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At least 145 records · Page 8

Role of a Multivalent Ion–Solvent Interaction on Restricted Mg 2+ Diffusion in Dimethoxyethane Electrolytes

The diffusion behavior of Mg 2+ in electrolytes is not as readily accessible as that from Li + or Na + utilizing PFG NMR, due to the low sensitivity, poor resolution, and rapid relaxation encountered when attempting 25 Mg NMR. In MgTFSI 2 /DME solutions, “bound” DME (coordinating to Mg 2+ ) and “free” DME (bulk) are distinguishable from 1 H NMR. With the exchange rates between them obtained from 2D 1 H EXSY NMR, we can extract the self-diffusivities of free DME and bound DME (which are equal to that of Mg 2+ ) before the exchange occurs using PFG diffusion NMR measurements coupled with analytical formulas describing diffusion under two-site exchange. Further, the high activation enthalpy for exhange (65–70 kJ/mol) can be explained by the structural change of bound DME as evidenced by its reduced C–H bond length. Comparison of the diffusion behaviors of Mg 2+ , TFSI – , DME, and Li + reveals a relative restriction to Mg 2+ diffusion that is caused by the long-range interaction between Mg 2+ and solvent molecules, especially those with suppressed motions at high concentrations and low temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Refinery Perspective on Decarbonizing with Marine Biofuels

This work seeks to understand what biofuel production pathways a refinery might prefer to produce very low sulfur fuel oil (VLSFO) for marine applications. A comprehensive refinery optimization model was modified to allow for (1) direct blending of soy biodiesel, renewable diesel, Fischer-Tropsch diesel, and several pyrolysis oils and (2) indirect blending of all pyrolysis oils via co-processing in a fluidized catalytic cracker (FCC) and diesel hydrotreater into the marine fuel pool. Results showed that preferred pathways to bio-VLSFO production included co-processing low-quality pyrolysis oil in a FCC to blend the resulting biogenic light cycle oil, directly blending soy biodiesel, and directly blending small quantities of pyrolysis oil. Bio-VLSFO production costs were compared to those of fossil VLSFO subject to different marine fuel demands, benchmark crude oil prices, and biogenic fractions in the finished product. Given benchmark crude oil prices over 60 $/bbl, bio-VLSFO production appeared to be significantly cheaper than fossil VLSFO. Corresponding marginal abatement costs of CO 2 mostly ranging from -300 to 350 $/ton of CO 2 were also determined using a simplified but novel approach to allow for a comparison to other decarbonization strategies. In conclusion, this work indicates that low-sulfur contents in biofuels, relatively relaxed specifications for marine fuels, and current difficulties in meeting VLSFO specifications with crude oils can combine to make bio-VLSFO production cost-effective. Moreover, marine fuels appear to be a good entry point for refiners to start decarbonizing with biofuel pathways that could eventually be extended to other product pools.

09 BIOMASS FUELS↗

Structural relaxation of water during rapid cooling from ambient temperatures

Experiments investigating the properties of deeply supercooled liquid water are needed to develop a comprehensive understanding of water’s anomalous properties. One approach involves transiently heating nanoscale water films into the supercooled region for several nanoseconds at a time and then interrogating the water films after they have quenched to cryogenic temperatures. To relate the results obtained with this approach to other experiments and simulations on supercooled water, it is important to understand how closely the quenched structure tracks the (metastable) equilibrium structure of water as a function of the transient heating temperature. A key step involves quantifying the extent to which water that is transiently heated to ambient temperatures [hyperquenched water (HQW)] subsequently relaxes toward the structure of low-density amorphous (LDA) ice as it cools. We analyzed the infrared reflection–absorption spectra of LDA, HQW, and crystalline ice films to determine their complex indices of refraction. With this information, we estimate that HQW retains ~50%–60% of a structural motif characteristic of water at high temperatures with the balance comprised of a low-temperature motif. This result, along with results from x-ray diffraction experiments on water and amorphous ices, allows one to quantify the fraction of the high-temperature motif at approximately zero pressure as a function of temperature from 150 to 350 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identifying the gene responsible for non‐photochemical quenching reversal in Phaeodactylum tricornutum

SUMMARY Algae such as diatoms and haptophytes have distinct photosynthetic pigments from plants, including a novel set of carotenoids. This includes a primary xanthophyll cycle comprised of diadinoxanthin and its de‐epoxidation product diatoxanthin that enables the switch between light harvesting and non‐photochemical quenching (NPQ)‐mediated dissipation of light energy. The enzyme responsible for the reversal of this cycle was previously unknown. Here, we identified zeaxanthin epoxidase 3 (ZEP3) from Phaeodactylum tricornutum as the candidate diatoxanthin epoxidase. Knocking out the ZEP3 gene caused a loss of rapidly reversible NPQ following saturating light exposure. This correlated with the maintenance of high concentrations of diatoxanthin during recovery in low light. Xanthophyll cycling and NPQ relaxation were restored via complementation of the wild‐type ZEP3 gene. The zep3 knockout strains showed reduced photosynthetic rates at higher light fluxes and reduced specific growth rate in variable light regimes, likely due to the mutant strains becoming locked in a light energy dissipation state. We were able to toggle the level of NPQ capacity in a time and dose dependent manner by placing the ZEP3 gene under the control of a β‐estradiol inducible promoter. Identification of this gene provides a deeper understanding of the diversification of photosynthetic control in algae compared to plants and suggests a potential target to improve the productivity of industrial‐scale cultures.

Ware, Maxwell A.↗

Low Forward Voltage III-Nitride Red Micro-Light-Emitting Diodes on a Strain Relaxed Template with an InGaN Decomposition Layer

In this study, III-nitride red micro-light-emitting diodes (µLEDs) with ultralow forward voltage are demonstrated on a strain relaxed template. The forward voltage ranges between 2.00 V and 2.05 V at 20 A/cm 2 for device dimensions from 5 x 5 to 100 x 100 µm 2 . The µLEDs emit at 692 nm at 5 A/cm 2 and 637 nm at 100 A/cm 2 , corresponding to a blueshift of 55 nm due to the screening of the internal electric field in the quantum wells. The maximum external quantum efficiency and wall-plug efficiency of µLEDs are 0.31% and 0.21%, respectively. This suggests that efficient III-nitride red µLEDs can be realized with further material optimizations.

36 MATERIALS SCIENCE↗

Radiative decay in carbon dioxide.

Thermal disturbance radiative decay time in carbon dioxide at low pressures and for nonzero vibrational relaxation times

Hodges, R. R., Jr.↗

Material damping in aluminum and metal matrix composites

The material damping in beam-like specimens of aluminum and metal matrix composites was measured. A unique apparatus to determine damping by free decay while the specimens are in free fall in a vacuum was used. The specimens tested include 2024-T3 and 6061-T4 aluminum, and unidirectional graphite/metal matrix specimens with P55 and P100 fibers and 6061 Aluminum and AZ91C Magnesium as matrix materials. Tests were conducted to determine the dependence of damping on frequency and stress level. For the aluminum specimens, the material damping followed the Zener model at very low stress levels. Below the Zener relaxation frequency, a strong dependence of damping on stress was found for even moderate stress levels. Damping for the aluminum matrix materials was slightly above that predicted by the Zener model for a homogeneous bar of the matrix aluminum. For the magnesium matrix specimens, damping significantly above the Zener prediction for the homogeneous matrix material was observed.

Crawley, Edward F.↗

MISSE 6 Polymer Film Tensile Experiment

The Polymer Film Tensile Experiment (PFTE) was flown as part of Materials International Space Station Experiment 6 (MISSE 6). The purpose of the experiment was to expose a variety of polymer films to the low Earth orbital environment under both relaxed and tension conditions. The polymers selected are those commonly used for spacecraft thermal control and those under consideration for use in spacecraft applications such as sunshields, solar sails, and inflatable and deployable structures. The dog-bone shaped samples of polymers that were flown were exposed on both the side of the MISSE 6 Passive Experiment Container (PEC) that was facing into the ram direction (receiving atomic oxygen, ultraviolet (UV) radiation, ionizing radiation, and thermal cycling) and the wake facing side (which was supposed to have experienced predominantly the same environmental effects except for atomic oxygen which was present due to reorientation of the International Space Station). A few of the tensile samples were coated with vapor deposited aluminum on the back and wired to determine the point in the flight when the tensile sample broke as recorded by a change in voltage that was stored on battery powered data loggers for post flight retrieval and analysis. The data returned on the data loggers was not usable. However, post retrieval observation and analysis of the samples was performed. This paper describes the preliminary analysis and observations of the polymers exposed on the MISSE 6 PFTE.

Miller, Sharon K. R.↗

An Examination of Radiation Induced Tensile Failure of Stressed and Unstressed Polymer Films Flown on MISSE-6

Thin film polymers are used in many spacecraft applications for thermal control (multilayer insulation and sunshields), as lightweight structural members (solar array blankets, inflatable/deployable structures) and have been proposed for propulsion (solar sails). Polymers in these applications are often under a tensile load and are directly exposed to the space environment, therefore it is important to understand the effect of stress in combination with the environment on the durability of these polymer films. The purpose of the Polymer Film Tensile Experiment, flown as part of Materials International Space Station Experiment 6 (MISSE 6), was to expose a variety of polymer films to the low Earth orbital environment under both relaxed and tension conditions. This paper describes the results of post flight tensile testing of these samples.

Miller, Sharon K.↗

A new method for predicting response in complex linear systems. II

The paper describes convergence and response studies in the low frequency range of complex systems, particularly with low values of damping of different distributions, and reports on the modification of the relaxation procedure required under these conditions. A new method is presented for response estimation in complex lumped parameter linear systems under random or deterministic steady state excitation. The essence of the method is the use of relaxation procedures with a suitable error function to find the estimated response; natural frequencies and normal modes are not computed. For a 45 degree of freedom system, and two relaxation procedures, convergence studies and frequency response estimates were performed. The low frequency studies are considered in the framework of earlier studies (Kayser and Bogdanoff, 1975) involving the mid to high frequency range.

Bogdanoff, J. L.↗

Seismic velocity, attenuation and rheology of the upper mantle

Seismic and rheological properties of the upper mantle in the vicinity of the low-velocity zone are expressed in terms of relaxation by dislocation glide. Dislocation bowing in the glide plane explains seismic velocities and attenuation. Climbing at higher stresses for longer periods of time give the observed viscosity, and explain the low velocity and high temperature attenuation found at seismic frequencies. Due to differing parameters, separate terms for thermal, seismic and rheological lithospheres are proposed. All three lithospheres, however, are related and are functions of temperature, and must be specified by parameters such as period, stress, and stress duration.

Anderson, D. L.↗

Dielectric Relaxation by Quantum Critical Magnons

We report the experimental observation of dielectric relaxation by quantum critical magnons. Complex capacitance measurements reveal a dissipative feature with a temperature-dependent amplitude due to low-energy lattice excitations and an activation behavior of the relaxation time. The activation energy softens close to a field-tuned magnetic quantum critical point at H = H c and follows single-magnon energy for H > H c , showing its magnetic origin. Furthermore, our study demonstrates the electrical activity of coupled low-energy spin and lattice excitations, an example of quantum multiferroic behavior.

1-dimensional spin chains↗

Clustering Nuclear Magnetic Resonance: Machine learning assistive rapid two‐dimensional relaxometry mapping

Abstract Low‐field nuclear magnetic resonance (NMR) relaxometry is an attractive approach from point‐of‐care testing medical diagnosis to in situ oil‐gas exploration. One of the problems, however, is the inherently long relaxation time of the (liquid) samples, (and hence low signal‐to‐noise ratio) which causes unnecessarily long repetition time. In this work, a new class of methodology is presented for rapid and accurate object classification using NMR relaxometry with the aid of machine learning. It is demonstrated that the sensitivity and specificity of the classification is substantially improved with higher order of (pseudo)‐dimensionality (e.g., 2D‐ or multi‐dimensional). This new methodology (termed as ‘Clustering NMR’) may be extremely useful for rapid and accurate object classification (in less than a minute) using low‐field NMR.

Peng, Weng Kung↗

Segmental relaxation of sequence defined polymers

For this work, the dynamical behavior of sequence defined polymers, P(C n EG 4 ), was studied using dielectric spectroscopy showing one segmental relaxation in addition to a secondary relaxation. In case of segmental relaxation, the relaxation times strongly depend on the molecular weight at low temperatures, while at higher temperatures, unlike to linear homo polymers, this effect levels out. With increasing length of C-units, the segmental relaxation accelerates. This is also reflected in the glass transition temperature, extracted from dielectric spectroscopy. With increasing length of C-units the glass transition temperature decreases, compatible with the accelerated segmental relaxation.

36 MATERIALS SCIENCE↗

Smoothers for Matrix-Free Algebraic Multigrid Preconditioning of High-Order Finite Elements

We investigate smoothers for use in matrix-free algebraic multigrid (AMG) preconditioning of high-order finite element problems. These AMG preconditioners are matrix-free in the sense that they are built from a related low-order refined finite element problem whose system matrix can be much more rapidly assembled than the high-order problem. Our proposed smoother, which we call distributive relaxation, is more robust to the anisotropy present in many low-order refined meshes which feature a clustering of nodes near the boundaries between high-order finite elements. For solving the low-order refined problem, we show that this new distributive relaxation smoother possesses significantly improved performance compared to more traditional smoothers.

97 MATHEMATICS AND COMPUTING↗

Transient polar motions and the nature of the asthenosphere for short time scales

A uniformly valid mathematical formalism is developed to study the secular motions of the rotational axis of a layered viscoelastic earth due to seismic excitation. The changes required for implementing the formulation within the framework of the faulting problem. The rationale of adopting the chosen nrheological model, which contains a low-viscosity zone beneath the lithosphere and is based on linear Maxell constitutive relationship, is discussed. The impact of this low-viscosity channel on thhe two families of relaxation time, governing both isostatic readjustment and rotational processes, is considered. It is found that the polar motions depend sensitively on the viscosity structure of the asthenosphere and not at all on the underlying mantle. A gloal low-velocity zone with short-term asthenospheric viscosities less than about 5 x 10 to the 18th Pa-s and widths greater than 50 km is ruled out.

Boschi, E.↗

Stress relaxation of high strength A-286 bolts in simulated storage at room temperature

It was concluded that thermally activated relaxation of the type customarily encountered at high temperatures was not expected to occur at the low temperatures where long time NERVA storage conditions will prevail. Instances where relaxation occurred by a different mechanism at such moderate temperatures were also reported. Twelve simulated bolted flange test specimens were prepared. Parameters that were varied among the twelve specimens were the flange material, the bolt shank diameter, and the bolt loading in terms of percent of yield strength.

Sampson, R. C.↗