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At least 19 records

Mars aqueous chemistry experiment

The Mars Aqueous Chemistry Experiment (MACE) is designed to conduct a variety of measurements on regolith samples, encompassing mineral phase analyses, chemical interactions with H2O, and physical properties determinations. From these data, much can be learned or inferred regarding the past weathering environment, the contemporaneous soil micro-environments, and the general chemical and physical state of the Martian regolith. By analyzing both soil and duricrust samples, the nature of the latter may become more apparent. Sites may be characterized for comparative purposes and criteria could be set for selection of high priority materials on future sample return missions. Progress for the first year MACE PIDDP is reported in two major areas of effort: (1) fluids handling concepts, definition, and breadboard fabrication and (2) aqueous chemistry ion sensing technology and test facility integration. A fluids handling breadboard was designed, fabricated, and tested at Mars ambient pressure. The breadboard allows fluid manipulation scenarios to be tested under the reduced pressure conditions expected in the Martian atmosphere in order to validate valve operations, orchestrate analysis sequences, investigate sealing integrity, and to demonstrate efficacy of the fluid handling concept. Additional fluid manipulation concepts have also been developed based on updated MESUR spacecraft definition. The Mars Aqueous Chemistry Experiment Ion Selective Electrode (ISE) facility was designed as a test bed to develop a multifunction interface for measurements of chemical ion concentrations in aqueous solution. The interface allows acquisition of real time data concerning the kinetics and heats of salt dissolution, and transient response to calibration and solubility events. An array of ion selective electrodes has been interfaced and preliminary calibration studies performed.

Clark, Benton C.↗

Phase diagram of KHF2 and non-equilibrium effects

The equilibrium diagram for the KHF2-H2O system was constructed from cooling and heating curves for the compositions between 5 wt% and 40 wt% KHF2 and the results are shown. The phase diagrams shown is typical of that of a two component system with miscible liquid phases and whole solid phases consist of pure components. A eutectic point was found at approximately 15% KHF2 which remains completely liquid down to a temperature of -9.0 C. No hydrate formation was observed and no anomalous behavior such as the occurrence of solid transitions or metastable states was observed. The effect of rapid freezing on the equilibrium diagram did not appear, and cooling curves exhibited only one halt. Also, at rapid freezing rates, the supercooling of the solutions was smaller than those observed at the slow cooling rates. The existence of a eutectic composition and the slow rate of dissolution of the salt are used to interpret heat absorption behavior in practical applications of the KHF2-H2O system.

Hobson, M. C.↗

Modeling the Salar de Uyuni, Bolivia as an Equipotential Surface of Earth's Gravity Field

The salar de Uyuni is a massive dry salt lake that lies at the lowest point of an internal/drainage basin in the Bolivian Altiplano. Its topography is remarkable for its extraordinary flatness over almost a full degree of latitude and longitude. We surveyed a 54 x 45 km region of the salar with kinematic GPS in September, 2002 and found a topographic range of only 80 cm over the entire surveyed area. Furthermore, the survey revealed distinct surface features with several dominant wavelengths and orientations. Some of these appear to be aligned with orographic features that intersect the salar, leading us to conjecture that they are the surface expression of high-density mountains that have been buried by low-density basin sediments. Over the oceans, a similar correspondence between basin bathymetry and surface topography is exploited to map the seafloor using sea-surface satellite altimetry measurements, with the sea surface following geoid undulations due to the underwater mass distribution. On the salar, annual flooding creates a shallow lake whose surface also lies on a equipotential surface shaped by the distribution of underlying mass. The link to the actual salar surface is via the dissolution and redeposition of salt by the lake waters, which appears to push the system to an equilibrium of constant water depth and the coincidence of the shapes of the lake surface and bottom. To test our hypothesis about the origin of the surface features on the salar, we compare our GPS survey elevations with the equipotential surface generated from local gravity measurements in conjunction with gravity and potential values from the EGM96 global geopotential model. 50% of the variance of the GPS elevations can be explained by equipotential surface undulations from the EGM96 model alone, and an additional 40% is explained by the shorter-wavelength equipotential surface derived from local gravity. We examine the unexplained 10% of elevation variance from the standpoint of errors in the equipotential surface calculation and possible unmodelled surface processes.

Borsa, Adrian↗

Turbine Airfoil Deposition Models

Gas turbine failures associated with sea-salt ingestion and sulfur-containing fuel impurities have directed attention to alkali sulfate deposition and the associated hot corrosion of gas turbine (GT) blades under some GT operating conditions. These salt deposits form thin, molten films which undermine the protective metal oxide coating normally found on GT blades. The prediction of molten salt deposition, flow and oxide dissolution, and their effects on the lifetime of turbine blades are examined. Goals include rationalizing and helping to predict corrosion patterns on operational GT rotor blades and stators, and ultimately providing some of the tools required to design laboratory simulators and future corrosion-resistant high-performance engines. Necessary background developments are reviewed first, and then recent results and tentative conclusions are presented along with a brief account of the present research plans.

Rosner, D. E.↗

Hot corrosion of silicon carbide and silicon nitride at 1000 C

The sodium sulfate hot corrosion of silicon-based ceramics at 1000 C has been extensively studied. Deposition of the sodium sulfate corrodant from combustion products is discussed in relation to sodium air impurity and sulfur fuel impurity content. Corrosion occurs by the combined processes of oxidation to form protective silica scales and dissolution of these scales to form nonprotective sodium silicates. The chemical corrosion mechanisms are presented in terms of acidic/basic dissolution of oxides in molten salts. The reactions are strongly influenced by the presence of free carbon in the ceramic. Strength reductions have been measured and are attributed to pitting in SiC and grain boundary attack in Si3N4. Initial results of burner corrosion of two ceramic matrix composites are consistent with the models developed for monolithic ceramics.

Fox, Dennis S.↗

Turbine airfoil deposition models and their hot corrosion implications

This research project deals with the prediction of single- and multi-component salt(-solution) deposition, flow and oxide dissolution and their effects on the lifetime of turbine blades. Goals include rationalizing and helping to predict corrosion patterns on operational gas turbine (GT) rotor blades and stator vanes, and ultimately providing some of the tools required to design laboratory simulators and future corrosion resistant high-performance engines. Necessary background developments are reviewed. Results and tentative conclusions for single species (Na sub 2 SO sub 4 (1)) condensation, binary salt-solution (Na sub 2 SO sub 4-K sub 2 SO sub 4) condensation, and burner-rig testing of alloy materials are outlined.

Rosner, D. E.↗

Method of cross-linking polyvinyl alcohol and other water soluble resins

A self supporting sheet structure comprising a water soluble, noncrosslinked polymer such as polyvinyl alcohol which is capable of being crosslinked by reaction with hydrogen atom radicals and hydroxyl molecule radicals is contacted with an aqueous solution having a pH of less than 8 and containing a dissolved salt in an amount sufficient to prevent substantial dissolution of the noncrosslinked polymer in the aqueous solution. The aqueous solution is then irradiated with ionizing radiation to form hydrogen atom radicals and hydroxyl molecule radicals and the irradiation is continued for a time sufficient to effect crosslinking of the water soluble polymer to produce a water insoluble polymer sheet structure. The method has particular application in the production of battery separators and electrode envelopes for alkaline batteries.

Phillipp, W. H.↗

Iodine addition using triiodide solutions

The study develops: a triiodide solution for use in preparing ground service equipment (GSE) water for Shuttle support, an iodine dissolution method that is reliable and requires minimal time and effort to prepare, and an iodine dissolution agent with a minimal concentration of sodium salt. Sodium iodide and hydriodic acid were both found to dissolve iodine to attain the desired GSE iodine concentrations of 7.5 +/- 2.5 mg/L and 25 +/- 5 mg/L. The 1.75:1 and 2:1 sodium iodide solutions produced higher iodine recoveries than the 1.2:1 hydriodic acid solution. A two-hour preparation time is required for the three sodium iodide solutions. The 1.2:1 hydriodic acid solution can be prepared in less than 5 min. Two sodium iodide stock solutions (2.5:1 and 2:1) were found to dissolve iodine without undergoing precipitation.

Rutz, Jeffrey A.↗

Self-discharge in bimetallic cells containing alkali metal

Theoretical analysis of thermally regenerative bimetallic cells with alkali metal anodes shows a relation between the current drawn and the rate of discharge under open-circuit conditions. The self-discharge rate of the cell is due to the dissolution and ionization of alkali metal atoms in the fused-salt electrolyte

Foster, M. S.↗

Aircraft measurements of ammonia and nitric acid in the lower troposphere

The first simultaneous measurements of ammonia and nitric acid in the troposphere have been made from an aircraft using a tungsten oxide denuder system. Vertical profiles of NH3 and HNO3 taken over coastal Virginia and Maryland in March and September, 1983, at altitudes from 150 m to 3000 m, show mixing ratios that decrease with altitude. Ammonia profiles show substantial seasonal variation, while nitric acid profiles do not. Using the measured profiles and a one-dimensional photochemical model, lifetimes due to heterogeneous loss of one day for HNO3 and ten days for NH3 are calculated. In contrast, NH3 profiles up to 5300 m over the North Atlantic Ocean during August 1982 show mixing ratios that increase slightly with altitude. These data represent the first ammonia profiles measured over the ocean. It is suggested that the increase in NH3 with altitude is a result of an ammonia-rich continental air mass advected over the ocean, followed by the dissolution of NH3 in the marine boundary layer on water-covered sea salt particles.

Lebel, P. J.↗

Potential Lifestyles in Ancient Environments of Gusev Crater, Mars

Habitable environments must sustain liquid water at least intermittently and also provide both chemical building blocks and useful sources of energy for life. Observations by Spirit rover indicate that conditions have probably been too dry to sustain life, at least since the emplacement of the extensive basalts that underlie the plains around the Columbia Memorial Station landing site. Local evidence of relatively minor aqueous alteration probably occurred under conditions where the activity of water was too low to sustain biological processes as we know them. In contrast, multiple bedrock units in West Spur and Husband Hill in the Columbia Wills have been extensively altered, probably by aqueous processes. The Fe in several of these units has been extensively oxidized, indicating that, in principle, any microbiota present during the aqueous alteration of these rocks could have obtained energy from Fe oxidation. Spirit discovered oliving-rich ultramafic rocks during her descent from Husband Hill southward into Inner Basin. Alteration of similar ultramafic rocks on Earth can yield H2 that can provide both energy and reducing power for microorganisms. Spirit s discovery of "salty" soil horizons rich in Fe and/or Mg is consistent with the aqueous dissolution and/or alteration of olivine. Such processes can oxidize Fe and also yield H2 under appropriate conditions. Very high S concentrations in these salty deposits indicate that soluble salts were mobilized by water and/or that S oxidation, a potential energy source for life, occurred. The Athena team has not yet established whether these salt components were deposited as large beds in ancient water bodies or, for example, were concentrated by more recent groundwater activity. Collectively these observations are consistent with the possibility that habitable environments existed at least intermittently in the distant geologic past.

DesMarais, David J.↗

Vapor deposition and condensate flow on combustion turbine blades - Theoretical model to predict/understand some corrosion rate consequences of molten alkali sulfate deposition in the field or laboratory

An analysis is undertaken of aerodynamically- and centrifugally-driven liquid condensate layers on nonisothermal combustion turbines' stator vanes and rotor blades. Attention is given to the quantitative consequences of one possible mechanism for the initiation of 'hot corrosion' in the underlying blade material through a 'fluxing' of the protective oxide coating by the molten salt of the Newtonian condensate film. Illustrative calculations are presented for the condensate streamline pattern and the distributions of the steady-state condensate layer thickness, together with the corresponding oxide dissolution rate, for a test turbine blade.

Rosner, Daniel E.↗

Modification by food of the calcium absorbability and physicochemical effects of calcium citrate

The food-calcium (Ca) interaction was examined in 12 healthy women (mean age 38 years) maintained on a constant metabolic diet. They underwent three phases of study, comprised of control (no Ca), Ca citrate (1 g Ca/day) during meals, and Ca citrate separately from meals. Each phase was 7 days in length and two 24-hour urine samples were collected on days 6 and 7. The rise from the control phase in urinary Ca was slightly more prominent when Ca citrate was given with meals than without (68 and 62%, respectively). The fall in urinary phosphorus was equivalent at about 25% between Ca citrate phases. The rise in urinary citrate and pH and the decline in urinary ammonium were more prominent when Ca citrate was given with meals; however, the changes were small or nonsignificant. The urinary saturation of Ca oxalate, brushite or monosodium urate did not differ between the two Ca citrate phases. There was a nonsignificant rise in serum iron during Ca citrate phases. The results suggest that: 1) dissolution and absorption of Ca citrate might be slightly greater when given with food than without; 2) that the ability of Ca citrate to attenuate crystallization of stone-forming Ca salts in urine is not modified by food; and 3) that Ca citrate may not impair iron absorption from food.

Non-NASA Center↗

Evidence for Halite at Meridiani Planum

The outcrop rocks investigated by the Mars Exploration Rover (MER) Opportunity at Meridiani Planum consist of altered basaltic fines emplaced through aeolian and aqueous processes. Diagenesis through episodes of groundwater influx is likely responsible for lithification of the sediments, formation and subsequent dissolution of embedded crystals, and development of hematitic spherules with occasional cemented overgrowths [1]. The action of liquid water in the development of these rocks prompts the search for pure evaporative salts such as chlorides. Extensive deposits of this nature have not yet been discovered and may be a result of erosion and removal from stratigraphic layers above those sampled by Opportunity, or burial beneath accessible depths [2]. Nonetheless, the presence of small amounts of halite (NaCl) associated with coatings and rinds is indicated by the available data.

Yen, Albert S.↗

The Alteration History of Clovis Class Rocks in Gusev Crater as Determined by Ti-Normalzed Mass Balance Analysis

The West Spur Clovis class rocks in Gusev Crater are some of the most altered rocks in Gusev Crater and likely contain a mixed sulfate and phyllosilicate mineralogy [1,2]. The high S and Cl content of the Clovis rocks suggests that acidic vapors or fluids of H2SO4 and HCl reacted with the Clovis parent rock to form Ca, Mg,- sulfates, iron-oxyhydroxides and secondary aluminosilicates (approx.60 wt.%) of a poorly crystalline nature (e.g., allophane) [1]. Up to 14-17 wt.% phyllosilicates (e.g., kaolinite, chlorite, serpentine) are hypothesized to exist in the Clovis materials suggesting that Clovis parent materials while possibly exposed to acidic pHs were likely neutralized by basalt dissolution which resulted in mildly acidic pHs (4-6) [1, 2]. This work proposes that subsequent to the alteration of the Clovis rocks, alteration fluids became concentrated in ions resulting in the addition of silicate and salts. The objective of this work is to utilize Ti-normalized mass balance analysis to evaluate (1) mineral gains and losses and (2) elemental gains and losses in the Clovis rocks. Results of this work will be used evaluate the nature of geochemical conditions that affect phyllosilicate and sulfate formation at Gusev crater.

Sutter, Brat↗

Molten salt corrosion of SiC: Pitting mechanism

Thin films of Na2SO4 and Na2CO3 at 1000 C lead to severe pitting of sintered alpha-SiC. These pits are important as they cause a strength reduction in this material. The growth of product layers is related to pit formation for the Na2CO3 case. The early reaction stages involve repeated oxidation and dissolution to form sodium silicate. This results in severe grain boundary attack. After this a porous silica layer forms between the sodium silicate melt and the SiC. The pores in this layer appear to act as paths for the melt to reach the SiC and create larger pits.

Jacobson, N. S.↗

Kinetics and mechanism of corrosion of SiC by molten salts

Corrosion of sintered alpha-SiC under thin films of Na2CO3/CO2, Na2SO4/O2, and Na2SO4/SO3 was investigated at 1000 C. Chemical analysis was used to follow silicate and silica evolution as a function of time. This information coupled with morphology observations leads to a detailed corrosion mechanism. In all cases the corrosion reactions occur primarily in the first few hours. In the Na2CO3/CO2 case, rapid oxidation and dissolution lead to a thick layer of silicate melt in about 0.25 h. After this, silica forms a protective layer on the carbide. In the Na2SO4/O2 case, a similar mechanism occurs. In the Na2SO4/SO3 case, a porous nonprotective layer of SiO2 grows directly on the carbide, and a silicate melt forms above this. In addition, SiO2 and regenerated Na2SO4 form at the melt/gas interface due to reaction of silicate with SO3 and SO2 + O2. The reaction slows when the lower silica layer becomes nonporous.

Jacobson, N. S.↗

Weathering of basaltic rocks under cold, arid conditions - Antarctica and Mars

The processes taking part in the chemical weathering of nonvesicular dolerite cobbles producing etch pits and secondary minerals including clays, under cold arid conditions of high-altitude ice-free areas of Victoria Land (Antarctica) are investigated as a possible analog to processes that produced the pitted rocks and clay minerals on Mars. Results suggest that the pits in the dolerite cobbles are formed by the dissolution of the rock by rare snow-melt water during the austral summer, followed by wind erosion of weathered material. The upper interior walls of the pits are lined with a yellow precipitate consisting of illite and quartz mixture, while the pit bottoms contain alteration products including Fe-rich clay minerals and soluble salts. A model is proposed for rock pitting on Mars analogous to that of the Antarctic dolerites.

Allen, C. C.↗