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At least 361 records · Page 20

Chemical durability of high-temperature superconductor YBa2Cu3O(7-x) in aqueous environments

The stability of YBa2Cu3O(7-x) in water and 100-percent humidity has been investigated at three temperatures, using pH measurements, X-ray diffraction, and scanning electron microscopy. The oxide-ceramic superconductor is highly unstable; it reacts rapidly with water and degrades in moisture. Dissolution of the oxide perovskite in water is highly incongruent. The corrosion products are found to be BaCO3, CuO, O2, etc. Barium hydroxide is first formed and further reacts with atmospheric CO2 to form needle-shaped crystals of BaCO3. For any practical applications, devices made from these materials would have to be protected with an impermeable coating to prevent deterioration from atmosphere.

Bansal, Narottam P.↗

Cell separation by immunoaffinity partitioning with polyethylene glycol-modified Protein A in aqueous polymer two-phase systems

Previous work has shown that polyethylene glycol (PEG)-bound antibodies can be used as affinity ligands in PEG-dextran two-phase systems to provide selective partitioning of cells to the PEG-rich phase. In the present work it is shown that immunoaffinity partitioning can be simplified by use of PEG-modified Protein A which complexes with unmodified antibody and cells and shifts their partitioning into the PEG-rich phase, thus eliminating the need to prepare a PEG-modified antibody for each cell type. In addition, the paper provides a more rigorous test of the original technique with PEG-bound antibodies by showing that it is effective at shifting the partitioning of either cell type of a mixture of two cell populations.

Karr, Laurel J.↗

Demixing of aqueous polymer two-phase systems in low gravity

Experiments on the effect of gravity on phase emulsion demixing were performed in order to study the potential of two-phase partitioning in space. The behavior of phase systems possessing phase density differences and systems with essentially identical phase densities was investigated during one-g and low-g parabolic aircraft maneuvers. It is found that demixing can occur rather rapidly in space, although more slowly than on earth. The Ostwald ripening theory predicts demixing rates many orders of magnitude lower than the observed values.

Bamberger, S.↗

Interactions of silicate glasses with aqueous environments under conditions of prolonged contact and flow

This paper discusses mechanisms involving saturation and reactions that lead to the formation of altered phases in silicate glasses considered for use in geologic repositories for nuclear waste. It is shown that the rate of dissolution of silicate glasses exposed to a broad range of contact times, leachant compositions, and surface-to-volume ratios is strongly affected by the presence of reactive species such as Al, Mg, and Fe. The reactive materials may originate in the leachant or, under conditions of high surface-to-volume ratio, in the glass itself. The effects of glass composition on the course of the corrosion process can be viewed in terms of the formation of a surface layer on the leached glass; the type, composition, and structure of this layer control the dissolution behavior of the glass.

Barkatt, Aaron↗

Mineral catalysis of the formation of the phosphodiester bond in aqueous solution - The possible role of montmorillonite clays

The possible role of montmorillonite clays in the spontaneous formation on the primitive earth of the phosphodiester bond in the presence of water was investigated in experiments measuring the binding of various nucleosides and nucleotides with Na(+)-montmorillonite 22A and the reactions of these compounds with a water-soluble carbodiimide. It was found that, at neutral pH, adenine derivatives bind stronger than the corresponding uracil derivatives, consistent with the protonation of the adenine by the acidic clay surface and a cationic binding of the protonated ring to the anionic clay surface. The reaction of the 5-prime-AMP with carbodiimide resulted in the formation of 2-prime,5-prime-pApA (18.9 percent), 3-prime,5-prime-pApA (11 percent), and AppA (4.8 percent). The yields of these oligomers obtained when poly(U) was used in place of the clay were 15.5 percent, 3.7 percent, and 14.9 percent AppA, respectively.

Ferris, James P.↗

Measurements and mechanisms of localized aqueous corrosion in aluminum-lithium alloys

Like most heat treatable aluminum alloys, localized corrosion and stress corrosion of Al-Li-Cu alloys is strongly dependent on the nature and distribution of second phase particles. To develop a mechanistic understanding of the role of localized corrosion in the stress corrosion process, bulk samples of T(sub 1) (Al2CuLi) and a range of Al-Cu-Fe impurity phases were prepared for electrochemical experiments. Potentiodynamic polarization and galvanic couple experiments were performed in standard 0.6 M NaCl and in simulated crevice solutions to assess corrosion behavior of these particles with respect to the alpha-Al matrix. A comparison of time to failure versus applied potential using a constant load, smooth bar SCC test technique in Cl(-), Cl(-)/CrO4(2-), and Cl(-)/CO3(2-) environments shows that rapid failures are to be expected when applied potentials are more positive than the breakaway potential (E sub br) of T(sub 1) (crack tip) but less than E(sub br) of alpha-Al (crack walls). It is shown that this criterion is not satisfied in aerated Cl(-) solutions. Accordingly, SCC resistance is good. This criterion is satisfied, however, in an alkaline isolated fissure exposed to a CO2 containing atmosphere. Rapid failure induced by these fissures was recently termed preexposure embrittlement. Anodic polarization shows that the corrosion behavior of T(sub 1) is relatively unaffected in alkaline CO3(2-) environments but the alpha-Al phase is rapidly passivated. X ray diffraction of crevice walls from artificial crevices suggests that passivation of alpha-Al occurs as hydrotalcite-type compound (LiAl2(OH)6)2(+) - CO3(2-) - nH2O.

Buchheit, Rudolph G., Jr.↗

Cell separation in immunoaffinity partition in aqueous polymer two-phase systems

Two methods for immunoaffinity partitioning are described. One technique involves the covalent coupling of poly (ethylene glycol) (PEG) to immunoglobulin G antibody preparations. In the second method PEG-modified Protein A is used to complex with cells and unmodified antibody. The effects of PEG molecular weight, the degree of modification, and varying phase system composition on antibody activity and its affinity for the upper phase are studied. It is observed that both methods resulted in effective cell separation.

Karr, Laurel J.↗

Numerical simulation of solidification in a horizontal cylindrical annulus charged with an aqueous salt solution

A computational study of solidification of a binary Na2CO3 solution in a horizontal cylindrical annulus is performed using a continuum formulation with a control-volume based, finite-difference scheme. The initial conditions were selected to facilitate the study of counter thermal and solutal convection, accompanied by extensive mushy region growth. Numerical results are compared with experimental data with mixed success. Qualitative agreement is obtained for the overall solidification process and associated physical phenomena. However, the plume thickness calculated for the solutally-driven convective upflow is substantially smaller than the observed value. Evolution of double-diffusive layers is predicted, but over a time scale much smaller than that observed experimentally. Good agreement is obtained between predicted and measured results for solid growth, but the mushy region thickness is significantly overpredicted.

Neilson, D. G.↗

Measurements and mechanisms of localized aqueous corrosion in aluminum-lithium-copper alloys

Summary information is included for electrochemical aspects of stress corrosion cracking in alloy 2090 and an introduction to the work to be initiated on the new X2095 (Weldalite) alloy system. Stress corrosion cracking (SCC) was studied in both S-T and L-T orientations in alloy 2090. A constant load TTF test was performed in several environments with a potentiostatically applied potential. In the same environments the electrochemical behavior of phases found along subgrain boundaries was assessed. It was found that rapid failure due to SCC occurred when the following criteria was met: E(sub BR,T1) is less than E(sub applied) is less than E(sub Br, matrix phase). Although the L-T orientation is usually considered more resistant to SCC, failures in this orientation occurred when the stated criteria was met. This may be due to the relatively isotropic geometry of the subgrains which measure approximately 12 to 25 microns in diameters. Initial studies of alloy X2095 includes electrochemical characterization of three compositional variations each at three temperatures. The role of T(sub 1) dissolution in SCC behavior is addressed using techniques similar to those used in the research of 2090 described. SCC susceptibility is also studied using alternate immersion facilities at Reynolds Metals Corporation. Pitting is investigated in terms of stability, role of precipitate phases and constituent particles, and as initiation sites for SCC. In all research endeavors, attempts are made to link electrochemistry to microstructure. Previous work on 2090 provides a convenient basis for comparison since both alloys contain T(sub 1) precipitates but with different distributions. In 2090 T(sub 1) forms preferentially on subgrain boundaries whereas in X2095 the microstructure appears to be more homogeneous with finer T(sub 1) particles. Another point for comparison is the delta prime strengthening phase found in 2090 but absent in X2095.

Wall, Douglas↗

Dissolution of quartz in aqueous basic solution, 106-236 C - Surface kinetics of 'perfect' crystallographic faces

A highly accurate method, called the negative crystal method, for determining the rate of dissolution on specific crystallographic faces of crystals was developed, in which the dissolution rates of nominally perfect crystal faces are obtained by measuring the size of individual negative crystals during a sequence of dissolution steps. The method was applied to determine the apparent activation energy and rate constants for the dissolution of quartz in 0.01 M KOH solutions at temperatures from 106 to 236 C. Also investigated were the effects of hydroxyl activity and ionic strength. The apparent activation energies for the dissolution of the prism and of the rhomb were determined.

Gratz, Andrew J.↗

Ancient aqueous sedimentation on Mars

Viking orbiter images are presently used to calculate approximate volumes for the inflow valleys of the ancient cratered terrain of Mars; a sediment-transport model is then used to conservatively estimate the amount of water required for the removal of this volume of debris from the valleys. The results obtained for four basins with well-developed inflow networks indicate basin sediment thicknesses of the order of tens to hundreds of meters. The calculations further suggest that the quantity of water required to transport the sediment is greater than that which could be produced by a single discharge of the associated aquifer, unless the material of the Martian highlands was very fine-grained and noncohesive to depths of hundreds of meters.

Goldspiel, Jules M.↗

Experimental study of directional solidification of aqueous ammonium chloride solution

Directional solidification experiments have been carried out using the analog casting system of NH4Cl-H2O solution by cooling it from below with a constant-temperature surface ranging from -31.5 C to +11.9 C. The NH4Cl concentration was 26 percent in all solutions, with a liquidus temperature of 15 C. It was found that finger convection occurred in the fluid region just above the mushy layer in all experiments. Plume convection with associated chimneys in the mush occurred in experiments with bottom temperatures as high as +11.0 C. However, when the bottom temperature was raised to +11.9 C, no plume convection was observed, although finger convection continued as usual. A method has been devised to determine the porosity of the mush by computed tomography. Using the mean value of the porosity across the mush layer and the permeability calculated by the Kozeny-Carman relationship, the critical solute Rayleigh number across the mush layer for onset of plume convection was estimated to be between 200 and 250.

Chen, C. F.↗

The corrosion behavior of the T1 (Al2CuLi) intermetallic compound in aqueous environments

The intermetallic compound T1 (Al2CuLi) is suspected to play an important role in the localized corrosion at subgrain boundaries in Al-Li-Cu alloys. The intermetallic was synthesized for characterization of its corrosion behavior. Experiments performed included open circuit potential measurements, potentiodynamic polarization, and corrosion rate vs. pH in solutions whose pH was varied over the range of 3 to 11. Subgrain boundary pitting and continuous subgrain boundary corrosion are discussed in terms of the data obtained. Evidence suggesting the dealloying of copper from this compound is also presented.

Buchheit, R. G.↗

A carbonate-silicate aqueous geochemical cycle model for Mars

A model for the carbonate-silicate geochemical cycle of an early, wet Mars is under development. The results of this study will be used to constrain models of the geochemical history of Mars and the likely mineralogy of its present surface. Although Mars today is a cold, dry planet, it may once have been much warmer and wetter. Values of total outgassed CO2 from several to about 10 bars are consistent with present knowledge (Pollack et al. 1987), and this amount of CO2 implies an amount of water outgassed at least equal to an equivalent depth of 500-1000 meters (Carr 1986). Pollack et al. (1987), in addition, estimate that a thick CO2 atmosphere may have existed for an extended period of time, perhaps as long as a billion years. The greenhouse effect of such an atmosphere would permit the presence of liquid water on the surface, most likely in the form of a shallow sea in the lowest regions of the planet, such as the northern plains (Schaefer 1990). The treatment of geochemical cycles as complex kinetic chemical reactions has been undertaken for terrestrial systems in recent years with much success (Lasaga 1980, 1981; Berner et al. 1983; Lasaga et al. 1985). Although the Martian system is vastly less well understood, and hence less well-constrained, it is also a much simpler system, due to the lack of biogenic reactions that make the terrestrial system so complex. It should be possible, therefore, to use the same techniques to model the Martian system as have been used for terrestrial systems, and to produce useful results. A diagram of the carbonate-silicate cycle for Mars (simplified from the terrestrial system) is given.

Schaefer, M. W.↗

Carbonate formation on Mars: History of the CO2 atmosphere from models of diffusion-limited growth in non-aqueous environments

We conducted preliminary experiments designed to measure the amount of CO2 reacted from a simulated Martian atmosphere to form carbonate on silicate grains. Warm experiments at constant T (300-350 K) and with no water (vapor or liquid) yielded no detectable reaction, suggesting the following result. If we are indeed operating in the thermodynamically-favorable regime (supported by Gooding (1978) for the gas-solid reaction), then the lack of a reaction at warm temperatures suggests that a reaction in the 200-300 K regime will be less favored if reaction kinetics dominate. The completely dry scenario is thus not favored. An additional experiment, with abundant water vapor and at T approx. 300 K (constant), yielded a negative result as well. However, this is not inconsistent with Booth's findings, since lower temperatures may be required for the absorption of a monolayer of water. We plan further (lower-T) experiments.

Stephens, Stuart K.↗

Aqueous-alteration products in S-N-C meteorites and implications for volatile/regolith interactions on Mars

The shergottite, nakhlite, and Chassigny (SNC) meteorites are inferred to be samples from the Martian surface, and so provide a wealth of information on Martian petrology and geochemistry. Because the SNCs are igneous rocks, it has not been obvious that they could reveal much about low-temperature geochemical processes and atmosphere surface interactions on Mars. However, five of the eight SNCs are known to contain low-temperature hydrous minerals and related phase of likely martian origin. Here, we review these martian weathering and alteration products in SNCs and outline possible implications for volatile/regolith interactions and regolith sinks for volatiles on Mars.

Treiman, A. H.↗

Aqueous organic geochemistry at high temperature/high pressure

A description of the fate and chemical alterations of organic matter under hydrothermal conditions is given, with a brief overview of the geographic localities where these processes have been investigated to date. Two major aspects are examined: (1) alteration and degradation processes and reactions, both reductive and oxidative; and (2) synthesis processes and reactions which are primarily reductive. Examples of industrial applications of the related supercritical fluid technology are discussed.

Simoneit, Bernd R. T.↗

Preterrestrial aqueous alteration of the Lafayette (SNC) meteorite

The structure and chemical composition of the Lafayette meteorite were examined using several methods. The meteorite contains abundant hydrous post-magnetic alteration material consisting of ferroan smectite clays, magnetite, and ferrihydrite. The textural relations, mineralogy, and composition of these materials were examined and their preterrestrial nature was documented. Olivine, pyroxene, and glass alteration are described and the bulk compositions of the alteration veinlets is discussed. Essential features of the geochemistry of the alteration processes are described. It is suggested that the alteration of the Lafayette meteorite occurred during episodic infiltrations of small volumes of saline water. Constraints placed on water chemistry and water-rock interactions in the Martian crust are outlined.

Treiman, Allan H.↗