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At least 1,441 records · Page 80

A Groundmass Composition for EET 79001A Using a Novel Microprobe Technique for Estimating Bulk Compositions. Lithology A as an Impact Melt?

Petrologic investigation of the shergottites has been hampered by the fact that most of these meteorites are partial cumulates. Two lines of inquiry have been used to evaluate the compositions of parental liquids: (i) perform melting experiments at different pressures and temperatures until the compositions of cumulate crystal cores are reproduced [e.g., 1]; and (ii) use point-counting techniques to reconstruct the compositions of intercumulus liquids [e.g., 2]. The second of these methods is hampered by the approximate nature of the technique. In effect, element maps are used to construct mineral modes; and average mineral compositions are then converted into bulk compositions. This method works well when the mineral phases are homogeneous [3]. However, when minerals are zoned, with narrow rims contributing disproportionately to the mineral volume, this method becomes problematic. Decisions need to be made about the average composition of the various zones within crystals. And, further, the proportions of those zones also need to be defined. We have developed a new microprobe technique to see whether the point-count method of determining intercumulus liquid composition is realistic. In our technique, the approximating decisions of earlier methods are unnecessary because each pixel of our x-ray maps is turned into a complete eleven-element quantitative analysis. The success or failure of our technique can then be determined by experimentation. As discussed earlier, experiments on our point-count composition can then be used to see whether experimental liquidus phases successfully reproduce natural mineral compositions. Regardless of our ultimate outcome in retrieving shergottite parent liquids, we believe our pixel-bypixel analysis technique represents a giant step forward in documenting thin-section modes and compositions. For a third time, we have analyzed the groundmass composition of EET 79001, 68 [Eg]. The first estimate of Eg was made by [4] and later modified by [5], to take phase diagram considerations into account. The Eg composition of [4] was too olivine normative to be the true Eg composition, because the ,68 groundmass contains no forsteritic olivine. A later mapping by [2] basically reconfirmed the modifications of [5]. However, even the modified composition of [5] has olivine on the liquidus for ~50 C before low-Ca pyroxene appears [6].

Jones, John H.↗

Optimal design of multi-stage vacuum membrane distillation and integration with supercritical water desalination for improved zero liquid discharge desalination

Herein this paper proposes a novel concept for the optimal design of multi-stage vacuum membrane distillation (VMD). Generally, a multi-stage VMD is designed with an equal temperature difference between each stage. However, such a design is energy inefficient and increases VMD area. An analytical methodology for calculating the optimal stage temperature is proposed. By selecting the optimal stage temperature, the energy efficiency and required membrane area can be potentially improved by 16% and 30%, respectively. The proposed concept applies to all heat sources, including latent, sensible, and waste heat. To illustrate the method, multi-stage VMD is integrated with the waste heat from a supercritical water desalination (SCWD) system to achieve zero liquid discharge. SCWD is an energy-intensive process, requires high-quality thermal heat (>450 °C), and exhibits high waste heat rejection. The integrated VMD-SCWD approach is approximately 50% more energy-efficient and 35% more cost-efficient than the standalone SCWD system. Compared to the commercially used brine concentrator and crystallizer, the multi-stage VMD-SCWD system is more energy efficient for feed concentrations >5%. VMD-SCWD system is 30% cheaper, due to less expensive membrane distillation modules compared to a brine concentrator. The proposed design concept can replace the brine concentrator and crystallizer as an improved alternative for a zero-liquid discharge desalination system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Meniscus Shapes in Detached Bridgman Growth

In detached Bridgman crystal growth, most of the melt is in contact with the ampoule wall, but the crystal is separated from the wall by a small gap, typically 1-100 micrometers. A liquid free surface, or meniscus, bridges across this gap at the position of the melt-crystal interface. Meniscus shapes have been calculated for the case of detached Bridgman growth in cylindrical ampoules by solving the Young-Laplace equation. Key parameters affecting meniscus shapes are the growth angle, contact angle of the meniscus to the ampoule wall, the pressure differential across the meniscus, and the Bond number, a measure of the ratio of gravitational to capillary forces. In general, for specified values of growth and contact angles, solutions exist only over a finite range of pressure differentials. For intermediate values of the Bond number, there are multiple solutions to the Young-Laplace equations. There are also cases where, as a function of pressure differential, existence intervals alternate with intervals where no solutions exist. The implications of the meniscus shape calculations on meniscus stability are discussed.

Volz, M. P.↗

Dynamic Heterogeneity and Kovacs’ Memory Effects in Supercooled Water

Understanding the properties of supercooled water is important for developing a comprehensive theory for liquid water and amorphous ices. Because of rapid crystallization for deeply supercooled water, experiments on it are typically carried out under conditions in which the temperature and/or pressure are rapidly changing. As a result, information on the structural relaxation kinetics of supercooled water as it approaches (metastable) equilibrium is useful for interpreting results obtained in this experimentally challenging region of phase space. Here, we used infrared spectroscopy and the fast time resolution obtained by transiently heating nanoscale water films to investigate relaxation kinetics (aging) in supercooled water. When the structural relaxation of the water films was followed using a temperature jump protocol analogous to the classic experiments of Kovacs, similar memory effects were observed. In particular, after suitable aging at one temperature, water’s structure displayed an extremum versus the number of heat pulses upon changing to a second temperature before eventually relaxing to a steady-state structure characteristic of that temperature. A random double well model based on the idea of dynamic heterogeneity in supercooled water accounts for the observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mantle–melt partitioning of the highly siderophile elements: New results and application to Mars

Trace elements and extant and extinct isotopic attributes in Martian meteorites have been used to argue that Mars accreted quickly, differentiated into core and mantle, and established several mantle reservoirs, possibly within 10 Ma of T0. The partitioning of trace elements in the deep mantle has been relatively unstudied, despite the need for such knowledge in understanding magma ocean crystallization and the origin of depleted and enriched mantle reservoirs. The siderophile element composition of the Martian mantle and lithophile isotopic systems such as Sr, Hf, and Nd are thought to record evidence for early metal–silicate equilibrium and deep magma ocean at an intermediate depth and pressure of 800 km or 14 GPa. We have carried out experiments across this pressure range to better understand the mineral/melt partitioning of a wide range of elements. These new data are used to evaluate differentiation models for Mars and to help interpret the available isotopic data. The relatively incompatible nature of Re compared to mildly compatible Os means that the crystallization of a deep magma ocean will lead to residual liquids with superchondritic Re/Os, and solids with subchondritic Re/Os. Such material available in the mantle could be the source of enriched isotopic reservoir that produced shergottites with +γOs values. Slightly subchondritic Re/Os ratios in the crystallizing solids would provide a reservoir that could produce -γOs values. Finally, melting of mixtures of these two enriched and depleted endmembers could explain the Nd-Os isotopic correlations and systematics of shergottites.

58 GEOSCIENCES↗

Measuring Thicknesses Of Vacuum-Deposited Organic Thin Films

Method of measuring thickness of thin organic liquid film deposited in vacuum involves use of quartz-crystal monitor (QCM) calibrated by use of witness plate that has, in turn, calibrated by measurement of absorption of infrared light in deposited material. Present procedure somewhat tedious, but once calibration accomplished, thicknesses of organic liquid deposits monitored in real time and in situ by use of QCM.

David, Carey E.↗

Homogeneous crystal nucleation in binary metallic melts

A method for calculating the homogeneous crystal nucleation frequency in binary metallic melts is developed. The free energy of crystallization is derived from regular solution models for the liquid and solid and is used, together with model-based estimates of the interfacial tension, to calculate the nucleation frequency from the classical theory. The method can account for the composition dependence of the maximum undercooling observed in a number of experiments on small droplet dispersions. It can also be used to calculate the driving force for crystal growth and to obtain more precise estimates of the homogeneous crystal nucleation frequency in glass-forming alloys. This method, although approximate, is simple to apply, and requires only knowledge of the phase diagram and a few readily available thermodynamic quantities as input data.

Thompson, C. V.↗

Studies of convection in a solidifying binary mixture at reduced gravity

A great deal of interest was generated recently in the possibility of producing new materials in the reduced gravity environment provided during the forthcoming missions of Spacelab. The range of possibilities extend from producing large crystals of uniform properties to manufacturing materials with unique properties. Most of these processes involve the solidification of materials from the liquid state. Convective motions within the liquid during solidification can influence the local material composite and the shape of the solid-liquid interface which may result in solids with non-uniform properties and crystal defects. The microgravity environment of Spacelab is being viewed as one in which the buoyancy forces are eliminated so that convection driven by thermal gradients does occur, resulting in an improved solidification process. However, convection may occur for other reasons and whether convection is negligible or not during solidification constitutes processing in low-gravity environment. Little information exists presently on convection during solidification under such circumstances. A continuation of an analytical investigation into the nature of convective motion in a binary liquid layer due to surface tension forces during its solidification is reported. The onset of convection will be determined through a stability analysis which is described.

Antar, B. N.↗

Fluoroalkyl-functional imidazoles and imidazolium–based ionic liquids prepared via thiol-ene/yne click chemistry

A fluorinated thiol was systematically investigated against a diverse set of –ene- and –yne-bearing imidazole and imidazolium substrates in the pursuit of new cation-fluorinated, omniphobic (hydrophobic and oleophobic) ionic liquids for aerospace applications. Compounds were prepared using UV-initiated click chemistry at quantitative conversion and purified with relative ease. Seven ionic liquids were synthesized and have isolated yields ranging from 74% to >99%. Five of the new cation-fluorinated ionic liquids are hydrophobic and two are liquids at room temperature. In addition to hydrophobicity, the seven ionic liquids’ solubilities were qualitatively examined across a wide spectrum of conventional organic solvents. Of note, the majority of the prepared ionic liquids are insoluble in water and hexanes yet soluble in methanol, acetone, acetonitrile, and dichloromethane. In addition to intriguing solubility properties, the ionic liquids in this study have high densities without the incorporation of heavy atoms, ranging from 1.596 to 1.924 g cm –3 . The fluorinated salts also show good short-term thermal stability in air, with decomposition temperatures ranging from 215 °C to 320 °C. Other relevant characterization methods include spectroscopy, thermal analysis, and physical property measurements where appropriate. The X-ray crystal structure of a divalent, cation-fluorinated ionic liquid from this study was also obtained and shows unique fluorous domains in the extended structure, providing valuable insight into the materials’ physical properties. Furthermore, this work highlights a family of compounds moving towards omniphobic ionic liquids yielding potential possibilities for future applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication of Single Crystal MgO Capsules

A method has been developed for machining MgO crystal blocks into forms for containing metallic and silicate liquids at temperatures up to 2,400 C, and pressures up to at least 320 kilobars. Possible custom shapes include tubes, rods, insulators, capsules, and guides. Key differences in this innovative method include drilling along the crystallographic zone axes, use of a vibration minimizing material to secure the workpiece, and constant flushing of material swarf with a cooling medium/lubricant (water). A single crystal MgO block is cut into a section .5 mm thick, 1 cm on a side, using a low-speed saw with a 0.004 blade. The cut is made parallel to the direction of cleavage. The block may be cut to any thickness to achieve the desired length of the piece. To minimize drilling vibrations, the MgO block is mounted on a piece of adhesive putty in a vise. The putty wad cradles the bottom half of the entire block. Diamond coring tools are used to drill the MgO to the desired custom shape, with water used to wet and wash the surface of swarf. Compressed air may also be used to remove swarf during breaks in drilling. The MgO workpiece must be kept cool at all times with water. After all the swarf is rinsed off, the piece is left to dry overnight. If the workpiece is still attached to the base of the MgO block after drilling, it may be cut off by using a diamond cutoff wheel on a rotary hand tool or by using a low-speed saw.

Danielson, Lisa↗

Infrared Database for Process Support Materials

Process support materials' compatibility with cleaning processes is critical to ensure final hardware cleanliness and that performance requirements are met. Previous discovery of potential contaminants in process materials shows the need for incoming materials testing and establishment of a process materials database. The Contamination Control Team of the Materials, Processes, and Manufacturing (MP&M) Department at Marshall Space Flight Center (MSFC) has initiated the development of such an infrared (IR) database, called the MSFC Process Materials IR database, of the common process support materials used at MSFC. These process support materials include solvents, wiper cloths, gloves, bagging materials, etc. Testing includes evaluation of the potential of gloves, wiper cloths, and other items to transfer contamination to handled articles in the absence of solvent exposure, and the potential for solvent exposure to induce material degradation. This Technical Memorandum (TM) summarizes the initial testing completed through December 2002. It is anticipated that additional testing will be conducted with updates provided in future TMs.Materials were analyzed using two different IR techniques: (1) Dry transference and (2) liquid extraction testing. The first of these techniques utilized the Nicolet Magna 750 IR spectrometer outfitted with a horizontal attenuated total reflectance (HATR) crystal accessory. The region from 650 to 4,000 wave numbers was analyzed, and 50 scans were performed per IR spectrum. A dry transference test was conducted by applying each sample with hand pressure to the HATR crystal to first obtain a spectrum of the parent material. The material was then removed from the HATR crystal and analyzed to determine the presence of any residues. If volatile, liquid samples were examined both prior to and following evaporation.The second technique was to perform an extraction test with each sample in five different solvents.Once the scans were complete for both the dry transference and the extraction tests, the residue from each scan was interpreted.

Bennett, K. E.↗

Highland materials at Apollo 17 - Contributions from 72275

A set of Apollo 17 feldspathic highland clasts from polymict breccia 72275 have been studied. The clasts include six granulites and a rare Apollo 17 ferroan anorthosite (FAN). The composition of these clasts is discussed in detail. It is suggested that there are three possibilities regarding the petrogenesis of Apollo 17 FAN: (1) the rocks are products of late-stage crystallization from their parent magma, (2) the rocks solidified with a high amount of trapped liquid relative to FANs from other sites, or (3) the highlands rocks that formed at this site crystallized from a parent magma with a composition distinct from that of other lunar highland sites.

Salpas, Peter A.↗

SU(4) Chiral Spin Liquid, Exciton Supersolid, and Electric Detection in Moiré Bilayers

We propose a moiré bilayer as a platform where exotic quantum phases can be stabilized and electrically detected. Moiré bilayers consist of two separate moiré superlattice layers coupled through the interlayer Coulomb repulsion. In the small distance limit, an SU(4) spin can be formed by combining layer pseudospin and the real spin. As a concrete example, we study an SU(4) spin model on triangular lattice in the fundamental representation. By tuning a three-site ring exchange term K ~ ( t 3 /U 2 ), we find the SU(4) symmetric crystallized phase and an SU (4) 1 chiral spin liquid at the balanced filling. We also predict two different exciton supersolid phases with interlayer coherence at imbalanced filling under displacement field. Especially, the system can simulate an SU(2) Bose-Einstein condensation by injecting interlayer excitons into the magnetically ordered Mott insulator at the layer polarized limit. Smoking gun evidences of these phases can be obtained by measuring the pseudospin transport in the counterflow channel.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Study of liquid-solid transition for materials processing in space. Analysis of field effects on dense liquid materials

The behavior of dense liquids near the solidification point under the influence of magnetic fields or near-zero gravity conditions were analyzed within the framework of existing liquid state models and classical field theory. The dynamic body forces which are an effect of the magnetic field on liquids are discussed. It is concluded that both magnetic fields and low gravity conditions produce an increase in the diffusion coefficient which result in an increased growth rate of crystals, and time varying magnetic fields induce eddy currents in the liquid which produce body forces and tend to disrupt convection.

Miller, R. I.↗

Band gap dependence of exciton Lande factor in lead halide perovskites

The optical properties of lead halide perovskite semiconductors in vicinity of the bandgap are controlled by excitons, so that investigation of their fundamental properties is of critical importance. The exciton Landé or g-factor g X is the key parameter, determining the exciton Zeeman spin splitting in magnetic fields. The exciton, electron, and hole carrier g-factors provide information on the band structure, including its anisotropy, and the parameters contributing to the electron and hole effective masses. Here, g X is measured by reflectivity in magnetic fields up to 60 T for lead halide perovskite crystals. The materials band gap energies at a liquid helium temperature vary widely across the visible spectral range from 1.520 up to 3.213 eV in hybrid organic–inorganic and fully inorganic perovskites with different cations and halogens: FA 0.9 Cs 0.1 PbI 2.8 Br 0.2 , MAPbI 3 , FAPbBr 3 , CsPbBr 3 , and MAPb(Br 0.05 Cl 0.95 ) 3 . The exciton g-factors are found to be nearly constant, ranging from +2.3 to +2.7. Thus, the strong dependences of the electron and hole g-factors on the bandgap roughly compensate each other when combining to the exciton g-factor. The same is true for the anisotropies of the carrier g-factors, resulting in a nearly isotropic exciton g-factor. The experimental data are compared favorably with model calculation results.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

In situ polymerized succinonitrile-based solid polymer electrolytes for lithium ion batteries

Novel solid polymer electrolytes based on succinonitrile (SN) plastic crystal electrolyte (SN-PCE) and polymerized ionic liquid (PIL) has been successfully synthesized via an in-situ method. The fabricated electrolyte (PIL-SN-PCE) is uniformly inlayed into the supporting matrix of polyimide, which effectively ameliorates the mechanical properties of the electrolyte. PIL can effectively enhance the thermal stability of electrolytes up to 300 °C and mitigate the parasitic reactions between the electrolytes and the electrodes. PIL-SN-PCE exhibits a remarkable oxidation ability up to 5.4 V vs Li/Li + and a high room temperature ionic conductivity of 6.54 × 10 -4 S cm -1 . Furthermore, in-situ formed interface in PIL-SN-PCE guarantee an excellent compatibility with different electrodes, which can effectively improve the cycle stability and rate performances of both half-cells and full cells. Finally, PIL-SN-PCE is considered as a promising electrolyte for high energy density lithium-ion batteries.

25 ENERGY STORAGE↗

Bismuth as a Reactive Solvent in the Synthesis of Multicomponent Transition-Metal-Bearing Bismuthides

Employment of liquid bismuth (Bi) allows the facile single-crystal growth of compounds containing elements with high melting points, provided that these elements have reasonably high solubility in Bi. Utilization of the Bi flux approach yielded two new ternary bismuthides, SrNi 0.17(1) Bi 2 [a defect variant of the BaCuSn 2 type, space group Cmcm , α = 4.879(2) Å, b = 17.580(6) Å, and c = 4.696(2) Å] and CaTi 3 Bi 4 [NdTi 3 (Sn 0.1 Sb 0.9 ) 4 structure type, space group Fmmm , a = 5.6295(7) Å, b = 9.8389(1) Å, and c = 23.905(3) Å]. In addition, the ternary antimonide CaV3Sb4, isostructural with CaTi 3 Bi 4 , was synthesized from antimony (Sb) flux, and analyzed with the goal of validating structural assessment of the bismuthide analogue, where the X-ray crystallographic work proved to be very challenging. All synthesized compounds exhibit complex crystal structures featuring quasi-two-dimensional building blocks of different topologies. First-principle calculations reveal hypervalent bonding in the homoatomic Bi subunits. Lastly, physical property measurements indicate metallic conductivity and the absence of localized magnetism in the studied compounds.

36 MATERIALS SCIENCE↗