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At least 361 records · Page 20

Environmental Degradation of Materials: Surface Chemistry Related to Stress Corrosion Cracking

Parallel experiments have been performed in order to develop a comprehensive model for stress cracking (SCC) in structural materials. The central objective is to determine the relationship between the activity and selectivity of the microstructure of structural materials to their dissolution kinetics and experimentally measured SCC kinetics. Zinc was chosen as a prototype metal system. The SCC behavior of two oriented single-crystal disks of zinc in a chromic oxide/sodium sulfate solution (Palmerton solution) were determined. It was found that: (1) the dissolution rate is strongly (hkil)-dependent and proportional to the exposure time in the aggressive environment; and (2) a specific slip system is selectively active to dissolution under applied stress and this slip line controls crack initiation and propagation. As a precursor to potential microgrvity experiments, electrophoretic mobility measurements of zinc particles were obtained in solutions of sodium sulfate (0.0033 M) with concentrations of dissolved oxygen from 2 to 8 ppm. The equilibrium distribution of exposed oriented planes as well as their correlation will determine the particle mobility.

Schwarz, J. A.↗

Numerical solutions of chemically reacting and radiating flows

The two-dimensional spatially elliptic Navier-Stokes equations are used to investigate the chemically reacting and radiating supersonic flow of the hydrogen-air system between two parallel plates and in a channel with a ten-degree compression-expansion ramp at the lower boundary. The explicit unsplit finite-difference technique of MacCormack is used to advance the governing equations in time until convergence is achieved. The chemistry source term in the species equation is treated implicitly to alleviate the stiffness associated with fast reactions. The tangent slab approximation is employed in the radiative flux formulation. Both pseudo-gray and nongray models are used to represent the absorption-emission characteristics of the participating species. Results obtained for specific conditions indicate that the radiative interaction can have a significant influence on the flow field.

Mani, M.↗

Supersonic combusting flow - A comparison of numerical and experimental results

The flow field of an unconfined coaxial supersonic burner (SSB) was obtained numerically, using a CFD code. The explicit MacCormack algorithm, with point implicit treatment of chemistry source terms, was employed in the CFD code. Combustion of hydrogen and air was simulated by a two-step finite-rate combustion model whereas turbulence was accounted for by a Prandtl mixing length scheme. Boundary conditions and some important features of the numerical scheme were discussed. The qualitative features of the numerical solution were compared with those obtained by regular as well as schlieren photographs. General agreements of the CFD solution and the experimental photographs were observed.

Chitsomboon, T.↗

A coupled implicit method for chemical non-equilibrium flows at all speeds

The present time-accurate coupled-solution procedure addresses the chemical nonequilibrium Navier-Stokes equations over a wide Mach-number range uses, in conjunction with the strong conservation form of the governing equations, five unknown primitive variables. The numerical tests undertaken address steady convergent-divergent nozzle flows with air dissociation/recombination, dump combustor flows with n-pentane/air chemistry, and unsteady nonreacting cavity flows.

Shuen, Jian-Shun↗

Developing Optimized Trajectories Derived from Mission and Thermo-Structural Constraints

In conjunction with NASA and the Department of Defense, the Johns Hopkins University Applied Physics Laboratory (JHU/APL) has been investigating analytical techniques to address many of the fundamental issues associated with solar exploration spacecraft and high-speed atmospheric vehicle systems. These issues include: thermo-structural response including the effects of thermal management via the use of surface optical properties for high-temperature composite structures; aerodynamics with the effects of non-equilibrium chemistry and gas radiation; and aero-thermodynamics with the effects of material ablation for a wide range of thermal protection system (TPS) materials. The need exists to integrate these discrete tools into a common framework that enables the investigation of interdisciplinary interactions (including analysis tool, applied load, and environment uncertainties) to provide high fidelity solutions. In addition to developing robust tools for the coupling of aerodynamically induced thermal and mechanical loads, JHU/APL has been studying the optimal design of high-speed vehicles as a function of their trajectory. Under traditional design methodology the optimization of system level mission parameters such as range and time of flight is performed independently of the optimization for thermal and mechanical constraints such as stress and temperature. A truly optimal trajectory should optimize over the entire range of mission and thermo-mechanical constraints. Under this research, a framework for the robust analysis of high-speed spacecraft and atmospheric vehicle systems has been developed. It has been built around a generic, loosely coupled framework such that a variety of readily available analysis tools can be used. The methodology immediately addresses many of the current analysis inadequacies and allows for future extension in order to handle more complex problems.

Lear, Matthew H.↗

Heterogeneous chemical reaction of chlorine nitrate and water on sulfuric-acid surfaces at room temperature

The use of H2SO4 as a catalyst for aerosol production of chlorine compounds in the chemistry of the antarctic stratosphere was investigated in laboratory trials. The experiments involved the gas surface collision rate of a molecule on a given surface during its residence time in a Knudsen cell in molecular flow conditions. Chlorine nitrate gas was made to flow through a chamber exposed to a container holding a 95.6 pct H2SO4 solution. Gas leaving the cell was scanned with a mass spectrometer. A sticking coefficient of 0.00032 was found for the chlorine nitrate, a value five times that previously reported.

Rossi, Michel J.↗

Numerical study of supersonic combustors by multi-block grids with mismatched interfaces

A three dimensional, finite rate chemistry, Navier-Stokes code was extended to a multi-block code with mismatched interface for practical calculations of supersonic combustors. To ensure global conservation, a conservative algorithm was used for the treatment of mismatched interfaces. The extended code was checked against one test case, i.e., a generic supersonic combustor with transverse fuel injection, examining solution accuracy, convergence, and local mass flux error. After testing, the code was used to simulate the chemically reacting flow fields in a scramjet combustor with parallel fuel injectors (unswept and swept ramps). Computational results were compared with experimental shadowgraph and pressure measurements. Fuel-air mixing characteristics of the unswept and swept ramps were compared and investigated.

Moon, Young J.↗

A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

Cho, S. Y.↗

Effects of Rhenium Addition on the Temporal Evolution of the Nanostructure and Chemistry of a Model Ni-Cr-Al Superalloy: Analysis of the Coarsening Behavior - 2

The temporal evolution of the nanostructure and chemistry of a model Ni-8.5 at.% Cr-10 at.% Al alloy with the addition of 2 at.% Re was studied using transmission electron microscopy and atom-probe tomography in order to measure the number density and mean radius of the y' (LIZ) precipitates and the chemistry of the y'-precipitates and the y (fcc)-matrix. In this article, the coarsening behavior of the y'-precipitates is discussed in detail and compared with the Umantsev-Olson model for multi-component alloys. In addition, the experimental results are evaluated with PrecipiCalc(TradeMark) simulations. The results show that the diffusivities of the solute elements play a major role in the coarsening behavior of the y'-precipitates and that the addition of Re retards the coarsening kinetics and stabilizes the spheroidal morphology of the precipitates by reducing the interfacial energy.

Yoon, Kevin E.↗

Numerical study of supersonic combustors by multi-block grids with mismatched interfaces

A three-dimensional, finite-rate chemistry, Navier-Stokes code has been extended to a multi-block with mismatched interface code for practical calculations of supersonic combustors. To ensure global conservation, a conservative algorithm was used for the treatment of mismatched interfaces. The extended code was checked against one test case, i.e., a generic supersonic combustor with transverse fuel injection, examining solution accuracy, convergence, and local mass flux error. After testing, the code was used to simulate the chemically reacting flow fields in a scramjet combustor with parallel fuel injectors (unswept and swept ramps). Computational results were compared with experimental shadowgraph and pressure measurements. Fuel-air mixing characteristics of the unswept and swept ramps were compared and investigated.

Moon, Young J.↗

Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗

Characterization of Errors in Satellite-Based HCHO/NO 2 Tropospheric Column Ratios With Respect to Chemistry, Column-to-PBL Translation, Spatial Representation, and Retrieval Uncertainties

The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO 2 ) (a proxy for nitrogen oxides) tropospheric columns from ultraviolet–visible (UV–Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to quantify those errors carefully. Concerning the chemistry error, a well-characterized box model constrained by more than 500 h of aircraft data from NASA's air quality campaigns is used to simulate the ratio of the chemical loss of HO 2 + RO 2 (LRO x ) to the chemical loss of NO x (LNO x ). Subsequently, we challenge the predictive power of HCHO/NO 2 ratios (FNRs), which are commonly applied in current research, in detecting the underlying ozone regimes by comparing them to LRO x /LNO x . FNRs show a strongly linear (R 2 =0.94) relationship with LRO x /LNO x , but only on the logarithmic scale. Following the baseline (i.e., ln(LRO x /LNO x ) = −1.0 ± 0.2) with the model and mechanism (CB06, r2) used for segregating NO x -sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that the FNR has an inherent 20 % standard error (1σ) resulting from not accurately describing the RO x –HO x cycle. We calculate high ozone production rates (PO 3 ) dominated by large HCHO × NO 2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO 3 and HCHO × NO 2 becomes more pronounced when moving towards NO x -sensitive regions due to nonlinear chemistry; our results indicate that there is fruitful information in the HCHO × NO 2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO 2 concentrations from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns into the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. Based on summertime-averaged data, the Ozone Monitoring Instrument (OMI) loses 12 % of its spatial information at its native resolution with respect to a high-resolution sensor like the TROPOspheric Monitoring Instrument (TROPOMI) (> 5.5 × 3.5 km 2 ). A pixel with a grid size of 216 km 2 fails at capturing ∼ 65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO 2 and HCHO columns. At a 68 % confidence interval (1σ), errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO 2 columns, should be above 1.2–1.5 × 10 16 molec. cm −2 to attain a 20 %–30 % standard error in the ratio. This level of error is almost non-achievable with the OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40 %–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (< 50 %) tends to be mild, whereas areas with low vegetation and anthropogenic sources (e.g., the Rocky Mountains) are markedly uncertain (> 100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric.

Amir H. Souri↗

High Efficiency Space Power Systems Project Advanced Space-Rated Batteries

Case Western Reserve University (CWRU) has an agreement with China National Offshore Oil Corporation New Energy Investment Company, Ltd. (CNOOC), under the United States-China EcoPartnerships Framework, to create a bi-national entity seeking to develop technically feasible and economically viable solutions to energy and environmental issues. Advanced batteries have been identified as one of the initial areas targeted for collaborations. CWRU invited NASA Glenn Research Center (GRC) personnel from the Electrochemistry Branch to CWRU to discuss various aspects of advanced battery development as they might apply to this partnership. Topics discussed included: the process for the selection of a battery chemistry; the establishment of an integrated development program; project management/technical interactions; new technology developments; and synergies between batteries for automotive and space operations. Additional collaborations between CWRU and NASA GRC's Electrochemistry Branch were also discussed.

Reid, Concha M.↗

Comparison of numerical techniques for integration of stiff ordinary differential equations arising in combustion chemistry

The efficiency and accuracy of several algorithms recently developed for the efficient numerical integration of stiff ordinary differential equations are compared. The methods examined include two general-purpose codes, EPISODE and LSODE, and three codes (CHEMEQ, CREK1D, and GCKP84) developed specifically to integrate chemical kinetic rate equations. The codes are applied to two test problems drawn from combustion kinetics. The comparisons show that LSODE is the fastest code currently available for the integration of combustion kinetic rate equations. An important finding is that an interactive solution of the algebraic energy conservation equation to compute the temperature does not result in significant errors. In addition, this method is more efficient than evaluating the temperature by integrating its time derivative. Significant reductions in computational work are realized by updating the rate constants (k = at(supra N) N exp(-E/RT) only when the temperature change exceeds an amount delta T that is problem dependent. An approximate expression for the automatic evaluation of delta T is derived and is shown to result in increased efficiency.

Radhakrishnan, K.↗

Computation of hypersonic flow fields

The present discussion of the theory, solution methods, and development status of chemically reactive flow CFD codes pertaining to the flow field around a hypersonic vehicle encompasses the formulation of multicomponent viscous equations, grid-generation techniques, and finite-difference algorithms. The Navier-Stokes equations presented focus on such particularities of high speed vehicles as their aerodynamic configuration, lee and wake flow, bow shock, and chemistry and low density effects. Issues for which further development is desirable encompass boundary treatments, grid quality, shock capturing, and the decoupling of chemistry from flow variables.

Li, Chien-Peng↗

LDEF polymeric materials: 10 months versus 5.8 years of exposure

The chemical characterization of several polymeric materials which received 10 months of exposure and 5.8 years of exposure on a Row 9 Long Duration Exposure Facility (LDEF) experiment (A0134) is reported. Specimens include fluorinated ethylene propylene (FEP) teflon film, polysulfone film, and graphite fiber reinforced epoxy amd polysulfone matrix composites. The responses of these materials to the two LEO exposures are compared. The results of infrared, thermal, x-ray photoelectron, and scanning electron microscope analyses are reported. Solution property measurements of various molecular weight parameters are presented for the thermoplastic polysulfone materials. Molecular level effects attributable to exposure that were present in 10-month exposed specimens were not found in 5.8-year exposed specimens. This result suggests that increased atomic oxygen fluence toward the end of the LDEF mission may have eroded away selected environmentally induced changes in surface chemistry for 5.8-year exposure specimens.

Young, Philip R.↗

Long Duration Venus Probes and Landers

Planetary probes have long been a tool used by scientists to gain early clues on environments and systems of new planetary targets. This not only fueled the scientific process but also helped prepare for future missions, such as landers, and helped ensure their success. Venus, Earth's sister planet, has been the target of more probes and landers than any other body in our solar system except for Earth and yet many fundamental questions are unanswered. Challenge for Venus Surface Science: This lack of knowledge is a result of the challenging Venus environments. Remote sensing of the surface and portions of the atmosphere is difficult at best due to the thick layers of sulfuric acid clouds and the high pressure supercritical CO2 atmosphere below those clouds. This has hampered the ability of orbiting missions to provide us insight into surface features and processes and thus hides potential clues on interior process from our view. Surface probes and landers face an even more daunting challenge, which is the extreme temperature, pressure and unfriendly chemical composition of the near surface atmosphere. Over 10 assets have landed on the surface yet the longest surviving asset Venera-13 lasted only 127 minutes before succumbing to the extreme temperature. While this and other landers provided valuable new data, the short life impacted ability to understand any temporal processes, for example meteorology, seismic active, and therefore very little is known about the interior and surface atmosphere interactions. New Capability Offering Potential Solutions: Re-cent developments by NASA are offering hope of overcoming the technical challenges of surface operations and life with the use of high temperature electronics and systems. Wide band gap, SiC based electronics have been demonstrated to function successfully for extended periods of time both at 500C, Venus surface temperatures as well as when temperature is combined with the reactive chemistry of the surface atmosphere and the high pressures (over 90 bar pressure at the surface). In addition to electronics a number of other subsystems are in development including power in the form of high temperature batteries and power management devices, communications including antennas, transmitters and other components, materials, and structures and mechanisms. These are all activities under NASA's Long Lived In situ Solar System Exploration (LLISSE) project. Other activities are also funded under NASA's HOTTech program.

Kremic, T.↗

High-temperature resins

The basic chemistry, cure processes, properties, and applications of high temperature resins known as polyimides are surveyed. Condensation aromatic polymides are prepared by reacting aromatic diamines with aromatic dianhydrides, aromatic tetracarboxylic acids, or with dialkyl esters of aromatic tetracarboxylic acids, depending on the intended end use. The first is for coatings or films while the latter two are more suitable for polyimide matrix resins. Prepreg solutions are made by dissolving reactants in an aprotic solvent, and advances in the addition of a diamine on the double bond and radical polymerization of the double bond are noted to have yielded a final cure product with void-free characteristics. Attention is given to properties of the Skybond, Pyralin, and NR-150B polyimide prepreg materials and characteristics of aging in the NP-150 polyimides. Finally, features of the NASA-developed PMR polyimides are reviewed.

Serafini, T. T.↗