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At least 1,045 records · Page 58

Polymer Composition Influence on Optical Properties of Laser-Generated Au Nanoparticles Based Nanocomposites

Au nanoparticles (AuNPs) stable colloid solution were prepared by laser ablation and fragmentation in liquid monomer isodecyl acrylate (IDA). Sizes of obtained nanoparticles were determined by scanning transmission electron microscopy (STEM) and were about 20 nm. Nanocomposites films were prepared from obtained stable colloid solution by UV-photocuring. To prepare solid polymer films different crosslinking diacrylates were used. Third-order nonlinear optical responses of prepared nanomaterials with different polymer matrix compositions were estimated by z-scan technique and compared.

36 MATERIALS SCIENCE↗

NASA Flexible Screen Propellant Management Device (PMD) Demonstration With Cryogenic Liquid

While evaluating various options for liquid methane and liquid oxygen propellant management for lunar missions, Innovative Engineering Solutions (IES) conceived the flexible screen device as a potential simple alternative to conventional propellant management devices (PMD). An apparatus was designed and fabricated to test flexible screen devices in liquid nitrogen. After resolution of a number of issues (discussed in detail in the paper), a fine mesh screen (325 by 2300 wires per inch) spring return assembly was successfully tested. No significant degradation in the screen bubble point was observed either due to the screen stretching process or due to cyclic fatigue during testing. An estimated 30 to 50 deflection cycles, and approximately 3 to 5 thermal cycles, were performed on the final screen specimen, prior to and between formally recorded testing. These cycles included some "abusive" pressure cycling, where gas or liquid was driven through the screen at rates that produced differential pressures across the screen of several times the bubble point pressure. No obvious performance degradation or other changes were observed over the duration of testing. In summary, it is felt by the author that these simple tests validated the feasibility of the flexible screen PMD concept for use with cryogenic propellants.

Wollen, Mark↗

Modeling of Chill Down in Cryogenic Transfer Lines

A numerical model to predict chill down in cryogenic transfer lines has been developed. Three chill down cases using hydrogen as the working fluid are solved: 1) a simplified model amenable to analytical solution, 2) a realistic model of superheated vapor flow, and 3) a realistic model of initially subcooled liquid flow. The first case compares a numerical model with an analytical solution with very good agreement between the two. Additionally, the analytical solution provides a convenient way to look at parametric effects on the chill down. The second and third cases are numerical models which provide temperature histories of the fluid and solid tube wall during chill down as well as several other quantities of interest such as pressure and mass flow rate. Of great interest is the ability to predict accurate values of chill down time (the time required to achieve steady-state cryogenic flow). The models predict that a 26 in. long, 3/16 in. ID aluminum tube has a shorter chill down time (approx. equal to 100 sec) and uses less hydrogen with superheated vapor flow than with initially subcooled liquid flow (greater than 200 sec for chill down).

Cross, Matthew F.↗

Study of propellant dynamics in a shuttle type launch vehicle

A method and an associated digital computer program for evaluating the vibrational characteristics of large liquid-filled rigid wall tanks of general shape are presented. A solution procedure was developed in which slosh modes and frequencies are computed for systems mathematically modeled as assemblages of liquid finite elements. To retain sparsity in the assembled system mass and stiffness matrices, a compressible liquid element formulation was incorporated in the program. The approach taken in the liquid finite element formulation is compatible with triangular and quadrilateral structural finite elements so that the analysis of liquid motion can be coupled with flexible tank wall motion at some future time. The liquid element repertoire developed during the course of this study consists of a two-dimensional triangular element and a three-dimensional tetrahedral element.

Jones, C. E.↗

Selective Recovery of Rare Earth Elements from Coal Fly Ash Leachates Using Liquid Membrane Processes

Coal combustion residues and other geological waste materials have been proposed as a resource for rare earth elements (REEs, herein defined as the 14 stable lanthanides, yttrium, and scandium). The extraction of REEs from residues often generate acidified leachates that require highly selective separation methods to recover the REEs from other major soluble ions in the leachates. We studied two liquid membrane processes (liquid emulsion membranes, LEM, and supported liquid membranes, SLM) and compared them to standard solvent extraction techniques for selective recovery and concentration of REEs from a leachate of coal fly ash. All separation methods involved an organic solution of di(2-ethylhexyl)phosphoric acid dissolved in kerosene or mineral oil and an acid strippant solution of 5 M nitric acid for the liquid-based separations. The LEM configuration, which separated REEs by immersing an acid-in-oil emulsion in the ash leachate, resulted in similar recovery percentages of individual REEs as the conventional solvent extraction approach. The recovery of REEs in the SLM configuration, which involved the impregnation of the solvent in a hydrophobic membrane, was slower than the LEM process. However, the SLM process was notably more selective for the heavy (and higher value) REEs, while the conventional extraction and LEM processes were more selective for the light REEs. A flux-based model of the extraction processes suggested that recovery rates were limited by REE affinity for the solvent chelator in the SLM, while the rates of REEs separation via LEM were limited by diffusive mass transfer across the liquid membrane. Altogether, these results help to identify specific steps in the recovery process that future work should target in the development of scalable liquid membrane separations for REE recovery.

42 ENGINEERING↗

Impact of gravity on hydrate saturation in gas‐rich environments

Abstract We extend a one‐dimensional analytical solution by including buoyancy‐driven flow to explore the impact of gravity on hydrate formation from gas injection into brine‐saturated sediments within the hydrate stability zone. This solution includes the fully coupled gas and liquid phase flow and the associated advective transport in a homogeneous system. We obtain the saturations assuming Darcy flow under combined pressure and gravity gradients; capillary forces are neglected. At a high gas supply rate, the overpressure gradient (gradient of water pressure deviation from the hydrostatic pressure) dominates the gas flow, and the hydrate saturation is independent of the flow rate and flow direction. At a low gas supply rate, the buoyancy (the drive for gas flow induced by the density difference between gas and liquid) dominates the gas flow, and the hydrate saturation depends on the flow rate and flow direction. Hydrate saturation is highest for upward flow, and lowest for downward flow. Hydrate saturation decreases with flow rate for upward flow, and increases with flow rate for downward flow. In all cases, hydrate saturation is constant behind the hydrate solidification front. Gas saturation is homogeneous and close to the residual value for upward flow at a low rate; gas flows at the rate it is supplied. Gas saturation is much greater than the residual value, and decreases from the gas inlet to the hydrate solidification front for downward flow at a very low rate. The effect of gravity is usually negligible in laboratory experiments, yet is significant in natural hydrate systems.

You, Kehua↗

Crystallization kinetics of poly(ethylene oxide) confined in semicrystalline poly(vinylidene) fluoride

ABSTRACT Polymer blends based on poly(vinylidene fluoride) (PVDF) and poly(ethylene oxide) (PEO) have been prepared to analyze the crystallization kinetics of poly(ethylene oxide) confined in semicrystalline PVDF with different ratios of both polymers. Both blend components were dissolved in a common solvent, dimethyl formamide. Blend films were obtained by casting from the solution at 70 °C. Thus, PVDF crystals are formed by crystallization from the solution while PEO (which is in the liquid state during the whole process) is confined between PVDF crystallites. The kinetics of crystallization of the confined PEO phase was studied by isothermal and nonisothermal experiments. Fitting of Avrami model to the experimental DSC traces allows a quantitative comparison of the influence of the PVDF/PEO ratio in the blend on the crystallization behavior. The effect of melting and further recrystallization of the PVDF matrix on PEO confinement is also studied. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56 , 588–597

Tamaño‐Machiavello, Maria Noel↗

Characterization of the scintillation anisotropy in crystalline stilbene scintillator detectors

This study reports a series of measurements that characterize the directional dependence of the scintillation response of crystalline melt-grown and solution-grown trans-stilbene to incident DT and DD neutrons. These measurements give the amplitude and pulse shape dependence on the proton recoil direction over one hemisphere of the crystal, confirming and extending previous results in the literature for melt-grown stilbene and providing the first measurements for solution-grown stilbene. In similar measurements of liquid and plastic detectors, no directional dependence was observed, confirming the hypothesis that the anisotropy in stilbene and other organic crystal scintillators is a result of internal effects due to the molecular or crystal structure and not an external effect on the measurement system.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Characterization and Application of a Hybrid Optical Microscopy/Laser Ablation Liquid Vortex Capture/Electrospray Ionization System for Mass Spectrometry Imaging with Sub-micrometer Spatial Resolution

Herein, a commercial optical microscope, laser microdissection instrument was coupled with an electrospray ionization mass spectrometer via a low profile liquid vortex capture probe to yield a hybrid optical microscopy/mass spectrometry imaging system. The instrument has bright-field and fluorescence microscopy capabilities in addition to a highly focused UV laser beam that is utilized for laser ablation of samples. With this system, material laser ablated from a sample using the microscope was caught by a liquid vortex capture probe and transported in solution for analysis by electrospray ionization mass spectrometry. Both lane scanning and spot sampling mass spectral imaging modes were used. The smallest area the system was able to ablate was ~0.544 μm × ~0.544 μm, achieved by oversampling of the smallest laser ablation spot size that could be obtained (~1.9 μm). With use of a model photoresist surface, known features as small as ~1.5 μm were resolved. The capabilities of the system with real world samples were demonstrated first with a blended polymer thin film containing poly(2-vinylpyridine) and poly(N-vinylcarbazole). Using spot sampling imaging, sub-micrometer sized features (0.62, 0.86, and 0.98 μm) visible by optical microscopy were clearly distinguished in the mass spectral images. A second real world example showed the imaging of trace amounts of cocaine in mouse brain thin tissue sections. Lastly, with use of a lane scanning mode with ~6 μm × ~6 μm data pixels, features in the tissue as small as 15 μm in size could be distinguished in both the mass spectral and optical images.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites

Liquid-phase processing of molecules using heterogeneous catalysts – an important strategy for obtaining renewable chemicals sustainably from biomass – involves reactions that occur at solid-liquid interfaces. In glucose isomerization catalyzed by basic faujasite zeolites, the catalytic activity depends strongly on the solvent composition: initially, it declines precipitously when water is mixed with a small amount of the organic co-solvent γ-valerolactone (GVL), then recovers as the GVL content increases. Using solid-state 13C NMR spectroscopy, we observed glucose isomers located inside the zeolite pores directly, and followed their transformations into fructose and mannose in real time. At low GVL concentrations, glucose is depleted in the zeolite pores relative to the liquid phase, while higher GVL concentrations in solution drive glucose inside the pores, resulting in up to a 32 enhancement in the local glucose concentration. Although their populations exchange rapidly, molecules present at the reactive interface experience a significantly different environment from the bulk solution.

carbohydrate isomerization↗

Direct Observation of Aggregative Nanoparticle Growth: Kinetic Modeling of the Size Distribution and Growth Rate

Direct observations of solution-phase nanoparticle growth using in situ liquid transmission electron microscopy (TEM) have demonstrated the importance of “non-classical” growth mechanisms, such as aggregation and coalescence, on the growth and final morphology of nanocrystals at the atomic and single nanoparticle scales. To date, groups have quantitatively interpreted the mean growth rate of nanoparticles in terms of the Lifshitz-Slyozov-Wagner (LSW) model for Ostwald ripening, but less attention has been paid to modeling the corresponding particle size distribution. Here we use in situ fluid stage scanning TEM to demonstrate that silver nanoparticles grow by a length-scale dependent mechanism, where individual nanoparticles grow by monomer attachment but ensemble-scale growth is dominated by aggregation. Although our observed mean nanoparticle growth rate is consistent with the LSW model, we show that the corresponding particle size distribution is broader and more symmetric than predicted by LSW. Following direct observations of aggregation, we interpret the ensemble-scale growth using Smoluchowski kinetics and demonstrate that the Smoluchowski model quantitatively captures the mean growth rate and particle size distribution.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A review of whole cell wall NMR by the direct-dissolution of biomass

To fully realize the potential of lignocellulosic biomass as a renewable resource for the production of fuels, chemicals, and materials, an improved understanding of the chemical and molecular structures within biomass and how those structures are formed during biosynthesis and transformed during (thermochemical and biological) conversion must be developed. This effort will require analytical techniques which are not only in-depth, rapid, and cost-effective, but also leave native cell wall features intact. Whole plant cell wall nuclear magnetic resonance (NMR) analysis facilitates unparalleled structural characterization of lignocellulosic biomass without causing (or with minimal) structural modification. The objective of this review is to summarize research pertaining to solution- or gel-state whole plant cell wall NMR analysis of biomass, demonstrating the capability of NMR to delineate the structural features and transformations of biomass. In particular, this review will focus on the application of a two-dimensional solution-state NMR technique and perdeuterated ionic liquid based organic electrolyte solvents for the direct dissolution and analysis of biomass. Furthermore, we believe this type of analysis will be critical to advancing biofuel research, improving bioprocessing methodology, and enhancing plant bioengineering efforts.

09 BIOMASS FUELS↗

Group-V Doping Impact on Cd-Rich CdTe Single Crystals Grown by Traveling-Heater Method

Cd-rich CdTe single crystals were grown from Cd solvent in the traveling-heater method (THM) rather than the more common Te solvent used for high-resistivity CdTe. The growth process from Cd solution in terms of the solid-liquid interface shape and group-V doping under Cd-rich condition were investigated. Stable, flat solid-liquid interfaces can be obtained by optimizing THM furnace temperature profile. An apparent doping limit in the 10^16 to 10^17 cm^ -3 range which scales weakly with increasing group-V element concentrations in the Cd-rich CdTe samples were indicated from capacitance-voltage measurement. The two-photon excitation time-resolved photoluminescence revealed a bulk lifetime of 20-40 ns.

14 SOLAR ENERGY↗

Experimental study of the tritium distribution in the effluents resulting from the sodium hydrolysis

Within the framework of the dismantling of fast breeder reactors in France several processes are under investigation regarding sodium disposal. One of them, called ELA (radioactive sodium waste treatment process), is based on the implementation of the sodium-water reaction, in a controlled and progressive way, to remove residual sodium. This sodium contains impurities such as sodium hydride, sodium oxide and tritiated sodium hydride. The hydrolysis of these various chemical species leads to the production of a liquid effluent, mainly composed of an aqueous solution of sodium hydroxide, and a gaseous effluent, mainly composed of nitrogen (inert gas), hydrogen and steam. The tritium is distributed between these effluents, and, within the gaseous effluent, according to its forms HT and HTO (tritiated water). HTO being 10,000 times more radio-toxic than HT, a precise knowledge of the mechanisms governing the phase distribution of tritium is necessary. This paper presents the first experimental results from a parametric study on the tritium distribution between the various effluents generated during hydrolysis operations. A series of experiments have been performed in order to study the influence of water flow rate, argon flow rate, initial mass and specific activity of the hydrolyzed sodium sample. An important influence of the total tritium concentration in the hydrolyzed sample has been highlighted. As for the phenomena suspected to be responsible for the phase change of tritiated water, in the studied range of parameters, vaporization induced by the heat of reactions seems to be dominant over the evaporation induced by the inert gas flow rate.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Selective Sorption of Dissolved Organic Carbon Compounds by Temperate Soils

Physico-chemical sorption of dissolved organic carbon (DOC) on soil minerals is one of the major processes of organic carbon (OC) stabilization in soils, especially in deeper layers. The attachment of C on soil solids is related to the reactivity of the soil minerals and the chemistry of the sorbate functional groups, but the sorption studies conducted without controlling microbial activity may overestimate the sorption potential of soil. This study was conducted to examine the sorptive characteristics of a diverse functional groups of simple OC compounds (D-glucose, L-alanine, oxalic acid, salicylic acid, and sinapyl alcohol) on temperate climate soil orders (Mollisols, Ultisols and Alfisols) with and without biological degradative processes. Equilibrium batch experiments were conducted using 0-100 mg C L-1 at a solid-solution ratio of 1:60 for 48 hrs and the sorption parameters were calculated by Langmuir model fitting. The amount of added compounds that remained in the solution phase was detected by high performance liquid chromatography (HPLC) and total organic C (TOC) analysis. Soil sterilization was performed by -irradiation technique and experiments were repeated to determine the contribution of microbial degradation to apparent sorption. Overall, Ultisols did not show a marked preference for apparent sorption of any of the model compounds, as indicated by a narrower range of maximum sorption capacity (Smax) of 173-527 mg kg soil-1 across compounds. Mollisols exhibited a strong preference for apparent sorption of oxalic acid (Smax of 5290 mg kg soil-1) and sinapyl alcohol (Smax of 2031 mg kg soil-1) over the other compounds. The propensity for sorption of oxalic acid is mainly attributed to the precipitation of insoluble Ca-oxalate due to the calcareous nature of most Mollisol subsoils and its preference for sinapyl alcohol could be linked to the polymerization of this lignin monomer on 2:2 mineral dominated soils. The reactivity of Alfisols to DOC was in between that of Ultisols and Mollisols. HPLC results revealed significantly higher sorption of D-glucose and L-alanine than did TOC results, and duplicate experiments with sterilized soils confirmed that glucose and alanine were mineralized leading to higher apparent sorption values via HPLC. This study demonstrated that three common temperate soil orders experienced differential sorption of simple OC compounds, indicating that sorbate chemistry plays a significant role in the sorptive stabilization of DOC.

Jagadamma, Sindhu↗

LNAPL Removal from Unsaturated Porous Media using Surfactant Infiltration

A series of unsaturated column experiments was performed to evaluate light non-aqueous phase liquid (LNAPL) fate and removal during surfactant solution infiltration. Surfactant-LNAPL phase behavior tests were conducted to optimize the remedial solutions. Packed sand and site sediment columns were first processed to establish representative LNAPL smear zone under unsaturated conditions. Infiltration of low-concentration surfactant was then applied in a stepwise flush mode, with 0.3 column pore volume (PV) of solution in each flush. The influence of infiltrated surfactant solution volume and pH on LNAPL removal was assessed. A LNAPL bank was observed at the very front of the first surfactant infiltration in each column, indicating that a very low surfactant concentration is needed to reduce the LNAPL-water interfacial tension sufficiently enough to mobilize trapped LNAPL under unsaturated conditions. More LNAPL was recovered as additional steps of surfactant infiltration were applied. Up to 99% LNAPL was removed after six infiltration steps, with less than 2.0 PV of total surfactant solution application, suggesting surfactant infiltration may be an effective method for vadose zone LNAPL remediation. The influence of pH tested in this study (3.99~10.85) was insignificant because the buffering capacity of the sediment kept the pH in the column higher than the zero point charge, pHzpc, of the sediment and therefore the difference between surfactant sorption was negligible.

Zhong, Lirong↗

CO 2 Absorption and Magnesium Carbonate Precipitation in MgCl 2 –NH 3 –NH 4 Cl Solutions: Implications for Carbon Capture and Storage

CO 2 absorption and carbonate precipitation are the two core processes controlling the reaction rate and path of CO 2 mineral sequestration. Whereas previous studies have focused on testing reactive crystallization and precipitation kinetics, much less attention has been paid to absorption, the key process determining the removal efficiency of CO 2 . In this study, adopting a novel wetted wall column reactor, we systematically explore the rates and mechanisms of carbon transformation from CO 2 gas to carbonates in MgCl 2 –NH 3 –NH 4 Cl solutions. We find that reactive diffusion in liquid film of the wetted wall column is the rate-limiting step of CO 2 absorption when proceeding chiefly through interactions between CO 2 (aq) and NH 3 (aq). We further quantified the reaction kinetic constant of the CO 2 –NH 3 reaction. Our results indicate that higher initial concentration of NH 4 Cl ( ≥2mol∙L -1 ) leads to the precipitation of roguinite [(NH 4 ) 2 Mg(CO 3 ) 2 ∙4H 2 O], while nesquehonite appears to be the dominant Mg-carbonate without NH 4 Cl addition. We also noticed dypingite formation via phase transformation in hot water. This study provides new insight into the reaction kinetics of CO 2 mineral carbonation that indicates the potential of this technique for future application to industrial-scale CO 2 sequestration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗