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At least 91 records · Page 5

Surface Finishing and Coating Parameters Impact on Additively Manufactured Binder-Jetted Steel–Bronze Composites

In this paper, electroless nickel plating is explored for the protection of binder-jetting-based additively manufactured (AM) composite materials. Electroless nickel plating was attempted on binder-jetted composites composed of stainless steel and bronze, resulting in differences in the physicochemical properties. We investigated the impact of surface finishing, plating solution chemistry, and plating parameters to attain a wide range of surface morphologies and roughness levels. We employed the Keyence microscope to quantitatively evaluate dramatically different surface properties before and after the coating of AM composites. Scanning electron microscopy revealed a wide range of microstructural properties in relation to each combination of surface finishing and coating parameters. We studied chempolishing, plasma cleaning, and organic cleaning as the surface preparation methods prior to coating. We found that surface preparation dictated the surface roughness. Taguchi statistical analysis was performed to investigate the relative strength of experimental factors and interconnectedness among process parameters to attain optimum coating qualities. The quantitative impacts of phosphorous level, temperature, surface preparation, and time factor on the roughness of the nickel-plated surface were 17.95%, 8.2%, 50.02%, and 13.21%, respectively. On the other hand, the quantitative impacts of phosphorous level, temperature, surface preparation, and time factor on the thickness of nickel plating were 35.12%, 41.40%, 3.87%, and 18.24%, respectively. The optimum combination of the factors’ level projected the lowest roughness of Ra at 7.76 µm. The optimum combination of the factors’ level projected the maximum achievable thickness of ~149 µm. This paper provides insights into coating process for overcoming the sensitivity of AM composites in hazardous application spaces via robust coating.

36 MATERIALS SCIENCE↗

Baltimore Ecosystem Study: Soil atmosphere fluxes of carbon dioxide, nitrous oxide and methane, 1998 - ongoing

The Baltimore Ecosystem Study (BES) established a network of long-term permanent biogeochemical study plots in 1998. These plots provide long-term data on vegetation, soil and hydrologic processes in the key ecosystem types within the urban ecosystem. The network of study plots includes forest plots (upland and riparian), chosen to represent the range of forest conditions in the area and grass plots (to represent home lawns). Plots are instrumented with lysimeters (drainage and tension) to sample soil solution chemistry, time domain reflectometry probes to measure soil moisture, dataloggers to measure and record soil temperature, and trace gas flux chambers to measure the flux of carbon dioxide, nitrous oxide and methane from soil to the atmosphere. Measurements of in situ nitrogen mineralization, nitrification and denitrification were made at approximately monthly intervals from Fall 1998 - Fall 2000. Detailed vegetation characterization (all layers) was done in summer 1998 and 2015. Data from these plots has been published in Groffman et al. (2006, 2009), Groffman and Pouyat (2009), Savva et al. (2010), Costa and Groffman (2013), Duncan et al. (2013), Waters et al. (2014), Ni and Groffman (2018), Templeton et al. (2019). Literature Cited Costa, K.H. and P.M. Groffman. 2013. Factors regulating net methane flux in urban forests and grasslands. Soil Science Society of America Journal 77:850 - 855. Duncan, J. M., L. E. Band, and P. M. Groffman. 2013. Towards closing the watershed nitrogen budget: Spatial and temporal scaling of denitrification. Journal of Geophysical Research Biogeosciences 118:1-5; DOI: 10.1002/jgrg.20090 Groffman PM, Pouyat RV, Cadenasso ML, Zipperer WC, Szlavecz K, Yesilonis IC,. Band LE and Brush GS. 2006. Land use context and natural soil controls on plant community composition and soil nitrogen and carbon dynamics in urban and rural forests. Forest Ecology and Management 236:177-192. Groffman, P.M., C.O. Williams, R.V. Pouyat, L.E. Band and I.C. Yesilonis. 2009. Nitrate leaching and nitrous oxide flux in urban forests and grasslands. Journal of Environmental Quality 38:1848-1860. Groffman, P.M. and R.V. Pouyat. 2009. Methane uptake in urban forests and lawns. Environmental Science and Technology 43:5229-5235. DOI: 10.1021/es803720h. Ni, X. and P.M. Groffman. 2018. Declines in methane uptake in forest soils. Proceedings of the National Academies of Science of the United States of America 115:8587-8590. Savva, Y., K. Szlavecz, R. V. Pouyat, P. M. Groffman, and G. Heisler. 2010. Effects of land use and vegetation cover on soil temperature in an urban ecosystem. Soil Science Society of America Journal 74:469-480. Templeton, L., M.L. Cadenasso, J. Sullivan, M. Neel and P.M. Groffman. 2019. Changes in vegetation structure and composition of urban and rural forest patches in Baltimore from 1998 to 2015. Forest Ecology and Management. In press. Waters, E.R., J.L. Morse, N.D. Bettez and P.M. Groffman. 2014. Differential carbon and nitrogen controls of denitrification in riparian zones and streams along an urban to exurban gradient. Journal of Environmental Quality 43:955–963.

Groffman, Peter M↗

Performance of advanced chromium electrodes for the NASA Redox Energy Storage System

Chromium electrodes were prepared for the NASA Redox Storage System with meet the performance requirements for solar-photovoltaic, wind-turbine and electric utility applications. Gold-lead catalyzed carbon felt electrodes up tp 930 sq cm were fabricated and tested in single cells and multicell stacks for hydrogen evolution, coulombic efficiency, catalyst stability and electrochemical activity. Factors which affect the overall performance of a particular electrode include the carbon felt lot, the cleaning treatment and the gold catalyzation method. Effects of the chromium solution chemistry and impurities on charge/discharge performance are also presented.

Gahn, R. F.↗

Electrochemical performance and transport properties of a Nafion membrane in a hydrogen-bromine cell environment

The overall energy conversion efficiency of a hydrogen-bromine energy storage system is highly dependent upon the characteristics and performance of the ion-exchange membrane utilized as a half-cell separator. The electrochemical performance and transport properties of a duPont Nafion membrane in an aqueous HBr-Br2 environment were investigated. Membrane conductivity data are presented as a function of HBr concentration and temperature for the determination of ohmic voltage losses across the membrane in an operational cell. Diffusion-controlled bromine permeation rates and permeabilities are presented as functions of solution composition and temperature. Relationships between the degree of membrane hydration and the membrane transport characteristics are discussed. The solution chemistry of an operational hydrogen-bromine cell undergoing charge from 45% HBr to 5% HBr is discussed, and, based upon the experimentally observed bromine permeation behavior, predicted cell coulombic losses due to bromine diffusion through the membrane are presented as a function of the cell state-of-charge.

Baldwin, Richard S.↗

The formation of peroxonitrites and oxygen on Mars

When Martian regolith samples are moistened with water, a strong oxidant and oxygen gas are released. The many possible oxidants which have been suggested as present, including superoxide (O2(-)) hydrogen peroxide (H2O2(-)), and manganese (IV) oxide (MnO2), as well as peroxonitrite (ONOO(-)), can be distinguished by their ability to account for the numerous observations of the Viking Labelled Release (LR) and Gas Exchange (GEX) experiments. The magnitudes, kinetics, and heat labilities of the LR experiments and the magnitudes and heat labilities of the GEX experiments have been quantitatively replicated with peroxonitrites. Further, it is to be expected from information about the photochemistry of nitrogen in the atmosphere, the calculated fluxes of the NO(x) to the surface, the known reactions of NO(x) with carbonates to produce nitrates and photolysis studies of nitrates, that peroxonitrites are present on Mars. However, considerable uncertainty has existed about the form in which oxygen is stored in photolyzed nitrate crystals. Models have ranged from micropores of O2 to chemically bound oxygen as peroxonitrite (O2NOO(-)), as well as peroxonitrite. Studies of the solution chemistry and solid state photochemistry were completed, which show that much of the oxygen evolved on wetting comes from thermal breakdown of peroxonitrite after it is dissolved. A chemical model is developed for the photochemical processes occurring during UV irradiation of solid nitrates which resolves the several contradictory models discussed in the literature in recent years.

Plumb, Robert C.↗

CFD evaluation of Mach 17 HYPULSE scramjet combustor data

Three-dimensional finite rate chemistry solutions are performed on a single fuel injector configuration. The results are compared with limited experimental data obtained from the HYPULSE expansion tube facility at simulated flight Mach 17 flow conditions. All comparisons, except for wall heat flux, were in excellent agreement. Key findings from this study are useful in interpretation of the experimental measurements.

Bobskill, Glenn J.↗

Quartz dissolution. I - Negative crystal experiments and a rate law. II - Theory of rough and smooth surfaces

The range of the measured quartz dissolution rates, as a function of temperature and pOH, extent of saturation, and ionic strength, is extended to cover a wider range of solution chemistries, using the negative crystal methodology of Gratz et al. (1990) to measure the dissolution rate. A simple rate law describing the quartz dissolution kinetics above the point of zero charge of quartz is derived for ionic strengths above 0.003 m. Measurements were performed on some defective crystals, and the mathematics of step motion was developed for quartz dissolution and was compared with rough-face behavior using two different models.

Gratz, Andrew J.↗

Liquid propellant rocket engine combustion simulation with a time-accurate CFD method

Time-accurate computational fluid dynamics (CFD) algorithms are among the basic requirements as an engineering or research tool for realistic simulations of transient combustion phenomena, such as combustion instability, transient start-up, etc., inside the rocket engine combustion chamber. A time-accurate pressure based method is employed in the FDNS code for combustion model development. This is in connection with other program development activities such as spray combustion model development and efficient finite-rate chemistry solution method implementation. In the present study, a second-order time-accurate time-marching scheme is employed. For better spatial resolutions near discontinuities (e.g., shocks, contact discontinuities), a 3rd-order accurate TVD scheme for modeling the convection terms is implemented in the FDNS code. Necessary modification to the predictor/multi-corrector solution algorithm in order to maintain time-accurate wave propagation is also investigated. Benchmark 1-D and multidimensional test cases, which include the classical shock tube wave propagation problems, resonant pipe test case, unsteady flow development of a blast tube test case, and H2/O2 rocket engine chamber combustion start-up transient simulation, etc., are investigated to validate and demonstrate the accuracy and robustness of the present numerical scheme and solution algorithm.

Chen, Y. S.↗

Demonstration of a Porous Tube Hydroponic System to Control Plant Moisture and Growth

Accurate remote detection of plant health indicators such as moisture, plant pigment concentrations, photosynthetic flux, and other biochemicals in canopies is a major goal in plant research. Influencing factors include complex interactions between wavelength dependent absorbing and scattering features from backgrounds as well as canopy biochemical and biophysical constituents. Accurately controlling these factors in outdoor field studies is difficult. Early testing of a porous tube plant culture system has indicated that plant biomass production, biomass partitioning, and leaf moisture of plants can be controlled by precisely managing the root water potential. Managing nutrient solution chemistry can also control plant pigments, biochemical concentrations, plant biomass production, and photosynthetic rates. A test bed was developed which utilized the porous tube technology with the intent of evaluating remote sensing systems, spectral analyses procedures, gas-exchange, and fluorescence measurements for their ability to detect small differences in plant water status. Spectral analysis was able to detect small differences in the mean leaf water content between the treatments. However these small differences were not detectable in the gas-exchange or fluorescence measurements.

Dreschel, T. W.↗

Aerogel/Particle Composites for Thermoelectric Devices

Optimizing solution chemistry and the addition of titania and fumed silica powder reduces shrinkage. These materials would serve to increase thermal efficiency by providing thermal insulation to suppress lateral heat leaks. They would also serve to prolong operational lifetime by suppressing sublimation of certain constituents of thermoelectric materials (e.g., sublimation of Sb from CoSb3) at typical high operating temperatures. [The use of pure silica aerogels as cast-in-place thermal-insulation and sublimation-suppression materials was described in "Aerogels for Thermal Insulation of Thermoelectric Devices" (NPO-40630), NASA Tech Briefs, Vol. 30, No. 7 (July 2006), page 50.] A silica aerogel is synthesized in a solgel process that includes preparation of a silica sol, gelation of the sol, and drying of the gel in a solvent at a supercritical temperature and pressure. The utility of pure silica aerogel is diminished by a tendency to shrink (and, therefore, also to crack) during the gelation and supercritical-drying stages. Moreover, to increase suppression of sublimation, it is advantageous to make an aerogel having greater density, but shrinkage and cracking tend to increase with density. A composite material of the type under investigation consists mostly of titania oxide powder particles and a small addition of fumed silica powder, which are mixed into the sol along with other ingredients prior to the gelation stage of processing. The silica aerogel and fumed silica act as a binder, gluing the titania particles together. It is believed that the addition of fumed silica stiffens the aerogel network and reduces shrinkage during the supercritical-drying stage. Minimization of shrinkage enables establishment of intimate contact between thermoelectric legs and the composite material, thereby maximizing the effectiveness of the material for thermal insulation and suppression of sublimation. To some extent, the properties of the composite can be tailored via the proportions of titania and other ingredients. In particular (see figure), the addition of a suitably large proportion of titania (e.g., 0.6 g/cu cm) along with a 10-percent increase in the amount of tetraethylorthosilicate [TEOS (an ingredient of the sol)] to an aerogel component having a density 40 mg/cm3makes it possible to cast a high-average-density (>0.1 g/cm3) aerogel/particle composite having low shrinkage (2.3 percent).

Paik, Jong-Ah↗

Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution

Despite the significant impact of radiation-induced redox reactions on the accessibility and lifetimes of actinide oxidation states, fundamental knowledge of aqueous actinide metal ion radiation chemistry is limited, especially for the late actinides. A quantitative understanding of these intrinsic radiation-induced processes is essential for investigating the fundamental properties of these actinides. We present here a picosecond electron pulse reaction kinetics study into the radiation-induced redox chemistry of trivalent berkelium (Bk(III)) and californium (Cf(III)) ions in acidic aqueous solutions at ambient temperature. New, and first of a kind, second-order rate coefficients are reported for the transient radical-induced reduction of Bk(III) and Cf(III) by the hydrated electron (eaq−) and hydrogen atom (H•), demonstrating significant reactivity (up to 1011M-1s-1) indicative of a preference of these metals to adopt divalent states. Additionally, we reportthe first-ever second-order rate coefficients for the transient radical-induced oxidation of these elements by reaction with hydroxyl (•OH) and nitrate (NO3•) radicals, which also exhibited fast reactivity (ca. 108 M-1s-1). Transient Cf(II), Cf(IV), and Bk(IV) absorption spectra are also reported. Overall, the presented data highlight the existence of rich, complex, intrinsic late actinide radiation-induced redox chemistry that has the potential to influence the findings of other areas of actinide science.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Study of actinide chemistry in saturated potassium fluoride solution

Study concerning the chemistry of actinides in saturated KF solution included work with neptunium, uranium, and americium. Solubilities, absorption spectra, oxidation-reduction reactions, and solid compounds which can be produced in KF solution were examined. The information is used for preparation of various materials from salts of the actinides.

Cohen, D.↗

Nuclear Fuel and Pu Redox Studies from The Glenn T. Seaborg Institute at Idaho National Laboratory

The Glenn T. Seaborg Institute at Idaho National Laboratory (INL-GTSI) focuses on advancing fundamental research in the actinide sciences by providing unique opportunities to early career scientists and engineers to gain experience studying the actinide elements and their associated systems. The INL-GTSI is built from three focus areas that are based on the expertise and supporting infrastructure at INL and include solid state chemistry and physics, solution phase chemistry and physics, and forensic and isotope science. INL is the lead Laboratory for nuclear energy research and development in the U. S. and the research on nuclear fuels performed under the INL-GTSI gives good examples of solid state studies. Uranium-Molybdenum (U-Mo) alloys are leading fuel candidates for conversion of high performance research and test reactors to low-enriched fuels. During irradiation, generated fission gas accumulates into bubbles and self-organizes into a gas bubble superlattice (GBS) that effectively stores fission gases and inhibits fuel swelling. A study on the early self- organizing behavior of the GBS shows that not only grain boundaries but the interfaces between the U-Mo matrix and uranium carbide (UC) impurities are important to GBS formation.[1] In solution, understanding the complex redox behavior of plutonium in aqueous environments is critical for establishing optimized nuclear waste reprocessing solvent systems and storage tank environments. INL-GTSI researchers have produced an experimentally validated multi-scale model of the gamma radiation induced behavior of plutonium ions in concentrated aqueous HNO3 solutions.[2] Here, gamma radiation effected only minimal steady state changes in the redox distribution of the plutonium oxidation states. The redox cycling between Pu(IV) and Pu(III) is demonstrated to be mediated by the •OH/NO3• radical oxidation of Pu(III) and the H2O2/HNO3 driven reduction of Pu(IV). The INL-GTSI offers young researchers the unique chance to work directly with actinide bearing materials in a U. S. National Laboratory environment. Further topical areas of interest to the INL-GTSI include, but are not limited to, fundamental actinide properties, structure/property (electronic, magnetic, thermal) relations, actinide quantum criticality, f- electron interactions, electron correlations, computational studies, new phases, defect effects, interface interactions, isotope production and separation, forensic analytical chemistry, structure and dynamic properties of actinides in non-aqueous media, separations chemistry and kinetics for advanced nuclear fuel cycles, radiation effects, and innovative and advanced ligand design for complexation of the actinides.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Current Needs in Radiochemistry

There are a number of current needs in the development of the Pu and Am separations that underpin larger interest areas including nuclear waste issues, nuclear weapons, nuclear forensics, nuclear fuels and similarly related fields. In the large areas of interest, there are a number of sub-fields that include corrosion chemistry, pyrochemistry, solution-phase chemistry, rapid separations, environmental speciation, and other similar efforts. However, in all of the these fields it is important to realize that the underlying chemistry that underpins these efforts is similar in that Pu and Am are bound to ligands that can be in the solid, aqueous, or gas phase and separations occurs due to the preferential binding of the ligand to Pu or Am based on a number of factors that include pH, concentration, oxidation state, etc. In the past, most of the Pu and Am chemistry has occurred in limited scope within universities where micro-scale and bench-top scale chemistry are the dominate investigative theme. At US national laboratory and their international counterparts, larger scale reactions have been attempted such that industrial scale chemistry has been completed. Some of this technology has been harnessed in radiopharmaceuticals and nuclear fuel reprocessing. However, such bench-top research is expensive to due to the safety and security that is concerned when dealing with Pu, and scale-up of reactions is even more resource intensive. In an effort to offset this expensive, it would be of interest to explore the ability to predict selectivity based on the computational modeling of actinide chemistry. This has historically been limited by the abilities of large supercomputers, but with the emphasis on developing exascale computers within the US and similar efforts by other countries this predictive modeling has potential to produce significant results that would yield improved understanding of actinide chemistry.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Computational solution of atmospheric chemistry problems

Extensive studies were performed on problems of interest in atmospheric chemistry. In addition to several minor projects, four major projects were performed and described (theoretical studies of ground and low-lying excited states of ClO2; ground and excited state potential energy surfaces of the methyl peroxy radical; electronic states ot the FO radical; and theoretical studies S02 (H2O) (sub n)).

Jafri, J.↗