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At least 649 records · Page 36

Investigating the Effect of Added Salt on the Chain Dimensions of Poly(ethylene oxide) through Small-Angle Neutron Scattering

We have measured the effect of added salt on the chain dimensions of mixtures of poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI) in the melt state through small-angle neutron scattering (SANS) experiments. Scattering profiles from blends of hydrogenated and deuterated PEO mixed with LiTFSI were measured as a function of salt concentration. Scattering profiles from pure deuterated PEO/LiTFSI mixtures were used for background-subtraction purposes. The densities of PEO/LiTFSI mixtures of varying salt concentrations were measured to calculate partial molar monomer volumes of PEO and LiTFSI to account for nonideal mixing. Kratky plots of the scattering profiles were used to calculate the salt concentration dependence of statistical segment length. At low salt concentrations, segment length decreases with increasing salt concentration, before increasing with increasing salt concentration in the high salt concentration regime. The random phase approximation was used to predict theoretical scattering profiles from the calculated segment lengths and partial molar volumes; there is excellent agreement between the theoretical and measured scattering profiles at all salt concentrations. There appears to be a correlation between chain dimensions and coordination between lithium ions and EO monomers. Finally, the scattering profiles of the pure deuterated PEO/LiTFSI mixtures suggested the presence of ion clusters of characteristic size of 0.6 nm at high salt concentrations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The effect of polymer-induced attraction on dynamical arrests of polymer composites with bimodal particle size distributions

We explore the flow properties of nanocomposite melts where the particles have bimodal size distributions and experience a weak attraction produced by suspending silica particles in polyethylene glycol melts with a molecular weight of 2000 (PEG2000). The polymer is unentangled and adsorbs to the particle surface. Here, the volume fraction ratio of large particles to total particle volume fraction, R, is systematically varied to study the effects of this polymer-induced attraction on suspension rheology. The maximum volume fraction, Φm, of the particles varies in a nonmonotonic manner of R as demonstrated in studies of the same mixtures when suspended in polyethylene glycol with a molecular weight of 400 (PEG400), where the particles experience excluded volume interactions. The dynamical arrest volume fraction Φx, of nanocomposite melts in PEG2000 monotonically increases with R. In frequency sweep experiments, the plateau elastic modulus is dominated by attractive interactions and increases with the total particle volume fraction, Φc, proportionally with 1/(h2< D >), where < D > is the volume average particle diameter and h is the average particle-particle surface separation. As R is varied, this universal yielding behavior occurs at constant surface separation, h, suggesting that the flow properties of the mixtures can be understood as being equivalent to flow properties of homogeneous particle suspensions experiencing short-range attractions with an extent independent of particle size.

36 MATERIALS SCIENCE↗

Flame balls - Past, present and future

This paper discusses analytical and numerical work that has been carried out in order to understand flame-balls and related phenomena that have been observed in microgravity experiments. The importance of heat losses is identified, whether from conduction, convection, or radiation. Accurate numerical simulations for hydrogen-air mixtures with radiation losses reveal a flammability limit of 3.5 percent of hydrogen by volume, a value close to the experimental one. The important role of stability analyses is emphasized, with particular attention to the role of three-dimensional instabilities in explaining unsteady spheroidal flames and flame-strings, objects that are observed in the experiments. We speculate that the dynamics of flame-strings is affected by in-depth radiation absorption for mixtures containing SF6, and report on some preliminary calculations in which this phenomenon is accounted for.

Buckmaster, J.↗

Structure and Dynamics of Interfaces: Drops and Films

We aim to acquire measurements of the structure and dynamics of certain liquid-fluid interfaces using an ensemble of techniques in collaboration: (1) Total internal reflection (TIR) Surface light scattering spectroscopy (SLSS), (2) Brewster angle microscopy (BAM), and (3) Drop-shape analysis. SLSS and BAM can be done on a shared interfacial footprint. Results using a 50-50 mixture of pentane-isohexane, which extends the range of NASA's Confined Vapor Bubble (CVB) experiment, yield surface tension results that differ from the expected Langmuir Fit. These results were confirmed using both the SLSS and drop-shape analysis approaches.

pentane-isohexane mixture↗

Fluid physics, thermodynamics, and heat transfer experiments in space

An overstudy committee was formed to study and recommend fundamental experiments in fluid physics, thermodynamics, and heat transfer for experimentation in orbit, using the space shuttle system and a space laboratory. The space environment, particularly the low-gravity condition, is an indispensable requirement for all the recommended experiments. The experiments fell broadly into five groups: critical-point thermophysical phenomena, fluid surface dynamics and capillarity, convection at reduced gravity, non-heated multiphase mixtures, and multiphase heat transfer. The Committee attempted to assess the effects of g-jitter and other perturbations of the gravitational field on the conduct of the experiments. A series of ground-based experiments are recommended to define some of the phenomena and to develop reliable instrumentation.

Dodge, F. T.↗

Gouge formation and dilation impacts to flow during fracture shearing

We report flow in fractures is of critical importance to fluid flow in low-permeability shales, particularly when they restrict vertical migration from reservoirs. The Mt. Simon Sandstone is a target for geologic CO 2 sequestration and the overlying Eau Claire Formation is the sealing formation capping this reservoir. The lower Eau Claire, a primary barrier to upward migration of CO 2 from the Mt. Simon, is lithologically heterogenous with a mixture of sandstone and shale. We use a series of flow-through experiments on fractured samples from the Eau Claire to document the morphological changes taking place in the fracture and surrounding rock as it is sheared in a stepwise fashion. The samples were imaged using computed tomography after each shearing episode and flow resistance was calculated based on the pressure differential across each core. We found that gouge accumulations in the fracture plane led to specific instances of self-sealing behavior despite the fact that most samples increased in average fracture aperture and transmissivity. Gouge limited the increase or, in some cases, decreased flow through these samples. Fractures adjacent to shale-rich zones and concordant with bedding were more likely to show evidence of self-sealing, while increased sandstone content and fracture orientation perpendicular to bedding planes was more likely to result in fracture dilation and fracture permeability increases. Reactivation and shearing of vertical fractures in lithologically heterogenous caprocks is more likely to pose risks to long term CO 2 storage scenarios.

58 GEOSCIENCES↗

Segmental Dynamics Measured by Quasi-Elastic Neutron Scattering and Ion Transport in Chemically Distinct Polymer Electrolytes

We investigate the segmental dynamics and ion transport in two chemically distinct polymer electrolytes, poly(2-cyanoethyl acrylate) (PCEA) and poly(ethylene oxide) (PEO), and their mixtures with lithium bis(trifluoromethane)sulfonimide (LiTFSI) salt. Quasi-elastic neutron scattering experiments reveal slow dynamics in PCEA/LiTFSI relative to that in PEO/LiTFSI, translating to monomeric friction coefficients that are orders of magnitude different. In spite of the enhanced salt dissociation in PCEA due to the presence of polar groups, ion transport is largely dominated by the effect of increased monomeric friction in the pure polymer. Conductivity in these systems is quantified through a simple expression combining salt dissociation, the monomeric friction in the pure polymer, and the effect of added salt on the monomeric friction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Data-Efficient Methods for Determining Flory–Huggins χ Parameters in Multicomponent Polymer Formulations

Polymer formulations are essential in diverse applications including personal care products, coatings, paints, adhesives, and plastic materials. Designing these formulations requires navigating large, complex design spaces, where phase and self-assembly behavior critically impact performance. The Flory–Huggins χ parameter, which quantifies segmental miscibility, is widely used to parametrize the excess free energy of mixing in formulation models. In this work, we introduce two data-efficient, top-down methods for estimating χ parameters using the Random Phase Approximation (RPA): (i) Boundary Nonlinear Regression (Boundary-NLR), which fits theoretical spinodal boundaries to experimental phase boundaries, and (ii) Surrogate Model Inverse Parameter Estimation (SMIPE), which uses a Gaussian Process Classifier to fit sparse phase maps via a surrogate model. Both methods allow rapid parametrization of polymer field-theoretic models without the need for additional experiments. We evaluate these approaches on data sets involving polymer–solvent–nonsolvent ternary mixtures and block copolymer–solvent systems, demonstrating their robustness to experimental noise and their relevance for real-world formulation design.

copolymers↗

Non-Intrusive Energy Disaggregation Using Non-Negative Matrix Factorization With Sum-to-k Constraint

Energy disaggregation or non-intrusive load monitoring addresses the issue of extracting device-level energy consumption information by monitoring the aggregated signal at one single measurement point without installing meters on each individual device. Energy disaggregation can be formulated as a source separation problem, where the aggregated signal is expressed as linear combination of basis vectors in a matrix factorization framework. In this paper, an approach based on Sum-to-k constrained non-negative matrix factorization (S2K-NMF) is proposed. By imposing the sum-to-k constraint and the non-negative constraint, S2K-NMF is able to effectively extract perceptually meaningful sources from complex mixtures. The strength of the proposed algorithm is demonstrated through two sets of experiments: Energy disaggregation in a residential smart home; and heating, ventilating, and air conditioning components energy monitoring in an industrial building testbed maintained at the Oak Ridge National Laboratory. Furthermore, extensive experimental results demonstrate the superior performance of S2K-NMF as compared to state-of-the-art decomposition-based disaggregation algorithms.

42 ENGINEERING↗

Probing the Effects of NO x and SO x Impurities on Oxy-Fuel Combustion in Supercritical CO 2 : Shock Tube Experiments and Chemical Kinetic Modeling

The direct-fired supercritical carbon dioxide cycles are one of the most promising power generation methods in terms of their efficiency and environmental friendliness. Two important challenges in implementing these cycles are the high pressure (300 bar) and high CO 2 dilution (>80%) in the combustor. The design and development of supercritical oxy-combustors for natural gas require accurate reaction kinetic models to predict the combustion outcomes. The presence of a small amount of impurities in natural gas and other feed streams to oxy-combustors makes these predictions even more complex. During oxy-combustion, trace amounts of nitrogen present in the oxidizer is converted to NO x and gets into the combustion chamber along with the recirculated CO 2 . Similarly, natural gas can contain a trace amount of ammonia and sulfurous impurities that get converted to NO x and SO x and get back into the combustion chamber with recirculated CO 2 . In this work, a reaction model is developed for predicting the effect of impurities such as NO x and SO x on supercritical methane combustion. The base mechanism used in this work is GRI Mech 3.0. H 2 S combustion chemistry is obtained from Bongartz et al. while NOx chemistry is from Konnov. The reaction model is then optimized for a pressure range of 30–300 bar using high-pressure shock tube data from the literature. It is then validated with data obtained from the literature for methane combustion, H 2 S oxidation, and NO x effects on ignition delay. The effect of impurities on CH 4 combustion up to 16 atm is validated using NO x -doped methane studies obtained from the literature. In order to validate the model for high-pressure conditions, experiments are conducted at the UCF shock tube facility using natural gas identical mixtures with N 2 O as an impurity at ~100 bar. Current results show that there is a significant change in ignition delay with the presence of impurities. A comparison is made with experimental data using the developed model and predictions are found to be in good agreement. The model developed was used to study the effect of impurities on CO formation from sCO 2 combustors. It was found that NO x helps in reducing CO formation while the presence of H 2 S results in the formation of more CO. The reaction mechanism developed herein can also be used as a base mechanism to develop reduced mechanisms for use in CFD simulations.

Energy & Fuels↗

Exobiology, Jupiter and life.

Recent experiments in an environmental chamber have shown that not even hardy terrestrial bacteria can survive on the Martian surface. The planet Jupiter is now considered by many to be the most likely place to find nonterrestrial life. Atmospheric simulation experiments for Jupiter that have been performed involve spark or semicorona discharges in mixtures of methane and ammonia at room temperature and a pressure lower than atmospheric. Terrestrial microorganisms have been shown capable of surviving 24 hr under a range of possible Jovian atmospheric conditions. The final mode of approach to the question of Jovian life concerns theoretical studies on the sort of chemical systems from which life could be generated.

Molton, P. M.↗

Validation of scramjet exhaust simulation technique at Mach 6

Current design philosophy for hydrogen-fueled, scramjet-powered hypersonic aircraft results in configurations with strong couplings between the engine plume and vehicle aerodynamics. The experimental verification of the scramjet exhaust simulation is described. The scramjet exhaust was reproduced for the Mach 6 flight condition by the detonation tube simulator. The exhaust flow pressure profiles, and to a large extent the heat transfer rate profiles, were then duplicated by cool gas mixtures of Argon and Freon 13B1 or Freon 12. The results of these experiments indicate that a cool gas simulation of the hot scramjet exhaust is a viable simulation technique except for phenomena which are dependent on the wall temperature relative to flow temperature.

Hopkins, H. B.↗

Potential Bedforms on Venus: Wind Tunnel Simulations

Wind tunnel studies involving mixtures of particle sizes (bimodal and multimodal distributions) indicate the microdunes and related ridge- and wave-like structures can occur over a wider range of conditions. The results indicate that the bedforms develop as a consequence of the effective sorting capability of the high-density Venusian atmosphere. Four mixtures of different particle-size distributions were investigated. The results of these experiments suggest that: (1) small-scale bedforms on Venus may be more common than previously anticipated from simulations involving only unimodal sands; (2) small particles are rapidly sorted on Venus if winds slightly above threshold are available; (3) coarse particles are transported in traction within the bedforms as well as rolled by saltating fines, suggesting that the capacity of wind on Venus to transport material is greater than anticipated from previous flux studies and (4) microdunes and related ridges and waves with coarse and fine layers can be produced during sorting.

Bougan, S. J.↗

Catalytic recombination of dissociation products with Pt/SnO2 for rare and common isotope long-life, closed-cycle CO2 lasers

This paper reports results on recombination of pulsed CO2 laser dissociation products with Pt/SnO2 catalysts, and supporting studies in a surrogate laboratory catalyst reactor. The closed-cycle, pulsed CO2 laser has been continuously operated for one million pulses with an overall power degradation of less than 5 percent by flowing the laser gas mixture through a 2-percent Pt/SnO2 catalyst bed. In the surrogate laboratory reactor, experiments have been conducted to determine isotopic exchange with the catalyst when using rare-isotope gases. The effects of catalyst pretreatment, sample weight, composition, and temperature on catalyst efficiency have also been determined.

Brown, Kenneth G.↗

On the isotope analysis of cometary dust

It is thought that comets are an intimate mixture of ices and sub-micron to pebble sized silicates. Based on experience with carbonaceous chrondrites, part of the smallest grains are expected to be primary condensates carrying the unadulterated isotopic signature of their place of origin. In order to extract this information a grain-by-grain analysis will be necessary.

Begemann, Friedrich↗

Space Station Freedom pressurized element interior design process

The process used to develop the on-orbit working and living environment of the Space Station Freedom has some very unique constraints and conditions to satisfy. The goal is to provide maximum efficiency and utilization of the available space, in on-orbit, zero G conditions that establishes a comfortable, productive, and safe working environment for the crew. The Space Station Freedom on-orbit living and working space can be divided into support for three major functions: (1) operations, maintenance, and management of the station; (2) conduct of experiments, both directly in the laboratories and remotely for experiments outside the pressurized environment; and (3) crew related functions for food preparation, housekeeping, storage, personal hygiene, health maintenance, zero G environment conditioning, and individual privacy, and rest. The process used to implement these functions, the major requirements driving the design, unique considerations and constraints that influence the design, and summaries of the analysis performed to establish the current configurations are described. Sketches and pictures showing the layout and internal arrangement of the Nodes, U.S. Laboratory and Habitation modules identify the current design relationships of the common and unique station housekeeping subsystems. The crew facilities, work stations, food preparation and eating areas (galley and wardroom), and exercise/health maintenance configurations, waste management and personal hygiene area configuration are shown. U.S. Laboratory experiment facilities and maintenance work areas planned to support the wide variety and mixtures of life science and materials processing payloads are described.

Hopson, George D.↗