of high-dose DNA fragment-size data to low doses or to high LETs.

NASA Center JSC↗

Morphing Wing Weight Predictors and Their Application in a Template-Based Morphing Aircraft Sizing Environment II: Morphing Aircraft Sizing via Multi-level Optimization - Part 2

This report presents an approach for sizing of a morphing aircraft based upon a multi-level design optimization approach. For this effort, a morphing wing is one whose planform can make significant shape changes in flight - increasing wing area by 50% or more from the lowest possible area, changing sweep 30 or more, and/or increasing aspect ratio by as much as 200% from the lowest possible value. The top-level optimization problem seeks to minimize the gross weight of the aircraft by determining a set of "baseline" variables - these are common aircraft sizing variables, along with a set of "morphing limit" variables - these describe the maximum shape change for a particular morphing strategy. The sub-level optimization problems represent each segment in the morphing aircraft's design mission; here, each sub-level optimizer minimizes fuel consumed during each mission segment by changing the wing planform within the bounds set by the baseline and morphing limit variables from the top-level problem.

Skillen, Michael D.↗

Small-Scale Drop-Size Variability: Empirical Models for Drop-Size-Dependent Clustering in Clouds

By analyzing aircraft measurements of individual drop sizes in clouds, it has been shown in a companion paper that the probability of finding a drop of radius r at a linear scale l decreases as l(sup D(r)), where 0 less than or equals D(r) less than or equals 1. This paper shows striking examples of the spatial distribution of large cloud drops using models that simulate the observed power laws. In contrast to currently used models that assume homogeneity and a Poisson distribution of cloud drops, these models illustrate strong drop clustering, especially with larger drops. The degree of clustering is determined by the observed exponents D(r). The strong clustering of large drops arises naturally from the observed power-law statistics. This clustering has vital consequences for rain physics, including how fast rain can form. For radiative transfer theory, clustering of large drops enhances their impact on the cloud optical path. The clustering phenomenon also helps explain why remotely sensed cloud drop size is generally larger than that measured in situ.

Marshak, Alexander↗

Minimizing Optimal Transport for Functions with Fixed-Size Nodal Sets

Consider the class of zero-mean functions with fixed L ∞ and L 1 norms and exactly N ϵ N nodal points. Which functions f minimize W p (f + ,f – ), the Wasserstein distance between the measures whose densities are the positive and negative parts? We provide a complete solution to this minimization problem on the line and the circle, which provides sharp constants for previously proven “uncertainty principle”-type inequalities, i.e., lower bounds on N • W p (f + ,f – ). We further show that, while such inequalities hold in many metric measure spaces, they are no longer sharp when the non-branching assumption is violated; indeed, for metric star-graphs, the optimal lower bound on W p (f + ,f – ) is not inversely proportional to the size of the nodal set, N. Here, based on similar reductions, we make connections between the analogous problem of minimizing W p (f + ,f – ) for f defined on Ω C R d with an equivalent optimal domain partition problem.

97 MATHEMATICS AND COMPUTING↗

Effect of microalgae cell composition and size on responsiveness to ultrasonic harvesting

Ultrasonic harvesting could reduce the energy consumption and costs associated with separating microalgae from growth media. The responsiveness of microalgae cells to an ultrasonic standing wave depends on the cell radius and acoustic contrast factor (ACF). The ACF can vary as cell composition (e.g. lipid, protein, carbohydrate content) varies depending on the algae strain, cultivation conditions, and growth stage. Here, two independent experimental methods were used to characterize the ACF of three algae ;strains—Nannochloropsis salina, Chlamydomonas reinhardtii, and Tetraselmis chuii—as a function of dynamic cellular composition over 9- to 14-day growth periods. For N. salina, lipid content increased from 25 ± 1% to 33 ± 1% ash-free dry weight (AFDW) and ACF decreased by 46% (from 0.041 ± 0.002 to 0.022 ± 0.002) between growth days 3 and 10. For C. reinhardtii, lipid content increased from 26 ± 1% to 40 ± 1% AFDW and ACF decreased by 33% (from 0.051 ± 0.013 to 0.034 ± 0.006) between growth days 3 and 9. For T. chuii, lipid content and ACF remained stable (~ 10% AFDW and ~ 0.3) over the growth period. ACF decreased as lipid content increased because lipids have a negative ACF in the growth media; however, cell size had a greater impact on cell responsiveness because the ratio of the acoustic radiation force to the drag force is proportional to cell radius squared.

09 BIOMASS FUELS↗

Complexation of lanthanides and other metal ions by the polypyridyl ligand quaterpyridine: Relation between metal ion size, chelate ring size, and complex stability

Metal ion complexing properties of the ligand QPY (2,2':6',2'':6'',2'''-quaterpyridine) are reported in relation to its possible use as a functional group for reagents in the extraction and separation of Ln(III) (lanthanide) ions. QPY is almost totally insoluble in water, but variation of the intense π-π* transitions in the UV spectrum of 1 × 10 –5 M QPY solutions in 50% CH 3 OH/H 2 O (v/v) as a function of pH or metal ion concentration allowed for the determination of the protonation constant (pK) and log K 1 values with metal ions. The pK a values of QPY are 4.54 ± 0.02 and 3.47 ± 0.02 in 50% CH 3 OH/H 2 O. The log K 1 values determined by UV–visible spectroscopy for the Ln(III) ions by titration of 1:1 solutions of 1.0 × 10­ 5 M Ln(III) ion and QPY between pH 2 and 6 were: La(III), 3.79; Pr(III), 4.34; Nd(III) 4.57; Sm(III), 4.78; Gd(III) 4.69; Dy(III), 4.76, Ho(III), 4.94; Er(III), 5.36, Tm(III), 5.84, and Lu(III) 5.54, all at 25 °C and ionic strength zero. The log K 1 values for the Ln(III) ions show quite strong increases from La(III) to Lu(III), with a local maximum at Sm(III), and a local minimum at Gd(III). The local maxium at Sm(III) is attributed to this ion being the best-fit size for coordinating with polypyridyl ligands. The effect of preorganization of polypyridyls such as QPY with bridging benzo groups in the ligand backbone to yield DPP (2,9-dipyrid-2-yl-1,10-phenanthroline) is to produce significant increases in log K 1 for large metal ions such as Ln(III) ions, but for small metal ions such as Zn(II), there is a large decrease in log K 1 in passing from QPY to DPP: this shows how rigidification of the ligand can enhance the selectivity against small metal ions of polypyridyls forming five-membered chelate rings. DFT calculations are used to analyze the variation in log K 1 in passing from the La(III) complexes of QPY to DPP compared to those for the smaller Lu(III) ion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogenation of Diesters on Copper Catalyst Anchored on Ordered Hierarchical Porous Silica: Pore size effect

An ordered hierarchically porous silica (HPS) with the coexistence of both mesopores and abundant micropores was fabricated and used as support for the preparation of copper-based catalysts (Cu/HPS). The ordered mesoporous structure of the Cu/HPS catalysts was retained. In addition, both Cu0 and Cu+ species are found to be highly dispersed. It might be attributed to the anchoring effect of micropores and the formation of Cu-O-Si species derived from the strong interaction between surface silica and copper precursor. The Cu/HPS catalysts showed excellent performances in the hydrogenation of dimethyl adipate. The catalytic activity in dimethyl oxalate hydrogenation depended on the surface reaction, while the activity in dimethyl adipate hydrogenation will be readily controlled by pore diffusion, which can be improved by tailoring the pore size of HPS. These findings could be meaningful instruction for the rational design of industrial catalysts for the hydrogenation of various diesters.

ester, hydrogenation, higherarchical, copper, diff↗

Pushing the size limit of de novo structure ensemble prediction guided by sparse SDSL-EPR restraints to 200 residues: The monomeric and homodimeric forms of BAX

Structure determination remains a challenge for many biologically important proteins. In particular, proteins that adopt multiple conformations often evade crystallization in all biologically relevant states. Although computational de novo protein folding approaches often sample biologically relevant conformations, the selection of the most accurate model for different functional states remains a formidable challenge, in particular, for proteins with more than about 150 residues. Electron paramagnetic resonance (EPR) spectroscopy can obtain limited structural information for proteins in well-defined biological states and thereby assist in selecting biologically relevant conformations. The present study demonstrates that de novo folding methods are able to accurately sample the folds of 192-residue long soluble monomeric Bcl-2-associated X protein (BAX). The tertiary structures of the monomeric and homodimeric forms of BAX were predicted using the primary structure as well as 25 and 11 EPR distance restraints, respectively. The predicted models were subsequently compared to respective NMR/X-ray structures of BAX. EPR restraints improve the protein-size normalized root-mean-square-deviation (RMSD100) of the most accurate models with respect to the NMR/crystal structure from 5.9 Å to 3.9 Å and from 5.7 Å to 3.3 Å, respectively. Additionally, the model discrimination is improved, which is demonstrated by an improvement of the enrichment from 5% to 15% and from 13% to 21%, respectively.

Biochemistry & Molecular Biology↗

Electric double layer capacitance for ionic liquids in nanoporous electrodes: Effects of pore size and ion composition

The energy density of an electric double layer (EDL) capacitor, a type of supercapacitor, depends on the ion distribution within the micropores of electrodes that are typically made of amorphous carbon. By using coarse-grained models and the classical density functional theory, we investigate the distributions of ionic species among different idealized nanopores in contact with an asymmetric ionic liquid mixture and the effects of the bulk electrolyte composition on capacitive energy storage. We find that a charged pore is always small-ion selective, provided all ions have the same valence and similar non-electrostatic interactions. While small ions enhance both the EDL capacitance and the accessibility of micropores, an ionic mixture containing ions of different sizes may yield a capacitance higher than those corresponding to pure ionic liquids. Furthermore, the increased capacitance may be attributed to more efficient ion packing near the charged surface. At certain conditions, the improvement is on a par with the anomalous capacitance rise for pure ionic liquids in electrodes with ultranarrow pores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗