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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. A new environmental chamber for evaluation of gas-phase chemical mechanisms and secondary aerosol formation

    NASA Astrophysics Data System (ADS)

    Carter, William P. L.; Cocker, David R.; Fitz, Dennis R.; Malkina, Irina L.; Bumiller, Kurt; Sauer, Claudia G.; Pisano, John T.; Bufalino, Charles; Song, Chen

    A new state-of-the-art indoor environmental chamber facility for the study of atmospheric processes leading to the formation of ozone and secondary organic aerosol (SOA) has been constructed and characterized. The chamber is designed for atmospheric chemical mechanism evaluation at low reactant concentrations under well-controlled environmental conditions. It consists of two collapsible 90 m 3 FEP Teflon film reactors on pressure-controlled moveable frameworks inside a temperature-controlled enclosure flushed with purified air. Solar radiation is simulated with either a 200 kW Argon arc lamp or multiple blacklamps. Results of initial characterization experiments, all carried out at ˜300-305 K under dry conditions, concerning NO x and formaldehyde offgasing, radical sources, particle loss rates, and background PM formation are described. Results of initial single organic-NO x and simplified ambient surrogate-NO x experiments to demonstrate the utility of the facility for mechanism evaluation under low NO x conditions are summarized and compared with the predictions of the SAPRC-99 chemical mechanism. Overall, the results of the initial characterization and evaluation indicate that this new environmental chamber can provide high quality mechanism evaluation data for experiments with NO x levels as low as ˜2 ppb, though the results indicate some problems with the gas-phase mechanism that need further study. Initial evaluation experiments for SOA formation, also carried out under dry conditions, indicate that the chamber can provide high quality secondary aerosol formation data at relatively low hydrocarbon concentrations.

  7. The Mechanism of Porosity Formation During Solvent-Mediated Phase Transformations

    SciTech Connect

    Christophe Raufaste; Bjorn Jamtveit; Timm John; Paul Meakin; Dag Kristian Dysthe

    2011-05-01

    Solvent-mediated solid–solid phase transformations often result in the formation of a porous medium, which may be stable on long time scales or undergo ripening and consolidation. We have studied replacement processes in the KBr–KCl–H2O system using both in situ and ex situ experiments. The replacement of a KBr crystal by a K(Br,Cl) solid solution in the presence of an aqueous solution is facilitated by the generation of a surprisingly stable, highly anisotropic and connected pore structure that pervades the product phase. This pore structure ensures efficient solute transport from the bulk solution to the reacting KBr and K(Br,Cl) surfaces. The compositional profile of the K(Br,Cl) solid solution exhibits striking discontinuities across disc-like cavities in the product phase. Similar transformation mechanisms are probably important in controlling phase-transformation processes and rates in a variety of natural and man-made systems.

  8. 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.

  9. 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)

  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. Improving cutaneous scar formation by controlling the mechanical environment: large animal and phase I studies.

    PubMed

    Gurtner, Geoffrey C; Dauskardt, Reinhold H; Wong, Victor W; Bhatt, Kirit A; Wu, Kenneth; Vial, Ivan N; Padois, Karine; Korman, Joshua M; Longaker, Michael T

    2011-08-01

    To test the hypothesis that the mechanical environment of cutaneous wounds can control scar formation. Mechanical forces have been recognized to modulate myriad biologic processes, but the role of physical force in scar formation remains unclear. Furthermore, the therapeutic benefits of offloading cutaneous wounds with a device have not been rigorously tested. A mechanomodulating polymer device was utilized to manipulate the mechanical environment of closed cutaneous wounds in red Duroc swine. After 8 weeks, wounds subjected to different mechanical stress states underwent immunohistochemical analysis for fibrotic markers. In a phase I clinical study, 9 human patients undergoing elective abdominal surgery were treated postoperatively with a stress-shielding polymer on one side whereas the other side was treated as standard of care. Professional photographs were taken between 8 and 12 months postsurgery and evaluated using a visual analog scale by lay and professional panels. This study is registered with ClinicalTrials.gov, number NCT00766727. Stress shielding of swine incisions reduced histologic scar area by 6- and 9-fold compared to control and elevated stress states, respectively (P < 0.01 for both) and dramatically decreased the histologic expression of profibrotic markers. Closure of high-tension wounds induced human-like scar formation in the red Duroc, a phenotype effectively mitigated with stress shielding of wounds. In the study on humans, stress shielding of abdominal incisions significantly improved scar appearance (P = 0.004) compared with within-patient controls. These results indicate that mechanical manipulation of the wound environment with a dynamic stress-shielding polymer device can significantly reduce scar formation.

  12. 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.

  13. Gold catalyzed nickel disilicide formation: a new solid-liquid-solid phase growth mechanism.

    PubMed

    Tang, Wei; Picraux, S Tom; Huang, Jian Yu; Liu, Xiaohua; Tu, K N; Dayeh, Shadi A

    2013-01-01

    The vapor-liquid-solid (VLS) mechanism is the predominate growth mechanism for semiconductor nanowires (NWs). We report here a new solid-liquid-solid (SLS) growth mechanism of a silicide phase in Si NWs using in situ transmission electron microcopy (TEM). The new SLS mechanism is analogous to the VLS one in relying on a liquid-mediating growth seed, but it is fundamentally different in terms of nucleation and mass transport. In SLS growth of Ni disilicide, the Ni atoms are supplied from remote Ni particles by interstitial diffusion through a Si NW to the pre-existing Au-Si liquid alloy drop at the tip of the NW. Upon supersaturation of both Ni and Si in Au, an octahedral nucleus of Ni disilicide (NiSi2) forms at the center of the Au liquid alloy, which thereafter sweeps through the Si NW and transforms Si into NiSi2. The dissolution of Si by the Au alloy liquid mediating layer proceeds with contact angle oscillation at the triple point where Si, oxide of Si, and the Au alloy meet, whereas NiSi2 is grown from the liquid mediating layer in an atomic stepwise manner. By using in situ quenching experiments, we are able to measure the solubility of Ni and Si in the Au-Ni-Si ternary alloy. The Au-catalyzed mechanism can lower the formation temperature of NiSi2 by 100 °C compared with an all solid state reaction.

  14. 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.

  15. Understanding the facet formation mechanisms of Si thin-film solidification through three-dimensional phase-field modeling

    NASA Astrophysics Data System (ADS)

    Chen, G. Y.; Lan, C. W.

    2017-09-01

    Adaptive phase field modeling is used in order to model the formation mechanism of a silicon faceted interface in three dimensions. We investigate the faceting condition for equilibrium shapes and dynamic situations. In this study, we propose a new anisotropic function of surface energy for the phase-field simulations in three-dimension, and negative stiffness is further considered. The morphological evolutions are presented and compare well with experimental findings. The growth mechanism is further discussed.

  16. 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.

  17. 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.

  18. Liquid nanodroplet formation through phase explosion mechanism in laser-irradiated metal targets

    NASA Astrophysics Data System (ADS)

    Mazzi, Alberto; Gorrini, Federico; Miotello, Antonio

    2015-09-01

    Some quantitative aspects of laser-irradiated pure metals, while approaching phase explosion, are still not completely understood. Here, we develop a model that describes the main quantities regulating the liquid-vapor explosive phase transition and the expulsion of liquid nanodroplets that, by solidifying, give rise to nanoparticle formation. The model combines both a thermodynamics description of the explosive phase change and a Monte Carlo simulation of the randomly generated critical vapor bubbles. The calculation is performed on a set of seven metals (Al, Fe, Co, Ni, Cu, Ag, and Au) which are frequently used in pulsed laser ablation experiments. Our final predictions about the size distribution of the liquid nanodroplets and the number ratio of liquid/vapor ejected atoms are compared, whenever possible, with available molecular dynamics simulations and experimental data.

  19. Synthesis, characterization and formation mechanism of metastable phase VO{sub 2}(A) nanorods

    SciTech Connect

    Cheng, X.H.; Xu, H.F.; Wang, Z.Z.; Zhu, K.R.; Li, G.; Jin, Shaowei

    2013-09-01

    Graphical abstract: - Highlights: • Pure phases of VO{sub 2}(B) and VO{sub 2}(A) were prepared by a facile hydrothermal method. • Belt-like particles prepared at 180 °C was indexed as monoclinic VO{sub 2}(B) phase. • Rod-like particles prepared at 230 °C was indexed as tetragonal VO{sub 2}(A) phase. • VO{sub 2}(A) nanorods resulted from VO{sub 2}(B) nanobelts by assembly and crystal adjustment. - Abstract: Pure phase VO{sub 2}(A) nanorods were synthesized via the reduction of V{sub 2}O{sub 5} by oxalic acid during the hydrothermal treatment. Two sets of samples were prepared by varying both system temperature and reaction time under a filling ratio of 0.40 for observing the formation and evolution of VO{sub 2}(A) nanorods. Structures were characterized by X-ray diffraction, scanning and transmission electron microscopies, respectively. It was found that VO{sub 2}(B) was firstly formed and then transformed into VO{sub 2}(A) as the increasing system temperature or extending reaction time. An assembling and following crystal adjustment was proposed for explanation the formation process of VO{sub 2}(A) from VO{sub 2}(B). For VO{sub 2}(A) nanorods, the phase transition temperature of 169.7 °C was higher than that of the VO{sub 2}(A) bulk, it might be ascribed to the lower crystallinity or nonstoichiometry in VO{sub 2}(A) nanorods. VO{sub 2} nanostructures with controllable phases and properties should find their promising applications in a single VO{sub 2} nanodevice.

  20. 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).

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Microstructural characterization, formation mechanism and fracture behavior of the needle δ phase in Fe–Ni–Cr type superalloys with high Nb content

    SciTech Connect

    Ning, Yongquan; Huang, Shibo; Fu, M.W.; Dong, Jie

    2015-11-15

    Microstructural characterization, formation mechanism and fracture behavior of the needle δ phase in Fe–Ni–Cr type superalloys with high Nb content (GH4169, equivalent to Inconel 718) have been quantitatively investigated in this research. The typical microstructures of δ phases with the stick, mixed and needle shapes obviously present in Inconel 718 after the isothermal upsetting at the temperature of 980–1060 °C with the initial strain rate of 10{sup −3}–10{sup −1} s{sup −1}. It is found that the shape of the δ phase has a great effect on the mechanical properties of the alloy, viz., the stick δ phase behaves good plasticity and the needle δ phase has good strength. In addition, the needle δ phase can be used to control the grain size as it can prevent grain growth. The combined effect of the localized necking and microvoid coalescence leads to the final ductile fracture of the GH4169 components with the needle δ phase. Both dislocation motion and atom diffusion are the root-cause for the needle δ phase to be firstly separated at grain boundary and then at sub-boundary. The formation mechanism of the needle δ phase is the new finding in this research. Furthermore, it is the primary mechanism for controlling the needle δ phase in Fe–Ni–Cr type superalloys with high Nb content. - Highlights: • Shape of the δ phase takes great effect on mechanical property. • Needle δ phase plays a great role to prevent grain growth. • Needle δ phase can enhance the fracture strength. • Microstructure mechanism of the needle δ phase has been investigated. • Fracture behavior of the needle δ phase has been studied.

  12. 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.

  13. 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

  14. 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

  15. Mechanisms of senile cataract formation.

    PubMed

    Chylack, L T

    1984-06-01

    Research on the mechanisms of lens opacification during the past 20 years has revealed a number of individual, identifiable cataractogenic stresses in man. They include osmotic cataract formation (diabetic, galactosemic and hypoglycemic cataracts), radiation cataracts (X-irradiation, near U.V. radiation and microwave radiation) and in senile cataract the conversion of soluble low molecular weight cytoplasmic proteins to soluble high molecular weight aggregates, insoluble phases, and insoluble membrane-protein matrices. Oxidative stress has emerged as a common denominator of many changes in senile cataract. As we increase our understanding of these mechanisms, we may be able to intervene therapeutically to delay or prevent human cataract formation in man.

  16. 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.

  17. Receptor-independent fluid-phase pinocytosis mechanisms for induction of foam cell formation with native LDL particles

    PubMed Central

    Kruth, Howard S.

    2014-01-01

    Purpose of review Because early findings indicated that native low density lipoprotein (LDL) did not substantially increase macrophage cholesterol content during in vitro incubations, investigators presumed that LDL must be modified in some way to trigger its uptake by the macrophage. The purpose of this review is to discuss recent findings showing that native unmodified LDL can induce massive macrophage cholesterol accumulation mimicking macrophage foam cell formation that occurs within atherosclerotic plaques. Recent findings Macrophages that show high rates of fluid-phase pinocytosis also show similar high rates of uptake of native unmodified LDL through non-receptor mediated uptake within both macropinosomes and micropinosomes. Non-saturable fluid-phase uptake of LDL by macrophages converts the macrophages into foam cells. Different macrophage phenotypes demonstrate either constitutive fluid-phase pinocytosis or inducible fluid-phase pinocytosis. Fluid-phase pinocytosis has been demonstrated by macrophages within mouse atherosclerotic plaques indicating that this pathway contributes to plaque macrophage cholesterol accumulation. Summary Contrary to what has been believed previously, macrophages can take up large amounts of native unmodified LDL by receptor-independent, fluid-phase pinocytosis converting these macrophages into foam cells. Thus, targeting macrophage fluid-phase pinocytosis should be considered when investigating strategies to limit macrophage cholesterol accumulation in atherosclerotic plaques. PMID:21881499

  18. Electronic and mechanical properties, phase stability, and formation energies of point defects of niobium boronitride Nb2BN

    NASA Astrophysics Data System (ADS)

    Suetin, D. V.; Shein, I. R.

    2017-08-01

    The electronic structure, Fermi surface, Sommerfeld and Pauli paramagnetic susceptibility coefficients, cohesive energies, phase and point defect formation energies, elastic constants, bulk, shear, and Young moduli, Poisson ratios, and Vickers microhardness of niobium boronitride Nb2BN are determined by the ab initio FLAPW-GGA full-potential method. The obtained values are discussed in comparison with similar data for Mo2BC and other related binary carbides, nitrides, and borides of transition metals, and with available experimental data.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Ion Yields for Some Salts in MALDI: Mechanism for the Gas-Phase Ion Formation from Preformed Ions

    NASA Astrophysics Data System (ADS)

    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.

  10. 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. © American Society for Mass Spectrometry, 2011

  11. 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

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

    PubMed

    Chandran, Preethi K; Kuttan, Ramadasan

    2008-09-01

    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.

  13. 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.

  14. 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.

  15. Three-Dimensional Multiscale Modeling of Stable Intermediate State Formation Mechanism in a Single Active Layer- Phase Change Memory Cell

    NASA Astrophysics Data System (ADS)

    Dincer, Onur; Cinar, Ibrahim; Karakas, Vedat; Aslan, Ozgur Burak; Gokce, Aisha; Stipe, Barry; Katine, Jordan A.; Aktas, Gulen; Ozatay, Ozhan

    2014-03-01

    Phase change memory (PCM) appears as a potential memory technology with its superior scalability which could be enhanced by a boost in storage density via multiple-bit per cell functionality. Given the large contrast between set and reset states of a PCM cell it is yet unclear whether it is possible to create intermediate logic states reproducibly and controllably in a device with a single active phase change layer. Here we report the results of a 3D finite element model that pinpoints the direct effect of current distribution and the indirect effect of device top contact fabrication induced defects through modification of phase change kinetics (crystallite nucleation and growth rates) on stabilization of intermediate states. A comprehensive picture of the electrical, thermal and phase change dynamics is obtained using a multiphysics approach. Our study shows that homogeneous and heterogeneous phase transition can be induced in the active region such that nonuniform temperature distribution and modification of switching dynamics with various contact shapes and sizes play a major role in the stabilization of a mixed phase state. This work has been supported by the European Commission FP7 Marie Curie IRG grant: PCM-256281 and TUBITAK grant: 113F385.

  16. 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.

  17. 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

  18. Mechanical and kinetic study on gas-phase formation of dinitro-naphthalene from 1- and 2-nitronaphthalene.

    PubMed

    Huang, Zixiao; Zhang, Qingzhu; Wang, Wenxing

    2016-08-01

    Nitrated polycyclic aromatic hydrocarbons have received an increasing number of considerations because of their higher mutagens than parent PAHs. In this paper, the formation of dinitro-naphthalene was investigated mechanistically using 1- and 2-nitronaphthalene as precursors with the aid of high-accuracy quantum chemistry calculation. The geometrical parameters, as well as vibrational frequencies, were calculated at the BB1K/6-31+G(d,p) level. Water molecule plays an important role in the formation of dinitro-naphthalene. The rate constants were deduced by canonical variational transition-state theory with small curvature tunneling contribution over the temperature range of 273-333 K. Meanwhile, the Arrhenius formulas were fitted for the OH addition of both 1- and 2-nitronaphthalene. The calculated overall rate constants for 1-nitronaphthalene and 2-nitronaphthalene at 298 K and 1 atm are 7.43 × 10(-13) and 7.48 × 10(-13) cm(3) molecule(-1) s(-1), respectively. The rate constants of NO3 addition to 1-nitronaphthalene and 2-nitronaphthalene by RRKM method at 298 K and 1 atm are 3.55 × 10(-15) and 3.47 × 10(-15) cm(3) molecule(-1) s(-1), respectively. This study provides a comprehensive investigation of the formation process of dinitro-naphthalenes, initiated by OH and NO3 radicals and should facilitate to illuminate its atmospheric source. Oxygen may probably be competitive with the second NO2 addition step when the concentration of NO2 is at low level. Copyright © 2016. Published by Elsevier Ltd.

  19. 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.

  20. Aqueous-Phase Mechanism for Secondary Organic Aerosol Formation from Isoprene: Application to the Southeast United States and Co-Benefit of SO2 Emission Controls

    NASA Technical Reports Server (NTRS)

    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.; hide

    2016-01-01

    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 (gamma) 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 42 on aerosol acidity and volume). The US EPA projects 2013-2025 decreases in anthropogenic emissions of 34% for NOx (leading to 7

  1. 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

  2. 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.

    2015-11-01

    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 probabilities (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 OA and formaldehyde (a product of isoprene oxidation). The yield 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 indirect effect of sulfate on aerosol acidity and volume, rather than a direct mechanistic role for sulfate. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation), but decrease as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US EPA projects 2013-2025 decreases in anthropogenic emissions of 34 % for NOx (leading to

  3. Impact of solid second phases on deformation mechanisms of naturally deformed salt rocks (Kuh-e-Namak, Dashti, Iran) and rheological stratification of the Hormuz Salt Formation

    NASA Astrophysics Data System (ADS)

    Závada, P.; Desbois, G.; Urai, J. L.; Schulmann, K.; Rahmati, M.; Lexa, O.; Wollenberg, U.

    2015-05-01

    Viscosity contrasts displayed in flow structures of a mountain namakier (Kuh-e-Namak - Dashti), between 'weak' second phase bearing rock salt and 'strong' pure rock salt types are studied for deformation mechanisms using detailed quantitative microstructural study. While the solid inclusions rich ("dirty") rock salts contain disaggregated siltstone and dolomite interlayers, "clean" salts reveal microscopic hematite and remnants of abundant fluid inclusions in non-recrystallized cores of porphyroclasts. Although the flow in both, the recrystallized "dirty" and "clean" salt types is accommodated by combined mechanisms of pressure-solution creep (PS), grain boundary sliding (GBS), transgranular microcracking and dislocation creep accommodated grain boundary migration (GBM), their viscosity contrasts observed in the field outcrops are explained by: 1) enhanced ductility of "dirty" salts due to increased diffusion rates along the solid inclusion-halite contacts than along halite-halite contacts, and 2) slow rates of intergranular diffusion due to dissolved iron and inhibited dislocation creep due to hematite inclusions for "clean" salt types Rheological contrasts inferred by microstructural analysis between both salt rock classes apply in general for the "dirty" salt forming Lower Hormuz and the "clean" salt forming the Upper Hormuz of the Hormuz Formation and imply strain rate gradients or decoupling along horizons of mobilized salt types of different composition and microstructure.

  4. Mechanism of formation of perovskite phase and dielectric properties of Pb(Zn,Mg){sub 1/3}Nb{sub 2/3}O{sub 3} ceramics prepared by columbite precursor routes

    SciTech Connect

    Jang, H.M.; Cho, S.R.; Lee, K.M.

    1995-02-01

    The mechanism of formation of the perovskite phase and the dielectric properties of Pb(Zn,Mg){sub 1/3}Nb{sub 2/3}O{sub 3} (PZMN) ceramics were examined using two different types of columbite precursors, (Mg,Zn)Nb{sub 2}O{sub 6} (MZN) and MgNb{sub 2}O{sub 6} + ZnNb{sub 2}O{sub 6} (MN + ZN). The formation of perovskite phase in the PbO + MN + ZN system is characterized by an initial rapid formation of Mg-rich perovskite phase, followed by a sluggish formation of Zn-rich perovskite phase. On the other hand, due to the formation of pyrochlore phase of mixed divalent cations Pb{sub 2{minus}x}(Zn,Mg){sub y}Nb{sub 2{minus}y}O{sub 7{minus}x{minus}3y/2}, the pyrochlore/perovskite transformation in the PbO + MZN system proceeded uniformly with a spatial homogeneity. Further analysis suggested that the formation of perovskite phase is a diffusion-controlled process. The degree of diffuseness of the rhombohedral/cubic phase transition (DPT) is higher in the PbO + MN + ZN system than in the PbO + MZN specimen for T > T{sub max} (temperature of the dielectric permittivity maximum), indicating a broadened compositional distribution of the B-site cations in the PbO + MN + ZN system.

  5. Quantitative reproducibility of mass spectra in matrix-assisted laser desorption ionization and unraveling of the mechanism for gas-phase peptide ion formation.

    PubMed

    Ahn, Sung Hee; Park, Kyung Man; Bae, Yong Jin; Kim, Myung Soo

    2013-03-01

    In a previous study on matrix-assisted laser desorption ionization (MALDI) of peptides using α-cyano-4-hydroxycinnamic acid (CHCA) as a matrix, we found that the patterns of single-shot spectra obtained under different experimental conditions became similar upon temperature selection. In this paper, we report that absolute ion abundances are also similar in temperature-selected MALDI spectra, even when laser fluence is varied. The result that has been obtained using CHCA and 2,5-dihydroxybenzoic acid as matrices is in disagreement with the hypothesis of laser-induced ionization of matrix as the mechanism for primary ion formation in MALDI. We also report that the total number of ions in such a spectrum is unaffected by the identity, concentration and number of analytes, i.e. it is the same as that in the spectrum of pure matrix. We propose that the generation of gas-phase ions in MALDI can be explained in terms of two thermal reactions, i.e. the autoprotolysis of matrix molecules and the matrix-to-analyte proton transfer, both of which are in quasi-equilibrium in the early matrix plume. Copyright © 2013 John Wiley & Sons, Ltd.

  6. 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...

  7. 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...

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  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. Receptor-independent fluid-phase pinocytosis mechanisms for induction of foam cell formation with native low-density lipoprotein particles.

    PubMed

    Kruth, Howard S

    2011-10-01

    Because early findings indicated that native low-density lipoprotein (LDL) did not substantially increase macrophage cholesterol content during in-vitro incubations, investigators presumed that LDL must be modified in some way to trigger its uptake by the macrophage. The purpose of this review is to discuss recent findings showing that native unmodified LDL can induce massive macrophage cholesterol accumulation mimicking macrophage foam cell formation that occurs within atherosclerotic plaques. Macrophages that show high rates of fluid-phase pinocytosis also show similar high rates of uptake of native unmodified LDL through nonreceptor mediated uptake within both macropinosomes and micropinosomes. Nonsaturable fluid-phase uptake of LDL by macrophages converts the macrophages into foam cells. Different macrophage phenotypes demonstrate either constitutive fluid-phase pinocytosis or inducible fluid-phase pinocytosis. Fluid-phase pinocytosis has been demonstrated by macrophages within mouse atherosclerotic plaques indicating that this pathway contributes to plaque macrophage cholesterol accumulation. Contrary to what has been believed previously, macrophages can take up large amounts of native unmodified LDL by receptor-independent, fluid-phase pinocytosis converting these macrophages into foam cells. Thus, targeting macrophage fluid-phase pinocytosis should be considered when investigating strategies to limit macrophage cholesterol accumulation in atherosclerotic plaques.

  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. 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

  18. 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.

  19. Core-Shell Fibers Electrospun from Phase-Separated Blend Solutions: Fiber Formation Mechanism and Unique Energy Dissipation for Synergistic Fiber Toughness.

    PubMed

    Wang, Chi; Hsiue, Ting-Ting

    2017-09-11

    Through single-tube electrospinning, the biodegradable core-shell fibers of poly(3-hydroxybutyrate) (PHB) and poly(d,l-lactic acid) (PDLLA) were obtained from blend solutions with different compositions at a total polymer concentration of 7 wt %. Regardless whether PHB is the major or minor component (PHB/PDLLA = 90/10, 75/25, 50/50, and 25/75 wt. ratio), these phase-separated solutions all yielded core-shell fibers with PHB as core and PDLLA as shell. A new scenario of core-shell fiber formation was proposed on the basis of the relative magnitude of the intrinsic relaxation rate of fluids and external extension rate during electrospinning. The effects of blend compositions on the morphologies of the Taylor cone, whipping jet, and as-spun fibers were investigated. The diameters of core-shell fibers can be tailored by simply varying the PHB/PDLLA ratios. Two scaling laws describing the apparent viscosity (ηo) dependence of the outer fiber diameter (dfo) and core fiber diameter (dfc) were derived. That is, dfo ∼ ηo(0.38) and dfc ∼ ηo(0.86). The microstructures of the as-spun fibers were determined by differential scanning calorimetry, Fourier transform infrared spectroscopy, and synchrotron wide-angle and small-angle X-ray scatterings. Results showed that the PDLLA component was in the amorphous state, and the crystallizability of PHB component remained unchanged, except the amorphous 10/90 fibers electrospun from a miscible solution state. The synergistic mechanical properties of the core-shell fibers were obtained, along with the ductile PDLLA shell enclosing the brittle PHB core. The enhanced toughness was attributed to the fragmentation of the brittle PHB core and necking fracture of the ductile PDLLA shell, which served as an effective route for energy dissipation. Compared with the neat PHB fiber, the 90/10 and 75/25 core-shell fibers possessed larger elastic moduli, which was attributed to the high PHB crystal orientation in their core sections despite

  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. 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.

  2. 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

  3. 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

  4. 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.

  5. Mechanisms for formation of organic acids in gas-phase reactions of ozone and hydroxyl radical with dialkenes and unsaturated carbonyls

    NASA Astrophysics Data System (ADS)

    Chien, Chao-Jung

    2001-07-01

    Carboxylic acids are ubiquitous throughout the troposphere and may contribute significant fractions of the free acidity in some remote areas. One of the important sources of these carboxylic acids is thought to be photochemical transformation of biogenic hydrocarbons such as isoprene. For the work reported here, atmospheric samples from University of North Carolina dual outdoor environmental chamber under simulated urban atmospheric conditions were analyzed for carboxylic acids. Both OH radicals and O3 initiated photooxidation reaction experiments were performed for isoprene, along with its structural analogs, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene, and their primary photooxidation products, methacrolein, acrolein, and methyl vinyl ketone. Among the detected carboxylic acids were formic, acetic, and several multifunctional carboxylic acids, including methacrylic, acrylic, glyoxylic, and glycolic acids. Quantification of most carboxylic acid products was also established. Formation yields of carboxylic acids from the reactions of O3 with studied compounds were determined, and time-concentration series of the reactants and carboxylic acid products were measured to facilitate mechanism formulation. While the reaction mechanisms of Criegee biradicals arising from decomposition of primary ozonides are proposed to account for the observed carboxylic acid products in the ozonolysis of unsaturated hydrocarbons, reactions of peroxy acyl radicals with HO2 and/or other peroxy radicals are thought to be responsible for the formation of carboxylic acids during the OH-initiated reactions in the presence of NOx. In this study, smog chamber simulations have also been performed for selected compounds using Morpho, a photochemical kinetic simulation software package. Explicit photochemical mechanisms with O 3 and OH radicals that lead to formation of carboxylic acids were elaborated and implemented, and the simulation results were compared with those from other chemical

  6. 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.

  7. 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.

  8. Epigenetic Mechanisms of Memory Formation and Reconsolidation

    PubMed Central

    Jarome, Timothy J.; Lubin, Farah D.

    2014-01-01

    Memory consolidation involves transcriptional control of genes in neurons to stabilize a newly formed memory. Following retrieval, a once consolidated memory destabilizes and again requires gene transcription changes in order to restabilize, a process referred to as reconsolidation. Understanding the molecular mechanisms of gene transcription during the consolidation and reconsolidation processes could provide crucial insights into normal memory formation and memory dysfunction associated with psychiatric disorders. In the past decade, modifications of epigenetic markers such as DNA methylation and posttranslational modifications of histone proteins have emerged as critical transcriptional regulators of gene expression during initial memory formation and after retrieval. In light of the rapidly growing literature in this exciting area of research, we here examine the most recent and latest evidence demonstrating how memory acquisition and retrieval trigger epigenetic changes during the consolidation and reconsolidation phases to impact behavior. In particular we focus on the reconsolidation process, where we discuss the already identified epigenetic regulators of gene transcription during memory reconsolidation, while exploring other potential epigenetic modifications that may also be involved, and expand on how these epigenetic modifications may be precisely and temporally controlled by important signaling cascades critical to the reconsolidation process. Finally, we explore the possibility that epigenetic mechanisms may serve to regulate a system or circuit level reconsolidation process and may be involved in retrieval-dependent memory updating. Hence, we propose that epigenetic mechanisms coordinate changes in neuronal gene transcription, not only during the initial memory consolidation phase, but are triggered by retrieval to regulate molecular and cellular processes during memory reconsolidation. PMID:25130533

  9. Nugget formation and its mechanism of resistance spot welded joints in DP600 dual-phase and DC54D ultralow carbon steel

    NASA Astrophysics Data System (ADS)

    Li, Ci; Yuan, Xinjian; Wu, Kanglong; Wang, Haodong; Hu, Zhan; Pan, Xueyu

    2017-05-01

    Resistance spot welded joints in different configurations of DP600 and DC54D were investigated to elucidate the nugget formation process and mechanical properties of the resultant joints. Results show that, when the welding time was less than 4 cycles, the fusion zone (FZ) was not formed, but the heat-affected zone (HAZ) occurred with a "butterfly" shape. In 4 cycles, the FZ in dissimilar sheets occurred with an "abnormal butterfly" shape because of nugget shift. When the welding time increased to 14 cycles, the FZ exhibited a "bread loaf" shape and the weld shifted to "dog bones." The nugget can be divided into three regions, namely, FZ, HAZ1, and HAZ2, and the FZ consisted of lath martensite. The micro hardness of DP600 FZ was lower than that of HAZ because of the dilution of DC54D. The failure mode of B changed from interfacial failure to plug failure during the nugget formation process. The tensile-shear load of sound weld is 6.375, 6.016, and 19.131 kN.

  10. 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.

  11. Polymorphic phase transition mechanism of compressed coesite.

    PubMed

    Hu, Q Y; Shu, J-F; Cadien, A; Meng, Y; Yang, W G; Sheng, H W; Mao, H-K

    2015-03-20

    Silicon dioxide is one of the most abundant natural compounds. Polymorphs of SiO₂ and their phase transitions have long been a focus of great interest and intense theoretical and experimental pursuits. Here, compressing single-crystal coesite SiO₂ under hydrostatic pressures of 26-53 GPa at room temperature, we discover a new polymorphic phase transition mechanism of coesite to post-stishovite, by means of single-crystal synchrotron X-ray diffraction experiment and first-principles computational modelling. The transition features the formation of multiple previously unknown triclinic phases of SiO₂ on the transition pathway as structural intermediates. Coexistence of the low-symmetry phases results in extensive splitting of the original coesite X-ray diffraction peaks that appear as dramatic peak broadening and weakening, resembling an amorphous material. This work sheds light on the long-debated pressure-induced amorphization phenomenon of SiO₂, but also provides new insights into the densification mechanism of tetrahedrally bonded structures common in nature.

  12. Polymorphic phase transition mechanism of compressed coesite

    NASA Astrophysics Data System (ADS)

    Hu, Q. Y.; Shu, J.-F.; Cadien, A.; Meng, Y.; Yang, W. G.; Sheng, H. W.; Mao, H.-K.

    2015-03-01

    Silicon dioxide is one of the most abundant natural compounds. Polymorphs of SiO2 and their phase transitions have long been a focus of great interest and intense theoretical and experimental pursuits. Here, compressing single-crystal coesite SiO2 under hydrostatic pressures of 26-53 GPa at room temperature, we discover a new polymorphic phase transition mechanism of coesite to post-stishovite, by means of single-crystal synchrotron X-ray diffraction experiment and first-principles computational modelling. The transition features the formation of multiple previously unknown triclinic phases of SiO2 on the transition pathway as structural intermediates. Coexistence of the low-symmetry phases results in extensive splitting of the original coesite X-ray diffraction peaks that appear as dramatic peak broadening and weakening, resembling an amorphous material. This work sheds light on the long-debated pressure-induced amorphization phenomenon of SiO2, but also provides new insights into the densification mechanism of tetrahedrally bonded structures common in nature.

  13. 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.

  14. 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.

  15. Novel two-component gels of cetylpyridinium chloride and the bola-amphiphile 6-amino caproic acid: phase evolution and mechanism of gel formation.

    PubMed

    Ramakanth, Illa; Patnaik, Archita

    2012-03-08

    A two-component gel resulting from the amphiphilic cationic surfactant cetylpyridinium chloride (CPC) in the presence of a structure-forming bola-amphiphilic additive 6-aminocaproic acid (6-ACA) was realized and investigated. At a critical 6 wt % of 1:1 CPC:6-ACA, the yellow colored gel resulted from a 3:1 v/v CHCl(3):H(2)O critical binary solvent composition. The mixed amphiphilic system formed a 1:1 complex with a binding constant ~0.83 × 10(4) M(-1). Phase evolution and mechanism of gelation in the mixed CPC:6-ACA system was unraveled upon investigating the gel microstructure, based on spectroscopic, microscopic, and small-angle X-ray scattering (SAXS) investigations. The gel assembled as a lamellar organization, maintaining a loosely interdigitated bilayer structure of CPC and 6-ACA molecules through predominant charge transfer, H-bonding, and hydrophobic and intercomplex interactions. The SAXS pattern indicated a semicrystalline form to be the stable phase with alternating crystalline and amorphous layers; a novel mode of gelation with a widely disparate semicrystalline form of the lamellar gel was thus indicated, where the lamellar structure was deduced from the interplanar spacings. A transition from low viscosity reverse micellar solution to a yellow rigid gel upon aging was thus comprehended. The mixed amphiphile in varying polarity organic solvents in the presence of water indicated the nonconducive nature of gelation in very highly polar solvents, methanol, and DMF or, in very low polarity solvents, such as, cyclohexane and carbon tetrachloride.

  16. 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.

  17. Nanostructure and Phases Formation under Mechanical Alloying of Bynary Powder Mixtures of Fe and sp-Element (M); M = C,B,Al,Si,Ge,Sn

    NASA Astrophysics Data System (ADS)

    Yelsukov, E. P.; Dorofeev, G. A.

    2005-07-01

    The processes of mechanical alloying of iron and sp-elements (C, B, Al, Si, Ge, Sn) under identical conditions of mechanical treatment have been studied. General regularities and differences in the mechanisms and kinetics of solid state reactions have been ascertained. A microscopic model of mechanical alloying in these systems is suggested.

  18. On the lag phase in amyloid fibril formation

    PubMed Central

    Arosio, Paolo; Knowles, Tuomas P. J.

    2015-01-01

    The formation of nanoscale amyloid fibrils from normally soluble peptides and proteins is a common form of self-assembly phenomenon that has fundamental connections with biological functions and human diseases. The kinetics of this process has been widely studied and exhibits on a macroscopic level three characteristic stages: a lag phase, a growth phase and a final plateau regime. The question of which molecular events take place during each one of these phases has been a central element in the quest for a mechanism of amyloid formation. In this review, we discuss the nature and molecular origin of the lag-phase in amyloid formation by making use of tools and concepts from physical chemistry, in particular from chemical reaction kinetics. We discuss how, in macroscopic samples, it has become apparent that the lag-phase is not a waiting time for nuclei to form. Rather, multiple parallel processes exist and typically millions of primary nuclei form during the lag phase from monomers in solution. Thus, the lag-time represents a time that is required for the nuclei that are formed early on in the reaction to grow and proliferate in order to reach an aggregate concentration that is readily detected in bulk assays. In many cases, this proliferation takes place through secondary nucleation, where fibrils may present a catalytic surface for the formation of new aggregates. Fibrils may also break (fragmentation) and thereby provide new ends for elongation. Thus, at least two – primary nucleation and elongation – and in many systems at least four – primary nucleation, elongation, secondary nucleation and fragmentation – microscopic processes occur during the lag phase. Moreover, these same processes occur during all three phases of the macroscopic aggregation process, albeit at different rates as governed by rate constants and by the concentration of reacting species at each point in time. PMID:25719972

  19. 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.

  20. OH radical formation from the gas-phase reaction of ozone with terminal alkenes and the relationship between structure and mechanism

    SciTech Connect

    Paulson, S.E.; Chung, M.Y.; Hasson, A.S.

    1999-10-14

    The reactions of ozone with alkenes have been shown recently to lead to the direct production of OH radicals in quantities that vary from 7 to 100% depending on the structure of the alkene. OH radicals are the most important oxidizing species in the lower atmosphere, and the OH-alkene reaction is a large source of new OH radicals, important in urban and rural air during both day and night. Evidence for OH formation comes both from low-pressure direct measurements and from tracer experiments at high pressure. With the goal of measuring OH formation yields with good precision, a small-ratio relative rate technique was developed. This method uses small amounts of fast-reacting aromatics and aliphatic ethers to trace OH formation yields. Here, the authors report OH formation yields for a series of terminal alkenes reacting with ozone. Measured OH yields were 0.29 {+-} 0.05, 0.24 {+-} 0.05, 0.18 {+-} 0.04, and 0.10 {+-} 0.03 for 1-butene, 1-pentene, 1-hexene, and 1-octene, respectively. For the methyl-substituted terminal alkenes methyl propene and 2-methyl-1-butene, OH yields were 0.72 {+-} 0.12 and 0.67 {+-} 0.12, respectively. The results are discussed both in terms of their atmospheric implications and the relationship between structure and OH formation.

  1. A simplified reaction mechanism for soot formation in nonpremixed flames

    SciTech Connect

    Leung, K.M.; Lindstedt, R.P. ); Jones, W.P. )

    1991-12-01

    The present article outlines a simplified reaction mechanism for the formation, growth, and combustion of soot particles in laminar nonpremixed flames. The model can be combined with detailed chemistry descriptions for the gas phase, as in the present case, or with reduced chemical reaction mechanisms. The reaction mechanism involves nucleation, surface growth, particle coagulation, and combustion steps. The model outlined has been created with the intention of being applicable to the prediction of turbulent flames via different approaches. The soot nucleation and surface growth reactions are linked to the gas phase by presuming that pyrolysis products, in the present case acetylene, and not the fuel itself, are of primary importance in the soot formation process. The deduced reaction mechanism is applied to counterflow ethylene and propane flames burning with a range of oxygen-enriched and depleted air streams. The results obtained show excellent qualitative and quantitative agreement with measured data for soot volume fraction, particle growth, and number density.

  2. 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.

  3. Gas phase dynamics of triplet formation in benzophenone.

    PubMed

    Spighi, Gloria; Gaveau, Marc-André; Mestdagh, Jean-Michel; Poisson, Lionel; Soep, Benoît

    2014-05-28

    Benzophenone is a prototype molecule for photochemistry in the triplet state through its high triplet yield and reactivity. We have investigated its dynamics of triplet formation under the isolated gas phase conditions via femtosecond and nanosecond time resolved photoelectron spectroscopy. This represents the complete evolution from the excitation in S2 to the final decay of T1 to the ground state S0. We have found that the triplet formation can be described almost as a direct process in preparing T1, the lowest reacting triplet state, from the S1 state after S2 → S1 internal conversion. The molecule was also deposited by a pick-up technique on cold argon clusters providing a soft relaxation medium without evaporation of the molecule and the mechanism was identical. This cluster technique is a model for medium influenced electronic relaxation and provides a continuous transition from the isolated gas phase to the relaxation dynamics in solution.

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

    SciTech Connect

    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.

  5. The in situ gas-phase formation of a C-glycoside ion obtained during electrospray ionization tandem mass spectrometry. A unique intramolecular mechanism involving an ion-molecule reaction.

    PubMed

    Banoub, Joseph H; Demian, Wael L L; Piazzetta, Paolo; Sarkis, George; Kanawati, Basem; Lafont, Dominique; Laurent, Nicolas; Vaillant, Celine; Randell, Edward; Giorgi, Gianluca; Fridgen, Travis D

    2015-10-15

    This study examines the electrospray ionization mass spectrometry (ESI-MS), in-source collision-induced dissociation (CID) fragmentation and low-energy collision-induced dissociation tandem mass spectrometry (CID-MS/MS) of a synthetic pair of β- and α-anomers of the amphiphilic cholesteryl polyethoxy neoglycolipids containing the 2-azido-2-deoxy-D-galactosyl-D-GalN3 moiety. We describe the novel and unique in situ gas-phase formation of a C-glycoside ion formed during all these gas-phase processes and propose a reasonable mechanism for its formation. The synthetic amphiphilic glycolipids were composed of the 2-deoxy-2-azido-D-galactosyl moiety (GalN3, the hydrophilic part) covalently attached to a polyethoxy spacer which is covalently linked to the cholesteryl moiety (hydrophobic part). The 2-azido-2-deoxy-α- and β-D-galactosyl-containing glycolipids were studied by in-time and in-space ESI-MS and CID-MS/MS in positive ion mode, with quadrupole ion trap (QIT), quadrupole-quadrupole-time-of-flight (QqTOF), and Fourier transform ion cyclotron resonance (FTICR) instruments. Conventional single-stage ESI-MS analysis showed the formation of the protonated molecule. During the single-stage ESI-MS analysis and the CID-MS/MS of the [M+H](+) and [M+NH4](+) adducts obtained from both glycolipid anomers, the presence of a series of specific product ions with different intensities was observed, consistent with the [C-glycoside+H-N2](+), [cholestadiene+H](+), 2-deoxy-2-D-azido-galactosyl [GalN3](+), [GalNH](+) and [sugar-Spacer+H](+) ions. The gas-phase formation of the [C-glycoside+H-N2](+) ion isolated from the glycolipid anomers was observed during both the ESI-MS of the glycolipids and the CID-MS/MS analyses of the [M+H](+) ions and it was found to occur by an intramolecular rearrangement involving an ion-molecule complex. CID-QqTOF-MS/MS and CID-FTICR-MS(2) analysis allowed the differentiation of the two glycolipid anomers and showed noticeable variation in the

  6. 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.

  7. Ionic Mechanisms of Soot Formation in Flames.

    DTIC Science & Technology

    1984-05-01

    I. INTRODUCTION AND STATEMENT OF WORK I II. STATUS OF RESEARCH 3 A. The Ionic Mechanism of Soot Formation 3 B. Particle Electronics 6 C. Sooting Flame Structure...2.28. At 2.2 u ivehrlr25’. cmj6~e1unr s TP-443 C. SOOTING FLAME STRUCTURE STUDI.__ 1. Langmuir Probe Measurements Olson and Calcote’ previously

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. MECHANISMS OF HUMAN KIDNEY STONE FORMATION

    PubMed Central

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

    2014-01-01

    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 (ICSF) 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. PMID:25108546

  13. Stratigraphic Signatures of Forearc Basin Formation Mechanisms

    NASA Astrophysics Data System (ADS)

    Mannu, U.; Ueda, K.; Gerya, T.; Willett, S.; Strasser, M.

    2014-12-01

    Forearc basins are loci of active sedimentation above the landward portion of accretionary prisms. Although these basins typically remain separated from the frontal prism by a forearc high, their evolution has a significant impact on the structure and deformation of the entire wedge. Formation of forearc basins has been proposed as a consequence of changes in wedge stability due to an increase of slab dip in subduction zones. Another hypothesis attributes this to higher hinterland sedimentation, which causes the rear of the wedge to stabilize and eventually develop a forearc basin. Basin stratigraphic architecture, revealed by high-resolution reflection seismic data and borehole data allows interpretation of structural development of the accretionary prism and associated basins with the goal of determining the underlying driving mechanism(s) of basin formation. In this study we supplement data interpretation with thermo-mechanical numerical models including high-resolution isochronal surface tracking to visualize the developing stratigraphy of basins that develop in subduction zone and wedge dynamic models. We use a dynamic 2D thermo mechanical model incorporating surface processes, strain weakening and sediment subduction. The model is a modification of I2VIS model, which is based on conservative, fully staggered finite differences and a non-diffusive marker- in-cell technique capable of modelling mantle convection. In the model different driving mechanisms for basin formation can be explored. Stratigraphic simulations obtained by isochronal surface tracking are compared to reflection pattern and stratigraphy of seismic and borehole data, respectively. Initial results from a model roughly representing the Nankai Trough Subduction Zone offshore Japan are compared to available seismic and Integrated Ocean Drilling (IODP) data. A calibrated model predicting forearc basin stratigraphy will be used to discern the underlying process of basins formation and wedge

  14. 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.

  15. 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.

  16. An analysis of the mechanism of white spot formation

    NASA Astrophysics Data System (ADS)

    Shved, Felix I.

    1994-01-01

    In this article, an attempt is made to describe the mechanism for the formation of solute-lean white spot defects in vacuum-arc remelted ingots. The new explanation includes falling to the pool of metal pieces that are not necessarily different in composition from base metal. The residues of these pieces that survive on their way to the deep regions of the pool serve as nuclei for an equilibrium atom-exchange process between solid and liquid phases, which leads to the selective solute depletion at their boundary. The width of layers thus formed depends on the solid-liquid phase contact time.

  17. 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

  18. 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.

  19. 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.

  20. 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.

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

    NASA Astrophysics Data System (ADS)

    Kruve, Anneli; Kaupmees, Karl

    2017-05-01

    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. 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

  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. [Mechanisms of immune deposit formation in glomerulonephritis].

    PubMed

    Bussolati, B; Camussi, G

    1996-03-01

    Recent experimental studies allowed the identification of several mechanisms of immune deposit formation, which are able to reproduce the morphological and clinical pattern of human glomerulonephritis. Moreover, it was shown that most of the lesions considered, in the past, as due to circulating immune complexes (IC), are instead caused by the "in situ" formation of IC. As a result of these studies, the following schematic classification was proposed: 1) immune deposits formed by glomerular localization of IC primarily formed in the circulation; 2) immune deposits formed "in situ" by reaction of circulating antibodies with fixed structural antigens; 3) immune deposits formed "in situ" by antibodies reactive with movable structural antigens; 4) immune deposits formed "in situ" by antibodies reactive with sequestered antigens leaking out of tissues; 5) IC formed "in situ" by antibodies reactive with exogenous or non-glomerular endogenous antigens planted in the glomeruli; 6) ANCA-associated glomerular disease.

  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. 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.

  11. EUV Dimmings: Formation Mechanisms and Associated Phenomena

    NASA Astrophysics Data System (ADS)

    Thompson, B. J.; Mays, M. L.; West, M. J.

    2012-12-01

    Large-scale coronal EUV dimmings, developing on timescales of minutes to hours in association with a flare or filament eruption, are known to exhibit a high correlation with coronal mass ejections. While most observations indicate that the decrease in emission in a dimming is due, at least in part, to a density decrease, a complete understanding requires us to examine at least four mechanisms that have been observed to cause darkened regions in the corona: 1) mass loss, 2) cooling, 3) heating, and 4) absorption/obscuration. Recent advances in automatic detection, observations with improved cadence and resolution, multi-viewpoint imaging, and spectroscopic studies have continued to shed light on dimming formation, evolution, and recovery. However, there are still some outstanding questions, including 1) Why do some CMEs show dimming and some do not? 2) What determines the location of a dimming? 3) What determines the temporal evolution of a dimming? 4) How does the post-eruption dimming connect to the ICME? 5) What is the relationship between dimmings and other CME-associated phenomena? The talk will emphasize the different formation mechanisms of dimmings and their relationship to CMEs and CME-associated phenomena.

  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. 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.

  14. 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.

  15. 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

  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. A collective mechanism for phase variation in biofilms

    NASA Astrophysics Data System (ADS)

    Chia, Nicholas; Woese, Carl; Goldenfeld, Nigel

    2009-03-01

    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.

  19. A collective mechanism for phase variation in biofilms.

    PubMed

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

    2008-09-23

    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.

  20. Metastable phases in mechanically alloyed aluminum germanium powders

    SciTech Connect

    Yvon, P.J.; Schwarz, R.B.

    1993-03-01

    Aluminum and germanium form a simple eutectic system with no stable intermetallic phase, and limited mutual solubility. We report the formation of a metastable rhombohedral,{gamma}{sub 1} phase by mechanically alloying aluminum and germanium powders. This phase, which appears for compositions between 20 and 50 at. % germanium, has also been observed in rapidly quenched alloys, but there is disagreement as to its composition. By measuring the heat of crystallization as a function of composition, we determined the composition of the {gamma}{sub 1} phase to be Al{sub 70}Ge{sub 30}. We also produced Al{sub 70}Ge{sub 30} by arc melting the pure elements, followed by splat-quenching at a cooling rate in the range of 10{sup 8} K s{sup {minus}1}. This method produced two metastable phases, one of which was found to be the {gamma}{sub 1} phase obtained by mechanical alloying. The other was a monoclinic phase reported earlier in the literature as {gamma}{sub 2}.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Formation of nanostructural materials induced by mechanical processings (overview)

    NASA Astrophysics Data System (ADS)

    Gaffet, E.; Abdellaoui, M.; Malhouroux-Gaffet, N.

    1995-02-01

    Mechanical alloying (MA) was firstly developed to synthesize metallic matrix composite by mechanically incorporating preformed oxide and or carbide particles into a metallic matrix. A compaction process is then applied to obtain bulk materials. During MA, powders are repeatedly welded, fractured and rewelded in a high-energy mill leading to an intimate mixing on a nano/micro-scale with the possible formation of far-from-equilibrium phases. The versatility of MA is well-known; high-volume, low-energy mills can be used to commercially produce dispersion-strengthened Al, Ni and other transition metal alloys. An overview of the dynamics of the process is presented to help gain a full appreciation of the industrial potential of the technique for synthesizing materials.

  8. Phase imaging of mechanical properties of live cells (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Wax, Adam

    2017-02-01

    The mechanisms by which cells respond to mechanical stimuli are essential for cell function yet not well understood. Many rheological tools have been developed to characterize cellular viscoelastic properties but these typically require direct mechanical contact, limiting their throughput. We have developed a new approach for characterizing the organization of subcellular structures using a label free, noncontact, single-shot phase imaging method that correlates to measured cellular mechanical stiffness. The new analysis approach measures refractive index variance and relates it to disorder strength. These measurements are compared to cellular stiffness, measured using the same imaging tool to visualize nanoscale responses to flow shear stimulus. The utility of the technique is shown by comparing shear stiffness and phase disorder strength across five cellular populations with varying mechanical properties. An inverse relationship between disorder strength and shear stiffness is shown, suggesting that cell mechanical properties can be assessed in a format amenable to high throughput studies using this novel, non-contact technique. Further studies will be presented which include examination of mechanical stiffness in early carcinogenic events and investigation of the role of specific cellular structural proteins in mechanotransduction.

  9. Physical mechanisms for multiphase flow associated with hydrate formation

    NASA Astrophysics Data System (ADS)

    Behseresht, Javad; Bryant, Steven L.

    2017-05-01

    Many Arctic hydrate reservoirs such as those of the Prudhoe Bay and Kuparuk River area on the Alaska North Slope (ANS) are believed originally to be natural gas accumulations converted to hydrate accumulations after being placed in the gas hydrate stability zone (GHSZ) in response to ancient climate cooling. In this work, the implications of a previously described mechanistic model for the transport of gaseous and aqueous phases are studied using a transient 1-D transport model during the conversion of a gas reservoir to a hydrate reservoir. The mechanistic model predicts/explains the vertical profile of hydrate saturation in "converted free gas" hydrate reservoirs. The initial gas phase saturation with depth is estimated from the profile of capillary entry pressure, which is estimated from grain size distributions measured in cores. The gas accumulation is assumed to be disconnected from its original source so that methane transport occurs only within it. As the base of the GHSZ descends through the sediment, hydrate forms within the GHSZ. The net volume reduction associated with hydrate formation creates a "sink" which drives flow of gaseous and aqueous phases to the hydrate formation zone. Mechanisms by which this fluid movement could have occurred are analyzed. Flow driven by saturation gradients plays a key role in creating reservoirs of large hydrate saturations, as observed in Mount Elbert stratigraphic test well in the Milne Point Unit of Alaska North Slope (ANS). Viscous-dominated pressure-driven flow of gaseous and aqueous phases cannot explain large hydrate saturations originated from large-saturation gas accumulations. The mode of hydrate formation for a wide range of rate of hydrate formation, the rate of descent of the base of GHSZ, and host sediment characteristics are analyzed and characterized based on dimensionless groups. The proposed transport model is also consistent with field data from hydrate-bearing sand units in Mount Elbert well. Results

  10. A Unified Mechanism for the Formation of Oscillation Marks

    NASA Astrophysics Data System (ADS)

    Ramirez Lopez, Pavel E.; Mills, Kenneth C.; Lee, Peter D.; Santillana, Begoña

    2012-02-01

    Oscillation marks (OMs) are regular, transverse indentations formed on the surface of continuously cast (CC) steel products. OMs are widely considered defects because these are associated with segregation and transverse cracking. A variety of mechanisms for their formation has been proposed ( e.g., overflow, folding, and meniscus freezing), whereas different mark types have also been described ( e.g., folded, hooks, and depressions). The current work uses numerical modeling to formulate a unified theory for the onset of OMs. The initial formation mechanism is demonstrated to be caused by fluctuations in the metal and slag flow near the meniscus, which in turn causes thermal fluctuations and successive thickening and thinning of the shell, matching the thermal fluctuations observed experimentally in a mold simulator. This multiphysics modeling of the transient shell growth and explicit prediction of OMs morphology was possible for the first time through a model for heat transfer, fluid flow, and solidification coupled with mold oscillation, including the slag phase. Strategies for reducing OMs in the industrial practice fit with the proposed mechanism. Furthermore, the model provides quantitative results regarding the influence of slag infiltration on shell solidification and OM morphology. Control of the precise moment when infiltration occurs during the cycle could lead to enhanced mold powder consumption and decreased OM depth, thereby reducing the probability for transverse cracking and related casting problems.

  11. 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

  12. Gel phase formation in dilute triblock copolyelectrolyte complexes.

    PubMed

    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

    2017-02-23

    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-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.

  13. 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.

  14. Formation Mechanisms for Dunes Observed on Titan

    NASA Astrophysics Data System (ADS)

    Vinson, Alec; Hays, C. C.; Lopes-Gautier, R. M.; Mitchell, K. L.; Diniega, S.; Farr, T. G.

    2013-01-01

    The Cassini spacecraft has discovered massive dune fields on Saturn’s largest moon, Titan. The dunes were observed with the Cassini Synthetic Aperture Radar Imaging (SARS) instrument. The radar instrument operates at a frequency of 13.78 GHz, corresponding to a wavelength 2.2 cm. The resolution for the images examined are ~ 1 pixel = 175 m (varies from image to image). These dunes, or at least what’s visible to radar, through the thick nitrogen Titan atmosphere, seem to be almost exclusively longitudinal dunes (with crests forming parallel to prevailing wind directions). Many unanswered questions remain about these dunes. One goal of this project is to attempt to calculate the heights of these dunes, which has not yet been systematically attempted. We will use radar parallax analyses to calculate the height of the dunes. The Cassini radar determines position based on how long the radar wave took to return to the spacecraft, making an assumption that the surface is a perfect sphere. With changes in height, the time return for radar will change, distorting the image. Looking at these distortions (specifically, the shortening or elongation of the side of a dune) and knowing the inclination angle, we can determine height or depth. We will also use this same method with radar images of the Namib dunes, in southwest Africa, as an Earth analog, to test and determine how accurate our method is. This approach should give useful information on the morphology of the dunes on Titan. Knowing more about the morphology of the dunes can teach us more about the dune’s composition and formation mechanisms.

  15. 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.

  16. 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

  17. 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

  18. Formation of a two-phase microstructure in Fe-Cr-Ni alloy during directional solidification

    NASA Astrophysics Data System (ADS)

    Fu, J. W.; Yang, Y. S.; Guo, J. J.; Ma, J. C.; Tong, W. H.

    2008-12-01

    The formation and evolution of a two-phase coupled growth microstructure in AISI 304 stainless steel are investigated using a quenching method during directional solidification. It is found that the two-phase microstructure, which is composed of coupled growth of thin lathy delta ferrite (δ) and austenite (γ), forms from the melt first during solidification. As solidification proceeds, the retained liquid transforms into austenite directly. On cooling, the subsequent incomplete solid-state transformation from ferrite to austenite results in the disappearance of the thinner lathy delta ferrite, and the final two-phase coupled growth microstructure is formed. The formation mechanism of the two-phase coupled growth microstructure is analyzed theoretically based on the nucleation and constitutional undercooling (NCU) criterion. Transmission electron microscope (TEM) and EDS analyses were carried out to identify the phases and determine the phase composition, respectively.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. Mechanisms for indirect effects from aerosol pollution on mixed-phase clouds

    NASA Astrophysics Data System (ADS)

    Phillips, Vaughan

    2015-04-01

    Aerosol pollution can have various effects on mixed-phase clouds. They can alter coalescence and raindrop-freezing for droplet activation by CCN aerosols. They can alter aggregation of ice crystals and snow formation. This can alter the lifetime of mixed-phase clouds, as well as the reflectivity for solar radiation. Simulations of observed cases of mixed-phase clouds have been performed to examine the mechanisms for effects from aerosol pollution on them. Such mechanisms are discussed in the presentation.

  4. Grain damage, phase mixing and plate-boundary formation

    NASA Astrophysics Data System (ADS)

    Bercovici, David; Skemer, Philip

    2017-07-01

    The generation of plate tectonics on Earth relies on complex mechanisms for shear localization, as well as for the retention and reactivation of weak zones in the cold ductile lithosphere. Pervasive mylonitization, wherein zones of high deformation coincide with extensive mineral grain size reduction, is an important clue to this process. In that regard, the grain-damage model of lithospheric weakening provides a physical framework for both mylonitization and plate generation, and accounts for the competition between grain size reduction by deformation and damage, and healing by grain growth. Zener pinning at the evolving interface between mineral components, such as olivine and pyroxene, plays a key role in helping drive grains to small mylonitic sizes during deformation, and then retards their growth once deformation ceases. The combined effects of damage and pinning, however, rely on the efficiency of inter-grain mixing between phases (e.g., olivine and pyroxene) and grain dispersal, which likely depends on grain size itself. Here we present a new model for inter-grain mixing and damage and the onset of rapid mixing. The model considers the competition between the formation of new grains behind a receding interphase triple junction (e.g., olivine growing into a boundary between two pyroxene grains) and their severance or spalling during progressive deformation and damage. The newly formed grains of one phase are then transported along the opposing phase's grain-boundaries and the two phases become dispersed at the grain-scale in a growing mixed layer. The small intermixed grains also affect the grain evolution of the surrounding host grains by Zener pinning, and hence influence the rheology and growth of the mixed layer. As the grains in the mixed layer shrink, subsequently spalled new grains are also smaller, causing a feedback that leads to more rapid mixing and shear localization in the mixed layer. The early stages of mixing can be compared to laboratory

  5. 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.

  6. 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.

  7. The short-term reduction of uranium by nanoscale zero-valent iron (nZVI): role of oxide shell, reduction mechanism and the formation of U( v )-carbonate phases

    SciTech Connect

    Tsarev, Sergey; Collins, Richard N.; Ilton, Eugene S.; Fahy, Adam; Waite, T. David

    2017-01-01

    Nanoscale zero-valent iron (nZVI) is a potential remediation agent for uranium-contaminated groundwaters, however, a complete mechanistic understanding of the processes that lead to uranium immobilization has yet to be achieved. In this study, the short-term anoxic reaction of U(VI) with fresh, (anoxic) aged and corroded nZVI particles was investigated under aqueous conditions conducive to the formation of thermodynamically stable U(VI)-Ca-CO3 ternary aqueous complexes. The first stage of the reaction between U(VI) and nZVI was assigned to sorption processes with the formation of surface U(VI)-carbonate complexes. Aged nZVI removed U(VI) faster than either fresh or corroded nZVI and it is hypothesized that U reduction initially occurs through the transfer of one electron from Fe(II) in the nZVI surface oxide layer. Evidence for reduction to U(V) was obtained through X-ray photoelectron spectroscopy and by determination of U-O bond distances of ~2.05 Å and 2.27 Å by U LIII-edge X-ray absorption spectroscopy detection of U-O bond distances at ~2.05 Å and 2.27 Å with these distances , similar to thoseat observed for the U(V) site in the mixed U(V)/U(VI) carbonate mineral wyartite. Scanning transmission electron microscopy also demonstrated that U was present as a nanoparticulate phase after one day of reaction, rather than a surface complex. Further reduction to U(IV), as observed in previous studies, would appear to be rate-limiting and coincident with the transformation of this meta-stable U-carbonate phase to uraninite (UO2).

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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).

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. Dynamic Phases, Pinning, and Pattern Formation for Driven Dislocation Assemblies

    PubMed Central

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

    2015-01-01

    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. 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. PMID:25613839

  6. Phase formation and microstructure in lithium-carbon intercalation compounds during lithium uptake and release

    NASA Astrophysics Data System (ADS)

    Drüe, Martin; Seyring, Martin; Rettenmayr, Markus

    2017-06-01

    The intercalation and de-intercalation behavior of lithium in graphite was investigated with respect to the formation of lithium graphite intercalation compounds (Li-GICs) using a combination of XRD measurements and metallography. Microstructural features and the evolution of phases and structural details of Li-GICs during Li uptake and release are correlated for the first time, giving new insight into the formation of Li-GICs. Lithium evaporation loss during annealing was exploited for studying the phase evolution during lithium de-intercalation, whereas phase formation during lithium uptake was studied in a sample exhibiting a lithium concentration gradient. The experiments indicate that growth and dissolution of the compound LiC6 do not occur by an inverse mechanism, as shown by the formation of different intermediate phases. The compound LiC12 was found to be a non-stoichiometric solid solution. LiC6 can be clearly identified in micrographs by the color and distinct phase boundaries, while LiC12 is situated in the vicinity of the LiC6 phase with varying coloration depending on the Li content.

  7. 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

  8. 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.

  9. 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.

  10. 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…

  11. 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…

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. Isopropylammonium Formate as a Mobile Phase Modifier for Liquid Chromatography

    PubMed Central

    Collins, Matthew P.; Zhou, Ling; Camp, Suzanne E.; Danielson, Neil D.

    2012-01-01

    Isopropylammonium formate (IPAF), a new alkylammonium formate (AAF) room temperature ionic liquid, has been synthesized from isopropylamine and formic acid and characterized as an organic solvent mobile phase replacement for reversed-phase liquid chromatography (LC). Characterization of IPAF solvent properties in water such as pH, conductivity, and viscosity, as well as its synthesis, is described. The LC polarity (P′) and the solvent strength (S) parameters are determined to be 6.0 and 2.4, respectively, similar to those same parameters for methanol and acetonitrile. Application of this RTIL is demonstrated as an organic solvent replacement for reversed-phase LC to separate a test mixture of niacinamide, acetophenone and p-nitroaniline. The van Deemter plot profile for several columns of different dimensions, particle size, pore size and stationary phase are compared using an IPAF–water mobile phase. At flow rates above 2 mL/min, on-line mixing of the viscous IPAF with water appears not to be uniform. A flattening of the van Deemter profile is noted for particularly short (50 mm) wide bore (4.6 mm) columns packed with larger particles (10 µm). Small particle longer columns likely facilitated mixing at the beginning of the column generating typical linearly increasing van Deemeter curves. IPAF has been further shown as a function of temperature to be a non-denaturing modifier solvent for the separation of the protein cytochrome c from tryptophan compared to methanol. This is important to show, because the semi-preparative separation of native proteins using AAF mobile phases is the long-term goal of this research program. PMID:22718743

  20. The Embedded Phase of Star Formation : Outflows, Envelopes, First Conditions of Disk Formation

    NASA Astrophysics Data System (ADS)

    Vorobyov, Eduard

    2017-06-01

    The embedded phase of star formation witnesses the birth of stars, the formation of circumstellar disks, and the launch of jets and outflows. It sets the stage for the disk and star evolution in the subsequent optically visible T Tauri phase, largely determining disk and stellar masses and paving the way for planet assembly. This phase is hard to observe and theory can provide valuable insights into the processes that take place in the depth of collapsing clouds. I will overview processes that are linked with the disk early evolution, such as gravitational instability and its implications, variable protostellar accretion with episodic bursts and its effect on the disk dynamical and chemical evolution, and initial stages of dust growth. The nature of very low luminosity objects (VELLOs) will also be discussed.

  1. 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

  2. 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.

  3. Mechanisms behind signet ring cell carcinoma formation.

    PubMed

    Fukui, Yasuhisa

    2014-08-08

    Signet ring cell carcinomas are highly malignant dedifferentiated adenocarcinomas. There are no cell-cell interactions between these round-shaped cells. They contain huge numbers of vacuoles, filled with mucins, which are secreted from the cells. The mechanism behind this phenotype has recently begun to be elucidated. In highly differentiated adenocarcinomas the ErbB2/ErbB3 complex is activated, which is followed by phosphatidylinositol 3-kinase (PI3K) activation. p38 MAP kinase is activated downstream of PI3K and adherens junctions are disrupted via Rac1 activation. Loss of adherens junctions leads to the disappearance of tight junctions, which results in a loss of cell-cell interactions. Secretion of mucin is enhanced by activation of PI3K. One of the mucins - Muc4 - can activate ErbB2. Under normal conditions Muc4 and ErbB2 are separated by adherens and tight junctions, however in signet ring cells they are able to interact, since these junctions have been lost. Therefore, an activation loop is formed, consisting of ERbB2/ErbB3-Muc4-ErbB2/ErbB3. As a result, the ErbB2/ErbB3 signaling pathway becomes constitutively activated, cell-cell interactions are lost, and signet ring carcinomas are formed. As a result of constitutive activation of the ErbB2/ErbB3 complex, cell growth is continuously enhanced. Some signet ring cell carcinomas have been found to have mutations in the E-cadherin gene, which fits the above hypothesis. Copyright © 2014 Elsevier Inc. All rights reserved.

  4. 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

  5. [Mechanism of scar formation and strategy of treatment].

    PubMed

    Lu, Shu-liang

    2013-04-01

    So far, studies on the mechanism of scar formation have mainly focused on cells, cytokines and extracellular matrix. Some studies have shown that fibroblast is one of the most important element in the process of scar formation, while epidermal and endothelial cells exert synergistic effects as well. Genetic factor can not be ignored in scar formation, either. Recently, studies have shown decisively the loss or damage of the three-dimensional structure of dermal tissue is the initiator of scar formation. Thus, the defect of epidermis template is proposed as a theory in order to explain the mechanism of scar formation. There are various techniques for scar treatment. The commonly accepted methods are physical therapy, pressure therapy, pharmaceutical therapy, radiotherapy, etc.

  6. A FIB induced boiling mechanism for rapid nanopore formation

    PubMed Central

    Das, K; Freund, J B; Johnson, H T

    2015-01-01

    Focused ion beam (FIB) technology is widely used to fabricate nanopores in solid-state membranes. These nanopores have desirable thermomechanical properties for applications such as high-throughput DNA sequencing. Using large scale molecular dynamics simulations of the FIB nanopore formation process, we show that there is a threshold ion delivery rate above which the mechanism underlying nanopore formation changes. At low rates nanopore formation is slow, with the rate proportional to the ion flux and therefore limited by the sputter rate of the target material. However, at higher fluxes nanopores form via a thermally dominated process, consistent with an explosive boiling mechanism. In this case, mass is rapidly rearranged via bubble growth and coalescence, much more quickly than would occur during sputtering. This mechanism has the potential to greatly speed up nanopore formation. PMID:24356374

  7. Prediction of an Autocatalytic Replication Mechanism for Micelle Formation

    NASA Astrophysics Data System (ADS)

    Pool, René; Bolhuis, Peter G.

    2006-07-01

    We report molecular simulations suggesting that the kinetics of surfactant micelle formation can be sped up significantly by a replication mechanism, in which growing micelles become unstable and split into two similar sized micelles. We argue that for certain surfactants types around the critical micelle concentration, such a mechanism becomes more dominant than the commonly accepted nucleation pathway.

  8. 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.

  9. 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...

  10. 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...

  11. 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.

  12. 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.

  13. Epigenetic mechanisms in experience-driven memory formation and behavior.

    PubMed

    Puckett, Rosemary E; Lubin, Farah D

    2011-10-01

    Epigenetic mechanisms have long been associated with the regulation of gene-expression changes accompanying normal neuronal development and cellular differentiation; however, until recently these mechanisms were believed to be statically quiet in the adult brain. Behavioral neuroscientists have now begun to investigate these epigenetic mechanisms as potential regulators of gene-transcription changes in the CNS subserving synaptic plasticity and long-term memory (LTM) formation. Experimental evidence from learning and memory animal models has demonstrated that active chromatin remodeling occurs in terminally differentiated postmitotic neurons, suggesting that these molecular processes are indeed intimately involved in several stages of LTM formation, including consolidation, reconsolidation and extinction. Such chromatin modifications include the phosphorylation, acetylation and methylation of histone proteins and the methylation of associated DNA to subsequently affect transcriptional gene readout triggered by learning. The present article examines how such learning-induced epigenetic changes contribute to LTM formation and influence behavior. In particular, this article is a survey of the specific epigenetic mechanisms that have been demonstrated to regulate gene expression for both transcription factors and growth factors in the CNS, which are critical for LTM formation and storage, as well as how aberrant epigenetic processing can contribute to psychological states such as schizophrenia and drug addiction. Together, the findings highlighted in this article support a novel role for epigenetic mechanisms in the adult CNS serving as potential key molecular regulators of gene-transcription changes necessary for LTM formation and adult behavior.

  14. 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).

  15. Gas-phase formation of silicon carbides, oxides, and sulphides from atomic silicon ions

    NASA Technical Reports Server (NTRS)

    Bohme, Diethard K.; Wlodek, Stanislaw; Fox, Arnold

    1989-01-01

    A systematic experimental study of the kinetics and mechanisms of the chemical reactions in the gas phase between ground-state Si(+)2p and a variety of astrophysical molecules. The aim of this study is to identify the reactions which trigger the formation of chemical bonds between silicon and carbon, oxygen and sulphur, and the chemical pathways which lead to further molecular growth. Such knowledge is valuable in the identification of new extraterrestrial silicon-bearing molecules and for an assessment of the gas-phase transition from atomic silicon to silicon carbide and silicate grain particles in carbon-rich and oxygen-rich astrophysical environments.

  16. 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.

  17. Collisionless Weibel shocks: Full formation mechanism and timing

    SciTech Connect

    Bret, A.; Stockem, A.; Narayan, R.; Silva, L. O.

    2014-07-15

    Collisionless shocks in plasmas play an important role in space physics (Earth's bow shock) and astrophysics (supernova remnants, relativistic jets, gamma-ray bursts, high energy cosmic rays). While the formation of a fluid shock through the steepening of a large amplitude sound wave has been understood for long, there is currently no detailed picture of the mechanism responsible for the formation of a collisionless shock. We unravel the physical mechanism at work and show that an electromagnetic Weibel shock always forms when two relativistic collisionless, initially unmagnetized, plasma shells encounter. The predicted shock formation time is in good agreement with 2D and 3D particle-in-cell simulations of counterstreaming pair plasmas. By predicting the shock formation time, experimental setups aiming at producing such shocks can be optimised to favourable conditions.

  18. 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.

  19. 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).

  20. Phase separation like dynamics during Myxococcus xanthus fruiting body formation

    NASA Astrophysics Data System (ADS)

    Liu, Guannan; Thutupalli, Shashi; Wigbers, Manon; Shaevitz, Joshua

    2015-03-01

    Collective motion exists in many living organisms as an advantageous strategy to help the entire group with predation, forage, and survival. However, the principles of self-organization underlying such collective motions remain unclear. During various developmental stages of the soil-dwelling bacterium, Myxococcus xanthus, different types of collective motions are observed. In particular, when starved, M. xanthus cells eventually aggregate together to form 3-dimensional structures (fruiting bodies), inside which cells sporulate in response to the stress. We study the fruiting body formation process as an out of equilibrium phase separation process. As local cell density increases, the dynamics of the aggregation M. xanthus cells switch from a spatio-temporally random process, resembling nucleation and growth, to an emergent pattern formation process similar to a spinodal decomposition. By employing high-resolution microscopy and a video analysis system, we are able to track the motion of single cells within motile collective groups, while separately tuning local cell density, cell velocity and reversal frequency, probing the multi-dimensional phase space of M. xanthus development.

  1. 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.

  2. 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

  3. Formation Mechanism of Spherical TiC in Ni-Ti-C System during Combustion Synthesis.

    PubMed

    Zhu, Guoliang; Wang, Wei; Wang, Rui; Zhao, Chuanbao; Pan, Weitao; Huang, Haijun; Du, Dafan; Wang, Donghong; Shu, Da; Dong, Anping; Sun, Baode; Jiang, Sheng; Pu, Yilong

    2017-08-29

    The formation mechanism of TiC particles in a Ni-Ti-C system were revealed by using differential thermal analysis (DTA), XRD, and SEM to identify the reaction products in different temperature ranges. The results indicated that the synthesis mechanism of TiC in Ni-Ti-C system was complex; several reactions were involved in the combustion synthesis of TiC-Ni composite. The Ni-Ti intermediate phases play important roles during the formation of TiC. Moreover, the influence of heating rate on the size range of TiC was also discussed.

  4. 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

  5. Formation mechanism of robust silver nanoparticle film with superhydrophobicity

    NASA Astrophysics Data System (ADS)

    Guo, Zhiguang; Liu, Weimin

    2010-12-01

    The promising formation mechanism of Ag nanoparticles on a Si wafer displaying superhydrophobicity, generated by means of a facile in situ galvanic cell route, is discussed. The results showed that the promising formation of Ag nanoparticles is based on a microelectrochemical redox reaction in which both the anodic process and the cathodic process occur simultaneously on the silicon substrate surface. This discovery could be of great importance in the design of other metal/semiconductor systems.

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

    PubMed

    Hordichok, Andrew J; Steyger, Peter S

    2007-10-01

    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 (6h), and allowed to recover (18h). 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.

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. Metastable bcc phase formation in the Nb-Cr system

    SciTech Connect

    Thoma, D.J.; Schwarz, R.B.; Perepezko, J.H.; Plantz, D.H.

    1993-08-01

    Extended metastable bcc solid solutions of Nb-Xat.%Cr (X = 35, 50, 57, 77, 82, and 94) were synthesized by two-anvil splat-quenching. In addition, bcc (Nb-67at.%Cr) was prepared by mechanically alloying mixtures of niobium and chromium powders. The lattice parameters were measured by X-ray diffraction and the Young`s moduli were measured by low-load microindentation. The composition dependence of the lattice parameters and elastic moduli show a positive deviation with respect to a rule of mixtures. During continuous heating at 15C/min., the metastable precursor bcc phases decomposed at temperatures above 750C to uniformly refined microstructures.

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

    NASA Astrophysics Data System (ADS)

    Lee, Shan-Hu; Uin, Janek; Guenther, Alex B.; de 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.

  14. Methylammonium formate as a mobile phase modifier for reversed-phase liquid chromatography

    PubMed Central

    Grossman, Shau; Danielson, Neil D.

    2009-01-01

    Although alkylammonium ionic liquids such as ethylammonium nitrate and ethylammonium formate have been used as mobile phase “solvents” for liquid chromatography (LC), we have shown that methylammonium formate (MAF), in part because of its lower viscosity, can be an effective replacement for methanol (MeOH) in reversed-phase LC. Plots of log retention factor versus the fraction of MeOH and MAF in the mobile phase indicate quite comparable solvent strength slope values of 2.50 and 2.05, respectively. Using a polar endcapped C18 column, furazolidone and nitrofurantoin using 20% MAF-80% water could be separated in 22 min but no baseline separation was possible using MeOH as the modifier, even down to 10%. Suppression of silanol peak broadening effects by MAF is important permitting a baseline separation of pyridoxine, thiamine, and nicotinamide using 5% MAF-95% water at 0.7 mL/min. Using 5% MeOH-95% water, severe peak broadening for thiamine is evident. The compatibility of MAF as a mobile phase modifer for LC with mass spectrometry detection of water soluble vitamins is also shown. PMID:18849044

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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

  20. Mechanism of New Bone Formation in Axial Spondyloarthritis.

    PubMed

    Poddubnyy, Denis; Sieper, Joachim

    2017-09-01

    The purpose of this review is to discuss new evidence explaining the progress from bony inflammation over repair tissue to new bone formation in axial spondyloartrhitis and its correlations in imaging and histology of the bone. Data from imaging, histology and treatment interventions indicates that the disease starts with inflammation, followed by replacement of subchondral bone marrow by repair tissue which presence is crucial for the stimulation of new bone formation. The magnetic resonance imaging (MRI) sequences of STIR and T1 are currently the most commonly used imaging techniques to follow this process; explanations are offered for the limited sensitivity to detect these bony changes on MRI in their different phases. Early and effective anti-inflammatory treatment is crucial for the prevention of long-term ankylosis. Whether there are currently also treatment options targeting new bone formation in these patients directly is less clear.

  1. 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.

  2. 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.

  3. Recent Advances in Molecular Mechanisms of Abdominal Aortic Aneurysm Formation

    PubMed Central

    Annambhotla, Suman; Bourgeois, Sebastian; Wang, Xinwen; Lin, Peter H.; Yao, Qizhi; Chen, Changyi

    2010-01-01

    Abdominal Aortic Aneurysm (AAA) is an increasingly common clinical condition with fatal implications. It is associated with advanced age, male gender, cigarette smoking, atherosclerosis, hypertension, and genetic predisposition. Although significant evidence has emerged in the last decade, the molecular mechanisms of AAA formation remains poorly understood. Currently, the treatment for AAA remains primarily surgical with the lone innovation of endovascular therapy. With advance in the human genome, understanding precisely which molecules and genes mediate AAA development and blocking their activity at the molecular level could lead to important new discoveries and therapies. This review summarizes recent updates in molecular mechanisms of AAA formation including animal models, autoimmune components, infection, key molecules and cytokines, mechanical forces, genetics and pharmacotherapy. This review will be helpful to those who want to recognize the newest endeavors within the field and identify possible lines of investigation in AAA. PMID:18259804

  4. 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.

  5. 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

  6. Statistical mechanical and quantum mechanical modeling of condensed phase systems

    NASA Astrophysics Data System (ADS)

    Labrosse, Matthew R.

    Understanding adsorption in nanoporous media is vital to improving their use in industrial applications such as fluid storage and separations processes. One major objective of this research is to shed light on an on-going controversy in literature over where gases adsorb on single walled carbon nanotube bundles. Grand-canonical Monte Carlo simulations have been performed using models of carbon nanotube bundles composed of tubes of all the same diameter (homogeneous) and tubes of different diameters (heterogeneous). We used three metrics with which we compared our simulation results to those found in experiments on carbon nanotubes: the specific surface area, the isosteric heat of adsorption, and the adsorption capacity. Simulations of classically behaved fluids Ar, CH4, and Xe indicate that nanotubes prepared by the HiPco process are best described by a heterogeneous bundle model with ˜11% of the nanotubes opened. Ne gas requires additional considerations to describe the quantum effects at the temperatures of interest, which have been implemented by the Feynman-Hibbs approximation. Overall, calculated results from Ne simulations are consistent with those from classical fluids. However, Ne simulations strongly indicate that the small interstitial channels formed by exactly three nanotubes are closed. Combined with previous studies on classically behaved fluids Ar, CH4, and Xe, experimental data including Ne are best matched by hetergeneous bundles with ˜11% open-ended nanotubes. The development of a heterogeneous Co/C/O reactive force field (ReaxFF) potential has also been a major objective of this research. ReaxFF provides a method to describe bond-breaking and bond-forming events that can be applied to large-scale molecular dynamics (MD) simulations. This many-bodied semi-empirical potential has been trained from ab initio density functional theory (DFT) calculations. The training set originally included descriptions of bulk and surface condensed phase cobalt

  7. Quasi-Hermitian quantum mechanics in phase space

    SciTech Connect

    Curtright, Thomas; Veitia, Andrzej

    2007-10-15

    We investigate quasi-Hermitian quantum mechanics in phase space using standard deformation quantization methods: Groenewold star products and Wigner transforms. We focus on imaginary Liouville theory as a representative example where exact results are easily obtained. We emphasize spatially periodic solutions, compute various distribution functions and phase-space metrics, and explore the relationships between them.

  8. 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.

  9. 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.

  10. 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

  11. 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).

  12. 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

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

    PubMed

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

    2016-07-15

    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 ((3)B1), which may be accessed by near-UV solar excitation of SO2 to its excited (1)B1 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. 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.

  15. Novel mechanism of conjoined gene formation in the human genome.

    PubMed

    Kim, Ryong Nam; Kim, Aeri; Choi, Sang-Haeng; Kim, Dae-Soo; Nam, Seong-Hyeuk; Kim, Dae-Won; Kim, Dong-Wook; Kang, Aram; Kim, Min-Young; Park, Kun-Hyang; Yoon, Byoung-Ha; Lee, Kang Seon; Park, Hong-Seog

    2012-03-01

    Recently, conjoined genes (CGs) have emerged as important genetic factors necessary for understanding the human genome. However, their formation mechanism and precise structures have remained mysterious. Based on a detailed structural analysis of 57 human CG transcript variants (CGTVs, discovered in this study) and all (833) known CGs in the human genome, we discovered that the poly(A) signal site from the upstream parent gene region is completely removed via the skipping or truncation of the final exon; consequently, CG transcription is terminated at the poly(A) signal site of the downstream parent gene. This result led us to propose a novel mechanism of CG formation: the complete removal of the poly(A) signal site from the upstream parent gene is a prerequisite for the CG transcriptional machinery to continue transcribing uninterrupted into the intergenic region and downstream parent gene. The removal of the poly(A) signal sequence from the upstream gene region appears to be caused by a deletion or truncation mutation in the human genome rather than post-transcriptional trans-splicing events. With respect to the characteristics of CG sequence structures, we found that intergenic regions are hot spots for novel exon creation during CGTV formation and that exons farther from the intergenic regions are more highly conserved in the CGTVs. Interestingly, many novel exons newly created within the intergenic and intragenic regions originated from transposable element sequences. Additionally, the CGTVs showed tumor tissue-biased expression. In conclusion, our study provides novel insights into the CG formation mechanism and expands the present concepts of the genetic structural landscape, gene regulation, and gene formation mechanisms in the human genome.

  16. Formation mechanism and prevention analysis in plateau damp environment

    NASA Astrophysics Data System (ADS)

    Meng, Yongjun; Chi, Fengxia

    2017-06-01

    This paper analyses and researches road condensation ice formation mechanism, so as to find out the effective and economical method to prevent road frozen ice and govern it. The method of prevention can be divided into passive inhibition technology and proactive inhibition technology. Passive inhibition technology cannot inhibit the formation of condensation. In the process of research of prevention condensation, early warning system for snow and ice research also should not ignore. To establish early warning systems and take it into implementation will greatly reduce the extent of the ice and snow disasters.

  17. 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

  18. 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.

  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. CLEPS 1.0: A new protocol for cloud aqueous phase oxidation of VOC mechanisms

    NASA Astrophysics Data System (ADS)

    Mouchel-Vallon, Camille; Deguillaume, Laurent; Monod, Anne; Perroux, Hélène; Rose, Clémence; Ghigo, Giovanni; Long, Yoann; Leriche, Maud; Aumont, Bernard; Patryl, Luc; Armand, Patrick; Chaumerliac, Nadine

    2017-03-01

    A new detailed aqueous phase mechanism named the Cloud Explicit Physico-chemical Scheme (CLEPS 1.0) is proposed to describe the oxidation of water soluble organic compounds resulting from isoprene oxidation. It is based on structure activity relationships (SARs) which provide global rate constants together with branching ratios for HOṡ abstraction and addition on atmospheric organic compounds. The GROMHE SAR allows the evaluation of Henry's law constants for undocumented organic compounds. This new aqueous phase mechanism is coupled with the MCM v3.3.1 gas phase mechanism through a mass transfer scheme between gas phase and aqueous phase. The resulting multiphase mechanism has then been implemented in a model based on the Dynamically Simple Model for Atmospheric Chemical Complexity (DSMACC) using the Kinetic PreProcessor (KPP) that can serve to analyze data from cloud chamber experiments and field campaigns. The simulation of permanent cloud under low-NOx conditions describes the formation of oxidized monoacids and diacids in the aqueous phase as well as a significant influence on the gas phase chemistry and composition and shows that the aqueous phase reactivity leads to an efficient fragmentation and functionalization of organic compounds.

  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. On the mechanism of nanoparticle formation in a flame doped by iron pentacarbonyl.

    PubMed

    Poliak, Marina; Fomin, Alexey; Tsionsky, Vladimir; Cheskis, Sergey; Wlokas, Irenaeus; Rahinov, Igor

    2015-01-07

    In this work we have investigated the mechanism of nanoparticle synthesis in a low pressure, premixed, laminar flat flame of CH4-O2, doped with iron pentacarbonyl using a combined quartz-crystal-microbalance-particle-mass-spectrometry apparatus. We have unambiguously demonstrated that the formation of nanoparticles in iron pentacarbonyl-doped flames occurs very early, in close proximity to the burner surface, prior to the flame front. This early rise of nanoparticle mass concentration is followed by a sharp drop in nanoparticle concentration at the high temperature flame front. This "prompt" nanoparticle generation is consistent with kinetic models describing iron cluster formation. The observation of this phenomenon in a quasi-one-dimensional premixed flat flame strengthens our previous findings and points out that the "prompt" nanoparticle formation is a general phenomenon, not limited to diffusion flames. It presents a challenge and a trigger for further development of the existing mechanisms for gas phase synthesis of iron oxide particles in flames.

  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. 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.

  6. 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.

  7. 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

  8. Mechanism of frost formation on lubricant-impregnated surfaces.

    PubMed

    Rykaczewski, Konrad; Anand, Sushant; Subramanyam, Srinivas Bengaluru; Varanasi, Kripa K

    2013-04-30

    Frost formation is a major problem affecting a variety of industries including transportation, power generation, construction, and agriculture. Currently used active chemical, thermal, and mechanical techniques of ice removal are time-consuming and costly. The use of nanotextured coatings infused with perfluorinated oil has recently been proposed as a simple passive antifrosting and anti-icing method. However, we demonstrate that the process of freezing subcooled condensate and frost formation on such lubricant-impregnated surfaces is accompanied by the migration of the lubricant from the wetting ridge and from within the textured substrate to the surface of frozen droplets. For practical applications, this mechanism can comprise the self-healing and frost-repelling characteristics of lubricant impregnated-surfaces, regardless of the underlying substrate's topography. Thus, further research is necessary to develop liquid-texture pairs that will provide a sustainable frost suppression method.

  9. Defect formation mechanism during PECVD of a-Si:H

    SciTech Connect

    Maeda, Keiji; Umezu, Ikurou

    1997-07-01

    Defect formation mechanism in a-Si:H during PECVD at substrate temperature below 250 C is considered to be breaking of weak bonds in the Urbach tail. To break weak bonds, an extra energy is necessary. This energy is supplied by the reaction energy of SiH{sub 3} precursor at the growing surface incorporating SiH{sub 2} into the network. The defect density is experimentally shown to be proportional to a product of the energy supply frequency, i.e., SiH{sub 2} density, and the weak bond density which is obtained by the Urbach energy. By analysis using the configurational coordinate diagram the energy level of the broken weak bond is determined to be 0.2 eV above the valence band mobility edge. There is similarity of the defect formation mechanism during deposition to that of the Staebler-Wronski effect.

  10. 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

  11. 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.

  12. 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.

  13. Coffee melanoidins: structures, mechanisms of formation and potential health impacts.

    PubMed

    Moreira, Ana S P; Nunes, Fernando M; Domingues, M Rosário; Coimbra, Manuel A

    2012-09-01

    During the roasting process, coffee bean components undergo structural changes leading to the formation of melanoidins, which are defined as high molecular weight nitrogenous and brown-colored compounds. As coffee brew is one of the main sources of melanoidins in the human diet, their health implications are of great interest. In fact, several biological activities, such as antioxidant, antimicrobial, anticariogenic, anti-inflammatory, antihypertensive, and antiglycative activities, have been attributed to coffee melanoidins. To understand the potential of coffee melanoidin health benefits, it is essential to know their chemical structures. The studies undertaken to date dealing with the structural characterization of coffee melanoidins have shown that polysaccharides, proteins, and chlorogenic acids are involved in coffee melanoidin formation. However, exact structures of coffee melanoidins and mechanisms involved in their formation are far to be elucidated. This paper systematizes the available information and provides a critical overview of the knowledge obtained so far about the structure of coffee melanoidins, mechanisms of their formation, and their potential health implications.

  14. 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

  15. 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

  16. Peptide Formation Mechanism on Montmorillonite Under Thermal Conditions

    NASA Astrophysics Data System (ADS)

    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.

  17. 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.

  18. 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.

  19. Dynamic phases, clustering, and chain formation for driven disk systems in the presence of quenched disorder

    NASA Astrophysics Data System (ADS)

    Yang, Y.; McDermott, D.; Reichhardt, C. J. Olson; Reichhardt, C.

    2017-04-01

    We numerically examine the dynamic phases and pattern formation of two-dimensional monodisperse repulsive disks driven over random quenched disorder. We show that there is a series of distinct dynamic regimes as a function of increasing drive, including a clogged or pile-up phase near depinning, a homogeneous disordered flow state, and a dynamically phase separated regime consisting of high-density crystalline regions surrounded by a low density of disordered disks. At the highest drives the disks arrange into one-dimensional moving chains. The phase separated regime has parallels with the phase separation observed in active matter systems, but arises from a distinct mechanism consisting of the combination of nonequilibrium fluctuations with density-dependent mobility. We discuss the pronounced differences between this system and previous studies of driven particles with longer-range repulsive interactions moving over random substrates, such as superconducting vortices or electron crystals, where dynamical phase separation and distinct one-dimensional moving chains are not observed. Our results should be generic to a broad class of systems in which the particle-particle interactions are short ranged, such as sterically interacting colloids or Yukawa particles with strong screening driven over random pinning arrays, superconducting vortices in the limit of small penetration depths, or quasi-two-dimensional granular matter flowing over rough landscapes.

  20. 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

  1. Importance of silicon and mechanisms of biosilica formation in plants.

    PubMed

    Sahebi, Mahbod; Hanafi, Mohamed M; Siti Nor Akmar, Abdullah; Rafii, Mohd Y; Azizi, Parisa; 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.

  2. 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.

  3. 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}.

  4. Differential Effects of the Hydrophobic Surfactant Proteins on the Formation of Inverse Bicontinuous Cubic Phases

    PubMed Central

    Chavarha, Mariya; Loney, Ryan W.; Kumar, Kamlesh; Rananavare, Shankar B.; Hall, Stephen B.

    2012-01-01

    Prior studies have shown that the biological mixture of the two hydrophobic surfactant proteins, SP–B and SP–C, produces faster adsorption of the surfactant lipids to an air/water interface, and that they induce 1-palmitoyl-2-oleoyl phosphatidylethanolamine (POPE) to form inverse bicontinuous cubic phases. Previous studies have shown that SP–B has a much greater effect than SP–C on adsorption. If the two proteins induce faster adsorption and formation of the bicontinuous structures by similar mechanisms, then they should also have different abilities to form the cubic phases. To test this hypothesis, we measured small angle X-ray scattering on the individual proteins combined with POPE. SP–B replicated the dose-related ability of the combined proteins to induce the cubic phases at temperatures more than 25°C below the point at which POPE alone forms the curved inverse-hexagonal phase. With SP–C, diffraction from cubic structures was either absent or present at very low intensities only with larger amounts of protein. The correlation between the structural effects of inducing curved structures and the functional effects on the rate of adsorption fits with the model in which SP–B promotes adsorption by facilitating formation of an inversely curved, rate-limiting structure. PMID:23140329

  5. Nucleation mechanism for the direct graphite-to-diamond phase transition.

    PubMed

    Khaliullin, Rustam Z; Eshet, Hagai; Kühne, Thomas D; Behler, Jörg; Parrinello, Michele

    2011-07-24

    Graphite and diamond have comparable free energies, yet forming diamond from graphite in the absence of a catalyst requires pressures that are significantly higher than those at equilibrium coexistence. At lower temperatures, the formation of the metastable hexagonal polymorph of diamond is favoured instead of the more stable cubic diamond. These phenomena cannot be explained by the concerted mechanism suggested in previous theoretical studies. Using an ab initio quality neural-network potential, we carried out a large-scale study of the graphite-to-diamond transition assuming that it occurs through nucleation. The nucleation mechanism accounts for the observed phenomenology and reveals its microscopic origins. We demonstrate that the large lattice distortions that accompany the formation of diamond nuclei inhibit the phase transition at low pressure, and direct it towards the hexagonal diamond phase at higher pressure. The proposed nucleation mechanism should improve our understanding of structural transformations in a wide range of carbon-based materials.

  6. 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.

  7. 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.

  8. Morphogengineering roots: comparing mechanisms of morphogen gradient formation

    PubMed Central

    2012-01-01

    Background In developmental biology, there has been a recent focus on the robustness of morphogen gradients as possible providers of positional information. It was shown that functional morphogen gradients present strong biophysical constraints and lack of robustness to noise. Here we explore how the details of the mechanism which underlies the generation of a morphogen gradient can influence those properties. Results We contrast three gradient-generating mechanisms, (i) a source-decay mechanism; and (ii) a unidirectional transport mechanism; and (iii) a so-called reflux-loop mechanism. Focusing on the dynamics of the phytohormone auxin in the root, we show that only the reflux-loop mechanism can generate a gradient that would be adequate to supply functional positional information for the Arabidopsis root, for biophysically reasonable kinetic parameters. Conclusions We argue that traits that differ in spatial and temporal time-scales can impose complex selective pressures on the mechanism of morphogen gradient formation used for the development of the particular organism. PMID:22583698

  9. Neural mechanisms underlying binocular fusion and stereopsis: position vs. phase.

    PubMed

    Anzai, A; Ohzawa, I; Freeman, R D

    1997-05-13

    The visual system utilizes binocular disparity to discriminate the relative depth of objects in space. Since the striate cortex is the first site along the central visual pathways at which signals from the left and right eyes converge onto a single neuron, encoding of binocular disparity is thought to begin in this region. There are two possible mechanisms for encoding binocular disparity through simple cells in the striate cortex: a difference in receptive field (RF) position between the two eyes (RF position disparity) and a difference in RF profile between the two eyes (RF phase disparity). Although there have been studies supporting each of the two encoding mechanisms, both mechanisms have not been examined in a single study. Therefore, the relative roles of the two mechanisms have not been determined. To address this issue, we have mapped left and right eye RFs of simple cells in the cat's striate cortex using binary m-sequence noise, and then we have estimated RF position and phase disparities. We find that RF position disparities are generally limited to small values that are not sufficient to encode large binocular disparities. In contrast, RF phase disparities cover a wide range of binocular disparities and exhibit dependencies on orientation and spatial frequency in a manner expected for a mechanism that encodes binocular disparity. These results indicate that binocular disparity is mainly encoded through RF phase disparity. However, RF position disparity may play a significant role for cells with high spatial frequency selectivity, which are constrained to small RF phase disparities.

  10. 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.

  11. 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.

  12. 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.

  13. Observation and prediction of first phase formation in binary Cu-metal thin films

    NASA Astrophysics Data System (ADS)

    Li, Jian; Strane, J. W.; Russell, S. W.; Hong, S. Q.; Mayer, J. W.; Marais, T. K.; Theron, C. C.; Pretorius, R.

    1992-10-01

    First phase formation has been determined in Cu binary thin film systems with Ti, Zr, Mg, Sb, Pd, and Pt using transmission electron microscopy and Rutherford backscattering spectrometry. CuTi, CuZr, CuMg2, Cu2Sb, Cu3Pd, and Cu3Pt are the first phases to form upon annealing the Cu/metal bilayers. The effective heat of formation model is used to predict first phase formation in 14 Cu/metal systems.

  14. Mantle-slab interaction and redox mechanism of diamond formation.

    PubMed

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

    2013-12-17

    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.

  15. 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

  16. The physical mechanisms of subcritical collisionless shock-wave formation

    NASA Technical Reports Server (NTRS)

    Mellott, M. M.

    1984-01-01

    The key process in shock wave formation is related to energy dissipation, and the nature of the operative dissipation mechanism determines the basic character of the resulting shock. In the case of collisionless plasmas, the primary problem consists in the identification of the processes which can provide the necessary dissipation in relatively short spatial scale lengths. The present investigation is concerned with the various collisionless dissipation mechanisms which can operate in weak shocks, taking into account the effects of different mechanisms on shock structure. Particular attention is given to a restricted class of quasi-perpendicular low beta low Mach number shocks. Such shocks are traditionally called 'laminar shocks'. Resistive shocks are considered along with subcritical shocks observed with the aid of the ISEE spacecraft.

  17. 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.

  18. 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

  19. Rheological controls on the terrestrial core formation mechanism

    NASA Astrophysics Data System (ADS)

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

    2008-09-01

    Knowledge about the formation mechanism for the Earth's core is still very limited. The fracturing mechanism was proposed by Stevenson [1981] 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 [Karato and Murthy, 1997a; Ziethe and Spohn, 2007]. 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 [Gerya and Yuen, 2007]. In the model the planet is surrounded by a low viscosity (η=1019 Pa s), massless fluid ("sticky air") to simulate a free surface [Schmeling et al., 2008]. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. The Mechanism of Amyloid Spherulite Formation by Bovine Insulin

    PubMed Central

    Krebs, M. R. H.; Bromley, E. H. C.; Rogers, S. S.; Donald, A. M.

    2005-01-01

    The formation of amyloid-containing spherulite-like structures has been observed in some instances of amyloid diseases, as well as in amyloid fibril-containing solutions in vitro. In this article we describe the structure and kinetics of bovine insulin amyloid fibril spherulites formed in the presence and absence of different salts and at different salt concentrations. The general spherulite structure consists of radially oriented amyloid fibrils, as shown by optical microscopy and environmental scanning electron microscopy. In the center of each spherulite, a “core” of less regularly oriented material is observed, whose size decreases when the spherulites are formed in the presence of increasing concentrations of NaCl. Similarly, amyloid fibrils form faster in the presence of NaCl than in its absence. A smaller enhancement of the rate of formation with salt concentration is observed for spherulites. These data suggest that both amyloid fibril formation and random aggregation occur concurrently under the conditions tested. Changes in their relative rates result in the different-sized cores observed in the spherulites. This mechanism can be likened to that leading to the formation of spherulites of polyethylene, in agreement with observations that polypeptide chains under partially denaturing conditions can exhibit behavior not dissimilar to that of synthetic polymers. PMID:15596515

  7. The probabilistic mechanism of formation of block structures

    NASA Astrophysics Data System (ADS)

    Ivanov, V. I.

    2012-03-01

    Questions on the formation of block structures are considered. It is shown that the block structure is characteristic of bodies in a wide range of scales from microscopic to astronomic and from the bodies of nonliving nature to living organisms and communities. A scheme of the mechanism of the probabilistic formation of block structures is suggested. The characteristics general for structures of all scales are revealed. Evidence is presented that the hierarchical pattern of element sizes is characteristic of natural structures in which the ratio of linear sizes of elements neighboring by hierarchy is 2-5, while the characteristic scale coefficient is √ N , where N is the total number of elements of which the system is formed. The block-probabilistic approach ensures knowledge of rare catastrophic events, including earthquakes, market crashes, floods, and industrial catastrophes, or creative events such as the formation of hypercomplex systems similar to organisms and communities. The statistics of rare events follows the power distribution (the distribution with a "heavy tail") rather than the exponential one and especially the Poisson distribution, the Gaussian distribution, or the distributions with "light tails" close to them. The expression for the factor of increasing the formation probability of the systems, which is of many orders of magnitude even for the simplest systems, is acquired.

  8. 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.

  9. 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

  10. Multiple repressive mechanisms in the hippocampus during memory formation.

    PubMed

    Cho, Jun; Yu, Nam-Kyung; Choi, Jun-Hyeok; Sim, Su-Eon; Kang, SukJae Joshua; Kwak, Chuljung; Lee, Seung-Woo; Kim, Ji-il; Choi, Dong Il; Kim, V Narry; Kaang, Bong-Kiun

    2015-10-02

    Memory stabilization after learning requires translational and transcriptional regulations in the brain, yet the temporal molecular changes that occur after learning have not been explored at the genomic scale. We used ribosome profiling and RNA sequencing to quantify the translational status and transcript levels in the mouse hippocampus after contextual fear conditioning. We revealed three types of repressive regulations: translational suppression of ribosomal protein-coding genes in the hippocampus, learning-induced early translational repression of specific genes, and late persistent suppression of a subset of genes via inhibition of estrogen receptor 1 (ESR1/ERα) signaling. In behavioral analyses, overexpressing Nrsn1, one of the newly identified genes undergoing rapid translational repression, or activating ESR1 in the hippocampus impaired memory formation. Collectively, this study unveils the yet-unappreciated importance of gene repression mechanisms for memory formation. Copyright © 2015, American Association for the Advancement of Science.

  11. 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.

  12. 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.

  13. 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.

  14. Upwash exploitation and downwash avoidance by flap phasing in ibis formation flight.

    PubMed

    Portugal, Steven J; Hubel, Tatjana Y; Fritz, Johannes; Heese, Stefanie; Trobe, Daniela; Voelkl, Bernhard; Hailes, Stephen; Wilson, Alan M; Usherwood, James R

    2014-01-16

    Many species travel in highly organized groups. The most quoted function of these configurations is to reduce energy expenditure and enhance locomotor performance of individuals in the assemblage. The distinctive V formation of bird flocks has long intrigued researchers and continues to attract both scientific and popular attention. The well-held belief is that such aggregations give an energetic benefit for those birds that are flying behind and to one side of another bird through using the regions of upwash generated by the wings of the preceding bird, although a definitive account of the aerodynamic implications of these formations has remained elusive. Here we show that individuals of northern bald ibises (Geronticus eremita) flying in a V flock position themselves in aerodynamically optimum positions, in that they agree with theoretical aerodynamic predictions. Furthermore, we demonstrate that birds show wingtip path coherence when flying in V positions, flapping spatially in phase and thus enabling upwash capture to be maximized throughout the entire flap cycle. In contrast, when birds fly immediately behind another bird--in a streamwise position--there is no wingtip path coherence; the wing-beats are in spatial anti-phase. This could potentially reduce the adverse effects of downwash for the following bird. These aerodynamic accomplishments were previously not thought possible for birds because of the complex flight dynamics and sensory feedback that would be required to perform such a feat. We conclude that the intricate mechanisms involved in V formation flight indicate awareness of the spatial wake structures of nearby flock-mates, and remarkable ability either to sense or predict it. We suggest that birds in V formation have phasing strategies to cope with the dynamic wakes produced by flapping wings.

  15. Spontaneous formation of stable capillary bridges for firming compact colloidal microstructures in phase separating liquids: a computational study.

    PubMed

    Cheng, Tian-Le; Wang, Yu U

    2012-02-07

    Computer modeling and simulations are performed to investigate capillary bridges spontaneously formed between closely packed colloidal particles in phase separating liquids. The simulations reveal a self-stabilization mechanism that operates through diffusive equilibrium of two-phase liquid morphologies. Such mechanism renders desired microstructural stability and uniformity to the capillary bridges that are spontaneously formed during liquid solution phase separation. This self-stabilization behavior is in contrast to conventional coarsening processes during phase separation. The volume fraction limit of the separated liquid phases as well as the adhesion strength and thermodynamic stability of the capillary bridges are discussed. Capillary bridge formations in various compact colloid assemblies are considered. The study sheds light on a promising route to in situ (in-liquid) firming of fragile colloidal crystals and other compact colloidal microstructures via capillary bridges.

  16. 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.

  17. Proposed Mechanism for the Formation of Dust Horizons on Bauxite Residue Disposal Areas

    NASA Astrophysics Data System (ADS)

    Klauber, Craig; Harwood, Nicole; Hockridge, Renee; Middleton, Campbell

    Without some form of mitigation control bauxite residue disposal areas in Mediterranean climates can be subject to large-scale dust lift-off events during summer, with significant environmental impact. Intuitively dust formation relates simply to the process of drying. However, whilst wet solids will not produce dust, the converse is not always true. Both the rate of drying and the composition of the bauxite residue are critical factors in determining whether a potential dust event will occur. In this work a dust formation mechanism is proposed in which caustic salts transport and effloresce along with a changing phase composition in the brine solids from sodium bicarbonate through to trona and then to carbonate monohydrate. The efflorescence leads to a white dust event, but the carbonate phase change and the associated reduction in sodium molar volume critically breaks inter-particulate bonding between the residue particles leading to a more severe underlying red dust event.

  18. Pessimum effect of externally applied chlorides on expansion due to delayed ettringite formation: Proposed mechanism

    SciTech Connect

    Ekolu, S.O. . E-mail: s.ekolu@utoronto.ca; Thomas, M.D.A.; Hooton, R.D.

    2006-04-15

    Mortars and concretes were subjected to a heat treatment cycle consisting of a pre-set period of 4 h at 23 deg. C followed by accelerated curing at 95 deg. C prior to storage at room temperature in water or limewater, 0.5 M, 2.8 M sodium chloride solutions. It was found that the specimens stored in 0.5 M sodium chloride solution gave a much greater expansion than those stored in limewater or 2.8 M sodium chloride solution. This pessimum influence of chlorides on expansion due to delayed ettringite formation deviates from the commonly held view that chlorides mitigate sulphate attack in concretes. The mechanism of the pessimum effect of chlorides on expansion due to delayed ettringite formation, and the final products of the associated phase transformations have been proposed. X-ray diffraction and differential thermal analysis techniques were used to follow phase transformations.

  19. 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

  20. 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.

  1. Nanoscale self-assembly of starch: Phase relations, formation, and structure

    NASA Astrophysics Data System (ADS)

    Creek, John A.

    This project has been undertaken to develop a fundamental understanding of the spherulitic self-assembly of starch polymers from aqueous solution, both as a model for starch granule initiation in vivo and as a biologically-inspired material with applications in the food and pharmaceutical industries. Botanical starches were observed to form semi-crystalline spherulites from aqueous solution when cooled after a high temperature treatment, and the processes resulting in spherulite formation were investigated. Based on the influence of cooling rate on spherulite formation from a botanical starch, liquid-liquid demixing in competition with crystallization was proposed as the mechanism leading to spherulite formation (summarized in a hypothetical phase diagram). Study of amylose and amylopectin self-assembly demonstrated that the linear polymer plays the primary role in forming spherulites. As a result, the roles of degree of polymerization, concentration, and thermal processing conditions on amylose self-assembly were explored. Thermal properties, final system morphology, and crystalline allomorph were characterized. In all cases the experimental findings supported the proposed phase diagram. Finally, the crystalline nanostructure of the spherulites was probed using atomic force microscopy (AFM), revealing a seemingly universal level of structure in crystalline starch materials. This was compared to an existing model of crystallization for synthetic polymers involving a transitional liquid crystalline-like ordering---a comparison that makes sense in light of the known helical structure of starch.

  2. Role of diffusion in amorphous-phase formation and crystallization of amorphous Ni--Zr

    SciTech Connect

    Barbour, J.C.; de Reus, R.; Denier van der Gon, A.W.; Saris, F.W.

    1987-03-01

    The Ni--Zr system is examined as a representative system for the formation of an amorphous phase by diffusion and for the crystallization of an amorphous phase by diffusion. High-resolution electron microscopy (HREM) is used to show that the amorphous phase grows by bulk diffusion through the amorphous material rather than by short-circuit diffusion. Also, the HREM shows that the amorphous phase formed by diffusion appears to be the same as the vapor-deposited amorphous phase. A correlation between crystallization temperatures (T/sub x/) and the enthalpy of large-atom hole formation is given. This correlation predicts values of T/sub x/ that are lower than those predicted from the small-atom hole-formation model. The difference in hole-formation enthalpies for the large and small atoms is given as a criterion for amorphous-phase formation via diffusion.

  3. 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

  4. 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

  5. Sensitivity analysis of a mixed-phase chemical mechanism using automatic differentiation

    SciTech Connect

    Zhang, Y.; Easter, R.C.

    1998-08-01

    A sensitivity analysis of a comprehensive mixed-phase chemical mechanism is conducted under a variety of atmospheric conditions. The local sensitivities of gas and aqueous phase species concentrations with respect to a variety of model parameters are calculated using the novel automatic differentiation ADIFOR tool. The main chemical reaction pathways in all phases, interfacial mass transfer processes, and ambient physical parameters that affect tropospheric O{sub 3} formation and O{sub 3}-precursor relations under all modeled conditions are identified and analyzed. The results show that the presence of clouds not only reduces many gas phase species concentrations and the total oxidizing capacity but alters O{sub 3}-precursor relations. Decreases in gas phase concentrations and photochemical formation rates of O{sub 3} can be up to 9{percent} and 100{percent}, respectively, depending on the preexisting atmospheric conditions. The decrease in O{sub 3} formation is primarily caused by the aqueous phase reactions of O{sub 2}{sup {minus}} with dissolved HO{sub 2} and O{sub 3} under most cloudy conditions. {copyright} 1998 American Geophysical Union

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Phase resetting as a mechanism for supramodal attentional control.

    PubMed

    Kayser, Christoph

    2009-11-12

    Attentional modulation and cross-modal integration might partly rely on the same neurophysiological mechanisms. As a new study by Lakatos et al. in this issue of Neuron shows, attended stimuli in one sensory modality not only modulate oscillatory activity within the primary cortex of the same modality but also reset the phase of ongoing oscillations in primary cortices of other modalities.

  14. 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…

  15. Atomic Simulations of Alane Phase Transformations and Dehydrogenation Mechanisms

    NASA Astrophysics Data System (ADS)

    Opalka, Susanne; Saxe, Paul; Lovvik, Ole Martin

    2007-03-01

    Density functional theory atomic ground state, molecular dynamics, and direct method lattice dynamic simulations were used to mechanistically probe phase transformations between the various crystallographically refined α, α', β, and γ AlH3 phases. Lattice dynamic predictions of the AlH3 structures provided an ideal test case for systematically accessing the accuracy of the vibrational thermodynamic property contributions with the harmonic approximation. The predicted transformation pathways involved coordinated tilting and rotation mechanisms, similar to that observed in perovskite structures. Further simulations were conducted to elucidate the mechanism for α AlH3 phase decomposition to the Al and H2 products and to identify probable barriers to reversible rehydrogenation.

  16. 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.

  17. 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.

  18. Boron nitride hollow nanospheres: Synthesis, formation mechanism and dielectric property

    SciTech Connect

    Zhong, B.; Tang, X.H.; Huang, X.X.; Xia, L.; Zhang, X.D.; Wang, C.J.; Wen, G.W.

    2015-04-15

    Highlights: • BN hollow nanospheres are fabricated in large scale via a new CVD method. • Morphology and structure are elucidated by complementary analytical techniques. • Formation mechanism is proposed based on experimental observations. • Dielectric properties are investigated in the X-band microwave frequencies. • BN hollow nanospheres show lower dielectric loss than regular BN powders. - Abstract: Boron nitride (BN) hollow nanospheres have been successfully fabricated by pyrolyzing vapors decomposed from ammonia borane (NH{sub 3}BH{sub 3}) at 1300 °C. The final products have been extensively characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The BN hollow nanospheres were ranging from 100 to 300 nm in diameter and around 30–100 nm in thickness. The internal structure of the products was found dependent on the reaction temperatures. A possible formation mechanism of the BN hollow nanospheres was proposed on the basis of the experimental observations. Dielectric measurements in the X-band microwave frequencies (8–12 GHz) showed that the dielectric loss of the paraffin filled by the BN hollow nanospheres was lower than that filled by regular BN powders, which indicated that the BN hollow nanospheres could be potentially used as low-density fillers for microwave radomes.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. Formation of porous crystals via viscoelastic phase separation

    NASA Astrophysics Data System (ADS)

    Tsurusawa, Hideyo; Russo, John; Leocmach, Mathieu; Tanaka, Hajime

    2017-10-01

    Viscoelastic phase separation of colloidal suspensions can be interrupted to form gels either by glass transition or by crystallization. With a new confocal microscopy protocol, we follow the entire kinetics of phase separation, from homogeneous phase to different arrested states. For the first time in experiments, our results unveil a novel crystallization pathway to sponge-like porous crystal structures. In the early stages, we show that nucleation requires a structural reorganization of the liquid phase, called stress-driven ageing. Once nucleation starts, we observe that crystallization follows three different routes: direct crystallization of the liquid phase, the Bergeron process, and Ostwald ripening. Nucleation starts inside the reorganized network, but crystals grow past it by direct condensation of the gas phase on their surface, driving liquid evaporation, and producing a network structure different from the original phase separation pattern. We argue that similar crystal-gel states can be formed in monatomic and molecular systems if the liquid phase is slow enough to induce viscoelastic phase separation, but fast enough to prevent immediate vitrification. This provides a novel pathway to form nanoporous crystals of metals and semiconductors without dealloying, which may be important for catalytic, optical, sensing, and filtration applications.

  4. 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…

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Arrested phase separation in reproducing bacteria: a generic route to pattern formation?

    NASA Astrophysics Data System (ADS)

    Tailleur, Julien

    2011-03-01

    In this talk I will present a generic mechanism by which reproducing microorganisms can form stable patterns. This mechanism is based on the competition between two separate ingredients. First, a diffusivity that depends on the local population density can promote phase separation, generating alternating regions of high and low densities. Then, this is opposed by the logistic law for birth and death of microorganisms which allows only a single uniform density to be stable. The result of this contest is an arrested nonequilibrium phase separation in which dense droplets or rings become separated by less dense regions, with a characteristic steady-state length scale. I will illustrate this mechanism by considering a model of run-and-tumble bacteria, for which a density dependent diffusivity can stem from either a decrease of the swim speed or an increase of the tumbling rate at high density. No chemotaxis is assumed in this model, yet it predicts the formation of patterns strikingly similar to those believed to result from chemotactic behavior.

  13. 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

  14. 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.

  15. Mechanisms of detonation formation due to a temperature gradient

    NASA Astrophysics Data System (ADS)

    Kapila, A. K.; Schwendeman, D. W.; Quirk, J. J.; Hawa, T.

    2002-12-01

    Emergence of a detonation in a homogeneous, exothermically reacting medium can be deemed to occur in two phases. The first phase processes the medium so as to create conditions ripe for the onset of detonation. The actual events leading up to preconditioning may vary from one experiment to the next, but typically, at the end of this stage the medium is hot and in a state of nonuniformity. The second phase consists of the actual formation of the detonation wave via chemico-gasdynamic interactions. This paper considers an idealized medium with simple, rate-sensitive kinetics for which the preconditioned state is modelled as one with an initially prescribed linear gradient of temperature. Accurate and well-resolved numerical computations are carrried out to determine the mode of detonation formation as a function of the size of the initial gradient. For shallow gradients, the result is a decelerating supersonic reaction wave, a weak detonation, whose trajectory is dictated by the initial temperature profile, with only weak intervention from hydrodynamics. If the domain is long enough, or the gradient less shallow, the wave slows down to the Chapman-Jouguet speed and undergoes a swift transition to the ZND structure. For sharp gradients, gasdynamic nonlinearity plays a much stronger role. Now the path to detonation is through an accelerating pulse that runs ahead of the reaction wave and rearranges the induction-time distribution there to one that bears little resemblance to that corresponding to the initial temperature gradient. The pulse amplifies and steepens, transforming itself into a complex consisting of a lead shock, an induction zone, and a following fast deflagration. As the pulse advances, its three constituent entities attain progressively higher levels of mutual coherence, to emerge as a ZND detonation. For initial gradients that are intermediate in size, aspects of both the extreme scenarios appear in the path to detonation. The novel aspect of this study

  16. 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

  17. Formation Mechanism of Titanium Silicon Carbide: The Effect of Different Composition of Starting Materials

    NASA Astrophysics Data System (ADS)

    Solihin; Mursito, Anggoro Tri; Sun, Zhengming

    2017-07-01

    Titanium silicon carbide (Ti3SiC2) is a kind of ceramic that has physical property value similar with metal. Ti3SiC2 has been synthesized through various methods based on solid state reaction. Although Ti3SiC2 has been synthesized through various methods by using various starting materials consisting titanium (Ti), silicon (Si), and carbon (C) the mechanism of Ti3SiC2 formation through sintering has not fully understood. The aim of this research is to reveal the mechanism happening during sintering. Two composition of starting material was used, 2Ti/2Si/3TiC and 5Ti/2Si/3C. The analysis through XRD and SEM-EDS shows that the formation of intermediate phases, TiC and Ti5Si3, takes place prior to the formation of Ti3SiC2. In other words, Ti3SiC2 can only be formed through solid state reaction between TiC and Ti5Si3. Since TiC has already available in the system 2Ti/2Si/3TiC, the phase purity of Ti3SiC2 in 2Ti/2Si/3TiC is always higher than that of 5Ti/2Si/3C.

  18. Dissipative melting as a mechanism for core formation

    NASA Technical Reports Server (NTRS)

    Turcotte, D. L.; Emerman, S. H.

    1983-01-01

    Cosmochemical studies strongly favor a near-homogeneous accretion of the earth. These studies also show that core segregation probably occurred within the first 100,000 years of earth history. Mechanisms of core formation have received relatively little attention. The principal purpose of this paper is to examine dissipative melting as a possible mechanism for core segregation. For a large iron body migrating through the mantle, the potential energy lost by the body is dissipated by frictional heating. If the body has a radius greater than about 30 km, the frictional heating is sufficient to melt a path through which the body can fall. If the iron body is liquid (as expected) with a low viscosity, it would penetrate the mantle as a diapir. The problem of an immiscible liquid body melting its way through a solid is solved, and a family of diapir shapes is obtained. It is found that dissipative heating may be a viable mechanism for core segregation if sufficiently large bodies of liquid iron can form.

  19. Influence of Supercooling on Formation of Primary Phase

    NASA Astrophysics Data System (ADS)

    Yoshimura, R.; Esaka, H.; Shinozuka, K.

    2015-06-01

    It is reported actual volume fraction of primary phase in alloys is larger than the equilibrium value. Larger volume fraction of the primary phase may cause shrinkage cavities and surface or internal cracks. Although control of solidified structure is important for the quality of cast products, this problem has not been elucidated. Taking these results into account, this study has been carried out in order to comprehend a phenomenon of larger volume fraction of primary phase. Sn-Pballoy has been used as a test alloy and to examine the relation between supercooling for nucleation and the volume fraction of primary phase has been mainly characterized. Actually, volume fraction of primary phase in Sn-Pballoy is larger than that of lever rule. It was also observed that the volume fraction of β-Sn decreases with decreasing the supercooling in early stage of solidification. In the final stage of solidification, however, the effect of supercooling on volume fraction of primary phase is small. Furthermore, when the supercooling was low, volume fraction of primary phase was slowly increased.

  20. 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

  1. 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

  2. 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.

  3. 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

  4. 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.

  5. Wind a potential mechanism of Mars gully formation

    NASA Astrophysics Data System (ADS)

    Yue, Z.; Xie, H.

    2007-12-01

    Since Mars gullies were first revealed with the Mars Global Surveyor (MGS) Mars Orbiter Camera (MOC) in 2000, they rapidly became a hotspot in Mars studying in that some of them are very young features on Mars surface. The previous studies focused on their formation and erosion mechanisms. As a result, several mechanisms have been proposed. But none of them can interpret the formation of all gullies perfectly. High resolution HiRISE images give us a good opportunity to examine it. In this study, we propose that wind could play an important role in some of the gullies formation. Wind is the most important agent acting on Mars surface (Fenton, 2003) and produced many features on Mars surface, including ubiquitous dunes, yardangs, deflation pits, dust storms, and dust deposits. Similarly, wind can also affect the inner edge of craters and valleys, where the gullies have been found mostly. Under the erosion of wind, the small channel will turn to a big gully. Wind could be a major reason to explain (1) why gullies formed in one side of a crater wall, while small wind-blown sand deposits in the opposite side of the same crater, as found in the crater of this HiRISE image (PSP_001697_1390_RED.JP2) and (2) why two craters next to each other, but only the big one has gullies developed. The reason for this is that big crater can form a strong wind circulation. In another HiRISE image (PSP_001330_1395_RED.JP2), we found a rock in the lower end of a gully course in a crater wall, for which we explain this gully is in the process of formation. This rock could be moving down and carving in to form the course due to the wind force. Based on the common characteristics of wind abrasion mechanics (Greeley and Iversen, 1985), we propose the following processes of gully formation by wind: (1) Embryonic stage: one side of a crater wall or valley wall was "softened" by the wind storm and formed some irregular and V-shaped fractured channels. (2) Youthful stage: small impact pits formed

  6. 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

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. Biosynthesis of riboflavin: mechanism of formation of the ribitylamino linkage

    SciTech Connect

    Keller, P.J.; Van, Q.L.; Kim, S.U.; Bown, D.H.; Chen, H.C.; Kohnle, A.; Bacher, A.; Floss, H.G.

    1988-02-23

    Feeding experiments with Ashbya gossypii followed by NMR analysis of the resulting riboflavin showed incorporation of deuterium from D-(2-/sup 2/H)ribose at C-2' and from D-(1-/sup 2/H) ribose in the pro-R position at C-1' of the ribityl side chain. The results rule out an Amadori rearrangement mechanism for the reduction of the ribosylamino to the ribitylamino linkage and point to formation of a Schiff base that is reduced stereospecifically opposite to the face from which the oxygen has departed. As prerequisite for the analysis, the /sup 1/H NMR signals for the pro-R and pro-S hydrogens at C-1' of 6,7-dimethyl-8-ribityllumazine and riboflavin and its tetraacetate were assigned with the aid of synthetic stereospecifically deuteriated samples.

  12. A Mechanism for E xB0 Structure Formation

    NASA Astrophysics Data System (ADS)

    Diamond, Patrick; Gurcan, Ozgur; Hahm, T. S.; Dif-Pradalier, Guilhem

    2012-10-01

    A novel mechanism for E xB0 staircase formation is proposed. Staircases are quasi-regular patterns of strong, localized shear layers and profile corrugations interspersed with regions of avalanching. The critical question is how do such quasi-regular patterns self-consistently form. We propose a simple model based on a.) symmetry constraints on the form of the flux, b.) the existence of a fluctuation amplitude dependent time delay between the profile perturbation and the flux. The time delay leads to the development of quasi-periodic jams or clusters in the transport flux. These in turn nucleate profile corrugations and a shear layer staircase. The implication for avalanche structure will be discussed. The aim of this work is a self-consistent treatment of the spatio-temporal structure of transport and flows.

  13. Formation Mechanisms for Spur and Groove Features on Fringing Reefs

    NASA Astrophysics Data System (ADS)

    Bramante, J. F.; Ashton, A. D.; Perron, J. T.

    2016-12-01

    Spur and groove systems (SAGs) are ubiquitous morphological features found on fore-reef slopes globally. SAGs consist of parallel, roughly shore-normal ridges of actively growing coral and coralline algae (spurs) separated by offshore-sloping depressions typically carpeted by a veneer of sediment (grooves). Although anecdotal observations and recent statistical analyses have reported correlations between wave exposure and the distribution of SAGs on fore-reef slopes, the physical mechanisms driving SAG formation remain poorly understood. For example, there remains significant debate regarding the importance of coral growth versus bed erosion for SAG formation. Here we investigate a hypothesis that SAG formation is controlled by feedbacks between sediment production and diffusion and coral growth. Using linear stability analysis, we find that sediment production, coral growth, and the feedbacks between them are unable to produce stable periodic structures without a sediment sink. However, if incipient grooves act as conduits for sediment transport offshore, a positive feedback can develop as the groove bed erodes through wave-driven abrasion during offshore transport. Eventually a negative feedback slows groove deepening when the groove bed is armored by sediment, and the groove bed relaxes to a sediment-veneered equilibrium profile analogous to sediment-rich shorefaces. To test this hypothesis, we apply a numerical model that incorporates coral growth and sediment production, sediment diffusion, non-linear wave-driven abrasion, and sediment advection offshore. This model produces the periodic, linear features characteristic of SAG morphology. The relative magnitude of growth, production, diffusion, abrasion, and advection rates affect periodic spacing or wavelength of the modeled SAGs. Finally, we evaluate the ability of the model to replicate geographical variability in SAG characteristics using previously published datasets and reanalysis wave data.

  14. 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

  15. 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

  16. Mechanisms of kinetic trapping in self-assembly and phase transformation

    PubMed Central

    Hagan, Michael F.; Elrad, Oren M.; Jack, Robert L.

    2011-01-01

    In self-assembly processes, kinetic trapping effects often hinder the formation of thermodynamically stable ordered states. In a model of viral capsid assembly and in the phase transformation of a lattice gas, we show how simulations in a self-assembling steady state can be used to identify two distinct mechanisms of kinetic trapping. We argue that one of these mechanisms can be adequately captured by kinetic rate equations, while the other involves a breakdown of theories that rely on cluster size as a reaction coordinate. We discuss how these observations might be useful in designing and optimising self-assembly reactions. PMID:21932884

  17. Feasibility of formation of nanocrystalline Fe-Cr-Y alloys: Mechanical properties and thermal stability

    SciTech Connect

    Muthaiah, V.M. Suntharavel; Babu, L. Hari; Koch, Carl C.; Mula, Suhrit

    2016-04-15

    Aim of the present study is to investigate the feasibility of formation of Fe-Cr-Y disordered solid solutions by mechanical alloying and effect of Y on the thermal stability and mechanical properties of such nanocrystalline alloys. Thermodynamic analysis by Miedema's and Toop's models confirms that the energy barrier required to form the disordered solid solutions has been overcome by the stored energy due to strain dislocations and grain boundary defects. Although limited grain growth was observed during annealing of metastable Fe-15Cr-1Y alloy, the grains size found to stabilize at ~ 53 nm after annealing at 1000 °C; and the corresponding hardness value measured to be also quite high (8 GPa). The grain size analysis by TEM and AFM is well-corroborated with the XRD crystallite size. The high thermal stability and large strengthening effect have been discussed in the light of grain boundary pinning by solute segregation, solute drag effect and Zener pinning due to intermetallic phase(s). - Highlights: • Metastable Fe-Cr-Y alloys were developed by mechanical alloying for nuclear applications. • Formation of Fe-Cr-Y solid solutions was explained from the Gibbs free energy change using Toop's model. • 1 at.% Y found to be very effective in the stabilization of Fe-Cr alloys at high temperatures. • Solute drag effect and/or segregation of Y atoms played a pivotal role in the stabilization.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Mechanism of chimera formation during the Multiple Displacement Amplification reaction

    PubMed Central

    Lasken, Roger S; Stockwell, Timothy B

    2007-01-01

    Background Multiple Displacement Amplification (MDA) is a method used for amplifying limiting DNA sources. The high molecular weight amplified DNA is ideal for DNA library construction. While this has enabled genomic sequencing from one or a few cells of unculturable microorganisms, the process is complicated by the tendency of MDA to generate chimeric DNA rearrangements in the amplified DNA. Determining the source of the DNA rearrangements would be an important step towards reducing or eliminating them. Results Here, we characterize the major types of chimeras formed by carrying out an MDA whole genome amplification from a single E. coli cell and sequencing by the 454 Life Sciences method. Analysis of 475 chimeras revealed the predominant reaction mechanisms that create the DNA rearrangements. The highly branched DNA synthesized in MDA can assume many alternative secondary structures. DNA strands extended on an initial template can be displaced becoming available to prime on a second template creating the chimeras. Evidence supports a model in which branch migration can displace 3'-ends freeing them to prime on the new templates. More than 85% of the resulting DNA rearrangements were inverted sequences with intervening deletions that the model predicts. Intramolecular rearrangements were favored, with displaced 3'-ends reannealing to single stranded 5'-strands contained within the same branched DNA molecule. In over 70% of the chimeric junctions, the 3' termini had initiated priming at complimentary sequences of 2–21 nucleotides (nts) in the new templates. Conclusion Formation of chimeras is an important limitation to the MDA method, particularly for whole genome sequencing. Identification of the mechanism for chimera formation provides new insight into the MDA reaction and suggests methods to reduce chimeras. The 454 sequencing approach used here will provide a rapid method to assess the utility of reaction modifications. PMID:17430586

  5. 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.

  6. Phase space view of quantum mechanical systems and Fisher information

    NASA Astrophysics Data System (ADS)

    Nagy, Á.

    2016-06-01

    Pennini and Plastino showed that the form of the Fisher information generated by the canonical distribution function reflects the intrinsic structure of classical mechanics. Now, a quantum mechanical generalization of the Pennini-Plastino theory is presented based on the thermodynamical transcription of the density functional theory. Comparing to the classical case, the phase-space Fisher information contains an extra term due to the position dependence of the temperature. However, for the special case of constant temperature, the expression derived bears resemblance to the classical one. A complete analogy to the classical case is demonstrated for the linear harmonic oscillator.

  7. 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.

  8. Self-Gravitating Relativistic Fluids: The Formation of a Free Phase Boundary in the Phase Transition from Hard to Soft

    NASA Astrophysics Data System (ADS)

    Christodoulou, Demetrios; Lisibach, André

    2016-11-01

    In the 1990s Christodoulou introduced an idealized fluid model intended to capture some of the features of the gravitational collapse of a massive star to form a neutron star or a black hole. This was the two-phase model introduced in `Self-gravitating relativistic fluids: a two phase model' (Demeterios, Arch Ration Mech Anal 130:343-400, 1995). The present work deals with the formation of a free phase boundary in the phase transition from hard to soft in this model. In this case the phase boundary has corners at the null points; the points which separate the timelike and spacelike components of the interface between the two phases. We prove the existence and uniqueness of a free phase boundary. Also the local form of the shock near the null point is established.

  9. 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.

  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. 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.

  12. 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

  13. A fracture mechanics study of the phase separating planar electrodes: Phase field modeling and analytical results

    NASA Astrophysics Data System (ADS)

    Haftbaradaran, H.; Maddahian, A.; Mossaiby, F.

    2017-05-01

    It is well known that phase separation could severely intensify mechanical degradation and expedite capacity fading in lithium-ion battery electrodes during electrochemical cycling. Experiments have frequently revealed that such degradation effects could be substantially mitigated via reducing the electrode feature size to the nanoscale. The purpose of this work is to present a fracture mechanics study of the phase separating planar electrodes. To this end, a phase field model is utilized to predict how phase separation affects evolution of the solute distribution and stress profile in a planar electrode. Behavior of the preexisting flaws in the electrode in response to the diffusion induced stresses is then examined via computing the time dependent stress intensity factor arising at the tip of flaws during both the insertion and extraction half-cycles. Further, adopting a sharp-interphase approximation of the system, a critical electrode thickness is derived below which the phase separating electrode becomes flaw tolerant. Numerical results of the phase field model are also compared against analytical predictions of the sharp-interphase model. The results are further discussed with reference to the available experiments in the literature. Finally, some of the limitations of the model are cautioned.

  14. Molecular mechanisms in the formation of the medial longitudinal fascicle

    PubMed Central

    Ahsan, Mansoor; Riley, Kerry-lyn; Schubert, Frank R

    2007-01-01

    The first neurons in the vertebrate brain form a stereotypical array of longitudinal and transversal axon tracts, the early axon scaffold. This scaffold is thought to lay down the basic structure for the later, more complex neuronal pathways in the brain. The ventral longitudinal tract is pioneered by neurons located at the ventral midbrain–forebrain boundary, which form the medial longitudinal fascicle. Recent studies have shed some light on the molecular mechanisms that control the development of the medial longitudinal fascicle. Here, we show that patterning molecules, notably the ventralizing signalling molecule Shh, are involved in the formation of medial longitudinal fascicle neurons and in medial longitudinal fascicle axon guidance. Downstream of Shh, several homeobox genes are expressed in the tegmentum. We describe the expression patterns of Sax1, Emx2, Six3, Nkx2.2 and Pax6 in the mesencephalon and pretectum in detail. Furthermore, we review the evidence of their molecular interactions, and their involvement in neuronal fate specification. In particular, Sax1 plays a major role in fate determination of medial longitudinal fascicle neurons. Finally, we discuss the available data on axon guidance mechanisms for the medial longitudinal fascicle, which suggest that different guidance molecules such as class 3 Semaphorins, Slits and Netrins act to determine the caudal and ventral course of the medial longitudinal fascicle axons. PMID:17623036

  15. 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.

  16. Formation of pyrimidine dimer radical anions in the gas phase.

    PubMed

    Edtbauer, Achim; Russell, Katherine; Feketeová, Linda; Taubitz, Jörg; Mitterdorfer, Christian; Denifl, Stephan; O'Hair, Richard A J; Märk, Tilmann D; Scheier, Paul; Wille, Uta

    2009-12-21

    Crossed-beam experiments revealed that attachment of a free electron to the cyclobutane pyrimidine dimers c,s-DMT<>DMT and c,a-DMT<>DMT leads to the formation of dimer radical anions with the lifetime of at least 80 micros, thus showing that the latter are much more stable than previously believed.

  17. 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

  18. 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

  19. 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

  20. Crystallization of transmembrane proteins in cubo: mechanisms of crystal growth and defect formation.

    PubMed

    Qutub, Yasser; Reviakine, Ilya; Maxwell, Carrie; Navarro, Javier; Landau, Ehud M; Vekilov, Peter G

    2004-11-05

    Crystallization of membrane proteins is a major stumbling block en route to elucidating their structure and understanding their function. The novel concept of membrane protein crystallization from lipidic cubic phases, "in cubo", has yielded well-ordered crystals and high-resolution structures of several membrane proteins, yet progress has been slow due to the lack of understanding of the molecular mechanisms of protein transport, crystal nucleation, growth, and defect formation in cubo. Here, we examine at molecular and mesoscopic resolution with atomic force microscopy the morphology of in cubo grown bacteriorhodopsin crystals in inert buffers and during etching by detergent. The results reveal that crystal nucleation occurs following local rearrangement of the highly curved lipidic cubic phase into a lamellar structure, which is akin to that of the native membrane. Crystals grow within the bulk cubic phase surrounded by such lamellar structures, whereby transport towards a growing crystalline layer is constrained to within an individual lamella. This mechanism leads to lack of dislocations, generation of new crystalline layers at numerous locations, and to voids and block boundaries. The characteristic macroscopic lengthscale of these defects suggests that the crystals grow by attachment of single molecules to the nuclei. These insights into the mechanisms of nucleation, growth and transport in cubo provide guidance en route to a rational design of membrane protein crystallization, and promise to further advance the field.

  1. 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.

  2. 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.

  3. 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.

  4. Laser-driven formation of a high-pressure phase in amorphous silica

    SciTech Connect

    Salleo, Alberto; Taylor, Seth T.; Martin, Michael C.; Panero, Wendy R.; Jeanloz, Raymond; Genin, Francois Y.; Sands, Timothy

    2002-05-31

    A combination of electron diffraction and infrared reflectance measurements shows that synthetic silica transforms partially into stishovite under high-intensity (GW/cm2) laser irradiation, probably by the formation of a dense ionized plasma above the silica surface. During the transformation the silicon coordination changes from four-fold to six-fold and the silicon-oxygen bond changes from mostly covalent to mostly ionic, such that optical properties of the transformed material differ significantly from those of the original glass. This phase transformation offers one suitable mechanism by which laser-induced damage grows catastrophically once initiated, thereby dramatically shortening the service lifetime of optics used for high-power photonics applications such as inertial confinement fusion.

  5. 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

  6. 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.

  7. 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.

  8. VO{sub 2} (A): Reinvestigation of crystal structure, phase transition and crystal growth mechanisms

    SciTech Connect

    Rao Popuri, Srinivasa; Artemenko, Alla; Labrugere, Christine; Miclau, Marinela; Villesuzanne, Antoine; Pollet, Michaël

    2014-05-01

    Well crystallized VO{sub 2} (A) microrods were grown via a single step hydrothermal reaction in the presence of V{sub 2}O{sub 5} and oxalic acid. With the advantage of high crystalline samples, we propose P4/ncc as an appropriate space group at room temperature. From morphological studies, we found that the oriented attachment and layer by layer growth mechanisms are responsible for the formation of VO{sub 2} (A) micro rods. The structural and electronic transitions in VO{sub 2} (A) are strongly first order in nature, and a marked difference between the structural transition temperatures and electronic transitions temperature was evidenced. The reversible intra- (LTP-A to HTP-A) and irreversible inter- (HTP-A to VO{sub 2} (M1)) structural phase transformations were studied by in-situ powder X-ray diffraction. Attempts to increase the size of the VO{sub 2} (A) microrods are presented and the possible formation steps for the flower-like morphologies of VO{sub 2} (M1) are described. - Graphical abstract: Using a single step and template free hydrothermal synthesis, well crystallized VO{sub 2} (A) microrods were prepared and the P4/ncc space group was assigned to the room temperature crystal structure. Reversible and irreversible phase transitions among different VO{sub 2} polymorphs were identified and their progressive nature was highlighted. Attempts to increase the microrods size, involving layer by layer formation mechanisms, are presented. - Highlights: • Highly crystallized VO{sub 2} (A) microrods were grown via a single step hydrothermal process. • The P4/ncc space group was determined for VO{sub 2} (A) at room temperature. • The electronic structure and progressive nature of the structural phase transition were investigated. • A weak coupling between structural and electronic phase transitions was identified. • Different crystallite morphologies were discussed in relation with growth mechanisms.

  9. 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.

  10. 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

  11. 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

  12. 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.

  13. 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

  14. Kinetics for the subgel phase formation in DPPC/DOPC mixed bilayers.

    PubMed

    Kinoshita, Masanao; Ito, Keisuke; Kato, Satoru

    2010-09-01

    We analyzed the kinetics for the subgel (SGI) phase formation in DPPC/DOPC binary bilayers paying attention to DOPC-induced modification of the bilayer physical properties. Differential scanning calorimetry and X-ray diffraction revealed that addition of DOPC reduced the apparent initial lag time to start the SGI phase formation, and that the SGI phase in the binary bilayers had basically the same structure as that in pure DPPC bilayers though addition of DOPC markedly increased the peak temperature and enthalpy of the subtransition in heating. Moreover, addition of DOPC abolished the prolongation of the initial lag time in pure DPPC bilayers induced by lowering the incubation temperature from 0 to -5 degrees C. Our results suggested that DOPC molecules work as a diffusion enhancer to promote the nucleation of the SGI phase, and relatively destabilize the gel phase so that the formed SGI phase transforms into the ripple phase in heating. Copyright 2010 Elsevier Ireland Ltd. All rights reserved.

  15. 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.

  16. Mechanism of IAPP amyloid fibril formation involves an intermediate with a transient {beta}-sheet.

    SciTech Connect

    Buchanan, Lauren E.; Dunkelberger, Emily B.; Tran, Huong Q.; Cheng, Pin-Nan; Chiu, Chi-cheng; Cao, Ping; Raleigh, Daniel P.; De Pablo, Juan J.; Nowick, James; Zanni, Martin T.

    2013-11-26

    Amyloid formation is implicated in more than 20 human diseases, yet the mechanism by which fibrils form is not well understood. We use 2D infrared spectroscopy and isotope labeling to monitor the kinetics of fibril formation by human islet amyloid polypeptide (hIAPP or amylin) that is associated with type 2 diabetes. We find that an oligomeric intermediate forms during the lag phase with parallel β-sheet structure in a region that is ultimately a partially disordered loop in the fibril. We confirm the presence of this intermediate, using a set of homologous macrocyclic peptides designed to recognize β-sheets. Mutations and molecular dynamics simulations indicate that the intermediate is on pathway. Disrupting the oligomeric β-sheet to form the partially disordered loop of the fibrils creates a free energy barrier that is the origin of the lag phase during aggregation. These results help rationalize a wide range of previous fragment and mutation studies including mutations in other species that prevent the formation of amyloid plaques.

  17. 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).

  18. Statistics of errors in fibre communication lines with a phase-modulation format and optical phase conjugation

    SciTech Connect

    Shapiro, Elena G; Fedoruk, Mikhail P

    2011-06-30

    Analytical formulas are derived to approximate the probability density functions of 'zero' and 'one' bits in a linear communication channel with a binary format of optical signal phase modulation. Direct numerical simulation of the propagation of optical pulses in a communication line with optical phase conjugation is performed. The results of the numerical simulation are in good agreement with the analytical approximation. (fibreoptic communication lines)

  19. 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.

  20. 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.

  1. Phase Transformation Volume Change Control of Strain and Instability Mechanisms

    NASA Astrophysics Data System (ADS)

    Green, H. W.

    2011-12-01

    Phase transformations that are accompanied by significant change in volume self-organize the transformation process under stress to enhance strain and/or decrease stress. When the kinetics of the reaction are reasonably rapid, this occurs by nucleation and growth of phase(s) on grain boundaries of appropriate orientation to facilitate strain. When the kinetics of reaction are sluggish (ratio of nucleation rate to growth rate >> 1) and the reaction is polymorphic and exothermic, under specific conditions this process can lead to shearing instability in which the volume change of reaction drives runaway nucleation at stress concentrations leading to macroscopic faulting. Under these conditions, the detailed processes and microstructures produced depend on the sign of volume change but the failure is very similar whether volume change is positive or negative. The microstructures confirm that the mesoscale physics of this process (self-organization of primary features and nucleation/propagation of a fault) is the same as for brittle shear fracture, despite the large difference in the fundamental microscopic physics (formation of nanocrystalline microlenses instead of tensile cracks, and fault propagation by grain-boundary sliding rather than frictional sliding). When volume change is negative and the kinetics of reaction are less sluggish (ratio of nucleation rate to growth rate of order 1), nucleation of the new (denser) phase occurs preferentially on grain boundaries normal to maximum compression and new crystals nucleated on any orientation of grain boundary grow parallel to maximum compression. The result is stylolite-like volume loss normal to maximum compression. Observations of polyphase metamorphic rocks suggest that similar creep can occur during prograde metamorphism by nucleation of more-dense phases and less-dense phases on different populations of phase-boundary orientations such that the overall pattern achieves a macroscopic strain by volume transfer

  2. 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.

  3. Unified Mechanism for the Formation of Moving Magnetic Features

    NASA Astrophysics Data System (ADS)

    Ryutova, M. P.; Hagenaar, H. J.

    2005-05-01

    In the highly dynamic environment around sunspots there are small scale magnetic features, MMF's, that show clear regularities and may be thus categorized according their observed properties. For now there are at least 4 types of "MMF's" (Moving Magnetic Features). Type I MMF's are compact pairs of opposite polarity elements that may emerge anywhere in penumbra or moat region and move radially outward gradually separating; their velocities exceed the velocities of ambient flows, and their inner " foot" shares the sunspot's polarity. Type II MMF's are seen as unipolar features of the same polarity as the sunspot, moving outward from the sunspot with higher velocities than type I. Type III MMF's are also seen as unipolar features but have the polarity opposite to the sunspot's and travel with higher velocities than the other two types of MMF's. Recently the "type IV" features were observed in a sunspot formation region, that appear as compact bipoles flowing into sunspots and with an inner foot of a polarity opposite to the sunspot's. These were dubbed the MDF's (Moving Dipolar Features). The observed properties of all types of MMF's clearly violate the energy and momentum conservation laws, and thus require the application of physical mechanisms adequate for energetically open systems. Such mechanisms have been applied to type I and type II MMF's (Ryutova, Shine, Title, and Sakai, 1998, ApJ, 492, 402) with a good agreement between the theory and observations. Here we show that the same approach not only explains the origin, structure and dynamics of MDF's and type III MMF's, but consolidates all types of MMF's into one scheme. Theoretical results are compared with the observed properties of MMF's using time series of several data sets.

  4. Study of mechanism which causes film formation on mercury surfaces

    NASA Technical Reports Server (NTRS)

    Frohnsdorff, G.; Dunn, D.

    1972-01-01

    The mechanism by which small quantities of dissolved tin, sodium, and lithium lower the rate of evaporation of mercury in vacuum is determined. An apparatus was built in which dilute amalgams could be prepared and studied in an oxygen-free environment before being exposed to oxygen under controlled conditions. The apparatus was able to maintain a pressure of less than 1.3 x 0.000001 N/sqm (10 to the minus 8th power torr) of gases and vapors other than mercury and less than 1.3 x 10 to the minus 8th N/sq m (10 to the minus 10th power torr) partial pressure of oxygen; also, it provided for mechanical sweeping of the liquid metal surfaces in the vacuum environment. The rates of evaporation of pure mercury and of dilute amalgams of tin (52 ppm), sodium (229 ppm), and lithium (165 ppm) were determined at temperature between 25 and 55 C both before and after 70 minute exposures to an approximately 270 N/sq m (2 torr) pressure of oxygen. The rates of evaporation of the pure mercury and the amalgams as first prepared were similar but the rates for the amalgams were reduced by at least 80% at 25 C as a result of the exposure to oxygen. The effect of the oxygen treatment could be completely removed by sweeping the amalgam surfaces. It was concluded that the reduced rates of evaporation resulted from the formation of transparent, insoluble, oxide films on the amalgam surfaces.

  5. 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.

  6. Superconducting phase diagrams of cuprates and pnictides as a key to understanding the HTSC mechanism

    NASA Astrophysics Data System (ADS)

    Mitsen, K. V.; Ivanenko, O. M.

    2017-04-01

    This paper reviews experimental phase diagrams of cuprates and pnictides to demonstrate that specific features of the superconducting phase diagrams in both HTSC families can be understood within the framework of the proposed approach, which assumes the formation, under heterovalent doping, of localized trion complexes consisting of a doped carrier and charge transfer (CT) excitons. The geometry of such cells containing CT excitons (CT plaquettes) in the basal plane of the crystal is determined by its crystal structure and the type of dopant, so that the dopant concentration range corresponding to the existence of a percolation cluster of CT plaquettes can be readily determined for each particular compound. These dopant concentration ranges coincide with good accuracy with the experimental ranges of superconducting domes in the phase diagrams of the HTSC compounds considered. The generation of free carriers and the mechanism of superconducting pairing in this pattern is related to biexciton complexes (Heitler-London centers) emerging in neighboring CT plaquettes.

  7. Phase Formation in PZT Phosphorus-Doped Ceramics

    SciTech Connect

    Celi, L. A.; Caballero, A. C.; Villegas, M.; Moure, C.; Fernandez, J. F.; Eiras, J. A.

    2009-04-19

    The surface modification of lead zirconate titanate (PZT) ceramics with phosphate ester leaves a phosphorus residue absorbed onto the particle surface. During the sintering processes, this surface layer reacts with the PZT to form lead-rich compounds, such as Pb{sub 3}(PO{sub 4}){sub 2} and Pb{sub 4}(P{sub 2}O{sub 9}). The formation of such a compounds may be the responsible for the grain growth inhibition observed in PZT-modified ceramics, as well as the lead loss reduction.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. From Phase Locking to Phase Slips: A Mechanism for a Quiescent H mode

    NASA Astrophysics Data System (ADS)

    Guo, Z. B.; Diamond, P. H.

    2015-04-01

    We demonstrate that E ×B shear, VE×B ' , governs the dynamics of the cross phase of the peeling-ballooning-(PB-)mode-driven heat flux, and so determines the evolution from the edge-localized (ELMy) H mode to the quiescent (Q ) H mode. A physics-based scaling of the critical E ×B shearing rate (VE×B ,c r ' ) for accessing the Q H mode is predicted. The ELMy H mode to the Q H -mode evolution is shown to follow from the conversion from a phase locked state to a phase slip state. In the phase locked state, PB modes are pumped continuously, so bursts occur. In the slip state, the PB activity is a coherent oscillation. Stronger E ×B shearing implies a higher phase slip frequency. This finding predicts a new state of cross phase dynamics and shows a new way to understand the physics mechanism for ELMy to the Q H -mode evolution.

  13. Mechanism and microstructures in Ga2O3 pseudomartensitic solid phase transition.

    PubMed

    Zhu, Sheng-Cai; Guan, Shu-Hui; Liu, Zhi-Pan

    2016-07-21

    Solid-to-solid phase transition, although widely exploited in making new materials, challenges persistently our current theory for predicting its complex kinetics and rich microstructures in transition. The Ga2O3α-β phase transformation represents such a common but complex reaction with marked change in cation coordination and crystal density, which was known to yield either amorphous or crystalline products under different synthetic conditions. Here we, via recently developed stochastic surface walking (SSW) method, resolve for the first time the atomistic mechanism of Ga2O3α-β phase transformation, the pathway of which turns out to be the first reaction pathway ever determined for a new type of diffusionless solid phase transition, namely, pseudomartensitic phase transition. We demonstrate that the sensitivity of product crystallinity is caused by its multi-step, multi-type reaction pathway, which bypasses seven intermediate phases and involves all types of elementary solid phase transition steps, i.e. the shearing of O layers (martensitic type), the local diffusion of Ga atoms (reconstructive type) and the significant lattice dilation (dilation type). While the migration of Ga atoms across the close-packed O layers is the rate-determining step and yields "amorphous-like" high energy intermediates, the shearing of O layers contributes to the formation of coherent biphase junctions and the presence of a crystallographic orientation relation, (001)α//(201[combining macron])β + [120]α//[13[combining macron]2]β. Our experiment using high-resolution transmission electron microscopy further confirms the theoretical predictions on the atomic structure of biphase junction and the formation of (201[combining macron])β twin, and also discovers the late occurrence of lattice expansion in the nascent β phase that grows out from the parent α phase. By distinguishing pseudomartensitic transition from other types of mechanisms, we propose general rules to predict the

  14. Luster decoration of ceramics: mechanisms of metallic luster formation

    NASA Astrophysics Data System (ADS)

    Pradell, T.; Molera, J.; Bayés, C.; Roura, P.

    2006-05-01

    Luster is a metallic decoration produced since early Islamic times (9th century AD in Iraq). Different studies have shown that medieval lusters are a metal-glass nanocomposite (metal nanoparticles embodied in a silica glassy matrix) obtained from the reaction of a copper and/or silver containing paint with a glaze. The mechanisms of formation of these metallic-like layers are investigated by laboratory reproductions of Medieval luster. Copper and silver lusters are obtained based on different thermal paths and atmospheres, and by using different glaze compositions. The ionic exchange between Cu+ and Ag+ ions from the luster paint with Na+ and K+ of the glaze, is demonstrated in either oxidizing or inert atmospheres and at firing temperatures between 500 °C and 600 °C. The reduction of copper and silver to their metallic state is obtained by introducing a reducing gas afterwards. The lusters are non-metallic red ruby copper or green with brown spots silver when developed over alkaline glazes, while they appear coppery and golden metallic when developed over mixed alkaline-lead glazes. SR-XRD, optical absorption and microprobe chemical analysis of the lusters indicate that the total amount of copper and silver, and the nature and size of the nanoparticles, are similar in both cases. Further work is needed to clarify the origin of these differences.

  15. 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).

  16. Modeling the mechanism of CLN025 beta-hairpin formation.

    PubMed

    McKiernan, Keri A; Husic, Brooke E; Pande, Vijay S

    2017-09-14

    Beta-hairpins are substructures found in proteins that can lend insight into more complex systems. Furthermore, the folding of beta-hairpins is a valuable test case for benchmarking experimental and theoretical methods. Here, we simulate the folding of CLN025, a miniprotein with a beta-hairpin structure, at its experimental melting temperature using a range of state-of-the-art protein force fields. We construct Markov state models in order to examine the thermodynamics, kinetics, mechanism, and rate-determining step of folding. Mechanistically, we find the folding process is rate-limited by the formation of the turn region hydrogen bonds, which occurs following the downhill hydrophobic collapse of the extended denatured protein. These results are presented in the context of established and contradictory theories of the beta-hairpin folding process. Furthermore, our analysis suggests that the AMBER-FB15 force field, at this temperature, best describes the characteristics of the full experimental CLN025 conformational ensemble, while the AMBER ff99SB-ILDN and CHARMM22* force fields display a tendency to overstabilize the native state.

  17. 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

  18. 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.

  19. 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.

  20. Hydrodynamic mechanism of temperature gradient formation in thin nematic films

    NASA Astrophysics Data System (ADS)

    Zakharov, A. V.

    2017-07-01

    The temperature gradient formation mechanism in an initially uniformly heated hybrid-oriented liquid-crystal (HOLC) channel of microscopic sizes upon exposure to a steady hydrodynamic flow is theoretically studied within the nonlinear generalization of the Ericksen-Leslie theory, taking into account the heat conduction equation. The case of total thermal insulation of one of the HOLC channel is considered provided that a constant temperature is maintained on the other surface. It is shown that the temperature difference χmax(ζ) in the HOLC channel section, caused by the horizontal steady flow with the "triangular" velocity profile u( z, ζ) is significantly affected by the position ζ of the maximum velocity. It is shown that, in the case of the LC system formed by 4- n-pentyl- n'-cyanobiphenyl molecules, the hydrodynamic flow characterized by the peak position ζ = 0.98 of the velocity u( z, ζ = 0.98) 0.9 μm/s forms a maximum temperature difference χmax(ζ) = 0.03 ( 9 K) over the HOLC channel section.

  1. Modeling the mechanism of CLN025 beta-hairpin formation

    NASA Astrophysics Data System (ADS)

    McKiernan, Keri A.; Husic, Brooke E.; Pande, Vijay S.

    2017-09-01

    Beta-hairpins are substructures found in proteins that can lend insight into more complex systems. Furthermore, the folding of beta-hairpins is a valuable test case for benchmarking experimental and theoretical methods. Here, we simulate the folding of CLN025, a miniprotein with a beta-hairpin structure, at its experimental melting temperature using a range of state-of-the-art protein force fields. We construct Markov state models in order to examine the thermodynamics, kinetics, mechanism, and rate-determining step of folding. Mechanistically, we find the folding process is rate-limited by the formation of the turn region hydrogen bonds, which occurs following the downhill hydrophobic collapse of the extended denatured protein. These results are presented in the context of established and contradictory theories of the beta-hairpin folding process. Furthermore, our analysis suggests that the AMBER-FB15 force field, at this temperature, best describes the characteristics of the full experimental CLN025 conformational ensemble, while the AMBER ff99SB-ILDN and CHARMM22* force fields display a tendency to overstabilize the native state.

  2. 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.

  3. A phase field study of stress effects on microstructure formation during laser-aided direct metal deposition process

    NASA Astrophysics Data System (ADS)

    Mirzade, Fikret K.

    2017-06-01

    We present a phase-field model for predicting elastic effects on microstructure evolution at the process of laser sintering with powder injection. We derive a system of governing equations describing coupling effects among phase variable, concentration, thermal and elastic displacement fields based on the principle of entropy production positiveness, in which thermal and concentration expansions, mechanical anisotropy effects, transformation dilatation, and strain dependency on phase transformation are considered. The microstructure model is coupled with a macroscopic thermodynamic model. Effects of thermo-capillary and thermo-gravitation convections are included. The possibility to describe the process of structure formation at the phase interface during the melt crystallization is discussed. This model enables prediction and visualization of grain structures during and after the laser sintering process.

  4. 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.

  5. Polarization Mechanisms in Phase II Poly(Vinylidene Fluoride) Films.

    DTIC Science & Technology

    1981-11-12

    34 OdRO a mnk W) Poly(Vinylidene Fluoride), x-rays, piezelectricity, polarization, poling FAWWRmCT ffls~ -ew nam 9 Uf"Oo me..Mv £*mM NOWsA Unoriented...phase II films were poled with fields up to 3.2 MV/cm at room o) temperature. A determination of the piezoelectric strain coefficient provided a measure...sT. VW OtU.4LF-41U.4" ". . -. I u CIImVP CLAI IaICATIOM OV- VPI PU.I (Ul... O111 111..41 the poling field and different polarization mechanisms appear

  6. The normal-auxeticity mechanical phase transition in graphene

    NASA Astrophysics Data System (ADS)

    Deng, Binghui; Hou, Jie; Zhu, Hanxing; Liu, Sheng; Liu, Emily; Shi, Yunfeng; Peng, Qing

    2017-06-01

    When a solid object is stretched, in general, it shrinks transversely. However, the abnormal ones are auxetic, which exhibit lateral expansion, or negative Poisson ratio. While graphene is a paradigm 2D material, surprisingly, graphene converts from normal to auxetic at certain strains. Here, we show via molecular dynamics simulations that the normal-auxeticity mechanical phase transition only occurs in uniaxial tension along the armchair direction or the nearest neighbor direction. Such a characteristic persists at temperatures up to 2400 K. Besides monolayer, bilayer and multi-layer graphene also possess such a normal-auxeticity transition. This unique property could extend the applications of graphene to new horizons.

  7. Three Distinct Phases of Isoprene Formation during Growth and Sporulation of Bacillus subtilis

    PubMed Central

    Wagner, William P.; Nemecek-Marshall, Michele; Fall, Ray

    1999-01-01

    During growth on a glucose-tryptone medium, Bacillus subtilis 6051 (Marburg strain) exhibited three phases of isoprene (2-methyl-1,3-butadiene) formation, corresponding to (i) glucose catabolism and secretion of acetoin, (ii) catabolism of acetoin, and (iii) the early stages of sporulation. These results establish an experimental system for studying the biological role of isoprene formation. PMID:10419976

  8. 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.

  9. 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

  10. 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

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Asymptotic formation and orbital stability of phase-locked states for the Kuramoto model

    NASA Astrophysics Data System (ADS)

    Choi, Young-Pil; Ha, Seung-Yeal; Jung, Sungeun; Kim, Yongduck

    2012-04-01

    We discuss the asymptotic formation and nonlinear orbital stability of phase-locked states arising from the ensemble of non-identical Kuramoto oscillators. We provide an explicit lower bound for a coupling strength on the formation of phase-locked states, which only depends on the diameters of natural frequencies and initial phase configurations. We show that, when the phases of non-identical oscillators are distributed over the half circle and the coupling strength is sufficiently large, the dynamics of Kuramoto oscillators exhibits two stages (transition and relaxation stages). In a transition stage, initial configurations shrink to configurations whose diameters are strictly less than {π}/{2} in a finite-time, and then the configurations tend to phase-locked states asymptotically. This improves previous results on the formation of phase-locked states by Chopra-Spong (2009) [26] and Ha-Ha-Kim (2010) [27] where their attention were focused only on the latter relaxation stage. We also show that the Kuramoto model is ℓ1-contractive in the sense that the ℓ1-distance along two smooth Kuramoto flows is less than or equal to that of initial configurations. In particular, when two initial configurations have the same averaged phases, the ℓ1-distance between them decays to zero exponentially fast. For the configurations with different phase averages, we use the method of average adjustment and translation-invariant of the Kuramoto model to show that one solution converges to the translation of the other solution exponentially fast. This establishes the orbital stability of the phase-locked states. Our stability analysis does not employ any standard linearization technique around the given phase-locked states, but instead, we use a robust ℓ1-metric functional as a Lyapunov functional. In the formation process of phase-locked states, we estimate the number of collisions between oscillators, and lower-upper bounds of the transversal phase differences.

  20. 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.

  1. Formation of unequilibrated R chondrite chondrules and opaque phases

    NASA Astrophysics Data System (ADS)

    Miller, K. E.; Lauretta, D. S.; Connolly, H. C.; Berger, E. L.; Nagashima, K.; Domanik, K.

    2017-07-01

    Sulfide assemblages are commonly found in chondritic meteorites as small inclusions in the matrix or in association with chondrules. These assemblages are widely hypothesized to form through pre-accretionary corrosion of metal by H2S gas or through parent body processes. We report here on two unequilibrated R chondrite samples that contain large, chondrule-sized sulfide nodules in the matrix. Both samples are from Mount Prestrud (PRE) 95404. Chemical maps and spot and broad-beam electron microprobe analyses (EMPA) were used to assess the distribution, stoichiometry, and bulk composition of sulfide nodules and silicate chondrules in the clasts. Oxygen isotope data were collected via secondary ion mass spectrometry (SIMS) to assess the relationship of chondrules to other chondrite groups. Scanning electron microscopy (SEM), focused ion beam (FIB), and transmission electron microscopy (TEM) analyses were used to assess fine-scale features and identify crystal structures in sulfide assemblages. Thermodynamic models were used to assess the temperature, sulfur fugacity (fS2), total pressure, dust-to-gas ratio, and oxygen fugacity (fO2) conditions during sulfide nodule and chondrule formation. The unequilibrated clasts include a mixture of type I and type II chondrules, as well as non-porphyritic chondrules. Chondrule oxygen isotopes overlap with ordinary-chondrite chondrules. Sulfide nodules average 200 μm in diameter, have rounded shapes, and are primarily composed of pyrrhotite, pentlandite, and magnetite. Some are deformed around chondrules in a petrologic relationship similar in appearance to compound chondrules. Both nodules and sulfides in chondrules include phosphate inclusions and Cu-rich lamellae, which suggests a genetic relationship between sulfides in chondrules and in the matrix. Ni/Co ratios for matrix and chondrule sulfides are solar, while Fe and Ni are non-solar and inversely related. We hypothesize that sulfide nodules formed via pre-accretionary melt

  2. 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.

  3. Laser-driven formation of a high-pressure phase in amorphous silica.

    PubMed

    Salleo, Alberto; Taylor, Seth T; Martin, Michael C; Panero, Wendy R; Jeanloz, Raymond; Sands, Timothy; Génin, François Y

    2003-12-01

    Because of its simple composition, vast availability in pure form and ease of processing, vitreous silica is often used as a model to study the physics of amorphous solids. Research in amorphous silica is also motivated by its ubiquity in modern technology, a prominent example being as bulk material in transmissive and diffractive optics for high-power laser applications such as inertial confinement fusion (ICF). In these applications, stability under high-fluence laser irradiation is a key requirement, with optical breakdown occurring when the fluence of the beam is higher than the laser-induced damage threshold (LIDT) of the material. The optical strength of polished fused silica transmissive optics is limited by their surface LIDT. Surface optical breakdown is accompanied by densification, formation of point defects, cratering, material ejection, melting and cracking. Through a combination of electron diffraction and infrared reflectance measurements we show here that synthetic vitreous silica transforms partially into a defective form of the high-pressure stishovite phase under high-intensity (GW cm(-2)) laser irradiation. This phase transformation offers one suitable mechanism by which laser-induced damage grows catastrophically once initiated, thereby dramatically shortening the service lifetime of optics used for high-power photonics.

  4. Quantum mechanical force fields for condensed phase molecular simulations

    NASA Astrophysics Data System (ADS)

    Giese, Timothy J.; York, Darrin M.

    2017-09-01

    Molecular simulations are powerful tools for providing atomic-level details into complex chemical and physical processes that occur in the condensed phase. For strongly interacting systems where quantum many-body effects are known to play an important role, density-functional methods are often used to provide the model with the potential energy used to drive dynamics. These methods, however, suffer from two major drawbacks. First, they are often too computationally intensive to practically apply to large systems over long time scales, limiting their scope of application. Second, there remain challenges for these models to obtain the necessary level of accuracy for weak non-bonded interactions to obtain quantitative accuracy for a wide range of condensed phase properties. Quantum mechanical force fields (QMFFs) provide a potential solution to both of these limitations. In this review, we address recent advances in the development of QMFFs for condensed phase simulations. In particular, we examine the development of QMFF models using both approximate and ab initio density-functional models, the treatment of short-ranged non-bonded and long-ranged electrostatic interactions, and stability issues in molecular dynamics calculations. Example calculations are provided for crystalline systems, liquid water, and ionic liquids. We conclude with a perspective for emerging challenges and future research directions.

  5. 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.

  6. 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.

  7. Coupled Thermo-Hydro-Mechanical Numerical Framework for Simulating Unconventional Formations

    NASA Astrophysics Data System (ADS)

    Garipov, T. T.; White, J. A.; Lapene, A.; Tchelepi, H.

    2016-12-01

    Unconventional deposits are found in all world oil provinces. Modeling these systems is challenging, however, due to complex thermo-hydro-mechanical processes that govern their behavior. As a motivating example, we consider in situ thermal processing of oil shale deposits. When oil shale is heated to sufficient temperatures, kerogen can be converted to oil and gas products over a relatively short timespan. This phase change dramatically impact both the mechanical and hydrologic properties of the rock, leading to strongly coupled THMC interactions. Here, we present a numerical framework for simulating tightly-coupled chemistry, geomechanics, and multiphase flow within a reservoir simulator (the AD-GPRS General Purpose Research Simulator). We model changes in constitutive behavior of the rock using a thermoplasticity model that accounts for microstructural evolution. The multi-component, multiphase flow and transport processes of both mass and heat are modeled at the macroscopic (e.g., Darcy) scale. The phase compositions and properties are described by a cubic equation of state; Arrhenius-type chemical reactions are used to represent kerogen conversion. The system of partial differential equations is discretized using a combination of finite-volumes and finite-elements, respectively, for the flow and mechanics problems. Fully implicit and sequentially implicit method are used to solve resulting nonlinear problem. The proposed framework is verified against available analytical and numerical benchmark cases. We demonstrate the efficiency, performance, and capabilities of the proposed simulation framework by analyzing near well deformation in an oil shale formation.

  8. 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.

  9. 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.

  10. Multi-scale investigation into the mechanisms of fault mirror formation in seismically active carbonate rocks

    NASA Astrophysics Data System (ADS)

    Ohl, Markus; Chatzaras, Vasileios; Niemeijer, Andre; King, Helen; Drury, Martyn; Plümper, Oliver

    2017-04-01

    Mirror surfaces along principal slip zones in carbonate rocks have recently received considerable attention as they are thought to form during fault slip at seismic velocities and thus may be a marker for paleo-seismicity (Siman-Tov et al., 2013). Therefore, these structures represent an opportunity to improve our understanding of earthquake mechanics in carbonate faults. Recent investigations reported the formation of fault mirrors in natural rocks as well as in laboratory experiments and connected their occurrence to the development of nano-sized granular material (Spagnuolo et al., 2015). However, the underlying formation and deformation mechanisms of these fault mirrors are still poorly constrained and warrant further research. In order to understand the influence and significance of these fault products on the overall fault behavior, we analysed the micro-, and nanostructural inventory of natural fault samples containing mirror slip surfaces. Here we present first results on the possible formation mechanisms of fault mirrors and associated deformation mechanisms operating in the carbonate fault gouge from two seismically active fault zones in central Greece. Our study specifically focuses on mirror slip surfaces obtained from the Arkitsa fault in the Gulf of Evia and the Schinos fault in the Gulf of Corinth. The Schinos fault was reactivated by a magnitude 6.7 earthquake in 1981 while the Arkitsa fault is thought to have been reactivated by a magnitude 6.9 earthquake in 1894. Our investigations encompass a combination of state-of-the-art analytical techniques including X-ray computed tomography, focused ion beam scanning electron microscopy (FIB-SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Using this multiscale analytical approach, we report decarbonation-reaction structures, considerable calcite twinning and grain welding immediately below the mirror slip surface. Grains or areas indicating decarbonation reactions show a foam

  11. 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

  12. 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).

  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. 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

  15. Formation of titanosilicate precursors of an active adsorption phase

    NASA Astrophysics Data System (ADS)

    Kuznetsova, T. F.; Ivanets, A. I.; Katsoshvili, L. L.

    2017-04-01

    Micro-mesoporous titanosilicate precursors of the active absorption phase of a composite ceramic membrane are synthesized, and their textural and adsorption properties are investigated by means of low-temperature nitrogen adsorption/desorption. Low-temperature isotherms of nitrogen adsorption/desorption are analyzed using the BET, Langmuir, comparative t-plot, Barrett-Joyner-Halenda, and density functional theory methods. It is found that at high contents of silicon(IV) oxide, the resulting xerogels have surface areas of 656 and 890 m2/g according to the BET and Langmuir approaches, respectively, while the micropores' inner and outer surfaces are 453 and 466 m2/g, respectively, according to the t-plot. According to the DFT distributions, the mesopore diameters of a sample can be adjusted in the range of 3-9 nm. By analyzing the type of capillary condensation hysteresis in the adsorption/desorption isotherms, it is shown that the pores in the samples are very bottle-like, even though their shape may be different in reality. It is found that in samples with high contents of titanium(IV) oxide, the pore throats are blocked during adsorbate desorption, due to the percolation effect. It is assumed that the stabilization of particles of titanium(IV) oxide by amorphous layers of silica protects the texture of titanosilicate xerogels from full contraction and the coalescence of particles during heat treatment ranging from 393 to 923 K.

  16. 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.

  17. 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 implic