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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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At least 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Direct in situ measurement of specific capacitance, monolayer tension, and bilayer tension in a droplet interface bilayer

In this study, thickness and tension are important physical parameters of model cell membranes. However, traditional methods to measure these quantities require multiple experiments using separate equipment. This work introduces a new multi-step procedure for directly accessing in situ multiple physical properties of droplet interface bilayers (DIB), including specific capacitance (related to thickness), lipid monolayer tension in the Plateau-Gibbs border, and bilayer tension. The procedure employs a combination of mechanical manipulation of bilayer area followed by electrowetting of the capacitive interface to examine the sensitivities of bilayer capacitance to area and contact angle to voltage, respectively. These data allow for determining the specific capacitance of the membrane and surface tension of the lipid monolayer, which are then used to compute bilayer thickness and tension, respectively. The use of DIBs affords accurate optical imaging of the connected droplets in addition to electrical measurements of bilayer capacitance, and it allows for reversibly varying bilayer area. After validating the accuracy of the technique with diphytanoyl phosphatidylcholine (DPhPC) DIBs in hexadecane, the method is applied herein to quantify separately the effects on membrane thickness and tension caused by varying the solvent in which the DIB is formed and introducing cholesterol into the bilayer. Because the technique relies only on capacitance measurements and optical images to determine both thickness and tension, this approach is specifically well-suited for studying the effects of peptides, biomolecules, natural and synthetic nanoparticles, and other species that accumulate within membranes without altering bilayer conductance.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Natural deep eutectic solvent mediated extrusion for continuous high-solid pretreatment of lignocellulosic biomass

Several deep eutectic solvents (DESs) have been demonstrated to be highly effective for lignocellulosic biomass pretreatment, combining the advantages of simple synthesis, relatively low chemical cost and better biocompatibility. However, low biomass loading that is usually involved with DES pretreatment hinders its practical use. Here, a twin-screw extruder was used for pretreating biomass sorghum bagasse at solid loadings up to 50%, mediated by a neutral-pH DES, choline chloride : glycerol (ChCl : Gly). This continuous extrusion process led to high glucose and xylose yields of >85% from enzymatic saccharification of the pretreated sorghum. A combination of microscopic, spectroscopic, and X-ray diffraction analyses demonstrate a high degree of defibration and disruption of the biomass cell wall structures; however, little or no change in chemical compositions. Further results from gel permeation chromatographic (GPC) and nuclear magnetic resonance (NMR) spectroscopic analyses indicate that ChCl : Gly-mediated extrusion preserved the basic lignin structural characteristics with no significant differences between extruded biomass at a solid loading of 30% and 50%. This study demonstrates the potential of DES-mediated extrusion as a highly effective continuous high-solid biomass pretreatment technology for industrially relevant applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

A water-processable organic electron-selective layer for solution-processed inverted organic solar cells

A triazine- and pyridinium-containing water-soluble material of 1,1′,1″-(4,4′,4″-(1,3,5-triazine-2,4,6-triyl)tris(benzene-4,1-diyl)) tris(methylene)tripyridinium bromide (TzPyBr) was developed as an organic electron-selective layer in solution-processed inverted organic solar cells due to its strong anti-erosion capacity against non-polar organic solvents commonly used for the active layer. Ohmic-like contact with the adjacent active materials like fullerene derivatives is speculated to be formed, as confirmed by the work-function measurements with scanning Kelvin probe and ultraviolet photoelectron spectroscopy techniques. Besides, considering the deep highest occupied molecular orbital energy level of TzPyBr, excellent hole-blocking property of the electron-selective layer is also anticipated. The inverted organic photovoltaic devices based on the TzPyBr/ITO (indium tin oxide) bilayer cathode exhibit dramatically enhanced performance compared to the control devices with bare ITO as the cathode and even higher efficiency than the conventional type devices with ITO and Al as the electrodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Doubly self-consistent field theory of grafted polymers under simple shear in steady state

We present a generalization of the numerical self-consistent mean-field theory of polymers to the case of grafted polymers under simple shear. The general theoretical framework is presented, and then applied to three different chain models: rods, Gaussian chains, and finitely extensible nonlinear elastic (FENE) chains. The approach is self-consistent at two levels. First, for any flow field, the polymer density profile and effective potential are calculated self-consistently in a manner similar to the usual self-consistent field theory of polymers, except that the calculation is inherently two-dimensional even for a laterally homogeneous system. Second, through the use of a modified Brinkman equation, the flow field and the polymer profile are made self-consistent with respect to each other. For all chain models, we find that reasonable levels of shear cause the chains to tilt, but it has very little effect on the overall thickness of the polymer layer, causing a small decrease for rods, and an increase of no more than a few percent for the Gaussian and FENE chains. Using the FENE model, we also probe the individual bond lengths, bond correlations, and bond angles along the chains, the effects of the shear on them, and the solvent and bonded stress profiles. We find that the approximations needed within the theory for the Brinkman equation affect the bonded stress, but none of the other quantities.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Structure and tunneling dynamics in a model system of peptide co-solvents: Rotational spectroscopy of the 2,2,2-trifluoroethanol⋯water complex

The hydrogen-bonding topology and tunneling dynamics of the binary adduct, 2,2,2-trifluoroethanol (TFE)⋯water, were investigated using chirped pulse and cavity based Fourier transform microwave spectroscopy with the aid of high level ab initio calculations. Rotational spectra of the most stable binary TFE⋯water conformer and five of its deuterium isotopologues were assigned. A strong preference for the insertion binding topology where water is inserted into the existing intramolecular hydrogen-bonded ring of TFE was observed. Tunneling splittings were detected in all of the measured rotational transitions of TFE⋯water. Based on the relative intensity of the two tunneling components and additional isotopic data, the splitting can be unambiguously attributed to the tunneling motion of the water subunit, i.e., the interchange of the bonded and nonbonded hydrogen atoms of water. The absence of any other splitting in the rotational transitions of all isotopologues observed indicates that the tunneling between g+ and g− TFE is quenched in the TFE⋯H{sub 2}O complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Solvation thermodynamics of amino acid side chains on a short peptide backbone

The hydration process of side chain analogue molecules differs from that of the actual amino acid side chains in peptides and proteins owing to the effects of the peptide backbone on the aqueous solvent environment. A recent molecular simulation study has provided evidence that all nonpolar side chains, attached to a short peptide backbone, are considerably less hydrophobic than the free side chain analogue molecules. In contrast to this, the hydrophilicity of the polar side chains is hardly affected by the backbone. To analyze the origin of these observations, we here present a molecular simulation study on temperature dependent solvation free energies of nonpolar and polar side chains attached to a short peptide backbone. The estimated solvation entropies and enthalpies of the various amino acid side chains are compared with existing side chain analogue data. The solvation entropies and enthalpies of the polar side chains are negative, but in absolute magnitude smaller compared with the corresponding analogue data. The observed differences are large; however, owing to a nearly perfect enthalpy-entropy compensation, the solvation free energies of polar side chains remain largely unaffected by the peptide backbone. We find that a similar compensation does not apply to the nonpolar side chains; while the backbone greatly reduces the unfavorable solvation entropies, the solvation enthalpies are either more favorable or only marginally affected. This results in a very small unfavorable free energy cost, or even free energy gain, of solvating the nonpolar side chains in strong contrast to solvation of small hydrophobic or nonpolar molecules in bulk water. The solvation free energies of nonpolar side chains have been furthermore decomposed into a repulsive cavity formation contribution and an attractive dispersion free energy contribution. We find that cavity formation next to the peptide backbone is entropically favored over formation of similar sized nonpolar side chain cavities in bulk water, in agreement with earlier work in the literature on analysis of cavity fluctuations at nonpolar molecular surfaces. The cavity and dispersion interaction contributions correlate quite well with the solvent accessible surface area of the nonpolar side chains attached to the backbone. This correlation however is weak for the overall solvation free energies owing to the fact that the cavity and dispersion free energy contributions are almost exactly cancelling each other.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

In vitro fibrillization of Alzheimer’s amyloid-β peptide (1-42)

The amyloid deposition in the form of extracellular fibrillar aggregates of amyloid-β (Aβ) peptide is a critical pathological event in Alzheimer’s disease. Here, we report a systematic investigation of the effects of environmental factors on the kinetics of Aβ fibrillization in vitro. The effects of Aβ42 peptide concentration, temperature, pH, added solvents and the ratio of Aβ40 and Aβ42 on the peptide fibrillization under agitated conditions was studied. The analysis show that the rate of fibril growth by monomer addition is not limited by diffusion but by rearrangement in the monomer structure, which is enhanced by low concentrations of fluorinated alcohols and characterized by the activation energy of 12 kcal/mol. Fibrillization rate decreases at pH values below 7.0 where simultaneous protonation of His 13 and 14 inhibits fibril formation. The lag period for Aβ42 was only twofold shorter and the fibril growth rate twofold faster than those of Aβ40. Lag period was shortened and the fibrillization rate was increased only at 90% content of Aβ42.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Electronic structure, pore size distribution, and sorption characterization of an unusual MOF, {[Ni(dpbz)][Ni(CN) 4 ]} n , dpbz = 1,4-bis(4-pyridyl)benzene

The monoclinic (Ni(L)[Ni(CN) 4 ] (L= 1,4-Bis(4-pyridyl) benzene) compound (defined as Ni-dpbz) is a flexible metal organic framework which assumes a pillared structure with layers defined by 2D Ni[Ni(CN) 4 ] n nets and dpbz ligands as pillars. The structure features an entrapped dpbz ligand that links between the open ends of four-fold Ni sites from two neighboring chains. This arrangement results in an unusual 5-fold pseudo square-pyramid environment for Ni and a significantly long Ni-N distance of 2.369(4) Å. Herein, using Density Functional Theory calculations, the different bonding characteristics between the 5-fold and 6-fold Ni's were determined. We found that there is weak covalent bonding between the 5-fold Ni and N in the entrapped ligand, and the 6-fold Ni-N bonds provide effective electronic conduction. The disordered dimethyl sulfoxide (DMSO) solvent molecules are not bonded to the framework. The material has a single pore with a diameter of 4.1 Å. This pore includes approximately 55% of the total free volume (based on a zero-diameter probe). The accessible pore surface area and pore volume were calculated to be 507 m 2 /g and 6.99 cm 3 /kg, respectively. The maximum amount of CO 2 that can be accommodated in the pores after DMSO is removed was found to be 204 mg/g, agreeing with the results of adsorption/desorption experiments of about 220 mg/g.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Pathways for Nucleation and Growth in Confined Spaces and at Interfaces

Mineral crystallization is central to myriad natural processes from the formation of snowflakes to stalagmites, but the molecular-scale mechanisms are often far more complex than models reflect. Feedbacks between the hydro-, bio-, and geo-spheres drive complex crystallization processes that challenge our ability to observe and quantify them, motivating an expansion of crystallization theories. Here, in this article, we discuss how the driving forces and timescales of nucleation are influenced by factors ranging from simple geometric confinement to distinct interfacial solution structures involving solvent organization, electrical double layers, and surface charging effects. Taken together, these ubiquitous natural phenomena can preserve metastable intermediates, drive precipitation of undersaturated phases, and modulate crystallization in time and space.

biosphere↗
DOE OSTI2012

Computational Fluid Dynamics of rising droplets

The main goal of this study is to perform simulations of droplet dynamics using Truchas, a LANL-developed computational fluid dynamics (CFD) software, and compare them to a computational study of Hysing et al.[IJNMF, 2009, 60:1259]. Understanding droplet dynamics is of fundamental importance in liquid-liquid extraction, a process used in the nuclear fuel cycle to separate various components. Simulations of a single droplet rising by buoyancy are conducted in two-dimensions. Multiple parametric studies are carried out to ensure the problem set-up is optimized.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1995

Replacing Chlorinated-Solvent-Based Cleaners And Adhesives

Brief report describes tests conducted to assess feasibility of using selected chemicals as replacements for selected cleaners, primers, and adhesives containing chlorinated solvents. Cleaners, primers, and adhesives in question used in bonding insulating material in steel cases of solid-fuel rocket motors. Necessary to phase out use of chlorinated solvents because of concerns over toxicity and adverse effects on ozone layer in upper atmosphere.

Heaton, Harley↗
NASA NTRSDate not supplied

Colloids in Microgravity

Colloidal particles are important in a broad range of applications in technology and materials processing. Due to high sensitivity to thermal fluctuations, a suspension of colloidal particles is considered as an assembly of super-atoms in condensed matter physics. This feature provides an excellent experimental model in statistical mechanics for fundamental studies of microstructural evolution and phase transformation at the individual particle level. However, using colloids to probe three-dimensional phase transitions on Earth remains a challenge as they can be influenced by the gravity force causing the particles to sediment and the solvent to flow. To suppress the undesirable gravity effects, experiments on concentrated colloids were carried out in the International Space Station (ISS) Light Microscopy Module. We will present results of these experiments.

Colloids↗
DOE OSTI2017

Geothermal Desalination GeoVision Case Study Analysis: Multiple Effect Distillation

Multiple effect distillation (MED) was evaluated as the baseline technology for geothermal desalination. MED desalination plant mass & energy balances were modeled using a simplified method described in the open literature. GETEM was used to calculate hydrothermal and EGS resource costs in the Business-As-Usual and Exploration De-Risk GeoVision Study Scenarios. The levelized cost of water (LCOW) was evaluated for geothermal resources in the temperature range of 100°C to 200°C. The LCOH from geothermal resources in the scenarios evaluated is cost competitive with many of the heat sources examined for MED desalination applications discussed in the literature. In the Business-As-Usual Scenario a hydrothermal resource achieves the LCOW cost target of $1.50/m³ with resource temperatures of approximately 150°C and greater. A hydrothermal resource in the Exploration De-Risk Scenario achieves the LCOW cost target of $1.00/m³ at a resource temperature of 200°C. In all cases evaluated, higher temperature geothermal resources demonstrate increased ability to achieve the specified LCOW cost targets. The degree to which the geothermal resource, feed water source, cooling water, water market, and concentrate disposal site are co-located will have a significant impact on the viability of any geothermal desalination application. In practice, due to large variations in resource characteristics, site attributes, and application requirements, the economic and logistical feasibility of geothermal desalination is likely to be highly site- and application- dependent. Although EGS resources in the Exploration De-Risk Scenario do not achieve the LCOW cost target at the resource temperatures evaluated, EGS resources could be deployed at locations where hydrothermal resources do not exist, which would help to address co-location challenges.

15 GEOTHERMAL ENERGY↗
DOE OSTI2016

Magnetite Dissolution using Hydrazine-Acid Solution for Chemical Decontamination

Chemical decontamination is committed to giving safe decommissioning of nuclear facilities as well as maintenance during the normal operation under sufficiently reduced radiation field. The removal of radioisotopes from the primary coolant system of nuclear power plant takes place with the dissolution of metal oxide layer. Dissolution of metal oxides in aqueous acidic solutions is primarily controlled by the protonation of metal-oxygen bonding to release the metal ions from the oxide lattices but in the presence of reducing or chelating agents dissolution is often facilitated by the enhanced mass transfer of metal ions together with chelating reagents as well as metal reduction to soluble state such as insoluble ferric ions to soluble ferrous ions of hematite. The mechanisms and kinetics related to the metal oxides dissolution in varied acidic reagents have been reported for many decades even though a general picture of dissolution is not available due to the peculiarity of each oxide in structure, stability of metal ions, solubility, and reactivity. In a number of experimental results and practical reports, organic acids such as oxalic acid, citric acid, ascorbic acid, malonic acid, thioglycolic acid, etc. were used as solvent reagents and many other literatures reported the effectiveness of the chelating agents in dissolution rate such as iminodiacetic acid (IDA), diethylene triamine pentaacetic acid (DTPA), nitrilo triacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA) by the sorption of dissolved metal ions forming stable metal chelates. Also reductive dissolution by the addition of reducing reagents such as hydrazine, vanadium as well as organic acids was reported with effective experimental results. However, organic acids and chelating ligands are often problematic on the safety of radioactive wastes. Organic compounds in a repository potentially form a complex with radionuclides, which increases the mobility of radionuclides and consequently increases the probability of the radioactive contamination of groundwater. Furthermore oxalic acid can cause a severe intergranular attack (IGA) to the type 304 stainless steel. Therefore, the use of organic acids or chelating reagents even though those effects to the dissolution performance is much greater than other chemical components must be minimized or carefully determined with appropriate treatment processes. Alternatively dissolution accommodated by inorganic reducing reagents or catalysts in inorganic acid solutions have been extensively studied for the feasible dissolution outcomes. The mixture of sulfuric acid and sulfurous acids as a dissolution media was reported to increase dissolution rate due to the effect of protonation by H{sub 2}SO{sub 4} and reducing effect of H{sub 2}SO{sub 3}. The increased dissolution of magnetite was also found in sulfur dioxide solution containing copper ions because SO{sub 2} plays as a reducing catalyst to form FeHSO{sub 3}{sup +} with Fe(III) from iron oxides and accordingly the concentration of Fe(III) ions decreases to accelerate the iron oxide dissolution. The present study is concerned with the feasibility of not using the organic compounds for the dissolution of oxide layers. We propose an acidic solution containing sulfuric acid, hydrazine, and copper ions for the effective dissolution of magnetite powders. The effects of both hydrazine and copper ions as a reducing agent and a catalyst respectively to promote the reducing power, as well as temperature will be investigated on the dissolution of magnetite powder. (authors)

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2014

Self-consistent field theory of tethered polymers: One dimensional, three dimensional, strong stretching theories and the effects of excluded-volume-only interactions

We examine end-tethered polymers in good solvents, using one- and three-dimensional self-consistent field theory, and strong stretching theories. We also discuss different tethering scenarios, namely, mobile tethers, fixed but random ones, and fixed but ordered ones, and the effects and important limitations of including only binary interactions (excluded volume terms). We find that there is a “mushroom” regime in which the layer thickness is independent of the tethering density, σ, for systems with ordered tethers, but we argue that there is no such plateau for mobile or disordered anchors, nor is there one in the 1D theory. In the other limit of brushes, all approaches predict that the layer thickness scales linearly with N. However, the σ{sup 1/3} scaling is a result of keeping only excluded volume interactions: when the full potential is included, the dependence is faster and more complicated than σ{sup 1/3}. In fact, there does not appear to be any regime in which the layer thickness scales in the combination Nσ{sup 1/3}. We also compare the results for two different solvents with each other, and with earlier Θ solvent results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Understanding How Processing Additives Tune the Nanoscale Morphology of High Efficiency Organic Photovoltaic Blends: From Casting Solution to Spun-Cast Thin Film

Adding a small amount of a processing additive to the casting solution of photoactive organic blends has been demonstrated to be an effective method for achieving improved power conversion efficiency (PCE) in organic photovoltaics (OPVs). However, an understanding of the nano-structural evolution occurring in the transformation from casting solution to thin photoactive films is still lacking. In this report, the effects of the processing additive diiodooctane (DIO) on the morphology of the established blend of PBDTTT-C-T polymer and the fullerene derivative PC71BM used for OPVs are investigated, starting in the casting solution and tracing the effects in spun-cast thin films by using neutron/X-ray scattering, neutron reflectometry, and other characterization techniques. The results reveal that DIO has no observable effect on the structures of PBDTTT-C-T and PC71BM in solution; however, in the spun-cast films, it significantly promotes their molecular ordering and phase segregation, resulting in improved PCE. Thermodynamic analysis based on Flory-Huggins theory provides a rationale for the effects of DIO on different characteristics of phase segregation due to changes in concentration resulting from evaporation of the solvent and additive during film formation. Such information may help improve the rational design of ternary blends to more consistently achieve improved PCE for OPVs.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Hydrodynamic coupling of particle inclusions embedded in curved lipid bilayer membranes

Here, we develop theory and computational methods to investigate particle inclusions embedded within curved lipid bilayer membranes. We consider the case of spherical lipid vesicles where inclusion particles are coupled through (i) intramembrane hydrodynamics, (ii) traction stresses with the external and trapped solvent fluid, and (iii) intermonolayer slip between the two leaflets of the bilayer. We investigate relative to flat membranes how the membrane curvature and topology augment hydrodynamic responses. We show how both the translational and rotational mobility of protein inclusions are effected by the membrane curvature, ratio of intramembrane viscosity to solvent viscosity, and intermonolayer slip. For general investigations of many-particle dynamics, we also discuss how our approaches can be used to treat the collective diffusion and hydrodynamic coupling within spherical bilayers.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Deep eutectic solvents as green and sustainable diluents in headspace gas chromatography for the determination of trace level genotoxic impurities in pharmaceuticals

Genotoxic impurities (GTIs) are potential carcinogens that need to be controlled down to ppm or lower concentration levels in pharmaceuticals under strict regulations. The static headspace gas chromatography (HS-GC) coupled with electron capture detection (ECD) is an effective approach to monitor halogenated and nitroaromatic genotoxins. Deep eutectic solvents (DESs) possess tunable physico-chemical properties and low vapor pressure for HS-GC methods. In this study, zwitterionic and non-ionic DESs have been used for the first time to develop and validate a sensitive analytical method for the analysis of 24 genotoxins at sub-ppm concentrations. Compared to non-ionic diluents, zwitterionic DESs produced exceptional analytical performance and the betaine: 7 (1,4- butane diol) DES outperformed the betaine: 5 (1,4-butane diol) DES. Limits of detection (LOD) down to the 5-ppb concentration level were achieved in DESs. Wide linear ranges spanning over 5 orders of magnitude (0.005–100 µg g –1 ) were obtained for most analytes with exceptional sensitivities and high precision. The method accuracy and precision were validated using 3 commercially available drug substances and excellent recoveries were obtained. Finally, this study broadens the applicability of HS-GC in the determination of less volatile GTIs by establishing DESs as viable diluent substitutes for organic solvents in routine pharmaceutical analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗