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NASA NTRS1991

Finite-rate chemistry effects in a Mach 2 reacting flow

UV spontaneous vibrational Raman scattering and laser-induced predissociative fluorescence (LIPF) are combined and applied to a supersonic flame. For the first time, simultaneous measurements of temperature, major species (H2, O2, N2, H2O), and minor species (OH) concentrations are obtained with a 'single' excimer laser in a supersonic-lifted hydrogen-air diffusion flame. In the supersonic flame, a small amount of reaction occurs upstream of the lifted flame base, due to shock wave interactions and mixing with hot vitiated air. The strong turbulent mixing and high total enthalpy fluctuations lead to nonequilibrium values of temperature, and major and minor species concentrations. Combustion occurs farther downstream of the lifted region where slow three-body recombination reactions result in superequilibrium OH concentrations that depress the temperatures below their equilibrium values. Farther downstream, ambient air entrainment contaminates flame properties.

Cheng, T. S.↗

DOE OSTI2025

Numerical simulation of flow and mixing in fracture intersections

Fluid transport through fractured geological formations is strongly influenced by the redistribution of solutes at fracture intersections. In this study, we perform detailed numerical simulations of flow and scalar transport within the intersection of two smooth, planar fractures. The analysis focuses on the mixing ratio, the proportion of solute flux exiting along the outlet branch aligned with the primary inlet flow direction, relative to the total solute flux at the outlets. We systematically investigate how the mixing ratio varies with four key parameters: Peclet number, Reynolds number, flow rate ratio between outlet branches, and fracture intersection angle. Results show that the mixing ratio decreases with increasing Peclet number and outlet flow rate ratio, consistent with reduced diffusive spreading and enhanced streamline routing. While low Reynolds numbers have minimal impact, inertial effects at higher Reynolds numbers significantly increase the mixing ratio. Additionally, acute and obtuse intersection angles alter flow partitioning and modify the solute distribution at the outlets. These findings provide a quantitative basis for incorporating physically realistic mixing behavior—intermediate between complete mixing and streamline-following assumptions—into network-scale transport models. The results have direct relevance to subsurface energy systems, including geothermal energy production, carbon sequestration, and contaminant remediation.

58 GEOSCIENCES↗

DOE OSTI2023

Differential multi-probe thermal transport measurements of multi-walled carbon nanotubes grown by chemical vapor deposition

Carbon nanotubes (CNTs) are quasi-one dimensional nanostructures that display both high thermal conductivity for potential thermal management applications and intriguing low-dimensional phonon transport phenomena. In comparison to the advances made in the theoretical calculation of the lattice thermal conductivity of CNTs, thermal transport measurements of CNTs have been limited by either the poor temperature sensitivity of Raman thermometry technique or the presence of contact thermal resistance errors in sensitive two-probe resistance thermometry measurements. Here we report advances in a multi-probe measurement of the intrinsic thermal conductivity of individual multi-walled CNT samples that are transferred from the growth substrate onto the measurement device. The sample-thermometer thermal interface resistance is directly measured by this multi-probe method and used to model the temperature distribution along the contacted sample segment. The detailed temperature profile helps to eliminate the contact thermal resistance error in the obtained thermal conductivity of the suspended sample segment. A differential electro-thermal bridge measurement method is established to enhance the signal-to-noise ratio and reduce the measurement uncertainty by over 40%. The obtained thermal resistances of multiple suspended segments of the same MWCNT samples increase nearly linearly with increasing length, revealing diffusive phonon transport as a result of phonon-defect scattering in these MWCNT samples. The measured thermal conductivity increases with temperature and reaches up to 390 ± 20 W m –1 K –1 at room temperature for a 9-walled MWCNT. In conclusion, theoretical analysis of the measurement results suggests submicron phonon mean free paths due to extrinsic phonon scattering by extended defects such as grain boundaries. The obtained thermal conductivity is decreased by a factor of 3 upon electron beam damage and surface contamination of the CNT sample.

42 ENGINEERING↗

NASA NTRS1974

Inversion layer solar cell fabrication and evaluation

Inversion layer solar cells were fabricated by etching through the diffused layer on p-type silicon wafers in a comb-like contact pattern. The charge separation comes from an induced p-n junction at the surface. The inverted surface is caused by a layer of transparent material applied to the surface that either contains free positive ions or that creates donor states at the interface. Cells are increased from 3 ma I sub sc to 100 ma by application of sodium silicate. The action is unstable, however, and decays. Non-mesa contaminated oxide cells were fabricated with short circuit currents of over 100 ma measured in the sun. Cells of this type have demonstrated stability.

Call, R. L.↗

DOE OSTI2021

A solution framework for linear PDE-constrained mixed-integer problems

Abstract We present a general numerical solution method for control problems with state variables defined by a linear PDE over a finite set of binary or continuous control variables. We show empirically that a naive approach that applies a numerical discretization scheme to the PDEs to derive constraints for a mixed-integer linear program (MILP) leads to systems that are too large to be solved with state-of-the-art solvers for MILPs, especially if we desire an accurate approximation of the state variables. Our framework comprises two techniques to mitigate the rise of computation times with increasing discretization level: First, the linear system is solved for a basis of the control space in a preprocessing step. Second, certain constraints are just imposed on demand via the IBM ILOG CPLEX feature of a lazy constraint callback. These techniques are compared with an approach where the relations obtained by the discretization of the continuous constraints are directly included in the MILP. We demonstrate our approach on two examples: modeling of the spread of wildfire and the mitigation of water contamination. In both examples the computational results demonstrate that the solution time is significantly reduced by our methods. In particular, the dependence of the computation time on the size of the spatial discretization of the PDE is significantly reduced.

97 MATHEMATICS AND COMPUTING↗

NASA NTRS1993

Optical characterization of LDEF contaminant film

Dark brown molecular film deposits were found at numerous locations on the Long Duration Exposure Facility (LDEF) and have been documented in great detail by several investigators. The exact deposition mechanism for these deposits is as yet unknown, although direct and scattered atomic oxygen, and solar radiation interacting with materials outgassing products have all been implicated in the formation process. Specimens of the brown molecular film were taken from below the flange of the experimental tray located at position D10 on the LDEF. The tray was one of two, comprising the same experiment, the other being located on the wake facing side of the LDEF satellite at position B4. Having access to both trays, we were able to directly compare the effect that orientation with respect to the atomic oxygen flux vector had on the formation of the brown molecular film deposits. The film is thickest on surfaces facing toward the exterior, i.e. the tray corner, as can be seen by comparing the lee and wake aspects of the rivets. The patterns appear to be aligned not with the velocity vector but with the corner of the tray suggesting that flux to the surface is due to scattered atomic oxygen rather than direct ram impingement. The role of scattered flux is further supported by more faint plume patterns on the sides of the tray. The angle of these plumes is strongly aligned with the ram direction but the outline of the deposit implies that incident atoms are scattered by collisions with the edges of the opening resulting in a directed, but diffuse, flux of atomic oxygen to the surface. Spectral reflectance measurements in the 2 to 10 micron (4000 to 1000 wavenumbers) spectral range are presented for the film in the 'as deposited' condition and for the free standing film. The material was analyzed by FTIR (Fourier Transform Infrared) microspectroscopy using gold as the reference standard. The 'as deposited' specimen was on an aluminum rivet taken from beneath the tray flange while the free film was obtained by chipping some of the material from the rivet. The transmission spectrum over the 2 to 10 micron range for the free film is presented. This spectrum appears to be essentially the same as that presented by Crutcher et.al. for films formed at vent sites which faced into the ram direction and suggested to originate from urethanes and silicones used on the LDEF. Banks et. al. state that silicones, when exposed to atomic oxygen, release polymeric scission fragments which deposit on surfaces and form a glassy, dark contaminant layer upon further atomic oxygen exposure and solar irradiation.

Blakkolb, Brian K.↗

DOE OSTI2020

Wash Penalty Factors: Insight into the Effects of Water Wash Down of Building Materials for Radionuclide/Nuclear (Rn) Decontamination - 20153

The release of radiological material to the urban environment can have a devastating socio-economic impact. In an urban release scenario, areas around the dispersal epicenter and any areas contaminated via atmospheric deposition may require extensive decontamination. Most recently, our group reported the decontamination efficacy of pressurized water washing of common porous building materials, and compared the penetration depth of the contaminations before and after exposure to pressurized tap water. Here, we continue evaluation of the decontamination efficacy of wash solutions based on potassium (K{sup +}) salt for cesium (Cs), strontium (Sr), and europium (Eu) contaminations on common building surfaces. The surfaces included: the cement used in concrete, the aggregate used in concrete, intact concrete, roadway asphalt, asphalt shingles, and latex paint. We deposited solutions of {sup 137}Cs, {sup 85}Sr, and {sup 152}Eu onto numerous common building materials and exposed these materials to a static bath or low-pressure flow of tap water, 0.1 M potassium chloride (KCl), and 0.5 M KCl. The decontamination efficacy and the depth profile for residual contamination were measured to determine the conditions under which applying a wash solution has benefit compared to physically removing the surface material. To aid in these analyses, we introduced a 'wash penalty factor' to quantify the degree to which contamination migrated into the bulk material by the action of the wash method. On asphalt, 70-80% of the radionuclides were found to be within 0.02 mm of the surface. Cs{sup +} bonded to negative charge sites on the surface of the mineral aggregate (used in concrete) so decontamination was improved by ion exchange with K{sup +}. Sr{sup 2+} is soluble and removed by water, while not bonding to aggregate or demonstrating solubility in the liquid asphalt. Eu{sup 3+} is precipitated and not removed in gentle wash but displays mobility within the pore space that suggests its presence as a colloid. Concrete is more porous than asphalt, and 80% of the radionuclides were within 0.2 mm of the surface for {sup 137}Cs and {sup 152}Eu and 50- 80% for {sup 85}Sr. On concrete, Cs{sup +} bonds similarly to asphalt. Sr{sup 2+} bonds to the cement or precipitates from the alkaline pore water. Eu{sup 3+} sorbs to the cement and then precipitates. In brick, the results for Cs{sup +} and Sr{sup 2+} suggested that diffusion of ions from deeper in the coupon was important. Eu{sup 3+} is removed poorly due to precipitation. We will explain and report example wash penalty factors that vary from 0 to > 1 for the various methods and the implications for deciding when to implement wash down methods. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS2000

Determination of Interfacial Rheological Properties through Microgravity Oscillations of Bubbles and Drops

This report summarizes our derivations of analytical expressions for the frequencies and damping constants for small-amplitude axisymmetric shape oscillations of a liquid drop suspended in an immiscible fluid host in microgravity. In particular, this work addresses large Reynolds number shape oscillations and focuses on the surface rheological effects that arise from the presence of insoluble surfactants at the interface. Parameters characterizing viscous effects from the bulk phases, surface viscous effects, Marangoni effects from the surface advection and diffusion of surfactants, and the Gibbs elasticity are all considered and analyzed to determine the relative importance of each contribution. Supplementing the analytical treatment for small-amplitude oscillations, a numerical boundary integral equation formulation is developed for the study of large-amplittide axisymmetric oscillations of a drop in vacuum. The boundary integral formulation is an extension of classical potential flow theory and approximately accounts for viscous effects in the bulk fluid as well as the surface viscous and Marangoni effects resulting from an insoluble surfactant contaminating the interface. Theoretical and numerical results are presented for four distinct cases. These, range from the case when the effects of the surfactants are 'negligible' to 'large' when compared to the viscous effects in the bulk phases. The feasibility of the non-contact measurement of the surface parameters, using experimental observations for the oscillation frequencies and damping constants of drops and bubbles, is discussed.

Nadim, Ali↗

DOE OSTI2020

Reducing dielectric loss and enhancing electrical insulation for multilayer polymer films by nanoconfined ion transport under high poling electric fields

High temperature polar polymers have demonstrated potential for good thermal stability and high dielectric constant at the same time. However, polarization of contaminated impurity ions in polar polymers, even at the ppm level, can significantly increase the dielectric loss at high temperature and low frequencies. One effective strategy to mitigate this problem is to multilayer them with a high temperature nonpolar dielectric polymer to confine impurity ion transport at the nanometer scale. In this study, confined ion transport in high temperature polycarbonate (HTPC)/poly(vinylidene fluoride) (PVDF) multilayer films under high AC electric fields was studied using a direct analytical simulation method. Different from the ion transport under low fields, the ion diffusion model failed to describe the ion transport under high electric fields. An exponential ion distribution profile, which was observed for the DC poling situation, was employed to implement the direct analytical simulation. Confined impurity ion transport under high AC fields was quantitatively understood. As the AC field increased, the mobile ion concentration decreased whereas the diffusion coefficient increased. The decrease of mobile ion concentration was explained by the blockage of impurity ions by the HTPC layers. This knowledge helped in the determination of optimal conditions to polarize impurity ions from the PVDF layers into the HTPC layers. After cooling below the glass transition temperature of HTPC, polarized impurity ions were locked inside the HTPC layers. As a result, increased discharge efficiency and enhanced electrical insulation (i.e., increased dielectric breakdown strength) were achieved for the polarized multilayer films.

36 MATERIALS SCIENCE↗

NASA NTRS1984

Ceramic microstructure and adhesion

When a ceramic is brought into contact with a ceramic, a polymer, or a metal, strong bond forces can develop between the materials. The bonding forces will depend upon the state of the surfaces, cleanliness and the fundamental properties of the two solids, both surface and bulk. Adhesion between a ceramic and another solid are discussed from a theoretical consideration of the nature of the surfaces and experimentally by relating bond forces to interface resulting from solid state contact. Surface properties of ceramics correlated with adhesion include, orientation, reconstruction and diffusion as well as the chemistry of the surface specie. Where a ceramic is in contact with a metal their interactive chemistry and bond strength is considered. Bulk properties examined include elastic and plastic behavior in the surficial regions, cohesive binding energies, crystal structures and crystallographic orientation. Materials examined with respect to interfacial adhesive interactions include silicon carbide, nickel zinc ferrite, manganese zinc ferrite, and aluminum oxide. The surfaces of the contacting solids are studied both in the atomic or molecularly clean state and in the presence of selected surface contaminants.

Buckley, D. H.↗

NASA NTRS1985

Ceramic microstructure and adhesion

Buckley, D. H.↗

NASA NTRS2003

In Situ Remediation of Polychlorinated Bephenyls Using Palladium Coated Iron or Magnesium

The remediation of polychlorinated biphenyls (PCBs) and other chlorinated synthetic aromatic compounds are of great concern due to their toxicity and persistence in the environment. When released into the environment, PCBs are sorbed to particulate matter that can then disperse over large areas. Although the US Environmental Protection Agency (EPA) has banned the manufacture of PCBs since 1979, they are still present in the environment posing possible adverse health affects to both humans and animals. Thus, it is of utmost importance to develop a method that remediates PCB-contaminated soil, sediments, and water. The objective of our research was to develop an in-situ PCB remediation technique that is applicable for the treatment of soils and sediments. Previous research conducted at the University of Central Florida (UCF) proved the feasibility of using an emulsified system to dehalogenate a dense non-aqueous phase liquid (DNAPL) source, such as TCE, in the subsurface by means of an in-situ injection. The generation of a hydrophobic emulsion system drew the DNAPL TCE, through the oil membrane where it diffused to the iron particle and underwent degradation. TCE continued to enter, diffuse, degrade and exit the droplet maintaining a concentration gradient across the membrane, thus maintaining the driving force of the reaction.

Geiger, Cherie L.↗

NASA NTRS2015

Final Report on the Detection of Green Monopropellants

In 2014, National Aeronautics and Space Administration (NASA) Kennedy Space Center (KSC) funded a project titled "Familiarization and Detection of Green Monopropellants" utilizing Independent Research and Technology Development (IR&TD) and Center Innovation Fund (CIF) funding. The purpose of the project was to evaluate methods of detection for ammonium dinitramide (ADN) and hydroxylammonium nitrate (HAN). An Engineering Services Contract (ESC) task order was created with the scope of evaluation of several methods of detecting ADN- and HAN-based propellants, as well as development of methods for detection. Detection methods include developed methods such as colorimetric indicating absorbent socks, and commercial-off-the- shelf (COTS) units for ammonia detection. An additional goal of the task order was for ESC to become familiar with ADN's and HAN's material properties and material compatibility. Two approaches were initially investigated as possible methods for the detection of HAN (or AFM315E) and ADN (or LMP-103S). These approaches were colorimetric analysis and instrumentation-based COTS vapor sensors utilization. Initial testing showed that the relatively non-existent vapor pressure of the AF-M315E (of which HAN is a major component) propellant would make the use of COTS sensors difficult for real-time area monitoring of HAN; a small response was detected through the use of active COTS sensors, including the RAE Systems MultiRAE Lite and Drager X-act (registered) 5000, but the levels detected were below the threshold limit value for the toxic gas ammonia. Therefore, a detection system ased upon a colorimetric indicator impregnated into an absorbent material was developed. Preliminary analysis (ESC-245-FDG-001) identified a particularly outstanding candidate as a colorimetric indicator for the detection of the presence of AF-M315E in the form of a Methyl Red (Basic) indicator. Materials impregnated with this indicator exhibit significant color change and the materials are not susceptible to interference from exposure to water or carbon dioxide. The completed detection system for HAN/AF-M315E consists of absorbent socks packed with Fisher Universal Spill Absorbent capable of absorbing and containing any propellant spills that they come into contact with along with indicating wipes. The absorbent socks are also chemically treated with a Methyl Red (Basic) indicator solution to provide the end user with a visual indication that a leak has occurred and proper protective precautions must be undertaken. An added benefit of this detection system is that the absorbent socks should neutralize/absorb any commodity that it comes into contact with (until saturation is reached). Additional adsorbent socks can be deployed until a color change is not seen, indicating that the HAN/AF-M315E contamination has been contained. The indicating wipes provide the user the opportunity to wipe surfaces to determine if there is any HAN/AF-M315E or HAN/AFM315E residue present. The wipes should allow the detection of fuel levels that may be too small to detect with the absorbent socks. The development of a detection system for the ADN/LMP-103S focused on the use of various COTS sensors used as real-time area monitoring devices and personal dosimeters. These COTS based sensor systems were of several different types, including both actively pumped and diffusion-based passive systems, as well as a "rope"-type chemical sensing cable. The results highlighted some of the major differences between the two monopropellants undergoing evaluation. Unlike HAN, ADN (which is the major constituent of LMP-103S) exhibits a much more volatile nature in comparison to AF-M315E. In fact, testing showed that a large percentage of the fuel was lost during the sampling measurement (greater than 10 percent by mass); although this testing cannot tell if the volatile component is the ADN itself or another component of the monopropellant solution. Not surprisingly, all four of the procured vapor-based COTS sensors showed positive results when exposed to solutions of the LMP-103S (ESC-245-FDG-002). The completed detection system for ADN/LMP-103S consists of a combination of two of the tested COTS sensor systems, the RAE Systems MultiRAE Lite and the BW Technologies GasAlert Extreme. These systems are meant to be used in conjunction with one another, which allows for the end-user to have both real-time area monitoring (MultiRAE Lite) as well as a personal dosimeter device (GasAlert Extreme) which can be worn as additional personal protective equipment. An stainless steel extension wand was fabricated and included in the detection system for the MultiRAE Lite to allow for more remote sensing, and connects via the active pumping inlet of the sensor. As stated, the final results of this testing resulted in the production of two "kits" which can be used for the detection of HAN/AF-M315E and ADN/LMP-103s (ESC-245-FDG-003).

Detection↗

NASA NTRS2001

Formation of Residual Gases from Source Materials in Closed Crystal Growth Systems

Different, non-constituent cases are present in crystal growth systems and may affect processes like growth rate in PVT or voids formation and detached solidification in melt growth systems. The presence of the gas may be detrimental or advantageous depending on its amount and composition, and on the process in question. The presence of the cases, their amount and composition, can be caused and changed by diffusion through and desorption from the growth container material. We have investigated these phenomena for silica glass ampoules. We also found, that residual cases can be generated by the source materials: even very high purity commercial elements and compounds may contain trace amounts of impurities, particularly oxides. The oxides may have low volatilities themselves but their reaction with other species, particularly carbon and hydrogen, may produce volatile compounds like water or carbon oxides. The amount of the gas and its composition is dependent on the original purity of the material (oxide contaminants) and the heat treatment of the source prior to sealing. In many cases. particularly at temperatures below about 900 C and in well-outgassed ampoules, this mechanism dominates. The problem is of a particular importance in sealed systems where the amount and composition of the gas cannot be directly controlled. Therefore, a reasonable knowledge and understanding of the origin, composition, magnitude, and change with time of gases present in sealed ampoules may be important for a meaningful control and interpretation of crystal growth processes. We have investigated this phenomenon in more details for a number of elements and compounds, primarily for II-VI and IV-VI materials. Different source pre-treatment and annealing procedures were applied, and subsequent consecutive annealings and measurements were done to determine the origin and development of the gas in the systems.

Palosz, W.↗

NASA NTRS2012

Observed Limits on Charge Exchange Contributions to the Diffuse X-Ray Background

We present a high-resolution spectrum of the diffuse X-ray background from 0.1 to 1 keV for an approximately 1 sr region of the sky centered at l = 90 degrees b = +60 degrees using a 36 pixel array of microcalorimeters flown on a sounding rocket. With an energy resolution of 11 eV FWHM below 1 keV, the spectrum s observed line ratios help separate charge exchange contributions originating within the heliosphere from thermal emission of hot gas in the interstellar medium. The X-ray sensitivity below 1 keV was reduced by about a factor of four from contamination that occurred early in the flight, limiting the significance of the results. The observed centroid of helium-like O VII is 568 (sup +2 (sub -3) eV at 90% confidence. Since the centroid expected for thermal emission is 568.4 eV and for charge exchange is 564.2 eV, thermal emission appears to dominate for this line complex. The dominance of thermal emission is consistent with much of the high-latitude O VII emission originating in 2-3 x 10(exp 6) K gas in the Galactic halo. On the other hand, the observed ratio of C VI Lygamma to Lyalpha is 0.3 plus or minus 0.2. The expected ratios are 0.04 for thermal emission and 0.24 for charge exchange, indicating that charge exchange must contribute strongly to this line and therefore potentially to the rest of the ROSAT R12 band usually associated with 10(sup 6) K emission from the Local Hot Bubble. The limited statistics of this experiment and systematic uncertainties due to the contamination require only greater than 32% thermal emission for O VII and greater than 20% from charge exchange for C VI at the 90% confidence level. An experimental gold coating on the silicon substrate of the array greatly reduced extraneous signals induced on nearby pixels from cosmic rays passing through the substrate, reducing the triggered event rate by a factor of 15 from a previous flight of the instrument.

Crowder, S. G.↗

NASA NTRS2012

Observed Limits on Charge Exchange Contributions to the Diffuse X-Ray Background

Crowder, S. G.↗

NASA NTRS1988

Two puzzling aspects of protein crystal growth

A study is presented of several mechanisms which may reduce crystal growth rates and or terminate crystal growth. It is found that salt gradients which change the local chemical potential of the protein are insufficient to account for the slow crystal growth rates which have been reported. Contaminants which adsorb protein from solution may reduce the effective protein concentration, but the impurity's concentration and its affinity for protein are unknown. Association of protein molecules in bulk solution can reduce the monomer concentration significantly, but extant theory and experiment are not sensitive enough to determine the actual concentration of aggregates in solution. For systems of interest, shear-induced effects were found to be too weak to interfere with normal binding of incoming protein molecules. Although we found that most crystal growth occurs in a regime where both interfacial kinetics and diffusion influence crystal growth, the role of mass transfer rates on the terminal size of crystals is unknown, primarily because no data exist which cover the size range of interest (0.1 mm to 1 mm in length).

Grant, M. L.↗

NASA NTRS1990

The theoretical relationship between foliage temperature and canopy resistance in sparse crops

One-dimensional, sparse-crop interaction theory is reformulated to allow calculation of the canopy resistance from measurements of foliage temperature. A submodel is introduced to describe eddy diffusion within the canopy which provides a simple, empirical simulation of the reported behavior obtained from a second-order closure model. The sensitivity of the calculated canopy resistance to the parameters and formulas assumed in the model is investigated. The calculation is shown to exhibit a significant but acceptable sensitivity to extreme changes in canopy aerodynamics, and to changes in the surface resistance of the substrate beneath the canopy at high and intermediate values of leaf area index. In very sparse crops changes in the surface resistance of the substrate are shown to contaminate the calculated canopy resistance, tending to amplify the apparent response to changes in water availability. The theory is developed to allow the use of a measurement of substrate temperature as an option to mitigate this contamination.

Shuttleworth, W. James↗