WorldWideScience

Sample records for vycor

  1. Acoustic properties of a porous glass (vycor) at hypersonic frequencies.

    Science.gov (United States)

    Levelut, C; Pelous, J

    2007-10-17

    Brillouin scattering experiments have been performed from 5 to 1600 K in vycor, a porous silica glass. The acoustic velocity and attenuation at hypersonic frequencies are compared to those of bulk silica and others porous silica samples. The experimental evidence for the influence of porosity on the scattering by acoustic waves is compared to calculations. The correlation between internal friction and thermal conductivity at low temperature is discussed.

  2. Temperature-dependent adsorption of nitrogen on porous vycor glass

    Science.gov (United States)

    Huber, Tito E.; Tsou, Hsi Lung

    1998-03-01

    Adsorption isotherms of N2 have been measured in the temperature range from 77 to 120 K in samples of porous vycor glass. From the Brunauer-Emmett-Teller theory the surface layer coverages are determined. These are found to be temperature dependent. When adsorption-isotherm coverage data are expressed as a function of the adsorption potential δμ, the result is roughly temperature independent for coverages ranging from submonolayer to thin film, below capillary condensation. This characteristic curve, which represents the distribution of adsorption sites vs the adsorption potential, is compared with results from two models for the adsorbate: Dubinin's isotherm for microporous solids and its extension to rough surfaces, which places importance on the porosity of the surface, and Halsey's extension of the Frankel-Halsey-Hill isotherm, which takes into account the long-range variations of the substrate adsorption potential. The impact of this work on the interpretation of N2 adsorption data in terms of a surface area is discussed.

  3. Positron lifetimes at the initial stage of pore formation in Vycor glass

    CERN Document Server

    Jasinska, B; Goworek, T

    2000-01-01

    The formation of narrow pores during leaching of Vycor glass by sulphuric acid was investigated using the positron lifetime technique. During the leaching process the pore diameter remained roughly constant (except for the case of cold leaching). The time of processing changed the total length of capillaries, but not their number; at the temperature 50 deg. C during 20 min of leaching the average leaching depth was 24 mu m.

  4. Temperature-dependent adsorption of hydrogen, deuterium, and neon on porous Vycor glass

    Science.gov (United States)

    Huber, T. E.; Scardino, D.; Tsou, H. L.

    1995-10-01

    Adsorption isotherms of H2, D2, and Ne have been measured in the temperature range from 15 K to the corresponding critical points in samples of porous Vycor glass. From the Brunauer-Emmett-Teller theory the surface layer coverages are determined. These are found to be temperature dependent. A model-independent approach allows us to fit the data for coverages ranging from submonolayer to thin film, below capillary condensation, for each adsorbate at all temperatures with a temperature-independent curve. This characteristic curve represents the distribution of adsorption sites versus the adsorption potential. In the intermediate coverage range, the isotherms exhibit the modified Frenkel-Halsey-Hill (FHH) behavior. The adsorption saturates for low-adsorption potentials. The characteristic curve is a useful universal curve since it is roughly the same for the three species investigated. We examine the relative strengths of the surface potentials and densities of the two isotopic modifications of hydrogen and of the more classical Ne adsorbed on porous Vycor glass. The characteristic adsorption curve is compared with results from two models for the adsorbate: Dubinin's isotherm for microporous solids and its extension to rough surfaces which places importance on the porosity of the surface, and Halsey's model, which is an extension of the FHH isotherm that takes into account the long-range variations of substrate adsorption potential.

  5. Interplay of vapor adsorption and liquid imbibition in nanoporous Vycor glass

    Science.gov (United States)

    Kiepsch, Sebastian; Pelster, Rolf

    2016-04-01

    We have studied the kinetics of spontaneous capillary rise and of the concurrent vapor adsorption in nanoporous, monolithic samples of Vycor glass with a mean pore diameter of 7.5 nm. As liquids, we have chosen n -alcohols (n =4 -10 ) whose vapor pressures at room temperature range from p0=965 Pa down to p0=0.743 Pa. Dielectric measurements allow us to achieve spatial selectivity to predefined parts of the porous Vycor glass. In this way, we are able to measure the overall uptake of molecules as well as vapor adsorption from the surroundings in unfilled parts of the pore network, i.e., above the liquid menisci of the rising imbibition front. We show that the latter process is unaltered compared to free adsorption in samples suspended above a liquid reservoir. Only at low vapor pressures, i.e., for long alcohols, vapor adsorption can be neglected and the capillary rise follows the theoretical predictions of the Lucas-Washburn √{t } law. The more volatile the alcohol, the more important the additional adsorption of molecules becomes. We show that the overall filling process in the pore network is well described by a superposition of the Lucas-Washburn law and the measured vapor adsorption. In addition, the experiments give insight into the vapor diffusion dynamics in the porous matrix.

  6. On the Formation of Nanobubbles in Vycor Porous Glass during the Desorption of Halogenated Hydrocarbons

    Science.gov (United States)

    Mitropoulos, A. C.; Stefanopoulos, K. L.; Favvas, E. P.; Vansant, E.; Hankins, N. P.

    2015-06-01

    Vycor porous glass has long served as a model mesoporous material. During the physical adsorption of halogenated hydrocarbon vapours, such as dibromomethane, the adsorption isotherm exhibits an hysteresis loop; a gradual ascent is observed at higher pressures during adsorption, and a sharp drop is observed at lower pressures during desorption. For fully wetting fluids, an early hypothesis attributed the hysteresis to mechanistic differences between capillary condensation (adsorption) and evaporation (desorption) processes occurring in the wide bodies and narrow necks, respectively, of ‘ink-bottle’ pores. This was later recognized as oversimplified when the role of network percolation was included. For the first time, we present in-situ small angle x-ray scattering measurements on the hysteresis effect which indicate nanobubble formation during desorption, and support an extended picture of network percolation. The desorption pattern can indeed result from network percolation; but this can sometimes be initiated by a local cavitation process without pore blocking, which is preceded by the temporary, heterogeneous formation of nanobubbles involving a change in wetting states. The capacity of the system to sustain such metastable states is governed by the steepness of the desorption boundary.

  7. Comparative study of the thermoluminescence between the materials {alpha}-Al{sub 2}O{sub 3}:C, KCl:Eu{sup 2+}, KBr: Eu{sup 2+} and VYCOR; Estudio comparativo de la termoluminiscencia entre los materiales {alpha}-Al{sub 2}O{sub 3}: C, KCl:Eu{sup 2+}, KBr: Eu{sup 2+} y VYCOR

    Energy Technology Data Exchange (ETDEWEB)

    Pedroza M, M. [Programa de Posgrado en Fisica de Materiales, Centro de Investigacion Cientifica y de Educacion Superior de Ensenada, Apdo. Postal 2681, C.P. 22800, Ensenada, Baja California (Mexico); Melendrez, R.; Perez S, R.; Aceves, R.; Piters, T.M.; Barboza F, M. [Centro de Investigacion en Fisica, Universidad de Sonora, Apdo. Postal 5-088, C.P. 83190 Hermosillo, Sonora (Mexico)

    1999-07-01

    It is presented some investigation results related to the thermoluminescence curves (Tl), Tl emission and the spectra of excitation of thermoluminescence in the ultraviolet region of 190 to 250 nm in the materials {alpha}-Al{sub 2}O{sub 3}:C, KCl: Eu{sup 2+}, KBr: Eu{sup 2+} and the Vycor glass. It was able to be observed that the Tl emission for the first three materials exists around 420 nm and in the case of Vycor the emission consists of two Tl peaks where the most low temperature is a band more wide centered in 460 nm and the other band of high temperature emits in 470 nm. In the excitation curves of Tl were obtained centered bands around 230 nm for KCl: Eu{sup 2+}, 235 nm for KBr: Eu{sup 2+}, 220 nm for the alumina and 195 nm for the Vycor. From the results it was able to be appreciated that this last has a minor relative intensity with respect to the others materials but also the region in which works there was an alone band between the 190 to 205 nm. This fact makes the material be very selective in the ultraviolet region of greatest energy. (Author)

  8. Existence of liquid helium above melting curve pressures

    Energy Technology Data Exchange (ETDEWEB)

    Thomson, A.L.; Brewer, D.F.; Naji, T.; Haynes, S. (Sussex Univ., Brighton (UK). Dept. of Physics); Reppy, J.D. (Cornell Univ., Ithaca, NY (USA))

    Data are presented on the specific heat of helium confined at a high externally applied pressure within the 60 A pores of vycor glass. The specific heat shows that the helium within the pores remains in the liquid state down to temperatures well below 1 K. On the other hand the helium outside the vycor behaves normally, changing phase from solid to liquid as it warms.

  9. Temperature variations of average o-Ps lifetime in porous media

    CERN Document Server

    Goworek, T; Jasinska, B; Wawryszczuk, J

    2000-01-01

    Modification of the Tao-Eldrup model is proposed in order to extend its usefulness to the case of porous media. The modification consists in the transition from spherical to capillary geometry and in inclusion of pick-off annihilation from the excited states of a particle in the well. Approximated equations for pick-off constant in these states are given. The model was tested by observing the temperature dependences of o-Ps lifetime in various media. In the case of silica gels and Vycor glass with narrow pores, the model seems to work well, while for larger pores in Vycor unexpectedly long lifetimes appear in the range of lowest temperatures.

  10. Transparent Nanoporous Glass-Polymer Composite for U.S. Army Applications

    Science.gov (United States)

    2008-10-01

    a nitrogen environment until infiltration and polymerization. Infiltration and curing procedures varied for each of the prepolymers . Samples...manufacturing a nanocomposite from nanoporous glass was first tested by infiltrating Vycor glass with various prepolymers (MMA, IBA, and a low-viscosity

  11. Isosteric Vapor Pressure – Temperature Data for Water Sorption in Hardened Cement Paste: Enthalpy, Entropy and Sorption Isotherms at Different Temperatures

    DEFF Research Database (Denmark)

    Radjy, Fariborz; Sellevold, Erik J.; Hansen, Kurt Kielsgaard

    . The accuracies for pressure, enthalpy and entropy are found to be 0.5% or less. PART II: The TPA-system has been used to generate water vapor pressure – temperature data for room temperature – and steam cured hardened cement pastes as well as porous vycor glass. The moisture contents range from saturated to dry...

  12. Suitability of various materials for porous filters in diffusion experiments

    Energy Technology Data Exchange (ETDEWEB)

    Aldaba, David; Vidal, Miquel; Rigol, Anna [Univ. de Barcelona (Spain). Dept. de Quimica Analitica; Glaus, Martin; Van Loon, Luc [Paul Scherrer Institut, Villigen PSI (Switzerland). Lab. for Waste Management; Leupin, Olivier [Nagra, Wettingen (Switzerland)

    2014-10-01

    The suitability of different porous materials (stainless steel, VYCOR {sup registered} glass, Al{sub 2}O{sub 3} and PEEK) for use as confining filters in diffusion experiments was evaluated by measuring the effective diffusion coefficients (D{sub e}) of neutral (HTO) and ionic solutes (Na{sup +}, Cs{sup +}, Sr{sup 2+}, Cl{sup -}, SeO{sub 4}{sup 2-}) in the materials in through-diffusion experiments. For stainless steel filters, the D{sub e} values of the target solutes correlated satisfactorily with their bulk diffusion coefficient in water (D{sub w}); thus, the diffusion process in the stainless steel filters was primarily controlled by the diffusivity of the solvated ions. For the remaining materials, the D{sub e} and D{sub w} values were also correlated for the target solutes, and the geometric factors were in the sequence: VYCOR {sup registered} glass < Al{sub 2}O{sub 3} < PEEK. Stainless steel and VYCOR {sup registered} glass were the most appropriate materials because of their high D{sub e} values, but a specific interaction of caesium with VYCOR {sup registered} glass was hypothesised because the D{sub e} values obtained for this solute were slightly higher than expected.

  13. Silicates materials of high vacuum technology

    CERN Document Server

    Espe, Werner

    2013-01-01

    Materials of High Vacuum Technology, Volume 2: Silicates covers silicate insulators of special importance to vacuum technology. The book discusses the manufacture, composition, and physical and chemical properties of technical glasses, quartz glass, quartzware, vycor glass, ceramic materials, mica, and asbestos.

  14. In Pursuit of the Elusive Supersolid

    Science.gov (United States)

    Mi, X.; Reppy, J. D.

    2014-04-01

    The excitement following the initial report of supersolid behavior for 4He embedded in porous Vycor glass has been tempered by the realization that many of the early supersolid observations were contaminated by effects arising from an anomaly in the elastic properties of solid 4He. In an attempt to separate dynamic elastic effects from a true supersolid signal, we employed a torsional oscillator with two eigen-frequencies to study the 4He-Vycor system. We found that frequency-dependent elastic signals can entirely account for the observed period shift signals. Although, we conclude that supersolid does not exist for the 4He-Vycor case, the question of its presence in bulk samples remains open. In our current experiments we apply the two-frequency test to bulk samples of solid 4He. Again we find a frequency-dependent contribution arising from elastic effects; however, in some cases we also find a small frequency-independent contribution, which may indicate the existence of a remnant supersolid phase. Given the history of this subject such results must be treated with caution.

  15. Pursuit of the Elusive Supersolid

    Science.gov (United States)

    Mi, Xiao; Reppy, John D.

    2013-03-01

    The excitement following the initial report of supersolid behavior for 4He embedded in porous Vycor glass has been tempered by the realization that many of the early supersolid observations were contaminated by effects arising from an anomaly in the elastic properties of solid 4He. In an attempt to separate dynamic elastic effects from a true supersolid signal, we employed a torsional oscillator with two eigen frequencies to study the 4He-Vycor system. We found that frequency dependent elastic signals can entirely account for the observed period shift signals. Although, we conclude that supersolid does not exist for the 4He-Vycor case, the question of its presence in bulk samples remains open. In our current experiments we apply the two-frequency test to bulk samples of solid 4He. Again we find a frequency dependent contribution arising from elastic effects. However, in some cases we also find a small frequency independent contribution, which may indicate the existence of a remnant supersolid phase. Given the history of this subject such results must be treated with caution. This work is supported by the National Science Foundation through Grant DMR-060586, DMR-0965698 and CCMR Grant DMR-050404.

  16. Structure of polymer chains under confinement

    Indian Academy of Sciences (India)

    Jyotsana Lal

    2008-11-01

    We observe by SANS the structure of neutral polystyrene and charged polystyrene sulphonate chains in semi-dilute solutions confined in a model nanoporous glass, Vycor. The size of the free chains in solution is always larger than the pore diameter, 70. The use of a suitable mixture of hydrogenated and deuterated solvents and polymers enables us to measure directly the form factor of one single chain among the others. Single chain form factor was observed both for bulk and confined chains using the condition of zero average contrast. Our measurements on neutral polymer chains are in agreement with the theoretical predictions established by Daoud and de Gennes for chains confined in a cylindrical pore when the chains are entangled and laterally squeezed but remain ideal at large scale along the cylinder axis because of the screening of the excluded volume interactions (so-called regime of ``semi-dilute cigars"). For confined charged polymers, a peak is observed whose intensity increases with molecular weight and the asymptotic 1/ scattering region is extended compared to the bulk. We infer that the chains are sufficiently extended, under the influence of confinement, to highlight the large scale disordered structure of Vycor even under contrast matched conditions. The asymptotic behaviour of the observed interchain structure factor is ≈ 1/2 and ≈ 1/ for free and confined chains respectively.

  17. Methane storage in nanoporous media as observed via high field NMR relaxometry

    CERN Document Server

    Papaioannou, Antonios

    2015-01-01

    The storage properties of methane gas in Vycor porous glass (5.7 nm) are characterized in a wide pressure range from 0.7 MPa-89.7 MPa using Nuclear Magnetic Resonance (NMR). We demonstrate the capability of high field NMR relaxometry for the determination of the methane gas storage capacity and the measurement of the Hydrogen Index, to a high degree of accuracy. This helps determine the excess gas in the pore space which can be identified to exhibit Langmuir properties in the low pressure regime of 0.7 MPa to 39.6 Mpa. The Langmuir model enables us to determine the equilibrium density of the monolayer of adsorbed gas to be 8.5% lower than that of liquid methane. We also identify the signatures of multilayer adsorption at the high pressure regime from 39.6 Mpa to 89.7 Mpa and use the Brunauer-Emmet-Teller (BET) theory to determine the number of adsorbed layers of methane gas. We show how these measurements help us differentiate the gas stored in the Vycor pore space into free and adsorbed fractions for the ent...

  18. Development of hollow fiber catalytic membrane reactors for high temperature gas cleanup. Final report, September 1989--March 1994

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Yi Hua; Moser, W.R.; Pien, S.; Shelekhin, A.B.

    1994-07-01

    The objective of this project was to develop economically and technically viable catalytic membrane reactors for high temperature, high pressure gaseous contaminant control in Integrated Gasification Combined Cycle (IGCC) systems. These catalytic membrane reactors decompose H{sub 2}S and separate the reaction products. The reactors were designed to operate in the hostile process environment of the IGCC systems, and at temperatures ranging from 500 to 1000{degrees}C. Severe conditions encountered in the IGCC process (e.g., 900{degrees}C, containing of H{sub 2}S, CO{sub 2} and H{sub 2}O) make it impossible to use polymeric membranes in the process. A list of inorganic membranes that can be employed in the membrane reactor includes Pd metallic membranes, molecular-sieve glass membranes (PPG Industries), porous Vycor glass membranes and porous sol-gel derived membranes such as alumina, zirconia. Alumina and zirconia membranes, however, cannot withstand for a long time at high temperatures in the presence of water vapors. Palladium membranes are a very promising class of inorganic membranes for gas separations that is currently under development. In this project two different types of membranes were used in the design of the membrane reactor -- molecular-sieve glass membrane and Vycor glass porous membrane.

  19. Hydraulic Transport Across Hydrophilic and Hydrophobic Nanopores: Flow Experiments with Water and n-Hexane

    CERN Document Server

    Gruener, Simon; Greulich, Stefanie; Busch, Mark; Huber, Patrick

    2015-01-01

    We experimentally explore pressure-driven flow of water and n-hexane across nanoporous silica (Vycor glass monoliths with 7 or 10 nm pore diameters, respectively) as a function of temperature and surface functionalization (native and silanized glass surfaces). Hydraulic flow rates are measured by applying hydrostatic pressures via inert gases (argon and helium, pressurized up to 70 bar) on the upstream side in a capacitor-based membrane permeability setup. For the native, hydrophilic silica walls, the measured hydraulic permeabilities can be quantitatively accounted for by bulk fluidity provided we assume a sticking boundary layer, i.e. a negative velocity slip length of molecular dimensions. The thickness of this boundary layer is discussed with regard to previous capillarity-driven flow experiments (spontaneous imbibition) and with regard to velocity slippage at the pore walls resulting from dissolved gas. Water flow across the silanized, hydrophobic nanopores is blocked up to a hydrostatic pressure of at l...

  20. Isosteric Vapor Pressure – Temperature Data for Water Sorption in Hardened Cement Paste: Enthalpy, Entropy and Sorption Isotherms at Different Temperatures

    DEFF Research Database (Denmark)

    Radjy, Fariborz; Sellevold, Erik J.; Hansen, Kurt Kielsgaard

    and the temperatures range from 2 to 95 °C, differing for the specimen types. The data has been analyzed to yield differential enthalpy and entropy of adsorption, as well as the dependence of the relative vapor pressure on temperature at various constant moisture contents. The implications for the coefficient......PART I: In order to generate isosteric (constant mass) vapor pressure – temperature data (P-T data) for adsorbed pore water in hydrated cement paste, the Thermo Piestic Analysis system (the TPA system) described herein was developed. The TPA system generates high precision equilibrium isosteric P....... The accuracies for pressure, enthalpy and entropy are found to be 0.5% or less. PART II: The TPA-system has been used to generate water vapor pressure – temperature data for room temperature – and steam cured hardened cement pastes as well as porous vycor glass. The moisture contents range from saturated to dry...

  1. Statistical similarity between the compression of a porous material and earthquakes

    CERN Document Server

    Baro, Jordi; Illa, Xavier; Planes, Antoni; Salje, Ekhard K H; Schranz, Wilfried; Soto-Parra, Daniel E; Vives, Eduard

    2012-01-01

    It has been long stated that there are profound analogies between fracture experiments and earthquakes; however, few works attempt a complete characterization of the parallelisms between these so separate phenomena. We study the Acoustic Emission events produced during the compression of Vycor (SiO2). The Gutenberg-Richter law, the modified Omori's law, and the law of aftershock productivity are found to hold for a minimum of 5 decades, are independent of the compression rate, and keep stationary for all the duration of the experiments. The waiting-time distribution fulfills a unified scaling law with a power-law exponent close to 2.45 for long times, which is explained in terms of the temporal variations of the activity rate.

  2. How do rod-like molecules freeze and arrange in mesopores?

    CERN Document Server

    Huber, P; Hofmann, T; Knorr, K

    2003-01-01

    We present an x-ray diffraction study on rod-like molecules, i.e. the normal alkanes C sub 1 sub 9 H sub 4 sub 0 and C sub 9 H sub 2 sub 0 condensed in nanoporous Vycor glass. Temperature-dependent diffraction patterns elucidate how the structure and phase behaviour of these molecules are affected by the random substrate disorder and the geometric confinement. For the medium-length alkane C sub 1 sub 9 H sub 4 sub 0 a quenching of the lamellar ordering is observed, whereas this geometric ordering principle survives in the case of the short-length C sub 9 H sub 2 sub 0 , although in a modified fashion.

  3. A study of freezing-melting hysteresis of water in different porous materials. Part II: surfactant-templated silicas.

    Science.gov (United States)

    Petrov, Oleg; Furó, István

    2011-09-28

    The freezing-melting hysteresis of water in mesoporous silicas MCM-48, MCM-41 and SBA-16 has been studied by NMR cryoporometry. The hysteresis in MCM-48 was found to exhibit nearly parallel branches, matching type H1 hysteresis that had been observed earlier in controlled pore glass. The same type of hysteresis is observed in two of three different-sized MCM-41 under study (a pore diameter of 3.6 and 3 nm), superimposed with a secondary, extremely broad, type H3 hysteresis. No hysteresis was found in the smallest MCM-41 with a pore diameter hysteresis with the freezing branch being essentially steeper than the melting one, which is attributed to a pore blockage upon freezing, similar to what we observed earlier in Vycor porous glass. The data were analyzed using the model of curvature-dependent metastability of a solid phase upon melting; the validity of this model has been discussed.

  4. Thin film fuel cell electrodes.

    Science.gov (United States)

    Asher, W. J.; Batzold, J. S.

    1972-01-01

    Earlier work shows that fuel cell electrodes prepared by sputtering thin films of platinum on porous vycor substrates avoid diffusion limitations even at high current densities. The presented study shows that the specific activity of sputtered platinum is not unusually high. Performance limitations are found to be controlled by physical processes, even at low loadings. Catalyst activity is strongly influenced by platinum sputtering parameters, which seemingly change the surface area of the catalyst layer. The use of porous nickel as a substrate shows that pore size of the substrate is an important parameter. It is noted that electrode performance increases with increasing loading for catalyst layers up to two microns thick, thus showing the physical properties of the sputtered layer to be different from platinum foil. Electrode performance is also sensitive to changing differential pressure across the electrode. The application of sputtered catalyst layers to fuel cell matrices for the purpose of obtaining thin total cells appears feasible.

  5. Frameless Stereotactic Insertion of Viewsite Brain Access System with Microscope-Mounted Tracking Device for Resection of Deep Brain Lesions: Technical Report.

    Science.gov (United States)

    White, Tim; Chakraborty, Shamik; Lall, Rohan; Fanous, Andrew A; Boockvar, John; Langer, David J

    2017-02-04

    The surgical management of deep brain tumors is often challenging due to the limitations of stereotactic needle biopsies and the morbidity associated with transcortical approaches. We present a novel microscopic navigational technique utilizing the Viewsite Brain Access System (VBAS) (Vycor Medical, Boca Raton, FL, USA) for resection of a deep parietal periventricular high-grade glioma as well as another glioma and a cavernoma with no related morbidity. The approach utilized a navigational tracker mounted on a microscope, which was set to the desired trajectory and depth. It allowed gentle continuous insertion of the VBAS directly to a deep lesion under continuous microscopic visualization, increasing safety by obviating the need to look up from the microscope and thus avoiding loss of trajectory. This technique has broad value for the resection of a variety of deep brain lesions.

  6. Development of lightweight, glass mirror segments for the Large Deployable Reflector

    Science.gov (United States)

    Melugin, R. K.; Miller, J. H.; Angel, J. R. P.; Wangsness, P. A. A.; Parks, R. E.

    1986-01-01

    Accomplishments in the development of lightweight, honeycomb-core, sandwich mirror blanks made of borosilicate and high-silica glasses at the University of Arizona for the Large Deployable Reflector program are described. In this paper, work spanning the last 2 years is reported, highlighting a new mirror blank fabrication technique that permits the fabrication of the honeycomb core integrally with the front and back plates of the blank in a single furnace cycle. Two types of mirror blanks made by this method, an off-axis, aspheric segment and a smaller Vycor circular piece, are described. The fabrication of two off-axis, aspheric mirror segments is also described. Cryogenic test results are included on the test of a 38-cm diameter, lightweight, honeycomb core, sandwich mirror made of Pyrex.

  7. Combination of small angle neutron scattering data and mesoscopic simulation techniques as a tool for the structural characterization and prediction of properties of bi-phasic media

    Energy Technology Data Exchange (ETDEWEB)

    Kainourgiakis, M.E. [National Center for Scientific Research ' Demokritos' , Institute of Physical Chemistry, Agia Paraskevi Attikis, 15310 Athens (Greece); Steriotis, Th.A. [National Center for Scientific Research ' Demokritos' , Institute of Physical Chemistry, Agia Paraskevi Attikis, 15310 Athens (Greece)], E-mail: tster@chem.demokritos.gr; Kikkinides, E.S. [Department of Engineering and Management of Energy Resources, University of Western Macedonia, Kastorias and Fleming Str., 50100 Kozani (Greece); Chemical Process Engineering Research Institute, Center for Research and Technology Hellas, P.O. Box 361, 57001 Thermi, Thessaloniki (Greece); Charalambopoulou, G.Ch. [National Center for Scientific Research ' Demokritos' , Institute of Physical Chemistry, Agia Paraskevi Attikis, 15310 Athens (Greece); Ramsay, J.D.F. [Laboratoire des Materiaux et Procedes Membranaires, UMR CNRS 5635, Universite Montpellier II, Montpellier (France); Stubos, A.K. [National Center for Scientific Research ' Demokritos' , Institute of Physical Chemistry, Agia Paraskevi Attikis, 15310 Athens (Greece)

    2005-10-31

    A powerful, versatile methodology based on the combination of small angle neutron scattering (SANS) with mesoscopic simulation techniques is developed in an effort to relate in a sufficiently accurate manner the structure of biphasic media to their macroscopic physicochemical (equilibrium and dynamic) properties. Appropriate mathematical transformation of SANS spectra provides valuable information about the disordered geometry of a wide range of biphasic materials spanning from typical porous materials (Vycor porous glass, silica gel, alumina membrane) to complex biological tissues (stratum corneum), in terms of the corresponding autocorrelation function. Digital reconstruction (stochastic or process-based) is employed to generate two- or three-dimensional binary images of the respective structures, on the basis of the statistical properties obtained from the SANS spectra of the original materials. The resulting reconstructed domains are further used for the simulation of equilibrium (sorption) and dynamic (diffusion and permeation) processes, addressing the most common applications of the materials under consideration.

  8. Capillary rise of water in hydrophilic nanopores

    CERN Document Server

    Gruener, Simon; Wallacher, Dirk; Kityk, Andriy V; Huber, Patrick; 10.1103/PhysRevE.79.067301

    2009-01-01

    We report on the capillary rise of water in three-dimensional networks of hydrophilic silica pores with 3.5nm and 5nm mean radii, respectively (porous Vycor monoliths). We find classical square root of time Lucas-Washburn laws for the imbibition dynamics over the entire capillary rise times of up to 16h investigated. Provided we assume two preadsorbed strongly bound layers of water molecules resting at the silica walls, which corresponds to a negative velocity slip length of -0.5nm for water flow in silica nanopores, we can describe the filling process by a retained fluidity and capillarity of water in the pore center. This anticipated partitioning in two dynamic components reflects the structural-thermodynamic partitioning in strongly silica bound water layers and capillary condensed water in the pore center which is documented by sorption isotherm measurements.

  9. Spontaneous Imbibition Dynamics of an n-Alkane in Nanopores: Evidence of Meniscus Freezing and Monolayer Sticking

    CERN Document Server

    Gruener, Simon; 10.1103/PhysRevLett.103.174501

    2009-01-01

    Capillary filling dynamics of liquid n-tetracosane (n-C24H50) in a network of cylindrical pores with 7 and 10 nm mean diameter in monolithic silica glass (Vycor) exhibit an abrupt temperature-slope change at Ts=54 deg C, ~4 deg C above bulk and ~16 deg C, 8 deg C, respectively, above pore freezing. It can be traced to a sudden inversion of the surface tension's T slope, and thus to a decrease in surface entropy at the advancing pore menisci, characteristic of the formation of a single solid monolayer of rectified molecules, known as surface freezing from macroscopic, quiescent tetracosane melts. The imbibition speeds, that are the squared prefactors of the observed square-root-of-time Lucas-Washburn invasion kinetics, indicate a conserved bulk fluidity and capillarity of the nanopore-confined liquid, if we assume a flat lying, sticky hydrocarbon backbone monolayer at the silica walls.

  10. Structure and dynamics of interfacial water. Role of hydratation water in the globular proteins dynamics; Structure et dynamique de l`eau interfaciale. Role de l`eau d`hydratation dans la dynamique des proteines globulaires

    Energy Technology Data Exchange (ETDEWEB)

    Zanotti, J.M.

    1997-01-27

    This memoir includes five chapters. In the first chapter, are given the elements of the neutrons scattering theory that is used in this study. the second chapter is devoted to a general presentation of the interaction between biological macro molecule and water. The third part is dedicated to the study of the structure and the dynamics of interfacial water in the neighbouring of model systems, the vycor and the amorphous carbon. The results presented in this part are compared with these one relative to water dynamics at the C-phycocyanin surface. This study makes the object of the fourth chapter. Then, in the fifth and last chapter are discussed the results relative to the role of hydratation on the parv-albumin dynamics for which have been combined the neutron quasi elastic incoherent scattering and the nuclear magnetic resonance of the carbon 13 solid in natural abundance.

  11. Characterization of control mesoporous glasses (CPGs) using positron annihilation lifetime spectroscopy (PALS)

    Energy Technology Data Exchange (ETDEWEB)

    Sayed Ahmed, Essmat Mahmoud Hassan

    2008-01-30

    This thesis has two main goals. Firstly and for the first time, the positron annihilation lifetime technique (PALS) is used to characterize the control porous glasses (CPGs) media. All the positron annihilation spectroscopy (PAS) investigations have been interested in the commercial Vycor glass media of pores size {<=} 4 nm. Therefore, the PALS is used to establish basic correlations between the important physical properties of the CPG (pore size, surface area, and porosity) and the orthopositronium (o-Ps) lifetime. The second goal is to use these correlations to verify the validity of some suggested models and theories to discover possible deviations from the expected behaviour and to discuss the physical point of view for these deviations. Chapter 1 presents an overview of positron, positronium and their interaction with solid materials. Chapter 2 of this thesis is concerned with characterization of porous glass materials. This chapter discusses in detail the preparation methods of porous glasses specially control porous glass and Vycor glass. The gas adsorption phenomenon in porous glass and the related definitions are discussed. The most important terms of the porous glass such as pore size, shape, volume, pore size distribution, surface area, and porosity are discussed. Chapter 3 presents in detail the well known models and the derived equations which correlate between the lifetime of the o-Ps long-lived component and the pore size, pore shape and the temperature dependence of the porous media. Chapter 4 presents an overview of the main experimental techniques used in this thesis, namely positron annihilation lifetime spectroscopy. Chapter 5 explains the sample preparation for the measurements. The chapter represents also the experimental data for the correlation between the o-Ps lifetime and pore sizes for a system of CPG media (from 1 nm to 64 nm). I also studied the temperature dependence of the o-Ps long-lived component in different pore sizes. In this

  12. Capillary rise dynamics of liquid hydrocarbons in mesoporous silica as explored by gravimetry, optical and neutron imaging: Nano-rheology and determination of pore size distributions from the shape of imbibition fronts

    CERN Document Server

    Gruener, Simon; Schillinger, Burkhard; Egelhaaf, Stefan U; Huber, Patrick

    2015-01-01

    We present gravimetrical, optical, and neutron imaging measurements of the capillarity-driven infiltration of mesoporous silica glass by hydrocarbons. Square-root-of-time Lucas-Washburn invasion kinetics are found for linear alkanes from n-decane (C10) to n-hexacontane (C60) and for squalane, a branched alkane, in porous Vycor with 6.5 nm or 10 nm pore diameter, respectively. Humidity-dependent experiments allow us to study the influence on the imbibition kinetics of water layers adsorbed on the pore walls. Except for the longest molecule studied, C60, the invasion kinetics can be described by bulk fluidity and bulk capillarity, provided we assume a sticking, pore-wall adsorbed boundary layer, i.e. a monolayer of water covered by a monolayer of flat-laying hydrocarbons. For C60, however, an enhanced imbibition speed compared to the value expected in the bulk is found. This suggests the onset of velocity slippage at the silica walls or a reduced shear viscosity due to the transition towards a polymer-like flow...

  13. A Superfluid Pulse Tube Refrigerator Without Moving Parts for Sub-Kelvin Cooling

    Science.gov (United States)

    Miller, Franklin K.

    2012-01-01

    A report describes a pulse tube refrigerator that uses a mixture of He-3 and superfluid He-4 to cool to temperatures below 300 mK, while rejecting heat at temperatures up to 1.7 K. The refrigerator is driven by a novel thermodynamically reversible pump that is capable of pumping the He-3 He-4 mixture without the need for moving parts. The refrigerator consists of a reversible thermal magnetic pump module, two warm heat exchangers, a recuperative heat exchanger, two cold heat exchangers, two pulse tubes, and an orifice. It is two superfluid pulse tubes that run 180 out of phase. All components of this machine except the reversible thermal pump have been demonstrated at least as proof-of-concept physical models in previous superfluid Stirling cycle machines. The pump consists of two canisters packed with pieces of gadolinium gallium garnet (GGG). The canisters are connected by a superleak (a porous piece of VYCOR glass). A superconducting magnetic coil surrounds each of the canisters.

  14. Simultaneous measurement of arginine vasopressin and oxytocin in plasma and neurohypophysis by radioimmunoassay

    Energy Technology Data Exchange (ETDEWEB)

    Landgraf, R. (Deutsche Hochschule fuer Koerperkultur, Leipzig (German Democratic Republic). Forschungsinstitut Koerperkultur und Sport)

    1981-12-01

    Arginine vasopressin (AVP) and oxytocin (OXT) were measured simultaneously in the same sample by specific and sensitive radioimmunoassays (RIAs). The antibodies used did not cross-react to a variety of analogs and related peptides. The extraction procedure using Vycor glass powder resulted in mean recoveries of 84.4% (AVP) and 64.6% (OXT). In both assays, the sensitivity was 1 to 2 pg/ml plasma. A preincubation procedure that depresses plasma levels of both AVP and OXT selectively, provided specific blank values for a given plasma sample. To confirm the validity of the RIAs, dehydration experiments were performed. In rats, the basal levels of plasma AVP and OXT (means: 2,63 pg/ml and 6.80 pg/ml, respectively) are increased significantly after 24 h, 48 h and 72 h of water deprivation. Relationships are presented between both neurohormones in the plasma and neurohypophyses of control and dehydrated animals. As shown in cows, a significant correlation exists between plasma AVP and plasma osmolality but not between plasma OXT and osmolality or plasma AVP and OXT. Basal levels as well as physiological changes in plasma and neurohypophyseal AVP and OXT can be measured by the RIAs described.

  15. Hydraulic transport across hydrophilic and hydrophobic nanopores: Flow experiments with water and n-hexane.

    Science.gov (United States)

    Gruener, Simon; Wallacher, Dirk; Greulich, Stefanie; Busch, Mark; Huber, Patrick

    2016-01-01

    We experimentally explore pressure-driven flow of water and n-hexane across nanoporous silica (Vycor glass monoliths with 7- or 10-nm pore diameters, respectively) as a function of temperature and surface functionalization (native and silanized glass surfaces). Hydraulic flow rates are measured by applying hydrostatic pressures via inert gases (argon and helium, pressurized up to 70 bar) on the upstream side in a capacitor-based membrane permeability setup. For the native, hydrophilic silica walls, the measured hydraulic permeabilities can be quantitatively accounted for by bulk fluidity provided we assume a sticking boundary layer, i.e., a negative velocity slip length of molecular dimensions. The thickness of this boundary layer is discussed with regard to previous capillarity-driven flow experiments (spontaneous imbibition) and with regard to velocity slippage at the pore walls resulting from dissolved gas. Water flow across the silanized, hydrophobic nanopores is blocked up to a hydrostatic pressure of at least 70 bar. The absence of a sticking boundary layer quantitatively accounts for an enhanced n-hexane permeability in the hydrophobic compared to the hydrophilic nanopores.

  16. Properties of two-photon pumped cavity lasing in novel dye doped solid matrices

    Energy Technology Data Exchange (ETDEWEB)

    He, G.S.; Bhawalkar, J.D.; Zhao, C.; Prasad, P.N. [State Univ. of New York, Buffalo, NY (United States). Dept. of Chemistry

    1996-05-01

    Two-photon pumped frequency upconversion cavity lasing at {approximately}600 nm is accomplished in three types of dye-doped solid rods pumped with {approximately}10 ns and 1.06-{micro}m IR laser pulses. The dopant is a new dye, trans-4-[p-(N-ethyl-N-(hydroxyethyl)amino)styryl]-N-methylpyridinium tetraphenylborate, abbreviated as ASPT, which possesses a greater two-photon absorption cross section and stronger upconversion fluorescence emission than common commercial dyes (such as rhodamine). Three different materials were chosen as solid matrices: poly(2-hydroxyethyl methacrylate), VYCOR porous glass, and sol-gel glass. Using a Q-switched Nd:YAG pulse laser as the pump source, strong cavity lasing could be achieved in these three ASPT doped solid rods as well as in ASPT solution in a liquid cell. The spectral, temporal, and spatial characteristics of the cavity lasing output have been systematically investigated. The measured output-input characteristics, lasing lifetime, and damage threshold for the three different rods are presented.

  17. Adherence of Molecules to Silica Glass Surface: Experimental Results and Theoretical Calculations

    Science.gov (United States)

    Rivera, Edison; Prado, Miguel Oscar; Nuñez, Matias

    The adherence of molecules to surfaces is used in a wide scope of technological applications. In this work we study the attachment of molecules onto porous silica glass surface obtained from a Vycor glass, after glass- glass phase separation and leaching of the soluble phase with water. Nitrogen adsorption at 77 K was used for the determination of the specific surface area (BET area) and pore size distribution on the leached glass. The adherence onto the glass surface, of model molecules methylene blue (MB) and eosine yellow (EY), with positive and negative electrical charges respectively, was studied. The adsorption kinetics was determined from aqueous solutions using UV-VIS spectroscopy. It was found that the silica glass surface as prepared in this work is selective for positively charged molecules at pH≈5.20, an adsorption of 1 mg MB per gram of glass was found for methylene blue, and almost null adsorption for eosine yellow. First principles calculations were performed using the Density Functional Theory in order to model the interaction between both molecules and the glass surface.

  18. Cavitation and pore blocking in nanoporous glasses.

    Science.gov (United States)

    Reichenbach, C; Kalies, G; Enke, D; Klank, D

    2011-09-06

    In gas adsorption studies, porous glasses are frequently referred to as model materials for highly disordered mesopore systems. Numerous works suggest that an accurate interpretation of physisorption isotherms requires a complete understanding of network effects upon adsorption and desorption, respectively. The present article deals with nitrogen and argon adsorption at different temperatures (77 and 87 K) performed on a series of novel nanoporous glasses (NPG) with different mean pore widths. NPG samples contain smaller mesopores and significantly higher microporosity than porous Vycor glass or controlled pore glass. Since the mean pore width of NPG can be tuned sensitively, the evolution of adsorption characteristics with respect to a broadening pore network can be investigated starting from the narrowest nanopore width. With an increasing mean pore width, a H2-type hysteresis develops gradually which finally transforms into a H1-type. In this connection, a transition from a cavitation-induced desorption toward desorption controlled by pore blocking can be observed. Furthermore, we find concrete hints for a pore size dependence of the relative pressure of cavitation in highly disordered pore systems. By comparing nitrogen and argon adsorption, a comprehensive insight into adsorption mechanisms in novel disordered materials is provided.

  19. Preparation of H{sub 2}-permselective silica membranes by alternating reactant deposition. Quarterly progress report, September 1, 1993--December 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Soojin; Gavalas, G.R.

    1993-12-31

    Thin SiO{sub 2} layers were deposited on the surface of porous Vycor glass by alternating vapor phase reaction with SiCl{sub 4} and H{sub 2}O. The membranes prepared by this technique had H{sub 2} permeance of 0.3--0.4 cm{sup 3} (STP)/(min{center_dot}cm{sup 2}{center_dot}atm) and H{sub 2}:N{sub 2} selectivity of 500--1000 at 600{degrees}C. The SiCl{sub 4} dosage at each silylation cycle, the concentration of initial surface -OH groups, and the reaction temperature influence significantly the deposit layer thickness- After two weeks of heating at 550{degrees}C under 3 atmospheres of water vapor, the membrane H{sub 2} permeance decreased by about 20%, and the selectivity increased to more than 2000. The membrane properties after this hydrothermal treatment are superior to those of membranes prepared earlier by one-sided (steady flow) deposition. A simple model incorporating diffusion and surface reaction was used to study the effect of various parameters on the formation of the deposit layer.

  20. Ultrasonic measurements of normal and superfluid He-3 in high porosity aerogel

    Science.gov (United States)

    Lee, Yoonseok

    2014-03-01

    Ultrasound spectroscopy and nuclear magnetic resonance have been proven to be the most valuable spectroscopic tools in the study of superfluid 3He. These experimental methods provide complementary information on the orbital and spin structure of the Cooper pairs. In particular, the rich spectrum of the order parameter collective modes, a direct consequence of the exotic broken symmetry in the superfluid phases, have been mapped out by ultrasonic spectroscopic techniques. Aerogel possesses a unique structure, whose topology is at the antipode of conventional porous media such as Vycor glass and metallic sinters. High porosity aerogel presents additional scattering channel that substantially changes the ultrasonic behavior in both normal and superfluid phase of 3He. For example, in the normal fluid the classic first to zero sound crossover is effectively prohibited due to the residual elastic scattering from aerogel. However, the hydrodynamic-Knudsen crossover arises owing to the unique structure and the widely varying inelastic mean free path in 3He. In superfluid, no signatures of the order parameter collective modes were observed but the gapless superfluidity has been clearly verified through ultrasound measurements. In this paper, we will present the experimental results obtained in the past decade using ultrasonic techniques. Supported by NSF DMR-0803516 and DMR-1205891, and DMR-0654118 through National High Magnetic Field Laboratory and the State of Florida.

  1. Slow dynamics of supercooled water confined in nanoporous silica materials

    Energy Technology Data Exchange (ETDEWEB)

    Liu, L [Department of Nuclear Engineering, 24-209 MIT, Cambridge, MA 02139 (United States); Faraone, A [Department of Nuclear Engineering, 24-209 MIT, Cambridge, MA 02139 (United States); Mou, C-Y [Department of Chemistry, National Taiwan University, Taipei, 106, Taiwan (China); Yen, C-W [Department of Chemistry, National Taiwan University, Taipei, 106, Taiwan (China); Chen, S-H [Department of Nuclear Engineering, 24-209 MIT, Cambridge, MA 02139 (United States)

    2004-11-17

    We review our incoherent quasielastic neutron scattering (QENS) studies of the dynamics of supercooled water confined in nanoporous silica materials. QENS data were analysed by using the relaxing cage model (RCM) previously developed by us. We first use molecular dynamics (MD) simulation of the extended simple point charge model (SPC/E) for bulk supercooled water to establish the validity of the RCM, which applies to both the translational and rotational motion of water molecules. We then assume that the dynamics of water molecules in the vicinity of a hydrophilic surface is similar to a bulk water at an equivalent lower supercooled temperature. This analogy was experimentally demonstrated in previous investigations of water in Vycor glasses and near hydrophilic protein surfaces. Studies were made of supercooled water in MCM-41-S (pore sizes 25, 18, and 14 A) and MCM-48-S (pore size 22 A) using three QENS spectrometers of respective energy resolutions 1, 30, and 60 {mu}eV, covering the temperature range from 325 to 200 K. Five quantities are extracted from the analysis: they are {beta}, the stretch exponent characterizing the {alpha}-relaxation; {beta}{gamma}, the exponent determining the power-law dependence of the relaxation time on Q; <{tau}{sub 0}>, the Q-independent pre-factor for the average translational relaxation time; <{tau}{sub R{sub 1}}>, the relaxation time for the first-order rotational correlation function; and <{tau}{sub R{sub 3}}>, the relaxation time for the second-order rotational correlation function. We discuss the temperature dependence of these parameters and note that, in particular, the dynamics is rapidly slowing down at temperature around 220 K, signalling the onset of a structural arrest transition of liquid water into an amorphous solid water.

  2. Singlet oxygen chemistry in water. 2. Photoexcited sensitizer quenching by O2 at the water-porous glass interface.

    Science.gov (United States)

    Giaimuccio, Jovan; Zamadar, Matibur; Aebisher, David; Meyer, Gerald J; Greer, Alexander

    2008-12-11

    Insight into the O2 quenching mechanism of a photosensitizer (static or dynamic) would be useful for the design of heterogeneous systems to control the mode of generation of 1O2 in water. Here, we describe the use of a photosensitizer, meso-tetra(N-methyl-4-pyridyl)porphine (1), which was adsorbed onto porous Vycor glass (PVG). A maximum loading of 1.1 x 10(-6) mol 1 per g PVG was achieved. Less than 1% of the PVG surface was covered with photosensitizer 1, and the penetration of 1 reaches a depth of 0.32 mm along all faces of the glass. Time-resolved measurements showed that the lifetime of triplet 1*-ads was 57 microseconds in water. Triplet O2 quenched the transient absorption of triplet 1*-ads; for samples containing 0.9 x 10(-6)-0.9 x 10(-8) mol 1 adsorbed per g PVG, the Stern-Volmer constant, K(D), ranged from 23,700 to 32,100 M(-1). The adduct formation constant, Ks, ranged from 1310 to 510 M(-1). The amplitude of the absorption at 470 nm decreased slightly (by about 0.1) with increased O2 concentrations. Thus, the quenching behavior of triplet 1*-ads by O2 was proposed to be strongly dependent on dynamic quenching. Only approximately 10% of the quenching was attributed to the static quenching mechanism. The quenching of triplet 1*-ads was similar to that observed for photosensitizers in homogeneous solution which are often quenched dynamically by O2.

  3. Structural evolution in crystalline MoO{sub 3} nanoparticles with tunable size

    Energy Technology Data Exchange (ETDEWEB)

    Barros Santos, Elias de; Aparecido Sigoli, Fernando [Functional Materials Laboratory, Institute of Chemistry, University of Campinas, UNICAMP, PO Box 6154, Zip Code 13083-970 Campinas, SP (Brazil); Odone Mazali, Italo, E-mail: mazali@iqm.unicamp.br [Functional Materials Laboratory, Institute of Chemistry, University of Campinas, UNICAMP, PO Box 6154, Zip Code 13083-970 Campinas, SP (Brazil)

    2012-06-15

    In this study MoO{sub 3} nanoparticles were prepared in porous Vycor glass by impregnation-decomposition cycles (IDC) with molybdenum(VI) 2-ethylhexanoate. X-ray diffraction data show that the nanoparticles are crystalline and are in the orthorhombic {alpha}-MoO{sub 3} phase. Raman spectroscopy data also indicate the formation of this phase. The profiles in the Raman spectra changed with the number of IDC, indicating a structural evolution of the MoO{sub 3} nanoparticles. The IDC methodology promoted a linear mass increase and allowed tuning the nanoparticle size. Analysis of HRTEM images revealed that for 3, 5 and 7 IDC, the MoO{sub 3} nanoparticle average diameters are 3.2, 3.6 and 4.2 nm. Diffuse reflectance spectroscopy indicates a consistent red shift in the band gap from 3.35 to 3.29 eV as the size increases from 3.2 to 4.2 nm. This observed red shift in the band gap of the MoO{sub 3} nanoparticles is presumably due to quantum confinement effects. - Graphical abstract: Modification of profile Raman spectra for crystalline MoO{sub 3} nanoparticles in function of the particle size. Highlights: Black-Right-Pointing-Pointer Structural evolution of the MoO{sub 3} nanoparticles as a function of the crystallite size. Black-Right-Pointing-Pointer Tunable optical properties by controlling the MoO{sub 3} nanoparticle size. Black-Right-Pointing-Pointer The impregnation-decomposition methodology allowed tuning the nanoparticle size. Black-Right-Pointing-Pointer The red shift in the band gap of the MoO{sub 3} nanoparticles is due to quantum size effect. Black-Right-Pointing-Pointer The short-distance order in MoO{sub 3} nanoparticle is function to area/volume ratio.

  4. Coordination variation of hydrated Cu2+/Br1- ions traversing the interfacial water in mesopores

    Science.gov (United States)

    Wang, Q.; Huang, X. F.; Li, C. X.; Pan, L. Q.; Wu, Z. H.; Hu, T. D.; Jiang, Z.; Huang, Y. Y.; Cao, Z. X.; Sun, G.; Lu, K. Q.

    2012-06-01

    Resolution of the atomistic and electronic details about the coordination structure variation of hydrated ions in the interfacial water is still a tough challenge, which is, however, essentially important for the understanding of ion adsorption, permeation and other similar processes in aqueous solutions. Here we report the tracing of coordination structure variation for hydrated Cu2+/Br1- ions traversing the interfacial water in Vycor mesopores (ϕ = 7.6 nm) by employing both X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopies. By controlled desorption/adsorption of water, the filling fraction of the mesopores, thus the water layer thickness, can be adjusted, which in turn effects the variation of coordination structure of the ions therein. It is found that both Cu2+ and Br1- ions prefer staying exclusively in the core water, and in this circumstance no ion pairs have been detected in the solution of concentrations up to 1.0 M. Following capillary decondensation occurring at a filling fraction of ˜35% which corresponds to a water layer of about three monolayers, Br1- ions begin immediately to reconstruct their first coordination shell, characterized by ionic dehydration, shrinkage of ion-water bond length, and formation of ion pairs. In contrast, Cu2+ ions can retain a bulk-like coordination structure till being driven to bond directly to the pore surface when the filling fraction is below 20%. At the final stage of dehydration via thermal vacuum treatment at 110°C, Cu2+ ions can be completely reduced to the Cu1+ state, and recover at room temperature only when the filling fraction is above 14%. These results may be inspirable for the investigation of similar problems concerning hydrated ions in water solution under different confining conditions.

  5. Coordination variation of hydrated Cu2+/Br1− ions traversing the interfacial water in mesopores

    Directory of Open Access Journals (Sweden)

    Q. Wang

    2012-06-01

    Full Text Available Resolution of the atomistic and electronic details about the coordination structure variation of hydrated ions in the interfacial water is still a tough challenge, which is, however, essentially important for the understanding of ion adsorption, permeation and other similar processes in aqueous solutions. Here we report the tracing of coordination structure variation for hydrated Cu2+/Br1- ions traversing the interfacial water in Vycor mesopores (ϕ = 7.6 nm by employing both X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopies. By controlled desorption/adsorption of water, the filling fraction of the mesopores, thus the water layer thickness, can be adjusted, which in turn effects the variation of coordination structure of the ions therein. It is found that both Cu2+ and Br1- ions prefer staying exclusively in the core water, and in this circumstance no ion pairs have been detected in the solution of concentrations up to 1.0 M. Following capillary decondensation occurring at a filling fraction of ∼35% which corresponds to a water layer of about three monolayers, Br1- ions begin immediately to reconstruct their first coordination shell, characterized by ionic dehydration, shrinkage of ion-water bond length, and formation of ion pairs. In contrast, Cu2+ ions can retain a bulk-like coordination structure till being driven to bond directly to the pore surface when the filling fraction is below 20%. At the final stage of dehydration via thermal vacuum treatment at 110°C, Cu2+ ions can be completely reduced to the Cu1+ state, and recover at room temperature only when the filling fraction is above 14%. These results may be inspirable for the investigation of similar problems concerning hydrated ions in water solution under different confining conditions.

  6. Detection of the oxygen consumption rate of migrating zebrafish by electrochemical equalization systems.

    Science.gov (United States)

    Yasukawa, Tomoyuki; Koide, Masahiro; Tatarazako, Norihisa; Abe, Ryoko; Shiku, Hitoshi; Mizutani, Fumio; Matsue, Tomokazu

    2014-01-07

    A novel measurement system to determine oxygen consumption rates via respiration in migrating Zebrafish (Danio rerio) has been developed. A signal equalization system was adapted to detect oxygen in a chamber with one fish, because typical electrochemical techniques cannot measure respiration activities for migrating organisms. A closed chamber was fabricated using a pipet tip attached to a Pt electrode, and a columnar Vycor glass tip was used as the salt bridge. Pt electrode, which was attached to the chamber with one zebrafish, and Ag electrode were immersed in 10 mM potassium iodide (KI), and both the electrodes were connected externally to form a galvanic cell. Pt and Ag electrodes act as the cathode and anode to reduce oxygen and oxidize silver, respectively, allowing the deposition of insoluble silver iodide (AgI). The AgI acts as the signal source accumulated on the Ag electrode by conversion of oxygen. The amount of AgI deposited on the Ag electrode was determined by cathodic stripping voltammetry. The presence of zebrafish or its embryo led to a decrease in the stripping currents generated by a 10 min conversion of oxygen to AgI. The conversion of oxygen to AgI is disturbed by the migration of the zebrafish and allows the detection of different equalized signals corresponding to respiration activity. The oxygen consumption rates of the zebrafish and its embryo were estimated and determined to be ∼4.1 and 2.4 pmol·s(-1), respectively. The deposited AgI almost completely disappeared with a single stripping process. The signal equalization system provides a method to determine the respiration activities for migrating zebrafish and could be used to estimate environmental risk and for effective drug screening.

  7. Silica membranes for hydrogen separation in coal gas processing

    Energy Technology Data Exchange (ETDEWEB)

    Gavalas, G.R.

    1993-01-01

    The general objective of this project was to synthesize permselective membranes suitable for hydrogen separation from coal gas. The specific objectives were: (i) to synthesize membranes by chemical vapor deposition (CVD) of SiO[sub 2] or other oxides on porous support tubes, (ii) characterize the membranes by permeation measurements of various gases and by electron microscopy, and (iii) obtain information about the mechanism and kinetics Of SiO[sub 2] deposition, and model the process of membrane formation. Silica glass and certain other glasses, in dense (nonporous) form, are highly selective to hydrogen permeation. Since this high selectivity is accompanied by low permeability, however, a practical membrane must have a composite structure consisting of a thin layer of the active oxide supported on a porous tube or plate providing mechanical support. In this project the membranes were synthesized by chemical vapor deposition (CVD) of SiO[sub 2], TiO[sub 2], Al[sub 2]O[sub 3] and B[sub 2]O[sub 3] layers inside the walls of porous Vycor tubes (5 mm ID, 7 mm OD, 40 [Angstrom] mean pore diameter). Deposition of the oxide layer was carried out using the reaction of SiCl[sub 4] (or TiCl[sub 4], AlCl[sub 3], BCl[sub 3]) and water vapor at elevated temperatures. The porous support tube was inserted concentrically into a larger quartz tube and fitted with flow lines and pressure gauges. The flow of the two reactant streams was regulated by mass flow controllers, while the temperature was controlled by placing the reactor into a split-tube electric furnace.

  8. Silica membranes for hydrogen separation in coal gas processing. Final report, January 1993

    Energy Technology Data Exchange (ETDEWEB)

    Gavalas, G.R.

    1993-03-01

    The general objective of this project was to synthesize permselective membranes suitable for hydrogen separation from coal gas. The specific objectives were: (i) to synthesize membranes by chemical vapor deposition (CVD) of SiO{sub 2} or other oxides on porous support tubes, (ii) characterize the membranes by permeation measurements of various gases and by electron microscopy, and (iii) obtain information about the mechanism and kinetics Of SiO{sub 2} deposition, and model the process of membrane formation. Silica glass and certain other glasses, in dense (nonporous) form, are highly selective to hydrogen permeation. Since this high selectivity is accompanied by low permeability, however, a practical membrane must have a composite structure consisting of a thin layer of the active oxide supported on a porous tube or plate providing mechanical support. In this project the membranes were synthesized by chemical vapor deposition (CVD) of SiO{sub 2}, TiO{sub 2}, Al{sub 2}O{sub 3} and B{sub 2}O{sub 3} layers inside the walls of porous Vycor tubes (5 mm ID, 7 mm OD, 40 {Angstrom} mean pore diameter). Deposition of the oxide layer was carried out using the reaction of SiCl{sub 4} (or TiCl{sub 4}, AlCl{sub 3}, BCl{sub 3}) and water vapor at elevated temperatures. The porous support tube was inserted concentrically into a larger quartz tube and fitted with flow lines and pressure gauges. The flow of the two reactant streams was regulated by mass flow controllers, while the temperature was controlled by placing the reactor into a split-tube electric furnace.

  9. Preparation and characterization of new zeolite membranes. Application to gaseous separation; Preparation et caracterisation de nouvelles membranes de zeolithe application a la separation gazeuse

    Energy Technology Data Exchange (ETDEWEB)

    Anstett, M.

    1996-11-25

    Zeolites are interesting for the preparation of inorganic membranes which could be used for the continuous separation of gas and liquids by gas permeation and pervaporation. Zeolites membranes are obtained by hydrothermal synthesis and are characterized by XRD, SEM, TDA, IR, chemical analysis, EPMA, NMR, MAS NMR and gas permeation. After some tests of preparation of zeolite CHA and MFI self supporting membranes, the work is turned towards the preparation of zeolite MFI membranes supported by porous disks or {alpha} alumina, glass and tubes of carbon covered with a thin layer or zirconium dioxide. It is shown that the characteristics of the support (reactivity, pores dimensions, ...) strongly influence the quality of the prepared membrane. Two originals preparation processes are finalized. For the alumina disks, a gel precursor of zeolite is firs formed at the surface of the support by immersing successively that support in two non miscible liquids before the crystallisation. The gel is then converted into the zeolite by contact with water vapor. The zeolite layer obtained is localized at the surface of the support and present not only at the outside but also at the inside of the support. The characteristics of the zeolite layer can be controlled and the method can be adapted to various porous supports. The membrane obtained is interesting for hydrocarbons separations, for example the separation of methane and isobutane. In the case of Vycor glass disks, the reactivity of the support is first enhanced by contact with saturated water vapour. The temperature of the synthesis is then chosen relatively low in order to limit the attack of the support. With that method, a basic solution can be used without degradation of the support.The basicity leads to the formation of little crystals whose assembling is compact and homogeneous. The membrane obtained is interesting for example for the separation of normal butane and isobutane. (author) 71 refs.

  10. Classical transport in disordered systems

    Science.gov (United States)

    Papaioannou, Antonios

    This thesis reports on the manifestation of structural disorder on molecular transport and it consists of two parts. Part I discusses the relations between classical transport and the underlying structural complexity of the system. Both types of molecular diffusion, namely Gaussian and non- Gaussian are presented and the relevant time regimes are discussed. In addition the concept of structural universality is introduced and connected with the diffusion metrics. One of the most robust techniques for measuring molecular mean square displacements is magnetic resonance. This method requires encoding and subsequently reading out after an experimentally controlled time, a phase φ to the spins using magnetic field gradients. The main limitation for probing short diffusion lengths L(t) ˜ 1micro m with magnetic resonance is the requirement to encode and decode the phase φ in very short time intervals. Therefore, to probe such displacements a special probe was developed equipped with a gradient coil capable of delivering magnetic field gradients of approximately 90 G/cmA . The design of the probe is reported. Part I also includes a discussion of experiments of transport in two qualitatively different disordered phantoms and reports on a direct observation of universality in one-dimension. The results reveal the universal power law scaling of the diffusion coefficient at the long-time regime and illustrate the essence of structural universality by experimentally determining the structure correlation function of the phantoms. In addition, the scaling of the diffusive permeability of the phantoms with respect to the pore size is investigated. Additional work presented includes a detailed study of adsorption of methane gas in Vycor disordered glass. The techniques described in Part I of this thesis are widely used for measuring structural parameters of porous media, such as the surface-to-volume ratio or diffusive permeability. Part II of this thesis discusses the

  11. Measuring permeability, Young's modulus, and stress relaxation by the beam-bending technique

    Science.gov (United States)

    Vichit-Vadakan, Wilasa

    Recent interest in the permeability of cement paste, mortars, and concrete lies in the need to gain further understanding of mechanisms affecting the durability of these materials. Conventional techniques for measuring permeability are cumbersome and often take days to complete just one measurement. This thesis proposes a new technique for measuring the permeability. The advantage of this technique is that the results are obtained in a few minutes to a few hours; moreover, there is no problem with leaks or need for high pressures. The method is particularly well suited for examining the changes in permeability and viscoelastic properties of young cement paste samples. When a saturated rod of a porous material is instantaneously deflected under three-point bending, two types of relaxation processes occur simultaneously: hydrodynamic relaxation, caused by the flow of liquid in the porous body to restore ambient pressure, and viscoelastic relaxation of the solid network. By measuring the decrease in the force required to sustain a constant deflection, it is possible to obtain the permeability and Young's modulus from the hydrodynamic relaxation function, in addition to the stress relaxation function of the sample. The exact viscoelastic solution is developed and the total relaxation is shown to be very closely approximated as the product of the hydrodynamic and stress relaxation functions. The analytical results are verified on porous VycorRTM glass saturated in various solvents, including normal alcohols, water, and glycerol. The results show excellent agreement with the theory. Consistent with observations of previous workers, the permeability is found to be influenced by the size of the solvent molecule; by assuming that the pore surfaces are covered with a monolayer of immobile solvent, the observed variation can be explained. The evolution of the permeability, Young's modulus, and stress relaxation function are reported for Type III Portland cement paste with

  12. PREFACE: Water at interfaces Water at interfaces

    Science.gov (United States)

    Gallo, P.; Rovere, M.

    2010-07-01

    scales. Silicalite and tobermorite, a layered calcio-silicate model of cement and Vycor are analyzed. Gordillo and Martí consider structural and dynamical properties of water confined or close to carbon nanotubes or inside a slit pore of a single graphene sheet. Jedlovszky et al introduce a new method to determine the molecules located right at the boundary of two phases in a computer simulation. The new method is applied to the analysis of the interface of water with different apolar phases. Melchionna et al consider phenomena related to water in contact with thermophilic protein interfaces. In particular, they discuss the role of water in stabilizing these proteins. Rotenberg et al report results on the structure and dynamics of water at a clay surface. They analyze, in particular, the influence on the H-bond network of the surface oxygens and ions and investigate the surface H-bond formation and dissociation dynamics. Smirnov and Bougeard present examples of the spatial organization of molecules and of the short- and long-time dynamical behaviour of water confined in the pores of crystalline aluminosilicates, such as zeolites and clays, and in nanostructured materials. The last group opens with Sulpizi and Sprik who present density functional calculations of the dissociation constant of liquid water, implemented with a proton insertion/removal method. Jung and Marcus consider, more specifically, the properties of water in organic catalysis and discuss theoretical models and results obtained with quantum mechanical calculations. As organizers of the CECAM workshop 'Modeling and Simulation of Water at Interfaces from Ambient to Supercooled Conditions' we would like to thank CECAM, ESF-Simbioma, Wanda Andreoni, Emilie Bernard and Jordi Brusa. As guest editors of this special issue we would like to thank Gerhard Kahl and Philip Semple.