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Sample records for phase formation mechanism

  1. Formation of Protein Condensed Phases: Nucleation Mechanisms.

    PubMed

    Vekilov, Peter G

    2012-04-04

    Proteins in solution form a number of condensed phases. Even omitting the amyloid structures formed after partial protein unfolding, these phases include crystals, polymers, and other solid aggregates, as well as dense liquids and gels. Some of these condensed phases underlie pathological conditions, others play a crucial role in the biological function of the respective protein or are an essential part of its laboratory or industrial processing. In this review, we summarize the fundamentals and recent findings on the kinetics of nucleation of dense liquid droplets and crystals. We define the transition from nucleation to spinodal decomposition for these two phase transitions. We review the two-step mechanism of protein crystal nucleation, in which mesoscopic metastable protein clusters serve as precursors to the ordered crystal nuclei. The concepts and mechanisms reviewed here provide powerful tools for control of the nucleation process by varying the solution thermodynamic parameters.

  2. Amorphous phase formation in mechanically alloyed iron-based systems

    NASA Astrophysics Data System (ADS)

    Sharma, Satyajeet

    Bulk metallic glasses have interesting combination of physical, chemical, mechanical, and magnetic properties which make them attractive for a variety of applications. Consequently there has been a lot of interest in understanding the structure and properties of these materials. More varied applications can be sought if one understands the reasons for glass formation and the methods to control them. The glass-forming ability (GFA) of alloys can be substantially increased by a proper selection of alloying elements and the chemical composition of the alloy. High GFA will enable in obtaining large section thickness of amorphous alloys. Ability to produce glassy alloys in larger section thicknesses enables exploitation of these advanced materials for a variety of different applications. The technique of mechanical alloying (MA) is a powerful non-equilibrium processing technique and is known to produce glassy (or amorphous) alloys in several alloy systems. Metallic amorphous alloys have been produced by MA starting from either blended elemental metal powders or pre-alloyed powders. Subsequently, these amorphous alloy powders could be consolidated to full density in the temperature range between the glass transition and crystallization temperatures, where the amorphous phase has a very low viscosity. This Dissertation focuses on identifying the various Fe-based multicomponent alloy systems that can be amorphized using the MA technique, studying the GFA of alloys with emphasis on improving it, and also on analyzing the effect of extended milling time on the constitution of the amorphous alloy powder produced at earlier times. The Dissertation contains seven chapters, where the lead chapter deals with the background, history and introduction to bulk metallic glasses. The following four chapters are the published/to be published work, where the criterion for predicting glass formation, effect of Niobium addition on glass-forming ability (GFA), lattice contraction on

  3. Membrane formation mechanism of cross-linked polyurea microcapsules by phase separation method.

    PubMed

    Yoshizawa, H; Kamio, E; Hirabayashi, N; Jacobson, J; Kitamura, Y

    2004-05-01

    This research was conducted to clarify the membrane formation mechanism of cross-linked polyurea microcapsules by phase separation method, especially the role of polymeric surfactant, such as poly(ethylene-alt-maleic anhydride) (poly(E-MA)) at the interface of O/W emulsion. It was found that poly(E-MA) was necessary for the formation of cross-linked polyurea membrane. The addition of sodium dodecyl sulphate (SDS) prohibited the membrane formation reaction at the interface, even in the case of poly(E-MA) concentration enough for polymeric microcapsule formation. From the results in this study, poly(E-MA) was found to be adsorbed on the O/W emulsion and provide the reaction site for the membrane formation of polymeric microcapsules.

  4. Comparison of different gas-phase mechanisms and aerosol modules for simulating particulate matter formation.

    PubMed

    Kim, Youngseob; Couvidat, Florian; Sartelet, Karine; Seigneur, Christian

    2011-11-01

    The effects of two gas-phase chemical kinetic mechanisms, Regional Atmospheric Chemistry Mechanism version 2 (RACM2) and Carbon-Bond 05 (CB05), and two secondary organic aerosol (SOA) modules, the Secondary Organic Aerosoi Model (SORGAM) and AER/EPRI/Caltech model (AEC), on fine (aerodynamic diameter < or =2.5 microm) particulate matter (PM2.5) formation is studied. The major sources of uncertainty in the chemistry of SOA formation are investigated. The use of all major SOA precursors and the treatment of SOA oligomerization are found to be the most important factors for SOA formation, leading to 66% and 60% more SOA, respectively. The explicit representation of high-NO, and low-NOx gas-phase chemical regimes is also important with increases in SOA of 30-120% depending on the approach used to implement the distinct SOA yields within the gas-phase chemical kinetic mechanism; further work is needed to develop gas-phase mechanisms that are fully compatible with SOA formation algorithms. The treatment of isoprene SOA as hydrophobic or hydrophilic leads to a significant difference, with more SOA being formed in the latter case. The activity coefficients may also be a major source of uncertainty, as they may differ significantly between atmospheric particles, which contain a myriad of SOA, primary organic aerosol (POA), and inorganic aerosol species, and particles formed in a smog chamber from a single precursor under dry conditions. Significant interactions exist between the uncertainties of the gas-phase chemistry and those of the SOA module.

  5. Mechanism of carboxylic acid photooxidation in atmospheric aqueous phase: Formation, fate and reactivity

    NASA Astrophysics Data System (ADS)

    Charbouillot, Tiffany; Gorini, Sophie; Voyard, Guillaume; Parazols, Marius; Brigante, Marcello; Deguillaume, Laurent; Delort, Anne-Marie; Mailhot, Gilles

    2012-09-01

    In the first part of the work, we investigated the reactivity toward photogenerated hydroxyl radicals (rad OH) of seven monocarboxylic acids and six dicarboxylic acids found in natural cloud water. This leads to the proposition of a schematic degradation pathway linking glutaric acid (C5) to complete mineralization into CO2. We report a detailed mechanism on the succinic acid reactivity toward rad OH leading to the formation of malonic, glyoxylic and consequently oxalic acids and a comparison with reported pathways proposed by the CAPRAM (Chemical Aqueous Phase RAdical Mechanism) is discussed. We also investigated the photooxidation of formic acid under atmospherically relevant conditions leading to the possible formation of oxalic acid via radical mediated recombination. The second part focuses on the polychromatic irradiation (closed to solar irradiation) of a collected cloud aqueous phase showing that irradiation of cloud water leads to the formation of both formic and acetic acids. Carboxylic acid formation increases in the presence of photogenerated hydroxyl radicals from hydrogen peroxide, showing that photooxidation could play a key role in the formation of carboxylic acids under atmospherically relevant conditions.

  6. Amorphous phase formation in Fe-6.0wt%Si alloy by mechanical alloying

    SciTech Connect

    Filho, A.F.; Bolfarini, C.; Xu, Y.; Kiminami, C.S.

    1999-12-31

    Mechanical alloying, MA, is a high-energy ball milling technique, in which elemental blends are milled to achieve alloying at atomic level. This communication describes the results of an investigation on the phase transformation of a mixture of Fe and Si powders with 6wt%Si during MA processing. Besides the verification of the effect of milling time on the structure and on the compositional homogeneity, this study was undertaken in order to confirm, by using TEM technique, the possibility of amorphous phase formation for Si content lower than 17.7wt%.

  7. Phase formation and superconducting properties of mechanically alloyed Nb3(Al1-x Ge x ) system

    NASA Astrophysics Data System (ADS)

    Li, Pingyuan; Chen, Yongliang; Xu, Liyuan; Zhang, Yun; Pan, Xifeng; Yan, Guo; Zhang, Yong; Cheng, C. H.; Feng, Yong; Zhao, Yong

    2016-07-01

    Mechanically alloyed Nb3(Al1-x Ge x ) compounds with nominal composition x = 0%, 10%, 15%, 20%, 25% and 30% were synthesized using high-energy ball milling. The effects of Ge content and sintering temperature on the formation of the Nb3Al superconducting phase at a relatively low temperature without the extremely high-temperature rapid heating, quenching and transformation process were studied. The results revealed that Ge doping in Nb3Al improved the formation of the A15 phase at low temperatures, enhanced the superconducting transition temperature (T c), and refined the grain structure, thus improving the overall superconducting properties. The pinning behavior was also studied for the optimized sample.

  8. Mechanism of Phase Formation in the Batch Mixtures for Slag-Bearing Glass Ceramics - 12207

    SciTech Connect

    Stefanovsky, Sergey V.; Stefanovsky, Olga I.; Malinina, Galina A.

    2012-07-01

    Slag surrogate was produced from chemicals by heating to 900 deg. C and keeping at this temperature for 1 hr. The product obtained was intermixed with either sodium di-silicate (75 wt.% waste loading) or borax (85 wt.% slag loading). The mixtures were heat-treated within a temperature range of 25 to 1300 deg. C. The products were examined by X-ray diffraction and infrared spectroscopy. The products prepared at temperatures of up to 1000 deg. C contained both phase typical of the source slag and intermediate phases as well as phases typical of the materials melted at 1350 deg. C such as nepheline, britholite, magnetite and matrix vitreous phase. Vitrification process in batch mixtures consisting of slag surrogate and either sodium di-silicate or sodium tetraborate runs through formation of intermediate phases mainly silico-phosphates capable to incorporate Sm as trivalent actinides surrogate. Reactions in the batch mixtures are in the whole completed by ∼1000 deg. C but higher temperatures are required to homogenize the products. If in the borate-based system the mechanism is close to simple dissolution of slag constituents in the low viscous borate melt, then in the silicate-based system the mechanism was found to be much complicated and includes re-crystallization during melting with segregation of newly-formed nepheline type phase. (authors)

  9. Phenomenological thermodynamics and the structure formation mechanism of the CuTi₂S₄ rhombohedral phase.

    PubMed

    Talanov, Michail V; Shirokov, Vladimir B; Talanov, Valery M

    2016-04-21

    The theory of structural phase transition in CuTi2S4 is proposed. The symmetry of order parameters, thermodynamics and the mechanism of the atomic structure formation of the rhombohedral Cu-Ti-thiospinel have been studied. The critical order parameter inducing the phase transition has been found. Within the Landau theory of phase transitions, it is shown that the phase state may change from the high-symmetry cubic disordered Fd3[combining macron]m phase to the low-symmetry ordered rhombohedral R3[combining macron]m phase as a result of phase transition of the first order close to the second order. It is shown that the rhombohedral structure of CuTi2S4 is formed as a result of the displacements of all types of atoms and the ordering of Cu-atoms (1 : 1 order type in tetrahedral spinel sites), Ti-atoms (1 : 1 : 6 order type in octahedral spinel sites), and S-atoms (1 : 1 : 3 : 3 order type). The Cu- and Ti-atoms form metal nanoclusters which are named a "bunch" of dimers. The "bunch" of dimers in CuTi2S4 is a new type of self-organization of atoms in frustrated spinel-like structures. It is shown that Ti-atoms also form other types of metal nanoclusters: trimers and tetrahedra.

  10. Phase formation and mechanical properties of Cu-Zr-Ti bulk metallic glass composites

    NASA Astrophysics Data System (ADS)

    Kim, Byoung Jin; Yun, Young Su; Kim, Won Tae; Kim, Do Hyang

    2016-11-01

    The effect of the type of the crystalline phase and its volume fraction on the mechanical property of Cu50Zr50-xTix alloys (x = 0-10) bulk metallic glass composites has been investigated in this study. Up to 6 at% of Ti, B19' phase particles distributed in the glassy matrix, while at 8 and 10% of Ti, B2 phase particles are retained in the glass matrix due to suppression of the eutectoid transformation of B2 phase and by avoidance of martensitic transformation of B2 into B19'. The volume fraction of crystalline phase is strongly dependent on the cooling rate. The larger volume fraction of the crystalline phases results in the lower yield stress, the higher plastic strain, and the more pronounced work hardening behavior. At the crystalline volume fraction below 30%, the variation of the yield strength can be described by the rule of mixture model (ROM), while at the crystalline volume fraction higher than 50% by the load-bearing model (LBM). At the crystal fractions between 30 and 50%, there is a yield strength drop and a transition from the ROM to the LBM. This transition is due to the formation of the crystalline structural framework at higher crystal fraction.

  11. Formation mechanism of gas bubble superlattice in UMo metal fuels: Phase-field modeling investigation

    NASA Astrophysics Data System (ADS)

    Hu, Shenyang; Burkes, Douglas E.; Lavender, Curt A.; Senor, David J.; Setyawan, Wahyu; Xu, Zhijie

    2016-10-01

    Nano-gas bubble superlattices are often observed in irradiated UMo nuclear fuels. However, the formation mechanism of gas bubble superlattices is not well understood. A number of physical processes may affect the gas bubble nucleation and growth; hence, the morphology of gas bubble microstructures including size and spatial distributions. In this work, a phase-field model integrating a first-passage Monte Carlo method to investigate the formation mechanism of gas bubble superlattices was developed. Six physical processes are taken into account in the model: 1) heterogeneous generation of gas atoms, vacancies, and interstitials informed from atomistic simulations; 2) one-dimensional (1-D) migration of interstitials; 3) irradiation-induced dissolution of gas atoms; 4) recombination between vacancies and interstitials; 5) elastic interaction; and 6) heterogeneous nucleation of gas bubbles. We found that the elastic interaction doesn't cause the gas bubble alignment, and fast 1-D migration of interstitials along <110> directions in the body-centered cubic U matrix causes the gas bubble alignment along <110> directions. It implies that 1-D interstitial migration along [110] direction should be the primary mechanism of a fcc gas bubble superlattice which is observed in bcc UMo alloys. Simulations also show that fission rates, saturated gas concentration, and elastic interaction all affect the morphology of gas bubble microstructures.

  12. Formation mechanism of gas bubble superlattice in UMo metal fuels: Phase-field modeling investigation

    SciTech Connect

    Hu, Shenyang; Burkes, Douglas E.; Lavender, Curt A.; Senor, David J.; Setyawan, Wahyu; Xu, Zhijie

    2016-07-08

    Nano-gas bubble superlattices are often observed in irradiated UMo nuclear fuels. However, the for- mation mechanism of gas bubble superlattices is not well understood. A number of physical processes may affect the gas bubble nucleation and growth; hence, the morphology of gas bubble microstructures including size and spatial distributions. In this work, a phase-field model integrating a first-passage Monte Carlo method to investigate the formation mechanism of gas bubble superlattices was devel- oped. Six physical processes are taken into account in the model: 1) heterogeneous generation of gas atoms, vacancies, and interstitials informed from atomistic simulations; 2) one-dimensional (1-D) migration of interstitials; 3) irradiation-induced dissolution of gas atoms; 4) recombination between vacancies and interstitials; 5) elastic interaction; and 6) heterogeneous nucleation of gas bubbles. We found that the elastic interaction doesn’t cause the gas bubble alignment, and fast 1-D migration of interstitials along $\\langle$110$\\rangle$ directions in the body-centered cubic U matrix causes the gas bubble alignment along $\\langle$110$\\rangle$ directions. It implies that 1-D interstitial migration along [110] direction should be the primary mechanism of a fcc gas bubble superlattice which is observed in bcc UMo alloys. Simulations also show that fission rates, saturated gas concentration, and elastic interaction all affect the morphology of gas bubble microstructures.

  13. Mechanisms for the formation of secondary organic aerosol components from the gas-phase ozonolysis of alpha-pinene.

    PubMed

    Ma, Yan; Russell, Andrew T; Marston, George

    2008-08-07

    Gas-phase ozonolysis of alpha-pinene was studied in static chamber experiments under 'OH-free' conditions. A range of multifunctional products-in particular low-volatility carboxylic acids-were identified in the condensed phase using gas chromatography coupled to mass spectrometry after derivatisation. The dependence of product yields on reaction conditions (humidity, choice of OH radical scavengers, added Criegee intermediate scavengers, NO(2)etc.) was investigated to probe the mechanisms of formation of these products; additional information was obtained by studying the ozonolysis of an enal and an enone derived from alpha-pinene. On the basis of experimental findings, previously suggested mechanisms were evaluated and detailed gas-phase mechanisms were developed to explain the observed product formation. Atmospheric implications of this work are discussed.

  14. Comparison of Phases Formation Process in Initial and Mechanically Activated Ceramic Batches with Pyrochlore Formulations

    SciTech Connect

    Stefanovsky, S. V.; Chizhevskaya, S. V.; Yudintsev, S. V.

    2002-02-25

    Formation of two pyrochlore ceramics with formulations CaZr0.25U0.75Ti2O7 and CaUTi2O7 within the temperature range 1000-1500 C from batches prepared by grinding of oxide powders in a mortar and an activator with hydrostatic yokes AGO-2U as well as soaking of a Ca, Zr, and Ti oxide mixture with uranylnitrate solution was studied. The pyrochlore ceramics are produced through intermediate calcium uranate formation. Phase formation reactions in the batch pre-treated in the AGO-2U unit were completed within the temperature range 1000-1100 C that is lower than in the batches prepared by two other methods.

  15. Creation and formation mechanism of new carbon phases constructed by amorphous carbon

    NASA Astrophysics Data System (ADS)

    Yao, Mingguang; Cui, Wen; Liu, Bingbing

    Our recent effort is focusing on the creation of new hard/superhard carbon phases constructed by disordered carbons or amorphous carbon clusters under high pressure. We showed that the pressure-induced amorphous hard carbon clusters from collapsed fullerenes can be used as building blocks (BBs) for constructing novel carbon structures. This new strategy has been verified by compressing a series of intercalated fullerides, pre-designed by selecting various dopants with special features. We demonstrate that the boundaries of the amorphous BBs are mediated by intercalated dopants and several new superhard materials have been prepared. We also found that the dopant-mediated BBs can be arranged in either ordered or disordered structures, both of which can be hard enough to indent the diamond anvils. The hardening mechanisms of the new phases have also been discussed. For the glassy carbon (GC) constructructed by disordered fullerene-like nanosized fragments, we also found that these disordered fragments can bond and the compressed GC transformed into a transparent superhard phase. Such pressure-induced transformation has been discovered to be driven by a novel mechanism (unpublished). By understanding the mechanisms we can clarify the controversial results on glassy carbon reported recently. The authors would like to thank the financial support from the National Natural Science Foundation of China (No. 11474121, 51320105007).

  16. Formation Mechanism and Control of Perovskite Films from Solution to Crystalline Phase Studied by in Situ Synchrotron Scattering.

    PubMed

    Chang, Chun-Yu; Huang, Yu-Ching; Tsao, Cheng-Si; Su, Wei-Fang

    2016-10-12

    Controlling the crystallization and morphology of perovskite films is crucial for the fabrication of high-efficiency perovskite solar cells. For the first time, we investigate the formation mechanism of the drop-cast perovskite film from its precursor solution, PbCl2 and CH3NH3I in N,N-dimethylformamide, to a crystalline CH3NH3PbI3-xClx film at different substrate temperatures from 70 to 180 °C in ambient air and humidity. We employed an in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) technique for this study. When the substrate temperature is at or below 100 °C, the perovskite film is formed in three stages: the initial solution stage, transition-to-solid film stage, and transformation stage from intermediates into a crystalline perovskite film. In each stage, the multiple routes for phase transformations are preceded concurrently. However, when the substrate temperature is increased from 100 to 180 °C, the formation mechanism of the perovskite film is changed from the "multistage formation mechanism" to the "direct formation mechanism". The proposed mechanism has been applied to understand the formation of a perovskite film containing an additive. The result of this study provides a fundamental understanding of the functions of the solvent and additive in the solution and transition states to the crystalline film. It provides useful knowledge to design and fabricate crystalline perovskite films for high-efficiency solar cells.

  17. Identification of Abnormal Phase and its Formation Mechanism in Synthesizing Chalcogenide Films

    NASA Astrophysics Data System (ADS)

    Liu, Kegao; Ji, Nianjing; Xu, Yong; Liu, Hong

    2016-09-01

    Chalcogenide films can be used in thin-film solar cells due to their high photoelectric conversion efficiencies. It was difficult to identify one abnormal phase with high X-ray diffraction (XRD) intensity and preferred orientation in the samples for preparing chalcogenide films by spin-coating and co-reduction on soda-lime glass (Na2OṡCaOṡ6SiO2) substrates. The raw materials and reductant are metal chlorides and hydrazine hydrate respectively. In order to identify this phase, a series of experiments were done under different conditions. The phases of obtained products were analyzed by XRD and the size and morphology were characterized by scanning electron microscope (SEM) and atomic force microscopy (AFM). From the experimental results, first it was proved that the abnormal phase was water-soluble by water immersion experiment, then it was identified as NaCl crystal through XRD, energy dispersive spectrometer (EDS) and SEM. The cubic NaCl crystals have high crystallinity with size lengths of about 0.5-2μm and show a <100> preferred orientation. The reaction mechanism of NaCl crystal was proposed as follows: The NaCl crystal was formed by reaction of Na2O and HCl in a certain experimental conditions.

  18. Study on the Formation and Precipitation Mechanism of Mn5Si3 Phase in the MBA-2 Brass Alloy

    NASA Astrophysics Data System (ADS)

    Li, Hang; Jie, Jinchuan; Zhang, Pengchao; Jia, Chunxu; Wang, Tongmin; Li, Tingju

    2016-06-01

    Mn5Si3 is an attractive dispersion in the special brass, owing to its high hardness and high wear resistance. In the present study, synchrotron X-ray radiography and rapid cooling were applied to investigate the formation mechanism of Mn5Si3 phase in the MBA-2 brass alloy. The primary Mn5Si3 phase is proved to exist stably in the alloy melt and nucleate from the melt at temperatures above 1373 K (1100 °C). In addition, the precipitation mechanism of Mn5Si3 phase is addressed systematically by the isothermal heat treatment. The Mn5Si3 particles are observed to precipitate from the matrix at temperatures above 1023 K (750 °C), and a crystallographic orientation relationship is found between the precipitated Mn5Si3 particle and β phase: (110)_{β } //(1overline{1} 00)_{{{{Mn}}5 {{Si}}3 }} and [overline{1} 11]_{β } //[11overline{2} overline{2} ]_{{{{Mn}}5 {{Si}}3 }} . However, the precipitation of Mn5Si3 phase is thermodynamically inhibited at lower temperatures, which can be ascribed to the increase in the Gibbs free energy of formation of Mn5Si3 with decreasing the temperature.

  19. Synthesis and formation mechanism of pinnoite by the phase transition process

    NASA Astrophysics Data System (ADS)

    Lin, Feng; Dong, Yaping; Peng, Jiaoyu; Wang, Liping; Li, Wu

    2016-06-01

    Pinnoite (MgB2O(OH)6) for the first time was synthesized using the solid-liquid-solid conversion method. The effects of reaction time, pH value and concentrations of magnesium and borate were investigated. Pinnoite was synthesized under the optimum condition of 8 mmol hungtsaoite and 1% boric acid solution at 80 °C. The products were determined using X-ray diffraction, Fourier-transform infrared spectroscopy, TG-DSC and a UV-vis spectrometer. The change processes of the surface morphology of pinnoite were investigated using scanning electron microscopy. In addition, the formation mechanism of pinnoite was discussed according to the changes in the content of precipitation and pH value.

  20. The Mechanism of 2-Furaldehyde Formation from d-Xylose Dehydration in the Gas Phase. A Tandem Mass Spectrometric Study

    NASA Astrophysics Data System (ADS)

    Ricci, Andreina; Piccolella, Simona; Pepi, Federico; Garzoli, Stefania; Giacomello, Pierluigi

    2013-07-01

    The mechanism of reactions occurring in solution can be investigated also in the gas phase by suited mass spectrometric techniques, which allow to highlight fundamental mechanistic features independent of the influence of the medium and to clarifying controversial hypotheses proposed in solution studies. In this work, we report a gas-phase study performed by electrospray triple stage quadrupole mass spectrometry (ESI-TSQ/MS) on the dehydration of d-xylose, leading mainly to the formation of 2-furaldehyde (2-FA). It is generally known in carbohydrate chemistry that the thermal acid catalyzed dehydration of pentoses leads to the formation of 2-FA, but several aspects on the solution-phase mechanism are controversial. Here, gaseous reactant ions corresponding to protonated xylose molecules obtained from ESI of a solution containing d-xylose and ammonium acetate as protonating reagent were allowed to undergo collisionally activated decomposition (CAD) into the triple stage quadrupole analyzer. The product ion mass spectra of protonated xylose are characterized by the presence of ionic intermediates arising from xylose dehydration, which were structurally characterized by their fragmentation patterns. As expected, the xylose triple dehydration leads to the formation of the ion at m/z 97, corresponding to protonated 2-FA. On the basis of mass spectrometric evidences, we demonstrated that in the gas phase, the formation of 2-FA involves protonation at the OH group bound to the C1 atom of the sugar, the first ionic intermediate being characterized by a cyclic structure. Finally, energy resolved product ion mass spectra allowed to obtain information on the energetic features of the d-xylose→2-FA conversion.

  1. Structure, properties, and possible mechanisms of formation of diamond-like phases

    NASA Astrophysics Data System (ADS)

    Belenkov, E. A.; Greshnyakov, V. A.

    2016-10-01

    An analysis was performed for relations between the structural parameters and the properties of 36 carbon diamond-like phases consisting of atoms occupying crystallographically equivalent positions. It was found that the crystal lattices of these phases were in stressed states with respect to the cubic diamond lattice. The density of diamond-like phases, their sublimation energies, bulk moduli, hardnesses, and band gaps depend on the deformation parameters Def and Str. The most stable phases must be phases with minimal parameters Def and Str and also with ring parameter Rng that is most close to the corresponding parameter of cubic diamond. The structures and energy characteristics of fullerites, nanotube bundles, and graphene layers of which diamond-like phases can be obtained as a result of polymerization at high pressures have been calculated.

  2. MECHANISMS OF PHASE FORMATION IN THE VITRIFICATION OF HIGH-FERROUS SAVANNAH RIVER SITE SB2 HLW SLUDGE SURROGATE - 9300

    SciTech Connect

    Marra, J

    2008-08-27

    Phase formation mechanisms associated with the vitrification of high-ferrous Savannah River Site (SRS) Sludge Batch 2 (SB2) high level waste surrogate were studied by infrared spectroscopy (IRS) and X-ray diffraction (XRD). Two mixtures at 50 wt% waste loading with commercially available Frit 320 (Li{sub 2}O - 8 wt %, B{sub 2}O{sub 3} - 8 wt %, Na{sub 2}O - 12 wt %, SiO{sub 2} - 72 wt %) and batch chemicals (LiOH {center_dot} H{sub 2}O, H{sub 3}BO{sub 3}, NaNO{sub 3}, SiO{sub 2}) to represent the frit formulation were prepared as slurries with a water content of {approx}50 wt%. The mixtures were air-dried at a temperature of 115 C and heat-treated at 500, 700, 900, 1000, 1100, 1200, and 1300 C for 1 hr at each temperature. Infrared spectra and XRD patterns of the products produced at each temperature were recorded. In both mixtures prepared using frit and batch chemicals to represent the frit, phase formation reactions were completed within the temperature range between 900 and 1000 C. However, residual quartz was still present in glass produced from the mixture with batch chemicals even at 1100 C. Although, the phase composition and structure of the glassy products obtained from both mixtures at temperatures over 1000 C were similar, the products obtained from the mixture using actual frit were more homogeneous than those from the mixture with batch chemicals. Thus, the use of frit rather than batch chemicals reduced the temperature range of phase formation and provided for production of higher quality glass.

  3. Formation mechanism of primary phases and eutectic structures within undercooled Pb-Sb-Sn ternary alloys

    NASA Astrophysics Data System (ADS)

    Wang, Weili; Dai, Fuping; Wei, Bingbo

    2007-08-01

    The solidification characteristics of three types of Pb-Sb-Sn ternary alloys with different primary phases were studied under substantial undercooling conditions. The experimental results show that primary (Pb) and SbSn phases grow in the dendritic mode, whereas primary (Sb) phase exhibits faceted growth in the form of polygonal blocks and long strips. (Pb) solid solution phase displays strong affinity with SbSn intermetallic compound so that they produce various morphologies of pseudobinary eutectics, but it can only grow in the divorced eutectic mode together with (Sb) phase. Although (Sb) solid solution phase and SbSn intermetallic compound may grow cooperatively within ternary eutectic microstructures, they seldom form pseudobinary eutectics independently. The (Pb)+(Sb)+SbSn ternary eutectic structure usually shows lamellar morphology, but appears as anomalous eutectic when its volume fraction becomes small. EDS analyses reveal that all of the three primary (Pb), (Sb) and SbSn phases exhibit conspicuous solute trapping effect during rapid solidification, which results in the remarkable extension of solute solubility.

  4. A solid-phase mechanism of shock-wave formation of dust particles of heavy metals

    NASA Astrophysics Data System (ADS)

    Lin, E. E.; Mikhailov, A. L.; Khvorostin, V. N.

    2016-08-01

    The possibility of formation of dust particles in solid as a result of shock-wave destruction of the initial crystalline material structure and subsequent coalescence of atomic clusters (nanoparticles), which leads to the aggregation of mesocrystalline particles (grains) in the shocked layer, is discussed.

  5. Synthesis of thermo-responsive polymers recycling aqueous two-phase systems and phase formation mechanism with partition of ε-polylysine.

    PubMed

    Xu, Chengning; Dong, Wenying; Wan, Junfen; Cao, Xuejun

    2016-11-11

    Aqueous two-phase systems (ATPS) have the potential application in bioseparation and biocatalysis engineering. In this paper, a recyclable ATPS was developed by two thermo-responsive copolymers, PVBAm and PN. Copolymer PVBAm was copolymerized using N-vinylcaprolactam, Butyl methacrylate and Acrylamide as monomers, and PN was synthesized by N-isopropylacrylamide. The lower critical solution temperature (LCST) of PVBAm and PN were 45.0°C and 33.5°C, respectively. The recoveries of both polymers could achieve over 95.0%. The phase behavior and formation mechanism of PVBAm/PN ATPS was studied. Low-field nuclear magnetic resonance (LF-NMR) was applied in the phase-forming mechanism study in ATPS. In addition, combining the analysis results of surface tension, transmission electron microscopy and dynamic light scattering, the phase-forming of the PVBAm/PN ATPS was proved. The application was performed by partition of ε-polylysine in the 2% PVBAm/2% PN (w/w) ATPS. The results demonstrated that ε-polylysine was extracted into the PN-rich phase, the maximal partition coefficient (1/K) and extraction recovery of pure ε-polylysine were 6.87 and 96.36%, respectively, and 7.41 partition coefficient and 97.85% extraction recovery for ε-polylysine fermentation broth were obtained in the presence of 50mM (NH4)2SO4 at room temperature. And this method can effectively remove the most impurities from fermentation broth when (NH4)2SO4 exists in the ATPS. It is believed that the thermo-responsive recycling ATPS has a good application prospect in the field of bio-separation.

  6. Phase formation and mechanical/tribological modification induced by nitrogen high temperature plasma based ion implantation into molybdenum

    NASA Astrophysics Data System (ADS)

    Carreri, F. C.; Oliveira, R. M.; Oliveira, A. C.; Silva, M. M. N. F.; Ueda, M.; Silva, M. M.; Pichon, L.

    2014-08-01

    Transition metal nitrides present high hardness, good wear resistance and chemical stability. The formation of a surface layer of these materials on different types of substrates can improve surface properties without changing bulk characteristics. Molybdenum is used in many technological applications and the search for ways to effectively improve its properties is justified. In this work nitrogen ions were implanted into molybdenum by means of high temperature plasma based ion implantation (HTPBII), in order to produce a layer of molybdenum nitride on the surface of the material. The treatment was performed in the temperature range of 800-1200 °C, for 1 h. X-ray diffraction spectra showed the presence of the cubic-Mo2N phase in most of the samples. The tetragonal-Mo2N phase was also observed, depending on treatment conditions. Glow discharge optical emission spectroscopy was used to study the composition and thickness of the nitride layer. A 12 μm thick Mo2N layer was observed for samples treated at 1100 °C, although beyond this temperature threshold, a significant amount of nitride can no longer be produced. In relation to the surface mechanical properties, a ninefold increase in surface hardness was obtained, as well as a decrease in the friction coefficient. Wear against an alumina ball was not observed.

  7. Diagenetic Microcrystalline Opal Varieties from the Monterey Formation, CA: HRTEM Study of Structures and Phase Transformation Mechanisms

    NASA Technical Reports Server (NTRS)

    Cady, Sherry L.; Wenk, H.-R.; DeVincenzi, Don (Technical Monitor)

    1994-01-01

    Microcrystalline opal varieties form as intermediary precipitates during the diagenetic transformation of biogenically precipitated non-crystalline opal (opal-A) to microquartz. With regard to the Monterey Formation of California, X-ray powder diffraction studies have shown that a decrease in the primary d-spacing of opal-CT toward that of cristobalite occurs with increasing diagenesis. The initial timing of opal-CT/quartz formation and the value of the primary opal-CT d-spacing, are influenced by the sediment. lithology. Transmission electron microscopy methods (CTEM/HRTEM) were used to investigate the structure of the diagenetic phases and establish transformation mechanisms between the varieties of microcrystalline opals in charts and porcelanites from the Monterey Formation. HRTEM images revealed that the most common fibrous varieties of microcrystalline opals contain varying amounts of structural disorder. Finite lamellar units of cristobalite-and tridymite-type. layer sequences were found to be randomly stacked in a direction perpendicular to the fiber axis. Disordered and ordered fibers were found to have coprecipitated within the same radial fiber bundles that formed within the matrix of the Most siliceous samples. HRTEM images, which reveal that the fibers within radial and lepispheric fiber bundles branch non-crystallographically, support an earlier proposal that microspheres in chert grow via a spherulitic growth mechanism. A less common variety of opal-CT was found to be characterized by non-parallel (low-angle) stacking sequences that often contain twinned lamellae. Tabular-shaped crystals of orthorhombic tridymite (PO-2) were also identified in the porcelanite samples. A shift in the primary d-spacing of opal-CT has been interpreted as an indication of solid-state ordering g toward a predominantly cristobalite structure, (opal-C). Domains of opal-C were identified as topotactically-oriented overgrowths on discrete Sections of opal-CT fibers and as

  8. Control of Y₂O₃ phase and its nanostructure formation through a very high energy mechanical milling

    SciTech Connect

    Lee, M.K.; Park, E.K.; Park, J.J.; Rhee, C.K.

    2013-05-01

    The formation behavior of Y₂O₃ ceramic particles was studied by employing a very high energy ball milling (milling energy: ~165 kJ/g·hit, milling speed: 1000 rpm). Both the XRD and HRTEM studies revealed that the high impact strain energy generated during the milling caused a drastic phase transition from the original C-type cubic (space group Ia3, a=10.58 Å) to the metastable B-type monoclinic (space group C2/m, a=13.89 Å), finally followed by a partial solid-state amorphization. The cubic phase was difficult to be reduced down to smaller than 10 nm, while the monoclinic phase was stabilized at sizes smaller than 10 nm with a mean crystallite size of 7.57 nm. Consequently, the existence of Y₂O₃ at a nanoscale smaller than 10 nm is possible by forming metastable monoclinic crystals, which are strain-induced. - Graphical abstract: The fig shows the solid-state phase formation of Y₂O₃ by very high energy input into the particles during milling: ordered body-centered cubic phase (space group Ia3, a=10.58 Å) nanocrystalline monoclinic phase (space group C2/m, a=13.89 Å) disordered monoclinic phase partial amorphous phase. The formation of Y₂O₃ smaller than 10 nm was strongly dependent on whether the phase transition from cubic to monoclinic occurred. Highlights: • This paper analyses very high energy milling behavior of coarse Y₂O₃ particles. • A drastic phase transition from cubic to monoclinic occurred with a partial amorphization. • An existence of Y₂O₃ smaller than 10 nm is possible by forming strain-induced monoclinic crystals.

  9. The α-Effect and Competing Mechanisms: The Gas-Phase Reactions of Microsolvated Anions with Methyl Formate

    NASA Astrophysics Data System (ADS)

    Thomsen, Ditte L.; Nichols, Charles M.; Reece, Jennifer N.; Hammerum, Steen; Bierbaum, Veronica M.

    2013-12-01

    The enhanced reactivity of α-nucleophiles, which contain an electron lone pair adjacent to the reactive site, has been demonstrated in solution and in the gas phase and, recently, for the gas-phase SN2 reactions of the microsolvated HOO-(H2O) ion with methyl chloride. In the present work, we continue to explore the significance of microsolvation on the α-effect as we compare the gas-phase reactivity of the microsolvated α-nucleophile HOO-(H2O) with that of microsolvated normal alkoxy nucleophiles, RO-(H2O), in reactions with methyl formate, where three competing reactions are possible. The results reveal enhanced reactivity of HOO-(H2O) towards methyl formate, and clearly demonstrate the presence of an overall α-effect for the reactions of the microsolvated α-nucleophile. The association of the nucleophiles with a single water molecule significantly lowers the degree of proton abstraction and increases the SN2 and BAC2 reactivity compared with the unsolvated analogs. HOO-(H2O) reacts with methyl formate exclusively via the BAC2 channel. While microsolvation lowers the overall reaction efficiency, it enhances the BAC2 reaction efficiency for all anions compared with the unsolvated analogs. This may be explained by participation of the solvent water molecule in the BAC2 reaction in a way that continuously stabilizes the negative charge throughout the reaction.

  10. Impacts of aqueous phase radical mechanism of oligomerization of methyl vinyl ketone (MVK) on SOA formation: on the prevailing role of dissolved oxygen

    NASA Astrophysics Data System (ADS)

    Renard, P.; Ervens, B.; Siekmann, F.; Vassalo, L.; Ravier, S.; Clement, J.; Monod, A.

    2012-12-01

    It is now recognized that the aqueous phase photochemistry of organic compounds in cloud droplets and deliquescent aerosol particles lead to the formation of oligomers and thus it might produce a substantial amount of atmospheric Secondary Organic Aerosol (SOA) with unique properties. However, the chemical mechanisms leading to these oligomers are still poorly understood, and consequently, their atmospheric impacts are difficult to assess. The goal of this study was to investigate the atmospheric impact of an aqueous phase radical mechanism of oligomerization of methyl vinyl ketone (MVK: one of the main reaction products of isoprene) on SOA formation. Aqueous phase photooxidation of MVK was investigated in a photoreactor using photolysis of H2O2 as OH radical generator. Electrospray high resolution mass spectrometry analysis of the solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1800 Da within less than 15 minutes of reaction. Highest oligomer formation rates were obtained under conditions of low dissolved oxygen, highest temperature and highest MVK initial concentrations. A radical mechanism of polymerization is proposed to explain this oligomer formation. Furthermore, we quantified the total amount of carbon present in oligomers, and the initial radical branching ratios. Kinetic parameters of the proposed oligomerization mechanism are constrained by means of a box model that is able to reproduce the temporal evolution of intermediates and products as observed in the laboratory experiments. Additional model simulations for atmospherically-relevant conditions will be presented that show the extent to which these radical processes contribute to SOA formation in the multiphase system as compared to other aqueous phase as well as traditional SOA sources.

  11. Release of gas-phase halogens by photolytic generation of OH in frozen halide-nitrate solutions: an active halogen formation mechanism?

    PubMed

    Abbatt, J; Oldridge, N; Symington, A; Chukalovskiy, V; McWhinney, R D; Sjostedt, S; Cox, R A

    2010-06-17

    To better define the mechanisms by which condensed-phase halides may be oxidized to form gas-phase halogens under polar conditions, experiments have been conducted whereby frozen solutions containing chloride (1 M), bromide (1.6 x 10(-3) to 5 x 10(-2) M), iodide (<1 x 10(-5) M), and nitrate (0.01 to 1 M) have been illuminated by ultraviolet light in a continually flushed cell. Gas-phase products are quantified using chemical ionization mass spectrometry, and experiments were conducted at both 248 and 263 K. Br(2) was the dominant product, along with smaller yields of IBr and trace BrCl and I(2). The Br(2) yields were largely independent of the Br(-)/Cl(-) ratio of the frozen solution, down to seawater composition. However, the yields of halogens were strongly dependent on the levels of NO(3)(-) and acidity in solution, consistent with a mechanism whereby NO(3)(-) photolysis yields OH that oxidizes the condensed-phase halides. In support, we observed the formation of gas-phase NO(2), formed simultaneously with OH. Gas-phase HONO was also observed, suggesting that halide oxidation by HONO in the condensed phase may also occur to some degree. By measuring the production rate of condensed-phase OH, using benzoic acid as a radical trap, we determine that the molar yield of Br(2) formation relative to OH generation is 0.6, consistent with each OH being involved in halide oxidation. These studies suggest that gas-phase halogen formation should occur simultaneously with NO(x) release from frozen sea ice and snow surfaces that contain sufficient halides and deposited nitrate.

  12. Effects of sigma-phase formation on some mechanical properties of a wrought nickel-base superalloy (IN-100)

    NASA Technical Reports Server (NTRS)

    Dreshfield, R. L.; Ashbrook, R. L.

    1974-01-01

    The effect of sigma phase formation on an extruded and forged nickel base superalloy with the composition of the casting alloy IN-100 was studied. By adding only aluminum and titanium to remelt stock, three compositions were produced which had varying propensities for sigma formation. These compositions were given a four step heat treatment and were stress-ruptured or tensile tested. The very sigma prone composition had a shorter rupture life than the sigma-free or moderately sigma prone compositions when tested at 843 and 885 C. Elongation in room temperature tensile tests was considerably lower for the very sigma prone composition than for the other two wrought compositions after prolonged exposure at 732 or 843 C.

  13. Simulation of aromatic SOA formation using the lumping model integrated with explicit gas-phase kinetic mechanisms and aerosol-phase reactions

    NASA Astrophysics Data System (ADS)

    Im, Y.; Jang, M.; Beardsley, R. L.

    2013-03-01

    The Unified Partitioning-Aerosol phase Reaction (UNIPAR) model has been developed to predict the secondary organic aerosol (SOA) formation through multiphase reactions. An explicit gas-kinetic model was employed to express gas-phase oxidation of aromatic hydrocarbons. Gas-phase products are grouped based on volatility (6 levels) and reactivity (5 levels) and used to construct the stoichiometric coefficients (αi,j) matrix, the set of parameters used to describe the concentrations of organic compounds in multiphase. Weighting of the αi,j matrix as a function of NOx improved the evaluation of NOx effects on SOA. The total amount of organic matter (OMT) is predicted by two modules in the UNIPAR model: OMP by a partitioning process and OMAR by aerosol-phase reactions. OMP is estimated using the SOA partitioning model that has been used in a regional air quality model (CMAQ 5.0.1). OMAR predicts multiphase reactions of organic compounds, such as oligomerization, acid-catalyzed reactions, and organosulfate (OS) formation. The model was evaluated with the SOA data produced from the photooxidation of toluene and 1,3,5-trimethylbenzene using an outdoor reactor (UF-APHOR chamber). The model reasonably simulates SOA formation under various aerosol acidities, NOx concentrations, humidities and temperatures. Furthermore, the OS fraction in the SOA predicted by the model was in good agreement with the experimentally measured OS fraction.

  14. Formation mechanism of superconducting phase and its three-dimensional architecture in pseudo-single-crystal KxFe2-ySe2

    DOE PAGES

    Liu, Yong; Xing, Qingfeng; Straszheim, Warren E.; ...

    2016-02-11

    Here, we report how the superconducting phase forms in pseudo-single-crystal KxFe2-ySe2. In situ scanning electron microscopy (SEM) observation reveals that, as an order-disorder transition occurs, on cooling, most of the high-temperature iron-vacancy-disordered phase gradually changes into the iron-vacancy-ordered phase whereas a small quantity of the high-temperature phase retains its structure and aggregates to the stripes with more iron concentration but less potassium concentration compared to the iron-vacancy-ordered phase. The stripes that are generally recognized as the superconducting phase are actually formed as a remnant of the high-temperature phase with a compositional change after an “imperfect” order-disorder transition. It should bemore » emphasized that the phase separation in pseudo-single-crystal KxFe2-ySe2 is caused by the iron-vacancy order-disorder transition. The shrinkage of the high-temperature phase and the expansion of the newly created iron-vacancy-ordered phase during the phase separation rule out the mechanism of spinodal decomposition proposed in an early report [Wang et al, Phys. Rev. B 91, 064513 (2015)]. Since the formation of the superconducting phase relies on the occurrence of the iron-vacancy order-disorder transition, it is impossible to synthesize a pure superconducting phase by a conventional solid state reaction or melt growth. By focused ion beam-scanning electron microscopy, we further demonstrate that the superconducting phase forms a contiguous three-dimensional architecture composed of parallelepipeds that have a coherent orientation relationship with the iron-vacancy-ordered phase.« less

  15. Simulation of aromatic SOA formation using the lumping model integrated with explicit gas-phase kinetic mechanisms and aerosol-phase reactions

    NASA Astrophysics Data System (ADS)

    Im, Y.; Jang, M.; Beardsley, R. L.

    2014-04-01

    The Unified Partitioning-Aerosol phase Reaction (UNIPAR) model has been developed to predict the secondary organic aerosol (SOA) formation through multiphase reactions. The model was evaluated with aromatic SOA data produced from the photooxidation of toluene and 1,3,5-trimethylbenzene (135-TMB) under various concentrations of NOx and SO2 using an outdoor reactor (University of Florida Atmospheric PHotochemical Outdoor Reactor (UF-APHOR) chamber). When inorganic species (sulfate, ammonium and water) are present in aerosol, the prediction of both toluene SOA and 135-TMB SOA, in which the oxygen-to-carbon (O : C) ratio is lower than 0.62, are approached under the assumption of a complete organic/electrolyte-phase separation below a certain relative humidity. An explicit gas-kinetic model was employed to express gas-phase oxidation of aromatic hydrocarbons. Gas-phase products are grouped based on their volatility (6 levels) and reactivity (5 levels) and exploited to construct the stoichiometric coefficient (αi,j) matrix, the set of parameters used to describe the concentrations of organic compounds in multiphase. Weighting of the αi,j matrix as a function of NOx improved the evaluation of NOx effects on aromatic SOA. The total amount of organic matter (OMT) is predicted by two modules in the UNIPAR model: OMP by a partitioning process and OMAR by aerosol-phase reactions. The OMAR module predicts multiphase reactions of organic compounds, such as oligomerization, acid-catalyzed reactions, and organosulfate (OS) formation. The model reasonably simulates SOA formation under various aerosol acidities, NOx concentrations, humidities and temperatures. Furthermore, the OS fractions in the SOA predicted by the model were in good agreement with the experimentally measured OS fractions.

  16. Mechanism of GEMS formation

    SciTech Connect

    Bradley, J P; Dai, Z R

    2004-03-10

    GEMS (glass with embedded metal and sulfides) in interplanetary dust particles (IDPs) were examined using 200 keV analytical transmission electron microscopy. The morphologies and crystallography of embedded relict grains reveal that GEMS are pseudomorphs formed by irradiation processing of crystals free-floating in space. Some GEMS retain a compositional and morphological ''memory'' of the crystal from which they formed. Pseudomorphism rules out condensation, annealing, flash heating, or shock melting as alternative mechanisms of GEMS formation. A significant and often dominant fraction of the atoms in GEMS were sputtered deposited from other grains. Therefore, a normal (solar) isotopic composition is not a reliable indicator of whether GEMS formed in the solar system or in presolar interstellar or circumstellar environments.

  17. Mechanistic Studies Of Combustion And Structure Formation During Combustion Synthesis Of Advanced Materials: Phase Separation Mechanism For Bio-Alloys

    NASA Technical Reports Server (NTRS)

    Varma, A.; Lau, C.; Mukasyan, A.

    2003-01-01

    Among all implant materials, Co-Cr-Mo alloys demonstrate perhaps the most useful balance of resistance to corrosion, fatigue and wear, along with strength and biocompatibility [1]. Currently, these widely used alloys are produced by conventional furnace technology. Owing to high melting points of the main alloy elements (e.g. Tm.p.(Co) 1768 K), high-temperature furnaces and long process times (several hours) are required. Therefore, attempts to develop more efficient and flexible methods for production of such alloys with superior properties are of great interest. The synthesis of materials using combustion phenomena is an advanced approach in powder metallurgy [2]. The process is characterized by unique conditions involving extremely fast heating rates (up to 10(exp 6 K/s), high temperatures (up to 3500 K), and short reaction times (on the order of seconds). As a result, combustion synthesis (CS) offers several attractive advantages over conventional metallurgical processing and alloy development technologies. The foremost is that solely the heat of chemical reaction (instead of an external source) supplies the energy for the synthesis. Also, simple equipment, rather than energy-intensive high-temperature furnaces, is sufficient. This work was devoted to experiments on CS of Co-based alloys by utilizing thermite (metal oxide-reducing metal) reactions, where phase separation subsequently produces materials with tailored compositions and properties. Owing to high reaction exothermicity, the CS process results in a significant increase of temperature (up to 3000 C), which is higher than melting points of all products. Since the products differ in density, phase separation may be a gravitydriven process: the heavy (metallic phase) settles while the light (slag) phase floats. The goal was to determine if buoyancy is indeed the major mechanism that controls phase segregation.

  18. Phase Field Fracture Mechanics.

    SciTech Connect

    Robertson, Brett Anthony

    2015-11-01

    For this assignment, a newer technique of fracture mechanics using a phase field approach, will be examined and compared with experimental data for a bend test and a tension test. The software being used is Sierra Solid Mechanics, an implicit/explicit finite element code developed at Sandia National Labs in Albuquerque, New Mexico. The bend test experimental data was also obtained at Sandia Labs while the tension test data was found in a report online from Purdue University.

  19. Ion yields for some salts in MALDI: mechanism for the gas-phase ion formation from preformed ions.

    PubMed

    Moon, Jeong Hee; Shin, Young Sik; Bae, Yong Jin; Kim, Myung Soo

    2012-01-01

    Preformed ion emission is the main assumption in one of the prevailing theories for peptide and protein ion formation in matrix-assisted laser desorption ionization (MALDI). Since salts are in preformed ion forms in the matrix-analyte mixture, they are ideal systems to study the characteristics of preformed ion emission. In this work, a reliable method to measure the ion yield (IY) in MALDI was developed and used for a solid salt benzyltriphenylphosphonium chloride and two room-temperature ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate and trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate. IY for the matrix (α-cyano-4-hydroxycinnamic acid, CHCA) was also measured. Taking 1 pmol salts in 25 nmol CHCA as examples, IYs for three salts were similar, (4-8) × 10(-4), and those for CHCA were (0.8-1.2) × 10(-7). Even though IYs for the salts and CHCA remained virtually constant at low analyte concentration, they decreased as the salt concentrations increased. Two models, Model 1 and Model 2, were proposed to explain low IYs for the salts and the concentration dependences. Both models are based on the fact that the ion-pair formation equilibrium is highly shifted toward the neutral ion pair. In Model 1, the gas-phase analyte cations were proposed to originate from the same cations in the solid that were dielectrically screened from counter anions by matrix neutrals. In Model 2, preformed ions were assumed to be released from the solid sample in the form of neutral ion pairs and the anions in the ion pairs were assumed to be eliminated via reactions with matrix-derived cations.

  20. Deformation-phase transformation coupling mechanism of white layer formation in high speed machining of FGH95 Ni-based superalloy

    NASA Astrophysics Data System (ADS)

    Du, Jin; Liu, zhanqiang; Lv, Shaoyu

    2014-02-01

    Ni-based superalloy represents a significant metal portion of the aircraft critical structural and engine components. When these critical structural components in aerospace industry are manufactured with the objective to reach high reliability levels and excellent service performance, surface integrity is one of the most relevant parameter used for evaluating the quality of finish machined surfaces. In the study of surface integrity, the formation white layer is a very important research topic. The formation of white layer on the Ni-based superalloy machined surface will reduce the machined parts service performance and fatigue life. This paper was conducted to determine the effects of cutting speed on white layer formation in high speed machining of FGH95 Ni-based superalloy. Optical microscope, scanning electron microscope and X-ray diffraction were employed to analyze the elements and microstructures of white layer and bulk materials. The statistical analysis for grain numbers was executed to study the influence of cutting speed on the grain refinement in the machined surface. The investigation results showed that white layer exhibits significantly different microstructures with the bulk materials. It shows densification, no obvious structural features characteristic. The microstructure and phase of Ni-based solid solution changed during cutting process. The increase of cutting speed causes the increase of white layer thickness when the cutting speed is less than 2000 m/min. However, white layer thickness reduces with the cutting speed further increase. The higher the cutting speed, the more serious grains refinement in machined surface. 2-D FEM for machining FGH95 were carried out to simulate the cutting process and obtained the cutting temperature field, cutting strain field and strain rate field. The impact mechanisms of cutting temperature, cutting strain and strain rates on white layer formation were analyzed. At last, deformation-phase transformation

  1. Effect of Calendula officinalis Flower Extract on Acute Phase Proteins, Antioxidant Defense Mechanism and Granuloma Formation During Thermal Burns

    PubMed Central

    Chandran, Preethi K.; Kuttan, Ramadasan

    2008-01-01

    Effect of Calendula officinalis flower extract was investigated against experimentally induced thermal burns in rats. Burn injury was made on the shaven back of the rats under anesthesia and the animals were treated orally with different doses of the flower extract (20 mg, 100 mg and 200 mg/kg body weight). The animals treated with the extract showed significant improvement in healing when compared with the control untreated animals. The indicators of the wound healing such as collagen-hydroxyproline and hexosamine contents were significantly increased in the treated group indicating accelerated wound healing in the treated animals. The acute phase proteins—haptoglobin and orosomucoid which were increased due to burn injury were found to be decreased significantly in 200 mg/kg body weight extract treated animals. The antioxidant defense mechanism, which was decreased in the liver during burn injury, was found to be enhanced in treated animals. The lipid peroxidation was significantly lowered in the treated group when compared to control animals. Tissue damage marker enzymes- alkaline phosphatase, alanine and aspartate transaminases were significantly lowered in the treated groups in a dose dependant manner. The histopathological analyses of skin tissue also give the evidence of the increased healing potential of the extract after burn injury. PMID:18818737

  2. Formation mechanism of calcium hexaluminate

    NASA Astrophysics Data System (ADS)

    Chen, Jun-hong; Chen, Hai-yang; Yan, Ming-wei; Cao, Zheng; Mi, Wen-jun

    2016-10-01

    To investigate the formation mechanism of calcium hexaluminate (CaAl12O19, CA6), the analytically pure alumina and calcia used as raw materials were mixed in CaO/Al2O3 ratio of 12.57:137.43 by mass. The raw materials were ball-milled and shaped into green specimens, and fired at 1300-1600°C. Then, the phase composition and microstructure evolution of the fired specimen were studied, and a first principle calculation was performed. The results show that in the reaction system of CaO and Al2O3, a small amount of CA6 forms at 1300°C, and greater amounts are formed at 1400°C and higher temperatures. The reaction is as follows: CaO·2Al2O3 (CA2) + 4Al2O3 → CA6. The diffusions of Ca2+ in CA2 towards Al2O3 and Al3+ in Al2O3 towards CA2 change the structures in different degrees of difficulty. Compared with the difficulty of structural change and the corresponding lattice energy change, it is deduced that the main formation mechanism is the diffusion of Ca2+ in CA2 towards Al2O3.

  3. Kinetics and Mechanisms of Cr(VI) Formation via the Oxidation of Cr(III) Solid Phases by Chlorine in Drinking Water.

    PubMed

    Chebeir, Michelle; Liu, Haizhou

    2016-01-19

    Hexavalent chromium Cr(VI), typically existing as the oxyanion form of CrO4(2-), is being considered for more stringent drinking water standards by regulatory agencies. Cr(VI) can be inadvertently produced via the oxidation of trivalent chromium Cr(III) solids. This study investigated the kinetics and mechanisms of Cr(III) solids oxidation by chlorine in drinking water and associated Cr(VI) formation. Batch experiments were carried out with three Cr(III) solids of environmental relevance, i.e., chromium hydroxide Cr(OH)3(s), chromium oxide Cr2O3(s), and copper chromite Cu2Cr2O5(s). Impacts of water chemical parameters including pH (6.0-8.5) and bromide concentration (0-5 mg/L) were examined. Results showed that the rapid oxidation of Cr(III) solid phases by chlorine was accompanied by Cr(VI) formation and an unexpected production of dissolved oxygen. Analysis of reaction stoichiometry indicated the existence of Cr intermediate species that promoted the autocatalytic decay of chlorine. An increase in pH modestly enhanced Cr(VI) formation due to changes of reactive Cr(III) surface hydroxo species. Bromide, a trace chemical constituent in source waters, exhibited a catalytic effect on Cr(VI) formation due to an electron shuttle mechanism between Cr(III) and chlorine and the bypass of Cr intermediate formation. The kinetics data obtained from this study suggest that the oxidation of Cr(III) solids by chlorine in water distribution systems can contribute to Cr(VI) occurrence in tap water, especially in the presence of a trace level of bromide.

  4. Comparison of experimental approaches to study selective properties of thick phase-amplitude holograms recorded in materials with diffusion-based formation mechanisms

    NASA Astrophysics Data System (ADS)

    Borisov, Vladimir; Klepinina, Mariia; Veniaminov, Andrey; Angervaks, Aleksandr; Shcheulin, Aleksandr; Ryskin, Aleksandr

    2016-04-01

    Volume holographic gratings, both transmission and reflection-type, may be employed as one-dimensional pho- tonic crystals. More complex two- and three-dimensional holographic photonic-crystalline structures can be recorded using several properly organized beams. As compared to colloidal photonic crystals, their holographic counterparts let minimize distortions caused by multiple inner boundaries of the media. Unfortunately, it's still hard to analyze spectral response of holographic structures. This work presents the results of thick holographic gratings analysis based on spectral-angular selectivity contours approximation. The gratings were recorded in an additively colored fluorite crystal and a glassy polymer doped with phenanthrenequinone (PQ-PMMA). The two materials known as promising candidates for 3D diffraction optics including photonic crystals, employ diffusion-based mechanisms of grating formation. The surfaces of spectral-angular selectivity were obtained in a single scan using a white-light LED, rotable table and a matrix spectrometer. The data expressed as 3D plots make apparent visual estimation of the grating phase/amplitude nature, noninearity of recording, etc., and provide sufficient information for numerical analysis. The grating recorded in the crystal was found to be a mixed phase-amplitude one, with different contributions of refractive index and absorbance modulation at different wavelengths, and demonstrated three diffraction orders corresponding to its three spatial harmonics originating from intrinsically nonlinear diffusion-drift recording mechanism. Contrastingly, the grating in the polymeric medium appeared purely phase and linearly recorded.

  5. Formation mechanism of axial macrosegregation of primary phases induced by a static magnetic field during directional solidification

    PubMed Central

    Li, Xi; Fautrelle, Yves; Ren, Zhongming; Moreau, Rene

    2017-01-01

    Understanding the macrosegregation formed by applying magnetic fields is of high commercial importance. This work investigates how static magnetic fields control the solute and primary phase distributions in four directionally solidified alloys (i.e., Al-Cu, Al-Si, Al-Ni and Zn-Cu alloys). Experimental results demonstrate that significant axial macrosegregation of the solute and primary phases (i.e., Al2Cu, Si, Al3Ni and Zn5Cu phases) occurs at the initial solidification stage of the samples. This finding is accompanied by two interface transitions in the mushy zone: quasi planar → sloping → quasi planar. The amplitude of the macrosegregation of the primary phases under the magnetic field is related to the magnetic field intensity, temperature gradient and growth speed. The corresponding numerical simulations present a unidirectional thermoelectric (TE) magnetic convection pattern in the mushy zone as a consequence of the interaction between the magnetic field and TE current. Furthermore, a model is proposed to explain the peculiar macrosegregation phenomenon by considering the effect of the forced TE magnetic convection on the solute distribution. The present study not only offers a new approach to control the solute distribution by applying a static magnetic field but also facilitates the understanding of crystal growth in the solute that is controlled by the static magnetic field during directional solidification. PMID:28367991

  6. Analysis of interface formation mechanism in GaN double-polarity selective-area growth by metalorganic vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Kuze, Kenta; Osumi, Noriyuki; Fujita, Yohei; Inoue, Yoku; Nakano, Takayuki

    2016-05-01

    The fabrication of quasi-phase-matching (QPM) crystals by selective-area growth on the two asymmetrically polar surfaces of GaN is examined. We attempted the fabrication of GaN-QPM crystals by one-time growth using a carbon mask. For GaN double-polarity selective-area growth (DP-SAG), we investigated the effect of varied nitriding times of the Al2O3 templates patterned with the carbon mask. We optimized the nitriding conditions for the DP-SAG process, and evaluated the substrate fabricated by the optimized DP-SAG process. In addition, we examined the interface formation mechanism of DP-GaN fabricated by GaN DP-SAG process. We determined that it is possible to fabricate DP-GaN with a sharp interface by optimizing the growth conditions.

  7. Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

    NASA Astrophysics Data System (ADS)

    Marais, E. A.; Jacob, D. J.; Jimenez, J. L.; Campuzano-Jost, P.; Day, D. A.; Hu, W.; Krechmer, J.; Zhu, L.; Kim, P. S.; Miller, C. C.; Fisher, J. A.; Travis, K.; Yu, K.; Hanisco, T. F.; Wolfe, G. M.; Arkinson, H. L.; Pye, H. O. T.; Froyd, K. D.; Liao, J.; McNeill, V. F.

    2016-02-01

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx ≡ NO + NO2) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation), but decrease more strongly as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US Environmental Protection Agency (EPA) projects 2013-2025 decreases in anthropogenic emissions of

  8. Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

    EPA Science Inventory

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for...

  9. Mechanism of polymer nanoparticle formation by nanoprecipitation

    NASA Astrophysics Data System (ADS)

    Zhao, Chen; Li, Tingting; van Keuren, Edward

    Nanoprecipitation method is a simple and convenient way to produce nanoparticles from polymers in solution. The control of nanoparticle size and size distribution plays a pivotal role in the use of nanoprecipitation for drug delivery. We investigated various factors and initial conditions that affect the particle size, such as the initial solute concentration, solvent/non-solvent ratio and the molecular weight of the polymer samples. The results shed light on the mechanisms of particle formation and phase separation which occurs in nanoprecipitation. Spinodal decomposition, which takes place as a result of a quench to a sufficiently high supersaturation, is believed to be the main mechanism that governs the phase separation. In addition, the glass transition of the polymers will also be a key factor that contributes to the thermodynamics and kinetics of the phase separation and the resulting particle size and morphology.

  10. Geometric phase in Bohmian mechanics

    SciTech Connect

    Chou, Chia-Chun; Wyatt, Robert E.

    2010-10-15

    Using the quantum kinematic approach of Mukunda and Simon, we propose a geometric phase in Bohmian mechanics. A reparametrization and gauge invariant geometric phase is derived along an arbitrary path in configuration space. The single valuedness of the wave function implies that the geometric phase along a path must be equal to an integer multiple of 2{pi}. The nonzero geometric phase indicates that we go through the branch cut of the action function from one Riemann sheet to another when we locally travel along the path. For stationary states, quantum vortices exhibiting the quantized circulation integral can be regarded as a manifestation of the geometric phase. The bound-state Aharonov-Bohm effect demonstrates that the geometric phase along a closed path contains not only the circulation integral term but also an additional term associated with the magnetic flux. In addition, it is shown that the geometric phase proposed previously from the ensemble theory is not gauge invariant.

  11. Structure and mechanism of the formation of core–shell nanoparticles obtained through a one-step gas-phase synthesis by electron beam evaporation

    PubMed Central

    Bardakhanov, Sergey P; Schreiber, Makoto; Bazarova, Dashima G; Romanov, Nikolai A; Baldanov, Boris B; Radnaev, Bair R; Syzrantsev, Viacheslav V

    2015-01-01

    Summary The structure of core–shell Cu@silica and Ag@Si nanoparticles obtained in one-step through evaporation of elemental precursors by a high-powered electron beam are investigated. The structure of the core and shell of the particles are investigated in order to elucidate their mechanisms of formation and factors affecting the synthesis. It is proposed that the formation of Cu@silica particles is mainly driven by surface tension differences between Cu and Si while the formation of Ag@Si particles is mainly driven by differences in the vapour concentration of the two components. PMID:25977857

  12. Structure and mechanism of the formation of core-shell nanoparticles obtained through a one-step gas-phase synthesis by electron beam evaporation.

    PubMed

    Nomoev, Andrey V; Bardakhanov, Sergey P; Schreiber, Makoto; Bazarova, Dashima G; Romanov, Nikolai A; Baldanov, Boris B; Radnaev, Bair R; Syzrantsev, Viacheslav V

    2015-01-01

    The structure of core-shell Cu@silica and Ag@Si nanoparticles obtained in one-step through evaporation of elemental precursors by a high-powered electron beam are investigated. The structure of the core and shell of the particles are investigated in order to elucidate their mechanisms of formation and factors affecting the synthesis. It is proposed that the formation of Cu@silica particles is mainly driven by surface tension differences between Cu and Si while the formation of Ag@Si particles is mainly driven by differences in the vapour concentration of the two components.

  13. Possible mechanisms of macrolayer formation

    SciTech Connect

    Sadasivan, P.; Chappidi, P.R.; Unal, C.; Nelson, R.A.

    1992-05-01

    The high heat flux nucleate boiling region, also called the vapor mushroom region, has been shown to have a thin liquid layer on the heater surface under the large mushroom-shaped vapor bubbles that grow from the heater surface. The name given to this liquid layer is the macrolayer to differentiate it from the microlayer that exists under the discrete bubbles found at lower heat fluxes in the nucleate boiling region. Typical thicknesses of this macrolayer range from 50 to 500 {mu}m for water on a flat horizontal boiling surface and depend upon the heat flux. Thus, the macrolayer is thicker than the wedge-shaped microlayers, found under discrete bubbles, which range in thickness from 1 to 10 {mu}m. Although the mechanism of microlayer formation and its evaporation is conceptually simple that of the macrolayer is still not understood. This paper critically compares the potential mechanisms proposed for macrolayer formation. These mechanisms include the Helmholtz instability applied to the vapor stem above active nucleation sites, liquid trapped by lateral coalescence of discrete bubbles that initially form during the mushroom bubble`s waiting period, and the limitation of liquid resupply at mushroom departure as a result of vapor flow from the active nucleation sites.

  14. Possible mechanisms of macrolayer formation

    SciTech Connect

    Sadasivan, P.; Chappidi, P.R.; Unal, C.; Nelson, R.A.

    1992-01-01

    The high heat flux nucleate boiling region, also called the vapor mushroom region, has been shown to have a thin liquid layer on the heater surface under the large mushroom-shaped vapor bubbles that grow from the heater surface. The name given to this liquid layer is the macrolayer to differentiate it from the microlayer that exists under the discrete bubbles found at lower heat fluxes in the nucleate boiling region. Typical thicknesses of this macrolayer range from 50 to 500 {mu}m for water on a flat horizontal boiling surface and depend upon the heat flux. Thus, the macrolayer is thicker than the wedge-shaped microlayers, found under discrete bubbles, which range in thickness from 1 to 10 {mu}m. Although the mechanism of microlayer formation and its evaporation is conceptually simple that of the macrolayer is still not understood. This paper critically compares the potential mechanisms proposed for macrolayer formation. These mechanisms include the Helmholtz instability applied to the vapor stem above active nucleation sites, liquid trapped by lateral coalescence of discrete bubbles that initially form during the mushroom bubble's waiting period, and the limitation of liquid resupply at mushroom departure as a result of vapor flow from the active nucleation sites.

  15. New phase formation in titanium aluminide during chemical etching

    SciTech Connect

    Takasaki, Akito; Ojima, Kozo; Taneda, Youji . Dept. of Mathematics and Physics)

    1994-05-01

    A chemical etching technique is widely used for metallographic observation. Because this technique is based on a local corrosion phenomenon on a sample, the etching mechanism, particularly for two-phase alloys, can be understood by electrochemical consideration. This paper describes formation of a new phase in a Ti-45Al (at.%) titanium aluminide during chemical etching, and the experimental results are discussed electrochemically.

  16. Formation mechanisms of metal colloids

    NASA Astrophysics Data System (ADS)

    Halaciuga, Ionel

    Highly dispersed uniform metallic particles are widely used in various areas of technology and medicine and are likely to be incorporated into many other applications in the future. It is commonly accepted that size, shape and composition of the particles represent critical factors in most applications. Thus, understanding the mechanisms of formation of metal particles and the ways to control the physical (e.g. shape, size) and chemical (e.g. composition) properties is of great importance. In the current research, the formation of uniform silver spheres is investigated experimentally. The parameters that influence the formation of silver particles when concentrated iso-ascorbic acid and silver-polyamine complex solutions are rapidly mixed were studied in the absence of dispersants. We found that by varying the nature of the amine, temperature, concentration of reactants, silver/amine molar ratio, and the nature of the silver salt, the size of the resulting silver particles can be varied in a wide range (0.08--1.5 microm). The silver particles were formed by aggregation of nanosize subunits as substantiated by both electron microscopy and X-ray diffraction techniques and by the vivid rapid color changes during the chemical precipitation process. From the practical standpoint, the goal of this research was to prepare well dispersed spherical silver particles having a relatively smooth surface and a diameter of about 1 microm to satisfy the demands of the current electronic materials market. A two stage particle growth model previously developed to explain the narrow size distribution occurring in synthesis of gold spheres was applied to the present experimental system, and the parameters that control the size distribution characteristics were identified. The kinetic parameter required to match the final particle size was found to be in agreement with the one used previously in modeling formation of gold spheres, suggesting that similar kinetics governs the

  17. Shape without Structure: An Intriguing Formation Mechanism in the Solvothermal Synthesis of the Phase-Change Material Sb2 Te3.

    PubMed

    Saltzmann, Tobias; Bornhöfft, Manuel; Mayer, Joachim; Simon, Ulrich

    2015-05-26

    We introduce a novel solvothermal synthesis of individual single crystalline Sb2 Te3 micro- and nanocrystals as a model material for phase-change switching. We identified different intermediates along the reaction path to the final Sb2 Te3 hexagonal platelets (HPs) and discuss their forming mechanism. By means of nanodiffraction (ND) in a scanning transmission electron microscope we demonstrate that the intermediates follow a hexagonal shape evolution in the amorphous state. In situ nanomanipulator measurements reveal electrical phase-change switching properties of the individual Sb2 Te3 hexagonal platelets.

  18. Geometrical Phases in Quantum Mechanics

    NASA Astrophysics Data System (ADS)

    Christian, Joy Julius

    In quantum mechanics, the path-dependent geometrical phase associated with a physical system, over and above the familiar dynamical phase, was initially discovered in the context of adiabatically changing environments. Subsequently, Aharonov and Anandan liberated this phase from the original formulation of Berry, which used Hamiltonians, dependent on curves in a classical parameter space, to represent the cyclic variations of the environments. Their purely quantum mechanical treatment, independent of Hamiltonians, instead used the non-trivial topological structure of the projective space of one-dimensional subspaces of an appropriate Hilbert space. The geometrical phase, in their treatment, results from a parallel transport of the time-dependent pure quantum states along a curve in this space, which is endowed with an abelian connection. Unlike Berry, they were able to achieve this without resort to an adiabatic approximation or to a time-independent eigenvalue equation. Prima facie, these two approaches are conceptually quite different. After a review of both approaches, an exposition bridging this apparent conceptual gap is given; by rigorously analyzing a model composite system, it is shown that, in an appropriate correspondence limit, the Berry phase can be recovered as a special case from the Aharonov-Anandan phase. Moreover, the model composite system is used to show that Berry's correction to the traditional Born-Oppenheimer energy spectra indeed brings the spectra closer to the exact results. Then, an experimental arrangement to measure geometrical phases associated with cyclic and non-cyclic variations of quantum states of an entangled composite system is proposed, utilizing the fundamental ideas of the recently opened field of two-particle interferometry. This arrangement not only resolves the controversy regarding the true nature of the phases associated with photon states, but also unequivocally predicts experimentally accessible geometrical phases in a

  19. Gas-Phase Infrared; JCAMP Format

    National Institute of Standards and Technology Data Gateway

    SRD 35 NIST/EPA Gas-Phase Infrared; JCAMP Format (PC database for purchase)   This data collection contains 5,228 infrared spectra in the JCAMP-DX (Joint Committee for Atomic and Molecular Physical Data "Data Exchange") format.

  20. Structure Formation Mechanisms during Solid Ti with Molten Al Interaction

    NASA Astrophysics Data System (ADS)

    Gurevich, L.; Pronichev, D.; Trunov, M.

    2016-02-01

    The study discuses advantages and disadvantages of previously proposed mechanisms of the formation of structure between solid Ti and molten Al and presents a new mechanism based on the reviewed and experimental data. The previously proposed mechanisms were classified into three groups: mechanisms of precipitation, mechanisms of destruction and mechanisms of chemical interaction between intermetallics and melt. The reviewed mechanisms did not explain the formation of heterogeneous interlayer with globular aluminide particles and thin layers of pure Al, while the present study reveals variation in the solid Ti/molten Al reaction kinetics during various phases of laminated metal-intermetallic composite formation. The proposed mechanism considers formed during composite fabrication thin oxide interlayers between Ti and Al evolution and its impact on the intermetallic compound formation and explains the initial slow rate of intermetallic interlayer formation and its subsequent acceleration when the oxide foils are ruptured.

  1. Study of Formation Mechanisms of Gas Hydrate

    NASA Astrophysics Data System (ADS)

    Yang, Jia-Sheng; Wu, Cheng-Yueh; Hsieh, Bieng-Zih

    2015-04-01

    Gas hydrates, which had been found in subsurface geological environments of deep-sea sediments and permafrost regions, are solid crystalline compounds of gas molecules and water. The estimated energy resources of hydrates are at least twice of that of the conventional fossil fuel in the world. Gas hydrates have a great opportunity to become a dominating future energy. In the past years, many laboratory experiments had been conducted to study chemical and thermodynamic characteristics of gas hydrates in order to investigate the formation and dissociation mechanisms of hydrates. However, it is difficult to observe the formation and dissociation of hydrates in a porous media from a physical experiment directly. The purpose of this study was to model the dynamic formation mechanisms of gas hydrate in porous media by reservoir simulation. Two models were designed for this study: 1) a closed-system static model with separated gas and water zones; this model was a hydrate equilibrium model to investigate the behavior of the formation of hydrates near the initial gas-water contact; and 2) an open-system dynamic model with a continuous bottom-up gas flow; this model simulated the behavior of gas migration and studied the formation of hydrates from flowed gas and static formation water in porous media. A phase behavior module was developed in this study for reservoir simulator to model the pressure-volume-temperature (PVT) behavior of hydrates. The thermodynamic equilibriums and chemical reactions were coupled with the phase behavior module to have functions modelling the formation and dissociation of hydrates from/to water and gas. The simulation models used in this study were validated from the code-comparison project proposed by the NETL. According to the modelling results of the closed-system static model, we found that predominated location for the formation of hydrates was below the gas-water contact (or at the top of water zone). The maximum hydrate saturation

  2. Formation of metastable phases by spinodal decomposition

    PubMed Central

    Alert, Ricard; Tierno, Pietro; Casademunt, Jaume

    2016-01-01

    Metastable phases may be spontaneously formed from other metastable phases through nucleation. Here we demonstrate the spontaneous formation of a metastable phase from an unstable equilibrium by spinodal decomposition, which leads to a transient coexistence of stable and metastable phases. This phenomenon is generic within the recently introduced scenario of the landscape-inversion phase transitions, which we experimentally realize as a structural transition in a colloidal crystal. This transition exhibits a rich repertoire of new phase-ordering phenomena, including the coexistence of two equilibrium phases connected by two physically different interfaces. In addition, this scenario enables the control of sizes and lifetimes of metastable domains. Our findings open a new setting that broadens the fundamental understanding of phase-ordering kinetics, and yield new prospects of applications in materials science. PMID:27713406

  3. Formation of metastable phases by spinodal decomposition

    NASA Astrophysics Data System (ADS)

    Alert, Ricard; Tierno, Pietro; Casademunt, Jaume

    2016-10-01

    Metastable phases may be spontaneously formed from other metastable phases through nucleation. Here we demonstrate the spontaneous formation of a metastable phase from an unstable equilibrium by spinodal decomposition, which leads to a transient coexistence of stable and metastable phases. This phenomenon is generic within the recently introduced scenario of the landscape-inversion phase transitions, which we experimentally realize as a structural transition in a colloidal crystal. This transition exhibits a rich repertoire of new phase-ordering phenomena, including the coexistence of two equilibrium phases connected by two physically different interfaces. In addition, this scenario enables the control of sizes and lifetimes of metastable domains. Our findings open a new setting that broadens the fundamental understanding of phase-ordering kinetics, and yield new prospects of applications in materials science.

  4. Formation mechanism of superconducting phase and its three-dimensional architecture in pseudo-single-crystal KxFe2-ySe2

    SciTech Connect

    Liu, Yong; Xing, Qingfeng; Straszheim, Warren E.; Marshman, Jeff; Pedersen, Pal; McLaughlin, Richard; Lograsso, Thomas A.

    2016-02-11

    Here, we report how the superconducting phase forms in pseudo-single-crystal KxFe2-ySe2. In situ scanning electron microscopy (SEM) observation reveals that, as an order-disorder transition occurs, on cooling, most of the high-temperature iron-vacancy-disordered phase gradually changes into the iron-vacancy-ordered phase whereas a small quantity of the high-temperature phase retains its structure and aggregates to the stripes with more iron concentration but less potassium concentration compared to the iron-vacancy-ordered phase. The stripes that are generally recognized as the superconducting phase are actually formed as a remnant of the high-temperature phase with a compositional change after an “imperfect” order-disorder transition. It should be emphasized that the phase separation in pseudo-single-crystal KxFe2-ySe2 is caused by the iron-vacancy order-disorder transition. The shrinkage of the high-temperature phase and the expansion of the newly created iron-vacancy-ordered phase during the phase separation rule out the mechanism of spinodal decomposition proposed in an early report [Wang et al, Phys. Rev. B 91, 064513 (2015)]. Since the formation of the superconducting phase relies on the occurrence of the iron-vacancy order-disorder transition, it is impossible to synthesize a pure superconducting phase by a conventional solid state reaction or melt growth. By focused ion beam-scanning electron microscopy, we further demonstrate that the superconducting phase forms a contiguous three-dimensional architecture composed of parallelepipeds that have a coherent orientation relationship with the iron-vacancy-ordered phase.

  5. Phase separation and the formation of cellular bodies

    NASA Astrophysics Data System (ADS)

    Xu, Bin; Broedersz, Chase P.; Meir, Yigal; Wingreen, Ned S.

    Cellular bodies in eukaryotic cells spontaneously assemble to form cellular compartments. Among other functions, these bodies carry out essential biochemical reactions. Cellular bodies form micron-sized structures, which, unlike canonical cell organelles, are not surrounded by membranes. A recent in vitro experiment has shown that phase separation of polymers in solution can explain the formation of cellular bodies. We constructed a lattice-polymer model to capture the essential mechanism leading to this phase separation. We used both analytical and numerical tools to predict the phase diagram of a system of two interacting polymers, including the concentration of each polymer type in the condensed and dilute phase.

  6. Magnetohydrodynamic mechanism for pedestal formation.

    PubMed

    Guazzotto, L; Betti, R

    2011-09-16

    Time-dependent two-dimensional magnetohydrodynamic simulations are carried out for tokamak plasmas with edge poloidal flow. Differently from conventional equilibrium theory, a density pedestal all around the edge is obtained when the poloidal velocity exceeds the poloidal sound speed. The outboard pedestal is induced by the transonic discontinuity, the inboard one by mass redistribution. The density pedestal follows the formation of a highly sheared flow at the transonic surface. These results may be relevant to the L-H transition and pedestal formation in high performance tokamak plasmas.

  7. Interplay between micelle formation and waterlike phase transitions

    NASA Astrophysics Data System (ADS)

    Heinzelmann, G.; Figueiredo, W.; Girardi, M.

    2010-02-01

    A lattice model for amphiphilic aggregation in the presence of a structured waterlike solvent is studied through Monte Carlo simulations. We investigate the interplay between the micelle formation and the solvent phase transition in two different regions of temperature-density phase diagram of pure water. A second order phase transition between the gaseous (G) and high density liquid (HDL) phases that occurs at very high temperatures, and a first order phase transition between the low density liquid (LDL) and (HDL) phases that takes place at lower temperatures. In both cases, we find the aggregate size distribution curve and the critical micellar concentration as a function of the solvent density across the transitions. We show that micelle formation drives the LDL-HDL first order phase transition to lower solvent densities, while the transition G-HDL is driven to higher densities, which can be explained by the markedly different degrees of micellization in both cases. The diffusion coefficient of surfactants was also calculated in the LDL and HDL phases, changing abruptly its behavior due to the restructuring of waterlike solvent when we cross the first order LDL-HDL phase transition. To understand such behavior, we calculate the solvent density and the number of hydrogen bonds per water molecule close to micelles. The curves of the interfacial solvent density and the number of hydrogen bonds per water molecule in the first hydration signal a local phase change of the interfacial water, clarifying the diffusion mechanism of free surfactants in the solvent.

  8. Phase Formation Behavior in Ultrathin Iron Oxide.

    PubMed

    Jõgi, Indrek; Jacobsson, T Jesper; Fondell, Mattis; Wätjen, Timo; Carlsson, Jan-Otto; Boman, Mats; Edvinsson, Tomas

    2015-11-17

    Nanostructured iron oxides, and especially hematite, are interesting for a wide range of applications ranging from gas sensors to renewable solar hydrogen production. A promising method for deposition of low-dimensional films is atomic layer deposition (ALD). Although a potent technique, ALD of ultrathin films is critically sensitive to the substrate and temperature conditions where initial formation of islands and crystallites influences the properties of the films. In this work, deposition at the border of the ALD window forming a hybrid ALD/pulsed CVD (pCVD) deposition is utilized to obtain a deposition less sensitive to the substrate. A thorough analysis of iron oxide phases formation on two different substrates, Si(100) and SiO2, was performed. Films between 3 and 50 nm were deposited and analyzed with diffraction techniques, high-resolution Raman spectroscopy, and optical spectroscopy. Below 10 nm nominal film thickness, island formation and phase dependent particle crystallization impose constraints for deposition of phase pure iron oxides on non-lattice-matching substrates. Films between 10 and 20 nm thickness on SiO2 could effectively be recrystallized into hematite whereas for the corresponding films on Si(100), no recrystallization occurred. For films thicker than 20 nm, phase pure hematite can be formed directly with ALD/pCVD with very low influence of the substrate on either Si or SiO2. For more lattice matched substrates such as SnO2:F, Raman spectroscopy indicated formation of the hematite phase already for films with 3 nm nominal thickness and clearly for 6 nm films. Analysis of the optical properties corroborated the analysis and showed a quantum confined blue-shift of the absorption edge for the thinnest films.

  9. Mechanisms of FGF gradient formation during embryogenesis.

    PubMed

    Balasubramanian, Revathi; Zhang, Xin

    2016-05-01

    Fibroblast growth factors (FGFs) have long been attributed to influence morphogenesis in embryonic development. Signaling by FGF morphogen encodes positional identity of tissues by creating a concentration gradient over the developing embryo. Various mechanisms that influence the development of such gradient have been elucidated in the recent past. These mechanisms of FGF gradient formation present either as an extracellular control over FGF ligand diffusion or as a subcellular control of FGF propagation and signaling. In this review, we describe our current understanding of FGF as a morphogen, the extracellular control of FGF gradient formation by heparan sulfate proteoglycans (HSPGs) and mechanisms of intracellular regulation of FGF signaling that influence gradient formation.

  10. Kinetically driven ordered phase formation in binary colloidal crystals

    NASA Astrophysics Data System (ADS)

    Bochicchio, D.; Videcoq, A.; Ferrando, R.

    2013-02-01

    The aggregation of binary colloids of the same size and balanced charges is studied by Brownian dynamics simulations for dilute suspensions. It is shown that, under appropriate conditions, the formation of colloidal crystals is dominated by kinetic effects leading to the growth of well-ordered crystallites of the sodium-chloride (NaCl) bulk phase. These crystallites form with very high probability even when the cesium-chloride (CsCl) phase is more stable thermodynamically. Global optimization searches show that this result is not related to the most favorable structures of small clusters, which are either amorphous or of the CsCl structure. The formation of the NaCl phase is related to the specific kinetics of the crystallization process, which takes place by a two-step mechanism. In this mechanism, dense fluid aggregates form at first and then crystallization follows. It is shown that the type of short-range order in these dense fluid aggregates determines which phase is finally formed in the crystallites. The role of hydrodynamic effects in the aggregation process is analyzed by stochastic rotation dynamics - molecular dynamics simulations, and we find that these effects do not play a major role in the formation of the crystallites.

  11. Film formation and mechanical behavior of polymer latexes

    SciTech Connect

    Gauthier, C.; Sindt, O.; Perez, J.

    1995-12-31

    The purpose of this lecture is to review the present state of the art in the field of film formation in relation with the mechanical behavior of polymer films. After a review of the theoretical approaches concerning film forming process, we show the influence of some experimental parameters (temperature, hygrometry {hor_ellipsis}) in the case of a core-shell latex obtained from polystyrene/Poly (Styrene co. butyl acrylate). Then, the mechanical behavior of polymer films is considered. The improvement of the mechanical strength of latex films during the last stage of film formation (i.e., gradual coalescence) is illustrated. Further analysis of the molecular process yielding mechanical behavior allows us to show how the comparison between prediction and experimental data can provide information on morphological changes, on the stability of this one, or on the formation of an interphase between constituting phases.

  12. Mechanism for the formation of gas-phase protonated alcohol-ether adducts by VUV laser ionization and density-functional calculations.

    PubMed

    Lam, Selay; Shi, Y J; Mosey, N J; Woo, T K; Lipson, R H

    2004-11-22

    The neutral vapors above liquid alcohol/ether mixtures, (diethyl ether/methanol, diethyl ether/ethanol, tetrahydrofuran/methanol, and tetrahydrofuran/ethanol) were co-expanded with He in a supersonic jet, ionized with a 118-nm vacuum ultraviolet laser, and detected in a time-of-flight mass spectrometer. In each case, features attributed to protonated alcohol-ether dimers and protonated ether monomers were observed, as well as those ions obtained by ionizing neat alcohol or ether samples alone. Theoretical calculations, carried out to establish the energetics of the various possible reactions leading to the formation of the observed binary adducts, indicate that the most thermodynamically favorable pathway corresponds to the addition of a protonated alcohol monomer to neutral ether.

  13. Molecular mechanisms of bone formation in spondyloarthritis.

    PubMed

    González-Chávez, Susana Aideé; Quiñonez-Flores, Celia María; Pacheco-Tena, César

    2016-07-01

    Spondyloarthritis comprise a group of inflammatory rheumatic diseases characterized by its association to HLA-B27 and the presence of arthritis and enthesitis. The pathogenesis involves both an inflammatory process and new bone formation, which eventually lead to ankylosis of the spine. To date, the intrinsic mechanisms of the pathogenic process have not been fully elucidated, and our progress is remarkable in the identification of therapeutic targets to achieve the control of the inflammatory process, yet our ability to inhibit the excessive bone formation is still insufficient. The study of new bone formation in spondyloarthritis has been mostly conducted in animal models of the disease and only few experiments have been done using human biopsies. The deregulation and overexpression of molecules involved in the osteogenesis process have been observed in bone cells, mesenchymal cells, and fibroblasts. The signaling associated to the excessive bone formation is congruent with those involved in the physiological processes of bone remodeling. Bone morphogenetic proteins and Wnt pathways have been found deregulated in this disease; however, the cause for uncontrolled stimulation remains unknown. Mechanical stress appears to play an important role in the pathological osteogenesis process; nevertheless, the association of other important factors, such as the presence of HLA-B27 and environmental factors, remains uncertain. The present review summarizes the experimental findings that describe the signaling pathways involved in the new bone formation process in spondyloarthritis in animal models and in human biopsies. The role of mechanical stress as the trigger of these pathways is also reviewed.

  14. Mechanics of membrane fusion/pore formation.

    PubMed

    Fuhrmans, Marc; Marelli, Giovanni; Smirnova, Yuliya G; Müller, Marcus

    2015-01-01

    Lipid bilayers play a fundamental role in many biological processes, and a considerable effort has been invested in understanding their behavior and the mechanism of topological changes like fusion and pore formation. Due to the time- and length-scale on which these processes occur, computational methods have proven to be an especially useful tool in their study. With their help, a number of interesting findings about the shape of fusion intermediates could be obtained, and novel hypotheses about the mechanism of topological changes and the involvement of peptides therein were suggested. In this work, we try to present a summary of these developments together with some hitherto unpublished results, featuring, among others, the shape of stalks and fusion pores, possible modes of action of the influenza HA fusion peptide and the SNARE protein complex, the mechanism of supported lipid bilayer formation by vesicle spreading, and the free energy and transition pathway of the fusion process.

  15. Histopathology Predicts the Mechanism of Stone Formation

    NASA Astrophysics Data System (ADS)

    Evan, Andrew P.

    2007-04-01

    About 5% of American women and 12% of men will develop a kidney stone at some time in their life and these numbers appear to be on the rise. Despite years of scientific research into the mechanisms of stone formation and growth, limited advances have been made until recently. Randall's original observations and thoughts on the mechanisms for kidney stone formation have been validated for idiopathic calcium oxalate stone formers (ICSF) but not for most other stone forming groups. Our current studies on selected groups of human stone formers using intraoperative papillary biopsies has shown overwhelming evidence for the presence of Randall's plaque in ICSF and that stone formation and growth are exclusively linked to its availability to urinary ions and proteins. Intense investigation of the plaque-stone junction is needed if we are to understand the factors leading to the overgrowth process on exposed regions of plaque. Such information should allow the development of treatment strategies to block stone formation in ICSF patients. Patients who form brushite stones, or who form apatite stones because of distal renal tubular acidosis (dRTA), or patients with calcium oxalate stones due to obesity bypass procedures, or patients with cystinuria, get plugged inner medullary collecting ducts (IMCD) which leads to total destruction of the lining cells and focal sites of interstitial fibrosis. These stone formers have plaque but at levels equal to or below non-stone formers, which would suggest that they form stones by a different mechanism than do ICSF patients.

  16. Investigating materials formation with liquid-phase and cryogenic TEM

    NASA Astrophysics Data System (ADS)

    de Yoreo, J. J.; N. A. J. M., Sommerdijk

    2016-08-01

    The recent advent of liquid-phase transmission electron microscopy (TEM) and advances in cryogenic TEM are transforming our understanding of the physical and chemical mechanisms underlying the formation of materials in synthetic, biological and geochemical systems. These techniques have been applied to study the dynamic processes of nucleation, self-assembly, crystal growth and coarsening for metallic and semiconductor nanoparticles, (bio)minerals, electrochemical systems, macromolecular complexes, and organic and inorganic self-assembling systems. New instrumentation and methodologies that are currently on the horizon promise new opportunities for advancing the science of materials synthesis.

  17. Mechanics of formation of sawtooth chips

    NASA Astrophysics Data System (ADS)

    Vyas, Amitabh

    Formation of sawtooth chips was studied while machining case carburized 8620 steel (of varying degrees of hardness--upto Rc62), Titanium and Brass. Cutting forces were measured and an attempt was made to measure temperature during machining of case carburized 8620 steel. Conventional tool-chip thermocouple technique was modified to accommodate the effects due to design of Cubic Boron Nitride (CBN) cutting inserts. The chips produced were examined under Optical Microscope, Scanning Electron Microscope and Transmission Electron Microscope. A technique was developed for specimen preparation to study the microstructure of a non-etching white layer under a transmission electron microscope. All the experiments done during this study for an investigation into the root cause of a sawtooth chip formation suggest that a cyclic crack formation on the free surface side of the chip is responsible for the formation of the sawtooth chips; contrary to the widely accepted view of adiabatic shear being the root cause of the sawtooth chip formation. A Quick-Stop device was also used to determine the mechanism of the sawtooth chip formation. A new method of evaluating cutting ratio for the sawtooth chips is proposed and was verified experimentally.

  18. Mechanisms of human kidney stone formation.

    PubMed

    Evan, Andrew P; Worcester, Elaine M; Coe, Fredric L; Williams, James; Lingeman, James E

    2015-01-01

    The precise mechanisms of kidney stone formation and growth are not completely known, even though human stone disease appears to be one of the oldest diseases known to medicine. With the advent of the new digital endoscope and detailed renal physiological studies performed on well phenotyped stone formers, substantial advances have been made in our knowledge of the pathogenesis of the most common type of stone former, the idiopathic calcium oxalate stone former as well as nine other stone forming groups. The observations from our group on human stone formers and those of others on model systems have suggested four entirely different pathways for kidney stone formation. Calcium oxalate stone growth over sites of Randall's plaque appear to be the primary mode of stone formation for those patients with hypercalciuria. Overgrowths off the ends of Bellini duct plugs have been noted in most stone phenotypes, do they result in a clinical stone? Micro-lith formation does occur within the lumens of dilated inner medullary collecting ducts of cystinuric stone formers and appear to be confined to this space. Lastly, cystinuric stone formers also have numerous small, oval, smooth yellow appearing calyceal stones suggestive of formation in free solution. The scientific basis for each of these four modes of stone formation are reviewed and used to explore novel research opportunities.

  19. Investigation of formation mechanisms of chips in orthogonal cutting process

    NASA Astrophysics Data System (ADS)

    Ma, W.

    2012-08-01

    This work investigates the formation mechanisms of chips in orthogonal cutting of mild steel and the transformation conditions between various morphology chips. It is supposed that the modeling material follows the Johnson-Cook constitutive model. In orthogonal cutting process, both the plastic flow and the instability behaviors of chip materials are caused by the plane strain loadings. Therefore, the general instability behaviors of materials in plane strain state are first analyzed with linear perturbation method and a universal instability criterion is established. Based on the analytical results, the formation mechanisms of chips and the transformation conditions between continuous and serrated chips are further studied by instability phase diagram method. The results show that the chip formation strongly depends on the intensity ratios between shear and normal stresses. The ratios of dissipative rates of plastic work done by compression and shear stresses govern the transformation from continuous to serrated chips. These results are verified by the numerical simulations on the orthogonal cutting process.

  20. Phase optimized skeletal mechanisms for engine simulations

    NASA Astrophysics Data System (ADS)

    Blurock, Edward S.; Tuner, Martin; Mauss, Fabian

    2010-07-01

    Adaptive chemistry is based on the principle that instead of having one comprehensive model describing the entire range of chemical source term space (typically parameters related to temperature, pressure and species concentrations), a set of computationally simpler models are used, each describing a local region (in multidimensional space) or phases (in zero-dimensional space). In this work, an adaptive chemistry method based on phase optimized skeletal mechanisms (POSM) is applied to a 96 species n-heptane-isooctane mechanism within a two-zone zero-dimensional stochastic reactor model (SRM) for an spark-ignition (SI) Engine. Two models differing only in the extent of reduction in the phase mechanism, gave speed-up factors of 2.7 and 10. The novelty and emphasis of this study is the use of machine learning techniques to decide where the phases are and to produce a usable phase recognition. The combustion process is automatically divided up into an 'optimal' set of phases through machine learning clustering based on fuzzy logic predicates involving a necessity parameter (a measure giving an indication whether a species should be included in the mechanism or not). The mechanism of each phase is reduced from the full mechanism based on this necessity parameter with respect to the conditions of that phase. The algorithm to decide which phase the process is in is automatically determined by another machine learning method that produces decision trees. The decision tree is made up of asking whether the mass fraction values were above or below given values. Two POSM studies were done, a conservative POSM where the species in each phase are eliminated based on a necessity parameter threshold (speed-up 2.7) and a further reduced POSM where each phase was further reduced by hand (speed-up 10). The automated techniques of determining the phases and for creating the decision tree are very general and are not limited to the parameter choices of this paper. There is also no

  1. Adduct Formation in ESI/MS by Mobile Phase Additives

    NASA Astrophysics Data System (ADS)

    Kruve, Anneli; Kaupmees, Karl

    2017-03-01

    Adduct formation is a common ionization method in electrospray ionization mass spectrometry (ESI/MS). However, this process is poorly understood and complicated to control. We demonstrate possibilities to control adduct formation via mobile phase additives in ESI positive mode for 17 oxygen and nitrogen bases. Mobile phase additives were found to be a very effective measure for manipulating the formation efficiencies of adducts. An appropriate choice of additive may increase sensitivity by up to three orders of magnitude. In general, sodium adduct [M + Na]+ and protonated molecule [M + H]+ formation efficiencies were found to be in good correlation; however, the former were significantly more influenced by mobile phase properties. Although the highest formation efficiencies for both species were observed in water/acetonitrile mixtures not containing additives, the repeatability of the formation efficiencies was found to be improved by additives. It is concluded that mobile phase additives are powerful, yet not limiting factors, for altering adduct formation.

  2. Planet formation - Mechanism of early growth

    NASA Technical Reports Server (NTRS)

    Hartmann, W. K.

    1978-01-01

    Experiments in vacuum (approx. 0.5 to 1 mbar) and in air quantify mechanics of collisions, rebound, and fragmentation at low velocities (1-50 m/sec), under the conditions usually postulated for the preplanetary environment in the primitive solar nebula. Such collisions have been little studied experimentally. Contrary to widespread assumptions, accretionary growth of the largest meteoroid- and asteroid-sized bodies in a given swarm results spontaneously from the simple mechanics of these collisions, without other ad hoc sticking mechanisms. The smaller bodies in the swarm are less likely to grow. Granular surfaces form, either by gravitational collapse of dust swarms or by rapid formation of regolith surfaces on solid planetesimals; these surfaces strongly promote further growth by retarding rebound. Growth of large bodies increases modal collision velocities, causing fragmentation of smaller bodies and eventual production of interstellar dust as a by-product of planetesimal interactions.

  3. Space Shuttle Pinhole Formation Mechanism Studies

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.

    1998-01-01

    Pinholes have been observed to form on the wing leading edge of the space shuttle after about 10-15 flights. In this report we expand upon previous observations by Christensen (1) that these pinholes often form along cracks and are associated with a locally zinc-rich area. The zinc appears to come from weathering and peeling paint on the launch structure. Three types of experimental examinations are performed to understand this issue further: (A) Detailed microstructural examination of actual shuttle pinholes (B) Mass spectrometric studies of coupons containing, actual shuttle pinholes and (C) Laboratory furnace studies of ZnO/SiC reactions and ZnO/SiC protected carbon/carbon reaction. On basis of these observations we present a detailed mechanism of pinhole formation due to formation of a corrosive ZnO-Na-2-O-SiO2 ternary glass, which flows into existing cracks and enlarges them.

  4. Chemical mechanisms governing atmospheric new particle formation

    NASA Astrophysics Data System (ADS)

    Bzdek, Bryan Richard

    The goal of this dissertation is to understand the chemistry that governs new particle formation, a ubiquitous and important atmospheric process. New particle formation occurs when gas phase precursors condense to create small molecular clusters on the order of 1 nm diameter. Those clusters must then grow rapidly and ultimately may serve as the seeds for cloud droplets. However, modelers have substantial difficulty predicting the frequency and efficiency of new particle formation. This predictive difficulty is an important contributor to the uncertainty in aerosol effects on global climate and therefore also contributes to the large uncertainty in anthropogenic effects on climate. To reduce these uncertainties, a more precise understanding of how particles nucleate and grow in the atmospheric is required. In this dissertation, mass spectrometry is used to determine the chemical processes involved in new particle formation. Gas phase species such as sulfuric acid, ammonia, amines, and organic matter are contributors but exactly how and how much each contributes to the growth of nanoparticles is not well understood. Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and Nano Aerosol Mass Spectrometry (NAMS) are used to study the chemical composition and reactivity of clusters < 3 nm diameter and nanoparticles 10-20 nm diameter, respectively. The FTICR-MS studies are laboratory based, whereas the NAMS studies are field based. Measurements of cluster composition and reactivity using FTICR-MS permit prediction of the composition of ambient molecular clusters. For ambient molecular clusters to become relevant to climate by serving as cloud condensation nuclei, they must grow rapidly. NAMS measurements at 20 nm diameter permit determination of nanoparticle growth pathways. This dissertation shows that sulfuric acid adds to both clusters and nanoparticles in a collision limited manner. On the other hand, ammonia uptake in both size regimes may not

  5. Peptide Bond Formation Mechanism Catalyzed by Ribosome.

    PubMed

    Świderek, Katarzyna; Marti, Sergio; Tuñón, Iñaki; Moliner, Vicent; Bertran, Juan

    2015-09-23

    In this paper we present a study of the peptide bond formation reaction catalyzed by ribosome. Different mechanistic proposals have been explored by means of Free Energy Perturbation methods within hybrid QM/MM potentials, where the chemical system has been described by the M06-2X functional and the environment by means of the AMBER force field. According to our results, the most favorable mechanism in the ribosome would proceed through an eight-membered ring transition state, involving a proton shuttle mechanism through the hydroxyl group of the sugar and a water molecule. This transition state is similar to that described for the reaction in solution (J. Am. Chem. Soc. 2013, 135, 8708-8719), but the reaction mechanisms are noticeably different. Our simulations reproduce the experimentally determined catalytic effect of ribosome that can be explained by the different behavior of the two environments. While the solvent reorganizes during the chemical process involving an entropic penalty, the ribosome is preorganized in the formation of the Michaelis complex and does not suffer important changes along the reaction, dampening the charge redistribution of the chemical system.

  6. Peptide Bond Formation Mechanism Catalyzed by Ribosome

    PubMed Central

    Świderek, Katarzyna; Marti, Sergio; Tuñón, Iñaki; Moliner, Vicent; Bertran, Juan

    2015-01-01

    In this paper we present a study of the peptide bond formation reaction catalyzed by ribosome. Different mechanistic proposals have been explored by means of Free Energy Perturbation methods within hybrid QM/MM potentials, where the chemical system has been described by the M06-2X functional and the environment by means of the AMBER force field. According to our results, the most favourable mechanism in the ribosome would proceed through an eight-membered ring transition state, involving a proton shuttle mechanism through the hydroxyl group of the sugar and a water molecule. This transition state is similar to that described for the reaction in solution (J. Am. Chem. Soc. 2013, 135, 8708–8719) but the reaction mechanisms are noticeable different. Our simulations reproduce the experimentally determined catalytic effect of ribosome that can be explained by the different behaviour of the two environments. While the solvent reorganizes during the chemical process involving an entropic penalty, the ribosome is preorganized in the formation of the Michaelis complex and does not suffer important changes along the reaction, dampening the charge redistribution of the chemical system. PMID:26325003

  7. Mechanism of methane formation in potassium catalyzed carbon gasification

    SciTech Connect

    Mims, C.A.; Krajewski, J.J.

    1986-11-01

    The authors have performed a kinetics and isotope tracer study of the mechanism of CH/sub 4/ formation from a potassium catalyzed carbon during gasification in atmospheres containing H/sub 2/O, H/sub 2/, CO/sub 2/, and CO Temperatures from 925 to 1025 K and pressures up to 8 atm were studied. The authors found that although potassium salts catalyze the formation of CH/sub 4/, there is not a one-to-one correspondence between CH/sub 4/ and CO formation rates implying different sites for generation of the two products. At low gas phase carbon activity the CH/sub 4/ product is formed by direct hydrogenation of substrate carbon and not by secondary reaction of gas phase CO or CO/sub 2/. At higher gas phase carbon activities some CH/sub 4/ is produced from gas phase carbon oxides as a result of carbon deposition. In some cases the deposited carbon shows higher reactivity than the original carbon substrate so that this can be legitimately viewed as a secondary pathway.

  8. Modeling of metastable phase formation diagrams for sputtered thin films

    PubMed Central

    Chang, Keke; Music, Denis; to Baben, Moritz; Lange, Dennis; Bolvardi, Hamid; Schneider, Jochen M.

    2016-01-01

    Abstract A method to model the metastable phase formation in the Cu–W system based on the critical surface diffusion distance has been developed. The driver for the formation of a second phase is the critical diffusion distance which is dependent on the solubility of W in Cu and on the solubility of Cu in W. Based on comparative theoretical and experimental data, we can describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation. Metastable phase formation diagrams for Cu–W and Cu–V thin films are predicted and validated by combinatorial magnetron sputtering experiments. The correlative experimental and theoretical research strategy adopted here enables us to efficiently describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation during magnetron sputtering. PMID:27877871

  9. Modeling of metastable phase formation diagrams for sputtered thin films.

    PubMed

    Chang, Keke; Music, Denis; To Baben, Moritz; Lange, Dennis; Bolvardi, Hamid; Schneider, Jochen M

    2016-01-01

    A method to model the metastable phase formation in the Cu-W system based on the critical surface diffusion distance has been developed. The driver for the formation of a second phase is the critical diffusion distance which is dependent on the solubility of W in Cu and on the solubility of Cu in W. Based on comparative theoretical and experimental data, we can describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation. Metastable phase formation diagrams for Cu-W and Cu-V thin films are predicted and validated by combinatorial magnetron sputtering experiments. The correlative experimental and theoretical research strategy adopted here enables us to efficiently describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation during magnetron sputtering.

  10. Deformation mechanisms in a Laves phase

    SciTech Connect

    Liu, Yaping; Allen, S.M.; Livingston, J.D.

    1992-12-31

    The stress-induced phase transformation between C36 and C15 structures in Fe{sub 2}Zr is studied by electron microscopy. Nucleus of transformation is believed to be pre-existing C15 layers in C36 particles. Microstructural evidence for three mechanisms of growth of a new phase were found: Fault accumulation and rearrangement, moving of a individual partial dislocations between two phases, and the migration of microscopic ledges composed of a series of Shockley partials between C36 and C15. Plastic deformation by slip on non-basal planes of C36 caused by indentation is studied.

  11. Strain phase separation: Formation of ferroelastic domain structures

    NASA Astrophysics Data System (ADS)

    Xue, Fei; Li, Yongjun; Gu, Yijia; Zhang, Jinxing; Chen, Long-Qing

    2016-12-01

    Phase decomposition is a well-known process leading to the formation of two-phase mixtures. Here we show that a strain imposed on a ferroelastic crystal promotes the formation of mixed phases and domains, i.e., strain phase separation with local strains determined by a common tangent construction on the free energy versus strain curves. It is demonstrated that a domain structure can be understood using the concepts of domain/phase rule, lever rule, and coherent and incoherent strain phase separation, in a complete analogy to phase decomposition. The proposed strain phase separation model is validated using phase-field simulations and experimental observations of PbTi O3 and BiFe O3 thin films as examples. The proposed model provides a simple tool to guide and design domain structures of ferroelastic systems.

  12. Mechanisms of lamellar collagen formation in connective tissues.

    PubMed

    Ghazanfari, Samaneh; Khademhosseini, Ali; Smit, Theodoor H

    2016-08-01

    The objective of tissue engineering is to regenerate functional tissues. Engineering functional tissues requires an understanding of the mechanisms that guide the formation and evolution of structure in the extracellular matrix (ECM). In particular, the three-dimensional (3D) collagen fiber arrangement is important as it is the key structural determinant that provides mechanical integrity and biological function. In this review, we survey the current knowledge on collagen organization mechanisms that can be applied to create well-structured functional lamellar tissues and in particular intervertebral disc and cornea. Thus far, the mechanisms behind the formation of cross-aligned collagen fibers in the lamellar structures is not fully understood. We start with cell-induced collagen alignment and strain-stabilization behavior mechanisms which can explain a single anisotropically aligned collagen fiber layer. These mechanisms may explain why there is anisotropy in a single layer in the first place. However, they cannot explain why a consecutive collagen layer is laid down with an alternating alignment. Therefore, we explored another mechanism, called liquid crystal phasing. While dense concentrations of collagen show such behavior, there is little evidence that the conditions for liquid crystal phasing are actually met in vivo. Instead, lysyl aldehyde-derived collagen cross-links have been found essential for correct lamellar matrix deposition. Furthermore, we suggest that supra-cellular (tissue-level) shear stress may be instrumental in the alignment of collagen fibers. Understanding the potential mechanisms behind the lamellar collagen structure in connective tissues will lead to further improvement of the regeneration strategies of functional complex lamellar tissues.

  13. Peptide bond formation via glycine condensation in the gas phase.

    PubMed

    Van Dornshuld, Eric; Vergenz, Robert A; Tschumper, Gregory S

    2014-07-24

    Four unique gas phase mechanisms for peptide bond formation between two glycine molecules have been mapped out with quantum mechanical electronic structure methods. Both concerted and stepwise mechanisms, each leading to a cis and trans glycylglycine product (four mechanisms total), were examined with the B3LYP and MP2 methods and Gaussian atomic orbital basis sets as large as aug-cc-pVTZ. Electronic energies of the stationary points along the reaction pathways were also computed with explicitly correlated MP2-F12 and CCSD(T)-F12 methods. The CCSD(T)-F12 computations indicate that the electronic barriers to peptide bond formation are similar for all four mechanisms (ca. 32-39 kcal mol(-1) relative to two isolated glycine fragments). The smallest barrier (32 kcal mol(-1)) is associated with the lone transition state for the concerted mechanism leading to the formation of a trans peptide bond, whereas the largest barrier (39 kcal mol(-1)) was encountered along the concerted pathway leading to the cis configuration of the glycylglycine dipeptide. Two significant barriers are encountered for the stepwise mechanisms. For both the cis and trans pathways, the early electronic barrier is 36 kcal mol(-1) and the subsequent barrier is approximately 1 kcal mol(-1) lower. A host of intermediates and transition states lie between these two barriers, but they all have very small relative electronic energies (ca. ± 4 kcal mol(-1)). The isolated cis products (glycylglycine + H2O) are virtually isoenergetic with the isolated reactants (within -1 kcal mol(-1)), whereas the trans products are about 5 kcal mol(-1) lower in energy. In both products, however, the water can hydrogen bond to the dipeptide and lower the energy by roughly 5-9 kcal mol(-1). This study indicates that the concerted process leading to a trans configuration about the peptide bond is marginally favored both thermodynamically (exothermic by ca. 5 kcal mol(-1)) and kinetically (barrier height ≈ 32 kcal mol(-1

  14. String Mechanism for Relativistic Jet Formation

    NASA Astrophysics Data System (ADS)

    Dyadechkin, S. A.; Semenov, V. S.; Punsly, B.; Biernat, H. K.

    Here we present our latest studies of relativistic jet formation in the vicinity of a rotating black hole where the reconnection process has been taken into account. In order to simplify the problem, we use Lagrangian formalism and develop a method which enables us to consider a magnetized plasma as a set of magnetic flux tubes [5,6]. Within the limits of the Lagrangian approach, we perform numerical simulations of the flux tube (nonlinear string) behavior which clearly demonstrates the process of relativistic jet formation in the form of outgoing torsional nonlinear aves. It turns out that the jet is produced deep inside the ergosphere where the flux tube takes away spinning energy from the black hole due to the nonlocal Penrose process [2]. This is similar to the Blandford-Znajek (BZ) mechanism to some extent [8], however, the string mechanism is essentially time dependent. It is shown that the leading part of the accreting tube gains negative energy and therefore has to stay in the ergosphere forever. Simultaneously, another part of the tube propagates along the spinning axis away from the hole with nearly the speed of light. As a result, the tube is continuously stretching and our mechanism is essentially time dependent. Obviously, such process cannot last infinitely long and we have to take into account the reconnection process. Due to reconnection, the topology of the flux tube is changed and it gives rise to a plasmoid creation which propagates along spin axis of the hole with relativistic speed carrying off the energy and angular momentum away from the black hole.

  15. Molecular mechanisms of phase change in locusts.

    PubMed

    Wang, Xianhui; Kang, Le

    2014-01-01

    Phase change in locusts is an ideal model for studying the genetic architectures and regulatory mechanisms associated with phenotypic plasticity. The recent development of genomic and metabolomic tools and resources has furthered our understanding of the molecular basis of phase change in locusts. Thousands of phase-related genes and metabolites have been highlighted using large-scale expressed sequence tags, microarrays, high-throughput transcriptomic sequences, or metabolomic approaches. However, only several key factors, including genes, metabolites, and pathways, have a critical role in phase transition in locusts. For example, CSP (chemosensory protein) and takeout genes, the dopamine pathway, protein kinase A, and carnitines were found to be involved in the regulation of behavioral phase change and gram-negative bacteria-binding proteins in prophylaxical disease resistance of gregarious locusts. Epigenetic mechanisms including small noncoding RNAs and DNA methylation have been implicated. We review these new advances in the molecular basis of phase change in locusts and present some challenges that need to be addressed.

  16. The free energy of mechanically unstable phases

    PubMed Central

    van de Walle, A.; Hong, Q.; Kadkhodaei, S.; Sun, R.

    2015-01-01

    Phase diagrams provide ‘roadmaps' to the possible states of matter. Their determination traditionally rests on the assumption that all phases, even unstable ones, have well-defined free energies under all conditions. However, this assumption is commonly violated in condensed phases due to mechanical instabilities. This long-standing problem impedes thermodynamic database development, as pragmatic attempts at solving this problem involve delicate extrapolations that are highly nonunique and that lack an underlying theoretical justification. Here we propose an efficient computational solution to this problem that has a simple interpretation, both as a topological partitioning of atomic configuration space and as a minimally constrained physical system. Our natural scheme smoothly extends the free energy of stable phases, without relying on extrapolation, thus enabling a formal assessment of widely used extrapolation schemes. PMID:26130613

  17. A collective mechanism for phase variation in biofilms

    PubMed Central

    Chia, Nicholas; Woese, Carl R.; Goldenfeld, Nigel

    2008-01-01

    Understanding how microbes gather into biofilm communities and maintain diversity remains one of the central questions of microbiology, requiring an understanding of microbes as communal rather then individual organisms. Phase variation plays an integral role in the formation of diverse phenotypes within biofilms. We propose a collective mechanism for phase variation based on gene transfer agents, and apply the theory to predict the population structure and growth dynamics of a biofilm. Our results describe quantitatively recent experiments, with the only adjustable parameter being the rate of intercellular horizontal gene transfer. Our approach derives from a more general picture for the emergence of cooperation between microbes. PMID:18799735

  18. Phase diagram of hopping conduction mechanisms in polymer nanofiber network

    SciTech Connect

    Li, Jeng-Ting; Lu, Yu-Cheng; Jiang, Shiau-Bin; Zhong, Yuan-Liang; Yeh, Jui-Ming

    2015-12-07

    Network formation by nanofiber crosslinking is usually in polymer materials as application in organic semiconductor devices. Electron hopping transport mechanisms depend on polymer morphology in network. Conducting polymers morphology in a random network structure is modeled by a quasi-one-dimensional system coupled of chains or fibers. We observe the varying hopping conduction mechanisms in the polyaniline nanofibers of the random network structure. The average diameter d of the nanofibers is varied from approximately 10 to 100 nm. The different dominant hopping mechanisms including Efros-Shklovskii variable-range hopping (VRH), Mott VRH, and nearest-neighbor hopping are dependent on temperature range and d in crossover changes. The result of this study is first presented in a phase diagram of hopping conduction mechanisms based on the theories of the random network model. The hopping conduction mechanism is unlike in normal semiconductor materials.

  19. Graphite formation in cast iron, phase 2

    NASA Technical Reports Server (NTRS)

    Stefanescu, D. M.; Fiske, M. R.

    1985-01-01

    Several types of cast irons are directionally solidified aboard the KC-135 aircraft. Also, control samples are run on Earth for comparison. Some of these samples are unusable because of various mechanical problems; the analysis and the interpretation of results on the samples that are run successfully is discussed.

  20. Co-phasing the planet formation imager

    NASA Astrophysics Data System (ADS)

    Petrov, Romain G.; Boskri, Abdelkarim; Elhalkouj, Thami; Monnier, John; Ireland, Michael; Kraus, Stefan

    2016-08-01

    The Planet Formation Imager (PFI) is a project for a very large optical interferometer intended to obtain images of the planet formation process at scales as small as the Hill sphere of giant exoplanets. Its main science instruments will work in the thermal infrared but it will be cophased in the near infrared, where it requires also some capacity for scientific imaging. PFI imaging and resolution specifications imply an array of 12 to 20 apertures and baselines up to a few kilometers cophased at near infrared coherent magnitudes as large as 10. This paper discusses various cophasing architectures and the corresponding minimum diameter of individual apertures, which is the dominant element of PFI cost estimates. From a global analysis of the possible combinations of pairwise fringe sensors, we show that conventional approaches used in current interferometers imply the use of prohibitively large telescopes and we indicate the innovative strategies that would allow building PFI with affordable apertures smaller than 2 m in diameter. The approach with the best potential appears to be Hierarchical Fringe Tracking based on "two beams spatial filters" that cophase pairs of neighboring telescopes with all the efficiency of a two telescopes fringe tracker and transmit most of the flux as if it was produced by an unique single mode aperture to cophase pairs of pairs and then pairs of groups of apertures. We consider also the adaptation to PFI of more conventional approaches such as a combination of GRAVITY like fringe trackers or single or multiple chains of 2T fringe trackers.

  1. Soliton formation in the FFLO phase

    NASA Astrophysics Data System (ADS)

    Croitoru, M. D.; Buzdin, A. I.

    2016-12-01

    There is increasing body of experimental evidences of the Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) phase in quasi-low-dimensional organic and heavy-fermion superconductors. The emergence of the FFLO phase has been demonstrated mainly based on a thermodynamic quantity or microscopically with spin polarization distribution that exhibit anomalies within the superconducting state in the presence of the in-plane magnetic field. However, the direct observation of superconducting order parameter modulation is so far (still) missing. Within the quasiclassical approach and Ginzburg-Landau formalism we study how the orbital effect of the in-plane field influences the FFLO instability in quasi-one-dimensional superconductors with a sufficiently weak interlayer coupling locking the magnetic flux to Josephson-type vortices. By making use of the continuum limit approximation of the Frenkel-Kontorova model for competing periodicities, we find and characterize the locking behavior of the modulation wave vector, when it remains equal to the magnetic length through some range of values of the external field.

  2. O2 on ganymede: Spectral characteristics and plasma formation mechanisms

    USGS Publications Warehouse

    Calvin, W.M.; Johnson, R.E.; Spencer, J.R.

    1996-01-01

    Weak absorption features in the visible reflectance spectrum of Jupiter's satellite Ganymede have been correlated to those observed in the spectrum of molecular oxygen. We examine the spectral characteristics of these absorption features in all phases of O2 and conclude that the molecular oxygen is most likely present at densities similar to the liquid or solid ??-phase. The contribution of O2 to spectral features observed on Ganymede in the near-infrared wavelength region affects the previous estimates of photon pathlength in ice. The concentration of the visible absorption features on the trailing hemisphere of Ganymede suggests an origin due to bombardment by magneto-spheric ions. We derive an approximate O2 formation rate from this mechanism and consider the state of O2 within the surface.

  3. Symbiotic Control in Mechanical Bond Formation.

    PubMed

    Wang, Yuping; Sun, Junling; Liu, Zhichang; Nassar, Majed S; Botros, Youssry Y; Stoddart, J Fraser

    2016-09-26

    Since the advent of mechanically interlocked molecules (MIMs), many approaches to templating their formation using various different noncovalent bonding interactions have been introduced and explored. In particular, employing radical-pairing interactions between BIPY(.+) units, the radical cationic state of 4,4'-bipyridinium (BIPY(2+) ) units, in syntheses is not only a convenient but also an attractive source of templation because of the unique properties residing in the resulting catenanes and rotaxanes. Herein, we report a copper-mediated procedure that enables the generation, in the MIM-precursors, of BIPY(.+) radical cations, while the metal itself, which is oxidized to Cu(I) , catalyzes the azide-alkyne cycloaddition reactions that result in the efficient syntheses of two catenanes and one rotaxane, assisted by radical-pairing interactions between the BIPY(.+) radical cations. This procedure not only provides a fillip for making and investigating the properties of Coulombically challenged catenanes and rotaxanes, but it also opens up the possibility of synthesizing artificial molecular machines which operate away from equilibrium.

  4. Gel phase formation in dilute triblock copolyelectrolyte complexes

    NASA Astrophysics Data System (ADS)

    Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

    2017-02-01

    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

  5. Gel phase formation in dilute triblock copolyelectrolyte complexes

    PubMed Central

    Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

    2017-01-01

    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics. PMID:28230046

  6. Metastable phase formation in Be-Nb intermetallic compounds

    SciTech Connect

    Brimhall, J.L.; Charlot, L.A.; Bruemmer, S.M.

    1990-11-01

    Amorphous structures or metastable crystalline phases are produced in sputter-deposited Beryllium-Niobium (Be-Nb) alloys (5-15 at. % Nb) depending on the substrate temperature. The metastable phases transform to the stable Be{sub 12}Nb, Be{sub 17}Nb{sub 2}Nb phases on annealing at temperatures >800{degree}C. No Be{sub 5}Nb phase was found and the Be{sub 17}Nb{sub 2} phase is stable to low temperature. The Be{sub 12}Nb phase appeared to have a stoichiometric range of about 5.5 to 7.7 at. % Nb. The formation of the metastable phases is consistent with current models and theories. 17 refs., 1 fig., 2 tabs.

  7. Formation of laves phase in a refractory austenitic steel due to long-term heating

    NASA Astrophysics Data System (ADS)

    Tarasenko, L. V.; Shal'kevich, A. B.

    2011-07-01

    Steels of the Fe - Cr - Ni -Mo - Nb - Al - C system are studied by methods of phase physicochemical analysis and electron microscopy with the aim to determine the causes of changes in mechanical properties after long-term heating at a temperature of 600 - 700°C. Grain-boundary formation of particles of a Laves phase is shown to cause decrease in the impact toughness and transformation of particles of γ'-phase under conditions of creep. The effect of alloying elements on the chemical composition of the multicomponent Laves phase is studied depending on the temperatures of hardening, aging, and subsequent heating. Concentration correspondence between the chemical composition of the austenite and the intermetallic tcp phase formed in aging is discovered. A computational scheme for predicting the possibility of formation of Laves phases in multicomponent alloys is suggested.

  8. Aqueous-phase mechanism for secondary organic aerosol ...

    EPA Pesticide Factsheets

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx  ≡  NO + NO2) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observati

  9. Dynamical phase transitions in quantum mechanics

    NASA Astrophysics Data System (ADS)

    Rotter, Ingrid

    2012-02-01

    The nucleus is described as an open many-body quantum system with a non-Hermitian Hamilton operator the eigenvalues of which are complex, in general. The eigenvalues may cross in the complex plane (exceptional points), the phases of the eigenfunctions are not rigid in approaching the crossing points and the widths bifurcate. By varying only one parameter, the eigenvalue trajectories usually avoid crossing and width bifurcation occurs at the critical value of avoided crossing. An analog spectroscopic redistribution takes place for discrete states below the particle decay threshold. By this means, a dynamical phase transition occurs in the many-level system starting at a critical value of the level density. Hence the properties of the low-lying nuclear states (described well by the shell model) and those of highly excited nuclear states (described by random ensembles) differ fundamentally from one another. The statement of Niels Bohr on the collective features of compound nucleus states at high level density is therefore not in contradiction to the shell-model description of nuclear (and atomic) states at low level density. Dynamical phase transitions are observed experimentally in different quantum mechanical systems by varying one or two parameters.

  10. Modeling liquid-liquid phase transitions and quasicrystal formation

    NASA Astrophysics Data System (ADS)

    Skibinsky, Anna

    In this thesis, studies which concern two different subjects related to phase transitions in fluids and crystalline solids are presented. Condensed matter formation, structure, and phase transitions are modeled using molecular dynamics simulations of simple discontinuous potentials with attractive and repulsive interactions. Novel phase diagrams are proposed for quasicrystals, crystals, and liquids. In the first part of the thesis, the formation of a quasicrystal in a two dimensional monodisperse system is investigated using molecular dynamics simulations of hard sphere particles interacting via a two-dimensional square-well potential. It is found that for certain values of the square-well parameters more than one stable crystalline phase can form. By quenching the liquid phase at a very low temperature, an amorphous phase is obtained. When this the amorphous phase is heated, a quasicrystalline structure with five-fold symmetry forms. From estimations of the Helmholtz potentials of the stable crystalline phases and of the quasicrystal, it is concluded that within a specific temperature range, the observed quasicrystal phase can be the stable phase. The second part of the thesis concerns a study of the liquid-liquid phase transition for a single-component system in three dimensions, interacting via an isotropic potential with a repulsive soft-core shoulder at short distance and an attractive well at an intermediate distance. The potential is similar to potentials used to describe such liquid systems as colloids, protein solutions, or liquid metals. It is shown that the phase diagram for such a potential can have two lines of first-order fluid-fluid phase transitions: one separating a gas and a low-density liquid (LDL), and another between the LDL and a high-density liquid (HDL). Both phase transition lines end in a critical point, a gas-LDL critical point and, depending on the potential parameters, either a gas-HDL critical point or a LDL-HDL critical point. A

  11. Formative pluripotency: the executive phase in a developmental continuum.

    PubMed

    Smith, Austin

    2017-02-01

    The regulative capability of single cells to give rise to all primary embryonic lineages is termed pluripotency. Observations of fluctuating gene expression and phenotypic heterogeneity in vitro have fostered a conception of pluripotency as an intrinsically metastable and precarious state. However, in the embryo and in defined culture environments the properties of pluripotent cells change in an orderly sequence. Two phases of pluripotency, called naïve and primed, have previously been described. In this Hypothesis article, a third phase, called formative pluripotency, is proposed to exist as part of a developmental continuum between the naïve and primed phases. The formative phase is hypothesised to be enabling for the execution of pluripotency, entailing remodelling of transcriptional, epigenetic, signalling and metabolic networks to constitute multi-lineage competence and responsiveness to specification cues.

  12. Ionic Mechanisms of Carbon Formation in Flames.

    DTIC Science & Technology

    1981-05-01

    It was concluded that neutral free radical, polyacetylene, and polycyclic aromatic hydrocarbon mechanisms are not consistent with this description...free radicals, polyacetylenes, or polycyclic aromatic hydrocarbons add in a series of fast ion-molecule reactions, a mechanism could be developed which...flame. Neutral free radical, polyacetylene, and polycyclic aromatic hydrocarbon mechanisms are not consistent with this description. However, when

  13. A Gas-phase Formation Route to Interstellar Trans-methyl Formate

    NASA Astrophysics Data System (ADS)

    Cole, Callie A.; Wehres, Nadine; Yang, Zhibo; Thomsen, Ditte L.; Snow, Theodore P.; Bierbaum, Veronica M.

    2012-07-01

    The abundance of methyl formate in the interstellar medium has previously been underpredicted by chemical models. Additionally, grain surface chemistry cannot account for the relative abundance of the cis- and trans-conformers of methyl formate, and the trans-conformer is not even formed at detectable abundance on these surfaces. This highlights the importance of studying formation pathways to methyl formate in the gas phase. The rate constant and branching fractions are reported for the gas-phase reaction between protonated methanol and formic acid to form protonated trans-methyl formate and water as well as adduct ion: Rate constants were experimentally determined using a flowing afterglow-selected ion flow tube apparatus at 300 K and a pressure of 530 mTorr helium. The results indicate a moderate overall rate constant of (3.19 ± 0.39) × 10-10 cm3 s-1 (± 1σ) and an average branching fraction of 0.05 ± 0.04 for protonated trans-methyl formate and 0.95 ± 0.04 for the adduct ion. These experimental results are reinforced by ab initio calculations at the MP2(full)/aug-cc-pVTZ level of theory to examine the reaction coordinate and complement previous density functional theory calculations. This study underscores the need for continued observational studies of trans-methyl formate and for the exploration of other gas-phase formation routes to complex organic molecules.

  14. Statistical mechanics of soft-boson phase transitions

    NASA Technical Reports Server (NTRS)

    Gupta, Arun K.; Hill, Christopher T.; Holman, Richard; Kolb, Edward W.

    1991-01-01

    The existence of structure on large (100 Mpc) scales, and limits to anisotropies in the cosmic microwave background radiation (CMBR), have imperiled models of structure formation based solely upon the standard cold dark matter scenario. Novel scenarios, which may be compatible with large scale structure and small CMBR anisotropies, invoke nonlinear fluctuations in the density appearing after recombination, accomplished via the use of late time phase transitions involving ultralow mass scalar bosons. Herein, the statistical mechanics are studied of such phase transitions in several models involving naturally ultralow mass pseudo-Nambu-Goldstone bosons (pNGB's). These models can exhibit several interesting effects at high temperature, which is believed to be the most general possibilities for pNGB's.

  15. Formation of Frank-Kasper σ-phase from polydisperse diblock copolymers

    NASA Astrophysics Data System (ADS)

    Liu, Meijiao; Li, Weihua; Shi, An-Chang

    Recent experimental and theoretical studies have revealed a number of complex spherical phases including the complex Frank-Kasper σ-phase, which consists of 30 spheres in a unit cell. It is desirable to understand the mechanisms for the formation of the complex spherical phases such as the A15-phase and the Frank-Kasper σ-phase in block copolymers. Based on the observation that the A15-phase and the Frank-Kasper σ-phase are composed of spherical domains with different sizes, we hypothesize that polydispersity of the block copolymers could be used to obtain these complex phases. We tested this hypothesis by carrying out self-consistent field theory for polydisperse AB diblock copolymers. Specially we studied the relative stability of various spherical phases, including the fcc, bcc, A15 and Frank_Kasper σ-phase, in binary blends composed of AB block copolymers different lengths of the A-blocks. Our results revealed that the Frank-Kasper σ-phase could be stabilized by tailoring the length ratio as well as the compositions of the two diblock copolymers. The distribution of the diblocks in the system indicates that copolymer segregation is the origin of the formation of spherical domains with different sizes.

  16. Kinetic Study to Predict Sigma Phase Formation in Duplex Stainless Steels

    NASA Astrophysics Data System (ADS)

    dos Santos, Daniella Caluscio; Magnabosco, Rodrigo

    2016-04-01

    This work presents an improved kinetic study of sigma phase formation during isothermal aging between 973 K and 1223 K (700 °C and 950 °C), based on Kolmogorov-Johnson-Mehl-Avrami (K-J-M-A) model, established from volume fraction of sigma phase determined in backscattered electron images over polished surfaces of aged samples. The kinetic study shows a change in the main mechanism of sigma formation between 973 K and 1173 K (700 °C and 900 °C), from a nucleation-governed stage to a diffusion-controlled growth-coarsening stage, confirmed by a double inclination in K-J-M-A plots and microstructural observations. A single inclination in K-J-M-A plots was observed for the 1223 K (950 °C) aging temperature, showing that kinetic behavior in this temperature is only related to diffusion-controlled growth of sigma phase. The estimated activation energies for the nucleation of sigma phase are close to the molybdenum diffusion in ferrite, probably the controlling mechanism of sigma phase nucleation. The proposed time-temperature-transformation (TTT) diagram shows a "double c curve" configuration, probably associated to the presence of chi-phase formed between 973 K and 1073 K (700 °C and 800 °C), which acts as heterogeneous nuclei for sigma phase formation in low aging temperatures.

  17. Effect of electron irradiation exposure on phase formation, microstructure and mechanical strength of Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} superconductor prepared via co-precipitation method

    SciTech Connect

    Mohiju, Zaahidah 'Atiqah; Hamid, Nasri A. Kannan, V.; Abdullah, Yusof

    2015-04-29

    In this work the effect of electron irradiation on the mechanical properties of Bi2Sr2CaCu2O8 (Bi-2212) superconductor was studied by exposing the Bi-2212 superconductor with different doses of electron irradiation. Bi-2212 samples were prepared by using co-precipitation method. Irradiation was performed with irradiation dose of 100 kGray and 200 kGray, respectively. Characterization of the samples was performed by using X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Instron Universal Testing machine was used to measure the strength of the samples. The XRD patterns for the non-irradiated and irradiated samples show well-defined peaks of which could be indexed on the basis of a Bi-2212 phase structure. XRD patterns also indicate that electron irradiation did not affect the Bi-2212 superconducting phase. SEM micrographs show disorientation in the texture of the microstructure for irradiated samples. Sample exposed to 200 kGray electron irradiation dose shows enhancement of grain size. Their grain growth and texture improved slightly compared to other sample. The results also show that enlargement of grain size resulted in higher mechanical strength.

  18. Ionic Mechanisms of Carbon Formation in Flames.

    DTIC Science & Technology

    1980-03-01

    Office of Scientific Research/l 10 Mar 8 Building 410 13a/T 0FPAr-- Boiling AFB, DC 20332 34______________ 14. MONITORING AGENCY NAME & ADDRESS(utf...particular the hypothesis that soot nucleates on chemically formed ions whose growth is thermochemically favored and proceeds by very rapid ion-molecule...and on the ion chemistry in laboratory flames. b. Determine whether and how chemical additives affect nucleation (ini- tial particle formation) or

  19. Formation of vortices in first order phase transitions

    SciTech Connect

    Melfo, A. |; Perivolaropoulos, L. |

    1995-07-15

    Using a toy model Langrangian we investigate the formation of vortices in first order phase transitions. The evolution and interactions of vacuum bubbles are also studied using both analytical approximations and a numerical simulation of scalar field dynamics. A long-lived bubble wall bound state is discovered and its existence is justified by using a simplified potential for the bubble wall interaction. The conditions that need to be satisfied for vortex formation by bubble collisions are also studied with particular emphasis placed on geometrical considerations. These conditions are then implemented in a Monte Carlo simulation for the study of the probability of defect formation. It is shown that the probability of vortex formation by the collision of relativistically expanding bubbles gets reduced by about 10% due to the above-mentioned geometric effects.

  20. Stalk Phase Formation: Effects of Dehydration and Saddle Splay Modulus

    PubMed Central

    Kozlovsky, Yonathan; Efrat, Avishay; Siegel, David A.; Kozlov, Michael M.

    2004-01-01

    One of the earliest lipid intermediates forming in the course of membrane fusion is the lipid stalk. Although many aspects of the stalk hypothesis were elaborated theoretically and confirmed by experiments it remained unresolved whether stalk formation is always an energy consuming process or if there are conditions where the stalks are energetically favorable and form spontaneously resulting in an equilibrium stalk phase. Motivated by a recent breakthrough experiments we analyze the physical factors determining the spontaneous stalk formation. We show that this process can be driven by interplay between two factors: the elastic energy of lipid monolayers including a contribution of the saddle splay deformation and the energy of hydration repulsion acting between apposing membranes. We analyze the dependence of stalk formation on the saddle splay (Gaussian) modulus of the lipid monolayers and estimate the values of this modulus based on the experimentally established phase boundary between the lamellar and the stalk phases. We suggest that fusion proteins can induce stalk formation just by bringing the membranes into close contact, and accumulating, at least locally, a sufficiently large energy of the hydration repulsion. PMID:15454446

  1. Molecular mechanisms of dental enamel formation.

    PubMed

    Simmer, J P; Fincham, A G

    1995-01-01

    Tooth enamel is a unique mineralized tissue in that it is acellular, is more highly mineralized, and is comprised of individual crystallites that are larger and more oriented than other mineralized tissues. Dental enamel forms by matrix-mediated biomineralization. Enamel crystallites precipitate from a supersaturated solution within a well-delineated biological compartment. Mature enamel crystallites are comprised of non-stoichiometric carbonated calcium hydroxyapatite. The earliest crystallites appear suddenly at the dentino-enamel junction (DEJ) as rapidly growing thin ribbons. The shape and growth patterns of these crystallites can be interpreted as evidence for a precursor phase of octacalcium phosphate (OCP). An OCP crystal displays on its (100) face a surface that may act as a template for hydroxyapatite (OHAp) precipitation. Octacalcium phosphate is less stable than hydroxyapatite and can hydrolyze to OHAp. During this process, one unit cell of octacalcium phosphate is converted into two unit cells of hydroxyapatite. During the precipitation of the mineral phase, the degree of saturation of the enamel fluid is regulated. Proteins in the enamel matrix may buffer calcium and hydrogen ion concentrations as a strategy to preclude the precipitation of competing calcium phosphate solid phases. Tuftelin is an acidic enamel protein that concentrates at the DEJ and may participate in the nucleation of enamel crystals. Other enamel proteins may regulate crystal habit by binding to specific faces of the mineral and inhibiting growth. Structural analyses of recombinant amelogenin are consistent with a functional role in establishing and maintaining the spacing between enamel crystallites.

  2. The kinetics of composite particle formation during mechanical alloying

    NASA Technical Reports Server (NTRS)

    Aikin, B. J. M.; Courtney, T. H.

    1993-01-01

    The kinetics of composite particle formation during attritor milling of insoluble binary elemental powders have been examined. The effects of processing conditions (i.e., mill power, temperature, and charge ratio) on these kinetics were studied. Particle size distributions and fractions of elemental and composite particles were determined as functions of milling time and processing conditions. This allowed the deduction of phenomenological rate constants describing the propensity for fracture and welding during processing. For the mill-operating conditions investigated, the number of particles in the mill generally decreased with milling time, indicating a greater tendency for particle welding than fracture. Moreover, a bimodal size distribution is often obtained as a result of preferential welding. Copper and chromium 'alloy' primarily by encapsulation of Cr particles within Cu. This form of alloying also occurs in Cu-Nb alloys processed at low mill power and/or for short milling times. For other conditions, however, Cu-Nb alloys develop a lamellar morphology characteristic of mechanically alloyed two-phase ductile metals. Increasing mill power or charge (ball-to-powder weight) ratio (CR) increases the rate of composite particle formation.

  3. Star formation and gas phase history of the cosmic web

    NASA Astrophysics Data System (ADS)

    Snedden, Ali; Coughlin, Jared; Phillips, Lara Arielle; Mathews, Grant; Suh, In-Saeng

    2016-01-01

    We present a new method of tracking and characterizing the environment in which galaxies and their associated circumgalactic medium evolve. We have developed a structure finding algorithm that uses the rate of change of the density gradient to self-consistently parse and follow the evolution of groups/clusters, filaments and voids in large-scale structure simulations. We use this to trace the complete evolution of the baryons in the gas phase and the star formation history within each structure in our simulated volume. We vary the structure measure threshold to probe the complex inner structure of star-forming regions in poor clusters, filaments and voids. We find that the majority of star formation occurs in cold, condensed gas in filaments at intermediate redshifts (z ˜ 3). We also show that much of the star formation above a redshift z = 3 occurs in low-contrast regions of filaments, but as the density contrast increases at lower redshift, star formation switches to the high-contrast regions, or inner parts, of filaments. Since filaments bridge the void and cluster regions, it suggests that the majority of star formation occurs in galaxies in intermediate density regions prior to the accretion on to groups/clusters. We find that both filaments and poor clusters are multiphase environments distinguishing themselves by different distributions of gas phases.

  4. The mechanism of the formation of hydantoins

    SciTech Connect

    Worman, J.J.; Uhrich, K.; Olson, E.; Diehl, J.; Farnum, S.; Hawthorne, S.

    1986-04-01

    N-substituted hydantoins, specifically the N-(carbamylisopropyl)-5,5-dimethylhydantoin, form in water at room temperature from the N-..cap alpha..-carbamylisopropyl-N'-..cap alpha..isobutyronitrile urea. Only a small amount of the 5,5-dimethylhydantoin, IX, is produced from the N-substituted urea, IX, or its carbamate salt, X. Thus, they are not likely intermediates in the formation of the DMH in water in the presence of acetone, hydrogen cyanide, carbon dioxide, and ammonia. Instead the hydantoins are believed to result from the hydrated conjugate base of the carbamic acid (VI).

  5. Mechanisms of coke formation and fouling in thermal cracking

    SciTech Connect

    Lott, R.K.; Rangwala, H.A.; Hsi, C.

    1995-12-31

    When heavy oil is cracked to produce distillate, coking of the reacting liquid is, in general, preceded by formation of a new, highly viscous liquid phase, rich in coke precursors. Results from pilot-scale experiments using feedstocks from Gudao (China) reported here show that inert-gas stripping of light distillates from the reacting liquid strongly inhibits coking and possibly the partition of precursors into the new phase. Heavy oil, rich in asphaltene, is often reported to have a high coking propensity. This paper provides experimental evidence to show that the asphaltene concentration is not the most critical factor in the coking propensity of heavy oil. Autoclave tests show that the liquid product could contain more than 40% of asphaltene, and yield only 60% of the coke produced by similar tests in which the liquid product contains less than 20% asphaltene. The solubility of asphaltene in the reaction liquid is the most crucial factor affecting coke yield. It controls the coking mechanisms and the fouling tendency of the resulting coke.

  6. Gel phase formation in dilute triblock copolyelectrolyte complexes

    DOE PAGES

    Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; ...

    2017-02-23

    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chainmore » aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Finally, our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.« less

  7. Dynamic phases, pinning, and pattern formation for driven dislocation assemblies

    DOE PAGES

    Zhou, Caizhi; Reichhardt, Charles; Olson Reichhardt, Cynthia J.; ...

    2015-01-23

    We examine driven dislocation assemblies and show that they can exhibit a set of dynamical phases remarkably similar to those of driven systems with quenched disorder such as vortices in superconductors, magnetic domain walls, and charge density wave materials. These phases include pinned-jammed, fluctuating, and dynamically ordered states, and each produces distinct dislocation patterns as well as specific features in the noise fluctuations and transport properties. Lastly, our work suggests that many of the results established for systems with quenched disorder undergoing plastic depinning transitions can be applied to dislocation systems, providing a new approach for understanding pattern formation andmore » dynamics in these systems.« less

  8. Dynamic phases, pinning, and pattern formation for driven dislocation assemblies

    SciTech Connect

    Zhou, Caizhi; Reichhardt, Charles; Olson Reichhardt, Cynthia J.; Beyerlein, Irene J.

    2015-01-23

    We examine driven dislocation assemblies and show that they can exhibit a set of dynamical phases remarkably similar to those of driven systems with quenched disorder such as vortices in superconductors, magnetic domain walls, and charge density wave materials. These phases include pinned-jammed, fluctuating, and dynamically ordered states, and each produces distinct dislocation patterns as well as specific features in the noise fluctuations and transport properties. Lastly, our work suggests that many of the results established for systems with quenched disorder undergoing plastic depinning transitions can be applied to dislocation systems, providing a new approach for understanding pattern formation and dynamics in these systems.

  9. Fluid Mechanics of Blood Clot Formation

    NASA Astrophysics Data System (ADS)

    Fogelson, Aaron L.; Neeves, Keith B.

    2015-01-01

    Intravascular blood clots form in an environment in which hydrodynamic forces dominate and in which fluid-mediated transport is the primary means of moving material. The clotting system has evolved to exploit fluid dynamic mechanisms and to overcome fluid dynamic challenges to ensure that clots that preserve vascular integrity can form over the wide range of flow conditions found in the circulation. Fluid-mediated interactions between the many large deformable red blood cells and the few small rigid platelets lead to high platelet concentrations near vessel walls where platelets contribute to clotting. Receptor-ligand pairs with diverse kinetic and mechanical characteristics work synergistically to arrest rapidly flowing cells on an injured vessel. Variations in hydrodynamic stresses switch on and off the function of key clotting polymers. Protein transport to, from, and within a developing clot determines whether and how fast it grows. We review ongoing experimental and modeling research to understand these and related phenomena.

  10. Mechanisms of Basalt-plains Ridge Formation

    NASA Technical Reports Server (NTRS)

    Watters, T. R.; Maxwell, T. A.

    1985-01-01

    The morphologic similarities between the Columbia Plateau ridges and ridges on the Moon, Mercury and Mars form a strong basis for the interpretation of basalt-plains ridges as compressional folds. The basalt-plains ridges appear to have formed on competent flood basalt units deformed at the surface with essentially no confining pressure. Estimates of compressive strain for planetary ridges range from a few tenths of a percent on the Moon to up to 0.4% on Mars, to as high as 35% for Columbia Plateau folds with associated thrust faults. Such values have strong implications for both deformational mechanisms as well as for the source of stress. Deformational mechanisms that will attempt to account for the morphology, fold geometry, possible associated thrust faulting and regular spacing of the basalt-plains ridges on the terrestrial planets are under investigation.

  11. Fluid Mechanics of Blood Clot Formation.

    PubMed

    Fogelson, Aaron L; Neeves, Keith B

    2015-01-01

    Intravascular blood clots form in an environment in which hydrodynamic forces dominate and in which fluid-mediated transport is the primary means of moving material. The clotting system has evolved to exploit fluid dynamic mechanisms and to overcome fluid dynamic challenges to ensure that clots that preserve vascular integrity can form over the wide range of flow conditions found in the circulation. Fluid-mediated interactions between the many large deformable red blood cells and the few small rigid platelets lead to high platelet concentrations near vessel walls where platelets contribute to clotting. Receptor-ligand pairs with diverse kinetic and mechanical characteristics work synergistically to arrest rapidly flowing cells on an injured vessel. Variations in hydrodynamic stresses switch on and off the function of key clotting polymers. Protein transport to, from, and within a developing clot determines whether and how fast it grows. We review ongoing experimental and modeling research to understand these and related phenomena.

  12. Enabling Technologies for Direct Detection Optical Phase Modulation Formats

    NASA Astrophysics Data System (ADS)

    Xu, Xian

    Phase modulation formats are believed to be one of the key enabling techniques for next generation high speed long haul fiber-optic communication systems due to the following main advantages: (1) with a balanced detection, a better receiver sensitivity over conventional intensity modulation formats, e.g., a ˜3-dB sensitivity improvement using differential phase shift keying (DPSK) and a ˜1.3-dB sensitivity improvement using differential quadrature phase shift keying (DQPSK); (2) excellent robustness against fiber nonlinearities; (3) high spectrum efficiency when using multilevel phase modulation formats, such as DQPSK. As the information is encoded in the phase of the optical field, the phase modulation formats are sensitive to the phase-related impairments and the deterioration induced in the phase-intensity conversion. This consequently creates new challenging issues. The research objective of this thesis is to depict some of the challenging issues and provide possible solutions. The first challenge is the cross-phase modulation (XPM) penalty for the phase modulated channels co-propagating with the intensity modulated channels. The penalty comes from the pattern dependent intensity fluctuations of the neighboring intensity modulated channels being converted into phase noise in the phase modulation channels. We propose a model to theoretically analyze the XPM penalty dependence on the walk off effect. From this model, we suggest that using fibers with large local dispersion or intentionally introducing some residual dispersion per span would help mitigate the XPM penalty. The second challenge is the polarization dependent frequency shift (PDf) induced penalty during the phase-intensity conversion. The direct detection DPSK is usually demodulated in a Mach-Zehnder delay interferometer (DI). The polarization dependence of DI introduces a PDf causing a frequency offset between the laser's frequency and the transmissivity peak of DI, degrading the demodulated DPSK

  13. Multi-phase galaxy formation and quasar absorption systems

    NASA Astrophysics Data System (ADS)

    Maller, Ariyeh H.

    2005-03-01

    The central problem of galaxy formation is understanding the cooling and condensation of gas in dark matter halos. It is now clear that to match observations this requires further physics than the simple assumptions of single phase gas cooling. A model of multi-phase cooling (maller & bullock 2004) can successfully account for the upper cutoff in the masses of galaxies and provides a natural explanation of many types of absorption systems (mo & miralda-escude 1996). Absorption systems are our best probes of the gaseous content of galaxy halos and therefore provide important constraints on models for gas cooling into galaxies. All physical processes that effect gas cooling redistribute gas and therefore are detectable in absorption systems. Detailed studies of the nature of gas in galaxy halos using absorption systems are crucial for building a correct theory of galaxy formation.

  14. Simulating the Phases of the Moon Shortly after Its Formation

    ERIC Educational Resources Information Center

    Noordeh, Emil; Hall, Patrick; Cuk, Matija

    2014-01-01

    The leading theory for the origin of the Moon is the giant impact hypothesis, in which the Moon was formed out of the debris left over from the collision of a Mars sized body with the Earth. Soon after its formation, the orbit of the Moon may have been very different than it is today. We have simulated the phases of the Moon in a model for its…

  15. Solid-state graphene formation via a nickel carbide intermediate phase [Nickel carbide (Ni3C) as an intermediate phase for graphene formation

    SciTech Connect

    Xiong, W; Zhou, Yunshen; Hou, Wenjia; Guillemet, Thomas; Silvain, Jean-François; Lahaye, Michel; Lebraud, Eric; Xu, Shen; Wang, Xinwei; Cullen, David A; More, Karren Leslie; Lu, Yong Feng

    2015-11-10

    Direct formation of graphene with controlled number of graphitic layers on dielectric surfaces is highly desired for practical applications. Despite significant progress achieved in understanding the formation of graphene on metallic surfaces through chemical vapor deposition (CVD) of hydrocarbons, very limited research is available elucidating the graphene formation process via rapid thermal processing (RTP) of solid-state amorphous carbon, through which graphene is formed directly on dielectric surfaces accompanied by autonomous nickel evaporation. It is suggested that a metastable hexagonal nickel carbide (Ni3C) intermediate phase plays a critical role in transforming amorphous carbon to 2D crystalline graphene and contributing to the autonomous Ni evaporation. Temperature resolved carbon and nickel evolution in the RTP process is investigated using Auger electron spectroscopic (AES) depth profiling and glancing-angle X-ray diffraction (GAXRD). Formation, migration and decomposition of the hexagonal Ni3C are confirmed to be responsible for the formation of graphene and the evaporation of Ni at 1100 °C. The Ni3C-assisted graphene formation mechanism expands the understanding of Ni-catalyzed graphene formation, and provides insightful guidance for controlled growth of graphene through the solid-state transformation process.

  16. Solid-state graphene formation via a nickel carbide intermediate phase [Nickel carbide (Ni3C) as an intermediate phase for graphene formation

    DOE PAGES

    Xiong, W; Zhou, Yunshen; Hou, Wenjia; ...

    2015-11-10

    Direct formation of graphene with controlled number of graphitic layers on dielectric surfaces is highly desired for practical applications. Despite significant progress achieved in understanding the formation of graphene on metallic surfaces through chemical vapor deposition (CVD) of hydrocarbons, very limited research is available elucidating the graphene formation process via rapid thermal processing (RTP) of solid-state amorphous carbon, through which graphene is formed directly on dielectric surfaces accompanied by autonomous nickel evaporation. It is suggested that a metastable hexagonal nickel carbide (Ni3C) intermediate phase plays a critical role in transforming amorphous carbon to 2D crystalline graphene and contributing to themore » autonomous Ni evaporation. Temperature resolved carbon and nickel evolution in the RTP process is investigated using Auger electron spectroscopic (AES) depth profiling and glancing-angle X-ray diffraction (GAXRD). Formation, migration and decomposition of the hexagonal Ni3C are confirmed to be responsible for the formation of graphene and the evaporation of Ni at 1100 °C. The Ni3C-assisted graphene formation mechanism expands the understanding of Ni-catalyzed graphene formation, and provides insightful guidance for controlled growth of graphene through the solid-state transformation process.« less

  17. The fluid mechanics of thrombus formation

    NASA Technical Reports Server (NTRS)

    1972-01-01

    Experimental data are presented for the growth of thrombi (blood clots) in a stagnation point flow of fresh blood. Thrombus shape, size and structure are shown to depend on local flow conditions. The evolution of a thrombus is described in terms of a physical model that includes platelet diffusion, a platelet aggregation mechanism, and diffusion and convection of the chemical species responsible for aggregation. Diffusion-controlled and convection-controlled regimes are defined by flow parameters and thrombus location, and the characteristic growth pattern in each regime is explained. Quantitative comparisons with an approximate theoretical model are presented, and a more general model is formulated.

  18. Phase separation dynamics during Myxococcus xanthus fruiting body formation

    NASA Astrophysics Data System (ADS)

    Liu, Guannan; Bahar, Fatmagul; Patch, Adam; Thutupalli, Shashi; Yllanes, David; Marchetti, M. Cristina; Welch, Roy; Shaevitz, Joshua

    Many living systems take advantage of collective behavior for group survival. We use the soil-dwelling bacterium Myxococcus xanthus as a model to study out-of-equilibrium phase separation during fruiting body formation. M. xanthus cells have the ability to glide on solid surfaces and reverse their direction periodically. When starved, M. xanthus cells aggregate together and form structures called fruiting bodies, inside of which cells sporulate to survive stressful conditions. We show that at high cell density the formation of fruiting bodies is a phase separation process. From experimental data that combines single-cell tracking, population-scale imaging, mutants, and drug applications, we construct the phase diagram of M. xanthus in the space of Péclet number and cell density. When wild type cells are starved, we find that they actively increase their Péclet number by modulating gliding speed and reversal frequency which induces a phase separation from a gas-like state to an aggregated fruiting body state.

  19. Phase formation in Cu-Si and Cu-Ge

    NASA Astrophysics Data System (ADS)

    Hong, Stella Q.; Comrie, Craig M.; Russell, Stephen W.; Mayer, James W.

    1991-10-01

    Phase formation and growth kinetics have been investigated with lateral diffusion couples in Cu-Si and Cu-Ge systems. Analytical electron microscopy was used to determine the crystal structures and chemical compositions of the growing phases. Cu3Si is found to be the dominant phase in the Cu-Si system. The growth of the silicide follows a (time)1/2 dependence with an activation energy of 0.95 eV in the temperature range of 200-260 °C. Cu3Ge is the only phase observed in Cu-Ge lateral diffusion couples with its length up to 20 μm. The growth of Cu3Ge is a diffusion controlled process at a rate similar to that of Cu3Si. The activation energy of Cu3Ge growth is 0.94 eV at 200-420 °C. In Cu-silicide or Cu-germanide formation, Cu appears to be the dominant diffusing species.

  20. Anomalous surface phase formation on Pt sub 3 Sn <110>

    SciTech Connect

    Haner, A.N.; Ross, P.N. ); Bardi, U. . Dipt. di Chimica)

    1990-06-01

    LEED analysis of the clean annealed surface of a {l angle}110{r angle} oriented Pt{sub 3}Sn single crystal surface indicates the formation of a multilayer surface phase which does not have the L1{sub 2} bulk structure. LEISS analysis indicates a surface stoichiometry of ca. 1:1 with Sn atoms displaced ca. 1.4 above the plane of Pt atoms. The surface phase is hypothesized to be a rhombic distortion of the {l angle}0001{r angle} plant of PtSn, which has a B8{sub 1} (NiAs-type) bulk structure. It is not clear whether the phase forms by precipitation of PtSn due to a slight (0.5%) stoichiometric excess of Sn in the bulk, or due to multilayer reconstruction driven by surface segregation. 20 refs., 3 figs.

  1. Nonrainfall water origins and formation mechanisms.

    PubMed

    Kaseke, Kudzai Farai; Wang, Lixin; Seely, Mary K

    2017-03-01

    Dryland ecosystems cover 40% of the total land surface on Earth and are defined broadly as zones where precipitation is considerably less than the potential evapotranspiration. Nonrainfall waters (for example, fog and dew) are the least-studied and least-characterized components of the hydrological cycle, although they supply critical amounts of water for dryland ecosystems. The sources of nonrainfall waters are largely unknown for most systems. In addition, most field and modeling studies tend to consider all nonrainfall inputs as a single category because of technical constraints, which hinders prediction of dryland responses to future warming conditions. This study uses multiple stable isotopes ((2)H, (18)O, and (17)O) to show that fog and dew have multiple origins and that groundwater in drylands can be recycled via evapotranspiration and redistributed to the upper soil profile as nonrainfall water. Surprisingly, the non-ocean-derived (locally generated) fog accounts for more than half of the total fog events, suggesting a potential shift from advection-dominated fog to radiation-dominated fog in the fog zone of the Namib Desert. This shift will have implications on the flora and fauna distribution in this fog-dependent system. We also demonstrate that fog and dew can be differentiated on the basis of the dominant fractionation (equilibrium and kinetic) processes during their formation using the (17)O-(18)O relationship. Our results are of great significance in an era of global climate change where the importance of nonrainfall water increases because rainfall is predicted to decline in many dryland ecosystems.

  2. Nonrainfall water origins and formation mechanisms

    PubMed Central

    Kaseke, Kudzai Farai; Wang, Lixin; Seely, Mary K.

    2017-01-01

    Dryland ecosystems cover 40% of the total land surface on Earth and are defined broadly as zones where precipitation is considerably less than the potential evapotranspiration. Nonrainfall waters (for example, fog and dew) are the least-studied and least-characterized components of the hydrological cycle, although they supply critical amounts of water for dryland ecosystems. The sources of nonrainfall waters are largely unknown for most systems. In addition, most field and modeling studies tend to consider all nonrainfall inputs as a single category because of technical constraints, which hinders prediction of dryland responses to future warming conditions. This study uses multiple stable isotopes (2H, 18O, and 17O) to show that fog and dew have multiple origins and that groundwater in drylands can be recycled via evapotranspiration and redistributed to the upper soil profile as nonrainfall water. Surprisingly, the non–ocean-derived (locally generated) fog accounts for more than half of the total fog events, suggesting a potential shift from advection-dominated fog to radiation-dominated fog in the fog zone of the Namib Desert. This shift will have implications on the flora and fauna distribution in this fog-dependent system. We also demonstrate that fog and dew can be differentiated on the basis of the dominant fractionation (equilibrium and kinetic) processes during their formation using the 17O-18O relationship. Our results are of great significance in an era of global climate change where the importance of nonrainfall water increases because rainfall is predicted to decline in many dryland ecosystems. PMID:28345058

  3. The formation of topological defects in phase transitions

    NASA Technical Reports Server (NTRS)

    Hodges, Hardy M.

    1989-01-01

    It was argued, and fought through numerical work that the results of non-dynamical Monte Carlo computer simulations cannot be applied to describe the formation of topological defects when the correlation length at the Ginzburg temperature is significantly smaller than the horizon size. To test the current hypothesis that infinite strings at formation are essentially described by Brownian walks of size the correlation length at the Ginzburg temperature, fields at the Ginzburg temperature were equilibrated. Infinite structure do not exist in equilibrium for reasonable definitions of the Ginzburg temperature, and horizons must be included in a proper treatment. A phase transition, from small-scale to large-scale string or domain wall structure, is found to occur very close to the Ginzburg temperature, in agreement with recent work. The formation process of domain walls and global strings were investigated through the breaking of initially ordered states. To mimic conditions in the early Universe, cooling times are chosen so that horizons exist in the sample volume when topological structure formation occurs. The classical fields are evolved in real-time by the numerical solution of Langevin equations of motion on a three dimensional spatial lattice. The results indicate that it is possible for most of the string energy to be in small loops, rather than in long strings, at formation.

  4. PLETHORA gradient formation mechanism separates auxin responses

    PubMed Central

    Siligato, Riccardo; Smetana, Ondřej; Díaz-Triviño, Sara; Salojärvi, Jarkko; Wachsman, Guy; Prasad, Kalika; Heidstra, Renze; Scheres, Ben

    2015-01-01

    During plant growth, dividing cells in meristems must coordinate transitions from division to expansion and differentiation, thus generating three distinct developmental zones: the meristem, elongation zone and differentiation zone1. Simultaneously, plants display tropisms, rapid adjustments of their direction of growth to adapt to environmental conditions. It is unclear how stable zonation is maintained during transient adjustments in growth direction. In Arabidopsis roots, many aspects of zonation are controlled by the phytohormone auxin and auxin-induced PLETHORA (PLT) transcription factors, both of which display a graded distribution with a maximum near the root tip2-12. In addition, auxin is also pivotal for tropic responses13,14. Here, using an iterative experimental and computational approach, we show how an interplay between auxin and PLTs controls zonation and gravitropism. We find that the PLT gradient is not a direct, proportionate readout of the auxin gradient. Rather, prolonged high auxin levels generate a narrow PLT transcription domain from which a gradient of PLT protein is subsequently generated through slow growth dilution and cell-to-cell movement. The resulting PLT levels define the location of developmental zones. In addition to slowly promoting PLT transcription, auxin also rapidly influences division, expansion and differentiation rates. We demonstrate how this specific regulatory design in which auxin cooperates with PLTs through different mechanisms and on different timescales enables both the fast tropic environmental responses and stable zonation dynamics necessary for coordinated cell differentiation. PMID:25156253

  5. Role of Nucleation and Growth in Two-Phase Microstructure Formation

    SciTech Connect

    Shin, Jong Ho

    2007-01-01

    During the directional solidification of peritectic alloys, a rich variety of two-phase microstructures develop, and the selection process of a specific microstructure is complicated due to the following two considerations. (1) In contrast to many single phase and eutectic microstructures that grow under steady state conditions, two-phase microstructures in a peritectic system often evolve under non-steady-state conditions that can lead to oscillatory microstructures, and (2) the microstructure is often governed by both the nucleation and the competitive growth of the two phases in which repeated nucleation can occur due to the change in the local conditions during growth. In this research, experimental studies in the Sn-Cd system were designed to isolate the effects of nucleation and competitive growth on the dynamics of complex microstructure formation. Experiments were carried out in capillary samples to obtain diffusive growth conditions so that the results can be analyzed quantitatively. At high thermal gradient and low velocity, oscillatory microstructures were observed in which repeated nucleation of the two phases was observed at the wall-solid-liquid junction. Quantitative measurements of nucleation undercooling were obtained for both the primary and the peritectic phase nucleation, and three different ampoule materials were used to examine the effect of different contact angles at the wall on nucleation undercooling. Nucleation undercooling for each phase was found to be very small, and the experimental undercooling values were orders of magnitude smaller than that predicted by the classical theory of nucleation. A new nucleation mechanism is proposed in which the clusters of atoms at the wall ahead of the interface can become a critical nucleus when the cluster encounters the triple junction. Once the nucleation of a new phase occurs, the microstructure is found to be controlled by the relative growth of the two phases that give rise to different

  6. Multifunctional acid formation from the gas-phase ozonolysis of beta-pinene.

    PubMed

    Ma, Yan; Marston, George

    2008-10-28

    The gas-phase ozonolysis of beta-pinene was studied in static chamber experiments, using gas chromatography coupled to mass spectrometric and flame ionisation detection to separate and detect products. A range of multifunctional organic acids-including pinic acid, norpinic acid, pinalic-3-acid, pinalic-4-acid, norpinalic acid and OH-pinalic acid-were identified in the condensed phase after derivatisation. Formation yields for these products under systematically varying reaction conditions (by adding different OH radical scavengers and Criegee intermediate scavengers) were investigated and compared with those observed from alpha-pinene ozonolysis, allowing detailed information on product formation mechanisms to be elucidated. In addition, branching ratios for the initial steps of the reaction were inferred from quantitative measurements of primary carbonyl formation. Atmospheric implications of this work are discussed.

  7. Impact of Gas-Phase Mechanisms on Weather Research Forecasting Model with Chemistry (WRF/Chem) Predictions: Mechanism Implementation and Comparative Evaluation

    EPA Science Inventory

    Gas-phase mechanisms provide important oxidant and gaseous precursors for secondary aerosol formation. Different gas-phase mechanisms may lead to different predictions of gases, aerosols, and aerosol direct and indirect effects. In this study, WRF/Chem-MADRID simulations are cond...

  8. Domain wall formation in late-time phase transitions

    NASA Technical Reports Server (NTRS)

    Kolb, Edward W.; Wang, Yun

    1992-01-01

    We examine domain wall formulation in late time phase transitions. We find that in the invisible axion domain wall phenomenon, thermal effects alone are insufficient to drive different parts of the disconnected vacuum manifold. This suggests that domain walls do not form unless either there is some supplemental (but perhaps not unreasonable) dynamics to localize the scalar field responsible for the phase transition to the low temperature maximum (to an extraordinary precision) before the onset of the phase transition, or there is some non-thermal mechanism to produce large fluctuations in the scalar field. The fact that domain wall production is not a robust prediction of late time transitions may suggest future directions in model building.

  9. Invariance principles for cochlear mechanics: hearing phases.

    PubMed

    Reimann, H M

    2006-02-01

    A functional model of the cochlea is devised on the basis of the results from classical experiments. The basilar membrane filter is investigated in detail. Its phase is close to linear in the region around the peak of the amplification. On one side this has consequences for the time analysis and on the other side this has led to a prediction on phase perception for very simple combinations of tones, a prediction which is now confirmed by experiments. Equivariance under the dilation group permits one to describe the model by a wavelet transform [Daubechies, Ten Lectures on Wavelets (SIAM, Philadelphia, 1992)]. The wavelet is discussed in reference to the phase analysis of the basilar membrane filter.

  10. Shock Formation in Electron-Ion Plasmas: Mechanism and Timing

    NASA Astrophysics Data System (ADS)

    Bret, Antoine; Stockem Novo, Anne; Ricardo, Fonseca; Luis, Silva

    2016-10-01

    We analyze the formation of a collisionless shock in electron-ion plasmas in theory and simulations. In initially un-magnetized relativistic plasmas, such shocks are triggered by the Weibel instability. While in pair plasmas the shock starts forming right after the instability saturates, it is not so in electron-ion plasmas because the Weibel filaments at saturation are too small. An additional merging phase is therefore necessary for them to efficiently stop the flow. We derive a theoretical model for the shock formation time, taking into account filament merging in the nonlinear phase of the Weibel instability. This process is much slower than in electron-positron pair shocks, and so the shock formation is longer by a factor proportional to √{mi /me } ln(mi /me).

  11. PRISMA—A formation flying project in implementation phase

    NASA Astrophysics Data System (ADS)

    Persson, Staffan; Veldman, Sytze; Bodin, Per

    2009-11-01

    The PRISMA project for autonomous formation flying and rendezvous has passed its critical design review in February-March 2007. The project comprises two satellites which are an in-orbit testbed for Guidance, Navigation and Control (GNC) algorithms and sensors for advanced formation flying and rendezvous. Several experiments involving GNC algorithms, sensors and thrusters will be performed during a 10 month mission with launch planned for the second half of 2009. The project is run by the Swedish Space Corporation (SSC) in close cooperation with the German Aerospace Center (DLR), the French Space Agency (CNES) and the Technical University of Denmark (DTU). Additionally, the project also will demonstrate flight worthiness of two novel motor technologies: one that uses environmentally clean and non-hazardous propellant, and one that consists of a microthruster system based on MEMS technology. The project will demonstrate autonomous formation flying and rendezvous based on several sensors—GPS, RF-based and vision based—with different objectives and in different combinations. The GPS-based onboard navigation system, contributed by DLR, offers relative orbit information in real-time in decimetre range. The RF-based navigation instrument intended for DARWIN, under CNES development, will be tested for the first time on PRISMA, both for instrument performance, but also in closed loop as main sensor for formation flying. Several rendezvous and proximity manoeuvre experiments will be demonstrated using only vision based sensor information coming from the modified star camera provided by DTU. Semi-autonomous operations ranging from 200 km to 1 m separation between the satellites will be demonstrated. With the project now in the verification phase particular attention is given to the specific formation flying and rendezvous functionality on instrument, GNC-software and system level.

  12. Formation of ion clusters in the phase separated structures of neutral-charged polymer blends

    NASA Astrophysics Data System (ADS)

    Kwon, Ha-Kyung; Olvera de La Cruz, Monica

    2015-03-01

    Polyelectrolyte blends, consisting of at least one charged species, are promising candidate materials for fuel cell membranes, for their mechanical stability and high selectivity for proton conduction. The phase behavior of the blends is important to understand, as this can significantly affect the performance of the device. The phase behavior is controlled by χN, the Flory-Huggins parameter multiplied by the number of mers, as well as the electrostatic interactions between the charged backbone and the counterions. It has recently been shown that local ionic correlations, incorporated via liquid state (LS) theory, enhance phase separation of the blend, even in the absence of polymer interactions. In this study, we show phase diagrams of neutral-charged polymer blends including ionic correlations via LS theory. In addition to enhanced phase separation at low χN, the blends show liquid-liquid phase separation at high electrostatic interaction strengths. Above the critical strength, the charged polymer phase separates into ion-rich and ion-poor regions, resulting in the formation of ion clusters within the charged polymer phase. This can be shown by the appearance of multiple spinodal and critical points, indicating the coexistence of several charge separated phases. This work was performed under the following financial assistance award 70NANB14H012 from U.S. Department of Commerce, National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design (CHiMaD).

  13. Droplets formation and merging in two-phase flow microfluidics.

    PubMed

    Gu, Hao; Duits, Michel H G; Mugele, Frieder

    2011-01-01

    Two-phase flow microfluidics is emerging as a popular technology for a wide range of applications involving high throughput such as encapsulation, chemical synthesis and biochemical assays. Within this platform, the formation and merging of droplets inside an immiscible carrier fluid are two key procedures: (i) the emulsification step should lead to a very well controlled drop size (distribution); and (ii) the use of droplet as micro-reactors requires a reliable merging. A novel trend within this field is the use of additional active means of control besides the commonly used hydrodynamic manipulation. Electric fields are especially suitable for this, due to quantitative control over the amplitude and time dependence of the signals, and the flexibility in designing micro-electrode geometries. With this, the formation and merging of droplets can be achieved on-demand and with high precision. In this review on two-phase flow microfluidics, particular emphasis is given on these aspects. Also recent innovations in microfabrication technologies used for this purpose will be discussed.

  14. Droplets Formation and Merging in Two-Phase Flow Microfluidics

    PubMed Central

    Gu, Hao; Duits, Michel H. G.; Mugele, Frieder

    2011-01-01

    Two-phase flow microfluidics is emerging as a popular technology for a wide range of applications involving high throughput such as encapsulation, chemical synthesis and biochemical assays. Within this platform, the formation and merging of droplets inside an immiscible carrier fluid are two key procedures: (i) the emulsification step should lead to a very well controlled drop size (distribution); and (ii) the use of droplet as micro-reactors requires a reliable merging. A novel trend within this field is the use of additional active means of control besides the commonly used hydrodynamic manipulation. Electric fields are especially suitable for this, due to quantitative control over the amplitude and time dependence of the signals, and the flexibility in designing micro-electrode geometries. With this, the formation and merging of droplets can be achieved on-demand and with high precision. In this review on two-phase flow microfluidics, particular emphasis is given on these aspects. Also recent innovations in microfabrication technologies used for this purpose will be discussed. PMID:21731459

  15. Mechanism of vacancy formation induced by hydrogen in tungsten

    SciTech Connect

    Liu, Yi-Nan; Ahlgren, T.; Bukonte, L.; Nordlund, K.; Shu, Xiaolin; Yu, Yi; Lu, Guang-Hong; Li, Xiao-Chun

    2013-12-15

    We report a hydrogen induced vacancy formation mechanism in tungsten based on classical molecular dynamics simulations. We demonstrate the vacancy formation in tungsten due to the presence of hydrogen associated directly with a stable hexagonal self-interstitial cluster as well as a linear crowdion. The stability of different self-interstitial structures has been further studied and it is particularly shown that hydrogen plays a crucial role in determining the configuration of SIAs, in which the hexagonal cluster structure is preferred. Energetic analysis has been carried out to prove that the formation of SIA clusters facilitates the formation of vacancies. Such a mechanism contributes to the understanding of the early stage of the hydrogen blistering in tungsten under a fusion reactor environment.

  16. Shared mechanisms in physiological and pathological nucleoplasmic reticulum formation

    PubMed Central

    Drozdz, Marek Mateusz; Vaux, David John

    2017-01-01

    ABSTRACT The mammalian nuclear envelope (NE) can develop complex dynamic membrane-bounded invaginations in response to both physiological and pathological stimuli. Since the formation of these nucleoplasmic reticulum (NR) structures can occur during interphase, without mitotic NE breakdown and reassembly, some other mechanism must drive their development. Here we consider models for deformation of the interphase NE, together with the evidence for their potential roles in NR formation. PMID:27797635

  17. Closure of supporting cell scar formations requires dynamic actin mechanisms

    PubMed Central

    Hordichok, Andrew J.; Steyger, Peter S.

    2007-01-01

    In many vertebrate inner ear sensory epithelia, dying sensory hair cells are extruded, and the apices of surrounding supporting cells converge to re-seal the epithelial barrier between the electrochemically-distinct endolymph and perilymph. These cellular mechanisms remain poorly understood. Dynamic microtubular mechanisms have been proposed for hair cell extrusion; while contractile actomyosin-based mechanisms are required for cellular extrusion and closure in epithelial monolayers. The hypothesis that cytoskeletal mechanisms are required for hair cell extrusion and supporting cell scar formation was tested using bullfrog saccules incubated with gentamicin (6 hours), and allowed to recover (18 hours). Explants were then fixed, labeled for actin and cytokeratins, and viewed with confocal microscopy. To block dynamic cytoskeletal processes, disruption agents for microtubules (colchicine, paclitaxel) myosin (Y-27632, ML-9) or actin (cytochalasin D, latrunculin A) were added during treatment and recovery. Microtubule disruption agents had no effect on hair cell extrusion or supporting cell scar formation. Myosin disruption agents appeared to slow down scar formation but not hair cell extrusion. Actin disruption agents blocked scar formation, and largely prevented hair cell extrusion. These data suggest that actin-based cytoskeletal processes are required for hair cell extrusion and supporting cell scar formation in bullfrog saccules. PMID:17716843

  18. Polymer interdiffusion and mechanical property development during latex film formation

    SciTech Connect

    Fu, Z.; Boczar, E.M.; Kirk, A.B.

    1995-12-31

    The interdiffusion of polymer chains across the latex boundaries during latex film formation has been studied using the fluorescence technique of direct energy transfer (DET) or small-angle neutron scattering technique (SANS) by several groups. The increase in mechanical strength and the interdiffusion depth determined by SANS has been correlated for several polystyrene latex systems during film formation. In this paper, we will present the correlation between the increase in mechanical strength and the interdiffusion depth for a poly (amyl methacrylate) latex system. Volume fractions of mixing (Fm) as a function of annealing time for two poly (amyl methacrylate) latex blend films were measured.

  19. Fibril Formation and Phase Separation in Aqueous Cellulose Ethers

    NASA Astrophysics Data System (ADS)

    Maxwell, Amanda; Schmidt, Peter; McAllister, John; Lott, Joseph; Bates, Frank; Lodge, Timothy

    Aqueous solutions of many cellulose ethers are known to undergo thermoreversible gelation and phase separation upon heating to form turbid hydrogels, but the mechanism and resulting structures have not been well understood. Turbidity, light scattering and small-angle neutron scattering (SANS) are used to show that hydroxypropyl methylcellulose (HPMC) chains are dissolved in water below 50 °C and undergo phase separation at higher temperatures. At 70 °C, at sufficiently high concentrations in water, HPMC orders into fibrillar structures with a well-defined radius of 18 +/- 2 nm, as characterized by cryogenic transmission electron microscopy and SANS. The HPMC fibril structure is independent of concentration and heating rate. However, HPMC fibrils do not form a percolating network as readily as is seen in methylcellulose, resulting in a lower hot-gel modulus, as demonstrated by rheology.

  20. Nematic phase formation in suspensions of graphene oxide

    NASA Astrophysics Data System (ADS)

    Fresneau, Nathalie; Campidelli, Stéphane

    The last decade has seen the rise of graphene. Graphene is a single layer of graphite; it can be obtained by direct liquid phase exfoliation of the latter through harsh sonication. This technique presents the disadvantage to produce small graphene flakes (typically in the 0.05 to 0.4 μm2 range for the monolayers) and multilayer graphene with uncontrolled thickness distributions. In order to improve the exfoliation process, one has to counter the strong van der Waals interactions between the carbon planes of graphite. This implies to increase the distance between two planes and it can be done, for example, by oxidizing graphite to introduce oxygen species in the graphenic planes. The fabrication of graphite oxide is known for almost 150 years, and it became popular again these last ten years. Generally, the oxidation of graphite is performed following a method described by Hummers in the 1950's and the material produced by this technique exfoliates quasi-spontaneously into monolayer species called graphene oxide (GO). The highly anisotropic shape of GO (several μm in length and width for a thickness of ca. 1 nm) combined with the presence of oxygenated functions on the sp2 carbon structure of graphene lead to the formation of a lyotropic liquid crystalline phase in water. Above a certain concentration of graphene flakes the gain in translational entropy for a long-range ordered phase outweighs the loss in rotational entropy, and the liquid crystal phase then forms. The value of the threshold is affected by the aspect ratio of the graphene flakes but other factors such as the interactions also play a strong role.

  1. Reinvestigation of the nitrosamine-formation mechanism during ozonation.

    PubMed

    Yang, Lei; Chen, Zhonglin; Shen, Jimin; Xu, Zhenzhen; Liang, Heng; Tian, Jiayu; Ben, Yue; Zhai, Xu; Shi, Wenxin; Li, Guibai

    2009-07-15

    Previous studies have linked nitrosamine formation during ozonation to a nitrosation process in which nitrosation is catalyzed by formaldehyde, a normal byproduct of ozonation. This mechanism cannot explain the increase in N-nitrosodimethylamine (NDMA) formation with an increase of pH. This study reinvestigates the pathway of N-nitrosamine formation during ozonation. Our observations demonstrated the critical importance of some reactive inorganic nitrogenous intermediates, such as hydroxylamine and dinitrogen tetroxide (N2O4). We report two altemative pathways that possibly explain nitrosamine formation during ozonation at neutral and alkaline pH: (i) secondary amine precursors reacting with hydroxylamine to form unsymmetrical dialkylhydrazine intermediates, which are further oxidized to their relevant nitrosamines; and (ii) a nitrosation pathway in which N2O4 acts as the nitrosating reagent. The key variables of pathway (i) (including reaction time, pH, dissolved oxygen) were investigated. Since hydroxylamine is a common intermediate of dimethylamine oxidation, it is reasonable to assume that hydroxylamine is a possible inorganic precursor for NDMA formation during oxidation processes using strong oxidants. With an improved understanding of the pathway of nitrosamine formation, it should be apparent that the reactive nitrogenous intermediates play an important role in the N-nitrosamine-formation, so future studies of N-nitrosamine-formation control should be focused on the transformation of nitrogen in water treatment

  2. Isoprene suppression of new particle formation: Potential mechanisms and implications

    NASA Astrophysics Data System (ADS)

    Lee, Shan-Hu; Uin, Janek; Guenther, Alex B.; Gouw, Joost A.; Yu, Fangqun; Nadykto, Alex B.; Herb, Jason; Ng, Nga L.; Koss, Abigail; Brune, William H.; Baumann, Karsten; Kanawade, Vijay P.; Keutsch, Frank N.; Nenes, Athanasios; Olsen, Kevin; Goldstein, Allen; Ouyang, Qi

    2016-12-01

    Secondary aerosols formed from anthropogenic pollutants and natural emissions have substantial impacts on human health, air quality, and the Earth's climate. New particle formation (NPF) contributes up to 70% of the global production of cloud condensation nuclei (CCN), but the effects of biogenic volatile organic compounds (BVOCs) and their oxidation products on NPF processes in forests are poorly understood. Observations show that isoprene, the most abundant BVOC, suppresses NPF in forests. But the previously proposed chemical mechanism underlying this suppression process contradicts atmospheric observations. By reviewing observations made in other forests, it is clear that NPF rarely takes place during the summer when emissions of isoprene are high, even though there are sufficient concentrations of monoterpenes. But at present it is not clear how isoprene and its oxidation products may change the oxidation chemistry of terpenes and how NOx and other atmospheric key species affect NPF in forest environments. Future laboratory experiments with chemical speciation of gas phase nucleation precursors and clusters and chemical composition of particles smaller than 10 nm are required to understand the role of isoprene in NPF. Our results show that climate models can overpredict aerosol's first indirect effect when not considering the absence of NPF in the southeastern U.S. forests during the summer using the current nucleation algorithm that includes only sulfuric acid and total concentrations of low-volatility organic compounds. This highlights the importance of understanding NPF processes as function of temperature, relative humidity, and BVOC compositions to make valid predictions of NPF and CCN at a wide range of atmospheric conditions.

  3. Characterising the acceleration phase of blast wave formation

    SciTech Connect

    Fox, T. E. Pasley, J.; Robinson, A. P. L.; Schmitz, H.

    2014-10-15

    Intensely heated, localised regions in uniform fluids will rapidly expand and generate an outwardly propagating blast wave. The Sedov-Taylor self-similar solution for such blast waves has long been studied and applied to a variety of scenarios. A characteristic time for their formation has also long been identified using dimensional analysis, which by its very nature, can offer several interpretations. We propose that, rather than simply being a characteristic time, it may be interpreted as the definitive time taken for a blast wave resulting from an intense explosion in a uniform media to contain its maximum kinetic energy. A scaling relation for this measure of the acceleration phase, preceding the establishment of the blast wave, is presented and confirmed using a 1D planar hydrodynamic model.

  4. Atomic scale analysis of phase formation and diffusion kinetics in Ag/Al multilayer thin films

    NASA Astrophysics Data System (ADS)

    Aboulfadl, Hisham; Gallino, Isabella; Busch, Ralf; Mücklich, Frank

    2016-11-01

    Thin films generally exhibit unusual kinetics leading to chemical reactions far from equilibrium conditions. Binary metallic multilayer thin films with miscible elements show some similar behaviors with respect to interdiffusion and phase formation mechanisms. Interfacial density, lattice defects, internal stresses, layer morphologies and deposition conditions strongly control the mass transport between the individual layers. In the present work, Ag/Al multilayer thin films are used as a simple model system, in which the effects of the sputtering power and the bilayer period thickness on the interdiffusion and film reactions are investigated. Multilayers deposited by DC magnetron sputtering undergo calorimetric and microstructural analyses. In particular, atom probe tomography is extensively used to provide quantitative information on concentration gradients, grain boundary segregations, and reaction mechanisms. The magnitude of interdiffusion was found to be inversely proportional to the period thickness for the films deposited under the same conditions, and was reduced using low sputtering power. Both the local segregation at grain boundaries as well as pronounced non-equilibrium supersaturation effects play crucial roles during the early stages of the film reactions. For multilayers with small periods of 10 nm supersaturation of the Al layers with Ag precedes the polymorphic nucleation and growth of the hcp γ-Ag2Al phase. In larger periods the γ phase formation is triggered at junctions between grain boundaries and layers interfaces, where the pathway to heterogeneous nucleation is local supersaturation. Other Ag-rich phases also form as intermediate phases due to asymmetric diffusion rates of parent phases in the γ phase during annealing.

  5. Molecular Mechanisms of Floral Boundary Formation in Arabidopsis

    PubMed Central

    Yu, Hongyang; Huang, Tengbo

    2016-01-01

    Boundary formation is a crucial developmental process in plant organogenesis. Boundaries separate cells with distinct identities and act as organizing centers to control the development of adjacent organs. In flower development, initiation of floral primordia requires the formation of the meristem-to-organ (M–O) boundaries and floral organ development depends on the establishment of organ-to-organ (O–O) boundaries. Studies in this field have revealed a suite of genes and regulatory pathways controlling floral boundary formation. Many of these genes are transcription factors that interact with phytohormone pathways. This review will focus on the functions and interactions of the genes that play important roles in the floral boundaries and discuss the molecular mechanisms that integrate these regulatory pathways to control the floral boundary formation. PMID:26950117

  6. Importance of Aqueous-phase Secondary Organic Aerosol Formation from Aromatics in an Atmospheric Hydrocarbon Mixture

    NASA Astrophysics Data System (ADS)

    Parikh, H. M.; Carlton, A. G.; Vizuete, W.; Zhang, H.; Zhou, Y.; Chen, E.; Kamens, R. M.

    2010-12-01

    Two new secondary organic aerosol (SOA) modeling frameworks are developed, one based on an aromatic gas and particle-phase kinetic mechanism and another based on a parameterized SOA model used in conjunction with an underlying gas-phase mechanism, both of which simulate SOA formation through partitioning to two stable liquid phases: one hydrophilic containing particle aqueous-phase and the other hydrophobic comprising mainly organic components. The models were evaluated against outdoor smog chamber experiments with different combinations of initial toluene, o-xylene, p-xylene, toluene and xylene mixtures, NOx, non-SOA-forming hydrocarbon mixture, initial seed type, and humidity. Aerosol data for experiments with either ammonium sulfate or initial background seed particles, in the presence of an atmospheric hydrocarbon mixture, NOx and in sunlight under a dry atmosphere (RH = 6 to 10%) show reduced SOA formation when compared to experiments with similar initial gas and particle concentrations at higher relative humidities (RH = 40 to 90%). Both frameworks simulated reasonable fits to the total observed SOA concentrations under all conditions. For both dry and wet experiments with low initial seed, semi-volatile product partitioning in particle organic-phase is mass-transfer limited and is modeled using a dynamic gas-particle partitioning algorithm with accommodation coefficient as the primary pseudo-transport parameter. Further, the modeled SOA product distributions for both frameworks clearly show the importance of the contribution of aqueous-phase SOA particularly under conditions of low initial seed concentrations and high-humidity. For both models, under these conditions, aqueous-phase SOA from uptake of glyoxal, methylglyoxal and related polar products to particle water phase dominates as compared to the partitioning of semi-volatiles to particle organic phase. Interestingly, both the kinetic and parameterized SOA frameworks simulate similar amounts of aqueous-phase

  7. Dynamic phase separation: from coarsening to turbulence via structure formation.

    PubMed

    Golovin, A A; Pismen, L M

    2004-09-01

    We investigate some new two-dimensional evolution models belonging to the class of convective Cahn-Hilliard models: (i) a local model with a scalar order parameter, (ii) a nonlocal model with a scalar order parameter, and (iii) a model with a vector order parameter. These models are applicable to phase-separating system where concentration gradients cause hydrodynamic motion due to buoyancy or Marangoni effect. The numerical study of the models shows transition from coarsening, typical of Cahn-Hilliard systems, to spatiotemporally irregular behavior (turbulence), typical of the Kuramoto-Sivashinsky equation, which is obtained in the limit of very strong driving. The transition occurs not in a straightforward way, but through the formation of spatial patterns that emerge for intermediate values of the driving intensity. As in driven one-dimensional models studied before, the mere presence of the driving force, however small, breaks the symmetry between the two separating phases, as well as increases the coarsening rate. With increasing driving, coarsening stops. The dynamics is generally irregular at strong driving, but exhibits specific structural features.

  8. Formation of Asymmetrical Structured Silica Controlled by a Phase Separation Process and Implication for Biosilicification

    PubMed Central

    Shi, Jia-Yuan; Yao, Qi-Zhi; Li, Xi-Ming; Zhou, Gen-Tao; Fu, Sheng-Quan

    2013-01-01

    Biogenetic silica displays intricate patterns assembling from nano- to microsize level and interesting non-spherical structures differentiating in specific directions. Several model systems have been proposed to explain the formation of biosilica nanostructures. Of them, phase separation based on the physicochemical properties of organic amines was considered to be responsible for the pattern formation of biosilica. In this paper, using tetraethyl orthosilicate (TEOS, Si(OCH2CH3)4) as silica precursor, phospholipid (PL) and dodecylamine (DA) were introduced to initiate phase separation of organic components and influence silica precipitation. Morphology, structure and composition of the mineralized products were characterized using a range of techniques including field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG-DTA), infrared spectra (IR), and nitrogen physisorption. The results demonstrate that the phase separation process of the organic components leads to the formation of asymmetrically non-spherical silica structures, and the aspect ratios of the asymmetrical structures can be well controlled by varying the concentration of PL and DA. On the basis of the time-dependent experiments, a tentative mechanism is also proposed to illustrate the asymmetrical morphogenesis. Therefore, our results imply that in addition to explaining the hierarchical porous nanopatterning of biosilica, the phase separation process may also be responsible for the growth differentiation of siliceous structures in specific directions. Because organic amine (e.g., long-chair polyamines), phospholipids (e.g., silicalemma) and the phase separation process are associated with the biosilicification of diatoms, our results may provide a new insight into the mechanism of biosilicification. PMID:23585878

  9. Formation of asymmetrical structured silica controlled by a phase separation process and implication for biosilicification.

    PubMed

    Shi, Jia-Yuan; Yao, Qi-Zhi; Li, Xi-Ming; Zhou, Gen-Tao; Fu, Sheng-Quan

    2013-01-01

    Biogenetic silica displays intricate patterns assembling from nano- to microsize level and interesting non-spherical structures differentiating in specific directions. Several model systems have been proposed to explain the formation of biosilica nanostructures. Of them, phase separation based on the physicochemical properties of organic amines was considered to be responsible for the pattern formation of biosilica. In this paper, using tetraethyl orthosilicate (TEOS, Si(OCH2CH3)4) as silica precursor, phospholipid (PL) and dodecylamine (DA) were introduced to initiate phase separation of organic components and influence silica precipitation. Morphology, structure and composition of the mineralized products were characterized using a range of techniques including field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG-DTA), infrared spectra (IR), and nitrogen physisorption. The results demonstrate that the phase separation process of the organic components leads to the formation of asymmetrically non-spherical silica structures, and the aspect ratios of the asymmetrical structures can be well controlled by varying the concentration of PL and DA. On the basis of the time-dependent experiments, a tentative mechanism is also proposed to illustrate the asymmetrical morphogenesis. Therefore, our results imply that in addition to explaining the hierarchical porous nanopatterning of biosilica, the phase separation process may also be responsible for the growth differentiation of siliceous structures in specific directions. Because organic amine (e.g., long-chair polyamines), phospholipids (e.g., silicalemma) and the phase separation process are associated with the biosilicification of diatoms, our results may provide a new insight into the mechanism of biosilicification.

  10. Mechanics of Metals with Phase Changes

    SciTech Connect

    Lashley, Jason C.

    2001-01-01

    New experimental data is presented on some exotic metals that exhibit phase changes at cryogenic temperatures. The types of phase changes that were detected in the specific heat data range from martensitic (diffusion less) transitions to superconducting transitions. In addition, the charge density wave (CDW) state in uranium metal was detected in the specific heat. Specific-heat measurements were made in zero-magnetic field using an apparatus capable of obtaining temperatures as low as 0.4 K. Calibration performed on this apparatus, using a single-crystal copper sample, show its accuracy to be 0.50%, while the resolution was better than 0.1%. Our measurements demonstrate that similar high precision and accurate specific-heat measurements can be obtained on milligram-scale samples. In Chapters 2 and 3, specific-heat measurements are presented for the B2 (CsCl structure) alloy AuZn and for α-uranium (orthorhombic symmetry). The AuZn alloy exhibits a continuous transition at 64.75 K and an entropy of transition of (ΔStr) 2.02 J K-1 mol-1. Calculation of the Debye temperature, by extrapolating of the high temperature phase elastic constants to T = 0 K yields a value of 207 K (±2 K), in favorable agreement with the calorimetric value of 219 K (±0.50 K), despite the intervening martensitic transition. Reported results for single-crystal α-U show a low-temperature limiting θD of 256 K (±0.50 K) and four low-temperature anomalies: a superconducting transition below 1 K, an electronic transition at 22 K, and two anomalies at 38 K and at 42 K indicative of the CDW state. In order to continue the study of the actinide series of elements, a program was initiated to first purify and then grow single crystals of plutonium. Accordingly, the focus of Chapters 4 through 6 will be a description of plutonium sample preparation. In this program plutonium metal was purified via zone refining, using a levitated molten zone to minimize

  11. Formation mechanisms of spatially-directed zincblende gallium nitride nanocrystals

    SciTech Connect

    Wood, A. W.; Collino, R. R.; Cardozo, B. L.; Naab, F.; Wang, Y. Q.; Goldman, R. S.

    2011-12-15

    We report on the spatially selective formation of GaN nanocrystals embedded in GaAs. Broad-area N{sup +} implantation followed by rapid thermal annealing leads to the formation of nanocrystals at the depth of maximum ion damage. With additional irradiation using a Ga{sup +} focused ion beam, selective lateral positioning of the nanocrystals within the GaAs matrix is observed in isolated regions of increased vacancy concentration. Following rapid thermal annealing, the formation of zincblende GaN is observed in the regions of highest vacancy concentration. The nucleation of zincblende nanocrystals over the wurtzite phase of bulk GaN is consistent with the predictions of a thermodynamic model for the nanoscale size-dependence of GaN nucleation.

  12. New understanding of microstructure formation of the rubber phase in thermoplastic vulcanizates (TPV).

    PubMed

    Wu, Hanguang; Tian, Ming; Zhang, Liqun; Tian, Hongchi; Wu, Youping; Ning, Nanying

    2014-03-21

    The breakup of the rubber phase in an ethylene-propylene-diene monomer (EPDM)/polypropylene (PP) blend at the early stage of dynamic vulcanization is similar to that in an unvulcanized EPDM/PP blend because of the low crosslink density of the EPDM phase. In this work, the minimum size of the rubber phase in the unvulcanized EPDM/PP blend was first calculated by using the critical breakup law of viscoelastic droplets in a matrix. The calculated results showed that the minimum size of the rubber phase in the unvulcanized blend was in the nanometer scale (25-46 nm), not the micrometer scale as reported in many works. Meanwhile, the actual size of the rubber phase in the thermoplastic vulcanizate (TPV) at both the early stage and the final stage of dynamic vulcanization was observed by using peak force tapping atomic force microscopy (PF-AFM). The results indicated that the EPDM phase indeed broke up into nanoparticles at the early stage of dynamic vulcanization, in good agreement with the calculated results. More interestingly, we first revealed that the micrometer-sized rubber particles commonly observed in TPV were actually the agglomerates of rubber nanoparticles with diameters between 40 and 60 nm. The mechanism for the formation of rubber nanoparticles and their agglomerates during dynamic vulcanization was then discussed. Our work provides guidance to control the microstructure of the rubber phase in TPV to prepare high performance TPV products for a wide range of applications in the automobile and electronic industries.

  13. Gas-phase hydrolysis of triplet SO2: A possible direct route to atmospheric acid formation

    NASA Astrophysics Data System (ADS)

    Donaldson, D. James; Kroll, Jay A.; Vaida, Veronica

    2016-07-01

    Sulfur chemistry is of great interest to the atmospheric chemistry of several planets. In the presence of water, oxidized sulfur can lead to new particle formation, influencing climate in significant ways. Observations of sulfur compounds in planetary atmospheres when compared with model results suggest that there are missing chemical mechanisms. Here we propose a novel mechanism for the formation of sulfurous acid, which may act as a seed for new particle formation. In this proposed mechanism, the lowest triplet state of SO2 (3B1), which may be accessed by near-UV solar excitation of SO2 to its excited 1B1 state followed by rapid intersystem crossing, reacts directly with water to form H2SO3 in the gas phase. For ground state SO2, this reaction is endothermic and has a very high activation barrier; our quantum chemical calculations point to a facile reaction being possible in the triplet state of SO2. This hygroscopic H2SO3 molecule may act as a condensation nucleus for water, giving rise to facile new particle formation (NPF).

  14. Gas-phase hydrolysis of triplet SO2: A possible direct route to atmospheric acid formation

    PubMed Central

    Donaldson, D. James; Kroll, Jay A.; Vaida, Veronica

    2016-01-01

    Sulfur chemistry is of great interest to the atmospheric chemistry of several planets. In the presence of water, oxidized sulfur can lead to new particle formation, influencing climate in significant ways. Observations of sulfur compounds in planetary atmospheres when compared with model results suggest that there are missing chemical mechanisms. Here we propose a novel mechanism for the formation of sulfurous acid, which may act as a seed for new particle formation. In this proposed mechanism, the lowest triplet state of SO2 (3B1), which may be accessed by near-UV solar excitation of SO2 to its excited 1B1 state followed by rapid intersystem crossing, reacts directly with water to form H2SO3 in the gas phase. For ground state SO2, this reaction is endothermic and has a very high activation barrier; our quantum chemical calculations point to a facile reaction being possible in the triplet state of SO2. This hygroscopic H2SO3 molecule may act as a condensation nucleus for water, giving rise to facile new particle formation (NPF). PMID:27417675

  15. Formation of an interstitially alloyed phase in Mg/C60 composite

    NASA Astrophysics Data System (ADS)

    Shin, Jaehyuck; Yoon, Sock-yeon; Choi, Hyunjoo; Shin, Seeun; Bae, Donghyun

    2013-07-01

    The formation of an interstitially alloyed phase and its effects on mechanical properties are investigated for a magnesium-based composite containing fullerene (Mg/C60). The Mg/C60 composite was fabricated using the ball milling method followed by hot rolling and then the composite sheet was annealed at 425°C for up to 37 h. The fullerene was dispersed during the ball milling process and it was decomposed. The carbon atoms from the decomposed fullerene diffused into the magnesium matrix, which increasingly occupied the octahedral sites of the magnesium as the annealing continued. The formed interstitially alloyed phase expanded as the annealing time increased, and magnesium carbide was formed after 37 h. Vickers hardness value increased as the interstitially alloyed phase continuously formed and it decreased when the magnesium carbide was formed, because the carbon atoms at the magnesium interstices may interact with moving dislocations, resulting in an increase in the hardness of the magnesium.

  16. A directional nucleation-zipping mechanism for triple helix formation.

    PubMed

    Alberti, Patrizia; Arimondo, Paola B; Mergny, Jean-Louis; Garestier, Thérèse; Hélène, Claude; Sun, Jian-Sheng

    2002-12-15

    A detailed kinetic study of triple helix formation was performed by surface plasmon resonance. Three systems were investigated involving 15mer pyrimidine oligonucleotides as third strands. Rate constants and activation energies were validated by comparison with thermodynamic values calculated from UV-melting analysis. Replacement of a T.A base pair by a C.G pair at either the 5' or the 3' end of the target sequence allowed us to assess mismatch effects and to delineate the mechanism of triple helix formation. Our data show that the association rate constant is governed by the sequence of base triplets on the 5' side of the triplex (referred to as the 5' side of the target oligopurine strand) and provides evidence that the reaction pathway for triple helix formation in the pyrimidine motif proceeds from the 5' end to the 3' end of the triplex according to the nucleation-zipping model. It seems that this is a general feature for all triple helices formation, probably due to the right-handedness of the DNA double helix that provides a stronger base stacking at the 5' than at the 3' duplex-triplex junction. Understanding the mechanism of triple helix formation is not only of fundamental interest, but may also help in designing better triple helix-forming oligonucleotides for gene targeting and control of gene expression.

  17. Mechanism of 3-(glutathion-S-yl)-benzidine formation.

    PubMed

    Lakshmi, V M; Zenser, T V; Davis, B B

    1994-04-01

    The formation of thioether conjugates is an important mechanism for inactivation of carcinogens. 3-(Glutathion-S-yl)-benzidine (BZ-SG) formation prevents benzidinediimine and peroxidase-mediated benzidine binding to DNA. Benzidinediimine is the two-electron oxidized product of benzidine thought to be the reactive intermediate involved in peroxidase-mediated binding of benzidine to DNA. Diimine interacts with benzidine to form a dimeric complex known as the charge-transfer complex. The latter is in equilibrium with the cation radical. This study evaluated the mechanism by which BZ-SG forms. Benzidinediimine was synthesized and used to study the formation of BZ-SG. With 0.05 mM benzidinediimine, BZ-SG formation was optimum at pH 4.5 and with glutathione at 0.05 to 0.1 mM. By monitoring specific absorption spectra, the reduction of benzidinediimine at pH 4.5 was evaluated. The t1/2 for diimine decay (425 nm) and maximum absorbance of the charge-transfer complex (600 nm) were each at approximately 5 min. Within 10 min, the maximum amount of benzidine had formed from diimine. BZ-SG formation followed the decay of diimine. The relationship between benzidinediimine and benzidine, with respect to BZ-SG formation, was assessed at a fixed concentration of glutathione (0.05 mM) and a fixed total concentration of amine and diimine (0.05 mM). In three separate experiments, each of these three components was radiolabeled independent of the other two components. Experiments with [3H]glutathione indicated that conjugate formation was dependent upon diimine, and not benzidine. With [3H]benzidinediimine or [3H]benzidine, two different calculations were necessary to assess conjugate formation. For [3H]benzidinediimine, the calculation considered that only the radiolabeled diimine formed conjugate, while with [3H]benzidine, a specific activity calculation was necessary to demonstrate that conjugate formation was dependent upon diimine. With 0.05 mM [3H]benzidine, horseradish

  18. Hebbian and neuromodulatory mechanisms interact to trigger associative memory formation

    PubMed Central

    Johansen, Joshua P.; Diaz-Mataix, Lorenzo; Hamanaka, Hiroki; Ozawa, Takaaki; Ycu, Edgar; Koivumaa, Jenny; Kumar, Ashwani; Hou, Mian; Deisseroth, Karl; Boyden, Edward S.; LeDoux, Joseph E.

    2014-01-01

    A long-standing hypothesis termed “Hebbian plasticity” suggests that memories are formed through strengthening of synaptic connections between neurons with correlated activity. In contrast, other theories propose that coactivation of Hebbian and neuromodulatory processes produce the synaptic strengthening that underlies memory formation. Using optogenetics we directly tested whether Hebbian plasticity alone is both necessary and sufficient to produce physiological changes mediating actual memory formation in behaving animals. Our previous work with this method suggested that Hebbian mechanisms are sufficient to produce aversive associative learning under artificial conditions involving strong, iterative training. Here we systematically tested whether Hebbian mechanisms are necessary and sufficient to produce associative learning under more moderate training conditions that are similar to those that occur in daily life. We measured neural plasticity in the lateral amygdala, a brain region important for associative memory storage about danger. Our findings provide evidence that Hebbian mechanisms are necessary to produce neural plasticity in the lateral amygdala and behavioral memory formation. However, under these conditions Hebbian mechanisms alone were not sufficient to produce these physiological and behavioral effects unless neuromodulatory systems were coactivated. These results provide insight into how aversive experiences trigger memories and suggest that combined Hebbian and neuromodulatory processes interact to engage associative aversive learning. PMID:25489081

  19. Magnetic fields during the early phase of massive star formation

    NASA Astrophysics Data System (ADS)

    Seifried, Daniel Jürgen

    2013-01-01

    The goal of this work is to improve our current understanding of the formation process of massive stars in the presence of magnetic fields by means of numerical simulations. In particular, I focus on protostellar accretion rates, the evolution and the properties of protostellar discs and their associated outflows, and the interplay of turbulence and magnetic fields and its impact on protostellar disc formation. In a systematic parameter study I show that the accretion rates are remarkably constant over a wide range of initial conditions. Furthermore, I show that in the absence of turbulence for strong initial magnetic fields only sub-Keplerian discs can form which is attributed to the strong magnetic braking effect. This result seems to be in contrast to observational results. The morphology of the outflows, which shows a strong dependence on the initial conditions, can ultimately be linked to the structure of the underlying disc. Well-collimated outflows with high outflows velocities only develop if a Keplerian protostellar disc is present, otherwise slowly expanding, sphere-like outflows develop. Furthermore, I analyse the driving mechanism of outflows with an analytical criterion derived in the course of this work. When including supersonic, turbulent motions in the simulations, Keplerian protostellar discs form in contrast to the non-turbulent simulations. This result is in agreement with observations of early-type protostellar objects.

  20. Roasting effects on formation mechanisms of coffee brew melanoidins.

    PubMed

    Bekedam, E Koen; Loots, Mirjam J; Schols, Henk A; Van Boekel, Martinus A J S; Smit, Gerrit

    2008-08-27

    The effect of the roasting degree on coffee brew melanoidin properties and formation mechanisms was studied. Coffee brew fractions differing in molecular weight (Mw) were isolated from green and light-, medium-, and dark-roasted coffee beans. Isolated fractions were characterized for their melanoidin, nitrogen, protein, phenolic groups, chlorogenic acid, quinic acid, caffeic acid, and sugar content. It was found that the melanoidin level in all fractions correlated with both the nitrogen and the protein content. The melanoidin level also correlated with the phenolic groups' level and ester-linked quinic acid level. It was concluded that proteins and chlorogenic acids should be primarily involved in melanoidin formation. Initial roasting, from green to light-roasted beans, especially led to the formation of intermediate Mw (IMw) melanoidins when compared to high Mw (HMw) melanoidins. Indications were found that this IMw melanoidin formation is mainly due to Maillard reactions and chlorogenic acid incorporation reactions between chlorogenic acids, sucrose, and amino acids/protein fragments. Additionally, it was found that prolonged roasting predominantly led to formation melanoidins with a high Mw. Furthermore, arabinogalactans seem to be relatively more involved in melanoidin formation than galactomannans. It was hypothesized that chromophores may be formed or attached through the arabinose moiety of arabinogalactan proteins (AGP). Finally, it could be concluded that galactomannans are continuously incorporated in AGP-melanoidins upon roasting.

  1. Computational study of peptide bond formation in the gas phase through ion-molecule reactions.

    PubMed

    Redondo, Pilar; Martínez, Henar; Cimas, Alvaro; Barrientos, Carmen; Largo, Antonio

    2013-08-21

    A computational study of peptide bond formation from gas-phase ion-molecule reactions has been carried out. We have considered the reaction between protonated glycine and neutral glycine, as well as the reaction between two neutral glycine molecules for comparison purposes. Two different mechanisms, concerted and stepwise, were studied. Both mechanisms show significant energy barriers for the neutral reaction. The energy requirements for peptide bond formation are considerably reduced upon protonation of one of the glycine molecules. For the reaction between neutral glycine and N-protonated glycine the lowest energy barrier is observed for the concerted mechanism. For the reaction between neutral glycine and protonated glycine at carbonyl oxygen, the preferred mechanism is the stepwise one, with a relatively small energy barrier (23 kJ mol(-1) at 0 K) and leading to the lowest-lying protonated glycylglycine isomer. In the case that the reaction could be initiated by protonated glycine at hydroxyl oxygen the process would be barrier-free and clearly exothermic. In that case peptide bond formation could take place even under interstellar conditions if glycine is present in space.

  2. COMPETING MECHANISMS OF MOLECULAR HYDROGEN FORMATION IN CONDITIONS RELEVANT TO THE INTERSTELLAR MEDIUM

    SciTech Connect

    Lemaire, J. L.; Vidali, G.; Baouche, S.; Chehrouri, M.; Chaabouni, H.; Mokrane, H.

    2010-12-20

    The most efficient mechanism of the formation of molecular hydrogen in the current universe is by association of hydrogen atoms on the surface of interstellar dust grains. The details of the processes of its formation and release from the grain are of great importance in the physical and chemical evolution of the space environments where it takes place. The main puzzle is still the fate of the 4.5 eV released in H{sub 2} formation and whether it goes into internal energy (rovibrational excitation), translational kinetic energy, or heating of the grain. The modality of the release of this energy affects the dynamics of the ISM and its evolution toward star formation. We present results of the detection of the rovibrational states of the just-formed H{sub 2} as it leaves the surface of a silicate. We find that rovibrationally excited molecules are ejected into the gas phase immediately after formation over a much wider range of grain temperatures than anticipated. Our results can be explained by the presence of two mechanisms of molecule formation that operate in partially overlapping ranges of grain temperature. A preliminary analysis of the relative importance of these two mechanisms is given. These unexpected findings, which will be complemented with experiments on the influence of factors such as silicate morphology, should be of great interest to the astrophysics and astrochemistry communities.

  3. FRAGMENTATION AT THE EARLIEST PHASE OF MASSIVE STAR FORMATION

    SciTech Connect

    Zhang Qizhou; Wang Yang; Pillai, Thushara; Rathborne, Jill

    2009-05-01

    We present 1.3 mm continuum and spectral line images of two massive molecular clumps P1 and P2 in the G28.34+0.06 region with the Submillimeter Array (SMA). While the two clumps contain masses of 1000 and 880 M {sub sun}, respectively, P1 has a luminosity OF <10{sup 2} L {sub sun}, and a lower gas temperature and smaller line width than P2. Thus, P1 appears to be at a much earlier stage of massive star formation than P2. The high-resolution SMA observations reveal two distinctive cores in P2 with masses of 97 and 49 M {sub sun}, respectively. The 4 GHz spectral bandpass captures line emission from CO isotopologues, SO, CH{sub 3}OH, and CH{sub 3}CN, similar to hot molecular cores harboring massive young stars. The P1 clump, on the other hand, is resolved into five cores along the filament with masses from 22 to 64 M {sub sun} and an average projected separation of 0.19 pc. Except {sup 12}CO, no molecular line emission is detected toward the P1 cores at a 1{sigma} rms of 0.1 K. Since strong {sup 12}CO and C{sup 18}O emissions are seen with the single-dish telescope at a resolution of 11'', the nondetection of these lines with the SMA indicates a depletion factor up to 10{sup 3}. While the spatial resolution of the SMA is better than the expected Jeans length, the masses in P1 cores are much larger than the thermal Jeans mass, indicating the importance of turbulence and/or magnetic fields in cloud fragmentation. The hierarchical structures in the P1 region provide a glimpse of the initial phase of massive star and cluster formation.

  4. Physical Mechanisms of Pattern Formation in the Early Chick Embryo

    NASA Astrophysics Data System (ADS)

    Balter, Ariel; Glazier, James; Zaitlen, Benji; Chaplain, Mark; Weijer, Cornelis

    2007-03-01

    Gastrulation marks a critical step in early embryogenesis when the first recognizable patterns are laid down. Although the genome maintains ultimate responsibility for this pattern formation, it cannot actually control the organization of individual cells. The robustness of embryogenic pattern formation suggests that a few simple, physical mechanisms are unleashed and that self-organization results. We perform numerical simulations of early chick gastrulation using an agent based method in which individual cells interact via a handful of behaviors including adhesivity, secretion and chemotaxis. Through these simulations we have identified certain behaviors as being important for various stages and morphological events. For instance, experimental results on primitive streak formation are best reproduced by a model in which the Kohler's Sickle secretes a chemo repellant for streak tip cells, and cell polarization appears to be important for initiating polonaise motion during streak elongation.

  5. Neural and Cellular Mechanisms of Fear and Extinction Memory Formation

    PubMed Central

    Orsini, Caitlin A.; Maren, Stephen

    2012-01-01

    Over the course of natural history, countless animal species have evolved adaptive behavioral systems to cope with dangerous situations and promote survival. Emotional memories are central to these defense systems because they are rapidly acquired and prepare organisms for future threat. Unfortunately, the persistence and intrusion of memories of fearful experiences are quite common and can lead to pathogenic conditions, such as anxiety and phobias. Over the course of the last thirty years, neuroscientists and psychologists alike have attempted to understand the mechanisms by which the brain encodes and maintains these aversive memories. Of equal interest, though, is the neurobiology of extinction memory formation as this may shape current therapeutic techniques. Here we review the extant literature on the neurobiology of fear and extinction memory formation, with a strong focus on the cellular and molecular mechanisms underlying these processes. PMID:22230704

  6. Resolving the molecular mechanism of cadherin catch bond formation

    SciTech Connect

    Manibog, Kristine; Li, Hui; Rakshit, Sabyasachi; Sivasankar, Sanjeevi

    2014-06-02

    Classical cadherin Ca(2+)-dependent cell-cell adhesion proteins play key roles in embryogenesis and in maintaining tissue integrity. Cadherins mediate robust adhesion by binding in multiple conformations. One of these adhesive states, called an X-dimer, forms catch bonds that strengthen and become longer lived in the presence of mechanical force. Here we use single-molecule force-clamp spectroscopy with an atomic force microscope along with molecular dynamics and steered molecular dynamics simulations to resolve the molecular mechanisms underlying catch bond formation and the role of Ca(2+) ions in this process. Our data suggest that tensile force bends the cadherin extracellular region such that they form long-lived, force-induced hydrogen bonds that lock X-dimers into tighter contact. When Ca(2+) concentration is decreased, fewer de novo hydrogen bonds are formed and catch bond formation is eliminated

  7. Wine protein haze: mechanisms of formation and advances in prevention.

    PubMed

    Van Sluyter, Steven C; McRae, Jacqui M; Falconer, Robert J; Smith, Paul A; Bacic, Antony; Waters, Elizabeth J; Marangon, Matteo

    2015-04-29

    Protein haze is an aesthetic problem in white wines that can be prevented by removing the grape proteins that have survived the winemaking process. The haze-forming proteins are grape pathogenesis-related proteins that are highly stable during winemaking, but some of them precipitate over time and with elevated temperatures. Protein removal is currently achieved by bentonite addition, an inefficient process that can lead to higher costs and quality losses in winemaking. The development of more efficient processes for protein removal and haze prevention requires understanding the mechanisms such as the main drivers of protein instability and the impacts of various wine matrix components on haze formation. This review covers recent developments in wine protein instability and removal and proposes a revised mechanism of protein haze formation.

  8. Formation of binary phase gratings in photopolymer-liquid crystal composites by a surface-controlled anisotropic phase separation

    SciTech Connect

    Park, Jae-Hong; Khoo, Iam Choon; Yu, Chang-Jae; Jung, Min-Sik; Lee, Sin-Doo

    2005-01-10

    We report on formation of binary phase gratings in photopolymer-liquid crystal (PLC) composites using a surface-controlled phase separation method. The binary nature of the PLC phase gratings is produced by employing a single step photo-ablation through an amplitude photomask which precisely controls the interfacial interactions between the LC and the photopolymer on the alignment layer. A subsequent illumination of the ultraviolet light onto the whole PLC promotes an anisotropic phase separation resulting in the formation of distinct binary patterns for the PLC structure. The electrically tunable diffraction properties of the binary phase gratings are presented.

  9. Exchange anisotropy as mechanism for spin-stripe formation in frustrated spin chains

    NASA Astrophysics Data System (ADS)

    Pregelj, M.; Zaharko, O.; Herak, M.; Gomilšek, M.; Zorko, A.; Chapon, L. C.; Bourdarot, F.; Berger, H.; Arčon, D.

    2016-08-01

    We investigate the spin-stripe mechanism responsible for the peculiar nanometer modulation of the incommensurate magnetic order that emerges between the vector-chiral and the spin-density-wave phase in the frustrated zigzag spin-1/2 chain compound β -TeVO4 . A combination of magnetic-torque, neutron-diffraction, and spherical-neutron-polarimetry measurements is employed to determine the complex magnetic structures of all three ordered phases. Based on these results, we develop a simple phenomenological model, which exposes the exchange anisotropy as the key ingredient for the spin-stripe formation in frustrated spin systems.

  10. Peptide formation mechanism on montmorillonite under thermal conditions.

    PubMed

    Fuchida, Shigeshi; Masuda, Harue; Shinoda, Keiji

    2014-02-01

    The oligomerization of amino acids is an essential process in the chemical evolution of proteins, which are precursors to life on Earth. Although some researchers have observed peptide formation on clay mineral surfaces, the mechanism of peptide bond formation on the clay mineral surface has not been clarified. In this study, the thermal behavior of glycine (Gly) adsorbed on montmorillonite was observed during heating experiments conducted at 150 °C for 336 h under dry, wet, and dry-wet conditions to clarify the mechanism. Approximately 13.9 % of the Gly monomers became peptides on montmorillonite under dry conditions, with diketopiperazine (cyclic dimer) being the main product. On the other hand, peptides were not synthesized in the absence of montmorillonite. Results of IR analysis showed that the Gly monomer was mainly adsorbed via hydrogen bonding between the positively charged amino groups and negatively charged surface sites (i.e., Lewis base sites) on the montmorillonite surface, indicating that the Lewis base site acts as a catalyst for peptide formation. In contrast, peptides were not detected on montmorillonite heated under wet conditions, since excess water shifted the equilibrium towards hydrolysis of the peptides. The presence of water is likely to control thermodynamic peptide production, and clay minerals, especially those with electrophilic defect sites, seem to act as a kinetic catalyst for the peptide formation reaction.

  11. Mechanism of Consistent Gyrus Formation: an Experimental and Computational Study

    NASA Astrophysics Data System (ADS)

    Zhang, Tuo; Razavi, Mir Jalil; Li, Xiao; Chen, Hanbo; Liu, Tianming; Wang, Xianqiao

    2016-11-01

    As a significant type of cerebral cortical convolution pattern, the gyrus is widely preserved across species. Although many hypotheses have been proposed to study the underlying mechanisms of gyrus formation, it is currently still far from clear which factors contribute to the regulation of consistent gyrus formation. In this paper, we employ a joint analysis scheme of experimental data and computational modeling to investigate the fundamental mechanism of gyrus formation. Experimental data on mature human brains and fetal brains show that thicker cortices are consistently found in gyral regions and gyral cortices have higher growth rates. We hypothesize that gyral convolution patterns might stem from heterogeneous regional growth in the cortex. Our computational simulations show that gyral convex patterns may occur in locations where the cortical plate grows faster than the cortex of the brain. Global differential growth can only produce a random gyrification pattern, but it cannot guarantee gyrus formation at certain locations. Based on extensive computational modeling and simulations, it is suggested that a special area in the cerebral cortex with a relatively faster growth speed could consistently engender gyri.

  12. Mechanism of Consistent Gyrus Formation: an Experimental and Computational Study

    PubMed Central

    Zhang, Tuo; Razavi, Mir Jalil; Li, Xiao; Chen, Hanbo; Liu, Tianming; Wang, Xianqiao

    2016-01-01

    As a significant type of cerebral cortical convolution pattern, the gyrus is widely preserved across species. Although many hypotheses have been proposed to study the underlying mechanisms of gyrus formation, it is currently still far from clear which factors contribute to the regulation of consistent gyrus formation. In this paper, we employ a joint analysis scheme of experimental data and computational modeling to investigate the fundamental mechanism of gyrus formation. Experimental data on mature human brains and fetal brains show that thicker cortices are consistently found in gyral regions and gyral cortices have higher growth rates. We hypothesize that gyral convolution patterns might stem from heterogeneous regional growth in the cortex. Our computational simulations show that gyral convex patterns may occur in locations where the cortical plate grows faster than the cortex of the brain. Global differential growth can only produce a random gyrification pattern, but it cannot guarantee gyrus formation at certain locations. Based on extensive computational modeling and simulations, it is suggested that a special area in the cerebral cortex with a relatively faster growth speed could consistently engender gyri. PMID:27853245

  13. Vesicle Formation and Endocytosis: Function, Machinery, Mechanisms, and Modeling

    PubMed Central

    Parkar, Nihal S.; Akpa, Belinda S.; Nitsche, Ludwig C.; Wedgewood, Lewis E.; Place, Aaron T.; Sverdlov, Maria S.; Chaga, Oleg

    2009-01-01

    Abstract Vesicle formation provides a means of cellular entry for extracellular substances and for recycling of membrane constituents. Mechanisms governing the two primary endocytic pathways (i.e., caveolae- and clathrin-mediated endocytosis, as well as newly emerging vesicular pathways) have become the focus of intense investigation to improve our understanding of nutrient, hormone, and drug delivery, as well as opportunistic invasion of pathogens. In this review of endocytosis, we broadly discuss the structural and signaling proteins that compose the molecular machinery governing endocytic vesicle formation (budding, invagination, and fission from the membrane), with some regard for the specificity observed in certain cell types and species. Important biochemical functions of endocytosis and diseases caused by their disruption also are discussed, along with the structures of key components of endocytic pathways and their known mechanistic contributions. The mechanisms by which principal components of the endocytic machinery are recruited to the plasma membrane, where they interact to induce vesicle formation, are discussed, together with computational approaches used to simulate simplified versions of endocytosis with the hope of clarifying aspects of vesicle formation that may be difficult to determine experimentally. Finally, we pose several unanswered questions intended to stimulate further research interest in the cell biology and modeling of endocytosis. Antioxid. Redox Signal. 11, 1301–1312. PMID:19113823

  14. Different pathways of phase transition in a V-Si system driven by mechanical alloying

    SciTech Connect

    Liu, L.; Lu, L.; Lai, M.O.; Magini, M.; Fei, G.T.; Zhang, L.D.

    1998-04-01

    Solid state reactions induced by mechanical alloying of an elemental powder mixture of V and Si with a composition of V{sub 75}Si{sub 25} were investigated using X-ray diffraction and scanning and transmission electron microscopy. It was found that the phase transitions in this system are closely related to the milling intensity. High-energy milling mainly causes the formation of intermetallic compounds, whereas low-energy milling leads to amorphization. The thermodynamics and kinetics related to the different pathways of V-Si phase transition are briefly discussed in this paper. The effect of air contamination on phase transition is also addressed.

  15. Wettability and phase formation in the TiC{sub x}/Al system

    SciTech Connect

    Frumin, N.; Frage, N.; Polak, M.; Dariel, M.P.

    1997-10-15

    The introduction of reinforcements such as carbide or oxide ceramics into a metallic matrix improves high temperature strength, creep resistance and low temperature toughness. Modification of the ceramic phase can also be used in order to improve wetting in a metal/ceramic system. The wettability of ceramic surfaces by metallic melts is strongly dependent on the stoichiometry of the ceramic compound (oxide or carbide). Titanium carbide has a wide range of stability (0.55 < C/Ti {le} 1), and its chemical, physical and mechanical properties largely depend on the composition. For instance, chemical inertness and hardness increase with increasing C/Ti ratio. The use of TiC as a reinforcing phase in aluminum alloys or in TiC/Al cermets has not been exploited fully. Titanium carbide exhibits adequate wetting by Al{sub (L)} due to chemical interactions at high temperatures that may also lead to the formation of the Al{sub 4}C{sub 3} phase. The presence of this phase at the interface is undesirable because it is weak and brittle. Moreover, Al{sub 4}C{sub 3} decomposes in the presence of water to form Al{sub 2}O{sub 3} and methane gas. The present work was aimed at finding the proper conditions and the Ti/C ratio in non-stoichiometric TiC{sub x} that would improve wetting and prevent the formation of Al{sub 4}C{sub 3}.

  16. Importance of Silicon and Mechanisms of Biosilica Formation in Plants

    PubMed Central

    Siti Nor Akmar, Abdullah; Rafii, Mohd Y.; Tengoua, F. F.; Nurul Mayzaitul Azwa, Jamaludin; Shabanimofrad, M.

    2015-01-01

    Silicon (Si) is one of the most prevalent macroelements, performing an essential function in healing plants in response to environmental stresses. The purpose of using Si is to induce resistance to distinct stresses, diseases, and pathogens. Additionally, Si can improve the condition of soils, which contain toxic levels of heavy metals along with other chemical elements. Silicon minimizes toxicity of Fe, Al, and Mn, increases the availability of P, and enhances drought along with salt tolerance in plants through the formation of silicified tissues in plants. However, the concentration of Si depends on the plants genotype and organisms. Hence, the physiological mechanisms and metabolic activities of plants may be affected by Si application. Peptides as well as amino acids can effectively create polysilicic species through interactions with different species of silicate inside solution. The carboxylic acid and the alcohol groups of serine and asparagine tend not to engage in any significant role in polysilicates formation, but the hydroxyl group side chain can be involved in the formation of hydrogen bond with Si(OH)4. The mechanisms and trend of Si absorption are different between plant species. Furthermore, the transportation of Si requires an energy mechanism; thus, low temperatures and metabolic repressors inhibit Si transportation. PMID:25685787

  17. Physical Mechanisms of Glaze Ice Scallop Formations on Swept Wings

    NASA Technical Reports Server (NTRS)

    Vargas, Mario; Reshotko, Eli

    1998-01-01

    An experiment was conducted to understand the physical mechanisms that lead to the formation of scallops on swept wings. Icing runs were performed on a NACA 0012 swept wing tip at 45 deg, 30 deg, and 15 deg sweep angles. A baseline case was chosen and direct measurements of scallop height and spacing, castings, video data and close-up photographic data were obtained. The results showed the scallops are made of glaze ice feathers that grow from roughness elements that have reached a minimum height and are located beyond a given distance from the attachment line. This distance depends on tunnel conditions and sweep angle, and is the critical parameter in the formation of scallops. It determines if complete scallops, incomplete scallops or no scallops are going to be formed. The mechanisms of growth for complete and incomplete scallops were identified. The effect of velocity, temperature and LWC on scallop formation was studied. The possibility that cross flow instability may be the physical mechanism that triggers the growth of roughness elements into glaze ice feathers is examined.

  18. Investigating Processes of Materials Formation via Liquid Phase and Cryogenic TEM

    SciTech Connect

    De Yoreo, James J.; Sommerdijk, Nico

    2016-06-14

    The formation of materials in solutions is a widespread phenomenon in synthetic, biological and geochemical systems, occurring through dynamic processes of nucleation, self-assembly, crystal growth, and coarsening. The recent advent of liquid phase TEM and advances in cryogenic TEM are transforming our understanding of these phenomena by providing new insights into the underlying physical and chemical mechanisms. The techniques have been applied to metallic and semiconductor nanoparticles, geochemical and biological minerals, electrochemical systems, macromolecular complexes, and selfassembling systems, both organic and inorganic. New instrumentation and methodologies currently on the horizon promise new opportunities for advancing the science of materials synthesis.

  19. Project ARGO: Gas phase formation in simulated microgravity

    NASA Technical Reports Server (NTRS)

    Powell, Michael R.; Waligora, James M.; Norfleet, William T.; Kumar, K. Vasantha

    1993-01-01

    The ARGO study investigated the reduced incidence of joint pain decompression sickness (DCS) encountered in microgravity as compared with an expected incidence of joint pain DCS experienced by test subjects in Earth-based laboratories (unit gravity) with similar protocols. Individuals who are decompressed from saturated conditions usually acquire joint pain DCS in the lower extremities. Our hypothesis is that the incidence of joint pain DCS can be limited by a significant reduction in the tissue gas micronuclei formed by stress-assisted nucleation. Reductions in dynamic and kinetic stresses in vivo are linked to hypokinetic and adynamic conditions of individuals in zero g. We employed the Doppler ultrasound bubble detection technique in simulated microgravity studies to determine quantitatively the degree of gas phase formation in the upper and lower extremities of test subjects during decompression. We found no evidence of right-to-left shunting through pulmonary vasculature. The volume of gas bubble following decompression was examined and compared with the number following saline contrast injection. From this, we predict a reduced incidence of DCS on orbit, although the incidence of predicted mild DCS still remains larger than that encountered on orbit.

  20. Mechanisms of the formation of biological signaling profiles

    NASA Astrophysics Data System (ADS)

    Teimouri, Hamid; Kolomeisky, Anatoly B.

    2016-12-01

    The formation and growth of multi-cellular organisms and tissues from several genetically identical embryo cells is one of the most fundamental natural phenomena. These processes are stimulated and governed by multiple biological signaling molecules, which are also called morphogens. Embryo cells are able to read and pass genetic information by measuring the non-uniform concentration profiles of signaling molecules. It is widely believed that the establishment of concentration profiles of morphogens, commonly referred as morphogen gradients, is a result of complex biophysical and biochemical processes that might involve diffusion and degradation of locally produced signaling molecules. In this review, we discuss various theoretical aspects of the mechanisms for morphogen gradient formation, including stationary and transient dynamics, the effect of source delocalization, diffusion, different degradation mechanisms, and the role of spatial dimensions. Theoretical predictions are compared with experimental observations. In addition, we analyze the potential alternative mechanisms of the delivery of biological signals in embryo cells and tissues. Current challenges in understanding the mechanisms of morphogen gradients and future directions are also discussed.

  1. Formation Mechanism of Barrier Layer in the Subtropical Pacific

    NASA Astrophysics Data System (ADS)

    Katsura, S.; Oka, E.; Sato, K.

    2014-12-01

    Formation mechanism of barrier layers (BLs) in the subtropical Pacific was investigated by using Argo profiling float data and shipboard hydrographic section data. In this region, BLs were formed mainly in winter in association with the sea surface salinity (SSS) front, which was located on the equator side of the SSS maximum region. While BLs from gridded Argo data were broadly distributed, their distribution from raw Argo profiles was patchy and their temporal scale was shorter than 10 days. Formation mechanism of BLs was attributed to two processes: freshening near the sea surface and salinification in the subsurface. As for the former process, poleward Ekman advection of fresher water from the tropics across the SSS front was dominant, while the effect of precipitation was small. As for the latter process, inflow of high salinity water into mixed layers associated with the SSS front can contribute to the BL formation, but actually the core of subducted Tropical Water was too deep to affect salinity structure in the mixed layers across the seasonal thermocline. These features strongly suggest that tilting of the SSS front is essentially important for the BL formation in the subtropical Pacific. This tilting process can only occur where the contribution of horizontal SSS gradient to the horizontal density gradient is strong, and explains why spatial distribution of BLs corresponded to the SSS front. Seasonal variation of BLs corresponded well to that of mixed layer depth, indicating that the deeper mixed layers are before the BL formation, the thicker BLs are formed when the SSS front is tilted.

  2. Numerical analysis of fume formation mechanism in arc welding

    NASA Astrophysics Data System (ADS)

    Tashiro, Shinichi; Zeniya, Tasuku; Yamamoto, Kentaro; Tanaka, Manabu; Nakata, Kazuhiro; Murphy, Anthony B.; Yamamoto, Eri; Yamazaki, Kei; Suzuki, Keiichi

    2010-11-01

    In order to clarify the fume formation mechanism in arc welding, a quantitative investigation based on the knowledge of interaction among the electrode, arc and weld pool is indispensable. A fume formation model consisting of a heterogeneous condensation model, a homogeneous nucleation model and a coagulation model has been developed and coupled with the GTA or GMA welding model. A series of processes from evaporation of metal vapour to fume formation from the metal vapour was totally investigated by employing this simulation model. The aim of this paper is to visualize the fume formation process and clarify the fume formation mechanism theoretically through a numerical analysis. Furthermore, the reliability of the simulation model was also evaluated through a comparison of the simulation result with the experimental result. As a result, it was found that the size of the secondary particles consisting of small particles with a size of several tens of nanometres reached 300 nm at maximum and the secondary particle was in a U-shaped chain form in helium GTA welding. Furthermore, it was also clarified that most part of the fume was produced in the downstream region of the arc originating from the metal vapour evaporated mainly from the droplet in argon GMA welding. The fume was constituted by particles with a size of several tens of nanometres and had similar characteristics to that of GTA welding. On the other hand, if the metal transfer becomes unstable and the metal vapour near the droplet diffuses directly towards the surroundings of the arc not getting into the plasma flow, the size of the particles reaches several hundred nanometres.

  3. Mantle–slab interaction and redox mechanism of diamond formation

    PubMed Central

    Palyanov, Yuri N.; Bataleva, Yuliya V.; Sokol, Alexander G.; Borzdov, Yuri M.; Kupriyanov, Igor N.; Reutsky, Vadim N.; Sobolev, Nikolai V.

    2013-01-01

    Subduction tectonics imposes an important role in the evolution of the interior of the Earth and its global carbon cycle; however, the mechanism of the mantle–slab interaction remains unclear. Here, we demonstrate the results of high-pressure redox-gradient experiments on the interactions between Mg-Ca-carbonate and metallic iron, modeling the processes at the mantle–slab boundary; thereby, we present mechanisms of diamond formation both ahead of and behind the redox front. It is determined that, at oxidized conditions, a low-temperature Ca-rich carbonate melt is generated. This melt acts as both the carbon source and crystallization medium for diamond, whereas at reduced conditions, diamond crystallizes only from the Fe-C melt. The redox mechanism revealed in this study is used to explain the contrasting heterogeneity of natural diamonds, as seen in the composition of inclusions, carbon isotopic composition, and nitrogen impurity content. PMID:24297876

  4. Effects of Strain Rates on Mechanical Properties and Fracture Mechanism of DP780 Dual Phase Steel

    NASA Astrophysics Data System (ADS)

    Li, Shengci; Kang, Yonglin; Zhu, Guoming; Kuang, Shuang

    2015-06-01

    The mechanical properties of DP780 dual phase steel were measured by quasi-static and high-speed tensile tests at strain rates between 0.001 and 1000 s-1 at room temperature. The deformation and fracture mechanisms were analyzed by observation of the tensile fracture and microstructure near the fracture. Dynamic factor and feret ratio quantitative methods were applied to study the effect of strain rate on the microstructure and properties of DP780 steel. The constitutive relation was described by a modified Johnson-Cook and Zerilli-Armstrong model. The results showed that the strain rate sensitivity of yield strength is bigger than that of ultimate tensile strength; as strain rate increased, the formation of microcracks and voids at the ferrite/martensite interface can be alleviated; the strain rate effect is unevenly distributed in the plastic deformation region. Moreover, both models can effectively describe the experimental results, while the modified Zerilli-Armstrong model is more accurate because the strain-hardening rate of this model is independent of strain rate.

  5. Rheological controls on the terrestrial core formation mechanism

    NASA Astrophysics Data System (ADS)

    Golabek, G. J.; Gerya, G. V.; Tackley, P. J.

    2008-09-01

    Abstract Knowledge about the formation mechanism for the Earth's core is still very limited. The fracturing mechanism was proposed by [1] for cold central protocores surrounded by an iron layer, which develops from the overlying magma ocean. In this case the cold protocore is displaced from the centre of the accreting planet and fractured due to the large stresses, whereas the consideration of short-lived radioactive radioactive heating may result in warmer central regions and the preference of iron diapirism as core formation mechanism [2,3]. Until now most numerical models of core formation via diapirism were limited to the simulation of the sinking of a single diapir. We performed 2D spherical simulations using the code I2ELVIS applying the newly developed "spherical-Cartesian" methodology combining finite differences on a fully staggered rectangular Eulerian grid and Lagrangian marker-in-cell technique for solving momentum, continuity and temperature equations as well as Poisson equation for gravity potential in a self-gravitating planetary body [4]. In the model the planet is surrounded by a low viscosity (η=1019 Pa s), massless fluid ("sticky air") to simulate a free surface [5]. We applied a temperature and stress dependent viscoplastic rheology inside an Earth-sized planet and included heat release due to radioactive decay. As initial condition we use randomly distributed diapirs with random sizes in the range 50 to 100 km radius inside the accreting planet, which represent the iron delivered by predifferentiated impactors. A systematic investigation of the diapir behaviour for different activation volumes and yield stresses is being performed, and results are being compared to the isotopic time scale of core formation on terrestrial planets. We show that the rheology controls which formation mechanism becomes dominant. We observe 3 major regimes of core formation: First a weak viscous protocore for low activation volumes and low yield stress, which is

  6. Molecular mechanism of parallel fiber-Purkinje cell synapse formation.

    PubMed

    Mishina, Masayoshi; Uemura, Takeshi; Yasumura, Misato; Yoshida, Tomoyuki

    2012-01-01

    The cerebellum receives two excitatory afferents, the climbing fiber (CF) and the mossy fiber-parallel fiber (PF) pathway, both converging onto Purkinje cells (PCs) that are the sole neurons sending outputs from the cerebellar cortex. Glutamate receptor δ2 (GluRδ2) is expressed selectively in cerebellar PCs and localized exclusively at the PF-PC synapses. We found that a significant number of PC spines lack synaptic contacts with PF terminals and some of residual PF-PC synapses show mismatching between pre- and postsynaptic specializations in conventional and conditional GluRδ2 knockout mice. Studies with mutant mice revealed that in addition to PF-PC synapse formation, GluRδ2 is essential for synaptic plasticity, motor learning, and the restriction of CF territory. GluRδ2 regulates synapse formation through the amino-terminal domain, while the control of synaptic plasticity, motor learning, and CF territory is mediated through the carboxyl-terminal domain. Thus, GluRδ2 is the molecule that bridges synapse formation and motor learning. We found that the trans-synaptic interaction of postsynaptic GluRδ2 and presynaptic neurexins (NRXNs) through cerebellin 1 (Cbln1) mediates PF-PC synapse formation. The synaptogenic triad is composed of one molecule of tetrameric GluRδ2, two molecules of hexameric Cbln1 and four molecules of monomeric NRXN. Thus, GluRδ2 triggers synapse formation by clustering four NRXNs. These findings provide a molecular insight into the mechanism of synapse formation in the brain.

  7. Intermetallic Phase Formation in Explosively Welded Al/Cu Bimetals

    NASA Astrophysics Data System (ADS)

    Amani, H.; Soltanieh, M.

    2016-08-01

    Diffusion couples of aluminum and copper were fabricated by explosive welding process. The interface evolution caused by annealing at different temperatures and time durations was investigated by means of optical microscopy, scanning electron microscopy equipped with energy dispersive spectroscopy, and x-ray diffraction. Annealing in the temperature range of 573 K to 773 K (300 °C to 500 °C) up to 408 hours showed that four types of intermetallic layers have been formed at the interface, namely Al2Cu, AlCu, Al3Cu4, and Al4Cu9. Moreover, it was observed that iron trace in aluminum caused the formation of Fe-bearing intermetallics in Al, which is near the interface of the Al-Cu intermetallic layers. Finally, the activation energies for the growth of Al2Cu, AlCu + Al3Cu4, Al4Cu9, and the total intermetallic layer were calculated to be about 83.3, 112.8, 121.6, and 109.4 kJ/mol, respectively. Considering common welding methods ( i.e., explosive welding, cold rolling, and friction welding), although there is a great difference in welding mechanism, it is found that the total activation energy is approximately the same.

  8. Atomistic mechanism of α - β phase transition in vanadium pentoxide

    NASA Astrophysics Data System (ADS)

    Smirnov, Mikhail B.; Kazimirov, Viatcheslav Yu.; Baddour-Hadjean, Rita; Smirnov, Konstantin S.; Pereira-Ramos, Jean-Pierre

    2014-01-01

    A mechanism of the α - β structural phase transition (SPT) in V2O5 is proposed. The driving force of the SPT is suggested to be the U5 shear strain transforming the orthorhombic unit cell of the α-phase into the monoclinic unit cell of the β-phase. According to the model, the SPT is characterized by a concerted displacement of V2O5 chains and is of martensitic type. Results of periodic DFT calculations performed for structures along the transformation path corroborate the proposed mechanism. The calculated height of the energy barrier is in a good agreement with the heat of transition determined experimentally for the inverse β - α transformation. Possible ways of the experimental verification of the proposed mechanism are discussed.

  9. Mechanisms of amyloid formation revealed by solution NMR

    PubMed Central

    Karamanos, Theodoros K.; Kalverda, Arnout P.; Thompson, Gary S.; Radford, Sheena E.

    2015-01-01

    Amyloid fibrils are proteinaceous elongated aggregates involved in more than fifty human diseases. Recent advances in electron microscopy and solid state NMR have allowed the characterization of fibril structures to different extents of refinement. However, structural details about the mechanism of fibril formation remain relatively poorly defined. This is mainly due to the complex, heterogeneous and transient nature of the species responsible for assembly; properties that make them difficult to detect and characterize in structural detail using biophysical techniques. The ability of solution NMR spectroscopy to investigate exchange between multiple protein states, to characterize transient and low-population species, and to study high molecular weight assemblies, render NMR an invaluable technique for studies of amyloid assembly. In this article we review state-of-the-art solution NMR methods for investigations of: (a) protein dynamics that lead to the formation of aggregation-prone species; (b) amyloidogenic intrinsically disordered proteins; and (c) protein–protein interactions on pathway to fibril formation. Together, these topics highlight the power and potential of NMR to provide atomic level information about the molecular mechanisms of one of the most fascinating problems in structural biology. PMID:26282197

  10. A mechanical device to study geometric phases and curvatures

    NASA Astrophysics Data System (ADS)

    Gil, Salvador

    2010-04-01

    A simple mechanical device is introduced that can be used to illustrate the parallel transport of a vector along a curved surface and the geometric phase shift that occurs when a vector is carried along a loop on a curved surface. Its connection with the Foucault pendulum and Berry phases is discussed. The experimental results are in close agreement with the theoretical expectations. The experiment is inexpensive and conceptually easy to understand and perform.

  11. NGC 1097:Constraining mechanisms for star formation with the VLA

    NASA Astrophysics Data System (ADS)

    Wood, Sarah; Sheth, Kartik; Balser, Dana S.; Yarber, Aara'L.

    2015-01-01

    The project goal is to trace the precise location of star forming regions in the barred spiral NGC 1097. Specifically we want to better understand how the star formation progresses in the bar and at the bar ends. Our hydrodynamic gas flow model indicates gas flow should never cross dust lanes yet previous azimuthal cross-correlation analysis have indicated that the Hα emission is offset on the leading side of the bar dust lanes. It is critical to verify the precise locations of the stars forming regions. Is the star formation initiated in the dust lanes, or perhaps in dust spurs on the trailing side of the galaxy? We will measure synchrotron and thermal radiation contributions to quantify recent activity and compare to existing Hα, GALEX, archival VLA, and new ALMA Cycle 0 and Cycle 1 observations. This project will help catalog current and past star formation activity in the bar of NGC 1097 and thus help constrain the mechanisms for star formation.

  12. Broadband opto-mechanical phase shifter for photonic integrated circuits

    NASA Astrophysics Data System (ADS)

    Guo, Xiang; Zou, Chang-Ling; Ren, Xi-Feng; Sun, Fang-Wen; Guo, Guang-Can

    2012-08-01

    A broadband opto-mechanical phase shifter for photonic integrated circuits is proposed and numerically investigated. The structure consists of a mode-carrying waveguide and a deformable non-mode-carrying nanostring, which are parallel with each other. Since the nanostring can be deflected by the optical gradient force between the waveguide and the nanostring, the effective refractive indices of the waveguide will be changed and a phase shift will be generated. The phase shift under different geometry sizes, launched powers and boundary conditions are calculated and the dynamical properties as well as the thermal noise's effect are also discussed. It is demonstrated that a π phase shift can be realized with only about 0.64 mW launched power and 50 μm long nanostring. The proposed phase shifter may find potential usage in future investigation of photonic integrated circuits.

  13. Mechanism for direct graphite-to-diamond phase transition

    PubMed Central

    Xie, Hongxian; Yin, Fuxing; Yu, Tao; Wang, Jian-Tao; Liang, Chunyong

    2014-01-01

    Using classical molecular dynamics with a more reliable reactive LCBOPII potential, we have performed a detailed study on the direct graphite-to-diamond phase transition. Our results reveal a new so-called “wave-like buckling and slipping” mechanism, which controls the transformation from hexagonal graphite to cubic diamond. Based on this mechanism, we have explained how polycrystalline cubic diamond is converted from hexagonal graphite, and demonstrated that the initial interlayer distance of compressed hexagonal graphite play a key role to determine the grain size of cubic diamond. These results can broaden our understanding of the high pressure graphite-to-diamond phase transition. PMID:25088720

  14. Clarifying the dominant sources and mechanisms of cirrus cloud formation.

    PubMed

    Cziczo, Daniel J; Froyd, Karl D; Hoose, Corinna; Jensen, Eric J; Diao, Minghui; Zondlo, Mark A; Smith, Jessica B; Twohy, Cynthia H; Murphy, Daniel M

    2013-06-14

    Formation of cirrus clouds depends on the availability of ice nuclei to begin condensation of atmospheric water vapor. Although it is known that only a small fraction of atmospheric aerosols are efficient ice nuclei, the critical ingredients that make those aerosols so effective have not been established. We have determined in situ the composition of the residual particles within cirrus crystals after the ice was sublimated. Our results demonstrate that mineral dust and metallic particles are the dominant source of residual particles, whereas sulfate and organic particles are underrepresented, and elemental carbon and biological materials are essentially absent. Further, composition analysis combined with relative humidity measurements suggests that heterogeneous freezing was the dominant formation mechanism of these clouds.

  15. Mechanical development of folded chert beds in Monterey Formation, California

    SciTech Connect

    Crowther, D.; Snyder, W.S.

    1988-03-01

    Small-scale folds in the upper siliceous facies of the Miocene Monterey Formation, at Lions Head, California (Santa Maria basin) are of tectonic origin. Folding is well developed in the chert-dominated zones and dies out rapidly in the adjacent siliceous mudstones. A tectonic origin is evidenced by the dominantly brittle deformation of the competent chert layers. Mechanically, the folds formed through a complex interrelationship between fracture and flexural slip. Opal-CT and quartz-chert layers display brittle fractures and rotated fracture blocks that responded to shortening. Thrusting of the chert layers is common in folds where fold propagation was impeded. Dilation breccia and void space occur in the hinges and reflect room problems during development of these disharmonic folds. Subsequent diagenesis has partially healed the fractures and slip surfaces, creating the erroneous appearance that ductile deformation was an important factor in the formation of the folds.

  16. Experimental evidence for formation mechanism of regular circular fringes

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Zhu, R.; Wang, G.; Wang, P.; Li, H.; Zhang, W.; Ren, G.

    2016-10-01

    Laser active suppressing jamming is one of the most effective technologies to cope with optoelectric imaging systems. In the process of carrying out laser disturbing experiment, regular circular fringes often appeared on the detector, besides laser spot converging by optical system. First of all, the formation of circular fringes has been experimentally investigated by using a simple converging lens to replace the complex optical system. Moreover, circular fringes have been simulated based on the interference theory of coherent light. The coherence between the experimental phenomena and the simulated results showed that the formation mechanism of regular circular fringes was the interference effect between reflected light by back surface of lens and directly refractive light on the detector. At last, the visibility of circular fringes has been calculated from 0.05 to 0.22 according to the current plating standard of lens surface and manufacture technique of optoelectric detector.

  17. Characterizing molecular clouds in the earliest phases of high-mass star formation

    NASA Astrophysics Data System (ADS)

    Sanhueza, Patricio A.

    High-mass stars play a key role in the energetics and chemical evolution. of molecular clouds and galaxies. However, the mechanisms that allow. the formation of high-mass stars are far less clear than those of. their low-mass. counterparts. Most of the research on high-mass star formation has focused. on regions currently undergoing star formation. In contrast, objects. in the earlier prestellar stage have been more difficult to identify. Recently, it has been. suggested that the cold, massive, and dense Infrared Dark Clouds (IRDCs) host. the earliest stages of high-mass star formation. The chemistry of IRDCs remains poorly explored. In this dissertation, an. observational program to search for chemical. variations in IRDC clumps as a function of their age is described. An increase in N2H+ and HCO+ abundances. is found from the quiescent, cold phase to the protostellar, warmer phases, reflecting chemical. evolution. For HCO+ abundances, the observed trend is consistent with. theoretical predictions. However, chemical models fail to explain the observed. trend of increasing N2H+ abundances. Pristine high-mass prestellar clumps are ideal for testing and constraining. theories of high-mass star formation because their predictions differ. the most at the early stages of evolution. From the initial IRDC sample, a high-mass clump that is the best candidate to be in the prestellar phase. was selected (IRDC G028.23-00.19 MM1). With a new set of observations, the prestellar nature of the clump is confirmed. High-angular resolution. observations of IRDC G028.23-00.19 suggest that in. order to form high-mass stars, the detected cores have to accrete a large. amount of material, passing through a low- to intermediate-mass phase. before having the necessary mass to form a. high-mass star. The turbulent core accretion model. is inconsistent with this observational result, but on the other hand, the. observations support the competitive accretion model. Embedded cores have. to

  18. Formation of Secondary Particulate Matter by Reactions of Gas Phase Hexanal with Sulfate Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Zhang, J.

    2003-12-01

    The formation of secondary particulate matter from the atmospheric oxidation of organic compounds can significantly contribute to the particulate burden, but the formation of organic secondary particulate matter is poorly understood. One way of producing organic secondary particulate matter is the oxidation of hydrocarbons with seven or more carbon atoms to get products with low vapor pressure. However, several recent reports suggest that relatively low molecular weight carbonyls can enter the particle phase by undergoing heterogeneous reactions. This may be a very important mechanism for the formation of organic secondary particulate matter. Atmospheric aldehydes are important carbonyls in the gas phase, which form via the oxidation of hydrocarbons emitted from anthropogenic and biogenic sources. In this poster, we report the results on particle growth by the heterogeneous reactions of hexanal. A 5 L Continuous Stirred Tank Reactor (CSTR) is set up to conduct the reactions in the presence of seed aerosol particles of deliquesced ammonia bisulfate. Hexanal is added into CSTR by syringe pump, meanwhile the concentrations of hexanal are monitored with High Pressure Liquid Chromatograph (HPLC 1050). A differential Mobility Analyzer (TSI 3071) set to an appropriate voltage is employed to obtain monodisperse aerosols, and another DMA associated with a Condensation Nuclear Counter (TSI 7610) is used to measure the secondary particle size distribution by the reaction in CSTR. This permits the sensitive determination of particle growth due to the heterogeneous reaction, very little growth occurs when hexanal added alone. Results for the simultaneous addition of hexanal and alcohols will also be presented.

  19. Formation mechanism of the protective layer in a blast furnace hearth

    NASA Astrophysics Data System (ADS)

    Jiao, Ke-xin; Zhang, Jian-liang; Liu, Zheng-jian; Xu, Meng; Liu, Feng

    2015-10-01

    A variety of techniques, such as chemical analysis, scanning electron microscopy-energy dispersive spectroscopy, and X-ray diffraction, were applied to characterize the adhesion protective layer formed below the blast furnace taphole level when a certain amount of titanium- bearing burden was used. Samples of the protective layer were extracted to identify the chemical composition, phase assemblage, and distribution. Furthermore, the formation mechanism of the protective layer was determined after clarifying the source of each component. Finally, a technical strategy was proposed for achieving a stable protective layer in the hearth. The results show that the protective layer mainly exists in a bilayer form in the sidewall, namely, a titanium-bearing layer and a graphite layer. Both the layers contain the slag phase whose major crystalline phase is magnesium melilite (Ca2MgSi2O7) and the main source of the slag phase is coke ash. It is clearly determined that solid particles such as graphite, Ti(C,N) and MgAl2O4 play an important role in the formation of the protective layer, and the key factor for promoting the formation of a stable protective layer is reasonable control of the evolution behavior of coke.

  20. Mechanisms of nascent fiber formation during avian skeletal muscle hypertrophy

    NASA Technical Reports Server (NTRS)

    McCormick, K. M.; Schultz, E.

    1992-01-01

    This study examined two putative mechanisms of new fiber formation in postnatal skeletal muscle, namely longitudinal fragmentation of existing fibers and de novo formation. The relative contributions of these two mechanisms to fiber formation in hypertrophying anterior latissimus dorsi (ALD) muscle were assessed by quantitative analysis of their nuclear populations. Muscle hypertrophy was induced by wing-weighting for 1 week. All nuclei formed during the weighting period were labeled by continuous infusion of 5-bromo-2'-deoxyuridine (BrdU), a thymidine analog, and embryonic-like fibers were identified using an antibody to ventricular-like embryonic (V-EMB) myosin. The number of BrdU-labeled and unlabeled nuclei in V-EMB-positive fibers were counted. Wing-weighting resulted in significant muscle enlargement and the appearance of many V-EMB+ fibers. The majority of V-EMB+ fibers were completely independent of mature fibers and had a nuclear density characteristics of developing fibers. Furthermore, nearly 100% of the nuclei in independent V-EMB+ fibers were labeled. These findings strongly suggest that most V-EMB+ fibers were nascent fibers formed de novo during the weighting period by satellite cell activation and fusion. Nascent fibers were found primarily in the space between fascicles where they formed a complex anastomosing network of fibers running at angles to one another. Although wing-weighting induced an increase in the number of branched fibers, there was no evidence that V-EMB+ fibers were formed by longitudinal fragmentation. The location of newly formed fibers in wing-weighted and regenerating ALD muscle was compared to determine whether satellite cells in the ALD muscle were unusual in that, if stimulated to divide, they would form fibers in the inter- and intrafascicular space. In contrast to wing-weighted muscle, nascent fibers were always found closely associated with necrotic fibers. These results suggest that wing-weighting is not simply another

  1. Aqueous phase oligomerization of methyl vinyl ketone through photooxidation - Part 2: Development of the chemical mechanism and atmospheric implications

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Renard, P.; Ravier, S.; Clément, J.-L.; Monod, A.

    2014-08-01

    We developed a chemical mechanism based on laboratory experiments that have shown efficient oligomerization from methyl vinyl ketone (MVK) in the bulk aqueous phase. Kinetic data are applied (if known) or fitted to the observed MVK decay and oligomer mass increase. The mechanism is then implemented into a multiphase box model that simulates (i) oligomer formation upon uptake of MVK from the gas phase, and (ii) SOA formation from isoprene, as a precursor of MVK and methacrolein (MACR) in the aqueous and gas phases. Model results show that under atmospheric conditions, the oligomer formation rate strongly depends on the availability of dissolved oxygen. If oxygen is consumed too quickly or its solubility is kinetically or thermodynamically limited, oligomerization is accelerated, in agreement with the laboratory studies. The comparison of predicted oligomer formation shows that for most model assumptions (e.g. depending on the assumed partitioning of MVK and MACR), SOA formation from isoprene in the gas phase exceeds aqueous SOA formation by a factor 3-4. However, at high aerosol liquid water content and potentially high partitioning of oligomer precursors into the aqueous phase, SOA formation in both phases might be equally efficient.

  2. Postsurgical intrapericardial adhesions: mechanisms of formation and prevention.

    PubMed

    Cannata, Aldo; Petrella, Duccio; Russo, Claudio Francesco; Bruschi, Giuseppe; Fratto, Pasquale; Gambacorta, Marcello; Martinelli, Luigi

    2013-05-01

    Postsurgical intrapericardial adhesions are still considered an unavoidable consequence of cardiothoracic operations. They increase the technical difficulty and the risk of reoperations. The pathogenesis of postsurgical adhesions is a multistep process, and the main key players are (1) loss of mesothelial cells, (2) accumulation of fibrin in areas devoid of mesothelial cells, (3) loss of normal pericardial fibrinolysis, and (4) local inflammation. Today, very promising methods to reduce adhesions are available for clinical use. This report reviews the process of formation of adhesions and the methods to prevent them, classified according to the mechanism of action.

  3. New hetero silicon-carbon nanostructure formation mechanism.

    PubMed

    Song, S P; Crimp, M A; Ayres, V M; Collard, C J; Holloway, J P; Brake, M L

    2004-09-01

    We report the formation of silicon and carbon hetero-nanostructures in an inductively coupled plasma system by a simultaneous growth/etching mechanism. Multi-walled carbon nanotubes were grown during one, three and five hour depositions, while tapered silicon nanowires were progressively etched. The carbon and silicon nanostructures and the interfaces between them were studied by electron microscopies and micro Raman spectroscopies. The potential of this method for large-scale controlled production of nano heterostructures without the requirement of a common catalyst is explored.

  4. Reexamination of CO formation during formic acid decomposition on the Pt(1 1 1) surface in the gas phase

    NASA Astrophysics Data System (ADS)

    Wang, Yingying; Zhang, Dongju; Liu, Peng; Liu, Chengbu

    2016-08-01

    Existing theoretical results for formic acid (HCOOH) decomposition on Pt(1 1 1) cannot rationalize the easy CO poisoning of the catalysts in the gas phase. The present work reexamined HCOOH decomposition on Pt(1 1 1) by considering the effect of the initial adsorption structure of the reactant on the reactivity. Our calculations present a new adsorption configuration of HCOOH on Pt(1 1 1), from which the formation of CO is found to be competing with the formation of CO2. The newly proposed mechanism improves our understanding for the mechanism of HCOOH decomposition catalyzed by Pt-based catalysts.

  5. A unifying picture of gas-phase formation and growth of PAH (Polycyclic Aromatic Hydrocarbons), soot, diamond and graphite

    NASA Technical Reports Server (NTRS)

    Frenklach, Michael

    1990-01-01

    A variety of seemingly different carbon formation processes -- polycyclic aromatic hydrocarbons and diamond in the interstellar medium, soot in hydrocarbon flames, graphite and diamond in plasma-assisted-chemical vapor deposition reactors -- may all have closely related underlying chemical reaction mechanisms. Two distinct mechanisms for gas-phase carbon growth are discussed. At high temperatures it proceeds via the formation of carbon clusters. At lower temperatures it follows a polymerization-type kinetic sequence of chemical reactions of acetylene addition to a radical, and reactivation of the resultant species through H-abstraction by a hydrogen atom.

  6. Motionless electromagnetic phase stepping versus mechanical phase stepping in x-ray phase-contrast imaging with a compact source.

    PubMed

    Harmon, Katherine J; Miao, Houxun; Gomella, Andrew A; Bennett, Eric E; Foster, Barbara A; Bhandarkar, Priya; Wen, Han

    2015-04-21

    X-ray phase contrast imaging based on grating interferometers detects the refractive index distribution of an object without relying on radiation attenuation, thereby having the potential for reduced radiation absorption. These techniques belong to the broader category of optical wavefront measurement, which requires stepping the phase of the interference pattern to obtain a pixel-wise map of the phase distortion of the wavefront. While phase stepping traditionally involves mechanical scanning of a grating or mirror, we developed electromagnetic phase stepping (EPS) for imaging with compact sources to obviate the need for mechanical movement. In EPS a solenoid coil is placed outside the x-ray tube to shift its focal spot with a magnetic field, causing a relative movement between the projection of the sample and the interference pattern in the image. Here we present two embodiments of this method. We verified experimentally that electromagnetic and mechanical phase stepping give the same results and attain the same signal-to-noise ratios under the same radiation dose. We found that the relative changes of interference fringe visibility were within 3.0% when the x-ray focal spot was shifted by up to 1.0 mm in either direction. We conclude that when using x-ray tube sources, EPS is an effective means of phase stepping without the need for mechanical movement.

  7. Noise and disorder: Phase transitions and universality in a model of opinion formation

    NASA Astrophysics Data System (ADS)

    Crokidakis, Nuno

    2016-02-01

    In this work, we study a three-state opinion formation model considering two distinct mechanisms, namely independence and conviction. Independence is introduced in the model as a noise by means of a probability of occurrence q. On the other hand, conviction acts as a disorder in the system, and it is introduced by two discrete probability distributions. We analyze the effects of such two mechanisms on the phase transitions of the model, and we found that the critical exponents are universal over the order-disorder frontier, presenting the same universality class of the mean-field Ising model. In addition, for one of the probability distributions, the transition may be eliminated for a wide range of the parameters.

  8. Auto Mechanics. Pre-Apprenticeship Phase 1 Training. Instructor's Guide.

    ERIC Educational Resources Information Center

    Lane Community Coll., Eugene, OR.

    This instructor's guide accompanies the self-paced student training modules on auto mechanics, one of which is available separately as CE 032 867. Introductory materials include an introduction to pre-apprenticeship and its three phases of training, a recommended preocedure for conducting pre-apprenticeship training, and a course outline. Teaching…

  9. A new mechanism for dendritic pattern formation in dense systems

    NASA Astrophysics Data System (ADS)

    Oikawa, Noriko; Kurita, Rei

    2016-06-01

    Patterns are often formed when particles cluster: Since patterns reflect the connectivity of different types of material, the emergence of patterns affects the physical and chemical properties of systems and shares a close relationship to their macroscopic functions. A radial dendritic pattern (RDP) is observed in many systems such as snow crystals, polymer crystals and biological systems. Although most of these systems are considered as dense particle suspensions, the mechanism of RDP formation in dense particle systems is not yet understood. It should be noted that the diffusion limited aggregation model is not applicable to RDP formation in dense systems, but in dilute particle systems. Here, we propose a simple model that exhibits RDP formation in a dense particle system. The model potential for the inter-particle interaction is composed of two parts, a repulsive and an attractive force. The repulsive force is applied to all the particles all the time and the attractive force is exerted only among particles inside a circular domain, which expands at a certain speed as a wave front propagating from a preselected centre. It is found that an RDP is formed if the velocity of the wave front that triggers the attractive interaction is of the same order of magnitude as the time scale defined by the aggregation speed.

  10. Determination of mechanism of flock sediment formation in tea beverages.

    PubMed

    Niino, Hitoshi; Sakane, Iwao; Okanoya, Kazunori; Kuribayashi, Syuhei; Kinugasa, Hitoshi

    2005-05-18

    The mechanism of sediment formation during the storage of green tea beverage was investigated. Green tea extract was separated by Diaion HP-20 column chromatography, and a sediment-formation test was performed. Results showed that at least one compound of the substance causing flock sediment was contained in each of the HP-20 nonadsorbed and adsorbed fractions. From the following fractionations and structure analyses, the substance in the HP-20 adsorbed fraction was determined to be 1-O-galloyl-4,6-O-(S)-hexahydroxydiphenoyl-beta-D-glucose (strictinin), which is one of the ellagitannins. Strictinin was hydrolyzed to ellagic acid by heat-sterilization processes such as retort sterilization or the ultra-high temperature processing used during the manufacturing of tea beverages. Ellagic acid combined with proteins in the HP-20 nonadsorbed fraction to form an irreversible sediment of green tea beverage; ellagic acid and proteins were confirmed to be present in that sediment. The HP-20 adsorbed fraction contained little strictinin and formed hardly any sediment, suggesting that control of the strictinin content is significant in avoiding sediment formation during the manufacturing process of tea beverages.

  11. Leading Formative Assessment Change: A 3-Phase Approach

    ERIC Educational Resources Information Center

    Northwest Evaluation Association, 2016

    2016-01-01

    If you are seeking greater student engagement and growth, you need to integrate high-impact formative assessment practices into daily instruction. Read the final article in our five-part series to find advice aimed at leaders determined to bring classroom formative assessment practices district wide. Learn: (1) what you MUST consider when…

  12. Simulation of semi-explicit mechanisms of SOA formation from glyoxal in a 3-D model

    NASA Astrophysics Data System (ADS)

    Knote, C.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J.; Fast, J.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R.; Tyndall, G.; Washenfelder, R.; Waxman, E.; Zhang, Q.

    2013-10-01

    New pathways to form secondary organic aerosols (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous-phase of cloud droplets and deliquesced aerosols where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include a detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aqueous-phase of aerosols. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. In all simulations the LA basin was found to be the hotspot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a simple uptake coefficient, as frequently employed in global modeling studies, leads to higher SOA contributions from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to be the main contributor to SOA mass compared to a volume process and reversible formation. We find that contribution of the latter is limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A kinetic limitation in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume pathways contribute >20% of glyoxal SOA mass, and the total mass formed (5.8% of total SOA in the LA

  13. Preparation and mechanisms of formation of monodispersed colloidal gold

    NASA Astrophysics Data System (ADS)

    Goia, Dan Viorel

    1998-12-01

    Monodispersed gold particles of various sizes, morphologies, and internal structures were prepared by the reduction in homogeneous solutions of tetrachloroauric(III) acid (HAuCl4) with iso-ascorbic acid. The mechanisms responsible for their formation were investigated with special reference to the composition of the solute species as a function of the reaction parameters, and their effect on the nucleation and growth processes. The precipitation experiments carried out in dilute solutions, in the absence of any protective agent, revealed important relations between the nature of the reactants in the solution and the characteristics (particle size, stability, optical properties) of the resulting dispersions of nanosize gold. Larger (micrometer) gold particles of various shapes and internal structure could be also produced using the same reactants in concentrated solutions, in the presence of gum arabic as a stabilizer, and it was established that such uniform particles are formed by the aggregation of nanosize precursors. A new model of the process was proposed, which showed that under specific conditions the aggregation can indeed result in the size selection mechanism. The results of the computer simulations agree reasonably well with the experimental facts observed in the formation of monodispersed gold spheres.

  14. Analysis of Europan Cycloid Morphology and Implications for Formation Mechanisms

    NASA Technical Reports Server (NTRS)

    Marshall, S. T.; Kattenhorn, S. A.

    2004-01-01

    Europa's highly fractured crust has been shown to contain features with a range of differing morphologies. Most lineaments on Europa are believed to have initiated as cracks, although the type of cracking (e.g. tensile vs. shear) remains unclear and may vary for different morphologies. Arcuate lineaments, called cycloids or flexi, have been observed in nearly all imaged regions of Europa and have been modeled as tensile fractures that were initiated in response to diurnal variations in tides. Despite this hypothesis about the formation mechanism, there have been no detailed analyses of the variable morphologies of cycloids. We have examined Galileo images of numerous locations on Europa to develop a catalog of the different morphologies of cycloids. This study focuses on variations in morphology along individual cycloid segments and differences in cusp styles between segments, while illustrating how morphologic evidence can help unravel formation mechanisms. In so doing, we present evidence for cycloid cusps forming due to secondary fracturing during strike-slip sliding on pre-existing cycloid segments.

  15. THE FORMATION MECHANISM OF GAS GIANTS ON WIDE ORBITS

    SciTech Connect

    Dodson-Robinson, Sarah E.; Veras, Dimitri; Ford, Eric B.; Beichman, C. A.

    2009-12-10

    The recent discoveries of massive planets on ultra-wide orbits of HR 8799 and Fomalhaut present a new challenge for planet formation theorists. Our goal is to figure out which of three giant planet formation mechanisms-core accretion (with or without migration), scattering from the inner disk, or gravitational instability-could be responsible for Fomalhaut b, HR 8799 b, c and d, and similar planets discovered in the future. This paper presents the results of numerical experiments comparing the long-period planet formation efficiency of each possible mechanism in model A star, G star, and M star disks. First, a simple core accretion simulation shows that planet cores forming beyond 35 AU cannot reach critical mass, even under the most favorable conditions one can construct. Second, a set of N-body simulations demonstrates that planet-planet scattering does not create stable, wide-orbit systems such as HR 8799. Finally, a linear stability analysis verifies previous work showing that global spiral instabilities naturally arise in high-mass disks. We conclude that massive gas giants on stable orbits with semimajor axes a approx> 35 AU form by gravitational instability in the disk. We recommend that observers examine the planet detection rate as a function of stellar age, controlling for the planets' dimming with time. Any age trend would indicate that planets on wide orbits are transient relics of scattering from the inner disk. If planet detection rate is found to be independent of stellar age, it would confirm our prediction that gravitational instability is the dominant mode of producing detectable planets on wide orbits. We also predict that the occurrence ratio of long-period to short-period gas giants should be highest for M dwarfs due to the inefficiency of core accretion and the expected small fragment mass (approx10 M {sub Jup}) in their disks.

  16. Mechanisms in environmentally assisted one-photon phase control

    NASA Astrophysics Data System (ADS)

    Pachón, Leonardo A.; Brumer, Paul

    2013-10-01

    The ability of an environment to assist in one-photon phase control relies upon entanglement between the system and bath and on the breaking of the time reversal symmetry. Here, one-photon phase control is examined analytically and numerically in a model system, allowing an analysis of the relative strength of these contributions. Further, the significant role of non-Markovian dynamics and of moderate system-bath coupling in enhancing one-photon phase control is demonstrated, and an explicit role for quantum mechanics is noted in the existence of initial non-zero stationary coherences. Finally, desirable conditions are shown to be required to observe such environmentally assisted control, since the system will naturally equilibrate with its environment at longer times, ultimately resulting in the loss of phase control.

  17. Influence of Powder Metallurgical Processing Routes on Phase Formations in a Multicomponent NbSi-Alloy

    NASA Astrophysics Data System (ADS)

    Seemüller, C.; Hartwig, T.; Mulser, M.; Adkins, N.; Wickins, M.; Heilmaier, M.

    2014-09-01

    Refractory metal silicide composites on the basis of Nbss-Nb5Si3 have been investigated as potential alternatives for nickel-base superalloys for years because of their low densities and good high-temperature strengths. NbSi-based composites are typically produced by arc-melting or casting. Samples in this study, however, were produced by powder metallurgy because of the potential for near net-shape component fabrication with very homogeneous microstructures. Either gas atomized powder or high-energy mechanically alloyed elemental powders were compacted by powder injection molding or hot isostatic pressing. Heat treatments were applied for phase stability evaluation. Slight compositional changes (oxygen, nitrogen, or iron) introduced by the processing route, i.e., powder production and consolidation, can affect phase formations and phase transitions during the process. Special focus is put on the distinction between different silicides (Nb5Si3 and Nb3Si) and silicide modifications (α-, β-, and γ-Nb5Si3), respectively. These were evaluated by x-ray diffraction and energy-dispersive spectroscopy measurements with the additional inclusion of thermodynamic calculations using the calculated phase diagram method.

  18. Phase stability, electronic structure and mechanical properties of molybdenum disilicide: a first-principles investigation

    NASA Astrophysics Data System (ADS)

    Qiao, Yingjie; Zhang, Hexin; Hong, Changqing; Zhang, Xiaohong

    2009-05-01

    The phase stability, electronic structure and mechanical properties of MoSi2 at different phases were systematically investigated by first-principles density functional theory calculations. The results indicated that both tetragonal and hexagonal MoSi2 are thermodynamically and mechanically stable. The formation energy of the hexagonal phase is 6.27 kJ mol-1 smaller than that of the tetragonal one. In tetragonal MoSi2, Mo 4dxz, 4dyz and 4d_{z}^{2} orbitals overlap effectively with Si sp_{z}^{1} , px and py ones, while interactions between Mo 4d_{{x}^{2}-{y}^{2}} (4dxy) and Si 2p orbitals are confirmed in the hexagonal phase. However, the bond strengths of the hexagonal phase are smaller, leading to changes in the mechanical properties. Young's modulus decreases from 443.33 to 341.37 GPa as the phase transforms from the tetragonal to the hexagonal phase. The weakness of the Si-Mo bonds along the [0 0 1] direction and the Si-Si bonds within the (0 0 1) plane make the shear deformations of the hexagonal phase much easier to occur, and the G/B ratio correspondingly decreases, suggesting improvement in ductility. Moreover, the calculated Vicker's hardness of the hexagonal phase is 10.15 GPa, 48% smaller than the value in the tetragonal one. Besides the structural transformation, the external pressure can also affect the mechanical properties of the system. Different from the structural change, the external pressure enhances the Si-Si interactions while it reduces the Si-Mo (II) bond populations. Both the Vicker's hardness and ductility are improved as the hydrostatic pressure increases. The present calculations confirmed that the Si-Si (I) interactions play a central role in the hardness and ductility of MoSi2 materials.

  19. Prediction of Phase Formation in Nanoscale Sn-Ag-Cu Solder Alloy

    NASA Astrophysics Data System (ADS)

    Wu, Min; Lv, Bailin

    2016-01-01

    In a dynamic nonequilibrium process, the effective heat of formation allows the heat of formation to be calculated as a function of concentrations of the reacting atoms. In this work, we used the effective heat of formation rule to predict the formation and size of compound phases in a nanoscale Sn-Ag-Cu lead-free solder. We calculated the formation enthalpy and effective formation enthalpy of compounds in the Sn-Ag, Sn-Cu, and Ag-Cu systems by using the Miedema model and effective heat of formation. Our results show that, considering the surface effect of the nanoparticle, the effective heat of formation rule successfully predicts the phase formation and sizes of Ag3Sn and Cu6Sn5 compounds, which agrees well with experimental data.

  20. Mechanical modulation method for ultrasensitive phase measurements in photonics biosensing.

    PubMed

    Patskovsky, S; Maisonneuve, M; Meunier, M; Kabashin, A V

    2008-12-22

    A novel polarimetry methodology for phase-sensitive measurements in single reflection geometry is proposed for applications in optical transduction-based biological sensing. The methodology uses altering step-like chopper-based mechanical phase modulation for orthogonal s- and p- polarizations of light reflected from the sensing interface and the extraction of phase information at different harmonics of the modulation. We show that even under a relatively simple experimental arrangement, the methodology provides the resolution of phase measurements as low as 0.007 deg. We also examine the proposed approach using Total Internal Reflection (TIR) and Surface Plasmon Resonance (SPR) geometries. For TIR geometry, the response appears to be strongly dependent on the prism material with the best values for high refractive index Si. The detection limit for Si-based TIR is estimated as 10(-5) in terms Refractive Index Units (RIU) change. SPR geometry offers much stronger phase response due to a much sharper phase characteristics. With the detection limit of 3.2*10(-7) RIU, the proposed methodology provides one of best sensitivities for phase-sensitive SPR devices. Advantages of the proposed method include high sensitivity, simplicity of experimental setup and noise immunity as a result of a high stability modulation.

  1. Formation of tetragonal hydrogen tungsten bronze by reactive mechanical alloying

    SciTech Connect

    Urretavizcaya, G. Tonus, F.; Gaudin, E.; Bobet, J.-L.; Castro, F.J.

    2007-10-15

    Hydrogen tungsten bronzes have been synthesized by reactive mechanical alloying monoclinic tungsten (VI) oxide under hydrogen atmosphere. Two milling devices with different energy ranges were used. Regardless of the distinct reaction times, a similar phase evolution was observed with both apparatus. The characterization of the materials was performed by XRD, SEM, DSC and total hydrogen content determination. The final product obtained was a mixture of tetragonal H{sub 0.33}WO{sub 3} and H{sub 0.23}WO{sub 3} bronzes. - Graphical abstract: Hydrogen tungsten bronzes have been synthesized by reactive mechanical alloying (RMA) monoclinic WO{sub 3} under H{sub 2} atmosphere. By using two milling devices with different energy ranges a similar phase evolution with distinct reaction times was observed. The materials were characterized by XRD, SEM, DSC and total hydrogen content determination. The final product obtained was a mixture of tetragonal H{sub 0.33}WO{sub 3} and H{sub 0.23}WO{sub 3} bronzes. Display Omitted.

  2. Secondary Aerosol: Precursors and Formation Mechanisms. Technical Report on Grant

    SciTech Connect

    Weinstein-Lloyd, Judith B

    2009-05-04

    This project focused on studying trace gases that participate in chemical reactions that form atmospheric aerosols. Ammonium sulfate is a major constituent of these tiny particles, and one important pathway to sulfate formation is oxidation of dissolved sulfur dioxide by hydrogen peroxide in cloud, fog and rainwater. Sulfate aerosols influence the number and size of cloud droplets, and since these factors determine cloud radiative properties, sulfate aerosols also influence climate. Peroxide measurements, in conjunction with those of other gaseous species, can used to distinguish the contribution of in-cloud reaction to new sulfate aerosol formation from gas-phase nucleation reactions. This will lead to more reliable global climate models. We constructed and tested a new 4-channel fluorescence detector for airborne detection of peroxides. We integrated the instrument on the G-1 in January, 2006 and took a test flight in anticipation of the MAX-Mex field program, where we planned to fly under pressurized conditions for the first time. We participated in the 2006 Megacity Initiative: Local and Global Research Observations (MILAGRO) - Megacity Aerosol EXperiment Mexico City (MAX-Mex) field measurement campaign. Peroxide instrumentation was deployed on the DOE G-1 research aircraft based in Veracruz, and at the surface site at Tecamac University.

  3. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Yee, L. D.; Schilling, K.; Loza, C. L.; Craven, J. S.; Zuend, A.; Ziemann, P. J.; Seinfeld, J.

    2013-12-01

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosol (SOA). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multi-generation gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a mid-experiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. The results of the current work have a number of implications for SOA models. While the dynamics of an aerosol size distribution reflects the mechanism of growth, we demonstrate here that it provides a key constraint in interpreting laboratory and ambient SOA formation. This work, although carried out specifically for the long chain alkane, dodecane, is expected to be widely applicable to other major classes of SOA precursors. SOA consists of a myriad of organic compounds containing various functional groups, which can generally undergo heterogeneous/multiphase reactions forming low-volatility products such as oligomers and other high molecular mass compounds. If particle-phase chemistry is indeed

  4. In situ real-time studies of nickel silicide phase formation

    NASA Astrophysics Data System (ADS)

    Tinani, Manisha

    2000-10-01

    Metal silicides have attracted considerable attention in recent years as low resistivity metal contact and interconnect materials in microelectronics. Historically, polycrystalline silicon has been used as the gate contact material. However, as device size decreases, the higher resistance of polycrystalline silicon can degrade device performance. Metal silicides provide low metal like resistivities and high temperature stability. Ideal silicides for practical applications need to have stable phases, low processing temperatures and mechanical compatibility with silicon, in order to reduce defects and roughness at the silicon-silicide interface. NiSi, one of the nickel silicide phases, fulfills all these criteria. It has a resistivity of 14muO-cm, and a large processing temperature window (350--750°C). NiSi actually surpasses other commonly used silicides such as COSi2 and TiSi2 1 in these properties, while avoiding problems generally faced with these silicides2. Prior to the use of NiSi, its formation mechanism must be understood. The objective of this research is to develop analytical procedures to monitor phase transformations, in our case NiSi, in real-time, using non-destructive techniques. To this end, we studied the formation of NiSi films on Si using Rutherford Backscattering spectrometry, atomic force microscopy, X-ray photoelectron spectroscopy, and real-time single wavelength and spectroscopic ellipsometry. Several nickel silicide phases (Ni2Si, NiSi, NiSi2), with different properties, form in various temperature ranges below 1000°C. Three phases, Ni2Si, NiSi, NiSi2, were identified in this temperature range, and their optical databases in the 2--4 eV range were established. We demonstrated that we can identify the phases and the extent of phase formation from optical data obtained via spectroscopic ellipsometry in real-time, and modeled the data using the optical databases established. We have also observed the onset of agglomeration of the silicide for

  5. Shocked cobbles in Lower Cretaceous Duwon Formation, South Korea: their classification and possible formation mechanisms

    NASA Astrophysics Data System (ADS)

    Lim, Hyoun Soo; Chae, Yong-Un; Kim, Kyung Soo; Kim, Cheng-Bin; Huh, Min

    2016-04-01

    Shocked cobbles are the cobbles having shock-induced deformation structures on the surfaces. The most distinctive macroscopic features are the subparallel fractures and the pervasive surface craters, with or without radial fractures. Until now, these shocked cobbles have been reported mainly in Europe, America, and Africa, but never been found or reported in Korea. Shocked cobbles have recently found in the Lower Cretaceous Duwon Formation in South Korea, which was the second report in Asia. The Duwon Formation consists mainly of conglomerates, gravelly sandstones and intercalated mudstone and shale layers. The shocked cobbles are commonly found in the lowermost clast-supported conglomerate layers, and they show various deformation features, such as pockmarked (circular or elliptical) cobbles, cratered (Hertzian or bowl-shaped) cobbles with or without radial fractures, cobbles showing subparallel fractures, and strongly squashed or heavily dissected cobbles. In general, these deformation structures are considered to have resulted from pressure dissolution by overburden, tectonic compression, and seismic or meteorite impacts. However, the exact formation mechanism is not clearly understood, and still in debate. The shocked cobbles found in the Duwon Formation have similar features to those of previously reported shocked cobbles, especially to Triassic Buntsandstein conglomerates in northeastern Spain. Based on the degree of deformation, the Duwon shocked cobbles can be divided into four types, which are (1) faint contact marks, (2) pitted marks without any fractures, (3) pitted marks with radial or sub-parallel fractures affected by pits, and (4) intensive fractures and heavily dissected fragments. The possible mechanisms for the Duwon shocked cobbles are thought to be crushing process by shear stress and pressure solution.

  6. Bridging the gap: disk formation in the Class 0 phase with ambipolar diffusion and Ohmic dissipation

    NASA Astrophysics Data System (ADS)

    Dapp, Wolf B.; Basu, Shantanu; Kunz, Matthew W.

    2012-05-01

    Context. Ideal magnetohydrodynamical (MHD) simulations have revealed catastrophic magnetic braking in the protostellar phase, which prevents the formation of a centrifugal disk around a nascent protostar. Aims: We determine if non-ideal MHD, including the effects of ambipolar diffusion and Ohmic dissipation determined from a detailed chemical network model, will allow for disk formation at the earliest stages of star formation. Methods: We employ the axisymmetric thin-disk approximation in order to resolve a dynamic range of 9 orders of magnitude in length and 16 orders of magnitude in density, while also calculating partial ionization using up to 19 species in a detailed chemical equilibrium model. Magnetic braking is applied to the rotation using a steady-state approximation, and a barotropic relation is used to capture the thermal evolution. Results: We resolve the formation of the first and second cores, with expansion waves at the periphery of each, a magnetic diffusion shock, and prestellar infall profiles at larger radii. Power-law profiles in each region can be understood analytically. After the formation of the second core, the centrifugal support rises rapidly and a low-mass disk of radius ≈ 10 R⊙ is formed at the earliest stage of star formation, when the second core has mass ~10-3 M⊙. The mass-to-flux ratio is ~104 times the critical value in the central region. Conclusions: A small centrifugal disk can form in the earliest stage of star formation, due to a shut-off of magnetic braking caused by magnetic field dissipation in the first core region. There is enough angular momentum loss to allow the second collapse to occur directly, and a low-mass stellar core to form with a surrounding disk. The disk mass and size will depend upon how the angular momentum transport mechanisms within the disk can keep up with mass infall onto the disk. Accounting only for direct infall, we estimate that the disk will remain ≲10 AU, undetectable even by ALMA, for

  7. Effect of temperature on the reaction pathway of calcium carbonate formation via precursor phases

    NASA Astrophysics Data System (ADS)

    Purgstaller, Bettina; Mavromatis, Vasileios; Konrad, Florian; Dietzel, Martin

    2016-04-01

    It has been earlier postulated that some biogenic and sedimentary calcium carbonate (CaCO3) minerals (e.g. calcite and aragonite) are secondary in origin and have originally formed via a metastable calcium carbonate precursor phase (e.g. amorphous CaCO3, [1-2]). Such formation pathways are likely affected by various physicochemical parameters including aqueous Mg and temperature. In an effort to improve our understanding on the formation mechanism of CaCO3 minerals, precipitation experiments were carried out by the addition of a 0.6 M (Ca,Mg)Cl2 solution at distinct Mg/Ca ratios (1/4 and 1/8) into a 1 M NaHCO3 solution under constant pH conditions(8.3 ±0.1). The formation of CaCO3 was systematically examined as a function of temperature (6, 12, 18 and 25 ±0.3° C). During the experimental runs mineral precipitation was monitored by in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. The results revealed two pathways of CaCO3 formation depending on the initial Mg/Ca ratio and temperature: (i) In experiments with a Mg/Ca ratio of 1/4 at ≤ 12° C as well as in experiments with a Mg/Ca ratio of 1/8 at ≤ 18° C, ikaite (CaCO3 6H2O) acts as a precursor phase for aragonite formation. (ii) In contrast higher temperatures induced the formation of Mg-rich amorphous CaCO3 (Mg-ACC) which was subsequently transformed to Mg-rich calcite. In situ Raman spectra showed that the transformation of Mg-ACC to Mg-calcite occurs at a higher rate (˜ 8 min) compared to that of ikaite to aragonite (> 2 h). Thus, the formation of aragonite rather than of Mg-calcite occurs due to the slower release of Ca2+and CO32- ions into the Mg-rich reactive solution during retarded ikaite dissolution. This behavior is generally consistent with the observation that calcite precipitation is inhibited at elevated aqueous Mg/Ca ratios. [1] Addadi L., Raz S. and Weiner S. (2003) Advanced Materials 15, 959-970. [2] Rodriguez-Blanco J. D

  8. Properties of aerosols and formation mechanisms over southern China during the monsoon season

    NASA Astrophysics Data System (ADS)

    Chen, Weihua; Wang, Xuemei; Blake Cohen, Jason; Zhou, Shengzhen; Zhang, Zhisheng; Chang, Ming; Chan, Chuen-Yu

    2016-10-01

    Measurements of size-resolved aerosols from 0.25 to 18 µm were conducted at three sites (urban, suburban and background sites) and used in tandem with an atmospheric transport model to study the size distribution and formation of atmospheric aerosols in southern China during the monsoon season (May-June) in 2010. The mass distribution showed the majority of chemical components were found in the smaller size bins (< 2.5 µm). Sulfate was found to be strongly correlated with aerosol water and anticorrelated with atmospheric SO2, hinting at aqueous-phase reactions being the main formation pathway. Nitrate was the only major species that showed a bimodal distribution at the urban site and was dominated by the coarse mode in the other two sites, suggesting that an important component of nitrate formation is chloride depletion of sea salt transported from the South China Sea. In addition to these aqueous-phase reactions and interactions with sea salt aerosols, new particle formation, chemical aging, and long-range transport from upwind urban or biomass burning regions was also found to be important in at least some of the sites on some of the days. This work therefore summarizes the different mechanisms that significantly impact the aerosol chemical composition during the monsoon over southern China.

  9. Reducing Mechanical Formation Damage by Minimizing Interfacial Tension and Capillary Pressure in Tight Gas

    NASA Astrophysics Data System (ADS)

    Ahmed, Arshad; Talib Shuker, Muhannad; Rehman, Khalil; Bahrami, Hassan; Memon, Muhammad Khan

    2013-12-01

    Tight gas reservoirs incur problems and significant damage caused by low permeability during drilling, completion, stimulation and production. They require advanced improvement techniques to achieve flow gas at optimum rates. Water blocking damage (phase Trapping/retention of fluids) is a form of mechanical formation damage mechanism, which is caused by filtrate invasion in drilling operations mostly in fracturing. Water blocking has a noticeable impact on formation damage in gas reservoirs which tends to decrease relative permeability near the wellbore. Proper evaluation of damage and the factors which influence its severity is essential to optimize well productivity. Reliable data regarding interfacial tension between gas and water is required in order to minimize mechanical formation damage potential and to optimize gas production. This study was based on the laboratory experiments of interfacial tension by rising drop method between gas-brine, gas-condensate and gas-brine. The results showed gas condensate has low interfacial tension value 6 - 11 dynes/cm when compared to gas-brine and gas- diesel which were 44 - 58 dynes/cm and 14 - 19 dynes/cm respectively. In this way, the capillary pressure of brine-gas system was estimated as 0.488 psi, therefore diesel-gas system was noticed about 0.164 psi and 0.098 psi for condensate-gas system. A forecast model was used by using IFT values to predict the phase trapping which shows less severe phase trapping damage in case of condensate than diesel and brine. A reservoir simulation study was also carried out in order to better understand the effect of hysteresis on well productivity and flow efficiency affected due to water blocking damage in tight gas reservoirs.

  10. Phase nucleation and evolution mechanisms in heterogeneous solids

    NASA Astrophysics Data System (ADS)

    Udupa, Anirudh

    nucleation theory. The experimental results are consistent with the developed theory and show that the theory of entropic dissipation is incorrect. A diffuse-interface computational technique was then developed to simulate the problem of electromigration driven void nucleation and growth in arbitrary geometries. Experimentally known results such as Black's law, existence of the Blech length, effect of interface adhesion energy were reproduced. The simulations were also used to infer the numerical value of the nucleation criterion, based on experimental results in the literature. The problem of electromigration is the result of species diffusion due to imparted momentum from the electrons, and the resulting motion of interface is influenced by surface diffusion along the interface, bulk diffusion, and the current density. Similarly, the formation of intermetallic compounds (IMC) and the resulting interface shape in many systems is the result of limiting effects of bulk diffusion, interfacial reaction, surface energy, and surface diffusion. Thus, the dynamics and stability of the interface formed when Cu and Sn react to form the IMC compound Cu6Sn5 is explored next. This system is of significant relevance to modern microelectronic chip assemblies, where solder joints with significant Cu6Sn5 volume fraction are known to be prone to brittle fracture and shorter useful life. Prior experimental observations have shown the interface to possess either a scalloped, flat or needle shaped morphology. The governing mechanism leading to the observed shape of the interface is not clearly known, and is the focus of the present study. In research unrelated to diffusion driven phase evolution, but involving interfaces nevertheless, in the appendix, the problem of interfacial delamination in Through Silicon Vias (TSV) is studied analytically. Three-dimensional (3D) packages utilizing TSVs are seen as enablers of increased performance and "More than Moore" functionality at the present time

  11. Axion field and the quark nugget's formation at the QCD phase transition

    NASA Astrophysics Data System (ADS)

    Liang, Xunyu; Zhitnitsky, Ariel

    2016-10-01

    We study a testable dark-matter (DM) model outside of the standard weakly interacting massive particle paradigm in which the observed ratio Ωdark≃Ωvisible for visible and dark-matter densities finds its natural explanation as a result of their common QCD origin when both types of matter (DM and visible) are formed at the QCD phase transition and both are proportional to ΛQCD. Instead of the conventional "baryogenesis" mechanism, we advocate a paradigm when the "baryogenesis" is actually a charge separation process which always occurs in the presence of the C P odd axion field a (x ). In this scenario, the global baryon number of the Universe remains zero, while the unobserved antibaryon charge is hidden in the form of heavy nuggets, similar to Witten's strangelets and compromise the DM of the Universe. In the present work, we study in great detail a possible formation mechanism of such macroscopically large heavy objects. We argue that the nuggets will be inevitably produced during the QCD phase transition as a result of Kibble-Zurek mechanism on formation of the topological defects during a phase transition. Relevant topological defects in our scenario are the closed bubbles made of the NDW=1 axion domain walls. These bubbles, in general, accrete the baryon (or antibaryon) charge, which eventually results in the formation of the nuggets and antinuggets carrying a huge baryon (antibaryon) charge. A typical size and the baryon charge of these macroscopically large objects are mainly determined by the axion mass ma. However, the main consequence of the model, Ωdark≈Ωvisible, is insensitive to the axion mass which may assume any value within the observationally allowed window 10-6 eV ≲ma≲10-3 eV . We also estimate the baryon-to-entropy ratio η ≡nB/nγ˜10-10 within this scenario. Finally, we comment on implications of these results to the axion search experiments, including the microwave cavity and the Orpheus experiments.

  12. Kinetics of the reactions of isoprene-derived hydroxynitrates: gas phase epoxide formation and solution phase hydrolysis

    NASA Astrophysics Data System (ADS)

    Jacobs, M. I.; Burke, W. J.; Elrod, M. J.

    2014-09-01

    Isoprene, the most abundant non-methane volatile organic compound (VOC) emitted into the atmosphere, is known to undergo gas phase oxidation to form eight different hydroxynitrate isomers in "high-NOx" environments. These hydroxynitrates are known to affect the global and regional formation of ozone and secondary organic aerosol (SOA), as well as affect the distribution of nitrogen. In the present study, we have synthesized three of the eight possible hydroxynitrates: 4-hydroxy-3-nitroxy isoprene (4,3-HNI) and E / Z-1-hydroxy-4-nitroxy isoprene (1,4-HNI). Oxidation of the 4,3-HNI isomer by the OH radical was monitored using a flow tube chemical ionization mass spectrometer (FT-CIMS), and its OH rate constant was determined to be (3.64 ± 0.41) × 10-11 cm3 molecule-1 s-1. The products of 4,3-HNI oxidation were monitored, and a mechanism to explain the products was developed. An isoprene epoxide (IEPOX) - a species important in SOA chemistry and thought to originate only from "low-NOx" isoprene oxidation - was found as a minor, but significant, product. Additionally, hydrolysis kinetics of the three synthesized isomers were monitored with nuclear magnetic resonance (NMR). The bulk, neutral solution hydrolysis rate constants for 4,3-HNI and the 1,4-HNI isomers were (1.59 ± 0.03) × 10-5 s-1 and (6.76 ± 0.09) × 10-3 s-1, respectively. The hydrolysis reactions of each isomer were found to be general acid-catalyzed. The reaction pathways, product yields and atmospheric implications for both the gas phase and aerosol phase reactions are discussed.

  13. Kinetics of the reactions of isoprene-derived hydroxynitrates: gas phase epoxide formation and solution phase hydrolysis

    NASA Astrophysics Data System (ADS)

    Jacobs, M. I.; Burke, W. J.; Elrod, M. J.

    2014-05-01

    Isoprene, the most abundant non-methane volatile organic compound (VOC) emitted into the atmosphere, is known to undergo gas phase oxidation to form eight different hydroxynitrate isomers in "high NOx" environments. These hydroxynitrates are known to affect the global and regional formation of ozone and secondary organic aerosol (SOA), as well as affect the distribution of nitrogen. In the present study, we have synthesized three of the eight possible hydroxynitrates: 4-hydroxy-3-nitroxy isoprene (4,3-HNI) and E/Z-1-hydroxy-4-nitroxy isoprene (1,4-HNI). Oxidation of the 4,3-HNI isomer by the OH radical was monitored using a flow tube chemical ionization mass spectrometer (FT-CIMS), and its OH rate constant was determined to be (3.64 ± 0.41) × 10-11 cm3 molecule-1 s-1. The products of 4,3-HNI oxidation were monitored, and a mechanism to explain the products was developed. An isoprene epoxide (IEPOX) - a species important in SOA chemistry and thought to originate only from "low NOx" isoprene oxidation - was found as a minor, but significant product. Additionally, hydrolysis kinetics of the three synthesized isomers were monitored with NMR. The bulk, neutral solution hydrolysis rate constants for 4,3-HNI and the 1,4-HNI isomers were (1.59±0.03 × 10-5 s-1 and (6.76 ± 0.09) × 10-3 s-1, respectively. The hydrolysis reactions of each isomer were found to be general acid-catalyzed. The reaction pathways, product yields and atmospheric implications for both the gas phase and aerosol-phase reactions are discussed.

  14. Insight into the mechanism of Sb promoted Cu(In,Ga)Se{sub 2} formation

    SciTech Connect

    Xiang, Yong Zhang, Xiaokun; Zhang, Shu

    2013-08-15

    Sb-doping has been demonstrated to be a new approach to promote Cu(In,Ga)Se{sub 2} (CIGS) thin film formation. To study the mechanism of Sb-promoted CIGS formation, we investigated the influence of Sb on the evolution of the critical intermediate Cu–Se phases, and found that Cu{sub 3}SbSe{sub 3} species was formed. Phase change of the as-prepared Cu–Se compounds at elevated temperature was determined using the differential scanning calorimetry analysis. For samples containing Sb, the melting decomposition occurred at 507.1 °C, along with aggregation of nanocrystals into a bulk, while the morphology of the sample without Sb barely changed after heating. This result suggests that the mobile Cu{sub 3}SbSe{sub 3} is likely the key intermediate responsible for Sb-promoted CIGS formation. Furthermore, we extended the scope of Sb-doping approach to solvothermal synthesis and CIGS nanocrystals were synthesized with significantly promoted kinetics in the presence of Sb. Based on these results, we propose the mechanism of Sb promoted CIGS formation. - Graphical abstract: Cu{sub 3}SbSe{sub 3} mobile phase is likely the key species to promote the formation of Cu(In,Ga)Se{sub 2}, and significantly promoting effect by Sb is also found in the synthesis of Cu(In,Ga)Se{sub 2} nanocrystals. Highlights: • In the presence of Sb, Cu{sub 3}SbSe{sub 3} is formed while synthesizing the essential intermediate Cu–Se compounds for Cu(In,Ga)Se{sub 2} materials. • Cu{sub 3}SbSe{sub 3} shows high mobility at elevated temperature. • Cu{sub 3}SbSe{sub 3} mobile phase is likely the key species to improve Cu(In,Ga)Se{sub 2} thin film formation. • A synthesis methodology is developed to produce Cu(In,Ga)Se{sub 2} nanocrystals with significantly promoted reaction kinetics.

  15. Locations and formation-mechanisms of hollows on Mercury

    NASA Astrophysics Data System (ADS)

    Thomas, Rebecca; Rothery, David; Conway, Susan; Anand, Mahesh

    2013-04-01

    Hollows on Mercury are sub-kilometre scale shallow, steep-sided rimless pits. Seemingly a result of loss of material to space, they are among several lines of evidence suggesting that the volatile budget of Mercury is higher than previously thought. They tend to occur in clusters and are associated with relatively high-albedo blue material ('bright crater floor deposits'). To further investigate the source and release mechanism of volatiles in hollow formation, we have surveyed hollowed areas within several pole-to-pole strips on Mercury. The majority of hollows occur in impact craters: on the walls and rims of simple craters and on the terraces, peaks and smooth floors of complex craters. Where they occur on only a part of a smooth crater floor, they cluster close to and concentric with the walls and peaks. Hollows that are not in craters are often associated with crater ejecta. Craters with hollows have a morphology that suggests a Calorian age or younger, however a few are very degraded and much older. In these older craters, hollows are observed associated with smaller superposed craters and the hanging wall of thrusts crossing the crater, in addition to tectonic lines of weakness such as crater walls and peak rings. A preferred slope aspect for hollows occurs in about one-third of cases. This is always towards the south in the northern hemisphere and towards the north in the southern hemisphere. The majority of hollow clusters superpose either low-reflectance material (LRM) or intermediate terrain (IT). Very few are observed on smooth plains except within large impact craters. This may be because smooth plains are not a good source of hollow-forming material and/or because they form a barrier to the release of volatiles. The occurrence of hollows in curved clusters following the walls and rims of impact craters, within slumped material from their walls and in uplifted central peaks suggests a structural control on their formation. However, hollowing is not

  16. The mechanism of hexamethylenetetramine (HMT) formation in the solid state at low temperature.

    PubMed

    Vinogradoff, Vassilissa; Rimola, Albert; Duvernay, Fabrice; Danger, Gregoire; Theulé, Patrice; Chiavassa, Thierry

    2012-09-21

    There is convincing evidence that the formation of complex organic molecules occurred in a variety of environments. One possible scenario highlights the universe as a giant reactor for the synthesis of organic complex molecules, which is confirmed by numerous identifications of interstellar molecules. Among them, precursors of biomolecules are of particular significance due to their exobiological implications, and some current targets concern their search in the interstellar medium as well as understanding the mechanisms of their formation. Hexamethylenetetramine (HMT, C(6)H(12)N(4)) is one of these complex organic molecules and is of prime interest since its acid hydrolysis seems to form amino acids. In the present work, the mechanism for HMT formation at low temperature and pressure (i.e. resembling interstellar conditions) has been determined by combining experimental techniques and DFT calculations. Fourier transform infra-red spectroscopy and mass spectrometry techniques have been used to follow experimentally the formation of HMT as well as its precursors from thermal reaction of NH(3):H(2)CO:HCOOH and CH(2)NH:HCOOH ice mixtures, from 20 K to 330 K. DFT calculations have been used to compute the mechanistic steps through which HMT can be formed starting from the experimental reactants observed in solid phase. The fruitful interplay between theory and experiment has allowed establishing that the mechanism in the solid state at low temperature is different from the one proposed in liquid phase, in which a new intermediate (1,3,5-triazinane, C(3)H(9)N(3)) has been identified. In the meantime, aminomethanol has been unambiguously confirmed as the first intermediate whereas the hypothesis of methylenimine as the second is further strengthened.

  17. Wavelength preserved phase erasure and PSK to conventional OOK data format conversion based on phase sensitive amplification

    NASA Astrophysics Data System (ADS)

    Yu, Kan; Yang, Weili; Yu, Yu

    2016-10-01

    In this paper, a phase erasure and format conversion of phase-shift keying (PSK) to conventional on-off keying (OOK) is proposed and demonstrated theoretically and experimentally. Using a single-pump nondegenerate phase sensitive amplification process in a highly nonlinear fiber, the 0 and 1-bits of the PSK signal obtain different gains through amplification and de-amplification. As a result, the modulation information is transferred onto the amplitude. With an optimized input power difference between the signal and idler, the signal phase information is erased with wavelength preservation after the PSA. The output constellation and eye diagrams show an effective phase erasure and format conversion of PSK to conventional OOK. The error vector magnitude is utilized to evaluate the scheme performance. The proposed scheme provides the flexibility and resiliency for future photonic networks.

  18. Phase behavior, formation, and rheology of cubic phase and related gel emulsion in Tween 80/water/oil systems.

    PubMed

    Alam, Mohammad Mydul; Ushiyama, Kousuke; Aramaki, Kenji

    2009-01-01

    We investigated the phase behavior, formation, and rheology of the cubic phase (I(1)) and related O/I(1) gel emulsion in water/Tween 80/oil systems using squalane, liquid paraffin (LP), and decane as oil components. In the phase behavior study, the phase sequences were similar for squalane and LP systems, while a lamellar liquid crystal (L(alpha)) was observed for decane system. In all the systems the addition of oil to W(m) or H(1) phase induced the I(1) phase, which can solubilize some amounts of oil followed by the appearance of I(1)+O phase. The formation of the O/I(1) gel emulsion has been studied at a fixed w/s (50/50) and we found that 30 wt% decane, 70 wt% squalane, and 60 wt% LP can form the gel emulsion. The water/Tween 80/squalane system has been taken as a model system to study viscoelastic properties of the I(1) phase and O/I(1) gel emulsion. The I(1) phase shows a typical hard gel cubic structure under the frequency and the values of the complex viscosity, /eta*/ and the elastic modulus, G ' increase with the addition of squalane, which could be due to the neighboring micellar interaction. On the other hand, the decreasing values of the viscoelastic parameters in the O/I(1) gel emulsion simply relate to the volume fraction of the I(1) phase in the system.

  19. Circuit Mechanisms Underlying Motor Memory Formation in the Cerebellum

    PubMed Central

    Lee, Ka Hung; Mathews, Paul J.; Reeves, Alexander M.B.; Choe, Katrina Y.; Jami, Shekib A.; Serrano, Raul E.; Otis, Thomas S.

    2015-01-01

    SUMMARY The cerebellum stores associative motor memories essential for properly timed movement; however, the mechanisms by which these memories form and are acted upon remain unclear. To determine how cerebellar activity relates to movement and motor learning, we used optogenetics to manipulate spontaneously firing Purkinje neurons (PNs) in mouse simplex lobe. Using high-speed videography and motion tracking, we found that altering PN activity produced rapid forelimb movement. PN inhibition drove movements time-locked to stimulus onset, whereas PN excitation drove delayed movements time-locked to stimulus offset. Pairing either PN inhibition or excitation with sensory stimuli triggered the formation of robust, associative motor memories; however, PN excitation led to learned movements whose timing more closely matched training intervals. These findings implicate inhibition of PNs as a teaching signal, consistent with a model whereby learning leads first to reductions in PN firing that subsequently instruct circuit changes in the cerebellar nucleus. PMID:25843404

  20. Lamellipodial actin mechanically links myosin activity with adhesion site formation

    PubMed Central

    Giannone, Gregory; Dubin-Thaler, Benjamin; Rossier, Olivier; Cai, Yunfei; Chaga, Oleg; Jiang, Guoying; Beaver, William; Döbereiner, Hans-Günther; Freund, Yoav; Borisy, Gary; Sheetz, Michael P.

    2013-01-01

    Summary Cell motility proceeds by cycles of edge protrusion, adhesion and retraction. Whether these functions are coordinated by biochemical or biomechanical processes is unknown. We find that myosin II pulls the rear of the lamellipodial actin network, causing upward bending, edge retraction and initiation of new adhesion sites. The network then separates from the edge and condenses over the myosin. Protrusion resumes as lamellipodial actin regenerates from the front and extends rearward until it reaches newly assembled myosin, initiating the next cycle. Upward bending, observed by evanescence and electron microscopy, results in ruffle formation when adhesion strength is low. Correlative fluorescence and electron microscopy shows that the regenerating lamellipodium forms a cohesive, separable layer of actin above the lamellum. Thus, actin polymerization periodically builds a mechanical link, the lamellipodium, connecting myosin motors with the initiation of adhesion sites, suggesting that the major functions driving motility are coordinated by a biomechanical process. PMID:17289574

  1. Directed networks' different link formation mechanisms causing degree distribution distinction

    NASA Astrophysics Data System (ADS)

    Behfar, Stefan Kambiz; Turkina, Ekaterina; Cohendet, Patrick; Burger-Helmchen, Thierry

    2016-11-01

    Within undirected networks, scientists have shown much interest in presenting power-law features. For instance, Barabási and Albert (1999) claimed that a common property of many large networks is that vertex connectivity follows scale-free power-law distribution, and in another study Barabási et al. (2002) showed power law evolution in the social network of scientific collaboration. At the same time, Jiang et al. (2011) discussed deviation from power-law distribution; others indicated that size effect (Bagrow et al., 2008), information filtering mechanism (Mossa et al., 2002), and birth and death process (Shi et al., 2005) could account for this deviation. Within directed networks, many authors have considered that outlinks follow a similar mechanism of creation as inlinks' (Faloutsos et al., 1999; Krapivsky et al., 2001; Tanimoto, 2009) with link creation rate being the linear function of node degree, resulting in a power-law shape for both indegree and outdegree distribution. Some other authors have made an assumption that directed networks, such as scientific collaboration or citation, behave as undirected, resulting in a power-law degree distribution accordingly (Barabási et al., 2002). At the same time, we claim (1) Outlinks feature different degree distributions than inlinks; where different link formation mechanisms cause the distribution distinctions, (2) in/outdegree distribution distinction holds for different levels of system decomposition; therefore this distribution distinction is a property of directed networks. First, we emphasize in/outlink formation mechanisms as causal factors for distinction between indegree and outdegree distributions (where this distinction has already been noticed in Barker et al. (2010) and Baxter et al. (2006)) within a sample network of OSS projects as well as Java software corpus as a network. Second, we analyze whether this distribution distinction holds for different levels of system decomposition: open

  2. Formation of silicon nanoparticles by a pressure induced nucleation mechanism

    NASA Astrophysics Data System (ADS)

    Kang, Myung-Koo; Kim, Si Joon; Kim, Hyun Jae

    2013-03-01

    Formation of silicon nanoparticles (SiNPs) was achieved using excimer laser crystallization of an amorphous Si (a-Si) thin film using a SiO2 capping layer (C/L) with improved thin-film transistor (TFT) performance due to the enlarged grain size of polycrystalline Si (poly-Si). After laser irradiation of an a-Si thin film covered with C/L, fluctuation in the surface morphology of the C/L was observed above the critical laser energy density (Ecr) with the formation of SiNPs. The grain size of the poly-Si layer after crystallization increased abruptly at the same time. A non-uniform pressure distribution beneath the SiO2 C/L was proposed for the initiation of nucleation, which is named pressure induced nucleation (PIN) mechanism. Following nucleation, the release of latent heat made it difficult for the remnant liquid Si to solidify and the volume increased due to the density difference between the liquid and solid Si. Consequently, the pressure on the liquid Si caused SiNPs to sprout through the SiO2 C/L as grains grew from the low temperature to high temperature point. This study offers not only a simple method to fabricate SiNPs with controllable size/density but also larger grain size with lower laser energy density, which leads to higher TFT performance.

  3. Martian gullies: possible formation mechanism by dry granular material..

    NASA Astrophysics Data System (ADS)

    Cedillo-Flores, Y.; Durand-Manterola, H. J.

    section Some of the geomorphological features in Mars are the gullies Some theories developed tried explain its origin either by liquid water liquid carbon dioxide or flows of dry granular material We made a comparative analysis of the Martian gullies with the terrestrial ones We propose that the mechanism of formation of the gullies is as follows In winter CO 2 snow mixed with sand falls in the terrain In spring the CO 2 snow sublimate and gaseous CO 2 make fluid the sand which flows like liquid eroding the terrain and forming the gullies By experimental work with dry granular material we simulated the development of the Martian gullies injecting air in the granular material section We present the characteristics of some terrestrial gullies forms at cold environment sited at Nevado de Toluca Volcano near Toluca City M e xico We compare them with Martian gullies choose from four different areas to target goal recognize or to distinguish to identify possible processes evolved in its formation Also we measured the lengths of those Martian gullies and the range was from 24 m to 1775 meters Finally we present results of our experimental work at laboratory with dry granular material

  4. Deformation quantization: Quantum mechanics lives and works in phase space

    NASA Astrophysics Data System (ADS)

    Zachos, Cosmas K.

    2014-09-01

    Wigner's 1932 quasi-probability Distribution Function in phase-space, his first paper in English, is a special (Weyl) representation of the density matrix. It has been useful in describing quantum flows in semiclassical limits; quantum optics; nuclear and physics; decoherence (eg, quantum computing); quantum chaos; "Welcher Weg" puzzles; molecular Talbot-Lau interferometry; atomic measurements. It is further of great importance in signal processing (time-frequency analysis). Nevertheless, a remarkable aspect of its internal logic, pioneered by H. Groenewold and J. Moyal, has only blossomed in the last quarter-century: It furnishes a third, alternate, formulation of Quantum Mechanics, independent of the conventional Hilbert Space (the gold medal), or Path Integral (the silver medal) formulations, and perhaps more intuitive, since it shares language with classical mechanics: one need not choose sides between coordinate or momentum space variables, since it is formulated simultaneously in terms of position and momentum. This bronze medal formulation is logically complete and self-standing, and accommodates the uncertainty principle in an unexpected manner, so that it offers unique insights into the classical limit of quantum theory. The observables in this formulation are cnumber functions in phase space instead of operators, with the same interpretation as their classical counterparts, only now composed together in novel algebraic ways using star products. One might then envision an imaginary world in which this formulation of quantum mechanics had preceded the conventional Hilbert-space formulation, and its own techniques and methods had arisen independently, perhaps out of generalizations of classical mechanics and statistical mechanics. A sampling of such intriguing techniques and methods has already been published in C. K. Zachos, Int Jou Mod Phys A17 297-316 (2002), and T. L. Curtright, D. B. Fairlie, and C. K. Zachos, A Concise Treatise on Quantum Mechanics in

  5. Quantum mechanics on phase space and the Coulomb potential

    NASA Astrophysics Data System (ADS)

    Campos, P.; Martins, M. G. R.; Vianna, J. D. M.

    2017-04-01

    Symplectic quantum mechanics (SMQ) makes possible to derive the Wigner function without the use of the Liouville-von Neumann equation. In this formulation of the quantum theory the Galilei Lie algebra is constructed using the Weyl (or star) product with Q ˆ = q ⋆ = q +iħ/2∂p , P ˆ = p ⋆ = p -iħ/2∂q, and the Schrödinger equation is rewritten in phase space; in consequence physical applications involving the Coulomb potential present some specific difficulties. Within this context, in order to treat the Schrödinger equation in phase space, a procedure based on the Levi-Civita (or Bohlin) transformation is presented and applied to two-dimensional (2D) hydrogen atom. Amplitudes of probability in phase space and the correspondent Wigner quasi-distribution functions are derived and discussed.

  6. Investigation of the mechanism of impurity assisted nanoripple formation on Si induced by low energy ion beam erosion

    SciTech Connect

    Koyiloth Vayalil, Sarathlal; Gupta, Ajay; Roth, Stephan V.; Ganesan, V.

    2015-01-14

    A detailed mechanism of the nanoripple pattern formation on Si substrates generated by the simultaneous incorporation of pure Fe impurities at low energy (1 keV) ion beam erosion has been studied. To understand and clarify the mechanism of the pattern formation, a comparative analysis of the samples prepared for various ion fluence values using two complimentary methods for nanostructure analysis, atomic force microscopy, and grazing incidence small angle x-ray scattering has been done. We observed that phase separation of the metal silicide formed during the erosion does not precede the ripple formation. It rather concurrently develops along with the ripple structure. Our work is able to differentiate among various models existing in the literature and provides an insight into the mechanism of pattern formation under ion beam erosion with impurity incorporation.

  7. A THREE-PHASE CHEMICAL MODEL OF HOT CORES: THE FORMATION OF GLYCINE

    SciTech Connect

    Garrod, Robin T.

    2013-03-01

    A new chemical model is presented that simulates fully coupled gas-phase, grain-surface, and bulk-ice chemistry in hot cores. Glycine (NH{sub 2}CH{sub 2}COOH), the simplest amino acid, and related molecules such as glycinal, propionic acid, and propanal, are included in the chemical network. Glycine is found to form in moderate abundance within and upon dust-grain ices via three radical-addition mechanisms, with no single mechanism strongly dominant. Glycine production in the ice occurs over temperatures {approx}40-120 K. Peak gas-phase glycine fractional abundances lie in the range 8 Multiplication-Sign 10{sup -11}-8 Multiplication-Sign 10{sup -9}, occurring at {approx}200 K, the evaporation temperature of glycine. A gas-phase mechanism for glycine production is tested and found insignificant, even under optimal conditions. A new spectroscopic radiative-transfer model is used, allowing the translation and comparison of the chemical-model results with observations of specific sources. Comparison with the nearby hot-core source NGC 6334 IRS1 shows excellent agreement with integrated line intensities of observed species, including methyl formate. The results for glycine are consistent with the current lack of a detection of this molecule toward other sources; the high evaporation temperature of glycine renders the emission region extremely compact. Glycine detection with ALMA is predicted to be highly plausible, for bright, nearby sources with narrow emission lines. Photodissociation of water and subsequent hydrogen abstraction from organic molecules by OH, and NH{sub 2}, are crucial to the buildup of complex organic species in the ice. The inclusion of alternative branches within the network of radical-addition reactions appears important to the abundances of hot-core molecules; less favorable branching ratios may remedy the anomalously high abundance of glycolaldehyde predicted by this and previous models.

  8. Genome-Wide Transcription Profiling of the Early Phase of Biofilm Formation by Candida albicans†

    PubMed Central

    Murillo, Luis A.; Newport, George; Lan, Chung-Yu; Habelitz, Stefan; Dungan, Jan; Agabian, Nina M.

    2005-01-01

    The ability to adhere to surfaces and develop as a multicellular community is an adaptation used by most microorganisms to survive in changing environments. Biofilm formation proceeds through distinct developmental phases and impacts not only medicine but also industry and evolution. In organisms such as the opportunistic pathogen Candida albicans, the ability to grow as biofilms is also an important mechanism for persistence, facilitating its growth on different tissues and a broad range of abiotic surfaces used in medical devices. The early stage of C. albicans biofilm is characterized by the adhesion of single cells to the substratum, followed by the formation of an intricate network of hyphae and the beginning of a dense structure. Changes in the transcriptome begin within 30 min of contact with the substrate and include expression of genes related to sulfur metabolism, in particular MET3, and the equivalent gene homologues of the Ribi regulon in Saccharomyces cerevisiae. Some of these changes are initiated early and maintained throughout the process; others are restricted to the earliest stages of biofilm formation. We identify here a potential alternative pathway for cysteine metabolism and the biofilm-associated expression of genes involved in glutathione production in C. albicans. PMID:16151249

  9. Numerical modeling of experimental observations on gas formation and multi-phase flow of carbon dioxide in subsurface formations

    NASA Astrophysics Data System (ADS)

    Pawar, R.; Dash, Z.; Sakaki, T.; Plampin, M. R.; Lassen, R. N.; Illangasekare, T. H.; Zyvoloski, G.

    2011-12-01

    One of the concerns related to geologic CO2 sequestration is potential leakage of CO2 and its subsequent migration to shallow groundwater resources leading to geochemical impacts. Developing approaches to monitor CO2 migration in shallow aquifer and mitigate leakage impacts will require improving our understanding of gas phase formation and multi-phase flow subsequent to CO2 leakage in shallow aquifers. We are utilizing an integrated approach combining laboratory experiments and numerical simulations to characterize the multi-phase flow of CO2 in shallow aquifers. The laboratory experiments involve a series of highly controlled experiments in which CO2 dissolved water is injected in homogeneous and heterogeneous soil columns and tanks. The experimental results are used to study the effects of soil properties, temperature, pressure gradients and heterogeneities on gas formation and migration. We utilize the Finite Element Heat and Mass (FEHM) simulator (Zyvoloski et al, 2010) to numerically model the experimental results. The numerical models capture the physics of CO2 exsolution, multi-phase fluid flow as well as sand heterogeneity. Experimental observations of pressure, temperature and gas saturations are used to develop and constrain conceptual models for CO2 gas-phase formation and multi-phase CO2 flow in porous media. This talk will provide details of development of conceptual models based on experimental observation, development of numerical models for laboratory experiments and modelling results.

  10. The formation and transformation mechanism of calcium carbonate in water

    SciTech Connect

    Ogino, Takeshi; Suzuki, Toshio; Sawada, Kiyoshi )

    1987-10-01

    High supersaturated solutions of Ca{sup 2+} and CO{sub 3}{sup 2{minus}} ions rapidly precipitate amorphous calcium carbonate, ACC, the logarithmic thermodynamic solubility product of which is about {minus}6.0 at 25{degree}C. The ACC initially formed is transformed to a mixture of several crystalline calcium carbonate polymorphs within several minutes. The transformed polymorphs are vaterite and calcite at low temperature (14 to 30{degree}C), and aragonite and calcite at high temperature (60 to 80{degree}C). At intermediate temperatures (40 to 50{degree}C) the formation of all three polymorphs was observed. Metastable polymorphs are gradually transformed to the stable form, calcite. It takes about 200 min at 25{degree}C and 370 min at 30{degree}C for the complete transformation of vaterite to calcite, and 100-1300 min for that of aragonite to calcite at 60-80{degree}C. At 50{degree}C, vaterite is predominantly transformed at first to aragonite within 60 min, and then the aragonite is transformed to calcite in about 900 min. The results of the change in the ion activity product of the solution and the abundances of the polymorphs strongly suggest that the polymorphic transformation of vaterite and aragonite to calcite takes place through dissolution of the metastable phase and growth of the stable phase, calcite. The rate-determining step of the transformation is the growth of calcite. The relative abundance of vaterite becomes higher at 25{degree}C with increasing concentrations of calcium and carbonate ions in the supersaturated solution. When the ion activity product of the initial supersaturated solution is lower than the solubility product of ACC at 25{degree}c, only vaterite directly precipitates after some induction period. The vaterite crystals formed are free of calcite seeds and the vaterite saturated solutions are stable for several days.

  11. Amyloid β Oligomeric Species Present in the Lag Phase of Amyloid Formation

    PubMed Central

    Wolff, Martin; Unuchek, Dmitry; Zhang, Bo; Gordeliy, Valentin; Willbold, Dieter; Nagel-Steger, Luitgard

    2015-01-01

    Alzheimer’s disease (AD)-associated amyloid β peptide (Aβ) is one of the main actors in AD pathogenesis. Aβ is characterized by its high tendency to self-associate, leading to the generation of oligomers and amyloid fibrils. The elucidation of pathways and intermediates is crucial for the understanding of protein assembly mechanisms in general and in conjunction with neurodegenerative diseases, e.g., for the identification of new therapeutic targets. Our study focused on Aβ42 and its oligomeric assemblies in the lag phase of amyloid formation, as studied by sedimentation velocity (SV) centrifugation. The assembly state of Aβ during the lag phase, the time required by an Aβ solution to reach the exponential growth phase of aggregation, was characterized by a dominant monomer fraction below 1 S and a population of oligomeric species between 4 and 16 S. From the oligomer population, two major species close to a 12-mer and an 18-mer with a globular shape were identified. The recurrence of these two species at different initial concentrations and experimental conditions as the smallest assemblies present in solution supports the existence of distinct, energetically favored assemblies in solution. The sizes of the two species suggest an Aβ42 aggregation pathway that is based on a basic hexameric building block. The study demonstrates the potential of SV analysis for the evaluation of protein aggregation pathways. PMID:26024352

  12. An ionic mechanism of carbon formation in flames

    NASA Technical Reports Server (NTRS)

    Calcote, H. F.

    1990-01-01

    The formation of incipient carbon in flames can be described by a series of elementary reactions in which the precursor of soot is the ion C3H3+, and the major building block is acetylene, polyacetylenes, or other hydrocarbon fragments which are present in large concentrations. The precursor ion is produced by nonequilibrium chemi-ionization reactions, e.g., CH asterisk plus C2H2 yields C3H3+ plus e or CH asterisk plus O yields CHO+ plus e. The CHO+ rapidly becomes C3H3+ through a series of ion-molecule reactions. The chemi-ion then adds acetylene in a series of very rapid ion-molecule reactions producing larger and larger ions. Ions isomerize very rapidly to produce aromatic structures overcoming one of the major problems with neutral species mechanisms: how to form the first carbon ring. As the ions grow, their recombination rate coefficients with electrons increase so that the larger ions are removed by dissociative recombination. These neutral species now continue to grow by the addition of more acetylene producing even larger neutral species. With increasing size, the rate coefficient of electron attachment also increases causing the reaction to become important, depending upon the temperature. Appreciable concentrations of negative ions shift the ion removal process to dissociative ion-ion recombination, which is orders of magnitude slower than ion-electron recombination. As the neutral species continue to grow by the addition of acetylene, they gradually take on the aspect of particles, i.e., the bulk properties of the substance CxHy dominate over the chemical properties. This change is gradual and there is no distinct size at which a large molecule becomes a particle. Evidence will be presented supporting the above mechanism. All of the ions proposed in the mechanism have been observed by mass spectrometric analysis, their concentrations measured, and their rates of reaction in the flame environment determined to be adequate to account for the observed rate

  13. Nematic phase formation in suspensions of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Zakri, Cecile; Poulin, Philippe

    This chapter describes the chemical composition, phase behavior and structure of recently investigated carbon nanotube (CNT) based liquid crystals. Because nanotubes are long and thin rigid cylinders, their phase behavior shares several similarities with many other systems such as rigid polymers and rod-like particle suspensions. CNT liquid crystals are achieved in highly concentrated suspensions comprised of raw or chemically functionalized particles. But extreme aspect ratio, rigidity, high sensitivity to interactions, optical properties and structural features of CNTs make their liquid crystalline phases unique in several ways. In particular, the chapter discusses the importance of the CNT waviness on the phase ordering and the role of excess surfactant or biomolecules used to stabilize the CNTs. The unique resonant Raman scattering of CNT allows original and accurate measurements of order parameters at a micron-scale. Highly oriented nematic tactoids could even be characterized by polarized Raman microscopy. From a more applied point of view, nematic ordering is shown to be a route towards the processing of new materials such as anisotropic conductive films and high strength fibers made of oriented carbon nanotubes. Examples of functional materials and nanocomposites achieved from CNT liquid crystals are given.

  14. Polymer fullerene solution phase behaviour and film formation pathways.

    PubMed

    Dattani, Rajeev; Cabral, João T

    2015-04-28

    We report the phase behaviour of polymer/fullerene/solvent ternary mixtures and its consequence for the morphology of the resulting composite thin films. We focus particularly on solutions of polystyrene (PS), C60 fullerene and toluene, which are examined by static and dynamic light scattering, and films obtained from various solution ages and thermal annealing conditions, using atomic force and light microscopy. Unexpectedly, the solution phase behaviour below the polymer overlap concentration, c*, is found to be described by a simple excluded volume argument (occupied by the polymer chains) and the neat C60/solvent miscibility. Scaling consistent with full exclusion is found when the miscibility of the fullerene in the solvent is much lower than that of the polymer, giving way to partial exclusion with more soluble fullerenes (phenyl-C61-butyric acid methyl ester, PCBM) and a less asymmetric solvent (chlorobenzene), employed in photovoltaic devices. Spun cast and drop cast films were prepared from PS/C60/toluene solutions across the phase diagram to yield an identical PS/C60 composition and film thickness, resulting in qualitatively different morphologies in agreement with our measured solution phase boundaries. Our findings are relevant to the solution processing of polymer/fullerene composites (including organic photovoltaic devices), which generally require effective solubilisation of fullerene derivatives and polymer pairs in this concentration range, and the design of well-defined thin film morphologies.

  15. New signals of quark-gluon-hadron mixed phase formation

    NASA Astrophysics Data System (ADS)

    Bugaev, K. A.; Sagun, V. V.; Ivanytskyi, A. I.; Oliinychenko, D. R.; Ilgenfritz, E.-M.; Nikonov, E. G.; Taranenko, A. V.; Zinovjev, G. M.

    2016-08-01

    Here we present several remarkable irregularities at chemical freeze-out which are found using an advanced version of the hadron resonance gas model. The most prominent of them are the sharp peak of the trace anomaly existing at chemical freeze-out at the center-of-mass energy 4.9 GeV and two sets of highly correlated quasi-plateaus in the collision energy dependence of the entropy per baryon, total pion number per baryon, and thermal pion number per baryon which we found at the center-of-mass energies 3.8-4.9 GeV and 7.6-10 GeV. The low-energy set of quasi-plateaus was predicted a long time ago. On the basis of the generalized shock-adiabat model we demonstrate that the low-energy correlated quasi-plateaus give evidence for the anomalous thermodynamic properties inside the quark-gluon-hadron mixed phase. It is also shown that the trace anomaly sharp peak at chemical freeze-out corresponds to the trace anomaly peak at the boundary between the mixed phase and quark gluon plasma. We argue that the high-energy correlated quasi-plateaus may correspond to a second phase transition and discuss its possible origin and location. Besides we suggest two new observables which may serve as clear signals of these phase transformations.

  16. Laboratory Investigations of Titan Haze Formation: Characterization of Gas Phase and Particle Phase Nitrogen

    NASA Astrophysics Data System (ADS)

    Horst, Sarah; Yoon, Heidi; Li, Rui; deGouw, Joost; Tolbert, Margaret

    2014-11-01

    Prior to the arrival of the Cassini-Huygens spacecraft, aerosol production in Titan’s atmosphere was believed to begin in the stratosphere where chemical processes are predominantly initiated by far ultraviolet (FUV) radiation. However, the discovery of very heavy ions, coupled with Cassini Ultraviolet Imaging Spectrograph (UVIS) occultation measurements that show haze absorption up to 1000 km altitude (Liang et al., 2007), indicates that haze formation initiates in the thermosphere. The energy environment of the thermosphere is significantly different from the stratosphere; in particular there is a greater flux of extreme ultraviolet (EUV) photons and energetic particles available to initiate chemical reactions, including the destruction of N2, in the upper atmosphere. The discovery of previously unpredicted nitrogen species in measurements of Titan’s atmosphere by the Cassini Ion and Neutral Mass Spectrometer (INMS) indicates that nitrogen participates in the chemistry to a much greater extent than was appreciated before Cassini (Vuitton et al., 2007). Additionally, measurements obtained by the Aerosol Collector Pyrolyzer (ACP) carried by Huygens to Titan’s surface may indicate that Titan’s aerosols contain significant amounts of nitrogen (Israël et al., 2005, 2006). The degree of nitrogen incorporation in the haze particles is important for understanding the diversity of molecules that may be present in Titan’s atmosphere and on its surface. We have conducted a series of Titan atmosphere simulation experiments using either spark discharge (tesla coil) or FUV photons (deuterium lamp) to initiate chemistry in CH4/N2 gas mixtures ranging from 0.01% CH4/99.99% N2 to 10% CH4/90% N2. We obtained in situ measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) to measure the particle composition as a function of particle size and a proton-transfer ion-trap mass spectrometer (PIT-MS) to measure the composition of gas phase

  17. Catalytic formation of ammonia: a lattice gas non-thermal Langmuir Hinshelwood mechanism

    NASA Astrophysics Data System (ADS)

    Khan, K. M.; Ahmad, N.; Albano, E. V.

    2001-11-01

    The catalytic formation of ammonia synthesis through dimers N 2 and H 2 has been studied through Monte-Carlo simulation via a model based on lattice gas non-thermal Langmuir-Hinshelwood mechanism, which involves the precursor motion of H 2 molecule. The most interesting feature of this model is it yields a steady reactive window, which is separated by continuous and discontinuous irreversible phase transitions. The phase diagram is qualitatively similar to well-known ZGB model. The width of the window depends upon the mobility of precursors. The continuous transition disappears when mobility of precursors is extended to third nearest neighbourhood. The dependence of production rate on partial pressure of hydrogen is predicted by simple mathematical equations in our model. Some more interesting results are observed when reaction between precursors and chemisorbed hydrogen atoms is considered.

  18. The formation mechanism of the Bonin high in August

    NASA Astrophysics Data System (ADS)

    Enomoto, Takeshi; Hoskins, Brian J.; Matsuda, Yoshihisa

    2003-01-01

    The Bonin high is a subtropical anticyclone that is predominant near Japan in the summer. This anticyclone is associated with an equivalent-barotropic structure, often extending throughout the entire troposphere. Although the equivalent-barotropic structure of the Bonin high has been known for years among synopticians because of its importance to the summer climate in east Asia, there are few dynamical explanations for such a structure. The present paper attempts to provide a formation mechanism for the deep ridge near Japan. We propose a new hypothesis that this equivalent-barotropic ridge near Japan is formed as a result of the propagation of stationary Rossby waves along the Asian jet in the upper troposphere ('the Silk Road pattern'). First, the monthly mean climatology is examined in order to demonstrate this hypothesis. It is shown that the enhanced Asian jet in August is favourable for the propagation of stationary Rossby waves and that the regions of descent over the eastern Mediterranean Sea and the Aral Sea act as two major wave sources. Second, a primitive-equation model is used to simulate the climatology of August. The model successfully simulates the Bonin high with an equivalent-barotropic structure. The upper-tropospheric ridge is found to be enhanced by a height anomaly of more than 80 m at 200 hPa, when a wave packet arrives. Sensitivity experiments are conducted to show that the removal of the diabatic cooling over the Asian jet suppresses the Silk Road pattern and formation of an equivalent-barotropic ridge near Japan, while the removal of the diabatic heating in the western Pacific does not.

  19. Coupling Field Theory with Continuum Mechanics: A Simulation of Domain Formation in Giant Unilamellar Vesicles

    PubMed Central

    Ayton, Gary S.; McWhirter, J. Liam; McMurtry, Patrick; Voth, Gregory A.

    2005-01-01

    Domain formation is modeled on the surface of giant unilamellar vesicles using a Landau field theory model for phase coexistence coupled to elastic deformation mechanics (e.g., membrane curvature). Smooth particle applied mechanics, a form of smoothed particle continuum mechanics, is used to solve either the time-dependent Landau-Ginzburg or Cahn-Hilliard free-energy models for the composition dynamics. At the same time, the underlying elastic membrane is modeled using smooth particle applied mechanics, resulting in a unified computational scheme capable of treating the response of the composition fields to arbitrary deformations of the vesicle and vice versa. The results indicate that curvature coupling, along with the field theory model for composition free energy, gives domain formations that are correlated with surface defects on the vesicle. In the case that external deformations are included, the domain structures are seen to respond to such deformations. The present simulation capability provides a significant step forward toward the simulation of realistic cellular membrane processes. PMID:15792968

  20. Coupling field theory with continuum mechanics: a simulation of domain formation in giant unilamellar vesicles.

    PubMed

    Ayton, Gary S; McWhirter, J Liam; McMurtry, Patrick; Voth, Gregory A

    2005-06-01

    Domain formation is modeled on the surface of giant unilamellar vesicles using a Landau field theory model for phase coexistence coupled to elastic deformation mechanics (e.g., membrane curvature). Smooth particle applied mechanics, a form of smoothed particle continuum mechanics, is used to solve either the time-dependent Landau-Ginzburg or Cahn-Hilliard free-energy models for the composition dynamics. At the same time, the underlying elastic membrane is modeled using smooth particle applied mechanics, resulting in a unified computational scheme capable of treating the response of the composition fields to arbitrary deformations of the vesicle and vice versa. The results indicate that curvature coupling, along with the field theory model for composition free energy, gives domain formations that are correlated with surface defects on the vesicle. In the case that external deformations are included, the domain structures are seen to respond to such deformations. The present simulation capability provides a significant step forward toward the simulation of realistic cellular membrane processes.

  1. Formation of quasicrystalline phase in Al70-x Ga x Pd17Mn13 alloys

    NASA Astrophysics Data System (ADS)

    Yadav, T. P.; Singh, Devinder; Shahi, Rohit R.; Shaz, M. A.; Tiwari, R. S.; Srivastava, O. N.

    2011-07-01

    In the present investigation, the formation and stability of icosahedral phase in Al70- x Ga x Pd17Mn13 alloys has been explored using X-ray diffraction, scanning, transmission electron microscopy and energy dispersive X-ray analysis. Cast alloys and melt-spun ribbons with x = 2.5, 5, 7.5, 10, 12.5, 15 and 20 have been investigated. In both cases, the alloys up to 5 at% Ga exhibit the formation of pure icosahedral phase. However, for x ≥5 at% Ga content, the cast alloy exhibits the formation of multiphase material, consisting of an icosahedral phase along with AlPd-type B2 and ξ‧ crystalline (orthorhombic structure with unit cell a = 23.5 Å, b = 16.6 Å and c = 12.4 Å) phases. In the case of the melt spun ribbon for x = 5 at% Ga, only an icosahedral phase has been found, but for 15 > x > 5 at% Ga, an icosahedral phase is the majority phase with AlPd-type B2 phase being the minority component. For x = 15 at% Ga, a Al3Pd2-type hexagonal phase together with a small amount of quasicrystalline phase is formed. However, for x = 20, only a hexagonal Al3Pd2 phase results.

  2. Formation mechanism of the graphite-rich protective layer in blast furnace hearths

    NASA Astrophysics Data System (ADS)

    Jiao, Ke-xin; Zhang, Jian-liang; Liu, Zheng-jian; Liu, Feng; Liang, Li-sheng

    2016-01-01

    A long campaign life of blast furnaces is heavily linked to the existence of a protective layer in their hearths. In this work, we conducted dissection studies and investigated damage in blast furnace hearths to estimate the formation mechanism of the protective layer. The results illustrate that a significant amount of graphite phase was trapped within the hearth protective layer. Furthermore, on the basis of the thermodynamic and kinetic calculations of the graphite precipitation process, a precipitation potential index related to the formation of the graphite-rich protective layer was proposed to characterize the formation ability of this layer. We determined that, under normal operating conditions, the precipitation of graphite phase from hot metal was thermodynamically possible. Among elements that exist in hot metal, C, Si, and P favor graphite precipitation, whereas Mn and Cr inhibit this process. Moreover, at the same hot-face temperature, an increase of carbon concentration in hot metal can shorten the precipitation time. Finally, the results suggest that measures such as reducing the hot-face temperature and increasing the degree of carbon saturation in hot metal are critically important to improve the precipitation potential index.

  3. Kinetics, products, and mechanisms of secondary organic aerosol formation.

    PubMed

    Ziemann, Paul J; Atkinson, Roger

    2012-10-07

    Secondary organic aerosol (SOA) is formed in the atmosphere when volatile organic compounds (VOCs) emitted from anthropogenic and biogenic sources are oxidized by reactions with OH radicals, O(3), NO(3) radicals, or Cl atoms to form less volatile products that subsequently partition into aerosol particles. Once in particles, these organic compounds can undergo heterogenous/multiphase reactions to form more highly oxidized or oligomeric products. SOA comprises a large fraction of atmospheric aerosol mass and can have significant effects on atmospheric chemistry, visibility, human health, and climate. Previous articles have reviewed the kinetics, products, and mechanisms of atmospheric VOC reactions and the general chemistry and physics involved in SOA formation. In this article we present a detailed review of VOC and heterogeneous/multiphase chemistry as they apply to SOA formation, with a focus on the effects of VOC molecular structure on the kinetics of initial reactions with the major atmospheric oxidants, the subsequent reactions of alkyl, alkyl peroxy, and alkoxy radical intermediates, and the composition of the resulting products. Structural features of reactants and products discussed include compound carbon number; linear, branched, and cyclic configurations; the presence of C[double bond, length as m-dash]C bonds and aromatic rings; and functional groups such as carbonyl, hydroxyl, ester, hydroxperoxy, carboxyl, peroxycarboxyl, nitrate, and peroxynitrate. The intention of this review is to provide atmospheric chemists with sufficient information to understand the dominant pathways by which the major classes of atmospheric VOCs react to form SOA products, and the further reactions of these products in particles. This will allow reasonable predictions to be made, based on molecular structure, about the kinetics, products, and mechanisms of VOC and heterogeneous/multiphase reactions, including the effects of important variables such as VOC, oxidant, and NO

  4. Mechanism of pyranopterin ring formation in molybdenum cofactor biosynthesis

    SciTech Connect

    Hover, Bradley M.; Tonthat, Nam K.; Schumacher, Maria A.; Yokoyama, Kenichi

    2015-05-04

    The molybdenum cofactor (Moco) is essential for all kingdoms of life, plays central roles in various biological processes, and must be biosynthesized de novo. During Moco biosynthesis, the characteristic pyranopterin ring is constructed by a complex rearrangement of guanosine 5'-triphosphate (GTP) into cyclic pyranopterin (cPMP) through the action of two enzymes, MoaA and MoaC (molybdenum cofactor biosynthesis protein A and C, respectively). Conventionally, MoaA was considered to catalyze the majority of this transformation, with MoaC playing little or no role in the pyranopterin formation. Recently, this view was challenged by the isolation of 3',8-cyclo-7,8-dihydro-guanosine 5'-triphosphate (3',8-cH2GTP) as the product of in vitro MoaA reactions. To elucidate the mechanism of formation of Moco pyranopterin backbone, in this paper we performed biochemical characterization of 3',8-cH2GTP and functional and X-ray crystallographic characterizations of MoaC. These studies revealed that 3',8-cH2GTP is the only product of MoaA that can be converted to cPMP by MoaC. Our structural studies captured the specific binding of 3',8-cH2GTP in the active site of MoaC. These observations provided strong evidence that the physiological function of MoaA is the conversion of GTP to 3',8-cH2GTP (GTP 3',8-cyclase), and that of MoaC is to catalyze the rearrangement of 3',8-cH2GTP into cPMP (cPMP synthase). Furthermore, our structure-guided studies suggest that MoaC catalysis involves the dynamic motions of enzyme active-site loops as a way to control the timing of interaction between the reaction intermediates and catalytically essential amino acid residues. In conclusion, these results reveal the previously unidentified mechanism behind Moco biosynthesis and provide mechanistic and structural insights into how enzymes catalyze complex rearrangement reactions.

  5. Mechanism of pyranopterin ring formation in molybdenum cofactor biosynthesis

    DOE PAGES

    Hover, Bradley M.; Tonthat, Nam K.; Schumacher, Maria A.; ...

    2015-05-04

    The molybdenum cofactor (Moco) is essential for all kingdoms of life, plays central roles in various biological processes, and must be biosynthesized de novo. During Moco biosynthesis, the characteristic pyranopterin ring is constructed by a complex rearrangement of guanosine 5'-triphosphate (GTP) into cyclic pyranopterin (cPMP) through the action of two enzymes, MoaA and MoaC (molybdenum cofactor biosynthesis protein A and C, respectively). Conventionally, MoaA was considered to catalyze the majority of this transformation, with MoaC playing little or no role in the pyranopterin formation. Recently, this view was challenged by the isolation of 3',8-cyclo-7,8-dihydro-guanosine 5'-triphosphate (3',8-cH2GTP) as the product ofmore » in vitro MoaA reactions. To elucidate the mechanism of formation of Moco pyranopterin backbone, in this paper we performed biochemical characterization of 3',8-cH2GTP and functional and X-ray crystallographic characterizations of MoaC. These studies revealed that 3',8-cH2GTP is the only product of MoaA that can be converted to cPMP by MoaC. Our structural studies captured the specific binding of 3',8-cH2GTP in the active site of MoaC. These observations provided strong evidence that the physiological function of MoaA is the conversion of GTP to 3',8-cH2GTP (GTP 3',8-cyclase), and that of MoaC is to catalyze the rearrangement of 3',8-cH2GTP into cPMP (cPMP synthase). Furthermore, our structure-guided studies suggest that MoaC catalysis involves the dynamic motions of enzyme active-site loops as a way to control the timing of interaction between the reaction intermediates and catalytically essential amino acid residues. In conclusion, these results reveal the previously unidentified mechanism behind Moco biosynthesis and provide mechanistic and structural insights into how enzymes catalyze complex rearrangement reactions.« less

  6. Phase-field elasticity model based on mechanical jump conditions

    NASA Astrophysics Data System (ADS)

    Schneider, Daniel; Tschukin, Oleg; Choudhury, Abhik; Selzer, Michael; Böhlke, Thomas; Nestler, Britta

    2015-05-01

    Computational models based on the phase-field method typically operate on a mesoscopic length scale and resolve structural changes of the material and furthermore provide valuable information about microstructure and mechanical property relations. An accurate calculation of the stresses and mechanical energy at the transition region is therefore indispensable. We derive a quantitative phase-field elasticity model based on force balance and Hadamard jump conditions at the interface. Comparing the simulated stress profiles calculated with Voigt/Taylor (Annalen der Physik 274(12):573, 1889), Reuss/Sachs (Z Angew Math Mech 9:49, 1929) and the proposed model with the theoretically predicted stress fields in a plate with a round inclusion under hydrostatic tension, we show the quantitative characteristics of the model. In order to validate the elastic contribution to the driving force for phase transition, we demonstrate the absence of excess energy, calculated by Durga et al. (Model Simul Mater Sci Eng 21(5):055018, 2013), in a one-dimensional equilibrium condition of serial and parallel material chains. To validate the driving force for systems with curved transition regions, we relate simulations to the Gibbs-Thompson equilibrium condition (Johnson and Alexander, J Appl Phys 59(8):2735, 1986).

  7. Quantum-mechanical study on the mechanism of peptide bond formation in the ribosome.

    PubMed

    Acosta-Silva, Carles; Bertran, Joan; Branchadell, Vicenç; Oliva, Antoni

    2012-04-04

    Ribosomes transform the genetic information encoded within genes into proteins. In recent years, there has been much progress in the study of this complex molecular machine, but the mechanism of peptide bond formation and the origin of the catalytic power of this ancient enzymatic system are still an unsolved puzzle. A quantum-mechanical study of different possible mechanisms of peptide synthesis in the ribosome has been carried out using the M06-2X density functional. The uncatalyzed processes in solution have been treated with the SMD solvation model. Concerted and two-step mechanisms have been explored. Three main points suggested in this work deserve to be deeply analyzed. First, no zwitterionic intermediates are found when the process takes place in the ribosome. Second, the proton shuttle mechanism is suggested to be efficient only through the participation of the A2451 2'-OH and two crystallographic water molecules. Finally, the mechanisms in solution and in the ribosome are very different, and this difference may help us to understand the origin of the efficient catalytic role played by the ribosome.

  8. Microstructural Formations and Phase Transformation Pathways in Hot Isostatically Pressed Tantalum Carbides

    DTIC Science & Technology

    2012-01-01

    REPORT Microstructural formations and phase transformation pathways in hot isostatically pressed tantalum carbides 14. ABSTRACT 16. SECURITY...CLASSIFICATION OF: A series of XTa:(1 X)C (0.5 < X < 1) compositions have been fabricated by hot isostatic pressing (HIP) of Ta and TaC powder blends...ANSI Std. Z39.18 - Microstructural formations and phase transformation pathways in hot isostatically pressed tantalum carbides Report Title ABSTRACT A

  9. Mechanism of phase transition, from vapor to solid: Transient liquid phase is between the two

    NASA Astrophysics Data System (ADS)

    Mahapatra, A. K.; Wang, Junyong; Zhang, Hongwei; Han, Min

    2016-08-01

    The mechanism of phase transition, from vapor to solid, is studied by producing non-stoichiometric ZnO and CdS nanoclusters (NCs) by low-energy cluster beam deposition technique, and examining their morphological and compositional evolution over a long span of time. It is concluded that the transition of vapor to solid goes through a transient liquid phase: coagulation of a large number of atomic clusters first forms liquid NCs which then solidify. The nature of the material and the experimental conditions determine crystallinity and shape of the NCs during the solidification process.

  10. Study on Pure Phase Formation of Lead Oxide Nanowires by Oxidation of Lead Nanowires

    NASA Astrophysics Data System (ADS)

    Hai, Kuo; Wang, Xiaogang

    2012-02-01

    Lead-oxide nanowires were synthesized by oxidizing lead metal nanowires. The phase structures, sizes and morphologies of the nanowires were investigated by atomic force microscopy and x-ray diffraction, and the band gap of the nanowires was determined by UV-Vis-NIR reflectance diffusion spectrums. The thermodynamic environment for the pure phase formation has been studied. The first-principle computation has been done to help understand the phase formation. Our results reveal that the pure phase formation strongly relies on both the process temperature and the oxygen flow/oxygen partial pressure, and the pure phase ?-PbO nanowires can be obtained only in a narrow, low temperature range under a low oxygen flow.

  11. Shock tube study of the fuel molecular structure effects on the chemical kinetic mechanisms for soot formation

    NASA Technical Reports Server (NTRS)

    Krech, R. H.; Cowles, L. M.; Rawlins, W. T.

    1983-01-01

    The objective of this research effort is to investigate the gas-phase mechanisms which lead to soot formation in the combustion of complex hydrocarbon fuels. The fuel decomposition is studied under pyrolytic and oxidative conditions behind incident shock waves, using various optical diagnostics to monitor particle appearance and the behavior of gas phase species. In particular, we are investigating: (1) improved quantification of UV/visible soot yield measurements using infrared attenuation and emission techniques; (2) spectral characteristics of gas-phase emission and absorption in the ultraviolet, visible, and infrared; and (3) a conceptual view of the chemical pathways for fuel decomposition and the gas-phase reactions leading to soot formation.

  12. Characterization of single phase copper selenide nanoparticles and their growth mechanism

    NASA Astrophysics Data System (ADS)

    Patidar, D.; Saxena, N. S.

    2012-03-01

    The high quality Cu3Se2 phase of copper selenide nanoparticles was synthesized through the solution-phase chemical reaction between copper and selenium. In this synthesis process, hydrazine hydrate acts as reducing agent whereas ethylene glycol controls the nucleation and growth of particles. An effort has been made to explain the growth mechanism to form copper selenide nanoparticles through the coordination of selenium to the Cu2+ complexes with OH groups of ethylene glycol. Result indicates the formation of Cu3Se2 single phase nanoparticles. The particles with the average particle size 25 nm are spherical in shape having tetragonal structure. The particles are well crystallized having 94% degree of crystallinity. An effort has also been made to determine the energy band gap of copper selenide nanoparticles through the absorption spectra.

  13. Phase formation at bonded vanadium and stainless steel interfaces

    SciTech Connect

    Summers, T.S.E.

    1992-01-01

    The interface between vanadium bonded to stainless steel was studies to determine whether a brittle phase formed during three joining operations. Inertia friction welds between V and 21-6-9 stainless steel were examined using TEM. In the as-welded condition, a continuous, polygranular intermetallic layer about 0.25 {mu}m thick was present at the interface. This layer grew to about 50 {mu}m thick during heat treatment at 1000{degrees}C for two hours. Analysis of electron diffraction patterns confirmed that this intermetallic was the {omega} phase. The interface between vanadium and type 304, SANDVIK SAF 2205, and 21-6-9 stainless steel bonded by a co-extrusion process had intermetallic particles at the interface in the as-extruded condition. Heat treatment at 1000{degrees}C for two hours caused these particles to grow into continuous layers in all three cases. Based on the appearance, composition and hardness of this interfacial intermetallic, it was also concluded to be {omega} phase. Bonding V to type 430 stainless steel by co-extrusion caused V-rich carbides to form at the interface due to the higher concentration of C in the type 430 than in the other stainless steels investigated. The carbide particles initially present grew into a continuous layer during a two-hour heat treatment at 1000{degrees}C. Co-hipping 21-6-9 stainless steel tubing with V rod resulted in slightly more concentric specimens than the co-extruded ones, but a continuous layer of the {omega} phase formed during the hipping operation. This brittle layer could initiate failure during subsequent forming operations. The vanadium near the stainless steel interface in the co-extruded and co-hipped tubing in some cases was harder than before heat treatment. It was concluded that this hardening was due to thermal straining during cooling following heat treatment and that thermal strains might present a greater problem than seen here when longer tubes are used in actual applications.

  14. Planetary Embryo Bow Shocks as a Mechanism for Chondrule Formation

    NASA Astrophysics Data System (ADS)

    Mann, Christopher; Boley, Aaron C.; Morris, Melissa A.

    2015-01-01

    We investigate the plausibility of a planetary embryo bow shock as a mechanism for chondrule formation in the early solar system. A Mars-size planetary embryo traveling on a moderately excited orbit through the dusty early environment of the solar system will experience supersonic velocities relative to the circularly orbiting gas and dust. The resulting bow shock can thermally process solids that pass through it, with a wide range of possible conditions depending on impact radius. Volatile outgassing by the embryo along with some gas capture from the surrounding nebula can produce temporary atmospheres. We use radiation hydrodynamics simulations with direct particle integration to model the consequences of solids that encounter a bow shock produced by a 3000 km embryo with relative speeds to the gas of 5, 6, and 7 km/s. The embryos are envisaged to be surrounded by low- and high-mass atmospheres (0.75 and 6.25 Martian-mass atmospheres, respectively), and we explore different opacities for the gas. We find that a high-mass atmosphere and low dust opacity can produce peak temperatures and cooling rates that are most consistent with constraints set by chondrule furnace studies for plausible shock speeds.

  15. Cortical mechanisms for afterimage formation: evidence from interocular grouping

    PubMed Central

    Dong, Bo; Holm, Linus; Bao, Min

    2017-01-01

    Whether the retinal process alone or retinal and cortical processes jointly determine afterimage (AI) formation has long been debated. Based on the retinal rebound responses, recent work proposes that afterimage signals are exclusively generated in the retina, although later modified by cortical mechanisms. We tested this notion with the method of “indirect proof”. Each eye was presented with a 2-by-2 checkerboard of horizontal and vertical grating patches. Each corresponding patch of the two checkerboards was perpendicular to each other, which produces binocular rivalry, and can generate percepts ranging from complete interocular grouping to either monocular pattern. The monocular percepts became more frequent with higher contrast. Due to adaptation, the visual system is less sensitive during the AIs than during the inductions with AI-similar contrast. If the retina is the only origin of AIs, comparable contrast appearance would require stronger retinal signals in the AIs than in the inductions, thus leading to more frequent monocular percepts in the AIs than in the inductions. Surprisingly, subjects saw the fully coherent stripes significantly more often in AIs. Our results thus contradict the retinal generation notion, and suggest that in addition to the retina, cortex is directly involved in the generation of AI signals. PMID:28112230

  16. Numerical simulations of a siphon mechanism for quiescent prominence formation

    NASA Technical Reports Server (NTRS)

    Poland, A. I.; Mariska, J. T.; Klimchuk, J. A.

    1986-01-01

    Quiescent prominences represent a significant challenge to our understanding of the flow of mass and energy in the outer layers of the solar atmosphere. A small number of quiescent prominences contain as much mass as the entire corona (Athay, 1976). The problem then is how to get that much material into the relatively small volume of a prominence and maintain it at a temperature of 10,000 K in close proximity to material at one million K. The thermal insulation to conduction provided by the magnetic field explains the disparate temperatures. The mass source problem is less well understood. One method for supplying mass to the prominence is to siphon it from the chromosphere. The siphon mechanism begins with a magnetic loop that evolves into a configuration with a gravitational well, such as that described by Kippenhahn and Schluter (1957). This could be formed, for example, by a twist in the magnetic field. A gravitational well could also be formed by a condensation induced sag in the field. This could further enhance the condensation process. Once this well has formed, or as it is forming, the material in the well area of the loop must cool and condense to the point where radiative losses exceed any heat input. Additional material must also flow into the well from the underlying chromosphere to supply the mass required to form the prominence. One example from a series of numerical simulations that were performed to study the formation of quiescent prominences is presented.

  17. Mechanism of the formation for thoracic impedance change.

    PubMed

    Kuang, Ming-Xing; Xiao, Qiu-Jin; Cui, Chao-Ying; Kuang, Nan-Zhen; Hong, Wen-Qin; Hu, Ai-Rong

    2010-03-01

    The purpose of this study is to investigate the mechanism of the formation for thoracic impedance change. On the basis of Ohm's law and the electrical field distribution in the cylindrical volume conductor, the formula about the thoracic impedance change are deduced, and they are demonstrated with the model experiment. The results indicate that the thoracic impedance change caused by single blood vessel is directly proportional to the ratio of the impedance change to the basal impedance of the blood vessel itself, to the length of the blood vessel appearing between the current electrodes, and to the basal impedance between two detective electrodes on the chest surface, while it is inversely proportional to the distance between the blood vessel and the line joining two detective electrodes. The thoracic impedance change caused by multiple blood vessels together is equal to the algebraic addition of all thoracic impedance changes resulting from the individual blood vessels. That is, the impedance changes obey the principle of adding scalars in the measurement of the electrical impedance graph. The present study can offer the theoretical basis for the waveform reconstruction of Impedance cardiography (ICG).

  18. Modification of linear prepolymers to tailor heterogeneous network formation through photo-initiated Polymerization-Induced Phase Separation.

    PubMed

    Szczepanski, Caroline R; Stansbury, Jeffrey W

    2015-07-23

    Polymerization-induced phase separation (PIPS) was studied in ambient photopolymerizations of triethylene glycol dimethacrylate (TEGDMA) modified by poly(methyl methacrylate) (PMMA). The molecular weight of PMMA and the rate of network formation (through incident UV-irradiation) were varied to influence both the promotion of phase separation through increases in overall free energy, as well as the extent to which phase development occurs during polymerization through diffusion prior to network gelation. The overall free energy of the polymerizing system increases with PMMA molecular weight, such that PIPS is promoted thermodynamically at low loading levels (5 wt%) of a higher molecular weight PMMA (120 kDa), while a higher loading level (20 wt%) is needed to induce PIPS with lower PMMA molecular weight (11 kDa), and phase separation was not promoted at any loading level tested of the lowest molecular weight PMMA (1 kDa). Due to these differences in overall free energy, systems modified by PMMA (11 kDa) underwent phase separation via Nucleation and Growth, and systems modified by PMMA (120 kDa), followed the Spinodal Decomposition mechanism. Despite differences in phase structure, all materials form a continuous phase rich in TEGDMA homopolymer. At high irradiation intensity (Io=20mW/cm(2)), the rate of network formation prohibited significant phase separation, even when thermodynamically preferred. A staged curing approach, which utilizes low intensity irradiation (Io=300µW/cm(2)) for the first ~50% of reaction to allow phase separation via diffusion, followed by a high intensity flood-cure to achieve a high degree of conversion, was employed to form phase-separated networks with reduced polymerization stress yet equivalent final conversion and modulus.

  19. Modification of linear prepolymers to tailor heterogeneous network formation through photo-initiated Polymerization-Induced Phase Separation

    PubMed Central

    Szczepanski, Caroline R.; Stansbury, Jeffrey W.

    2015-01-01

    Polymerization-induced phase separation (PIPS) was studied in ambient photopolymerizations of triethylene glycol dimethacrylate (TEGDMA) modified by poly(methyl methacrylate) (PMMA). The molecular weight of PMMA and the rate of network formation (through incident UV-irradiation) were varied to influence both the promotion of phase separation through increases in overall free energy, as well as the extent to which phase development occurs during polymerization through diffusion prior to network gelation. The overall free energy of the polymerizing system increases with PMMA molecular weight, such that PIPS is promoted thermodynamically at low loading levels (5 wt%) of a higher molecular weight PMMA (120 kDa), while a higher loading level (20 wt%) is needed to induce PIPS with lower PMMA molecular weight (11 kDa), and phase separation was not promoted at any loading level tested of the lowest molecular weight PMMA (1 kDa). Due to these differences in overall free energy, systems modified by PMMA (11 kDa) underwent phase separation via Nucleation and Growth, and systems modified by PMMA (120 kDa), followed the Spinodal Decomposition mechanism. Despite differences in phase structure, all materials form a continuous phase rich in TEGDMA homopolymer. At high irradiation intensity (Io=20mW/cm2), the rate of network formation prohibited significant phase separation, even when thermodynamically preferred. A staged curing approach, which utilizes low intensity irradiation (Io=300µW/cm2) for the first ~50% of reaction to allow phase separation via diffusion, followed by a high intensity flood-cure to achieve a high degree of conversion, was employed to form phase-separated networks with reduced polymerization stress yet equivalent final conversion and modulus. PMID:26190865

  20. Mechanisms Engineering Test Loop - Phase 1 Status Report

    SciTech Connect

    Kultgen, D.; Grandy, C.; Hvasta, M.; Lisowski, D.; Toter, W.; Borowski, A.

    2016-09-01

    This report documents the current status of the Mechanisms Engineering Test Loop (METL) as of the end of FY2016. Currently, METL is in Phase I of its design and construction. Once operational, the METL facility will test small to intermediate-scale components and systems in order to develop advanced liquid metal technologies. Testing different components in METL is essential for the future of advanced fast reactors as it will provide invaluable performance data and reduce the risk of failures during plant operation.

  1. Surfactants from the gas phase may promote cloud droplet formation

    PubMed Central

    Sareen, Neha; Schwier, Allison N.; Lathem, Terry L.; Nenes, Athanasios; McNeill, V. Faye

    2013-01-01

    Clouds, a key component of the climate system, form when water vapor condenses upon atmospheric particulates termed cloud condensation nuclei (CCN). Variations in CCN concentrations can profoundly impact cloud properties, with important effects on local and global climate. Organic matter constitutes a significant fraction of tropospheric aerosol mass, and can influence CCN activity by depressing surface tension, contributing solute, and influencing droplet activation kinetics by forming a barrier to water uptake. We present direct evidence that two ubiquitous atmospheric trace gases, methylglyoxal (MG) and acetaldehyde, known to be surface-active, can enhance aerosol CCN activity upon uptake. This effect is demonstrated by exposing acidified ammonium sulfate particles to 250 parts per billion (ppb) or 8 ppb gas-phase MG and/or acetaldehyde in an aerosol reaction chamber for up to 5 h. For the more atmospherically relevant experiments, i.e., the 8-ppb organic precursor concentrations, significant enhancements in CCN activity, up to 7.5% reduction in critical dry diameter for activation, are observed over a timescale of hours, without any detectable limitation in activation kinetics. This reduction in critical diameter enhances the apparent particle hygroscopicity up to 26%, which for ambient aerosol would lead to cloud droplet number concentration increases of 8–10% on average. The observed enhancements exceed what would be expected based on Köhler theory and bulk properties. Therefore, the effect may be attributed to the adsorption of MG and acetaldehyde to the gas–aerosol interface, leading to surface tension depression of the aerosol. We conclude that gas-phase surfactants may enhance CCN activity in the atmosphere. PMID:23382211

  2. Surfactants from the gas phase may promote cloud droplet formation.

    PubMed

    Sareen, Neha; Schwier, Allison N; Lathem, Terry L; Nenes, Athanasios; McNeill, V Faye

    2013-02-19

    Clouds, a key component of the climate system, form when water vapor condenses upon atmospheric particulates termed cloud condensation nuclei (CCN). Variations in CCN concentrations can profoundly impact cloud properties, with important effects on local and global climate. Organic matter constitutes a significant fraction of tropospheric aerosol mass, and can influence CCN activity by depressing surface tension, contributing solute, and influencing droplet activation kinetics by forming a barrier to water uptake. We present direct evidence that two ubiquitous atmospheric trace gases, methylglyoxal (MG) and acetaldehyde, known to be surface-active, can enhance aerosol CCN activity upon uptake. This effect is demonstrated by exposing acidified ammonium sulfate particles to 250 parts per billion (ppb) or 8 ppb gas-phase MG and/or acetaldehyde in an aerosol reaction chamber for up to 5 h. For the more atmospherically relevant experiments, i.e., the 8-ppb organic precursor concentrations, significant enhancements in CCN activity, up to 7.5% reduction in critical dry diameter for activation, are observed over a timescale of hours, without any detectable limitation in activation kinetics. This reduction in critical diameter enhances the apparent particle hygroscopicity up to 26%, which for ambient aerosol would lead to cloud droplet number concentration increases of 8-10% on average. The observed enhancements exceed what would be expected based on Köhler theory and bulk properties. Therefore, the effect may be attributed to the adsorption of MG and acetaldehyde to the gas-aerosol interface, leading to surface tension depression of the aerosol. We conclude that gas-phase surfactants may enhance CCN activity in the atmosphere.

  3. Formation of aqueous-phase α-hydroxyhydroperoxides (α-HHP): potential atmospheric impacts

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Lee, A. K. Y.; Soong, R.; Simpson, A. J.; Abbatt, J. P. D.

    2013-06-01

    The focus of this work is on quantifying the degree of the aqueous-phase formation of α-hydroxyhydroperoxides (α-HHPs) via reversible nucleophilic addition of H2O2 to aldehydes. Formation of this class of highly oxygenated organic hydroperoxides represents a poorly characterized aqueous-phase processing pathway that may lead to enhanced SOA formation and aerosol toxicity. Specifically, the equilibrium constants of α-HHP formation have been determined using proton nuclear-magnetic-resonance (1H NMR) spectroscopy and proton-transfer-reaction mass spectrometry (PTR-MS). Significant α-HHP formation was observed from formaldehyde, acetaldehyde, propionaldehyde, glycolaldehyde, glyoxylic acid, and methylglyoxal, but not from methacrolein and ketones. Low temperatures enhanced the formation of α-HHPs but slowed their formation rates. High inorganic salt concentrations shifted the equilibria toward the hydrated form of the aldehydes and slightly suppressed α-HHP formation. Using the experimental equilibrium constants, we predict the equilibrium concentration of α-HHPs to be in the μM level in cloud water, but it may also be present in the mM level in aerosol liquid water (ALW), where the concentrations of H2O2 and aldehydes can be high. Formation of α-HHPs in ALW may significantly affect the effective Henry's law constants of H2O2 and aldehydes but may not affect their gas-phase levels. The photochemistry and reactivity of this class of atmospheric species have not been studied.

  4. Formation of aqueous-phase α-hydroxyhydroperoxides (α-HHP): potential atmospheric impacts

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Lee, A. K. Y.; Soong, R.; Simpson, A. J.; Abbatt, J. P. D.

    2013-02-01

    The focus of this work is on quantifying the degree of the aqueous-phase formation of α-hydroxyhydroperoxides (α-HHPs) via reversible nucleophilic addition of H2O2 to aldehydes. Formation of this class of highly oxygenated organic hydroperoxides represents a poorly characterized aqueous-phase processing pathway that may lead to enhanced SOA formation and aerosol toxicity. Specifically, the equilibrium constants of α-HHP formation have been determined using proton nuclear resonance (1H NMR) spectroscopy and proton transfer reaction mass spectrometry (PTR-MS). Significant α-HHP formation was observed from formaldehyde, acetaldehyde, propionaldehyde, glycolaldehyde, glyoxylic acid, methylglyoxal, but not from methacrolein and ketones. Low temperatures enhanced the formation of α-HHPs but slowed their formation rates. High inorganic salt concentrations shifted the equilibria toward the hydrated form of the aldehydes and slightly suppressed α-HHP formation. Using the experimental equilibrium constants, we predict the equilibrium concentration of α-HHPs to be in the μM level in cloud water but may be present in the mM level in aerosol liquid water (ALW), where the concentrations of H2O2 and aldehydes can be high. Formation of α-HHPs in ALW may significantly affect the effective Henry's law constants of H2O2 and aldehydes but may not affect their gas-phase levels. The photochemistry and reactivity of this class of atmospheric species have not been studied.

  5. Formamidopyrimidines in DNA: mechanisms of formation, repair, and biological effects.

    PubMed

    Dizdaroglu, Miral; Kirkali, Güldal; Jaruga, Pawel

    2008-12-15

    Oxidatively induced damage to DNA results in a plethora of lesions comprising modified bases and sugars, DNA-protein cross-links, tandem lesions, strand breaks, and clustered lesions. Formamidopyrimidines, 4,6-diamino-5-formamidopyrimidine (FapyAde) and 2,6-diamino-4-hydroxy-5-formamidopyrimidine (FapyGua), are among the major lesions generated in DNA by hydroxyl radical attack, UV radiation, or photosensitization under numerous in vitro and in vivo conditions. They are formed by one-electron reduction of C8-OH-adduct radicals of purines and thus have a common precursor with 8-hydroxypurines generated upon one-electron oxidation. Methodologies using mass spectrometry exist to accurately measure FapyAde and FapyGua in vitro and in vivo. Formamidopyrimidines are repaired by base excision repair. Numerous prokaryotic and eukaryotic DNA glycosylases are highly specific for removal of these lesions from DNA in the first step of this repair pathway, indicating their biological importance. FapyAde and FapyGua are bypassed by DNA polymerases with the insertion of the wrong intact base opposite them, leading to mutagenesis. In mammalian cells, the mutagenicity of FapyGua exceeds that of 8-hydroxyguanine, which is thought to be the most mutagenic of the oxidatively induced lesions in DNA. The background and formation levels of the former in vitro and in vivo equal or exceed those of the latter under various conditions. FapyAde and FapyGua exist in living cells at significant background levels and are abundantly generated upon exposure to oxidative stress. Mice lacking the genes that encode specific DNA glycosylases accumulate these lesions in different organs and, in some cases, exhibit a series of pathological conditions including metabolic syndrome and cancer. Animals exposed to environmental toxins accumulate formamidopyrimidines in their organs. Here, we extensively review the mechanisms of formation, measurement, repair, and biological effects of formamidopyrimidines

  6. Phase separation and bistability in a three-dimensional model for protein domain formation at biomembranes

    NASA Astrophysics Data System (ADS)

    Alonso, Sergio; Bär, Markus

    2010-12-01

    Proteins in living cells interact with membranes. They may bind to or unbind from the membrane to the cytosol depending on the lipid composition of the membrane and their interaction with cytosolic enzymes. Moreover, proteins can accumulate at the membrane and assemble in spatial domains. Here, a simple model of protein cycling at biomembranes is studied, when the total number of proteins is conserved. Specifically, we consider the spatio-temporal dynamics of MARCKS proteins and their interactions with enzymes facilitating translocation from and rebinding to the membrane. The model exhibits two qualitatively different mechanisms of protein domain formation: phase separation related to a long-wave instability of a membrane state with homogeneous protein coverage and stable coexistence of two states with different homogeneous protein coverage in bistable media. We evaluate the impact of the cytosolic volume on the occurrence of protein pattern formation by simulations in a three-dimensional model. We show that the explicit treatment of the volume in the model leads to an effective rescaling of the reaction rates. For a simplified model of protein cycling, we can derive analytical expressions for the rescaling coefficients and verify them by direct simulations with the complete three-dimensional model.

  7. Coupling between pore formation and phase separation in charged lipid membranes

    NASA Astrophysics Data System (ADS)

    Himeno, Hiroki; Ito, Hiroaki; Higuchi, Yuji; Hamada, Tsutomu; Shimokawa, Naofumi; Takagi, Masahiro

    2015-12-01

    We investigated the effect of charge on the membrane morphology of giant unilamellar vesicles (GUVs) composed of various mixtures containing charged lipids. We observed the membrane morphologies by fluorescent and confocal laser microscopy in lipid mixtures consisting of a neutral unsaturated lipid [dioleoylphosphatidylcholine (DOPC)], a neutral saturated lipid [dipalmitoylphosphatidylcholine (DPPC)], a charged unsaturated lipid [dioleoylphosphatidylglycerol (DOP G(-)) ], a charged saturated lipid [dipalmitoylphosphatidylglycerol (DPP G(-)) ], and cholesterol (Chol). In binary mixtures of neutral DOPC-DPPC and charged DOPC -DPP G(-) , spherical vesicles were formed. On the other hand, pore formation was often observed with GUVs consisting of DOP G(-) and DPPC. In a DPPC-DPPG(-) -Chol ternary mixture, pore-formed vesicles were also frequently observed. The percentage of pore-formed vesicles increased with the DPP G(-) concentration. Moreover, when the head group charges of charged lipids were screened by the addition of salt, pore-formed vesicles were suppressed in both the binary and ternary charged lipid mixtures. We discuss the mechanisms of pore formation in charged lipid mixtures and the relationship between phase separation and the membrane morphology. Finally, we reproduce the results seen in experimental systems by using coarse-grained molecular dynamics simulations.

  8. Cross-phase Modification: A mechanism for the I-mode and other enhanced confinement regimes?

    NASA Astrophysics Data System (ADS)

    Newman, David; Terry, Paul; Sanchez, Raul; Bustos, A.

    2016-10-01

    New confinement regimes such as the I-mode offer good confinement properties with reduced density limit issues and better control. Previously, a number of different mechanisms have been identified for the formation and maintenance of enhanced confinement regimes. However, few if any allow enhanced confinement in one channel but not another as is seen in the I-mode. We propose modifications of cross-phases as a possible mechanism for different transport in different channels. Using simple dynamical models which have been able to capture a remarkable amount of the dynamics of the core and edge transport barriers found in many devices, we add cross phase to investigate the new mechanism. To this basic 7 field transport framework a simple model for phase effects, due to multiple instabilities, between the transported fields such as density and temperature is added with which we can investigate whether the dynamics of more continuous transitions such as the I-mode can be captured and understood. It can. This is backed up by multi-scale simulations on full gyro-kinetic codes. We then look at the question: If this mechanism is valid, what can the model tell us about control knobs for these promising regimes? Work supported by DOE Grant DE-FG02-04ER54741.

  9. The Formation Mechanism of Mesoporous Materials studied by EPR Spectroscopy and Cryo-TEM

    NASA Astrophysics Data System (ADS)

    Ruthstein, Sharon

    Ordered mesoporous materials raised a wide interest in the scientific community due to their unique structural properties which encompasses nanosize ordered channels. These materials have potential applications in diverse technological fields such as catalysis, membranes, microelectronics and sensors. The formation of these materials is initiated by the interaction of micelle of surfactant molecules with precursors of an inorganic oxide, usually silica, which further polymerizes to form solids with a well defined pore structure and amorphous walls. The aim of this study is to explore the details of this intriguing reaction mechanism on two types of materials, hexagonal and cubic, prepared with Pluronic block-copolymers as surfactants. The Pluronic micelles are characterized by a hydrophobic polypropylene oxide core and a hydrophilic polyethylene oxide corona. Examples of questions we address are: How does a homogeneous micellar solution transforms into an ordered phase? What kinds of interactions are responsible to this transformation? Our work focused on processes that take place on two levels, the molecular one and the mesoscale, which were investigated by combining electron paramagnetic resonance (EPR) and cryogenic transmission electron microscopy (cryo-TEM) techniques. The molecular level studies combine in-situ and freeze quench EPR spectroscopic techniques applied to nitroxide spin-probes introduced (at minute quantities) into the reaction mixtures. The nitroxide radicals serve as paramagnetic probes in the reaction mixture. They do not react or affect the reaction product but they sense in-situ the changes that occur in their environment during the reaction. The EPR spectrum provides information regarding the dynamic of the probe, which is affected by its surrounding, and the polarity of its environment. Fine structural details, such as the distribution of water and additives within the micelle, can be obtained from Electron Spin Echo Envelope Modulation

  10. Modulation-format-independent blind phase search algorithm for coherent optical square M-QAM systems.

    PubMed

    Zhou, Xian; Zhong, Kangping; Gao, Yuliang; Lu, Chao; Lau, Alan Pak Tao; Long, Keping

    2014-10-06

    Modulation format independence is one of the key challenges in digital signal processing (DSP) techniques for future elastic optical transmissions. We proposed a modulation-format-independent blind phase search (MFI-BPS) algorithm for square M-ary quadrature amplitude modulation (M-QAM) systems, in which modulation format recognition (MFR) and carrier phase estimation (CPE), are included and implemented both in a feed-forward manner. Comprehensive simulation and the experimental studies on 224 Gbit/s polarization multiplexing 16-QAM (PM-16QAM) systems demonstrate the feasibility and the effectiveness of the proposed MFI-BPS algorithm.

  11. The provenance and formation of reduced carbon phases on Mars from the study of Martian meteorites.

    NASA Astrophysics Data System (ADS)

    Steele, A.; McCubbin, F. M.; Fries, M.

    2015-12-01

    Organic carbon compounds are essential building blocks of terrestrial life, so the occurrence and origin (biotic or abiotic) of organic compounds on Mars is of great significance. Indeed, the question of Martian organic matter is among the highest priority targets for robotic spacecraft missions in the next decade includ- ing the Mars Science Laboratory and Mars 2020. Sev- eral Martian meteorites contain organic carbon (i.e., macromolecular reduced carbon-rich material, not nec- essarily related to biota), but there is little agreement on its origins. Initial hypotheses for the origin of this organic carbon included: terrestrial contamination; chondritic meteoritic input; thermal decomposition of Martian carbonate minerals; direct precipitation from cooling aqueous fluids; and the remains of ancient Martian biota. We report on results from the analysis of 14 martian meteorites and show the distribution of organic phases throughout the samples analyzed. We will present formation scearios for each of the types of organic matter discovered. These studies when combined show 4 possible pools of reduced carbon on Mars. 1) impact generated graphite in the Tissint meteorite, 2) secondary hydrothermal generated graphite in ALH 84001, 3) primary igneous reduced carbon in 12 Martian meteorites associated with spinel inclusions in olivine and pyroxene 4) and potentially primary hydrothermally formed organic carbon / nitrogen containing organic species in the maskelynite phases of the Tissint meteorite. These studies show that Mars has produced reduced carbon / organic carbon via several mechanisms and reveal that the building blocks of life, if not life itself, are present on Mars.

  12. Mechanisms of the early phases of plant gravitropism

    NASA Technical Reports Server (NTRS)

    Kiss, J. Z.

    2000-01-01

    Gravitropism is directed growth of a plant or plant organ in response to gravity and can be divided into the following temporal sequence: perception, transduction, and response. This article is a review of the research on the early events of gravitropism (i.e., phenomena associated with the perception and transduction phases). The two major hypotheses for graviperception are the protoplast-pressure and starch-statolith models. While most researchers support the concept of statoliths, there are suggestions that plants have multiple mechanisms of perception. Evidence supports the hypothesis that the actin cytoskeleton is involved in graviperception/transduction, but the details of these mechanisms remain elusive. A number of recent developments, such as increased use of the molecular genetic approach, magnetophoresis, and laser ablation, have facilitated research in graviperception and have allowed for refinement of the current models. In addition, the entire continuum of acceleration forces from hypo- to hyper-gravity have been useful in studying perception mechanisms. Future interdisciplinary molecular approaches and the availability of sophisticated laboratories on the International Space Station should help to develop new insights into mechanisms of gravitropism in plants.

  13. A HRMS study of oligomer formation through aqueous phase photooxidation of methylvinyl-ketone and methacrolein

    NASA Astrophysics Data System (ADS)

    Salque-moreton, G.; Liu, Y.; Voisin, D.; Siekmann, F.; Renard, P.; Monod, A.; Thissen, R.

    2012-04-01

    Global estimates of secondary organic aerosol (SOA) formation flux show that the current descriptions miss a large fraction of the sources. Aqueous phase photochemistry in cloud droplets and deliquescent aerosol may provide some of this missing flux. Organic reactions in those media, particularly leading to higher molecular weight products thus need better understanding. Here, we investigated the aqueous phase photooxidation of methacrolein (MACR) and methylvinyl-ketone (MVK), which are the two main oxidation products of isoprene, the volatile organic compound (VOC) that is mostly emitted on the global scale. In our experiments, photolysis of H2O2 provided OH radicals whose reaction with MACR or MVK produced oligomers. Firstly, oligomers were analyzed using electrospray ionization coupled with high-resolution linear ion trap Orbitrap™ (Thermo Corp.) mass spectrometer (HRMS). This technique enabled to propose the unambiguous elemental composition of the produced compounds as data were collected for a mass range of m/z 50-2000 amu. The mass of oligomers increased strongly in positive and negative ionization modes when initial concentrations of MACR and MVK were increased from 2 to 20 mM. Typical regular patterns of oligomer formation were observed for both precursors, and extended up to 1400 amu. These patterns were very different from each other for the two precursors although both showed regular mass differences of 70 amu. In addition, we used a Kendrick analysis and identified more than 20 distinct chemical oligomer series produced by photooxidation of both MACR and MVK, some of which reaching more than 1400 amu. The HRMS investigations allowed us to propose a mechanism of production of oligomers. Upon nebulization, both oligomer systems produce SOA with a mass yield of 2-12%. This mass yield increases with reaction time and precursor concentration. Moreover, time evolution of the oligomer systems observed with the Orbitrap will be compared to HR

  14. Illuminating the Atmospheric Oxidation Mechanisms, SOA Formation Pathways and Radical Yields of the Monoterpene Myrcene

    NASA Astrophysics Data System (ADS)

    Wyche, Kevin; Carr, Timo; Monks, Paul; Ellis, Andrew; Alfarra, Rami; McFiggans, Gordon; Hamilton, Jacqueline; Ward, Martyn; Boss, William; Camredon, Marie

    2010-05-01

    Biogenic Volatile Organic Compounds (BVOCs) are ubiquitous in the global troposphere, being emitted primarily from terrestrial plant life in significant quantities. Indeed, it is estimated that the total annual emission rate of all (non-methane) BVOCs is roughly ten times that of all anthropogenic volatile organic compounds (Guenther et al., 1995). With the exception of methane, the most dominant species of BVOC, in terms of emission strength, reactivity and their impact upon the atmosphere, are terpenes. Terpenes are a subdivision of BVOCs, composed primarily of hemiterpenes (C5), monoterpenes (C10), sesquiterpenes (C15) and diterpenes (C20). Under troposheric conditions terpenes react via complex and extensive gas phase oxidation pathways, have strong photochemical ozone creation potentials, constitute a significant radical source and are known to generate secondary organic aerosol (SOA) in high yields. At present there exists a certain lack of understanding regarding the oxidation mechanisms of certain terpenes and their role in SOA and radical formation. Consequently, as part of the NERC funded Aerosol Coupling in the Earth's System (ACES) and Total RAdical Production from the OZonolysis of alkenes (TRAPOZ) projects, a comprehensive series of simulation chamber experiments were conducted at the University of Manchester aerosol chamber facility, and at the EUropean PHOto REactor (EUPHORE) in order to investigate the gas phase degradation mechanisms, and SOA and radical formation potentials of a number of atmospherically significant terpenes. Both simulation chambers were highly instrumented during all experiments such that detailed and concomitant gas and aerosol phase measurements were made across a range of conditions. The work presented here describes the findings obtained from both photooxidation and ozonolysis experiments involving the common, but less well studied, aliphatic monoterpene, myrcene. The data presented include NOx and ozone measurements and

  15. Local structure, composition, and crystallization mechanism of a model two-phase “composite nanoglass”

    SciTech Connect

    Chattopadhyay, Soma; Kelly, S. D.; Shibata, Tomohiro; Balasubramanian, M.; Srinivasan, S. G.; Du, Jincheng; Banerjee, Rajarshi; Ayyub, Pushan

    2016-02-14

    We report a detailed study of the local composition and structure of a model, bi-phasic nanoglass with nominal stoichiometry Cu55Nb45. Three dimensional atom probe data suggest a nanoscale-phase-separated glassy structure having well defined Cu-rich and Nb-rich regions with a characteristic length scale of ≈3 nm. However, extended x-ray absorption fine structure analysis indicates subtle differences in the local environments of Cu and Nb. While the Cu atoms displayed a strong tendency to cluster and negligible structural order beyond the first coordination shell, the Nb atoms had a larger fraction of unlike neighbors (higher chemical order) and a distinctly better-ordered structural environment (higher topological order). This provides the first experimental indication that metallic glass formation may occur due to frustration arising from the competition between chemical ordering and clustering. These observations are complemented by classical as well as ab initio molecular dynamics simulations. Our study indicates that these nanoscale phase-separated glasses are quite distinct from the single phase nanoglasses (studied by Gleiter and others) in the following three respects: (i) they contain at least two structurally and compositionally distinct, nanodispersed, glassy phases, (ii) these phases are separated by comparatively sharp inter-phase boundaries, and (iii) thermally induced crystallization occurs via a complex, multi-step mechanism. Such materials, therefore, appear to constitute a new class of disordered systems that may be called a composite nanoglass.

  16. Local structure, composition, and crystallization mechanism of a model two-phase “composite nanoglass”

    SciTech Connect

    Chattopadhyay, Soma; Shibata, Tomohiro; Kelly, S. D.; Balasubramanian, M.; Srinivasan, S. G.; Du, Jincheng; Banerjee, Rajarshi; Ayyub, Pushan

    2016-02-14

    We report a detailed study of the local composition and structure of a model, bi-phasic nanoglass with nominal stoichiometry Cu{sub 55}Nb{sub 45}. Three dimensional atom probe data suggest a nanoscale-phase-separated glassy structure having well defined Cu-rich and Nb-rich regions with a characteristic length scale of ≈3 nm. However, extended x-ray absorption fine structure analysis indicates subtle differences in the local environments of Cu and Nb. While the Cu atoms displayed a strong tendency to cluster and negligible structural order beyond the first coordination shell, the Nb atoms had a larger fraction of unlike neighbors (higher chemical order) and a distinctly better-ordered structural environment (higher topological order). This provides the first experimental indication that metallic glass formation may occur due to frustration arising from the competition between chemical ordering and clustering. These observations are complemented by classical as well as ab initio molecular dynamics simulations. Our study indicates that these nanoscale phase-separated glasses are quite distinct from the single phase nanoglasses (studied by Gleiter and others) in the following three respects: (i) they contain at least two structurally and compositionally distinct, nanodispersed, glassy phases, (ii) these phases are separated by comparatively sharp inter-phase boundaries, and (iii) thermally induced crystallization occurs via a complex, multi-step mechanism. Such materials, therefore, appear to constitute a new class of disordered systems that may be called a composite nanoglass.

  17. GT1_cdedes_1: Heating and cooling mechanics in massive star formation

    NASA Astrophysics Data System (ADS)

    Dedes, C.

    2010-03-01

    Massive stars are important constituents of the interstellar medium (ISM) in our Galaxy and beyond. Their strong feedback processes influence the dynamics, energetics and chemistry of the surrounding interstellar medium both locally and on large scales. An important question to be answered is the one of cooling and heating mechanisms in regions of massive star formation. In the vicinity of massive stars, heating is provided mostly by far-UV (FUV) and infra-red radiation. Cooling is mostly provided by emission in the fine structure lines of CII. There are however other atomic and molecular lines such as OI, CO, OH and H_2O which can become significant coolants in the dense, embedded regions of massive star formation. This early phase when the forming massive star is still deeply embedded in its natal envelope, yet already interacting with, and potentially destroying, its environment through copious amounts of UV radiation, massive outflows and ultra compact HII (UCHII) regions, is an important phase in the star formation process. To understand the heating and cooling balance in this phase, one has to consider the contributions of various radiative and dynamical processes such as the FUV radiation from the young star itself, shocks created by strong stellar winds and the photon dominated regions (PDRs) where the radiation impinges on the molecular material. The tracers of these processes can be observed in the far-infrared, a wavelength range that is now accessible at unprecedented high spectral and spatial resolution with the Herschel Space Observatory. We propose to observe the aformentioned tracers of cooling and heating in the massive star forming region IRAS 12326-6245 to obtain a complete picture of the different processes, the regions they originate from and how they interact. This proposal is for time granted to the HIFI hardware team (PI: Frank Helmich) and to be accounted as part of the Swiss guaranteed time (Lead-Co-I: Arnold O. Benz).

  18. Acceleration of Classical Mechanics by Phase Space Constraints.

    PubMed

    Martínez-Núñez, Emilio; Shalashilin, Dmitrii V

    2006-07-01

    In this article phase space constrained classical mechanics (PSCCM), a version of accelerated dynamics, is suggested to speed up classical trajectory simulations of slow chemical processes. The approach is based on introducing constraints which lock trajectories in the region of the phase space close to the dividing surface, which separates reactants and products. This results in substantial (up to more than 2 orders of magnitude) speeding up of the trajectory simulation. Actual microcanonical rates are calculated by introducing a correction factor equal to the fraction of the phase volume which is allowed by the constraints. The constraints can be more complex than previously used boosting potentials. The approach has its origin in Intramolecular Dynamics Diffusion Theory, which shows that the majority of nonstatistical effects are localized near the transition state. An excellent agreement with standard trajectory simulation at high energies and Monte Carlo Transition State Theory at low energies is demonstrated for the unimolecular dissociation of methyl nitrite, proving that PSCCM works both in statistical and nonstatistical regimes.

  19. Phase behavior, rheological and mechanical properties of hydrophilic polymer dispersions.

    PubMed

    Bhattarai, Sushila; Bunt, Craig; Rathbone, Michael; Alany, Raid G

    2011-06-01

    Liquid polymeric systems that can undergo phase change (sol to gel) upon administration into the teat canal of cow's mammary gland can serve as a physical barrier to invading pathogens and can also serve as a reservoir for controlled release of therapeutic agents. The aim of the study was to investigate the phase behavior, rheological and mechanical properties of selected in situ gelling systems. Six in situ gelling polymer formulations were identified using phase behavior studies. Rheological studies revealed pseudoplastic flow with thixotropy. All six formulations showed significantly different viscosity, pseudoplasticity and thixotropy values except for CMC1 and HPMC2 which where statistically similar. The gel strength was dependent on the solvent system used and amount of water in the system. These in situ gelling systems have the potential to serve as a platform for development of intramammary formulations intended for administration into the teat canal of the cow's mammary gland. They can serve as a physical barrier or a matrix for controlled drug release.

  20. Formation of quark phases in compact stars and SN explosion

    SciTech Connect

    Drago, A.; Pagliara, G.; Pagliaroli, G.; Villante, F. L.; Vissani, F.

    2008-10-13

    We describe possible scenarios of quark deconfinement in compact stars and we analyze their astrophysical implications. The quark deconfinement process can proceed rapidly, as a strong deflagration, releasing a huge amount of energy in a short time and generating an extra neutrino burst. If energy is tranferred efficiently to the surface, like e.g. in the presence of convective instabilities, this burst could contribute to revitalize a partially failed SN explosion. We discuss how the neutrino observations from SN1987A would fit in this scenario. Finally, we focus on the fate of massive and rapidly rotating progenitors, discussing possible time separations between the moment of the core collapse and the moment of quark deconfinement. This mechanism can be at the basis of the interpretation of gamma ray bursts in which lines associated with heavy elements are present in the spectrum.

  1. Coupled dissolution-precipitation as a mechanism for amorphous-to-crystalline calcium carbonate phase transition

    NASA Astrophysics Data System (ADS)

    Rodriguez-Navarro, Carlos Manuel; Kudłacz, Krzysztof; Ruiz-Agudo, Encarnacion

    2014-05-01

    Growing evidence shows that several calcium carbonate biominerals form via an amorphous precursor phase. Such a biomineralization strategy could also be applicable for the biomimetic synthesis of novel functional materials. A crucial step in this process is the transformation of amorphous calcium carbonate (ACC) into calcite. However, controversy exists as to what is the actual mechanism of this transformation: Is it a solid-solid (solid state) or a dissolution/precipitation mechanism? Determining the transition mechanism is critical for example in interpreting the formation of oriented crystalline structures in biominerals (e.g., echinoderm spicles). We studied calcium carbonate precipitation and phase transitions according to the overall reaction Ca(OH)2 + CO2 = CaCO3+ H2O. Mineral phase transformations during this reaction were studied using transmission electron microscopy (TEM). Our TEM analysis showed that two different types of ACC are sequentially formed during this reaction. Type I ACC shows no well-defined short-range order, while Type II ACC shows a short-range order corresponding to calcite. Following e-beam irradiation, Type I ACC particles transform into randomly oriented CaO nanocrystals, while irradiation of Type II ACC leads to the formation of pseudomorphs made up of perfectly oriented aggregates of calcite nanocrystals. Moreover, calcite crystals formed in solution or in air (85 % relative humidity) after Type II ACC are also pseudomorphs made up of porous aggregates of preferentially oriented calcite nanocrystals. Our results give experimental evidence showing that the ACC to calcite transformation under relevant biomineralization conditions (low T and P), also applicable in the biomimetic synthesis of calcite, is a pseudomorphic dissolution-precipitation process. This mechanism involves the tightly interface-coupled dissolution of the precursor amorphous phase (with the crystalline phase protostructure) and concomitant deposition of the

  2. Fundamental studies of the mechanisms of slag deposit formation

    SciTech Connect

    Austin, L.G.; Tangsathitkulchai, M.; Gomez, C.; Malchenson, D.; Benson, S.

    1985-06-01

    A laboratory test furnace was used to investigate the slagging tendencies of pulverized coal under conditions which simulate the combustion conditions in a full-scale boiler. The accomplishments during this reporting period include: (1) Preliminary results of tests using polymer-mineral mixtures have shown that the deposits produced are similar in morphology to deposits produced from coals. (2) Temperature profiles in the region bewteen the constrictor and the substrate were determined by the use of pyrometric cones. (3) The performance of the fluidized spouting-bed feeder was tested to determine whether it was feeding a representative sample of coal. (4) Quantitative SEM-microprobe analysis was performed on a cross-section of an Indian Head lignite ash deposit. The results showed trends in composition with respect to height and distance from the centerline to outer edges of the deposit. Development work has continued on the computer-controlled SEM system. The sintering characteristics of Beulah and Upper Freeport fly ashes were examined. The compressive strength and shrinkage of the Beulah fly ash remained essentially unchanged with time at heat treatment temperatures below 1150/sup 0/C, whereas significant changes in compressive strength and shrinkage occurred in the sintering of the Upper Freeport fly ash. Strength tests of the HF-washed Upper Freeport fly ash were performed to verify the hypothesis that glassy phases in fly ash promote deposit strength. In addition, sintering studies on a model system consisting of a soda glass and alumina mixture were performed to illustrate the viscous flow mechanism of sintering. 11 refs., 29 figs., 7 tabs.

  3. Mechanism modeling for phase fraction measurement with ultrasound attenuation in oil–water two-phase flow

    NASA Astrophysics Data System (ADS)

    Su, Qian; Tan, Chao; Dong, Feng

    2017-03-01

    When measuring the phase fraction of oil–water two-phase flow with the ultrasound attenuation, the phase distribution and fraction have direct influence on the attenuation coefficient. Therefore, the ultrasound propagation at various phase fractions and distributions were investigated. Mechanism models describing phase fraction with the ultrasound attenuation coefficient were established by analyzing the interaction between ultrasound and two-phase flow by considering the scattering, absorption and diffusion effect. Experiments were performed to verify the theoretical analysis, and the test results gave good agreement with the theoretical analysis. When the dispersed phase fraction is low, the relationship between ultrasound attenuation coefficient and phase fraction is of monotonic linearity; at higher dispersed phase fraction, ultrasound attenuation coefficient presents an irregular response to the dispersed phase fraction. The presented mechanism models give reasonable explanations about the trend of ultrasound attenuation.

  4. Ultrasound Microbubble Treatment Enhances Clathrin-Mediated Endocytosis and Fluid-Phase Uptake through Distinct Mechanisms

    PubMed Central

    Fekri, Farnaz; Delos Santos, Ralph Christian; Karshafian, Raffi

    2016-01-01

    Drug delivery to tumors is limited by several factors, including drug permeability of the target cell plasma membrane. Ultrasound in combination with microbubbles (USMB) is a promising strategy to overcome these limitations. USMB treatment elicits enhanced cellular uptake of materials such as drugs, in part as a result of sheer stress and formation of transient membrane pores. Pores formed upon USMB treatment are rapidly resealed, suggesting that other processes such as enhanced endocytosis may contribute to the enhanced material uptake by cells upon USMB treatment. How USMB regulates endocytic processes remains incompletely understood. Cells constitutively utilize several distinct mechanisms of endocytosis, including clathrin-mediated endocytosis (CME) for the internalization of receptor-bound macromolecules such as Transferrin Receptor (TfR), and distinct mechanism(s) that mediate the majority of fluid-phase endocytosis. Tracking the abundance of TfR on the cell surface and the internalization of its ligand transferrin revealed that USMB acutely enhances the rate of CME. Total internal reflection fluorescence microscopy experiments revealed that USMB treatment altered the assembly of clathrin-coated pits, the basic structural units of CME. In addition, the rate of fluid-phase endocytosis was enhanced, but with delayed onset upon USMB treatment relative to the enhancement of CME, suggesting that the two processes are distinctly regulated by USMB. Indeed, vacuolin-1 or desipramine treatment prevented the enhancement of CME but not of fluid phase endocytosis upon USMB, suggesting that lysosome exocytosis and acid sphingomyelinase, respectively, are required for the regulation of CME but not fluid phase endocytosis upon USMB treatment. These results indicate that USMB enhances both CME and fluid phase endocytosis through distinct signaling mechanisms, and suggest that strategies for potentiating the enhancement of endocytosis upon USMB treatment may improve targeted

  5. Gas-phase Mechanisms of Sulfur Isotope Mass-independent Fractionation

    NASA Astrophysics Data System (ADS)

    Lyons, J. R.

    2006-12-01

    Mass-independent fractionation (MIF) in sulfur isotopes in ancient sulfur-bearing rocks (Farquhar et al. 2000a) is interpreted as evidence for gas-phase MIF processes in the early Earth atmosphere. This interpretation is made by analogy with oxygen isotope MIF in the modern atmosphere (produced during ozone formation), and by laboratory photolysis experiments on SO2 (Farquhar et al. 2001; Wing et al. 2004) that yield both elemental sulfur and sulfate with S MIF signatures at wavelengths above and below the SO2 dissociation limit. What is lacking is a quantitative understanding of the mechanisms of gas-phase S MIF. Quantification is essential in order to extract the full implications of sulfur MIF throughout Earth history, including for bacterial sulfate reduction processes which largely conserve D33S and D36S. Several sulfur MIF mechanisms are possible. The most obvious is the gas-phase thiozone reaction, which is isovalent to the ozone formation reaction. Ozone formation produces a well-known MIF signature in oxygen isotopes (Thiemens and Heidenreich 1983), and a symmetry-dependent non-RRKM mechanism has been proposed as the origin of O MIF (Gao and Marcus 2001). It is possible and perhaps likely that S3 formation also proceeds by a non-RRKM process. Data are lacking on isotopic (an even non-isotopic) rates of S3 formation, so it is not possible to make definitive statements about MIF in S3 at this time. However modeling results suggest that the vapor pressure of S2 is too low for gas-phase S3 formation to be significant. Two additional species that may exhibit a non-RRKM MIF signature are S2O2 and S4. Again, there is a lack of isotopomer-specific kinetic data for these reactions, and gas-phase formation of S4 is likely inconsequential. Perhaps the most obvious mechanism is simply the primary act of SO2 photolysis. The SO2 absorption spectrum is highly structured, with strong vibronic bands above and below the dissociation limit. In contrast H2S, with its mostly

  6. Gas-Phase Anionic σ-Adduct (Trans)formations in Heteroaromatic Systems1

    NASA Astrophysics Data System (ADS)

    Zimnicka, Magdalena; Danikiewicz, Witold

    2015-07-01

    Anions of nitroderivatives of thiophene and furan were subjected to the reactions with selected C-H acids in the gas phase. Various structures and reaction pathways were proposed for the observed ionic products. In general, the reactions of heteroaromatic anions with C-H acids may be divided into three groups, depending on the proton affinity difference between C-H acid's conjugate base and heteroaromatic anion (ΔPA). The proton transfer from C-H acid to heteroaromatic anion is a dominant process in the reactions for which ΔPA < 0 kcal mol-1, whereas the reactions with high ΔPA (ΔPA > 16 kcal mol-1) do not lead to any ionic products. The formation of σ-adducts and products of their further transformations according to the VNS, SNAr, cine, and tele substitution mechanisms have been proposed for reactions with moderate ΔPA. The other possible mechanisms as SN2 reaction, nucleophilic addition to the cyano group, ring-opening pathway, and halogenophilic reaction have also been discussed to contribute in the reactions between heteroaromatic anions and C-H acids.

  7. Theoretical Mechanistic and Kinetic Studies on Homogeneous Gas-Phase Formation of Polychlorinated Naphthalene from 2-Chlorophenol as Forerunner

    PubMed Central

    Xu, Fei; Zhang, Ruiming; Li, Yunfeng; Zhang, Qingzhu; Wang, Wenxing

    2015-01-01

    Polychlorinated naphthalenes (PCNs) are dioxins-like compounds and are formed along with polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in thermal and combustion procedures. Chlorophenols (CPs) are the most important forerunners of PCNs. A comprehensive comprehension of PCN formation procedure from CPs is a precondition for reducing the discharge of PCNs. Experiments on the formation of PCNs from CPs have been hindered by PCN toxicity and short of precise detection methods for active intermediate radicals. In this work, PCN formation mechanism in gas-phase condition from 2-chlorophenol (2-CP) as forerunner was studied by quantum chemistry calculations. Numbers of energetically advantaged formation routes were proposed. The rate constants of key elementary steps were calculated over 600–1200 K using canonical variational transition-state theory (CVT) with small curvature tunneling contribution (SCT) method. This study illustrates formation of PCNs with one chlorine atom loss from 2-CP is preferred over that without chlorine atom loss. In comparison with formation of PCDFs from 2-CP, PCN products are less chlorinated and have lower formation potential. PMID:26516839

  8. Effect of high temperature deposition on CoSi{sub 2} phase formation

    SciTech Connect

    Comrie, C. M.; Ahmed, H.; Smeets, D.; Demeulemeester, J.; Vantomme, A.; Turner, S.; Van Tendeloo, G.; Detavernier, C.

    2013-06-21

    This paper discusses the nucleation behaviour of the CoSi to CoSi{sub 2} transformation from cobalt silicide thin films grown by deposition at elevated substrate temperatures ranging from 375 Degree-Sign C to 600 Degree-Sign C. A combination of channelling, real-time Rutherford backscattering spectrometry, real-time x-ray diffraction, and transmission electron microscopy was used to investigate the effect of the deposition temperature on the subsequent formation temperature of CoSi{sub 2}, its growth behaviour, and the epitaxial quality of the CoSi{sub 2} thus formed. The temperature at which deposition took place was observed to exert a significant and systematic influence on both the formation temperature of CoSi{sub 2} and its growth mechanism. CoSi films grown at the lowest temperatures were found to increase the CoSi{sub 2} nucleation temperature above that of CoSi{sub 2} grown by conventional solid phase reaction, whereas the higher deposition temperatures reduced the nucleation temperature significantly. In addition, a systematic change in growth mechanism of the subsequent CoSi{sub 2} growth occurs as a function of deposition temperature. First, the CoSi{sub 2} growth rate from films grown at the lower reactive deposition temperatures is substantially lower than that grown at higher reactive deposition temperatures, even though the onset of growth occurs at a higher temperature, Second, for deposition temperatures below 450 Degree-Sign C, the growth appears columnar, indicating nucleation controlled growth. Elevated deposition temperatures, on the other hand, render the CoSi{sub 2} formation process layer-by-layer which indicates enhanced nucleation of the CoSi{sub 2} and diffusion controlled growth. Our results further indicate that this observed trend is most likely related to stress and changes in microstructure introduced during reactive deposition of the CoSi film. The deposition temperature therefore provides a handle to tune the CoSi{sub 2} growth

  9. Mechanisms of polar lobe formation in fertilized eggs of molluscs.

    PubMed

    Conrad, G W; Schantz, A R; Patron, R R

    1990-01-01

    Polar lobe formation in the marine mudsnail, Ilyanassa obsoleta, involves formation of a microtubule-, microfilament-dependent furrow that constricts at two rates, then stops and relaxes. Some artificial seawater mixtures allow relatively normal development, facilitate insertion of microelectrode tips, and prevent artifactual bleb formation during such punctures. Membrane events may affect formation of polar lobe constrictions: (1) Brief treatment with digitonin prevents constrictions, but not cytokinesis per se, and the suppression of constrictions is permanent. Tomatine (but not tomatidine) and filipin act similarly, although filipin often also stops cytokinesis as well. (2) Responses to digitonin, tomatine, and filipin occur with little change in membrane potential. (3) Adhesion to substrata in response to brief treatment at low pH prevents both constrictions and cytokinesis. (4) Adhesion to substrata via polylysine allows both constrictions and cytokinesis, but embryos are smaller in volume and develop abnormally. Formation of lobe constrictions may be sensitive to perturbations of the plasma membrane.

  10. Structure and Mechanism of a Pentameric Formate Channel

    SciTech Connect

    Waight, A.; Love, J; Wang, D

    2010-01-01

    Formate transport across the inner membrane is a critical step in anaerobic bacterial respiration. Members of the formate/nitrite transport protein family function to shuttle substrate across the cytoplasmic membrane. In bacterial pathogens, the nitrite transport protein is involved in protecting bacteria from peroxynitrite released by host macrophages. We have determined the 2.13-{angstrom} structure of the formate channel FocA from Vibrio cholerae, which reveals a pentamer in which each monomer possesses its own substrate translocation pore. Unexpectedly, the fold of the FocA monomer resembles that found in water and glycerol channels. The selectivity filter in FocA consists of a cytoplasmic slit and a central constriction ring. A 2.5-{angstrom} high-formate structure shows two formate ions bound to the cytoplasmic slit via both hydrogen bonding and van der Waals interactions, providing a structural basis for the substrate selectivity of the channel.

  11. Enhancement of polar crystalline phase formation in transparent PVDF-CaF2 composite films

    NASA Astrophysics Data System (ADS)

    Lee, Sang Goo; Ha, Jong-Wook; Sohn, Eun-Ho; Park, In Jun; Lee, Soo-Bok

    2016-12-01

    We consider the influence of calcium fluoride (CaF2) nanoparticles on the crystalline phase formation of poly(vinylidene fluoride) (PVDF) for the first time. The transparent PVDF-CaF2 composite films were prepared by casting on PET substrates using N,N-dimethylacetamide (DMAc) as a solvent. It was found that CaF2 promoted the formation of polar crystalline phase of PVDF in composites, whereas nonpolar α-phase was dominant in the neat PVDF film prepared at the same condition. The portion of polar crystalline phase increased in proportional to the weight fraction of CaF2 in the composite films up to 10 wt%. Further addition of CaF2 suppressed completely the α-phase formation. Polar crystalline phase observed in as-cast composite films was a mixture of β- and γ-polymorph structures. It was also shown that much ordered γ-phase could be obtained through thermal treatment of as-cast PVDF-CaF2 composite film at the temperatures above the melting temperature of the composite films, but below that of γ-phase.

  12. Effect of annealing process on the phase formation in poly(vinylidene fluoride) thin films

    SciTech Connect

    Abdullah, Ibtisam Yahya; Yahaya, Muhammad; Jumali, Mohd Hafizuddin Haji; Shanshool, Haider Mohammed

    2014-09-03

    This work reports the initial study on the effect of annealing process on the crystalline phase of poly(vinylidene fluoride) (PVDF) thin film. PVDF powder was dissolved in N,N-dimethylformamide before spin-coated onto a glass substrate to form a film. The films were annealed at 30°C, 90°C and 110°C for 5 hrs. The crystalline phase of the powder PVDF as received was investigated by using XRD and FTIR techniques. Moreover, the crystalline phases of thin films after annealing were investigated by using the same techniques. XRD analysis showed that in powder form PVDF exists in α-phase. Each annealed PVDF thin films exhibited identical formation of three-phases material namely γ (as major phase) while α and β phases as the minor phases. The FTIR analysis showed that the powder form of PVDF exists in α and β phases. FTIR measurement further confirmed the XRD results implying that the annealing process has no significant effect on the phase formation in PVDF films.

  13. Phase separation driven by density-dependent movement: A novel mechanism for ecological patterns.

    PubMed

    Liu, Quan-Xing; Rietkerk, Max; Herman, Peter M J; Piersma, Theunis; Fryxell, John M; van de Koppel, Johan

    2016-12-01

    Many ecosystems develop strikingly regular spatial patterns because of small-scale interactions between organisms, a process generally referred to as spatial self-organization. Self-organized spatial patterns are important determinants of the functioning of ecosystems, promoting the growth and survival of the involved organisms, and affecting the capacity of the organisms to cope with changing environmental conditions. The predominant explanation for self-organized pattern formation is spatial heterogeneity in establishment, growth and mortality, resulting from the self-organization processes. A number of recent studies, however, have revealed that movement of organisms can be an important driving process creating extensive spatial patterning in many ecosystems. Here, we review studies that detail movement-based pattern formation in contrasting ecological settings. Our review highlights that a common principle, where movement of organisms is density-dependent, explains observed spatial regular patterns in all of these studies. This principle, well known to physics as the Cahn-Hilliard principle of phase separation, has so-far remained unrecognized as a general mechanism for self-organized complexity in ecology. Using the examples presented in this paper, we explain how this movement principle can be discerned in ecological settings, and clarify how to test this mechanism experimentally. Our study highlights that animal movement, both in isolation and in unison with other processes, is an important mechanism for regular pattern formation in ecosystems.

  14. Hexagonal phase based gel-emulsion (O/H1 gel-emulsion): formation and rheology.

    PubMed

    Alam, Mohammad Mydul; Aramaki, Kenji

    2008-11-04

    The formation, stability, and rheological behavior of a hexagonal phase based gel-emulsion (O/H1 gel-emulsion) have been studied in water/C12EO8/hydrocarbon oil systems. A partial phase behavior study indicates that the oil nature has no effect on the phase sequences in the ternary phase diagram of water/C12EO8/oil systems but the domain size of the phases or the oil solubilization capacity considerably changes with oil nature. Excess oil is in equilibrium with the hexagonal phase (H1) in the ternary phase diagram in the H1+O region. The O/H1 gel-emulsion was prepared (formation) and kept at 25 degrees C to check stability. It has been found that the formation and stability of the O/H1 gel-emulsion depends on the oil nature. After 2 min observation (formation), the results show that short chain linear hydrocarbon oils (heptane, octane) are more apt to form a O/H1 gel-emulsion compared to long chain linear hydrocarbon oils (tetradecane, hexadecane), though the stability is not good enough in either system, that is, oil separates within 24 h. Nevertheless, the formation and stability of the O/H1 gel-emulsion is appreciably increased in squalane and liquid paraffin. It is surmised that the high transition temperature of the H1+O phase and the presence of a bicontinuous cubic phase (V1) might hamper the formation of a gel-emulsion. It has been pointed out that the solubilization of oil in the H1 phase could be related to emulsion stability. On the other hand, the oil nature has little or no effect on the formation and stability of a cubic phase based gel-emulsion (O/I1 gel-emulsion). From rheological measurements, it has found that the rheogram of the O/H1 gel-emulsion indicates gel-type structure and shows shear thinning behavior similar to the case of the O/I1 gel-emulsion. Rheological data infer that the O/I1 gel-emulsion is more viscous than the O/H1 gel-emulsion at room temperature but the O/H1 gel-emulsion shows consistency at elevated temperature.

  15. Sedimentary iron monosulfides: Kinetics and mechanism of formation

    NASA Astrophysics Data System (ADS)

    Pyzik, Albert J.; Sommer, Sheldon E.

    1981-05-01

    The reaction between hydrous iron oxides and aqueous sulfide species was studied at estuarine conditions of pH, total sulfide, and ionic strength to determine the kinetics and formation mechanism of the initial iron sulfide. Total, dissolved and acid extractable sulfide, thiosulfate, sulfate, and elemental sulfur were determined by spectrophotometric methods. Polysulfides, S 42- and S 52-, were determined from ultraviolet absorbance measurements and equilibrium calculations, while product hydroxyl ion was determined from pH measurements and solution buffer capacity. Elemental sulfur, as free and polysulfide sulfur, was 86% of the sulfide oxidation products; the remainder was thiosulfate. Rate expressions for the reduction and precipitation reactions were determined from analysis of electron balance and acid extractable iron monosulfide vs time, respectively, by the initial rate method. The rate of iron reduction in moles/liter/minute was given by d( reduction Fe) /dt = kS t0.5(J +) 0.5 A FeOOH1 where St was the total dissolved sulfide concentration, (H +) the hydrogen ion activity, both in moles/ liter; and AFeOOH the goethite specific surface area in square meters/liter. The rate constant, k, was 0.017 ± 0.002m -2 min -1. The rate of reduction was apparently determined by the rate of dissolution of the surface layer of ferrous hydroxide. The rate expression for the precipitation reaction was d(FeS)/dt = kS t1(H +) 1 A FeOOH1 where d(FeS)/dt was the rate of precipitation of acid extractable iron monosulfide in moles/liter/minute, and k = 82 ± 18 mol -1l2m-2 min -1. A model is proposed with the following steps: protonation of goethite surface layer; exchange of bisulfide for hydroxide in the mobile layer; reduction of surface ferric ions of goethite by dissolved bisulfide species which produces ferrous hydroxide surface layer elemental sulfur and thiosulfate; dissolution of surface layer of ferrous hydroxide; and precipitation of dissolved ferrous specie and

  16. A new mechanism for the formation of regolith on asteroids

    NASA Astrophysics Data System (ADS)

    Delbo, Marco; Libourel, Guy; Wilkerson, Justin; Murdoch, Naomi; Michel, Patrick; Ramesh, Kt; Ganino, Clement; Verati, Chrystele; Marchi, Simone

    2014-11-01

    The soil of asteroids, like that of the Moon, and other rocky, airless bodies in the Solar System, is made of a layer of pebbles, sand, and dust called regolith.Previous works suggested that the regolith on asteroids is made from material ejected from impacts and re-accumulated on the surface and from surface rocks that are broken down by micrometeoroid impacts. However, this regolith formation process has problems to explain the regolith on km-sized and smaller asteroids: it is known that impact fragments can reach escape velocities and breaks free from the gravitational forces of these small asteroids, indicating the impact mechanism is not the dominant process for regolith creation. Other studies also reveal that there is too much regolith on small asteroids’ surfaces to have been deposited there solely by impacts over the millions of years of asteroids’ evolution.We proposed that another process is capable of gently breaking rocks at the surface of asteroids: thermal fatigue by temperature cycling. As asteroids spin about their rotation axes, their surfaces go in and out of shadow resulting in large surface temperature variations. The rapid heating and cooling creates thermal expansion and contraction in the asteroid material, initiating cracking and propagating existing cracks. As the process is repeated over and over, the crack damage increases with time, leading eventually to rock fragmentation (and production of new regolith).To study this process, in the laboratory, we subjected meteorites, used as asteroid material analogs, to 37 days of thermal cycles similar to those occurring on asteroids. We measured cracks widening at an average rate of 0.5 mm/y. Some fragments were also produced, indicating meteorite fragmentation. To scale our results to asteroid lifetime, we incorporated our measurements into a fracture model and we deduced that thermal cycling is more efficient than micrometeorite bombardment at fragmenting rock over millions of years on

  17. A new mechanism for the formation of regolith on asteroids

    NASA Astrophysics Data System (ADS)

    Delbo, M.; Libourel, G.; Wilkerson, J.; Murdoch, N.; Michel, P.; Ramesh, K. T.; Ganino, C.; Verati, C.; Marchi, S.

    2014-12-01

    The soil of asteroids, like that of the Moon, Mars, and other rocky bodies in the Solar System, is made of a layer of pebbles, sand, and dust called regolith. Previous studies suggested that the regolith of asteroids is made from material ejected from impacts and re-accumulated on the surface and from boulders that are comminuted by micrometeoroid impacts. However, this classical scenario of regolith formation has problems to explain the regolith on km-sized and smaller asteroids: laboratory experiments and impact modelling have shown that the impact fragments can reach escape velocities and breaks free from the gravitational pull of these small asteroids, indicating the impact mechanism is not the dominant process for regolith creation. Other studies also reveal that there is too much regolith on small asteroids' surfaces to have been deposited there solely through impacts over the millions of years of asteroids' evolution. We discovered that another process is capable of gently breaking rocks at the surface of asteroids: thermal fatigue by temperature cycling. As asteroids spin about their rotation axes, their surfaces plunge in and out of shadow resulting in large surface temperature variations. The rapid heating and cooling creates thermal expansion and contraction in the asteroid material, initiating cracking and propagating existing cracks. As the process is repeated over and over, the crack damage increases with time, leading eventually to rock fragmentation (and production of new regolith). To study this process, in the laboratory, we subjected meteorites, used as asteroid material analogs, to 37 days of thermal cycles similar to those occurring on asteroids. We measured cracks widening at an average rate of 0.5 mm/y. Some fragments were also produced, indicating meteorite fragmentation. To scale our results to asteroid lifetime, we incorporated our measurements into a fracture model and we deduced that thermal cycling is more efficient than micrometeorite

  18. Reversible work of formation of an embryo of a new phase within a uniform macroscopic mother phase

    SciTech Connect

    Debenedetti, P.G.; Reiss, H. |

    1998-04-01

    A thermodynamically consistent formalism is derived for calculating the reversible work needed to form a small amount of a new phase (embryo) within a uniform macroscopic mother phase. The treatment goes beyond the classic work of Gibbs, who solved the problem for the particular case in which the embryo is in equilibrium with the mother phase, constituting a so-called critical nucleus. The formalism results in a new expression for the reversible work of embryo formation, the extrema conditions for which yield the correct conditions of equilibrium between the critical nucleus and the mother phase, as well as Gibbs{close_quote} result for the reversible work needed to form the critical nucleus. The new expression for the work of embryo formation differs from the one commonly used in the nucleation literature. In order to extend the Gibbsian formalism to noncritical nuclei, it is necessary to introduce a constraint that prevents the free transfer of matter between the embryo and the mother phase. The present approach is valid in the limit in which curvature contributions to the interfacial energy can be neglected. {copyright} {ital 1998 American Institute of Physics.}

  19. A photo-oxidation mechanism for patterning and hologram formation in conjugated polymer/glass composites

    NASA Astrophysics Data System (ADS)

    Levi, Ofer; Perepelitsa, Galina; Davidov, Dan; Shalom, Shoshy; Benjamin, Iris; Neumann, Ronny; Agranat, Aharon J.; Avny, Yair

    2000-08-01

    Improved diffraction efficiency was observed in holograms stored in disordered conjugated polymer/glass composites. The conjugated polymers used were alkoxy substituted poly(phenylenevinylne) analogs and the glass matrices were zirconia-organosilica xerogels. Investigation of the mechanism of hologram formation revealed evidence of a photochromic process consisting of light induced photo-oxidation (bleaching) of the embedded conjugated polymer resulting in the formation of an absorption grating and a phase grating. Investigation of the hologram formation revealed that the process was oxygen dependent. Oxygen removal increases hologram formation time by more than an order of magnitude and halves the total hologram efficiency. The oxygen dependence was also highly correlated with photobleaching of the samples and beam interaction of the writing beams. The chemical transformations upon photobleaching were shown by infrared and Raman spectroscopy to involve chain scission and oxidation of the polymer at the vinylic position of the conjugated polymer. Film preparation of the composites was optimized showing a tenfold improvement in the holographic properties compared to our previous results. The optimized treatment method allows for a high, >20%, diffraction efficiency, η, to be obtained for the 2.5-μm-thick polymer/glass films. Light sensitivity was compared for several polymer/glass composites and was correlated to the absorption curves and holographic diffraction efficiency showing that the new composites and film preparation techniques are promising for holographic materials sensitive in the blue and ultraviolet spectral regions. A method of information fixing by preventing oxygen entry to the composite film resulted in a fourfold increase of the erasure time. These findings suggest that holograms can be fixed for a long term by nonoxygen permeable coating, applied after hologram formation.

  20. Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM

    SciTech Connect

    Roldin, P.; Eriksson, A. C.; Nordin, E. Z.; Hermansson, E.; Mogensen, Ditte; Rusanen, A.; Boy, Michael; Swietlicki, E.; Svenningsson, Birgitta; Zelenyuk, Alla; Pagels, J.

    2014-08-11

    We have developed the novel Aerosol Dynamics, gas- and particle- phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas phase Master Chemical Mechanism version 3.2, an aerosol dynamics and particle phase chemistry module (which considers acid catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study: 1) the mass transfer limited uptake of ammonia (NH3) and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), 2) the slow and almost particle size independent evaporation of α-pinene secondary organic aerosol (SOA) particles, and 3) the influence of chamber wall effects on the observed SOA formation in smog chambers.

  1. EXPERIMENTAL AND COMPUTATIONAL STUDIES OF THE FORMATION MECHANISM OF PROTONATED INTERSTELLAR DIAZINES

    SciTech Connect

    Wang, Zhe-Chen; Cole, Callie A.; Bierbaum, Veronica M.; Snow, Theodore P.

    2015-01-10

    Studies of interstellar chemistry have grown in number and complexity by both observations and laboratory measurements, and nitrogen-containing aromatics have been implicated as important interstellar molecules. In this paper, the gas-phase collision induced dissociation (CID) processes of protonated pyridazine (1,2-diazine), pyrimidine (1,3-diazine), and pyrazine (1,4-diazine) cations (C{sub 4}H{sub 5}N{sub 2} {sup +}) are investigated in detail both experimentally and theoretically. The major neutral loss for all three CID processes is HCN, leading to the formation of C{sub 3}H{sub 4}N{sup +} isomers; our density functional theory (DFT) calculations support and elucidate our experimental results. The formation of C{sub 3}H{sub 4}N{sup +} isomers from the reaction of abundant interstellar acrylonitrile (CH{sub 2}CHCN) and H{sup +}is also studied employing DFT calculations. Our results lead to a novel mechanism for interstellar protonated diazine formation from the consecutive reactions of CH{sub 2}CHCN+ H{sup +} + HCN. Moreover, our results motivate the continuing search for interstellar C{sub 3}H{sub 4}N{sup +} isomers as well as polycyclic aromatic N-containing hydrocarbons (PANHs)

  2. Formation of prismatic loops from C15 Laves phase interstitial clusters in body-centered cubic iron

    SciTech Connect

    Zhang, Yongfeng; Bai, Xian-Ming; Tonks, Michael R.; Biner, S. Bulent

    2015-03-01

    This Letter reports the transition of C15 phase self-interstitial clusters to loops in body-centered-cubic Iron. Molecular dynamics simulations are performed to evaluate the relative stabilities of difference interstitial cluster configurations including C15 phase structure and <100> and <111>/2 loops. Within a certain size range, C15 cluster are found more stable than loops, and the relative stabilities are reversed beyond that range. In accordance to the crossover in relative stabilities, C15 clusters may grow by absorbing individual interstitials at small sizes and transitions into loops eventually. The transition takes place by nucleation and reaction of <111>/2 loop segments. These observations explain the absence of C15 phase interstitial clusters predicted by density-functional-theory calculations in previous experimental observations. More importantly, the current results provide a new formation mechanism of <100> loops which requires no interaction of loops.

  3. Phase-field-crystal models and mechanical equilibrium

    NASA Astrophysics Data System (ADS)

    Heinonen, V.; Achim, C. V.; Elder, K. R.; Buyukdagli, S.; Ala-Nissila, T.

    2014-03-01

    Phase-field-crystal (PFC) models constitute a field theoretical approach to solidification, melting, and related phenomena at atomic length and diffusive time scales. One of the advantages of these models is that they naturally contain elastic excitations associated with strain in crystalline bodies. However, instabilities that are diffusively driven towards equilibrium are often orders of magnitude slower than the dynamics of the elastic excitations, and are thus not included in the standard PFC model dynamics. We derive a method to isolate the time evolution of the elastic excitations from the diffusive dynamics in the PFC approach and set up a two-stage process, in which elastic excitations are equilibrated separately. This ensures mechanical equilibrium at all times. We show concrete examples demonstrating the necessity of the separation of the elastic and diffusive time scales. In the small-deformation limit this approach is shown to agree with the theory of linear elasticity.

  4. The mechanical properties of phase separated protein droplets

    NASA Astrophysics Data System (ADS)

    Jawerth, Louise; Ijavi, Mahdiye; Patel, Avinash; Saha, Shambaditya; Jülicher, Frank; Hyman, Anthony

    In vivo, numerous proteins associate into liquid compartments by de-mixing from the surrounding solution, similar to oil molecules in water. Many of these proteins and their corresponding liquid compartments play a crucial role in important biological processes, for instance germ line specification in C. elegans or in neurodegenerative diseases such as Amyotrophic lateral sclerosis (ALS). However, despite their importance, very little is known about the physical properties of the resulting droplets as well as the physical mechanisms that control their phase separation from solution. To gain a deeper understanding of these aspects, we study a few such proteins in vitro. When these proteins are purified and added to a physiological buffer, they phase separate into droplets ranging in size from a few to tens of microns with liquid-like behavior similar to their physiological counterparts. By attaching small beads to the surface of the droplets, we can deform the droplets by manipulating the beads directly using optical tweezers. By measuring the force required to deform the droplets we determine their surface tension, elasticity and viscosity as well as the frequency response of these properties. We also measure these properties using passive micro-rheology.

  5. The Role of Possible Feedback Mechanisms in the Effects of Altered Gravity on Formation and Function of Gravireceptors of Mollusks and Fish

    NASA Technical Reports Server (NTRS)

    Kondrachuk, Alexander V.; Boyle, Richard D.

    2005-01-01

    The variety of the effects of altered gravity (AG) on development and function of gravireceptors cannot be explained by simple feedback mechanism that correlates gravity level and weight of test mass. The reaction of organisms to the change of gravity depends on the phase of their development. To predict this reaction we need to know the details of the mechanisms of gravireceptor formation

  6. Secondary organic aerosol formation from low-NO(x) photooxidation of dodecane: evolution of multigeneration gas-phase chemistry and aerosol composition.

    PubMed

    Yee, Lindsay D; Craven, Jill S; Loza, Christine L; Schilling, Katherine A; Ng, Nga Lee; Canagaratna, Manjula R; Ziemann, Paul J; Flagan, Richard C; Seinfeld, John H

    2012-06-21

    The extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions. Production of semivolatile hydroperoxide species within three generations of chemistry is consistent with observed initial aerosol growth. Continued gas-phase oxidation of these semivolatile species produces multifunctional low volatility compounds. This study elucidates the complex evolution of the gas-phase photooxidation chemistry and subsequent SOA formation through a novel approach comparing molecular level information from a chemical ionization mass spectrometer (CIMS) and high m/z ion fragments from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Combination of these techniques reveals that particle-phase chemistry leading to peroxyhemiacetal formation is the likely mechanism by which these species are incorporated in the particle phase. The current findings are relevant toward understanding atmospheric SOA formation and aging from the "unresolved complex mixture," comprising, in part, long-chain alkanes.

  7. Mechanisms of zinc incorporation in aluminosilicate crystalline structures and the leaching behaviour of product phases.

    PubMed

    Tang, Yuanyuan; Shih, Kaimin

    2015-01-01

    This study quantitatively evaluates a waste-to-resource strategy of blending zinc-laden sludge and clay material for low-cost ceramic products. Using ZnO as the simulated zinc-laden sludge to sinter with kaolinite, both zinc aluminate spinel (ZnAl₂O₄) and willemite (Zn₂SiO₄) phases were formed during the sintering process. To analyse the details of zinc incorporation reactions, γ-Al₂O₃and quartz were further used as precursors to observe ZnAl₂O₄and Zn₂SiO₄formations. By firing the ZnO mixtures and their corresponding precursors at 750-1350°C for 3 h, the efficiency of zinc transformation was determined through Rietveld refinement analyses of X-ray diffraction data. The results also show different incorporation behaviour for kaolinite and mullite precursors during the formation of ZnAl2O₄and Zn2SiO₄in the system. In addition, with a competitive formation between ZnAl₂O₄and Zn₂SiO₄, the ZnAl₂O₄spinel phase is predominant at temperatures higher than 1050°C. This study used a prolonged leaching test modified from the US Environmental Protection Agency's toxicity characteristic leaching procedure to evaluate ZnO, ZnAl₂O₄, and Zn₂SiO₄product phases. The zinc concentrations in ZnO and Zn₂SiO₄leachates were about two orders of magnitude higher than that of ZnAl₂O₄ leachate at the end of the experiment, indicating that ZnAl₂O₄formation is the preferred stabilization mechanism for incorporating zinc in ceramic products.

  8. Insights into secondary organic aerosol formation mechanisms from measured gas/particle partitioning of specific organic tracer compounds.

    PubMed

    Zhao, Yunliang; Kreisberg, Nathan M; Worton, David R; Isaacman, Gabriel; Weber, Robin J; Liu, Shang; Day, Douglas A; Russell, Lynn M; Markovic, Milos Z; VandenBoer, Trevor C; Murphy, Jennifer G; Hering, Susanne V; Goldstein, Allen H

    2013-04-16

    In situ measurements of organic compounds in both gas and particle phases were made with a thermal desorption aerosol gas chromatography (TAG) instrument. The gas/particle partitioning of phthalic acid, pinonaldehyde, and 6,10,14-trimethyl-2-pentadecanone is discussed in detail to explore secondary organic aerosol (SOA) formation mechanisms. Measured fractions in the particle phase (f(part)) of 6,10,14-trimethyl-2-pentadecanone were similar to those expected from the absorptive gas/particle partitioning theory, suggesting that its partitioning is dominated by absorption processes. However, f(part) of phthalic acid and pinonaldehyde were substantially higher than predicted. The formation of low-volatility products from reactions of phthalic acid with ammonia is proposed as one possible mechanism to explain the high f(part) of phthalic acid. The observations of particle-phase pinonaldehyde when inorganic acids were fully neutralized indicate that inorganic acids are not required for the occurrence of reactive uptake of pinonaldehyde on particles. The observed relationship between f(part) of pinonaldehyde and relative humidity suggests that the aerosol water plays a significant role in the formation of particle-phase pinonaldehyde. Our results clearly show it is necessary to include multiple gas/particle partitioning pathways in models to predict SOA and multiple SOA tracers in source apportionment models to reconstruct SOA.

  9. Third phase formation in extraction of thorium nitrate by mixtures of trialkyl phosphates

    SciTech Connect

    Srinivasan, T.G.; Dhamodaran, R.; Suresh, A.; Vasudeva Rao, P.R.; Vijayasaradhi, S.

    1998-07-01

    This paper reports the results of the studies on third place formation during the extraction of thorium nitrate from zero free acidity solutions by mixtures of trialkyl phosphates. The phosphates used are tri n-butyl phosphate(TBP), triiso butyl phosphate(TiBP), tri sec butyl phosphate (TsBP) and tri n-amyl phosphate(TAP). The results indicate that small additions of a homologous phosphate can alter the Limiting Organic Concentration (LOC) above which the third phase formation takes place and thus can be advantageously utilized. Use of mixtures of the trialkyl phosphates as extractant can thus obviate the need for adding modifiers such as alcohols to the organic phase for avoiding third phase formation.

  10. Thalamic theta phase alignment predicts human memory formation and anterior thalamic cross-frequency coupling.

    PubMed

    Sweeney-Reed, Catherine M; Zaehle, Tino; Voges, Jürgen; Schmitt, Friedhelm C; Buentjen, Lars; Kopitzki, Klaus; Hinrichs, Hermann; Heinze, Hans-Jochen; Rugg, Michael D; Knight, Robert T; Richardson-Klavehn, Alan

    2015-05-20

    Previously we reported electrophysiological evidence for a role for the anterior thalamic nucleus (ATN) in human memory formation (Sweeney-Reed et al., 2014). Theta-gamma cross-frequency coupling (CFC) predicted successful memory formation, with the involvement of gamma oscillations suggesting memory-relevant local processing in the ATN. The importance of the theta frequency range in memory processing is well-established, and phase alignment of oscillations is considered to be necessary for synaptic plasticity. We hypothesized that theta phase alignment in the ATN would be necessary for memory encoding. Further analysis of the electrophysiological data reveal that phase alignment in the theta rhythm was greater during successful compared with unsuccessful encoding, and that this alignment was correlated with the CFC. These findings support an active processing role for the ATN during memory formation.

  11. Solvothermal Synthesis and Formation Mechanism of Potassium Sodium Niobate Mesocrystals Under Low Alkaline Conditions.

    PubMed

    Gu, QiLin; Zhu, Kongjun; Liu, Jinsong; Wang, Jing; Qiu, Jinhao; Cao, Yang; Liu, Pengcheng; Yao, Linlin

    2015-07-01

    Pure-phase (K, Na)NbO3 (KNN) powders with orthorhombic symmetry were successfully synthesized by solvothermal method using isopropanol as solvent, without the addition of water. The as-prepared powders were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectrometry to show the variation of phase, morphology, size distribution and chemical composition under different synthetic conditions, such as fill factors (FF) of the solvothermal system and alkalinity of the starting solution. Compared with the traditional hydrothermal method and the so-called solvothermal method (water aided in fact), small grains with well crystallinity were obtained using 100% isopropanol as reaction medium. The results indicate that both fill factor and alkalinity have significant effects on the phase structure and size distribution of the as-obtained KNN powders. Pure orthorhombic perovskite-structured KNN powders with a grain size of 100 nm were synthesized at the following condition: reaction time, 16 h; reaction temperature, 240 °C; fill factor, 70%; and alkalinity, 1 M. Small grains (~100 nm) tend to form mesocrystals (~10 µm) with tetrakaidecahedron structures, and the possible formation mechanism was proposed. The solvothermal method without the addition of water is a promising alternative to synthesize pure and refined powders under mild reaction conditions.

  12. Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

    PubMed

    Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

    2016-03-10

    Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

  13. Structural, electronic and mechanical properties of sp(3)-hybridized BN phases.

    PubMed

    Zhou, Rulong; Dai, Jun; Cheng Zeng, Xiao

    2017-03-30

    Motivated by the discovery of new phases of carbon under cold high-pressure compression, we performed a global structure search of high-pressure phases of boron nitride (BN). Ten new bulk phases were identified, each energetically more stable than the graphite-like hexagonal BN (h-BN) under high pressures. All ten high-pressure phases could be viewed as involving a stacking of buckled h-BN layers. Some of these solid structures can be fabricated through the cold high-pressure compression of h-BN films. According to the buckling of the h-BN layers, the new BN phases could be classified into three groups. The atomic structures, relative stabilities, electronic structures, and mechanical properties were studied in detail. A strong dependence of the relative stability, band structure, and mechanical properties on the buckling of h-BN was observed. The computed electronic band structures suggested that most of the high-pressure BN phases were insulators with wide and indirect band gaps. The calculated elastic constants and hardness suggested that several of the BN structures were superhard materials with potential applications in materials science and engineering. The computed transition paths indicated that the direct transition from h-BN to four of the new sp(3)-hybridized BN structures, or specifically to w-BN or bct-BN, were likely to occur through cold compression. For the other five of the new BN structures, although deeper local minima existed in the transition path, their formation through cold compression of h-BN was still plausible due to the low transition barrier from the deeper local minima to the targeted structure.

  14. Investigation of phase separation behavior and formation of plasmonic nanocomposites from polypeptide-gold nanorod nanoassemblies.

    PubMed

    Huang, Huang-Chiao; Nanda, Alisha; Rege, Kaushal

    2012-04-24

    Genetically engineered elastin-like polypeptides (ELP) can be interfaced with cetyltrimethyl ammonium bromide (CTAB)-stabilized gold nanorods (GNRs) resulting in the formation of stable dispersions (nanoassemblies). Increasing the dispersion temperature beyond the ELP transition temperature results in phase separation and formation of solid-phase ELP-GNR matrices (nanocomposites). Here, we investigated different physicochemical conditions that influence nanocomposite formation from temperature-induced phase separation of ELP-GNR nanoassemblies. The presence of cetyltrimethyl ammonium bromide (CTAB), used to template the formation of gold nanorods, plays a significant role in the phase separation behavior, with high concentrations of the surfactant leading to dramatic enhancements in ELP transition temperature. Nanocomposites could be generated at 37 °C in the presence of low CTAB concentrations (<1.5 mM); higher concentrations of CTAB necessitated higher temperatures (60 °C) due to elevated transition temperatures. The concentration of gold nanorods, however, had minimal influence on the phase separation behavior and nanocomposite formation. Further analysis of the kinetics of nanocomposite formation using a mathematical model indicated that CTAB largely influenced the early event of coacervation of ELP-GNR nanoassemblies leading to nanocomposites, but had minimal effect on nanocomposite maturation, which is a later-stage longer event. Finally, nanocomposites prepared in the presence of low CTAB concentrations demonstrated a superior photothermal response following laser irradiation compared to those generated using higher CTAB concentrations. Our results on understanding the formation of plasmonic/photothermal ELP-GNR nanocomposites have significant implications for tissue engineering, regenerative medicine, and drug delivery.

  15. Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

    NASA Astrophysics Data System (ADS)

    Beardsley, Ross L.; Jang, Myoseon

    2016-05-01

    The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+], mol L-1) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of photooxidation products and sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (eight groups) and aerosol phase reactivity (six groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid-catalyzed reactions and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx (VOC - volatile organic compound). The model is validated using isoprene photooxidation experiments performed in the dual, outdoor University of Florida Atmospheric PHotochemical Outdoor Reactor (UF APHOR) chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total organic mass formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H

  16. Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

    NASA Astrophysics Data System (ADS)

    Beardsley, R. L.; Jang, M.

    2015-11-01

    The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+]) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of the photooxidation products and the sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (8 groups) and aerosol phase reactivity (6 groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid catalyzed reactions, and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx. The model is validated using isoprene photooxidation experiments performed in the dual, outdoor UF APHOR chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total OM formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC, and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H+] but is dynamically related to all three parameters. For VOC / NOx > 10, with increasing NOx both experimental and

  17. The Mechanism of First Raindrops Formation in Deep Convective Clouds

    SciTech Connect

    Khain, Alexander; Prabha, Thara; Benmoshe, Nir; Pandithurai, G.; Ovchinnikov, Mikhail

    2013-08-22

    The formation of first raindrops in deep convective clouds is investigated. A combination of observational data analysis and 2-D and 3-D numerical bin microphysical simulations of deep convective clouds suggests that the first raindrops form at the top of undiluted or slightly diluted cores. It is shown that droplet size distributions in these regions are wider and contain more large droplets than in diluted volumes. The results of the study indicate that the initial raindrop formation is determined by the basic microphysical processes within ascending adiabatic volumes. It allows one to predict the height of the formation of first raindrops considering the processes of nucleation, diffusion growth and collisions. The results obtained in the study explain observational results reported by Freud and Rosenfeld (2012) according to which the height of first raindrop formation depends linearly on the droplet number concentration at cloud base. The results also explain why a simple adiabatic parcel model can reproduce this dependence. The present study provides a physical basis for retrieval algorithms of cloud microphysical properties and aerosol properties using satellites proposed by Rosenfeld et al. ( 2012). The study indicates that the role of mixing and entrainment in the formation of the first raindrops is not of crucial importance. It is also shown that low variability of effective and mean volume radii along horizontal traverses, as regularly observed by in situ measurements, can be simulated by high-resolution cloud models, in which mixing is parameterized by a traditional 1.5 order turbulence closure scheme.

  18. Study the formation of metastable crystalline phases from amorphous metallic systems with an integrated approach

    NASA Astrophysics Data System (ADS)

    Ye, Zhuo; Zhang, Feng; Sun, Yang; Mendelev, Mikhail; Ott, Ryan; Park, Eun-Soo; Besser, Matt; Kramer, Matt; Wang, Cai-Zhuang; Ho, Kai-Ming

    2015-03-01

    An efficient genetic algorithm (GA) is integrated with experimental diffraction data to solve a metastable Al20Sm4 phase that evolves during rapid solidification of an amorphous Al-10%Sm alloy produced by magnetron sputtering. The excellent match between calculated and experimental X-ray diffraction patterns confirms that this new phase appeared in the crystallization of the alloy. We discover the strong similarity of the underlying atomic structure between the amorphous alloy and this phase. Both phases share the same Sm-centered motif, providing a low-barrier pathway to form this Al20Sm4phase in the glass matrix at low temperatures. Molecular dynamic simulations of crystal growth from the liquid phase predict the formation of disordered anti-site defects in the devitrified crystal.

  19. Investigation of wing crack formation with a combined phase-field and experimental approach

    NASA Astrophysics Data System (ADS)

    Lee, Sanghyun; Reber, Jacqueline E.; Hayman, Nicholas W.; Wheeler, Mary F.

    2016-08-01

    Fractures that propagate off of weak slip planes are known as wing cracks and often play important roles in both tectonic deformation and fluid flow across reservoir seals. Previous numerical models have produced the basic kinematics of wing crack openings but generally have not been able to capture fracture geometries seen in nature. Here we present both a phase-field modeling approach and a physical experiment using gelatin for a wing crack formation. By treating the fracture surfaces as diffusive zones instead of as discontinuities, the phase-field model does not require consideration of unpredictable rock properties or stress inhomogeneities around crack tips. It is shown by benchmarking the models with physical experiments that the numerical assumptions in the phase-field approach do not affect the final model predictions of wing crack nucleation and growth. With this study, we demonstrate that it is feasible to implement the formation of wing cracks in large scale phase-field reservoir models.

  20. Variations in cometary dust composition from Giotto to Rosetta, clues to their formation mechanisms

    NASA Astrophysics Data System (ADS)

    Engrand, Cécile; Duprat, Jean; Dartois, Emmanuel; Benzerara, Karim; Leroux, Hugues; Baklouti, Donia; Bardyn, Anaïs; Briois, Christelle; Cottin, Hervé; Fischer, Henning; Fray, Nicolas; Godard, Marie; Hilchenbach, Martin; Langevin, Yves; Paquette, John; Rynö, Jouni; Schulz, Rita; Silén, Johan; Stenzel, Oliver; Thirkell, Laurent; Cosima Team

    2016-11-01

    This paper reviews the current knowledge on the composition of cometary dust (ice, minerals and organics) in order to constrain their origin and formation mechanisms. Comets have been investigated by astronomical observations, space missions (Giotto to Rosetta), and by the analysis of cometary dust particles collected on Earth, chondritic porous interplanetary dust particles (CP-IDPs) and ultracarbonaceous Antarctic micrometeorites (UCAMMs). Most ices detected in the dense phases of the interstellar medium (ISM) have been identified in cometary volatiles. However, differences also suggest that cometary ices cannot be completely inherited from the ISM. Cometary minerals are dominated by crystalline Mg-rich silicates, Fe sulphides and glassy phases including GEMS (glass with embedded metals and sulphides). The crystalline nature and refractory composition of a significant fraction of the minerals in comets imply a high temperature formation/processing close to the proto-Sun, resetting a possible presolar signature of these phases. These minerals were further transported up to the external regions of the disc and incorporated in comet nuclei. Cometary matter contains a low abundance of isotopically anomalous minerals directly inherited from the presolar cloud. At least two different kinds of organic matter are found in dust of cometary origin, with low or high nitrogen content. N-poor organic matter is also observed in primitive interplanetary materials (like carbonaceous chondrites) and its origin is debated. The N-rich organic matter is only observed in CP-IDPs and UCAMMs and can be formed by Galactic cosmic ray irradiation of N2- and CH4-rich icy surface at large heliocentric distance beyond a `nitrogen snow line'.

  1. Development of theory-based health messages: three-phase programme of formative research.

    PubMed

    Epton, Tracy; Norman, Paul; Harris, Peter; Webb, Thomas; Snowsill, F Alexandra; Sheeran, Paschal

    2015-09-01

    Online health behaviour interventions have great potential but their effectiveness may be hindered by a lack of formative and theoretical work. This paper describes the process of formative research to develop theoretically and empirically based health messages that are culturally relevant and can be used in an online intervention to promote healthy lifestyle behaviours among new university students. Drawing on the Theory of Planned Behaviour, a three-phase programme of formative research was conducted with prospective and current undergraduate students to identify (i) modal salient beliefs (the most commonly held beliefs) about fruit and vegetable intake, physical activity, binge drinking and smoking, (ii) which beliefs predicted intentions/behaviour and (iii) reasons underlying each of the beliefs that could be targeted in health messages. Phase 1, conducted with 96 pre-university college students, elicited 56 beliefs about the behaviours. Phase 2, conducted with 3026 incoming university students, identified 32 of these beliefs that predicted intentions/behaviour. Phase 3, conducted with 627 current university students, elicited 102 reasons underlying the 32 beliefs to be used to construct health messages to bolster or challenge these beliefs. The three-phase programme of formative research provides researchers with an example of how to develop health messages with a strong theoretical- and empirical base for use in health behaviour change interventions.

  2. Development of theory-based health messages: three-phase programme of formative research

    PubMed Central

    Epton, Tracy; Norman, Paul; Harris, Peter; Webb, Thomas; Snowsill, F. Alexandra; Sheeran, Paschal

    2015-01-01

    Online health behaviour interventions have great potential but their effectiveness may be hindered by a lack of formative and theoretical work. This paper describes the process of formative research to develop theoretically and empirically based health messages that are culturally relevant and can be used in an online intervention to promote healthy lifestyle behaviours among new university students. Drawing on the Theory of Planned Behaviour, a three-phase programme of formative research was conducted with prospective and current undergraduate students to identify (i) modal salient beliefs (the most commonly held beliefs) about fruit and vegetable intake, physical activity, binge drinking and smoking, (ii) which beliefs predicted intentions/behaviour and (iii) reasons underlying each of the beliefs that could be targeted in health messages. Phase 1, conducted with 96 pre-university college students, elicited 56 beliefs about the behaviours. Phase 2, conducted with 3026 incoming university students, identified 32 of these beliefs that predicted intentions/behaviour. Phase 3, conducted with 627 current university students, elicited 102 reasons underlying the 32 beliefs to be used to construct health messages to bolster or challenge these beliefs. The three-phase programme of formative research provides researchers with an example of how to develop health messages with a strong theoretical- and empirical base for use in health behaviour change interventions. PMID:24504361

  3. Identification of the formation phases of filamentary damage induced by nanosecond laser pulses in bulk fused silica

    SciTech Connect

    Shen, Chao; Xu, Zhongjie; Chambonneau, Maxime E-mail: jiangtian198611@163.com; Cheng, Xiang'ai; Jiang, Tian E-mail: jiangtian198611@163.com

    2015-09-14

    Employing a pump-probe polarization-based two-frame shadowgraphy setup, the formation of filamentary damage induced in bulk fused silica by a nanosecond pulse at 1064 nm is investigated with a picosecond probe. Three different phases are exhibited in the damage experiments. The first phase is the formation of a micrometric plasma channel along the laser direction during the beginning of the pulse likely caused by multi-photon ionization. This channel exhibits growth during ∼400 ps, and the newly grown plasma is discrete. Then, during the end of the pulse, this channel evolves into a tadpole-like morphology showing an elliptical head upstream the laser flux followed by a thin tail. This observed asymmetry is attributed to shielding effects caused by both the plasma and hot modified silica. Once the damage shows its almost final morphology, a last phase consists in the launch of a pressure wave enlarging it after the laser pulse. The physical mechanisms that might be involved in the formation of plasma channels are discussed. The experimental data are first confronted to the moving breakdown model which overestimates the filamentary damage length. Finally, taking into account the temporal shape of the laser pulses, the coupling between Kerr-induced self-focusing and stimulated Brillouin scattering is discussed to interpret the observations.

  4. What is the mechanism of formation of hydroxyaluminosilicates?

    PubMed Central

    Beardmore, James; Lopez, Xabier; Mujika, Jon I.; Exley, Christopher

    2016-01-01

    The formation of hydroxyaluminosilicates is integral to the biogeochemical cycles of aluminium and silicon. The unique inorganic chemistry which underlies their formation explains the non-essentiality in biota of both of these elements. However, the first steps in the formation of hydroxyaluminosilicates were hitherto only theoretical and plausibly only accessible in silico. Herein we have used computational chemistry to identify and define for the first time these unique and ultimately critically important reaction steps. We have used density-functional theory combined with solvent continuum models to confirm first, the nature of the reactants, an aluminium hydroxide dimer and silicic acid, second, the reaction products, two distinct hydroxyaluminosilicates A and B and finally, how these are the precursors to highly insoluble hydroxyaluminosilicates the role of which has been and continues to be to keep inimical aluminium out of biota. PMID:27477995

  5. Examination of Mechanisms and Fuel-Molecular Effects on Soot Formation.

    DTIC Science & Technology

    1988-02-13

    11 TABLE V - REACTIONS AND RATE COEFFICIENTS FOR STEPS LEADING TO FORMATION OF AROMATIC RING .... .............. . 12 S TABLE...VI REACTIONS LEADING TO FORMATION OF POLYCYCLIC HYDROCARBONS ....... ..................... . 13 -V; R88-957047 Examination of Mechanisms and Fuel...corporate-sponsorship to facilitate interpreting data from CHEMKIN and CHEMSEN. Plots of 1. Species concentrations 2. Reaction contribution to the formation

  6. Delta ferrite-containing austenitic stainless steel resistant to the formation of undesirable phases upon aging

    DOEpatents

    Leitnaker, J.M.

    Austenitic stainless steel alloys containing delta ferrite, such as are used as weld deposits, are protected against the transformation of delta ferrite to sigma phase during aging by the presence of carbon plus nitrogen in a weight percent 0.015 to 0.030 times the volume percent ferrite present in the alloy. The formation of chi phase upon aging is controlled by controlling the Mo content.

  7. Delta ferrite-containing austenitic stainless steel resistant to the formation of undesirable phases upon aging

    DOEpatents

    Leitnaker, James M.

    1981-01-01

    Austenitic stainless steel alloys containing delta ferrite, such as are used as weld deposits, are protected against the transformation of delta ferrite to sigma phase during aging by the presence of carbon plus nitrogen in a weight percent 0.015-0.030 times the volume percent ferrite present in the alloy. The formation of chi phase upon aging is controlled by controlling the Mo content.

  8. Mechanism of membrane tube formation induced by adhesive nanocomponents.

    PubMed

    Šarić, Anđela; Cacciuto, Angelo

    2012-11-02

    We report numerical simulations of membrane tubulation driven by large colloidal particles. Using Monte Carlo simulations we study how the process depends on particle size and binding strength, and present accurate free energy calculations to sort out how tube formation compares with the competing budding process. We find that tube formation is a result of the collective behavior of the particles adhering on the surface, and it occurs for binding strengths that are smaller than those required for budding. We also find that long linear aggregates of particles forming on the membrane surface act as nucleation seeds for tubulation by lowering the free energy barrier associated to the process.

  9. [Mechanisms of formation and biological role of protein carbamates].

    PubMed

    Mel'nichuk, D A

    1985-01-01

    Experimental data are presented evidencing for the fact that tissue proteins under conditions in vivo are subjected to enzymic carboxylation with formation of carbaminic groups. In this case a charge variation in definite sites of protein molecule is observed, which specifies variation of the protein conformation and biological properties. Basic regularities of protein carbamate formation reactions are revealed with factors affecting their intensity enumerated. The reactions are shown to be of great biological significance for the respiration processes, realization of hormonal effects of peptide and protein hormones as well as for regulation of tissue homeostasis under conditions of acidic-alkaline state variation in the organism.

  10. Molecule formation mechanisms of strontium mono fluoride in high-resolution continuum source electrothermal atomic absorption spectrometry.

    PubMed

    Ozbek, Nil; Akman, Suleyman

    2013-01-01

    In this study, the molecule formation mechanisms of strontium mono fluoride used for the determination of fluorine in a high-resolution continuum source atomic absorption spectrophotometer was investigated. To distinguish between the gas-phase and the condensed-phase mechanisms, the analyte (F) and the molecule forming element (Sr) were injected on the solid sampling platform manually, as mixed or separately, and the absorbances/peak shapes were compared. There was no significant difference between the absorbances. In addition, the peak shapes and the appearance times were almost the same for the two cases. It was proposed that the main pathway for SrF formation is a gas-phase combination reaction between Sr and F. When Sr and F were mixed on the platform, it was expected that at first SrF2 would be formed in the condensed phase, and then at elevated temperatures it was partly decomposed while either losing one F atom to form SrF, or completely decomposed to its atoms in the gas phase.

  11. Role of nitric oxide and prostaglandins in the bone formation response to mechanical loading.

    PubMed

    Chow, J W

    2000-10-01

    Nitric oxide and prostaglandins are crucial early mediators in mechanically induced bone formation. They are also responsible for the associated induction of gene expression of c-fos and IGF-1 in osteocytes, key mechanosensory cells in bone. Insight into the cellular and molecular mechanisms underlying bone formation has important implications for the maintenance of structural competence of bone.

  12. MECHANISMS OF NITROUS OXIDE FORMATION IN COAL FLAMES

    EPA Science Inventory

    The paper gives results of a study, using both detailed kinetic modeling and plug-flow simulator experiments, to investigate an unknown mechanism by which N2O is formed in coal flames. This mechanism has considerable importance in determining the influence of common and advanced ...

  13. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation.

    PubMed

    Shiraiwa, Manabu; Yee, Lindsay D; Schilling, Katherine A; Loza, Christine L; Craven, Jill S; Zuend, Andreas; Ziemann, Paul J; Seinfeld, John H

    2013-07-16

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.

  14. Triggering star formation by both radiative and mechanical AGN feedback

    NASA Astrophysics Data System (ADS)

    Liu, Chao; Gan, Zhao-Ming; Xie, Fu-Guo

    2013-08-01

    We perform two dimensional hydrodynamic numerical simulations to study the positive active galactic nucleus (AGN) feedback which triggers, rather than suppresses, star formation. Recently, it was shown by Nayakshin et al. and Ishibashi et al. that star formation occurs when the cold interstellar medium (ISM) is squeezed by the impact of mass outflow or radiation pressure, respectively. Mass outflow is ubiquitous in this astrophysical context, and radiation pressure is also important if the AGN is luminous. For the first time in this subject, we incorporate both mass outflow feedback and radiative feedback into our model. Consequently, the ISM is shocked into shells by the AGN feedback, and these shells soon fragment into clumps and filaments because of Rayleigh-Taylor and thermal instabilities. We have two major findings: (1) the star formation rate can indeed be very large in the clumps and filaments. However, the resultant star formation rate density is too large compared with previous works, which is mainly because we ignore the fact that most of the stars that are formed would be disrupted when they move away from the galactic center. (2) Although radiation pressure feedback has a limited effect, when mass outflow feedback is also included, they reinforce each other. Specifically, in the gas-poor case, mass outflow is always the dominant contributor to feedback.

  15. Kinetics and mechanism of soot formation in hydrocarbon combustion

    NASA Technical Reports Server (NTRS)

    Frenklach, Michael

    1990-01-01

    The focus of this work was on kinetic modeling. The specific objectives were: detailed modeling of soot formation in premixed flames, elucidation of the effects of fuel structure on the pathway to soot, and the development of a numerical technique for accurate modeling of soot particle coagulation and surface growth. Those tasks were successfully completed and are briefly summarized.

  16. Exploring Technology Supported Collaborative and Cooperative Group Formation Mechanisms

    ERIC Educational Resources Information Center

    Carapina, Mia; Boticki, Ivica

    2015-01-01

    This paper reflects on the systematic literature review paper (in progress), which analyzes technology enhanced collaborative and cooperative learning in elementary education worldwide from 2004 to 2015, focusing on the exploration of technology mediated group formation. The review paper reports on only a few cases of technology supported methods…

  17. Phase Formation and Transformations in Transmutation Fuel Materials for the LIFE Engine Part I - Path Forward

    SciTech Connect

    Turchi, P E; Kaufman, L; Fluss, M J

    2008-11-10

    The current specifications of the LLNL fusion-fission hybrid proposal, namely LIFE, impose severe constraints on materials, and in particular on the nuclear fissile or fertile nuclear fuel and its immediate environment. This constitutes the focus of the present report with special emphasis on phase formation and phase transformations of the transmutation fuel and their consequences on particle and pebble thermal, chemical and mechanical integrities. We first review the work that has been done in recent years to improve materials properties under the Gen-IV project, and with in particular applications to HTGR and MSR, and also under GNEP and AFCI in the USA. Our goal is to assess the nuclear fuel options that currently exist together with their issues. Among the options, it is worth mentioning TRISO, IMF, and molten salts. The later option will not be discussed in details since an entire report is dedicated to it. Then, in a second part, with the specific LIFE specifications in mind, the various fuel options with their most critical issues are revisited with a path forward for each of them in terms of research, both experimental and theoretical. Since LIFE is applicable to very high burn-up of various fuels, distinctions will be made depending on the mission, i.e., energy production or incineration. Finally a few conclusions are drawn in terms of the specific needs for integrated materials modeling and the in depth knowledge on time-evolution thermochemistry that controls and drastically affects the performance of the nuclear materials and their immediate environment. Although LIFE demands materials that very likely have not yet been fully optimized, the challenge are not insurmountable and a well concerted experimental-modeling effort should lead to dramatic advances that should well serve other fission programs such as Gen-IV, GNEP, AFCI as well as the international fusion program, ITER.

  18. Three-phase heaters with common overburden sections for heating subsurface formations

    SciTech Connect

    Vinegar, Harold J

    2012-02-14

    A heating system for a subsurface formation is described. The heating system includes three substantially u-shaped heaters with first end portions of the heaters being electrically coupled to a single, three-phase wye transformer and second end portions of the heaters being electrically coupled to each other and/or to ground. The three heaters may enter the formation through a first common wellbore and exit the formation through a second common wellbore so that the magnetic fields of the three heaters at least partially cancel out in the common wellbores.

  19. Phase field simulations of autocatalytic formation of alpha lamellar colonies in Ti-6Al-4V

    SciTech Connect

    Radhakrishnan, Bala; Gorti, Sarma; Babu, Suresh Sudharsanam

    2016-09-13

    Here, we present phase field simulations incorporating energy contributions due to thermodynamics, and anisotropic interfacial and strain energies, to demonstrate the nucleation and growth of multiple variants of alpha from beta in Ti-6Al-4V under isothermal conditions. The simulations focused on the effect of thermodynamic driving force and nucleation rate on the morphology of the transformed alpha assuming that the partitioning of V between beta and alpha is negligible for short isothermal holds. The results indicate that a high nucleation rate favors the formation of the basket-weave structure. However, at a lower nucleation rate the simulations show the intragranular nucleation of a colony structure by an autocatalytic nucleation mechanism adjacent to a pre-existing alpha variant. New side-plates of the same variant appear to nucleate progressively and grow to form the colony. The isothermal simulation results are used to offer a possible explanation for the transition from a largely basket weave structure to a colony structure inside narrow layer bands occurring during continuous heating and cooling conditions encountered during laser additive manufacturing of Ti-6Al-4V.

  20. Phase field simulations of autocatalytic formation of alpha lamellar colonies in Ti-6Al-4V

    DOE PAGES

    Radhakrishnan, Bala; Gorti, Sarma; Babu, Suresh Sudharsanam

    2016-09-13

    Here, we present phase field simulations incorporating energy contributions due to thermodynamics, and anisotropic interfacial and strain energies, to demonstrate the nucleation and growth of multiple variants of alpha from beta in Ti-6Al-4V under isothermal conditions. The simulations focused on the effect of thermodynamic driving force and nucleation rate on the morphology of the transformed alpha assuming that the partitioning of V between beta and alpha is negligible for short isothermal holds. The results indicate that a high nucleation rate favors the formation of the basket-weave structure. However, at a lower nucleation rate the simulations show the intragranular nucleation ofmore » a colony structure by an autocatalytic nucleation mechanism adjacent to a pre-existing alpha variant. New side-plates of the same variant appear to nucleate progressively and grow to form the colony. The isothermal simulation results are used to offer a possible explanation for the transition from a largely basket weave structure to a colony structure inside narrow layer bands occurring during continuous heating and cooling conditions encountered during laser additive manufacturing of Ti-6Al-4V.« less

  1. Formate hydrogen lyase mediates stationary-phase deacidification and increases survival during sugar fermentation in acetoin-producing enterobacteria

    PubMed Central

    Vivijs, Bram; Haberbeck, Leticia U.; Baiye Mfortaw Mbong, Victor; Bernaerts, Kristel; Geeraerd, Annemie H.; Aertsen, Abram; Michiels, Chris W.

    2015-01-01

    Two fermentation types exist in the Enterobacteriaceae family. Mixed-acid fermenters produce substantial amounts of lactate, formate, acetate, and succinate, resulting in lethal medium acidification. On the other hand, 2,3-butanediol fermenters switch to the production of the neutral compounds acetoin and 2,3-butanediol and even deacidify the environment after an initial acidification phase, thereby avoiding cell death. We equipped three mixed-acid fermenters (Salmonella Typhimurium, S. Enteritidis and Shigella flexneri) with the acetoin pathway from Serratia plymuthica to investigate the mechanisms of deacidification. Acetoin production caused attenuated acidification during exponential growth in all three bacteria, but stationary-phase deacidification was only observed in Escherichia coli and Salmonella, suggesting that it was not due to the consumption of protons accompanying acetoin production. To identify the mechanism, 34 transposon mutants of acetoin-producing E. coli that no longer deacidified the culture medium were isolated. The mutations mapped to 16 genes, all involved in formate metabolism. Formate is an end product of mixed-acid fermentation that can be converted to H2 and CO2 by the formate hydrogen lyase (FHL) complex, a reaction that consumes protons and thus can explain medium deacidification. When hycE, encoding the large subunit of hydrogenase 3 that is part of the FHL complex, was deleted in acetoin-producing E. coli, deacidification capacity was lost. Metabolite analysis in E. coli showed that introduction of the acetoin pathway reduced lactate and acetate production, but increased glucose consumption and formate and ethanol production. Analysis of a hycE mutant in S. plymuthica confirmed that medium deacidification in this organism is also mediated by FHL. These findings improve our understanding of the physiology and function of fermentation pathways in Enterobacteriaceae. PMID:25762991

  2. Microstructure and Mechanical Properties of Laves Phase-strengthened Fe-Cr-Zr Alloys

    SciTech Connect

    Tan, Lizhen; Yang, Ying

    2014-12-05

    Laves phase-reinforced alloys have shown some preliminary promising performance at room temperatures. This paper aims at evaluating mechanical properties of Laves phase-strengthened alloys at elevated temperatures. Three Fe-Cr-Zr alloys were designed to favor the formation of eutectic microstructures containing Laves and body-centered cubic phases with the aid of thermodynamic calculations. Microstructural characterization was carried out on the alloys in as-processed and aged states using optical microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction. The effect of thermal aging and alloy composition on microstructure has been discussed based on microstructural characterization results. Mechanical properties have been evaluated by means of Vickers microhardness measurements, tensile testing at temperatures up to 973.15 K (700.15 °C), and creep testing at 873.15 K (600.15 °C) and 260 MPa. Alloys close to the eutectic composition show significantly superior strength and creep resistance compared to P92. Finally, however, their low tensile ductility may limit their applications at relatively low temperatures.

  3. Microstructure and Mechanical Properties of Laves Phase-strengthened Fe-Cr-Zr Alloys

    DOE PAGES

    Tan, Lizhen; Yang, Ying

    2014-12-05

    Laves phase-reinforced alloys have shown some preliminary promising performance at room temperatures. This paper aims at evaluating mechanical properties of Laves phase-strengthened alloys at elevated temperatures. Three Fe-Cr-Zr alloys were designed to favor the formation of eutectic microstructures containing Laves and body-centered cubic phases with the aid of thermodynamic calculations. Microstructural characterization was carried out on the alloys in as-processed and aged states using optical microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction. The effect of thermal aging and alloy composition on microstructure has been discussed based on microstructural characterization results. Mechanical properties have been evaluated by meansmore » of Vickers microhardness measurements, tensile testing at temperatures up to 973.15 K (700.15 °C), and creep testing at 873.15 K (600.15 °C) and 260 MPa. Alloys close to the eutectic composition show significantly superior strength and creep resistance compared to P92. Finally, however, their low tensile ductility may limit their applications at relatively low temperatures.« less

  4. Star formation and multi-phase interstellar medium in the first galaxies

    NASA Astrophysics Data System (ADS)

    Ricotti, M.; Parry, O.; Polisensky, E.; Bovill, M.

    Star formation and metal enrichment in the first galaxies is discussed emphasizing similarities to the properties of dwarf spheroidal galaxies in the Local Universe. I present preliminary results from new radiation-hydrodynamic cosmological simulations for the formation of the first galaxies performed with the ART code. The simulations include a detailed model for star formation in a multi-phase ISM, including H_2 formation catalyzed by H- and on dust grains. The first metals are provided by Population III stars, while Population II star formation takes place in resolved molecular clouds. The properties of the first galaxies in these new simulations are in agreement with previous lower resolution simulations in which was found remarkable similarities between the fossils of the first galaxies and the faintest dwarf spheroidal galaxies in the Local Group.

  5. Structural basis of Staphylococcus epidermidis biofilm formation: mechanisms and molecular interactions.

    PubMed

    Büttner, Henning; Mack, Dietrich; Rohde, Holger

    2015-01-01

    Staphylococcus epidermidis is a usually harmless commensal bacterium highly abundant on the human skin. Under defined predisposing conditions, most importantly implantation of a medical device, S. epidermidis, however, can switch from a colonizing to an invasive life style. The emergence of S. epidermidis as an opportunistic pathogen is closely linked to the biofilm forming capability of the species. During the past decades, tremendous advance regarding our understanding of molecular mechanisms contributing to surface colonization has been made, and detailed information is available for several factors active during the primary attachment, accumulative or dispersal phase of biofilm formation. A picture evolved in which distinct factors, though appearing to be redundantly organized, take over specific and exclusive functions during biofilm development. In this review, these mechanisms are described in molecular detail, with a highlight on recent insights into multi-functional S. epidermidis cell surface proteins contributing to surface adherence and intercellular adhesion. The integration of distinct biofilm-promoting factors into regulatory networks is summarized, with an emphasis on mechanism that could allow S. epidermidis to flexibly adapt to changing environmental conditions present during colonizing or invasive life-styles.

  6. Structural basis of Staphylococcus epidermidis biofilm formation: mechanisms and molecular interactions

    PubMed Central

    Büttner, Henning; Mack, Dietrich; Rohde, Holger

    2015-01-01

    Staphylococcus epidermidis is a usually harmless commensal bacterium highly abundant on the human skin. Under defined predisposing conditions, most importantly implantation of a medical device, S. epidermidis, however, can switch from a colonizing to an invasive life style. The emergence of S. epidermidis as an opportunistic pathogen is closely linked to the biofilm forming capability of the species. During the past decades, tremendous advance regarding our understanding of molecular mechanisms contributing to surface colonization has been made, and detailed information is available for several factors active during the primary attachment, accumulative or dispersal phase of biofilm formation. A picture evolved in which distinct factors, though appearing to be redundantly organized, take over specific and exclusive functions during biofilm development. In this review, these mechanisms are described in molecular detail, with a highlight on recent insights into multi-functional S. epidermidis cell surface proteins contributing to surface adherence and intercellular adhesion. The integration of distinct biofilm-promoting factors into regulatory networks is summarized, with an emphasis on mechanism that could allow S. epidermidis to flexibly adapt to changing environmental conditions present during colonizing or invasive life-styles. PMID:25741476

  7. Santilli’s hadronic mechanics of formation of deuteron

    SciTech Connect

    Dhondge, Sudhakar S.

    2015-03-10

    In the present communication a brief review of the structure of deuteron proposed by Professor Santilli [1, 2] and its physical properties have been presented. Although Deuteron is a simple molecule, quantum mechanics has been unable to explain its different properties like the spin, magnetic moment, binding energy, stability, charge radius, dipole moment, etc. However, the Hadronic Mechanics developed by Santilli and applied by him [1, 2] to deuteron has succeeded in explaining the above properties to the scientific satisfaction. Santilli proposed Deuteron as a three body system which could take care of all the insufficiencies of quantum mechanics.

  8. Structural and phase transformations during copper and iron mechanical alloying in liquid medium studied by Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Eryomina, Marina Anatol'evna; Lomayeva, Svetlana Fedorovna; Ul'yanov, Alexandr Leonidovich; Yelsukov, Evgeny Petrovich

    2016-03-01

    Mössbauer spectroscopy and X-ray diffraction have been used to study the kinetics of structural and phase transformations in Cu + 2 at% 57Fe during mechanical activation in liquid media (heptane, distilled water) and subsequent heat treatment (600 and 700 °C). The initial stages of mechanical alloying are associated with the transition of components to the nanostructural state. Iron atom groups form near the grain boundaries, and isolated iron atoms penetrate from the boundaries into the grains. Oxidation of groups of iron atoms that form highly dispersed phases of ternary oxide and magnetite occur in the initial stages of mechanical alloying of Cu + 2 at% 57Fe in water. The formation of the solid solution in the form of isolated iron atoms in the lattice of copper proceeds, regardless of the milling media used. Samples prepared in heptane contain carbon and oxygen, and upon heat treatment, carbide and oxide phases are formed.

  9. Initial stages of soot formation in thermal pyrolysis of acetylene. I. Mechanism for homogeneous pyrolysis of acetylene

    SciTech Connect

    Merkulov, A.A.; Ovsyannikov, A.A.; Polak, L.S.; Popov, V.T.; Pustilnikov, V.Yu. )

    1989-03-01

    A probable mechanism for the homogeneous pyrolysis of acetylene, using carbene reactions, is considered. Analysis of the energetics for the probable mechanism of the initiation reactions shows the rearrangement C{sub 2}H{sub 2} {yields}:CCH{sub 2} to be the most probable. Using the energetic barriers for simple carbene reactions and formation enthalpies for more complicated carbenes, the authors evaluated the activation energies for the reactions mechanism. The vibrational excitation of the products of carbene reactions is taken into account. Calculations of the acetylene conversion kinetics and yields of the main gas-phase pyrolysis products, based on the carbene molecular mechanism, show significantly better agreement with available experimental data as compared to those based on traditional radical mechanisms. The calculated time for the appearance of aromatic products is close to the measured induction times for the appearance of soot particles.

  10. Acute formation of lumbar discal cyst: what is the mechanism?

    PubMed

    Aydin, S; Kucukyuruk, B; Yildirim, H; Abuzayed, B; Bozkus, H; Vural, M

    2010-12-01

    Lumbar discal cysts are extremely rare pathologies, with only few reports describing these lesions in the literature. Moreover, their definite pathogenesis is still unknown, with proposed theories based on radialogic and histologic findings. In this report, the authors present an acute formation of a discal cyst, which is reported for the first time. Also, we center our case on the discussion of the possible pathogenesis. Also, this is the first case of discal cyst reported in Turkey. A 67-year-old woman, whose complaints, and clinical and radiological findings demonstrated lumbar disc herniation with acute Modic 1 degererative changes of the adjacent end plates of L3-4 level. After medical and physical therapies, follow-up lumbar MRI has been taken to demonstrate a discal cyst formation on the adjacent intervertebral disc, showed cranially migrated cyst superior posterior on herniated disc, in 2 weeks period. The patient was treated by microsurgical resection of the cyst, and her complaints resolved completely.

  11. Aging behavior and mechanical properties of maraging steels in the presence of submicrocrystalline Laves phase particles

    SciTech Connect

    Mahmoudi, A.; Ghavidel, M.R. Zamanzad; Nedjad, S. Hossein; Heidarzadeh, A.; Ahmadabadi, M. Nili

    2011-10-15

    Cold rolling and annealing of homogenized Fe-Ni-Mn-Mo-Ti-Cr maraging steels resulted in the formation of submicrocrystalline Fe{sub 2}(Mo,Ti) Laves phase particles. Optical and scanning electron microscopy, X-ray diffraction, tensile and hardness tests were used to study the microstructure, aging behavior and mechanical properties of the annealed steels. The annealed microstructures showed age hardenability during subsequent isothermal aging at 753 K. Ultrahigh fracture stress but poor tensile ductility was obtained after substantial age hardening in the specimens with 2% and 4% chromium. Increasing chromium addition up to 6% toughened the aged microstructure at the expense of the fracture stress by increasing the volume fraction of retained austenite. The Laves phase particles acted as crack nucleation sites during tensile deformation. - Highlights: {yields} Laves phases dispersed in a BCC iron matrix by annealing of cold rolled samples. {yields} The samples showed age hardenability during subsequent isothermal aging at 753 K. {yields} Ultrahigh fracture stress but poor ductility was obtained after age hardening. {yields} Increasing chromium addition toughened the aged microstructure. {yields} Laves phase particles acting as crack nucleation sites during tensile deformation.

  12. Formation mechanisms of water-soluble organic compounds in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Huang, Xiaofeng

    Water-soluble organic compounds (WSOCs) are abundant in atmospheric aerosols, typically accounting for 20˜80% of particulate organic matter mass. Due to their affinity for water, WSOCs play an active role in aerosol-water interaction, and thus influence hygroscopic properties of aerosols, which in turn affect cloud formation processes and earth's radiation balance. Despite their abundance and significance, the sources of WSOCs are not well understood. Some primary sources (e.g., biomass burning) are known to emit WSOCs. It is also known from smog chamber experiments that photochemical oxidation of volatile organic compounds lead to less volatile oxygenated compounds that reside in the aerosol phase and are water-soluble because of the presence of polar functional groups. More recent work points to in-cloud/fog processes as a potentially important source for WSOCs. Work in this thesis aims to improve our understanding of the sources and formation mechanisms of WSOCs in atmospheric aerosols. Multiple approaches have been taken, including field measurements and controlled laboratory experiments. The thesis consists of the following four parts: (1) The formation mechanism of the most abundant WSOC species, oxalate, was investigated by synthesizing field measurement data obtained by our group and those available in the literature. Our measurements of aerosol sulfate and oxalate across a wide geographical span in the East Asia region, up to Beijing in the north and down to Hong Kong in the south, indicated that the two species were highly correlated. This good correlation was also found in measurements made elsewhere in the world by other researchers. Through a detailed analysis of factors influencing ambient oxalate, it can be argued that a common dominant formation pathway, likely in-cloud processing, explains the close tracking of the two chemically distinct species. This result also highlights the potential importance of in-cloud processing as a pathway leading to

  13. The ionic liquid isopropylammonium formate as a mobile phase modifier to improve protein stability during reversed phase liquid chromatography.

    PubMed

    Zhou, Ling; Danielson, Neil D

    2013-12-01

    The room temperature ionic liquid isopropylammonium formate (IPAF) is studied as a reversed phase HPLC mobile phase modifier for separation of native proteins using a polymeric column and the protein stability is compared to that using acetonitrile (MeCN) as the standard organic mobile phase modifier. A variety of important proteins with different numbers of subunits are investigated, including non-subunit proteins: albumin, and amyloglucosidase (AMY); a two subunit protein: thyroglobulin (THY); and four subunit proteins: glutamate dehydrogenase (GDH) and lactate dehydrogenase (LDH). A significant enhancement in protein stability is observed in the chromatograms upon using IPAF as a mobile phase modifier. The first sharper peak at about 2min represented protein in primarily the native form and a second broader peak more retained at about 5-6min represented substantially denatured or possibly aggregated protein. The investigated proteins (except LDH) could maintain the native form within up to 50% IPAF, while a mobile phase, with as low as 10% MeCN, induced protein denaturation. The assay for pyruvate using LDH has further shown that enzymatic activity can be maintained up to 30% IPAF in water in contrast to no activity using 30% MeCN.

  14. Cobalt-catalyzed formation of symmetrical biaryls and its mechanism.

    PubMed

    Moncomble, Aurélien; Le Floch, Pascal; Gosmini, Corinne

    2009-01-01

    Effective devotion: An efficient cobalt-catalyzed method devoted to the formation of symmetrical biaryls is described avoiding the preparation of organometallic reagents. Various aromatic halides functionalized by a variety of reactive group reagents are employed. Preliminary DFT calculations have shown that the involvement of a Co(I)/Co(III) couple is realistic at least in the case of 1,3-diazadienes as ligands (FG = functional group).

  15. The Mechanism of Formation of Lipid Tubules from Liposomes

    DTIC Science & Technology

    1988-01-01

    structures about 10 in diameter and as longt as hundreds of micrometers. To elucidate the nature of the conversion process. freeze fracture electron...microscopy was utilized to examine samples that were rapidly quenched during tubule fOrmation. Many transitional structures -Acre obserjed. typically...that form unusual tubular structures [1-61. tain trapped liposomes (Fig. 1). When liposomes The lecithin 1.2-bis( l.l2-tricosadiynoyl)-sn-gly- are

  16. Planetary Embryo Bow Shocks as a Mechanism for Chondrule Formation

    NASA Astrophysics Data System (ADS)

    Mann, Christopher R.; Boley, Aaron C.; Morris, Melissa A.

    2016-02-01

    We use radiation hydrodynamics with direct particle integration to explore the feasibility of chondrule formation in planetary embryo bow shocks. The calculations presented here are used to explore the consequences of a Mars-size planetary embryo traveling on a moderately excited orbit through the dusty, early environment of the solar system. The embryo’s eccentric orbit produces a range of supersonic relative velocities between the embryo and the circularly orbiting gas and dust, prompting the formation of bow shocks. Temporary atmospheres around these embryos, which can be created via volatile outgassing and gas capture from the surrounding nebula, can non-trivially affect thermal profiles of solids entering the shock. We explore the thermal environment of solids that traverse the bow shock at different impact radii, the effects that planetoid atmospheres have on shock morphologies, and the stripping efficiency of planetoidal atmospheres in the presence of high relative winds. Simulations are run using adiabatic and radiative conditions, with multiple treatments for the local opacities. Shock speeds of 5, 6, and 7 km s-1 are explored. We find that a high-mass atmosphere and inefficient radiative conditions can produce peak temperatures and cooling rates that are consistent with the constraints set by chondrule furnace studies. For most conditions, the derived cooling rates are potentially too high to be consistent with chondrule formation.

  17. PLANETARY EMBRYO BOW SHOCKS AS A MECHANISM FOR CHONDRULE FORMATION

    SciTech Connect

    Mann, Christopher R.; Boley, Aaron C.; Morris, Melissa A.

    2016-02-20

    We use radiation hydrodynamics with direct particle integration to explore the feasibility of chondrule formation in planetary embryo bow shocks. The calculations presented here are used to explore the consequences of a Mars-size planetary embryo traveling on a moderately excited orbit through the dusty, early environment of the solar system. The embryo’s eccentric orbit produces a range of supersonic relative velocities between the embryo and the circularly orbiting gas and dust, prompting the formation of bow shocks. Temporary atmospheres around these embryos, which can be created via volatile outgassing and gas capture from the surrounding nebula, can non-trivially affect thermal profiles of solids entering the shock. We explore the thermal environment of solids that traverse the bow shock at different impact radii, the effects that planetoid atmospheres have on shock morphologies, and the stripping efficiency of planetoidal atmospheres in the presence of high relative winds. Simulations are run using adiabatic and radiative conditions, with multiple treatments for the local opacities. Shock speeds of 5, 6, and 7 km s{sup −1} are explored. We find that a high-mass atmosphere and inefficient radiative conditions can produce peak temperatures and cooling rates that are consistent with the constraints set by chondrule furnace studies. For most conditions, the derived cooling rates are potentially too high to be consistent with chondrule formation.

  18. Studies of the underlying mechanisms for optical nonlinearities of blue phase liquid crystals (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Chen, Chun-Wei; Khoo, Iam Choon; Zhao, Shuo; Lin, Tsung-Hsien; Ho, Tsung-Jui

    2015-10-01

    We have investigated the mechanisms responsible for nonlinear optical processes occurring in azobenzene-doped blue phase liquid crystals (BPLC), which exhibit two thermodynamically stable BPs: BPI and BPII. In coherent two wave-mixing experiments, a slow (minutes) and a fast (few milliseconds) side diffractions are observed. The underlying mechanisms were disclosed by monitoring the dynamics of grating formation and relaxation as well as by some supplementary experiments. We found the photothermal indexing and dye/LC intermolecular torque leading to lattice distortion to be the dominant mechanisms for the observed nonlinear response in BPLC. Moreover, the response time of the nonlinear optical process varied with operating phase. The rise time of the thermal indexing process was in good agreement with our findings on the temperature dependence of BP refractive index: τ(ISO) > τ(BPI) > τ(BPII). The relaxation time of the torque-induced lattice distortion was analogue to its electrostriction counterpart: τ'(BPI) > τ'(BPII). In a separate experiment, lattice swelling with selective reflection of <110> direction changed from green to red was also observed. This was attributable to the isomerization-induced change in cholesteric pitch, which directly affects the lattice spacing. The phenomenon was confirmed by measuring the optical rotatory power of the BPLC.

  19. Cage occupancy and structural changes during hydrate formation from initial stages to resulting hydrate phase.

    PubMed

    Schicks, Judith M; Luzi-Helbing, Manja

    2013-11-01

    Hydrate formation processes and kinetics are still not sufficiently understood on a molecular level based on experimental data. In particular, the cavity formation and occupancy during the initial formation and growth processes of mixed gas hydrates are rarely investigated. In this study, we present the results of our time-depending Raman spectroscopic measurements during the formation of hydrates from ice and gases or gas mixtures such as CH4, CH4-CO2, CH4-H2S, CH4-C3H8, CH4-iso-C4H10, and CH4-neo-C5H12 at constant pressure and temperature conditions and constant composition of the feed gas phase. All investigated systems in this study show the incorporation of CH4 into the 5(12) cavities as first step in the initial stages of hydrate formation. Furthermore, the results imply that the initial hydrate phases differ from the resulting hydrate phase having reached a steady state regarding the occupancy and ratio of the small and large cavities of the hydrate.

  20. Palladium-modified aluminide coatings: Mechanisms of formation

    SciTech Connect

    Lamesle, P.; Steinmetz, P.; Steinmetz, J.; Alperine, S.

    1995-02-01

    The need to increase the efficiency of turbo engines has led manufacturers to increase the temperature of gases at the exhaust of the combustion chamber. Another limiting factor for the lifetime of blades or vanes used in gas turbines is hot corrosion due to the condensation of alkaline sulfate produced by the oxidation of sulfur contained in kerosene or fuels. To overcome these problems, the use of protective coatings has come into general use. A systematic investigation of the influence of Pd-Ni predeposit alloys on the microstructure and composition of aluminum diffusion coatings has been conducted on Ni base superalloys (mainly IN738). Their metallurgical structure has been studied with a special emphasis on the nature of the phases and distribution of the various elements throughout the coating section. A two-layer structure similar to that formed on simple aluminide coatings is observed whatever the type of aluminizing treatment (low and high aluminum activity, pack of vapor-phase coating). The superficial layer is, however, very different from that observed in simple aluminide coatings, since it is constituted with a ternary PdNi aluminide. Palladium concentration profiles, which significantly differ when using low or high activity cements, and the results of a study of the ternary Ni-Pd-Al phase diagram, provide qualitative indications concerning the coatings` growth processes. Palladium, if present at a sufficient level, enhances Al diffusion in the beta phase. In the case of low activity processes, a consequence of this increase of Al diffusion flux is the location of an NiAl reaction zone inside the coating.

  1. Formation of complex organic molecules in cold objects: the role of gas-phase reactions

    NASA Astrophysics Data System (ADS)

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-04-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

  2. A study of suppressed formation of low-conductivity phases in doped Li7La3Zr2O12 garnets by in situ neutron diffraction

    DOE PAGES

    Chen, Yan; Rangasamy, Ezhiylmurugan; dela Cruz, Clarina R.; ...

    2015-01-01

    Doped Li7La3Zr2O12 garnets, oxide-based solids with good Li+ conductivity and compatibility, show great potential as leading electrolyte material candidates for all-solid-state lithium ion batteries. Still yet, the conductive bulk usually suffers from the presence of secondary phases and the transition towards a low-conductivity tetragonal phase during synthesis. Dopants are designed to stabilize the high-conductive cubic phase and suppress the formation of the low-conductivity phases. In situ neutron diffraction enables a direct observation of the doping effects by monitoring the phase evolutions during garnet synthesis. It reveals the reaction mechanism involving the temporary presence of intermediate phases. The off-stoichiometry due tomore » the liquid Li2CO3 evaporation leads to the residual of the low-conductivity intermediate phase in the as-synthesized bulk. Appropriate doping of an active element may alter the component of the intermediate phases and promote the completion of the reaction. While the dopants aid to stabilize most of the cubic phase, a small amount of tetragonal phase tends to form under a diffusion process. Lastly, the in situ observations provide the guideline of process optimization to suppress the formation of unwanted low-conductivity phases.« less

  3. Formation mechanism of steep wave front in magnetized plasmas

    SciTech Connect

    Sasaki, M. Kasuya, N.; Itoh, S.-I.; Kobayashi, T.; Arakawa, H.; Itoh, K.; Fukunaga, K.; Yamada, T.; Yagi, M.

    2015-03-15

    Bifurcation from a streamer to a solitary drift wave is obtained in three dimensional simulation of resistive drift waves in cylindrical plasmas. The solitary drift wave is observed in the regime where the collisional transport is important as well as fluctuation induced transport. The solitary drift wave forms a steep wave front in the azimuthal direction. The phase of higher harmonic modes are locked to that of the fundamental mode, so that the steep wave front is sustained for a long time compared to the typical time scale of the drift wave oscillation. The phase entrainment between the fundamental and second harmonic modes is studied, and the azimuthal structure of the stationary solution is found to be characterized by a parameter which is determined by the deviation of the fluctuations from the Boltzmann relation. There are two solutions of the azimuthal structures, which have steep wave front facing forward and backward in the wave propagation direction, respectively. The selection criterion of these solutions is derived theoretically from the stability of the phase entrainment. The simulation result and experimental observations are found to be consistent with the theoretical prediction.

  4. Pseudogap formation and quantum phase transition in strongly-correlated electron systems

    SciTech Connect

    Chern, Chyh-Hong

    2014-11-15

    Pseudogap formation is a ubiquitous phenomenon in strongly-correlated superconductors, for example cuprates, heavy-fermion superconductors, and iron pnictides. As the system is cooled, an energy gap opens in the excitation spectrum before entering the superconducting phase. The origin of formation and the relevancy to the superconductivity remain unclear, which is the most challenging problem in condensed matter physics. Here, using the cuprate as a model, we demonstrate that the formation of pseudogap is due to a massive gauge interaction between electrons, where the mass of the gauge boson, determining the interaction length scale, is the consequence of the remnant antiferromagnetic fluctuation inherited from the parent compounds. Extracting from experimental data, we predict that there is a quantum phase transition belonging to the 2D XY universality class at the critical doping where pseudogap transition vanishes.

  5. Surface-Induced Phase of Tyrian Purple (6,6'-Dibromoindigo): Thin Film Formation and Stability.

    PubMed

    Truger, Magdalena; Roscioni, Otello M; Röthel, Christian; Kriegner, Dominik; Simbrunner, Clemens; Ahmed, Rizwan; Głowacki, Eric D; Simbrunner, Josef; Salzmann, Ingo; Coclite, Anna Maria; Jones, Andrew O F; Resel, Roland

    2016-07-06

    The appearance of surface-induced phases of molecular crystals is a frequently observed phenomenon in organic electronics. However, despite their fundamental importance, the origin of such phases is not yet fully resolved. The organic molecule 6,6'-dibromoindigo (Tyrian purple) forms two polymorphs within thin films. At growth temperatures of 150 °C, the well-known bulk structure forms, while at a substrate temperature of 50 °C, a surface-induced phase is observed instead. In the present work, the crystal structure of the surface-induced polymorph is solved by a combined experimental and theoretical approach using grazing incidence X-ray diffraction and molecular dynamics simulations. A comparison of both phases reveals that π-π stacking and hydrogen bonds are common motifs for the intermolecular packing. In-situ temperature studies reveal a phase transition from the surface-induced phase to the bulk phase at a temperature of 210 °C; the irreversibility of the transition indicates that the surface-induced phase is metastable. The crystallization behavior is investigated ex-situ starting from the sub-monolayer regime up to a nominal thickness of 9 nm using two different silicon oxide surfaces; island formation is observed together with a slight variation of the crystal structure. This work shows that surface-induced phases not only appear for compounds with weak, isotropic van der Waals bonds, but also for molecules exhibiting strong and highly directional hydrogen bonds.

  6. Defect formation and phase stability of Cu2ZnSnS4 photovoltaic material

    NASA Astrophysics Data System (ADS)

    Nagoya, Akihiro; Asahi, Ryoji; Wahl, Roman; Kresse, Georg

    2010-03-01

    First-principles studies of the phase stability of and defect formation in Cu2ZnSnS4 (CZTS) are performed. We show that CZTS is the thermodynamically stable phase for a rather small confined domain of chemical potentials. Even slight deviations from the optimal growth conditions will therefore result in the formation of other sulfidic precipitates, including ZnS, Cu2SnS3 , SnS, SnS2 , and CuS. In particular, under the prevalent experimental Cu-poor and Zn-rich growth conditions ZnS is the main competing phase. Furthermore, the calculations unambiguously predict that Cu at the Zn site is the most stable defect in the entire stability range of CZTS. This correlates with the experimental observation that CZTS is an intrinsic p -type semiconductor.

  7. Formation of free radicals during mechanical degradation of elastomers.

    NASA Technical Reports Server (NTRS)

    Devries, K. L.; Williams, M. L.; Roylance, D. K.

    1971-01-01

    Solithane 113 (an amorphous polyurethane elastomer) was prepared by curing equal proportions of castor oil and trifunctional isocyanate for 6 hr 45 min at 170 F. The sample material was mechanically degraded by grinding below and above its glass transition point at liquid nitrogen and room temperatures. The EPR spectra of ground samples were recorded and the number of free radicals were determined by a computer double-integration of the recorded spectra and by a comparison of the values with those of a standard material. Curves of EPR spectra suggest that different molecular mechanisms may be active in degradation of this material below and above its glass transition temperature.

  8. Mechanisms of endoderm formation in a cartilaginous fish reveal ancestral and homoplastic traits in jawed vertebrates.

    PubMed

    Godard, Benoit G; Coolen, Marion; Le Panse, Sophie; Gombault, Aurélie; Ferreiro-Galve, Susana; Laguerre, Laurent; Lagadec, Ronan; Wincker, Patrick; Poulain, Julie; Da Silva, Corinne; Kuraku, Shigehiro; Carre, Wilfrid; Boutet, Agnès; Mazan, Sylvie

    2014-10-31

    In order to gain insight into the impact of yolk increase on endoderm development, we have analyzed the mechanisms of endoderm formation in the catshark S. canicula, a species exhibiting telolecithal eggs and a distinct yolk sac. We show that in this species, endoderm markers are expressed in two distinct tissues, the deep mesenchyme, a mesenchymal population of deep blastomeres lying beneath the epithelial-like superficial layer, already specified at early blastula stages, and the involuting mesendoderm layer, which appears at the blastoderm posterior margin at the onset of gastrulation. Formation of the deep mesenchyme involves cell internalizations from the superficial layer prior to gastrulation, by a movement suggestive of ingressions. These cell movements were observed not only at the posterior margin, where massive internalizations take place prior to the start of involution, but also in the center of the blastoderm, where internalizations of single cells prevail. Like the adjacent involuting mesendoderm, the posterior deep mesenchyme expresses anterior mesendoderm markers under the control of Nodal/activin signaling. Comparisons across vertebrates support the conclusion that endoderm is specified in two distinct temporal phases in the catshark as in all major osteichthyan lineages, in line with an ancient origin of a biphasic mode of endoderm specification in gnathostomes. They also highlight unexpected similarities with amniotes, such as the occurrence of cell ingressions from the superficial layer prior to gastrulation. These similarities may correspond to homoplastic traits fixed separately in amniotes and chondrichthyans and related to the increase in egg yolk mass.

  9. Mechanisms of endoderm formation in a cartilaginous fish reveal ancestral and homoplastic traits in jawed vertebrates

    PubMed Central

    Godard, Benoit G.; Coolen, Marion; Le Panse, Sophie; Gombault, Aurélie; Ferreiro-Galve, Susana; Laguerre, Laurent; Lagadec, Ronan; Wincker, Patrick; Poulain, Julie; Da Silva, Corinne; Kuraku, Shigehiro; Carre, Wilfrid; Boutet, Agnès; Mazan, Sylvie

    2014-01-01

    ABSTRACT In order to gain insight into the impact of yolk increase on endoderm development, we have analyzed the mechanisms of endoderm formation in the catshark S. canicula, a species exhibiting telolecithal eggs and a distinct yolk sac. We show that in this species, endoderm markers are expressed in two distinct tissues, the deep mesenchyme, a mesenchymal population of deep blastomeres lying beneath the epithelial-like superficial layer, already specified at early blastula stages, and the involuting mesendoderm layer, which appears at the blastoderm posterior margin at the onset of gastrulation. Formation of the deep mesenchyme involves cell internalizations from the superficial layer prior to gastrulation, by a movement suggestive of ingressions. These cell movements were observed not only at the posterior margin, where massive internalizations take place prior to the start of involution, but also in the center of the blastoderm, where internalizations of single cells prevail. Like the adjacent involuting mesendoderm, the posterior deep mesenchyme expresses anterior mesendoderm markers under the control of Nodal/activin signaling. Comparisons across vertebrates support the conclusion that endoderm is specified in two distinct temporal phases in the catshark as in all major osteichthyan lineages, in line with an ancient origin of a biphasic mode of endoderm specification in gnathostomes. They also highlight unexpected similarities with amniotes, such as the occurrence of cell ingressions from the superficial layer prior to gastrulation. These similarities may correspond to homoplastic traits fixed separately in amniotes and chondrichthyans and related to the increase in egg yolk mass. PMID:25361580

  10. Nanobacteria: An alternative mechanism for pathogenic intra- and extracellular calcification and stone formation

    PubMed Central

    Kajander, E. Olavi; Çiftçioglu, Neva

    1998-01-01

    Calcium phosphate is deposited in many diseases, but formation mechanisms remain speculative. Nanobacteria are the smallest cell-walled bacteria, only recently discovered in human and cow blood and commercial cell culture serum. In this study, we identified with energy-dispersive x-ray microanalysis and chemical analysis that all growth phases of nanobacteria produce biogenic apatite on their cell envelope. Fourier transform IR spectroscopy revealed the mineral as carbonate apatite. The biomineralization in cell culture media resulted in biofilms and mineral aggregates closely resembling those found in tissue calcification and kidney stones. In nanobacteria-infected fibroblasts, electron microscopy revealed intra- and extracellular acicular crystal deposits, stainable with von Kossa staining and resembling calcospherules found in pathological calcification. Previous models for stone formation have led to an hypothesis that elevated pH due to urease and/or alkaline phosphatase activity is a lithogenic factor. Our results indicate that carbonate apatite can be formed without these factors at pH 7.4, at physiological phosphate and calcium concentrations. Nanobacteria can produce apatite in media mimicking tissue fluids and glomerular filtrate and provide a unique model for in vitro studies on calcification. PMID:9653177

  11. Nanobacteria: an alternative mechanism for pathogenic intra- and extracellular calcification and stone formation.

    PubMed

    Kajander, E O; Ciftçioglu, N

    1998-07-07

    Calcium phosphate is deposited in many diseases, but formation mechanisms remain speculative. Nanobacteria are the smallest cell-walled bacteria, only recently discovered in human and cow blood and commercial cell culture serum. In this study, we identified with energy-dispersive x-ray microanalysis and chemical analysis that all growth phases of nanobacteria produce biogenic apatite on their cell envelope. Fourier transform IR spectroscopy revealed the mineral as carbonate apatite. The biomineralization in cell culture media resulted in biofilms and mineral aggregates closely resembling those found in tissue calcification and kidney stones. In nanobacteria-infected fibroblasts, electron microscopy revealed intra- and extracellular acicular crystal deposits, stainable with von Kossa staining and resembling calcospherules found in pathological calcification. Previous models for stone formation have led to an hypothesis that elevated pH due to urease and/or alkaline phosphatase activity is a lithogenic factor. Our results indicate that carbonate apatite can be formed without these factors at pH 7.4, at physiological phosphate and calcium concentrations. Nanobacteria can produce apatite in media mimicking tissue fluids and glomerular filtrate and provide a unique model for in vitro studies on calcification.

  12. Synthesis, structural characterization and formation mechanism of ferroelectric bismuth vanadate nanotubes.

    PubMed

    Singh, Satyendra; Kumari, Neelam; Varma, K B R; Krupanidhi, S B

    2009-11-01

    We report the synthesis and structural characterization of ferroelectric bismuth vanadate (Bi2VO5.5) (BVO) nanotubes within the nanoporous anodic aluminum oxide (AAO) templates via sol-gel method. The as-prepared BVO nanotubes were characterized by X-ray powder diffraction (XRD), Scanning Electron Microscope (SEM), High-Resolution Transmission Electron Microscope (HRTEM) and the stoichiometry of the nanotubes was established by energy-dispersive X-ray spectroscopy (EDX). Postannealed (675 degrees C for 1 h), BVO nanotubes were a polycrystalline and the XRD studies confirmed the crystal structure to be orthorhombic. The uniformity in diameter and length of the nanotubes as reveled by the TEM and SEM suggested that these were influenced to a guest extent by the thickness and pore diameter of the nanoporous AAO template. EDX analysis demonstrated the formation of stoichiometric Bi2VO5.5 phase. HRTEM confirmed that the obtained BVO nanotubes were made up of nanoparticles of 5-9 nm range. The possible formation mechanism of nanotubes was elucidated.

  13. Kinetics and mechanism of the electrochemical formation of iron oxidation products on steel immersed in sour acid media.

    PubMed

    Hernández-Espejel, Antonio; Palomar-Pardavé, Manuel; Cabrera-Sierra, Román; Romero-Romo, Mario; Ramírez-Silva, María Teresa; Arce-Estrada, Elsa M

    2011-03-03

    From electrochemical techniques (cyclic voltammetry, potential steps, and EIS), XRD, and SEM-EDX, the kinetics and mechanism of anodic film formation applying anodic potential steps on steel immersed in sour acid media was determined. It was found, from a thermodynamic analysis, based on equilibrium phase diagrams of the system considered in this work, that iron oxidation may produce different new solid phases, depending on the applied potential, the first being the iron oxidation associated with formation of FeS((c)) species, which in turn can be reoxidized to FeS(2(c)) or even to Fe(2)O(3(c)) at higher potential values. From analysis of the corresponding experimental potentiostatic current density transients, it was concluded that the electrochemical anodic film formation involves an E(1)CE(2) mechanism, whereby the first of the two simultaneous processes were the Fe electrochemical oxidation (E(1)) followed by FeS precipitation (C) that occurs by 3D nucleation and growth limited by mass transfer reaction and FeS oxidation (E(2)) forming a mix of different stoichiometry iron sulphides and oxides. From EIS measurements, it was revealed that the anodic film's charge transfer resistance diminishes as the potential applied for its formation becomes more anodic, thus behaving poorly against corrosion.

  14. Hyaluronate-alginate gel as a novel biomaterial: mechanical properties and formation mechanism.

    PubMed

    Oerther, S; Le Gall, H; Payan, E; Lapicque, F; Presle, N; Hubert, P; Dexheimer, J; Netter, P

    1999-04-20

    With the aim of producing a biomaterial for surgical applications, the alginate-hyaluronate association has been investigated to combine the gel-forming properties of alginate with the healing properties of hyaluronate. Gels were prepared by diffusion of calcium into alginate-hyaluronate mixtures, with an alginate content of 20 mg/mL. The hyaluronate source was shown to have significant effect on the aspect and the properties of the gels. The gels have viscoelastic behaviour and the transient measurements carried out in creep mode could be interpreted through a Kelvin-Voigt generalised model: experimental data led to the steady state hardness and a characteristic viscosity of the gel. Gels prepared from Na rooster comb hyaluronate with weight ratio up to 0.50 have satisfactory mechanical properties, and fully stable gels are obtained after a few days; on the contrary, use of lower molecular weight hyaluronate led to loose gels for hyaluronate contents over 0.25. Gel formation was investigated by measurements of the exchange fluxes between the calcium chloride solution and the forming gel, which allowed thorough investigations of the occuring diffusion phenomena of water, calcium ion and hyaluronate. Strong interactions of water with hyaluronate reduce significantly the rate of weight loss from the gel beads and allows higher water content in steady-state gels. Calcium content in the gel samples could be correlated to the actual alginate concentration, whatever the nature and the weight ratio of hyaluronate.

  15. Electrical characteristics and formation mechanism of atmospheric pressure plasma jet

    SciTech Connect

    Liu, Lijuan; Zhang, Yu; Tian, Weijing; Meng, Ying; Ouyang, Jiting

    2014-06-16

    The behavior of atmospheric pressure plasma jet produced by a coplanar dielectric barrier discharge in helium in external electrostatic and magnetic field is investigated. Net negative charges in the plasma jet outside the tube were detected. The deflection of the plume in the external field was observed. The plasma jet is suggested to be formed by the electron beam from the temporal cathode which is accelerated by a longitudinal field induced by the surface charges on the dielectric tube or interface between the helium and ambient air. The helium flow is necessary for the jet formation in the surrounding air.

  16. Progress in spondylarthritis. Mechanisms of new bone formation in spondyloarthritis.

    PubMed

    Lories, Rik J U; Luyten, Frank P; de Vlam, Kurt

    2009-01-01

    Targeted therapies that neutralize tumour necrosis factor are often able to control the signs and symptoms of spondyloarthritis. However, recent animal model data and clinical observations indicate that control of inflammation may not be sufficient to impede disease progression toward ankylosis in these patients. Bone morphogenetic proteins and WNTs (wingless-type like) are likely to play an important role in ankylosis and could be therapeutic targets. The relationship between inflammation and new bone formation is still unclear. This review summarizes progress made in our understanding of ankylosis and offers an alternative view of the relationship between inflammation and ankylosis.

  17. Mechanisms underlying structural variant formation in genomic disorders

    PubMed Central

    Carvalho, Claudia M. B.; Lupski, James R.

    2016-01-01

    With the recent burst of technological developments in genomics, and the clinical implementation of genome-wide assays, our understanding of the molecular basis of genomic disorders, specifically the contribution of structural variation to disease burden, is evolving quickly. Ongoing studies have revealed a ubiquitous role for genome architecture in the formation of structural variants at a given locus, both in DNA recombination-based processes and in replication-based processes. These reports showcase the influence of repeat sequences on genomic stability and structural variant complexity and also highlight the tremendous plasticity and dynamic nature of our genome in evolution, health and disease susceptibility. PMID:26924765

  18. GAS PHASE SYNTHESIS OF (ISO)QUINOLINE AND ITS ROLE IN THE FORMATION OF NUCLEOBASES IN THE INTERSTELLAR MEDIUM

    SciTech Connect

    Parker, Dorian S. N.; Kaiser, Ralf I.; Kostko, Oleg; Troy, Tyler P.; Ahmed, Musahid; Mebel, Alexander M.; Tielens, Alexander G. G. M.

    2015-04-20

    Nitrogen-substituted polycyclic aromatic hydrocarbons (NPAHs) have been proposed to play a key role in the astrochemical evolution of the interstellar medium, yet the formation mechanisms of even their simplest prototypes—quinoline and isoquinoline—remain elusive. Here, we reveal a novel concept that under high temperature conditions representing circumstellar envelopes of carbon stars, (iso)quinoline can be synthesized via the reaction of pyridyl radicals with two acetylene molecules. The facile gas phase formation of (iso)quinoline in circumstellar envelopes defines a hitherto elusive reaction class synthesizing aromatic structures with embedded nitrogen atoms that are essential building blocks in contemporary biological-structural motifs. Once ejected from circumstellar shells and incorporated into icy interstellar grains in cold molecular clouds, these NPAHs can be functionalized by photo processing forming nucleobase-type structures as sampled in the Murchison meteorite.

  19. Formation of high-stress phase and extrusion of polyethylene due to nanoconfinements during Ziegler-Natta polymerization inside nanochannels.

    PubMed

    Nair, Sujith; Naredi, Prabhat; Kim, Seong H

    2005-06-30

    Polyethylene nanofibers were synthesized by heterogeneous Ziegler-Natta polymerization inside nanochannels of robust anodized aluminum oxide (AAO) membranes. The polymerization catalysts were chemisorbed at the inner wall of the nanochannels and monomers were provided through diffusion from the outside. Polyethylene is produced inside the nanochannels in the 10-20 mum region from the channel entrance. Polyethylene fibers were extruded from the nanochannels up to 3-5 mum during the polymerization. X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared analyses indicated formation of a highly stressed crystalline structure although the polymerization was carried out without any external pressure or mechanical work. The highly stressed phase formation inside nanochannels and some degree of polyethylene nanofiber extrusion from nanochannels were attributed to catalytic production of excess amounts of polyethylene inside nanoconfined templates.

  20. Geo-mechanical consequences of large scale fluid storage in the Utsira formation in the North Sea

    NASA Astrophysics Data System (ADS)

    Wangen, Magnus; Gasda, Sarah; Bjørnarå, Tore

    2016-04-01

    The Utsira formation in the North Sea is a more than 400 km long formation of Pliocene sand with a thickness in the range from 50m to 350m. The porosity of the Utsira formation is estimated to 35% and the permeability is of the order Darcy (1e-12 m2). This formation is being considered as a possible site for large scale CO2 storage, because of its large storage capacity and good permeability. In this work we look at the geo-mechanical implications of injecting "large'' volumes of fluid in the Utsira formation. Our modelling is based on Biot's poro-elasticity in combination with one-phase and two phase flow. We compare the pressure build-up from injection of brine with the pressure build-up from from injection of supercritical CO2. Well placement and near well modelling is not a part of the modelling. We study four different injection scenarios over 25 years, which have injection rates: 1 Mt/year, 10 Mt/year, 100 Mt/year and 1000 Mt/year. We observe that the pressure plume scales with the injection rate, which is the same behaviour as with Theis solution for pressure build-up. A particular concern is the mechanical properties of the Utsira sand and the cap rock. The cap rock is a Quaternary shale with a Young's modulus measured to 0.25 GPa and a Poisson ratio 0.25. A Young's modulus for the Utsira sand, which can be used to model expansion of the formation, is not measured. It is reasonable to assume that the loose sand has a low Young's modulus. We have tested low values of the Young's modulus for the sand and we get considerable mechanical expansion of the Utsira formation, even in the case of low pressure build-up from the fluid injection. Almost all the surface (seabed) uplift is linked to mechanical expansion of the sand. The strain of the Utsira formation and related surface uplift can be estimated with simple 1D models. Vertical 1D models apply because of the large lateral extent of the pressure plume compared to the thickness of the formation. The limits of

  1. Distinct Neural Mechanisms Mediate Olfactory Memory Formation at Different Timescales

    ERIC Educational Resources Information Center

    McNamara, Ann Marie; Magidson, Phillip D.; Linster, Christiane; Wilson, Donald A.; Cleland, Thomas A.

    2008-01-01

    Habituation is one of the oldest forms of learning, broadly expressed across sensory systems and taxa. Here, we demonstrate that olfactory habituation induced at different timescales (comprising different odor exposure and intertrial interval durations) is mediated by different neural mechanisms. First, the persistence of habituation memory is…

  2. Distributional Language Learning: Mechanisms and Models of Category Formation

    ERIC Educational Resources Information Center

    Aslin, Richard N.; Newport, Elissa L.

    2014-01-01

    In the past 15 years, a substantial body of evidence has confirmed that a powerful distributional learning mechanism is present in infants, children, adults and (at least to some degree) in nonhuman animals as well. The present article briefly reviews this literature and then examines some of the fundamental questions that must be addressed for…

  3. Mechanisms of Nitrogen Oxide Formation During Ensiling of Dairy Feeds

    EPA Science Inventory

    This product is the abstract of a proposed paper. The emission of NOx has been observed during the ensiling process (Peterson et al. 1958, Maw et al. 2002). Substantial NOx is not inherently present in corn. It is generated by an unknown mechanism during the early days of the ens...

  4. Glycerol effects on the formation and rheology of hexagonal phase and related gel emulsion.

    PubMed

    Alam, Mohammad Mydul; Aramaki, Kenji

    2009-08-15

    We have investigated the effects of glycerol on the formation and rheology of hexagonal phase (H(1)) and related O/H(1) gel emulsion in the water/C(12)EO(8)/dodecane system at 25 degrees C. It has been found that the aqueous solution of C(12)EO(8) forms H(1) phase, which could solubilize some amounts of dodecane. Beyond the solubilization limit, oil is separated and a two-phase region or H(1)+O phase appeared. Due to high viscosity of the H(1) phase, allows forming O/H(1) gel emulsion at the H(1)+O region. Rheological measurements (without glycerol) have shown that the rheogram of the H(1) phase does not change drastically with the addition of oil but the system is shifted to longer relaxation time. Simultaneously, the values of the absolute value(eta(*)) are found to increase with the addition of oil, which has been described with the neighboring micellar interaction. The rheogram of the O/H(1) gel emulsion shows gel type nature (G'>G'') but the viscosity monotonically decreases with increasing oil content, which could be due to the lower volume fraction of the continuous phase (H(1) phase). Addition of glycerol has brought an order-order transition or the microstructural transition from H(1)-lamellar (L(alpha)) phase, which is manifested from rheology and SAXS measurements. Viscosity of the O/H(1) gel emulsion also decreases with increasing glycerol content. Digital images show the physical appearance of the gel emulsion changes from turbid to transparent, which is depended on the glycerol concentration (since glycerol matches the refractive index of the H(1) phase and dodecane). Structural parameters of the H(1) phase have been evaluated with the help of Bohlin's model and found that the coordination number of the H(1) phase depends not only the oil and glycerol concentrations but also temperature.

  5. Commitment and exploration as mechanisms of identity formation.

    PubMed

    Meeus, W; Iedema, J; Maassen, G H

    2002-06-01

    We report a two-wave longitudinal study of 1,571 Dutch adolescents concerning the role of commitment and exploration in identity development. We used the Utrecht-Groningen Identity Development Scale to measure commitment and exploration in the domains of relational and societal identity. Our results can be summarized in three points. (1) Commitment and exploration are related processes in the development of identity. Adolescents with strong commitments also frequently explore them, and adolescents with low exploration in general have weak commitments. (2) The longitudinal stability of commitment and exploration has a medium effect size. For relational identity the stability of commitment is greater than that of exploration, but this is not the case for societal identity. The explanation we give for the lack of this difference in stability between commitment and exploration in societal identity is that the formative period for societal identity comes primarily at the end of adolescence. In that connection, we conclude that for present-day Dutch adolescents the formation of relational identity probably precedes that of societal identity. (3) In neither identity domain is commitment predictive of exploration three years later, nor is the reverse the case. We conclude that no long-term developmental sequentiality of commitment and exploration was found, but the results do not rule out the possibility of short-term developmental sequentiality.

  6. Annealing-induced change in quantum dot chain formation mechanism

    SciTech Connect

    Park, Tyler D.; Colton, John S.; Farrer, Jeffrey K.; Yang, Haeyeon; Kim, Dong Jun

    2014-12-15

    Self-assembled InGaAs quantum dot chains were grown using a modified Stranski-Krastanov method in which the InGaAs layer is deposited under a low growth temperature and high arsenic overpressure, which suppresses the formation of dots until a later annealing process. The dots are capped with a 100 nm GaAs layer. Three samples, having three different annealing temperatures of 460°C, 480°C, and 500°C, were studied by transmission electron microscopy. Results indicate two distinct types of dot formation processes: dots in the 460°C and 480°C samples form from platelet precursors in a one-to-one ratio whereas the dots in the sample annealed at 500°C form through the strain-driven self-assembly process, and then grow larger via an additional Ostwald ripening process whereby dots grow into larger dots at the expense of smaller seed islands. There are consequently significant morphological differences between the two types of dots, which explain many of the previously-reported differences in optical properties. Moreover, we also report evidence of indium segregation within the dots, with little or no indium intermixing between the dots and the surrounding GaAs barrier.

  7. Formation, stability, and crystal structure of σ phase in Mo-Re-Si alloys

    SciTech Connect

    Bei, Hongbin; Yang, Ying; Viswanathan, G.; Rawn, Claudia J; George, Easo P; Tiley, Jaimie; Chang, Y. Austin

    2010-01-01

    The formation, stability and crystal structure of the {sigma} phase in Mo-Re-Si alloys were investigated. Guided by thermodynamic calculations, six critically selected alloys were arc melted and annealed at 1600 C for 150 h. Their as-cast and annealed microstructures, including phase fractions and distributions, the compositions of the constituent phases and the crystal structure of the {sigma} phase were analyzed by thermodynamic modeling coupled with experimental characterization by scanning electron microscopy, electron probe microanalysis, X-ray diffraction and transmission electron microscopy. Two key findings resulted from this work. One is the large homogeneity range of the {sigma} phase region, extending from binary Mo-Re to ternary Mo-Re-Si. The other is the formation of a {sigma} phase in Mo-rich alloys either through the peritectic reaction of liquid + Mo{sub ss} {yields} {sigma} or primary solidification. These findings are important in understanding the effects of Re on the microstructure and providing guidance on the design of Mo-Re-Si alloys.

  8. Metastable bcc phase formation in the Nb-Cr-Ti system

    SciTech Connect

    Thoma, D.J.; Perepezko, J.H.

    1994-08-01

    Metastable disordered bcc phases have been formed from the melt in the Nb-Cr-Ti system where primary Laves phases would develop under equilibrium solidification conditions. Three vertical temperature-composition sections in the ternary system incorporating NbCr, were evaluated: the Nb-Cr binary, the TiCr{sub 2}-NbCr{sub 2} isoplethal section, and the NbCr{sub 2}-Ti plethal section. In the rapid solidification of NbCr{sub 2}, metastable bcc phase formation was not observed, but deviations from NbCr{sub 2} stoichiometry or alloying with Ti was found to promote bcc phase formation by decreasing the required liquid undercooling to reach the metastable bcc liquidus and solidus. The metastable phases were characterized through x-ray diffraction (XRD), and systematic deviations from Vegard`s Rule have been defined in the three plethal sections. The metastable bcc phases decompose at temperatures >800{degrees}C to uniformly refined microstructures. As a result, novel microstructural tailoring schemes are possible through the metastable precursor microstructures.

  9. Trace phase formation, crystallization kinetics and crystallographic evolution of a lithium disilicate glass probed by synchrotron XRD technique

    PubMed Central

    Huang, Saifang; Huang, Zhaohui; Gao, Wei; Cao, Peng

    2015-01-01

    X-ray diffraction technique using a laboratory radiation has generally shown limitation in detectability. In this work, we investigated the in situ high-temperature crystallization of a lithium disilicate glass-ceramic in the SiO2–Li2O–CaO–P2O5–ZrO2 system with the aid of synchrotron radiation. The formation of lithium metasilicate and other intermediate phases in trace amount was successfully observed by synchrotron X-ray diffraction (SXRD). The crystallization mechanism in this glass was thus intrinsically revised to be the co-nucleation of lithium metasilicate and disilicate, instead of the nucleation of lithium disilicate only. The phase content, crystallite size and crystallographic evolutions of Li2Si2O5 in the glass-ceramic as a function of annealing temperature were studied by performing Rietveld refinements. It is found that the growth of Li2Si2O5 is constrained by Li2SiO3 phase at 580–700°C. The relationship between the crystallographic evolution and phase transition was discussed, suggesting a common phenomenon of structural response of Li2Si2O5 along its c axis to other silicon-related phases during glass crystallization. PMID:25778878

  10. Atomic scale observation of phase separation and formation of silicon clusters in Hf higk-{kappa} silicates

    SciTech Connect

    Talbot, E.; Roussel, M.; Genevois, C.; Pareige, P.; Khomenkova, L.; Portier, X.; Gourbilleau, F.

    2012-05-15

    Hafnium silicate films were fabricated by RF reactive magnetron sputtering technique. Fine microstructural analyses of the films were performed by means of high-resolution transmission electron microscopy and atom probe tomography. A thermal treatment of as-grown homogeneous films leads to a phase separation process. The formation of SiO{sub 2} and HfO{sub 2} phases as well as pure Si one was revealed. This latter was found to be amorphous Si nanoclusters, distributed uniformly in the film volume. Their mean diameter and density were estimated to be about 2.8 nm and (2.9 {+-} 0.4) x 10{sup 17} Si-ncs/cm{sup 3}, respectively. The mechanism of the decomposition process was proposed. The obtained results pave the way for future microelectronic and photonic applications of Hf-based high-{kappa} dielectrics with embedded Si nanoclusters.

  11. Impacts of relative permeability on CO2 phase behavior, phase distribution, and trapping mechanisms

    NASA Astrophysics Data System (ADS)

    Moodie, N.; McPherson, B. J. O. L.; Pan, F.

    2015-12-01

    A critical aspect of geologic carbon storage, a carbon-emissions reduction method under extensive review and testing, is effective multiphase CO2 flow and transport simulation. Relative permeability is a flow parameter particularly critical for accurate forecasting of multiphase behavior of CO2 in the subsurface. The relative per­meability relationship assumed and especially the irreducible saturation of the gas phase greatly impacts predicted CO2 trapping mechanisms and long-term plume migration behavior. A primary goal of this study was to evaluate the impact of relative permeability on efficacy of regional-scale CO2 sequestration models. To accomplish this we built a 2-D vertical cross-section of the San Rafael Swell area of East-central Utah. This model simulated injection of CO2 into a brine aquifer for 30 years. The well was then shut-in and the CO2 plume behavior monitored for another 970 years. We evaluated five different relative permeability relationships to quantify their relative impacts on forecasted flow results of the model, with all other parameters maintained uniform and constant. Results of this analysis suggest that CO2 plume movement and behavior are significantly dependent on the specific relative permeability formulation assigned, including the assumed irreducible saturation values of CO2 and brine. More specifically, different relative permea­bility relationships translate to significant differences in CO2 plume behavior and corresponding trapping mechanisms.

  12. Kinetic study of model reactions in the gas phase at the early stage of coke formation

    SciTech Connect

    Nohara, D.; Sakai, T. )

    1992-01-01

    This paper reports that the most probable gas-phase reactions at the early stage of coke formation were elucidated by kinetic study on the model reactions adopted for formation of cyclic compounds and growth of ring. It was revealed that the formation and growth of ring proceeded mainly through cycloaddition of butadiene or allyl radicals to unsaturated hydrocarbons at relatively low temperatures ({approximately}600{degrees}C), i.e., through a Diels-Alder type reaction. On the other hand, such growth of ring as formation of biphenyl accompanying dehydrogenation from benzene can proceed only at the higher temperatures. It was also revealed that in the growth of the ring, cycloaddition of butadiene favors a cyclic olefin molecule that possesses a nonconjugated double bond and a nearly planar structure.

  13. Binary Formation Mechanisms: Constraints from the Companion Mass Ratio Distribution

    NASA Astrophysics Data System (ADS)

    Reggiani, Maddalena M.; Meyer, Michael R.

    2011-09-01

    We present a statistical comparison of the mass ratio distribution of companions, as observed in different multiplicity surveys, to the most recent estimate of the single-object mass function. The main goal of our analysis is to test whether or not the observed companion mass ratio distribution (CMRD) as a function of primary star mass and star formation environment is consistent with having been drawn from the field star initial mass function (IMF). We consider samples of companions for M dwarfs, solar-type stars, and intermediate-mass stars, both in the field as well as clusters or associations, and compare them with populations of binaries generated by random pairing from the assumed IMF for a fixed primary mass. With regard to the field we can reject the hypothesis that the CMRD was drawn from the IMF for different primary mass ranges: the observed CMRDs show a larger number of equal-mass systems than predicted by the IMF. This is in agreement with fragmentation theories of binary formation. For the open clusters α Persei and the Pleiades we also reject the IMF random-pairing hypothesis. Concerning young star-forming regions, currently we can rule out a connection between the CMRD and the field IMF in Taurus but not in Chamaeleon I. Larger and different samples are needed to better constrain the result as a function of the environment. We also consider other companion mass functions and we compare them with observations. Moreover the CMRD both in the field and clusters or associations appears to be independent of separation in the range covered by the observations. Combining therefore the CMRDs of M (1-2400 AU) and G (28-1590 AU) primaries in the field and intermediate-mass primary binaries in Sco OB2 (29-1612 AU) for mass ratios, q = M 2/M 1, from 0.2 to 1, we find that the best chi-square fit follows a power law dN/dqvpropq β, with β = -0.50 ± 0.29, consistent with previous results. Finally, we note that the Kolmogorov-Smirnov test gives a ~1% probability

  14. A possible oriented attachment growth mechanism for silver nanowire formation

    DOE PAGES

    Murph, Simona E. Hunyadi; Murphy, Catherine J.; Leach, Austin; ...

    2015-04-06

    Electron microscopy studies suggest that silver nanowires prepared by an approach reported earlier by us (Caswell, K. K., Bender, C. M., Murphy, C. J. Nano Lett.,2003, 3, 667–669) form through a coarsening process via an oriented attachment mechanism. Initially, silver nucleation centers were produced by chemical reduction of silver ions in boiling water, with sodium citrate and sodium hydroxide as additives in solution. These nucleation centers, with a twinned crystallographic orientation, ultimately merge into fully grown silver nanowires. This is a completely different mechanism from the seed-mediated growth approach, which has also been used to produce silver nanowires. Furthermore, companionmore » molecular dynamics performed with the embedded atom method are in agreement with our experimental data.« less

  15. A possible oriented attachment growth mechanism for silver nanowire formation

    SciTech Connect

    Murph, Simona E. Hunyadi; Murphy, Catherine J.; Leach, Austin; Gall, Kenneth

    2015-04-06

    Electron microscopy studies suggest that silver nanowires prepared by an approach reported earlier by us (Caswell, K. K., Bender, C. M., Murphy, C. J. Nano Lett.,2003, 3, 667–669) form through a coarsening process via an oriented attachment mechanism. Initially, silver nucleation centers were produced by chemical reduction of silver ions in boiling water, with sodium citrate and sodium hydroxide as additives in solution. These nucleation centers, with a twinned crystallographic orientation, ultimately merge into fully grown silver nanowires. This is a completely different mechanism from the seed-mediated growth approach, which has also been used to produce silver nanowires. Furthermore, companion molecular dynamics performed with the embedded atom method are in agreement with our experimental data.

  16. Formation mechanism of the photomask blanks material related haze

    NASA Astrophysics Data System (ADS)

    Kim, Jung-Jin; Choi, Junyoul; Koh, Soowan; Kim, Minho; Lee, Jiyoung; Lee, Han-Shin; Kim, Byung Gook; Jeon, Chan-uk

    2016-05-01

    We have observed a new type haze of which formation deviates from the generally accepted models with respect to the size, shape, and removability by chemicals. It has very small size of 50~100nm and are crowded around the cell boundary, while the typical haze doesn't prefer a special region on mask in the majority of cases. It is hard to remove by general cleaning, while the typical haze is easily removed by general cleaning process and even de-ionized water. It is confirmed that the source of the haze is blank material related ions which are formed by chemical etching of blanks during mask cleaning process or the photomask blanks itself.

  17. High-speed imagery captures new sea spray formation mechanism

    NASA Astrophysics Data System (ADS)

    Schultz, Colin

    2012-10-01

    When strong winds blow over ocean waves, small droplets of sea spray rise into the air, enhancing the exchange of heat, mass, and energy between the air and the sea. How effective sea spray is at mediating each of these dynamics depends on the rate at which droplets are created and the drop size distribution of the mist. Unfortunately, research has been limited by a dearth of observational evidence that could explain the details of sea spray generation, including understanding the drop size distribution or the effects of different wind speeds. Previous research with high-speed cameras aiming to capture the moment of drop formation was limited by camera resolutions too low to see all but the largest drops.

  18. All-optical phase modulated format conversion for high transmission rates based on fiber nonlinearity

    NASA Astrophysics Data System (ADS)

    Duarte, Vanessa C.; Drummond, Miguel V.; Nogueira, Rogério N.

    2013-11-01

    Advanced modulation formats are an emerging area since they allow reducing the symbol rate while encoding more bits per symbol. This allows higher spectral efficiencies. In addition, we can achieve higher data rates using lower-speed equipment like in all-optical format conversion systems, an important step for the development of systems with high transmission rates. In this paper we study the impact of some impairments found in all-optical advanced format conversions based on cross phase modulation (XPM) on a highly nonlinear fiber (HNLF), such as amplified spontaneous emission (ASE), nonlinear fiber length and group velocity dispersion (GVD), and analyze its performance based on error vector magnitude (EVM) for different bitrate transmissions. This simulation study is applied on earlier proposed phase modulated format conversion where n nonreturn-to-zero on-off keying (NRZ-OOK) channels at 10 Gb/s are converted into a return-to-zero m phase shift keying (RZ-mPSK) at 20Gb/s. We extend the work with simulations and show the results for n NRZ-OOK channels at 20Gb/s, 40 Gb/s and 50Gb/s to RZ-PSK at 40Gb/s, 80 Gb/s and 100Gb/s, respectively.

  19. Direct Observations of Sigma Phase Formation in Duplex Stainless Steels using In Situ Synchrotron X-Ray Diffraction

    SciTech Connect

    Elmer, J W; Palmer, T A; Specht, E D

    2006-07-03

    The formation and growth of sigma phase in 2205 duplex stainless steel was observed and measured in real time using synchrotron radiation during 10 hr isothermal heat treatments at temperatures between 700 C and 850 C. Sigma formed in near-equilibrium quantities during the isothermal holds, starting from a microstructure which contained a balanced mixture of metastable ferrite and austenite. In situ synchrotron diffraction continuously monitored the transformation, and these results were compared to those predicted by thermodynamic calculations. Differences between the calculated and measured amounts of sigma, ferrite and austenite suggest that the thermodynamic calculations underpredict the sigma dissolution temperature by approximately 50 C. The data were further analyzed using a modified Johnson-Mehl-Avrami (JMA) approach to determine kinetic parameters for sigma formation over this temperature range. The initial JMA exponent, n, at low fractions of sigma was found to be approximately 7.0, however, towards the end of the transformation, n decreased to values of approximately 0.75. The change in the JMA exponent was attributed to a change in the transformation mechanism from discontinuous precipitation with increasing nucleation rate, to growth of the existing sigma phase after nucleation site saturation occurred. Because of this change in mechanism, it was not possible to determine reliable values for the activation energy and pre-exponential terms for the JMA equation. While cooling back to room temperature, the partial transformation of austenite resulted in a substantial increase in the ferrite content, but sigma retained its high temperature value to room temperature.

  20. simpleGAMMA - a reduced model of secondary organic aerosol formation in the aqueous aerosol phase (aaSOA)

    NASA Astrophysics Data System (ADS)

    Woo, J. L.; McNeill, V. F.

    2015-01-01

    There is increasing evidence that the uptake and aqueous processing of water-soluble volatile organic compounds (VOCs) by wet aerosols or cloud droplets is an important source of secondary organic aerosol (SOA). We recently developed GAMMA (Gas-Aerosol Model for Mechanism Analysis), a zero-dimensional kinetic model that couples gas-phase and detailed aqueous-phase atmospheric chemistry for speciated prediction of SOA and organosulfate formation in cloudwater or aqueous aerosols. Results from GAMMA simulations of SOA formation in aerosol water (McNeill et al., 2012) indicate that it is dominated by two pathways: isoprene epoxydiol (IEPOX) uptake followed by ring-opening chemistry (under low-NOx conditions) and glyoxal uptake. This suggested that it is possible to model the majority of aqueous aerosol phase SOA mass using a highly simplified reaction scheme. We have therefore developed a reduced version of GAMMA, simpleGAMMA. Close agreement in predicted aaSOA mass is observed between simpleGAMMA and GAMMA under all conditions tested (between pH 1-4 and RH 40-80%) after 12 h of simulation. simpleGAMMA is computationally efficient and suitable for coupling with larger-scale atmospheric chemistry models.

  1. Formation of parallel two-phase flow in nanochannel and application to solvent extraction

    NASA Astrophysics Data System (ADS)

    Kazoe, Yutaka; Ugajin, Takuya; Ohta, Ryoichi; Mawatari, Kazuma; Kitamori, Takehiko; The University of Tokyo Team

    2015-11-01

    Micro chemical systems have realized high-throughput analysis in ultra small volumes. Our group has established unit operations such as extraction, separation and reaction, and a concept of integration of chemical processes using parallel multi-phase flows in microchannels. Recently, the research field has been extended to 10-1000 nm space (extended-nanospace). Exploiting extended-nanospace, we developed ultra high performance chemical operations such as aL-chromatography and single molecule immunoassay. However, formation of parallel multi-phase flow in nanochannels has been difficult. The challenge is to control liquid-liquid/gas-liquid interfaces in 100 nm-scale. For this purpose, this study developed a partial surface modification method of nanochannel and verified formation of parallel two-phase flow. We achieved partial hydrophobic modification using focused ion beam (FIB). Using this method, formation of parallel water/dodecane two-phase flow in a nanochannel of 1500 nm width and 890 nm depth was succeeded. Solvent extraction of lipid, which is a basic separation in bioanalysis, was achieved in 25 fL volume much smaller than single cell. This study will greatly contribute to develop novel nanofluidic devices for chemical analysis and chemical synthesis. This work was supported by Japan Science and Technology Agency, Core Research for Evolutional Science and Technology.

  2. Structural Evolution and Phase Stability of Hume-Rothery Phase in a Mechanically Driven Nanostructured Ag-15 at. pct Sn Alloy

    NASA Astrophysics Data System (ADS)

    Chithra, S.; Malviya, K. D.; Chattopadhyay, K.

    2013-10-01

    The paper reports phase evolution in mechanically driven Ag-15 at. pct Sn alloy powder starting with elemental powders in order to establish the feasibility of designing nanocomposites of a Ag-Sn solid solution. This alloy lies in the phase field of the hexagonal ζ-phase which is a well-known Hume-Rothery electron compound with an electron-to-atom ratio of about 1.45 and hexagonal crystal structure (a = 0.2966 nm, c = 0.4782 nm). Through a systematic use of X-ray diffraction and transmission electron microscopy, the results establish the formation of the ζ-phase which co-exists with the Ag solid solution during the initial phase of milling. Mechanical milling for long duration (55 hours) destabilizes the ζ-phase. A complete solid solution of Ag with a grain size of ~8 nm could be achieved after 60 hours of milling. Additional milling can induce decomposition of the solid solution that results in a reappearance of ζ-phase. We present a detailed thermodynamic calculation which indicates that complete Ag solid solution of the present alloy composition would be possible if the crystallites size can be reduced below a certain critical size. In particular, we show that both Ag and ζ-phase grain sizes need to be taken into account for determining the metastable equilibrium and the phase change that has been experimentally observed. Finally, we argue that recrystallization processes set a limit to the achievable size of the nanoparticles with metastable Ag solid solution.

  3. Mechanical loading, damping, and load-driven bone formation in mouse tibiae.

    PubMed

    Dodge, Todd; Wanis, Mina; Ayoub, Ramez; Zhao, Liming; Watts, Nelson B; Bhattacharya, Amit; Akkus, Ozan; Robling, Alexander; Yokota, Hiroki

    2012-10-01

    Mechanical loads play a pivotal role in the growth and maintenance of bone and joints. Although loading can activate anabolic genes and induce bone remodeling, damping is essential for preventing traumatic bone injury and fracture. In this study we investigated the damping capacity of bone, joint tissue, muscle, and skin using a mouse hindlimb model of enhanced loading in conjunction with finite element modeling to model bone curvature. Our hypothesis was that loads were primarily absorbed by the joints and muscle tissue, but that bone also contributed to damping through its compression and natural bending. To test this hypothesis, fresh mouse distal lower limb segments were cyclically loaded in axial compression in sequential bouts, with each subsequent bout having less surrounding tissue. A finite element model was generated to model effects of bone curvature in silico. Two damping-related parameters (phase shift angle and energy loss) were determined from the output of the loading experiments. Interestingly, the experimental results revealed that the knee joint contributed to the largest portion of the damping capacity of the limb, and bone itself accounted for approximately 38% of the total phase shift angle. Computational results showed that normal bone curvature enhanced the damping capacity of the bone by approximately 40%, and the damping effect grew at an accelerated pace as curvature was increased. Although structural curvature reduces critical loads for buckling in beam theory, evolution apparently favors maintaining curvature in the tibia. Histomorphometric analysis of the tibia revealed that in response to axial loading, bone formation was significantly enhanced in the regions that were predicted to receive a curvature-induced bending moment. These results suggest that in addition to bone's compressive damping capacity, surrounding tissues, as well as naturally-occurring bone curvature, also contribute to mechanical damping, which may ultimately affect

  4. Formation of lead-aluminate ceramics: Reaction mechanisms in immobilizing the simulated lead sludge.

    PubMed

    Lu, Xingwen; Shih, Kaimin

    2015-11-01

    We investigated a strategy of blending lead-laden sludge and an aluminum-rich precursor to reduce the release of hazardous lead from the stabilized end products. To quantify lead transformation and determine its incorporation behavior, PbO was used to simulate the lead-laden sludge fired with γ-Al2O3 by Pb/Al molar ratios of 1/2 and 1/12 at 600-1000 °C for 0.25-10 h. The sintered products were identified and quantified using Rietveld refinement analysis of X-ray diffraction data from the products generated under different conditions. The results indicated that the different crystallochemical incorporations of hazardous lead occurred through the formation of PbAl2O4 and PbAl12O19 in systems with Pb/Al ratios of 1/2 and 1/12, respectively. PbAl2O4 was observed as the only product phase at temperature of 950 °C for 3h heating in Pb/Al of 1/2 system. For Pb/Al of 1/12 system, significant growth of the PbAl12O19 phase clearly occurred at 1000 °C for 3 h sintering. Different product microstructures were found in the sintered products between the systems with the Pb/Al ratios 1/2 and 1/12. The leaching performances of the PbO, Pb9Al8O21, PbAl2O4 and PbAl12O19 phases were compared using a constant pH 4.9 leaching test over 92 h. The leachability data indicated that the incorporation of lead into PbAl12O19 crystal is a preferred stabilization mechanism in aluminate-ceramics.

  5. Mechanisms of Exhaust Pollutants and Plume Formation in Continuous Combustion.

    DTIC Science & Technology

    1984-06-01

    IN CONTINUOUS COMBUSTION E AFOSR 78-3586 G.S. Samuelsen UCI -ARTR-84-7 ci~LAi June 1984 Ř Mechanical Engineering Univgrsity of California Irvine...ORGANIZATION ’b- OFFICE SYMBOL 74. NAME OF MONITORING ORGANIZATION University of California I IfiapphuabielArFreOfi fSintfcRsac UCI Combustion ...SUPPLEMENTARY NOTATION 17 COSATI CODES iI19. SUBJaECT TERI,.S (Continue on pWar~tlee~r aid ida ify by blocir nurnbar, ’efLO TGROUP I sue. R ’ Combustion and

  6. Phase selection enabled formation of abrupt axial heterojunctions in branched oxide nanowires.

    PubMed

    Gao, Jing; Lebedev, Oleg I; Turner, Stuart; Li, Yong Feng; Lu, Yun Hao; Feng, Yuan Ping; Boullay, Philippe; Prellier, Wilfrid; van Tendeloo, Gustaaf; Wu, Tom

    2012-01-11

    Rational synthesis of nanowires via the vapor-liquid-solid (VLS) mechanism with compositional and structural controls is vitally important for fabricating functional nanodevices from bottom up. Here, we show that branched indium tin oxide nanowires can be in situ seeded in vapor transport growth using tailored Au-Cu alloys as catalyst. Furthermore, we demonstrate that VLS synthesis gives unprecedented freedom to navigate the ternary In-Sn-O phase diagram, and a rare and bulk-unstable cubic phase can be selectively stabilized in nanowires. The stabilized cubic fluorite phase possesses an unusual almost equimolar concentration of In and Sn, forming a defect-free epitaxial interface with the conventional bixbyite phase of tin-doped indium oxide that is the most employed transparent conducting oxide. This rational methodology of selecting phases and making abrupt axial heterojunctions in nanowires presents advantages over the conventional synthesis routes, promising novel composition-modulated nanomaterials.

  7. Formation of Structure, Phase Composition and Properties in Refractory Titanium Alloy Under Quenching

    NASA Astrophysics Data System (ADS)

    Gadeev, D. V.; Illarionov, A. G.; Demakov, S. L.

    2015-11-01

    The evolution of structure and phase composition in titanium alloy VT18U under cooling from 900 - 1035°C is studied by the methods of light and electron microscopy, x-ray imaging, hardness measurement and measurement of the modulus of elasticity. The critical temperature of heating for quenching and the dependence of the volume fraction of the phases on this temperature are determined. The effect of the structural and phase state of the alloy quenched from different temperatures on the combination of its physical and mechanical properties (modulus of elasticity, hardness) is analyzed.

  8. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: a kinetic study

    NASA Astrophysics Data System (ADS)

    Kroflič, Ana; Grgić, Irena

    2014-05-01

    It is well known that atmospheric aerosols play a crucial role in the Earth's climate and public health (Pöschl 2005). Despite a great effort invested in the studies of secondary organic aerosol (SOA) budget, composition, and its formation mechanisms, there is still a gap between field observations and atmospheric model predictions (Heald et al. 2005, Hallquist et al. 2009, and Lim et al. 2010). The insisting uncertainties surrounding SOA formation and aging thus gained an increasing interest in atmospheric aqueous phase chemistry; they call for more complex and time consuming studies at the environmentally relevant conditions allowing confident extrapolation to desired ambient conditions. In addition to the adverse health effects of atmospheric particulate matter (PM) as such, toxicity is also attributed to nitro-aromatic and other organic compounds which have already been detected in real aerosol samples (Traversi et al. 2009). Moreover, low-volatility aromatic derivatives are believed to form at least partly in the aerosol aqueous phase and not only in the gas phase from where they partition into water droplets (Ervens et al. 2011). Two nitro derivatives of biomass burning tracer guaiacol have recently been found in winter PM10 samples from the city of Ljubljana, Slovenia, and aqueous photonitration reaction was proposed as their possible production pathway (Kitanovski et al. 2012). In this study the kinetics of guaiacol nitration in aqueous solution was investigated in the presence of H2O2 and NO2¯ upon simulated solar irradiation (Xenon lamp, 300 W). During the experiment the DURAN® flask with the reaction mixture was held in the thermostated bath and thoroughly mixed. The reaction was monitored for 44 hours at different temperatures. Guaiacol and its main nitro-products (4-nitroguaiacol, 4-NG; 6-nitroguaiacol, 6-NG; and 4,6-dinitroguaiacol, 4,6-DNG) were quantified in every aliquot, taken from the reaction mixture, by use of high pressure liquid

  9. Single-phase and two-phase flow properties of mesaverde tight sandstone formation; random-network modeling approach

    NASA Astrophysics Data System (ADS)

    Bashtani, Farzad; Maini, Brij; Kantzas, Apostolos

    2016-08-01

    3D random networks are constructed in order to represent the tight Mesaverde formation which is located in north Wyoming, USA. The porous-space is represented by pore bodies of different shapes and sizes which are connected to each other by pore throats of varying length and diameter. Pore bodies are randomly distributed in space and their connectivity varies based on the connectivity number distribution which is used in order to generate the network. Network representations are then validated using publicly available mercury porosimetry experiments. The network modeling software solves the fundamental equations of two-phase immiscible flow incorporating wettability and contact angle variability. Quasi-static displacement is assumed. Single phase macroscopic properties (porosity, permeability) are calculated and whenever possible are compared to experimental data. Using this information drainage and imbibition capillary pressure, and relative permeability curves are predicted and (whenever possible) compared to experimental data. The calculated information is grouped and compared to available literature information on typical behavior of tight formations. Capillary pressure curve for primary drainage process is predicted and compared to experimental mercury porosimetry in order to validate the virtual porous media by history matching. Relative permeability curves are also calculated and presented.

  10. Modeling Multiple Time Scales during Glass Formation with Phase-Field Crystals

    SciTech Connect

    Berry, Joel; Grant, Martin

    2011-04-29

    The dynamics of glass formation in monatomic and binary liquids are studied numerically using a microscopic field theory for the evolution of the time-averaged atomic number density. A stochastic framework combining phase-field crystal free energies and dynamic density functional theory is shown to successfully describe several aspects of glass formation over multiple time scales. Agreement with mode coupling theory is demonstrated for underdamped liquids at moderate supercoolings, and a rapidly growing dynamic correlation length is found to be associated with fragile behavior.

  11. Mechanisms of Formation and Transformation of Ni-Fe Hydroxycarbonates

    SciTech Connect

    Refait, Ph.; Jeannin, M.; Reffass, M.; Drissi, S.H.; Abdelmoula, M.; Genin, J.-M.R.

    2005-04-26

    The mechanisms of the transformation of (Ni,Fe)(OH)2 precipitates in carbonated aqueous solutions were studied. The reactions were monitored by measuring the redox potential of the aqueous suspension, and end products were studied by Moessbauer spectroscopy, X-ray diffraction and Raman spectroscopy. The oxidation processes were compared to those occurring without Ni, that is when the initial hydroxide is Fe(OH)2. Schematically, the oxidation of Fe(OH)2 involves two intermediate compounds, the carbonated GR of formula Fe{sup II}{sub 4}Fe{sup III}{sub 2}(OH){sub 12}CO{sub 3} {center_dot} 2H{sub 2}O, and ferrihydrite, before to lead finally to goethite {alpha}-FeOOH. It proved possible to prepare Ni(II)-Fe(III) hydroxycarbonates with ratios Fe/Ni from 1/6 to 1/3. When the Fe/Ni ratio is larger than 1/3, a two stage oxidation process takes place. The first stage leads to a Ni(II)-Fe(II)-Fe(III) hydroxycarbonate. The second stage corresponds to the oxidation of the Fe(II) remaining inside the hydroxycarbonate and leads to a mixture of Ni(II)-Fe(III) hydroxycarbonate with ferrihydrite. The main effect of Ni is then to stop the reaction at an intermediate stage, as Ni(II) is not oxidised by O2, leaving unchanged the main features of the mechanisms of transformation.

  12. Mechanism of gas saturated oil viscosity anomaly near to phase transition point

    NASA Astrophysics Data System (ADS)

    Suleimanov, Baghir A.; Abbasov, Elkhan M.; Sisenbayeva, Marziya R.

    2017-01-01

    The article presents experimental studies of the phase behavior by the flash liberation test and of the viscosity of the live oil at different pressures. Unlike the typical studies at the pressure near the saturation pressure, the measurements were conducted at a relatively small pressure increment of 0.08-0.25 MPa. The viscosity anomaly was discovered experimentally near to the phase transition point in the range of the pressure levels P/Pb = 1-1.14 (Pb—bubble point pressure) and shows that it decreases about 70 times in comparison to the viscosity at the reservoir pressure. It was found that the bubble point pressure decreases significantly (up to 36%) with surfactant addition. Furthermore, the viscosity of the live oil at the surfactant concentration of 5 wt. % decreases almost 37 times in comparison to the viscosity at the reservoir pressure. The mechanism of observed effects was suggested based on the formation of the stable subcritical gas nuclei and associated slippage effect. The mechanism for the stabilization of the subcritical nuclei by the combined action of the surface and electrical forces, as well as the morphology of the formed nanobubbles, was considered. The model for determining the oil viscosity taking into account the slippage effect was suggested.

  13. Discontinuous phase formation and selective attack of SiC materials exposed to low oxygen partial pressure environments

    SciTech Connect

    Butt, D.P.; Tressler, R.E.; Spear, K.E.

    1993-09-01

    Three SiC materials were exposed to gas mixtures containing N{sub 2}, H{sub 2}, and CO at 1000-1300C, 1-740 torr for a few to 1000 h. Kinetic and thermodynamic studies indicate that CO is the predominant oxidizing species. A variety of corrosion processes were observed, including surface and internal pit formation, needle growth, grain boundary attack, and attack of impurities and surrounding material. In the case of a siliconized SiC, impurities such as Ca, Al, and Fe diffused rapidly through the Si matrix forming complex calcium aluminosilicates on the surface, leaving behind internal voids. Evaluation of the mechanical properties, including fractography, revealed a variety of degradative phenomena. Efforts to identify causes of pit formation suggested that the overall process was complex. Pits formed during attack of grain boundaries and regions containing transition metal impurities. Studies of single crystals showed preferential attack near impurities and crystalline defects, indicating that damaged crystals or certain crystal orientations in the polycrystalline materials are susceptible to attack. In addition, under some conditions where pit formation was observed, the strength of certain materials increased apparently due to flaw healing. It is suggested that flaws can heal in the absence of mechanical stress due to their high surface energy. However, second phases observed within partially healed surface cracks suggest impurities also contribute to the flaw healing processes.

  14. Barrier formation: potential molecular mechanism of enamel fluorosis.

    PubMed

    Lyaruu, D M; Medina, J F; Sarvide, S; Bervoets, T J M; Everts, V; Denbesten, P; Smith, C E; Bronckers, A L J J

    2014-01-01

    Enamel fluorosis is an irreversible structural enamel defect following exposure to supraoptimal levels of fluoride during amelogenesis. We hypothesized that fluorosis is associated with excess release of protons during formation of hypermineralized lines in the mineralizing enamel matrix. We tested this concept by analyzing fluorotic enamel defects in wild-type mice and mice deficient in anion exchanger-2a,b (Ae2a,b), a transmembrane protein in maturation ameloblasts that exchanges extracellular Cl(-) for bicarbonate. Defects were more pronounced in fluorotic Ae2a,b (-/-) mice than in fluorotic heterozygous or wild-type mice. Phenotypes included a hypermineralized surface, extensive subsurface hypomineralization, and multiple hypermineralized lines in deeper enamel. Mineral content decreased in all fluoride-exposed and Ae2a,b(-/-) mice and was strongly correlated with Cl(-). Exposure of enamel surfaces underlying maturation-stage ameloblasts to pH indicator dyes suggested the presence of diffusion barriers in fluorotic enamel. These results support the concept that fluoride stimulates hypermineralization at the mineralization front. This causes increased release of protons, which ameloblasts respond to by secreting more bicarbonates at the expense of Cl(-) levels in enamel. The fluoride-induced hypermineralized lines may form barriers that impede diffusion of proteins and mineral ions into the subsurface layers, thereby delaying biomineralization and causing retention of enamel matrix proteins.

  15. Analysis of mechanisms for anode plasma formation in ion diodes

    SciTech Connect

    Sweeney, M.A.; Brandenburg, J.E.; Gerber, R.A.; Johnson, D.J.; Hoffman, J.M.; Miller, P.A.; Quintenz, J.P.; Slutz, S.A.; Bieg, K.W.

    1983-01-01

    Understanding how anode plasma is formed in intense pulsed-power ion diodes by insulator breakdown is important in assessing the effect on ion beam quality. Formation of a passive flashover anode plasma source may involve one or more of the following: polarization of the anode dielectric, direct leakage electron bombardment, UV-stimulated desorption of excited gas in the gap or on the anode surface, ionization of desorbed neutrals in a surface plasma by electron return currents associated with ion extraction, or bombardment by low energy electrons or negative ions. At Sandia National Laboratories experiments have been done on Nereus, PI 110A, Proto I, Proto II, HydraMITE, and PBFA I using anodes with dielectric-filled surfaces. The experiments represent a variety of anode turn-on delays (2 to 15 ns), magnetic field strengths (7 to 30 kG), voltages (300 keV to 2 MeV), and anode configurations. Data include ion beam current from Faraday cups, holographic observation of plasma motion, the spatial and temporal character of visible light emitted from the plasma, and optical metallographic examination of the dielectric.

  16. The formation mechanism of aluminum oxide tunnel barriers.

    SciTech Connect

    Cerezo, A.; Petford-Long, A. K.; Larson, D. J.; Pinitsoontorn, S.; Singleton, E. W.; Materials Science Division; Univ. Oxford; Seagate Tech.

    2006-01-01

    The functional properties of magnetic tunnel junctions are critically dependant on the nanoscale morphology of the insulating barrier (usually only a few atomic layers thick) that separates the two ferromagnetic layers. Three-dimensional atom probe analysis has been used to study the chemistry of a magnetic tunnel junction structure comprising an aluminium oxide barrier formed by in situ oxidation, both in the under-oxidized and fully oxidized states and before and after annealing. Low oxidation times result in discrete oxide islands. Further oxidation leads to a more continuous, but still non-stoichiometric, barrier with evidence that oxidation proceeds along the top of grain boundaries in the underlying CoFe layer. Post-deposition annealing leads to an increase in the barrier area, but only in the case of the fully oxidized and annealed structure is a continuous planar layer formed, which is close to the stoichiometric Al:O ratio of 2:3. These results are surprising, in that the planar layers are usually considered unstable with respect to breaking up into separate islands. Analysis of the various driving forces suggests that the formation of a continuous layer requires a combination of factors, including the strain energy resulting from the expansion of the oxide during internal oxidation on annealing.

  17. Study of formation mechanism of incipient melting in thixo-cast Al–Si–Cu–Mg alloys

    SciTech Connect

    Du, Kang Zhu, Qiang Li, Daquan Zhang, Fan

    2015-08-15

    Mechanical properties of thixo-cast Al–Si–Cu–Mg alloys can be enhanced by T61 heat treatment. Copper and magnesium atoms in aluminum matrix can form homogeneously distributed precipitations after solution and aging treatment which harden the alloys. However, microsegregation of these alloying elements could form numerous tiny multi-compound phases during solidification. These phases could cause incipient melting defects in subsequent heat treatment process and degrade the macro-mechanical properties of productions. This study is to present heterogeneous distribution of Cu, Si, and Mg elements and formation of incipient melting defects (pores). In this study, incipient melting pores that occurred during solution treatment at various temperatures, even lower than common melting points of various intermetallic phases, were identified, in terms of a method of investigating the same surface area in the samples before and after solution treatment in a vacuum environment. The results also show that the incipient melting mostly originates at the clusters with fine intermetallic particles while also some at the edge of block-like Al{sub 2}Cu. The fine particles were determined being Al{sub 2}Cu, Al{sub 5}Cu{sub 2}Mg{sub 8}Si{sub 6} and Al{sub 8}Mg{sub 3}FeSi{sub 2}. Tendency of the incipient melting decreases with decreases of the width of the clusters. The formation mechanism of incipient melting pores in solution treatment process was discussed using both the Fick law and the LSW theory. Finally, a criterion of solution treatment to avoid incipient melting pores for the thixo-cast alloys is proposed. - Highlights: • In-situ comparison technique was used to analysis the change of eutectic phases. • The ralationship between eutectic phase size and incipient melting was studied. • Teat treatment criterion for higher incipient melting resistance was proposed.

  18. Study of Hind Limb Tissue Gas Phase Formation in Response to Suspended Adynamia and Hypokinesia

    NASA Technical Reports Server (NTRS)

    Butler, Bruce D.

    1996-01-01

    The purpose of this study was to investigate the hypothesis that reduced joint/muscle activity (hypo kinesia) as well as reduced or null loading of limbs (adynamia) in gravity would result in reduced decompression-induced gas phase and symptoms of decompression sickness (DCS). Finding a correlation between the two phenomena would correspond to the proposed reduction in tissue gas phase formation in astronauts undergoing decompression during extravehicular activity (EVA) in microgravity. The observation may further explain the reported low incidence of DCS in space.

  19. Hydride phase formation in carbon supported palladium hydride nanoparticles by in situ EXAFS and XRD

    NASA Astrophysics Data System (ADS)

    Bugaev, A. L.; Guda, A. A.; Lomachenko, K. A.; Lazzarini, A.; Srabionyan, V. V.; Vitillo, J. G.; Piovano, A.; Groppo, E.; Bugaev, L. A.; Soldatov, A. V.; Dmitriev, V. P.; Pellegrini, R.; van Bokhoven, J. A.; Lamberti, C.

    2016-05-01

    In the current work we present a detailed analysis of the hydride phase formation in industrial Pd/C nanocatalysts by means of combined in situ X-ray absorption spectroscopy (EXAFS), X-ray diffraction (XRD) and volumetric measurements for the temperatures from - 10 to 50 °C in the hydrogen pressure range from 0 to 1000 mbar. α- and β- hydride phases are clearly distinguished in XRD. For the first time, H/Pd atomic ratio were obtained by theoretical fitting of the near-edge region of the absorption spectra (XANES) and compared with volumetric measurements.

  20. Atmospheric fate of OH initiated oxidation of terpenes. Reaction mechanism of alpha-pinene degradation and secondary organic aerosol formation.

    PubMed

    Librando, Vito; Tringali, Giuseppe

    2005-05-01

    This paper studies the reaction products of alpha-pinene, beta-pinene, sabinene, 3-carene and limonene with OH radicals and of alpha-pinene with ozone using FT-IR spectroscopy for measuring gas phase products and HPLC-MS-MS to measure products in the aerosol phase. These techniques were used to investigate the secondary organic aerosol (SOA) formation from the terpenes. The gas phase reaction products were all quantified using reference compounds. At low terpene concentrations (0.9-2.1 ppm), the molar yields of gas phase reaction products were: HCHO 16-92%, HCOOH 10-54% (OH source: H2O2, 6-25 ppm); HCHO 127-148%, HCOOH 4-6% (OH source: CH3ONO, 5-8 ppm). At high terpene concentrations (4.1-13.2 ppm) the results were: HCHO 9-27%, HCOOH 15-23%, CH3(CO)CH3 0-14%, CH3COOH 0-5%, nopinone 24% (only from beta-pinene oxidation), limona ketone 61% (only from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source H2O2, 23-30 ppm); HCHO 76-183%, HCOOH 12-15%, CH3(CO)CH3 0-12%, nopinone 17% (from beta-pinene oxidation), limona ketone 48% (from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source CH3ONO, 14-16 ppm). Pinic acid, pinonic acid, limonic acid, limoninic acid, 3-caric acid, 3-caronic acid and sabinic acid were identified in the aerosol phase. On the basis of these results, we propose a formation mechanism for pinonic and pinic acid in the aerosol phase explaining how degradation products could influence SOA formation and growth in the troposphere.

  1. Optically transparent, mechanically durable, nanostructured superhydrophobic surfaces enabled by spinodally phase-separated glass thin films.

    PubMed

    Aytug, Tolga; Simpson, John T; Lupini, Andrew R; Trejo, Rosa M; Jellison, Gerald E; Ivanov, Ilia N; Pennycook, Stephen J; Hillesheim, Daniel A; Winter, Kyle O; Christen, David K; Hunter, Scott R; Haynes, J Allen

    2013-08-09

    We describe the formation and properties of atomically bonded, optical quality, nanostructured thin glass film coatings on glass plates, utilizing phase separation by spinodal decomposition in a sodium borosilicate glass system. Following deposition via magnetron sputtering, thermal processing and differential etching, these coatings are structurally superhydrophilic (i.e., display anti-fogging functionality) and demonstrate robust mechanical properties and superior abrasion resistance. After appropriate chemical surface modification, the surfaces display a stable, non-wetting Cassie-Baxter state and exhibit exceptional superhydrophobic performance, with water droplet contact angles as large as 172°. As an added benefit, in both superhydrophobic and superhydrophilic states these nanostructured surfaces can block ultraviolet radiation and can be engineered to be anti-reflective with broadband and omnidirectional transparency. Thus, the present approach could be tailored toward distinct coatings for numerous markets, such as residential windows, windshields, specialty optics, goggles, electronic and photovoltaic cover glasses, and optical components used throughout the US military.

  2. Waveguide formation mechanism generated by double doping in ferroelectric crystals

    NASA Astrophysics Data System (ADS)

    Atuchin, V. V.; Ziling, C. C.; Savatinova, I.; Armenise, M. N.; Passaro, V. M. N.

    1995-12-01

    Physical mechanisms causing the refractive index increase Δn in uniaxial oxidized ferroelectric crystals subjected to double doping are discussed. The analysis shows that the index changes of the two different dopants, ΔnA and ΔnB, are additive only if the corresponding changes of the spontaneous polarization are small. Ti indiffusion and proton exchange (TIPE) waveguides in LiNbO3 are considered as an example of the case when this condition is not fulfilled. The hydrogen-lithium substitution in such waveguides leads to a strong reduction of the spontaneous polarization of the virgin crystals and the final index change Δn is not a sum of ΔnA and ΔnB. A physical model is developed to explain light waveguiding in double-doped ferroelectric structures. Experimental data obtained for TIPE waveguides confirm the model.

  3. [Mechanism on differential gene expression and heterosis formation].

    PubMed

    Xu, Chen-Lu; Sun, Xiao-Mei; Zhang, Shou-Gong

    2013-06-01

    Despite the rediscovery of heterosis about a century ago and the suggestion of various genetic models to explain this phenomenon, little consensus has yet been reached about the genetic basis of heterosis. Following the genome organization variation and gene effects, an understanding of gene differential expression in hybrids and its parents provides a new opportunity to speculate on mechanisms that might lead to heterosis. Investigation on allele-specific gene expression in hybrid and gene differential expression between hybrids and its parents might contribute to improve our understanding of the molecular basis of heterosis and eventually guide breeding practices. In this review, we discussed the recent researches on allelic-specific expression in hybrid which was frequently observed in recent studies and analyzed its regulatory mechanism. All possible modes of gene action, including additivity, high- and low-parent dominance, underdominance, and over-dominance, were observed when investigating gene differential expression between hybrids and its parents. Data from transcriptomic studies screened several heterosis-associated genes and highlighted the importance of certain key biochemical pathways that may prove to be quintessential for the manifestation of heterosis. So far, no uniform global expression pat-terns were observed in these gene expression studies. Most heterosis-associated gene expression analyses have not revealed a predominant functional category to which differentially expressed genes belong. However, these gene expression profiling studies represent a first step towards the definition of the complex gene expression networks that might be relevant in the context of heterosis. New technique on gene expression profile and advancements in bioinformatics will facilitate our understanding of the genetic basis of heterosis at the gene-expression level.

  4. Phase stability, mechanical properties, hardness, and possible reactive routing of chromium triboride from first-principle investigations

    SciTech Connect

    Zhong, Ming-Min; Kuang, Xiao-Yu Wang, Zhen-Hua; Shao, Peng; Ding, Li-Ping; Huang, Xiao-Fen

    2013-12-21

    The first-principles calculations are employed to provide a fundamental understanding of the structural features and relative stability, mechanical and electronic properties, and possible reactive route for chromium triboride. The predicted new phase of CrB{sub 3} belongs to the rhombohedral phase with R-3m symmetry and it transforms into a hexagonal phase with P-6m2 symmetry at 64 GPa. The mechanical and thermodynamic stabilities of CrB{sub 3} are verified by the calculated elastic constants and formation enthalpies. Also, the full phonon dispersion calculations confirm the dynamic stability of predicted CrB{sub 3}. Considering the role of metallic contributions, the calculated hardness values from our semiempirical method for rhombohedral and hexagonal phases are 23.8 GPa and 22.1 GPa, respectively. In addition, the large shear moduli, Young's moduli, low Poisson's ratios, and small B/G ratios indicate that they are potential hard materials. Relative enthalpy calculations with respect to possible constituents are also investigated to assess the prospects for phase formation and an attempt at high-pressure synthesis is suggested to obtain chromium triboride.

  5. Phase stability, mechanical properties, hardness, and possible reactive routing of chromium triboride from first-principle investigations.

    PubMed

    Zhong, Ming-Min; Kuang, Xiao-Yu; Wang, Zhen-Hua; Shao, Peng; Ding, Li-Ping; Huang, Xiao-Fen

    2013-12-21

    The first-principles calculations are employed to provide a fundamental understanding of the structural features and relative stability, mechanical and electronic properties, and possible reactive route for chromium triboride. The predicted new phase of CrB3 belongs to the rhombohedral phase with R-3m symmetry and it transforms into a hexagonal phase with P-6m2 symmetry at 64 GPa. The mechanical and thermodynamic stabilities of CrB3 are verified by the calculated elastic constants and formation enthalpies. Also, the full phonon dispersion calculations confirm the dynamic stability of predicted CrB3. Considering the role of metallic contributions, the calculated hardness values from our semiempirical method for rhombohedral and hexagonal phases are 23.8 GPa and 22.1 GPa, respectively. In addition, the large shear moduli, Young's moduli, low Poisson's ratios, and small B∕G ratios indicate that they are potential hard materials. Relative enthalpy calculations with respect to possible constituents are also investigated to assess the prospects for phase formation and an attempt at high-pressure synthesis is suggested to obtain chromium triboride.

  6. Mechanisms of iron-silica aqueous interaction and the genesis of Precambrian iron formation

    NASA Astrophysics Data System (ADS)

    Chemtob, S. M.; Catalano, J. G.; Moynier, F.; Pringle, E. A.

    2015-12-01

    Iron formations (IFs), Fe- and Si-rich chemical sediments common in Precambrian successions, preserve key information about the compositional, biological, and oxidative evolution of the Precambrian ocean. Stable Si isotopes (δ30Si) of IF have been used to infer paleo-oceanic composition, and secular variations in δ30Si may reflect ancient biogeochemical cycles. The δ30Si of primary Fe-Si precipitates that formed IF depends not only on the δ30Si of aqueous silica but also on the precipitation mechanism. Multiple formation mechanisms for these primary precipitates are plausible. Aqueous Si may have adsorbed on newly precipitated iron oxyhydroxide surfaces; alternatively, Fe and Si may have coprecipitated as a single phase. Here we explore variations in the Si isotope fractionation factor (ɛ) with Fe-Si aqueous interaction mechanism (adsorption vs. coprecipitation). In adsorption experiments, sodium silicate solutions (pH 8.1, 125-2000 µM Si) were reacted with iron oxide particles (hematite, ferrihydrite, goethite, and magnetite) for 24 to 72 hours. Resultant solutions had δ30Si between 0 and +6‰. Calculated ɛ varied significantly with oxide mineralogy and morphology. For ferrihydrite, ɛ = -1.7‰; for hematite, ɛ = -2 to -5‰, depending on particle morphology. Apparent ɛ decreased upon surface site saturation, implying a smaller isotope effect for polymeric Si adsorption than monomeric adsorption. In coprecipitation experiments, solutions of Na-silicate and Fe(II) chloride (0.4-10 mM) were prepared anaerobically, then air-oxidized for 3 days to induce precipitation. At low Si concentrations, magnetite formed; near silica saturation, lepidocrocite and ferrihydrite formed. The Si isotope fractionation factor for coprecipitation was within the range of ɛ observed for adsorption (ɛ = -2.3 ± 1.0‰). These results indicate that the mechanism of Fe-Si interaction affects ɛ, presumably due to varying silicate coordination environments. These isotopic

  7. Selective covalent bond formation in polypeptide ions via gas-phase ion/ion reaction chemistry.

    PubMed

    Han, Hongling; McLuckey, Scott A

    2009-09-16

    Primary amines present in protonated polypeptides can be covalently modified via gas-phase ion/ion reactions using bifunctional reagent ions. The use of reagent anions with a charge-bearing site that leads to strong interactions with the polypeptide, such as sulfonic acid, gives rise to the formation of a long-lived adduct. A distinct reactive functional group, an aldehyde in the present case, can then undergo reaction with the peptide. Collisional activation of the adduct ion formed from a reagent with an aldehyde group and a peptide ion with a primary amine gives rise to water loss in conjunction with imine (Schiff base) formation. The covalently bound modification is retained upon subsequent collisional activation. This work demonstrates the ability to selectively modify polypeptide ions in the gas phase within the context of a multistage mass spectrometry experiment.

  8. A hydrogen-based oxidation mechanism relevant to planetary formation

    NASA Astrophysics Data System (ADS)

    Sharp, Zachary D.; McCubbin, Francis M.; Shearer, Charles K.

    2013-10-01

    It is now generally accepted that the Moon formed by collision of a Mars-sized impactor with the Earth (Hartmann and Davis, 1975), a process termed "the Giant Impact". The oxygen isotope compositions of both bodies are indistinguishable (Wiechert et al., 2001), a result that would require extensive chemical homogenization. Recent simulations have been developed that predict intimate mixing immediately following the impact (Canup, 2012; Ćuk and Stewart, 2012; Pahlevan and Stevenson, 2007), minimizing the oxygen isotope problem. Nevertheless, striking chemical differences remain. We propose that the process of hydrogen degassing and loss to space during magma cooling can explain differences in the water content, oxygen fugacity (f(O2)), and isotopic composition of Cl and H in the Earth-Moon system. At low f(O2), H2 gas is the stable O-H phase in basalts. The low solubility and rapid diffusivity of H2 explain the presently dry character of most lunar samples. Many of the apparently discrepant observations regarding the hydrous character of the Moon are reconciled by H2 degassing. Early H2 degassing also explains the high f(O2) of Earth's mantle. A loss of only 1/3 'ocean equivalent' water from Earth by hydrodynamic escape of H2 would shift the f(O2) of the upper mantle from the very low oxidation state equivalent to the Moon and other primitive differentiated bodies to its present oxidized state (near the fayalite-magnetite-quartz buffer). No other processes, such as late addition of material to Earth or injection of Fe3+-rich deep mantle materials to the upper mantle are required to explain the early elevated oxidation state of Earth's upper mantle.

  9. Isostructural solid-solid phase transition in monolayers of soft core-shell particles at fluid interfaces: structure and mechanics.

    PubMed

    Rey, Marcel; Fernández-Rodríguez, Miguel Ángel; Steinacher, Mathias; Scheidegger, Laura; Geisel, Karen; Richtering, Walter; Squires, Todd M; Isa, Lucio

    2016-04-21

    We have studied the complete two-dimensional phase diagram of a core-shell microgel-laden fluid interface by synchronizing its compression with the deposition of the interfacial monolayer. Applying a new protocol, different positions on the substrate correspond to different values of the monolayer surface pressure and specific area. Analyzing the microstructure of the deposited monolayers, we discovered an isostructural solid-solid phase transition between two crystalline phases with the same hexagonal symmetry, but with two different lattice constants. The two phases corresponded to shell-shell and core-core inter-particle contacts, respectively; with increasing surface pressure the former mechanically failed enabling the particle cores to come into contact. In the phase-transition region, clusters of particles in core-core contacts nucleate, melting the surrounding shell-shell crystal, until the whole monolayer moves into the second phase. We furthermore measured the interfacial rheology of the monolayers as a function of the surface pressure using an interfacial microdisk rheometer. The interfaces always showed a strong elastic response, with a dip in the shear elastic modulus in correspondence with the melting of the shell-shell phase, followed by a steep increase upon the formation of a percolating network of the core-core contacts. These results demonstrate that the core-shell nature of the particles leads to a rich mechanical and structural behavior that can be externally tuned by compressing the interface, indicating new routes for applications, e.g. in surface patterning or emulsion stabilization.

  10. Dual origins of measured phase-amplitude coupling reveal distinct neural mechanisms underlying episodic memory in the human cortex.

    PubMed

    Vaz, Alex P; Yaffe, Robert B; Wittig, John H; Inati, Sara K; Zaghloul, Kareem A

    2017-03-01

    Phase-amplitude coupling (PAC) is hypothesized to coordinate neural activity, but its role in successful memory formation in the human cortex is unknown. Measures of PAC are difficult to interpret, however. Both increases and decreases in PAC have been linked to memory encoding, and PAC may arise due to different neural mechanisms. Here, we use a waveform analysis to examine PAC in the human cortex as participants with intracranial electrodes performed a paired associates memory task. We found that successful memory formation exhibited significant decreases in left temporal lobe and prefrontal cortical PAC, and these two regions exhibited changes in PAC within different frequency bands. Two underlying neural mechanisms, nested oscillations and sharp waveforms, were responsible for the changes in these regions. Our data therefore suggest that decreases in measured cortical PAC during episodic memory reflect two distinct underlying mechanisms that are anatomically segregated in the human brain.

  11. The Formation of Nanocrystalline Semiconductor Particles within a Bicontinuous Cubic Phase

    DTIC Science & Technology

    1997-04-08

    zeolites have been used to control the particle size. Recently, other researchers have synthesized 1 DTIC QUALITY niEPEOTEB £ Docket No...Inventor’s Name: Yang et al PATENT APPLICATION 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 THE FORMATION OF...NANOCRYSTALLINE SEMICONDUCTOR PARTICLES WITHIN A BICONTINUOUS CUBIC PHASE Background of the Invention 1 . Field of the Invention The present

  12. Removal of Phosphorus in Silicon by the Formation of CaAl2Si2 Phase at the Solidification Interface

    NASA Astrophysics Data System (ADS)

    Sun, Liyuan; Wang, Zhi; Chen, Hang; Wang, Dong; Qian, Guoyu

    2017-02-01

    To fully understand the role of CaAl2Si2 phase in concentrating the non-metallic impurity phosphorus, an experiment of directional solidification of Al-70 at. pct Si alloy with extreme small lowering rate 0.05 mm min-1 was carried out. With good dynamic condition for the diffusion of impurity (Ca, Al, P) from silicon to the S/L interface, the CaAl2Si2 phase with 0.6-0.7 at. pct P was successfully observed by Electron Probe Micro Analyzer (EPMA), and its distribution character was originally presented. This impurity phase was widely detected in the refined sample but only at the interface of silicon crystal and Al-Si alloy which contributed to the deep removal of impurity P. The formation mechanism of CaAl2Si2-P phase was thus explored, in which the microsegregation and concentration of element P, Ca, Al in front of S/L interface were crucial. After acid leaching, the P content decreased from the original 23 ppm to below 5 ppm. Compared with normal solidification, a 16 pct higher removal efficiency of P was obtained in this study.

  13. Mechanisms underlying the formation of induced pluripotent stem cells.

    PubMed

    González, Federico; Huangfu, Danwei

    2016-01-01

    Human pluripotent stem cells (hPSCs) offer unique opportunities for studying human biology, modeling diseases, and therapeutic applications. The simplest approach so far to generate human PSC lines is through reprogramming of somatic cells from an individual by defined factors, referred to simply as reprogramming. Reprogramming circumvents the ethical controversies associated with human embryonic stem cells (hESCs) and nuclear transfer hESCs (nt-hESCs), and the resulting induced pluripotent stem cells (hiPSCs) retain the same basic genetic makeup as the somatic cell used for reprogramming. Since the first report of iPSCs by Takahashi and Yamanaka (Cell 2006, 126:663-676), the molecular mechanisms of reprogramming have been extensively investigated. A better mechanistic understanding of reprogramming is fundamental not only to iPSC biology and improving the quality of iPSCs for therapeutic use, but also to our understanding of the molecular basis of cell identity, pluripotency, and plasticity. Here, we summarize the genetic, epigenetic, and cellular events during reprogramming, and the roles of various factors identified thus far in the reprogramming process. WIREs Dev Biol 2016, 5:39-65. doi: 10.1002/wdev.206 For further resources related to this article, please visit the WIREs website.

  14. SURVIVAL OF INTERSTELLAR MOLECULES TO PRESTELLAR DENSE CORE COLLAPSE AND EARLY PHASES OF DISK FORMATION

    SciTech Connect

    Hincelin, U.; Wakelam, V.; Hersant, F.; Guilloteau, S.; Commerçon, B.

    2013-09-20

    An outstanding question of astrobiology is the link between the chemical composition of planets, comets, and other solar system bodies and the molecules formed in the interstellar medium. Understanding the chemical and physical evolution of the matter leading to the formation of protoplanetary disks is an important step for this. We provide some new clues to this long-standing problem using three-dimensional chemical simulations of the early phases of disk formation: we interfaced the full gas-grain chemical model Nautilus with the radiation-magnetohydrodynamic model RAMSES, for different configurations and intensities of the magnetic field. Our results show that the chemical content (gas and ices) is globally conserved during the collapsing process, from the parent molecular cloud to the young disk surrounding the first Larson core. A qualitative comparison with cometary composition suggests that comets are constituted of different phases, some molecules being direct tracers of interstellar chemistry, while others, including complex molecules, seem to have been formed in disks, where higher densities and temperatures allow for an active grain surface chemistry. The latter phase, and its connection with the formation of the first Larson core, remains to be modeled.

  15. Aging mechanisms in amorphous phase-change materials.

    PubMed

    Raty, Jean Yves; Zhang, Wei; Luckas, Jennifer; Chen, Chao; Mazzarello, Riccardo; Bichara, Christophe; Wuttig, Matthias

    2015-06-24

    Aging is a ubiquitous phenomenon in glasses. In the case of phase-change materials, it leads to a drift in the electrical resistance, which hinders the development of ultrahigh density storage devices. Here we elucidate the aging process in amorphous GeTe, a prototypical phase-change material, by advanced numerical simulations, photothermal deflection spectroscopy and impedance spectroscopy experiments. We show that aging is accompanied by a progressive change of the local chemical order towards the crystalline one. Yet, the glass evolves towards a covalent amorphous network with increasing Peierls distortion, whose structural and electronic properties drift away from those of the resonantly bonded crystal. This behaviour sets phase-change materials apart from conventional glass-forming systems, which display the same local structure and bonding in both phases.

  16. Instability of a Lamellar Phase under Shear Flow: Formation of Multilamellar Vesicles

    NASA Astrophysics Data System (ADS)

    Courbin, L.; Delville, J. P.; Rouch, J.; Panizza, P.

    2002-09-01

    The formation of closed-compact multilamellar vesicles (referred to in the literature as the ``onion texture'') obtained upon shearing lamellar phases is studied using small-angle light scattering and cross-polarized microscopy. By varying the shear rate γ ˙, the gap cell D, and the smectic distance d, we show that: (i)the formation of this structure occurs homogeneously in the cell at a well-defined wave vector qi, via a strain-controlled process, and (ii)the value of qi varies as (dγ ˙/D)1/3. These results strongly suggest that formation of multilamellar vesicles may be monitored by an undulation (buckling) instability of the membranes, as expected from theory.

  17. Hydride-phase formation and its influence on fatigue crack propagationbehavior in a Zircaloy-4 alloy

    SciTech Connect

    Garlea, Elena; Choo, H.; Wang, G Y; Liaw, Peter K; Clausen, B; Brown, D. W.; Park, Jae-Sung; Rack, P. D.; Kenik, Edward A

    2010-01-01

    The hydride-phase formation and its influence on the fatigue behavior of a Zircaloy-4 alloy charged with hydrogen gas are investigated. First, the microstructure and fatigue crack propagation rate of the alloy in the as-r