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All sourcesNASA NTRSDOE OSTI
NASA NTRS2021

Dissolution Rates of Allophane with Variable Fe Contents: Implications for Aqueous Alteration and the Preservation of X-ray Amorphous Materials on Mars

Recent measurements from Mars document X-ray amorphous/nano-crystalline materials in multiple locations across the planet. However, despite their prevalence, little is known about these materials or what their presence implies for the history of Mars. The X-ray amorphous component of the martian soil in Gale crater has an X-ray diffraction pattern that can be partially fit with allophane (approximately Al2O3•(SiO2)1.3-2•(H2O)2.5-3), and the low-temperature water release data are consistent with allophane. The chemical data from Gale crater suggest that other silicate materials similar to allophane, such as Fe-substituted allophane (approximately (Fe2O3)0.01-0.5(Al2O3)0.5-0.99•(SiO2)2•3H2O), may also be present. In order to investigate the properties of these potential poorly crystalline components of the martian soil, Fe-free allophane (Fe:Al = 0), Fe-poor allophane (Fe:Al = 1:99), and Fe-rich allophane (Fe:Al = 1:1) were synthesized and then characterized using electron microscopy and Mars-relevant techniques, including infrared spectroscopy, X-ray diffraction, and evolved gas analysis. Dissolution experiments were performed at acidic (initial pH values pH0 = 3.01, pH0 = 5.04), near-neutral (pH0 = 6.99), and alkaline (pH0 = 10.4) conditions in order to determine dissolution kinetics and alteration phases for these poorly crystalline materials. Dissolution rates (rdiss), based on the rate of Si release into solution, show that these poorly crystalline materials dissolve approximately an order of magnitude faster than crystalline phases with similar compositions at all pH conditions. For Fe-free allophane, logrdiss = -10.65 – 0.15 × pH; for Fe-poor allophane, logrdiss = -10.35 – 0.22 × pH; and for Fe-rich allophane, logrdiss = -11.46 – 0.042 × pH at 25°C, where rdiss has the units of mol m-2 s-1. The formation of incipient phyllosilicate-like phases was detected in Fe-free and Fe-rich allophane reacted in aqueous solutions with pH0 = 10.4 (steady-state pH ≈ 8). Mars-analog instrument analyses demonstrate that Fe-free allophane, Fe-poor allophane, and Fe-rich allophane are appropriate analogs for silicate phases in the martian amorphous soil component. Therefore, similar materials on Mars must have had limited interaction with liquid water since their formation. Combined with chemical changes expected from weathering, such as phyllosilicate formation, the rapid alteration of these poorly crystalline materials may be a useful tool for evaluating the extent of aqueous alteration in returned samples of martian soils.

S J Ralston↗
NASA NTRS1982

Preliminary study of the effects of a reversible chemical reaction on gas bubble dissolution

A preliminary investigation is carried out of the effects of a reversible chemical reaction on the dissolution of an isolated, stationary gas bubble in a glass melt. The exact governing equations for the model system are formulated and analyzed. The approximate quasi-steady-state version of these equations is solved analytically, and a calculation is made of bubble dissolution rates. The results are then compared with numerical solutions obtained from the finite difference form of the exact governing equations. It is pointed out that in the microgravity condition of space, the buoyant rise of a gas bubble in a glass melt will be negligible on the time scale of most experiments. For this reason, a determination of the behavior of a stationary gas bubble in a melt is relevant for an understanding of glass refining in space.

Weinberg, M. C.↗
NASA NTRS1991

High resolution electrolyte for thinning InP by anodic dissolution and its applications to EC-V profiling, defect revealing and surface passivation

An extensive experimental study was conducted using various electrolytes in an effort to find an appropriate electrolyte for anodic dissolution of InP. From the analysis of electrochemical characteristics in the dark and under different illumination levels, x ray photoelectron spectroscopy and SEM/Nomarski inspection of the surfaces, it was determined that the anodic dissolution of InP front surface layers by FAP electrolyte is a very good choice for rendering smooth surfaces, free of oxides and contaminants and with good electrical characteristics. The FAP electrolyte, based on HF, CH3COOH, and H2O2 appears to be inherently superior to previously reported electrolytes for performing accurate EC-V profiling of InP at current densities of up to 0.3 mA/sq cm. It can also be used for accurate electrochemical revealing of either precipitates or dislocation density with application to EPD mapping as a function of depth, and for defect revealing of multilayer InP structures at any depth and/or at the interfaces.

Faur, Maria↗
NASA NTRS1999

The Dissolution of an Interfween Miscible Liquids

The disappearance of the surface tension of the interface of a binary mixture, measured using the dynamic surface light scattering technique, is slower for a binary mixture of higher density contrast. A comparison with a naive diffusion model, expected to provide a lower limit for the speed of dissolution in the absence of gravity shows that the interfacial surface tension disappears much slower than even by diffusion with the effect becoming much more pronounced when density contrast between the liquid phases is increased. Thus, the factor most likely to be responsible for this anomalously slow dissolution is gravity. A mechanism could be based on the competition between diffusive relaxation and sedimentation at the dissolving interface.

Vlad, D.H.↗
NASA NTRS2003

Maximum Rates of Olivine Dissolution on Mars

This work is a first step in constraining olivine alteration rates on Mars. By bounding dissolution rates of olivine, we can make inferences about the temporal extent of aqueous alteration on the surface. Several hypothesized low-temperature surface aqueous alteration processes include valley network formation from release of groundwater during impact or gully formation from snow melt, both of which may occur over a period of several thousand years. Outflow channels may have formed during brief floods lasting less than a year. If large bodies of water were present during a warm, wet period, large standing bodies of water may have been present for 104 to 109 years. High-temperature alteration processes include hydrothermal activity associated with impacts and magmatic features. These features may remain active for 104 to 106 years. Table 2 summarizes speculated duration times of these aqueous processes. For comparison, we have determined minimum olivine residence times (time until complete dissolution) for 1 mm diameter particles to range from much less than one year to approximately 5,000 years.

J D Stopar↗
NASA NTRS2005

Dissolution kinetics of iron-, manganese-, and copper-containing synthetic hydroxyapatites

Micronutrient-substituted synthetic hydroxyapatite (SHA) is being evaluated by the National Aeronautics and Space Administration's (NASA) Advanced Life Support (ALS) Program for crop production on long-duration human missions to the International Space Station or for future Lunar or Martian outposts. The stirred-flow technique was utilized to characterize Ca, P, Fe, Mn, and Cu release characteristics from Fe-, Mn-, and Cu-containing SHA in deionized (DI) water, citric acid, and diethylene-triamine-pentaacetic acid (DTPA). Initially, Ca and P release rates decreased rapidly with time and were controlled by a non-SHA calcium phosphate phase(s) with low Ca/P solution molar ratios (0.91-1.51) relative to solid SHA ratios (1.56-1.64). At later times, Ca/P solution molar ratios (1.47-1.79) were near solid SHA ratios and release rates decreased slowly indicating that SHA controlled Ca and P release. Substituted SHA materials had faster dissolution rates relative to unsubstituted SHA. The initial metal release rate order was Mn >> Cu > Fe which followed metal-oxide/phosphate solubility suggesting that poorly crystalline metal-oxides/phosphates were dominating metal release. Similar metal release rates for all substituted SHA (approximately 0.01 cmol kg-1 min-1) at the end of the DTPA experiment indicated that SHA dissolution was supplying the metals into solution and that poorly crystalline metal-oxide/phosphates were not controlling metal release. Results indicate that non-SHA Ca-phosphate phases and poorly crystalline metal-oxide/phosphates will contribute Ca, P, and metals. After these phases have dissolved, substituted SHA will be the source of Ca, P, and metals for plants.

NASA Discipline Life Support Systems↗
NASA NTRS2023

Multiphysics Modeling of Electrode Dissolution under Hydrodynamic Conditions in Low Conductivity Water

Efficient plug-flow electrochemical reactors are characterized by their ability to effectively convert species with significant ionic strength and/or with the assistance of a well-behaved electrolyte. Because of the classic electroconductivity requirement, electrochemical reactors are not particularly attractive options for applications with low-conductivity conditions, especially for low-pressure feeds. However, these reactors can still find application in dedicated processes such as ultra-clean water conditioning and biological-coupled separation systems. Consequently, a multi-physics model was developed using COMSOL Multiphysics to characterize different reactor-design conditions based on the Tertiary Current Distribution which accounts for the effects of expected variations in electrolyte composition and ionic strength on the electrochemical process, as well as solution resistance and electrode kinetics. The modelling framework presented here employs single-phase laminar fluid flow, the Nernst-Planck equation, the water-based electroneutrality condition, and concentration-dependent overpotentials. This investigation particularly explores the electrolysis process of “anodic dissolution,” in which elemental species dissociate from the solid matrix of the electrode and enter the liquid phase of the electrolyte as soluble ions. The reactor configuration of interest has a rectangular parallel-electrode design and is operated galvanostatically. A series of parametric studies are carried out to inspect the response of the system when hydrodynamic, kinetic, and geometric conditions are changed. The parametric sweep resulted in variable effluent concentrations and system voltage, which reveal underlaying optimization patterns for electrode dissolution in low conductivity water.

Multiphysics↗
NASA NTRS1977

Stabilization of n-type semiconductors to photoanodic dissolution by competitive electron transfer processes

The behavior of n-type CdX (X = S, Se, Te) and GaP, GaAs, and InP in alkaline electrolytes containing X(--) and X sub n(--) ions is reviewed. Of the 18 combinations of electrode and electrolyte, 12 alliances are completely stable to photoanodic dissolution of the n-type photoanode. In each case the oxidation of the chalcogenide species at the photoanode is reversed at the cathode to complete an electrochemical cycle involving no net chemical change. The best system in terms of light-to-electric energy conversion seems to be the CdTe-based cell employing the Te(--)/Te2(--) electrolyte, with roughly 10% efficiency at an output voltage of 0.35 V for monochromatic 633 nm input optical energy at about 25 mW/sq cm.

Wrighton, M. S.↗
NASA NTRS1980

Dissolution of multicomponent bubbles

The behavior of an isolated, stationary, multicomponent gas bubble in a glassmelt containing several dissolved gases is considered. The relevant mass-transport equations are formulated and calculations are performed for the case of two diffusing gases using a quasi-stationary model and a numerical solution of the exact mass-transfer equations. The results obtained from these two approaches are compared. The factors which govern the dissolution or growth of a bubble are thermodynamic and kinetic in origin. The tendency of a bubble to grow or shrink at long times is controlled by departure from overall equilibrium, whereas the short-time bubble dynamics may be dominated by kinetic effects. As a result of the existence of these dual influences, maxima and/or minima occur in the functional dependence of the bubble radius on time.

Weinberg, M. C.↗
NASA NTRS1981

Dissolution of bulk specimens of silicon nitride

An accurate chemical characterization of silicon nitride has become important in connection with current efforts to incorporate components of this material into advanced heat engines. However, there are problems concerning a chemical analysis of bulk silicon nitride. Current analytical methods require the pulverization of bulk specimens. A pulverization procedure making use of grinding media, on the other hand, will introduce contaminants. A description is given of a dissolution procedure which overcomes these difficulties. It has been found that up to at least 0.6 g solid pieces of various samples of hot pressed and reaction bonded silicon nitride can be decomposed in a mixture of 3 mL hydrofluoric acid and 1 mL nitric acid overnight at 150 C in a Parr bomb. High-purity silicon nitride is completely soluble in nitric acid after treatment in the bomb. Following decomposition, silicon and hydrofluoric acid are volatilized and insoluble fluorides are converted to a soluble form.

Davis, W. F.↗
NASA NTRS1981

Behavior of bubbles in glassmelts. III - Dissolution and growth of a rising bubble containing a single gas

Finite difference solutions of the mass transport equations governing the dissolution (growth) of a rising gas bubble, containing a single gas, in a glassmelt were obtained. These solutions were compared with those obtained from an approximate procedure for a range of the controlling parameters. Applications were made to describe various aspects of O2 and CO2 gas-bubble behavior in a soda-lime-silicate melt.

Onorato, P. I. K.↗
NASA NTRS1986

Acid dissolution experiments - Carbonates and the 6.8-micrometer bands in interplanetary dust particles

A chemical dissolution experiment on an interplanetary dust particle (IDP) showed that carbonates, not acid-insoluble organic compounds, were responsible for virtually all the absorption at 6.8 micrometers seen in the infrared spectra of this particle. The IDP examined had an infrared spectrum characteristic of layer-lattice silicates and belongs to a class of IDP's whose spectra resemble those of protostellar objects like W33 A, which also exhibit a band at 6.8 micrometers.

Sandford, S. A.↗
NASA NTRS1986

Planetesimal dissolution in the envelopes of the forming, giant planets

An evaluation is made of the capacity of planetesimals to penetrate the envelopes of giant planets during their growth phase, by means of a core instability mechanism in which the growing core becomes gradually more adept in the gravitational concentration of gas from its solar nebula environment, until a runaway gas accretion occurs. If most of the accreted mass is contained in planetesimals larger that about 1 km, the critical core mass for runaway accretion will not significantly change when planetesimal dissolution is taken into account; it is accordingly suggested that giant planet envelopes should contain above-solar proportions of virtually all elements, relative to hydrogen.

Pollack, J. B.↗
NASA NTRS1984

The dissolution or growth of a sphere

The problem of the dissolution or growth of an isolated stationary sphere in a large fluid body is analyzed. The motion of the boundary as well as the the resulting motion in the liquid are properly taken into account. The governing equations are solved using a recently developed technique (Subramanian and Weinberg, 1981) which employs an asymptotic expansion in time. Results for the radius of the sphere as a function of time are calculated. The range of utility of the present solution is established by comparison with a numerical solution of the governing equations obtained by the method of finite differences.

Shankar, N.↗