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At least 793 records · Page 44

Numerical Study of Coupled Water and Vapor Flow, Heat Transfer, and Solute Transport in Variably-Saturated Deformable Soil During Freeze-Thaw Cycles

As climate change intensifies, soil water flow, heat transfer, and solute transport in the active, unfrozen zones within permafrost and seasonally frozen ground exhibit progressively more complex interactions that are difficult to elucidate with measurements alone. For example, frozen conditions impede water flow and solute transport in soil, while heat and mass transfer are significantly affected by high thermal inertia generated from water-ice phase change during the freeze-thaw cycle. To assist in understanding these subsurface processes, the current study presents a coupled two-dimensional model, which examines heat conduction-convection with water-ice phase change, soil water (liquid water and vapor) and groundwater flow, advective-dispersive solute transport with sorption, and soil deformation (frost heave and thaw settlement) in variably saturated soils subjected to freeze-thaw actions. This coupled multiphysics problem is numerically solved using the finite element method. The model's performance is first verified by comparison to a well-documented freezing test on unsaturated soil in a laboratory environment obtained from the literature. Then based on the proposed model, we quantify the impacts of freeze-thaw cycles on the distribution of temperature, water content, displacement history, and solute concentration in three distinct soil types, including sand, silt and clay textures. The influence of fluctuations in the air temperature, groundwater level, hydraulic conductivity, and solute transport parameters was also comparatively studied. The results show that (a) there is a significant bidirectional exchange between groundwater in the saturated zone and soil water in the vadose zone during freeze-thaw periods, and its magnitude increases with the combined influence of higher hydraulic conductivity and higher capillarity; (b) the rapid dewatering ahead of the freezing front causes local volume shrinkage within the non-frozen region when the freezing front propagates downward during the freezing stage and this volume shrinkage reduces the impact of frost heave due to ice formation. This gradually recovers when the thawed water replenishes the water loss zone during the thawing stage; and (c) the profiles of soil moisture, temperature, displacement, and solute concentration during freeze-thaw cycles are sensitive to the changes in amplitude and freeze-thaw period of the sinusoidal varying air temperature near the ground surface, hydraulic conductivity of soil texture, and the initial groundwater levels. Our modeling framework and simulation results highlight the need to account for coupled thermal-hydraulic-mechanical-chemical behaviors to better understand soil water and groundwater dynamics during freeze-thaw cycles and further help explain the observed changes in water cycles and landscape evolution in cold regions.

54 ENVIRONMENTAL SCIENCES↗

Silicate coprecipitation reduces green rust crystal size and limits dissolution-precipitation during air oxidation

Green rusts (GR) are mixed-valence iron (Fe) hydroxides which form in reducing redox environments like riparian and wetland soils and shallow groundwater. In these environments, silicon (Si) can influence Fe oxides’ chemical and physical properties but its role in GR formation and subsequent oxidative transformation have not been studied starting at initial nucleation. Green rust sulfate [GR(SO 4 )] and green rust carbonate [GR(CO 3 )] were both coprecipitated from salts by base titration in increasing % mol Si (0, 1, 10, and 50). The minerals were characterized before and after rapid (24 h) aqueous air-oxidation by x-ray diffraction (XRD), scanning electron microscopy (SEM), Fe extended x-ray absorption fine structure spectroscopy (EXAFS), and N 2 -BET surface area. Results showed that only GR(SO4) or GR(CO3) was formed at every tested Si concentration. Increasing % mol Si caused decreased plate size and increased surface area in GR(CO3) but not GR(SO4). GR plate basal thickness was not changed at any condition indicating a lack of Si interlayering. Air oxidation of GR(SO4) at all % mol Si contents transformed by dissolution and reprecipitation into lepidocrocite and goethite, favoring ferrihydrite with higher % Si content. Air oxidation of GR(CO3) transformed into magnetite and goethite but increasing Si caused GR to oxidize while retaining its hexagonal plate structure via solid-state oxidation. Our results indicate that Si has the potential to cause GR to form in smaller particles and upon air oxidation, Si can either stabilize the plate structure or alter transformation to ferrihydrite.

36 MATERIALS SCIENCE↗

Digital magnetic temperature transducer.

A new digital magnetic temperature transducer is reported. The device utilizes the discontinuous behavior of the initial permeability with temperature at the Curie temperature of some magnetic materials. Since the Curie temperature is determined by the chemical and crystallographic composition of the particular material only, the transducer requires no calibration and has extremely high stability and reproducibility with time. The output of the transducer is inherently digital and, therefore, is directly compatible with the digital information processing and control without A/D conversion. The temperature-sensing portion of the transducer consists only of magnetic cores and wire and, therefore, has extremely high reliability, is shock and radiation insensitive, small, and virtually indestructible.

Tchernev, D. I.↗

Development of Pyrrone structural forms for honeycomb filler

The development of techniques for the preparation of Pyrrone structural foams for use as honeycomb filler is described. The feasibility of preparing foams from polymers formed by the condensation of 3,3'-diaminobenzidine (DAB), or 3,3',4,4'-tetraaminobenzophenone (TABP), with 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA) was investigated. Initially, most of the effort was devoted to preparing Pyrrone prepolymers with improved and more reproducible foaming properties for making chemically blown foams. When it became apparent that very high curing shrinkages would not allow the use of unfilled Pyrrone prepolymers in a foam-in-place process, emphasis was shifted from chemically blown foams to syntactic foams. Syntactic foam formulations containing hollow carbon microspheres were developed. Syntactic foams made from selected formulations were found to have very low coefficients of thermal expansion. A technique was developed for the emplacement of Pyrrone syntactic foam formulations in honeycomb core structures.

Kimmel, B. G.↗

Analytical chemical kinetic investigation of the effects of oxygen, hydrogen, and hydroxyl radicals on hydrogen-air combustion

Quantitative values were computed which show the effects of the presence of small amounts of oxygen, hydrogen, and hydroxyl radicals on the finite-rate chemical kinetics of premixed hydrogen-air mixtures undergoing isobaric autoignition and combustion. The free radicals were considered to be initially present in hydrogen-air mixtures at equivalence ratios of 0.2, 0.6, 1.0, and 1.2. Initial mixture temperatures were 1100 K, 1200 K, and 1500 K, and pressures were 0.5, 1.0, 2.0, and 4.0 atm. Of the radicals investigated, atomic oxygen was found to be the most effective for reducing induction time, defined as the time to 5 percent of the total combustion temperature rise. The reaction time, the time between 5 percent and 95 percent of the temperature rise, is not decreased by the presence of free radicals in the initial hydrogen-air mixture. Fuel additives which yield free radicals might be used to effect a compact supersonic combustor design for efficient operation in an otherwise reaction-limited combustion regime.

Carson, G. T., Jr.↗

Wear studies on aircraft brake materials

An investigation of both worn surfaces of friction pads and steel rotors which are being applied in current aircraft brakes has been carried out by employing an X-ray diffraction technique. It consists of the analysis of chemical element distribution in the surface layers. The wear particles were also examined by using the scanning electron microscope. The initiation and growth of surface cracks and the oxidation were emphasized in this investigation. A wear model was proposed for the current aircraft brake materials. Essentially this model proposed that cracks are formed in the surface layer of the brake material due to the normal and frictional stresses. It is primarily surface temperature dependent.

Ho, T. L.↗

Chemical whitings and chlorophyll distributions in the Great Lakes as viewed by Landsat

A chemical precipitation of calcium carbonate, or whiting, was first observed by satellite in Lake Michigan during August 1973. Since that initial observation similar events have been noted in Lakes Michigan, Erie, and Ontario with imagery from Landsat, Skylab, and NOAA satellites. By the use of Landsat multispectral data together with NOAA thermal infrared data, it has been observed that whitings occur several meters below the lake surface in relatively warm water. They are most vividly displayed during and after periods of upwelling. As the epilimnetic waters become supersaturated with Ca(+2) ions during summer, a triggering mechanism (presumably biological or physical) initiates the whiting, which may continue for several months. The effects on the biota of the euphotic zone when this milky cloud is present in the upper layers are poorly understood. However, Great Lakes circulation studies are taking advantage of these natural dye tracers.

Strong, A. E.↗

Operational overview of Wallops Island instrument intercomparison - Carbon monoxide, nitric oxide, and hydroxyl instrumentation

NASA has initiated the Global Tropospheric Experiment (GTE) for the study of the chemistry of the global troposphere. One phase of GTE, Chemical Instrumentation Test and Evaluation (CITE), is concerned with the development and validation of measurement techniques for trace species which play important roles in the tropospheric chemical cycles. In connection with CITE 1 an intercomparison of instruments is conducted for the measurement of CO, NO, and OH. These species have been identified as critical for an understanding of homogeneous gas-phase chemistry in the troposphere. The present paper provides an operational overview of the first of three instrument intercomparison field missions conducted as part of GTE/CITE 1. The missions include one ground-based and two airborne missions, and were designed to characterize current capability of measuring ambient levels of CO, NO, and OH.

Gregory, G. L.↗

Evolution of a localized thermal explosion in a reactive gas

Experimental observations of ignition in premixed gaseous reactants indicate that perfectly homogeneous initiation is practically unrealizable. Instead, combustion first sets in, as a rule, at small, discrete sites where inherent inhomogeneities cause chemical activity to proceed preferentially and lead to localized explosions. Combustion waves propagating away from these hot spots or reaction centers eventually envelop the remaining bulk. This study examines the spatial structure and temporal evolution of a hot spot for a model involving Arrhenius kinetics. The hot spot, characterized by peaks in pressure and temperature with little diminution in local density, is shown to have one of two possible self-similar structures. The analysis employs a combination of asymptotics and numerics, and terminates when pressure and temperature in the explosion have peaked.

Jackson, T. L.↗

Multimegawatt electric propulsion for Mars missions

This paper summarizes an evaluation of multimegawatt (MMW) nuclear electric propulsion (NEP) and solar electric propulsion (SEP) for a piloted Mars exploration scenario. The figures of merit used in this study were total initial mass in low earth orbit (IMLEO) and the trip time. The MMW NEP and SEP systems to an aerobraked chemical (O2/H2) propulsion system are compared. A good performance compromise between a low IMLEO and short trip time can be obtained using MMW NEP systems; they can be both lighter and faster than the baseline chemical system. However, a MMW SEP system does not appear capable of providing as short a trip time as MMW NEP, in part due to the higher specific mass and non-constant power output of a SEP system.

Frisbee, Robert H.↗

The spin state and homogeneity of Comet Halley's nucleus

The present model of the spin rate of Comet Halley, which takes the form of an excited, axially symmetric rotator with prolate spheroid shape, accommodates both the imaging data from the Vega and Giotto encounters and a range of ground-based data for CN jets and shells, C2 production rates, and photometric variability. The model ratio of moments-of-inertia maxima to minima, at 2.28, implies a nearly constant density distribution throughout its interior. One of the five localized areas on the nucleus which dominate the activity observed appears to be uniquely responsible for the initiation of CN-shell boundaries which propagate through the coma, and may be indicative of either large-scale chemical inhomogeneity or a surface region with unusual physical structure.

Belton, Michael J. S.↗

Halogens and the Chemistry of the Free Troposphere

The role of halogens in both the marine boundary layer and the stratosphere has long been recognized, while their role in the free troposphere is often not considered in global chemical models. However, a careful examination of free-tropospheric chemistry constrained by observations using a full chemical data assimilation system shows that halogens do play a significant role in the free troposphere. In particular, the chlorine initiation of methane oxidation in the free troposphere can contribute more than 10%, and in some regions up to 50%, of the total rate of initiation. The initiation of methane oxidation by chlorine is particularly important below the polar vortex and in northern mid-latitudes. Likewise, the hydrolysis of BrONO2 alone can contribute more than 35% of the HNO3 production rate in the free-troposphere.

Lary, David John↗

GSDO Program Hexavalent Chrome Alternatives: Final Pretreatments Test Report

Hexavalent chrome free pretreatments should be considered for use on Ground Support Equipment (OSE) and Electrical Ground Support Equipment (EOSE). Both of the hexavalent chrome free pretreatments (Metalast TCP HF and SurTec 650C) evaluated by this project met, and in some instances exceeded, the requirements ofMIL-DTL-5541 "Chemical Conversion Coatings on Aluminum and Aluminum Alloys". For DC resistance measurements, both Metalast TCP HF and SurTec (!50C met initial requirements following assembly and in many cases continued to maintain passing readings for the duration of testing.

Kessel, Kurt↗

Heat Diffusion in Gases, Including Effects of Chemical Reaction

The diffusion of heat through gases is treated where the coefficients of thermal conductivity and diffusivity are functions of temperature. The diffusivity is taken proportional to the integral of thermal conductivity, where the gas is ideal, and is considered constant over the temperature interval in which a chemical reaction occurs. The heat diffusion equation is then solved numerically for a semi-infinite gas medium with constant initial and boundary conditions. These solutions are in a dimensionless form applicable to gases in general, and they are used, along with measured shock velocity and heat flux through a shock reflecting surface, to evaluate the integral of thermal conductivity for air up to 5000 degrees Kelvin. This integral has the properties of a heat flux potential and replaces temperature as the dependent variable for problems of heat diffusion in media with variable coefficients. Examples are given in which the heat flux at the stagnation region of blunt hypersonic bodies is expressed in terms of this potential.

Hansen, C. Frederick↗

Chemical abrasion: the mechanics of zircon dissolution

Chemical abrasion is a technique that combines thermal annealing and partial dissolution in hydrofluoric acid (HF) to selectively remove radiation-damaged portions of zircon crystals prior to U–Pb isotopic analysis, and it is applied ubiquitously to zircon prior to U–Pb isotope dilution thermal ionization mass spectrometry (ID-TIMS). The mechanics of zircon dissolution in HF and the impact of different leaching conditions on the zircon structure, however, are poorly resolved. We present a microstructural investigation that integrates microscale X-ray computed tomography (µCT), scanning electron microscopy, and Raman spectroscopy to evaluate zircon dissolution in HF. We show that µCT is an effective tool for imaging metamictization and complex dissolution networks in three dimensions. Acid frequently reaches crystal interiors via fractures spatially associated with radiation damage zoning and inclusions to dissolve soluble high-U zones, some inclusions, and material around fractures, leaving behind a more crystalline zircon residue. Other acid paths to crystal cores include the dissolution of surface-reaching inclusions and the percolation of acid across zones with high defect densities. In highly crystalline samples dissolution is crystallographically controlled with dissolution proceeding almost exclusively along the c axis. Increasing the leaching temperature from 180 to 210 °C results in deeper etching textures, wider acid paths, more complex internal dissolution networks, and greater volume losses. How a grain dissolves strongly depends on its initial radiation damage content and defect distribution as well as the size and position of inclusions. As such, the effectiveness of any chemical abrasion protocol for ID-TIMS U–Pb geochronology is likely sample-dependent. We also briefly discuss the implications of our findings for deep-time (U-Th)/He thermochronology.

58 GEOSCIENCES↗

Study of Ionic Mass Transport in Non-Conventional Electrolytes for Energy Storage and Carbon Capture Applications

In the field of energy storage, electrolytes are the materials or liquids used to transport ions or redox active chemicals to facilitate an electrochemical process. Conventional electrolytes are the most common form of electrolyte used and consist of salts dissolved in a liquid solvent medium. While conventional electrolytes are generally inexpensive and work well with lithium-ion batteries, they have many shortfalls however, such as corrosion of the cell, flammability, toxicity, price, and incompatibility with other metals. This project investigates the fundamental properties in nonconventional electrolyte systems with an initial focus on eutectics being made. Using electrochemical methods ( Cyclic Voltammetry (CV), Impedance, Conductance, etc.), we are studying the study of electrolyte systems containing ions used for thermal, chemical, or electrochemical energy storage such as Li + , Mg 2+ , Na + , K + , Al 3+ , CO 3 2- , Cl - , and O 2- . This research looks at how ion mobility effects the electrochemical characteristics and properties in green energy applications.

25 ENERGY STORAGE↗

Thematic Mapper research in the earth sciences

This paper's studies were initiated under the NASA program for the purpose of conducting the earth sciences research using the Landsat Thematic Mapper. The goals of the program include studies of the factors influencing the growth, health, condition, and distribution of vegetation on the earth; the processes controlling the evolution of the earth's crust; the earth's water budget and the hydrologic processes that operate at local, regional, and global scales; the physical and chemical interaction between different types of surficial materials; and the interaction between the earth's surface and its atmosphere. Twenty-seven domestic and five foreign investigations were initiated in 1985, with the results from most of them already published (one study was terminated due to the delay in the TDRSS). Twelve of the studies addressed hydrology, snow and ice, coastal processes, and near-shore oceanographic phenomena; seven addressed vegetation, soils, or animal habitat; and twelve addressed geologic subjects.

Salomonson, Vincent V.↗

AWSD Reactive Burn Model for the HMX‐Based High Explosive LX‐04

An Arrhenius–Wescott–Stewart–Davis (AWSD) reactive burn model is applied to describe shock initiation and detonation properties of the HMX-based high explosive LX-04. The parameters in the model are calibrated to data from multiple sources. The thermodynamic equations of state used in the model are calibrated to a combination of thermochemical calculations for HMX and LX-04 as well as experimentally-measured cylinder expansion results for LX-04. The kinetic parameters are calibrated to velocity data from gas gun experiments performed using EDC-32—a high explosive with the same chemical composition as LX-04 but different structural properties, and scaled rate stick data for PBX 9012. The AWSD model is shown to accurately describe the shock initiation and propagation of LX-04. Very good agreement is observed between the available experimental data and the AWSD model output. The presented results constitute an accurate LX-04 reactive burn model for use in engineering-scale models and simulations.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗