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Sample records for gas phase nucleation

  1. Gas Hydrate Nucleation Processes

    NASA Astrophysics Data System (ADS)

    David, R. E.; Zatsepina, O.; Phelps, T. J.

    2003-12-01

    The onset of gas hydrate nucleation is greatly affected by the thermal history of the water that forms its lattice structure. Hydrate formation experiments were performed in a 72 liter pressure vessel by bubbling carbon dioxide through a 1 liter column at hydrate formation pressures (1.4 to 3.7 MPa) and temperatures (275.0 to 278.0 K) to quantify this effect. They show that when even a fraction ( e. g. 20 %) of the water in which hydrate has formed was recently frozen and thawed, the overpressurization for nucleation was reduced by an average of 50 % versus experiments performed in distilled water. In those experiments where a lower overpressure is present when hydrate nucleated, they tended to form on the surface of bubbles, whereas when a higher amount of overpressure was necessary for hydrate to nucleate, they appeared to form abruptly on bubble surfaces as well as from the bulk liquid phase. In approximation of classical nucleation, hydrate formation could be described as occurring by the spontaneous joining together of arising components of the hydrate lattice. In water that was frozen, and kept at a low temperature (< 275 K), molecular simulation models predict the predominance of water molecules organized as penatmeters, a possible subunit of the hydrate lattice. Our results suggest that in nature, initiation of hydrate formation may be strongly influenced by temperature dependant pre-structuring of water molecules prior to their contact with gas.

  2. Onset conditions for gas phase reaction and nucleation in the CVD of transition metal oxides

    NASA Technical Reports Server (NTRS)

    Collins, J.; Rosner, D. E.; Castillo, J.

    1992-01-01

    A combined experimental/theoretical study is presented of the onset conditions for gas phase reaction and particle nucleation in hot substrate/cold gas CVD of transition metal oxides. Homogeneous reaction onset conditions are predicted using a simple high activation energy reacting gas film theory. Experimental tests of the basic theory are underway using an axisymmetric impinging jet CVD reactor. No vapor phase ignition has yet been observed in the TiCl4/O2 system under accessible operating conditions (below substrate temperature Tw = 1700 K). The goal of this research is to provide CVD reactor design and operation guidelines for achieving acceptable deposit microstructures at the maximum deposition rate while simultaneously avoiding homogeneous reaction/nucleation and diffusional limitations.

  3. Numerical Analysis of an Impinging Jet Reactor for the CVD and Gas-Phase Nucleation of Titania

    NASA Technical Reports Server (NTRS)

    Gokoglu, Suleyman A.; Stewart, Gregory D.; Collins, Joshua; Rosner, Daniel E.

    1994-01-01

    We model a cold-wall atmospheric pressure impinging jet reactor to study the CVD and gas-phase nucleation of TiO2 from a titanium tetra-iso-propoxide (TTIP)/oxygen dilute source gas mixture in nitrogen. The mathematical model uses the computational code FIDAP and complements our recent asymptotic theory for high activation energy gas-phase reactions in thin chemically reacting sublayers. The numerical predictions highlight deviations from ideality in various regions inside the experimental reactor. Model predictions of deposition rates and the onset of gas-phase nucleation compare favorably with experiments. Although variable property effects on deposition rates are not significant (approximately 11 percent at 1000 K), the reduction rates due to Soret transport is substantial (approximately 75 percent at 1000 K).

  4. Phase nucleation in curved space

    NASA Astrophysics Data System (ADS)

    Gómez, Leopoldo; García, Nicolás; Vitelli, Vincenzo; Lorenzana, José; Daniel, Vega

    Nucleation and growth is the dominant relaxation mechanism driving first-order phase transitions. In two-dimensional flat systems, nucleation has been applied to a wide range of problems in physics, chemistry and biology. Here we study nucleation and growth of two-dimensional phases lying on curved surfaces and show that curvature modifies both critical sizes of nuclei and paths towards the equilibrium phase. In curved space, nucleation and growth becomes inherently inhomogeneous and critical nuclei form faster on regions of positive Gaussian curvature. Substrates of varying shape display complex energy landscapes with several geometry-induced local minima, where initially propagating nuclei become stabilized and trapped by the underlying curvature (Gómez, L. R. et al. Phase nucleation in curved space. Nat. Commun. 6:6856 doi: 10.1038/ncomms7856 (2015).).

  5. Molecular dynamics simulations of cluster nucleation during inert gas condensation.

    PubMed

    Krasnochtchekov, Pavel; Averback, R S

    2005-01-22

    Molecular dynamics simulations of vapor-phase nucleation of germanium in an argon atmosphere were performed and a unexpected channel of nucleation was observed. This channel, vapor-induced cluster splitting, is important for more refractory materials since the critical nucleus size can fall below the size of a dimer. As opposed to conventional direct vapor nucleation of the dimer, which occurs by three-body collisions, cluster-splitting nucleation is a second-order reaction. The most important cluster-splitting reaction is the collision of a vapor atom and a trimer that leads to the formation of two dimers. The importance of the cluster-splitting nucleation channel relative to the direct vapor nucleation channel is observed to increase with decreasing vapor density and increasing ratio of vapor to carrier gas atoms.

  6. Studies of gas phase reactions, nucleation and growth mechanisms of plasma promoted chemical vapor deposition of aluminum using dimethylethylamine alane as source percursor

    NASA Astrophysics Data System (ADS)

    Knorr, Andreas H.

    The work presented herein focuses on the use of plasma promoted chemical vapor deposition (PPCVD) of aluminum (Al) using dimethylethylamine alane (DMEAA) as source precursor to provide an integrated, low temperature alternative to currently employed Al deposition methods in ultra large sale integration ULSI multilevel metal wiring schemes. In this respect, key findings are reported and discussed from critical scientific and technical aspects of an research and development effort, which was successfully executed to identify a viable Al CVD deposition process. In this respect, advanced atomic scale analytical techniques were successfully employed to characterize the PPCVD deposition process at the molecular level, and document the dependence of film's structural and compositional properties on key process parameters. This led to the development and optimization of a PPCVD Al process for ULSI applications. In addition, gas phase quadrupole mass spectrometry (QMS) was employed to study the gas phase evolution during TCVD and PPCVD in order to gain a thorough understanding of the potential chemical and physical reactions that could occur in the gas phase and derive corresponding optimized reaction pathways for both CVD processes. Key reaction mechanisms involved in thermal and plasma promoted CVD as a function of processing parameters were investigated, including the role of hydrogen plasma in providing an efficient pathway to aluminum nucleation and growth. The resulting reaction mechanisms were then employed to identify the most likely precursor decomposition pathways and explore relevant implications for thermal and plasma promoted CVD Al. Furthermore, the nucleation and growth of Al in both TCVD and PPCVD were thoroughly characterized. Time evolution studies were carried out employing a variety of relevant liners and seed layers under selected surface chemical states. The surface morphology of the resulting films were analyzed by means of scanning probe microscopy

  7. 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.

  8. Investigation of Metal and Metal Oxide Clusters Small Enough to Constitute the Critical Size for Gas Phase Nucleation in Combustion Processes.

    DTIC Science & Technology

    1980-11-01

    contract a variety of techniques have been employed to study the properties of small atomic and molecular clusters formed in the gas phase via...an inert carrier gas (e.g. helium), or as a mixing process using a hot condensable (e.g. lead, s-ilver, copper, indium or bismuth) and a cold carrier... gas (e.g. argon, j DD 0" 1473 EDITION OF I NOV81 IS OBSOLETE NS/N 0102-014736601 I SECURITY CLASSIFICATION OF THIS PAGE (U~h.. De Sneered) S’",A

  9. Free energy landscape and molecular pathways of gas hydrate nucleation

    NASA Astrophysics Data System (ADS)

    Bi, Yuanfei; Porras, Anna; Li, Tianshu

    2016-12-01

    Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), pB histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage order parameter (H-COP) which we developed for driving FFS, through conducting the pB histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.

  10. Nucleation in a Potts lattice gas model of crystallization from solution

    NASA Astrophysics Data System (ADS)

    Duff, Nathan; Peters, Baron

    2009-11-01

    Nucleation from solution is important in many pharmaceutical crystallization, biomineralization, material synthesis, and self-assembly processes. Simulation methodology has progressed rapidly for studies of nucleation in pure component and implicit solvent systems; however little progress has been made in the simulation of explicit solvent systems. The impasse stems from the inability of rare events simulation methodology to be combined with simulation techniques which maintain a constant chemical potential driving force (supersaturation) for nucleation. We present a Potts lattice gas (PLG) to aid in the development of new simulation strategies for nucleation from solution. The PLG captures common crystallization phase diagram features such as a eutectic point and solute/solvent melting points. Simulations of the PLG below the bulk solute melting temperature reveal a competition between amorphous and crystalline nuclei. As the temperature is increased toward the bulk melting temperature, the nucleation pathway changes from a one step crystalline nucleation pathway to a two step pathway, where an amorphous nucleus forms and then crystallizes. We explain these results in terms of classical nucleation theory with different size-dependant chemical potentials for the amorphous and crystalline nucleation pathways. The two step pathway may be particularly important when crystallization is favored only at postcritical sizes.

  11. Overview: Understanding nucleation phenomena from simulations of lattice gas models

    NASA Astrophysics Data System (ADS)

    Binder, Kurt; Virnau, Peter

    2016-12-01

    Monte Carlo simulations of homogeneous and heterogeneous nucleation in Ising/lattice gas models are reviewed with an emphasis on the general insight gained on the mechanisms by which metastable states decay. Attention is paid to the proper distinction of particles that belong to a cluster (droplet), that may trigger a nucleation event, from particles in its environment, a problem crucial near the critical point. Well below the critical point, the lattice structure causes an anisotropy of the interface tension, and hence nonspherical droplet shapes result, making the treatment nontrivial even within the conventional classical theory of homogeneous nucleation. For temperatures below the roughening transition temperature facetted crystals rather than spherical droplets result. The possibility to find nucleation barriers from a thermodynamic analysis avoiding a cluster identification on the particle level is discussed, as well as the question of curvature corrections to the interfacial tension. For the interpretation of heterogeneous nucleation at planar walls, knowledge of contact angles and line tensions is desirable, and methods to extract these quantities from simulations will be mentioned. Finally, also the problem of nucleation near the stability limit of metastable states and the significance of the spinodal curve will be discussed, in the light of simulations of Ising models with medium range interactions.

  12. Focus Article: Theoretical aspects of vapor/gas nucleation at structured surfaces

    NASA Astrophysics Data System (ADS)

    Meloni, Simone; Giacomello, Alberto; Casciola, Carlo Massimo

    2016-12-01

    Heterogeneous nucleation is the preferential means of formation of a new phase. Gas and vapor nucleation in fluids under confinement or at textured surfaces is central for many phenomena of technological relevance, such as bubble release, cavitation, and biological growth. Understanding and developing quantitative models for nucleation is the key to control how bubbles are formed and to exploit them in technological applications. An example is the in silico design of textured surfaces or particles with tailored nucleation properties. However, despite the fact that gas/vapor nucleation has been investigated for more than one century, many aspects still remain unclear and a quantitative theory is still lacking; this is especially true for heterogeneous systems with nanoscale corrugations, for which experiments are difficult. The objective of this focus article is analyzing the main results of the last 10-20 years in the field, selecting few representative works out of this impressive body of the literature, and highlighting the open theoretical questions. We start by introducing classical theories of nucleation in homogeneous and in simple heterogeneous systems and then discuss their extension to complex heterogeneous cases. Then we describe results from recent theories and computer simulations aimed at overcoming the limitations of the simpler theories by considering explicitly the diffuse nature of the interfaces, atomistic, kinetic, and inertial effects.

  13. Adiabatic nucleation in the liquid-vapor phase transition

    NASA Astrophysics Data System (ADS)

    de Sá, Elon M.; Meyer, Erich; Soares, Vitorvani

    2001-05-01

    The fundamental difference between classical (isothermal) nucleation theory (CNT) and adiabatic nucleation theory (ANT) is discussed. CNT uses the concept of isothermal heterophase fluctuations, while ANT depends on common fluctuations of the thermodynamic variables. Applications to the nonequilibrium liquid to vapor transition are shown. However, we cannot yet calculate nucleation frequencies. At present, we can only indicate at what temperatures and pressures copious homogeneous nucleation is expected in the liquid to vapor phase transition. It is also explained why a similar general indication cannot be made for the inverse vapor to liquid transition. Simultaneously, the validity of Peng-Robinson's equation of state [D.-Y. Peng and D. B. Robinson, Ind. Eng. Chem. Fundam. 15, 59 (1976)] is confirmed for highly supersaturated liquids.

  14. Nucleation and Growth of Gas Hydrate in Natural Seawater

    NASA Astrophysics Data System (ADS)

    Holman, S. A.; Osegovic, J. P.; Young, J. C.; Max, M. D.; Ames, A. L.

    2003-12-01

    Large-scale nucleation of gas hydrate takes place when hydrate-forming gas and seawater are brought together under suitable pressure-temperature conditions or where dissolved hydrate-forming gas in saturated or near-saturated seawater is chilled or brought to higher pressures. Profuse formation of hydrate shells on gas bubbles and nucleation of at least five different forms of gas hydrate have been achieved in fresh natural seawater. Growth of masses of solid gas hydrate takes place when hydrate-forming gas reactant dissolved in seawater is brought into the vicinity of the hydrate. The gas concentration of the enriched water in the vicinity of hydrate is higher than the hydrate equilibrium gas concentration. Hydrate growth under these conditions is accelerated due to the chemical potential difference between the enriched water and the hydrate crystals, which induces mass flux of dissolved hydrate forming gas into new hydrate crystals. As long as water enriched in the hydrate-forming gas is circulated into the vicinity of the hydrate, growth proceeds into the water space. Experimental approaches for growth of examples of solid masses of hydrate are presented. Results of these experiments provide an insight into the growth of gas hydrate under natural conditions where interstitial water in marine sediments is captured by burial from open seawater, and where solid gas hydrate forms on the seafloor. By using fresh natural seawater, which is a chemically and materially complex fluid, our experiments in pressurized, refrigerated reactors should closely track the growth history of solid hydrate in the natural environment. In our model for hydrate growth in sediments, nearly complete pore fill by diagenetic hydrate can best be accomplished by nucleation of hydrate at a point source within the pore water or at a particular point on sediment particulate, with growth outward into the water space that is refreshed with ground water having high concentrations of hydrate

  15. Quantum Nucleation of Phase Slips in 1-d Superfluids

    NASA Astrophysics Data System (ADS)

    Arovas, Daniel

    1998-03-01

    The rate for quantum nucleation of phase slips past an impurity in a one-dimensional superfluid is computed. Real time evolution of the nonlinear Schrödinger equation shows that there is a critical velocity vc below which solutions are time-independent [1,2]; this is the regime of quantum phase slip nucleation. We start with the Gross-Pitaevskii model in the presence of an impurity potential, and derive the Euclidean action for a space-time vortex-antivortex pair, which describes a phase slip event. The action is computed as a function of the superfluid velocity v and the impurity potential width and depth.l [1] V. Hakim, Phys. Rev. E 55, 2835 (1997).l [1] J. A. Freire, D. P. Arovas, and H. Levine, Phys. Rev. Lett (in press, 1997).l

  16. Nucleation and growth studies of crystalline carbon phases at nanoscale

    NASA Astrophysics Data System (ADS)

    Mani, Radhika C.

    Understanding the nucleation and early stage growth of crystals from the vapor phase is important for realizing large-area single-crystal quality films, controlled synthesis of nanocrystals, and the possible discovery of new phases of materials. Carbon provides the most interesting system because all its known crystalline phases (diamond, graphite and carbon nanotubes) are technologically important materials. Hence, this dissertation is focused on studying the nucleation and growth of carbon phases synthesized from the vapor phase. Nucleation experiments were performed in a microwave plasma chemical vapor deposition (CVD) reactor, and the resulting carbon nanocrystals were analyzed primarily using electron nanodiffraction and Raman spectroscopy. These studies led to the discovery of two new crystalline phases of sp 3 carbon other than diamond: face-centered and body-centered cubic carbon. Nanodiffraction results revealed possible hydrogen substitution into diamond-cubic lattices, indicating that these new phases probably act as intermediates in diamond nucleation. Nucleation experiments also led to the discovery of two new morphologies for sp2 carbon: nanocrystals of graphite and tapered, hollow 1-D structures termed here as "carbon nanopipettes". A Kinetic Monte Carlo (KMC) algorithm was developed to simulate the growth of individual diamond crystals from the vapor phase, starting with small clusters of carbon atoms (or seeds). Specifically, KMC simulations were used to distinguish the kinetic rules that give rise to a star-shaped decahedral morphology compared to decahedral crystals. KMC simulations revealed that slow adsorption on the {111} step-propagation sites compared to kink sites leads to star-decahedral crystals, and higher adsorption leads to decahedral crystals. Since the surfaces of the nanocrystals of graphite and nanopipettes were expected to be composed primarily of edge-plane sites, the electrochemical behavior of both these materials were

  17. Nucleation of the diamond phase in aluminium-solid solutions

    NASA Technical Reports Server (NTRS)

    Hornbogen, E.; Mukhopadhyay, A. K.; Starke, E. A., Jr.

    1993-01-01

    Precipitation was studied from fcc solid solutions with silicon, germanium, copper and magnesium. Of all these elements only silicon and germanium form diamond cubic (DC) precipitates in fcc Al. Nucleation of the DC structure is enhanced if both types of atom are dissolved in the fcc lattice. This is interpreted as due to atomic size effects in the prenucleation stage. There are two modes of interference of fourth elements with nucleation of the DC phase in Al + Si, Ge. The formation of the DC phase is hardly affected if the atoms (for example, copper) are rejected from the (Si, Ge)-rich clusters. If additional types of atom are attracted by silicon and/or germanium, DC nuclei are replaced by intermetallic compounds (for example Mg2Si).

  18. Magnetostatic Effects in the Nucleation of Rare Earth Ferromagnetic Phases

    SciTech Connect

    Durfee, C. S.; Flynn, C. P.

    2001-07-30

    It has been reported that superheating, supercooling, and explosive kinetics coupled to other degrees of freedom occur at the ferromagnetic transitions of Er and Dy, and that metastable phases occur during the transition kinetics of Er. We explain these observations in terms of magnetostatic energy, which requires highly eccentric nuclei in the homogeneous nucleation of magnetic transitions in heavy rare earths. The magnetostatics favor transitions through ferrimagnetic intermediaries. The unusual kinetics derive from effective spin lattice relaxation.

  19. Effect of the gas temperature and pressure on the nucleation time of particles in low pressure Ar-C2H2 rf plasmas

    NASA Astrophysics Data System (ADS)

    Lin, Jiashu; Henault, Marie; Orazbayev, Sagi; Boufendi, Laïa; Takahashi, Kazuo; Al Farabi Kazakh National University Collaboration; Kyoto Institute Of Technology Team; Gremi Team

    2016-09-01

    Particle formation in low pressure plasmas is a 3-step process. The first one corresponds to the nucleation and growth of nano-crystallites by ion-molecular reactions, the agglomeration phase to form large particles, and the growth by radical deposition on the particle surface. The nucleation phase was demonstrated to be sensitive to gas temperature and pressure. In this work, time of nucleation phase of particles formation in low pressure cold rf C2H2/Ar plasmas studied by varying gas temperature from 265 K to 375 K, gas pressure from 0.4 mbar to 0.8 mbar and rf power from 6 W to 20 W. The ratio of C2H2/Ar is fixed to 2/98 in terms of pressure. Several previous works reported that particle formation takes a few sec at room temperature in C2 H2 plasmas and the time is much shorter than 0.1 s in SiH4 plasmas. Time evolution of self-bias voltage was mainly used to determine nucleation time. The self-bias voltage was modified by phase transition between the steps from nucleation to coagulation. The experimental results showed that the nucleation time increased with gas temperature, decreased with gas pressure and discharge power. At constant gas pressure of 0.4 mbar and discharge power of 6 W, for example, the nucleation time increased from 5 sec to 30 sec with increas

  20. Ice nucleation properties of the most abundant mineral dust phases

    NASA Astrophysics Data System (ADS)

    Zimmermann, Frank; Weinbruch, Stephan; Schütz, Lothar; Hofmann, Heiko; Ebert, Martin; Kandler, Konrad; Worringen, Annette

    2008-12-01

    The ice nucleation properties of the nine most abundant minerals occurring in desert aerosols (quartz, albite, microcline, kaolinite, montmorillonite, illite, calcite, gypsum, and hematite) were investigated by environmental scanning electron microscopy (ESEM). In this instrument, the pure minerals are exposed to water vapor at variable pressures and temperatures. The crystallization of ice on the mineral particles is observed by secondary electron imaging, and the supersaturation for an activated particle fraction of 1-3% is determined as function of temperature. In all experiments, condensation of water prior to ice formation was not observed within detectable limits, even at water supersaturation. The highest temperatures for 1-3% activation vary between -10°C and -16°C for the nine minerals investigated, and the corresponding onset relative humidities relative to ice RHi between 107 and 117%. Supersaturation temperature curves for initial ice formation (1-3% activation) in the temperature range typical for mixed-phase clouds were measured for all nine minerals. The temperature dependence of the onset relative humidity is strongly dependent on mineralogy. Kaolinite, montmorillonite, and hematite show a strong increase in RHi with decreasing temperature, whereas RHi is almost constant for illite, albite, quartz, and calcite. The highly variable ice nucleation properties of the various mineral dust components should be considered for parameterization schemes. Illite and kaolinite are the most important minerals to consider, as they have high ice nucleation efficiency and are common components of desert aerosols.

  1. Phase nucleation and evolution mechanisms in heterogeneous solids

    NASA Astrophysics Data System (ADS)

    Udupa, Anirudh

    Phase nucleation and evolution is a problem of critical importance in many applications. As the length scales are reduced, it becomes increasingly important to consider interfacial and micro-structural effects that can be safely ignored at larger length scales owing to randomness. The theory of phase nucleation has been addressed usually by the classical nucleation theory, which was originally derived for single component fluid systems, after making an assumption of equilibrium. The criterion has not been rigorously derived for solids, which are far from equilibrium due to dissipation by multiple physical drivers. In this thesis, a thermodynamically sound nucleation criterion is derived for systems with multiple interacting physical phenomena and multiple dissipating mechanisms. This is done, using the tools of continuum mechanics, by determining the change in free energy upon the introduction of a new nucleus into the system. The developed theory is demonstrated to be a generalization of the classical nucleation theory (CNT). The developed theory is then applied to the problem of electromigration driven void nucleation, a serious reliability concern for the microelectronics industry. The void grows and eventually severs the line making the chip nonfunctional. There are two classes of theories at present in the electromigration literature to address the problem of void nucleation, the vacancy supersaturation theory and the entropic dissipation theory, both of which are empirical and based on intuition developed from experimental observations. When the developed theory was applied to the problem of electromigration, it was found to be consistent with the vacancy supersaturation theory, but provided the correct energetic quantity, the chemical potential, which has contribution from both the vacancy concentration as well as the hydrostatic stress. An experiment, consisting of electromigration tests on serpentine lines, was developed to validate the developed

  2. The nucleation rate surfaces design over diagram of phase equilibria and their applications for computational chemistry

    NASA Astrophysics Data System (ADS)

    Anisimov, M. P.

    2016-12-01

    One can find in scientific literature a pretty fresh idea of the nucleation rate surfaces design over the diagrams of phase equilibria. That idea looks like profitable for the nucleation theory development and for various practical applications where predictions of theory have no high enough accuracy for today. The common thermodynamics has no real ability to predict parameters of the first order phase transition. Nucleation experiment can be provided in very local nucleation conditions even the nucleation takes place from the critical line (in two-component case) down to the absolute zero temperature limit and from zero nucleation rates at phase equilibria up to the spinodal conditions. Theory predictions have low reliability as a rule. The computational chemistry has chance to make solution of that problem easier when a set of the used axiomatic statements will adapt enough progressive assumptions [1]. Semiempirical design of the nucleation rate surfaces over diagrams of phase equilibria have a potential ability to provide a reasonable quality information on nucleation rate for each channel of nucleation. Consideration and using of the nucleation rate surface topologies to optimize synthesis of a given phase of the target material can be available when data base on nucleation rates over diagrams of phase equilibria will be created.

  3. Gas Phase Nanoparticle Synthesis

    NASA Astrophysics Data System (ADS)

    Granqvist, Claes; Kish, Laszlo; Marlow, William

    This book deals with gas-phase nanoparticle synthesis and is intended for researchers and research students in nanomaterials science and engineering, condensed matter physics and chemistry, and aerosol science. Gas-phase nanoparticle synthesis is instrumental to nanotechnology - a field in current focus that raises hopes for environmentally benign, resource-lean manufacturing. Nanoparticles can be produced by many physical, chemical, and even biological routes. Gas-phase synthesis is particularly interesting since one can achieve accurate manufacturing control and hence industrial viability.

  4. Nucleation of protein crystals: critical nuclei, phase behavior, and control pathways

    NASA Astrophysics Data System (ADS)

    Galkin, Oleg; Vekilov, Peter G.

    2001-11-01

    We have studied the nucleation of crystals of the model protein lysozyme using a novel technique that allows direct determinations of homogeneous nucleation rates. At constant temperature of 12.6°C we varied the thermodynamic supersaturation by changing the concentrations of protein and precipitant. We found a broken dependence of the homogeneous nucleation rate on supersaturation that is beyond the predictions of the classical nucleation theory. The nucleation theorem allows us to relate this to discrete changes of the size of the crystal nuclei with increasing supersaturation as (10 or 11)→(4 or 5)→(1 or 2). Furthermore, we observe that the existence of a second liquid phase at high protein concentrations strongly affects crystal nucleation kinetics. We show that the rate of homogeneous nucleation of lysozyme crystals passes through a maximum in the vicinity of the liquid-liquid phase boundary hidden below the liquidus (solubility) line in the phase diagram of the protein solution. We found that glycerol and polyethylene glycol (PEG), which do not specifically bind to proteins, shift this phase boundary and significantly suppress or enhance the crystal nucleation rates, although no simple correlation exists between the action of PEG on the phase diagram and the nucleation kinetics. This provides for a control mechanism which does not require changes in the protein concentration, or the acidity and ionicity of the solution. The effects of the two additives on the phase diagram strongly depend on their concentration and this provides opportunities for further tuning of nucleation rates.

  5. Monte Carlo tests of nucleation concepts in the lattice gas model

    NASA Astrophysics Data System (ADS)

    Schmitz, Fabian; Virnau, Peter; Binder, Kurt

    2013-05-01

    The conventional theory of homogeneous and heterogeneous nucleation in a supersaturated vapor is tested by Monte Carlo simulations of the lattice gas (Ising) model with nearest-neighbor attractive interactions on the simple cubic lattice. The theory considers the nucleation process as a slow (quasistatic) cluster (droplet) growth over a free energy barrier ΔF*, constructed in terms of a balance of surface and bulk term of a critical droplet of radius R*, implying that the rates of droplet growth and shrinking essentially balance each other for droplet radius R=R*. For heterogeneous nucleation at surfaces, the barrier is reduced by a factor depending on the contact angle. Using the definition of physical clusters based on the Fortuin-Kasteleyn mapping, the time dependence of the cluster size distribution is studied for quenching experiments in the kinetic Ising model and the cluster size ℓ* where the cluster growth rate changes sign is estimated. These studies of nucleation kinetics are compared to studies where the relation between cluster size and supersaturation is estimated from equilibrium simulations of phase coexistence between droplet and vapor in the canonical ensemble. The chemical potential is estimated from a lattice version of the Widom particle insertion method. For large droplets it is shown that the physical clusters have a volume consistent with the estimates from the lever rule. Geometrical clusters (defined such that each site belonging to the cluster is occupied and has at least one occupied neighbor site) yield valid results only for temperatures less than 60% of the critical temperature, where the cluster shape is nonspherical. We show how the chemical potential can be used to numerically estimate ΔF* also for nonspherical cluster shapes.

  6. Nucleation of electrically charged droplets

    NASA Technical Reports Server (NTRS)

    De, B. R.

    1979-01-01

    The nucleating droplets or clusters in many nucleation environments (various colloidal plasmas in laboratory and technological applications, astrophysical condensation environments, etc.) are likely to be at a finite electric potential. This may be due either to the presence of electrons and ions in the gas phase or to the thermal ionization or photoionization of the droplets. The paper demonstrates that this potential may introduce a nontrivial modification in the conventional nucleation theory. Some results for the typical case of nucleation of water droplets are presented. The general conclusion is that the electric potential makes nucleation harder to achieve, thereby demonstrating the importance of a finite droplet potential in the theory of nucleation.

  7. Nucleation, kinetics and morphology of displacive phase transformations in iron

    NASA Astrophysics Data System (ADS)

    Suiker, A. S. J.; Thijsse, B. J.

    2013-11-01

    An extensive, systematic molecular dynamics (MD) study is performed for analysing the nucleation, kinetics and morphology characteristics of thermally-induced, displacive phase transformations from face-centred cubic (fcc) to body-centred cubic (bcc) iron. At the atomic level these transformation characteristics are influenced by a number of factors, including (i) the appearance of free surfaces, (ii) the initial presence of fcc-bcc grain boundaries, (iii) the existence of point defects (i.e., atomic vacancies) near a grain boundary, (iv) the initial thermal velocities of the atoms, and (v) the specific interatomic potential used. Other MD studies that capture the overall transformation behaviour of iron well have often underestimated or ignored the influence by these factors on the transformation response, with the risk of putting the accuracy, generality and physical explanation of the MD results on loose grounds. The present research illustrates the relative contribution of each of the above factors by means of a detailed comparison study for three different interatomic potentials. The accuracy of the interatomic potentials is established by validating for the fcc and bcc phases the calculated elastic moduli, cohesive energy, vacancy formation energy and interfacial energy against experimental and ab initio data reported in the literature. The importance of calibrating material data of both the stable bcc phase and the metastable fcc phase - instead of the stable bcc phase only - is demonstrated. The numerical results call for general caution when interpreting phenomena that start close to instability points and therefore are sensitive to small disturbances; a large spread in the overall transformation time is found under different initial thermal velocities, interfacial lattice incoherence, boundary conditions (free vs. periodic), and interatomic potentials, where for completely transformed atomic systems the discrepancy between the maximum and minimum

  8. Computer simulation of nucleation in a gas-saturated liquid.

    PubMed

    Protsenko, S P; Baidakov, V G; Teterin, A S; Zhdanov, E R

    2007-03-07

    Molecular dynamics methods have been used to investigate the kinetics of the liquid-gas phase transition in a two-component Lennard-Jones system at negative pressures and elastic stretches of the liquid to values close to spinodal ones. The molecular dynamics system consists of 2048 interacting particles with parameters of the Lennard-Jones potential for argon and neon. Density dependences of pressure and internal energy have been calculated for stable and metastable states of the mixture at a temperature T* approximately 0.7+/-0.01 and three values of the concentration. The location of mechanical and the diffusion spinodals has been determined. It has been established that a gas-saturated mixture retains its stability against finite variations of state variables up to stretches close to the values near the diffusion spinodal. The statistic laws of the process of destruction of the metastable state have been investigated. The lifetimes of the metastable phase have been determined. It is shown that owing to the small height of the potential barrier that separates the microheterogeneous from the homogeneous state a system of finite size has a possibility to make the reverse transition from the microheterogeneous into the homogeneous state. The lifetimes of the system in the microheterogeneous state, as well as the expectation times of the occurrence of a critical nucleus, are described by Poissonian distributions.

  9. Numerical study of the spontaneous nucleation of self-rotational moist gas in a converging-diverging nozzle

    NASA Astrophysics Data System (ADS)

    Ma, Qing-Fen; Hu, Da-Peng; Jiang, Jing-Zhi; Qiu, Zhong-Hua

    2010-01-01

    Spontaneous nucleation is the primary way of droplet formation in the supersonic gas separation technology, and the converging-diverging nozzle is the condensation and separation unit of supersonic gas separation devices. A three-dimensional geometrical model for the generation of self-rotational transonic gas flow is set up, based on which, the spontaneous nucleation of self-rotational transonic moist gas in the converging-diverging nozzle is carried out using an Eulerian multi-fluid model. The simulated results of the main flow and nucleation parameters indicate that the spontaneous nucleation can occur in the diverging part of the nozzle. However, different from the nucleation flow without self-rotation, the distributions of these parameters are unsymmetrical about the nozzle axis due to the irregular flow form caused by the self-rotation of gas flow. The nucleation region is located on the position where gas flows with intense rotation and the self-rotation impacts much on the nucleation process. Stronger rotation delays the onset of spontaneous nucleation and yields lower nucleation rate and narrow nucleation region. In addition, influences of other factors such as inlet total pressure p 0, inlet total temperature T 0, the nozzle-expanding ratio Ȧ and the inlet relative humidity ф 0 on the nucleation of self-rotational moist gas flow in the nozzle are also discussed.

  10. Phase transitions mediated by the nucleation of single vortices in a superconducting channel

    NASA Astrophysics Data System (ADS)

    Sobnack, M. B.; Kusmartsev, F. V.

    2013-10-01

    We study the nucleation of single vortices in a 2D channel in a superconducting/superfluid state which connects two bulk samples. Using real space renormalization group techniques, we show that boundary effects associated with the nucleation of single vortices drives the system to a phase transition at a temperature lower than the Berezinskĭ-Kosterlitz-Thouless temperature.

  11. Fluid phase thermodynamics : I) nucleate pool boiling of oxygen under magnetically enhanced gravity and II) superconducting cavity resonators for high-stability frequency references and precision density measurements of helium-4 gas

    NASA Astrophysics Data System (ADS)

    Corcovilos, Theodore Allen

    Although fluids are typically the first systems studied in undergraduate thermodynamics classes, we still have only a rudimentary phenomenological understanding of these systems outside of the classical and equilibrium regimes. Two experiments will be presented. First, we present progress on precise measurements of helium-4 gas at low temperatures (1 K-5 K). We study helium because at low densities it is an approximately ideal gas but at high densities the thermodynamic properties can be predicted by numerical solutions of Schroedinger's equation. By utilizing the high resolution and stability in frequency of a superconducting microwave cavity resonator we can measure the dielectric constant of helium-4 to parts in 109, corresponding to an equivalent resolution in density. These data will be used to calculate the virial coefficients of the helium gas so that we may compare with numerical predictions from the literature. Additionally, our data may allow us to measure Boltzmann's constant to parts in 108, a factor of 100 improvement over previous measurements. This work contains a description of the nearly-completed apparatus and the methods of operation and data analysis for this experiment. Data will be taken by future researchers.The second experiment discussed is a study of nucleate pool boiling. To date, no adequate quantitative model exists of this everyday phenomenon. In our experiment, we vary one parameter inaccessible to most researchers, gravity, by applying a magnetic force to our test fluid, oxygen. Using this technique, we may apply effective gravities of 0-80 times Earth's gravitational acceleration (g). In this work we present heat transfer data for the boiling of oxygen at one atmosphere ambient pressure for effective gravity values between 1g and 16g . Our data describe two relationships between applied heat flux and temperature differential: at low heat flux the system obeys a power law and at high heat flux the behavior is linear. We find that the

  12. Study of gypsum crystal nucleation and growth rates in simulated flue gas desulfurization liquors. Final report

    SciTech Connect

    Randolph, A.D.; Etherton, D.

    1981-06-01

    The kinetics of gypsum crystal nucleation and growth rates were measured in flue gas desulfurization (FGD) scrubber liquors. Variables studied were parent seed crystal size and mass; the organic additives citric acid, adipic acid, sodium dodecylbenzene sulfonate, and Calgon CL246 polyacrylic acid formulation; and pH. Citric acid produced gypsum crystals with a more favorable columnar structure. Lower pH resulted in increased nucleation rates. Stable secondary nucleation was observed in the presence of retained parent gypsum seed crystals of size >150 ..mu..m. Growth and nucleation rates were correlated using reaction kinetic models. These kinetics were then used in rigorous computer simulations to predict crystal-size distribution (CSD) with different scrubber configurations. Scrubber process configurations employing classified product removal were calculated to produce a gypsum sludge having a mean particle size up to twice as large as the particle size with unclassified operation.

  13. Role of Dynamic Nucleation at Moving Boundaries in Phase and Microstructure Selection

    NASA Technical Reports Server (NTRS)

    Karma, Alain; Trivedi, Rohit

    1999-01-01

    Solidification microstructures that form under steady-state growth conditions (cells, dendrites, regular eutectics, etc.) are reasonably well understood in comparison to other, more complex microstructures, which form under intrinsically non-steady-state growth conditions due to the competition between the nucleation and growth of several phases. Some important practical examples in this latter class include microstructures forming in peritectic systems in highly undercooled droplets, and in strip cast stainless steels. Prediction of phase and microstructure selection in these systems has been traditionally based on (1) heterogeneous nucleation on a static interface, and (2) comparing the relative growth rate of different phase/microstructures under steady-state growth conditions. The formation of new phases, however, occurs via nucleation on, or ahead of, a moving boundary. In addition, the actual selection process is controlled by a complex interaction between the nucleation process and the growth competition between the nuclei and the pre-existing phase under non-steady-state conditions. As a result, it is often difficult to predict which microstructure will form and which phases will be selected under prescribed processing conditions. This research addresses this critical role of nucleation at moving boundaries in the selection of phases and solidification microstructures through quantitative experiments and numerical modeling in peritectic systems. In order to create a well characterized system in which to study this problem, we focus on the directional solidification of hypo- and hyper-peritectic alloys in the two-phase region, imposing a large enough ratio of temperature gradient/growth rate (G/V(sub p)) to suppress the morphological instability of both the parent (alpha) and peritectic (Beta) phases, i.e. each phase alone would grow as a planar front. Our combined experimental and theoretical results show that, already in this simplified case, the growth

  14. Characterization of the α phase nucleation in a two-phase metastable β titanium alloy

    NASA Astrophysics Data System (ADS)

    Lenain, A.; Clément, N.; Jacques, P. J.; Véron, M.

    2005-12-01

    Beta titanium alloys are increasingly the best choice for automotive and aerospace applications due to their high performance-to-density ratio. Among these alloys, the TIMETAL Ti-LCB is already used in the automotive industry because it presents excellent mechanical properties and a lower cost compared with other Ti alloys. The current study deals with the characterization of the nucleation and growth of the α phase in several thermomechanical processes, because the distribution and size of the α phase strongly influence the mechanical properties of the resulting microstructures. Several heat treatments were conducted after either cold rolling or annealing. The resulting microstructures were characterized by scanning electron microscopy, transmission electron microscopy, x-ray diffraction, or electron backscatter diffraction. It was observed that the morphology and the volume fraction of the α phase are strongly dependent on the holding temperature, on the heating or cooling rate, and on the β grain size.

  15. Nucleation kinetics and crystal growth with fluctuating rates at the intermediate stage of phase transitions

    NASA Astrophysics Data System (ADS)

    Alexandrov, D. V.; Malygin, A. P.

    2014-01-01

    Crystal growth kinetics accompanied by particle growth with fluctuating rates at the intermediate stage of phase transitions is analyzed theoretically. The integro-differential model of governing equations is solved analytically for size-independent growth rates and arbitrary dependences of the nucleation frequency on supercooling/supersaturation. Two important cases of Weber-Volmer-Frenkel-Zel'dovich and Mier nucleation kinetics are detailed. A Fokker-Plank type equation for the crystal-size density distribution function is solved explicitly.

  16. Nonequilibrium thermodynamics of nucleation

    SciTech Connect

    Schweizer, M.; Sagis, L. M. C.

    2014-12-14

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects.

  17. Nonequilibrium thermodynamics of nucleation.

    PubMed

    Schweizer, M; Sagis, L M C

    2014-12-14

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects.

  18. Nonequilibrium thermodynamics of nucleation

    NASA Astrophysics Data System (ADS)

    Schweizer, M.; Sagis, L. M. C.

    2014-12-01

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects.

  19. 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

  20. Ice nucleation by combustion ash particles at conditions relevant to mixed-phase clouds

    NASA Astrophysics Data System (ADS)

    Umo, N. S.; Murray, B. J.; Baeza-Romero, M. T.; Jones, J. M.; Lea-Langton, A. R.; Malkin, T. L.; O'Sullivan, D.; Neve, L.; Plane, J. M. C.; Williams, A.

    2015-05-01

    Ice-nucleating particles can modify cloud properties with implications for climate and the hydrological cycle; hence, it is important to understand which aerosol particle types nucleate ice and how efficiently they do so. It has been shown that aerosol particles such as natural dusts, volcanic ash, bacteria and pollen can act as ice-nucleating particles, but the ice-nucleating ability of combustion ashes has not been studied. Combustion ashes are major by-products released during the combustion of solid fuels and a significant amount of these ashes are emitted into the atmosphere either during combustion or via aerosolization of bottom ashes. Here, we show that combustion ashes (coal fly ash, wood bottom ash, domestic bottom ash, and coal bottom ash) nucleate ice in the immersion mode at conditions relevant to mixed-phase clouds. Hence, combustion ashes could play an important role in primary ice formation in mixed-phase clouds, especially in clouds that are formed near the emission source of these aerosol particles. In order to quantitatively assess the impact of combustion ashes on mixed-phase clouds, we propose that the atmospheric abundance of combustion ashes should be quantified since up to now they have mostly been classified together with mineral dust particles. Also, in reporting ice residue compositions, a distinction should be made between natural mineral dusts and combustion ashes in order to quantify the contribution of combustion ashes to atmospheric ice nucleation.

  1. Interfacial free energy adjustable phase field crystal model for homogeneous nucleation.

    PubMed

    Guo, Can; Wang, Jincheng; Wang, Zhijun; Li, Junjie; Guo, Yaolin; Huang, Yunhao

    2016-05-18

    To describe the homogeneous nucleation process, an interfacial free energy adjustable phase-field crystal model (IPFC) was proposed by reconstructing the energy functional of the original phase field crystal (PFC) methodology. Compared with the original PFC model, the additional interface term in the IPFC model effectively can adjust the magnitude of the interfacial free energy, but does not affect the equilibrium phase diagram and the interfacial energy anisotropy. The IPFC model overcame the limitation that the interfacial free energy of the original PFC model is much less than the theoretical results. Using the IPFC model, we investigated some basic issues in homogeneous nucleation. From the viewpoint of simulation, we proceeded with an in situ observation of the process of cluster fluctuation and obtained quite similar snapshots to colloidal crystallization experiments. We also counted the size distribution of crystal-like clusters and the nucleation rate. Our simulations show that the size distribution is independent of the evolution time, and the nucleation rate remains constant after a period of relaxation, which are consistent with experimental observations. The linear relation between logarithmic nucleation rate and reciprocal driving force also conforms to the steady state nucleation theory.

  2. Theoretical study of vapor-liquid homogeneous nucleation using stability analysis of a macroscopic phase.

    PubMed

    Carreón-Calderón, Bernardo

    2012-10-14

    Stability analysis is generally used to verify that the solution to phase equilibrium calculations corresponds to a stable state (minimum of the free energy). In this work, tangent plane distance analysis for stability of macroscopic mixtures is also used for analyzing the nucleation process, reconciling thus this analysis with classical nucleation theories. In the context of the revised nucleation theory, the driving force and the nucleation work are expressed as a function of the Lagrange multiplier corresponding to the mole fraction constraint from the minimization problem of stability analysis. Using a van der Waals fluid applied to a ternary mixture, Lagrange multiplier properties are illustrated. In particular, it is shown how the Lagrange multiplier value is equal to one on the binodal and spinodal curves at the same time as the driving force of nucleation vanishes on these curves. Finally, it is shown that, on the spinodal curve, the nucleation work from the revised and generalized nucleation theories are characterized by two different local minima from stability analysis, irrespective of any interfacial tension models.

  3. Homogeneous nucleation rate measurements of 1-propanol in helium: the effect of carrier gas pressure.

    PubMed

    Brus, David; Zdímal, Vladimír; Stratmann, Frank

    2006-04-28

    Kinetics of homogeneous nucleation in supersaturated vapor of 1-propanol was studied using an upward thermal diffusion cloud chamber. Helium was used as a noncondensable carrier gas and the influence of its pressure on observed nucleation rates was investigated. The isothermal nucleation rates were determined by a photographic method that is independent on any nucleation theory. In this method, the trajectories of growing droplets are recorded using a charge coupled device camera and the distribution of local nucleation rates is determined by image analysis. The nucleation rate measurements of 1-propanol were carried out at four isotherms 260, 270, 280, and 290 K. In addition, the pressure dependence was investigated on the isotherms 290 K (50, 120, and 180 kPa) and 280 K (50 and 120 kPa). The isotherm 270 K was measured at 25 kPa and the isotherm 260 K at 20 kPa. The experiments confirm the earlier observations from several thermal diffusion chamber investigations that the homogeneous nucleation rate of 1-propanol tends to increase with decreasing total pressure in the chamber. In order to reduce the possibility that the observed phenomenon is an experimental artifact, connected with the generally used one-dimensional description of transfer processes in the chamber, a recently developed two-dimensional model of coupled heat, mass, and momentum transfer inside the chamber was used and results of both models were compared. It can be concluded that the implementation of the two-dimensional model does not explain the observed effect. Furthermore the obtained results were compared both to the predictions of the classical theory and to the results of other investigators using different experimental devices. Plotting the experimental data on the so-called Hale plot shows that our data seem to be consistent both internally and also with the data of others. Using the nucleation theorem the critical cluster sizes were obtained from the slopes of the individual isotherms

  4. Random-Walk Monte Carlo Simulation of Intergranular Gas Bubble Nucleation in UO2 Fuel

    SciTech Connect

    Yongfeng Zhang; Michael R. Tonks; S. B. Biner; D.A. Andersson

    2012-11-01

    Using a random-walk particle algorithm, we investigate the clustering of fission gas atoms on grain bound- aries in oxide fuels. The computational algorithm implemented in this work considers a planar surface representing a grain boundary on which particles appear at a rate dictated by the Booth flux, migrate two dimensionally according to their grain boundary diffusivity, and coalesce by random encounters. Specifically, the intergranular bubble nucleation density is the key variable we investigate using a parametric study in which the temperature, grain boundary gas diffusivity, and grain boundary segregation energy are varied. The results reveal that the grain boundary bubble nucleation density can vary widely due to these three parameters, which may be an important factor in the observed variability in intergranular bubble percolation among grain boundaries in oxide fuel during fission gas release.

  5. Phase field theory of interfaces and crystal nucleation in a eutectic system of fcc structure: II. Nucleation in the metastable liquid immiscibility region.

    PubMed

    Tóth, Gyula I; Gránásy, László

    2007-08-21

    In the second part of our paper, we address crystal nucleation in the metastable liquid miscibility region of eutectic systems that is always present, though experimentally often inaccessible. While this situation resembles the one seen in single component crystal nucleation in the presence of a metastable vapor-liquid critical point addressed in previous works, it is more complex because of the fact that here two crystal phases of significantly different compositions may nucleate. Accordingly, at a fixed temperature below the critical point, six different types of nuclei may form: two liquid-liquid nuclei: two solid-liquid nuclei; and two types of composite nuclei, in which the crystalline core has a liquid "skirt," whose composition falls in between the compositions of the solid and the initial liquid phases, in addition to nuclei with concentric alternating composition shells of prohibitively high free energy. We discuss crystalline phase selection via exploring/identifying the possible pathways for crystal nucleation.

  6. Optimization of crystal nucleation close to a metastable fluid-fluid phase transition.

    PubMed

    Wedekind, Jan; Xu, Limei; Buldyrev, Sergey V; Stanley, H Eugene; Reguera, David; Franzese, Giancarlo

    2015-06-22

    The presence of a metastable fluid-fluid critical point is thought to dramatically influence the crystallization pathway, increasing the nucleation rate by many orders of magnitude over the predictions of classical nucleation theory. We use molecular dynamics simulations to study the kinetics of crystallization in the vicinity of this metastable critical point and throughout the metastable fluid-fluid phase diagram. To quantitatively understand how the fluid-fluid phase separation affects the crystal nucleation, we evaluate accurately the kinetics and reconstruct the thermodynamic free-energy landscape of crystal formation. Contrary to expectations, we find no special advantage of the proximity of the metastable critical point on the crystallization rates. However, we find that the ultrafast formation of a dense liquid phase causes the crystallization to accelerate both near the metastable critical point and almost everywhere below the fluid-fluid spinodal line. These results unveil three different scenarios for crystallization that could guide the optimization of the process in experiments.

  7. Nucleation Chemical Physics: From Vapor Phase Clusters to Crystals in Solution

    SciTech Connect

    Kathmann, Shawn M.

    2007-08-03

    Both vapor-phase clusters and condensed-phase crystals are important in a wide variety of fundamental and applied problems in chemical physics. Favorable fluctuations in a supersaturated phase generate clusters of the new phase – exactly how one defines these new clusters as distinct from the mother phase represents a continuing challenge in molecular theories of nucleation. These incipient clusters can form homogeneously within the mother phase or heterogeneously on seeds, dust, impurities, ions, or others stability-inducing atomic/molecular structures (e.g., steps, edges, vacancies, etc.). Upon reaching a critical size the clusters may grow to macroscopic dimensions if enough nucleating material is present in surrounding environment or until relaxation processes dominate bringing the phase transformation to completion. This work was supported by the Chemical and Material Sciences Division, Office of Basic Energy Sciences, Department of Energy. The Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  8. Collector phase transitions during vapor-solid-solid nucleation of GaN nanowires.

    PubMed

    Chèze, Caroline; Geelhaar, Lutz; Trampert, Achim; Brandt, Oliver; Riechert, Henning

    2010-09-08

    We investigate the nucleation of Ni-induced GaN nanowires by in situ and ex situ experiments. Three nucleation stages are evidenced. In the first two stages, different crystal structures of the Ni collectors are identified. Real-time monitoring of the Ga desorption allows the amount of Ga incorporated in the collectors to be quantified. A transition of their crystal structure prior to nanowire growth is found to be in agreement with the thermodynamically stable phase sequence of the relevant phase diagrams.

  9. Reasons for crack nucleation in welded joints of main gas-pipelines after a long-term operation

    NASA Astrophysics Data System (ADS)

    Maruschak, P. O.; Bishchak, R. T.; Shlapak, L. S.; Panin, S. V.

    2017-02-01

    A crack of operational origin in the welded joint of the main gas pipeline is analyzed. The reasons for its nucleation and impact on technological microdefects that were formed earlier during the welding are found. Micromechanisms and stages of nucleation and propagation of the crack are investigated.

  10. Helmholtz free energy of a phase containing a sparse ensemble of heterophase clusters with application to nucleation theory.

    PubMed

    Tschudi, Hans Rudolf

    2010-03-11

    A decomposition of the Helmholtz free energy of a phase containing a sparse ensemble of heterophase clusters is derived based on classical statistical mechanics and on the general physical characteristics of such systems. It is not assumed that the phase is an ideal gas. The building blocks of this decomposition are the Helmholtz free energies of the constituents (phase and stationary heterophase clusters) and, for every cluster species, a volume V(k)(cm), which is of the magnitude of the thermal fluctuation volume of the center of mass of the stationary cluster containing k monomers. A definition of V(k)(cm) is given in terms of the configuration integrals of the clusters. V(k)(cm) is evaluated for k > 1, with the result that V(k)(cm) is proportional to k(-1/2) and is a function of temperature, the specific volume, and the isothermal compressibility of the phase in the cluster. A thermodynamically consistent expression for the work to form a stationary cluster, which reads as Delta g(k)/(k(B)T) = -ak + (3/2)bk(2/3) + 3ck(1/3) + d, is derived. The coefficients a, b, c, and d depend on the thermodynamic properties of the homogeneous phases, on the surface tension, and on one additional phenomenological material function of temperature and pressure. The description is general and covers a wide class of materials. It is shown that the heterogeneous system represents the thermodynamic equilibrium and not the pure phase without clusters. The resulting expression for the equilibrium particle number, which is different from the one used in classical nucleation theory, is by a standard procedure input for the calculation of the stationary Becker-Döring nucleation rate and entails a correction factor for the classical nucleation rate. Comparison with experiments is provided for nucleation onset measurements of argon and for measurements of the homogeneous nucleation rate of water. Measurements and theory can be brought to match within the limits of experimental precision

  11. Evaporation-triggered microdroplet nucleation and the four life phases of an evaporating Ouzo drop

    NASA Astrophysics Data System (ADS)

    Tan, Huanshu; Diddens, Christian; Lv, Pengyu; Kuerten, J. G. M.; Zhang, Xuehua; Lohse, Detlef

    2016-11-01

    Evaporating liquid droplets are omnipresent in nature and technology, such as in inkjet printing, coating, deposition of materials, medical diagnostics, agriculture, the food industry, cosmetics, or spills of liquids. Here we show that the evaporation of such ternary mixtures can trigger a phase transition and the nucleation of microdroplets of one of the components of the mixture. As a model system, we pick a sessile Ouzo droplet (as known from daily life) and reveal and theoretically explain its four life phases: In phase I, the spherical cap-shaped droplet remains transparent while the more volatile ethanol is evaporating, preferentially at the rim of the drop because of the singularity there. This leads to a local ethanol concentration reduction and correspondingly to oil droplet nucleation there. This is the beginning of phase II, in which oil microdroplets quickly nucleate in the whole drop, leading to its milky color that typifies the so-called "Ouzo effect." Once all ethanol has evaporated, the drop, which now has a characteristic nonspherical cap shape, has become clear again, with a water drop sitting on an oil ring (phase III), finalizing the phase inversion. Finally, in phase IV, all water has evaporated, leaving behind a tiny spherical cap-shaped oil drop.

  12. Gas-phase chemical dynamics

    SciTech Connect

    Weston, R.E. Jr.; Sears, T.J.; Preses, J.M.

    1993-12-01

    Research in this program is directed towards the spectroscopy of small free radicals and reactive molecules and the state-to-state dynamics of gas phase collision, energy transfer, and photodissociation phenomena. Work on several systems is summarized here.

  13. Quantized hard-x-ray phase vortices nucleated by aberrated nanolenses

    SciTech Connect

    Pavlov, Konstantin M.; Paganin, David M.; Vine, David J.; Schmalz, Jelena A.; Suzuki, Yoshio; Uesugi, Kentaro; Takeuchi, Akihisa; Yagi, Naoto; Jakubek, Jan; Altissimo, Matteo; Clark, Jesse N.

    2011-01-15

    Quantized x-ray phase vortices, namely, screw-type topological defects in the wave fronts of a coherent monochromatic scalar x-ray wave field, may be spontaneously nucleated by x-ray lenses. Phase retrieval is used to reconstruct the phase and amplitude of the complex disturbance created by aberrated gold nanolenses illuminated with hard x rays. A nanoscale quantized x-ray vortex-antivortex dipole is observed, manifest both as a pair of opposite-helicity branch points in the Riemann sheets of the multivalued x-ray phase map of the complex x-ray field and in the vorticity of the associated Poynting vector field.

  14. Heterogeneous nucleation and growth dynamics in the light-induced phase transition in vanadium dioxide

    DOE PAGES

    Brady, Nathaniel F.; Appavoo, Kannatassen; Seo, Minah; ...

    2016-03-02

    Here we report on ultrafast optical investigations of the light-induced insulator-to-metal phase transition in vanadium dioxide with controlled disorder generated by substrate mismatch. These results reveal common dynamics of this optically-induced phase transition that are independent of this disorder. Lastly, above the fluence threshold for completing the transition to the rutile crystalline phase, we find a common time scale, independent of sample morphology, of 40.5 ± 2 ps that is consistent with nucleation and growth dynamics of the R phase from the parent M1 ground state.

  15. Observation of the seismic nucleation phase in the Ridgecrest, California, earthquake sequence

    USGS Publications Warehouse

    Ellsworth, W.L.; Beroza, G.C.

    1998-01-01

    Near-source observations of five M 3.8-5.2 earthquakes near Ridgecrest, California are consistent with the presence of a seismic nucleation phase. These earthquakes start abruptly, but then slow or stop before rapidly growing again toward their maximum rate of moment release. Deconvolution of instrument and path effects by empirical Green's functions demonstrates that the initial complexity at the start of the earthquake is a source effect. The rapid growth of the P-wave arrival at the start of the seismic nucleation phase supports the conclusion of Mori and Kanamori [1996] that these earthquakes begin without a magnitude-scaled slow initial phase of the type observed by Iio [1992, 1995].

  16. The carrier gas pressure effect in a laminar flow diffusion chamber, homogeneous nucleation of n-butanol in helium.

    PubMed

    Hyvärinen, Antti-Pekka; Brus, David; Zdímal, Vladimír; Smolík, Jiri; Kulmala, Markku; Viisanen, Yrjö; Lihavainen, Heikki

    2006-06-14

    Homogeneous nucleation rate isotherms of n-butanol+helium were measured in a laminar flow diffusion chamber at total pressures ranging from 50 to 210 kPa to investigate the effect of carrier gas pressure on nucleation. Nucleation temperatures ranged from 265 to 280 K and the measured nucleation rates were between 10(2) and 10(6) cm(-3) s(-1). The measured nucleation rates decreased as a function of increasing pressure. The pressure effect was strongest at pressures below 100 kPa. This negative carrier gas effect was also temperature dependent. At nucleation temperature of 280 K and at the same saturation ratio, the maximum deviation between nucleation rates measured at 50 and 210 kPa was about three orders of magnitude. At nucleation temperature of 265 K, the effect was negligible. Qualitatively the results resemble those measured in a thermal diffusion cloud chamber. Also the slopes of the isothermal nucleation rates as a function of saturation ratio were different as a function of total pressure, 50 kPa isotherms yielded the steepest slopes, and 210 kPa isotherms the shallowest slopes. Several sources of inaccuracies were considered in the interpretation of the results: uncertainties in the transport properties, nonideal behavior of the vapor-carrier gas mixture, and shortcomings of the used mathematical model. Operation characteristics of the laminar flow diffusion chamber at both under-and over-pressure were determined to verify a correct and stable operation of the device. We conclude that a negative carrier gas pressure effect is seen in the laminar flow diffusion chamber and it cannot be totally explained with the aforementioned reasons.

  17. Nucleation of (He-3)-B from the A phase - A cosmic-ray effect?

    NASA Technical Reports Server (NTRS)

    Leggett, A. J.

    1984-01-01

    When He-3 is liquified and subsequently cooled, it undergoes, at a temperature of approximately 2.0-2.5 mK, a second-order transition into the so-called A phase. On further cooling, a first-order transition occurs, and the liquid passes into the B phase. Supercooling occurs with respect to the second transition, and the problem of nucleation arises. In connection with the experimental interest in studying metastable (He-3)-A down to the lowest temperatures in weak magnetic fields, the understanding of the mechanism of this transition and the feasibility of its inhibition is of some importance. The present investigation is concerned with the possibility that the transition is nucleated by the passage of a cosmic ray through the sample cell.

  18. First-order chiral phase transition in high-energy collisions: Can nucleation prevent spinodal decomposition?

    SciTech Connect

    Scavenius, O.; Dumitru, A.; Fraga, E. S.; Lenaghan, J. T.; Jackson, A. D.

    2001-06-01

    We discuss homogeneous nucleation in a first-order chiral phase transition within an effective field theory approach to low-energy QCD. Exact decay rates and bubble profiles are obtained numerically and compared to analytic results obtained with the thin-wall approximation. The thin-wall approximation overestimates the nucleation rate for any degree of supercooling. The time scale for critical thermal fluctuations is calculated and compared to typical expansion times for high-energy hadronic or heavy-ion collisions. We find that significant supercooling is possible, and the relevant mechanism for phase conversion might be that of spinodal decomposition. Some potential experimental signatures of supercooling, such as an increase in the correlation length of the scalar condensate, are also discussed.

  19. Heterogeneous ice nucleation and phase transition of viscous α-pinene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Virtanen, Annele; Stratmann, Frank

    2016-04-01

    There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate deposition ice nucleation and thus influence cirrus cloud properties. Global model simulations of monoterpene SOA particles suggest that viscous biogenic SOA are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle (INP) budget. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles at the CLOUD (Cosmics Leaving OUtdoor Droplets) experiment at CERN (Ignatius et al., 2015, Järvinen et al., 2015). In the CLOUD chamber, the SOA particles were produced from the ozone initiated oxidation of α-pinene at temperatures in the range from -38 to -10° C at 5-15 % relative humidity with respect to water (RHw) to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. As the RHw was increased to between 35 % at -10° C and 80 % at -38° C, a transition to spherical shape was observed with a new in-situ optical method. This transition confirms previous modelling of the viscosity transition conditions. The ice nucleation ability of SOA particles was investigated with a new continuous flow diffusion chamber SPIN (Spectrometer for Ice Nuclei) for different SOA particle sizes. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA in the deposition mode for ice saturation ratios between 1.3 and 1.4, significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -36.5 and -38.3° C ranged from 6 to 20 % and did not depend on the particle surface area. References Ignatius, K. et al., Heterogeneous ice

  20. Phase-field crystal modeling of heteroepitaxy and exotic modes of crystal nucleation

    NASA Astrophysics Data System (ADS)

    Podmaniczky, Frigyes; Tóth, Gyula I.; Tegze, György; Pusztai, Tamás; Gránásy, László

    2017-01-01

    We review recent advances made in modeling heteroepitaxy, two-step nucleation, and nucleation at the growth front within the framework of a simple dynamical density functional theory, the Phase-Field Crystal (PFC) model. The crystalline substrate is represented by spatially confined periodic potentials. We investigate the misfit dependence of the critical thickness in the StranskiKrastanov growth mode in isothermal studies. Apparently, the simulation results for stress release via the misfit dislocations fit better to the PeopleBean model than to the one by Matthews and Blakeslee. Next, we investigate structural aspects of two-step crystal nucleation at high undercoolings, where an amorphous precursor forms in the first stage. Finally, we present results for the formation of new grains at the solid-liquid interface at high supersaturations/supercoolings, a phenomenon termed Growth Front Nucleation (GFN). Results obtained with diffusive dynamics (applicable to colloids) and with a hydrodynamic extension of the PFC theory (HPFC, developed for simple liquids) will be compared. The HPFC simulations indicate two possible mechanisms for GFN.

  1. Optimization of crystal nucleation close to a metastable fluid-fluid phase transition

    PubMed Central

    Wedekind, Jan; Xu, Limei; Buldyrev, Sergey V.; Stanley, H. Eugene; Reguera, David; Franzese, Giancarlo

    2015-01-01

    The presence of a metastable fluid-fluid critical point is thought to dramatically influence the crystallization pathway, increasing the nucleation rate by many orders of magnitude over the predictions of classical nucleation theory. We use molecular dynamics simulations to study the kinetics of crystallization in the vicinity of this metastable critical point and throughout the metastable fluid-fluid phase diagram. To quantitatively understand how the fluid-fluid phase separation affects the crystal nucleation, we evaluate accurately the kinetics and reconstruct the thermodynamic free-energy landscape of crystal formation. Contrary to expectations, we find no special advantage of the proximity of the metastable critical point on the crystallization rates. However, we find that the ultrafast formation of a dense liquid phase causes the crystallization to accelerate both near the metastable critical point and almost everywhere below the fluid-fluid spinodal line. These results unveil three different scenarios for crystallization that could guide the optimization of the process in experiments PMID:26095898

  2. Evaporation-triggered microdroplet nucleation and the four life phases of an evaporating Ouzo drop

    NASA Astrophysics Data System (ADS)

    Tan, Huanshu; Diddens, Christian; Lv, Pengyu; Kuerten, J. G. M.; Zhang, Xuehua; Lohse, Detlef

    2016-08-01

    Evaporating liquid droplets are omnipresent in nature and technology, such as in inkjet printing, coating, deposition of materials, medical diagnostics, agriculture, the food industry, cosmetics, or spills of liquids. Whereas the evaporation of pure liquids, liquids with dispersed particles, or even liquid mixtures has intensively been studied over the past two decades, the evaporation of ternary mixtures of liquids with different volatilities and mutual solubilities has not yet been explored. Here we show that the evaporation of such ternary mixtures can trigger a phase transition and the nucleation of microdroplets of one of the components of the mixture. As a model system, we pick a sessile Ouzo droplet (as known from daily life—a transparent mixture of water, ethanol, and anise oil) and reveal and theoretically explain its four life phases: In phase I, the spherical cap-shaped droplet remains transparent while the more volatile ethanol is evaporating, preferentially at the rim of the drop because of the singularity there. This leads to a local ethanol concentration reduction and correspondingly to oil droplet nucleation there. This is the beginning of phase II, in which oil microdroplets quickly nucleate in the whole drop, leading to its milky color that typifies the so-called “Ouzo effect.” Once all ethanol has evaporated, the drop, which now has a characteristic nonspherical cap shape, has become clear again, with a water drop sitting on an oil ring (phase III), finalizing the phase inversion. Finally, in phase IV, all water has evaporated, leaving behind a tiny spherical cap-shaped oil drop.

  3. Evaporation-triggered microdroplet nucleation and the four life phases of an evaporating Ouzo drop

    PubMed Central

    Tan, Huanshu; Diddens, Christian; Lv, Pengyu; Kuerten, J. G. M.; Zhang, Xuehua; Lohse, Detlef

    2016-01-01

    Evaporating liquid droplets are omnipresent in nature and technology, such as in inkjet printing, coating, deposition of materials, medical diagnostics, agriculture, the food industry, cosmetics, or spills of liquids. Whereas the evaporation of pure liquids, liquids with dispersed particles, or even liquid mixtures has intensively been studied over the past two decades, the evaporation of ternary mixtures of liquids with different volatilities and mutual solubilities has not yet been explored. Here we show that the evaporation of such ternary mixtures can trigger a phase transition and the nucleation of microdroplets of one of the components of the mixture. As a model system, we pick a sessile Ouzo droplet (as known from daily life—a transparent mixture of water, ethanol, and anise oil) and reveal and theoretically explain its four life phases: In phase I, the spherical cap-shaped droplet remains transparent while the more volatile ethanol is evaporating, preferentially at the rim of the drop because of the singularity there. This leads to a local ethanol concentration reduction and correspondingly to oil droplet nucleation there. This is the beginning of phase II, in which oil microdroplets quickly nucleate in the whole drop, leading to its milky color that typifies the so-called “Ouzo effect.” Once all ethanol has evaporated, the drop, which now has a characteristic nonspherical cap shape, has become clear again, with a water drop sitting on an oil ring (phase III), finalizing the phase inversion. Finally, in phase IV, all water has evaporated, leaving behind a tiny spherical cap-shaped oil drop. PMID:27418601

  4. Evaporation-triggered microdroplet nucleation and the four life phases of an evaporating Ouzo drop.

    PubMed

    Tan, Huanshu; Diddens, Christian; Lv, Pengyu; Kuerten, J G M; Zhang, Xuehua; Lohse, Detlef

    2016-08-02

    Evaporating liquid droplets are omnipresent in nature and technology, such as in inkjet printing, coating, deposition of materials, medical diagnostics, agriculture, the food industry, cosmetics, or spills of liquids. Whereas the evaporation of pure liquids, liquids with dispersed particles, or even liquid mixtures has intensively been studied over the past two decades, the evaporation of ternary mixtures of liquids with different volatilities and mutual solubilities has not yet been explored. Here we show that the evaporation of such ternary mixtures can trigger a phase transition and the nucleation of microdroplets of one of the components of the mixture. As a model system, we pick a sessile Ouzo droplet (as known from daily life-a transparent mixture of water, ethanol, and anise oil) and reveal and theoretically explain its four life phases: In phase I, the spherical cap-shaped droplet remains transparent while the more volatile ethanol is evaporating, preferentially at the rim of the drop because of the singularity there. This leads to a local ethanol concentration reduction and correspondingly to oil droplet nucleation there. This is the beginning of phase II, in which oil microdroplets quickly nucleate in the whole drop, leading to its milky color that typifies the so-called "Ouzo effect." Once all ethanol has evaporated, the drop, which now has a characteristic nonspherical cap shape, has become clear again, with a water drop sitting on an oil ring (phase III), finalizing the phase inversion. Finally, in phase IV, all water has evaporated, leaving behind a tiny spherical cap-shaped oil drop.

  5. Nucleation and growth of the Alpha-Prime Phase martensitic phase in Pu-Ga Alloys

    SciTech Connect

    Blobaum, K M; Krenn, C R; Wall, M A; Massalski, T B; Schwartz, A J

    2005-02-09

    modeling approach based on classical nucleation theory is presented to describe the formation of alpha-phase embryos during conditioning. The reasons why the holding times during conditioning become eventually ineffective in promoting more alpha-prime formation on cooling are discussed in terms of the differences in the potency of the embryos created in the delta matrix during conditioning and in terms of growth-impeding volume strains in the matrix resulting from an increasing number of martensite particles, thus opposing further growth. It is suggested that the disparate amounts of the alpha-prime formation reported in the literature following various studies may be in part a consequence of the fact that conditioning times at ambient temperatures are inevitably involved in any handling of radioactive samples prior to testing.

  6. Gas phase chemistry in comets

    NASA Technical Reports Server (NTRS)

    Oppenheimer, M.

    1976-01-01

    The significance of gas phase reactions in determining the nuclear structure of comets is discussed. The sublimation of parent molecules such as H2O, CH4, CO2, and NH3 from the surface of the nucleus and their subsequent photodissociation and ionization in forming observed cometary molecular species are elaborated.

  7. Microphysical Consequences of the Spatial Distribution of Ice Nucleation in Mixed-Phase Stratiform Clouds

    SciTech Connect

    Yang, Fan; Ovchinnikov, Mikhail; Shaw, Raymond A.

    2014-07-28

    Mixed-phase stratiform clouds can persist even with steady ice precipitation fluxes, and the origin and microphysical properties of the ice crystals are of interest. Vapor deposition growth and sedimentation of ice particles along with a uniform volume source of ice nucleation, leads to a power law relation between ice water content wi and ice number concentration ni with exponent 2.5. The result is independent of assumptions about the vertical velocity structure of the cloud and is therefore more general than the related expression of Yang et al. [2013]. The sensitivity of the wi-ni relationship to the spatial distribution of ice nucleation is confirmed by Lagrangian tracking and ice growth with cloud-volume, cloud-top, and cloud-base sources of ice particles through a time-dependent cloud field. Based on observed wi and ni from ISDAC, a lower bound of 0.006 m^3/s is obtained for the ice crystal formation rate.

  8. A study to investigate phase transitions and nucleation kinetics of nickel and copper

    NASA Astrophysics Data System (ADS)

    Celik, F. A.; Yildiz, A. K.

    2016-04-01

    In this study, we investigate the homogeneous nucleation kinetics of copper and nickel system during cooling process using molecular dynamics simulation (MDS). The calculation is carried out for a different number of atoms consisting of 500, 2048, 8788 and 13,500 based on embedded atom method (EAM). It is observed that the melting points for the both model increases with increasing the size of systems (i.e. the number of atoms) as expected from Parrinello and Rahman MD method. The interfacial free energies and critical nucleus radius of nickel and copper are also determined by molecular dynamics, and the results are consistent with the classical nucleation theory. The structural development and phase transformation are also determined from the radial distribution function (RDF) and local bond orientational order parameters (LBOO).

  9. Nucleation of hcp and fcc phases in bcc iron under uniform compression: classical molecular dynamics simulations.

    PubMed

    Wang, B T; Shao, J L; Zhang, G C; Li, W D; Zhang, P

    2010-11-03

    By classical molecular dynamics simulations employing an embedded atom method potential, we have simulated the bcc to hcp/fcc structural transition in single-crystal iron under uniform compression. Results showed that the transition pressure is different from uniaxial compression and shock loading. The transformation occurs on a picosecond timescale and the transition time decreases along with the increase of pressure. The nucleation and growth of the hcp and fcc phases under constant pressure and temperature are analyzed in detail. The nucleation planes, all belonging to the {110}(bcc) family and parallel to the three compression directions [100], [010], and [001], have been observed. About 20% bcc atoms have transformed to fcc phase under pressure just over the critical point, and under higher pressure the fraction of the fcc phase increases steadily to exceed that of the hcp phase. We have investigated the transition mechanism of iron from initial bcc to hcp/fcc and found that the transition mainly consists of compression, rotation, and shuffle.

  10. Quantum Nucleation of Phase Slips in a 1D Model of a Superfluid

    SciTech Connect

    Freire, J.A.; Arovas, D.P.; Levine, H.

    1997-12-01

    We use a 1D model of a superfluid based on the Gross-Pitaevskii Lagrangian to illustrate a general numerical method designed to find quantum tunneling rates in extended bosonic systems. Specifically, we study flow past an obstacle and directly solve the imaginary time dynamics to find the {open_quotes}bounce{close_quotes} solution connected with the decay of the metastable laminar state via phase slip nucleation. The action for the tunneling configuration goes to zero at the threshold (in superfluid velocity) for classical production of these slips. Applications to other processes are briefly discussed. {copyright} {ital 1997} {ital The American Physical Society}

  11. Detached Melt Nucleation during Diffusion Brazing of a Technical Ni-based Superalloy: A Phase-Field Study

    NASA Astrophysics Data System (ADS)

    Böttger, B.; Apel, M.; Laux, B.; Piegert, S.

    2015-06-01

    Advanced solidification processes like welding, soldering, and brazing are often characterized by their specific solidification conditions. But they also may include different types of melting processes which themselves are strongly influenced by the initial microstructures and compositions of the applied materials and therefore are decisive for the final quality and mechanical properties of the joint. Such melting processes are often not well- understood because - compared to other fields of solidification science - relatively little research has been done on melting by now. Also, regarding microstructure simulation, melting has been strongly neglected in the past, although this process is substantially different from solidification due to the reversed diffusivities of the involved phases. In this paper we present phase-field simulations showing melting, solidification and precipitation of intermetallic phases during diffusion brazing of directionally solidified and heat-treated high-alloyed Ni- based gas turbine blade material using different boron containing braze alloys. Contrary to the common belief, melting of the base material is not always planar and can be further accompanied by detached nucleation and growth of a second liquid phase inside the base material leading to polycrystalline morphologies of the joint after solidification. These findings are consistent with results from brazed laboratory samples, which were characterized by EDX and optical microscopy, and can be explained in terms of specific alloy thermodynamics and inter-diffusion kinetics. Consequences of the gained new understanding for brazing of high- alloyed materials are discussed.

  12. An Effective Continuum Model for the Liquid-to-Gas Phase Change in a Porous Medium Driven by Solute Diffusion: II. Constant Liquid Withdrawal Rates

    SciTech Connect

    Tsimpanogiannis, Ioannis N.; Yortsos, Yanis C.

    2001-08-15

    This report describes the development of an effective continuum model to describe the nucleation and subsequent growth of a gas phase from a supersaturated, slightly compressible binary liquid in a porous medium, driven by solute diffusion.This report also focuses on the processes resulting from the withdrawal of the liquid at a constant rate. As before, the model addresses two stages before the onset of bulk gas flow, nucleation and gas phase growth. Because of negligible gradients due to gravity or viscous forces, the critical gas saturation, is only a function of the nucleation fraction.

  13. Report on the Implementation of Homogeneous Nucleation Scheme in MARMOT-based Phase Field Simulation

    SciTech Connect

    Li, Yulan; Hu, Shenyang Y.; Sun, Xin

    2013-09-30

    In this report, we summarized our effort in developing mesoscale phase field models for predicting precipitation kinetics in alloys during thermal aging and/or under irradiation in nuclear reactors. The first part focused on developing a method to predict the thermodynamic properties of critical nuclei such as the sizes and concentration profiles of critical nuclei, and nucleation barrier. These properties are crucial for quantitative simulations of precipitate evolution kinetics with phase field models. Fe-Cr alloy was chosen as a model alloy because it has valid thermodynamic and kinetic data as well as it is an important structural material in nuclear reactors. A constrained shrinking dimer dynamics (CSDD) method was developed to search for the energy minimum path during nucleation. With the method we are able to predict the concentration profiles of the critical nuclei of Cr-rich precipitates and nucleation energy barriers. Simulations showed that Cr concentration distribution in the critical nucleus strongly depends on the overall Cr concentration as well as temperature. The Cr concentration inside the critical nucleus is much smaller than the equilibrium concentration calculated by the equilibrium phase diagram. This implies that a non-classical nucleation theory should be used to deal with the nucleation of Cr precipitates in Fe-Cr alloys. The growth kinetics of both classical and non-classical nuclei was investigated by the phase field approach. A number of interesting phenomena were observed from the simulations: 1) a critical classical nucleus first shrinks toward its non-classical nucleus and then grows; 2) a non-classical nucleus has much slower growth kinetics at its earlier growth stage compared to the diffusion-controlled growth kinetics. 3) a critical classical nucleus grows faster at the earlier growth stage than the non-classical nucleus. All of these results demonstrated that it is critical to introduce the correct critical nuclei into phase

  14. Nucleation of the BCC phase from disorder in a diblock copolymer melt: Testing approximate theories through simulation

    NASA Astrophysics Data System (ADS)

    Spencer, Russell K. W.; Curry, Paul F.; Wickham, Robert A.

    2016-10-01

    We examine nucleation of the stable body-centred-cubic (BCC) phase from the metastable uniform disordered phase in an asymmetric diblock copolymer melt. Our comprehensive, large-scale simulations of the time-dependent, mean-field Landau-Brazovskii model find that spherical droplets of the BCC phase nucleate directly from disorder. Near the order-disorder transition, the critical nucleus is large and has a classical profile, attaining the bulk BCC phase in an interior that is separated from disorder by a sharp interface. At greater undercooling, the amplitude of BCC order in the interior decreases and the nucleus interface broadens, leading to a diffuse critical nucleus. This diffuse nucleus becomes large as the simulation approaches the disordered phase spinodal. We show that our simulation follows the same nucleation pathway that Cahn and Hilliard found for an incompressible two-component fluid, across the entire metastable region. In contrast, a classical nucleation theory calculation based on the free energy of a planar interface between coexisting BCC and disordered phases agrees with simulation only in the limit of very small undercooling; we can expand this region of validity somewhat by accounting for the curvature of the droplet interface. A nucleation pathway involving a classical droplet persists, however, to deep undercooling in our simulation, but this pathway is energetically unfavourable. As a droplet grows in the simulation, its interface moves with a constant speed, and this speed is approximately proportional to the undercooling.

  15. Nucleation of the BCC phase from disorder in a diblock copolymer melt: Testing approximate theories through simulation.

    PubMed

    Spencer, Russell K W; Curry, Paul F; Wickham, Robert A

    2016-10-14

    We examine nucleation of the stable body-centred-cubic (BCC) phase from the metastable uniform disordered phase in an asymmetric diblock copolymer melt. Our comprehensive, large-scale simulations of the time-dependent, mean-field Landau-Brazovskii model find that spherical droplets of the BCC phase nucleate directly from disorder. Near the order-disorder transition, the critical nucleus is large and has a classical profile, attaining the bulk BCC phase in an interior that is separated from disorder by a sharp interface. At greater undercooling, the amplitude of BCC order in the interior decreases and the nucleus interface broadens, leading to a diffuse critical nucleus. This diffuse nucleus becomes large as the simulation approaches the disordered phase spinodal. We show that our simulation follows the same nucleation pathway that Cahn and Hilliard found for an incompressible two-component fluid, across the entire metastable region. In contrast, a classical nucleation theory calculation based on the free energy of a planar interface between coexisting BCC and disordered phases agrees with simulation only in the limit of very small undercooling; we can expand this region of validity somewhat by accounting for the curvature of the droplet interface. A nucleation pathway involving a classical droplet persists, however, to deep undercooling in our simulation, but this pathway is energetically unfavourable. As a droplet grows in the simulation, its interface moves with a constant speed, and this speed is approximately proportional to the undercooling.

  16. Aerosol Inflluence on Ice Nucleation via the Immersion Mode in Mixed-Phase Arctic Stratiform Clouds

    NASA Astrophysics Data System (ADS)

    de Boer, G.; Hashino, T.; Tripoli, G. J.; Eloranta, E. W.

    2009-12-01

    Mixed-phase stratiform clouds are commonly observed at high latitudes (e.g. Shupe et al., 2006; de Boer et al., 2009a). Herman and Goody (1976), as well as Curry et al. (1996) present summaries of Arctic cloud climatologies that show low altitude stratus frequencies of up to 70% during transitional seasons. In addition to their frequent occurrence, these clouds have significant impacts on the near-surface atmospheric radiative budget, with estimates of wintertime reductions in net surface cooling of 40-50 Wm-2 (Curry et al., 1996) due predominantly to liquid in the mixed-phase layer. Both observational and modeling studies (e.g. Harrington et al., 1999; Jiang et al., 2000; Shupe et al., 2008; Klein et al., 2008) show a strong connection between the amount of ice present and the lifetime of the liquid portion of the cloud layer. This is thought to occur via the Bergeron-Findeissen mechanism (Pruppacher and Klett, 1997) in which ice grows at the expense of liquid due to its lower saturation vapor pressure. Unfortunately, the mechanisms by which ice is nucleated within these mixed-phase layers are not yet fully understood, and therefore an accurate depiction of this process for mixed-phase stratiform clouds has not yet been characterized. The nucleation mechanisms that are active in a given environment are sensitive to aerosol properties. Insoluble particles are typically good nuclei for ice particle formation, while soluble particles are typically better at nucleating water droplets. Aerosol observations from the Arctic often show mixed aerosol particles that feature both soluble and insoluble mass (Leaitch et al., 1984). Soluble mass fractions for these particles have been shown to be high, with estimates of 60-80% and are often made up of sulfates (Zhou et al., 2001; Bigg and Leck, 2001). It is believed that a significant portion of this sulfate mass comes from dimethyl sulfide (DMS) production in the Arctic Ocean and subsequent atmospheric oxidation. Since these

  17. PHASE-FIELD SIMULATION OF IRRADIATED METALS: PART II: GAS BUBBLE KINETICS

    SciTech Connect

    Paul C Millett; Anter El-Azab

    2011-01-01

    We present a phase-field model for inert gas bubble formation and evolution in irradiated metals. The model evolves vacancy, self-interstitial, and fission gas atoms through a coupled set of Cahn-Hilliard and Allen-Cahn equations, capturing the processes of defect generation, recombination, annihilation at GB sinks, as well as intragranular and intergranular bubble nucleation and growth in polycrystalline microstructures. Illustrative results are presented that characterize bubble growth and shrinkage, as well as the bubble density, size and nucleation rate as a function of varying irradiation conditions. Finally, intergranular bubble characteristics such as shape, pinning energy on GB motion, and bubble density are investigated.

  18. Studies of Nucleation and Growth, Specific Heat and Viscosity of Undercooled Melts of Quasicrystals and Polytetrahedral-Phase-Forming Alloys

    NASA Technical Reports Server (NTRS)

    Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rogers, J. R.; Robinson, M. B.; Rathz, T. J.; Krishnan, S.; Curreri, Peter A. (Technical Monitor)

    2002-01-01

    The local atomic structures of undercooled liquid metals are presumed to be icosahedral; this order is incompatible with translational periodicity, constituting a barrier to the nucleation of the crystal phase. The extended atomic structure of the icosahedral quasicrystal (i-phase) is similar to that presumed in the undercooled liquid. Therefore, a comparison of the maximum undercooling in alloys that form the i-phase with those that form crystal phases provides a probe of the liquid structure.

  19. Thermostability analysis of line-tension-associated nucleation at a gas-liquid interface

    NASA Astrophysics Data System (ADS)

    Singha, Sanat Kumar; Das, Prasanta Kumar; Maiti, Biswajit

    2017-01-01

    The influence of line tension on the thermostability of a droplet nucleated from an oversaturated vapor at the interface of the vapor and another immiscible liquid is investigated. Along with the condition of mechanical equilibrium, the notion of extremization of the reversible work of formation is considered to obtain the critical parameters related to heterogeneous nucleation. From the energetic formulation, the critical reversible work of formation is found to be greater than that of homogeneous nucleation for high value of the positive line tension. On the other hand, for high value of the negative line tension, the critical reversible work of formation becomes negative. Therefore, these thermodynamic instabilities under certain substrate wettability situations necessitate a free-energetics-based stability of the nucleated droplet, because the system energy is not minimized under these conditions. This thermostability is analogous to the transition-based stability proposed by Widom [B. Widom, J. Phys. Chem. 99, 2803 (1995)], 10.1021/j100009a041 in the case of partial wetting phenomena along with the positive line tension. The thermostability analysis limits the domain of the solution space of the present critical-value problem as the thermodynamic transformation in connection with homogeneous and workless nucleation is considered. Within the stability range of the geometry-based wetting parameters, three limiting modes of nucleation, i.e., total-dewetting-related homogeneous nucleation, and total-wetting-associated and total-submergence-associated workless nucleation scenarios, are identified. Either of the two related limiting wetting scenarios of workless nucleation, namely, total wetting and total submergence, is found to be favorable depending on the geometry-based wetting conditions. The line-tension-associated nucleation on a liquid surface can be differentiated from that on a rigid substrate, as in the former, the stability based on mechanical

  20. Studies of Nucleation and Growth, Specific Heat and Viscosity of Undercooled Melts of Quasicrystal and Polytetrahedral-Phase Forming Alloys

    NASA Technical Reports Server (NTRS)

    Kelton, K. F.; Gangopadhyay, Anup K.; Lee, G. W.; Hyers, Robert W.; Rathz, T. J.; Robinson, Michael B.; Rogers, Jan R.

    2003-01-01

    From extensive ground based work on the phase diagram and undercooling studies of Ti-Zr-Ni alloys, have clearly identified the composition of three different phases with progressively increasing polytetrahedral order such as, (Ti/Zr), the C14 Laves phase, and the i-phase, that nucleate directly from the undercooled liquid. The reduced undercooling decreases progressively with increasing polytetrahedral order in the solid, supporting Frank s hypothesis. A new facility for direct measurements of the structures and phase transitions in undercooled liquids (BESL) was developed and has provided direct proof of the primary nucleation of a metastable icosahedral phase in some Ti-Zr-Ni alloys. The first measurements of specific heat and viscosity in the undercooled liquid of this alloy system have been completed. Other than the importance of thermo-physical properties for modeling nucleation and growth processes in these materials, these studies have also revealed some interesting new results (such as a maximum of C(sup q, sub p) in the undercooled state). These ground-based results have clearly established the necessary background and the need for conducting benchmark nucleation experiments at the ISS on this alloy system.

  1. Ice nucleation by different types of soil dusts under mixed-phase cloud conditions: Laboratory studies and atmospheric implications

    NASA Astrophysics Data System (ADS)

    Tobo, Y.; DeMott, P. J.; Hill, T. C. J.; Prenni, A. J.; Swoboda-Colberg, N. G.; Franc, G. D.; Kreidenweis, S. M.

    2014-12-01

    It has been suggested that ice nucleation by desert soil dusts composed largely of minerals plays an important role in forming ice crystals in mixed-phase clouds and subsequent precipitation. More recently, several studies have suggested that soil dusts having higher contents of soil organic matter (SOM) may also contribute significantly to atmospheric ice nucleation. In this study, we examine the ice nucleation properties of soil dusts derived from different locations in the world. Our results show that the ice nucleating ability of agricultural soil dusts derived from the largest dust source regions in North America is almost comparable to that of desert soil dusts at temperatures colder than about -15°C. We also confirm that the agricultural soil dusts can serve as effective ice nuclei (IN) at much warmer temperatures. On the other hand, our results indicate that the ice nucleating ability of the agricultural soil dusts is significantly reduced after H2O2 digestion, while the reduction is not significant for the desert soil dusts. In this regard, based on single particle analysis, we demonstrate that such a significant reduction observed in the agricultural soil dusts is mainly attributable to the removal of organic-rich particles (namely, SOM particles), which have much higher ice nucleating ability than mineral particles. Moreover, we discuss the potential contributions of these soil dusts to atmospheric IN populations.

  2. The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation of Ordered Phases

    NASA Technical Reports Server (NTRS)

    Curreri, Peter A. (Technical Monitor); Kelton, K. F.; Gangopadhyay, A.; Lee, G. W.; Hyers, R. W.; Rathz, R. J.; Rogers, J.; Schenk, T.; Simonet, V.; Holland-Moritz, D.

    2003-01-01

    Over fifty years ago, David Turnbull showed that the temperature of many metallic liquids could be decreased far below their equilibrium melting temperature before crystallization occurred. To explain those surprising results, Charles Frank hypothesized that the local structures of undercooled metallic liquids are different from those of crystal phases, containing a significant degree of icosahedral order that is incompatible with extended periodicity. Such structural differences must create a barrier to the formation crystal phases, explaining the observed undercooling behavior. If true, the nucleation from the liquid of phases with extended icosahedral order should be easier. Icosahedral order is often favored in small clusters, as observed recently in liquid-like clusters of pure Pb on the (111) surface of Si, for example. However, it has never been shown that an increasing preference for icosahedral phase formation can be directly linked with the development of icosahedral order in the undercooled liquid. Owing to the combination of very recent advances in levitation techniques and the availability of synchrotron x-ray and high flux neutron facilities, this is shown here.

  3. The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation of Ordered Phases

    NASA Technical Reports Server (NTRS)

    Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.; Robinson, M. B.; Schenk, T.; Simonet, V.; Holland-Moritz, D.; Curreri, Peter A. (Technical Monitor)

    2002-01-01

    Over fifty years ago, David Turnbull showed that the temperature of many metallic liquids could be decreased far below their equilibrium melting temperature before crystallization occurred. To explain those surprising results, Charles Frank hypothesized that the local structures of undercooled metallic liquids are different from those of crystal phases, containing a significant degree of icosahedral order that is incompatible with extended periodicity. Such structural differences must create a barrier to the formation crystal phases, explaining the observed undercooling behavior. If true, the nucleation from the liquid of phases with extended icosahedral order should be easier. Icosahedral order is often favored in small clusters, as observed recently in liquid-like clusters of pure Pb on the (111) surface of Si(3), for example. However, it has never been shown that an increasing preference for icosahedral phase formation can be directly linked with the development of icosahedral order in the undercooled liquid. Owing to the combination of very recent advances in levitation techniques and the availability of synchrotron X-ray and high flux neutron facilities.

  4. The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation Behavior of Ordered Phases

    NASA Technical Reports Server (NTRS)

    Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.; Robinson, M. B.; Schenk, T.; Simonet, V.

    2003-01-01

    Over fifty years ago, David Turnbull showed that the temperature of many metallic liquids could be decreased far below their equilibrium melting temperature before crystallization occurred. To explain those surprising results, Charles Frank hypothesized that the local structures of undercooled metallic liquids are different from those of crystal phases, containing a significant degree of icosahedral order that is incompatible with extended periodicity. Such structural differences must create a barrier to the formation crystal phases, explaining the observed undercooling behavior. If true, the nucleation from the liquid of phases with extended icosahedral order should be easier. Icosahedral order is often favored in small clusters, as observed recently in liquid-like clusters of pure Pb on the (111) surface of Si[3], for example. However, it has never been shown that an increasing preference for icosahedral phase formation can be directly linked with the development of icosahedral order in the undercooled liquid. Owing to the combination of very recent advances in levitation techniques and the availability of synchrotron x-ray and high flux neutron facilities, this is shown here.

  5. Evidence of phase nucleation during olivine diffusion creep: A new perspective for mantle strain localisation

    NASA Astrophysics Data System (ADS)

    Précigout, Jacques; Stünitz, Holger

    2016-12-01

    For the past decades, grain size reduction leading to diffusion creep in olivine is believed to be a very important process for strain localisation in the lithospheric mantle. However, the mechanisms of grain size reduction in this regime are still poorly understood (e.g., Platt, 2015). Here we show new experimental results that document grain size reduction and material weakening during wet olivine diffusion creep. While occurring for both, mono-phase and two-phase aggregates, grain size reduction is coeval with strain localisation and local phase mixing in olivine-pyroxene aggregates. Based on evidence of fluid inclusions and cracks filled with a fine-grained phase mixture, we conclude that grain size reduces as a result of fluid-assisted nucleation that takes place in the presence of an aqueous fluid during diffusion creep. Cavitation induced by grain boundary sliding (creep cavitation) can be inferred, and may play a critical role for olivine grain size reduction. Amongst their implications for rock rheology in general, our findings highlight a key process for strain localisation in the ductile uppermost mantle.

  6. Distinct Nucleation and Propagation Phases of Northern Cascadia Episodic Tremor and Slip Events

    NASA Astrophysics Data System (ADS)

    Ulberg, C.; Creager, K. C.

    2013-12-01

    Northern Cascadia episodic tremor and slip (ETS) events appear to have distinct nucleation and propagation phases. We find that there is a roughly linear increase in tremor amplitude over the first ~5 days of each ETS event. We observe a corresponding linear increase in the areal distribution of tremor. These episodes typically initiate down dip, and after approximately 5 days have organized and migrated to fill the up-dip/down-dip width of the tremorgenic zone. After this time, tremor amplitudes vary wildly, modulated by tidal stresses, as the tremor propagates along strike in one or both directions at roughly 8 km/day, continuing for 4-5 weeks. Inter-ETS tremor swarms can begin similarly to ETS events, but do not reach the maximum area and amplitude of ETS events, and instead die away in less than 5-10 days. Since the increase in tremor amplitude during the nucleation phase is proportional to the increase in tremoring area, the source amplitude per unit area is approximately constant, indicating a constant radiated energy rate per unit area associated with tremor. In order to estimate tremor amplitude we use three-component seismograms from temporary deployments and permanent stations (Array of Arrays, CAFE, PNSN, TA) to estimate the amplitude of tremor bursts at the source location, using a method similar to Maeda and Obara (JGR, 2009). Source amplitude, or radiated energy rate, is proportional to the root-mean square of band limited (1.5-5.5 Hz) ground velocity for each 5-minute window. Station ground velocities and tremor locations, determined by a waveform envelope cross-correlation method (Wech and Creager, GRL, 2008), are inverted to obtain source amplitude and station statics, taking into account geometrical spreading and attenuation. The result is a catalog of source amplitudes for each of 40,000 tremor locations in northern Cascadia from 2006 to 2011.

  7. Rate processes in gas phase

    NASA Technical Reports Server (NTRS)

    Hansen, C. F.

    1983-01-01

    Reaction-rate theory and experiment are given a critical review from the engineers' point of view. Rates of heavy-particle, collision-induced reaction in gas phase are formulated in terms of the cross sections and activation energies for reaction. The effect of cross section function shape and of excited state contributions to reaction both cause the slope of Arrhenius plots to differ from the true activation energy, except at low temperature. The master equations for chemically reacting gases are introduced, and dissociation and ionization reactions are shown to proceed primarily from excited states about kT from the dissociation or ionization limit. Collision-induced vibration, vibration-rotation, and pure rotation transitions are treated, including three-dimensional effects and conservation of energy, which have usually been ignored. The quantum theory of transitions at potential surface crossing is derived, and results are found to be in fair agreement with experiment in spite of some questionable approximations involved.

  8. Polymorphism, crystal nucleation and growth in the phase-field crystal model in 2D and 3D

    NASA Astrophysics Data System (ADS)

    Tóth, Gyula I.; Tegze, György; Pusztai, Tamás; Tóth, Gergely; Gránásy, László

    2010-09-01

    We apply a simple dynamical density functional theory, the phase-field crystal (PFC) model of overdamped conservative dynamics, to address polymorphism, crystal nucleation, and crystal growth in the diffusion-controlled limit. We refine the phase diagram for 3D, and determine the line free energy in 2D and the height of the nucleation barrier in 2D and 3D for homogeneous and heterogeneous nucleation by solving the respective Euler-Lagrange (EL) equations. We demonstrate that, in the PFC model, the body-centered cubic (bcc), the face-centered cubic (fcc), and the hexagonal close-packed structures (hcp) compete, while the simple cubic structure is unstable, and that phase preference can be tuned by changing the model parameters: close to the critical point the bcc structure is stable, while far from the critical point the fcc prevails, with an hcp stability domain in between. We note that with increasing distance from the critical point the equilibrium shapes vary from the sphere to specific faceted shapes: rhombic dodecahedron (bcc), truncated octahedron (fcc), and hexagonal prism (hcp). Solving the equation of motion of the PFC model supplied with conserved noise, solidification starts with the nucleation of an amorphous precursor phase, into which the stable crystalline phase nucleates. The growth rate is found to be time dependent and anisotropic; this anisotropy depends on the driving force. We show that due to the diffusion-controlled growth mechanism, which is especially relevant for crystal aggregation in colloidal systems, dendritic growth structures evolve in large-scale isothermal single-component PFC simulations. An oscillatory effective pair potential resembling those for model glass formers has been evaluated from structural data of the amorphous phase obtained by instantaneous quenching. Finally, we present results for eutectic solidification in a binary PFC model.

  9. Studies of Nucleation, Growth, Specific Heat, and Viscosity of Undercooled Melts of Quasicrystals and Polytetrahedral-Phase-Forming Alloys

    NASA Technical Reports Server (NTRS)

    Kelton, K. F.; Croat, T. K.; Gangopadhyay, A.; Holland-Moritz, D.; Hyers, Robert W.; Rathz, Thomas J.; Robinson, Michael B.; Rogers, Jan R.

    2001-01-01

    Undercooling experiments and thermal physical property measurements of metallic alloys on the International Space Station (ISS) are planned. This recently-funded research focuses on fundamental issues of the formation and structure of highly-ordered non-crystallographic phases (quasicrystals) and related crystal phases (crystal approximants), and the connections between the atomic structures of these phases and those of liquids and glasses. It extends studies made previously by us of the composition dependence of crystal nucleation processes in silicate and metallic glasses, to the case of nucleation from the liquid phase. Motivating results from rf-levitation and drop-tube measurements of the undercooling of Ti/Zr-based liquids that form quasicrystals and crystal approximants are discussed. Preliminary measurements by electrostatic levitation (ESL) are presented.

  10. 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.

  11. 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.

  12. Reduced sediment melting at 7.5-12 GPa: phase relations, geochemical signals and diamond nucleation

    NASA Astrophysics Data System (ADS)

    Brey, G. P.; Girnis, A. V.; Bulatov, V. K.; Höfer, H. E.; Gerdes, A.; Woodland, A. B.

    2015-08-01

    ( D > 1). Aragonite and Fe-Mg carbonate have very different REE partition coefficients ( D Mst-Sd/L ~ 0.01 and D Arg/L ~ 1). Nb, Ta, Zr and Hf are strongly incompatible in both carbonates. The bearthite/melt partition coefficients are very high for LREE (>10) and decrease to ~1 for HREE. All HFSE are strongly incompatible in bearthite. In contrast, Ta, Nb, Zr and Hf are moderately to strongly compatible in ZrSiO4 and TiO2 phases. Based on the obtained partition coefficients, the composition of a mobile phase derived by sediment melting in deep subduction zones was calculated. This phase is strongly enriched in incompatible elements and displays a pronounced negative Ta-Nb anomaly but no Zr-Hf anomaly. Although all experiments were conducted in the diamond stability field, only graphite was observed in low-temperature experiments. Spontaneous diamond nucleation and the complete transformation of graphite to diamond were observed at temperatures above 1200-1300 °C. We speculate that the observed character of graphite-diamond transformation is controlled by relationships between the kinetics of metastable graphite dissolution and diamond nucleation in a hydrous silicocarbonate melt that is oversaturated in C.

  13. Gas phase kinetics during normal combustion

    NASA Technical Reports Server (NTRS)

    Price, C. F.; Boggs, T. L.; Eisel, J. L.; Atwood, A. I.; Zurn, D. E.

    1980-01-01

    The role of gas phase kinetics during combustion was explored in the steady state modeling efforts and in the analysis of ignition phenomena. In both cases it was shown that the combustion characteristics of some high energy ingredients and propellants are strongly affected, if not dictated, by the gas phase reactions which take place.

  14. Investigation of the Seismic Nucleation Phase of Large Earthquakes Using Broadband Teleseismic Data

    NASA Astrophysics Data System (ADS)

    Burkhart, Eryn Therese

    The dynamic motion of an earthquake begins abruptly, but is often initiated by a short interval of weak motion called the seismic nucleation phase (SNP). Ellsworth and Beroza [1995, 1996] concluded that the SNP was detectable in near-source records of 48 earthquakes with moment magnitude (Mw), ranging from 1.1 to 8.1. They found that the SNP accounted for approximately 0.5% of the total moment and 1/6 of the duration of the earthquake. Ji et al [2010] investigated the SNP of 19 earthquakes with Mw greater than 8.0 using teleseismic broadband data. This study concluded that roughly half of the earthquakes had detectable SNPs, inconsistent with the findings of Ellsworth and Beroza [1995]. Here 69 earthquakes of Mw 7.5-8.0 from 1994 to 2011 are further examined. The SNP is clearly detectable using teleseismic data in 32 events, with 35 events showing no nucleation phase, and 2 events had insufficient data to perform stacking, consistent with the previous analysis. Our study also reveals that the percentage of the SNP events is correlated with the focal mechanism and hypocenter depths. Strike-slip earthquakes are more likely to exhibit a clear SNP than normal or thrust earthquakes. Eleven of 14 strike-slip earthquakes (78.6%) have detectable NSPs. In contrast, only 16 of 40 (40%) thrust earthquakes have detectable SNPs. This percentage also became smaller for deep events (33% for events with hypocenter depth>250 km). To understand why certain thrust earthquakes have a visible SNP, we examined the sediment thickness, age, and angle of the subducting plate of all thrust earthquakes in the study. We found that thrust events with shallow (600 m) on the subducting plate tend to have clear SNPs. If the SNP can be better understood in the future, it may help seismologists better understand the rupture dynamics of large earthquakes. Potential applications of this work could attempt to predict the magnitude of an earthquake seconds before it begins by measuring the SNP, vastly

  15. Vapour–to–liquid nucleation: Nucleation theorems for nonisothermal–nonideal case

    SciTech Connect

    Malila, J.; McGraw, R.; Napari, I.; Laaksonen, A.

    2010-08-29

    Homogeneous vapour-to-liquid nucleation, a basic process of aerosol formation, is often considered as a type example of nucleation phenomena, while most treatment of the subject introduce several simplifying assumptions (ideal gas phase, incompressible nucleus, isothermal kinetics, size-independent surface free energy...). During last decades, nucleation theorems have provided new insights into properties of critical nuclei facilitating direct comparison between laboratory experiments and molecular simulations. These theorems are, despite of their generality, often applied in forms where the aforementioned assumptions are made. Here we present forms of nucleation theorems that explicitly take into account these effects and allow direct estimation of their importance. Only assumptions are Arrhenius-type kinetics of nucleation process and exclusion carrier gas molecules from the critical nucleus.

  16. Global model comparison of heterogeneous ice nucleation parameterizations in mixed phase clouds

    NASA Astrophysics Data System (ADS)

    Yun, Yuxing; Penner, Joyce E.

    2012-04-01

    A new aerosol-dependent mixed phase cloud parameterization for deposition/condensation/immersion (DCI) ice nucleation and one for contact freezing are compared to the original formulations in a coupled general circulation model and aerosol transport model. The present-day cloud liquid and ice water fields and cloud radiative forcing are analyzed and compared to observations. The new DCI freezing parameterization changes the spatial distribution of the cloud water field. Significant changes are found in the cloud ice water fraction and in the middle cloud fractions. The new DCI freezing parameterization predicts less ice water path (IWP) than the original formulation, especially in the Southern Hemisphere. The smaller IWP leads to a less efficient Bergeron-Findeisen process resulting in a larger liquid water path, shortwave cloud forcing, and longwave cloud forcing. It is found that contact freezing parameterizations have a greater impact on the cloud water field and radiative forcing than the two DCI freezing parameterizations that we compared. The net solar flux at top of atmosphere and net longwave flux at the top of the atmosphere change by up to 8.73 and 3.52 W m-2, respectively, due to the use of different DCI and contact freezing parameterizations in mixed phase clouds. The total climate forcing from anthropogenic black carbon/organic matter in mixed phase clouds is estimated to be 0.16-0.93 W m-2using the aerosol-dependent parameterizations. A sensitivity test with contact ice nuclei concentration in the original parameterization fit to that recommended by Young (1974) gives results that are closer to the new contact freezing parameterization.

  17. Hydrated metal ions in the gas phase.

    PubMed

    Beyer, Martin K

    2007-01-01

    Studying metal ion solvation, especially hydration, in the gas phase has developed into a field that is dominated by a tight interaction between experiment and theory. Since the studied species carry charge, mass spectrometry is an indispensable tool in all experiments. Whereas gas-phase coordination chemistry and reactions of bare metal ions are reasonably well understood, systems containing a larger number of solvent molecules are still difficult to understand. This review focuses on the rich chemistry of hydrated metal ions in the gas phase, covering coordination chemistry, charge separation in multiply charged systems, as well as intracluster and ion-molecule reactions. Key ideas of metal ion solvation in the gas phase are illustrated with rare-gas solvated metal ions.

  18. Combining Novel Simulation Methods and Nucleation Theory to Uncover the Secrets of Gas Hydrates

    SciTech Connect

    Keyes, Thomas

    2016-04-14

    Conventional computer simulation methods fail for some of the most important problems. With the design and application of innovative algorithms, this project achieved a breakthrough for the case of systems undergoing first-order phase transitions. We gave a complete simulation protocol based upon a well optimized version of our "generalized replica exchange method". The transition of primary interest was gas hydrate formation, a process of significance for climate science and natural gas retrieval. Since hydrates consist of guest molecules in the cages of a water matrix, β ice, the freezing and melting of water was also studied. New information was uncovered about the transition pathways and thermodynamics. Some highlights are 1. the finding that in a very dilute solution without deep supercooling, representative of real-world conditions and very challenging to conventional algorithms, methane can act as a catalyst to drive the formation of large amounts of β ice with empty cages as metastable intermediates, which might be filled by additional methane in a mechanism for hydrate formation, and 2. illumination of the role of metastable cubic ice in water freezing, with determination of the surface tensions of the cubic, hexagonal, and β ices, and the free energy difference of cubic vs hexagonal ice. Work was begun on lipid systems, bilayers and nanoreactors promising for energy-related photoreductions, and targets for future research. Our methods yielded what is arguably the most complete description of the composite lipid/water phases and the transition pathways among them.

  19. Gas bubble nucleation and tritium permeation through metallic walls in a liquid 83Pb-17Li blanket

    SciTech Connect

    Carta, R.; Dernini, S.; Polcaro, A.M.; Ricci, P.F.; Tola, G.; Pierini, G.

    1989-01-01

    Recent studies have given lower and lower values for the solubility of hydrogen isotopes in the eutectic 83Pb-17Li alloy, a candidate breeding material for the blanket of fusion machines. Therefore, thermodynamic stability for the gaseous phase under the high pressure reached at the bottom of the alloy containers can be achieved even for very low tritium concentrations in the liquid phase. A mathematical model to determine when tritium bubble nucleation occurs at an appreciable rate is presented. This model is used to predict tritium production behavior in the next European Torus (NET) tokamak.

  20. The effects of grain size distribution on cavity nucleation and creep deformation in ceramics containing viscous grain boundary phase

    SciTech Connect

    Dey, N.; Hsia, K.J.; Socie, D.F.

    1997-10-01

    The grain size distribution in a polycrystalline ceramic material is not uniform. Such microstructural inhomogeneity may give rise to nonuniform local stress distributions. Here the authors investigate the effect of grain size distribution on the generation of local stress concentration in ceramic materials creeping by localized flow of a viscous grain boundary phase. A simple bimodal grain size distribution is first considered. The critical stress for cavity nucleation, calculated using classical Becker-Doring nucleation theory, is compared with the local stress concentration. The results show that, because of the inhomogeneity, the local stress in the grain boundary viscous phase at the locations of large grains can exceed the critical stress for cavity nucleation. The creep rate due to localized viscous flow of the grain boundary phase and cavity growth is evaluated. Although the creep behavior owing solely to viscous flow is linear with respect to applied stress, it can be highly nonlinear when cavitation occurs. Moreover, as an example, the model has been used to study creep behavior of a whisker-reinforced Si{sub 3}N{sub 4} matrix composite in which long whiskers are surrounded by small equiaxed ceramic grains.

  1. Nucleation mechanism of nano-sized NaZn13-type and α-(Fe,Si) phases in La-Fe-Si alloys during rapid solidification

    NASA Astrophysics Data System (ADS)

    Hou, Xue-Ling; Xue, Yun; Liu, Chun-Yu; Xu, Hui; Han, Ning; Ma, Chun-Wei; Phan, Manh-Huong

    2015-03-01

    The nucleation mechanism involving rapid solidification of undercooled La-Fe-Si melts has been studied experimentally and theoretically. The classical nucleation theory-based simulations show a competitive nucleation process between the α-(Fe,Si) phase (size approximately 10 to 30 nm) and the cubic NaZn13-type phase (hereinafter 1:13 phase, size approximately 200 to 400 nm) during rapid solidification, and that the undercooled temperature change ∆ T plays an important factor in this process. The simulated results about the nucleation rates of the α-(Fe,Si) and 1:13 phases in La-Fe-Si ribbons fabricated by a melt-spinner using a copper wheel with a surface speed of 35 m/s agree well with the XRD, SEM, and TEM studies of the phase structure and microstructure of the ribbons. Our study paves the way for designing novel La-Fe-Si materials for a wide range of technological applications.

  2. Phase field theory of interfaces and crystal nucleation in a eutectic system of fcc structure: I. Transitions in the one-phase liquid region.

    PubMed

    Tóth, Gyula I; Gránásy, László

    2007-08-21

    The phase field theory (PFT) has been applied to predict equilibrium interfacial properties and nucleation barrier in the binary eutectic system Ag-Cu using double well and interpolation functions deduced from a Ginzburg-Landau expansion that considers fcc (face centered cubic) crystal symmetries. The temperature and composition dependent free energies of the liquid and solid phases are taken from CALculation of PHAse Diagrams-type calculations. The model parameters of PFT are fixed so as to recover an interface thickness of approximately 1 nm from molecular dynamics simulations and the interfacial free energies from the experimental dihedral angles available for the pure components. A nontrivial temperature and composition dependence for the equilibrium interfacial free energy is observed. Mapping the possible nucleation pathways, we find that the Ag and Cu rich critical fluctuations compete against each other in the neighborhood of the eutectic composition. The Tolman length is positive and shows a maximum as a function of undercooling. The PFT predictions for the critical undercooling are found to be consistent with experimental results. These results support the view that heterogeneous nucleation took place in the undercooling experiments available at present. We also present calculations using the classical droplet model [classical nucleation theory (CNT)] and a phenomenological diffuse interface theory (DIT). While the predictions of the CNT with a purely entropic interfacial free energy underestimate the critical undercooling, the DIT results appear to be in a reasonable agreement with the PFT predictions.

  3. Thermodynamics and kinetics of binary nucleation in ideal-gas mixtures

    NASA Astrophysics Data System (ADS)

    Alekseechkin, Nikolay V.

    2015-08-01

    The nonisothermal single-component theory of droplet nucleation [N. V. Alekseechkin, Physica A 412, 186 (2014)] is extended to binary case; the droplet volume V, composition x, and temperature T are the variables of the theory. An approach based on macroscopic kinetics (in contrast to the standard microscopic model of nucleation operating with the probabilities of monomer attachment and detachment) is developed for the droplet evolution and results in the derived droplet motion equations in the space (V, x, T)—equations for V ˙ ≡ d V / d t , x ˙ , and T ˙ . The work W(V, x, T) of the droplet formation is obtained in the vicinity of the saddle point as a quadratic form with diagonal matrix. Also, the problem of generalizing the single-component Kelvin equation for the equilibrium vapor pressure to binary case is solved; it is presented here as a problem of integrability of a Pfaffian equation. The equation for T ˙ is shown to be the first law of thermodynamics for the droplet, which is a consequence of Onsager's reciprocal relations and the linked-fluxes concept. As an example of ideal solution for demonstrative numerical calculations, the o-xylene-m-xylene system is employed. Both nonisothermal and enrichment effects are shown to exist; the mean steady-state overheat of droplets and their mean steady-state enrichment are calculated with the help of the 3D distribution function. Some qualitative peculiarities of the nucleation thermodynamics and kinetics in the water-sulfuric acid system are considered in the model of regular solution. It is shown that there is a small kinetic parameter in the theory due to the small amount of the acid in the vapor and, as a consequence, the nucleation process is isothermal.

  4. Thermodynamics and kinetics of binary nucleation in ideal-gas mixtures.

    PubMed

    Alekseechkin, Nikolay V

    2015-08-07

    The nonisothermal single-component theory of droplet nucleation [N. V. Alekseechkin, Physica A 412, 186 (2014)] is extended to binary case; the droplet volume V, composition x, and temperature T are the variables of the theory. An approach based on macroscopic kinetics (in contrast to the standard microscopic model of nucleation operating with the probabilities of monomer attachment and detachment) is developed for the droplet evolution and results in the derived droplet motion equations in the space (V, x, T)—equations for V̇≡dV/dt, ẋ, and Ṫ. The work W(V, x, T) of the droplet formation is obtained in the vicinity of the saddle point as a quadratic form with diagonal matrix. Also, the problem of generalizing the single-component Kelvin equation for the equilibrium vapor pressure to binary case is solved; it is presented here as a problem of integrability of a Pfaffian equation. The equation for Ṫ is shown to be the first law of thermodynamics for the droplet, which is a consequence of Onsager's reciprocal relations and the linked-fluxes concept. As an example of ideal solution for demonstrative numerical calculations, the o-xylene-m-xylene system is employed. Both nonisothermal and enrichment effects are shown to exist; the mean steady-state overheat of droplets and their mean steady-state enrichment are calculated with the help of the 3D distribution function. Some qualitative peculiarities of the nucleation thermodynamics and kinetics in the water-sulfuric acid system are considered in the model of regular solution. It is shown that there is a small kinetic parameter in the theory due to the small amount of the acid in the vapor and, as a consequence, the nucleation process is isothermal.

  5. Quantification of gypsum crystal nucleation, growth, and breakage rates in a wet flue gas desulfurization pilot plant

    SciTech Connect

    Hansen, B.B.; Kiil, S.; Johnsson, J.E.

    2009-10-15

    The aim of this work is to study the influence of nucleation, growth and breakage on the particle size distribution (PSD) of gypsum crystals produced by the wet flue gas desulfurization (FGD) process. The steady state PSD, obtained in a falling film wet FGD pilot plant during desulfurization of a 1000 ppm(V) SO{sub 2} gas stream, displayed a strong nonlinear behaviour (in a ln(n(l)) vs. I plot) at the lower end of the particle size range, compared to the well-known linear mixed suspension mixed product removal model. A transient population balance breakage model, fitted to experimental data, was able to model an increase in the fraction of small particles, but not to the extent observed experimentally. A three-parameter, size-dependent growth model, previously used for sodium sulphate decahydrate and potash alum, was able to describe the experimental data, indicating either size-dependent integration kinetics or growth rate dispersion.

  6. Phase-Modulation Gas-Correlation Spectroscopy

    NASA Technical Reports Server (NTRS)

    Rider, David M.; Schofield, John T.; Margolis, Jack S.; Mccleese, Daniel J.

    1989-01-01

    Electro-optic phase-modulation gas-correlation spectroscopy demonstrated in laboratory tests promising candidate technique for remote sensing of gases, temperatures, and wind velocities in atmosphere. In technique radiation emitted by sample atmosphere passed through electro-optic phase modulator, and modulated and unmodulated versions of spectrum alternately passed through reference absorption cell containing gas to be detected. Radiation emerging from reference cell band-pass filtered and detected. Correlation signal is difference in intensity between phase-modulated and unmodulated detected signals.

  7. Nucleation, growth, and coarsening of crystalline domains in order-order transitions between lamellar and hexagonal phases.

    PubMed

    Ohnogi, H; Shiwa, Y

    2011-07-01

    Using the numerical solution of the time-dependent Ginzburg-Landau equation, we study the entire process of transformation between the lamellar and the hexagonal phases from the early-stage nucleation and growth to the late-stage coarsening regime. The metastable crystalline structure that nucleates first is identified in terms of the mean-field theory under the single-wave-number approximation. This has been borne out by the numerically efficient preparation of single-crystal structure developed via the noise-induced self-organization. We also present results for the scaling of the late-time domain growth, which is quantified by two measures: the structure factor and the orientational correlation function. In particular, the growth exponent is shown to be robust and indifferent to conservation of the order parameter.

  8. 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.

  9. Thermal phases of interstellar and quasar gas

    NASA Technical Reports Server (NTRS)

    Lepp, S.; Mccray, R.; Shull, J. M.; Woods, D. T.; Kallman, T.

    1985-01-01

    Interstellar gas may be in a variety of thermal phases, depending on how it is heated and ionized; here a unified picture of the equation of state of interstellar and quasar gas is presented for a variety of such mechanisms over a broad range of temperatures, densities, and column densities of absorbing matter. It is found that for select ranges of gas pressure, photoionizing flux, and heating, three thermally stable phases are allowed: coronal gas (T above 100,000 K); warm gas (T about 10,000 K); and cold gas (T less than 100 K). With attenuation of ultraviolet and X-ray radiation, the cold phase may undergo a transition to molecules. In quasar broad-line clouds, this transition occurs at column density N(H) = about 10 to the 23rd/sq cm and could result in warm molecular cores and observable emission from H2 and OH. The underlying atomic physics behind each of these phase transitions and their relevance to interstellar matter and quasars are discussed.

  10. Real Gas/Blunt Cone. Phase 2

    NASA Technical Reports Server (NTRS)

    Deiwert, George S.; Eitelberg, Georg

    1998-01-01

    In this chapter recent activity in real-gas database definition and code validation will be summarized. In the Phase I report of the Working Group (WG) 181, aerothermodynamic problems were classified, for purpose of discussion, into seven types: aerodynamic parameters, viscous/shock interaction, boundary-layer transition, forebody-heating/heat-transfer, radiation and ablation, lee and base-region flow, and low-density flow. Several of these problem types were the subject of various chapters of the Phase 1 report describing real-gas effects and ground test facility issues. In this chapter some background and objectives outlined in the real-Gas effects Chapter V of the Phase 1 report will be reviewed. The results of the blunt cone test campaign developed under the auspices of the WG18 activity to study real-gas phenomena will be summarized, including the experimental and computational programs, issues and questions, and recommendations. Further, recent progress in other real-gas areas beyond the blunt cone test campaign will be discussed. Finally, a summary in which the present status of our understanding of real-gas issues will be presented.

  11. Comment on vapor phase homogeneous nucleation of CH 3CN and the scaling law for onset supersaturation ratios

    NASA Astrophysics Data System (ADS)

    Hale, Barbara N.; Kelly, Brendan

    1992-01-01

    We point out that the scaling law for onset vapor phase nucleation, ln Sonset ≈ 0.53 [Ω( Tc/ T-1)] 3/2, with Ω = 1.77 (from CH 3CN surface tension data) predicts the temperature dependence and approximate magnitude of CH 3CN supersaturation ratio data, S. This is contrary to the conclusions of Wright, Caldwell and El-Shall who estimate too large a value (2.14) for Ω. We note that Ω, the excess molecular surface entropy/ k, is more reliably extracted from the temperature derivative of the surface tension data.

  12. Laser Studies of Gas Phase Radical Reactions.

    DTIC Science & Technology

    1989-01-01

    Acremonium chrysogenum , was prepared according to the published procedure [6]. This fungal enzyme had a specific activity of 0.023 IUmg1, and was estimated to...Dist-lbitionj Avdielbiity Codes jAvail atidjor Dist 6a A-I . p -1- Laser Studies of Gas Phase Radical Reactions G. Hancock Physical Chemistry...some additional experiments concerning the formation of carbene radicals in liquid phase enzyme cleavage studies are described. Keywords Laser

  13. Homogeneous vs. heterogeneous nucleation in water-dicarboxylic acid systems

    NASA Astrophysics Data System (ADS)

    Hienola, A. I.; Vehkamäki, H.; Riipinen, I.; Kulmala, M.

    2009-03-01

    Binary heterogeneous nucleation of water-succinic/glutaric/malonic/adipic acid on nanometer-sized particles is investigated within the frame of classical heterogeneous nucleation theory. Homogeneous nucleation is also included for comparison. It is found that the nucleation probabilities depend on the contact angle and on the size of the seed particles. New thermodynamical properties, such as saturation vapor pressure, density and surface tension for all the dicarboxylic acid aqueous solutions are included in the calculations. While the new surface tension and density formulations do not bring any significant difference in the computed nucleation rate for homogeneous nucleation for succinic and glutaric acids, the use of the newly derived equations for the vapor pressure decrease the acid concentrations in gas phase by 3 orders of magnitude. According to our calculations, the binary heterogeneous nucleation of succinic acid-water and glutaric acid-water - although it requires a 3-4 orders of magnitude lower vapor concentrations than the homogeneous nucleation - cannot take place under atmospheric conditions. On the other hand binary homogeneous nucleation of adipic acid-water systems might be possible under conditions occuring in upper boundary layer. However, a more detailed characterization of the interaction between the surface and the molecules of the nucleating vapor should be considered in the future.

  14. Sublimating comets as the source of nucleation seeds for grain condensation in the gas outflow from AGB stars

    NASA Technical Reports Server (NTRS)

    Whitmire, D. P.; Matese, John J.; Reynolds, R. T.

    1989-01-01

    A growing amount of observational and theoretical evidence suggests that most main sequence stars are surrounded by disks of cometary material. The dust production by comets in such disks is investigated when the central stars evolve up the red giant and asymptotic giant branch (AGB). Once released, the dust is ablated and accelerated by the gas outflow and the fragments become the seeds necessary for condensation of the gas. The origin of the requisite seeds has presented a well known problem for classical nucleation theory. This model is consistent with the dust production observed in M giants and supergiants (which have increasing luminosities) and the fact that earlier supergiants and most WR stars (whose luminosities are unchanging) do not have significant dust clouds even though they have significant stellar winds. Another consequence of the model is that the spatial distribution of the dust does not, in general, coincide with that of the gas outflow, in contrast to the conventional condensation model. A further prediction is that the condensation radius is greater that that predicted by conventional theory which is in agreement with IR interferometry measurements of alpha-Ori.

  15. Continuous-Flow Gas-Phase Bioreactors

    NASA Technical Reports Server (NTRS)

    Wise, Donald L.; Trantolo, Debra J.

    1994-01-01

    Continuous-flow gas-phase bioreactors proposed for biochemical, food-processing, and related industries. Reactor contains one or more selected enzymes dehydrated or otherwise immobilized on solid carrier. Selected reactant gases fed into reactor, wherein chemical reactions catalyzed by enzyme(s) yield product biochemicals. Concept based on discovery that enzymes not necessarily placed in traditional aqueous environments to function as biocatalysts.

  16. EPA GAS PHASE CHEMISTRY CHAMBER STUDIES

    EPA Science Inventory

    Gas-phase smog chamber experiments are being performed at EPA in order to evaluate a number of current chemical mechanisms for inclusion in EPA regulatory and research models. The smog chambers are 9000 L in volume and constructed of 2-mil teflon film. One of the chambers is co...

  17. 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.

  18. Enzyme-catalyzed, gas-phase reactions.

    PubMed

    Barzana, E; Klibanov, A M; Karel, M

    1987-06-01

    Dehydrated preparations of alcohol oxidase adsorbed on DEAE-cellulose vigorously catalyze a gas-phase oxidation of ethanol vapors with molecular oxygen. The gas-phase reaction is strongly dependent on the water activity of the system. The enzymatic activity is severely inhibited by the product hydrogen peroxide. This inhibition can be alleviated, however, by an addition of catalase or peroxidase to the dry preparation. Such dehydrated, bienzymic catalysts afford a complete and selective conversion of the substrate to acetaldehyde. Dry alcohol oxidase is much more thermostable than in aqueous solution. The results of this work suggest that dehydrated enzymes have potential applications in the analysis of gaseous compounds and in the development of novel gas-solid bioreactors.

  19. Cryogenic two-phase flow during chilldown: Flow transition and nucleate boiling heat transfer

    NASA Astrophysics Data System (ADS)

    Jackson, Jelliffe Kevin

    The recent interest in space exploration has placed a renewed focus on rocket propulsion technology. Cryogenic propellants are the preferred fuel for rocket propulsion since they are more energetic and environmentally friendly compared with other storable fuels. Voracious evaporation occurs while transferring these fluids through a pipeline that is initially in thermal equilibrium with the environment. This phenomenon is referred to as line chilldown. Large temperature differences, rapid transients, pressure fluctuations and the transition from the film boiling to the nucleate boiling regime characterize the chilldown process. Although the existence of the chilldown phenomenon has been known for decades, the process is not well understood. Attempts have been made to model the chilldown process; however the results have been fair at best. A major shortcoming of these models is the use of correlations that were developed for steady, non-cryogenic flows. The development of reliable correlations for cryogenic chilldown has been hindered by the lack of experimental data. An experimental facility was constructed that allows the flow structure, the temperature history and the pressure history to be recorded during the line chilldown process. The temperature history is then utilized in conjunction with an inverse heat conduction procedure that was developed, which allows the unsteady heat transfer coefficient on the interior of the pipe wall to be extracted. This database is used to evaluate present predictive models and correlations for flow regime transition and nucleate boiling heat transfer. It is found that by calibrating the transition between the stratified-wavy and the intermittent/annular regimes of the Taitel and Dukler flow regime map, satisfactory predictions are obtained. It is also found that by utilizing a simple model that includes the effect of flow structure and incorporating the enhancement provided by the local heat flux, significant improvement in the

  20. Comparison of electrical and optical characteristics in gas-phase and gas-liquid phase discharges

    NASA Astrophysics Data System (ADS)

    Qazi, H. I. A.; Nie, Qiu-Yue; Li, He-Ping; Zhang, Xiao-Fei; Bao, Cheng-Yu

    2015-12-01

    This paper presents an AC-excited argon discharge generated using a gas-liquid (two-phase) hybrid plasma reactor, which mainly consists of a powered needle electrode enclosed in a conical quartz tube and grounded deionized water electrode. The discharges in the gas-phase, as well as in the two-phase, exhibit two discharge modes, i.e., the low current glow-like diffuse mode and the high current streamer-like constrict mode, with a mode transition, which exhibits a negative resistance of the discharges. The optical emission spectral analysis shows that the stronger diffusion of the water vapor into the discharge region in the two-phase discharges boosts up the generation of OH (A-X) radicals, and consequently, leads to a higher rotational temperature in the water-phase plasma plume than that of the gas-phase discharges. Both the increase of the power input and the decrease of the argon flow rate result in the increase of the rotational temperature in the plasma plume of the water-phase discharge. The stable two-phase discharges with a long plasma plume in the water-phase under a low power input and gas flow rate may show a promising prospect for the degradation of organic pollutants, e.g., printing and dyeing wastewater, in the field of environmental protection.

  1. Comparison of electrical and optical characteristics in gas-phase and gas-liquid phase discharges

    SciTech Connect

    Qazi, H. I. A.; Li, He-Ping Zhang, Xiao-Fei; Bao, Cheng-Yu; Nie, Qiu-Yue

    2015-12-15

    This paper presents an AC-excited argon discharge generated using a gas-liquid (two-phase) hybrid plasma reactor, which mainly consists of a powered needle electrode enclosed in a conical quartz tube and grounded deionized water electrode. The discharges in the gas-phase, as well as in the two-phase, exhibit two discharge modes, i.e., the low current glow-like diffuse mode and the high current streamer-like constrict mode, with a mode transition, which exhibits a negative resistance of the discharges. The optical emission spectral analysis shows that the stronger diffusion of the water vapor into the discharge region in the two-phase discharges boosts up the generation of OH (A–X) radicals, and consequently, leads to a higher rotational temperature in the water-phase plasma plume than that of the gas-phase discharges. Both the increase of the power input and the decrease of the argon flow rate result in the increase of the rotational temperature in the plasma plume of the water-phase discharge. The stable two-phase discharges with a long plasma plume in the water-phase under a low power input and gas flow rate may show a promising prospect for the degradation of organic pollutants, e.g., printing and dyeing wastewater, in the field of environmental protection.

  2. Receptors useful for gas phase chemical sensing

    DOEpatents

    Jaworski, Justyn W; Lee, Seung-Wuk; Majumdar, Arunava; Raorane, Digvijay A

    2015-02-17

    The invention provides for a receptor, capable of binding to a target molecule, linked to a hygroscopic polymer or hydrogel; and the use of this receptor in a device for detecting the target molecule in a gaseous and/or liquid phase. The invention also provides for a method for detecting the presence of a target molecule in the gas phase using the device. In particular, the receptor can be a peptide capable of binding a 2,4,6-trinitrotoluene (TNT) or 2,4,-dinitrotoluene (DNT).

  3. Experimental Thermochemistry of Gas Phase Cytosine Tautomers

    NASA Astrophysics Data System (ADS)

    Morrison, A. M.; Douberly, G. E.

    2011-06-01

    Enthalpies of interconversion are measured for the three lowest energy tautomers of isolated cytosine. The equilibrium distribution of tautomers near 600 K is frozen upon the capture of the gas phase species by low temperature helium nanodroplets. The temperature dependence of the gas phase cytosine tautomer populations is determined with infrared laser spectroscopy of the helium solvated species. The interconverison enthalpies obtained from the van't Hoff relation are 1.14 ± 0.21 and 1.63 ± 0.12 for the C31 rightleftharpoons C32 and C31 rightleftharpoons C1 equilibria, respectively. C31 and C32 are rotamers of an enol tautomer, and C1 is a keto tautomer. The interconversion enthalpies are compared to recent CCSD(T) thermochemistry calculations of cytosine tautomers.

  4. Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

    NASA Technical Reports Server (NTRS)

    Pusey, Marc L.; Forsythe, Elizabeth; Sumida, John; Maxwell, Daniel; Gorti, Sridhar

    2002-01-01

    Lysozyme, and most particularly the tetragonal form of the protein, has become the default standard protein for use in macromolecule crystal nucleation and growth studies. There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests this proteins crystal nucleation and growth is by addition of associated species that are preformed by standard reversible concentration-driven self association processes in the bulk solution. The evidence includes high resolution AFM studies of the surface packing and of growth unit size at incorporation, fluorescence resonance energy transfer measurements of intermolecular distances in dilute solution, dialysis kinetics, and modeling of the growth rate data. We have developed a selfassociation model for the proteins crystal nucleation and growth. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. Further, it indicates that nucleation and crystal growth are not distinct mechanistically, but identical, with the primary difference being the probability that the particle will continue to grow or dissolve. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small (M.W. = 14,400), a structured octamer in the 4(sub 3) helix configuration (the proposed average sized growth unit) would have a M.W. = 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm commonly attach to the crystal. These measurements were made at approximately saturation conditions, and they reflect the sizes of species that both added or desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it

  5. Nucleation of carbon nanostructures: Molecular dynamics with reactive potentials

    NASA Astrophysics Data System (ADS)

    Galiullina, G. M.; Orekhov, N. D.; Stegailov, V. V.

    2016-11-01

    In this paper, we present our first results in the study of the details of nucleation in the homogeneous carbon gas phase using computer calculations with molecular dynamics methods. Direct and controlled molecular-dynamics approaches are used and two reactive potentials (ReaxFF and AIREBO) are compared. The calculations have shown that the nucleation process in the AIREBO model is going more actively than in the ReaxFF one.

  6. Nucleation Behavior of Oxygen-Acetylene Torch-Produced Diamond Films

    NASA Technical Reports Server (NTRS)

    Roberts, F. E.

    2003-01-01

    A mechanism is presented for the nucleation of diamond in the combustion flame environment. A series of six experiments and two associated simulations provide results from which the mechanism was derived. A substantial portion of the prior literature was reviewed and the data and conclusions from the previous experimenters were found to support the proposed mechanism. The nucleation mechanism builds on the work of previous researchers but presents an approach to nucleation in a detail and direction not fully presented heretofore. This work identifies the gas phase as the controlling environment for the initial formation steps leading to nucleation. The developed mechanism explains some of the difficulty which has been found in producing single crystal epitaxial films. An experiment which modified the initial gas phase precursor using methane and carbon monoxide is presented. Addition of methane into the precursor gases was found to be responsible for pillaring of the films. Atomic force microscopy surface roughness data provides a reasonable look at suppression of nucleation by carbon monoxide. Surface finish data was taken on crystals which were open to the nucleation environment and generally parallel to the substrate surface. The test surfaces were measured as an independent measure of the instantaneous nucleation environent. A gas flow and substrate experiment changed the conditions on the surface of the sample by increasing the gas flow rate while remaining on a consistent point of the atomic constituent diagram, and by changing the carbide potential of the substrate. Two tip modification experiments looked at the behavior of gas phase nucleation by modifying the shape and behavior of the flame plasma in which the diamond nucleation is suspected to occur. Diamond nucleation and growth was additionally examined using a high-velocity oxygen fuel gun and C3H6 as the fuel gas phase precursor with addition of carbon monoxide gas 01 addition of liquid toluene.

  7. Gas-Phase Photoionization Of A Protein

    NASA Astrophysics Data System (ADS)

    Milosavljevic, A. R.; Giuliani, A.; Nicolas, C.; Gil, J.-F.; Lemaire, J.; Refregiers, M.; Nahon, L.

    2010-07-01

    We present preliminary results on gas phase photoionization of electrosprayproduced multiply protonated cytochrome c protein (104 amino acids; ˜12.4 kDa), which has been achieved with a newly developed experimental system for spectroscopy of electrosprayed ions in a linear quadrupole ion trap using a monochromatized vacuum ultraviolet (VUV) synchrotron radiation and tandem mass spectrometry method. The investigation of proteins in the gas phase, where they are free of the influence of counterions and solvent molecules, offer a possibility to understand their intrinsic molecular properties. However, due to limited both ion densities and available number of photons, the use of synchrotron radiation for the trapped ions spectroscopy is a rather challenging task. The feasibility of coupling a Fourier transform ion cyclotron resonance ion trap with soft x-ray synchrotron beamline and the first successful use of synchrotron radiation for spectroscopy of electrosprayed negative ions stored in a three-dimensional quadrupole ion trap have been demonstrated only recently (R. Thissen et al., 2008, Phys. Rev. Lett., 100, 223001; A. Giulliani et al., Proc. 57th ASMS Conf., Philadelphia, 2009). The present results are the first reported on photoionization of kDa species in the gas phase and are valuable regarding both a fundamental interest of accessing physical properties of large biological ions isolated in vacuo and potential development of a new technique for proteomics.

  8. Observations on the nucleation of ice VII in compressed water

    NASA Astrophysics Data System (ADS)

    Stafford, Samuel J. P.; Chapman, David J.; Bland, Simon N.; Eakins, Daniel E.

    2017-01-01

    Water can freeze upon multiple shock compression, but the window material determines the pressure of the phase transition. Several plate impact experiments were conducted with liquid targets on a single-stage gas gun, diagnosed simultaneously using photonic doppler velocimetry (PDV) and high speed imaging through the water. The experiments investigated why silica windows instigate freezing above 2.5 GPa whilst sapphire windows do not until 7 GPa. We find that the nucleation of ice occurs on the surfaces of windows and can be affected by the surface coating suggesting the surface energy of fused silica, likely due to hydroxyl groups, encourages nucleation of ice VII crystallites. Aluminium coatings prevent nucleation and sapphire surfaces do not nucleate until approximately 6.5 GPa. This is believed to be the threshold pressure for the homogeneous nucleation of water.

  9. Nucleation dynamics of nanostructural TiO2 films with controllable phases on (001) LaAlO3.

    PubMed

    Lin, Yuan; Zeng, Bo; Ji, Yanda; Liang, Weizheng; Feng, Dayu; Gao, Min; Zhang, Yin; Chen, Xinxin; Chen, Bin; Chen, Chonglin

    2014-01-10

    Microstructure evolution and nucleation dynamics of TiO2 nanostructural thin films on (001) LaAlO3 substrates grown by the polymer-assisted deposition technique have been systematically studied with the increase of annealing temperature. Epitaxial anatase TiO2 phase with nanometer-scaled periodic surface strip patterns can be achieved when the sample is annealed at 900 ° C. It is also found that the morphology of the surface pattern is related to the ramping rate of the temperature during annealing. The formation of the surface strip pattern can be considered to be associated with the diffusion limit growth dynamics. The surface pattern structure was found to strongly affect the hydrophilic properties of the thin films.

  10. Fuel Performance Experiments and Modeling: Fission Gas Bubble Nucleation and Growth in Alloy Nuclear Fuels

    SciTech Connect

    McDeavitt, Sean; Shao, Lin; Tsvetkov, Pavel; Wirth, Brian; Kennedy, Rory

    2014-04-07

    Advanced fast reactor systems being developed under the DOE's Advanced Fuel Cycle Initiative are designed to destroy TRU isotopes generated in existing and future nuclear energy systems. Over the past 40 years, multiple experiments and demonstrations have been completed using U-Zr, U-Pu-Zr, U-Mo and other metal alloys. As a result, multiple empirical and semi-empirical relationships have been established to develop empirical performance modeling codes. Many mechanistic questions about fission as mobility, bubble coalescience, and gas release have been answered through industrial experience, research, and empirical understanding. The advent of modern computational materials science, however, opens new doors of development such that physics-based multi-scale models may be developed to enable a new generation of predictive fuel performance codes that are not limited by empiricism.

  11. Overview: Nucleation of clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Warrier, Pramod; Khan, M. Naveed; Srivastava, Vishal; Maupin, C. Mark; Koh, Carolyn A.

    2016-12-01

    Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

  12. Gas phase thermochemistry of organogermanium compounds

    SciTech Connect

    Engel, J.P.

    1993-12-07

    A variety of silyl- and alkyl-germylene precursors have been synthesized and subsequently pyrolyzed in the gas phase. Arrhenius parameters were obtained employing a pulsed-stirred flow reactor for these unimolecular decompositions. These precursors are divided into two major categories by mechanism of germylene extrusion: {alpha}-elimination precursors and germylacetylenes. The extrusion of germylenes from germylacetylene precursors is of primary interest. A mechanism is proposed employing a germacyclopropene intermediate. Evidence supporting this mechanism is presented. In the process of exploring germylacetylenes as germylene precursors, an apparent dyatropic rearrangement between germanium and silicon was observed. This rearrangement was subsequently explored.

  13. Nucleation at the phase transition near 40 deg. C in MnAs nanodisks

    SciTech Connect

    Jenichen, B.; Takagaki, Y.; Ploog, K. H.; Darowski, N.; Feyerherm, R.; Zizak, I.

    2006-07-31

    The phase transition near 40 deg. C of both as-grown thin epitaxial MnAs films prepared by molecular beam epitaxy on GaAs(001) and nanometer-scale disks fabricated from the same films is studied. The disks are found to exhibit a pronounced hysteresis in the temperature curve of the phase composition. In contrast, supercooling and overheating take place far less in the samples of continuous layers. These phenomena are explained in terms of the necessary formation of nuclei of the other phase in each of the disks independent from each other. The influence of the elastic strains in the disks is reduced considerably.

  14. Vaccum Gas Tungsten Arc Welding, phase 1

    NASA Technical Reports Server (NTRS)

    Weeks, J. L.; Krotz, P. D.; Todd, D. T.; Liaw, Y. K.

    1995-01-01

    This two year program will investigate Vacuum Gas Tungsten Arc Welding (VGTAW) as a method to modify or improve the weldability of normally difficult-to-weld materials. VGTAW appears to offer a significant improvement in weldability because of the clean environment and lower heat input needed. The overall objective of the program is to develop the VGTAW technology and implement it into a manufacturing environment that will result in lower cost, better quality and higher reliability aerospace components for the space shuttle and other NASA space systems. Phase 1 of this program was aimed at demonstrating the process's ability to weld normally difficult-to-weld materials. Phase 2 will focus on further evaluation, a hardware demonstration and a plan to implement VGTAW technology into a manufacturing environment. During Phase 1, the following tasks were performed: (1) Task 11000 Facility Modification - an existing vacuum chamber was modified and adapted to a GTAW power supply; (2) Task 12000 Materials Selection - four difficult-to-weld materials typically used in the construction of aerospace hardware were chosen for study; (3) Task 13000 VGTAW Experiments - welding experiments were conducted under vacuum using the hollow tungsten electrode and evaluation. As a result of this effort, two materials, NARloy Z and Incoloy 903, were downselected for further characterization in Phase 2; and (4) Task 13100 Aluminum-Lithium Weld Studies - this task was added to the original work statement to investigate the effects of vacuum welding and weld pool vibration on aluminum-lithium alloys.

  15. Giddings Austin chalk enters deep lean-gas phase

    SciTech Connect

    Moritis, G.

    1995-12-25

    Deep lean gas is the latest phase in the growth of the Giddings field Austin chalk play. The first phase involved drilling vertical oil and gas wells. Next came the horizontal well boom in the shallower Austin chalk area, which is still continuing. And now this third phase places horizontal laterals in the Austen chalk at about 14,000--15,000 ft to produce lean gas. The article describes the producing wells and gas gathering.

  16. Initiation of the ice phase by marine biogenic surfaces in supersaturated gas and supercooled aqueous phases.

    PubMed

    Alpert, Peter A; Aller, Josephine Y; Knopf, Daniel A

    2011-11-28

    Biogenic particles have the potential to affect the formation of ice crystals in the atmosphere with subsequent consequences for the hydrological cycle and climate. We present laboratory observations of heterogeneous ice nucleation in immersion and deposition modes under atmospherically relevant conditions initiated by Nannochloris atomus and Emiliania huxleyi, marine phytoplankton with structurally and chemically distinct cell walls. Temperatures at which freezing, melting, and water uptake occur are observed using optical microscopy. The intact and fragmented unarmoured cells of N. atomus in aqueous NaCl droplets enhance ice nucleation by 10-20 K over the homogeneous freezing limit and can be described by a modified water activity based ice nucleation approach. E. huxleyi cells covered by calcite plates do not enhance droplet freezing temperatures. Both species nucleate ice in the deposition mode at an ice saturation ratio, S(ice), as low as ~1.2 and below 240 K, however, for each, different nucleation modes occur at warmer temperatures. These observations show that markedly different biogenic surfaces have both comparable and contrasting effects on ice nucleation behaviour depending on the presence of the aqueous phase and the extent of supercooling and water vapour supersaturation. We derive heterogeneous ice nucleation rate coefficients, J(het), and cumulative ice nuclei spectra, K, for quantification and analysis using time-dependent and time-independent approaches, respectively. Contact angles, α, derived from J(het)via immersion freezing depend on T, a(w), and S(ice). For deposition freezing, α can be described as a function of S(ice) only. The different approaches yield different predictions of atmospheric ice crystal numbers primarily due to the time evolution allowed for the time-dependent approach with implications for the evolution of mixed-phase and ice clouds.

  17. Infrared spectroscopy of homogeneously nucleated hydrazine aerosols - Disordered and crystalline phases. [in planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Dunder, T.; Clapp, M. L.; Miller, R. E.

    1993-01-01

    It is shown that aerosols generated at low temperatures and high condensation rate spontaneously form in a highly crystalline state. The resonant absorption bands in the IR spectra of these highly crystalline particles are much sharper than any reported previously in the bulk, and reveal details in the N-H vibrational bands that have not been previously observed. A disordered phase is also observed at somewhat higher temperatures. These results are consistent with this being a supercooled liquid. The fact that the spectra associated with these two aerosol phases are quite different is important to any future attempts at detecting hydrazine aerosols in planetary atmospheres by remote sensing techniques.

  18. Isothermal nucleation and growth kinetics of Pd/Ag alloy phase via in-situ time-resolved high-temperature x-ray diffraction (HTXRD) analysis

    SciTech Connect

    Ayturk, Mahmut Engin; Payzant, E Andrew; Speakman, Scott A; Ma, Yi Hua

    2008-01-01

    Among several different approaches to form Pd/Ag alloys for hydrogen separation applications, ex-situ studies carried by conventional X-ray point scanning detectors might fail to reveal the key aspects of the phase transformation between Pd and Ag metals. In this respect, in-situ time-resolved high temperature X-ray diffraction (HTXRD) was employed to study the Pd/Ag alloy phase nucleation and growth kinetics. By the use of linear position sensitive detectors, advanced optics and profile fitting with the use of JADE-6.5 software, isothermal phase evolution of the Pd/Ag alloy at 500 C, 550 C and 600 C under hydrogen atmosphere were quantified to elucidate the mechanistic details of the Pd/Ag alloy phase nucleation and growth pattern. Analysis of the HTXRD data by the Avrami model indicated that the nucleation of the Pd/Ag alloy phase was instantaneous where the growth mechanism was through diffusion-controlled one-dimensional thickening of the Pd/Ag alloy layer. The value of the Avrami exponent, n, was found to increase with temperature with the values of 0.34, 0.39 and 0.67 at 500oC, 550oC and 600oC, respectively. In addition, parabolic rate law analysis suggested that the nucleation of the Pd/Ag alloy phase was through a heterogeneous nucleation mode, in which the nucleation sites were defined as the non-equilibrium defects. The cross-sectional SEI micrographs indicated that the Pd/Ag alloy phase growth was strongly dependent upon the deposition morphology of the as-synthesized Pd and Ag layers formed by the electroless plating. Based on the Avrami model and the parabolic rate law, the estimated activation energies for the phase transformation were 236.5 and 185.6 kJ/mol and in excellent agreement with the literature values (183-239.5 kJ/mol).

  19. Polymorphic phase transition among the titania crystal structures using a solution-based approach: from precursor chemistry to nucleation process.

    PubMed

    Kumar, S Girish; Rao, K S R Koteswara

    2014-10-21

    Nanocrystalline titania are a robust candidate for various functional applications owing to its non-toxicity, cheap availability, ease of preparation and exceptional photochemical as well as thermal stability. The uniqueness in each lattice structure of titania leads to multifaceted physico-chemical and opto-electronic properties, which yield different functionalities and thus influence their performances in various green energy applications. The high temperature treatment for crystallizing titania triggers inevitable particle growth and the destruction of delicate nanostructural features. Thus, the preparation of crystalline titania with tunable phase/particle size/morphology at low to moderate temperatures using a solution-based approach has paved the way for further exciting areas of research. In this focused review, titania synthesis from hydrothermal/solvothermal method, conventional sol-gel method and sol-gel-assisted method via ultrasonication, photoillumination and ILs, thermolysis and microemulsion routes are discussed. These wet chemical methods have broader visibility, since multiple reaction parameters, such as precursor chemistry, surfactants, chelating agents, solvents, mineralizer, pH of the solution, aging time, reaction temperature/time, inorganic electrolytes, can be easily manipulated to tune the final physical structure. This review sheds light on the stabilization/phase transformation pathways of titania polymorphs like anatase, rutile, brookite and TiO2(B) under a variety of reaction conditions. The driving force for crystallization arising from complex species in solution coupled with pH of the solution and ion species facilitating the orientation of octahedral resulting in a crystalline phase are reviewed in detail. In addition to titanium halide/alkoxide, the nucleation of titania from other precursors like peroxo and layered titanates are also discussed. The non-aqueous route and ball milling-induced titania transformation is briefly

  20. Homogeneous nucleation kinetics

    NASA Technical Reports Server (NTRS)

    Rasmussen, D. H.; Appleby, M. R.; Leedom, G. L.; Babu, S. V.; Naumann, R. J.

    1983-01-01

    Homogeneous nucleation kinetics are rederived in a manner fundamentally similar to the approach of classical nucleation theory with the following modifications and improvements. First, the cluster is a parent phase cluster and does not require energization to the parent state. Second, the thermodynamic potential used to describe phase stability is a continuous function along the pathway of phase decomposition. Third, the kinetics of clustering corresponds directly to the diffusional flux of monomers through the cluster distribution and are formally similar to classical theory with the resulting kinetic equation modified by two terms in the preexponential factor. These terms correct for the influence of a supersaturation dependent clustering within the parent phase and for the influence of an asymmetrical cluster concentration as a function of cluster size at the critical cluster size. Fourth, the supersaturation dependence of the nucleation rate is of the same form as that given by classical nucleation theory. This supersaturation dependence must however be interpreted in terms of a size dependent surface tension. Finally, there are two scaling laws which describe supersaturation to either constant nucleation rate or to the thermodynamically determined physical spinodal.

  1. Simulation Study of Heterogeneous Nucleation at Grain Boundaries During the Austenite-Ferrite Phase Transformation: Comparing the Classical Model with the Multi-Phase Field Nudged Elastic Band Method

    NASA Astrophysics Data System (ADS)

    Song, Huajing; Shi, Rongpei; Wang, Yunzhi; Hoyt, Jeffrey J.

    2016-08-01

    In this work, molecular dynamics (MD) simulations have been used to study the heterogeneous nucleation occurring at grain boundaries (GBs) during the austenite (FCC) phase to ferrite (BCC) phase transformation in a pure Fe polycrystalline system. The critical nucleus properties (including size, shape, and activation energy) determined by classical nucleation theory are compared with those obtained by using a combination of the multi-phase field method (MPFM) and the nudged elastic band (NEB) method. For nucleation events that exhibit low-energy facets completely embedded within the parent FCC phase, there is a good agreement between the MD and the MPFM result with respect to the critical nucleus size, shape, and nucleation energy barrier. For systems where the emerging nucleus contains facets that cross the GB plane, the MPFM-NEB, when compared to MD, yields a better prediction than the classical approach for the nucleus morphology. New observations from the MPFM-NEB method indicate that the critical nucleus shape may change with volume and therefore depends on the nucleation driving force (undercooling).

  2. Fundamentals of gas phase plasmas for treatment of human tissue.

    PubMed

    Kushner, Mark J; Babaeva, Natalia Yu

    2011-01-01

    The use of gas phase plasmas for treating human tissue is at the intersection of two disciplines - plasma physics and engineering, and medicine. In this paper, a primer will be provided for the medical practitioner on the fundamentals of generating gas phase plasmas at atmospheric pressure in air for the treatment of human tissue. The mechanisms for gas phase plasmas interacting with tissue and biological fluids will also be discussed using results from computer modeling.

  3. In situ study of nucleation and aggregation phases for nanoparticles grown by laser-driven methods

    NASA Astrophysics Data System (ADS)

    Barberio, M.; Antici, P.

    2017-02-01

    In the last decades, nanomaterials and nanotechnologies have become fundamental and irreplaceable in many fields of science and technology. When used in applications, their properties depend on many factors such as size, shape, internal structure and composition. For this, exact knowledge of their structural features is essential when developing fabrication technologies and searching for new types of nanostructures or nanoparticles with specific properties. For the latter, the knowledge of the precise temporal evolution of the growth processes is fundamental when it comes to industrial production and applications. Here we present a method to control, with very high precision, the starting of the aggregation phase during the Laser Ablation in solution growth process. This is obtained by monitoring the optical absorption of the colloidal solution. We apply this control method on the most popular metallic nanoparticle materials (Ag, Al, Co, and Ti) and verify the technique using morphological analysis conducted by AFM and SEM microscopy. The experimental results are explained in terms of Mie extinction theory and Thermal Model for Laser Ablation.

  4. In situ study of nucleation and aggregation phases for nanoparticles grown by laser-driven methods

    PubMed Central

    Barberio, M.; Antici, P.

    2017-01-01

    In the last decades, nanomaterials and nanotechnologies have become fundamental and irreplaceable in many fields of science and technology. When used in applications, their properties depend on many factors such as size, shape, internal structure and composition. For this, exact knowledge of their structural features is essential when developing fabrication technologies and searching for new types of nanostructures or nanoparticles with specific properties. For the latter, the knowledge of the precise temporal evolution of the growth processes is fundamental when it comes to industrial production and applications. Here we present a method to control, with very high precision, the starting of the aggregation phase during the Laser Ablation in solution growth process. This is obtained by monitoring the optical absorption of the colloidal solution. We apply this control method on the most popular metallic nanoparticle materials (Ag, Al, Co, and Ti) and verify the technique using morphological analysis conducted by AFM and SEM microscopy. The experimental results are explained in terms of Mie extinction theory and Thermal Model for Laser Ablation. PMID:28195194

  5. Gas phase hydration of organic ions.

    PubMed

    Momoh, Paul O; El-Shall, M Samy

    2008-08-28

    In this work, we study the hydration phenomenon on a molecular level in the gas phase where a selected number of water molecules can interact with the organic ion of interest. The stepwise binding energies (DeltaH degrees (n-1,n)) of 1-7 water molecules to the phenyl acetylene cation are determined by equilibrium measurements using an ion mobility drift cell. The stepwise hydration energies DeltaH degrees (n-1,n) are nearly constant at 39.7 +/- 6.3 kJ mol(-1) from n = 1 to 7. The entropy change is larger in the n = 7 step, suggesting cyclic or cage-like water structures. No water addition is observed on the ionized phenyl acetylene trimer consistent with cyclization of the trimer ion to form triphenyl benzene cations C(24)H(18) (+) which are expected to interact weakly with the water molecules due to steric interactions and the delocalization of the charge on the large organic ion. The work demonstrates that hydration studies of organic ions can provide structural information on the organic ions.

  6. Intramolecular photoelectron diffraction in the gas phase

    NASA Astrophysics Data System (ADS)

    Ueda, K.; Miron, C.; Plésiat, E.; Argenti, L.; Patanen, M.; Kooser, K.; Ayuso, D.; Mondal, S.; Kimura, M.; Sakai, K.; Travnikova, O.; Palacios, A.; Decleva, P.; Kukk, E.; Martín, F.

    2013-09-01

    We report unambiguous experimental and theoretical evidence of intramolecular photoelectron diffraction in the collective vibrational excitation that accompanies high-energy photoionization of gas-phase CF4, BF3, and CH4 from the 1s orbital of the central atom. We show that the ratios between vibrationally resolved photoionization cross sections (v-ratios) exhibit pronounced oscillations as a function of photon energy, which is the fingerprint of electron diffraction by the surrounding atomic centers. This interpretation is supported by the excellent agreement between first-principles static-exchange and time-dependent density functional theory calculations and high resolution measurements, as well as by qualitative agreement at high energies with a model in which atomic displacements are treated to first order of perturbation theory. The latter model allows us to rationalize the results for all the v-ratios in terms of a generalized v-ratio, which contains information on the structure of the above three molecules and the corresponding molecular cations. A fit of the measured v-ratios to a simple formula based on this model suggests that the method could be used to obtain structural information of both neutral and ionic molecular species.

  7. Intramolecular photoelectron diffraction in the gas phase.

    PubMed

    Ueda, K; Miron, C; Plésiat, E; Argenti, L; Patanen, M; Kooser, K; Ayuso, D; Mondal, S; Kimura, M; Sakai, K; Travnikova, O; Palacios, A; Decleva, P; Kukk, E; Martín, F

    2013-09-28

    We report unambiguous experimental and theoretical evidence of intramolecular photoelectron diffraction in the collective vibrational excitation that accompanies high-energy photoionization of gas-phase CF4, BF3, and CH4 from the 1s orbital of the central atom. We show that the ratios between vibrationally resolved photoionization cross sections (v-ratios) exhibit pronounced oscillations as a function of photon energy, which is the fingerprint of electron diffraction by the surrounding atomic centers. This interpretation is supported by the excellent agreement between first-principles static-exchange and time-dependent density functional theory calculations and high resolution measurements, as well as by qualitative agreement at high energies with a model in which atomic displacements are treated to first order of perturbation theory. The latter model allows us to rationalize the results for all the v-ratios in terms of a generalized v-ratio, which contains information on the structure of the above three molecules and the corresponding molecular cations. A fit of the measured v-ratios to a simple formula based on this model suggests that the method could be used to obtain structural information of both neutral and ionic molecular species.

  8. Instabilities in Lean Gas-Phase Combustion

    NASA Astrophysics Data System (ADS)

    Schneider, K.; Bockhorn, H.; Eigenbrod, Ch.; Emerson, D.; Haldenwang, P.; Hoffmann, F.; Roekaerts, D.; Ronney, P.; Triebel, W.; Tummers, M.

    2005-06-01

    Lean burning is the burning of fuel-air mixtures with less than the chemically- balanced (stoichiometric) mixture. It produces a significant increase in fuel efficiency and reduction in pollution. However, the limits and control of lean burning are still not well understood.This is the motivation behind the study of instabilities in lean gas-phase combustion under microgravity conditions via direct numerical simulations and comparison of the results with experimental data.The goal is to gain fundamental insights in order to identify and understand the intrinsic chemical and fluid dynamical mechanisms responsible for these instabilities.The potential of this microgravity combustion research includes the development of technology that would reduce pollution and fire and explosion hazards, improve hazardous waste incineration and increase efficiency of the conversion of chemical energy to electric power or motive force.The results from this fundamental research will thus benefit chemical engineering and power generation. Its wide range of applications in industry includes lean-burning car engines.

  9. Nucleation at the Contact Line Observed on Nanotextured Surfaces

    NASA Astrophysics Data System (ADS)

    Kostinski, A. B.; Gurganus, C.; Charnawskas, J. C.; Shaw, R. A.

    2015-12-01

    Surface nucleation, and contact nucleation in particular, are important for many physical processes, including pharmaceutical drug synthesis, metallurgy, and heterogeneous ice nucleation. It has been conjectured that roughness plays a role in surface nucleation, the tendency for freezing to begin preferentially at the liquid-gas interface. Using high speed imaging, we sought evidence for freezing at the contact line on catalyst substrates with imposed characteristic length scales (texture). It is found that nano-scale texture causes a shift in the nucleation of ice in super-cooled water to the three-phase contact line, while micro-scale texture does not. The reduction in the Gibbs barrier for nucleation at the droplet triple line suggests that a line tension, inversely proportional to the surface feature length scale, may be the relevant physical mechanism. A survey of line tension values in literature supports this hypothesis. This work suggests that the physical morphology of a particle, and not just its chemical composition, is important for characterizing a nucleation catalyst.

  10. Hydrocarbon radical thermochemistry: Gas-phase ion chemistry techniques

    SciTech Connect

    Ervin, Kent M.

    2014-03-21

    Final Scientific/Technical Report for the project "Hydrocarbon Radical Thermochemistry: Gas-Phase Ion Chemistry Techniques." The objective of this project is to exploit gas-phase ion chemistry techniques for determination of thermochemical values for neutral hydrocarbon radicals of importance in combustion kinetics.

  11. Pressure Dependence of Gas-Phase Reaction Rates

    ERIC Educational Resources Information Center

    De Persis, Stephanie; Dollet, Alain; Teyssandier, Francis

    2004-01-01

    It is presented that only simple concepts, mainly taken from activated-complex or transition-state theory, are required to explain and analytically describe the influence of pressure on gas-phase reaction kinetics. The simplest kind of elementary gas-phase reaction is a unimolecular decomposition reaction.

  12. Modeling the Phase Composition of Gas Condensate in Pipelines

    NASA Astrophysics Data System (ADS)

    Dudin, S. M.; Zemenkov, Yu D.; Shabarov, A. B.

    2016-10-01

    Gas condensate fields demonstrate a number of thermodynamic characteristics to be considered when they are developed, as well as when gas condensate is transported and processed. A complicated phase behavior of the gas condensate system, as well as the dependence of the extracted raw materials on the phase state of the deposit other conditions being equal, is a key aspect. Therefore, when designing gas condensate lines the crucial task is to select the most appropriate methods of calculating thermophysical properties and phase equilibrium of the transported gas condensate. The paper describes a physical-mathematical model of a gas-liquid flow in the gas condensate line. It was developed based on balance equations of conservation of mass, impulse and energy of the transported medium within the framework of a quasi-1D approach. Constitutive relationships are given separately, and practical recommendations on how to apply the research results are provided as well.

  13. Dimers in nucleating vapors

    NASA Astrophysics Data System (ADS)

    Lushnikov, A. A.; Kulmala, M.

    1998-09-01

    The dimer stage of nucleation may affect considerably the rate of the nucleation process at high supersaturation of the nucleating vapor. Assuming that the dimer formation limits the nucleation rate, the kinetics of the particle formation-growth process is studied starting with the definition of dimers as bound states of two associating molecules. The partition function of dimer states is calculated by summing the Boltzmann factor over all classical bound states, and the equilibrium population of dimers is found for two types of intermolecular forces: the Lennard-Jones (LJ) and rectangular well+hard core (RW) potentials. The principle of detailed balance is used for calculating the evaporation rate of dimers. The kinetics of the particle formation-growth process is then investigated under the assumption that the trimers are stable with respect to evaporation and that the condensation rate is a power function of the particle mass. If the power exponent λ=n/(n+1) (n is a non-negative integer), the kinetics of the process is described by a finite set of moments of particle mass distribution. When the characteristic time of the particle formation by nucleation is much shorter than that of the condensational growth, n+2 universal functions of a nondimensional time define the kinetic process. These functions are calculated for λ=2/3 (gas-to-particle conversion in the free molecular regime) and λ=1/2 (formation of islands on surfaces).

  14. Time Dependent Studies of Reactive Shocks in the Gas Phase

    DTIC Science & Technology

    1978-11-16

    1 LEVEL NRL Memorandum Report 3W tO Time Dependent Studies of Reactive Shocks in the Gas Phase E.S. ORAN, ’T.R. YOUNG and J.P. BORIS Laboratory for...34-• TIME DEPENDENT STUDIES OF REACTIVE SHOCKS IN THE GAS PHASE I. Introduction This paper presents results obtained from a detailed numerical...chemical kinetics, reaction products, and intermediates produced in reactive gas mixtures ignited by the propagation of a shock front. The model is based

  15. A Distributed Activation Energy Model of Thermodynamically Inhibited Nucleation and Growth Reactions and its Application to the Phase Transition of HMX

    SciTech Connect

    Burnham, A K; Weese, R K; Weeks, B L

    2004-07-20

    Detailed and global models are presented for thermodynamically inhibited nucleation-growth reactions and applied to the {beta}-{delta} Phase Transition of HMX (nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine). The detailed model contains separate kinetic parameters for the nucleation process, including an activation energy distribution resulting from a distribution of defect energies, and for movement of the resulting reaction interface within a single particle. A thermodynamic inhibition term is added to both processes so that the rates go to zero at the transition temperature. The global model adds the thermodynamic inhibition term to the extended Prout-Tompkins nucleation-growth formalism for single particles or powders. Model parameters are calibrated from differential scanning calorimetry data. The activation energy for nucleation (333 kJ/mol) is substantially higher than that for growth (29.3 kJ/mol). Use of a small activation energy distribution ({approx}400 J/mol) for the defects improves the fit to a powered sample for both the early and late stages of the transition. The effective overall activation energy for the global model (208.8 kJ/mol) is in between that of nucleation and growth. Comparison of the two models with experiment indicates the thermodynamic inhibition term is more important than the energy distribution feature for this transition. Based on the applicability of the Prout-Tompkins kinetics approach to a wide range of organic and inorganic materials, both models should have equally broad applicability for thermodynamically constrained reactions.

  16. A Distributed Activation Energy Model of Thermodynamically Inhibited Nucleation and Growth Reactions and its Application to the beta-delta Phase Transition of HMX

    SciTech Connect

    Burnham, A K; Weese, R K; Weeks, B L

    2004-06-18

    Detailed and global models are presented for thermodynamically inhibited nucleation-growth reactions and applied to the {beta}-{delta} Phase Transition of HMX (nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine). The detailed model contains separate kinetic parameters for the nucleation process, including an activation energy distribution resulting from a distribution of defect energies, and for movement of the resulting reaction interface within a single particle. A thermodynamic inhibition term is added to both processes so that the rates go to zero at the transition temperature. The global model adds the thermodynamic inhibition term to the extended Prout-Tompkins nucleation-growth formalism for single particles or powders. Model parameters are calibrated from differential scanning calorimetry data. The activation energy for nucleation (333 kJ/mol) is substantially higher than that for growth (29.3 kJ/mol). Use of a small activation energy distribution ({approx}400 J/mol) for the defects improves the fit to a powered sample for both the early and late stages of the transition. The effective overall activation energy for the global model (208.8 kJ/mol) is in between that of nucleation and growth. Comparison of the two models with experiment indicates the thermodynamic inhibition term is more important than the energy distribution feature for this transition. Based on the applicability of the Prout-Tompkins kinetics approach to a wide range of organic and inorganic materials, both models should have equally broad applicability for thermodynamically constrained reactions.

  17. Pattern formation arising from condensation of a homogeneous gas into a binary, phase-separating liquid.

    PubMed

    Pooley, C M; Balazs, Anna C; Yeomans, J M

    2005-08-01

    We examine the nucleated growth of a binary, immiscible liquid drop within a homogeneous gas. The system couples the growth of the liquid drop with the phase separation of the immiscible components and, thus, can potentially reveal novel pattern formation. To carry out this study, we first characterize the thermodynamic properties of the system in terms of an appropriate Ginzburg-Landau free energy density. By minimizing this free energy, we construct the equilibrium phase diagram for the system. We then use a lattice Boltzmann algorithm to solve the hydrodynamic equations describing the dynamical evolution of the fluid. We observe intriguing tentaclelike structures within the nucleation and growth regime and explore how the formation of these structures depends on the thermodynamic and transport properties of the system. We give scaling laws describing domain growth in both the diffusion- and flow-limited regimes. The results highlight the novel physics that can emerge when there is interplay between the ordering of a density and a concentration field.

  18. Gas-phase nitronium ion affinities.

    PubMed Central

    Cacace, F; de Petris, G; Pepi, F; Angelelli, F

    1995-01-01

    Evaluation of nitronium ion-transfer equilibria, L1NO2+ + L2 = L2NO2+ + L1 (where L1 and L2 are ligands 1 and 2, respectively) by Fourier-transform ion cyclotron resonance mass spectrometry and application of the kinetic method, based on the metastable fragmentation of L1(NO2+)L2 nitronium ion-bound dimers led to a scale of relative gas-phase nitronium ion affinities. This scale, calibrated to a recent literature value for the NO2+ affinity of water, led for 18 ligands, including methanol, ammonia, representative ketones, nitriles, and nitroalkanes, to absolute NO2+ affinities, that fit a reasonably linear general correlation when plotted vs. the corresponding proton affinities (PAs). The slope of the plot depends to a certain extent on the specific nature of the ligands and, hence, the correlations between the NO2+ affinities, and the PAs of a given class of compounds display a better linearity than the general correlation and may afford a useful tool for predicting the NO2+ affinity of a molecule based on its PA. The NO2+ binding energies are considerably lower than the corresponding PAs and well below the binding energies of related polyatomic cations, such as NO+, a trend consistent with the available theoretical results on the structure and the stability of simple NO2+ complexes. The present study reports an example of extension of the kinetic method to dimers, such as L1(NO2+)L2, bound by polyatomic ions, which may considerably widen its scope. Finally, measurement of the NO2+ affinity of ammonia allowed evaluation of the otherwise inaccessible PA of the amino group of nitramide and, hence, direct experimental verification of previous theoretical estimates. PMID:11607578

  19. Molecular Ice Nucleation Activity of Birch Pollen

    NASA Astrophysics Data System (ADS)

    Felgitsch, Laura; Bichler, Magdalena; Häusler, Thomas; Weiss, Victor U.; Marchetti-Deschmann, Martina; Allmaier, Günter; Grothe, Hinrich

    2015-04-01

    Heterogeneous ice nucleation plays a major part in ecosystem and climate. Due to the triggering of ice cloud formation it influences the radiation balance of the earth, but also on the ground it can be found to be important in many processes of nature. So far the process of heterogeneous ice nucleation is not fully understood and many questions remain to be answered. Biological ice nucleation is hereby from great interest, because it shows the highest freezing temperatures. Several bacteria and fungi act as ice nuclei. A famous example is Pseudomonas syringae, a bacterium in commercial use (Snomax®), which increases the freezing from homogeneous freezing temperatures of approx. -40° C (for small volumes as in cloud droplets) to temperatures up to -2° C. In 2001 it was found that birch pollen can trigger ice nucleation (Diehl et al. 2001; Diehl et al. 2002). For a long time it was believed that this is due to macroscopic features of the pollen surface. Recent findings of Bernhard Pummer (2012) show a different picture. The ice nuclei are not attached on the pollen surface directly, but on surface material which can be easily washed off. This shows that not only the surface morphology, but also specific molecules or molecular structures are responsible for the ice nucleation activity of birch pollen. With various analytic methods we work on elucidating the structure of these molecules as well as the mechanism with which they trigger ice nucleation. To solve this we use various instrumental analytic techniques like Nuclear Magnetic Resonance spectroscopy (NMR), Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry (MALDI-MS), and Gas-phase Electrophoretic Mobility Molecular Analysis (GEMMA). Also standard techniques like various chromatographic separation techniques and solvent extraction are in use. We state here that this feature might be due to the aggregation of small molecules, with agglomerates showing a specific surface structure. Our results

  20. Gas Phase Organophosphate Detection Using Enzymes Encapsulated Within Peptide Nanotubes

    DTIC Science & Technology

    2014-03-27

    as gas and liquid chromatography, although very sensitive and reliable, have disadvantages. The US Air Force currently uses a field portable gas...biosensors to detect OPCs in liquid (Park et al., 2011; Stevens, 2012) and gas (Baker, 2013) phases. Detection is based upon a redox reaction... injecting a known volume of gas saturated at room temperature with malathion (vapor pressure = 25 ppbv), into a 40 ml vial purged with nitrogen at constant

  1. Density, phase behavior keys to acid gas injection

    SciTech Connect

    Carroll, J.J.; Lui, D.W.

    1997-06-23

    Acid gas injection requires an understanding of the complexities of gas phase behavior and physical properties. Injected acid gas streams typically come from the top of the regenerator reflux accumulator of an amine unit. Thus, they are composed mainly of hydrogen sulfide (H{sub 2}S) and carbon dioxide (CO{sub 2}) with significant amounts of methane and lesser amounts of other hydrocarbons. The stream is also saturated with water. The stream from the amine plant has a low pressure and must be compressed to a higher pressure for injection into a disposal well. This article summarizes the available research on acid gas phase behavior and density calculations.

  2. Gas-Liquid Flows and Phase Separation

    NASA Technical Reports Server (NTRS)

    McQuillen, John

    2004-01-01

    Common issues for space system designers include:Ability to Verify Performance in Normal Gravity prior to Deployment; System Stability; Phase Accumulation & Shedding; Phase Separation; Flow Distribution through Tees & Manifolds Boiling Crisis; Heat Transfer Coefficient; and Pressure Drop.The report concludes:Guidance similar to "A design that operates in a single phase is less complex than a design that has two-phase flow" is not always true considering the amount of effort spent on pressurizing, subcooling and phase separators to ensure single phase operation. While there is still much to learn about two-phase flow in reduced gravity, we have a good start. Focus now needs to be directed more towards system level problems .

  3. [Effect of inert gas xenon on the functional state of nucleated cells of peripheral blood during freezing].

    PubMed

    Laptev, D S; Polezhaeva, T V; Zaitseva, O O; Khudyakov, A N; Utemov, S V; Knyazev, M G; Kostyaev, A A

    2015-01-01

    A new method of preservation of nucleated cells in the electric refrigerator with xenon. After slow freezing and storage is even one day at -80 °C persists for more than 60% leukocytes. Cell membranes are resistant to the vital dye. In 85% of granulocytes stored baseline lysosomal-cationic protein, reduced lipid peroxidation and antioxidant activity. Cryopreservation of biological objects in inert gases is a promising direction in the practice of medicine and can be an alternative to the traditional method using liquid nitrogen.

  4. Real-Time Characterization of Particle and Gas Phase Diesel Emissions - Understanding the Influence of a Diesel Particulate Filter

    NASA Astrophysics Data System (ADS)

    Cross, E. S.; Sappok, A.; Carrasquillo, A. J.; Onasch, T. B.; Fortner, E.; Jayne, J.; Wong, V.; Worsnop, D. R.; Kroll, J. H.

    2010-12-01

    Diesel engine emissions constitute an important source of particulate black carbon (BC) and gas phase organics in the atmosphere. Particles composed of black carbon absorb incoming solar radiation having a net positive radiative forcing effect on the climate. Black carbon also has major air quality implications as BC particles from combustion sources are often coated with poly-aromatic hydrocarbons (PAHs), and are generally emitted in higher concentrations close to population centers. Regulations of diesel emissions target the mass of particulate matter (PM) and concentration of volatile gas phase organic compounds (VOC) produced. A third, potentially important component of diesel exhaust, is low volatility organic compounds (LVOC). Both the VOCs and LVOCs can lead to the formation of ultrafine particles (via homogeneous nucleation) and secondary organic aerosols (via oxidation). Recent development of mass spectrometric techniques to measure particulate black carbon and gas phase organics provide the opportunity to quantify and chemically characterize diesel emissions in real-time. Measurements of both the particulate and gas phase emissions from a medium-duty diesel engine will be presented. The experimental apparatus includes a diesel particulate filter (DPF) integrated in the exhaust line, which is a requirement for all 2007 and newer on-road diesel engines in the U.S. Measurements taken over the regeneration cycle of the DPF provide insight into how this after-treatment technology influences the gas phase and particle phase composition of the emissions. Gas phase measurements were made with a newly developed Total Gas-Phase Organic (TGO) instrument. Particulate species were characterized with a Soot Particle Aerosol Mass Spectrometer (SP-AMS). The combined utility of the TGO and SP-AMS instruments for emissions characterization studies will be demonstrated.

  5. Buckyball Nucleation of HiPco Tubes

    NASA Technical Reports Server (NTRS)

    Smalley, Richard E.

    2012-01-01

    The purpose of this innovation is to enhance nucleation of single-wall nanotubes (SWNTs) in the HiPco process, selectively producing 10,10 tubes, something which until now has not been thought possible. This is accomplished by injecting C60, or a derivative of C60, solubilized in supercritical CO2 together with a transition metal carboneal cocatalyst into the HiPco reactor. This is a variant on the supercritical disclosure. C60 has never been used to nucleate carbon nanotubes in the gas phase. C60 itself may not have adequate solubility in supercritical CO2. However, fluorinated C60, e.g., C60F36, is easy to make cheaply and should have much enhanced solubility.

  6. Mixed Stationary Liquid Phases for Gas-Liquid Chromatography.

    ERIC Educational Resources Information Center

    Koury, Albert M.; Parcher, Jon F.

    1979-01-01

    Describes a laboratory technique for use in an undergraduate instrumental analysis course that, using the interpretation of window diagrams, prepares a mixed liquid phase column for gas-liquid chromatography. A detailed procedure is provided. (BT)

  7. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry.

    PubMed

    Rondo, L; Ehrhart, S; Kürten, A; Adamov, A; Bianchi, F; Breitenlechner, M; Duplissy, J; Franchin, A; Dommen, J; Donahue, N M; Dunne, E M; Flagan, R C; Hakala, J; Hansel, A; Keskinen, H; Kim, J; Jokinen, T; Lehtipalo, K; Leiminger, M; Praplan, A; Riccobono, F; Rissanen, M P; Sarnela, N; Schobesberger, S; Simon, M; Sipilä, M; Smith, J N; Tomé, A; Tröstl, J; Tsagkogeorgas, G; Vaattovaara, P; Winkler, P M; Williamson, C; Wimmer, D; Baltensperger, U; Kirkby, J; Kulmala, M; Petäjä, T; Worsnop, D R; Curtius, J

    2016-03-27

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

  8. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Rondo, L.; Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-03-01

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

  9. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    PubMed Central

    Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-01-01

    Abstract Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI‐APi‐TOF (Chemical Ionization‐Atmospheric Pressure interface‐Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI‐APi‐TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4‐H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self‐contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit. PMID:27610289

  10. Optically-Based Diagnostics for Gas-Phase Laser Development

    DTIC Science & Technology

    2010-08-01

    Phase Laser Development Acknowledgement of Support and Disclaimer This material is based upon work supported by Air Force Office of Scientific...00-2010 4. TITLE AND SUBTITLE Optically-Based Diagnostics for Gas-Phase Laser Development 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM...Sciences Inc. Role of Optical Diagnostics in High Energy Gas Laser Development  Chemically rich, energetic, reacting flow with competing phenomena

  11. Experiments on Nucleation in Different Flow Regimes

    NASA Technical Reports Server (NTRS)

    Bayuzick, Robert J.; Hofmeister, W. H.; Morton, C. M.; Robinson, M. B.

    1998-01-01

    The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys.

  12. Nucleation in the presence of long-range interactions. [performed on ferroelectric barium titanate

    NASA Technical Reports Server (NTRS)

    Chandra, P.

    1989-01-01

    Unlike droplet nucleation near a liquid-gas critical point, the decay of metastable phases in crystalline materials is strongly affected by the presence of long-range forces. Field quench experiments performed on the ferroelectric barium titanate indicate that nucleation in this material is markedly different from that observed in liquids. In this paper, a theory for nucleation at a first-order phase transition in which the mediating forces are long range is presented. It is found that the long-range force induces cooperative nucleation and growth processes, and that this feedback mechanism produces a well-defined delay time with a sharp onset in the transformation to the stable phase. Closed-form expressions for the characteristic onset time and width of the transition are developed, in good agreement with numerical and experimental results.

  13. Preferential Nucleation during Polymorphic Transformations

    PubMed Central

    Sharma, H.; Sietsma, J.; Offerman, S. E.

    2016-01-01

    Polymorphism is the ability of a solid material to exist in more than one phase or crystal structure. Polymorphism may occur in metals, alloys, ceramics, minerals, polymers, and pharmaceutical substances. Unresolved are the conditions for preferential nucleation during polymorphic transformations in which structural relationships or special crystallographic orientation relationships (OR’s) form between the nucleus and surrounding matrix grains. We measured in-situ and simultaneously the nucleation rates of grains that have zero, one, two, three and four special OR’s with the surrounding parent grains. These experiments show a trend in which the activation energy for nucleation becomes smaller – and therefore nucleation more probable - with increasing number of special OR’s. These insights contribute to steering the processing of polymorphic materials with tailored properties, since preferential nucleation affects which crystal structure forms, the average grain size and texture of the material, and thereby - to a large extent - the final properties of the material. PMID:27484579

  14. Preferential Nucleation during Polymorphic Transformations.

    PubMed

    Sharma, H; Sietsma, J; Offerman, S E

    2016-08-03

    Polymorphism is the ability of a solid material to exist in more than one phase or crystal structure. Polymorphism may occur in metals, alloys, ceramics, minerals, polymers, and pharmaceutical substances. Unresolved are the conditions for preferential nucleation during polymorphic transformations in which structural relationships or special crystallographic orientation relationships (OR's) form between the nucleus and surrounding matrix grains. We measured in-situ and simultaneously the nucleation rates of grains that have zero, one, two, three and four special OR's with the surrounding parent grains. These experiments show a trend in which the activation energy for nucleation becomes smaller - and therefore nucleation more probable - with increasing number of special OR's. These insights contribute to steering the processing of polymorphic materials with tailored properties, since preferential nucleation affects which crystal structure forms, the average grain size and texture of the material, and thereby - to a large extent - the final properties of the material.

  15. Electron spectrometer for gas-phase spectroscopy

    SciTech Connect

    Bozek, J.D.; Schlachter, A.S.

    1997-04-01

    An electron spectrometer for high-resolution spectroscopy of gaseous samples using synchrotron radiation has been designed and constructed. The spectrometer consists of a gas cell, cylindrical electrostatic lens, spherical-sector electron energy analyzer, position-sensitive detector and associated power supplies, electronics and vacuum pumps. Details of the spectrometer design are presented together with some representative spectra.

  16. Single Particle Laser Mass Spectrometry Applied to Differential Ice Nucleation Experiments at the AIDA Chamber

    SciTech Connect

    Gallavardin, S. J.; Froyd, Karl D.; Lohmann, U.; Moehler, Ottmar; Murphy, Daniel M.; Cziczo, Dan

    2008-08-26

    Experiments conducted at the Aerosol Interactions and Dynamics in the Atmosphere (AIDA) chamber located in Karlsruhe, Germany permit investigation of particle properties that affect the nucleation of ice at temperature and water vapor conditions relevant to cloud microphysics and climate issues. Ice clouds were generated by heterogeneous nucleation of Arizona test dust (ATD), illite, and hematite and homogeneous nucleation of sulfuric acid. Ice crystals formed in the chamber were inertially separated from unactivated, or ‘interstitial’ aerosol particles with a pumped counterflow virtual impactor (PCVI), then evaporated. The ice residue (i.e., the aerosol which initiated ice nucleation plus any material which was scavenged from the gas- and/or particle-phase), was chemically characterized at the single particle level using a laser ionization mass spectrometer. In this manner the species that first nucleated ice could be identified out of a mixed aerosol population in the chamber. Bare mineral dust particles were more effective ice nuclei (IN) than similar particles with a coating. Metallic particles from contamination in the chamber initiated ice nucleation before other species but there were few enough that they did not compromise the experiments. Nitrate, sulfate, and organics were often detected on particles and ice residue, evidently from scavenging of trace gas-phase species in the chamber. Hematite was a more effective ice nucleus than illite. Ice residue was frequently larger than unactivated test aerosol due to the formation of aggregates due to scavenging, condensation of contaminant gases, and the predominance of larger aerosol in nucleation.

  17. Homogenous nucleation of sulfuric acid and water at close to atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Brus, D.; Neitola, K.; Hyvärinen, A.-P.; Petäjä, T.; Vanhanen, J.; Sipilä, M.; Paasonen, P.; Kulmala, M.; Lihavainen, H.

    2011-06-01

    In this study the homogeneous nucleation rates in the system of sulfuric acid and water were measured by using a flow tube technique. The goal was to directly compare particle formation rates obtained from atmospheric measurements with nucleation rates of freshly nucleated particles measured with particle size magnifier (PSM) which has detection efficiency of unity for particles having mobility diameter of 1.5 nm. The gas phase sulfuric acid concentration in this study was measured with the chemical ionization mass spectrometer (CIMS), commonly used in field measurements. The wall losses of sulfuric acid were estimated from measured concentration profiles along the flow tube. The initial concentrations of sulfuric acid estimated from loss measurements ranged from 108 to 3 × 109 molecules cm-3. The nucleation rates obtained in this study cover about three orders of magnitude from 10-1 to 102 cm-3 s-1 for commercial ultrafine condensation particle counter (UCPC) TSI model 3025A and from 101 to 104 cm-3 s-1 for PSM. The nucleation rates and the slopes (dlnJ/dln [H2SO4]) show satisfactory agreement when compared to empirical kinetic and activation models and the latest atmospheric nucleation data. To the best of our knowledge, this is the first experimental work providing temperature dependent nucleation rate measurements using a high efficiency particle counter with a cut-off-size of 1.5 nm together with direct measurements of gas phase sulfuric acid concentration.

  18. Evaluation of phase envelope on natural gas, condensate and gas hydrate

    NASA Astrophysics Data System (ADS)

    Promkotra, S.; Kangsadan, T.

    2015-03-01

    The experimentally gas hydrate are generated by condensate and natural gas. Natural gas and condensate samples are collected from a gas processing plant where is situated in the northeastern part of Thailand. Physical properties of the API gravity and density of condensate are presented in the range of 55-60° and 0.71-0.76 g/cm3. The chemical compositions of petroleum-field water are analyzed to evaluate the genesis of gas hydrate by experimental procedure. The hydrochemical compositions of petroleum-field waters are mostly the Na-Cl facies. This condition can estimate how the hydrate forms. Phase envelope of condensate is found only one phase which is liquid phase. The liquid fraction is 100% at 15°C and 101.327 kPa, with the critical pressure and temperature of 2,326 kPa and 611.5 K. However, natural gas can be separated in three phases which are vapor, liquid and solid phase with the pressure and temperature at 100 kPa and 274.2 K. The hydrate curves explicit both hydrate zone and nonhydrate zone. Phase envelope of gas hydrate from the phase diagram indicates the hydrate formation. The experimental results of hydrate form can correlate to the hydrate curve. Besides, the important factor of hydrate formation depends on impurity in the petroleum system.

  19. Dissolution of two-phase microsystems: Gas and liquid microparticle dissolution and dehydration of biomaterials

    NASA Astrophysics Data System (ADS)

    Duncan, Phillip Brent

    A main focus of this research is to develop techniques to study the dissolution process of two-phase microsystems on a single microparticle basis. This dissertation introduces a systematic approach to investigate the formation of microparticles to fulfill the need for rational design of microspheres for a range of applications. This novel method is based on the micropipet manipulation technique and can essentially test any system, where the continuous phase is a liquid and the dispersed phase is practically any phase, a gas (foam), a liquid (emulsion), or a solid (suspension). It is possible to study single microparticle volumes in the picoliter to nanoliter scale, which is on the same size-scale as particles created in bulk suspensions, microsphere processes, and applications. The ability to create, isolate, observe, and manipulate individual gas, liquid or solid microparticles in a well-defined and controlled liquid environment was found to be ideal to study gas microbubbles and microparticles, liquid microdroplets, and the dehydration of dissolved solutes. Subsequently, one can directly measure the dissolution rate and, when a solute is present, calculate its concentration during the dissolution process. Microbubble or microdroplet dissolution in a second phase is driven by two independent factors, a concentration gradient (undersaturation of the dispersed phase in the continuous phase) and a pressure gradient (due to the Laplace-overpressure inside the microparticle created by the surface tension). Experimentally, each of these driving forces can be independently tested. Both the gas microparticle and pure liquid microdroplet dissolution can be predicted by a simple theory based on the diffusion coefficient and solubility limit of the dispersed phase in the continuous phase. The dehydration of a salt ion solution microdroplet results in the nucleation and growth of a crystal, while the dehydration of proteins leads to glassification of the protein. The water

  20. High resolution ion mobility measurements for gas phase proteins: correlation between solution phase and gas phase conformations

    NASA Astrophysics Data System (ADS)

    Hudgins, Robert R.; Woenckhaus, Jürgen; Jarrold, Martin F.

    1997-11-01

    Our high resolution ion mobility apparatus has been modified by attaching an electrospray source to perform measurements for biological molecules. While the greater resolving power permits the resolution of more conformations for BPTI and cytochrome c, the resolved features are generally much broader than expected for a single rigid conformation. A major advantage of the new experimental configuration is the much gentler introduction of ions into the drift tube, so that the observed gas phase conformations appear to more closely reflect those present in solution. For example, it is possible to distinguish between the native state of cytochrome c and the methanol-denatured form on the basis of the ion mobility measurements; the mass spectra alone are not sensitive enough to detect this change. Thus this approach may provide a quick and sensitive tool for probing the solution phase conformations of biological molecules.

  1. Para-Hydrogen-Enhanced Gas-Phase Magnetic Resonance Imaging

    SciTech Connect

    Bouchard, Louis-S.; Kovtunov, Kirill V.; Burt, Scott R.; Anwar,M. Sabieh; Koptyug, Igor V.; Sagdeev, Renad Z.; Pines, Alexander

    2007-02-23

    Herein, we demonstrate magnetic resonance imaging (MRI) inthe gas phase using para-hydrogen (p-H2)-induced polarization. A reactantmixture of H2 enriched in the paraspin state and propylene gas is flowedthrough a reactor cell containing a heterogenized catalyst, Wilkinson'scatalyst immobilized on modified silica gel. The hydrogenation product,propane gas, is transferred to the NMR magnet and is spin-polarized as aresult of the ALTADENA (adiabatic longitudinal transport and dissociationengenders net alignment) effect. A polarization enhancement factor of 300relative to thermally polarized gas was observed in 1D1H NMR spectra.Enhancement was also evident in the magnetic resonance images. This isthe first demonstration of imaging a hyperpolarized gaseous productformed in a hydrogenation reaction catalyzed by a supported catalyst.This result may lead to several important applications, includingflow-through porous materials, gas-phase reaction kinetics and adsorptionstudies, and MRI in low fields, all using catalyst-free polarizedfluids.

  2. Constant volume gas cell optical phase-shifter

    DOEpatents

    Phillion, Donald W.

    2002-01-01

    A constant volume gas cell optical phase-shifter, particularly applicable for phase-shifting interferometry, contains a sealed volume of atmospheric gas at a pressure somewhat different than atmospheric. An optical window is present at each end of the cell, and as the length of the cell is changed, the optical path length of a laser beam traversing the cell changes. The cell comprises movable coaxial tubes with seals and a volume equalizing opening. Because the cell is constant volume, the pressure, temperature, and density of the contained gas do not change as the cell changes length. This produces an exactly linear relationship between the change in the length of the gas cell and the change in optical phase of the laser beam traversing it. Because the refractive index difference between the gas inside and the atmosphere outside is very much the same, a large motion must be made to change the optical phase by the small fraction of a wavelength that is required by phase-shifting interferometry for its phase step. This motion can be made to great fractional accuracy.

  3. Oscillatory burning of solid propellants including gas phase time lag.

    NASA Technical Reports Server (NTRS)

    T'Ien, J. S.

    1972-01-01

    An analysis has been performed for oscillatory burning of solid propellants including gas phase time lag. The gaseous flame is assumed to be premixed and laminar with a one-step overall chemical reaction. The propellant is assumed to decompose according to the Arrenhius Law, with no condensed phase reaction. With this model, strong gas phase resonance has been found in certain cases at the characteristic gas-phase frequencies, but the peaking of the acoustic admittance is in the direction favoring the damping of pressure waves. At still higher frequencies, moderate wave-amplifying ability was found. The limit of low frequency response obtained previously by Denison and Baum was recovered, and the limitations of the quasi-steady theory were investigated.

  4. Communication: Fourier-transform infrared probing of remarkable quantities of gas trapped in cold homogeneously nucleated nanodroplets

    NASA Astrophysics Data System (ADS)

    Uras-Aytemiz, Nevin; Devlin, J. Paul

    2013-07-01

    Studies of catalyzed all-vapor gas-hydrate formation on a sub-second timescale have been extended with a special focus on liquid-droplet compositions at the instant of hydrate crystallization. This focus has been enabled by inclusion of methanol in the all-vapor mixture. This slows droplet to gas-hydrate conversion near 200 K to a time scale suited for standard FTIR sampling. Such droplet data are sought as a guide to ongoing efforts to reduce the amount of guest catalyst required for instant formation of the gas hydrates. For the same reason, all-vapor sampling has also been extended to the generation of long-lived liquid droplets with reduced or no water content. Observations of single-solvent droplets show that surprising quantities of gas molecules are trapped during rapid droplet growth. For example, CO2 is trapped at levels near 50 mol. % in droplets of acetone, tetrahydrofuran, or trimethylene oxide formed under CO2 pressures of several Torr in a cold-chamber at 170 K. Less but significant amounts of gas are trapped at higher temperatures, or in methanol or water-methanol droplets. The droplet metastability appears to commonly lead to formation of bubbles larger than the original nanodroplets. Besides serving as a guide for the all-vapor gas-hydrate studies, the semiquantitative evidence of extensive trapping of gases is expected to have a role in future studies of atmospheric aerosols.

  5. Gas and particulate phase products from the ozonolysis of acenaphthylene

    NASA Astrophysics Data System (ADS)

    Riva, Matthieu; Healy, Robert M.; Tomaz, Sophie; Flaud, Pierre-Marie; Perraudin, Emilie; Wenger, John C.; Villenave, Eric

    2016-10-01

    Polycyclic aromatic hydrocarbons (PAHs) are recognized as important secondary organic aerosol (SOA) precursors in the urban atmosphere. In this work, the gas-phase ozonolysis of acenaphthylene was investigated in an atmospheric simulation chamber using a proton transfer reaction time-of-flight-mass spectrometer (PTR-TOF-MS) and an aerosol time-of-flight-mass spectrometer (ATOFMS) for on-line characterization of the oxidation products in the gas and particle phases, respectively. SOA samples were also collected on filters and analyzed by ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) and gas chromatography/electron impact ionization-mass spectrometry (GC/EI-MS). The major gas-phase products included a range of oxygenated naphthalene derivatives such as 1,8-naphthalic anhydride, naphthalene 1,8-dicarbaldehyde and naphthaldehyde, as well as a secondary ozonide. Possible reaction mechanisms are proposed for the formation of these products and favoured pathways have been suggested. Many of these products were also found in the particle phase along with a range of oligomeric compounds. The same range of gas and particle phase products was observed in the presence and absence of excess cyclohexane, an OH scavenger, indicating that OH radical production from the ozonolysis of acenaphthylene is negligible. SOA yields in the range 23-37% were determined and indicate that acenaphthylene ozonolysis may contribute to part of the SOA observed in urban areas.

  6. Collision-induced gas phase dissociation rates

    NASA Technical Reports Server (NTRS)

    Hansen, C. Frederick

    1990-01-01

    The Landau-Zener theory of reactive cross sections was applied to diatomic molecules dissociating from a ladder of vibrational states. The result predicts a dissociation rate that is quite well duplicated by an Arrhenius function having a preexponential temperature dependence of about T(sub -1/2), at least for inert collision partners. This relation fits experimental data reasonably well. The theory is then used to calculate the effect of vibrational nonequilibrium on dissociation rate. For Morse oscillators, the results are about the same as given by Hammerling, Kivel, and Teare in their analytic approximation for harmonic oscillators, though at very high temperature a correction for the partition function limit is included. The empirical correction for vibration nonequilibrium proposed by Park, which is a convenient algorithm for CFD calculations, is modified to prevent a drastic underestimation of dissociation rates that occurs with this method when vibrational temperature is much smaller than the kinetic temperature of the gas.

  7. Specific and reproducible gas sensors utilizing gas-phase chemical reaction on organic transistors.

    PubMed

    Zang, Yaping; Zhang, Fengjiao; Huang, Dazhen; Di, Chong-an; Meng, Qing; Gao, Xike; Zhu, Daoben

    2014-05-01

    Utilizing a textbook reaction on the surface of an organic active channel, achieves sensitive detection of HCl, NH3 and NO2, with good selectivity, excellent reproducibility, and satisfactory stability. These results reveal gas-phase reaction assisted detection as a unique and promising approach to construct practical applicable gas sensors with typical organic transistors.

  8. Enantiomeric phase separation in a lattice gas model: Guggenheim approximation

    NASA Astrophysics Data System (ADS)

    Huckaby, Dale A.; Shinmi, Masato; Ausloos, Marcel; Clippe, Paulette

    1986-05-01

    We consider a lattice gas in which the two enantiomeric forms of a tetrahedral molecule, consisting of a central carbon atom bonded to four different groups A, B, G, and H, are adsorbed onto a triangular lattice, such that the carbon atom is above a lattice site, the three bonds to A, B, and G point toward neighboring lattice sites, and the bond to H points perpendicular to and away from the plane of the lattice. For a certain choice of intermolecular interactions, such as may exist between the zwitterion forms of an amino acid, the phase diagram was investigated using a Guggenheim approximation with two order parameters. Enantiomeric phase separation into two symmetric condensed phases occurs at low temperatures. These condensed phases become a single racemic condensed phase at a critical line, and they are in equilibrium with a racemic gas phase along a line of triple points. These two lines coincide at a critical endpoint. The racemic condensed and gas phases are in equilibrium along a two phase coexistence line which begins at the critical endpoint and ends at a critical point. No tricritical point was found in the model for the special choice of interactions studied.

  9. Rupture of the cell envelope by induced intracellular gas phase expansion in gas vacuolate bacteria.

    PubMed Central

    Hemmingsen, B B; Hemmingsen, E A

    1980-01-01

    Using a new approach, we estimated the physical strength of the cell envelopes of three species of gram-negative, gas vacuolate bacteria (Microcyclus aquaticus, Prosthecomicrobium pneumaticum, and Meniscus glaucopis). Populations of cells were slowly (0.5 to 2.9 h) saturated with argon, nitrogen, or helium to final pressures up to 100 atm (10, 132 kPa). The gas phases of the vesicles remained intact and, upon rapid (1 to 2 s) decompression to atmospheric pressure, expanded and ruptured the cells; loss of colony-forming units was used as an index of rupture. Because the cell envelope is the cellular component most likely to resist the expanding intracellular gas phase, its strength can be estimated from the minimum gas pressures that produce rupture. The viable counts indicated that these minimum pressures were between 25 and 50 atm; the majority of the cell envelopes were ruptured at pressures between 50 and 100 atm. Cells in which the gas vesicles were collapsed and the gas phases were effectively dissolved by rapid compression tolerated decompression from much higher gas saturations. Cells that do not normally possess gas vesicles (Escherichia coli) or that had been prevented from forming them by addition of L-lysine to the medium (M. aquaticus) were not harmed by decompression from gas saturation pressures up to 300 atm. PMID:7204336

  10. Nucleation of ice and its management in ecosystems.

    PubMed

    Franks, Felix

    2003-03-15

    In addition to the gas and liquid phases, water can exist in many different solid states. Some of these are the well-studied crystalline ice polymorphs and the clathrate hydrates, but at least two distinguishable amorphous solid forms have also been shown to exist. This diversity of possible condensed states implies a multiplicity of transitions, each of them presumably associated with a nucleation step. Disagreement still exists as to whether the amorphous states can be regarded as metastable phases, and whether the phenomenon of polyamorphism can be treated in terms of phase transitions. In the Earth's hydrosphere, several of the crystalline and amorphous water phases can be formed from vapour, under given conditions of temperature, pressure and supersaturation, and classical nucleation theory is believed to account reasonably well for the observed growth of condensed forms of water in the upper atmosphere. Many terrestrial organisms are able to activate mechanisms to control the nucleation and growth of ice when exposed to sub-zero temperatures, thus enabling them to minimize the lethal effects of extreme freeze desiccation. The substances involved in these mechanisms include carbohydrates, amino acids and so-called cold-shock proteins, but the actual mechanisms of interfering with ice nucleation, although quite well documented, are as yet imperfectly understood. This is particularly true for the genetic control associated with biochemical processes that produce freeze resistance and freeze tolerance. The molecular biology of cold stress is currently a subject of intensive study.

  11. Gas Phase Chiral Separations By Ion Mobility Spectrometry

    PubMed Central

    Dwivedi, Prabha; Wu, Ching; Hill, Herbert H.

    2013-01-01

    This manuscript introduces the concept of Chiral Ion Mobility Spectrometry (CIMS) and presents examples demonstrating the gas phase separation of enantiomers of a wide range of racemates including pharmaceuticals, amino acids and carbohydrates. CIMS is similar to traditional ion mobility spectrometry (IMS), where gas phase ions, when subjected to a potential gradient are separated at atmospheric pressure due to differences in their shapes and sizes. In addition to size and shape, CIMS separates ions based on their stereospecific interaction with a chiral gas. In order to achieve chiral discrimination by CIMS, an asymmetric environment was provided by doping the drift gas with a volatile chiral reagent. In this study S-(+)-2-butanol was used as a chiral modifier to demonstrate enantiomeric separations of atenolol, serine, methionine, threonine, methyl-α-glucopyranoside, glucose, penicillamine, valinol, phenylalanine, and tryptophan from their respective racemic mixtures. PMID:17165808

  12. Gas phase metal cluster model systems for heterogeneous catalysis.

    PubMed

    Lang, Sandra M; Bernhardt, Thorsten M

    2012-07-14

    Since the advent of intense cluster sources, physical and chemical properties of isolated metal clusters are an active field of research. In particular, gas phase metal clusters represent ideal model systems to gain molecular level insight into the energetics and kinetics of metal-mediated catalytic reactions. Here we summarize experimental reactivity studies as well as investigations of thermal catalytic reaction cycles on small gas phase metal clusters, mostly in relation to the surprising catalytic activity of nanoscale gold particles. A particular emphasis is put on the importance of conceptual insights gained through the study of gas phase model systems. Based on these concepts future perspectives are formulated in terms of variation and optimization of catalytic materials e.g. by utilization of bimetals and metal oxides. Furthermore, the future potential of bio-inspired catalytic material systems are highlighted and technical developments are discussed.

  13. Effect of phase behavior on bypassing in enriched gas floods

    SciTech Connect

    Burger, J.E.; Bhogeswara, R.; Mohanty, K.K. )

    1994-05-01

    Enriched gas floods incorporate a complex interaction of heterogeneity, fingering, multiphase flow, and phase behavior. Experiments and simulations indicate that the optimum solvent enrichment in high-viscosity-ratio secondary gas floods can be below minimum miscibility enrichment (MME). The compositional path and resulting mobility profile in multidimensional multiple-contact miscible (MCM) or immiscible floods are different from their 1D counterparts for high-viscosity-ratio floods in heterogeneous media.

  14. Phase space analysis of some interacting Chaplygin gas models

    NASA Astrophysics Data System (ADS)

    Khurshudyan, M.; Myrzakulov, R.

    2017-02-01

    In this paper we discuss a phase space analysis of various interacting Chaplygin gas models in general relativity. Linear and nonlinear sign changeable interactions are considered. For each case appropriate late time attractors of field equations are found. The Chaplygin gas is one of the dark fluids actively considered in modern cosmology due to the fact that it is a joint model of dark energy and dark matter.

  15. Gas phase chemical detection with an integrated chemical analysis system

    SciTech Connect

    CASALNUOVO,STEPHEN A.; FRYE-MASON,GREGORY CHARLES; KOTTENSTETTE,RICHARD; HELLER,EDWIN J.; MATZKE,CAROLYN M.; LEWIS,PATRICK R.; MANGINELL,RONALD P.; BACA,ALBERT G.; HIETALA,VINCENT M.

    2000-04-12

    Microfabrication technology has been applied to the development of a miniature, multi-channel gas phase chemical laboratory that provides fast response, small size, and enhanced versatility and chemical discrimination. Each analysis channel includes a sample preconcentrator followed by a gas chromatographic separator and a chemically selective surface acoustic wave detector array to achieve high sensitivity and selectivity. The performance of the components, individually and collectively, is described.

  16. Freeze drying for gas chromatography stationary phase deposition

    DOEpatents

    Sylwester, Alan P.

    2007-01-02

    The present disclosure relates to methods for deposition of gas chromatography (GC) stationary phases into chromatography columns, for example gas chromatography columns. A chromatographic medium is dissolved or suspended in a solvent to form a composition. The composition may be inserted into a chromatographic column. Alternatively, portions of the chromatographic column may be exposed or filled with the composition. The composition is permitted to solidify, and at least a portion of the solvent is removed by vacuum sublimation.

  17. Gas-phase azide functionalization of carbon.

    PubMed

    Stenehjem, Eric D; Ziatdinov, Vadim R; Stack, T Daniel P; Chidsey, Christopher E D

    2013-01-23

    Tailoring the surface and interfacial properties of inexpensive and abundant carbon materials plays an increasingly important role for innovative applications including those in electrocatalysis, energy storage, gas separations, and composite materials. Described here is the novel preparation and subsequent use of gaseous iodine azide for the azide modification of carbon surfaces. In-line generation of gaseous iodine azide from iodine monochloride vapor and solid sodium azide is safe and convenient. Immediate treatment of carbon surfaces with this gaseous stream of iodine azide provides a highly reproducible, selective, and scalable azide functionalization that minimizes waste and reduces deleterious side reactions. Among the possible uses of azide-modified surfaces, they serve as versatile substrates for the attachment of additional functionality by coupling with terminal alkynes under the mild copper-catalyzed azide-alkyne cycloaddition (CuAAC) "click" reaction. For instance, coupling ethynylferrocene to azide-modified glassy carbon surfaces achieves ferrocene coverage up to 8 × 10(13) molecules/cm(2) by voltammetric and XPS analyses. The 1,2,3-triazole linker formed during the CuAAC reaction is robust and hydrolytically stable in both aqueous 1 M HClO(4) and 1 M NaOH for at least 12 h at 100 °C.

  18. Capillary gas chromatography with two new moderately high temperature phases.

    NASA Technical Reports Server (NTRS)

    Pollock, G. E.

    1972-01-01

    Gas chromatography test results are presented for two new moderately high-temperature phases of Dexsil 400-GC with free hydroxyl end groups (uncapped) and with end groups covered by trimethyl silyl groups (capped). The two Dexsil 400-GC phases were tested for their ability to resolve N-TFA-DL-(+)-2-butyl esters and n-butyl esters, as well as fatty acid methyl esters and hydrocarbon standards. Generally the more polar uncapped phase was superior to the capped phase in all separation comparisons, except for the hydrocarbons.

  19. Negative ion gas-phase chemistry of arenes.

    PubMed

    Danikiewicz, Witold; Zimnicka, Magdalena

    2016-01-01

    Reactions of aromatic and heteroaromatic compounds involving anions are of great importance in organic synthesis. Some of these reactions have been studied in the gas phase and are occasionally mentioned in reviews devoted to gas-phase negative ion chemistry, but no reviews exist that collect all existing information about these reactions. This work is intended to fill this gap. In the first part of this review, methods for generating arene anions in the gas phase and studying their physicochemical properties and fragmentation reactions are presented. The main topics in this part are as follows: processes in which gas-phase arene anions are formed, measurements and calculations of the proton affinities of arene anions, proton exchange reactions, and fragmentation processes of substituted arene anions, especially phenide ions. The second part is devoted to gas-phase reactions of arene anions. The most important of these are reactions with electrophiles such as carbonyl compounds and α,β-unsaturated carbonyl and related compounds (Michael acceptors). Other reactions including oxidation of arene anions and halogenophilic reactions are also presented. In the last part of the review, reactions of electrophilic arenes with nucleophiles are discussed. The best known of these is the aromatic nucleophilic substitution (SN Ar) reaction; however, other processes that lead to the substitution of a hydrogen atom in the aromatic ring are also very important. Aromatic substrates in these reactions are usually but not always nitroarenes bearing other substituents in the ring. The first step in these reactions is the formation of an anionic σ-adduct, which, depending on the substituents in the aromatic ring and the structure of the attacking nucleophile, is either an intermediate or a transition state in the reaction path. In the present review, we attempted to collect the results of both experimental and computational studies of the aforementioned reactions conducted since the

  20. Understanding Gas-Phase Ammonia Chemistry in Protoplanetary Disks

    NASA Astrophysics Data System (ADS)

    Chambers, Lauren; Oberg, Karin I.; Cleeves, Lauren Ilsedore

    2017-01-01

    Protoplanetary disks are dynamic regions of gas and dust around young stars, the remnants of star formation, that evolve and coagulate over millions of years in order to ultimately form planets. The chemical composition of protoplanetary disks is affected by both the chemical and physical conditions in which they develop, including the initial molecular abundances in the birth cloud, the spectrum and intensity of radiation from the host star and nearby systems, and mixing and turbulence within the disk. A more complete understanding of the chemical evolution of disks enables a more complete understanding of the chemical composition of planets that may form within them, and of their capability to support life. One element known to be essential for life on Earth is nitrogen, which often is present in the form of ammonia (NH3). Recent observations by Salinas et al. (2016) reveal a theoretical discrepancy in the gas-phase and ice-phase ammonia abundances in protoplanetary disks; while observations of comets and protostars estimate the ice-phase NH3/H2O ratio in disks to be 5%, Salinas reports a gas-phase NH3/H2O ratio of ~7-84% in the disk surrounding TW Hydra, a young nearby star. Through computational chemical modeling of the TW Hydra disk using a reaction network of over 5000 chemical reactions, I am investigating the possible sources of excess gas-phase NH3 by determining the primary reaction pathways of NH3 production; the downstream chemical effects of ionization by ultraviolet photons, X-rays, and cosmic rays; and the effects of altering the initial abundances of key molecules such as N and N2. Beyond providing a theoretical explanation for the NH3 ice/gas discrepancy, this new model may lead to fuller understanding of the gas-phase formation processes of all nitrogen hydrides (NHx), and thus fuller understanding of the nitrogen-bearing molecules that are fundamental for life as we know it.

  1. CHEMKIN2. General Gas-Phase Chemical Kinetics

    SciTech Connect

    Rupley, F.M.

    1992-01-24

    CHEMKIN is a high-level tool for chemists to use to describe arbitrary gas-phase chemical reaction mechanisms and systems of governing equations. It remains, however, for the user to select and implement a solution method; this is not provided. It consists of two major components: the Interpreter and the Gas-phase Subroutine Library. The Interpreter reads a symbolic description of an arbitrary, user-specified chemical reaction mechanism. A data file is generated which forms a link to the Gas-phase Subroutine Library, a collection of about 200 modular subroutines which may be called to return thermodynamic properties, chemical production rates, derivatives of thermodynamic properties, derivatives of chemical production rates, or sensitivity parameters. Both single and double precision versions of CHEMKIN are included. Also provided is a set of FORTRAN subroutines for evaluating gas-phase transport properties such as thermal conductivities, viscosities, and diffusion coefficients. These properties are an important part of any computational simulation of a chemically reacting flow. The transport properties subroutines are designed to be used in conjunction with the CHEMKIN Subroutine Library. The transport properties depend on the state of the gas and on certain molecular parameters. The parameters considered are the Lennard-Jones potential well depth and collision diameter, the dipole moment, the polarizability, and the rotational relaxation collision number.

  2. Gas purification in the dense phase at the CATS terminal

    SciTech Connect

    Openshaw, P.J.; Carnell, P.J.H.; Rhodes, E.F.

    1999-07-01

    The purification and transportation of natural gas at very high pressures can help to minimize the capital cost of pipelines and processing equipment. However, complex mixtures of hydrocarbons undergo unusual phase changes, such as retrograde condensation, as the temperature and pressure are altered. The Central Area Transmission System (CATS) is a joint venture of Amoci, BG, Amerada Hess, Phillips, Agip and Fina operated by Amoco on behalf of the owners. The design of the CATS terminal has provided an interesting processing challenge. The terminal receives a total of 1.6 Bscf/d of rich gas from a number of offshore fields. All are relatively sweet but the small amounts of H{sub 2}S and Hg are removed. Fixed bed technology was selected as the most economic purification process, while minimizing hydrocarbon loss and operator involvement. Conventionally, the raw gas would be split into the different hydrocarbon fractions and each would be processed separately. This would require the installation of a large number of reactors. A more elegant solution is to treat the gas on arrival at the terminal in the dense phase. This option raised questions around whether a fixed bed would be prone to fouling, could the pressure drop be kept low enough to avoid phase separation and would inadvertent wetting by condensation cause problems. Details are given of the test work carried out to prove the viability of using fixed bed technology for dense phase gas processing, the eventual design adopted and the performance over the first year of service.

  3. Enhancement of gas phase heat transfer by acoustic field application.

    PubMed

    Komarov, Sergey; Hirasawa, Masahiro

    2003-06-01

    This study discusses a possibility for enhancement of heat transfer between solids and ambient gas by application of powerful acoustic fields. Experiments are carried out by using preheated Pt wires (length 0.1-0.15 m, diameter 50 and 100 micro m) positioned at the velocity antinode of a standing wave (frequency range 216-1031 Hz) or in the path of a travelling wave (frequency range 6.9-17.2 kHz). A number of experiments were conducted under conditions of gas flowing across the wire surface. Effects of sound frequency, sound strength, gas flow velocity and wire preheating temperature on the Nusselt number are examined with and without sound application. The gas phase heat transfer rate is enhanced with acoustic field strength. Higher temperatures result in a vigorous radiation from the wire surface and attenuate the effect of sound. The larger the gas flow velocity, the smaller is the effect of sound wave on heat transfer enhancement.

  4. Gas Phase Hydration of Methyl Glyoxal to Form the Gemdiol

    NASA Astrophysics Data System (ADS)

    Kroll, Jay A.; Axson, Jessica L.; Vaida, Veronica

    2016-06-01

    Methylglyoxal is a known oxidation product of volatile organic compounds (VOCs) in Earth's atmosphere. While the gas phase chemistry of methylglyoxal is fairly well understood, its modeled concentration and role in the formation of secondary organic aerosol (SOA) continues to be controversial. The gas phase hydration of methylglyoxal to form a gemdiol has not been widely considered for water-restricted environments such as the atmosphere. However, this process may have important consequences for the atmospheric processing of VOCs. We will report on spectroscopic work done in the Vaida laboratory studying the hydration of methylglyoxal and discuss the implications for understanding the atmospheric processing and fate of methylglyoxal and similar molecules.

  5. Fischer Indole Synthesis in the Gas Phase, the Solution Phase, and at the Electrospray Droplet Interface

    NASA Astrophysics Data System (ADS)

    Bain, Ryan M.; Ayrton, Stephen T.; Cooks, R. Graham

    2017-02-01

    Previous reports have shown that reactions occurring in the microdroplets formed during electrospray ionization can, under the right conditions, exhibit significantly greater rates than the corresponding bulk solution-phase reactions. The observed acceleration under electrospray ionization could result from a solution-phase, a gas-phase, or an interfacial reaction. This study shows that a gas-phase ion/molecule (or ion/ion) reaction is not responsible for the observed rate enhancement in the particular case of the Fischer indole synthesis. The results show that the accelerated reaction proceeds in the microdroplets, and evidence is provided that an interfacial process is involved.

  6. A dynamic phase-field model for structural transformations and twinning: Regularized interfaces with transparent prescription of complex kinetics and nucleation. Part II: Two-dimensional characterization and boundary kinetics

    NASA Astrophysics Data System (ADS)

    Agrawal, Vaibhav; Dayal, Kaushik

    2015-12-01

    A companion paper presented the formulation of a phase-field model - i.e., a model with regularized interfaces that do not require explicit numerical tracking - that allows for easy and transparent prescription of complex interface kinetics and nucleation. The key ingredients were a re-parametrization of the energy density to clearly separate nucleation from kinetics; and an evolution law that comes from a conservation statement for interfaces. This enables clear prescription of nucleation through the source term of the conservation law and of kinetics through an interfacial velocity field. This model overcomes an important shortcoming of existing phase-field models, namely that the specification of kinetics and nucleation is both restrictive and extremely opaque. In this paper, we present a number of numerical calculations - in one and two dimensions - that characterize our formulation. These calculations illustrate (i) highly-sensitive rate-dependent nucleation; (ii) independent prescription of the forward and backward nucleation stresses without changing the energy landscape; (iii) stick-slip interface kinetics; (iii) the competition between nucleation and kinetics in determining the final microstructural state; (iv) the effect of anisotropic kinetics; and (v) the effect of non-monotone kinetics. These calculations demonstrate the ability of this formulation to precisely prescribe complex nucleation and kinetics in a simple and transparent manner. We also extend our conservation statement to describe the kinetics of the junction lines between microstructural interfaces and boundaries. This enables us to prescribe an additional kinetic relation for the boundary, and we examine the interplay between the bulk kinetics and the junction kinetics.

  7. An Atomistic View of Amyloidogenic Self-assembly: Structure and Dynamics of Heterogeneous Conformational States in the Pre-nucleation Phase

    PubMed Central

    Matthes, Dirk; Gapsys, Vytautas; Brennecke, Julian T.; de Groot, Bert L.

    2016-01-01

    The formation of well-defined filamentous amyloid structures involves a polydisperse collection of oligomeric states for which relatively little is known in terms of structural organization. Here we use extensive, unbiased explicit solvent molecular dynamics (MD) simulations to investigate the structural and dynamical features of oligomeric aggregates formed by a number of highly amyloidogenic peptides at atomistic resolution on the μs time scale. A consensus approach has been adopted to analyse the simulations in multiple force fields, yielding an in-depth characterization of pre-fibrillar oligomers and their global and local structure properties. A collision cross section analysis revealed structurally heterogeneous aggregate ensembles for the individual oligomeric states that lack a single defined quaternary structure during the pre-nucleation phase. To gain insight into the conformational space sampled in early aggregates, we probed their substructure and found emerging β-sheet subunit layers and a multitude of ordered intermolecular β-structure motifs with growing aggregate size. Among those, anti-parallel out-of-register β-strands compatible with toxic β-barrel oligomers were particularly prevalent already in smaller aggregates and formed prior to ordered fibrillar structure elements. Notably, also distinct fibril-like conformations emerged in the oligomeric state and underscore the notion that pre-nucleated oligomers serve as a critical intermediate step on-pathway to fibrils. PMID:27616019

  8. Heterogeneous nucleation of ice from supercooled water

    NASA Astrophysics Data System (ADS)

    Seeley, Lane Howard

    The relaxation of a metastable phase via the formation of a critical domain of the corresponding stable phase is a phenomenon that has been studied extensively in condensed matter physics. This dissertation describes laboratory studies of this phenomenon in the context of ice nucleation from undercooled liquid water. Such a study presents unique experimental challenges because the formation of a critical embryo is a statistical event, and once it occurs the entire sample relaxes to the stable phase. In order to study this statistical process it is necessary to create a large ensemble of separate, yet identical, domains of the metastable phase. The design of an apparatus is described which creates such an ensemble, in time, by repeatedly freezing and thawing a single water drop. This apparatus allows for the collection of a large data set and therefore can identify subtle changes in nucleation statistics that are produced by external controls. This dissertation describes a series of experiments intended to probe several aspects of ice nucleation. Results are presented for homogeneous ice nucleation as well as heterogeneous ice nucleation by; silanized and unsilanized glass, aliphatic alcohol Langmuir films, ionizing radiation, electric fields and motion at the three phase contact line. These experiments are analyzed largely in the context of classical nucleation theory. The unique experimental technique described here allows for sensitive tests of the temperature dependent nucleation rates, R( T), in these systems. Analysis of the R( T) within the context of classical nucleation theory constrains thermodynamic parameters and provides insight into these nucleation processes.

  9. Sigmoid kinetics of protein crystal nucleation

    NASA Astrophysics Data System (ADS)

    Nanev, Christo N.; Tonchev, Vesselin D.

    2015-10-01

    A non-linear differential equation expressing the new phase nucleation rate in the different steps of the process (non-stationary and stationary nucleation and in the plateau region) is derived from basic principles of the nucleation theory. It is shown that one and the same sigmoid (logistic) function describes both nucleation scenarios: the one according to the classical theory, and the other according to the modern two-stage mechanism of protein crystal formation. Comparison to experimental data on both insulin crystal nucleation kinetics and on bovine β-lactoglobulin crystallization indicates a good agreement with the sigmoidal prediction. Experimental data for electrochemical nucleation and glass crystallization obey the same sigmoid time dependence, and suggest universality of this nucleation kinetics law.

  10. Ion-Molecule Reactions in Gas Phase Radiation Chemistry.

    ERIC Educational Resources Information Center

    Willis, Clive

    1981-01-01

    Discusses some aspects of the radiation chemistry of gases, focusing on the ion-molecule and charge neutralization reactions which set study of the gas phase apart. Uses three examples that illustrate radiolysis, describing the radiolysis of (1) oxygen, (2) carbon dioxide, and (3) acetylene. (CS)

  11. The Dipeptide Ala-Gly in the Gas Phase

    NASA Astrophysics Data System (ADS)

    Bermúdez, Celina; Varela, Marcelino; Cabezas, Carlos; Peña, Isabel; Alonso, José L.

    2014-06-01

    The dipeptide Ala-Gly has been examined in gas phase by laser ablation molecular beam Fourier transform microwave (LA-MB-FTMW) spectroscopy in the frequency region 3-12 GHz. Three rotamers have been detected in the supersonic expansion. The quadrupole hyperfine structure of two 14N (I=1) nuclei has been totally resolved allowing the conclusive identification of one conformer.

  12. INVESTIGATION OF GAS-PHASE OZONE AS A POTENTIAL BIOCIDE

    EPA Science Inventory

    The paper presents data on the effect of ozone on both vegetative and spore-forming fungi as well as on spore-forming bacteria. (NOTE: Despite the wide use of ozone generators in indoor air cleaning, there is little research data on ozone's biocidal activity in the gas phase.) Dr...

  13. Fabrication of tensile-strained single-crystalline GeSn on transparent substrate by nucleation-controlled liquid-phase crystallization

    NASA Astrophysics Data System (ADS)

    Oka, Hiroshi; Amamoto, Takashi; Koyama, Masahiro; Imai, Yasuhiko; Kimura, Shigeru; Hosoi, Takuji; Shimura, Takayoshi; Watanabe, Heiji

    2017-01-01

    We developed a method of forming single-crystalline germanium-tin (GeSn) alloy on transparent substrates that is based on liquid-phase crystallization. By controlling and designing nucleation during the melting growth process, a highly tensile-strained single-crystalline GeSn layer was grown on a quartz substrate without using any crystal-seeds or catalysts. The peak field-effect hole mobility of 423 cm2/V s was obtained for a top-gate single-crystalline GeSn MOSFET on a quartz substrate with a Sn content of 2.6%, indicating excellent crystal quality and mobility enhancement due to Sn incorporation and tensile strain.

  14. Gas-phase chemistry of ruthenium and rhodium carbonyl complexes.

    PubMed

    Cao, Shiwei; Wang, Yang; Qin, Zhi; Fan, Fangli; Haba, Hiromitsu; Komori, Yukiko; Wu, Xiaolei; Tan, Cunmin; Zhang, Xin

    2016-01-07

    Short-lived ruthenium and rhodium isotopes were produced from a (252)Cf spontaneous fission (SF) source. Their volatile carbonyl complexes were formed in gas-phase reactions in situ with the carbon-monoxide containing gas. A gas-jet system was employed to transport the volatile carbonyls from the recoil chamber to the chemical separation apparatus. The gas-phase chemical behaviors of these carbonyl complexes were studied using an online low temperature isothermal chromatography (IC) technique. Long IC columns made up of FEP Teflon were used to obtain the chemical information of the high-volatile Ru and Rh carbonyls. By excluding the influence of precursor effects, short-lived isotopes of (109-110)Ru and (111-112)Rh were used to represent the chemical behaviours of Ru and Rh carbonyls. Relative chemical yields of about 75% and 20% were measured for Ru(CO)5 and Rh(CO)4, respectively, relative to the yields of KCl aerosols transported in Ar gas. The adsorption enthalpies of ruthenium and rhodium carbonyl complexes on a Teflon surface were determined to be around ΔHads = -33(+1)(-2) kJ mol(-1) and -36(+2)(-1) kJ mol(-1), respectively, by fitting the breakthrough curves of the corresponding carbonyl complexes with a Monte Carlo simulation program. Different from Mo and Tc carbonyls, a small amount of oxygen gas was found to be not effective for the chemical yields of ruthenium and rhodium carbonyl complexes. The general chemical behaviors of short-lived carbonyl complexes of group VI-IX elements were discussed, which can be used in the future study on the gas-phase chemistry of superheavy elements - Bh, Hs, and Mt carbonyls.

  15. Crystal nucleation of colloidal hard dumbbells.

    PubMed

    Ni, Ran; Dijkstra, Marjolein

    2011-01-21

    Using computer simulations, we investigate the homogeneous crystal nucleation in suspensions of colloidal hard dumbbells. The free energy barriers are determined by Monte Carlo simulations using the umbrella sampling technique. We calculate the nucleation rates for the plastic crystal and the aperiodic crystal phase using the kinetic prefactor as determined from event driven molecular dynamics simulations. We find good agreement with the nucleation rates determined from spontaneous nucleation events observed in event driven molecular dynamics simulations within error bars of one order of magnitude. We study the effect of aspect ratio of the dumbbells on the nucleation of plastic and aperiodic crystal phases, and we also determine the structure of the critical nuclei. Moreover, we find that the nucleation of the aligned close-packed crystal structure is strongly suppressed by a high free energy barrier at low supersaturations and slow dynamics at high supersaturations.

  16. Flavin Adenine Dinucleotide Structural Motifs: From Solution to Gas Phase

    PubMed Central

    2015-01-01

    Flavin adenine dinucleotide (FAD) is involved in important metabolic reactions where the biological function is intrinsically related to changes in conformation. In the present work, FAD conformational changes were studied in solution and in gas phase by measuring the fluorescence decay time and ion-neutral collision cross sections (CCS, in a trapped ion mobility spectrometer, TIMS) as a function of the solvent conditions (i.e., organic content) and gas-phase collisional partner (i.e., N2 doped with organic molecules). Changes in the fluorescence decay suggest that FAD can exist in four conformations in solution, where the abundance of the extended conformations increases with the organic content. TIMS-MS experiments showed that FAD can exist in the gas phase as deprotonated (M = C27H31N9O15P2) and protonated forms (M = C27H33N9O15P2) and that multiple conformations (up to 12) can be observed as a function of the starting solution for the [M + H]+ and [M + Na]+molecular ions. In addition, changes in the relative abundances of the gas-phase structures were observed from a “stack” to a “close” conformation when organic molecules were introduced in the TIMS cell as collision partners. Candidate structures optimized at the DFT/B3LYP/6-31G(d,p) were proposed for each IMS band, and results showed that the most abundant IMS band corresponds to the most stable candidate structure. Solution and gas-phase experiments suggest that the driving force that stabilizes the different conformations is based on the interaction of the adenine and isoalloxazine rings that can be tailored by the “solvation” effect created with the organic molecules. PMID:25222439

  17. Novel stationary phases based on asphaltenes for gas chromatography.

    PubMed

    Boczkaj, Grzegorz; Momotko, Malwina; Chruszczyk, Dorota; Przyjazny, Andrzej; Kamiński, Marian

    2016-07-01

    We present the results of investigations on the possibility of the application of the asphaltene fraction isolated from the oxidized residue from vacuum distillation of crude oil as a stationary phase for gas chromatography. The results of the investigation revealed that the asphaltene stationary phases can find use for the separation of a wide range of volatile organic compounds. The experimental values of Rohrschneider/McReynolds constants characterize the asphaltenes as stationary phases of medium polarity and selectivity similar to commercially available phases based on alkyl phthalates. Isolation of asphaltenes from the material obtained under controlled process conditions allows the production of a stationary phase having reproducible sorption properties and chromatographic columns having the same selectivity. Unique selectivity and high thermal stability make asphaltenes attractive as a material for stationary phases for gas chromatography. A low production cost from a readily available raw material (oxidized petroleum bitumens) is an important economic factor in case of application of the asphaltene stationary phases for preparative and process separations.

  18. Noble metal alloy clusters in the gas phase derived from protein templates: unusual recognition of palladium by gold

    NASA Astrophysics Data System (ADS)

    Baksi, Ananya; Pradeep, T.

    2013-11-01

    Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd+ in the gas phase. While a lysozyme-Au adduct forms Au18+, Au25+, Au38+ and Au102+ ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag+, Pt2+, Pd2+, Cu2+, Fe2+, Ni2+ and Cr3+) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38+. While other metal ions like Cu2+ help forming Au25+ selectively, Fe2+ catalyzes the formation of Au25+ over all other clusters. Gas phase cluster formation occurs from protein adducts where Au is in the 1+ state while Pd is in the 2+ state. The creation of alloys in the gas phase is not affected whether a physical mixture of Au and Pd adducts or a Au and Pd co-adduct is used as the precursor. The formation of Au cores and AuPd alloy cores of the kind comparable to monolayer protected clusters implies that naked clusters themselves may be nucleated in solution.Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd+ in the gas phase. While a lysozyme-Au adduct forms Au18+, Au25+, Au38+ and Au102+ ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag+, Pt2+, Pd2+, Cu2+, Fe2+, Ni2+ and Cr3+) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38+. While other metal ions like Cu2+ help forming Au25+ selectively, Fe2+ catalyzes the formation of Au25+ over all other clusters. Gas phase cluster

  19. Gas-Phase Studies of Formamidopyrimidine Glycosylase (Fpg) Substrates.

    PubMed

    Kiruba, G S M; Xu, Jiahui; Zelikson, Victoria; Lee, Jeehiun K

    2016-03-07

    Gas-phase thermochemical properties (tautomerism, acidity, and proton affinity) have been measured and calculated for a series of nucleobase derivatives that have not heretofore been examined under vacuum. The studied species are substrates for the enzyme formamidopyrimidine glycosylase (Fpg), which cleaves damaged nucleobases from DNA. The gas-phase results are compared and contrasted to solution-phase data, to afford insight into the Fpg mechanism. Calculations are also used to probe the energetics of various possible mechanisms and to predict isotope effects that could potentially allow for discrimination between different mechanisms. Specifically, (18) O substitution at the ribose O4' is predicted to result in a normal kinetic isotope effect (KIE) for a ring-opening "endocyclic" mechanism and an inverse KIE for a direct base excision "exocyclic" pathway.

  20. The physical chemistry of Criegee intermediates in the gas phase

    DOE PAGES

    Osborn, David L.; Taatjes, Craig A.

    2015-07-24

    Here, carbonyl oxides, also known as Criegee intermediates, are key intermediates in both gas phase ozonolysis of unsaturated hydrocarbons in the troposphere and solution phase organic synthesis via ozonolysis. Although the study of Criegee intermediates in both arenas has a long history, direct studies in the gas phase have only recently become possible through new methods of generating stabilised Criegee intermediates in sufficient quantities. This advance has catalysed a large number of new experimental and theoretical investigations of Criegee intermediate chemistry. In this article we review the physical chemistry of Criegee intermediates, focusing on their molecular structure, spectroscopy, unimolecular andmore » bimolecular reactions. These recent results have overturned conclusions from some previous studies, while confirming others, and have clarified areas of investigation that will be critical targets for future studies. In addition to expanding our fundamental understanding of Criegee intermediates, the rapidly expanding knowledge base will support increasingly predictive models of their impacts on society.« less

  1. The physical chemistry of Criegee intermediates in the gas phase

    SciTech Connect

    Osborn, David L.; Taatjes, Craig A.

    2015-07-24

    Here, carbonyl oxides, also known as Criegee intermediates, are key intermediates in both gas phase ozonolysis of unsaturated hydrocarbons in the troposphere and solution phase organic synthesis via ozonolysis. Although the study of Criegee intermediates in both arenas has a long history, direct studies in the gas phase have only recently become possible through new methods of generating stabilised Criegee intermediates in sufficient quantities. This advance has catalysed a large number of new experimental and theoretical investigations of Criegee intermediate chemistry. In this article we review the physical chemistry of Criegee intermediates, focusing on their molecular structure, spectroscopy, unimolecular and bimolecular reactions. These recent results have overturned conclusions from some previous studies, while confirming others, and have clarified areas of investigation that will be critical targets for future studies. In addition to expanding our fundamental understanding of Criegee intermediates, the rapidly expanding knowledge base will support increasingly predictive models of their impacts on society.

  2. Hydration of Gas-Phase Ions Formed by Electrospray Ionization

    PubMed Central

    Rodriguez-Cruz, Sandra E.; Klassen, John S.; Williams, Evan R.

    2005-01-01

    The hydration of gas-phase ions produced by electrospray ionization was investigated. Evidence that the hydrated ions are formed by two mechanisms is presented. First, solvent condensation during the expansion inside the electrospray source clearly occurs. Second, some solvent evaporation from more extensively solvated ions or droplets is apparent. To the extent that these highly solvated ions have solution-phase structures, then the final isolated gas-phase structure of the ion will be determined by the solvent evaporation process. This process was investigated for hydrated gramicidin S in a Fourier-transform mass spectrometer. Unimolecular dissociation rate constants of isolated gramicidin S ions with between 2 and 14 associated water molecules were measured. These rate constants increased from 16 to 230 s−1 with increasing hydration, with smaller values corresponding to magic numbers. PMID:10497808

  3. Gas Phase Reactivity of Carboxylates with N-Hydroxysuccinimide Esters

    PubMed Central

    Peng, Zhou; McGee, William M.; Bu, Jiexun; Barefoot, Nathan Z.; McLuckey, Scott A.

    2015-01-01

    N-hydroxysuccinimide (NHS) esters have been used for gas phase conjugation reactions with peptides at nucleophilic sites, such as primary amines (N-terminus, ε-amine of lysine) or guanidines, by forming amide bonds through a nucleophilic attack on the carbonyl carbon. The carboxylate has recently been found to also be a reactive nucleophile capable of initiating a similar nucleophilic attack to form a labile anhydride bond. The fragile bond is easily cleaved, resulting in an oxygen transfer from the carboxylate-containing species to the reagent, nominally observed as a water transfer. This reactivity is shown for both peptides and non-peptidic species. Reagents isotopically labeled with O18 were used to confirm reactivity. This constitutes an example of distinct differences in reactivity of carboxylates between the gas-phase, where they are shown to be reactive, and the solution-phase, where they are not regarded as reactive with NHS esters. PMID:25338221

  4. Gas Phase Reactivity of Carboxylates with N-Hydroxysuccinimide Esters

    NASA Astrophysics Data System (ADS)

    Peng, Zhou; McGee, William M.; Bu, Jiexun; Barefoot, Nathan Z.; McLuckey, Scott A.

    2015-01-01

    N-hydroxysuccinimide (NHS) esters have been used for gas-phase conjugation reactions with peptides at nucleophilic sites, such as primary amines (N-terminus, ɛ-amine of lysine) or guanidines, by forming amide bonds through a nucleophilic attack on the carbonyl carbon. The carboxylate has recently been found to also be a reactive nucleophile capable of initiating a similar nucleophilic attack to form a labile anhydride bond. The fragile bond is easily cleaved, resulting in an oxygen transfer from the carboxylate-containing species to the reagent, nominally observed as a water transfer. This reactivity is shown for both peptides and non-peptidic species. Reagents isotopically labeled with O18 were used to confirm reactivity. This constitutes an example of distinct differences in reactivity of carboxylates between the gas phase, where they are shown to be reactive, and the solution phase, where they are not regarded as reactive with NHS esters.

  5. Molecular dynamics of simulation of the nucleation, growth, inhibition and control of gas hydrates. Annual report, March 1992-June 1993

    SciTech Connect

    Clancy, P.

    1993-06-01

    This is the second year of a three-year project using molecular simulation techniques tailored specifically for the determination of early-stage kinetics of natural gas hydrate crystal growth and dissolution. This year, extensive simulations of the kinetics of growth of a model system showed the appearance of magic numbers' in the growth rate versus cluster size. The feasibility of monitoring the kinetics of hydrate growth and dissolution has been demonstrated. A preliminary mechanism for hydrate dissolution has been proposed. A building block' for hydrate growth has been identified as a long-lived entity in the liquid; this single dodecahedron has also been seen by preliminary NMR studies. Inhibition studies have begun with biopolymers and will continue next year with studies of simple inhibitors, in concert with molecular spectroscopic techniques.

  6. Improvement and further development in CESM/CAM5: gas-phase chemistry and inorganic aerosol treatments

    NASA Astrophysics Data System (ADS)

    He, J.; Zhang, Y.

    2014-09-01

    Gas-phase chemistry and subsequent gas-to-particle conversion processes such as new particle formation, condensation, and thermodynamic partitioning have large impacts on air quality, climate, and public health through influencing the amounts and distributions of gaseous precursors and secondary aerosols. Their roles in global air quality and climate are examined in this work using the Community Earth System Model version 1.0.5 (CESM1.0.5) with the Community Atmosphere Model version 5.1 (CAM5.1) (referred to as CESM1.0.5/CAM5.1). CAM5.1 includes a simple chemistry that is coupled with a 7-mode prognostic Modal Aerosol Model (MAM7). MAM7 includes classical homogenous nucleation (binary and ternary) and activation nucleation (empirical first-order power law) parameterizations, and a highly simplified inorganic aerosol thermodynamics treatment that only simulates particulate-phase sulfate and ammonium. In this work, a new gas-phase chemistry mechanism based on the 2005 Carbon Bond Mechanism for Global Extension (CB05_GE) and several advanced inorganic aerosol treatments for condensation of volatile species, ion-mediated nucleation (IMN), and explicit inorganic aerosol thermodynamics for sulfate, ammonium, nitrate, sodium, and chloride have been incorporated into CESM/CAM5.1-MAM7. Compared to the simple gas-phase chemistry, CB05_GE can predict many more gaseous species, and thus could improve model performance for PM2.5, PM10, PM components, and some PM gaseous precursors such as SO2 and NH3 in several regions as well as aerosol optical depth (AOD) and cloud properties (e.g., cloud fraction (CF), cloud droplet number concentration (CDNC), and shortwave cloud forcing, SWCF) on the global scale. The modified condensation and aqueous-phase chemistry could further improve the prediction of additional variables such as HNO3, NO2, and O3 in some regions, and new particle formation rate (J) and AOD on the global scale. IMN can improve the prediction of secondary PM2

  7. Preconceptual design of the gas-phase decontamination demonstration cart

    SciTech Connect

    Munday, E.B.

    1993-12-01

    Removal of uranium deposits from the interior surfaces of gaseous diffusion equipment will be a major portion of the overall multibillion dollar effort to decontaminate and decommission the gaseous diffusion plants. Long-term low-temperature (LTLT) gas-phase decontamination is being developed at the K-25 Site as an in situ decontamination process that is expected to significantly lower the decontamination costs, reduce worker exposure to radioactive materials, and reduce safeguard concerns. This report documents the preconceptual design of the process equipment that is necessary to conduct a full-scale demonstration of the LTLT method in accordance with the process steps listed above. The process equipment and method proposed in this report are not intended to represent a full-scale production campaign design and operation, since the gas evacuation, gas charging, and off-gas handling systems that would be cost effective in a production campaign are not cost effective for a first-time demonstration. However, the design presented here is expected to be applicable to special decontamination projects beyond the demonstration, which could include the Deposit Recovery Program. The equipment will therefore be sized to a 200 ft size 1 converter (plus a substantial conservative design margin), which is the largest item of interest for gas phase decontamination in the Deposit Recovery Program. The decontamination equipment will allow recovery of the UF{sub 6}, which is generated from the reaction of ClF{sub 3} with the uranium deposits, by use of NaF traps.

  8. A dynamic phase-field model for structural transformations and twinning: Regularized interfaces with transparent prescription of complex kinetics and nucleation. Part I: Formulation and one-dimensional characterization

    NASA Astrophysics Data System (ADS)

    Agrawal, Vaibhav; Dayal, Kaushik

    2015-12-01

    The motion of microstructural interfaces is important in modeling twinning and structural phase transformations. Continuum models fall into two classes: sharp-interface models, where interfaces are singular surfaces; and regularized-interface models, such as phase-field models, where interfaces are smeared out. The former are challenging for numerical solutions because the interfaces need to be explicitly tracked, but have the advantage that the kinetics of existing interfaces and the nucleation of new interfaces can be transparently and precisely prescribed. In contrast, phase-field models do not require explicit tracking of interfaces, thereby enabling relatively simple numerical calculations, but the specification of kinetics and nucleation is both restrictive and extremely opaque. This prevents straightforward calibration of phase-field models to experiment and/or molecular simulations, and breaks the multiscale hierarchy of passing information from atomic to continuum. Consequently, phase-field models cannot be confidently used in dynamic settings. This shortcoming of existing phase-field models motivates our work. We present the formulation of a phase-field model - i.e., a model with regularized interfaces that do not require explicit numerical tracking - that allows for easy and transparent prescription of complex interface kinetics and nucleation. The key ingredients are a re-parametrization of the energy density to clearly separate nucleation from kinetics; and an evolution law that comes from a conservation statement for interfaces. This enables clear prescription of nucleation - through the source term of the conservation law - and kinetics - through a distinct interfacial velocity field. A formal limit of the kinetic driving force recovers the classical continuum sharp-interface driving force, providing confidence in both the re-parametrized energy and the evolution statement. We present some 1D calculations characterizing the formulation; in a

  9. Unraveling the "pressure effect" in nucleation.

    PubMed

    Wedekind, Jan; Hyvärinen, Antti-Pekka; Brus, David; Reguera, David

    2008-09-19

    The influence of the pressure of a chemically inert carrier gas on the nucleation rate is one of the biggest puzzles in the research of gas-liquid nucleation. Experiments can show a positive effect, a negative effect, or no effect at all. The same experiment may show both trends for the same substance depending on temperature, or for different substances at the same temperature. We show how this ambiguous effect naturally arises from the competition of two contributions: nonisothermal effects and pressure-volume work. Our model clarifies seemingly contradictory experimental results and quantifies the variation of the nucleation ability of a substance in the presence of an ambient gas. Our findings are corroborated by molecular dynamics simulations and might have important implications since nucleation in experiments, technical applications, and nature practically always occurs in the presence of an ambient gas.

  10. Gas Phase Chemical Detection with an Integrated Chemical Analysis System

    SciTech Connect

    Baca, Albert G.; Casalnuovo, Stephen A.; Frye-Mason, Gregory C.; Heller, Edwin J.; Hietala, Susan L.; Hietala, Vincent M.; Kottenstette, Richard J.; Lewis, Patrick R.; Manginell, Ronald P.; Matzke, Carloyn M.; Reno, John L.; Sasaki, Darryl Y.; Schubert, W. Kent

    1999-07-08

    Microfabrication technology has been applied to the development of a miniature, multi-channel gas phase chemical laboratory that provides fast response, small size, and enhanced versatility and chemical discrimination. Each analysis channel includes a sample concentrator followed by a gas chromatographic separator and a chemically selective surface acoustic wave detector array to achieve high sensitivity and selectivity. The performance of the components, individually and collectively, is described. The design and performance of novel micromachined acoustic wave devices, with the potential for improved chemical sensitivity, are also described.

  11. Collaborative Advanced Gas Turbine Program: Phase 1. Final report

    SciTech Connect

    Hollenbacher, R.; Kesser, K.; Beishon, D.

    1994-12-01

    The Collaborative Advanced Gas Turbine (CAGT) Program is an advanced gas turbine research and development program whose goal is to accelerate the commercial availability, to within the turn of the century, of high efficiency aeroderivative gas turbines for electric power generating applications. In the first project phase, research was conducted to prove or disprove the research hypothesis that advanced aeroderivative gas turbine systems can provide a promising technology alternative, offering high efficiency and good environmental performance characteristics in modular sizes, for utility applications. This $5 million, Phase 1 research effort reflects the collaborative efforts of a broad and international coalition of industries and organizations, both public and private, that have pooled their resources to assist in this research. Included in this coalition are: electric and gas utilities, the Electric Power Research Institute, the Gas Research Institute and the principal aircraft engine manufacturers. Additionally, the US Department of Energy (DOE) and the California Energy Commission have interacted with the CAGT on both technical and executive levels as observers and sources of funding. The three aircraft engine manufacturer-led research teams participating in this research include: Rolls-Royce, Inc., and Bechtel; the Turbo Power and Marine Division of United Technologies and Fluor Daniel; and General Electric Power Generation, Stewart and Stevenson, and Bechtel. Each team has investigated advanced electric power generating systems based on their high-thrust (60,000 to 100,000 pounds) aircraft engines. The ultimate goal of the CAGT program is that the community of stakeholders in the growing market for natural-gas-fueled, electric power generation can collectively provide the right combination of market-pull and technology-push to substantially accelerate the commercialization of advanced, high efficiency aeroderivative technologies.

  12. A Uranyl Peroxide Dimer in the Gas Phase.

    PubMed

    Dau, Phuong D; Dau, Phuong V; Rao, Linfeng; Kovács, Attila; Gibson, John K

    2017-04-03

    The gas-phase uranyl peroxide dimer, [(UO2)2(O2)(L)2](2+) where L = 2,2'-trifluoroethylazanediyl)bis(N,N'-dimethylacetamide), was synthesized by electrospray ionization of a solution of UO2(2+) and L. Collision-induced dissociation of this dimer resulted in endothermic O atom elimination to give [(UO2)2(O)(L)2](2+), which was found to spontaneously react with water via exothermic hydrolytic chemisorption to yield [(UO2)2(OH)2(L)2](2+). Density functional theory computations of the energies for the gas-phase reactions are in accord with observations. The structures of the observed uranyl dimer were computed, with that of the peroxide of particular interest, as a basis to evaluate the formation of condensed phase uranyl peroxides with bent structures. The computed dihedral angle in [(UO2)2(O2)(L)2](2+) is 145°, indicating a substantial deviation from the planar structure with a dihedral angle of 180°. Energies needed to induce bending in the most elementary gas-phase uranyl peroxide complex, [(UO2)2(O2)](2+), were computed. It was found that bending from the lowest-energy planar structure to dihedral angles up to 140° required energies of <10 kJ/mol. The gas-phase results demonstrate the inherent stability of the uranyl peroxide moiety and support the notion that the uranyl-peroxide-uranyl structural unit is intrinsically planar, with only minor energy perturbations needed to form the bent structures found in studtite and uranyl peroxide nanostructures.

  13. Carbon Dioxide Separation from Flue Gas by Phase Enhanced Absorption

    SciTech Connect

    Liang Hu

    2006-06-30

    A new process, phase enhanced absorption, was invented. The method is carried out in an absorber, where a liquid carrier (aqueous solution), an organic mixture (or organic compound), and a gas mixture containing a gas to be absorbed are introduced from an inlet. Since the organic mixture is immiscible or at least partially immiscible with the liquid carrier, the organic mixture forms a layer or small parcels between the liquid carrier and the gas mixture. The organic mixture in the absorber improves mass transfer efficiency of the system and increases the absorption rate of the gas. The organic mixture serves as a transportation media. The gas is finally accumulated in the liquid carrier as in a conventional gas-liquid absorption system. The presence of the organic layer does not hinder the regeneration of the liquid carrier or recovery of the gas because the organic layer is removed by a settler after the absorption process is completed. In another aspect, the system exhibited increased gas-liquid separation efficiency, thereby reducing the costs of operation and maintenance. Our study focused on the search of the organic layer or transportation layer to enhance the absorption rate of carbon dioxide. The following systems were studied, (1) CO{sub 2}-water system and CO{sub 2}-water-organic layer system; (2) CO{sub 2}-Potassium Carbonate aqueous solution system and CO{sub 2}-Potassium Carbonate aqueous solution-organic layer system. CO{sub 2}-water and CO{sub 2}-Potassium Carbonate systems are the traditional gas-liquid absorption processes. The CO{sub 2}-water-organic layer and CO{sub 2}-Potassium Carbonate-organic layer systems are the novel absorption processes, phase enhanced absorption. As we mentioned early, organic layer (transportation layer phase) is used for the increase of absorption rate. Our study showed that the absorption rate can be increased by adding the organic layer. However, the enhanced factor is highly depended on the liquid mass transfer

  14. Experiments on Nucleation in Different Flow Regimes

    NASA Technical Reports Server (NTRS)

    Bayuzick, R. J.; Hofmeister, W. H.; Morton, C. M.; Robinson, M. B.

    1999-01-01

    The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods. Dilatometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov. The advantage of these experiments is that the samples are directly observable. The nucleation temperature

  15. Validity of commonly used formula of nucleation work for bubble nucleation

    NASA Astrophysics Data System (ADS)

    Mori, Atsushi

    2013-08-01

    Nishioka and Kusaka [Journal of Chemical Physics 96 (1992) 5370] showed that the commonly used formula, W=n(μα-μβ)+γA, for work of formation of critical nucleus is derived by integrating the isothermal Gibbs-Duhem relation for the incompressible nucleating phase, such as an incompressible liquid phase nucleation in a vapor phase. In their paper as well as in a subsequent paper [Li, Nishioka, Holcomb, Journal of Crystal Growth 171 (1997) 259] it was stated that the commonly used formula was valid for an incompressible nucleating phase and no longer held for such as a bubble nucleation. In this paper, we will amend this statement; that is, the commonly used formula is shown to hold for incompressible parent phase, such as a bubble nucleation in an incompressible parent phase.

  16. Spectroscopic studies of cold, gas-phase biomolecular ions

    NASA Astrophysics Data System (ADS)

    Rizzo, Thomas R.; Stearns, Jaime A.; Boyarkin, Oleg V.

    While the marriage of mass spectrometry and laser spectroscopy is not new, developments over the last few years in this relationship have opened up new horizons for the spectroscopic study of biological molecules. The combination of electrospray ionisation for producing large biological molecules in the gas phase together with cooled ion traps and multiple-resonance laser schemes are allowing spectroscopic investigation of individual conformations of peptides with more than a dozen amino acids. Highly resolved infrared spectra of single conformations of such species provide important benchmarks for testing the accuracy of theoretical calculations. This review presents a number of techniques employed in our laboratory and in others for measuring the spectroscopy of cold, gas-phase protonated peptides. We show examples that demonstrate the power of these techniques and evaluate their extension to still larger biological molecules.

  17. Substituent effects on the gas-phase acidity of silane

    SciTech Connect

    Gordon, M.S.; Volk, D.E. ); Gano, D.R. )

    1989-12-20

    In a previous paper, the gas-phase acidities of XH{sub n} compounds (X = C, N, O, F, Si, P, S, Cl) were predicted with ab initio wave functions. At the MP4{sup 2} level of theory with extended basis sets acidities for these species were determined to be within 2 kcal/mol of experimental value. In the present work, with 6-31G(d) geometries and full MP4/MC-311++G{sup 6}(3df,2pd) energies, the effects of CH{sub 3}, NH{sub 2}, OH, F, SiH{sub 3}, PH{sub 2}, SH, and Cl on the gas-phase acidity of silane are examined. Only a few related calculations have been carried out. All calculations were performed with Gaussian86, and all structures were verified as minima by diagonalizing the analytically determined hessians. Only the valence electrons were correlated in the perturbation theory calculations.

  18. The nucleoside uridine isolated in the gas phase.

    PubMed

    Peña, Isabel; Cabezas, Carlos; Alonso, José L

    2015-03-02

    Herein we present the first experimental observation of the isolated nucleoside uridine, placed in the gas phase by laser ablation and characterized by Fourier transform (FT) microwave techniques. Free from the bulk effects of their native environments, anti/C2'-endo-g+ conformation has been revealed as the most stable form of uridine. Intramolecular hydrogen bonds involving uracil and ribose moieties have been found to play an important role in the stabilization of the nucleoside.

  19. Gas phase fractionation method using porous ceramic membrane

    DOEpatents

    Peterson, Reid A.; Hill, Jr., Charles G.; Anderson, Marc A.

    1996-01-01

    Flaw-free porous ceramic membranes fabricated from metal sols and coated onto a porous support are advantageously used in gas phase fractionation methods. Mean pore diameters of less than 40 .ANG., preferably 5-20 .ANG. and most preferably about 15 .ANG., are permeable at lower pressures than existing membranes. Condensation of gases in small pores and non-Knudsen membrane transport mechanisms are employed to facilitate and increase membrane permeability and permselectivity.

  20. Research on Sources of Gas Phase Metastable Atoms and Molecules

    DTIC Science & Technology

    1982-05-01

    PAGI(Whi DeE# WA..teod) -systems of interest to such diverse areas as gas discharge physics, chemical physics, flame chemistry and plasma physics. "A...second task involved a literature review of prior basic research meta- stable sources followed by the development and experimental testing of appro...appropriate for this phase of the program. The operation of this type of metastable source wab investigated and tested for the production of metastable argon

  1. The Nucleoside Uridine Isolated in the Gas Phase**

    PubMed Central

    Peña, Isabel; Cabezas, Carlos; Alonso, José L.

    2016-01-01

    Herein we present the first experimental observation of the isolated nucleoside uridine, placed in the gas phase by laser ablation and characterized by Fourier transform microwave techniques. Free from the bulk effects of their native environments, anti/C2’-endo-g+ conformation has been revealed as the most stable form of uridine. Intramolecular hydrogen bonds involving uracil and ribose moieties have been found to play an important role in the stabilization of the nucleoside. PMID:25683559

  2. A varying polytropic gas universe and phase space analysis

    NASA Astrophysics Data System (ADS)

    Khurshudyan, M.

    2016-05-01

    In this paper, we will consider a phenomenological model of a dark fluid that is able to explain an accelerated expansion of our low redshift universe and the phase transition to this accelerated expanding universe. Recent developments in modern cosmology towards understanding of the accelerated expansion of the large scale universe involve various scenarios and approaches. Among these approaches, one of well-known and accepted practice is modeling of the content of our universe via dark fluid. There are various models of dark energy fluid actively studied in recent literature and polytropic gas is among them. In this work, we will consider a varying polytropic gas which is a phenomenological modification of polytropic gas. Our model of varying polytropic dark fluid has been constructed to analogue to a varying Chaplygin gas actively discussed in the literature. We will consider interacting models, where dark matter is a pressureless fluid, to have a comprehensive picture. Phase space analysis is an elegant mathematical tool to earn general understanding of large scale universe and easily see an existence of a solution to cosmological coincidence problem. Imposing some constraints on parameters of the models, we found late time attractors for each case analytically. Cosmological consequences for the obtained late time attractors are discussed.

  3. Field driven ferromagnetic phase nucleation and propagation from the domain boundaries in antiferromagnetically coupled perpendicular anisotropy films

    SciTech Connect

    Hauet, Thomas; Gunther, Christian M.; Hovorka, Ondrej; Berger, Andreas; Im, Mi-Young; Fischer, Peter; Hellwig, Olav

    2008-12-09

    We investigate the reversal process in antiferromagnetically coupled [Co/Pt]{sub X-1}/{l_brace}Co/Ru/[Co/Pt]{sub X-1}{r_brace}{sub 16} multilayer films by combining magnetometry and Magnetic soft X-ray Transmission Microscopy (MXTM). After out-of-plane demagnetization, a stable one dimensional ferromagnetic (FM) stripe domain phase (tiger-tail phase) for a thick stack sample (X=7 is obtained), while metastable sharp antiferromagnetic (AF) domain walls are observed in the remanent state for a thinner stack sample (X=6). When applying an external magnetic field the sharp domain walls of the thinner stack sample transform at a certain threshold field into the FM stripe domain wall phase. We present magnetic energy calculations that reveal the underlying energetics driving the overall reversal mechanisms.

  4. Carbon Dioxide Separation from Flue Gas by Phase Enhanced Absorption

    SciTech Connect

    Tim Fout

    2007-06-30

    A new process, phase enhanced absorption, was invented. The method is carried out in an absorber, where a liquid carrier (aqueous solution), an organic mixture (or organic compound), and a gas mixture containing a gas to be absorbed are introduced from an inlet. Since the organic mixture is immiscible or at least partially immiscible with the liquid carrier, the organic mixture forms a layer or small parcels between the liquid carrier and the gas mixture. The organic mixture in the absorber improves mass transfer efficiency of the system and increases the absorption rate of the gas. The organic mixture serves as a transportation media. The gas is finally accumulated in the liquid carrier as in a conventional gas-liquid absorption system. The presence of the organic layer does not hinder the regeneration of the liquid carrier or recovery of the gas because the organic layer is removed by a settler after the absorption process is completed. In another aspect, the system exhibited increased gas-liquid separation efficiency, thereby reducing the costs of operation and maintenance. Our study focused on the search of the organic layer or transportation layer to enhance the absorption rate of carbon dioxide. The following systems were studied, (1) CO{sub 2}-water system and CO{sub 2}-water-organic layer system; (2) CO{sub 2}-Potassium Carbonate aqueous solution system and CO{sub 2}-Potassium Carbonate aqueous solution-organic layer system. CO{sub 2}-water and CO{sub 2}-Potassium Carbonate systems are the traditional gas-liquid absorption processes. The CO{sub 2}-water-organic layer and CO{sub 2}-Potassium Carbonate-organic layer systems are the novel absorption processes, phase enhanced absorption. As we mentioned early, organic layer is used for the increase of absorption rate, and plays the role of transportation of CO{sub 2}. Our study showed that the absorption rate can be increased by adding the organic layer. However, the enhanced factor is highly depended on the

  5. The organic matter of Comet Halley as inferred by joint gas phase and solid phase analyses

    NASA Astrophysics Data System (ADS)

    Krueger, F. R.; Korth, A.; Kissel, J.

    1991-04-01

    During encounters with Comet Halley, the experiment PICCA onboard Giotto measured the gas-phase organic ion composition of the coma, and the experiment PUMA onboard Vega-1 measured the dust composition. Joining both results gives a consistent picture of the parent organic matter from which dust and gas is produced: a complex unsaturated polycondensate, which splits during coma formation into the more refractory C=C,C-N-containing dust part and the more volatile C=C,C-O-containing gas part. The responsible exothermal chemical reactions, which are triggered by sunlight, may play a major role in the dynamics of coma formation.

  6. Gas Phase Model of Surface Reactions for N{2} Afterglows

    NASA Astrophysics Data System (ADS)

    Marković, V. Lj.; Petrović, Z. Lj.; Pejović, M. M.

    1996-07-01

    The adequacy of the homogeneous gas phase model as a representation of the surface losses of diffusing active particles in gas phase is studied. As an example the recent data obtained for the surface recombination coefficients are reanalyzed. The data were obtained by the application of the breakdown delay times which consists of the measurements of the breakdown delay times t_d as a function of the afterglow period tau. It was found that for the conditions of our experiment, the diffusion should not be neglected as the final results are significantly different when obtained by approximate gas phase representation and by exact numerical solution to the diffusion equation. While application of the gas phase effective coefficients to represent surface losses gives an error in the value of the recombination coefficient, it reproduces correctly other characteristics such as order of the process which can be obtained from simple fits to the experimental data. Dans cet article, nous étudions la validité du modèle approximatif représentant les pertes superficielles des particules actives qui diffusent de la phase gazeuse comme pertes dans la phase homogène du gaz. Les données actuelles du coefficient de recombination en surface sont utilisées par cette vérification . Les données experimentales sont obtenues en utilisant la technique qui consiste en la mesure du temps de retard du début de la décharge en fonction de la période de relaxation. Nous avons trouvé que, pour nos conditions expérimentales, la diffusion ne peut être négligée. Aussi, les résultats finals sont considérablement différents quand ils sont obtenus en utilisant le modèle approximatif par comparaison aves les résultats obtenus par la solution numérique exacte de l'équation de la diffusion. L'application des coefficients effectifs dans la phase gaseuse pour la présentation des pertes superficielles donne, pour les coefficients de la recombinaison, des valeurs qui diffèrent en

  7. Gas-phase chemistry of technetium carbonyl complexes.

    PubMed

    Wang, Yang; Qin, Zhi; Fan, Fang-Li; Haba, Hiromitsu; Komori, Yukiko; Cao, Shi-Wei; Wu, Xiao-Lei; Tan, Cun-Min

    2015-05-28

    Gas-phase chemical behaviors of short-lived technetium carbonyl complexes were studied using a low temperature isothermal chromatograph (IC) coupled with a (252)Cf spontaneous fission (SF) source. Fission products recoiled from the (252)Cf SF source were thermalized in a mixed gas containing CO, and then technetium carbonyl complexes were formed from reactions between CO gas and various technetium isotopes. A gas-jet system was employed to transport the volatile carbonyl complexes from a recoil chamber to the IC. Short IC columns made of Fluorinated Ethylene Propylene (FEP) Teflon and quartz were used to obtain chemical information about the technetium carbonyl complexes. The results for the (104)Tc-(106)Tc carbonyl complexes were found to be strongly influenced by the precursors, and showed the chemical behaviors of (104)Mo-(106)Mo carbonyl complexes, respectively. However, (107)Tc and (108)Tc could represent the chemical information of the element technetium due to their high independent yields and the very short half-lives of their precursors (107)Mo and (108)Mo. An adsorption enthalpy of about ΔHads = -43 kJ mol(-1) was determined for the Tc carbonyl complexes on both the Teflon and quartz surfaces by fitting the breakthrough curves of the (107)Tc and (108)Tc carbonyl complexes with a Monte Carlo simulation program. Chemical yields of around 25% were measured for the Tc carbonyl complexes relative to the transport yields obtained with the gas-jet transport of KCl aerosol particles with Ar carrier gas. Furthermore, the influence of a small amount of O2 gas on the yields of the Mo and Tc carbonyl complexes was studied.

  8. Theory of Gas Injection: Interaction of Phase Behavior and Flow

    NASA Astrophysics Data System (ADS)

    Dindoruk, B.

    2015-12-01

    The theory of gas injection processes is a central element required to understand how components move and partition in the reservoir as one fluid is displacing another (i.e., gas is displacing oil). There is significant amount of work done in the area of interaction of phase-behavior and flow in multiphase flow conditions. We would like to present how the theory of gas injection is used in the industry to understand/design reservoir processes in various ways. The tools that are developed for the theory of gas injection originates from the fractional flow theory, as the first solution proposed by Buckley-Leveret in 1940's, for water displacing oil in porous media. After 1960's more and more complex/coupled equations were solved using the initial concept(s) developed by Buckley-Leverett, and then Welge et al. and others. However, the systematic use of the fractional flow theory for coupled set of equations that involves phase relationships (EOS) and phase appearance and disappearance was mainly due to the theory developed by Helfferich in early 80's (in petroleum literature) using method of characteristics primarily for gas injection process and later on by the systematic work done by Orr and his co-researchers during the last two decades. In this talk, we will present various cases that use and extend the theory developed by Helfferich and others (Orr et al., Lake et al. etc.). The review of various injection systems reveals that displacement in porous media has commonalities that can be represented with a unified theory for a class of problems originating from the theory of gas injection (which is in a way generalized Buckley-Leverett problem). The outcome of these solutions can be used for (and are not limited to): 1) Benchmark solutions for reservoir simulators (to quantify numerical dispersion, test numerical algorithms) 2) Streamline simulators 3) Design of laboratory experiments and their use (to invert the results) 4) Conceptual learning and to investigate

  9. Gas-Phase Synthesis of Gold- and Silica-Coated Nanoparticles

    NASA Astrophysics Data System (ADS)

    Boies, Adam Meyer

    2011-12-01

    Composite nanoparticles consisting of separate core-shell materials are of interest for a variety of biomedical and industrial applications. By combining different materials at the nanoscale, particles can exhibit enhanced or multi-functional behavior such as plasmon resonance combined with superparamagnetism. Gas-phase nanoparticle synthesis processes are promising because they can continuously produce particles with high mass-yield rates. In this dissertation, new methods are investigated for producing gas-phase coatings of nanoparticles in an "assembly-line" fashion. Separate processes are developed to create coatings from silica and gold that can be used with a variety of core-particle chemistries. A photoinduced chemical vapor deposition (photo-CVD) method is used to produce silica coatings from tetraethyl orthosilicate (TEOS) on the surface of nanoparticles (diameter ˜5--70 nm). Tandem differential mobility analysis (TDMA) of the process demonstrates that particle coatings can be produced with controllable thicknesses (˜1--10 nm) by varying system parameters such as precursor flow rate. Electron microscopy and infrared spectroscopy confirm that the photo-CVD films uniformly coat the particles and that the coatings are silica. In order to describe the coating process a chemical mechanism is proposed that includes gas-phase, surface and photochemical reactions. A chemical kinetics model of the mechanism indicates that photo-CVD coating proceeds primarily through the photodecomposition of TEOS which removes ethyl groups, thus creating activated TEOS species. The activated TEOS then adsorbs onto the surface of the particle where a series of subsequent reactions remove the remaining ethyl groups to produce a silica film with an open site for further attachment. The model results show good agreement with the experimentally measured coating trends, where increased TEOS flow increases coating thickness and increased nitrogen flow decreases coating thickness. Gold

  10. FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND CARBONACEOUS SOLIDS IN GAS-PHASE CONDENSATION EXPERIMENTS

    SciTech Connect

    Jaeger, C.; Huisken, F.; Henning, Th.; Mutschke, H.; Jansa, I. Llamas

    2009-05-01

    Carbonaceous grains represent a major component of cosmic dust. In order to understand their formation pathways, they have been prepared in the laboratory by gas-phase condensation reactions such as laser pyrolysis and laser ablation. Our studies demonstrate that the temperature in the condensation zone determines the formation pathway of carbonaceous particles. At temperatures lower than 1700 K, the condensation by-products are mainly polycyclic aromatic hydrocarbons (PAHs) that are also the precursors or building blocks for the condensing soot grains. The low-temperature condensates contain PAH mixtures that are mainly composed of volatile three to five ring systems. At condensation temperatures higher than 3500 K, fullerene-like carbon grains and fullerene compounds are formed. Fullerene fragments or complete fullerenes equip the nucleating particles. Fullerenes can be identified as soluble components. Consequently, condensation products in cool and hot astrophysical environments such as cool and hot asymptotic giant branch stars or Wolf-Rayet stars should be different and should have distinct spectral properties.

  11. Gas-phase and particulate products from the atmospheric degradation of an isoxazole fungicide.

    PubMed

    Tortajada-Genaro, Luis Antonio; Borrás, Esther; Muñoz, Amalia

    2013-08-01

    The isoxazole structure is present in several pesticides. However, there is a lack of information about its degradation products after the release to the atmosphere. The main atmospheric reactions of hymexazol (5-methylisoxazol-3-ol), selected as representative model, were investigated at a large outdoor simulation chamber. The predominant products of atmospheric degradations were gaseous nitrogen derivates (nitric acid, nitrogen dioxide, nitrogen oxide, nitrous acid, and peroxyacetylnitrate), ozone, and small oxygenated compounds (formic acid, formaldehyde, and methylglyoxal). The aerosol yields were lower than 5%, and an OH rate-dependence was observed in the nucleation, particle growth, and size distribution. Also, the chemical composition of minor multi-oxygenated products was studied for OH-photo-oxidations. More than 20 products were detected in the gas or particulate phase. The most abundant were heterocyclic cleavage products with C4-chain and oxygenated moieties at positions 1 and 3, such as 3,4-dioxobutanoic acid, 3-oxobutanoic acid, and 3-oxobutanal. The suggested reaction pathway is the opening of heterocycle ring by the cleavage of N-O bond and C-N bond, releasing nitrogen oxides.

  12. Nucleation processes of nanobubbles at a solid/water interface

    NASA Astrophysics Data System (ADS)

    Fang, Chung-Kai; Ko, Hsien-Chen; Yang, Chih-Wen; Lu, Yi-Hsien; Hwang, Ing-Shouh

    2016-04-01

    Experimental investigations of hydrophobic/water interfaces often return controversial results, possibly due to the unknown role of gas accumulation at the interfaces. Here, during advanced atomic force microscopy of the initial evolution of gas-containing structures at a highly ordered pyrolytic graphite/water interface, a fluid phase first appeared as a circular wetting layer ~0.3 nm in thickness and was later transformed into a cap-shaped nanostructure (an interfacial nanobubble). Two-dimensional ordered domains were nucleated and grew over time outside or at the perimeter of the fluid regions, eventually confining growth of the fluid regions to the vertical direction. We determined that interfacial nanobubbles and fluid layers have very similar mechanical properties, suggesting low interfacial tension with water and a liquid-like nature, explaining their high stability and their roles in boundary slip and bubble nucleation. These ordered domains may be the interfacial hydrophilic gas hydrates and/or the long-sought chemical surface heterogeneities responsible for contact line pinning and contact angle hysteresis. The gradual nucleation and growth of hydrophilic ordered domains renders the original homogeneous hydrophobic/water interface more heterogeneous over time, which would have great consequence for interfacial properties that affect diverse phenomena, including interactions in water, chemical reactions, and the self-assembly and function of biological molecules.

  13. Nucleation processes of nanobubbles at a solid/water interface

    PubMed Central

    Fang, Chung-Kai; Ko, Hsien-Chen; Yang, Chih-Wen; Lu, Yi-Hsien; Hwang, Ing-Shouh

    2016-01-01

    Experimental investigations of hydrophobic/water interfaces often return controversial results, possibly due to the unknown role of gas accumulation at the interfaces. Here, during advanced atomic force microscopy of the initial evolution of gas-containing structures at a highly ordered pyrolytic graphite/water interface, a fluid phase first appeared as a circular wetting layer ~0.3 nm in thickness and was later transformed into a cap-shaped nanostructure (an interfacial nanobubble). Two-dimensional ordered domains were nucleated and grew over time outside or at the perimeter of the fluid regions, eventually confining growth of the fluid regions to the vertical direction. We determined that interfacial nanobubbles and fluid layers have very similar mechanical properties, suggesting low interfacial tension with water and a liquid-like nature, explaining their high stability and their roles in boundary slip and bubble nucleation. These ordered domains may be the interfacial hydrophilic gas hydrates and/or the long-sought chemical surface heterogeneities responsible for contact line pinning and contact angle hysteresis. The gradual nucleation and growth of hydrophilic ordered domains renders the original homogeneous hydrophobic/water interface more heterogeneous over time, which would have great consequence for interfacial properties that affect diverse phenomena, including interactions in water, chemical reactions, and the self-assembly and function of biological molecules. PMID:27090291

  14. 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.

  15. Gas phase oxidation downstream of a catalytic combustor

    NASA Technical Reports Server (NTRS)

    Tien, J. S.; Anderson, D. N.

    1979-01-01

    Effect of the length available for gas-phase reactions downstream of the catalytic reactor on the emission of CO and unburned hydrocarbons was investigated. A premixed, prevaporized propane/air feed to a 12/cm/diameter catalytic/reactor test section was used. The catalytic reactor was made of four 2.5 cm long monolithic catalyst elements. Four water cooled gas sampling probes were located at positions between 0 and 22 cm downstream of the catalytic reactor. Measurements of unburned hydrocarbon, CO, and CO2 were made. Tests were performed with an inlet air temperature of 800 K, a reference velocity of 10 m/s, pressures of 3 and 600,000 Pa, and fuel air equivalence ratios of 0.14 to 0.24. For very lean mixtures, hydrocarbon emissions were high and CO continued to be formed downstream of the catalytic reactor. At the highest equivalence ratios tested, hydrocarbon levels were much lower and CO was oxidized to CO2 in the gas phase downstream. To achieve acceptable emissions, a downstream region several times longer than the catalytic reactor could be required.

  16. Preferential nucleation during polymorphic transformations

    DOE PAGES

    Sharma, H.; Sietsma, J.; Offerman, S. E.

    2016-08-03

    Polymorphism is the ability of a solid material to exist in more than one phase or crystal structure. Polymorphism may occur in metals, alloys, ceramics, minerals, polymers, and pharmaceutical substances. Unresolved are the conditions for preferential nucleation during polymorphic transformations in which structural relationships or special crystallographic orientation relationships (OR’s) form between the nucleus and surrounding matrix grains. We measured in-situ and simultaneously the nucleation rates of grains that have zero, one, two, three and four special OR’s with the surrounding parent grains. These experiments show a trend in which the activation energy for nucleation becomes smaller – and thereforemore » nucleation more probable - with increasing number of special OR’s. As a result, these insights contribute to steering the processing of polymorphic materials with tailored properties, since preferential nucleation affects which crystal structure forms, the average grain size and texture of the material, and thereby - to a large extent - the final properties of the material.« less

  17. Preferential nucleation during polymorphic transformations

    SciTech Connect

    Sharma, H.; Sietsma, J.; Offerman, S. E.

    2016-08-03

    Polymorphism is the ability of a solid material to exist in more than one phase or crystal structure. Polymorphism may occur in metals, alloys, ceramics, minerals, polymers, and pharmaceutical substances. Unresolved are the conditions for preferential nucleation during polymorphic transformations in which structural relationships or special crystallographic orientation relationships (OR’s) form between the nucleus and surrounding matrix grains. We measured in-situ and simultaneously the nucleation rates of grains that have zero, one, two, three and four special OR’s with the surrounding parent grains. These experiments show a trend in which the activation energy for nucleation becomes smaller – and therefore nucleation more probable - with increasing number of special OR’s. As a result, these insights contribute to steering the processing of polymorphic materials with tailored properties, since preferential nucleation affects which crystal structure forms, the average grain size and texture of the material, and thereby - to a large extent - the final properties of the material.

  18. Studies of Nucleation and Growth, Specific Heat and Viscosity of Undercooled Melts of Quasicrystals and Polytetrehedral-Phase-Forming Alloys

    NASA Technical Reports Server (NTRS)

    2003-01-01

    By investigating the properties of quasicrystals and quasicrystal-forming liquid alloys, we may determine the role of ordering of the liquid phase in the formation of quasicrystals, leading to a better fundamental understanding of both the quasicrystal and the liquid. A quasicrystal is solid characterized by a symmetric but non-periodic arrangement of atoms, usually in the form of an icosahedron (12 atoms, 20 triangular faces). It is theorized that the short-range order in liquids takes this same form. The degree of ordering depends on the temperature of the liquid, and affects many of the liquid s properties, including specific heat, viscosity, and electrical resistivity. The MSFC role in this project includes solidification studies, phase diagram determination, and thermophysical property measurements on the liquid quasicrystal-forming alloys, all by electrostatic levitation (ESL). The viscosity of liquid quasicrystal-forming alloys is measured by the oscillating drop method, both in the stable and undercooled liquid state. The specific heat of solid, undercooled liquid, and stable liquid are measured by the radiative cooling rate of the droplets.

  19. Phase-locked measurements of gas-liquid horizontal flows

    NASA Astrophysics Data System (ADS)

    Zadrazil, Ivan; Matar, Omar; Markides, Christos

    2014-11-01

    A flow of gas and liquid in a horizontal pipe can be described in terms of various flow regimes, e.g. wavy stratified, annular or slug flow. These flow regimes appear at characteristic gas and liquid Reynolds numbers and feature unique wave phenomena. Wavy stratified flow is populated by low amplitude waves whereas annular flow contains high amplitude and long lived waves, so called disturbance waves, that play a key role in a liquid entrainment into the gas phase (droplets). In a slug flow regime, liquid-continuous regions travel at high speeds through a pipe separated by regions of stratified flow. We use a refractive index matched dynamic shadowgraphy technique using a high-speed camera mounted on a moving robotic linear rail to track the formation and development of features characteristic for the aforementioned flow regimes. We show that the wave dynamics become progressively more complex with increasing liquid and gas Reynolds numbers. Based on the shadowgraphy measurements we present, over a range of conditions: (i) phenomenological observations of the formation, and (ii) statistical data on the downstream velocity distribution of different classes of waves. EPSRC Programme Grant, MEMPHIS, EP/K0039761/1.

  20. Effects of cloud condensation nuclei and ice nucleating particles on precipitation processes and supercooled liquid in mixed-phase orographic clouds

    DOE PAGES

    Fan, Jiwen; Leung, L. Ruby; Rosenfeld, Daniel; ...

    2017-01-23

    How orographic mixed-phase clouds respond to the change in cloud condensation nuclei (CCN) and ice nucleating particles (INPs) are highly uncertain. The main snow production mechanism in warm and cold mixed-phase orographic clouds (referred to as WMOCs and CMOCs, respectively, distinguished here as those having cloud tops warmer and colder than −20 °C) could be very different. We quantify the CCN and INP impacts on supercooled water content, cloud phases, and precipitation for a WMOC case and a CMOC case, with sensitivity tests using the same CCN and INP concentrations between the WMOC and CMOC cases. It was found that depositionmore » plays a more important role than riming for forming snow in the CMOC case, while the role of riming is dominant in the WMOC case. As expected, adding CCN suppresses precipitation, especially in WMOCs and low INPs. However, this reverses strongly for CCN of 1000 cm−3 and larger. We found a new mechanism through which CCN can invigorate mixed-phase clouds over the Sierra Nevada and drastically intensify snow precipitation when CCN concentrations are high (1000 cm−3 or higher). In this situation, more widespread shallow clouds with a greater amount of cloud water form in the Central Valley and foothills west of the mountain range. The increased latent heat release associated with the formation of these clouds strengthens the local transport of moisture to the windward slope, invigorating mixed-phase clouds over the mountains, and thereby producing higher amounts of snow precipitation. Under all CCN conditions, increasing the INPs leads to decreased riming and mixed-phase fraction in the CMOC as a result of liquid-limited conditions, but has the opposite effects in the WMOC as a result of ice-limited conditions. However, precipitation in both cases is increased by increasing INPs due to an increase in deposition for the CMOC but enhanced riming and deposition in the WMOC. Increasing the INPs dramatically reduces

  1. Effects of cloud condensation nuclei and ice nucleating particles on precipitation processes and supercooled liquid in mixed-phase orographic clouds

    SciTech Connect

    Fan, Jiwen; Leung, L. Ruby; Rosenfeld, Daniel; DeMott, Paul J.

    2017-01-01

    How orographic mixed-phase clouds respond to the change in cloud condensation nuclei (CCN) and ice nucleating particles (INPs) are highly uncertain. The main snow production mechanism in warm and cold mixed-phase orographic clouds (referred to as WMOCs and CMOCs, respectively, distinguished here as those having cloud tops warmer and colder than -20°C) could be very different. We quantify the CCN and INP impacts on supercooled water content, cloud phases, and precipitation for a WMOC case and a CMOC case, with sensitivity tests using the same CCN and INP concentrations between the WMOC and CMOC cases. It was found that deposition plays a more important role than riming for forming snow in the CMOC case, while the role of riming is dominant in the WMOC case. As expected, adding CCN suppresses precipitation, especially in WMOCs and low INPs. However, this reverses strongly for CCN of 1000 cm-3 and larger. We found a new mechanism through which CCN can invigorate mixed-phase clouds over the Sierra Nevada and drastically intensify snow precipitation when CCN concentrations are high (1000 cm-3 or higher). In this situation, more widespread shallow clouds with a greater amount of cloud water form in the Central Valley and foothills west of the mountain range. The increased latent heat release associated with the formation of these clouds strengthens the local transport of moisture to the windward slope, invigorating mixed-phase clouds over the mountains, and thereby producing higher amounts of snow precipitation. Under all CCN conditions, increasing the INPs leads to decreased riming and mixed-phase fraction in the CMOC as a result of liquid-limited conditions, but has the opposite effects in the WMOC as a result of ice-limited conditions. However, precipitation in both cases is increased by increasing INPs due to an increase in deposition for the CMOC but enhanced riming and deposition in the WMOC. Increasing the INPs dramatically reduces

  2. Effects of cloud condensation nuclei and ice nucleating particles on precipitation processes and supercooled liquid in mixed-phase orographic clouds

    NASA Astrophysics Data System (ADS)

    Fan, Jiwen; Leung, L. Ruby; Rosenfeld, Daniel; DeMott, Paul J.

    2017-01-01

    How orographic mixed-phase clouds respond to the change in cloud condensation nuclei (CCN) and ice nucleating particles (INPs) are highly uncertain. The main snow production mechanism in warm and cold mixed-phase orographic clouds (referred to as WMOCs and CMOCs, respectively, distinguished here as those having cloud tops warmer and colder than -20 °C) could be very different. We quantify the CCN and INP impacts on supercooled water content, cloud phases, and precipitation for a WMOC case and a CMOC case, with sensitivity tests using the same CCN and INP concentrations between the WMOC and CMOC cases. It was found that deposition plays a more important role than riming for forming snow in the CMOC case, while the role of riming is dominant in the WMOC case. As expected, adding CCN suppresses precipitation, especially in WMOCs and low INPs. However, this reverses strongly for CCN of 1000 cm-3 and larger. We found a new mechanism through which CCN can invigorate mixed-phase clouds over the Sierra Nevada and drastically intensify snow precipitation when CCN concentrations are high (1000 cm-3 or higher). In this situation, more widespread shallow clouds with a greater amount of cloud water form in the Central Valley and foothills west of the mountain range. The increased latent heat release associated with the formation of these clouds strengthens the local transport of moisture to the windward slope, invigorating mixed-phase clouds over the mountains, and thereby producing higher amounts of snow precipitation. Under all CCN conditions, increasing the INPs leads to decreased riming and mixed-phase fraction in the CMOC as a result of liquid-limited conditions, but has the opposite effects in the WMOC as a result of ice-limited conditions. However, precipitation in both cases is increased by increasing INPs due to an increase in deposition for the CMOC but enhanced riming and deposition in the WMOC. Increasing the INPs dramatically reduces supercooled water content and

  3. Computational phase diagrams of noble gas hydrates under pressure

    SciTech Connect

    Teeratchanan, Pattanasak Hermann, Andreas

    2015-10-21

    We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-I{sub h}, ice-I{sub c}, ice-II, and C{sub 0} interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C{sub 0} water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C{sub 0} hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.

  4. Computational phase diagrams of noble gas hydrates under pressure

    NASA Astrophysics Data System (ADS)

    Teeratchanan, Pattanasak; Hermann, Andreas

    2015-10-01

    We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-Ih, ice-Ic, ice-II, and C0 interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C0 water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C0 hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.

  5. Nucleation and growth of nanoscaled one-dimensional materials

    NASA Astrophysics Data System (ADS)

    Cui, Hongtao

    Nanoscaled one-dimensional materials have attracted great interest due to their novel physical and chemical properties. The purpose of this dissertation is to study the nucleation and growth mechanisms of carbon nanotubes and silicon nitride nanowires with their field emission applications in mind. As a result of this research, a novel methodology has been developed to deposit aligned bamboo-like carbon nanotubes on substrates using a methane and ammonia mixture in microwave plasma enhanced chemical deposition. Study of growth kinetics suggests that the carbon diffusion through bulk catalyst particles controls growth in the initial deposition process. Microstructures of carbon nanotubes are affected by the growth temperature and carbon concentration in the gas phase. High-resolution transmission electron microscope confirms the existence of the bamboo-like structure. Electron diffraction reveals that the iron-based catalyst nucleates and sustains the growth of carbon nanotubes. A nucleation and growth model has been constructed based upon experimental data and observations. In the study of silicon nitride nanoneedles, a vapor-liquid-solid model is employed to explain the nucleation and growth processes. Ammonia plasma etching is proposed to reduce the size of the catalyst and subsequently produce the novel needle-like nanostructure. High-resolution transmission electron microscope shows the structure is well crystallized and composed of alpha-silicon nitride. Other observations in the structure are also explained.

  6. Nucleation and growth of Ag islands on the (.sqroot.3 × .sqroot.3)R30° phase of Ag on Si(111)

    SciTech Connect

    Belianinov, A.; Unal, B.; Ho, K.-M.; Wang, C.-Z.; Evans, J. W.; Tringides, M. C.; Thiel, P. A.

    2011-06-06

    We use scanning tunneling microscopy to measure densities and characteristics of Ag islands that form on the ({radical}3 x {radical}3)R30{sup o}-Ag phase on Si(111), as a function of deposition temperature. Nucleation theory predicts that the logarithm of island density varies linearly with inverse deposition temperature. The data show two linear regimes. At 50-125 K, islands are relatively small, and island density decreases only slightly with increasing temperature. At 180-250 K, islands are larger and polycrystalline, and island density decreases strongly with increasing temperature. At 300 K, Ag atoms can travel for distances of the order of 1 {micro}m. Assuming that Ag diffusion occurs via thermally activated motion of single atoms between adjacent sites, the data can be explained as follows. At 50-125 K, the island density does not follow conventional Arrhenius scaling due to limited mobility and a consequent breakdown of the steady-state condition for the adatom density. At {approx} 115-125 K, a transition to conventional Arrhenius scaling with critical nucleus size (i = 1) begins, and at 180-250 K, i > 1 prevails. The transition points indicate a diffusion barrier of 0.20-0.23 eV and a pairwise Ag-Ag bond strength of 0.14 eV. These energy values lead to an estimate of i {approx} 3-4 in the regime 180-250 K, where island density varies strongly with temperature.

  7. Nucleation and growth of Ag islands on the (√3 × √3)R30° phase of Ag on Si(111).

    PubMed

    Belianinov, A; Unal, B; Ho, K-M; Wang, C-Z; Evans, J W; Tringides, M C; Thiel, P A

    2011-07-06

    We use scanning tunneling microscopy to measure densities and characteristics of Ag islands that form on the (√3 × √3)R30°-Ag phase on Si(111), as a function of deposition temperature. Nucleation theory predicts that the logarithm of island density varies linearly with inverse deposition temperature. The data show two linear regimes. At 50-125 K, islands are relatively small, and island density decreases only slightly with increasing temperature. At 180-250 K, islands are larger and polycrystalline, and island density decreases strongly with increasing temperature. At 300 K, Ag atoms can travel for distances of the order of 1 µm. Assuming that Ag diffusion occurs via thermally activated motion of single atoms between adjacent sites, the data can be explained as follows. At 50-125 K, the island density does not follow conventional Arrhenius scaling due to limited mobility and a consequent breakdown of the steady-state condition for the adatom density. At ∼ 115-125 K, a transition to conventional Arrhenius scaling with critical nucleus size (i = 1) begins, and at 180-250 K, i > 1 prevails. The transition points indicate a diffusion barrier of 0.20-0.23 eV and a pairwise Ag-Ag bond strength of 0.14 eV. These energy values lead to an estimate of i≈3-4 in the regime 180-250 K, where island density varies strongly with temperature.

  8. Femtosecond gas phase electron diffraction with MeV electrons.

    PubMed

    Yang, Jie; Guehr, Markus; Vecchione, Theodore; Robinson, Matthew S; Li, Renkai; Hartmann, Nick; Shen, Xiaozhe; Coffee, Ryan; Corbett, Jeff; Fry, Alan; Gaffney, Kelly; Gorkhover, Tais; Hast, Carsten; Jobe, Keith; Makasyuk, Igor; Reid, Alexander; Robinson, Joseph; Vetter, Sharon; Wang, Fenglin; Weathersby, Stephen; Yoneda, Charles; Wang, Xijie; Centurion, Martin

    2016-12-16

    We present results on ultrafast gas electron diffraction (UGED) experiments with femtosecond resolution using the MeV electron gun at SLAC National Accelerator Laboratory. UGED is a promising method to investigate molecular dynamics in the gas phase because electron pulses can probe the structure with a high spatial resolution. Until recently, however, it was not possible for UGED to reach the relevant timescale for the motion of the nuclei during a molecular reaction. Using MeV electron pulses has allowed us to overcome the main challenges in reaching femtosecond resolution, namely delivering short electron pulses on a gas target, overcoming the effect of velocity mismatch between pump laser pulses and the probe electron pulses, and maintaining a low timing jitter. At electron kinetic energies above 3 MeV, the velocity mismatch between laser and electron pulses becomes negligible. The relativistic electrons are also less susceptible to temporal broadening due to the Coulomb force. One of the challenges of diffraction with relativistic electrons is that the small de Broglie wavelength results in very small diffraction angles. In this paper we describe the new setup and its characterization, including capturing static diffraction patterns of molecules in the gas phase, finding time-zero with sub-picosecond accuracy and first time-resolved diffraction experiments. The new device can achieve a temporal resolution of 100 fs root-mean-square, and sub-angstrom spatial resolution. The collimation of the beam is sufficient to measure the diffraction pattern, and the transverse coherence is on the order of 2 nm. Currently, the temporal resolution is limited both by the pulse duration of the electron pulse on target and by the timing jitter, while the spatial resolution is limited by the average electron beam current and the signal-to-noise ratio of the detection system. We also discuss plans for improving both the temporal resolution and the spatial resolution.

  9. Fluorescence Spectroscopy of Gas-phase Polycyclic Aromatic Hydrocarbons

    NASA Technical Reports Server (NTRS)

    Thomas, J. D.; Witt, A. N.

    2006-01-01

    The purpose of this investigation was to produce fluorescence spectra of polycyclic aromatic hydrocarbon (PAH) molecules in the gas-phase for comparison with blue luminescence (BL) emission observed in astrophysical sources Vijh et al. (2004, 2005a,b). The BL occurs roughly from 350 to 450 nm, with a sharp peak near 380 nm. PAHs with three to four rings, e.g. anthracene and pyrene, were found to produce luminescence in the appropriate spectral region, based on existing studies. Relatively few studies of the gas-phase fluorescence of PAHs exist; those that do exist have dealt primarily with the same samples commonly available for purchase such as pyrene and anthracene. In an attempt to understand the chemistry of the nebular environment we also obtained several nitrogen substituted PAHs from our colleagues at NASA Ames. In order to simulate the astrophysical environment we also took spectra by heating the PAHs in a flame. The flame environment counteracts the formation of eximers and permits the spectroscopy of free-flying neutral molecules. Experiments with coal tar demonstrate that fluorescence spectroscopy reveals primarily the presence of the smallest molecules, which are most abundant and which possess the highest fluorescence efficiencies. One gas-phase PAH that seems to fit the BL spectrum most closely is phenanthridine. In view of the results from the spectroscopy of coal tar, a compound containing a mixture of PAHs ranging from small to very large PAH molecules, we can not preclude the presence of larger PAHs in interstellar sources exhibiting BL.

  10. Neurotransmitters in the Gas Phase: La-Mb Studies

    NASA Astrophysics Data System (ADS)

    Cabezas, C.; Mata, S.; López, J. C.; Alonso, J. L.

    2011-06-01

    LA-MB-FTMW spectroscopy combines laser ablation with Fourier transform microwave spectroscopy in supersonic jets overcoming the problems of thermal decomposition associated with conventional heating methods. We present here the results on LA-MB-FTMW studies of some neurotransmitters. Six conformers of dopamine, four of adrenaline, five of noradrenaline and three conformers of serotonin have been characterized in the gas phase. The rotational and nuclear quadrupole coupling constants extracted from the analysis of the rotational spectrum are directly compared with those predicted by ab initio methods to achieve the conclusive identification of different conformers and the experimental characterization of the intramolecular forces at play which control conformational preferences.

  11. Multiscale Aspects of Modeling Gas-Phase Nanoparticle Synthesis

    PubMed Central

    Buesser, B.; Gröhn, A.J.

    2013-01-01

    Aerosol reactors are utilized to manufacture nanoparticles in industrially relevant quantities. The development, understanding and scale-up of aerosol reactors can be facilitated with models and computer simulations. This review aims to provide an overview of recent developments of models and simulations and discuss their interconnection in a multiscale approach. A short introduction of the various aerosol reactor types and gas-phase particle dynamics is presented as a background for the later discussion of the models and simulations. Models are presented with decreasing time and length scales in sections on continuum, mesoscale, molecular dynamics and quantum mechanics models. PMID:23729992

  12. Theoretical calculations of EPR parameters of gas phase hydracrylonitrile radical

    NASA Astrophysics Data System (ADS)

    Sarikaya, Ebru Karakaş; Dereli, Ömer

    2017-02-01

    As a result of detailed conformational search of the hydracrylonitrile, four different conformers of molecule have been obtained. For these conformations, eleven possible radicals were modelled by using density functional theory (DFT) computations with respect to molecular structure. Electron Paramagnetic Resonance parameters of these model radicals were calculated and then they were compared with the experimental ones. Geometry optimizations of the molecule and modeled radicals were calculated by B3LYP method using 6-311++G(d,p) basis sets in gas phase.

  13. Seven Conformers of Pipecolic Acid Identified in the Gas Phase

    NASA Astrophysics Data System (ADS)

    Cabezas, Carlos; Simao, Alcides; Alonso, José L.

    2016-06-01

    The multiconformational landscape of the non-proteinogenic cyclic amino acid pipecolic acid has been explored in the gas phase. Solid pipecolic acid (m.p. 280°C) was vaporized by laser ablation (LA) and expanded in a supersonic jet where the rotational spectra of seven conformers were obtained by broadband microwave spectroscopy (CP-FTMW). All conformers were conclusively identified by comparison of the experimental spectroscopic constants with those predicted theoretically. The relative stability of the conformers rests on a delicate balance of the different intramolecular hydrogen bonds established between the carboxylic and the amino groups.

  14. Femtosecond analysis of free molecular rotation in the gas phase

    NASA Astrophysics Data System (ADS)

    Borisevich, N. A.; Khoroshilov, E. V.; Kryukov, I. V.; Kryukov, P. G.; Sharkov, A. V.; Blokhin, A. P.; Tolstorozhev, G. B.

    1992-04-01

    The time-resolved S 1→S *n absorption anisotropy decay resulting from rotation of free gas phase POPOP molecules at 593 K and PPO molecules at 483 K was studied after S 0→S *1 excitation by femtosecond linearly polarized pulses at 308 nm. The time evolution of the anisotropy measured through a few picoseconds after excitation is in agreement with the results of calculations made for POPOP and PPO using orientational correlation functions developed for rigid asymmetric top molecules.

  15. The solar system/interstellar medium connection - Gas phase abundances

    NASA Technical Reports Server (NTRS)

    Lutz, Barry L.

    1987-01-01

    Gas-phase abundances in the outer solar system are presented as diagnostics of the interstellar medium at the time of the solar system formation, some 4.55 billion years ago. Possible influences of the thermal and chemical histories of the primitive solar nebula and of the processes which led to the formation and evolution of the outer planets and comets on the elemental and molecular composition of the primordial matter are outlined. The major components of the atmospheres of the outer planets and of the comae of comets are identified, and the cosmogonical and cosmological implications are discussed.

  16. Gas-phase energetics of thorium fluorides and their ions.

    PubMed

    Irikura, Karl K

    2013-02-14

    Gas-phase thermochemistry for neutral ThF(n) and cations ThF(n)(+) (n = 1-4) is obtained from large-basis CCSD(T) calculations, with a small-core pseudopotential on thorium. Electronic partition functions are computed with the help of relativistic MRCI calculations. Geometries, vibrational spectra, electronic fine structure, and ion appearance energies are tabulated. These results support the experimental results by Lau, Brittain, and Hildenbrand for the neutral species, except for ThF. The ion thermochemistry is presented here for the first time.

  17. Collaborative Project: Understanding the Chemical Processes tat Affect Growth rates of Freshly Nucleated Particles

    SciTech Connect

    McMurry, Peter; Smuth, James

    2015-11-12

    This final technical report describes our research activities that have, as the ultimate goal, the development of a model that explains growth rates of freshly nucleated particles. The research activities, which combine field observations with laboratory experiments, explore the relationship between concentrations of gas-phase species that contribute to growth and the rates at which those species are taken up. We also describe measurements of the chemical composition of freshly nucleated particles in a variety of locales, as well as properties (especially hygroscopicity) that influence their effects on climate.

  18. The partitioning of ketones between the gas and aqueous phases

    NASA Astrophysics Data System (ADS)

    Betterton, Eric A.

    Most ketones are not significantly hydrated; they therefore retain their chromophore and they could be photolytically degraded in solution yielding a variety of products including carboxylic acids, aldehydes and radicals. It is difficult to accurately model the partitioning of ketones between the gas phase and aqueous phase because of the lack suitable estimates of the Henry's Law constants; consequently the fate and environmental effects of ketones cannot be confidently predicted. Here we report the experimental determination of the Henry's Law constants of a series of ketones that has yielded a simple straight line equation to predict the Henry's Law constants of simple aliphatic ketones: log H ∗ =0.23Σσ ∗ + 1.51; where H ∗ is the effective Henry's Law constant (M atm -1, and Σσ ∗ is the Taft polar substituents constants. The results for 25°C are (M atm -1) CH 3COCH 3, 32; C 6H 5COCH 3, 110; CH 2ClCOCH 3, 59; CH 3COCOCH 3, 74; CF 3COCH 3, 138. Acetophenone appears to have an abnormally high H ∗. Most low molecular weight aliphatic ketones are predicted to characterized by H ∗⩾30 M atm -1 and therefore they are expected to be found in the aqueous phase at concentrations of ⩾5 - 0.5 μM (given a typical gas-phase concentration range of 1-10 ppbv). The expected rate of decomposition of ketones due to photolysis in hydrometers is briefly discussed.

  19. Communication: Bubbles, crystals, and laser-induced nucleation

    NASA Astrophysics Data System (ADS)

    Knott, Brandon C.; LaRue, Jerry L.; Wodtke, Alec M.; Doherty, Michael F.; Peters, Baron

    2011-05-01

    Short intense laser pulses of visible and infrared light can dramatically accelerate crystal nucleation from transparent solutions; previous studies invoke mechanisms that are only applicable for nucleation of ordered phases or high dielectric phases. However, we show that similar laser pulses induce CO2 bubble nucleation in carbonated water. Additionally, in water that is cosupersaturated with argon and glycine, argon bubbles escaping from the water can induce crystal nucleation without a laser. Our findings suggest a possible link between laser-induced nucleation of bubbles and crystals.

  20. Carbon and Noble Gas Isotope Banks in Two-Phase Flow: Changes in Gas Composition During Migration

    NASA Astrophysics Data System (ADS)

    Sathaye, K.; Larson, T.; Hesse, M. A.

    2015-12-01

    In conjunction with the rise of unconventional oil and gas production, there has been a recent rise in interest in noble gas and carbon isotope changes that can occur during the migration of natural gas. Natural gas geochemistry studies use bulk hydrocarbon composition, carbon isotopes, and noble gas isotopes to determine the migration history of gases from source to reservoir, and to trace fugitive gas leaks from reservoirs to shallow groundwater. We present theoretical and experimental work, which helps to explain trends observed in gas composition in various migration scenarios. Noble gases are used as tracers for subsurface fluid flow due to distinct initial compositions in air-saturated water and natural gases. Numerous field studies have observed enrichments and depletions of noble gases after gas-water interaction. A theoretical two-phase gas displacement model shows that differences in noble gas solubility will cause volatile gas components will become enriched at the front of gas plumes, leaving the surrounding residual water stripped of dissolved gases. Changes in hydrocarbon gas composition are controlled by gas solubility in both formation water and residual oil. In addition to model results, we present results from a series of two-phase flow experiments. These results demonstrate the formation of a noble gas isotope banks ahead of a main CO2 gas plume. Additionally, we show that migrating hydrocarbon gas plumes can sweep biogenic methane from groundwater, significantly altering the isotope ratio of the gas itself. Results from multicomponent, two-phase flow experiments qualitatively agree with the theoretical model, and previous field studies. These experimentally verified models for gas composition changes can be used to aid source identification of subsurface gases.

  1. Gas-Phase Fragmentation Analysis of Nitro-Fatty Acids

    PubMed Central

    Bonacci, Gustavo; Asciutto, Eliana K.; Woodcock, Steven R.; Salvatore, Sonia R.; Freeman, Bruce A.; Schopfer, Francisco J.

    2012-01-01

    Nitro-fatty acids are electrophilic signaling mediators formed in increased amounts during inflammation by nitric oxide and nitrite-dependent redox reactions. A more rigorous characterization of endogenously-generated species requires additional understanding of their gas-phase induced fragmentation. Thus, collision induced dissociation (CID) of nitroalkane and nitroalkene groups in fatty acids were studied in the negative ion mode to provide mass spectrometric tools for their structural characterization. Fragmentation of nitroalkanes occurred mainly through loss of the NO2− anion or neutral loss of HNO2. The CID of nitroalkenes proceeds via a more complex cyclization, followed by fragmentation to nitrile and aldehyde products. Gas-phase fragmentation of nitroalkene functional groups with additional γ or δ unsaturation occurred through a multiple step cyclization reaction process, leading to 5 and 6 member ring heterocyclic products and carbon chain fragmentation. Cyclization products were not obtained during nitroalkane fragmentation, highlighting the role of double bond π electrons during NO2− rearrangements, stabilization and heterocycle formation. The proposed structures, mechanisms and products of fragmentation are supported by analysis of 13C and 15N labeled parent molecules, 6 different nitroalkene positional isomers, 6 nitroalkane positional isomers, accurate mass determinations at high resolution and quantum mechanics calculations. Multiple key diagnostic ion fragments were obtained through this analysis, allowing for the precise placement of double bonds and sites of fatty acid nitration, thus supporting an ability to predict nitro positions in biological samples. PMID:21953257

  2. High resolution dissociative electron attachment to gas phase adenine

    SciTech Connect

    Huber, D.; Beikircher, M.; Denifl, S.; Zappa, F.; Matejcik, S.; Bacher, A.; Grill, V.; Maerk, T. D.; Scheier, P.

    2006-08-28

    The dissociative electron attachment to the gas phase nucleobase adenine is studied using two different experiments. A double focusing sector field mass spectrometer is utilized for measurements requiring high mass resolution, high sensitivity, and relative ion yields for all the fragment anions and a hemispherical electron monochromator instrument for high electron energy resolution. The negative ion mass spectra are discussed at two different electron energies of 2 and 6 eV. In contrast to previous gas phase studies a number of new negative ions are discovered in the mass spectra. The ion efficiency curves for the negative ions of adenine are measured for the electron energy range from about 0 to 15 eV with an electron energy resolution of about 100 meV. The total anion yield derived via the summation of all measured fragment anions is compared with the total cross section for negative ion formation measured recently without mass spectrometry. For adenine the shape of the two cross section curves agrees well, taking into account the different electron energy resolutions; however, for thymine some peculiar differences are observed.

  3. Gas-phase Dissociation of homo-DNA Oligonucleotides

    NASA Astrophysics Data System (ADS)

    Stucki, Silvan R.; Désiron, Camille; Nyakas, Adrien; Marti, Simon; Leumann, Christian J.; Schürch, Stefan

    2013-12-01

    Synthetic modified oligonucleotides are of interest for diagnostic and therapeutic applications, as their biological stability, pairing selectivity, and binding strength can be considerably increased by the incorporation of unnatural structural elements. Homo-DNA is an oligonucleotide homologue based on dideoxy-hexopyranosyl sugar moieties, which follows the Watson-Crick A-T and G-C base pairing system, but does not hybridize with complementary natural DNA and RNA. Homo-DNA has found application as a bioorthogonal element in templated chemistry applications. The gas-phase dissociation of homo-DNA has been investigated by ESI-MS/MS and MALDI-MS/MS, and mechanistic aspects of its gas-phase dissociation are discussed. Experiments revealed a charge state dependent preference for the loss of nucleobases, which are released either as neutrals or as anions. In contrast to DNA, nucleobase loss from homo-DNA was found to be decoupled from backbone cleavage, thus resulting in stable products. This renders an additional stage of ion activation necessary in order to generate sequence-defining fragment ions. Upon MS3 of the primary base-loss ion, homo-DNA was found to exhibit unspecific backbone dissociation resulting in a balanced distribution of all fragment ion series.

  4. Nahoon: Time-dependent gas-phase chemical model

    NASA Astrophysics Data System (ADS)

    Wakelam, V.

    2014-09-01

    Nahoon is a gas-phase chemical model that computes the chemical evolution in a 1D temperature and density structure. It uses chemical networks downloaded from the KInetic Database for Astrochemistry (KIDA) but the model can be adapted to any network. The program is written in Fortran 90 and uses the DLSODES (double precision) solver from the ODEPACK package to solve the coupled stiff differential equations. The solver computes the chemical evolution of gas-phase species at a fixed temperature and density and can be used in one dimension (1D) if a grid of temperature, density, and visual extinction is provided. Grains, both neutral and negatively charged, and electrons are considered as chemical species and their concentrations are computed at the same time as those of the other species. Nahoon contains a test to check the temperature range of the validity of the rate coefficients and avoid extrapolations outside this range. A test is also included to check for duplication of chemical reactions, defined over complementary ranges of temperature.

  5. 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.

  6. Homogeneous nucleation and growth in supersaturated zinc vapor investigated by molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Römer, F.; Kraska, T.

    2007-12-01

    Homogeneous nucleation and growth of zinc from supersaturated vapor are investigated by nonequilibrium molecular dynamics simulations in the temperature range from 400to800K and for a supersaturation ranging from logS =2 to 11. Argon is added to the vapor phase as carrier gas to remove the latent heat from the forming zinc clusters. A new parametrization of the embedded atom method for zinc is employed for the interaction potential model. The simulation data are analyzed with respect to the nucleation rates and the critical cluster sizes by two different methods, namely, the threshold method of Yasuoka and Matsumoto [J. Chem. Phys. 109, 8451 (1998)] and the mean first passage time method for nucleation by Wedekind et al. [J. Chem. Phys. 126, 134103 (2007)]. The nucleation rates obtained by these methods differ approximately by one order of magnitude. Classical nucleation theory fails to describe the simulation data as well as the experimental data. The size of the critical cluster obtained by the mean first passage time method is significantly larger than that obtained from the nucleation theorem.

  7. Experimental study of Gas Phase Formation and Evolution in Low fO2 Planetary Basalts.

    NASA Astrophysics Data System (ADS)

    Rutherford, M. J.; Wetzel, D. T.; Saal, A. E.; Hauri, E. H.

    2012-12-01

    The existence of a gas phase in planetary basaltic magmas is demonstrated by the ubiquitous presence of vesicles in returned lunar samples and meteorites as well as basalts from Earth and Mars. Additionally, formation of the fine-grained glass bead deposits during eruption of lunar picritic glasses required a large gas-bubble volume (> 90%) at the time of eruption/fragmentation. Up to 100-200 ppm levels of H, S, Cl and F still remain as diffusion-loss profiles in individual lunar glass beads SIMS (1), and higher volatile concentrations occur in olivine melt inclusions (2). The composition and origin of such volcanic gases were investigated by experiments on a volatile (C-O-H-S-Cl-F)-bearing picritic glass composition as a function of fO2 near iron-wustite (IW). The C-O-H species dissolved in gas-saturated basaltic melt above IW-0.5 are carbonate, OH and H2O with 100 to 10,000 ppm H2O in the sample; below IW-0.5, the C-species present (Raman and FTIR) are Fe(CO)5 (iron pentacarbonyl) and lesser CH4 [3]. The change in melt speciation in part reflects a change in calculated speciation in the coexisting gas [4]. The carbon solubility in these experimental melts increases linearly with increasing pressure; the more oxidized glasses contain 32-620 ppm C for pressures of 98 to 980 MPa, the reduced glasses contain 8-240 ppm C for pressures between 36 and 900 MPa. Thus, the C solubility of the more reduced Fe-carbonyl and CH4 is about one-half that of carbonate at the same pressure, and indicates the carrying capacity for C in reduced (i.e., lunar) magmas is much lower than it is in present day terrestrial magmas. Varioles up to 200 um in diameter formed in some experiments with higher dissolved water contents (1%); they have radiating crystalline textures (olivine, glass and poorly crystallized graphite) initiated at a central nucleation site. A sharp peak in the variole Ramen spectra indicates methane as well as CO is released during variole formation and a reaction such

  8. Kinetics of nucleation of thermodynamically ordered ferroelectric phases in PbMg1/3Nb2/3O3- xPbTiO3 crystals with different compositions

    NASA Astrophysics Data System (ADS)

    Kamzina, L. S.

    2016-12-01

    The kinetics of electric field-induced nucleation of ordered ferroelectric phases from a mixed glassy relaxor state has been studied in a number of single-crystal (1- x)PbMg1/3Nb2/3O3- xPbTiO3 (PMN- xPT) solid solutions ( x = 29, 33, 35%) lying in a morphotropic phase region. It is shown that the formation of these phases and fast establishment of a macroscopic polarization are preceded by some delay time, depending on the electric field strength and temperature. It is found that the monoclinic phase is thermodynamically stable at room temperature in all the compounds in the time ( 3000 s) and electric field ( 1 kV/cm) ranges under study, whereas the monoclinic phase of the compound with x = 35% transforms, at temperatures near the temperature of the morphotropic phase transition after insignificant time interval of 100 s, to another stable ferroelectric tetragonal phase.

  9. Improvement and further development in CESM/CAM5: gas-phase chemistry and inorganic aerosol treatments

    NASA Astrophysics Data System (ADS)

    He, J.; Zhang, Y.

    2013-10-01

    Gas-phase chemistry and subsequent gas-to-particle conversion processes such as new particle formation, condensation, and thermodynamic partitioning have large impacts on air quality, climate, and public health through influencing the amounts and distributions of gaseous precursors and secondary aerosols. Their roles in global air quality and climate are examined in this work using the Community Earth System Model version 1.0.5 (CESM1.0.5) with the Community Atmosphere Model version 5.1 (CAM5.1) (referred to as CESM1.0.5/CAM5.1). CAM5.1 includes a simple chemistry that is coupled with a 7-mode prognostic Modal Aerosol Model (MAM7). MAM7 includes classical homogenous nucleation (binary and ternary) and activation nucleation (empirical first-order power law) parameterizations, and a highly-simplified inorganic aerosol thermodynamics treatment that only simulates sulfate (SO42-) and ammonium (NH4+). In this work, a new gas-phase chemistry mechanism based on the 2005 Carbon Bond Mechanism for Global Extension (CB05_GE) and several advanced inorganic aerosol treatments for condensation of volatile species, ion-mediated nucleation (IMN), and explicit inorganic aerosol thermodynamics have been incorporated into CESM/CAM5.1-MAM7. Comparing to the simple gas-phase chemistry, CB05_GE can predict many more gaseous species, and improve model performance for PM2.5, PM10, PM2.5 components, and some PM gaseous precursors such as SO2 and NH3 in several regions, as well as aerosol optical depth (AOD) and cloud properties (e.g., cloud fraction (CF), cloud droplet number concentration (CDNC), and shortwave cloud forcing (SWCF)) on globe. The modified condensation and aqueous-phase chemistry further improves the predictions of additional variables such as HNO3, NO2, and O3 in some regions, and new particle formation rate (J) and AOD over globe. IMN can improve the predictions of secondary PM2.5 components, PM2.5, and PM10 over Europe, as well as AOD and CDNC over globe. The explicit

  10. Beyond classical nucleation theory of bubble nucleation during explosive volcanic eruptions (Invited)

    NASA Astrophysics Data System (ADS)

    Gonnermann, H. M.; Gardner, J. E.

    2013-12-01

    Magma degassing, a consequence of the pressure-dependent solubilities of magmatic gases, determines how volcanoes erupt. As magma rises toward the surface, ambient pressure decreases and the melt becomes supersaturated in volatiles, first causing bubbles to nucleate and then grow by diffusion of volatiles from the melt. Consequently, bubble nucleation is a rate-limiting process for magma degassing. It is exceedingly sensitive to the surface energy of a nucleating bubble, which thus exerts a fundamental control on eruptive dynamics. The rate at which bubbles nucleate during explosive magma ascent determines the bubble number density (BND). The conventional view that BND is correlated with magma discharge rate, itself a proxy for explosive intensity, is however not universally true. This is perhaps a consequence of our incomplete understanding of the nucleation work, which depends on the surface tension of the interface between a bubble nucleus and surrounding bulk phase, and which is inaccessible to direct experimental determination. Its effective value can, however, be estimated from nucleation experiments. Because relatively small changes in surface tension result in exceedingly large changes in nucleation rate, current estimates of surface tension result in significant uncertainties in predicted nucleation rates across a wide range of conditions. We show, based on combined decompression-nucleation experiments and numerical modeling thereof, that the surface tension between critical bubble nuclei and the surrounding rhyolitic melt depends on the degree of supersaturation and is lower than the macroscopically measurable value. This is consistent with the view that, far from equilibrium, the interface between a nucleus and surrounding metastable bulk phase is diffuse instead of sharp. As a consequence, the increase in nucleation rate with supersaturation is smaller (larger) than would be predicted from classical nucleation theory for supersaturation pressures less

  11. The Diamagnetic Phase Transition of Dense Electron Gas: Astrophysical Applications

    NASA Astrophysics Data System (ADS)

    Wang, Zhaojun; Lü, Guoliang; Zhu, Chunhua; Wu, Baoshan

    2016-10-01

    Neutron stars are ideal astrophysical laboratories for testing theories of the de Haas-van Alphen effect and diamagnetic phase transition which is associated with magnetic domain formation. The “magnetic interaction” between delocalized magnetic moments of electrons (the Shoenberg effect), can result in an effect of the diamagnetic phase transition into domains of alternating magnetization (Condon's domains). Associated with the domain formation are prominent magnetic field oscillation and anisotropic magnetic stress which may be large enough to fracture the crust of magnetar with a super-strong field. Even if the fracture is impossible as in “low-field” magnetar, the depinning phase transition of domain wall (DW) motion driven by low field rate (mainly due to the Hall effect) in the randomly perturbed crust can result in a catastrophically variation of magnetic field. This intermittent motion, similar to the avalanche process, makes the Hall effect be dissipative. These qualitative consequences about magnetized electron gas are consistent with observations of magnetar emission, and especially the threshold critical dynamics of driven DW can partially overcome the difficulties of “low-field” magnetar bursts and the heating mechanism of transient, or “outbursting” magnetar.

  12. Nucleation and droplet growth at high pressure

    NASA Astrophysics Data System (ADS)

    Luijten, Carlo Cornelis Maria

    Homogeneous nucleation, the first stage of droplet formation in the absence of foreign particles, usually takes place in the presence of one or more supercritical carrier gases. The present work aimed at a systematic investigation of the effects of carrier gas pressure on nucleation and droplet growth. Using the so-called nucleation pulse method, nucleation and droplet growth can be separated in time, which facilitates quantitative study of these processes using Constant Angle Mie Scattering and light extinction. The method was implemented in a modified shock tube, using gas dynamic principles to create the pulse. In this way, nucleation and growth rates were measured as a function of temperature, pressure, and composition. Composition measurement at high pressure was achieved along two different routes. Water vapour concentrations were determined using a commercial humidity sensor, after calibration with total pressure as an independent parameter. Gas chromatography was used to determine hydrocarbon concentrations, after pressure reduction of the mixture over a thermostatic capillary tube. Using the above analysis techniques, nucleation and droplet growth experiments were performed for several vapour-gas mixtures, at pressures between 1 and 40 bar. Mixtures with a varying degree of interaction were selected, to allow for a systematic investigation of carrier gas influence. Besides these binary mixtures, the first quantitative nucleation and growth rates for- multicomponent-natural gas were obtained. Theoretical models for both nucleation and droplet growth were adapted to take into account the presence of a carrier gas, under condition of small carrier gas solubility. The main effects involved are the increase of saturated vapour density and decrease of surface tension with pressure. On the basis of our experiments, these effects were demonstrated to play important and counteracting roles in high pressure nucleation. Using Density Functional Theory, both effects

  13. Gas-phase reactions of halogen species of atmospheric importance

    NASA Astrophysics Data System (ADS)

    Heard, Anne C.

    A low-pressure discharge-flow technique, with various optical detection methods, has been used to determine bimolecular rate coefficients for a number of reactions in the gas-phase between OH radicals and organic halogen-containing molecules and between NO3 radicals and the iodine species I2 and I. These experiments have shown that: (1) the reaction of methyl iodide with OH accounts for approximately 2 percent of the removal of CH3I from the troposphere as compared with photolysis; (2) abstraction of I-atoms from a C-I bond by OH is probable in the gas-phase; (3) the halogen-containing anaesthetic substances halothane CF3CClBrH, enflurane CF2HOCF2CFClH, isoflurane CF2HOCClHCF3 and sevoflurane (CF3)2CHOCFH2 have significantly shorter tropospheric lifetimes than the fully halogenated CFCs and halons because of reaction with the OH radical and are thus unlikely to be transported up to the stratosphere where they could contribute to the depletion of ozone. Data obtained for reactions between OH and some 'CFC alternatives' along with measurements of the integrated absorption cross-sections of the compounds in the spectral region 800-1200 cm(exp -1) were used to calculate ozone depletion potentials (ODP) and greenhouse warming potentials relative to CFCl3 for each compound. The study of the reactions between OH and CF3CFBrH and CF2BrH was used to provide a useful first estimate of the environmental acceptability of these compounds in the context of their possible use as replacements for the conventional CFCs. A method was developed to provide a first estimate of the ODP of a halogenated alkane without use of a complicated (and expensive) computer modeling scheme. A reaction between molecular iodine and the nitrate radical in the gas-phase was discovered and the kinetics of this reaction have been studied. No temperature or pressure dependence was observed for the rate of reaction, the rate constant of which was found to be (1.5 +/- 0.5) x 10(exp -12)/cu cm

  14. Ice-Nucleating Bacteria

    NASA Astrophysics Data System (ADS)

    Obata, Hitoshi

    Since the discovery of ice-nucleating bacteria in 1974 by Maki et al., a large number of studies on the biological characteristics, ice-nucleating substance, ice nucleation gene and frost damage etc. of the bacteria have been carried out. Ice-nucleating bacteria can cause the freezing of water at relatively warm temperature (-2.3°C). Tween 20 was good substrates for ice-nucleating activity of Pseudomonas fluorescens KUIN-1. Major fatty acids of Isolate (Pseudomonas fluorescens) W-11 grown at 30°C were palmitic, cis-9-hexadecenoic and cis-11-octadecenoic which amounted to 90% of the total fatty acids. Sequence analysis shows that an ice nucleation gene from Pseudomonas fluorescens is related to the gene of Pseudomonas syringae.

  15. Ice Nucleation in Deep Convection

    NASA Technical Reports Server (NTRS)

    Jensen, Eric; Ackerman, Andrew; Stevens, David; Gore, Warren J. (Technical Monitor)

    2001-01-01

    The processes controlling production of ice crystals in deep, rapidly ascending convective columns are poorly understood due to the difficulties involved with either modeling or in situ sampling of these violent clouds. A large number of ice crystals are no doubt generated when droplets freeze at about -40 C. However, at higher levels, these crystals are likely depleted due to precipitation and detrainment. As the ice surface area decreases, the relative humidity can increase well above ice saturation, resulting in bursts of ice nucleation. We will present simulations of these processes using a large-eddy simulation model with detailed microphysics. Size bins are included for aerosols, liquid droplets, ice crystals, and mixed-phase (ice/liquid) hydrometers. Microphysical processes simulated include droplet activation, freezing, melting, homogeneous freezing of sulfate aerosols, and heterogeneous ice nucleation. We are focusing on the importance of ice nucleation events in the upper part of the cloud at temperatures below -40 C. We will show that the ultimate evolution of the cloud in this region (and the anvil produced by the convection) is sensitive to these ice nucleation events, and hence to the composition of upper tropospheric aerosols that get entrained into the convective column.

  16. Exploring Carbon Nanomaterial Diversity for Nucleation of Protein Crystals

    PubMed Central

    Govada, Lata; Leese, Hannah S.; Saridakis, Emmanuel; Kassen, Sean; Chain, Benny; Khurshid, Sahir; Menzel, Robert; Hu, Sheng; Shaffer, Milo S. P.; Chayen, Naomi E.

    2016-01-01

    Controlling crystal nucleation is a crucial step in obtaining high quality protein crystals for structure determination by X-ray crystallography. Carbon nanomaterials (CNMs) including carbon nanotubes, graphene oxide, and carbon black provide a range of surface topographies, porosities and length scales; functionalisation with two different approaches, gas phase radical grafting and liquid phase reductive grafting, provide routes to a range of oligomer functionalised products. These grafted materials, combined with a range of controls, were used in a large-scale assessment of the effectiveness for protein crystal nucleation of 20 different carbon nanomaterials on five proteins. This study has allowed a direct comparison of the key characteristics of carbon-based nucleants: appropriate surface chemistry, porosity and/or roughness are required. The most effective solid system tested in this study, carbon black nanoparticles functionalised with poly(ethylene glycol) methyl ether of mean molecular weight 5000, provides a novel highly effective nucleant, that was able to induce crystal nucleation of four out of the five proteins tested at metastable conditions. PMID:26843366

  17. Exploring Carbon Nanomaterial Diversity for Nucleation of Protein Crystals

    NASA Astrophysics Data System (ADS)

    Govada, Lata; Leese, Hannah S.; Saridakis, Emmanuel; Kassen, Sean; Chain, Benny; Khurshid, Sahir; Menzel, Robert; Hu, Sheng; Shaffer, Milo S. P.; Chayen, Naomi E.

    2016-02-01

    Controlling crystal nucleation is a crucial step in obtaining high quality protein crystals for structure determination by X-ray crystallography. Carbon nanomaterials (CNMs) including carbon nanotubes, graphene oxide, and carbon black provide a range of surface topographies, porosities and length scales; functionalisation with two different approaches, gas phase radical grafting and liquid phase reductive grafting, provide routes to a range of oligomer functionalised products. These grafted materials, combined with a range of controls, were used in a large-scale assessment of the effectiveness for protein crystal nucleation of 20 different carbon nanomaterials on five proteins. This study has allowed a direct comparison of the key characteristics of carbon-based nucleants: appropriate surface chemistry, porosity and/or roughness are required. The most effective solid system tested in this study, carbon black nanoparticles functionalised with poly(ethylene glycol) methyl ether of mean molecular weight 5000, provides a novel highly effective nucleant, that was able to induce crystal nucleation of four out of the five proteins tested at metastable conditions.

  18. Gas-phase folding and unfolding of cytochrome c cations.

    PubMed Central

    Wood, T D; Chorush, R A; Wampler, F M; Little, D P; O'Connor, P B; McLafferty, F W

    1995-01-01

    Water is thought to play a dominant role in protein folding, yet gaseous multiply protonated proteins from which the water has been completely removed show hydrogen/deuterium (H/D) exchange behavior similar to that used to identify conformations in solution. Indicative of the gas-phase accessibility to D2O, multiply-charged (6+ to 17+) cytochrome c cations exchange at six (or more) distinct levels of 64 to 173 out of 198 exchangeable H atoms, with the 132 H level found at charge values 8+ to 17+. Infrared laser heating and fast collisions can apparently induce ions to unfold to exchange at a higher distinct level, while charge-stripping ions to lower charge values yields apparent folding as well as unfolding. PMID:7708663

  19. Regenerable Air Purification System for Gas-Phase Contaminant Control

    NASA Technical Reports Server (NTRS)

    Constantinescu, Ileana C.; Finn, John E.; LeVan, M. Douglas; Lung, Bernadette (Technical Monitor)

    2000-01-01

    Tests of a pre-prototype regenerable air purification system (RAPS) that uses water vapor to displace adsorbed contaminants from an adsorbent column have been performed at NASA Ames Research Center. A unit based on this design can be used for removing trace gas-phase contaminants from spacecraft cabin air or from polluted process streams including incinerator exhaust. During the normal operation mode, contaminants are removed from the air on the column. Regeneration of the column is performed on-line. During regeneration, contaminants are displaced and destroyed inside the closed oxidation loop. In this presentation we discuss initial experimental results for the performance of RAPS in the removal and treatment of several important spacecraft contaminant species from air.

  20. Regenerable Air Purification System for Gas-Phase Contaminant Control

    NASA Technical Reports Server (NTRS)

    Constantinescu, Ileana C.; Qi, Nan; LeVan, M. Douglas; Finn, Cory K.; Finn, John E.; Luna, Bernadette (Technical Monitor)

    2000-01-01

    A regenerable air purification system (RAPS) that uses water vapor to displace adsorbed contaminants from an. adsorbent column into a closed oxidation loop is under development through cooperative R&D between Vanderbilt University and NASA Ames Research Center. A unit based on this design can be used for removing trace gas-phase contaminants from spacecraft cabin air or from polluted process streams including incinerator exhaust. Recent work has focused on fabrication and operation of a RAPS breadboard at NASA Ames, and on measurement of adsorption isotherm data for several important organic compounds at Vanderbilt. These activities support the use and validation of RAPS modeling software also under development at Vanderbilt, which will in turn be used to construct a prototype system later in the project.

  1. The intrinsic (gas-phase) acidities of bridgehead alcohols

    NASA Astrophysics Data System (ADS)

    Herrero, Rebeca; Dávalos, Juan Z.; Abboud, José-Luis M.; Alkorta, I.; Koppel, I.; Koppel, I. A.; Sonoda, T.; Mishima, M.

    2007-11-01

    The gas-phase acidities of 1-adamantanol and perfluoro1-adamantanol were determined by means of Fourier transform ion cyclotron resonance spectrometry (FT-ICR). The acidity of perfluoro1-adamantanol seems to be the highest ever reported for an alcohol. A computational study of these species and their anions at both the MP2/6-311 + G(d,p) and B3LYP/6-311 + G(d,p) levels was performed. Also studied were the tertiary alcohols (including their perfluorinated forms) derived from norbornane, bicyclo[2.2E2]octane and cubane. It was found that: (i) the intrinsic acidity of non-fluorinated bridgehead alcohols increases with the strain of the hydrocarbon framework and, (ii) perfluorination of these compounds strongly increases their acidity and, likely, significantly modifies their internal strain.

  2. Gas-phase synthesis of magnetic metal/polymer nanocomposites.

    PubMed

    Starsich, Fabian H L; Hirt, Ann M; Stark, Wendelin J; Grass, Robert N

    2014-12-19

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

  3. Gas-phase synthesis of magnetic metal/polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Starsich, Fabian H. L.; Hirt, Ann M.; Stark, Wendelin J.; Grass, Robert N.

    2014-12-01

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

  4. Uv Spectroscopy on Gas Phase Cu(I)-BIPYRIDYL Complexes

    NASA Astrophysics Data System (ADS)

    Xu, Shuang; Christopher, Casey; Weber, J. Mathias

    2015-06-01

    Transition metal complexes with bipyridine ligands are of great interest in metal-organic chemistry, since they are prototypes for many applications in photochemistry and homogeneous catalysis. Under-coordinated bipyridyl complexes are elusive species in the condensed phase, and the ligand-induced changes in electronic structure are of fundamental interest. We present UV photodissociation spectra of mass-selected monocationic copper(I)-bipyridyl complexes [bpy-Cu-L]+ with different ligands (L = H2O, D2, N2, MeOH, Cl). Complexes were prepared via electrospray ionization of copper/bipyridine solutions followed by accumulation and buffer gas cooling in a cryogenic Paul trap. In addition, we show spectra of similar species based on copper oxide, [bpy-CuO-L]+.

  5. Dissociative attachment reactions of electrons with gas phase superacids

    SciTech Connect

    Liu, X.

    1992-01-01

    Using the flowing afterglow Langmuir probe (FALP) technique, dissociative attachment coefficients [beta] for reactions of electrons with gas phase superacids HCo(PF[sub 3])[sub 4], HRh(PF[sub 3])[sub 4] and carbonyl hydride complexes HMn(CO)[sub 5], HRe(CO)[sub 5] have been determined under thermal conditions over the approximate temperature range 300[approximately]550 K. The superacids react relatively slowly (<1/20 of [beta][sub max]) with free electrons in a thermal plasma, and the values of [beta] obtained this far do not show a correlation between acidity and [beta]. The pioneer researchers in this field had speculated that any superacid would be a rapid attacher of electrons; it was found that this speculation is not true in general. The product distribution of electron attachment reaction to HCo(PF[sub 3])[sub 4] was found to be independent of temperature even though the [beta][HCo(PF[sub 3])[sub 4

  6. Gas and liquid phase acidity of natural antioxidants.

    PubMed

    Leopoldini, Monica; Russo, Nino; Toscano, Marirosa

    2006-04-19

    The gas phase and in solution absolute and relative acidities of nine natural systems contained in red and white wines were determined through theoretical B3LYP/6-311++G** calculations. The aim was to correlate these thermodynamic quantities to the ability that some of these compounds show in chelating metals ions to carry out an antioxidant action following a mechanism recently reported in the literature. Results indicated that both absolute and relative values are affected by molecular features such as electronic delocalization and conjugation and intramolecular hydrogen bonds. Polyphenols characterized by the ortho-dihydroxy functionality were found to be good candidates to act as metal cation chelating ligands. Some differences in absolute acidities values were encountered in going from vacuum to water solution.

  7. Silicon Nanowire-Based Devices for Gas-Phase Sensing

    PubMed Central

    Cao, Anping; Sudhölter, Ernst J.R.; de Smet, Louis C.P.M.

    2014-01-01

    Since their introduction in 2001, SiNW-based sensor devices have attracted considerable interest as a general platform for ultra-sensitive, electrical detection of biological and chemical species. Most studies focus on detecting, sensing and monitoring analytes in aqueous solution, but the number of studies on sensing gases and vapors using SiNW-based devices is increasing. This review gives an overview of selected research papers related to the application of electrical SiNW-based devices in the gas phase that have been reported over the past 10 years. Special attention is given to surface modification strategies and the sensing principles involved. In addition, future steps and technological challenges in this field are addressed. PMID:24368699

  8. Infrared photodissociation spectroscopy of protonated neurotransmitters in the gas phase

    NASA Astrophysics Data System (ADS)

    MacLeod, N. A.; Simons, J. P.

    2007-03-01

    Protonated neurotransmitters have been produced in the gas phase via a novel photochemical scheme: complexes of the species of interest, 1-phenylethylamine, 2-amino-1-phenylethanol and the diastereo-isomers, ephedrine and pseudoephedrine, with a suitable proton donor, phenol (or indole), are produced in a supersonic expansion and ionized by resonant two photon ionization of the donor. Efficient proton transfer generates the protonated neurotransmitters, complexed to a phenoxy radical. Absorption of infrared radiation, and subsequent evaporation of the phenoxy tag, coupled with time of flight mass spectrometry, provides vibrational spectra of the protonated (and also hydrated) complexes for comparison with the results of quantum chemical computation. Comparison with the conformational structures of the neutral neurotransmitters (established previously) reveals the effect of protonation on their structure. The photochemical proton transfer strategy allows spectra to be recorded from individual laser shots and their quality compares favourably with that obtained using electro-spray or matrix assisted laser desorption ion sources.

  9. Synthesis and Gas Phase Thermochemistry of Germanium-Containing Compounds

    SciTech Connect

    Classen, Nathan Robert

    2002-01-01

    The driving force behind much of the work in this dissertation was to gain further understanding of the unique olefin to carbene isomerization observed in the thermolysis of 1,1-dimethyl-2-methylenesilacyclobutane by finding new examples of it in other silicon and germanium compounds. This lead to the examination of a novel phenylmethylenesilacyclobut-2-ene, which did not undergo olefin to carbene rearrangement. A synthetic route to methylenegermacyclobutanes was developed, but the methylenegermacyclobutane system exhibited kinetic instability, making the study of the system difficult. In any case the germanium system decomposed through a complex mechanism which may not include olefin to carbene isomerization. However, this work lead to the study of the gas phase thermochemistry of a series of dialkylgermylene precursors in order to better understand the mechanism of the thermal decomposition of dialkylgermylenes. The resulting dialkylgermylenes were found to undergo a reversible intramolecular β C-H insertion mechanism.

  10. Ceramic microreactors for heterogeneously catalysed gas-phase reactions.

    PubMed

    Knitter, Regina; Liauw, Marcel A

    2004-08-01

    The high surface to volume ratio of microchannel components offers many advantages in micro chemical engineering. It is obvious, however, that the reactor material and corrosion phenomena play an important role when applying these components. For chemical reactions at very high temperatures or/and with corrosive reactants involved, microchannel components made of metals or polymers are not suited. Hence, a modular microreactor system made of alumina was developed and fabricated using a rapid prototyping process chain. With exchangeable inserts the system can be adapted to the requirements of various reactions. Two heterogeneously catalysed gas-phase reactions (oxidative coupling of methane, isoprene selective oxidation to citraconic anhydride) were investigated to check the suitability of the system at temperatures of up to 1000 degrees C. Apart from the high thermal and chemical resistance, the lack of any blind activity was found to be another advantage of ceramic components.

  11. 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

  12. Gas phase plasma impact on phenolic compounds in pomegranate juice.

    PubMed

    Herceg, Zoran; Kovačević, Danijela Bursać; Kljusurić, Jasenka Gajdoš; Jambrak, Anet Režek; Zorić, Zoran; Dragović-Uzelac, Verica

    2016-01-01

    The aim of the study was to evaluate the effect of gas phase plasma on phenolic compounds in pomegranate juice. The potential of near infrared reflectance spectroscopy combined with partial least squares for monitoring the stability of phenolic compounds during plasma treatment was explored, too. Experiments are designed to investigate the effect of plasma operating conditions (treatment time 3, 5, 7 min; sample volume 3, 4, 5 cm(3); gas flow 0.75, 1, 1.25 dm(3) min(-1)) on phenolic compounds and compared to pasteurized and untreated pomegranate juice. Pasteurization and plasma treatment resulted in total phenolic content increasing by 29.55% and 33.03%, respectively. Principal component analysis and sensitivity analysis outputted the optimal treatment design with plasma that could match the pasteurized sample concerning the phenolic stability (5 min/4 cm(3)/0.75 dm(3) min(-1)). Obtained results demonstrate the potential of near infrared reflectance spectroscopy that can be successfully used to evaluate the quality of pomegranate juice upon plasma treatment considering the phenolic compounds.

  13. Estimation of gas phase mixing in packed beds

    SciTech Connect

    Frigerio, S.; Thunman, H.; Leckner, B.; Hermansson, S.

    2008-04-15

    An improved model is presented for estimation of the mixing of gaseous species in a packed bed for fuel conversion. In particular, this work clarifies the main characteristics of mixing of volatiles and oxidizers in a burning bed of high-volatile solid fuel. Expressions are introduced to represent the active role of degradation of the solid particles in the mixing within the gas phase. During drying and devolatilization the solids modify the behavior of the gas flow: the volatiles released from the surface of the particles increase the turbulence in the system, and hence the rates of the homogeneous reactions under mixing-limited conditions. Numerical experiments are carried out to test the validity of this conclusion regarding mixing in different geometries. The flow of volatiles leaving the fuel particles is shown to contribute significantly to mixing, especially at low air flows through a bed. However, the fraction of the particle surface where volatiles are released and its orientation in the bed should be better determined in order to increase the accuracy of the estimates of turbulent mixing. (author)

  14. Gas phase structures of peroxides: experiments and computational problems.

    PubMed

    Oberhammer, Heinz

    2015-02-02

    Gas-phase structures of several organic and inorganic peroxides X-O-O-X and X-O-O-X', which have been determined experimentally by gas electron diffraction and/or microwave spectroscopy, are discussed. The OO bond length in these peroxides varies from 1.481(8) Å in Me3 SiOOSiMe3 to 1.214(2) Å in FOOF and the dihedral angle ϕ(XO-OX) between 0° in HC(O)O-OH and near 180° in Bu(t) O-OBu(t) . Some of the peroxides cause problems for quantum chemistry, since several computational methods fail to reproduce the experimental structures. Extreme examples are MeO-OMe and FO-OF. In the case of MeO-OMe only about half of the more than 100 computational methods reported in the literature reproduce the experimentally determined double-minimum shape of the torsional potential around the OO bond correctly. For FO-OF only a small number of close to 200 computational methods reproduce the OO and OF bond lengths better than ±0.02 Å.

  15. Gas phase hydrogen permeation in alpha titanium and carbon steels

    NASA Technical Reports Server (NTRS)

    Johnson, D. L.; Shah, K. K.; Reeves, B. H.; Gadgeel, V. L.

    1980-01-01

    Commercially pure titanium and heats of Armco ingot iron and steels containing from 0.008-1.23 w/oC were annealed or normalized and machined into hollow cylinders. Coefficients of diffusion for alpha-Ti and alpha-Fe were determined by the lag-time technique. Steady state permeation experiments yield first power pressure dependence for alpha-Ti and Sievert's law square root dependence for Armco iron and carbon steels. As in the case of diffusion, permeation data confirm that alpha-titanium is subject to at least partial phase boundary reaction control while the steels are purely diffusion controlled. The permeation rate in steels also decreases as the carbon content increases. As a consequence of Sievert's law, the computed hydrogen solubility decreases as the carbon content increases. This decreases in explained in terms of hydrogen trapping at carbide interfaces. Oxidizing and nitriding the surfaces of alpha-titanium membranes result in a decrease in the permeation rate for such treatment on the gas inlet surfaces but resulted in a slight increase in the rate for such treatment on the gas outlet surfaces. This is explained in terms of a discontinuous TiH2 layer.

  16. Phase separation in a polarized Fermi gas with spin-orbit coupling

    SciTech Connect

    Yi, W.; Guo, G.-C.

    2011-09-15

    We study the phase separation of a spin-polarized Fermi gas with spin-orbit coupling near a wide Feshbach resonance. As a result of the competition between spin-orbit coupling and population imbalance, the phase diagram for a uniform gas develops a rich structure of phase separation involving topologically nontrivial gapless superfluid states. We then demonstrate the phase separation induced by an external trapping potential and discuss the optimal parameter region for the experimental observation of the gapless superfluid phases.

  17. Full field gas phase velocity measurements in microgravity

    NASA Technical Reports Server (NTRS)

    Griffin, Devon W.; Yanis, William

    1995-01-01

    Measurement of full-field velocities via Particle Imaging Velocimetry (PIV) is common in research efforts involving fluid motion. While such measurements have been successfully performed in the liquid phase in a microgravity environment, gas-phase measurements have been beset by difficulties with seeding and laser strength. A synthesis of techniques developed at NASA LeRC exhibits promise in overcoming these difficulties. Typical implementation of PIV involves forming the light from a pulsed laser into a sheet that is some fraction of a millimeter thick and 50 or more millimeters wide. When a particle enters this sheet during a pulse, light scattered from the particle is recorded by a detector, which may be a film plane or a CCD array. Assuming that the particle remains within the boundaries of the sheet for the second pulse and can be distinguished from neighboring particles, comparison of the two images produces an average velocity vector for the time between the pulses. If the concentration of particles in the sampling volume is sufficiently large but the particles remain discrete, a full field map may be generated.

  18. Homogeneous nucleation rate measurements and the properties of critical clusters

    SciTech Connect

    Wyslouzil, Barbara E.; Strey, Reinhard; Wölk, Judith; Wilemski, Gerald; Kim, Yoojeong

    2009-10-06

    By combining a range of experimental techniques, quantitative nucleation rate measurements can now be made over {approx} 20 orders of magnitude. These rates can be used to directly test the predictions of nucleation theories or scaling laws. They can also provide direct information regarding the properties of the critical clusters - the first fragments of the new phase that are in unstable equilibrium with the supersaturated mother phase. This paper reviews recent progress in the field of vapor phase nucleation with a special focus on integrating the results from supersonic nozzle and nucleation pulse chamber studies.

  19. The gas-phase ozonolysis of α-humulene.

    PubMed

    Beck, M; Winterhalter, R; Herrmann, F; Moortgat, G K

    2011-06-21

    α-Humulene contains three double bonds (DB), and after ozonolysis of the first DB the first-generation products are still reactive towards O(3) and produce second- and third-generation products. The primary aim of this study consisted of identifying the products of the three generations, focusing on the carboxylic acids, which are known to have a high aerosol formation potential. The experiments were performed in a 570 litre spherical glass reactor at 295 K and 730 Torr. Initial mixing ratios were 260-2090 ppb for O(3) and 250-600 ppb for α-humulene in synthetic air. Reactants and gas-phase products were measured by in situ FTIR spectroscopy. Particulate products were sampled on Teflon filters, extracted with methanol and analyzed by LC-MS/MS-TOF. Using cyclohexane (10-100 ppm) as an OH-radical scavenger and by monitoring the yield of cyclohexanone by PTR-MS, an OH-yield of (10.5 ± 0.7)% was determined for the ozonolysis of the first DB, and (12.9 ± 0.7)% of the first-generation products. The rate constant of the reaction of O(3) with α-humulene is known as k(0) = 1.17 × 10(-14) cm(3) molecule(-1) s(-1) [Y. Shu and R. Atkinson, Int. J. Chem. Kinet., 1994, 26, 1193-1205]. The reaction rate constants of O(3) with the first-generation products and the second-generation products were, respectively, determined as k(1) = (3.6 ± 0.9) × 10(-16) and k(2) = (3.0 ± 0.7) × 10(-17) cm(3) molecule(-1) s(-1) by Facsimile-simulation of the observed ozone decay by FTIR. A total of 37 compounds in the aerosol phase and 5 products in the gas phase were tentatively identified: 25 compounds of the first-generation products contained C13-C15 species, 9 compounds of the second-generation products contained C8-C11 species, whereas 8 compounds of the third-generation products contained C4-C6 species. The products of all three generations consisted of a variety of dicarboxylic-, hydroxy-oxocarboxylic- and oxo-carboxylic acids. The formation mechanisms of some of the products are

  20. Nucleation and stabilization of carbon-rich structures in interstellar media

    SciTech Connect

    Patra, N.; Král, P.; Sadeghpour, H. R. E-mail: pkral@uic.edu

    2014-04-10

    We study the conditions under which carbon clusters of different sizes form and stabilize. We describe the approach to equilibrium by simulating tenuous carbon gas dynamics to long times. First, we use reactive molecular dynamics simulations to describe the nucleation of long chains, large clusters, and complex cage structures in carbon- and hydrogen-rich interstellar gas phases. We study how temperature, particle density, the presence of hydrogen, and carbon inflow affect the nucleation of molecular moieties with different characteristics, in accordance with astrophysical conditions. We extend the simulations to densities that are orders of magnitude lower than current laboratory densities, to temperatures that are relevant to circumstellar environments of planetary nebulae, and microsecond formation times. We correlate cluster size distributions from the simulations with thermodynamic equilibrium at low temperatures and gas densities, where entropy plays a significant role.

  1. Zinc Nucleation and Growth in Microgravity

    NASA Technical Reports Server (NTRS)

    Michael, B. Patrick; Nuth, J. A., III; Lilleleht, L. U.; Vondrak, Richard R. (Technical Monitor)

    2000-01-01

    We report our experiences with zinc nucleation in a microgravity environment aboard NASA's Reduced Gravity Research Facility. Zinc vapor is produced by a heater in a vacuum chamber containing argon gas. Nucleation is induced by cooling and its onset is easily detected visually by the appearance of a cloud of solid, at least partially crystalline zinc particles. Size distribution of these particles is monitored in situ by photon correlation spectroscopy. Samples of particles are also extracted for later analysis by SEM. The initially rapid increase in particle size is followed by a slower period of growth. We apply Scaled Nucleation Theory to our data and find that the derived critical temperature of zinc, the critical cluster size at nucleation, and the surface tension values are all in reasonably good agreement with their accepted literature values.

  2. Experiments on Nucleation in Different Flow Regimes

    NASA Technical Reports Server (NTRS)

    Bayuzick, Robert J.

    1999-01-01

    The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods [1-6]. Dilitometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics [7]. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov [8]. The advantage of these experiments is that the samples are directly observable. The nucleation

  3. Diamond nucleation using polyethene

    SciTech Connect

    Morell, Gerardo; Makarov, Vladimir; Varshney, Deepak; Weiner, Brad

    2013-07-23

    The invention presents a simple, non-destructive and non-abrasive method of diamond nucleation using polyethene. It particularly describes the nucleation of diamond on an electrically viable substrate surface using polyethene via chemical vapor deposition (CVD) technique in a gaseous environment.

  4. Diamond Nucleation Using Polyethene

    NASA Technical Reports Server (NTRS)

    Morell, Gerardo (Inventor); Makarov, Vladimir (Inventor); Varshney, Deepak (Inventor); Weiner, Brad (Inventor)

    2013-01-01

    The invention presents a simple, non-destructive and non-abrasive method of diamond nucleation using polyethene. It particularly describes the nucleation of diamond on an electrically viable substrate surface using polyethene via chemical vapor deposition (CVD) technique in a gaseous environment.

  5. Overview: Experimental studies of crystal nucleation: Metals and colloids

    NASA Astrophysics Data System (ADS)

    Herlach, Dieter M.; Palberg, Thomas; Klassen, Ina; Klein, Stefan; Kobold, Raphael

    2016-12-01

    Crystallization is one of the most important phase transformations of first order. In the case of metals and alloys, the liquid phase is the parent phase of materials production. The conditions of the crystallization process control the as-solidified material in its chemical and physical properties. Nucleation initiates the crystallization of a liquid. It selects the crystallographic phase, stable or meta-stable. Its detailed knowledge is therefore mandatory for the design of materials. We present techniques of containerless processing for nucleation studies of metals and alloys. Experimental results demonstrate the power of these methods not only for crystal nucleation of stable solids but in particular also for investigations of crystal nucleation of metastable solids at extreme undercooling. This concerns the physical nature of heterogeneous versus homogeneous nucleation and nucleation of phases nucleated under non-equilibrium conditions. The results are analyzed within classical nucleation theory that defines the activation energy of homogeneous nucleation in terms of the interfacial energy and the difference of Gibbs free energies of solid and liquid. The interfacial energy acts as barrier for the nucleation process. Its experimental determination is difficult in the case of metals. In the second part of this work we therefore explore the potential of colloidal suspensions as model systems for the crystallization process. The nucleation process of colloids is observed in situ by optical observation and ultra-small angle X-ray diffraction using high intensity synchrotron radiation. It allows an unambiguous discrimination of homogeneous and heterogeneous nucleation as well as the determination of the interfacial free energy of the solid-liquid interface. Our results are used to construct Turnbull plots of colloids, which are discussed in relation to Turnbull plots of metals and support the hypothesis that colloids are useful model systems to investigate crystal

  6. Gas-phase synthesis of semiconductor nanocrystals and its applications

    NASA Astrophysics Data System (ADS)

    Mandal, Rajib

    Luminescent nanomaterials is a newly emerging field that provides challenges not only to fundamental research but also to innovative technology in several areas such as electronics, photonics, nanotechnology, display, lighting, biomedical engineering and environmental control. These nanomaterials come in various forms, shapes and comprises of semiconductors, metals, oxides, and inorganic and organic polymers. Most importantly, these luminescent nanomaterials can have different properties owing to their size as compared to their bulk counterparts. Here we describe the use of plasmas in synthesis, modification, and deposition of semiconductor nanomaterials for luminescence applications. Nanocrystalline silicon is widely known as an efficient and tunable optical emitter and is attracting great interest for applications in several areas. To date, however, luminescent silicon nanocrystals (NCs) have been used exclusively in traditional rigid devices. For the field to advance towards new and versatile applications for nanocrystal-based devices, there is a need to investigate whether these NCs can be used in flexible and stretchable devices. We show how the optical and structural/morphological properties of plasma-synthesized silicon nanocrystals (Si NCs) change when they are deposited on stretchable substrates made of polydimethylsiloxane (PDMS). Synthesis of these NCs was performed in a nonthermal, low-pressure gas phase plasma reactor. To our knowledge, this is the first demonstration of direct deposition of NCs onto stretchable substrates. Additionally, in order to prevent oxidation and enhance the luminescence properties, a silicon nitride shell was grown around Si NCs. We have demonstrated surface nitridation of Si NCs in a single step process using non?thermal plasma in several schemes including a novel dual-plasma synthesis/shell growth process. These coated NCs exhibit SiNx shells with composition depending on process parameters. While measurements including

  7. Gas-Phase Reactions of Halogen Species of Atmospheric Importance.

    NASA Astrophysics Data System (ADS)

    Heard, Anne C.

    Available from UMI in association with The British Library. Requires signed TDF. A low-pressure discharge-flow technique, with various optical detection methods, has been used to determine bimolecular rate coefficients for a number of reactions in the gas-phase between OH radicals and organic halogen -containing molecules and between NO_3 radicals and the iodine species I_2 and I. These experiments have shown that: (i) the reaction of methyl iodide with OH accounts for approximately 2% of the removal of CH_3I from the troposphere as compared with photolysis; (ii) abstraction of I-atoms from a C-I bond by OH is probable in the gas -phase; (iii) the halogen-containing anaesthetic substances halothane CF_3CCl BrH, enflurane CF_2HOCF _2CFClH, isoflurane CF_2HOCClHCF _3 and sevoflurane (CF_3) _2CHOCFH_2 have significantly shorter tropospheric lifetimes than the fully halogenated CFCs and halons because of reaction with the OH radical and are thus unlikely to be transported up to the stratosphere where they could contribute to the depletion of ozone. Data obtained for reactions between OH and some 'CFC alternatives' along with measurements of the integrated absorption cross -sections of the compounds in the spectral region 800-1200 cm^{-1} were used to calculate ozone depletion potentials (ODP) and greenhouse warming potentials relative to CFCl_3 for each compound. The study of the reactions between OH and CF_3CFBrH and CF _2BrH was used to provide a useful first estimate of the environmental acceptability of these compounds in the context of their possible use as replacements for the conventional CFCs. A method was developed to provide a first estimate of the ODP of a halogenated alkane without use of a complicated (and expensive) computer modeling scheme. A reaction between molecular iodine and the nitrate radical in the gas-phase was discovered and the kinetics of this reaction have been studied. No temperature or pressure dependence was observed for the rate of

  8. Nucleation and Crystallization in nucleated Polymers

    NASA Astrophysics Data System (ADS)

    Schick, Christoph; Zhuravlev, Evgeny; Wurm, Andreas

    2012-02-01

    Crystallization is commonly considered as nucleation followed by a growth process. Here we apply the recently developed technique, differential fast scanning calorimetry (DFSC), for a unique, new look at the crystal growth of poly(epsilon-caprolactone) (PCL) and PCL carbon nanotube composites from 185 K, below the glass transition temperature, to 330 K, close to the equilibrium melting temperature. The DFSC allows temperature control of the sample and determination of its heat capacity during temperature treatments by employing cooling and heating rates from 50 to 50,000 K/s. First, the crystal nucleation and overall crystallization half times were determined simultaneously in the range of temperatures where crystallization of PCL occurs. After attempting to analyze the experiments with the classical nucleation and growth model a new methodology is described, which addresses the specific problems of crystallization of flexible linear macromolecules. The structures seem to range from having practically unmeasurable latent heats of ordering (nuclei) to being clearly-recognizable, ordered species with rather sharp disordering endotherms at temperatures from the glass transition to equilibrium melting (increasingly perfect and larger crystals). The mechanisms and kinetics of growth (if any) involve a detailed understanding of the interaction with the surrounding rigid amorphous fraction (RAF) in dependence of crystal size and perfection. E. Zhuravlev, J.W.P. Schmelzer, B. Wunderlich and C. Schick, Kinetics of nucleation and crystallization in poly(epsilon-caprolactone) (PCL), Polymer 52 (2011) 1983-1997.

  9. Measurement of Gas-phase Acids in Diesel Exhaust

    NASA Astrophysics Data System (ADS)

    Wentzell, J. J.; Liggio, J.; Li, S.; Vlasenko, A. L.; Staebler, R. M.; Brook, J.; Lu, G.; Poitras, M.; Chan, T.

    2012-12-01

    Gas-phase acids were measured using chemical ionization mass spectrometry (CIMS) as part of the Diesel Engine Emission Research Experiment (DEERE). The CIMS technique, utilizing acetate ion (CH3COO-) as a reagent ion, proved to be a rapid (measurements on the order of seconds) and sensitive (several counts/pptv) method of quantifying the acid emissions. Diluted diesel exhaust measurements were made from a Constant Volume Sampling dilution tunnel using a light duty (1.9L turbocharged Volkswagen Jetta TDI) diesel engine equipped with an OEM diesel oxidation catalyst and exhaust gas recirculation, mounted on an engine dynamometer. Acids measured included isocyanic, nitrous, nitric, propionic and sum of lactic and oxalic, as well as other unidentified compounds. Complimentary measurements of CO, CO2, Total Hydrocarbon (THC), and NOx, were also performed. Several engine modes (different engine rpm and torque outputs) at steady state were examined to determine their effect on acid emissions. Emission rates with respect to NOx and fuel based emission factors were determined. Measurements of HONO fuel emission factors agree well with real-world measurements within a traffic tunnel.1 The first estimate of isocyanic acid emission factors from a diesel engine is reported, and suggests that the emission of this highly toxic compound in diesel exhaust should not be ignored. 1. Kurtenbach, R., Becker, K. H., Gomes, J. A. G., Kleffmann, J.,Lorzer, J. C., Spittler, M., Wiesen, P., Ackermann, R., Geyer, A.,and Platt, U.: Investigations of emissions and heterogeneous formation of HONO in a road traffic tunnel, Atmos. Environ., 35, 3385-3394, doi:10.1016/S1352-2310(01)00138-8, 2001.

  10. Relating the hygroscopic properties of submicron aerosol to both gas- and particle-phase chemical composition in a boreal forest environment

    NASA Astrophysics Data System (ADS)

    Hong, J.; Kim, J.; Nieminen, T.; Duplissy, J.; Ehn, M.; Äijälä, M.; Hao, L. Q.; Nie, W.; Sarnela, N.; Prisle, N. L.; Kulmala, M.; Virtanen, A.; Petäjä, T.; Kerminen, V.-M.

    2015-10-01

    Measurements of the hygroscopicity of 15-145 nm particles in a boreal forest environment were conducted using two Hygroscopicity Tandem Differential Mobility Analyzer (HTDMA) systems during the Pan-European Gas-Aerosols-climate interaction Study (PEGASOS) campaign in spring 2013. Measurements of the chemical composition of non-size segregated particles were also performed using a high-resolution aerosol mass spectrometer (HR-AMS) in parallel with hygroscopicity measurements. On average, the hygroscopic growth factor (HGF) of particles was observed to increase from the morning until afternoon. In case of accumulation mode particles, the main reasons for this behavior were increases in the ratio of sulfate to organic matter and oxidation level (O : C ratio) of the organic matter in the particle phase. Using an O : C dependent hygroscopic growth factor of organic matter (HGForg), fitted using the inverse Zdanovskii-Stokes-Robinson (ZSR) mixing rule, clearly improved the agreement between measured HGF and that predicted based on HR-AMS composition data. Besides organic oxidation level, the influence of inorganic species was tested when using the ZSR mixing rule to estimate the hygroscopic growth factor of organics in the aerosols. While accumulation and Aitken mode particles were predicted fairly well by the bulk aerosol composition data, the hygroscopicity of nucleation mode particles showed little correlation. However, we observed them to be more sensitive to the gas phase concentration of condensable vapors: the more sulfuric acid in the gas phase, the more hygroscopic the nucleation mode particles were. No clear dependence was found between the extremely low-volatility organics concentration (ELVOC) and the HGF of particles of any size.

  11. Relating the hygroscopic properties of submicron aerosol to both gas- and particle-phase chemical composition in a boreal forest environment

    NASA Astrophysics Data System (ADS)

    Hong, J.; Kim, J.; Nieminen, T.; Duplissy, J.; Ehn, M.; Äijälä, M.; Hao, L.; Nie, W.; Sarnela, N.; Prisle, N. L.; Kulmala, M.; Virtanen, A.; Petäjä, T.; Kerminen, V.-M.

    2015-06-01

    Measurements of the hygroscopicity of 15-145 nm particles in a boreal forest environment were conducted using two Hygroscopicity Tandem Differential Mobility Analyzer (HTDMA) systems during the Pan-European Gas-AeroSOIs-climate interaction Study (PEGASOS) campaign in spring 2013. Measurements of the chemical composition of non-size segregated particles were also performed using a High-Resolution Aerosol Mass Spectrometer (HR-AMS) in parallel with hygroscopicity measurements. On average, the hygroscopic growth factor (HGF) of particles was observed to increase from the morning until afternoon. In case of accumulation mode particles, the main reasons for this behavior were increases in the ratio of sulfate to organic matter and oxidation level (O : C ratio) of the organic matter in the particle phase. Using an O : C dependent hygroscopic growth factor of organic matter (HGForg), fitted using the inverse Zdanovskii-Stokes-Robinson (ZSR) mixing rule, clearly improved the agreement between measured HGF and that predicted based on HR-AMS composition data. Besides organic oxidation level, the influence of inorganic species was tested when using the ZSR mixing rule to estimate the hygroscopic growth factor of organics in the aerosols. While accumulation and Aitken mode particles were predicted fairly well by the bulk aerosol composition data, the hygroscopicity of nucleation mode particles showed little correlation. However, we observed them to be more sensitive to the gas phase concentration of condensable vapors: the more there was sulfuric acid in the gas phase, the more hygroscopic the nucleation mode particles were. No clear dependence was found between the extremely low-volatility organics (ELVOCs) concentration and the HGF of particles of any size.

  12. Ozone Cross-Section Measurement by Gas Phase Titration.

    PubMed

    Viallon, Joële; Moussay, Philippe; Flores, Edgar; Wielgosz, Robert I

    2016-11-01

    Elevated values of ground-level ozone damage health, vegetation, and building materials and are the subject of air quality regulations. Levels are monitored by networks using mostly ultraviolet (UV) absorption instruments, with traceability to standard reference photometers, relying on the UV absorption of ozone at the 253.65 nm line of mercury. We have redetermined the ozone cross-section at this wavelength based on gas phase titration (GPT) measurements. This is a well-known chemical method using the reaction of ozone (O3) with nitrogen monoxide (NO) resulting in nitrogen dioxide (NO2) and oxygen (O2). The BIPM GPT facility uses state-of-the-art flow measurement, chemiluminescence for NO concentration measurements, a cavity phase shift analyzer (CAPS) for NO2 measurements, and a UV ozone analyzer. The titration experiment is performed over the concentration range 100-500 nmol/mol, with NO and NO2 reactants/calibrants diluted down from standards with nominal mole fractions of 50 μmol/mol. Accurate measurements of NO, NO2, and O3 mole fractions allow the calculation of ozone absorption cross section values at 253.65 nm, and we report a value of 11.24 × 10(-18) cm(2) molecule(-1) with a relative expanded uncertainty of 1.8% (coverage factor k = 2) based on nitrogen monoxide titration values and a value of 11.22 × 10(-18) cm(2) molecule(-1) with a relative expanded uncertainty of 1.4% (coverage factor k = 2) based on nitrogen dioxide titration values. The excellent agreement between these values and recently published absorption cross-section measurements directly on pure ozone provide strong evidence for revising the conventionally accepted value of ozone cross section at 253.65 nm.

  13. Uridine Nucleoside Thiation: Gas-Phase Structures and Energetics

    NASA Astrophysics Data System (ADS)

    Hamlow, Lucas; Lee, Justin; Rodgers, M. T.; Berden, Giel; Oomens, Jos

    2016-06-01

    The naturally occurring thiated uridine nucleosides, 4-thiouridine (s4Urd) and 2-thiouridine (s2Urd), play important roles in the function and analysis of a variety of RNAs. 2-Thiouridine and its C5 modified analogues are commonly found in tRNAs and are believed to play an important role in codon recognition possibly due to their different structure, which has been shown by NMR to be predominantly C3'-endo. 2-Thiouridine may also play an important role in facilitating nonenzymatic RNA replication and transcription. 4-Thiouridine is a commonly used photoactivatable crosslinker that is often used to study RNA-RNA and RNA-protein cross-linking behavior. Differences in the base pairing between uracil and 4-thiouracil with adenine and guanine are an important factor in their role as a cross linker. The photoactivity of s4Urd may also aid in preventing near-UV lethality in cells. An understanding of their intrinsic structure in the gas-phase may help further elucidate the roles these modified nucleosides play in the regulation of RNAs. In this work, infrared multiple photon dissociation (IRMPD) action spectra of the protonated forms of s2Urd and s4Urd were collected in the IR fingerprint region. Structural information is determined by comparison with theoretical linear IR spectra generated from density functional theory calculations using molecular modeling to generate low-energy candidate structures. Present results are compared with analogous results for the protonated forms of uridine and 2'-deoxyuridine as well as solution phase NMR data and crystal structures.

  14. Concurrence of aqueous and gas phase contamination of groundwater in the Wattenberg oil and gas field of northern Colorado.

    PubMed

    Li, Huishu; Son, Ji-Hee; Carlson, Kenneth H

    2016-01-01

    The potential impact of rapid development of unconventional oil and natural gas resources using hydraulic fracturing and horizontal drilling on regional groundwater quality has received significant attention. Major concerns are methane or oil/gas related hydrocarbon (such as TPHs, BTEX including benzene, toluene, ethybenzene and xylene) leaks into the aquifer due to the failure of casing and/or stray gas migration. Previously, we investigated the relationship between oil and gas activity and dissolved methane concentration in a drinking water aquifer with the major finding being the presence of thermogenic methane contamination, but did not find detectable concentrations of TPHs or BTEX. To understand if aqueous and gas phases from the producing formation were transported concurrently to drinking water aquifers without the presence of oil/gas related hydrocarbons, the ionic composition of three water groups was studied: (1) uncontaminated deep confined aquifer, (2) suspected contaminated groundwater - deep confined aquifer containing thermogenic methane, and (3) produced water from nearby oil and gas wells that would represent aqueous phase contaminants. On the basis of quantitative and spatial analysis, we identified that the "thermogenic methane contaminated" groundwater did not have similarities to produced water in terms of ionic character (e.g. Cl/TDS ratio), but rather to the "uncontaminated" groundwater. The analysis indicates that aquifer wells with demonstrated gas phase contamination have not been contacted by an aqueous phase from oil and gas operations according to the methodology we use in this study and the current groundwater quality data from COGCC. However, the research does not prove conclusively that this the case. The results may provide insight on contamination mechanisms since improperly sealed well casing may result in stray gas but not aqueous phase transport.

  15. Surface-Specific Nucleation and Deposition (?) of Heavy and Precious Metals on Minerals and Fibers Exposed to Fumarole Gas - FESEM/EDS Studies

    NASA Astrophysics Data System (ADS)

    Obenholzner, J. H.; Poelt, P.; Reichmann, A.

    2004-12-01

    Mineral grains, glass fibers and diatoms had been exposed to the F0 fumarole at Vulcano (Italy) between 2001 and 2004. On quartz grains patches of Pb-(Tl)-Cl (max.l=50 µm), Tl-(Fe)-(Br)-Cl, Al-S-Cl-(O), Al-Cl-(F)-(S)-(Mg)-(K)-(Ca)-(Fe) and needle-like Ca sulphate (+Cl-F) are growing. Pb-S nucleated on K feldspar, Ba-S-O and As-S on the surface of diatoms. Desert dust interacting with volcanic gases might transport heavy metals to environments far away from volcanoes. Si-rich glass fibers are the substratum for Tl-Cl, Hg-, As-, Tl- and Pb-bearing and Al-(S)-(O) crystals. Au-Ag alloys (l= ca. 3 µm) are detected on Si-rich fibers. These anhedral grains are embedded in an Al-O-(S)-(Ca) matrix. Available data do not indicate if deposition or nucleation are the responsible processes. Ba-S-O particles nucleated on borosilicate glass fibers. Rock wool of basaltic composition (Na-Mg-Al-Si-K-Ca-Ti-Fe-O) collected only S and shows surface modification. These preliminary results indicate that Si-rich surfaces might be useful in i.e. air conditioning systems to detoxicate volcanically polluted air. Quartz sand deployed on top of lava flows might reduce the release of heavy metals to the environment. According to the experiments utilizing glass fibers of different composition the eruptions of basaltic magma should release more heavy metals to the atmosphere relatively compared to the eruptions of rhyolitic magma.

  16. Nucleation Pathways of CO2 Condensation under Mesoporous Templated Glass

    NASA Astrophysics Data System (ADS)

    Wang, Bo; Byran, Matthew S.; Warren, Garfield T.; Sokol, Paul E.; Indiana University Team; NIST Collaboration

    2015-03-01

    Carbon capture and storage (CCS) are important elements in reducing greenhouse gas emission and combating global warming. The adsorption behavior of CO2 under mesoporous confinement at room temperature is particularly relevant. , Small Angle Scattering of X-ray (SAXS) and Neutron (SANS) were used to probe the adsorption process of CO2 under such mesoporous confinement MCM-41 and details of nucleation pathways were mapped out by fitting the scattering intensities with adsorption models. From both experiments, the nucleation of CO2 on the inner pore surface of MCM-41 is found to be a two-step process; high density liquid phase CO2 first forms uniform layers following the long range translational symmetry of the porous matrix, above one CO2 filling, determined by the pore size and temperature, capillary condensation initiates. The nucleation sites formed during capillary condensation start to separate the long range symmetry from the one at uniform layers. Finally, SAXS and SANS techniques are compared and they both showed their unique properties of probing the filling-dependent structures of adsorbed CO2 under such mesoporous system.

  17. Experimental Determination of Gas Phase Thermodynamic Properties of Bimolecular Complexes

    NASA Astrophysics Data System (ADS)

    Hansen, Anne S.; Maroun, Zeina; Mackeprang, Kasper; Kjaergaard, Henrik G.

    2016-06-01

    Accurate determination of the atmospheric abundance of hydrogen bound bimolecular complexes is necessary, as hydrogen bonds are partly responsible for the formation and growth of aerosol particles. The abundance of a complex is related to the Gibbs free energy of complex formation (Δ G), which is often obtained from quantum chemical calculations that rely on calculated values of the enthalpy (Δ H) and entropy (Δ S) of complex formation. However, calculations of Δ H and in particular Δ S are associated with large uncertainties, and accurate experimental values are therefore crucial for theoretical benchmarking studies. Infrared measurements of gas phase hydrogen bound complexes were performed in the 300 to 373 K range, and lead to a purely experimental determination of Δ H using the van't Hoff equation. Equilibrium constants were determined by combining an experimental and calculated OH-stretching intensity, from which values of Δ G and hence Δ S could be determined. Thus we can determine Δ G, Δ H and Δ S for a bimolecular complex. We find that in the 300 to 373 K temperature range the determined Δ H and Δ S values are independent of temperature.

  18. Gas phase production and loss of isoprene epoxydiols.

    PubMed

    Bates, Kelvin H; Crounse, John D; St Clair, Jason M; Bennett, Nathan B; Nguyen, Tran B; Seinfeld, John H; Stoltz, Brian M; Wennberg, Paul O

    2014-02-20

    Isoprene epoxydiols (IEPOX) form in high yields from the OH-initiated oxidation of isoprene under low-NO conditions. These compounds contribute significantly to secondary organic aerosol formation. Their gas-phase chemistry has, however, remained largely unexplored. In this study, we characterize the formation of IEPOX isomers from the oxidation of isoprene by OH. We find that cis-β- and trans-β-IEPOX are the dominant isomers produced, and that they are created in an approximate ratio of 1:2 from the low-NO oxidation of isoprene. Three isomers of IEPOX, including cis-β- and trans-β, were synthesized and oxidized by OH in environmental chambers under high- and low-NO conditions. We find that IEPOX reacts with OH at 299 K with rate coefficients of (0.84 ± 0.07) × 10(-11), (1.52 ± 0.07) × 10(-11), and (0.98 ± 0.05) × 10(-11) cm(3) molecule(-1) s(-1) for the δ1, cis-β, and trans-β isomers. Finally, yields of the first-generation products of IEPOX + OH oxidation were measured, and a new mechanism of IEPOX oxidation is proposed here to account for the observed products. The substantial yield of glyoxal and methylglyoxal from IEPOX oxidation may help explain elevated levels of those compounds observed in low-NO environments with high isoprene emissions.

  19. Gas-phase Electronic Spectra of Coronene and Corannulene Cations

    NASA Astrophysics Data System (ADS)

    Hardy, F.-X.; Rice, Corey A.; Maier, John P.

    2017-02-01

    Gas-phase electronic spectra of the coronene ({{{C}}}24{{{{H}}}12}+) and corannulene ({{{C}}}20{{{{H}}}10}+) cations complexed with helium have been recorded in a quadrupole ion trap at 5 K by photodissociation. The electronic spectrum of {{{C}}}20{{{{H}}}10}+ with two helium atoms was also measured to estimate the perturbation. This method is sufficient for an astronomical comparison because the shift due to the weakly bound helium is on the order of 0.2 Å. {{{C}}}24{{{{H}}}12}+{--}{He} has the origin band of the {{{A}}}2{{{E}}}1g≤ftarrow X{}2{{{E}}}2u transition at 9438.3 Å and that to a much higher state {{{D}}}3≤ftarrow X{}2{{{E}}}2u at 4570 Å. The corannulene cation is subject to a Jahn–Teller distortion in the electronic ground state, leading to the {3}2{{A}}\\prime ≤ftarrow {{X}}{}2{{A}}\\prime \\prime and {3}2{{A}}\\prime \\prime ≤ftarrow {{X}}{}2{{A}}\\prime transitions with origin band maxima when complexed with helium at 5996.1 and 5882.6 Å. These absorptions lie in a region where there is a congestion of diffuse interstellar bands (DIBs). However, the recorded features have no match with astronomical observations, removing coronene and corannulene cations and probably other aromatic hydrocarbons of this size as possible carriers of the DIBs.

  20. Microwave spectrum and the gas phase structure of phthalimide

    NASA Astrophysics Data System (ADS)

    Pejlovas, Aaron M.; Lin, Wei; Oncer, Onur; Kukolich, Stephen G.

    2015-11-01

    The microwave spectrum of phthalimide (PhI) was measured in the 4.8-9.5 GHz range using a Flygare-Balle type, pulsed-beam Fourier transform microwave spectrometer. Rotational transitions were measured for the parent and all unique single 13C substituted isotopologues. The rotational (MHz), centrifugal distortion (kHz), and quadrupole coupling constants (MHz) were determined for the parent to be A = 1745.6655(10), B = 1199.3309(6), C = 711.0864(3), DJ = 0.012(7), DJK = -0.05(9), 1.5χaa = 2.719(11), and 0.25(χbb - χcc) = 1.236(3). Using the measured rotational constants of the isotopologues, a nonlinear least squares fit was performed to obtain the best fit gas phase structure. The inertial defect is Δ = -0.175 amu Å2, indicating a planar structure for PhI. Calculations using B3LYP/aug-cc-pVQZ provided rotational constants which are much closer to the experimental values compared to the MP2/6-311++G∗∗ calculated values.

  1. Microwave spectrum and gas phase structure of maleimide

    NASA Astrophysics Data System (ADS)

    Pejlovas, Aaron M.; Oncer, Onur; Kang, Lu; Kukolich, Stephen G.

    2016-01-01

    The rotational spectrum of maleimide was measured in the 5-12 GHz range using a Flygare-Balle type, pulsed-beam Fourier transform microwave spectrometer. Rotational transitions were measured for the parent, all unique singly substituted 13C isotopologues, and an sbnd ND, deuterium substituted isotopologue. The parent (or normal isotopologue) rotational constants, centrifugal distortion constants, and quadrupole coupling constants are A = 6815.3251(12) MHz, B = 2361.85011(64) MHz, C = 1754.32750(64) MHz, DJ = 0.232(24) kHz, DJK = 0.546(54) kHz, 1.5χaa = 2.4227(53) MHz, and 0.25(χbb-χcc) = 1.3679(15) MHz. A best fit gas phase structure was determined using the experimental rotational constants of the isotopologues and some parameters from calculations. The inertial defect is Δ = -0.054 amu Å2, indicating a planar structure for maleimide, with no large amplitude motions observed on the sbnd NH hydrogen atom. Calculations using B3LYP/aug-cc-pVTZ provided rotational constants which are much closer (within 1-2%) to the experimental values compared to the MP2/aug-cc-pVTZ calculated values.

  2. Surface plasmon sensing of gas phase contaminants using optical fiber.

    SciTech Connect

    Thornberg, Steven Michael; White, Michael I.; Rumpf, Arthur Norman; Pfeifer, Kent Bryant

    2009-10-01

    Fiber-optic gas phase surface plasmon resonance (SPR) detection of several contaminant gases of interest to state-of-health monitoring in high-consequence sealed systems has been demonstrated. These contaminant gases include H{sub 2}, H{sub 2}S, and moisture using a single-ended optical fiber mode. Data demonstrate that results can be obtained and sensitivity is adequate in a dosimetric mode that allows periodic monitoring of system atmospheres. Modeling studies were performed to direct the design of the sensor probe for optimized dimensions and to allow simultaneous monitoring of several constituents with a single sensor fiber. Testing of the system demonstrates the ability to detect 70mTorr partial pressures of H{sub 2} using this technique and <280 {micro}Torr partial pressures of H{sub 2}S. In addition, a multiple sensor fiber has been demonstrated that allows a single fiber to measure H{sub 2}, H{sub 2}S, and H{sub 2}O without changing the fiber or the analytical system.

  3. Nucleation in food colloids

    NASA Astrophysics Data System (ADS)

    Povey, Malcolm J. W.

    2016-12-01

    Nucleation in food colloids has been studied in detail using ultrasound spectroscopy. Our data show that classical nucleation theory (CNT) remains a sound basis from which to understand nucleation in food colloids and analogous model systems using n-alkanes. Various interpretations and modifications of CNT are discussed with regard to their relevance to food colloids. Much of the evidence presented is based on the ultrasound velocity spectrometry measurements which has many advantages for the study of nucleating systems compared to light scattering and NMR due to its sensitivity at low solid contents and its ability to measure true solid contents in the nucleation and early crystal growth stages. Ultrasound attenuation spectroscopy also responds to critical fluctuations in the induction region. We show, however, that a periodic pressure fluctuation such as a quasi-continuous (as opposed to a pulse comprising only a few pressure cycles) ultrasound field can alter the nucleation process, even at very low acoustic intensity. Thus care must be taken when using ultrasound techniques that the measurements do not alter the studied processes. Quasi-continuous ultrasound fields may enhance or suppress nucleation and the criteria to determine such effects are derived. The conclusions of this paper are relevant to colloidal systems in foods, pharmaceuticals, agro-chemicals, cosmetics, and personal products.

  4. Musculoskeletal-induced Nucleation in Altitude Decompression Sickness

    NASA Technical Reports Server (NTRS)

    Pollock, N. W.; Natoli, M. J.; Conkin, J.; Wessel, J. H., III; Gernhardt, M. L.

    2014-01-01

    Musculoskeletal activity has the potential to both improve and compromise decompression safety. Exercise enhances inert gas elimination during oxygen breathing prior to decompression (prebreathe), but it may also promote bubble nuclei formation (nucleation), which can lead to gas phase separation and bubble growth and increase the risk of decompression sickness (DCS). The timing, pattern and intensity of musculoskeletal activity and the level of tissue supersaturation may be critical to the net effect. There are limited data available to evaluate cost-benefit relationships. Understanding the relationship is important to improve our understanding of the underlying mechanisms of nucleation in exercise prebreathe protocols and to quantify risk in gravity and microgravity environments. Data gathered during NASA's Prebreathe Reduction Program (PRP) studies combined oxygen prebreathe and exercise followed by low pressure (4.3 psi; altitude equivalent of 30,300 ft [9,235 m]) microgravity simulation to produce two protocols used by astronauts preparing for extravehicular activity. Both the Phase II/CEVIS (cycle ergometer vibration isolation system) and ISLE (in-suit light exercise) trials eliminated ambulation to more closely simulate the microgravity environment. The CEVIS results (35 male, 10 female) serve as control data for this NASA/Duke study to investigate the influence of ambulation exercise on bubble formation and the subsequent risk of DCS.

  5. GAS PHASE SELECTIVE PHOTOXIDATION OF ALCOHOLS USING LIGHT-ACTIVATED TITANIUM DIOXIDE AND MOLECULAR OXYGEN

    EPA Science Inventory

    Gas Phase Selective Oxidation of Alcohols Using Light-Activated Titanium Dioxide and Molecular Oxygen

    Gas phase selective oxidations of various primary and secondary alcohols are studied in an indigenously built stainless steel up-flow photochemical reactor using ultravi...

  6. DEMONSTRATION OF FUEL CELLS TO RECOVER ENERGY FROM LANDFILL GAS: PHASE II. PRETREATMENT SYSTEM PERFORMANCE MEASUREMENT

    EPA Science Inventory

    The report describes Phase II of a demonstration of the utilization of commercial phosphoric acid fuel cells to recover energy from landfill gas. This phase consisted primarily of the construction and testing of a Gas Pretreatment Unit (GPU) whose function is to remove those impu...

  7. Kinetic Monte Carlo simulations of electrodeposition: Crossover from continuous to instantaneous homogeneous nucleation within Avrami’s law

    NASA Astrophysics Data System (ADS)

    Frank, Stefan; Rikvold, Per Arne

    2006-06-01

    The influence of lateral adsorbate diffusion on the dynamics of the first-order phase transition in a two-dimensional Ising lattice gas with attractive nearest-neighbor interactions is investigated by means of kinetic Monte Carlo simulations. For example, electrochemical underpotential deposition proceeds by this mechanism. One major difference from adsorption in vacuum surface science is that under control of the electrode potential and in the absence of mass-transport limitations, local adsorption equilibrium is approximately established. We analyze our results using the theory of Kolmogorov, Johnson and Mehl, and Avrami (KJMA), which we extend to an exponentially decaying nucleation rate. Such a decay may occur due to a suppression of nucleation around existing clusters in the presence of lateral adsorbate diffusion. Correlation functions prove the existence of such exclusion zones. By comparison with microscopic results for the nucleation rate I and the interface velocity of the growing clusters v, we can show that the KJMA theory yields the correct order of magnitude for Iv2. This is true even though the spatial correlations mediated by diffusion are neglected. The decaying nucleation rate causes a gradual crossover from continuous to instantaneous nucleation, which is complete when the decay of the nucleation rate is very fast on the time scale of the phase transformation. Hence, instantaneous nucleation can be homogeneous, producing negative minima in the two-point correlation functions. We also present in this paper an n-fold way Monte Carlo algorithm for a square lattice gas with adsorption/desorption and lateral diffusion.

  8. Study on measures to improve gas-liquid phase mixing in a multiphase pump impeller under high gas void fraction

    NASA Astrophysics Data System (ADS)

    Zhang, J. Y.; Zhu, H. W.; Ding, K.; Qiang, R.

    2012-11-01

    Rotodynamic multiphase pump can transport crude gas-liquid mixture produced from oil well, and is regarded as the good choice of oil-gas multiphase transportation in offshore product system, for its advantages that compact structure, large flow rate, not sensitive to solid particles in the fluid. However, it is prone to bring about gas-liquid separation within the impeller under high gas void fraction. To solve the problem, this paper presents several measures to break gas packet and inhibit gas-liquid separation, such as, depositing the short blades, opening holes at the blades where gas packets gather, using T-shaped blades, etc. Then, CFD software was used to simulate the flow fields which were added measures to inhibit gas-liquid separation. The results show that streamlines in three new impellers distribute more evenly than in original impeller, the gas-liquid two phases mixed degree was improved, and the gas-liquid separation was inhibited to some extent. However, adding the short blades and using T-blade impeller failed to improve the differential pressure of impellers. So the placement and the geometrical parameters of the measures inhibiting gas-liquid separation should be further optimized.

  9. Triplet-state energies and substituent effects of excited aroyl compounds in the gas phase.

    PubMed

    Lin, Z P; Aue, W A

    2000-01-01

    Triplet-state energy values obtained from the gas phase are still scarce. In this study, the triplet-state energies of 58 aroyl compounds, introduced as gas chromatographic peaks at atmospheric pressure and typically 473 K, have been determined from the 0-0 bands of their n --> pi* type phosphorescence spectra in excited nitrogen. Correlations of those gas-phase triplet-state energies with Hammett constants could be observed for substituted acetophenones, benzaldehydes and benzophenones.

  10. Experiments on Nucleation in Different Flow Regimes

    NASA Technical Reports Server (NTRS)

    Bayuzick, R. J.; Hofmeister, W. H.; Morton, C. M.; Robinson, M. B.

    1998-01-01

    The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods. Dilitometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov. The advantage of these experiments is that the samples are directly observable. The nucleation temperature

  11. A nanoscale temperature-dependent heterogeneous nucleation theory

    SciTech Connect

    Cao, Y. Y.; Yang, G. W.

    2015-06-14

    Classical nucleation theory relies on the hypothetical equilibrium of the whole nucleation system, and neglects the thermal fluctuations of the surface; this is because the high entropic gains of the (thermodynamically extensive) surface would lead to multiple stable states. In fact, at the nanometer scale, the entropic gains of the surface are high enough to destroy the stability of the thermal equilibrium during nucleation, comparing with the whole system. We developed a temperature-dependent nucleation theory to elucidate the heterogeneous nucleation process, by considering the thermal fluctuations based on classical nucleation theory. It was found that the temperature not only affected the phase transformation, but also influenced the surface energy of the nuclei. With changes in the Gibbs free energy barrier, nucleation behaviors, such as the nucleation rate and the critical radius of the nuclei, showed temperature-dependent characteristics that were different from those predicted by classical nucleation theory. The temperature-dependent surface energy density of a nucleus was deduced based on our theoretical model. The agreement between the theoretical and experimental results suggested that the developed nucleation theory has the potential to contribute to the understanding and design of heterogeneous nucleation at the nanoscale.

  12. AEROSOL NUCLEATION AND GROWTH DURING LAMINAR TUBE FLOW: MAXIMUM SATURATIONS AND NUCLEATION RATES. (R827354C008)

    EPA Science Inventory

    An approximate method of estimating the maximum saturation, the nucleation rate, and the total number nucleated per second during the laminar flow of a hot vapour–gas mixture along a tube with cold walls is described. The basis of the approach is that the temperature an...

  13. Harvesting hydrogen gas from air pollutants with an un-biased gas phase photo-electrochemical cell.

    PubMed

    Verbruggen, Sammy W; Van Hal, Myrthe; Bosserez, Tom; Rongé, Jan; Hauchecorne, Birger; Martens, Johan A; Lenaerts, Silvia

    2017-02-08

    The concept of an all-gas-phase photo-electrochemical cell (PEC) producing hydrogen gas from volatile organic contaminated gas and light is presented. Without applying any external bias, organic contaminants are degraded and hydrogen gas is produced in separate electrode compartments. The system works most efficiently with organic pollutants in inert carrier gas. In the presence of oxygen gas, the cell performs less efficiently but still significant photocurrents are generated, showing the cell can be run on organic contaminated air. The purpose of this study is to demonstrate new application opportunities of PEC technology and to encourage further advancement toward photo-electrochemical remediation of air pollution with the attractive feature of simultaneous energy recovery and pollution abatement.

  14. Electron attachment to ? and ? in the gas phase

    NASA Astrophysics Data System (ADS)

    Smith, David; Spanel, Patrik

    1996-11-01

    The fullerene molecule 0953-4075/29/21/030/img3 is known to attach several electrons in the solid phase, but only recently has it been recognized that it can also attach electrons in the gas phase. The first electron - molecular beam results showed that 0953-4075/29/21/030/img3 and 0953-4075/29/21/030/img5 molecules non-dissociatively attached a single electron over the unusually wide electron energy range from near thermal to about 10 eV, but these studies were not able to provide either the magnitude of the cross sections or describe the low-energy attachment behaviour. But using our flowing afterglow - Langmuir probe (FALP) apparatus we have been able to determine the absolute attachment rate coefficients for both 0953-4075/29/21/030/img3 and 0953-4075/29/21/030/img5 over the electron temperature range 300 - 4500 K. These FALP experiments have shown that attachment to 0953-4075/29/21/030/img3 at low electron energies (<1 eV) proceeds predominantly by p-wave electron capture, and that a centrifugal barrier of 0.26 eV is evident which was corroborated by subsequent theory. A similar situation is observed for attachment to 0953-4075/29/21/030/img5 except that for this fullerene molecule there is evidence that at very low electron energies (< 0.05 eV) inefficient s-wave capture may also occur. These FALP data further indicate that at energies above about 0.3 eV extraordinarily efficient electron attachment occurs to both 0953-4075/29/21/030/img3 and 0953-4075/29/21/030/img5, and when the mean thermal cross sections derived from these FALP data are used to normalize the crossed electron - molecular beam data at the common low energies accessible in both experiments, it is clear that electron attachment to these fullerene molecules is very efficient over a wide electron energy range from about 0.3 - 10 eV above which electron thermionic emission occurs from the hot 0953-4075/29/21/030/img12 and 0953-4075/29/21/030/img13 nascent negative ions.

  15. Detection of Gas-Phase Ammonia Using Photothermal Interferometry.

    NASA Astrophysics Data System (ADS)

    Owens, Melody Avery

    1995-01-01

    Ammonia in the atmosphere plays an important chemical role in diverse ecological and physical systems. It is challenging to measure because it adheres to many commonly used sampling materials, is soluble in water, and forms particles. A new instrument has been built to detect gas -phase ammonia in ambient air by photothermal interferometry. Ammonia molecules in sampled air are excited to upper vibrational rotational states of the nu_2 band of ammonia by absorption of 9.22 mu m light from the 9R30 line of a carbon dioxide laser. Excited ammonia molecules transfer this energy as heat to the air by collisions. The temperature and consequent refractive index change is measured as a phase shift in one arm of a sensitive homodyne interferometer. The CO_2 laser output is modulated at 1.2 kHz, and the AC signal from the interferometer is measured with a lock -in amplifier. The +/-2sigma detection limit of the interferometer at this frequency is 1.2 times 10^{ -7} radians, only a factor of four above the quantum noise limit. The ammonia detector is calibrated by dynamic dilution of two permeation tube outputs and by standard addition. Permeation rates are verified by NH _3 conversion to nitric oxide on hot platinum foil followed by chemiluminescent NO detection, and are monitored by mass loss history. The sample cell, inlet and calibration plumbing is glass to minimize NH _3 sample loss by wall adsorption. Sample flow is 2 l/min, with residence time less than one second. The detector is zeroed by sampling through tubing filled with H_3PO_4-coated Teflon. A Stark signal shift of 7.9 mV was measured for 507 ppb of NH_3 with 925 V/mm of applied field density as an alternative zeroing method. The linear dynamic range of the detector is broad, (greater than 5 orders of magnitude), and the detector is sensitive, with a 31 ppt 4sigma lower detection limit measured in 100 s. Signal gain is insensitive to water vapor and CO_2. The instrument response is fast, with a 1 s e

  16. Gas-phase spin relaxation of Xe129

    NASA Astrophysics Data System (ADS)

    Anger, B. C.; Schrank, G.; Schoeck, A.; Butler, K. A.; Solum, M. S.; Pugmire, R. J.; Saam, B.

    2008-10-01

    We have completed an extensive study of Xe129 longitudinal spin relaxation in the gas phase, involving both intrinsic and extrinsic mechanisms. The dominant intrinsic relaxation is mediated by the formation of persistent Xe2 van der Waals dimers. The dependence of this relaxation on applied magnetic field yields the relative contributions of the spin-rotation and chemical-shift-anisotropy interactions; the former dominates at magnetic fields below a few tesla. This relaxation also shows an inverse quadratic dependence on temperature T ; the maximum low-field intrinsic relaxation for pure xenon at room temperature (measured here to be 4.6h , in agreement with previous work) increases by ≈60% for T=100°C . The dominant extrinsic relaxation is mediated by collisions with the walls of the glass container. Wall relaxation was studied in silicone-coated alkali-metal-free cells, which showed long (many hours or more) and robust relaxation times, even at the low magnetic fields typical for spin-exchange optical pumping (≈3mT) . The further suppression of wall relaxation for magnetic fields above a few tesla is consistent with the interaction of Xe129 with paramagnetic spins on or inside the surface coating. At 14.1T and sufficiently low xenon density, we measured a relaxation time T1=99h , with an inferred wall-relaxation time of 174h . A prototype large storage cell ( 12cm diameter) was constructed to take advantage of the apparent increase in wall-relaxation time for cells with a smaller surface-to-volume ratio. The measured relaxation time in this cell at 3mT and 100°C was 5.75h . Such a cell (or one even larger) could be used to store many liters of hyperpolarized Xe129 produced by a flow-through polarizer and accumulator for up to three times longer than currently implemented schemes involving freezing xenon in liquid nitrogen.

  17. Gas-Phase Combustion Synthesis of Nonoxide Nanoparticles in Microgravity

    NASA Technical Reports Server (NTRS)

    Axelbaum, R. L.; Kumfer, B. M.; Sun, Z.; Chao, B. H.

    2001-01-01

    Gas-phase combustion synthesis is a promising process for creating nanoparticles for the growing nanostructure materials industry. The challenges that must be addressed are controlling particle size, preventing hard agglomerates, maintaining purity, and, if nonoxides are synthesized, protecting the particles from oxidation and/or hydrolysis during post-processing. Sodium-halide Flame Encapsulation (SFE) is a unique methodology for producing nonoxide nanoparticles that addresses these challenges. This flame synthesis process incorporates sodium and metal-halide chemistry, resulting in nanoparticles that are encapsulated in salt during the early stages of their growth in the flame. Salt encapsulation has been shown to allow control of particle size and morphology, while serving as an effective protective coating for preserving the purity of the core particles. Metals and compounds that have been produced using this technology include Al, W, Ti, TiB2, AlN, and composites of W-Ti and Al-AlN. Oxygen content in SFE synthesized nano- AlN has been measured by neutron activation analysis to be as low as 0.54wt.%, as compared to over 5wt.% for unprotected AlN of comparable size. The overall objective of this work is to study the SFE process and nano-encapsulation so that they can be used to produce novel and superior materials. SFE experiments in microgravity allow the study of flame and particle dynamics without the influence of buoyancy forces. Spherical sodium-halide flames are produced in microgravity by ejecting the halide from a spherical porous burner into a quiescent atmosphere of sodium vapor and argon. Experiments are performed in the 2.2 sec Drop Tower at the NASA-Glenn Research Center. Numerical models of the flame and particle dynamics were developed and are compared with the experimental results.

  18. Gas-phase interactions of organotin compounds with cysteine.

    PubMed

    Latrous, Latifa; Salpin, Jean-Yves; Haldys, Violette; Léon, Emmanuelle; Correia, Catarina; Lamsabhi, Al Mokhtar

    2016-11-01

    The gas-phase interactions of cysteine with di-organotin and tri-organotin compounds have been studied by mass spectrometry experiments and quantum calculations. Positive-ion electrospray spectra show that the interaction of di- and tri-organotins with cysteine results in the formation of [(R)2 Sn(Cys-H)](+) and [(R)3 Sn(Cys)](+) ions, respectively. MS/MS spectra of [(R)2 Sn(Cys-H)](+) complexes are characterized by numerous fragmentation processes, notably associated with elimination of NH3 and (C,H2 ,O2 ). Several dissociation routes are characteristic of each given organic species. Upon collision, both the [(R)3 Sn(Gly)](+) and [(R)3 Sn(Cys)](+) complexes are associated with elimination of the intact amino acid, leading to the formation of [(R)3 Sn](+) cation. But for the latter complex, two additional fragmentation processes are observed, associated with the elimination of NH3 and C3 H4 O2 S. Calculations indicate that the interaction between organotins and cysteine is predominantly electrostatic but also exhibits a considerable covalent character, which is slightly more pronounced in tri-organotin complexes. A preferred bidentate interaction of the type -η(2) -S-NH2 , with sulfur and the amino group, is observed. As for the [(R)3 Sn(Cys)](+) complexes, their stability is due to the combination of the hydrogen bond taking place between the amino group and the sulfur lone pair and the interaction between the carboxylic oxygen atom and the metal. Copyright © 2016 John Wiley & Sons, Ltd.

  19. IV-VI semiconductor lasers for gas phase biomarker detection

    NASA Astrophysics Data System (ADS)

    McCann, Patrick; Namjou, Khosrow; Roller, Chad; McMillen, Gina; Kamat, Pratyuma

    2007-09-01

    A promising absorption spectroscopy application for mid-IR lasers is exhaled breath analysis where sensitive, selective, and speedy measurement of small gas phase biomarker molecules can be used to diagnose disease and monitor therapies. Many molecules such as nitric oxide, ethane, formaldehyde, acetaldehyde, acetone, carbonyl sulfide, and carbon disulfide have been connected to diseases or conditions such as asthma, oxidative stress, breast cancer, lung cancer, diabetes, organ transplant rejection, and schizophrenia. Measuring these and other, yet to be discovered, biomarker molecules in exhaled breath with mid-IR lasers offers great potential for improving health care since such tests are non-invasive, real-time, and do not require expensive consumables or chemical reagents. Motivated by these potential benefits, mid-IR laser spectrometers equipped with presently available cryogenically-cooled IV-VI lasers mounted in compact Stirling coolers have been developed for clinical research applications. This paper will begin with a description of the development of mid-IR laser instruments and their use in the largest known exhaled breath clinical study ever performed. It will then shift to a description of recent work on the development of new IV-VI semiconductor quantum well materials and laser fabrication methods that offer the promise of low power consumption (i.e. efficient) continuous wave emission at room temperature. Taken together, the demonstration of compelling clinical applications with large market opportunities and the clear identification of a viable pathway to develop low cost mid-IR laser instrumentation can create a renewed focus for future research and development efforts within the mid-IR materials and devices area.

  20. Dissociative electron attachment to the gas-phase nucleobase hypoxanthine

    SciTech Connect

    Dawley, M. Michele; Tanzer, Katrin; Denifl, Stephan E-mail: Sylwia.Ptasinska.1@nd.edu; Carmichael, Ian; Ptasińska, Sylwia E-mail: Sylwia.Ptasinska.1@nd.edu

    2015-06-07

    We present high-resolution measurements of the dissociative electron attachment (DEA) to isolated gas-phase hypoxanthine (C{sub 5}H{sub 4}N{sub 4}O, Hyp), a tRNA purine base. The anion mass spectra and individual ion efficiency curves from Hyp were measured as a function of electron energy below 9 eV. The mass spectra at 1 and 6 eV exhibit the highest anion yields, indicating possible common precursor ions that decay into the detectable anionic fragments. The (Hyp − H) anion (C{sub 5}H{sub 3}N{sub 4}O{sup −}) exhibits a sharp resonant peak at 1 eV, which we tentatively assign to a dipole-bound state of the keto-N1H,N9H tautomer in which dehydrogenation occurs at either the N1 or N9 position based upon our quantum chemical computations (B3LYP/6-311+G(d,p) and U(MP2-aug-cc-pVDZ+)) and prior studies with adenine. This closed-shell dehydrogenated anion is the dominant fragment formed upon electron attachment, as with other nucleobases. Seven other anions were also observed including (Hyp − NH){sup −}, C{sub 4}H{sub 3}N{sub 4}{sup −}/C{sub 4}HN{sub 3}O{sup −}, C{sub 4}H{sub 2}N{sub 3}{sup −}, C{sub 3}NO{sup −}/HC(HCN)CN{sup −}, OCN{sup −}, CN{sup −}, and O{sup −}. Most of these anions exhibit broad but weak resonances between 4 and 8 eV similar to many analogous anions from adenine. The DEA to Hyp involves significant fragmentation, which is relevant to understanding radiation damage of biomolecules.

  1. Gas phase depletion and flow dynamics in horizontal MOCVD reactors

    NASA Astrophysics Data System (ADS)

    Van de Ven, J.; Rutten, G. M. J.; Raaijmakers, M. J.; Giling, L. J.

    1986-08-01

    Growth rates of GaAs in the MOCVD process have been studied as a function of both lateral and axial position in horizontal reactor cells with rectangular cross-sections. A model to describe growth rates in laminar flow systems on the basis of concentration profiles under diffusion controlled conditions has been developed. The derivation of the growth rate equations includes the definition of an entrance length for the concentration profile to developed. In this region, growth rates appear to decrease with the 1/3 power of the axial position. Beyond this region, an exponential decrease is found. For low Rayleigh number conditions, the present experimental results show a very satisfactory agreement with the model without parameter fitting for both rectangular and tapered cells, and with both H 2 and N 2 as carrier gases. Theory also predicts that uniform deposition can be obtained over large areas in the flow direction for tapered cells, which has indeed been achieved experimentally. The influence of top-cooling in the present MOCVD system has been considered in more detail. From the experimental results, conclusions could be drawn concerning the flow characteristics. For low Rayleigh numbers (present study ≲ 700) it follows that growth rate distributions correspond with forced laminar flow characteristics. For relatively high Rayleigh numbers (present work 1700-2800), free convective effects with vortex formation are important. These conclusions are not specific for the present system, but apply to horizontal cold-wall reactors in general. On the basis of the present observations, recommendations for a cell design to obtain large area homogeneous deposition have been formulated. In addition, this work supports the conclusion that the final decomposition of trimethylgallium in the MOCVD process mainly takes place at the hot substrate and susceptor and not in the gas phase.

  2. Gas-Phase Combustion Synthesis of Aluminum Nitride Powder

    NASA Technical Reports Server (NTRS)

    Axelbaum, R. L.; Lottes, C. R.; Huertas, J. I.; Rosen, L. J.

    1996-01-01

    Due to its combined properties of high electrical resistivity and high thermal conductivity aluminum nitride (AlN) is a highly desirable material for electronics applications. Methods are being sought for synthesis of unagglomerated, nanometer-sized powders of this material, prepared in such a way that they can be consolidated into solid compacts having minimal oxygen content. A procedure for synthesizing these powders through gas-phase combustion is described. This novel approach involves reacting AlCl3, NH3, and Na vapors. Equilibrium thermodynamic calculations show that 100% yields can be obtained for these reactants with the products being AlN, NaCl, and H2. The NaCl by-product is used to coat the AlN particles in situ. The coating allows for control of AlN agglomeration and protects the powders from hydrolysis during post-flame handling. On the basis of thermodynamic and kinetic considerations, two different approaches were employed to produce the powder, in co-flow diffusion flame configurations. In the first approach, the three reactants were supplied in separate streams. In the second, the AlCl3 and NH3 were premixed with HCl and then reacted with Na vapor. X-ray diffraction (XRD) spectra of as-produced powders show only NaCl for the first case and NaCl and AlN for the second. After annealing at 775 C tinder dynamic vacuum, the salt was removed and XRD spectra of powders from both approaches show only AlN. Aluminum metal was also produced in the co-flow flame by reacting AlCl3 with Na. XRD spectra of as-produced powders show the products to be only NaCl and elemental aluminum.

  3. CHAOS III: Gas-phase Abundances in NGC 5457

    NASA Astrophysics Data System (ADS)

    Croxall, Kevin V.; Pogge, Richard W.; Berg, Danielle A.; Skillman, Evan D.; Moustakas, John

    2016-10-01

    We present Large Binocular Telescope observations of 109 H ii regions in NGC 5457 (M101) obtained with the Multi-Object Double Spectrograph. We have robust measurements of one or more temperature-sensitive auroral emission lines for 74 H ii regions, permitting the measurement of “direct” gas-phase abundances. Comparing the temperatures derived from the different ionic species, we find: (1) strong correlations of T[N ii] with T[S iii] and T[O iii], consistent with little or no intrinsic scatter; (2) a correlation of T[S iii] with T[O iii], but with significant intrinsic dispersion; (3) overall agreement between T[N ii], T[S ii], and T[O ii], as expected, but with significant outliers; (4) the correlations of T[N ii] with T[S iii] and T[O iii] match the predictions of photoionization modeling while the correlation of T[S iii] with T[O iii] is offset from the prediction of photoionization modeling. Based on these observations, which include significantly more observations of lower excitation H ii regions, missing in many analyses, we inspect the commonly used ionization correction factors (ICFs) for unobserved ionic species and propose new empirical ICFs for S and Ar. We have discovered an unexpected population of H ii regions with a significant offset to low values in Ne/O, which defies explanation. We derive radial gradients in O/H and N/O which agree with previous studies. Our large observational database allows us to examine the dispersion in abundances, and we find intrinsic dispersions of 0.074 ± 0.009 in O/H and 0.095 ± 0.009 in N/O (at a given radius). We stress that this measurement of the intrinsic dispersion comes exclusively from direct abundance measurements of H ii regions in NGC 5457.

  4. On the method of indirectly measuring gas and particulate phase velocities in shock induced dusty-gas flows

    NASA Astrophysics Data System (ADS)

    Lock, G. D.

    A method of indirectly measuring the temporally varying velocities of the gas and particulate phases in the nonequilibrium region of a shock wave moving at constant speed in a dusty-gas flow is described, and this method is assessed by using experimental data from shock-induced air flows containing 40-micron-diameter glass beads in a dusty-gas shock-tube facility featuring a large horizontal channel (19.7-cm by 7.6-cm in cross section). Simultaneous measurements of the shock-front speed with time-of-arrival gauges, particle concentration by light extinctiometry, and gas-particle mixture density by beta-ray absorption are used in conjunction with two mass conservation laws to obtain the indirect velocity measurements of both phases. A second indirect measurement of the gas-phase velocity is obtained when the gas pressure is simultaneously recorded along with the particle concentration and shock-front speed when used in conjunction with the conservation of mixture momentum. Direct measurements of the particulate-phase velocity by laser-Doppler velocimetry are also presented as a means of assessing the indirect velocity measurement method.

  5. The Noble Gas Record of Gas-Water Phase Interaction in the Tight-Gas-Sand Reservoirs of the Rocky Mountains

    NASA Astrophysics Data System (ADS)

    Ballentine, C. J.; Zhou, Z.; Harris, N. B.

    2015-12-01

    The mass of hydrocarbons that have migrated through tight-gas-sandstone systems before the permeability reduces to trap the hydrocarbon gases provides critical information in the hydrocarbon potential analysis of a basin. The noble gas content (Ne, Ar, Kr, Xe) of the groundwater has a unique isotopic and elemental composition. As gas migrates through the water column, the groundwater-derived noble gases partition into the hydrocarbon phase. Determination of the noble gases in the produced hydrocarbon phase then provides a record of the type of interaction (simple phase equilibrium or open system Rayleigh fractionation). The tight-gas-sand reservoirs of the Rocky Mountains represent one of the most significant gas resources in the United States. The producing reservoirs are generally developed in low permeability (averaging <0.1mD) Upper Cretaceous fluvial to marginal marine sandstones and commonly form isolated overpressured reservoir bodies encased in even lower permeability muddy sediments. We present noble gas data from producing fields in the Greater Green River Basin, Wyoming; the the Piceance Basin, Colorado; and in the Uinta Basin, Utah. The data is consistent from all three basins. We show how in each basin the noble gases record open system gas migration through a water column at maximum basin burial. The data within an open system model indicates that the gas now in-place represents the last ~10% of hydrocarbon gas to have passed through the water column, most likely prior to permeability closedown.

  6. Comparative study on methodology in molecular dynamics simulation of nucleation

    NASA Astrophysics Data System (ADS)

    Julin, Jan; Napari, Ismo; Vehkamäki, Hanna

    2007-06-01

    Gas-liquid nucleation of 1000 Lennard-Jones atoms is simulated to evaluate temperature regulation methods and methods to obtain nucleation rate. The Berendsen and the Andersen thermostats are compared. The Berendsen thermostat is unable to control the temperature of clusters larger than the critical size. Independent of the thermostating method the velocities of individual atoms and the translational velocities of clusters up to at least six atoms are accurately described by the Maxwell velocity distribution. Simulations with the Andersen thermostat yield about two times higher nucleation rates than those with the Berendsen thermostat. Nucleation rate is extracted from the simulations by direct observation of times of nucleation onset and by the method of Yasuoka and Matsumoto [J. Chem. Phys. 109, 8451 (1998)]. Compared to the direct observation, the nucleation rates obtained from the method of Yasuoka and Matsumoto are higher by a factor of 3.

  7. Capillary effects on gas hydrate three-phase stability in marine sediments

    NASA Astrophysics Data System (ADS)

    Liu, X.; Flemings, P. B.

    2013-12-01

    We study the three-phase (Liquid + Gas + Hydrate) stability of the methane hydrate system in marine sediments by considering the capillary effects on both hydrate and free gas phases. The aqueous CH4 solubilities required for forming hydrate (L+H) and free gas (L+G) in different pore sizes can be met in a three-phase zone. The top of the three-phase zone shifts upward in sediments as the water depth increases and the mean pore size decreases. The thickness of the three-phase zone increases as the pore size distribution widens. The top of the three-phase zone can either overlie the three-phase stability depth at deepwater Blake Ridge or underlie the three-phase stability depth at Hydrate Ridge in shallow water. Our model prediction is compatible with worldwide observations that the bottom-simulating reflector is systematically shifted upward relative to the bulk equilibrium depth as water depth (pressure) is increased. The gas hydrate and free gas saturations of the three-phase zone at Blake Ridge Comparison of the globally compiled BSR temperatures with the three-phase equilibrium curves for the systems of pure CH4 + 3.5 wt.% seawater (solid line) and pure CH4 + 2.0 wt.% seawater (dotted line). The discrepancies between the observed BSR temperature and the calculated three-phase temperature are systematically larger in deep water than in shallow water.

  8. Final Report: "Collaborative Project. Understanding the Chemical Processes That Affect Growth Rates of Freshly Nucleated Particles"

    SciTech Connect

    Smith, James N.; McMurry, Peter H.

    2015-11-12

    This final technical report describes our research activities that have, as the ultimate goal, the development of a model that explains growth rates of freshly nucleated particles. The research activities, which combine field observations with laboratory experiments, explore the relationship between concentrations of gas-phase species that contribute to growth and the rates at which those species are taken up. We also describe measurements of the chemical composition of freshly nucleated particles in a variety of locales, as well as properties (especially hygroscopicity) that influence their effects on climate. Our measurements include a self-organized, DOE-ARM funded project at the Southern Great Plains site, the New Particle Formation Study (NPFS), which took place during spring 2013. NPFS data are available to the research community on the ARM data archive, providing a unique suite observations of trace gas and aerosols that are associated with the formation and growth of atmospheric aerosol particles.

  9. CO2 Capture from Flue Gas by Phase Transitional Absorption

    SciTech Connect

    Liang Hu

    2009-06-30

    A novel absorption process called Phase Transitional Absorption was invented. What is the Phase Transitional Absorption? Phase Transitional Absorption is a two or multi phase absorption system, CO{sub 2} rich phase and CO{sub 2} lean phase. During Absorption, CO{sub 2} is accumulated in CO{sub 2} rich phase. After separating the two phases, CO{sub 2} rich phase is forward to regeneration. After regeneration, the regenerated CO{sub 2} rich phase combines CO{sub 2} lean phase to form absorbent again to complete the cycle. The advantage for Phase Transitional Absorption is obvious, significantly saving on regeneration energy. Because CO{sub 2} lean phase was separated before regeneration, only CO{sub 2} rich phase was forward to regeneration. The absorption system we developed has the features of high absorption rate, high loading and working capacity, low corrosion, low regeneration heat, no toxic to environment, etc. The process evaluation shows that our process is able to save 80% energy cost by comparing with MEA process.

  10. 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

  11. Assessing nucleation in cloud formation modelling for Brown Dwarf and Exoplanet atmospheres

    NASA Astrophysics Data System (ADS)

    Lee, Graham; Helling, Christiane; Giles, Helen; Bromley, Stefan

    2015-04-01

    Context. Substellar objects such as Brown Dwarfs and hot Jupiter exoplanets are cool enough that clouds can form in their atmospheres (Helling & Casewell 2014; A&ARv 22)). Unlike Earth, where cloud condensation nuclei are provided by the upward motion of sand or ash, in Brown Dwarf and hot Jupiters these condensation seeds form from the gas phase. This process proceeds in a stepwise chemical reaction of single monomer addition of a single nucleation species, referred to as homogeneous nucleation. The rate at which these seeds form is determined by the local thermodynamic conditions and the chemical composition of the local gas phase. Once the seed particles have formed, multiple materials are thermally stable and grow almost simultaneously by chemical surface reactions. This results in the growth of the condensation seeds to macroscopic particles of μm size. At the same time, the gas phase becomes depleted. Once temperatures become too high for thermal stability of the cloud particle, it evaporates until its constituents return to the gas phase. Convection from deeper atmospheric layers provides element replenishment to upper, cooler layers allowing the cloud formation process to reach a stationary state (Woitke & Helling 2003; A&A 399). Aims. The most efficient nucleation is a 'winner takes all' process as the losing molecules will condense on the surface of the faster nucleating seed particle. We apply new molecular (TiO2)N-cluster and SiO vapour data to our cloud formation model in order to re-asses the question of the primary nucleation species. Methods. We apply density functional theory (B3LYP, 6-311G(d)) using the computational chemistry package GAUSSIAN 09 to derive updated thermodynamical data for (TiO2)N-clusters as input for our TiO2 seed formation model. We test both TiO2 and SiO as primary nucleates assuming a homogeneous nucleation process and by solving a system of dust moment equations and element conservation for a pre-scribed Brown Dwarf

  12. A new method for measurement of gas-phase ammonia and amines in air

    NASA Astrophysics Data System (ADS)

    Dawson, M. L.; Gomez, A.; Arquero, K. D.; Perraud, V. M.; Finlayson-Pitts, B. J.

    2013-12-01

    Accurately predicting particle formation and growth from gas phase precursors is an essential component of modeling the impact of particulate matter on human health, visibility and climate. While the reactions of ammonia with nitric and sulfuric acids to form particulate nitrate and sulfate particles is well known, it has been recently recognized that gas-phase amines, even at low ppb levels, significantly enhance particle formation from common atmospheric acids. As a result, accurate data on the sources, sinks and typical background concentrations of gas-phase amines, are crucial to predicting new particle formation in the atmosphere. However, gas-phase amines are notoriously difficult to measure, as they have a tendency to stick to surfaces, including sampling lines and inlets. In addition, background amine concentrations in the atmosphere are typically a few ppb or lower, requiring low detection limits for ambient sampling techniques. Here we report the development of a simple, reliable method for detection of gas-phase amines at atmospherically relevant concentrations using collection on a cation exchange sorbent followed by in-line extraction and ion chromatography. Gas-phase standards of several amines and ammonia are used to characterize the technique and results from ambient samples in an agricultural area are presented. The application of this technique to field measurements as well as to laboratory measurements of new particle formation from gas-phase ammonia and amines are discussed.

  13. Wurtzite to rocksalt phase transformation of cadmium selenide nanocrystals via laser-induced shock waves: transition from single to multiple nucleation.

    PubMed

    Wittenberg, Joshua S; Merkle, Maxwell G; Alivisatos, A Paul

    2009-09-18

    The behavior of CdSe nanocrystals shocked to stresses of 2-3.75 GPa has been studied. Above 3 GPa a near-complete disappearance of the first excitonic feature and broadening of the low-energy absorption edge were observed, consistent with a wurtzite to rocksalt structural transformation. The transformation pressure is reduced relative to hydrostatic compression in a diamond anvil cell, and the rate increases, attributed to shock induced shear stress along the reaction coordinate. The especially rapid rate observed for a 3.75 GPa shock suggests multiple nucleation events per particle.

  14. Condensed-phase versus gas-phase ozonolysis of catechol: A combined experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Barnum, Timothy J.; Medeiros, Nicholas; Hinrichs, Ryan Z.

    2012-08-01

    Anthropogenic emissions of volatile aromatic compounds contribute to the formation of secondary organic aerosols (SOA), especially in urban environments. Aromatic SOA precursors typically require oxidation by hydroxyl radicals, although recent work suggests that ozonolysis of 1,2-benzenediols produces SOA in high yields. We employed attenuated total reflectance and transmission infrared spectroscopy to investigate the heterogeneous ozonolysis of catechol thin films. Formation of the dominant condensed-phase product muconic acid was highly dependent on relative humidity (RH) with few products detected below 40% RH and a maximum reactive uptake coefficient of γ = (5.6 ± 0.5) × 10-5 measured at 81.2% RH. We also performed quantum chemical calculations mapping out several reaction pathways for the homogeneous ozonolysis of gaseous catechol. 1,3-cycloaddition transition states were rate limiting with the most favorable activation energies at 45.4 and 47.1 kJ mol-1 [CCSD(T)/6-311++G(d,p)] corresponding to addition across and adjacent to the diol Cdbnd C, respectively. Gas-phase rate constants, calculated using transition state theory, were six orders of magnitude slower than experimental values. In contrast, a calculated activation energy was lower for the ozonolysis of a catechol•H2O complex, which serves as a first-approximation for modeling the ozonolysis of condensed-phase catechol. These combined results suggests that homogeneous ozonolysis of catechol may not be important for the formation of secondary organic aerosols but that ozonolysis of surface-adsorbed catechol may contribute to SOA growth.

  15. Gas phase dispersion in compost as a function of different water contents and air flow rates.

    PubMed

    Sharma, Prabhakar; Poulsen, Tjalfe G

    2009-07-21

    Gas phase dispersion in a natural porous medium (yard waste compost) was investigated as a function of gas flow velocity and compost volumetric water content using oxygen and nitrogen as tracer gases. The compost was chosen because it has a very wide water content range and because it represents a wide range of porous media, including soils and biofilter media. Column breakthrough curves for oxygen and nitrogen were measured at relatively low pore gas velocities, corresponding to those observed in for instance soil vapor extraction systems or biofilters for air cleaning at biogas plants or composting facilities. Total gas mechanical dispersion-molecular diffusion coefficients were fitted from the breakthrough curves using a one-dimensional numerical solution to the advection-dispersion equation and used to determine gas dispersivities at different volumetric gas contents. The results showed that gas mechanical dispersion dominated over molecular diffusion with mechanical dispersion for all water contents and pore gas velocities investigated. Importance of mechanical dispersion increased with increasing pore gas velocity and compost water content. The results further showed that gas dispersivity was relatively constant at high values of compost gas-filled porosity but increased with decreasing gas-filled porosity at lower values of gas-filled porosity. Results finally showed that measurement uncertainty in gas dispersivity is generally highest at low values of pore gas velocity.

  16. Size Dependant Nucleation of Confined 2-Decanol

    NASA Astrophysics Data System (ADS)

    Amanuel, Samuel; Bauer, Hillary; Safiq, Alexandrea; Dulmaa, Jargalsaikhan; Khraisat, Amer

    2012-02-01

    We have studied freezing and melting of physically confined 2-decanol in nano porous silica using a Differential Scanning Calorimeter (DSC). Both melting and freezing temperatures are suppressed for physically confined 2-decanol. In the presence of bulk, freezing of the confined system is triggered by freezing of the bulk where nucleation is heterogeneous. There is, however, a cutoff size between 100 nm and 300 nm where phase transition is no longer initiated through heterogeneous nucleation. Below the cutoff size, nucleation is homogeneous where the confined system has to be supercooled further before any phase transition can occur. Melting of the confined system, on the other hand, is not influenced by the presence or absence of the bulk.

  17. Vapor liquid solid-hydride vapor phase epitaxy (VLS-HVPE) growth of ultra-long defect-free GaAs nanowires: Ab initio simulations supporting center nucleation

    SciTech Connect

    André, Yamina Lekhal, Kaddour; Hoggan, Philip; Avit, Geoffrey; Réda Ramdani, M.; Monier, Guillaume; Colas, David; Ajib, Rabih; Castelluci, Dominique; Gil, Evelyne; Cadiz, Fabian; Rowe, Alistair; Paget, Daniel; Petit, Elodie; Leroux, Christine; Trassoudaine, Agnès

    2014-05-21

    High aspect ratio, rod-like and single crystal phase GaAs nanowires (NWs) were grown by gold catalyst-assisted hydride vapor phase epitaxy (HVPE). High resolution transmission electron microscopy and micro-Raman spectroscopy revealed polytypism-free zinc blende (ZB) NWs over lengths of several tens of micrometers for a mean diameter of 50 nm. Micro-photoluminescence studies of individual NWs showed linewidths smaller than those reported elsewhere which is consistent with the crystalline quality of the NWs. HVPE makes use of chloride growth precursors GaCl of which high decomposition frequency after adsorption onto the liquid droplet catalysts, favors a direct and rapid introduction of the Ga atoms from the vapor phase into the droplets. High influxes of Ga and As species then yield high axial growth rate of more than 100 μm/h. The diffusion of the Ga atoms in the liquid droplet towards the interface between the liquid and the solid nanowire was investigated by using density functional theory calculations. The diffusion coefficient of Ga atoms was estimated to be 3 × 10{sup −9} m{sup 2}/s. The fast diffusion of Ga in the droplet favors nucleation at the liquid-solid line interface at the center of the NW. This is further evidence, provided by an alternative epitaxial method with respect to metal-organic vapor phase epitaxy and molecular beam epitaxy, of the current assumption which states that this type of nucleation should always lead to the formation of the ZB cubic phase.

  18. 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

  19. Gas-phase interactions of organotin compounds with glycine.

    PubMed

    Latrous, Latifa; Tortajada, Jeanine; Haldys, Violette; Léon, Emmanuelle; Correia, Catarina; Salpin, Jean-Yves

    2013-07-01

    Gas-phase interactions of organotins with glycine have been studied by combining mass spectrometry experiments and quantum calculations. Positive-ion electrospray spectra show that the interaction of di- and tri-organotins with glycine results in the formation of [(R)2Sn(Gly)-H](+) and [(R)3Sn(Gly)](+) ions, respectively. Di-organotin complexes appear much more reactive than those involving tri-organotins. (MS/MS) spectra of the [(R)3Sn(Gly)](+) ions are indeed simple and only show elimination of intact glycine, generating the [(R)3Sn](+) carbocation. On the other hand, MS/MS spectra of [(R)2Sn(Gly)-H](+) complexes are characterized by numerous fragmentation processes. Six of them, associated with elimination of H2O, CO, H2O + CO and formation of [(R)2SnOH](+) (-57 u),[(R)2SnNH2](+) (-58 u) and [(R)2SnH](+) (-73 u), are systematically observed. Use of labeled glycines notably concludes that the hydrogen atoms eliminated in water and H2O + CO are labile hydrogens. A similar conclusion can be made for hydrogens of [(R2)SnOH](+) and [(R2)SnNH2](+) ions. Interestingly, formation [(R)2SnH](+) ions is characterized by a migration of one the α hydrogen of glycine onto the metallic center. Finally, several dissociation routes are observed and are characteristic of a given organic substituent. Calculations indicated that the interaction between organotins and glycine is mostly electrostatic. For [(R)2Sn(Gly)-H](+) complexes, a preferable bidentate interaction of the type η(2)-O,NH2 is observed, similar to that encountered for other metal ions. [(R)3Sn](+) ions strongly stabilize the zwitterionic form of glycine, which is practically degenerate with respect to neutral glycine. In addition, the interconversion between both forms is almost barrierless. Suitable mechanisms are proposed in order to account for the most relevant fragmentation processes.

  20. Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler.

    PubMed

    Meischen, Sandra J; Van Pelt, Vincent J; Zarate, Eugene A; Stephens, Edward A

    2004-01-01

    Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results.

  1. Spectroscopy of PAH species in the gas phase

    NASA Astrophysics Data System (ADS)

    Robinson, Michael S.; Beegle, Luther W.; Wdowiak, Thomas J.

    1995-02-01

    At elevated temperatures, the structured CH stretch absorption occurring at room temperature of polycyclic aromatic hydrocarbon (PAH) molecules encapsulated in KBr coalesces to a single peak whose wavelength is a very close match for that of the observed 3.3 μm unidentified infrared band (UIR) emission feature (Flickinger and Wdowiak. Astrophys. J.362, L71-L74. 1990). The temperature of approximately 800 K is significant because a PAH molecule in the interstellar radiation field, upon absorption of an ultraviolet photon, is expected to be excited to an energy equivalent to temperatures of this order (Sellgren, Astrophys. J.277, 623 1984). Our previous study of PAH molecules in the vapor phase at 600-800 K showed that the C-H stretch PAH feature near 3.3 μm is at a shorter wavelength than in the condensed state (Flickinger et al., Astrophys. J.380, L43-L46, 1991). Recent work by Joblin et al. ( 1st Symp. on the Infrared Cirrus and Diffuse Interstellar Clouds. 1994) in a short path length diamond cell indicates the gas phase wavelength of the 3.3 μm region C-H stretch feature of naphthalene is directly proportional to temperature over a large temperature range. Laser-excited IR fluorescence studies have also suggested that the wavelength is sensitive to laser photon energy in a direct relationship (Williams and Leone, The Diffuse Interstellar Bands Conf., 1994). Comprehensive studies of PAHs thermally excited up to the decomposition temperature are therefore important to carry out. We have utilized a long-path-length optical heat pipe to confirm that the wavelength of the peak of the C-H stretch band of naphthalene vapor obeys a direct relationship with temperature as reported by Joblin, and to demonstrate that this feature undergoes a strengthening with respect to the longer wavelength band due to an out-of-plane deformation (782 cm -1) as temperature increases. The shift from 3067.6 to 3063.7 cm -1 over the temperature range of 316-996 K seems to be linear

  2. Recycling of excavated asphalt from gas-pipeline installations to Gas Research Institute. Final report - Phase 1

    SciTech Connect

    Lucido, J.; Tobin, A.

    1988-12-01

    Recent estimates indicate that over 11,500 miles of gas distribution piping is installed under existing asphalt pavement annually. This estimate includes 25% of all new installations and 60% of all replacement work. As gas distribution systems grow to meet demands, more projects will involve restoration of asphalt pavements. Because gas distribution piping installed and/or replaced under asphalt pavement can be significantly more expensive than an installation in unpaved soil--it is cause for major concern to the gas industry. The Phase I study addressed the concept of on-site recycling of excavated asphalt for gas utility trenching applications. Commercialization of this concept will eliminate the need for disposal of existing asphalt concrete and the importing of new asphalt concrete, creating potentially significant advantages to the industry.

  3. Mm/submm Study of Gas-Phase Photoproducts from Methanol Interstellar Ice Analogues

    NASA Astrophysics Data System (ADS)

    Mesko, AJ; Smith, Houston Hartwell; Milam, Stefanie N.; Widicus Weaver, Susanna L.

    2016-06-01

    Icy grain reactions have gained quite the popularity in the astrochemistry community to explain the formation of complex organic molecules. Through temperature programmed desorption and photolysis experiments we use rotational spectroscopy to measure the gas-phase products of icy grain reactions. Previous results include testing detection limits of the system by temperature programmed desorption of methanol and water ices, photochemistry of gas-phase methanol, and detection of photodesorbed water from a pure water ice surface. Current work that will be discussed focuses on the detection of gas-phase CO and other photoproducts from an ice surface.

  4. Gas-phase production of single-walled carbon nanotubes from carbon monoxide: a review of the hipco process

    NASA Technical Reports Server (NTRS)

    Nikolaev, Pavel

    2004-01-01

    The latest process for producing large quantities of single-walled carbon nanotubes (SWNTs) to emerge from the Rice University, dubbed HiPco, is living up to its promise. The current production rates approach 450 mg/h (or 10 g/day), and nanotubes typically have no more than 7 mol % of iron impurities. Second-generation HiPco apparatus can run continuously for 7-10 days at a time. In the HiPco process nanotubes grow in high-pressure, high-temperature flowing CO on catalytic clusters of iron. Catalyst is formed in situ by thermal decomposition of iron pentacarbonyl, which is delivered intact within a cold CO flow and then rapidly mixed with hot CO in the reaction zone. Upon heating, the Fe(CO)5 decomposes into atoms that condense into larger clusters. SWNTs nucleate and grow on these particles in the gas phase via CO disproportionation: CO + CO --> CO2 + C (SWNT), catalyzed by the Fe surface. The concentration of CO2 produced in this reaction is equal to that of carbon and can therefore serve as a useful real-time feedback parameter. It was used to study and optimize SWNT production as a function of temperature, pressure, and Fe(CO)5 concentration. The results of the parametric study are in agreement with current understanding of the nanotube formation mechanism.

  5. Fragile-to-fragile liquid transition at Tg and stable-glass phase nucleation rate maximum at the Kauzmann temperature TK

    NASA Astrophysics Data System (ADS)

    Tournier, Robert F.

    2014-12-01

    An undercooled liquid is unstable. The driving force of the glass transition at Tg is a change of the undercooled-liquid Gibbs free energy. The classical Gibbs free energy change for a crystal formation is completed including an enthalpy saving. The crystal growth critical nucleus is used as a probe to observe the Laplace pressure change Δp accompanying the enthalpy change -Vm×Δp at Tg where Vm is the molar volume. A stable glass-liquid transition model predicts the specific heat jump of fragile liquids at T≤Tg, the Kauzmann temperature TK where the liquid entropy excess with regard to crystal goes to zero, the equilibrium enthalpy between TK and Tg, the maximum nucleation rate at TK of superclusters containing magic atom numbers, and the equilibrium latent heats at Tg and TK. Strong-to-fragile and strong-to-strong liquid transitions at Tg are also described and all their thermodynamic parameters are determined from their specific heat jumps. The existence of fragile liquids quenched in the amorphous state, which do not undergo liquid-liquid transition during heating preceding their crystallization, is predicted. Long ageing times leading to the formation at TK of a stable glass composed of superclusters containing up to 147 atom, touching and interpenetrating, are evaluated from nucleation rates. A fragile-to-fragile liquid transition occurs at Tg without stable-glass formation while a strong glass is stable after transition.

  6. Homogeneous nucleation of methane hydrates: unrealistic under realistic conditions.

    PubMed

    Knott, Brandon C; Molinero, Valeria; Doherty, Michael F; Peters, Baron

    2012-12-05

    Methane hydrates are ice-like inclusion compounds with importance to the oil and natural gas industry, global climate change, and gas transportation and storage. The molecular mechanism by which these compounds form under conditions relevant to industry and nature remains mysterious. To understand the mechanism of methane hydrate nucleation from supersaturated aqueous solutions, we performed simulations at controlled and realistic supersaturation. We found that critical nuclei are extremely large and that homogeneous nucleation rates are extremely low. Our findings suggest that nucleation of methane hydrates under these realistic conditions cannot occur by a homogeneous mechanism.

  7. Two-stage coal liquefaction without gas-phase hydrogen

    DOEpatents

    Stephens, H.P.

    1986-06-05

    A process is provided for the production of a hydrogen-donor solvent useful in the liquefaction of coal, wherein the water-gas shift reaction is used to produce hydrogen while simultaneously hydrogenating a donor solvent. A process for the liquefaction of coal using said solvent is also provided. The process enables avoiding the use of a separate water-gas shift reactor as well as high pressure equipment for liquefaction. 3 tabs.

  8. Temperature dependence of nucleation in Yukawa fluids

    NASA Astrophysics Data System (ADS)

    Li, J.-S.; Wilemski, G.

    2002-03-01

    We have studied the temperature dependence of gas-liquid nucleation in Yukawa fluids with gradient theory (GT) and density functional theory (DFT). Each of these nonclassical theories exhibits a weaker (i.e. better) temperature dependence than classical nucleation theory. At a given temperature, the difference between GT and DFT for the reversible work to form a critical nucleus gets smaller with increasing superaturation. For the temperature dependence, the reversible work for GT is very close to that for DFT at high temperatures. The difference between the two theories increases with decreasing temperature and supersaturation. Thus, in contrast to the behavior of a Peng-Robinson fluid, we find that GT can improve the temperature dependence over that of classical nucleation theory, although not always to the same degree as DFT.

  9. The gas-phase metallicity of central and satellite galaxies in the Sloan Digital Sky Survey

    NASA Astrophysics Data System (ADS)

    Pasquali, Anna; Gallazzi, Anna; van den Bosch, Frank C.

    2012-09-01

    We exploit the galaxy groups catalogue of Yang et al. and the galaxy properties measured in the Sloan Digital Sky Survey Data Releases 4 and 7 to study how the gas-phase metallicities of star-forming galaxies depend on environment. We find that satellite and central galaxies follow a qualitatively similar stellar mass (M★)-gas-phase metallicity relation, whereby their gas-phase metallicity increases with M★. Satellites, though, have higher gas-phase metallicities than equally massive centrals, and this difference increases with decreasing stellar mass. We find a maximum offset of 0.06 dex at log(M★/h-2 M⊙) ≃ 8.25. At fixed halo mass, centrals are more metal rich than satellites by ˜0.5 dex on average. This is simply due to the fact that, by definition, centrals are the most massive galaxies in their groups, and the fact that gas-phase metallicity increases with stellar mass. More interestingly, we also find that the gas-phase metallicity of satellites increases with halo mass (Mh) at fixed stellar mass. This increment is more pronounced for less massive galaxies, and, at M★ ≃ 109 h-2 M⊙, corresponds to ˜0.15 dex across the range 11 < log (Mh/h-1 M⊙) < 14. We also show that low-mass satellite galaxies have higher gas-phase metallicities than central galaxies of the same stellar metallicity. This difference becomes negligible for more massive galaxies of roughly solar metallicity. We demonstrate that the observed differences in gas-phase metallicity between centrals and satellites at fixed M★ are not a consequence of stellar mass stripping (advocated by Pasquali et al. in order to explain similar differences but in stellar metallicity), nor to the past star formation history of these galaxies as quantified by their surface mass density or gas mass fraction. Rather, we argue that these trends probably originate from a combination of three environmental effects: (i) strangulation, which prevents satellite galaxies from accreting new, low

  10. Industrial fuel gas plant project. Phase II. Memphis industrial fuel gas plant. Final report. [U-GAS process

    SciTech Connect

    Not Available

    1983-01-01

    The Industrial Fuel Gas Plant produces a nominal 50 billion Btu/day of product gas. The entire IFG production will be sold to MLGW. Under normal conditions, 20% of the output of the plant will be sold by MLGW to the local MAPCO refinery and exchanged for pipeline quality refinery gas. The MAPCO refinery gas will be inserted into the Memphis Natural Gas Distribution System. A portion (normally 10%) of the IFG output of the plant will be diverted to a Credit Generation Unit, owned by MLGW, where the IFG will be upgraded to pipeline quality (950 Btu/SCF). This gas will be inserted into MLGW's Natural Gas Distribution System. The remaining output of the IFG plant (gas with a gross heating value of 300 Btu/SCF) will be sold by MLGW as Industrial Fuel Gas. During periods when the IFG plant is partially or totally off-stream, natural gas from the Memphis Natural Gas Distribution System will be sent to an air mixing unit where the gas will be diluted to a medium Btu content and distributed to the IFG customers. Drawing 2200-1-50-00104 is the plant block flow diagram showing the process sequence and process related support facilities of this industrial plant. Each process unit as well as each process-related support facility is described briefly.

  11. An investigation into the flow behavior of a single phase gas system and a two phase gas/liquid system in normal gravity with nonuniform heating from above

    NASA Technical Reports Server (NTRS)

    Disimile, Peter J.; Heist, Timothy J.

    1990-01-01

    The fluid behavior in normal gravity of a single phase gas system and a two phase gas/liquid system in an enclosed circular cylinder heated suddenly and nonuniformly from above was investigated. Flow visualization was used to obtain qualitative data on both systems. The use of thermochromatic liquid crystal particles as liquid phase flow tracers was evaluated as a possible means of simultaneously gathering both flow pattern and temperature gradient data for the two phase system. The results of the flow visualization experiments performed on both systems can be used to gain a better understanding of the behavior of such systems in a reduced gravity environment and aid in the verification of a numerical model of the system.

  12. Pressure drop, heat transfer, critical heat flux, and flow stability of two-phase flow boiling of water and ethylene glycol/water mixtures - final report for project "Efficent cooling in engines with nucleate boiling."

    SciTech Connect

    Yu, W.; France, D. M.; Routbort, J. L.

    2011-01-19

    Because of its order-of-magnitude higher heat transfer rates, there is interest in using controllable two-phase nucleate boiling instead of conventional single-phase forced convection in vehicular cooling systems to remove ever increasing heat loads and to eliminate potential hot spots in engines. However, the fundamental understanding of flow boiling mechanisms of a 50/50 ethylene glycol/water mixture under engineering application conditions is still limited. In addition, it is impractical to precisely maintain the volume concentration ratio of the ethylene glycol/water mixture coolant at 50/50. Therefore, any investigation into engine coolant characteristics should include a range of volume concentration ratios around the nominal 50/50 mark. In this study, the forced convective boiling heat transfer of distilled water and ethylene glycol/water mixtures with volume concentration ratios of 40/60, 50/50, and 60/40 in a 2.98-mm-inner-diameter circular tube has been investigated in both the horizontal flow and the vertical flow. The two-phase pressure drop, the forced convective boiling heat transfer coefficient, and the critical heat flux of the test fluids were determined experimentally over a range of the mass flux, the vapor mass quality, and the inlet subcooling through a new boiling data reduction procedure that allowed the analytical calculation of the fluid boiling temperatures along the experimental test section by applying the ideal mixture assumption and the equilibrium assumption along with Raoult's law. Based on the experimental data, predictive methods for the two-phase pressure drop, the forced convective boiling heat transfer coefficient, and the critical heat flux under engine application conditions were developed. The results summarized in this final project report provide the necessary information for designing and implementing nucleate-boiling vehicular cooling systems.

  13. Colloids and Nucleation

    NASA Technical Reports Server (NTRS)

    Ackerson, Bruce

    1997-01-01

    The objectives of the work funded under this grant were to develop a microphotographic technique and use it to monitor the nucleation and growth of crystals of hard colloidal spheres. Special attention is given to the possible need for microgravity studies in future experiments. A number of persons have been involved in this work. A masters student, Keith Davis, began the project and developed a sheet illumination apparatus and an image processing system for detection and analysis. His work on a segmentation program for image processing was sufficient for his master's research and has been published. A post doctoral student Bernie Olivier and a graduate student Yueming He, who originally suggested the sheet illumination, were funded by another source but along with Keith made photographic series of several samples (that had been made by Keith Davis). Data extraction has been done by Keith, Bernie, Yueming and two undergraduates employed on the grant. Results are published in Langmuir. These results describe the sheet lighting technique as one which illuminates not only the Bragg scattering crystal, but all the crystals. Thus, accurate crystal counts can be made for nucleation rate measurements. The strange crystal length scale reduction, observed in small angle light scattering (SALS) studies, following the initial nucleation and growth period, has been observed directly. The Bragg scattering (and dark) crystal size decreases in the crossover region. This could be an effect due to gravitational forces or due to over- compression of the crystal during growth. Direct observations indicate a complex morphology for the resulting hard sphere crystals. The crystal edges are fairly sharp but the crystals have a large degree of internal structure. This structure is a result of (unstable) growth and not aggregation. As yet unpublished work compares growth exponents data with data obtained by SALS. The nucleation rate density is determined over a broad volume fraction range

  14. A detailed study of ice nucleation by feldspar minerals

    NASA Astrophysics Data System (ADS)

    Whale, T. F.; Murray, B. J.; Wilson, T. W.; Carpenter, M. A.; Harrison, A.; Holden, M. A.; Vergara Temprado, J.; Morris, J.; O'Sullivan, D.

    2015-12-01

    Immersion mode heterogeneous ice nucleation plays a crucial role in controlling the composition of mixed phase clouds, which contain both supercooled liquid water and ice particles. The amount of ice in mixed phase clouds can affect cloud particle size, lifetime and extent and so affects radiative properties and precipitation. Feldspar minerals are probably the most important minerals for ice nucleation in mixed phase clouds because they nucleate ice more efficiently than other components of atmospheric mineral dust (Atkinson et al. 2013). The feldspar class of minerals is complex, containing numerous chemical compositions, several crystal polymorphs and wide variations in microscopic structure. Here we present the results of a study into ice nucleation by a wide range of different feldspars. We found that, in general, alkali feldspars nucleate ice more efficiently than plagioclase feldspars. However, we also found that particular alkali feldspars nucleate ice relatively inefficiently, suggesting that chemical composition is not the only important factor that dictates the ice nucleation efficiency of feldspar minerals. Ice nucleation by feldspar is described well by the singular model and is probably site specific in nature. The alkali feldspars that do not nucleate ice efficiently possess relatively homogenous structure on the micrometre scale suggesting that the important sites for nucleation are related to surface topography. Ice nucleation active site densities for the majority of tested alkali feldspars are similar to those found by Atkinson et al (2013), meaning that the validity of global aerosol modelling conducted in that study is not affected. Additionally, we have found that ice nucleation by feldspars is strongly influenced, both positively and negatively, by the solute content of droplets. Most other nucleants we have tested are unaffected by solutes. This provides insight into the mechanism of ice nucleation by feldspars and could be of importance

  15. Gas Phase UTE MRI of Propane and Propene

    PubMed Central

    Kovtunov, Kirill V.; Romanov, Alexey S.; Salnikov, Oleg G.; Barskiy, Danila A.; Chekmenev, Eduard Y.; Koptyug, Igor V.

    2016-01-01

    1H MRI of gases can potentially enable functional lung imaging to probe gas ventilation and other functions. In this work, 1H MR images of hyperpolarized and thermally polarized propane gas were obtained using UTE (ultrashort echo time) pulse sequence. A 2D image of thermally polarized propane gas with ~0.9×0.9 mm2 spatial resolution was obtained in less than 2 seconds, demonstrating that even non-hyperpolarized hydrocarbon gases can be successfully utilized for conventional proton MRI. The experiments were also performed with hyperpolarized propane gas and demonstrated acquisition of high-resolution multi-slice FLASH 2D images in ca. 510 s and non slice-selective 2D UTE MRI images in ca. 2 s. The UTE approach adopted in this study can be potentially used for medical lung imaging. Furthermore, the possibility to combine UTE with selective suppression of 1H signals from one of the two gases in a mixture is demonstrated in this MRI study. The latter can be useful for visualizing industrially important processes where several gases may be present, e.g., gas-solid catalytic reactions. PMID:27478870

  16. Resonance Energy Transfer Relates the Gas-Phase Structure and Pharmacological Activity of Opioid Peptides.

    PubMed

    Kopysov, Vladimir; Boyarkin, Oleg V

    2016-01-11

    Enkephalins are efficient pain-relief drugs that bind to transmembrane opioid receptors. One key structural parameter that governs the pharmacological activity of these opioid peptides and is typically determined from condensed-phase structures is the distance between the aromatic rings of their Tyr and Phe residues. We use resonance energy transfer, detected by a combination of cold ion spectroscopy and mass spectrometry, to estimate the Tyr-Phe spacing for enkephalins in the gas phase. In contrast to the condensed-phase structures, these distances appear to differ substantially in enkephalins with different pharmacological efficiencies, suggesting that gas-phase structures might be a better pharmacophoric metric for ligand peptides.

  17. Titanium defect structure change after gas-phase hydrogenation at different temperatures and cooling rates

    NASA Astrophysics Data System (ADS)

    Mikhaylov, Andrey A.; Laptev, Roman S.; Kudiiarov, Viktor N.; Volokitina, Tatiana L.

    2016-11-01

    Influence of gas-phase hydrogenation temperature and cooling rate on defect structure of commercially pure titanium alloy was experimentally studied by means of positron annihilation spectroscopy. The change of temperature in the process of gas-phase hydrogenation was in the range of 500-700°C, while the change of cooling rate was in the range of 0.4-10.4°C/min. With increasing of gas-phase hydrogenation temperature, significant increase of hydrogen sorption rate was found. High temperature gas-phase hydrogenation of commercially pure titanium alloy lead to the formation of vacancy and hydrogen-vacancy complexes. For the same concentration of hydrogen, temperature variation or variation of cooling rate had no effect on the type of defect. However, this variation provides significant changes in defect concentration.

  18. FACTORS INFLUENCING THE DEPOSITION OF A COMPOUND THAT PARTITIONS BETWEEN GAS AND PARTICULATE PHASES

    EPA Science Inventory

    How will atmospheric deposition behave for a compound when it reversibly sorbs between gas and atmospheric particulate phases? Two factors influence the answer. What physical mechanisms occur in the sorption process? What are the concentration and composition of atmospheric par...

  19. DETERMINATION OF CHLOROETHENES IN ENVIRONMENTAL BIOLOGICAL SAMPLES USING GAS CHROMATOGRAPHY COUPLED WITH SOLID PHASE MICRO EXTRACTION

    EPA Science Inventory

    An analytical method has been developed to determine the chloroethene series, tetrachloroethene (PCE), trichloroethene (TCE),cisdichloroethene (cis-DCE) andtransdichloroethene (trans-DCE) in environmental biotreatment studies using gas chromatography coupled with a solid phase mi...

  20. Processes forming Gas, Tar, and Coke in Cellulose Gasification from Gas-Phase Reactions of Levoglucosan as Intermediate.

    PubMed

    Fukutome, Asuka; Kawamoto, Haruo; Saka, Shiro

    2015-07-08

    The gas-phase pyrolysis of levoglucosan (LG), the major intermediate species during cellulose gasification, was studied experimentally over the temperature range of 400-900 °C. Gaseous LG did not produce any dehydration products, which include coke, furans, and aromatic substances, although these are characteristic products of the pyrolysis of molten LG. Alternatively, at >500 °C, gaseous LG produced only fragmentation products, such as noncondensable gases and condensable C1 -C3 fragments, as intermediates during noncondensable gas formation. Therefore, it was determined that secondary reactions of gaseous LG can result in the clean (tar- and coke-free) gasification of cellulose. Cooling of the remaining LG in the gas phase caused coke formation by the transition of the LG to the molten state. The molecular mechanisms that govern the gas- and molten-phase reactions of LG are discussed in terms of the acid catalyst effect of intermolecular hydrogen bonding to promote the molten-phase dehydration reactions.

  1. Detection Of Gas-Phase Polymerization in SiH4 And GeH4

    NASA Technical Reports Server (NTRS)

    Shing, Yuh-Han; Perry, Joseph W.; Allevato, Camillo E.

    1990-01-01

    Inelastic scattering of laser light found to indicate onset of gas-phase polymerization in plasma-enhanced chemical-vapor deposition (PECVD) of photoconductive amorphous hydrogenated silicon/germanium alloy (a-SiGe:H) film. In PECVD process, film deposited from radio-frequency glow-discharge plasma of silane (SiH4) and germane (GeH4) diluted with hydrogen. Gas-phase polymerization undesirable because it causes formation of particulates and defective films.

  2. An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

    NASA Technical Reports Server (NTRS)

    Koontz, Steven L.; Davis, Dennis D.; Hansen, Merrill

    1988-01-01

    A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

  3. Gas-Phase Molecular Dynamics: High Resolution Spectroscopy and Collision Dynamics of Transient Species

    SciTech Connect

    Hall,G.E.; Sears, T.J.

    2009-04-03

    This research is carried out as part of the Gas-Phase Molecular Dynamics program in the Chemistry Department at Brookhaven National Laboratory. High-resolution spectroscopy, augmented by theoretical and computational methods, is used to investigate the structure and collision dynamics of chemical intermediates in the elementary gas-phase reactions involved in combustion chemistry. Applications and methods development are equally important experimental components of this work.

  4. Double phase (liquid/gas) xenon scintillation detector for WIMPs direct search

    NASA Astrophysics Data System (ADS)

    Yamashita, M.; Doke, T.; Kikuchi, J.; Suzuki, S.

    2003-10-01

    A double phase (liquid/gas) xenon prototype detector of a 0.3 l active volume for WIMPs direct search has been constructed and tested. Proportional scintillation signals are observed by a multi-wire anode mounted in gas phase after ionization electrons drifted successfully long distance in liquid xenon. Both direct and proportional scintillation were used to discriminate electron recoil from nuclear recoil. Basic performances of the detector and the rejection efficiency of background gamma rays were demonstrated.

  5. Theory and Computing of Gas Phase Chemical Reactions: From Exact Quantum to Approximates Dynamical Treatments

    DTIC Science & Technology

    2006-02-08

    Phys. 110, 5526 (1999); Chem. Phys. 242, 341(1999). [51] R. M. Dreizler and E. K. U. Gross, Density Functional Theory (Springer Verlag, Berlin, 1990...the right hand side member of expression 3 can be derived from the square modulus of the S matrix Theory and Computing of Gas Phase Chemical...deal at the same time with different terms of the electronic functions manifolds (15). In these approaches the Theory and Computing of Gas Phase

  6. Gas-Phase Molecular Dynamics: High Resolution Spectroscopy and Collision Dynamics of Transient Species

    SciTech Connect

    Hall, G.E.

    2011-05-31

    This research is carried out as part of the Gas-Phase Molecular Dynamics program in the Chemistry Department at Brookhaven National Laboratory. Chemical intermediates in the elementary gas-phase reactions involved in combustion chemistry are investigated by high resolution spectroscopic tools. Production, reaction, and energy transfer processes are investigated by transient, double resonance, polarization and saturation spectroscopies, with an emphasis on technique development and connection with theory, as well as specific molecular properties.

  7. Gas-Phase Molecular Dynamics: High Resolution Spectroscopy and Collision Dynamics of Transient Species

    SciTech Connect

    Hall G. E.; Goncharov, V.

    2012-05-29

    This research is carried out as part of the Gas-Phase Molecular Dynamics program in the Chemistry Department at Brookhaven National Laboratory. Chemical intermediates in the elementary gas-phase reactions involved in combustion chemistry are investigated by high resolution spectroscopic tools. Production, reaction, and energy transfer processes are investigated by transient, double resonance, polarization and saturation spectroscopies, with an emphasis on technique development and connection with theory, as well as specific molecular properties.

  8. On the role of ethenol in equilibrium gas-phase ethanal

    NASA Astrophysics Data System (ADS)

    Slanina, Zdeněk

    1984-03-01

    The ethenol content in gas-phase ethanal has been evaluated under equilibrium conditions within a broad temperature interval, and it has been shown that the content thresholds of 1% and 1% can be crossed at about 650 and 1000 K, respectively. At moderate and higher temperatures the presence of ethenol is manifested by contributions to thermodynamic functions of the equilibrium gas-phase ethanal which can be even higher than the usual anharmonicity and non-rigidity corrections.

  9. Constraining the Multi-Phase Gas Content of Galaxies in the Local Cosmic Web

    NASA Astrophysics Data System (ADS)

    Stark, David; Kannappan, S. J.; Wei, L. H.; Baker, A. J.; Haynes, M. P.; Giovanelli, R.; Heitsch, F.; RESOLVE Team; ALFALFA Team

    2010-01-01

    The RESOLVE (REsolved Spectroscopy Of a Local VolumE) Survey is a census of gas, stars, and dark matter in 1500 galaxies down to dwarf-scale baryonic masses of 109 Msun, occupying a range of cluster, group, and filament environments in the local cosmic web. We discuss strategies to estimate the gas mass in HI, H2, and warmer phases. RESOLVE falls largely within the footprint of the ongoing ALFALFA survey, allowing us to acquire accurate HI data for much of the sample. Any missing HI masses will be estimated from color and environment data, based on trends calibrated using the ALFALFA data set. Initially, our constraints on the molecular gas component will be largely indirect, based on either AKARI FIR data or a new technique presented here that links CO-derived H2/HI ratios to stellar-mass normalized color gradients. We discuss additional strategies under development to better measure molecular gas and constrain the mass in warmer phases. In particular, we describe observational constraints on the nature of additional gas that is detected dynamically in a sample of very blue, gas-dominated galaxies, possibly representing a warm-hot phase or a low-metallicity molecular component. Obtaining a full gas census for the RESOLVE survey will allow us to model gas phase transitions and star formation, specifically examining how baryonic mass component ratios and conversion timescales depend on galaxy mass and environment.

  10. DEMONSTRATION BULLETIN: GAS-PHASE CHEMICAL REDUCTION - ECO LOGIC INTERNATIONAL, INC.

    EPA Science Inventory

    The patented Eco Logic Process employs a gas-phase reduction reaction of hydrogen with organic and chlorinated organic compounds at elevated temperatures to convert aqueous and oily hazardous contaminants into a hydrocarbon-rich gas product. After passing through a scrubber, the ...

  11. Formation of complex organic molecules in cold objects: the role of gas-phase reactions

    NASA Astrophysics Data System (ADS)

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-04-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

  12. Microgravity nucleation and particle coagulation experiments support

    NASA Technical Reports Server (NTRS)

    Lilleleht, L. U.; Lass, T. J.

    1987-01-01

    A hollow sphere model is developed to predict the range of supersaturation ratio values for refractory metal vapors in a proposed experimental nucleation apparatus. Since the experiments are to be carried out in a microgravity environment, the model neglects the effects of convection and assumes that the only transfer of vapors through an inert gas atmosphere is by conduction and molecular diffusion. A consistent set of physical properties data is assembled for the various candidate metals and inert ambient gases expected to be used in the nucleation experiments. Transient partial pressure profiles are computed for the diffusing refractory species for two possible temperature distributions. The supersaturation ratio values from both candidate temperature profiles are compared with previously obtained experimetnal data on a silver-hydrogen system. The model is used to simulate the diffusion of magnesium vapor through argon and other inert gas atmospheres over ranges of initial and boundary conditions. These results identify different combinations of design and operating parameters which are liekly to produce supersaturation ratio values high enough to induce homogeneous nucleation in the apparatus being designed for the microgravity nucleation experiments.

  13. Ceramic stationary gas turbine development. Final report, Phase 1

    SciTech Connect

    1994-09-01

    This report summarizes work performed by Solar Turbines Inc. and its subcontractors during the period September 25, 1992 through April 30, 1993. The objective of the work is to improve the performance of stationary gas turbines in cogeneration through implementation of selected ceramic components.

  14. Selective transport of amino acids into the gas phase: driving forces for amino acid solubilization in gas-phase reverse micelles.

    PubMed

    Fang, Yigang; Bennett, Andrew; Liu, Jianbo

    2011-01-28

    We report a study on encapsulation of various amino acids into gas-phase sodium bis(2-ethylhexyl) sulfosuccinate (NaAOT) reverse micelles, using electrospray ionization guided-ion-beam tandem mass spectrometry. Collision-induced dissociation of mass-selected reverse micellar ions with Xe was performed to probe structures of gas-phase micellar assemblies, identify solute-surfactant interactions, and determine preferential incorporation sites of amino acids. Integration into gas-phase reverse micelles depends upon amino acid hydrophobicity and charge state. For examples, glycine and protonated amino acids (such as protonated tryptophan) are encapsulated within the micellar core via electrostatic interactions; while neutral tryptophan is adsorbed in the surfactant layer. As verified using model polar hydrophobic compounds, the hydrophobic effect and solute-interface hydrogen-bonding do not provide sufficient driving force needed for interfacial solubilization of neutral tryptophan. Neutral tryptophan, with a zwitterionic structure, is intercalated at the micellar interface between surfactant molecules through complementary effects of electrostatic interactions between tryptophan backbone and AOT polar heads, and hydrophobic interactions between tryptophan side chain and AOT alkyl tails. Protonation of tryptophan could significantly improve its incorporation capacity into gas-phase reverse micelles, and displace its incorporation site from the micellar interfacial zone to the core; protonation of glycine, on the other hand, has little effect on its encapsulation capacity. Another interesting observation is that amino acids of different isoelectric points could be selectively encapsulated into, and transported by, reverse micelles from solution to the gas phase, based upon their competition for protonation and subsequent encapsulation within the micellar core.

  15. Nonlinear Acoustical Assessment of Precipitate Nucleation

    NASA Technical Reports Server (NTRS)

    Cantrell, John H.; Yost, William T.

    2004-01-01

    The purpose of the present work is to show that measurements of the acoustic nonlinearity parameter in heat treatable alloys as a function of heat treatment time can provide quantitative information about the kinetics of precipitate nucleation and growth in such alloys. Generally, information on the kinetics of phase transformations is obtained from time-sequenced electron microscopical examination and differential scanning microcalorimetry. The present nonlinear acoustical assessment of precipitation kinetics is based on the development of a multiparameter analytical model of the effects on the nonlinearity parameter of precipitate nucleation and growth in the alloy system. A nonlinear curve fit of the model equation to the experimental data is then used to extract the kinetic parameters related to the nucleation and growth of the targeted precipitate. The analytical model and curve fit is applied to the assessment of S' precipitation in aluminum alloy 2024 during artificial aging from the T4 to the T6 temper.

  16. Improved thermodynamic analysis of gas reactions for compound semiconductor growth by vapor-phase epitaxy

    NASA Astrophysics Data System (ADS)

    Inatomi, Yuya; Kangawa, Yoshihiro; Kakimoto, Koichi; Koukitu, Akinori

    2017-03-01

    An improved thermodynamic analysis method for vapor-phase epitaxy is proposed. In the conventional method, the mass-balance constraint equations are expressed in terms of variations in partial pressure. Although the conventional method is appropriate for gas–solid reactions occurring near the growth surface, it is not suitable for gas reactions that involve changes in the number of gas molecules. We reconsider the constraint equations in order to predict the effect of gas reactions on semiconductor growth processes. To demonstrate the feasibility of the improved method, the growth process of group-III nitrides by metalorganic vapor-phase epitaxy has been investigated.

  17. Nonequilibrium Features of the Nuclear Liquid-Gas Phase Transition

    NASA Astrophysics Data System (ADS)

    Zwieglinski, B.; Odeh, T.; Gross, C.; Schwarz, C.; Bassini, R.; Begemann-Blaich, M.; Blaich, T.; Emling, H.; Ferrero, A.; Fritz, S.; Gaff, S. J.; Imme, G.; Iori, I.; Kleinevoss, U.; Kunde, G. J.; Kunze, W. D.; Lindenstruth, V.; Lynen, U.; Mahi, M.; Moroni, A.; Moehlenkamp, T.; Mueller, W. F. J.; Ocker, B.; Pochodzalla, J.; Raciti, G.; Rubehn, Th.; Sann, H.; Schnittker, M.; Schuettauf, A.; Seidel, W.; Serfling, V.; Stroth, J.; Trautmann, W.; Trzcinski, A.; Verde, G.; Woerner, A.; Xi, H.; Zude, E.

    1999-03-01

    Energy spectra of protons emitted by the target residue in Au + Au collisions at 1 GeV/u were measured for different excitation energy bins. They reveal two components with different slopes attributed to preequilibrium and equilibrium emission. The relative contribution of the latter decreases rapidly with excitation energy, so that its presence becomes not apparent for the highest energy bins. It is argued therefore, that equilibrium may not be reached on the gas branch of the caloric curve.

  18. Gas distribution equipment in hydrogen service - Phase II

    NASA Technical Reports Server (NTRS)

    Jasionowski, W. J.; Huang, H. D.

    1980-01-01

    The hydrogen permeability of three different types of commercially available natural gas polyethylene pipes was determined. Ring tensile tests were conducted on permeability-exposed and as-received samples. Hydrogen-methane leakage experiments were also performed. The results show no selective leakage of hydrogen via Poiseuille, turbulent, or orifice flow (through leaks) on the distribution of blends of hydrogen and methane. The data collected show that the polyethylene pipe is 4 to 6 times more permeable to hydrogen than to methane.

  19. An indirect method of measuring gas- and particulate-phase velocities of shock-induced dusty-gas flows

    NASA Astrophysics Data System (ADS)

    Gottlieb, James J.

    1992-03-01

    A method of indirectly measuring the temporally varying velocities of both the particulate and gas phases in the nonequilibrium region of a shock wave moving at constant speed in a dusty-gas mixture is described. This method is implemented by using experimental data from shock-induced air flows containing glass beads 40 microns in diameter in a dusty-gas shock-tube facility featuring a large horizontal channel 197 mm high by 76 mm wide with a special dust-injection device. Simultaneous measurements of the shock-front speed with time-of-arrival gauges, particulate concentration by light extinctiometry, and combined particulate concentration and gas density by beta-ray absorption are used in conjunction with two mass conservation laws to provide these indirect two-phase velocity measurements. Direct measurements of the particulate-phase velocity by laser-Doppler velocimetry are also presented for comparison, and the capability of the indirect velocity-measurement method is assessed.

  20. ANALYSIS OF A GAS-PHASE PARTITIONING TRACER TEST CONDUCTED THROUGH FRACTURED MEDIA

    EPA Science Inventory

    The gas-phase partitioning tracer method was used to estimate non-aqueous phase liquid (NAPL), water, and air saturations in the vadose zone at a chlorinated-solvent contaminated field site in Tucson, AZ. The tracer test was conducted in a fractured clay system that is the confin...

  1. Two parametric flow measurement in gas-liquid two-phase flow

    NASA Astrophysics Data System (ADS)

    Chen, Z.; Chen, C.; Xu, Y.; Zhao, Z.

    The importance and current development of two parametric measurement during two-phase flow are briefly reviewed in this paper. Gas-liquid two-phase two parametric metering experiments were conducted by using an oval gear meter and a sharp edged orifice mounted in series in a horizontal pipe. Compressed air and water were used as gas and liquid phases respectively. The correlations, which can be used to predict the total flow rate and volumetric quality of two-phase flow or volumetric flow rate of each phase, have also been proposed in this paper. Comparison of the calculated values of flow rate of each phase from the correlations with the test data showed that the root mean square fractional deviation for gas flow rate is 2.9 percent and for liquid flow rate 4.4 percent. The method proposed in this paper can be used to measure the gas and liquid flow rate in two-phase flow region without having to separate the phases.

  2. Molecular recognition properties of tartrates and metal-tartrates in solution and gas phase.

    PubMed

    Wijeratne, Aruna B; Schug, Kevin A

    2009-05-01

    Solution phase and gas phase chiral molecular recognition properties of tartrates (salts or esters of tartaric acid) and metal tartrates (binuclear tartrato(4-)-metal-bridged complexes) are reviewed in conjunction with their applications in enantiomeric separation science and their mass spectrometric chiral discrimination properties.

  3. Gas-liquid phase separation in oppositely charged colloids: stability and interfacial tension.

    PubMed

    Fortini, Andrea; Hynninen, Antti-Pekka; Dijkstra, Marjolein

    2006-09-07

    We study the phase behavior and the interfacial tension of the screened Coulomb (Yukawa) restricted primitive model (YRPM) of oppositely charged hard spheres with diameter sigma using Monte Carlo simulations. We determine the gas-liquid and gas-solid phase transitions using free energy calculations and grand-canonical Monte Carlo simulations for varying inverse Debye screening length kappa. We find that the gas-liquid phase separation is stable for kappasigmagas-liquid interfacial tension using grand-canonical Monte Carlo simulations. The interfacial tension decreases upon increasing the range of the interaction. In particular, we find that simple scaling can be used to relate the interfacial tension of the YRPM to that of the restricted primitive model, where particles interact with bare Coulomb interactions.

  4. Influence of gas phase equilibria on the chemical vapor deposition of graphene.

    PubMed

    Lewis, Amanda M; Derby, Brian; Kinloch, Ian A

    2013-04-23

    We have investigated the influence of gas phase chemistry on the chemical vapor deposition of graphene in a hot wall reactor. A new extended parameter space for graphene growth was defined through literature review and experimentation at low pressures (≥0.001 mbar). The deposited films were characterized by scanning electron microscopy, Raman spectroscopy, and dark field optical microscopy, with the latter showing promise as a rapid and nondestructive characterization technique for graphene films. The equilibrium gas compositions have been calculated across this parameter space. Correlations between the graphene films grown and prevalent species in the equilibrium gas phase revealed that deposition conditions associated with a high acetylene equilibrium concentration lead to good quality graphene deposition, and conditions that stabilize large hydrocarbon molecules in the gas phase result in films with multiple defects. The transition between lobed and hexagonal graphene islands was found to be linked to the concentration of the monatomic hydrogen radical, with low concentrations associated with hexagonal islands.

  5. Analysis of volatile phase transport in soils using natural radon gas as a tracer

    SciTech Connect

    Chen, C.; Thomas, D.M.

    1992-12-31

    We have conducted a field study of soil gas transport processes using radon gas as a naturally occurring tracer. The .experiment monitored soil gas radon activity, soil moisture, and soil temperature at three depths in the shallow soil column; barometric pressure, rainfall and wind speed were monitored at the soil surface. Linear and multiple regression analysis of the data sets has shown that the gas phase radon activities under natural environmental conditions are influenced by soil moisture content, barometric pressure variations, soil temperature and soil structure. The effect of wind speed on subsurface radon activities under our field conditions has not been demonstrated.

  6. Analysis of volatile phase transport in soils using natural radon gas as a tracer

    SciTech Connect

    Chen, C.; Thomas, D.M.

    1992-01-01

    We have conducted a field study of soil gas transport processes using radon gas as a naturally occurring tracer. The .experiment monitored soil gas radon activity, soil moisture, and soil temperature at three depths in the shallow soil column; barometric pressure, rainfall and wind speed were monitored at the soil surface. Linear and multiple regression analysis of the data sets has shown that the gas phase radon activities under natural environmental conditions are influenced by soil moisture content, barometric pressure variations, soil temperature and soil structure. The effect of wind speed on subsurface radon activities under our field conditions has not been demonstrated.

  7. Evolution of natural gas composition: Predictive multi-phase reaction-transport modeling

    SciTech Connect

    Ortoleva, P.J.; Chang, K.A.; Maxwell, J.M.

    1995-12-31

    A computational modeling approach is used to investigate reaction and transport processes affecting natural gas composition over geological time. Three basic stages are integrated -- gas generation from organic solids or liquids, interactions during source rock expulsion to the reservoir and reactions within the reservoir. Multi-phase dynamics is handled by solving the fully coupled problem of phase-to-phase transfer, intra-phase organic and inorganic reactions and redox and other reactions between fluid phase molecules and minerals. Effects of capillarity and relative permeability are accounted for. Correlations will be determined between gas composition, temperature history, the mineralogy of rocks with which the gas was in contact and the composition of source organic phases. Questions of H{sub 2}S scavenging by oxidizing minerals and the production or removal of CO{sub 2} are focused upon. Our three spatial dimensional, reaction-transport simulation approach has great promise for testing general concepts and as a practical tool for the exploration and production of natural gas.

  8. Liquid-gas phase transitions in a multicomponent nuclear system with Coulomb and surface effects

    SciTech Connect

    Lee, S. J.; Mekjian, A. Z.

    2001-04-01

    The liquid-gas phase transition is studied in a multicomponent nuclear system using a local Skyrme interaction with Coulomb and surface effects. Some features are qualitatively the same as the results of Mu''ller and Serot where a relativistic mean field was used without Coulomb and surface effects. Surface tension brings the coexistence binodal surface to lower pressure. The Coulomb interaction makes the binodal surface smaller and causes another pair of binodal points at low pressure and large proton fraction with fewer protons in the liquid phase and more protons in the gas phase.

  9. Gas phase condensation of superparamagnetic iron oxide-silica nanoparticles - control of the intraparticle phase distribution

    NASA Astrophysics Data System (ADS)

    Stötzel, C.; Kurland, H.-D.; Grabow, J.; Müller, F. A.

    2015-04-01

    Spherical, softly agglomerated and superparamagnetic nanoparticles (NPs) consisting of maghemite (γ-Fe2O3) and amorphous silica (SiO2) were prepared by CO2 laser co-vaporization (CoLAVA) of hematite powder (α-Fe2O3) and quartz sand (SiO2). The α-Fe2O3 portion of the homogeneous starting mixtures was gradually increased (15 mass%-95 mass%). It was found that (i) with increasing iron oxide content the NPs' morphology changes from a nanoscale SiO2 matrix with multiple γ-Fe2O3 inclusions to Janus NPs consisting of a γ-Fe2O3 and a SiO2 hemisphere to γ-Fe2O3 NPs each carrying one small SiO2 lens on its surface, (ii) the multiple γ-Fe2O3 inclusions accumulate at the NPs' inner surfaces, and (iii) all composite NPs are covered by a thin layer of amorphous SiO2. These morphological characteristics are attributed to (i) the phase segregation of iron oxide and silica within the condensed Fe2O3-SiO2 droplets, (ii) the temperature gradient within these droplets which arises during rapid cooling in the CoLAVA process, and (iii) the significantly lower surface energy of silica when compared to iron oxide. The proposed growth mechanism of these Fe2O3-SiO2 composite NPs during gas phase condensation can be transferred to other systems comprising a glass-network former and another component that is insoluble in the regarding glass. Thus, our model will facilitate the development of novel functional composite NPs for applications in biomedicine, optics, electronics, or catalysis.Spherical, softly agglomerated and superparamagnetic nanoparticles (NPs) consisting of maghemite (γ-Fe2O3) and amorphous silica (SiO2) were prepared by CO2 laser co-vaporization (CoLAVA) of hematite powder (α-Fe2O3) and quartz sand (SiO2). The α-Fe2O3 portion of the homogeneous starting mixtures was gradually increased (15 mass%-95 mass%). It was found that (i) with increasing iron oxide content the NPs' morphology changes from a nanoscale SiO2 matrix with multiple γ-Fe2O3 inclusions to Janus NPs

  10. Nucleation theorems, the statistical mechanics of molecular clusters, and a revision of classical nucleation theory

    NASA Astrophysics Data System (ADS)

    Ford, I. J.

    1997-11-01

    The nucleation theorems relate the temperature and supersaturation dependence of the rate of nucleation of droplets from a metastable vapor phase to properties of the critical molecular cluster, the size that is approximately equally likely to grow or decay. They are derived here using a combination of statistical mechanics and cluster population dynamics, using an arbitrary model cluster definition. The theorems are employed to test the validity of the classical theory of homogeneous nucleation and its ``internally consistent'' form. It is found that the properties of the critical cluster for these models are incorrect, and it emerges that this occurs because the classical theory employs the free energy of a fixed droplet, rather than one free to take any position in space. Thus a term representing positional, or mixing, entropy is missing from the cluster free energy. A revised model is proposed, based on the capillarity approximation but with such a term included, and it is shown that it is fully consistent with the nucleation theorems. The model increases classical rates by factors of approximately 104-106. Other nucleation models should be tested for internal consistency using the same methods. Finally, the nucleation theorems are used to extract the excess internal energies of molecular clusters from experimental data for several substances.

  11. Two-phase turbine engines. [using gas-liquid mixture accelerated in nozzles

    NASA Technical Reports Server (NTRS)

    Elliott, D. G.; Hays, L. G.

    1976-01-01

    A description is given of a two-phase turbine which utilizes a uniform mixture of gas and liquid accelerated in nozzles of the types reported by Elliott and Weinberg (1968). The mixture acts directly on an axial flow or tangential impulse turbine or is separated into gas and liquid streams which operate separately on a gas turbine and a hydraulic turbine. The basic two-phase cycles are examined, taking into account working fluids, aspects of nozzle expansion, details of turbine cycle operation, and the effect of mixture ratio variation. Attention is also given to two-phase nozzle efficiency, two-phase turbine operating characteristics and efficiencies, separator turbines, and impulse turbine experiments.

  12. Deposition nucleation viewed as homogeneous or immersion freezing in pores and cavities

    NASA Astrophysics Data System (ADS)

    Marcolli, C.

    2013-06-01

    Heterogeneous ice nucleation is an important mechanism for the glaciation of mixed phase clouds and may also be relevant for cloud formation and dehydration at the cirrus cloud level. It is thought to proceed through different mechanisms, namely contact, condensation, immersion and deposition nucleation. Supposedly, deposition nucleation is the only pathway which does not involve liquid water but occurs by direct water vapor deposition on a surface. This study challenges this classical view by putting forward the hypothesis that what is called deposition nucleation is in fact homogeneous or immersion nucleation occurring in pores and cavities that may form between aggregated primary particles and fill with water at relative humidity RHw < 100% because of the inverse Kelvin effect. Evidence for this hypothesis of pore condensation and freezing (PCF) originates from a number of only loosely connected scientific areas. The prime example for PCF is ice nucleation in clay minerals and mineral dusts, for which the data base is best. Studies on freezing in confinement carried out on mesoporous silica materials such as SBA-15, SBA-16, MCM-41, zeolites and KIT have shown that homogeneous ice nucleation occurs abruptly at T=230-235 K in pores with diameters (D) of 3.5-4 nm or larger but only gradually at T=210-230 K in pores with D=2.5-3.5 nm. Melting temperatures in pores are depressed by an amount that can be described by the Gibbs-Thomson equation. Water adsorption isotherms of MCM-41 show that pores with D=3.5-4 nm fill with water at RHw = 56-60% in accordance with an inverse Kelvin effect. Water in such pores should freeze homogeneously for T < 235 K even before relative humidity with respect to ice (RHi) reaches ice saturation. Ice crystal growth by water vapor deposition from the gas phase is therefore expected to set in as soon as RHw > 100%. Pores with D > 7.5 nm fill with water at RHi > 100% for T < 235 K and are likely to freeze homogeneously as soon as they are

  13. Characterizing the correlations between local phase fractions of gas-liquid two-phase flow with wire-mesh sensor.

    PubMed

    Tan, C; Liu, W L; Dong, F

    2016-06-28

    Understanding of flow patterns and their transitions is significant to uncover the flow mechanics of two-phase flow. The local phase distribution and its fluctuations contain rich information regarding the flow structures. A wire-mesh sensor (WMS) was used to study the local phase fluctuations of horizontal gas-liquid two-phase flow, which was verified through comparing the reconstructed three-dimensional flow structure with photographs taken during the experiments. Each crossing point of the WMS is treated as a node, so the measurement on each node is the phase fraction in this local area. An undirected and unweighted flow pattern network was established based on connections that are formed by cross-correlating the time series of each node under different flow patterns. The structure of the flow pattern network reveals the relationship of the phase fluctuations at each node during flow pattern transition, which is then quantified by introducing the topological index of the complex network. The proposed analysis method using the WMS not only provides three-dimensional visualizations of the gas-liquid two-phase flow, but is also a thorough analysis for the structure of flow patterns and the characteristics of flow pattern transition. This article is part of the themed issue 'Supersensing through industrial process tomography'.

  14. Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

    SciTech Connect

    Lin, Manhua; Wang, Xiang; Yeom, Younghoon

    2015-03-17

    A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase id dispersed.

  15. Advanced H2-HCl Gas Dynamic Laser, Phase 2

    DTIC Science & Technology

    1976-01-01

    available in limited quantities on a special order basis, but synthesis is a straightforward and a well-known process. Three candidate propellant...oxidizers. Both oxides react significantly with HL and HC1 at high temperatures to yield H20 and other contaminants (Ca, Mg, CaOH , MgOH, CaCl, CaCl2, MgCip...quantities. However, synthesis of this compound is straight forward and results in a product of good yield and high purity. It is the best H„ gas generator

  16. Electron-beam synthesis of fuel in the gas phase

    NASA Astrophysics Data System (ADS)

    Ponomarev, A. V.; Holodkova, E. M.; Ershov, B. G.

    2012-09-01

    Electron-beam synthesis of liquid fuel from gaseous alkanes was upgraded for formation of conventional and alternative fuel from biomass or pyrolysis oil. Bio-feedstock conversion algorithm includes two consecutive stages: (1) initial macromolecules' transformation to low-molecular-weight intermediates; (2) transformation of these intermediates to stable fuel in gaseous alkanes' atmosphere. Radicals originated from alkanes participate in alkylation/hydrogenation of biomass intermediates. Chemical fixation of gaseous alkanes is amplified in the presence of biomass derivatives due to suppression of gas regeneration reactions, higher molar mass of reagents and lower volatility of radiolytic intermediates.

  17. Simulation of two-phase flow using lattice gas automata methods

    SciTech Connect

    Tsumaya, Akira; Ohashi, Hirotada; Akiyama, Mamoru

    1996-08-01

    Two-phase flow simulation has been primarily based on experimental data in the sense that constitutive relations necessary for solving fundamental equations are experimentally determined. This assures validity of simulation of two-phase flow within the experimental conditions, but it is difficult to predict the behavior of two-phase flow under extreme or complex conditions which occur, for example, in severe accidents of nuclear reactors. Lattice gas automaton (LGA) simulation has recently attracted attention as a method for numerical simulation of multi phase flow. The authors extend phase-separation LGA models and develop methods for two-phase flow simulation. First, they newly added a flow model to the immiscible lattice gas model and applied it to two-dimensional Poiseuille flow. They obtained a result looking like lubricated pipelining of crude oil with water. Also, considering the gravity effect, they introduced a buoyancy force into the liquid-gas model. As a result, they demonstrated that gas bubbles of various diameters rise and gradually coalesce each other turning into larger bubbles. Using these newly developed LGA models, they succeeded in simulating various flow patterns of two-phase flow.

  18. Analysis of Developing Gas/liquid Two-Phase Flows

    SciTech Connect

    Elena A. Tselishcheva; Michael Z. Podowski; Steven P. Antal; Donna Post Guillen; Matthias Beyer; Dirk Lucas

    2010-06-01

    The goal of this work is to develop a mechanistically based CFD model that can be used to simulate process equipment operating in the churn-turbulent regime. The simulations were performed using a state-of-the-art computational multiphase fluid dynamics code, NPHASE–CMFD [Antal et al,2000]. A complete four-field model, including the continuous liquid field and three dispersed gas fields representing bubbles of different sizes, was first carefully tested for numerical convergence and accuracy, and then used to reproduce the experimental results from the TOPFLOW test facility at Forschungszentrum Dresden-Rossendorf e.V. Institute of Safety Research [Prasser et al,2007]. Good progress has been made in simulating the churn-turbulent flows and comparison the NPHASE-CMFD simulations with TOPFLOW experimental data. The main objective of the paper is to demonstrate capability to predict the evolution of adiabatic churn-turbulent gas/liquid flows. The proposed modelling concept uses transport equations for the continuous liquid field and for dispersed bubble fields [Tselishcheva et al, 2009]. Along with closure laws based on interaction between bubbles and continuous liquid, the effect of height on air density has been included in the model. The figure below presents the developing flow results of the study, namely total void fraction at different axial locations along the TOPFLOW facility test section. The complete model description, as well as results of simulations and validation will be presented in the full paper.

  19. Genetic Algorithms and Nucleation in VIH-AIDS transition.

    NASA Astrophysics Data System (ADS)

    Barranon, Armando

    2003-03-01

    VIH to AIDS transition has been modeled via a genetic algorithm that uses boom-boom principle and where population evolution is simulated with a cellular automaton based on SIR model. VIH to AIDS transition is signed by nucleation of infected cells and low probability of infection are obtained for different mutation rates in agreement with clinical results. A power law is obtained with a critical exponent close to the critical exponent of cubic, spherical percolation, colossal magnetic resonance, Ising Model and liquid-gas phase transition in heavy ion collisions. Computations were carried out at UAM-A Supercomputing Lab and author acknowledges financial support from Division of CBI at UAM-A.

  20. Gas-phase and solution-phase polymerization of epoxides by Cr(salen) complexes: evidence for a dinuclear cationic mechanism.

    PubMed

    Schön, Eva; Zhang, Xiangyang; Zhou, Zhiping; Chisholm, Malcolm H; Chen, Peter

    2004-11-15

    The gas-phase reactions of a series of mass-selected mononuclear and dinuclear Cr(salen) complexes with propylene oxide suggest that the enhanced reactivity of the dinuclear complexes in gas-phase and in solution may derive from a dicationic mechanism in which the alkoxide chain is mu(2)-coordinated to two Lewis acidic metal centers. The double coordination is proposed to suppress backbiting, and hence chain-transfer in the gas-phase homopolymerization of epoxides.

  1. Multistep nucleation of nanocrystals in aqueous solution

    NASA Astrophysics Data System (ADS)

    Loh, N. Duane; Sen, Soumyo; Bosman, Michel; Tan, Shu Fen; Zhong, Jun; Nijhuis, Christian A.; Král, Petr; Matsudaira, Paul; Mirsaidov, Utkur

    2017-01-01

    The nucleation and growth of solids from solutions impacts many natural processes and is fundamental to applications in materials engineering and medicine. For a crystalline solid, the nucleus is a nanoscale cluster of ordered atoms that forms through mechanisms still poorly understood. In particular, it is unclear whether a nucleus forms spontaneously from solution via a single- or multiple-step process. Here, using in situ electron microscopy, we show how gold and silver nanocrystals nucleate from supersaturated aqueous solutions in three distinct steps: spinodal decomposition into solute-rich and solute-poor liquid phases, nucleation of amorphous nanoclusters within the metal-rich liquid phase, followed by crystallization of these amorphous clusters. Our ab initio calculations on gold nucleation suggest that these steps might be associated with strong gold-gold atom coupling and water-mediated metastable gold complexes. The understanding of intermediate steps in nuclei formation has important implications for the formation and growth of both crystalline and amorphous materials.

  2. Injection of highly supersaturated oxygen solutions without nucleation.

    PubMed

    Creech, J; Divino, V; Patterson, W; Zalesky, P J; Brennen, C E

    2002-12-01

    It is possible to inject highly supersaturated aqueous solutions of gas through a small capillary into an aqueous environment without the formation of significant gas bubbles. Such a technique has considerable potential therapeutic value in the treatment, for example, of heart attacks and strokes. The present paper is the second in a series (see Brereton et al. [1]) investigating the basic phenomenon behind this surprising effect. Recent experiments clearly demonstrate that the nucleation, when it does occur, results from heterogeneous nucleation on the interior surface of the distal end of the capillary. This paper describes the effects of the treatment of this interior surface on the nucleation processes and the results of high speed video observations of the phenomena. A heterogeneous nucleation model is presented which is in accord with the experimental observations.

  3. Cold flame on Biofilm - Transport of Plasma Chemistry from Gas to Liquid Phase

    NASA Astrophysics Data System (ADS)

    Kong, Michael

    2014-10-01

    One of the most active and fastest growing fields in low-temperature plasma science today is biological effects of gas plasmas and their translation in many challenges of societal importance such as healthcare, environment, agriculture, and nanoscale fabrication and synthesis. Using medicine as an example, there are already three FDA-approved plasma-based surgical procedures for tissue ablation and blood coagulation and at least five phase-II clinical trials on plasma-assisted wound healing therapies. A key driver for realizing the immense application potential of near room-temperature ambient pressure gas plasmas, commonly known as cold atmospheric plasmas or CAP, is to build a sizeable interdisciplinary knowledge base with which to unravel, optimize, and indeed design how reactive plasma species interact with cells and their key components such as protein and DNA. Whilst a logical objective, it is a formidable challenge not least since existing knowledge of gas discharges is largely in the gas-phase and therefore not directly applicable to cell-containing matters that are covered by or embedded in liquid (e.g. biofluid). Here, we study plasma inactivation of biofilms, a jelly-like structure that bacteria use to protect themselves and a major source of antimicrobial resistance. As 60--90% of biofilm is made of water, we develop a holistic model incorporating physics and chemistry in the upstream CAP-generating region, a plasma-exit region as a buffer for as-phase transport, and a downstream liquid region bordering the gas buffer region. A special model is developed to account for rapid chemical reactions accompanied the transport of gas-phase plasma species through the gas-liquid interface and for liquid-phase chemical reactions. Numerical simulation is used to illustrate how key reactive oxygen species (ROS) are transported into the liquid, and this is supported with experimental data of both biofilm inactivation using plasmas and electron spin spectroscopy (ESR

  4. Efficient and directed peptide bond formation in the gas phase via ion/ion reactions.

    PubMed

    McGee, William M; McLuckey, Scott A

    2014-01-28

    Amide linkages are among the most important chemical bonds in living systems, constituting the connections between amino acids in peptides and proteins. We demonstrate the controlled formation of amide bonds between amino acids or peptides in the gas phase using ion/ion reactions in a mass spectrometer. Individual amino acids or peptides can be prepared as reagents by (i) incorporating gas phase-labile protecting groups to silence otherwise reactive functional groups, such as the N terminus; (ii) converting the carboxyl groups to the active ester of N-hydroxysuccinimide; and (iii) incorporating a charge site. Protonation renders basic sites (nucleophiles) unreactive toward the N-hydroxysuccinimide ester reagents, resulting in sites with the greatest gas phase basicities being, in large part, unreactive. The N-terminal amines of most naturally occurring amino acids have lower gas phase basicities than the side chains of the basic amino acids (i.e., those of histidine, lysine, or arginine). Therefore, reagents may be directed to the N terminus of an existing "anchor" peptide to form an amide bond by protonating the anchor peptide's basic residues, while leaving the N-terminal amine unprotonated and therefore reactive. Reaction efficiencies of greater than 30% have been observed. We propose this method as a step toward the controlled synthesis of peptides in the gas phase.

  5. In Situ Environmental TEM in Imaging Gas and Liquid Phase Chemical Reactions for Materials Research.

    PubMed

    Wu, Jianbo; Shan, Hao; Chen, Wenlong; Gu, Xin; Tao, Peng; Song, Chengyi; Shang, Wen; Deng, Tao

    2016-11-01

    Gas and liquid phase chemical reactions cover a broad range of research areas in materials science and engineering, including the synthesis of nanomaterials and application of nanomaterials, for example, in the areas of sensing, energy storage and conversion, catalysis, and bio-related applications. Environmental transmission electron microscopy (ETEM) provides a unique opportunity for monitoring gas and liquid phase reactions because it enables the observation of those reactions at the ultra-high spatial resolution, which is not achievable through other techniques. Here, the fundamental science and technology developments of gas and liquid phase TEM that facilitate the mechanistic study of the gas and liquid phase chemical reactions are discussed. Combined with other characterization tools integrated in TEM, unprecedented material behaviors and reaction mechanisms are observed through the use of the in situ gas and liquid phase TEM. These observations and also the recent applications in this emerging area are described. The current challenges in the imaging process are also discussed, including the imaging speed, imaging resolution, and data management.

  6. Effect of additives on gas-phase catalysis with immobilised Thermoanaerobacter species alcohol dehydrogenase (ADH T).

    PubMed

    Trivedi, A H; Spiess, A C; Daussmann, T; Büchs, J

    2006-07-01

    This paper presents a strategy for preparing an efficient immobilised alcohol dehydrogenase preparation for a gas-phase reaction. The effects of additives such as buffers and sucrose on the immobilisation efficiency (residual activity and protein loading) and on the gas-phase reaction efficiency (initial reaction rate and half-life) of Thermoanaerobacter sp. alcohol dehydrogenase were studied. The reduction of acetophenone to 1-phenylethanol under in situ cofactor regeneration using isopropanol as co-substrate was used as a model reaction at fixed reaction conditions (temperature and thermodynamic activities). A strongly enhanced thermostability of the enzyme in the gas-phase reaction was achieved when the enzyme was immobilised with 50 mM phosphate buffer (pH 7) containing sucrose five times the protein amount (on weight/weight basis). This resulted in a remarkable productivity of 200 g L(-1) day(-1) even at non-optimised reaction conditions. The interaction of additives with the enzyme and water affects the immobilisation and gas-phase efficiencies of the enzyme. However, it was not possible to predict the effect of additives on the gas-phase reaction efficiency even after knowing their effect on the immobilisation efficiency.

  7. Gas-phase chemistry of element 114, flerovium

    NASA Astrophysics Data System (ADS)

    Yakushev, Alexander; Eichler, Robert

    2016-12-01

    Element 114 was discovered in 2000 by the Dubna-Livermore collaboration, and in 2012 it was named flerovium. It belongs to the group 14 of the periodic table of elements. A strong relativistic stabilisation of the valence shell 7s27p is expected due to the orbital splitting and the contraction not only of the 7s2 but also of the spherical 7p closed subshell, resulting in the enhanced volatility and inertness. Flerovium was studied chemically by gas-solid chromatography upon its adsorption on a gold surface. Two experimental results on Fl chemistry have been published so far. Based on observation of three atoms, a weak interaction of flerovium with gold was suggested in the first study. Authors of the second study concluded on the metallic character after the observation of two Fl atoms deposited on gold at room temperature.

  8. Air-sea transfer of gas phase controlled compounds

    NASA Astrophysics Data System (ADS)

    Yang, M.; Bell, T. G.; Blomquist, B. W.; Fairall, C. W.; Brooks, I. M.; Nightingale, P. D.

    2016-05-01

    Gases in the atmosphere/ocean have solubility that spans several orders of magnitude. Resistance in the molecular sublayer on the waterside limits the air-sea exchange of sparingly soluble gases such as SF6 and CO2. In contrast, both aerodynamic and molecular diffusive resistances on the airside limit the exchange of highly soluble gases (as well as heat). Here we present direct measurements of air-sea methanol and acetone transfer from two open cruises: the Atlantic Meridional Transect in 2012 and the High Wind Gas Exchange Study in 2013. The transfer of the highly soluble methanol is essentially completely airside controlled, while the less soluble acetone is subject to both airside and waterside resistances. Both compounds were measured concurrently using a proton-transfer-reaction mass spectrometer, with their fluxes quantified by the eddy covariance method. Up to a wind speed of 15 m s-1, observed air-sea transfer velocities of these two gases are largely consistent with the expected near linear wind speed dependence. Measured acetone transfer velocity is ∼30% lower than that of methanol, which is primarily due to the lower solubility of acetone. From this difference we estimate the “zero bubble” waterside transfer velocity, which agrees fairly well with interfacial gas transfer velocities predicted by the COARE model. At wind speeds above 15 m s-1, the transfer velocities of both compounds are lower than expected in the mean. Air-sea transfer of sensible heat (also airside controlled) also appears to be reduced at wind speeds over 20 m s-1. During these conditions, large waves and abundant whitecaps generate large amounts of sea spray, which is predicted to alter heat transfer and could also affect the air-sea exchange of soluble trace gases. We make an order of magnitude estimate for the impacts of sea spray on air-sea methanol transfer.

  9. Nucleation in Synoptically Forced Cirrostratus

    NASA Technical Reports Server (NTRS)

    Lin, R.-F.; Starr, D. OC.; Reichardt, J.; DeMott, P. J.

    2004-01-01

    Formation and evolution of cirrostratus in response to weak, uniform and constant synoptic forcing is simulated using a one-dimensional numerical model with explicit microphysics, in which the particle size distribution in each grid box is fully resolved. A series of tests of the model response to nucleation modes (homogeneous-freezing-only/heterogeneous nucleation) and heterogeneous nucleation parameters are performed. In the case studied here, nucleation is first activated in the prescribed moist layer. A continuous cloud-top nucleation zone with a depth depending on the vertical humidity gradient and one of the nucleation parameters is developed afterward. For the heterogeneous nucleation cases, intermittent nucleation zones in the mid-upper portion of the cloud form where the relative humidity is on the rise, because existent ice crystals do not uptake excess water vapor efficiently, and ice nuclei (IN) are available. Vertical resolution as fine as 1 m is required for realistic simulation of the homogeneous-freezing-only scenario, while the model resolution requirement is more relaxed in the cases where heterogeneous nucleation dominates. Bulk microphysical and optical properties are evaluated and compared. Ice particle number flux divergence, which is due to the vertical gradient of the gravity-induced particle sedimentation, is constantly and rapidly changing the local ice number concentration, even in the nucleation zone. When the depth of the nucleation zone is shallow, particle number concentration decreases rapidly as ice particles grow and sediment away from the nucleation zone. When the depth of the nucleation zone is large, a region of high ice number concentration can be sustained. The depth of nucleation zone is an important parameter to be considered in parametric treatments of ice cloud generation.

  10. Strategies for the Gas Phase Modification of Cationized Arginine via Ion/ion Reactions.

    PubMed

    Prentice, Boone M; McGee, William M; Stutzman, John R; McLuckey, Scott A

    2013-11-15

    The gas phase acetylation of cationized arginine residues is demonstrated here using ion/ion reactions with sulfosuccinimidyl acetate (sulfo-NHS acetate) anions. Previous reports have demonstrated the gas phase modification of uncharged primary amine (the N-terminus and ε-amino side chain of lysine) and uncharged guanidine (the arginine side chain) functionalities via sulfo-NHS ester chemistry. Herein, charge-saturated arginine-containing peptides that contain sodium ions as the charge carriers, such as [ac-ARAAARA+2Na](2+), are shown to exhibit strong reactivity towards sulfo-NHS acetate whereas the protonated peptide analogues exhibit no such reactivity. This difference in reactivity is attributed to the lower sodium ion (as compared to proton) affinity of the arginine, which results in increased nucleophilicity of the cationized arginine guanidinium functionality. This increased nucleophilicity improves the arginine residue's reactivity towards sulfo-NHS esters and enhances the gas phase covalent modification pathway. No such dramatic increase in reactivity towards sulfo-NHS acetate has been observed upon sodium cationization of lysine amino acid residues, indicating that this behavior appears to be unique to arginine. The sodium cationization process is demonstrated in the condensed phase by simply spiking sodium chloride into the peptide sample solution and in the gas phase by a peptide-sodium cation exchange process with a sulfo-NHS acetate sodium-bound dimer cluster reagent. This methodology demonstrates several ways by which arginine can be covalently modified in the gas phase even when it is charged. Collisional activation of an acetylated arginine product can result in deguanidination of the residue, generating an ornithine. This gas phase ornithination exhibits similar site-specific fragmentation behavior to that observed with peptides ornithinated in solution and may represent a useful approach for inducing selective peptide cleavages.

  11. Numerical Computation of Flame Spread over a Thin Solid in Forced Concurrent Flow with Gas-phase Radiation

    NASA Technical Reports Server (NTRS)

    Jiang, Ching-Biau; T'ien, James S.

    1994-01-01

    Excerpts from a paper describing the numerical examination of concurrent-flow flame spread over a thin solid in purely forced flow with gas-phase radiation are presented. The computational model solves the two-dimensional, elliptic, steady, and laminar conservation equations for mass, momentum, energy, and chemical species. Gas-phase combustion is modeled via a one-step, second order finite rate Arrhenius reaction. Gas-phase radiation considering gray non-scattering medium is solved by a S-N discrete ordinates method. A simplified solid phase treatment assumes a zeroth order pyrolysis relation and includes radiative interaction between the surface and the gas phase.

  12. Microgravity nucleation and particle coagulation experiments support

    NASA Technical Reports Server (NTRS)

    Lilleleht, L. U.; Ferguson, F. T.; Stephens, J. R.

    1992-01-01

    Modifications to the nucleation apparatus suggested by our first microgravity flight campaign are complete. These included a complete 'repackaging' of the equipment into three racks along with an improved vapor spout shutter mechanism and additional thermocouples for gas temperature measurements. The 'repackaged' apparatus was used in two KC-135 campaigns: one during the week of June 3, 1991 consisting of two flights with Mg and two with Zn, and another series consisting of three flights with Zn during the week of September 23, 1991. Our effort then was focused on the analysis of these data, including further development of the mathematical models to generate the values of temperature and supersaturation at the observed points of nucleation. The efforts to apply Hale's Scaled Nucleation Theory to our experimental data have met with only limited success, most likely due to still inadequate temperature field determination. Work on the development of a preliminary particle collector system designed to capture particles from the region of nucleation and condensation, as well as from other parts of the chamber, are discussed.

  13. Chemical Ionization Mass Spectrometry Techniques for Measurements of Gas-Phase Ammonia

    NASA Astrophysics Data System (ADS)

    Nowak, J. B.; Neuman, J. A.; Yoshida, K.; Ryerson, T. B.; Huey, L. G.; Tanner, D. J.; Sjostedt, S. J.; Hubler, G.; Fortin, T. J.; Sueper, D. J.; Fehsenfeld, F. C.

    2005-12-01

    Chemical Ionization Mass Spectrometry (CIMS) can be a highly selective technique with fast time response for measuring many atmospheric trace gases (e.g., hydroxyl radical (OH), sulfuric acid (H2SO4), nitric acid (HNO3)). CIMS is highly versatile and has been used under a wide variety of conditions with many different ion-molecule detection schemes, even for detecting the same molecule. Because of its high proton affinity (853.6 kJ/mol), ammonia (NH3) is another ideal candidate for detection by CIMS. NH3, the dominant gas-phase base in the atmosphere, is a precursor of ammonium nitrate and ammonium sulfates, compounds that are important constituents of airborne fine particulate matter that affect air quality. The characterization of three NH3 CIMS instruments: an atmospheric pressure ionization instrument and a low-pressure flow tube reactor instrument, both utilizing protonated ethanol cluster ion chemistry, and a different low-pressure flow tube reactor instrument using protonated acetone dimer ion chemistry, is presented here. Instrument performance is assessed using ambient data from both ground-based and airborne field programs to examine detection sensitivity, background signal, and time response. Laboratory characterization of different inlet materials is also presented. All three instruments used PFA Teflon sampling inlets. Instrumental backgrounds were determined by scrubbing NH3 from ambient air using silicon phosphates that release phosphoric acid when exposed to ambient levels of humidity. Standard addition calibrations were performed using NH3 permeation devices whose output was determined via 185nm optical absorption. Regardless of CIMS technique or ion chemistry used, the observed detection sensitivities were all adequate for detecting changes in NH3 at the 10 pptv level on a 1s timescale. The time responses, defined by a 1/e2 decay in the calibration signal, ranged from 5s to 45s for the different sampling inlet configurations and are rapid enough

  14. Test plan for phase II of the Retained Gas Sampler system

    SciTech Connect

    Hey, B.E.

    1995-06-19

    The Retained Gas Sampler (RGS) system is being developed to permit characterization of the gas phase component of waste tank core samples. Several laboratory experiments have been conducted which have affirmed the proof-of-principle for separating the gas phase materials from waste tank material in a quantitative manner. However, experiments conducted thus far have dealt only with representative materials and simulated hardware mock-ups. This test plan deals with the operation and testing of actual devices in the hot cell environment. This test plan coves all aspects of the RGS system including: sampler load-in, extrusion, gas extraction, quantitative separation, sample collection, and quantitative analysis. Sample material used in this test plan will be waste tank simulants and will not be radioactive. The work environment, however, will be an operating hot cell facility and will have radioactive contaminated surfaces. Operation of the system will therefore require an official radiation work permit (RWP).

  15. Selective removal of ethylene, a deposit precursor, from a "dirty" synthesis gas stream via gas-phase partial oxidation.

    PubMed

    Villano, Stephanie M; Hoffmann, Jessica; Carstensen, Hans-Heinrich; Dean, Anthony M

    2010-06-17

    A fundamental issue in the gasification of biomass is that in addition to the desired synthesis gas product (a mixture of H(2) and CO), the gasifier effluent contains other undesirable products that need to be removed before any further downstream processing can occur. This work assesses the potential to selectively remove hydrocarbons from a synthesis gas stream via gas-phase partial oxidation. Specifically, the partial oxidation of methane-doped, ethylene-doped, and methane/ethylene-doped model synthesis gas mixtures has been investigated at ambient pressures over a temperature range of 760-910 degrees C and at residence times ranging from 0.4 to 2.4 s using a tubular flow reactor. For the synthesis gas mixtures that contain either methane or ethylene, the addition of oxygen substantially reduces the hydrocarbon concentration while only a small reduction in the hydrogen concentration is observed. For the synthesis gas mixtures doped with both methane and ethylene, the addition of oxygen preferentially removes ethylene while the concentrations of methane and hydrogen remain relatively unaffected. These results are compared to the predictions of a plug flow model using a reaction mechanism that is designed to describe the pyrolysis and partial oxidation of small hydrocarbon species. The agreement between the experimental observations and the model predictions is quite good, allowing us to explore the underlying chemistry that leads to the hydrocarbon selective oxidation. The implications of these results are briefly discussed in terms of using synthesis gas to produce liquid fuels and electrical power via a solid oxide fuel cell.

  16. Insights into diastereoisomeric characterization of tetrahydropyridazine amino acid derivatives: crystal structures and gas phase ion chemistry.

    PubMed

    Giorgi, Gianluca; Favi, Gianfranco; Attanasi, Orazio A

    2013-08-14

    Structural, conformational properties, and gas phase reactivity of two representative diastereoisomeric members of a series of α,α-tetrahydropyridazine amino acid derivatives have been investigated by using X-ray crystallography, tandem mass spectrometry and theoretical calculations. Both diastereoisomers show an unusual screw-boat conformation of the tetrahydropyridazine ring. While protonated molecules mainly decompose in the gas phase by loss of acetamide, the main reactivity of the [M + Na](+) species consists of loss of PhNCO followed by acetamide and it is strictly dependent upon the stereochemistry of the parent compound. The most stable energy minimized structures obtained by theoretical calculations are in full agreement with the experimental data and allowed us to rationalize the gas phase reaction pathways.

  17. Native biomolecules in the gas phase? The case of green fluorescent protein.

    PubMed

    Frankevich, Vladimir; Barylyuk, Konstantin; Chingin, Konstantin; Nieckarz, Robert; Zenobi, Renato

    2013-04-02

    Green fluorescent protein (GFP) was ionized by native electrospray ionization and trapped for many seconds in high vacuum, allowing fluorescence emission to be measured as a probe of its biological function, to answer the question whether GFP exists in the native form in the gas phase or not. Although a narrow charge-state distribution, a collision cross-section very close to that expected for correctly folded GFP, and a large stability against dissociation all support a near-native gas-phase structure, no fluorescence emission was observed. The loss of the native form is attributed to the absence of residual water in the gas phase, which normally stabilizes the para-hydroxybenzylidene imidazolone chromophore of GFP.

  18. Direct observation of the gas-phase Criegee intermediate (CH2OO).

    PubMed

    Taatjes, Craig A; Meloni, Giovanni; Selby, Talitha M; Trevitt, Adam J; Osborn, David L; Percival, Carl J; Shallcross, Dudley E

    2008-09-10

    Carbonyl oxide species play a key role in tropospheric oxidation of organic molecules and in low-temperature combustion processes. In the late 1940s, Criegee first postulated the participation of carbonyl oxides, now often called "Criegee intermediates," in ozonolysis of alkenes. However, despite decades of effort, no gas phase Criegee intermediate has before been observed. As a result, knowledge of gas phase carbonyl oxide reactions has heretofore been inferred by indirect means, with derived rate coefficients spanning orders of magnitude. We have directly detected the primary Criegee intermediate, formaldehyde oxide (CH2OO), in the chlorine-initiated gas-phase oxidation of dimethyl sulfoxide (DMSO). This work not only establishes that the Criegee intermediate is formed in DMSO oxidation also but opens the possibility for explicit kinetics studies on this critical atmospheric species.

  19. Device for two-dimensional gas-phase separation and characterization of ion mixtures

    DOEpatents

    Tang, Keqi; Shvartsburg, Alexandre A.; Smith, Richard D.

    2006-12-12

    The present invention relates to a device for separation and characterization of gas-phase ions. The device incorporates an ion source, a field asymmetric waveform ion mobility spectrometry (FAIMS) analyzer, an ion mobility spectrometry (IMS) drift tube, and an ion detector. In one aspect of the invention, FAIMS operating voltages are electrically floated on top of the IMS drift voltage. In the other aspect, the FAIMS/IMS interface is implemented employing an electrodynamic ion funnel, including in particular an hourglass ion funnel. The present invention improves the efficiency (peak capacity) and sensitivity of gas-phase separations; the online FAIMS/IMS coupling creates a fundamentally novel two-dimensional gas-phase separation technology with high peak capacity, specificity, and exceptional throughput.

  20. Metal-Organic Framework Thin Films as Stationary Phases in Microfabricated Gas-Chromatography Columns.

    SciTech Connect

    Read, Douglas; Sillerud, Colin Halliday

    2016-01-01

    The overarching goal of this project is to integrate Sandia's microfabricated gas-chromatography ( GC) columns with a stationary phase material that is capable of retaining high-volatility chemicals and permanent gases. The successful integration of such a material with GCs would dramatically expand the repertoire of detectable compounds for Sandia's various microanalysis systems. One such promising class of candidate materials is metal-organic frameworks (MOFs). In this report we detail our methods for controlled deposition of HKUST-1 MOF stationary phases within GC columns. We demonstrate: the chromatographic separation of natural gas; a method for determining MOF film thickness from chromatography alone; and the first-reported GC x GC separation of natural gas -- in general -- let alone for two disparate MOF stationary phases. In addition we determine the fundamental thermodynamic constant for mass sorption, the partition coefficient, for HKUST-1 and several light hydrocarbons and select toxic industrial chemicals.

  1. OMVPE growth and gas-phase reactions of AlGaN for UV emitters

    SciTech Connect

    Han, J.; Figiel, J.J.; Crawford, M.H.; Banas, M.A.; Bartram, M.E.; Biefeld, R.M.; Song, Y.K.; Nurmikko, A.V.

    1998-06-01

    Gas-phase parasitic reactions among TMG, TMA, and NH3, are investigated by monitoring of the growth rate/incorporation efficiency of GaN and AlN using an in-situ optical reflectometer. It is suggested that gas phase adduct (TMA: NH{sub 3}) reactions not only reduce the incorporation efficiency of TMA but also affect the incorporation behavior of TMGa. The observed phenomena can be explained by either a synergistic gas-phase scavenging effect or a surface site-blocking effect. Relatively low reactor pressures (30--50 Torr) are employed to grow an AlGaN/GaN QW p-n diode structure. The UV emission at 354 nm (FWHM {approximately} 6 nm) represents the first report of LED operation from an indium-free GaN QW diode.

  2. Abundant gas-phase H2O in absorption toward massive protostars

    NASA Astrophysics Data System (ADS)

    Boonman, A. M. S.; van Dishoeck, E. F.

    2003-06-01

    We present infrared spectra of gas-phase H2O around 6 mu m toward 12 deeply embedded massive protostars obtained with the Short Wavelength Spectrometer on board the Infrared Space Observatory (ISO). The nu2 ro-vibrational band has been detected toward 7 of the sources and the excitation temperatures indicate an origin in the warm gas at Tex>~ 250 K. Typical derived gas-phase H2O abundances are ~ 5*E-6-6*E-5, with the abundances increasing with the temperature of the warm gas. The inferred gas/solid ratios show a similar trend with temperature and suggest that grain-mantle evaporation is important. The increasing gas/solid ratio correlates with other indicators of increased temperatures. If the higher temperatures are due to a larger ratio of source luminosity to envelope mass, this makes gas-phase H2O a good evolutionary tracer. Comparison with chemical models shows that three different chemical processes, ice evaporation, high-T chemistry, and shocks, can reproduce the high inferred gas-phase H2O abundances. In a forthcoming paper each of these processes are investigated in more detail in comparison with data from the Long Wavelength Spectrometer on board ISO and the Submillimeter Wave Astronomy Satellite (SWAS). Comparison with existing SWAS data indicates that a jump in the H2O abundance is present and that the observed nu2 ro-vibrational band traces primarily the warm inner envelope. Based on observations with ISO, an ESA project with instruments funded by ESA Member States (especially the PI countries: France, Germany, the Netherlands and the United Kingdom) and with the participation of ISAS and NASA.

  3. Phase behavior and splitting analysis: An operational tool in gas transmission and distribution

    SciTech Connect

    Martinez A., F.F.; Infantini S., M.

    1998-12-31

    Most of the natural gas produced by Petroleos de Venezuela, S.A. (PDVSA) is associated gas that flows from the gathering systems to the processing plants, before it arrives at the transmission systems. Even if the gas transmission occurs after the necessary processing of the gas has been completed, condensation still happens in the transmission, regulating stations and/or distribution systems. The quantity of condensate will not only depend on composition, pressure and temperature, but also on the unequal splitting phenomenon that takes place at tee junctions in a network system. The splitting phenomenon determines the liquid distribution at the junction. This situation is more drastic when the processing plant is partially or totally shut down in a maintenance program. This work shows how the gas transmission and distribution engineer has to use the phase behavior and splitting analysis as an operational tool, in order to predict and prevent the presence of liquid in the system. Using process simulators, the phase behavior analysis is conducted to determine the bubble and dew point curve and to perform flash calculations at any pressure and temperature. Then, the operational pressure-temperature profile is over-plotted on the phase envelope diagram in order to evaluate the condensation possibility into the gas pipeline. Afterwards, the pressure and temperature drops in regulating stations are incorporated in the phase envelope diagram and the two-phase gas condensate study is completed. Finally, considering the concepts of the splitting phenomenon and the knowledge that it can really happen, the presence of liquid in particular customers can be explained and solved. Operational experiences are included to evaluate the methodology and to present the effectiveness of the results.

  4. Gas adsorption/absorption heat switch, phase 1

    NASA Technical Reports Server (NTRS)

    Chan, C. K.

    1987-01-01

    The service life and/or reliability of far-infrared sensors on surveillance satellites is presently limited by the cryocooler. The life and/or reliability, however, can be extended by using redundant cryocoolers. To reduce parasitic heat leak, each stage of the inactive redundant cryocooler must be thermally isolated from the optical system, while each stage of the active cryocooler must be thermally connected to the system. The thermal break or the thermal contact can be controlled by heat switches. Among different physical mechanisms for heat switching, mechanically activated heat switches tend to have low reliability and, furthermore, require a large contact force. Magnetoresistive heat switches are, except at very low temperatures, of very low efficiency. Heat switches operated by the heat pipe principle usually require a long response time. A sealed gas gap heat switch operated by an adsorption pump has no mechanical motion and should provide the reliability and long lifetime required in long-term space missions. Another potential application of a heat switch is the thermal isolation of the optical plane during decontamination.

  5. Gas-phase chemiluminescence and chemi-ionization

    SciTech Connect

    Fontijn, A.

    1985-01-01

    The phenomena of chemiluminescence (or more broadly chemi-excitation) and chemi-ionization have major similarities from a fundamental kinetic and dynamic point of view. However, since the former has primarily been investigated using optical spectroscopic techniques and the latter largely by mass spectroscopic (and other gaseous electronic) methods, the two phenomena have apparently never, explicitly been discussed together in one volume. In addition to a number of review articles on each individual subject, several meetings and books have had chemiluminescence and bioluminescence as their theme and those have been dominated by condensed phase work. On the other hand, chemi-ionization is often discussed in the contest of gaseous electronics, plasma chemistry and combustion. It is the goal of this book to present a more unified understanding of the two phenomena.

  6. Amphipols Outperform Dodecylmaltoside Micelles in Stabilizing Membrane Protein Structure in the Gas Phase

    PubMed Central

    2014-01-01

    Noncovalent mass spectrometry (MS) is emerging as an invaluable technique to probe the structure, interactions, and dynamics of membrane proteins (MPs). However, maintaining native-like MP conformations in the gas phase using detergent solubilized proteins is often challenging and may limit structural analysis. Amphipols, such as the well characterized A8-35, are alternative reagents able to maintain the solubility of MPs in detergent-free solution. In this work, the ability of A8-35 to retain the structural integrity of MPs for interrogation by electrospray ionization-ion mobility spectrometry-mass spectrometry (ESI-IMS-MS) is compared systematically with the commonly used detergent dodecylmaltoside. MPs from the two major structural classes were selected for analysis, including two β-barrel outer MPs, PagP and OmpT (20.2 and 33.5 kDa, respectively), and two α-helical proteins, Mhp1 and GalP (54.6 and 51.7 kDa, respectively). Evaluation of the rotationally averaged collision cross sections of the observed ions revealed that the native structures of detergent solubilized MPs were not always retained in the gas phase, with both collapsed and unfolded species being detected. In contrast, ESI-IMS-MS analysis of the amphipol solubilized MPs studied resulted in charge state distributions consistent with less gas phase induced unfolding, and the presence of lowly charged ions which exhibit collision cross sections comparable with those calculated from high resolution structural data. The data demonstrate that A8-35 can be more effective than dodecylmaltoside at maintaining native MP structure and interactions in the gas phase, permitting noncovalent ESI-IMS-MS analysis of MPs from the two major structural classes, while gas phase dissociation from dodecylmaltoside micelles leads to significant gas phase unfolding, especially for the α-helical MPs studied. PMID:25495802

  7. Probing the energetics of dissociation of carbonic anhydrase-ligand complexes in the gas phase.

    PubMed Central

    Gao, J; Wu, Q; Carbeck, J; Lei, Q P; Smith, R D; Whitesides, G M

    1999-01-01

    This paper describes the use of electrospray ionization-Fourier transform ion cyclotron mass spectrometry (ESI-FTICR-MS) to study the relative stabilities of noncovalent complexes of carbonic anhydrase II (CAII, EC 4.2.1.1) and benzenesulfonamide inhibitors in the gas phase. Sustained off-resonance irradiation collision-induced dissociation (SORI-CID) was used to determine the energetics of dissociation of these CAII-sulfonamide complexes in the gas phase. When two molecules of a benzenesulfonamide (1) were bound simultaneously to one molecule of CAII, one of them was found to exhibit significantly weaker binding (DeltaE50 = 0.4 V, where E50 is defined as the amplitude of sustained off-resonance irradiation when 50% of the protein-ligand complexes are dissociated). In solution, the benzenesulfonamide group coordinates as an anion to a Zn(II) ion bound at the active site of the enzyme. The gas phase stability of the complex with the weakly bound inhibitor was the same as that of the inhibitor complexed with apoCAII (i.e., CAII with the Zn(II) ion removed from the binding site). These results indicate that specific interactions between the sulfonamide group on the inhibitor and the Zn(II) ion on CAII were preserved in the gas phase. Experiments also showed a higher gas phase stability for the complex of para-NO2-benzenesulfonamide-CAII than that for ortho-NO2-benzenesulfonamide-CAII complex. This result further suggests that steric interactions of the inhibitors with the binding pocket of CAII parallel those in solution. Overall, these results are consistent with the hypothesis that CAII retains, at least partially, the structure of its binding pocket in the gas phase on the time scale (seconds to minutes) of the ESI-FTICR measurements. PMID:10354450

  8. Studies of cluster-assembled materials: From gas phase to condensed phase

    NASA Astrophysics Data System (ADS)

    Gao, Lin

    . After being mass gated in a reflectron equipped time-of-flight mass spectrometer (TOF-MS) and deposited onto TEM grids, the resultant specimens can be loaded onto high-resolution TEM investigation via electron diffraction. In conclusion, soft-landing of mass selected clusters has been shown to be a successful approach to obtain structural information on Zr-Met-Car cluster-assembled materials collected from the gas phase. TEM images indicate the richness of the morphologies associated with these cluster crystals. However, passivation methods are expected to be examined further to overcome the limited stabilities of these novel clusters. From this initial study, it's shown the promising opportunity to study other Met-Cars species and more cluster-based materials. Experimental results of reactions run with a solvothermal synthesis method obtained while searching for new Zr-C cluster assembled materials, are reported. One unexpected product in single crystal form was isolated and tentatively identified by X-ray diffraction to be [Zr6i O(OH)O12·2(Bu)4], with space group P2 1/n and lattice parameters of a = 12.44 A, b = 22.06 A, c = 18.40 A, alpha = 90°, beta = 105°, gamma = 90°, V = 4875 A3 and R 1 = 3.15% for the total observed data (I ≥ 2 sigma I) and oR2 = 2.82%. This novel hexanuclear Zr(IV)-oxo-hydroxide cluster anion may be the first member in polyoxometalates class with metal atoms from the IVB group and having Oh symmetry. Alternatively, it may be the first member in {[(Zr6Z)X 12]X6}m- class with halides replaced by oxo- and hydroxyl groups and with an increased oxidation state of Zr. It is predicted to bear application potentials directed by both families. This work could suggest a direction in which the preparation of Zr-C cluster-assembled materials in a liquid environment may be eventually fulfilled. 1,3-Bis(diethylphosphino)propane (depp) protected small gold clusters are studied via multiple techniques, including Electrospray Ionization Mass Spectrometry

  9. On the Ice Nucleation Spectrum

    NASA Technical Reports Server (NTRS)

    Barahona, D.

    2012-01-01

    This work presents a novel formulation of the ice nucleation spectrum, i.e. the function relating the ice crystal concentration to cloud formation conditions and aerosol properties. The new formulation is physically-based and explicitly accounts for the dependency of the ice crystal concentration on temperature, supersaturation, cooling rate, and particle size, surface area and composition. This is achieved by introducing the concepts of ice nucleation coefficient (the number of ice germs present in a particle) and nucleation probability dispersion function (the distribution of ice nucleation coefficients within the aerosol population). The new formulation is used to generate ice nucleation parameterizations for the homogeneous freezing of cloud droplets and the heterogeneous deposition ice nucleation on dust and soot ice nuclei. For homogeneous freezing, it was found that by increasing the dispersion in the droplet volume distribution the fraction of supercooled droplets in the population increases. For heterogeneous ice nucleation the new formulation consistently describes singular and stochastic behavior within a single framework. Using a fundamentally stochastic approach, both cooling rate independence and constancy of the ice nucleation fraction over time, features typically associated with singular behavior, were reproduced. Analysis of the temporal dependency of the ice nucleation spectrum suggested that experimental methods that measure the ice nucleation fraction over few seconds would tend to underestimate the ice nuclei concentration. It is shown that inferring the aerosol heterogeneous ice nucleation properties from measurements of the onset supersaturation and temperature may carry significant error as the variability in ice nucleation properties within the aerosol population is not accounted for. This work provides a simple and rigorous ice nucleation framework where theoretical predictions, laboratory measurements and field campaign data can be

  10. Plasma-produced phase-pure cuprous oxide nanowires for methane gas sensing

    SciTech Connect

    Cheng, Qijin Zhang, Fengyan; Yan, Wei; Randeniya, Lakshman; Ostrikov, Kostya

    2014-03-28

    Phase-selective synthesis of copper oxide nanowires is warranted by several applications, yet it remains challenging because of the narrow windows of the suitable temperature and precursor gas composition in thermal processes. Here, we report on the room-temperature synthesis of small-diameter, large-area, uniform, and phase-pure Cu{sub 2}O nanowires by exposing copper films to a custom-designed low-pressure, thermally non-equilibrium, high-density (typically, the electron number density is in the range of 10{sup 11}–10{sup 13} cm{sup −3}) inductively coupled plasmas. The mechanism of the plasma-enabled phase selectivity is proposed. The gas sensors based on the synthesized Cu{sub 2}O nanowires feature fast response and recovery for the low-temperature (∼140 °C) detection of methane gas in comparison with polycrystalline Cu{sub 2}O thin film-based gas sensors. Specifically, at a methane concentration of 4%, the response and the recovery times of the Cu{sub 2}O nanowire-based gas sensors are 125 and 147 s, respectively. The Cu{sub 2}O nanowire-based gas sensors have a potential for applications in the environmental monitoring, chemical industry, mining industry, and several other emerging areas.

  11. Direct Numerical Simulation of biomass pyrolysis and combustion with gas phase reactions

    NASA Astrophysics Data System (ADS)

    Awasthi, A.; Kuerten, J. G. M.; Geurts, B. J.

    2016-09-01

    We present Direct Numerical Simulation of biomass pyrolysis and combustion in a turbulent channel flow. The model includes simplified models for biomass pyrolysis and char combustion along with a model for particle tracking. The gas phase is modelled as a mixture of reacting gas species. The gas-particle interactions for mass, momentum, and energy exchange are included by two-way coupling terms. The effect of two-way coupling on the conversion time of biomass particles is found noticeable for particle volume fractions > 10-5. We also observe that at constant volume fraction the effect of two-way coupling increases as the particle size is reduced, due to the higher total heat exchange area in case of smaller particles. The inclusion of gas phase homogeneous reactions in the DNS model decreases the biomass pyrolysis time due to higher gas temperatures. In contrast, including gas phase reactions increases the combustion time of biomass due to the lower concentration of oxygen at the particle surface.

  12. Distribution of Organophosphate Esters between the Gas and Particle Phase-Model Predictions vs Measured Data.

    PubMed

    Sühring, Roxana; Wolschke, Hendrik; Diamond, Miriam L; Jantunen, Liisa M; Scheringer, Martin

    2016-07-05

    Gas-particle partitioning is one of the key factors that affect the environmental fate of semivolatile organic chemicals. Many organophosphate esters (OPEs) have been reported to primarily partition to particles in the atmosphere. However, because of the wide range of their physicochemical properties, it is unlikely that OPEs are mainly in the particle phase "as a class". We compared gas-particle partitioning predictions for 32 OPEs made by the commonly used OECD POV and LRTP Screening Tool ("the Tool") with the partitioning models of Junge-Pankow (J-P) and Harner-Bidleman (H-B), as well as recently measured data on OPE gas-particle partitioning. The results indicate that half of the tested OPEs partition into the gas phase. Partitioning into the gas phase seems to be determined by an octanol-air partition coefficient (log KOA) < 10 and a subcooled liquid vapor pressure (log PL) > -5 (PL in Pa), as well as the total suspended particle concentration (TSP) in the sampling area. The uncertainty of the physicochemical property data of the OPEs did not change this estimate. Furthermore, the predictions by the Tool, J-P- and H-B-models agreed with recently measured OPE gas-particle partitioning.

  13. Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multi-layer model ADCHAM

    NASA Astrophysics Data System (ADS)

    Roldin, P.; Eriksson, A. C.; Nordin, E. Z.; Hermansson, E.; Mogensen, D.; Rusanen, A.; Boy, M.; Swietlicki, E.; Svenningsson, B.; Zelenyuk, A.; Pagels, J.

    2014-01-01

    We have developed the novel Aerosol Dynamics, gas- and particle-phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas phase Master Chemical Mechanism version 3.2, an aerosol dynamics and particle phase chemistry module (which considers acid catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study: (1) the mass transfer limited uptake of ammonia (NH3) and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), (2) the slow and almost particle size independent evaporation of α-pinene secondary organic aerosol (SOA) particles, and (3) the influence of chamber wall effects on the observed SOA formation in smog chambers. ADCHAM is able to capture the observed α-pinene SOA mass increase in the presence of NH3(g). Organic salts of ammonium and carboxylic acids predominantly form during the early stage of SOA formation. These salts contribute substantially to the initial growth of the homogeneously nucleated particles. The model simulations of evaporating α-pinene SOA particles support the recent experimental findings that these particles have a semi-solid tar like amorphous phase state. ADCHAM is able to reproduce the main features of the observed slow evaporation rates if low-volatility and viscous oligomerized SOA material accumulates in the particle surface layer upon evaporation. The evaporation rate is mainly governed by the reversible decomposition of oligomers back to monomers. Finally, we demonstrate that the mass transfer limited uptake of condensable organic compounds onto wall deposited particles or directly onto the Teflon chamber walls of smog chambers can have profound influence on the

  14. Characterization of annular two-phase gas-liquid flows in microgravity

    NASA Astrophysics Data System (ADS)

    Bousman, W. Scott; McQuillen, John B.

    1994-08-01

    A series of two-phase gas-liquid flow experiments were developed to study annular flows in microgravity using the NASA Lewis Learjet. A test section was built to measure the liquid film thickness around the perimeter of the tube permitting the three dimensional nature of the gas-liquid interface to be observed. A second test section was used to measure the film thickness, pressure drop and wall shear stress in annular microgravity two-phase flows. Three liquids were studied to determine the effects of liquid viscosity and surface tension. The result of this study provide insight into the wave characteristics, pressure drop and droplet entrainment in microgravity annular flows.

  15. Study of Hind Limb Tissue Gas Phase Formation in Response to Suspended Adynamia and Hypokinesia

    NASA Technical Reports Server (NTRS)

    Butler, Bruce D.

    1996-01-01

    The purpose of this study was to investigate the hypothesis that reduced joint/muscle activity (hypo kinesia) as well as reduced or null loading of limbs (adynamia) in gravity would result in reduced decompression-induced gas phase and symptoms of decompression sickness (DCS). Finding a correlation between the two phenomena would correspond to the proposed reduction in tissue gas phase formation in astronauts undergoing decompression during extravehicular activity (EVA) in microgravity. The observation may further explain the reported low incidence of DCS in space.

  16. Gas-phase reactions in extraterrestrial environments: laboratory investigations by crossed molecular beams.

    PubMed

    Balucani, Nadia; Casavecchia, Piergiorgio

    2006-12-01

    We have investigated gas-phase reactions of N((2)D) with the most abundant hydrocarbons in the atmosphere of Titan by the crossed molecular beam technique. In all cases, molecular products containing a novel CN bond are formed, thus suggesting possible routes of formation of gas-phase nitriles in the atmosphere of Titan and primordial Earth. The same approach has been recently extended to the study of radical-radical reactions, such as the reaction of atomic oxygen with the CH(3) and C(3)H(5) radicals. Products other than those already considered in the modeling of planetary atmospheres and interstellar medium have been identified.

  17. Gas phase infrared spectra and corresponding DFT calculations of α, ω-diphenylpolyenes

    NASA Astrophysics Data System (ADS)

    Biemann, Lars; Braun, Michaela; Kleinermanns, Karl

    2010-01-01

    We present gas phase Fourier Transform Infrared (FTIR) spectra of the homologue series of α, ω-diphenylpolyenes consisting of trans- and cis-stilbene, diphenylbutadiene (DPB) and diphenylhexatriene (DPH) obtained by a fast thermal heating technique that enables vaporization without decomposition. Infrared marker bands for the cis-isomers of the polyenes have been identified by density functional calculations at the B3LYP/TZVP level of theory. The all trans isomers of DPB and DPH do not interconvert to the cis-isomers in the gas phase at 200 °C.

  18. Characterization of annular two-phase gas-liquid flows in microgravity

    NASA Technical Reports Server (NTRS)

    Bousman, W. Scott; Mcquillen, John B.

    1994-01-01

    A series of two-phase gas-liquid flow experiments were developed to study annular flows in microgravity using the NASA Lewis Learjet. A test section was built to measure the liquid film thickness around the perimeter of the tube permitting the three dimensional nature of the gas-liquid interface to be observed. A second test section was used to measure the film thickness, pressure drop and wall shear stress in annular microgravity two-phase flows. Three liquids were studied to determine the effects of liquid viscosity and surface tension. The result of this study provide insight into the wave characteristics, pressure drop and droplet entrainment in microgravity annular flows.

  19. A microcomputer-controlled gas phase microreactor system

    SciTech Connect

    Morris, R.M.

    1983-08-01

    Although automated reactors are effective tools for studying a single type of reaction or optimizing catalyst performance, they may not be well suited for exploratory research. These reactors generally have several shortcomings. First, they may have limited versatility since they are usually designed with a single application in mind. Second, computer systems used for process control and data acquisition are often expensive and complex, so that once they are set up for a given application, it is quite difficult to adapt them for another. Because of these restrictions, experimental reactors are often operated manually, requiring a full-time operator to monitor operations and acquire data. This is a greater problem in laboratories where projects are often short-term, and the costs of setting up an automated reactor may outweigh the benefits of automation. For an automated reactor to be cost-effective in such an environment, both reactor hardware and control software must be versatile enough that they can be easily modified and adapted for different experiments. An automated gas-flow microreactor has been designed and constructed which is both inexpensive and flexible. The reactor is capable of performing three different types of experiments, 1) continuous reagent feed with analysis of the product stream, 2) pulsed-flow experiments, and 3) temperature-programmed desorption (TPD) and reaction (TPR). Conversion of the reactor from one configuration to another requires less than one hour. Process control and data acquisition are performed using an Apple II Plus microcomputer (Apple Computer Corp., Cupertino, Calif.) and an ISAAC interface device (Cyborg Corp., Newton, Mass.).

  20. Crystallization and nucleation kinetics in volcanic systems

    NASA Astrophysics Data System (ADS)

    Agostini, C.; Fortunati, A.; Carroll, M. R.; Scaillet, B.; Landi, P.

    2011-12-01

    The main objective of this experimental study is to constrain and quantitatively model the complex solidification process that transforms a magma in a solid material. Of major interest are crystal nucleation and growth driven by isothermal decompression of hydrous magmas, and comparison with results from more abundant crystal growth/nucleation data obtained in isobaric cooling experiments. This research concerns two different volcanic systems, Pantelleria (peralkaline rhyolite) and Stromboli (basalt), to better understand how crystallization kinetics can affect different magma compositions. For Stromboli volcanic system TZM apparatus has been used to perform decompression runs at Bayerisches Geoinstitut in Bayreuth (DE). As for Pantelleria composition, cooling experiments has been done using IHPV devices at ISTO of Orléans (FR), on the basis of previous phase equilibrium work (Di Carlo et al., 2010). First obtained results for Stromboli case show high rates of nucleation and crystal growth during the initial stages of crystallization which were followed by crystal growth at approximately constant number densities as equilibrium was approached. Shapes of crystals growing in melts are controlled by the kinetics of crystallization and may provide information about the degree of undercooling experienced by batches of magma en route to the surface (Lofgren, 1980). The study of crystallization kinetics through phases growth rates (Couch et al., 2003), together with the calculation of nucleation density and nucleation rates (Hammer et al., 1999) represent a step toward the estimation of the time scales of magmatic processes in volcanic systems and the interpretation of shallow magmatic processes. The results for Stromboli suggest average crystal growth timescales on the order of weeks, but this is complicated by clear evidence that some crystals have experienced repeated periods of both dissolution and growth (Landi et al., 2004).

  1. Measurements of liquid-phase turbulence in gas-liquid two-phase flows using particle image velocimetry

    NASA Astrophysics Data System (ADS)

    Zhou, Xinquan; Doup, Benjamin; Sun, Xiaodong

    2013-12-01

    Liquid-phase turbulence measurements were performed in an air-water two-phase flow loop with a circular test section of 50 mm inner diameter using a particle image velocimetry (PIV) system. An optical phase separation method--planar laser-induced fluorescence (PLIF) technique—which uses fluorescent particles and an optical filtration technique, was employed to separate the signals of the fluorescent seeding particles from those due to bubbles and other noises. An image pre-processing scheme was applied to the raw PIV images to remove the noise residuals that are not removed by the PLIF technique. In addition, four-sensor conductivity probes were adopted to measure the radial distribution of the void fraction. Two benchmark tests were performed: the first was a comparison of the PIV measurement results with those of similar flow conditions using thermal anemometry from previous studies; the second quantitatively compared the superficial liquid velocities calculated from the local liquid velocity and void fraction measurements with the global liquid flow rate measurements. The differences of the superficial liquid velocity obtained from the two measurements were bounded within ±7% for single-phase flows and two-phase bubbly flows with the area-average void fraction up to 18%. Furthermore, a preliminary uncertainty analysis was conducted to investigate the accuracy of the two-phase PIV measurements. The systematic uncertainties due to the circular pipe curvature effects, bubble surface reflection effects and other potential uncertainty sources of the PIV measurements were discussed. The purpose of this work is to facilitate the development of a measurement technique (PIV-PLIF) combined with image pre-processing for the liquid-phase turbulence in gas-liquid two-phase flows of relatively high void fractions. The high-resolution data set can be used to more thoroughly understand two-phase flow behavior, develop liquid-phase turbulence models, and assess high

  2. Modeling the final phase of landfill gas generation from long-term observations.

    PubMed

    Tintner, Johannes; Kühleitner, Manfred; Binner, Erwin; Brunner, Norbert; Smidt, Ena

    2012-06-01

    For waste management, methane emissions from landfills and their effect on climate change are of serious concern. Current models for biogas generation that focus on the economic use of the landfill gas are usually based on first order chemical reactions (exponential decay), underestimating the long-term emissions of landfills. The presented study concentrated on the curve fitting and the quantification of the gas generation during the final degradation phase under optimal anaerobic conditions. For this purpose the long-term gas generation (240-1,830 days) of different mechanically biologically treated (MBT) waste materials was measured. In this study the late gas generation was modeled by a log-normal distribution curve to gather the maximum gas generation potential. According to the log-normal model the observed gas sum curve leads to higher values than commonly used exponential decay models. The prediction of the final phase of landfill gas generation by a fitting model provides a basis for CO(2) balances in waste management and some information to which extent landfills serve as carbon sink.

  3. Molecular simulation of excess isotherm and excess enthalpy change in gas-phase adsorption.

    PubMed

    Do, D D; Do, H D; Nicholson, D

    2009-01-29

    We present a new approach to calculating excess isotherm and differential enthalpy of adsorption on surfaces or in confined spaces by the Monte Carlo molecular simulation method. The approach is very general and, most importantly, is unambiguous in its application to any configuration of solid structure (crystalline, graphite layer or disordered porous glass), to any type of fluid (simple or complex molecule), and to any operating conditions (subcritical or supercritical). The behavior of the adsorbed phase is studied using the partial molar energy of the simulation box. However, to characterize adsorption for comparison with experimental data, the isotherm is best described by the excess amount, and the enthalpy of adsorption is defined as the change in the total enthalpy of the simulation box with the change in the excess amount, keeping the total number (gas + adsorbed phases) constant. The excess quantities (capacity and energy) require a choice of a reference gaseous phase, which is defined as the adsorptive gas phase occupying the accessible volume and having a density equal to the bulk gas density. The accessible volume is defined as the mean volume space accessible to the center of mass of the adsorbate under consideration. With this choice, the excess isotherm passes through a maximum but always remains positive. This is in stark contrast to the literature where helium void volume is used (which is always greater than the accessible volume) and the resulting excess can be negative. Our definition of enthalpy change is equivalent to the difference between the partial molar enthalpy of the gas phase and the partial molar enthalpy of the adsorbed phase. There is no need to assume ideal gas or negligible molar volume of the adsorbed phase as is traditionally done in the literature. We illustrate this new approach with adsorption of argon, nitrogen, and carbon dioxide under subcritical and supercritical conditions.

  4. An approximate calculation of advective gas-phase transport of 14C at Yucca Mountain, Nevada

    NASA Astrophysics Data System (ADS)

    Knapp, R. B.

    1990-01-01

    A quasilinear partial differential equation, which describes gas-phase transport of a 14C kinematic wave through a porous medium, is derived, its sensitivity to system variables is analyzed and it is applied to one possible release scenarion at the porposed Yucca Mountain, Nevada high-level radioactive waste repository. Advection, isotope exchange between CO 2 in a flowing gas phase and HCO 3- in a static aqueous phase, and radioactive decay are incorporated. The governing equation is solved analytically by the method of characteristics. The mass fraction of 14C in the gas phase,X 14g, is controlled by radioactive decay. The relatively long half-line of 14C, about 5720 years, and the relatively shallow proposed burial depth of the radioactive waste, about 350m, requires significant retardation of the 14C wave velocity for significant reduction in X 14g. 14C wave velocity is most sensitive to temperature and pH which control the distribution of total carbon between gas and liquid phase; the greater the partitioning of carbon into the liquid phase, the greater the retardation of the 14C wave velocity and the greater the ultimate reduction in X 14g from initial conditions. Partitioning of total carbon into the liquid phase is greatest at low temperatures, < 100° C, and high pH values, > 8. Increasing water saturation also tends to retard 14C wave velocity but to a lesser extent. The governing equation has been applied using conditions that may possibly occur at the proposed Yucca Mountain repository. Calculations indicate that the 14C wave takes about 5900 years to reach the surface with a X 14g equal to 25 ppm. Diffusion and dispersion are not of major importance for these conditions. These calculations are approximate due to the number of assumptions involved. Discharge of 14C into the gas before the selected time would accelerate wave arrival and increase the amount of 14C reaching the surface.

  5. Nucleation Rate Analysis of Methane Hydrate from Molecular Dynamics Simulations

    DOE PAGES

    Yuhara, Daisuke; Barnes, Brian C.; Suh, Donguk; ...

    2015-01-06

    Clathrate hydrates are solid crystalline structures most commonly formed from solutions that have nucleated to form a mixed solid composed of water and gas. Understanding the mechanism of clathrate hydrate nucleation is essential to grasp the fundamental chemistry of these complex structures and their applications. Molecular dynamics (MD) simulation is an ideal method to study nucleation at the molecular level because the size of the critical nucleus and formation rate occur on the nano scale. Moreover, various analysis methods for nucleation have been developed through MD to analyze nucleation. In particular, the mean first-passage time (MFPT) and survival probability (SP)more » methods have proven to be effective in procuring the nucleation rate and critical nucleus size for monatomic systems. This study assesses the MFPT and SP methods, previously used for monatomic systems, when applied to analyzing clathrate hydrate nucleation. Because clathrate hydrate nucleation is relatively difficult to observe in MD simulations (due to its high free energy barrier), these methods have yet to be applied to clathrate hydrate systems. In this study, we have analyzed the nucleation rate and critical nucleus size of methane hydrate using MFPT and SP methods from data generated by MD simulations at 255 K and 50 MPa. MFPT was modified for clathrate hydrate from the original version by adding the maximum likelihood estimate and growth effect term. The nucleation rates were calculated by MFPT and SP methods and are within 5%; the critical nucleus size estimated by the MFPT method was 50% higher, than values obtained through other more rigorous but computationally expensive estimates. These methods can also be extended to the analysis of other clathrate hydrates.« less

  6. Nucleation Rate Analysis of Methane Hydrate from Molecular Dynamics Simulations

    SciTech Connect

    Yuhara, Daisuke; Barnes, Brian C.; Suh, Donguk; Knott, Brandon C.; Beckham, Gregg T.; Yasuoka, Kenji; Wu, David T.; Amadeu K. Sum

    2015-01-06

    Clathrate hydrates are solid crystalline structures most commonly formed from solutions that have nucleated to form a mixed solid composed of water and gas. Understanding the mechanism of clathrate hydrate nucleation is essential to grasp the fundamental chemistry of these complex structures and their applications. Molecular dynamics (MD) simulation is an ideal method to study nucleation at the molecular level because the size of the critical nucleus and formation rate occur on the nano scale. Moreover, various analysis methods for nucleation have been developed through MD to analyze nucleation. In particular, the mean first-passage time (MFPT) and survival probability (SP) methods have proven to be effective in procuring the nucleation rate and critical nucleus size for monatomic systems. This study assesses the MFPT and SP methods, previously used for monatomic systems, when applied to analyzing clathrate hydrate nucleation. Because clathrate hydrate nucleation is relatively difficult to observe in MD simulations (due to its high free energy barrier), these methods have yet to be applied to clathrate hydrate systems. In this study, we have analyzed the nucleation rate and critical nucleus size of methane hydrate using MFPT and SP methods from data generated by MD simulations at 255 K and 50 MPa. MFPT was modified for clathrate hydrate from the original version by adding the maximum likelihood estimate and growth effect term. The nucleation rates were calculated by MFPT and SP methods and are within 5%; the critical nucleus size estimated by the MFPT method was 50% higher, than values obtained through other more rigorous but computationally expensive estimates. These methods can also be extended to the analysis of other clathrate hydrates.

  7. Nucleation rate analysis of methane hydrate from molecular dynamics simulations.

    PubMed

    Yuhara, Daisuke; Barnes, Brian C; Suh, Donguk; Knott, Brandon C; Beckham, Gregg T; Yasuoka, Kenji; Wu, David T; Sum, Amadeu K

    2015-01-01

    Clathrate hydrates are solid crystalline structures most commonly formed from solutions that have nucleated to form a mixed solid composed of water and gas. Understanding the mechanism of clathrate hydrate nucleation is essential to grasp the fundamental chemistry of these complex structures and their applications. Molecular dynamics (MD) simulation is an ideal method to study nucleation at the molecular level because the size of the critical nucleus and formation rate occur on the nano scale. Various analysis methods for nucleation have been developed through MD to analyze nucleation. In particular, the mean first-passage time (MFPT) and survival probability (SP) methods have proven to be effective in procuring the nucleation rate and critical nucleus size for monatomic systems. This study assesses the MFPT and SP methods, previously used for monatomic systems, when applied to analyzing clathrate hydrate nucleation. Because clathrate hydrate nucleation is relatively difficult to observe in MD simulations (due to its high free energy barrier), these methods have yet to be applied to clathrate hydrate systems. In this study, we have analyzed the nucleation rate and critical nucleus size of methane hydrate using MFPT and SP methods from data generated by MD simulations at 255 K and 50 MPa. MFPT was modified for clathrate hydrate from the original version by adding the maximum likelihood estimate and growth effect term. The nucleation rates calculated by MFPT and SP methods are within 5%, and the critical nucleus size estimated by the MFPT method was 50% higher, than values obtained through other more rigorous but computationally expensive estimates. These methods can also be extended to the analysis of other clathrate hydrates.

  8. Surface Nanobubbles Nucleate Microdroplets

    NASA Astrophysics Data System (ADS)

    Zhang, Xuehua; Lhuissier, Henri; Sun, Chao; Lohse, Detlef

    2014-04-01

    When a hydrophobic solid is in contact with water, surface nanobubbles often form at the interface. They have a lifetime many orders of magnitude longer than expected. Here, we show that they even withstand a temperature increase to temperatures close to the boiling point of bulk water; i.e., they do not nucleate larger bubbles ("superstability"). On the contrary, when the vapor-liquid contact line passes a nanobubble, a liquid film remains around it, which, after pinch-off, results in a microdroplet in which the nanobubbles continue to exist. Finally, the microdroplet evaporates and the nanobubble consequently bursts. Our results support that pinning plays a crucial role for nanobubble stability.

  9. Analytic determination of the number of nucleation sites in nucleate boiling of liquids on real surfaces

    SciTech Connect

    Kopp, I.Z. )

    1989-11-01

    The solution of the problem of intersection with a level is used as the basis for the probabilistic approach to describing the microtopography of a real surface on the assumption that the number of its projections is equal to the number of its pits. In this way one determines the number of nucleation sites. Starting with determination of the stable size of the vapor-phase nucleus generated in pits of rough surfaces, numerical solutions are obtained for the number of nucleation sites. This number provides to be in satisfactory agreement with the experimental data on the boiling of water on various surfaces.

  10. Translational invariance in nucleation theories: theoretical formulation.

    PubMed

    Drossinos, Y; Kevrekidis, P G; Georgopoulos, P G

    2001-03-01

    The consequences of spontaneously broken translational invariance on the nucleation-rate statistical prefactor in theories of first-order phase transitions are analyzed. A hybrid, semiphenomenological approach based on field-theoretic analyses of condensation and modern density-functional theories of nucleation is adopted to provide a unified prescription for the incorporation of translational-invariance corrections to nucleation-rate predictions. A connection between these theories is obtained starting from a quantum-mechanical Hamiltonian and using methods developed in the context of studies on Bose-Einstein condensation. An extremum principle is used to derive an integro-differential equation for the spatially nonuniform mean-field order-parameter profile; the appropriate order parameter becomes the square root of the fluid density. The importance of the attractive intermolecular potential is emphasized, whereas the repulsive two-body potential is approximated by considering hard-sphere collisions. The functional form of the degenerate translational eigenmodes in three dimensions is related to the mean-field order parameter, and their contribution to the nucleation-rate prefactor is evaluated. The solution of the Euler-Lagrange variational equation is discussed in terms of either a proposed variational trial function or the complete numerical solution of the associated boundary-value integro-differential problem. Alternatively, if the attractive potential is not explicitly known, an approach that allows its formal determination from its moments is presented.

  11. Amyloid fibril networks nucleated under oscillatory shear

    NASA Astrophysics Data System (ADS)

    Batzli, Kiersten; Love, Brian

    2013-03-01

    The process of amyloid fibril formation is of interest due to the link between these self-aggregating proteins and the progression of neurodegenerative disease. More recently, research has been directed at the exploitation of self-assembly properties of amyloid proteins for use as templates for nanowires and fibrillar networks. Insulin is an ideal protein for these purposes due to the ease of aggregation, as well as the large aspect ratio and high chemical stability of the produced fibrils. Insulin in pH 2 solution quickly forms aggregates in the presence of 65 °C heat. We have investigated the effect of oscillatory shear on the nucleation and growth of amyloid fibrillar networks using rheology and TEM to characterize the mechanical properties and structure of the network respectively. We contrast networks nucleated under oscillatory shear with networks nucleated in static and agitated conditions, and discuss network properties in the context of use in templating nanostructures. We find that the structural characteristics of the formed networks, including the density of fibrils, are affected by shear during the nucleation phase of amyloid growth.

  12. Effect of liquid distribution on gas-water phase mass transfer in an unsaturated sand during infiltration

    NASA Astrophysics Data System (ADS)

    Imhoff, Paul T.; Jaffé, Peter R.

    1994-09-01

    Gas-water phase mass transfer was examined in a homogeneous sand with both the gas and water phase mobile: water was infiltrated from the top of the sand column while benzene-laden air flowed upward from the bottom. Mass-transfer limitations for this situation may be important for applications of bioventing, where water and nutrients are added at the ground surface simultaneously with induced air movement to carry oxygen and volatile organics to microbial populations. Gas- and water-phase samples indicate that gas-water phase mass transfer was sufficiently fast that equilibrium between gas and water phases was achieved at all sampling locations within the porous medium. Lower-bound estimates for the gas-water mass-transfer rate coefficient show that mass transfer was at least 10-40 times larger than predictions made from an empirical model developed for gas-water phase mass transfer in an identical porous medium. A water-phase tracer test demonstrates that water flow was much more uniform in this study than in those earlier experiments, which is a likely explanation for the differing rates of gas-water phase mass transfer. It is hypothesized that the liquid distribution in previous laboratory experiments was less uniform because of preferential flow paths due to wetting front instabilities. Gas-water phase mass-transfer rate coefficients reported in this investigation are for an ideal situation of uniform water infiltration: mass-transfer rates in field soils are expected to be significantly smaller.

  13. The Nucleation of Cavitation in Aqueous Media

    DTIC Science & Technology

    1985-01-25

    37 9. TllIstration of interfacila motion during - the compression phase of a compression/ decompression process . .................. .. .- 10a...special subcommittee to investigate this phenomenon. In 1917, Lord Rayleigh 5 became involved. His solution - of the equations governing vapor cavity...at the interface between a flat solid and a pure liquid to account for nucleation at the interface between two pure liquids. Apfel’s crevice model was

  14. In situ measurements of gas/particle-phase transitions for atmospheric semivolatile organic compounds

    PubMed Central

    Williams, Brent J.; Goldstein, Allen H.; Kreisberg, Nathan M.; Hering, Susanne V.

    2010-01-01

    An understanding of the gas/particle-phase partitioning of semivolatile compounds is critical in determining atmospheric aerosol formation processes and growth rates, which in turn affect global climate and human health. The Study of Organic Aerosol at Riverside 2005 campaign was pe