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Sample records for adsorbed organic films

  1. Computer simulations of adsorbed liquid crystal films

    NASA Astrophysics Data System (ADS)

    Wall, Greg D.; Cleaver, Douglas J.

    2003-01-01

    The structures adopted by adsorbed thin films of Gay-Berne particles in the presence of a coexisting vapour phase are investigated by molecular dynamics simulation. The films are adsorbed at a flat substrate which favours planar anchoring, whereas the nematic-vapour interface favours normal alignment. On cooling, a system with a high molecule-substrate interaction strength exhibits substrate-induced planar orientational ordering and considerable stratification is observed in the density profiles. In contrast, a system with weak molecule-substrate coupling adopts a director orientation orthogonal to the substrate plane, owing to the increased influence of the nematic-vapour interface. There are significant differences between the structures adopted at the two interfaces, in contrast with the predictions of density functional treatments of such systems.

  2. Hydrophobic Porous Material Adsorbs Small Organic Molecules

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K.; Hickey, Gregory S.

    1994-01-01

    Composite molecular-sieve material has pore structure designed specifically for preferential adsorption of organic molecules for sizes ranging from 3 to 6 angstrom. Design based on principle that contaminant molecules become strongly bound to surface of adsorbent when size of contaminant molecules is nearly same as that of pores in adsorbent. Material used to remove small organic contaminant molecules from vacuum systems or from enclosed gaseous environments like closed-loop life-support systems.

  3. Performance of PF BL-13A, a vacuum ultraviolet and soft X-ray undulator beamline for studying organic thin films adsorbed on surfaces

    NASA Astrophysics Data System (ADS)

    Toyoshima, Akio; Kikuchi, Takashi; Tanaka, Hirokazu; Mase, Kazuhiko; Amemiya, Kenta; Ozawa, Kenichi

    2013-03-01

    We report on the present status of a vacuum ultraviolet and soft X-ray undulator beamline, BL-13A, located at the Photon Factory. BL-13A is mainly dedicated to the study of organic thin films adsorbed on well-defined surfaces, using angle-resolved photoelectron spectroscopy (ARPES), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS). The photon-energy resolution (E/ΔE) is estimated to be about 10000 at a photon energy of 64 eV with an exit-slit width of 30 μm. The photon intensity is estimated to be 2.9 × 1012 to 5.6 × 108 photons/s for photon energies of 30-1600 eV with an exit-slit width of 100 μm at the ring current of 450 mA. An ultrahigh vacuum (UHV) chamber equipped with an electron-energy analyzer (Gamma Data/Scienta, SES 200) is used as the main end station for ARPES, XPS, and XAS measurements. A sample can be transferred from a UHV chamber for sample preparation or from a UHV chamber for the evaporation of organic materials. The sample-holder acceptors are equipped with a heating and cooling system. The overall electron-energy resolution is estimated to be about 12 meV at a photon energy of 30 eV.

  4. Size selective hydrophobic adsorbent for organic molecules

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K. (Inventor); Hickey, Gregory S. (Inventor)

    1997-01-01

    The present invention relates to an adsorbent formed by the pyrolysis of a hydrophobic silica with a pore size greater than 5 .ANG., such as SILICALITE.TM., with a molecular sieving polymer precursor such as polyfurfuryl alcohol, polyacrylonitrile, polyvinylidene chloride, phenol-formaldehyde resin, polyvinylidene difluoride and mixtures thereof. Polyfurfuryl alcohol is the most preferred. The adsorbent produced by the pyrolysis has a silicon to carbon mole ratio of between about 10:1 and 1:3, and preferably about 2:1 to 1:2, most preferably 1:1. The pyrolysis is performed as a ramped temperature program between about 100.degree. and 800.degree. C., and preferably between about 100.degree. and 600.degree. C. The present invention also relates to a method for selectively adsorbing organic molecules having a molecular size (mean molecular diameter) of between about 3 and 6 .ANG. comprising contacting a vapor containing the small organic molecules to be adsorbed with the adsorbent composition of the present invention.

  5. Interactions of organic contaminants with mineral-adsorbed surfactants

    USGS Publications Warehouse

    Zhu, L.; Chen, B.; Tao, S.; Chiou, C.T.

    2003-01-01

    Sorption of organic contaminants (phenol, p-nitrophenol, and naphthalene) to natural solids (soils and bentonite) with and without myristylpyridinium bromide (MPB) cationic surfactant was studied to provide novel insight to interactions of contaminants with the mineral-adsorbed surfactant. Contaminant sorption coefficients with mineral-adsorbed surfactants, Kss, show a strong dependence on surfactant loading in the solid. At low surfactant levels, the Kss values increased with increasing sorbed surfactant mass, reached a maximum, and then decreased with increasing surfactant loading. The Kss values for contaminants were always higher than respective partition coefficients with surfactant micelles (Kmc) and natural organic matter (Koc). At examined MPB concentrations in water the three organic contaminants showed little solubility enhancement by MPB. At low sorbed-surfactant levels, the resulting mineral-adsorbed surfactant via the cation-exchange process appears to form a thin organic film, which effectively "adsorbs" the contaminants, resulting in very high Kss values. At high surfactant levels, the sorbed surfactant on minerals appears to form a bulklike medium that behaves essentially as a partition phase (rather than an adsorptive surface), with the resulting Kss being significantly decreased and less dependent on the MPB loading. The results provide a reference to the use of surfactants for remediation of contaminated soils/sediments or groundwater in engineered surfactant-enhanced washing.

  6. Structure and properties of water film adsorbed on mica surfaces

    NASA Astrophysics Data System (ADS)

    Zhao, Gutian; Tan, Qiyan; Xiang, Li; Cai, Di; Zeng, Hongbo; Yi, Hong; Ni, Zhonghua; Chen, Yunfei

    2015-09-01

    The structure profiles and physical properties of the adsorbed water film on a mica surface under conditions with different degrees of relative humidity are investigated by a surface force apparatus. The first layer of the adsorbed water film shows ice-like properties, including a lattice constant similar with ice crystal, a high bearing capacity that can support normal pressure as high as 4 MPa, a creep behavior under the action of even a small normal load, and a character of hydrogen bond. Adjacent to the first layer of the adsorbed water film, the water molecules in the outer layer are liquid-like that can flow freely under the action of external loads. Experimental results demonstrate that the adsorbed water layer makes the mica surface change from hydrophilic to weak hydrophobic. The weak hydrophobic surface may induce the latter adsorbed water molecules to form water islands on a mica sheet.

  7. Hydraulic properties of adsorbed water films in unsaturated porous media

    SciTech Connect

    Tokunaga, Tetsu K.

    2009-03-01

    Adsorbed water films strongly influence residual water saturations and hydraulic conductivities in porous media at low saturations. Hydraulic properties of adsorbed water films in unsaturated porous media were investigated through combining Langmuir's film model with scaling analysis, without use of any adjustable parameters. Diffuse double layer influences are predicted to be important through the strong dependence of adsorbed water film thickness (f) on matric potential ({Psi}) and ion charge (z). Film thickness, film velocity, and unsaturated hydraulic conductivity are predicted to vary with z{sup -1}, z{sup -2}, and z{sup -3}, respectively. In monodisperse granular media, the characteristic grain size ({lambda}) controls film hydraulics through {lambda}{sup -1} scaling of (1) the perimeter length per unit cross sectional area over which films occur, (2) the critical matric potential ({Psi}{sub c}) below which films control flow, and (3) the magnitude of the unsaturated hydraulic conductivity when {Psi} < {Psi}{sub c}. While it is recognized that finer textured sediments have higher unsaturated hydraulic conductivities than coarser sands at intermediate {Psi}, the {lambda}{sup -1} scaling of hydraulic conductivity predicted here extends this understanding to very low saturations where all pores are drained. Extremely low unsaturated hydraulic conductivities are predicted under adsorbed film-controlled conditions (generally < 0.1 mm y{sup -1}). On flat surfaces, the film hydraulic diffusivity is shown to be constant (invariant with respect to {Psi}).

  8. Optical spectroscopy and scanning tunneling microscopy studies of molecular adsorbates and anisotropic ultrathin films. Final report

    SciTech Connect

    Hemminger, J.C.

    1998-09-01

    The bonding, chemistry and ordering of molecular adsorbates on well defined single crystal surfaces and in ultrathin films was to be studied in an effort to develop sufficient fundamental understanding to allow the controlled preparation of anisotropic ultrathin films of organic monolayers. In this research the authors combine the use of optical probes (Raman spectroscopy, laser induced thermal desorption with Fourier transform mass spectrometry detection) with scanning tunneling microscopy (STM) and conventional methods of UHV surface science (Auger electron spectroscopy, x-ray photoelectron spectroscopy, low energy electron diffraction, and thermal desorption spectroscopy). The conventional surface probes provide well tested methods for the preparation and characterization of single crystal substrates. The optical probes used in the experiments provide powerful methods for the molecular identification of adsorbates in monolayers and ultrathin films. Scanning tunneling microscopy provides one with the ability to determine the detailed molecular level ordering of the molecular adsorbates. The emphasis of this research is on more complex molecular absorbates some of which are monomer precursors to ultrathin polymer films. Enhanced methods of Raman spectroscopy have been developed for the study of monolayer adsorbates on surfaces in ultrahigh vacuum environments. This report gives an overview of recent research results, including the construction of UHV variable temperature STM, analysis of STM images, growth and chemistry of intermetallic single crystal ultrathin films, and electron beam induced chemistry of tetracyanoquinodimethane.

  9. Alkylammonium montmorillonites as adsorbents for organic vapors from air

    SciTech Connect

    Harper, M.; Purnell, C.J. )

    1990-01-01

    Montmorillonite clays may be modified by the exchange of the inorganic interlayer cations with alkylammonium ions, resulting in a fixed internal porosity. The pore size and shape depend on the nature of the alkylammonium ion. A number of different ions were used to prepare adsorbents with varying properties, and these were examined for their potential application to sampling organic vapors in air. Characterization involved determination of nitrogen and water contents, surface area, interlayer spacing, thermal stability, and breakthrough volumes of organic vapors. The adsorbent that showed the most promise (tetramethylammonium montmorillonite (TMA)) was further evaluated for use as an adsorbent in both thermal- and solvent-desorable sampling systems.

  10. Complexation of trace metals by adsorbed natural organic matter

    USGS Publications Warehouse

    Davis, J.A.

    1984-01-01

    The adsorption behavior and solution speciation of Cu(II) and Cd(II) were studied in model systems containing colloidal alumina particles and dissolved natural organic matter. At equilibrium a significant fraction of the alumina surface was covered by adsorbed organic matter. Cu(II) was partitioned primarily between the surface-bound organic matter and dissolved Cu-organic complexes in the aqueous phase. Complexation of Cu2+ with the functional groups of adsorbed organic matter was stronger than complexation with uncovered alumina surface hydroxyls. It is shown that the complexation of Cu(II) by adsorbed organic matter can be described by an apparent stability constant approximately equal to the value found for solution phase equilibria. In contrast, Cd(II) adsorption was not significantly affected by the presence of organic matter at the surface, due to weak complex formation with the organic ligands. The results demonstrate that general models of trace element partitioning in natural waters must consider the presence of adsorbed organic matter. ?? 1984.

  11. AQUATIC PHOTOLYSIS OF OXY-ORGANIC COMPOUNDS ADSORBED ON GOETHITE.

    USGS Publications Warehouse

    Goldberg, Marvin C.

    1985-01-01

    Organic materials that will not absorb light at wavelengths longer than 295 nanometers (the solar wavelength cutoff) may nevertheless, undergo electron transfer reactions initiated by light. These reactions occur when the organic materials are adsorbed as ligand complexes to the surface of iron oxy-hydroxide (goethite). The adsorbed materials can be either inner or outer coordination sphere complexes. Goethite was chosen as the iron oxyhydroxide surface because it has the highest thermodynamic stability of any of the oxyhydroxides in water and it can be synthesized easily, with high purity.

  12. Adsorbed Methane Film Properties in Nanoporous Carbon Monoliths

    NASA Astrophysics Data System (ADS)

    Soo, Yuchoong; Chada, Nagaraju; Beckner, Matthew; Romanos, Jimmy; Burress, Jacob; Pfeifer, Peter

    2013-03-01

    Carbon briquetting can increase methane storage capacity by reducing the useless void volume resulting in a better packing density. It is a robust and efficient space-filling form for an adsorbed natural gas vehicle storage tank. To optimize methane storage capacity, we studied three fabrication process parameters: carbon-to-binder ratio, compaction temperature, and pyrolysis temperature. We found that carbon-to-binder ratio and pyrolysis temperature both have large influences on monolith uptakes. We have been able to optimize these parameters for high methane storage. All monolith uptakes (up to 260 bar) were measured by a custom-built, volumetric, reservoir-type instrument. The saturated film density and the film thickness was determined using linear extrapolation on the high pressure excess adsorption isotherms. The saturated film density was also determined using the monolayer Ono-Kondo model. Film densities ranged from ca. 0.32 g/cm3 - 0.37 g/cm3.The Ono-Kondo model also determines the binding energy of methane. Binding energies were also determined from isosteric heats calculated from the Clausius-Clapeyron equation and compared with the Ono-Kondo model method. Binding energies from Ono-Kondo were ca. 7.8 kJ/mol - 10 kJ/mol. Work funded by California Energy Commission Contract #500-08-022.

  13. DESIGNING FIXED-BED ADSORBERS TO REMOVE MIXTURES OF ORGANICS.

    EPA Science Inventory

    A liquid-phase granular activated carbon (GAC) pilot plant and a full-scale GAC adsorber were designed, built, and operated in order to evaluate their performance for treating a groundwater contaminated with several volatile and synthetic organic chemicals. Several empty bed con...

  14. Adsorbed water and thin liquid films on Mars

    NASA Astrophysics Data System (ADS)

    Boxe, C. S.; Hand, K. P.; Nealson, K. H.; Yung, Y. L.; Yen, A. S.; Saiz-Lopez, A.

    2012-07-01

    At present, bulk liquid water on the surface and near-subsurface of Mars does not exist due to the scarcity of condensed- and gas-phase water, pressure and temperature constraints. Given that the nuclei of soil and ice, that is, the soil solid and ice lattice, respectively, are coated with adsorbed and/or thin liquid films of water well below 273 K and the availability of water limits biological activity, we quantify lower and upper limits for the thickness of such adsorbed/water films on the surface of the Martian regolith and for subsurface ice. These limits were calculated based on experimental and theoretical data for pure water ice and water ice containing impurities, where water ice containing impurities exhibit thin liquid film enhancements, ranging from 3 to 90. Close to the cold limit of water stability (i.e. 273 K), thin liquid film thicknesses at the surface of the Martian regolith is 0.06 nm (pure water ice) and ranges from 0.2 to 5 nm (water ice with impurities). An adsorbed water layer of 0.06 nm implies a dessicated surface as the thickness of one monolayer of water is 0.3 nm but represents 0.001-0.02% of the Martian atmospheric water vapour inventory. Taking into account the specific surface area (SSA) of surface-soil (i.e. top 1 mm of regolith and 0.06 nm adsorbed water layer), shows Martian surface-soil may contain interfacial water that represents 6-66% of the upper- and lower-limit atmospheric water vapour inventory and almost four times and 33%, the lower- and upper-limit Martian atmospheric water vapour inventory. Similarly, taking the SSA of Martian soil, the top 1 mm or regolith at 5 nm thin liquid water thickness, yields 1.10×1013 and 6.50×1013 litres of waters, respectively, 55-325 times larger than Mars' atmospheric water vapour inventory. Film thicknesses of 0.2 and 5 nm represent 2.3×104-1.5×106 litres of water, which is 6.0×10-7-4.0×10-4%, respectively, of a 10 pr μm water vapour column, and 3.0×10-6-4.0×10-4% and 6.0×10

  15. Selective Gas Capture Ability of Gas-Adsorbent-Incorporated Cellulose Nanofiber Films.

    PubMed

    Shah, Kinjal J; Imae, Toyoko

    2016-05-01

    The 2,2,6,6-tetramethylpiperidine-1-oxyl radical-oxidized cellulose nanofibers (TOCNF) were hybridized with cation and anion-exchange organoclays, where poly(amido amine) dendrimers were loaded to enhance the functionality of gas adsorption, since dendrimers have the high adsorbability and the enough selectivity on the gas adsorption. The thin films were prepared from the organoclay-TOCNF hybrids and supplied to the gas adsorption. The adsorption of CO2 and NH3 gases increased with an increasing amount of organoclays in TOCNF films, but the behavior of the increase depended on gases, clays, and dendrimers. The hydrotalcite organoclay-TOCNF films displayed the highest adsorption of both gases, but the desorption of CO2 gas from hydrotalcite organoclay-TOCNF films was drastically high in comparison with the other systems. While the CO2 gas is adsorbed and remained on cationic dendrimer sites in cation-exchange organoclay-TOCNF films, the CO2 gas is adsorbed on cationic clay sites in anion exchange organoclay-TOCNF films, and it is easily desorbed from the films. The NH3 adsorption is inversive to the CO2 adsorption. Then the CO2 molecules adsorbed on the cationic dendrimers and the NH3 molecules adsorbed on the anionic dendrimers are preferably captured in these adsorbents. The present research incorporated dendrimers will be contributing to the development of gas-specialized adsorbents, which are selectively storable only in particular gases. PMID:27035217

  16. Enhanced photodegradation of organic dyes adsorbed on a clay.

    PubMed

    Tani, Seiji; Yamaki, Hiroshi; Sumiyoshi, Azumi; Suzuki, Yasutaka; Hasegawa, Shinya; Yamazaki, Suzuko; Kawamata, Jun

    2009-01-01

    The interaction of three photoactive organic dyes, Rhodamine B, Rhodamine 6G and a stilbazolium derivative 4'-dimethylamino-N-methyl-4-stilbazolium with synthetic sodium-saponite has been examined by UV-visible absorption spectroscopy. In all cases, bathochromic shifts and the reduction of peak absorbance for the dyes were observed in the absorption spectra at a low dye concentration (25% adsorption of the cation exchange capacity (CEC) of the clay), although the shape and the width of their absorption bands were similar to those in aqueous solution. This absorption behavior indicates that the organic dye molecules adsorbed onto the surface of the negatively charged clay particles and the adsorbed molecules were well dispersed. The photodegradation of the organic dyes in aqueous solution and in the clay suspension has been also examined by the irradiation of a laser beam at a wavelength of 532 nm. We have found that the hybridization of the organic dyes with the exfoliated clay particles largely enhanced a photodegradation. The clay particles acted as a catalyst even at a high concentration such as approximately 300% of CEC. PMID:19441365

  17. Effects of the Adsorbed Polymer Nanolayers on the Dewetting of Polystyrene Thin Films

    NASA Astrophysics Data System (ADS)

    Cheung, Justin; Wang, Jiaxun; Jiang, Naisheng; Endoh, Maya; Koga, Tadanori

    2015-03-01

    It was previously reported that irreversibly adsorbed polymer nanolayers can be produced on solid substrates by thermal annealing. This study sought to determine the impact of the adsorbed nanolayers on film stability of ultrathin polystyrene (PS) films. A series of bilayers composed of the bottom PS adsorbed nanolayers and PS overlayers with different molecular weights were prepared as model systems. The surface structures of the bilayer films annealed above the bulk glass transition temperature were analyzed by using optical and atomic force microscopes. We will discuss the unique roles of the adsorbed polymer chains in the stability of the liquid thin films. T. K. acknowledges the partial financial support from NSF Grant No. CMMI-1332499.

  18. Aging of the nanosized photochromic WO3 films and the role of adsorbed water in the photochromism

    NASA Astrophysics Data System (ADS)

    Gavrilyuk, A. I.

    2016-02-01

    Here it has been reported on aging of the nanosized WO3 film, which is revealed is continuous reduction of the photochromic sensitivity over time. Water molecules physically adsorbed on the film surface from ambient air form donor-acceptor and hydrogen bonds, changing gradually the adsorption state to chemisorption which prevents an access of organic molecules that serve as hydrogen donors by the photochromism. The mechanism of the process has been investigated and discussed. The role of water in the photochromism has been highlighted. The difference in the efficiency for being of a hydrogen donor in the photochromic process between water and organic molecules is discussed.

  19. Direct Measurement of the Adsorbed Film Volume for Estimating Heats of Adsorption

    NASA Astrophysics Data System (ADS)

    Gillespie, Andrew; Dohnke, Elmar; Rash, Tyler; Stalla, David; Knight, Ernest; Seydel, Florian; Sweany, Mark; Pfeifer, Peter

    Compressed hydrogen and methane require extremely high pressures or low temperatures in order to compete with the energy density of conventional fossil fuels. Adsorbent materials provide a means to increase the energy density of these gasses up to 6 times that of compressed gas at the same temperature and pressure. One major concern in engineering adsorbed gas systems is thermal management during charging and discharging. Adsorption is an exothermic process, releasing heat during charging and absorbing heat during discharging. To estimate the heat of adsorption, it is common to analyze excess adsorption isotherms by converting to absolute adsorption and employ the Clausius Clapeyron relation. However, this method requires an assumed volume of the adsorbed state. It is common for researchers to assume that the adsorbed film occupies the entire pore volume of the adsorbent material. However, the adsorbed film only occupies a fraction of the total pore volume. This yields heats of adsorption that are underestimated by as much as 10kJ/mol at high coverage. In this talk, we present a method to directly measure the adsorbed film volume as a function of temperature and present the resulting heats of adsorption for both methane and hydrogen.

  20. Heat capacity measurements of atoms and molecules adsorbed on evaporated metal films

    SciTech Connect

    Kenny, T.W.

    1989-05-01

    Investigations of the properties of absorbed monolayers have received great experimental and theoretical attention recently, both because of the importance of surface processes in practical applications such as catalysis, and the importance of such systems to the understanding of the fundamentals of thermodynamics in two dimensions. We have adapted the composite bolometer technology to the construction of microcalorimeters. For these calorimeters, the adsorption substrate is an evaporated film deposited on one surface of an optically polished sapphire wafer. This approach has allowed us to make the first measurements of the heat capacity of submonolayer films of /sup 4/He adsorbed on metallic films. In contrast to measurements of /sup 4/He adsorbed on all other insulating substrates, we have shown that /sup 4/He on silver films occupies a two-dimensional gas phase over a broad range of coverages and temperatures. Our apparatus has been used to study the heat capacity of Indium flakes. CO multilayers, /sup 4/He adsorbed on sapphire and on Ag films and H/sub 2/ adsorbed on Ag films. The results are compared with appropriate theories. 68 refs., 19 figs.

  1. Elastic mediated force between nanoparticles adsorbed on smectic films under an external field.

    PubMed

    Pereira, Maria S S; Lyra, Marcelo L; de Oliveira, Italo N

    2013-02-01

    Within the harmonic approximation, we analytically determine the elastic-mediated interaction between colloidal nanoparticles adsorbed on the surface of smectic films under the influence of an external field. Both cases of free-standing films and films deposited over a solid substrate are considered. We show that the asymptotic decay (1/R in free-standing and exponential in deposited films) is not altered by the external field. However, the external field plays distinct roles according to the film configuration, the interparticle distance, the film thickness, and the surface tension at the film-gas interface. We provide a detailed discussion under the light of the distinct mechanisms controlling the undulations of the surface layer. PMID:23496530

  2. Structure and dynamics of ultrathin organic films

    NASA Astrophysics Data System (ADS)

    Kiktyeva, Tatyana A.

    Existing and newly developed nonlinear optical methods have been used to characterize molecular structure, orientation and dynamics at interfaces. Optical second harmonic generation (SHG) studies have been conducted on molecular films of the organic dyes, rhodamine 6G and malachite green, adsorbed at the fused silica/air interface. The second harmonic response from the organic dye films was found to be a non-monotonic function of the surface concentration with discontinuities corresponding to completion of successive monolayers. This behavior reflects ordering of molecular adlayers, which extends for several layers. Polarized SHG studies in conjunction with optical absorbance and fluorescence measurements were used to determine the type of interactions responsible for the adsorption in the ordered layers. The results indicate that the well-defined order within the first layer is due to the specific adsorbate-substrate interactions. Orientation in subsequent layers is teed by adsorbate-adsorbate interactions, dependent on the nature of the adsorbate and consequently on its orientation within the first layer. These results provide a direct measure of the extent of the interfacial ordering and molecular interactions at the solid/air interface and can be used to determine an adsorbate's filling factor. Time and frequency resolved vibrational spectra of a monolayer of amphiphilic molecules at the CaF2/air interface were investigated using infrared-visible sum frequency generation. Vibrational wave packet dynamics following coherent excitation of CH3 vibrational modes with broad bandwidth infrared pulses is reported. The induced macroscopic polarization displays quantum interference effects (quantum beats) and decays on a time scale dependent on the nature of the interfacial environment. These observations provide a link between the degree of structural order of the monolayer and the vibrational coherence lifetime. Monitoring interfacial wave packet dynamics represents a

  3. Adsorbate-induced demagnetization and restructuring of ultrathin magnetic films: CO chemisorbed on γ-Fe/Cu(100)

    NASA Astrophysics Data System (ADS)

    Spišák, D.; Hafner, J.

    2001-09-01

    First-principles local-spin-density (LSD) investigations of the structural, magnetic, and electronic properties of clean and CO-adsorbed ultrathin γ-iron films epitaxially grown on Cu(100) surfaces demonstrate that both the geometrical and the magnetic structures of the films are profoundly modified by the adsorption of CO. The enhanced magnetic moments of the top-layer atoms are strongly quenched by the presence of the adsorbate. Due to the pronounced magnetovolume effect, this leads also to a correlated change in the interlayer relaxations. Strikingly, the adsorbate-induced demagnetization is primarily limited to those surface atoms directly bonded to the adsorbate. This leads to the formation of an in-plane magnetic pattern in a partially adsorbate-covered film. The comparison of the calculated vibrational eigenfrequencies of the CO adsorbate with experiment confirms the picture based on the LSD calculations.

  4. Thermodynamic study of argon films adsorbed on boron nitride

    SciTech Connect

    Migone, A.D.; Alkhafaji, M.T. ); Vidali, G. ); Karimi, M. )

    1993-03-15

    We have performed a detailed adsorption isotherm study of Ar on BN for temperatures between 65 and 80 K. The isothermal compressibility of the films was obtained from adsorption data. At monolayer coverages, a small isotherm substep is present at melting. We found two isothermal compressibility peaks in the first layer: a sharp peak, corresponding to the melting substep, and a smaller, broader peak that occurs at lower pressures. At multilayer coverages we found reentrant layering occurring in the third and fourth layers of the film. We compare our layering results with predictions for the preroughening transition. We also found a series of small steps in the isotherms between the second and third layers and between the third and fourth layers of the film. These small steps are evidence of individual layer melting for the second and third layers. Our results at monolayer and at multilayer coverages are extensively compared to those found for Ar on graphite. We have also performed calculations of the rare-gas--BN interaction potentials. Our calculations indicate the substrate corrugation is smaller for the rare-gas--BN systems than it is for the same rare gases on graphite. The implications of this result for the possible existence of monolayer-commensurate solids on BN are discussed.

  5. Influence of fluoride-detergent combinations on the visco-elasticity of adsorbed salivary protein films.

    PubMed

    Veeregowda, Deepak H; van der Mei, Henny C; Busscher, Henk J; Sharma, Prashant K

    2011-02-01

    The visco-elasticity of salivary-protein films is related to mouthfeel, lubrication, biofilm formation, and protection against erosion and is influenced by the adsorption of toothpaste components. The thickness and the visco-elasticity of hydrated films (determined using a quartz crystal microbalance) of 2-h-old in vitro-adsorbed salivary-protein films were 43.5 nm and 9.4 MHz, respectively, whereas the dehydrated thickness, measured using X-ray photoelectron spectroscopy, was 2.4 nm. Treatment with toothpaste slurries decreased the thickness of the film, depending on the fluoride-detergent combination involved. Secondary exposure to saliva resulted in a regained thickness of the film to a level similar to its original thickness; however, no association was found between the thickness of hydrated and dehydrated films, indicating differences in film structure. Treatment with stannous fluoride/sodium lauryl sulphate (SnF(2)/SLS)-containing toothpaste slurries yielded a strong, immediate two-fold increase in characteristic film frequency (f(c)) with respect to untreated films, indicating cross-linking in adsorbed salivary-protein films by Sn(2+) that was absent when SLS was replaced with sodium hexametaphosphate (NaHMP). Secondary exposure to saliva of films treated with SnF(2) caused a strong, six-fold increase in f(c) compared with primary salivary-protein films, regardless of whether SLS or NaHMP was the detergent. This suggests that ionized stannous is not directly available for cross-linking in combination with highly negatively charged NaHMP, but becomes slowly available after initial treatment to cause cross-linking during secondary exposure to saliva. PMID:21244507

  6. Electron-Stimulated Oxidation of Thin Water Films Adsorbed on TiO2(110)

    SciTech Connect

    Lane, Christopher D.; Petrik, Nikolay G.; Orlando, Thomas M.; Kimmel, Greg A.

    2007-11-08

    Electron-stimulated reactions in thin (< 3 monolayer, ML) water films adsorbed on TiO2(110) are investigated. For electron fluences less than ~1×1016 e-/cm2, irradiation with 100 eV electrons results in electron-stimulated desorption (ESD) of atomic and molecular hydrogen, but no measurable O2. The ESD leaves adsorbed hydroxyls which oxidize the TiO2(110) surface and change the post-irradiation TPD spectra of the remaining water in characteristic ways. The species remaining on the TiO2(110) after irradiation of adsorbed water films are apparently similar to those produced without irradiation by co-dosing water and O2. Annealing above ~600 K reduces the oxidized surfaces, and water TPD spectra characteristic of ion sputtered and annealed TiO2(110) are recovered. The rate of electron-stimulated “oxidation” of the water films is proportional to the coverage of water in the first layer for coverages less than 1 ML. However, higher coverages suppress this reaction. When thin water films are irradiated, the rate of electron-stimulated oxidation is independent of the initial oxygen vacancy concentration, as is the final oxidized state achieved at high electron fluences. To explain the results, we propose that electron excitation of water molecules adsorbed on Ti4+ sites leads to desorption of hydrogen atoms and leaves an OH adsorbed at the site. If hydroxyls are present in the bridging oxygen rows, these react with the OH’s on the Ti4+ sites to reform water and heal the oxygen vacancy associated with the bridging OH. Once the bridge bonded hydroxyls have been eliminated, further irradiation increases the concentration of OH’s in the Ti4+ rows leading to the creation of species which block sites in the Ti4+ rows, perhaps H2O2 and/or HO2.

  7. RADIOLYSIS OF ORGANIC COMPOUNDS IN THE ADSORBED STATE

    DOEpatents

    Sutherland, J.W.; Allen, A.O.

    1961-10-01

    >A method of forming branch chained hydrocarbons by means of energetic penetrating radiation is described. A solid zeolite substrate is admixed with a cobalt ion and is irradiated with a hydrocarbon adsorbed therein. Upon irradiation with gamma rays, there is an increased yield of branched and lower molecular straight chain compounds. (AEC)

  8. Anomalous conformational transitions in cytochrome C adsorbing to Langmuir-Blodgett films

    NASA Astrophysics Data System (ADS)

    Sankaranarayanan, Kamatchi; Nair, B. U.; Dhathathreyan, A.

    2013-05-01

    Helix to beta conformational transitions in proteins has attracted much attention due to their relevance to fibril formation which is implicated in many neurological diseases. This study reports on unusual conformational transition of cytochrome C adsorbing to hydrophilic surface containing pure cationic lipid and mixed Langmuir-Blodgett films (LB films) of cationic and neutral lipids. Evidence for conformational changes of the protein from its native helical state to beta sheet comes from Circular dichroic spectroscopy (CD spectroscopy). Analysis of these samples using High resolution TEM (HRTEM) shows a typical fibrillar pattern with each strand spacing of about 0.41 nm across which can be attributed to the repeat distance of interdigitated neighboring hydrogen-bonded ribbons in a beta sheet. Changes in contact angles of protein adsorbing to the LB films together with the increased mass uptake of water using quartz crystal microbalance (QCM) confirm the role of positive charges in the conformational transition. Dehydration of the protein resulting from the excess water entrainment in the polar planes of the cationic lipid in hydrophilic surface seems to trigger the refolding of the protein to beta sheet while it retains its native conformation in hydrophobic films. The results suggest that drastic conformational changes in CytC adsorbing to cationic lipids may be of significance in its role as a peripheral membrane protein.

  9. Unusual Morphologies of Poly(vinyl alcohol) Thin Films Adsorbed on Poly(dimethylsiloxane) Substrates.

    PubMed

    Karki, Akchheta; Nguyen, Lien; Sharma, Bhanushee; Yan, Yan; Chen, Wei

    2016-04-01

    Adsorption of poly(vinyl alcohol) (PVOH), 99% and 88% hydrolyzed poly(vinyl acetate), to poly(dimethylsiloxane) (PDMS) substrates was studied. The substrates were prepared by covalently attaching linear PDMS polymers of 2, 9, 17, 49, and 116 kDa onto silicon wafers. As the PDMS molecular weight/thickness increases, the adsorbed PVOH thin films progressively transition from continuous to discontinuous morphologies, including honeycomb and fractal/droplet. The structures are the result of thin film dewetting that occurs upon exposure to air. The PVOH film thickness does not vary significantly on these PDMS substrates, implicating the PDMS thickness as the cause for the morphology differences. The adsorbed PVOH thin films are less stable and have a stronger tendency to dewet on thicker, more liquid-like PDMS layers. When PVOH(99%) and PVOH(88%) thin films are compared, fractal and droplet morphologies are observed on high molecular weight PDMS substrates, respectively. The formation of the unique fractal features in the PVOH(99%) thin films as well as other crystalline and semicrystalline thin films is most likely driven by crystallization during the dehydration process in a diffusion-limited aggregation fashion. The only significant enhancement in hydrophilicity via PVOH adsorption was obtained on PDMS(2k), which is completely covered with a PVOH thin film. To mimic the lower receding contact angle and less liquid-like character of the PDMS(2k) substrate, light plasma treatment of the higher molecular weight PDMS substrates was carried out. On the treated PDMS substrates, the adsorbed PVOH thin films are in the more continuous honeycomb morphology, giving rise to significantly enhanced wettability. Furthermore, hydrophobic recovery of the hydrophilized PDMS substrates was not observed during a 1 week period. Thus, light plasma oxidation and subsequent PVOH adsorption can be utilized as a means to effectively hydrophilize conventional PDMS substrates. This study

  10. EVALUATION OF SOLID ADSORBENTS FOR THE COLLECTION AND ANALYSES OF AMBIENT BIOGENIC VOLATILE ORGANICS

    EPA Science Inventory

    Micrometeorological flux measurements of biogenic volatile organic compounds (BVOCs) usually require that large volumes of air be collected (whole air samples) or focused during the sampling process (cryogenic trapping or gas-solid partitioning on adsorbents) in order to achiev...

  11. Structural investigations of adsorbed films of Methyl Halides on Boron Nitride

    NASA Astrophysics Data System (ADS)

    Sprung, Michael; Freitag, Andrea; Hanson, Jonathan; Larese, John

    2000-03-01

    The Methyl Halides are a group of molecules whose properties of thin adsorbed films on Graphite have been well characterized. Boron Nitride forms a hexagonal structure with a slightly larger (about 2% ) unit cell than Graphite. The study of thin films of Methyl Halides (CH_3R, R=Cl, Br and I) on Boron Nitride is motivated by the hope to gain a better understanding of adsorbate-substrate interaction. High resolution adsorption isotherms and x-ray powder diffraction have been used to investigate the monolayer structures of CH_3R adsorbed on Boron Nitride. The experiments were carried out at the Beamline X7B of the NSLS. The gases were dosed onto the sample with an automated gas handling system, and a Mar345 image plate detector was used to collect the data. The measurements were performed in a temperature range between 50 and 175 K. All three adsorbates form a solid monolayer structure on Boron Nitride at low temperature. The structure of Methyl Chloride and Methyl Bromide is very similar to the high-density structure of CH_3Cl on Graphite. This is surprising for CH_3Br because it forms a different structure on Graphite. Methyl Iodide forms similar structures on both substrates.

  12. Aggregate formation of eosin-Y adsorbed on nanocrystalline TiO2 films

    NASA Astrophysics Data System (ADS)

    Yaguchi, Kaori; Furube, Akihiro; Katoh, Ryuzi

    2012-11-01

    We have studied the adsorption of eosin-Y on nanocrystalline TiO2 films with two different solvents namely acetonitrile (ACN) and ethanol (EtOH). A Langmuir-type adsorption isotherm was observed with ACN. In contrast, a Freundlich-type adsorption isotherm was observed with EtOH, suggesting that EtOH molecules co-adsorbed on TiO2 surface. Absorption spectra of the dye adsorbed films clearly show aggregate formation at high concentrations of dye in the solutions. From the analysis of the spectra, we conclude that head-to-tail type aggregates are observed with ACN, whereas various types of aggregates, including H-type and head-to-tail type aggregates, are observed with EtOH.

  13. Inhomogeneous distribution of organic molecules adsorbed in sol gel glasses

    NASA Astrophysics Data System (ADS)

    Meneses-Nava, M. A.; Chávez-Cerda, S.; Sánchez-Villicaña, V.; Sánchez-Mondragón, J. J.; King, T. A.

    1999-09-01

    The effects of the porous matrix upon the radiative characteristics of quinine sulphate doped sol-gel glasses are investigated. The broadenings of the absorption and fluorescence spectra are explained by the attachment of the molecules on distorted sites or in a non-planar fashion, creating an inhomogeneous distribution of adsorbed molecules. For this reason, each emitting center relaxes with its own characteristics. This inhomogeneous distribution is also supported by the non-exponential and the wavelength dependence of the fluorescence decay.

  14. Scandium-Triflate/Metal-Organic Frameworks: Remarkable Adsorbents for Desulfurization and Denitrogenation.

    PubMed

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2015-12-01

    Scandium-triflate (Sc(OTf)3) was introduced for the first time on metal-organic frameworks (MOFs), to utilize acidic Sc(OTf)3 for adsorptive desulfurization and denitrogenation of fuel containing benzothiophene (BT), dibenzothiophene (DBT), quinoline (QUI), and indole (IND). A remarkable improvement in the adsorption capacity (about 65% based on the weight of adsorbents; 90% based on the surface area of the adsorbents) was observed with the Sc(OTf)3/MOFs as compared to the virgin MOFs for the adsorption of BT from liquid fuel. The basic QUI was also adsorbed preferentially onto the acidic Sc(OTf)3/MOFs. However, nonsupported Sc(OTf)3 showed negligible adsorption capacities. The improved adsorptive performance for BT, DBT, and QUI might be derived from acid-base interactions between the acidic Sc(OTf)3 and basic adsorbates. On the other hand, the Sc(OTf)3, loaded on MOFs, reduced the adsorption capacity for neutral IND due to lack of interaction between the neutral adsorbate and acidic adsorbent and the reduced porosities of the modified adsorbents. The reusability of the adsorbents was found satisfactory up to the fourth run. On the basis of the result, it is suggested that metal-triflates, such as Sc(OTf)3, can be prospective materials for adsorptive desulfurization/denitrogenation of fuels when supported on porous materials such as MOFs. PMID:26575418

  15. Metallo-organic decomposition films

    NASA Technical Reports Server (NTRS)

    Gallagher, B. D.

    1985-01-01

    A summary of metallo-organic deposition (MOD) films for solar cells was presented. The MOD materials are metal ions compounded with organic radicals. The technology is evolving quickly for solar cell metallization. Silver compounds, especially silver neodecanoate, were developed which can be applied by thick-film screening, ink-jet printing, spin-on, spray, or dip methods. Some of the advantages of MOD are: high uniform metal content, lower firing temperatures, decomposition without leaving a carbon deposit or toxic materials, and a film that is stable under ambient conditions. Molecular design criteria were explained along with compounds formulated to date, and the accompanying reactions for these compounds. Phase stability and the other experimental and analytic results of MOD films were presented.

  16. Heat capacity of quantum adsorbates: Hydrogen and helium on evaporated gold films

    SciTech Connect

    Birmingham, J.T. |

    1996-06-01

    The author has constructed an apparatus to make specific heat measurements of quantum gases adsorbed on metallic films at temperatures between 0.3 and 4 K. He has used this apparatus to study quench-condensed hydrogen films between 4 and 923 layers thick with J = 1 concentrations between 0.28 and 0.75 deposited on an evaporated gold surface. He has observed that the orientational ordering of the J = 1 molecules depends on the substrate temperature during deposition of the hydrogen film. He has inferred that the density of the films condensed at the lowest temperatures is 25% higher than in bulk H{sub 2} crystals and have observed that the structure of those films is affected by annealing at 3.4 K. The author has measured the J = 1 to J = 0 conversion rate to be comparable to that of the bulk for thick films; however, he found evidence that the gold surface catalyzes conversion in the first two to four layers. He has also used this apparatus to study films of {sup 4}He less than one layer thick adsorbed on an evaporated gold surface. He shows that the phase diagram of the system is similar to that for {sup 4}He/graphite although not as rich in structure, and the phase boundaries occur at different coverages and temperatures. At coverages below about half a layer and at sufficiently high temperatures, the {sup 4}He behaves like a two-dimensional noninteracting Bose gas. At lower temperatures and higher coverages, liquidlike and solidlike behavior is observed. The Appendix shows measurements of the far-infrared absorptivity of the high-{Tc} superconductor La{sub 1.87}Sr{sub 0.13}CuO{sub 4}.

  17. Extra adsorption and adsorbate superlattice formation in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Sung Cho, Hae; Deng, Hexiang; Miyasaka, Keiichi; Dong, Zhiyue; Cho, Minhyung; Neimark, Alexander V.; Ku Kang, Jeung; Yaghi, Omar M.; Terasaki, Osamu

    2015-11-01

    Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition, which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage. The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface and also amongst themselves within individual pores have been extensively studied, adsorbate-adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate-adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption-desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of ‘extra adsorption domains’—that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically.

  18. AC microcalorimetry of adsorbates on evaporated metal films: Orientational ordering of H{sub 2} multilayers

    SciTech Connect

    Phelps, R.B.

    1991-11-01

    We have improved and extended a novel ac calorimetric technique for measuring the heat capacity of adsorbates on evaporated metal films. Metallic substrates are of particular interest in current studies of the thermodynamics of adsorbed molecules. The method described in the present work is only calorimetric technique which allows measurements of molecules on simple metallic surfaces. Among other improvements, we have achieved significant progress in the preparation and characterization of the evaporated metal film. We have applied this novel technique to a study of hydrogen multilayers on gold and sapphire substrates. We have shown that samples of normal-hydrogen with a nominal coverage n of approximately 25 monolayers (ML) undergo a bulk-like orientational ordering transition. The transition is suppressed as the coverage is decreased, and no sign of the transition remains above 1.6 K for n {approx} 1 ML. For n {approx_lt} 8 ML, the peak in the heat capacity exhibits signs of finite-size effects. At higher coverages, finite-size effects are not observed, and the shape of the peak depends strongly on the substrate. We conclude that the peak is inhomogeneously broadened for n {approx_lt} 8 ML. This work represents the first measurements of the heat capacity due to orientational ordering in adsorbed hydrogen. The results of an earlier experiment involving vibrational spectroscopy of adsorbed molecules are included in the Appendix. In this work, we have used infrared emission spectroscopy to study the spectral region in the vicinity of the C=O stretch vibration of bridge-bonded CO on Pt(111).

  19. AC microcalorimetry of adsorbates on evaporated metal films: Orientational ordering of H sub 2 multilayers

    SciTech Connect

    Phelps, R.B.

    1991-11-01

    We have improved and extended a novel ac calorimetric technique for measuring the heat capacity of adsorbates on evaporated metal films. Metallic substrates are of particular interest in current studies of the thermodynamics of adsorbed molecules. The method described in the present work is only calorimetric technique which allows measurements of molecules on simple metallic surfaces. Among other improvements, we have achieved significant progress in the preparation and characterization of the evaporated metal film. We have applied this novel technique to a study of hydrogen multilayers on gold and sapphire substrates. We have shown that samples of normal-hydrogen with a nominal coverage n of approximately 25 monolayers (ML) undergo a bulk-like orientational ordering transition. The transition is suppressed as the coverage is decreased, and no sign of the transition remains above 1.6 K for n {approx} 1 ML. For n {approx lt} 8 ML, the peak in the heat capacity exhibits signs of finite-size effects. At higher coverages, finite-size effects are not observed, and the shape of the peak depends strongly on the substrate. We conclude that the peak is inhomogeneously broadened for n {approx lt} 8 ML. This work represents the first measurements of the heat capacity due to orientational ordering in adsorbed hydrogen. The results of an earlier experiment involving vibrational spectroscopy of adsorbed molecules are included in the Appendix. In this work, we have used infrared emission spectroscopy to study the spectral region in the vicinity of the C=O stretch vibration of bridge-bonded CO on Pt(111).

  20. Atomic force microscopy of AgBr crystals and adsorbed gelatin films

    SciTech Connect

    Haugstad, G.; Gladfelter, W.L.; Keyes, M.P.; Weberg, E.B.

    1993-06-01

    Atomic force microscopy of the (111) surface of macroscopic AgBr crystals revealed steps ranging in height from two atomic layers up to 10 nm, lying predominantly along the (110) and (112) families of crystal directions. Rods of elemental Ag, formed via photoreduction, were observed along the (110) family of directions. Images of adsorbed gelatin films revealed circular pores with diameters of order 10-100 nm, extending to the AgBr surface. The length of deposition time, the pH and concentration of the gelatin solution, and the presence of steps on the AgBr surface were observed to affect the size, number, and location of pores in the gelatin films. 12 refs., 7 figs.

  1. Atomic Motion in Low-Coverage Helium Films Adsorbed in FSM Nanochannels

    NASA Astrophysics Data System (ADS)

    Matsushita, Taku; Kuze, Atsushi; Kawai, Ryosuke; Hieda, Mitsunori; Wada, Nobuo

    2013-06-01

    4He and 3He films adsorbed in nanoporous silicates have shown similar heat capacities until the quantum-fluid layer appears at coverages over the first-layer completion n 1. To obtain information on dynamics of adatoms at low coverages below the quantum fluid region, we have done pulsed-NMR experiment at 3.3 MHz for 3He films adsorbed in straight 2.4 nm nanochannels of FSM silicates. The spin-lattice and spin-spin relaxation times T 1 and T 2 observed at 0.54-7 K were well described by the two-dimensional version of the Bloembergen-Purcell-Pound model. At coverages 0.4-1.7 n 1, minima of T 1, indicating the spin correlation time τ c of 4.8×10-8 sec, were observed at temperatures between 6 and 3 K. With decreasing temperature, changes in T 1 and T 2 become small below about 1.5 K, suggesting crossover from thermally-activated motion to quantum tunneling. In contrast to large variations below n 1, both relaxation times above n 1 are almost independent of coverage, which is likely to indicate that τ c is determined by interlayer exchange of adatoms. Below n 1, onsets for localization of adatoms were suggested by a decrease in T 2.

  2. Nanotribological properties of water films adsorbing atop, and absorbing below, graphene layers supported by metal substrates

    NASA Astrophysics Data System (ADS)

    Liu, Zijian; Curtis, C. K.; Stine, R.; Sheehan, P.; Krim, J.

    The tribological properties of graphite, a common lubricant with known sensitivity to the presence of water, have been studied extensively at the macroscopic and microscopic scales. Although far less attention has been devoted to the tribological properties of graphene, it has been established that the tribological response to the presence of water is dissimilar from that of graphite. We report here a quartz crystal microbalance study of the nanotribological properties of water films adsorbed/absorbed on graphene layers prepared by either chemical decomposition on nickel(111) substrates or transfer of freestanding graphene layers to aluminum substrates. Sliding friction levels of the water films were also measured for metal surfaces in the absence of a graphene layer. We observe very high friction levels for water adsorbed atop graphene on Ni(111) and very low levels for water on aluminum. For the case of graphene/aluminum, the data indicate that the water is absorbing between the graphene layer and the aluminum. Dissipation levels moreover indicate the presence of an interstitial water increases sliding friction between the graphene and the aluminum substrate Work supported by NSF and NRL.

  3. Covalent organic frameworks: Potential adsorbent for carbon dioxide adsorption

    NASA Astrophysics Data System (ADS)

    Xie, Yinhuan

    A series of covalent organic frameworks (COFs) based on propeller shaped hexaphenylbenzene derivatives were obtained under solvothermal conditions via Schiff base reaction. The relationship between the geometry parameters of monomers and gas absorption behaviors of planar COFs was investigated. The FT-IR spectroscopy confirms the formation of imine double bond in the obtained COFs by showing a peak around 1620 cm-1. The resulting frameworks have high BET surface areas approaching 700 m2/g and CO2 uptake up to 14% at 273 K and 1 bar, which are better than most of the 2-D porous aromatic frameworks. The thermogravimetric analysis shows those frameworks are stable until 773 K, allowing for the practical application of the post-combustion CO2 technology. Moreover, a novel synthetic strategy for the trigonal pyramidal hydrozide monomers was established. It provides an efficient way to synthesize the hydrozide monomers at multi-gram scale, promising for the synthesis of hydrozane porous organic cages.

  4. COMPARISON OF SOLID ADSORBENT SAMPLING TECHNIQUES FOR VOLATILE ORGANIC COMPOUNDS IN AMBIENT AIR

    EPA Science Inventory

    The specific objective of the study was to compare the performance of three solid adsorbents (Tenax, an experimental polyimide resin, and Spherocarb) as well as cryogenic trapping/gas chromatography for sampling and analysis of a target list of volatile organic compounds in ambie...

  5. Influences of Dilute Organic Adsorbates on the Hydration of Low-Surface-Area Silicates.

    PubMed

    Sangodkar, Rahul P; Smith, Benjamin J; Gajan, David; Rossini, Aaron J; Roberts, Lawrence R; Funkhouser, Gary P; Lesage, Anne; Emsley, Lyndon; Chmelka, Bradley F

    2015-07-01

    Competitive adsorption of dilute quantities of certain organic molecules and water at silicate surfaces strongly influence the rates of silicate dissolution, hydration, and crystallization. Here, we determine the molecular-level structures, compositions, and site-specific interactions of adsorbed organic molecules at low absolute bulk concentrations on heterogeneous silicate particle surfaces at early stages of hydration. Specifically, dilute quantities (∼0.1% by weight of solids) of the disaccharide sucrose or industrially important phosphonic acid species slow dramatically the hydration of low-surface-area (∼1 m(2)/g) silicate particles. Here, the physicochemically distinct adsorption interactions of these organic species are established by using dynamic nuclear polarization (DNP) surface-enhanced solid-state NMR techniques. These measurements provide significantly improved signal sensitivity for near-surface species that is crucial for the detection and analysis of dilute adsorbed organic molecules and silicate species on low-surface-area particles, which until now have been infeasible to characterize. DNP-enhanced 2D (29)Si{(1)H}, (13)C{(1)H}, and (31)P{(1)H} heteronuclear correlation and 1D (29)Si{(13)C} rotational-echo double-resonance NMR measurements establish hydrogen-bond-mediated adsorption of sucrose at distinct nonhydrated and hydrated silicate surface sites and electrostatic interactions with surface Ca(2+) cations. By comparison, phosphonic acid molecules are found to adsorb electrostatically at or near cationic calcium surface sites to form Ca(2+)-phosphonate complexes. Although dilute quantities of both types of organic molecules effectively inhibit hydration, they do so by adsorbing in distinct ways that depend on their specific architectures and physicochemical interactions. The results demonstrate the feasibility of using DNP-enhanced NMR techniques to measure and assess dilute adsorbed molecules and their molecular interactions on low

  6. Transient magnetization of core excited organic molecules adsorbed on graphene

    NASA Astrophysics Data System (ADS)

    Ravikumar, Abhilash; Baby, Anu; Lin, He; Brivio, Gian Paolo; Fratesi, Guido

    This work presents a density functional theory based computational investigation of electronic and magnetic properties of physisorbed and chemisorbed organic molecules on graphene in the ground state and core excited one at low molecular coverage. For physisorbed molecules, where the interaction with graphene is dominated by van der Waals forces and the system is non-magnetic in the ground state, it is found that the valence electrons relax towards a spin polarized configuration upon excitation of a core-level electron. The magnetism depends on efficient electron transfer from graphene on the femtosecond time scale. On the contrary, when graphene is covalently functionalized, the system is magnetic in the ground state presenting two spin dependent mid gap states localized around the adsorption site. At variance with the physisorbed case upon core-level excitation, the LUMO of the molecule and the mid gap states of graphene hybridize and the relaxed valence shell is not magnetic anymore. This project has received funding from the European Union Seventh Framework Programme under grant agreement n∘ 607232 [THINFACE].

  7. Thermodynamic and dynamic characteristics of hydroxypropylmethylcellulose adsorbed films at the air-water interface.

    PubMed

    Pérez, Oscar E; Sánchez, Cecilio Carrera; Rodríguez Patino, Juan M; Pilosof, Ana M R

    2006-01-01

    Surface pressure isotherms and structural and surface dilatational properties of three hydroxypropylmethycelluloses (HPMCs, called E4M, E50LV, and F4M) adsorbed films at the air-water interface were determined. In this work we present evidence that HPMC molecules are able to diffuse and saturate the air-water interface at very low concentrations in the bulk phase. As bulk concentration increased, structural changes at a molecular level occurred at the interface. These changes corresponded to transition from an expanded structure (structure I) to a condensed one (structure II). When the surface concentration of HPMC was high enough, the collapse of the monolayer was observed. The three HPMCs formed very elastic films at the air-water interface, even at low surface pressures. E4M showed features that make it unique. For instance it showed the highest surface activity, mainly at low bulk concentrations (<10(-4) wt %). The differences observed in surface activity may be attributed to differences in the hydroxypropyl molar substitution and molecular weight of HPMC. All three HPMCs formed films of similar viscoelasticity and elastic dilatational modulus, which can be accounted for by their similar degree of methyl substitution. PMID:16398540

  8. Dissociative electron attachment and charging of SF6 adsorbed on rare-gas films

    NASA Astrophysics Data System (ADS)

    Weik, Fritz; Illenberger, Eugen

    1998-10-01

    Electron stimulated desorption (ESD) of fragment ions in the energy range between 0 and 18 eV from SF6 adsorbed on rare-gas films (Kr, Xe) is reported. The ESD results are compared with previous experiments on dissociative electron attachment (DA) to gas-phase SF6. At energies characteristic for the respective rare-gas substrate strong resonant enhancements in the ESD yield of F- are observed. This enhancement is explained by the appearance of an "electron-exciton complex" in the rare-gas film (the analogue to the anionic Feshbach resonances in single atoms) which couples to the first dipole allowed excitation of the SF6 molecule. After electron and energy transfer, the highly excited SF6*- ion dissociates at the surface resulting in the desorption of F- fragments. At low electron energies (in the range from 0 to 0.6 eV) charging of the rare-gas film covered with SF6 is observed. From these experiments a charging cross section of 2.1(±1.8)×10-15 cm2 is derived.

  9. Electrospun polystyrene nanofibers as a novel adsorbent to transfer an organic phase from an aqueous phase.

    PubMed

    Liu, Feilong; Song, Dandan; Huang, Xueying; Xu, Hui

    2016-04-01

    The aim of this work is to develop a simple phase-transfer method for dispersive liquid-liquid microextraction. For this purpose, a polystyrene nanofiber was prepared by a facile electrospinning strategy and used for the first time as an adsorbent to transfer the organic phase in dispersive liquid-liquid microextraction procedure. The fiber was characterized and its chemical stability and excellent hydrophobicity enable it to selectively adsorb the organic solvent in an aqueous sample. High porosity and specific surface area provide a large adsorption capacity. Under the optimal conditions, the developed dispersive liquid-liquid microextraction with high-performance liquid chromatography method was successfully applied to the analysis of aldehydes in environmental water samples. The merits of this approach are that it is easy-to-operate, low-cost, time-saving, and has satisfactory sensitivity. It provides an alternative way for fast and convenient phase transfer of the hydrophobic organic solvent from the aqueous phase. PMID:26841974

  10. Sputtering and secondary ion emission properties of alkali metal films and adsorbed monolayers

    SciTech Connect

    Krauss, A R; Gruen, D M

    1980-01-01

    The secondary ion emission of alkali metal adsorbed monlayer and multilayer films has been studied. Profiling with sub-monolayer resolution has been performed by Auger, x-ray photoemission and secondary ion mass spectroscopy. Characteristic differences in the sputtering yields, and ion fraction have been observed which are associated with both the surface bonding properties and the mechanism leading to the formation of secondary ions. By sputtering with a negative bias applied to the sample, positive secondary ions are returned to the surface, resulting in a reduced sputter-induced erosion rate. Comparison with the results obtained with K and Li overlayers sputtered without sample bias provides an experimental value of both the total and secondary ion sputtering yields. The first and second monolayers can be readily identified and the first monolayer exhibits a lower sputtering yield and higher secondary ion fraction. This result is related to adsorption theory and measured values are compared with those obtained by thermal desorption measurements.

  11. Mesoscopic Hamiltonian for the fluctuations of adsorbed Lennard-Jones liquid films.

    PubMed

    Fernández, Eva M; Chacón, Enrique; MacDowell, Luis G; Tarazona, Pedro

    2015-06-01

    We use Monte Carlo simulations of a Lennard-Jones fluid adsorbed on a short-range planar wall substrate to study the fluctuations in the thickness of the wetting layer, and we get a quantitative and consistent characterization of their mesoscopic Hamiltonian, H[ξ]. We have observed important finite-size effects, which were hampering the analysis of previous results obtained with smaller systems. The results presented here support an appealing simple functional form for H[ξ], close but not exactly equal to the theoretical nonlocal proposal made on the basis a generic density-functional analysis by Parry and coworkers. We have analyzed systems under different wetting conditions, as a proof of principle for a method that provides a quantitative bridge between the molecular interactions and the phenomenology of wetting films at mesoscopic scales. PMID:26172722

  12. Low cost adsorbents for the removal of organic pollutants from wastewater.

    PubMed

    Ali, Imran; Asim, Mohd; Khan, Tabrez A

    2012-12-30

    Water pollution due to organic contaminants is a serious issue because of acute toxicities and carcinogenic nature of the pollutants. Among various water treatment methods, adsorption is supposed as the best one due to its inexpensiveness, universal nature and ease of operation. Many waste materials used include fruit wastes, coconut shell, scrap tyres, bark and other tannin-rich materials, sawdust and other wood type materials, rice husk, petroleum wastes, fertilizer wastes, fly ash, sugar industry wastes blast furnace slag, chitosan and seafood processing wastes, seaweed and algae, peat moss, clays, red mud, zeolites, sediment and soil, ore minerals etc. These adsorbents have been found to remove various organic pollutants ranging from 80 to 99.9%. The present article describes the conversion of waste products into effective adsorbents and their application for water treatment. The possible mechanism of adsorption on these adsorbents has also been included in this article. Besides, attempts have been made to discuss the future perspectives of low cost adsorbents in water treatment. PMID:23023039

  13. Friction and transfer of copper, silver, and gold to iron in the presence of various adsorbed surface films

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1979-01-01

    Sliding friction experiments were conducted with the noble metals copper, silver, and gold and two binary alloys of these metals contacting iron in the presence of various adsorbates including, oxygen, methyl mercaptan, and methyl chloride. A pin on disk specimen configuration was used with a load of 100 grams, sliding velocity of 60 mm/min; at 25 C with the surfaces saturated with the adsorbates. Auger emission spectroscopy was used to monitor surface films. Results of the experiments indicate that friction and transfer characteristics are highly specific with respect to both the noble metal and surface film present. With all three metals and films transfer of the noble metal to iron occurred very rapidly. With all metals and films transfer of the noble metal to iron continuously increased with repeated passes except for silver and copper sliding on iron sulfide.

  14. Vibrational spectra of CO adsorbed on oxide thin films: A tool to probe the surface defects and phase changes of oxide thin films

    SciTech Connect

    Savara, Aditya

    2014-03-15

    Thin films of iron oxide were grown on Pt(111) single crystals using cycles of physical vapor deposition of iron followed by oxidative annealing in an ultrahigh vacuum apparatus. Two procedures were utilized for film growth of ∼15–30 ML thick films, where both procedures involved sequential deposition+oxidation cycles. In procedure 1, the iron oxide film was fully grown via sequential deposition+oxidation cycles, and then the fully grown film was exposed to a CO flux equivalent to 8 × 10{sup −7} millibars, and a vibrational spectrum of adsorbed CO was obtained using infrared reflection-absorption spectroscopy. The vibrational spectra of adsorbed CO from multiple preparations using procedure 1 show changes in the film termination structure and/or chemical nature of the surface defects—some of which are correlated with another phase that forms (“phase B”), even before enough of phase B has formed to be easily detected using low energy electron diffraction (LEED). During procedure 2, CO vibrational spectra were obtained between deposition+oxidation cycles, and these spectra show that the film termination structure and/or chemical nature of the surface defects changed as a function of sequential deposition+oxidation cycles. The authors conclude that measurement of vibrational spectra of adsorbed CO on oxide thin films provides a sensitive tool to probe chemical changes of defects on the surface and can thus complement LEED techniques by probing changes not visible by LEED. Increased use of vibrational spectra of adsorbed CO on thin films would enable better comparisons between films grown with different procedures and by different groups.

  15. Direct Measurement of Adsorbed Gas Redistribution in Metal–Organic Frameworks

    SciTech Connect

    Chen, Ying-Pin; Liu, Yangyang; Liu, Dahuan; Bosch, Mathieu; Zhou, Hong-Cai

    2015-03-04

    Knowledge about the interactions between gas molecules and adsorption sites is essential to customize metal-organic frameworks (MOFs) as adsorbents. The dynamic interactions occurring during adsorption/desorption working cycles with several states are especially complicated. Even so, the gas dynamics based upon experimental observations and the distribution of guest molecules under various conditions in MOFs have not been extensively studied yet. In this work, a direct time-resolved diffraction structure envelope (TRDSE) method using sequential measurements by in situ synchrotron powder X-ray diffraction has been developed to monitor several gas dynamic processes taking place in MOFs: infusion, desorption, and gas redistribution upon temperature change. The electron density maps indicate that gas molecules prefer to redistribute over heterogeneous types of sites rather than to exclusively occupy the primary binding sites. We found that the gas molecules are entropically driven from open metal sites to larger neighboring spaces during the gas infusion period, matching the localized-to-mobile mechanism. In addition, the partitioning ratio of molecules adsorbed at each site varies with different temperatures, as opposed to an invariant distribution mode. Equally important, the gas adsorption in MOFs is intensely influenced by the gas–gas interactions, which might induce more molecules to be accommodated in an orderly compact arrangement. This sequential TRDSE method is generally applicable to most crystalline adsorbents, yielding information on distribution ratios of adsorbates at each type of site.

  16. 4-Mercaptopyridine adsorbed on pure palladium island films: A combined SERS and DFT investigation

    NASA Astrophysics Data System (ADS)

    Guo, Hao; Ding, Li; Zhang, Tianjie; Mo, Yujun

    2013-03-01

    Surface-enhanced Raman scattering (SERS) can provide vibrational information with molecular specificity and potential single-molecule sensitivity. SERS studies on pure transition metals, however, remain challenging due to the weak SERS activity of transition metals compared to coinage metals. Here we fabricated alumina-supported Pd island films by depositing laser-ablated Pd colloids onto an Al substrate. Robust SERS signal employing 4-mercaptopyridine (4-Mpy) as a probe was registered from the as-prepared films. The adsorption information of 4-Mpy molecules such as orientation and coordinating site was discussed in detail based on SERS data. It was inferred that 4-Mpy adsorbs via its sulfur atom to Pd surface with a tilted binding configuration. The Raman wavenumber and intensity of an adsorption model including one 4-Mpy and Pd atom were computed using density functional theory (DFT) at the Beck's three-parameter Lee-Yang-Parr (B3LYP) level with the LANL2DZ basis set. The simulated Raman spectrum was in good agreement with the experimental one except for the relative intensity. The current investigation could be helpful to gain a comprehensive understanding of SERS.

  17. O the Transition from - to Three-Dimensional Behavior in Adsorbed Films

    NASA Astrophysics Data System (ADS)

    Day, Peter Kenneth

    1993-01-01

    Argon and krypton films adsorbed on graphite foam have been studied in detail using vapor pressure and high resolution, heat capacity measurements. Heat capacity features near the bulk triple point temperature, previously associated with the surface melting of the uniform film, are shown to be due to the melting of bulk material condensed in pores in the substrate. The melting curve of the capillary condensate agrees with the prediction of a modified Clausius -Claperon equation. The second and third layers in argon and the second layer in krypton have a triple point at which two-dimensional solid, liquid, and gas phases coexist atop a solid lower layer. Commensurate-incommensurate transitions are found in the first two layers of argon and in the second layer of krypton, so that monolayer argon melts from a registered phase, but the second layers of both systems melt from incommensurate bilayer phases. The melting of the second and third layers in both systems are likely to be first order, but the data are not conclusive. At coverages starting with 3{1over 2} layers, heat capacity features that are due to reentrant layering-transitions are seen in both systems, confirming the result of recent ellipsometry studies. Further heat capacity peaks suggest phase transitions that join the newly observed reentrant layering-transitions with the well studied layering-transitions at low temperature. These heat capacity peaks may be related to the recently proposed preroughening transition. A mean field theory is developed that reproduced the reentrant layering behavior for ratios of nearest and next nearest neighbor interaction energies greater than a critical value. The mean field theory gives an explanation for the appearance of reentrant layering -transitions at different film thicknesses depending on the substrate-adsorbate interaction parameter. Multilayer phase diagrams are drawn from the data that suggest a crossover from two-dimensional behavior in the second layer to

  18. Preparation of dye-adsorbing ZnO thin films by electroless deposition and their photoelectrochemical properties.

    PubMed

    Nagaya, Satoshi; Nishikiori, Hiromasa

    2013-09-25

    Dye-adsorbing ZnO thin films were prepared on ITO films by electroless deposition. The films were formed in an aqueous solution containing zinc nitrate, dimethylamine-borane, and eosin Y at 328 K. The film thickness was 1.2-2.0 μm. Thinner and larger-plane hexagonal columns were produced from the solution containing a higher concentration of eosin Y. A photocurrent was observed in the electrodes containing such ZnO films during light irradiation. The photoelectrochemical performance of the film was improved by increasing the concentration of eosin Y because of increases in the amount of absorbed photons and the electronic conductivity of ZnO. PMID:24020721

  19. Mercury removal from incineration flue gas by organic and inorganic adsorbents.

    PubMed

    Jurng, Jongsoo; Lee, Tai Gyu; Lee, Gyo Woo; Lee, Sung-Jun; Kim, Byung Hwa; Seier, Jochen

    2002-06-01

    Experiments were performed to investigate various adsorbents for their mercury removal capabilities from incineration flue gases. Four different materials were tested; Zeolite, Bentonite, activated carbon (AC), and wood char. Real incineration off-gas and in-lab simulated combustion flue gases (N2 + Hg) were used. Three cylindrical-shaped sorbent columns with 5 cm in diameter and 20 cm in length were used. The gas flow rate was fixed at 660 l/h at all times. Concentrations of NO, CO, O2, CO2, SO2, H2O, HCl, and mercury were continuously monitored. Mercury removal efficiencies of natural Zeolite and Bentonite were found to be much lower than those of the referenced AC. Amount of Hg removed were 9.2 and 7.4 microg/g of Zeolite and Bentonite, respectively. Removal efficiencies of each layer consisted of inorganic adsorbents were no higher than 7%. No significant improvement was observed with sulfur impregnation onto the inorganic adsorbents. Organic adsorbents (wood char and AC) showed much higher mercury removal efficiencies than those of inorganic ones (Zeolite and Bentonite). Mercury removal efficiency of wood char reached over 95% in the first layer, showing almost same effectiveness as AC which currently may be the most effective adsorbents for mercury. Amount of mercury captured by wood char was approximately 0.6 mg/g of wood char, close to the amount captured by AC tested in this study. Hence, wood char, made from the waste woods through a gasification process, should be considered as a possible alternative to relatively expensive AC. PMID:12108697

  20. Comparison of Gas and Adsorbed Phase X-ray Photoemission Spectra of Oxidized Organics on Ice

    NASA Astrophysics Data System (ADS)

    Newberg, J. T.; Bluhm, H.

    2011-12-01

    Most uptake studies of small chain organics on ice surfaces at near ambient conditions have been performed using flow tube and other methods which monitor the disappearance of the gas phase. We will present results using synchrotron based, ambient pressure X-ray photoemission spectroscopy which allows for the probing of the ice surface directly at near ambient conditions. C 1s XPS and C K-edge NEXAFS gas phase and adsorbed phase spectra will be compared for 2-propanol, acetone, and 1-propanal on ice at -45 C. Uptake experiments give rise to first order Langmuirian isotherms. Acetone and 2-propanol show little difference in the photoemission spectra between the gas phase and adsorbed phase, suggesting that adsorption occurs molecularly. However, adsorption of 1-propanal shows evidence of chemical transformation (oxidation) at the interface of ice. Further studies are underway to better understand this adsorption behavior.

  1. Removal of organic pollutants from aqueous solutions by adsorbents prepared from an agroalimentary by-product.

    PubMed

    Delval, Franck; Crini, Grégorio; Vebrel, Joël

    2006-11-01

    Two series of crosslinked starch polymers were tested for their ability to adsorb organic pollutants in aqueous solutions. The polymers were prepared by a crosslinking reaction of starch-enriched flour using epichlorohydrin as the crosslinking agent, without and in the presence of NH(4)OH. These polymers were used as sorbent materials for the removal of phenolic derivatives from wastewater. The influence of several parameters (kinetics, pH and polymer structure) on the sorption capacity was evaluated using the batch and the open column methods. Results of adsorption experiments showed that the starch-based materials exhibited high sorption capacities toward phenolic derivatives. The study of the kinetics of pollutant uptake revealed that the adsorbents presented a relatively fast rate of adsorption. The experimental data were examined using the Langmuir and Freundlich models and it was found that the Freundlich model appeared to fit the isotherm data better than the Langmuir model. PMID:16275061

  2. Adsorbed films of three-patch colloids: continuous and discontinuous transitions between thick and thin films.

    PubMed

    Dias, C S; Araújo, N A M; Telo da Gama, M M

    2014-09-01

    We investigate numerically the role of spatial arrangement of the patches on the irreversible adsorption of patchy colloids on a substrate. We consider spherical three-patch colloids and study the dependence of the kinetics on the opening angle between patches. We show that growth is suppressed below and above minimum and maximum opening angles, revealing two absorbing phase transitions between thick and thin film regimes. While the transition at the minimum angle is continuous, in the directed percolation class, that at the maximum angle is clearly discontinuous. For intermediate values of the opening angle, a rough colloidal network in the Kardar-Parisi-Zhang universality class grows indefinitely. The nature of the transitions was analyzed in detail by considering bond flexibility, defined as the dispersion of the angle between the bond and the center of the patch. For the range of flexibilities considered we always observe two phase transitions. However, the range of opening angles where growth is sustained increases with flexibility. At a tricritical flexibility, the discontinuous transition becomes continuous. The practical implications of our findings and the relation to other nonequilibrium transitions are discussed. PMID:25314441

  3. Microcrystalline organic thin-film solar cells.

    PubMed

    Verreet, Bregt; Heremans, Paul; Stesmans, Andre; Rand, Barry P

    2013-10-11

    Microcrystalline organic films with tunable thickness are produced directly on an indium-tin-oxide substrate, by crystallizing a thin amorphous rubrene film followed by its use as a template for subsequent homoepitaxial growth. These films, with exciton diffusion lengths exceeding 200 nm, produce solar cells with increasing photocurrents at thicknesses up to 400 nm with a fill factor >65%, demonstrating significant potential for microcrystalline organic electronic devices. PMID:23939936

  4. Third Sound in Superfluid 4He Films Adsorbed on Packed Multiwall Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Menachekanian, Emin

    Third sound is studied for superfluid films of 4He adsorbed on multiwall carbon nanotubes packed into an annular resonator. The third sound is generated with mechanical oscillation of the cell, and detected with carbon bolometers. A filling curve at temperatures near 250 mK shows oscillations in the third sound velocity, with maxima at the completion of the 4th and 5th atomic layers. Sharp changes in the Q factor of the third sound are found at partial layer fillings. Temperature sweeps at a number of fill points show strong broadening effects on the Kosterlitz-Thouless (KT) transition, and rapidly increasing dissipation, in qualitative agreement with the predictions of Machta and Guyer. At the 4th layer completion there is a sudden reduction of the transition temperature TKT , and then a recovery back to linear variation with fill, although the slope is considerably smaller than the KT prediction. These effects might be related to changes in the gas-liquid coexistence regions.

  5. Development of adsorbent for the simultaneous removal of organic and inorganic contaminants from aqueous solution.

    PubMed

    Choi, J W; Chung, S G; Hong, S W; Kim, D J; Lee, S H

    2011-01-01

    In this study, a modified adsorbent, alginate complex beads, was prepared and applied to the removal of mixed contaminants from wastewater. The alginate complex beads were generated by the immobilization of powdered activated carbon and synthetic zeolites onto alginate gel beads, which were then dried at 110 °C for 20 h until the diameter had been reduced to 1 mm. This dry technique increased the hardness of the adsorbent to assure its durability and application. The adsorption onto the alginate complex beads of organic and inorganic compounds, as target contaminants, was investigated by performing both equilibrium and kinetic batch experiments. From the adsorption isotherms, according to the Langmuir equation, the alginate complex bead was capable of effectively removing benzene, toluene, zinc and cadmium. From kinetic batch experiments, the removal efficiencies of benzene, toluene, zinc and cadmium were found to be 66.5, 92.4, 74.1 and 76.7%, respectively, for initial solution concentrations of 100 mg L(-1). The results indicated that the adsorbent developed in this study has the potential to be a promising material for the removal of mixed pollutants from industrial wastewater or contaminated groundwater. PMID:22020474

  6. Polyethyleneimine Incorporated Metal-Organic Frameworks Adsorbent for Highly Selective CO2 Capture

    PubMed Central

    Lin, Yichao; Yan, Qiuju; Kong, Chunlong; Chen, Liang

    2013-01-01

    A series of polyethyleneimine (PEI) incorporated MIL-101 adsorbents with different PEI loadings were reported for the first time in the present work. Although the surface area and pore volume of MIL-101 decreased significantly after loading PEI, all the resulting composites exhibited dramatically enhanced CO2 adsorption capacity at low pressures. At 100 wt% PEI loading, the CO2 adsorption capacity at 0.15 bar reached a very competitive value of 4.2 mmol g−1 at 25°C, and 3.4 mmol g−1 at 50°C. More importantly, the resulting adsorbents displayed rapid adsorption kinetics and ultrahigh selectivity for CO2 over N2 in the designed flue gas with 0.15 bar CO2 and 0.75 bar N2. The CO2 over N2 selectivity was up to 770 at 25°C, and 1200 at 50°C. We believe that the PEI based metal-organic frameworks is an attractive adsorbent for CO2 capture. PMID:23681218

  7. The effects of adsorbing organic pollutants from super heavy oil wastewater by lignite activated coke.

    PubMed

    Tong, Kun; Lin, Aiguo; Ji, Guodong; Wang, Dong; Wang, Xinghui

    2016-05-01

    The adsorption of organic pollutants from super heavy oil wastewater (SHOW) by lignite activated coke (LAC) was investigated. Specifically, the effects of LAC adsorption on pH, BOD5/COD(Cr)(B/C), and the main pollutants before and after adsorption were examined. The removed organic pollutants were characterized by Fourier transform infrared spectroscopy (FTIR), Boehm titrations, gas chromatography-mass spectrometry (GC-MS), and liquid chromatography with organic carbon detection (LC-OCD). FTIR spectra indicated that organic pollutants containing -COOH and -NH2 functional groups were adsorbed from the SHOW. Boehm titrations further demonstrated that carboxyl, phenolic hydroxyl, and lactonic groups on the surface of the LAC increased. GC-MS showed that the removed main organic compounds are difficult to be degraded or extremely toxics to aquatic organisms. According to the results of LC-OCD, 30.37 mg/L of dissolved organic carbons were removed by LAC adsorption. Among these, hydrophobic organic contaminants accounted for 25.03 mg/L. Furthermore, LAC adsorption was found to increase pH and B/C ratio of the SHOW. The mechanisms of adsorption were found to involve between the hydrogen bonding and the functional groups of carboxylic, phenolic, and lactonic on the LAC surface. In summary, all these results demonstrated that LAC adsorption can remove bio-refractory DOCs, which is beneficial for biodegradation. PMID:26808249

  8. Orientation and order of aqueous organic ions adsorbed to a solid surface

    SciTech Connect

    Sukhishvili, S.A.; Granick, S.

    1999-01-21

    The adsorption and orientation of an aqueous organic ion with anisotropic shape (1,4-dimethylpyridinium, P{sup +}) at the surface of oxidized silicon carrying opposite charge (produced by conditions of high pH) were studied using polarized infrared spectroscopy in attenuated total reflection (FTIR-ATR). Orientation relative to the surface was quantified from the dichroic ratio of in-plane skeletal vibrations of the pyridinium ring (1643 and 1523 cm{sup {minus}1}), and the adsorbed amount was inferred from the intensity of these bands. The sticking energy of the organic ion was slightly larger than that of small inorganic ions of the same charge (Li{sup +}, Na{sup +}, Cs{sup +}). From relative quantities adsorbed in competitive adsorption, the relative sticking energy was quantified ({approximately}7k{sub B}T relative to Na{sup +} at pH = 9.2 and varying in the order Cs{sup +} > Na{sup +} > Li{sup +} by the total amount of 0.6k{sub B}T). At low ionic strength (no inorganic ions present except those in the buffer solution), P{sup +} stood preferably parallel to the surface when the surface coverage was low but more nearly upright both as its surface coverage increased and as the concentration of coadsorbed small ions increased. This shows the influence of steric packing on the orientation of this ion of asymmetric shape. The larger the hydrated diameter of the coadsorbed ion, the more the P{sup +} ion tilted away from the surface (H{sup +} < Li{sup +}, Na{sup +}, Cs{sup +} < Mg{sup 2+}). Furthermore, if the mass adsorbed exceeded a critical level, both the tilt and the amount adsorbed jumped in response to increasing P{sup +} concentration in bulk solution, with hysteresis upon dilution. This jump, together with the measured ellipsometric thickness and contact angle, suggests that the discontinuity involved structural change within a single monolayer. The organic ion thus behaved at the surface as an embryonic amphiphile, although in the bulk, micelle formation has

  9. Influence of Chemical Composition on the Reaction Products Observed During Electron Stimulated Decomposition of Organohalides Adsorbed in Water (Ice) Films

    NASA Astrophysics Data System (ADS)

    Fairbrother, Howard; Perry, Christopher; Faradzhev, Nadir; Madey, Theodore

    2004-03-01

    We report on the reactions of CF_2Cl2 and other organohalides codeposited_ in water (ice) films (≈100 nm thick on Au) at ˜ 100K during X-ray or electron beam irradiation. X-ray irradiation produces a distribution of low energy secondary electrons that in CF_2Cl_2/H_2O(ice) films produce H_3O^+, CO2 and COF2 (carbonyl fluoride). Chloride and fluoride anions are also produced and solvated (trapped) within the ice film during X-ray or electron irradiation. Product partitioning is dependent on the film's chemical composition; in water rich films, CO2 and COF2 production is favored, while a thermally stable partially halogenated CF_xCly film is detected in CF_2Cl2 rich films. During the early stages of irradiation, the dominance of Cl^- anions indicates that DEA of CF_2Cl2 via C-Cl cleavage (CF_2Cl2 + e^- → ot CF_2Cl + Cl^-) is the primary initial process. These results obtained for CF_2Cl2 are compared with electron stimulated reactions of other organohalides (CCl_4, CDCl_3, CD_2Cl2 and CH_3I) adsorbed in water(ice)films.

  10. Investigation of organic, inorganic and synthetic adsorbents for the pretreatment of landfill leachate.

    PubMed

    Shahriari, H; Fernandes, L; Tezel, F H

    2008-05-01

    An investigation into the use of organic, inorganic and synthetic adsorbents for the pretreatment of landfill leachate, generated by the City of Ottawa Trail Road Landfill, was carried out. The purpose of this project was to reduce the concentration of contaminants in order to meet the local Sewer Use By-Laws, prior to transporting the leachate from the generating site to the local municipal sewage treatment plant, and thereby reducing the disposal fees. Peat moss, compost, clinoptilolite, basalt and two types of activated carbon (DSR-A and F400) were investigated to determine the adsorption capacity for contaminants from leachate. Kinetic studies were also performed. The results based on batch adsorption isotherms show that peat moss has the highest adsorption capacity for boron (B) and barium (Ba), compared with the other adsorbents. Also peat moss has good removals of Total Kjeldahl Nitrogen (TKN), Total Organic Carbon (TOC), and benzene, toluene, ethylbenzene and xylene (BTEX), but these are lower than the removals obtained with activated carbon. Because of its relatively low cost and higher adsorption of B and Ba, peat moss was selected as the filter media for the column studies. The treated leachate was tested for B, Ba, TKN, carbonaceous biological oxygen demand (CBOD5) and hydrogen sulfide (H2S). The breakthrough curves for B and Ba showed the effectiveness of peat moss in removing these contaminants. PMID:18661738

  11. Metallo-Organic Decomposition (MOD) film development

    NASA Technical Reports Server (NTRS)

    Parker, J.

    1986-01-01

    The processing techniques and problems encountered in formulating metallo-organic decomposition (MOD) films used in contracting structures for thin solar cells are described. The use of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques performed at Jet Propulsion Laboratory (JPL) in understanding the decomposition reactions lead to improvements in process procedures. The characteristics of the available MOD films were described in detail.

  12. Hollow Co@C prepared from a Co-ZIF@microporous organic network: magnetic adsorbents for aromatic pollutants in water.

    PubMed

    Hong, Seokjo; Yoo, Jin; Park, Nojin; Lee, Sang Moon; Park, Je-Geun; Park, Ji Hoon; Son, Seung Uk

    2015-12-28

    This work shows the new engineering strategy of magnetic adsorbents by the combination of zeolitic imidazolate framework (ZIF) and microporous organic network (MON) chemistry. ZIF-67 nanoparticles containing Co(2+) ions were coated with MON. The thermolysis of ZIF-67@MON under argon resulted in hollow carbon materials bearing cobalt nanoparticles which showed promising performance as magnetic adsorbents for aromatic pollutants in water. PMID:26490193

  13. Properties of Organic Films on Aqueous Subphases

    NASA Astrophysics Data System (ADS)

    Gilman, J.; Vaida, V.

    2003-12-01

    Recently, it has been determined that organics represent a significant percentage of the composition of certain atmospheric aerosols. The air/aqueous interface of such an aerosol has the ability to act as a concentrator and selector of organic surfactants. Amphiphilic organics, such as fatty acids and alcohols, have been found to partition to the interface of aerosols thus creating a hydrophobic organic coating on an aqueous core. The selectivity of the interface was studied by monitoring the composition of various films, via GC-MS, as a function of exposure time. A Langmuir-Blodgett trough was used to contain and collect the self-assembled films that were produced from the addition of binary solutions of surfactants to the surface of an aqueous subphase. Surfactants with differing carbon number and head group functionalities were studied. The stability of the films was examined by varying the thickness of the organic films and the pH of the subphase. For a multilayer film containing equimolar stearic acid and lauric acid on a distilled water subphase, it was found that the acid with the longer hydrocarbon tail (stearic acid) remained at the interface much longer that the shorter acid. Films containing 1-octadecanol and stearic acid, both of which have identical carbon numbers, showed similar lifetimes at the air/water interface. Octadecane was found to have a longer lifetime at the interface when dissolved in equimolar stearic acid than when in a homogeneous film. Multilayer films and films formed on acidic subphases were found to be the most stable for both fatty acids studied. The relevance of these findings as they relate to organic aerosol content and structure as well as atmospheric processing and transport will be discussed.

  14. Influence of structural fluctuations on lifetimes of adsorbate states at hybrid organic-semiconductor interfaces

    NASA Astrophysics Data System (ADS)

    Müller, M.; Sánchez-Portal, D.; Lin, H.; Fratesi, G.; Brivio, G. P.; Selloni, A.

    On the road towards a more realistic description of charge transfer processes at hybrid organic-semiconductor interfaces for photovoltaic applications we extend our first-principles scheme for the extraction of elastic linewidths to include the effects of structural fluctuations. Based on snapshots obtained from Car-Parinello molecular dynamics simulations at room temperature, we set up geometries in which dye molecules at interfaces are attached to a semi-infinite TiO2 substrate. The elastic linewidths are computed using a Green's function method. This effectively introduces the coupling to a continuum of states in the substrate. In particular we investigate catechol and isonicotinic acid on rutile(110) and anatase(101) at the level of semi-local density functional theory. We perform multiple calculations of linewidths and peak-positions associated with the adsorbate's frontier orbitals for different geometric configurations to obtain a time-averaged analysis of such physical properties. We compare the results from the considered systems to understand the effects of dynamics onto interfacial charge transfer and systematically assess the dependence of the extracted elastic lifetimes on the relative alignment between adsorbate and substrate states. This project has received funding from the European Union Seventh Framework Programme under Grant Agreement No. 607323 [THINFACE].

  15. Controlling the spatial arrangement of organic magnetic anions adsorbed on epitaxial graphene on Ru(0001).

    PubMed

    Stradi, Daniele; Garnica, Manuela; Díaz, Cristina; Calleja, Fabián; Barja, Sara; Martín, Nazario; Alcamí, Manuel; Vazquez de Parga, Amadeo L; Miranda, Rodolfo; Martín, Fernando

    2014-12-21

    Achieving control over the self-organization of functional molecules on graphene is critical for the development of graphene technology in organic electronic and spintronic. Here, by using a scanning tunneling microscope (STM), we show that the electron acceptor molecule 7,7',8,8'-tetracyano-p-quinodimethane (TCNQ) and its fluorinated derivative 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyano-p-quinodimethane (F4-TCNQ), co-deposited on the surface of epitaxial graphene on Ru(0001), transform spontaneously into their corresponding magnetic anions and self-organize in two remarkably different structures. TCNQ forms densely packed linear magnetic arrays, while F4-TCNQ molecules remain as isolated non interacting magnets. With the help of density functional theory (DFT) calculations, we trace back the origin of this behavior in the competition between the intermolecular repulsion experienced by the individual charged anions, which tends to separate the molecules, and the delocalization of the electrons transferred from the surface to the molecules, which promotes the formation of molecular oligomers. Our results demonstrate that it is possible to control the spatial arrangement of organic magnetic anions co-adsorbed on a surface by means of chemical substitution, paving the way for the design of two-dimensional fully organic magnetic structures on graphene and on other surfaces. PMID:25382549

  16. Influence of ionic strength changes on the structure of pre-adsorbed salivary films. A response of a natural multi-component layer.

    PubMed

    Macakova, Lubica; Yakubov, Gleb E; Plunkett, Mark A; Stokes, Jason R

    2010-05-01

    Salivary films coating oral surfaces are critically important for oral health. This study focuses on determining the underlying nature of this adsorbed film and how it responds to departures from physiological conditions due to changes in ionic strength. Under physiological conditions, it is found that pre-adsorbed in vitro salivary film on hydrophobic surfaces is present as a highly hydrated viscoelastic layer. We follow the evolution of this film in terms of its effective thickness, hydration and viscoelastic properties, as well as adsorbed mass of proteins, using complementary surface characterisation methods: a Surface Plasmon Resonance (SPR) and a Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D). Our results support a heterogeneous model for the structure of the salivary film with an inner dense anchoring layer and an outer highly extended hydrated layer. Further swelling of the film was observed upon decreasing the salt concentration down to 1mM NaCl. However, upon exposure to deionised water, a collapse of the film occurs that was associated with the loss of water contained within the adsorbed layer. We suggest that the collapse in deionised water is driven by an onset of electrostatic attraction between different parts of the multi-component salivary film. It is anticipated that such changes could also occur when the oral cavity is exposed to food, beverage, oral care and pharmaceutical formulations where drastic changes to the structural integrity of the film is likely to have implications on oral health, sensory perception and product performance. PMID:20133111

  17. Structure and friction of stearic acid and oleic acid films adsorbed on iron oxide surfaces in squalane.

    PubMed

    Doig, Michael; Warrens, Chris P; Camp, Philip J

    2014-01-14

    The structure and friction of fatty acid surfactant films adsorbed on iron oxide surfaces lubricated by squalane are examined using large-scale molecular dynamics simulations. The structures of stearic acid and oleic acid films under static and shear conditions, and at various surface coverages, are described in detail, and the effects of unsaturation in the tail group are highlighted. At high surface coverage, the measured properties of stearic acid and oleic acid films are seen to be very similar. At low and intermediate surface coverages, the presence of a double bond, as in oleic acid, is seen to give rise to less penetration of lubricant in to the surfactant film and less layering of the lubricant near to the film. The kinetic friction coefficient is measured as a function of shear rate within the hydrodynamic (high shear rate) lubrication regime. Lubricant penetration and layering are observed to be correlated with friction coefficient. The friction coefficient with oleic acid depends only weakly on surface coverage, while stearic acid admits more lubricant penetration, and its friction coefficient increases significantly with decreasing surface coverage. Connections between film structure and friction are discussed. PMID:24364665

  18. Selective Ni-P electroless plating on photopatterned cationic adsorption films influenced by alkyl chain lengths of polyelectrolyte adsorbates and additive surfactants.

    PubMed

    Nakagawa, Masaru; Nawa, Nozomi; Iyoda, Tomokazu

    2004-10-26

    We demonstrated that the photopatterned single-layer adsorption film of poly(1-dodecyl-4-pyridinium bromide) on a silica surface was available for a template of nickel-phosphorus (Ni-P) electroless plating through sensitization with a SnCl(2) aqueous solution and activation with a PdCl(2) aqueous solution. Four kinds of poly(1-alkyl-4-vinylpyridinium halide)s bearing methyl, propyl, hexyl, and dodecyl groups were prepared. The cationic polymers were adsorbed by a negatively charged silica surface from their solutions, to form single-layer adsorption films exhibiting desorption-resistance toward deionized water and ethanol. The organic adsorption films could be decomposed completely by exposure to 172 nm deep-UV light. The formation and decomposition of the single-layer films were confirmed by deep-UV absorption spectral measurement and zeta-potential measurement. Ni-P electroless plating was carried out on the photopatterned adsorption films, using three types of SnO(x) colloidal materials without and with cationic or anionic surfactant as catalyst precursors in the sensitization step. In the case of the negatively charged SnO(x) colloids surrounded by anionic surfactant, Ni-deposition took place preferentially on the cationic adsorption films remaining in unexposed regions. The Ni-deposition was accelerated significantly on the cationic adsorption film bearing dodecyl groups. It was obvious by ICP-AES analyses that the hydrophobic long-chain dodecyl groups in the adsorption film could promote the adsorption of the negative SnO(x) colloids on the film surface, followed by much nucleus formation of zerovalent Pd catalysts useful for the electroless plating. The result of our experiment clearly showed that, in addition to electrostatic interaction, van der Waals interaction generating between the hydrophobic long-chain hydrocarbons of the adsorption film and the surfactant improved significantly the adsorption stability of the SnO(x) colloids, resulting in highly

  19. Activated boron nitride as an effective adsorbent for metal ions and organic pollutants

    NASA Astrophysics Data System (ADS)

    Li, Jie; Xiao, Xing; Xu, Xuewen; Lin, Jing; Huang, Yang; Xue, Yanming; Jin, Peng; Zou, Jin; Tang, Chengchun

    2013-11-01

    Novel activated boron nitride (BN) as an effective adsorbent for pollutants in water and air has been reported in the present work. The activated BN was synthesized by a simple structure-directed method that enabled us to control the surface area, pore volume, crystal defects and surface groups. The obtained BN exhibits an super high surface area of 2078 m2/g, a large pore volume of 1.66 cm3/g and a special multimodal microporous/mesoporous structure located at ~ 1.3, ~ 2.7, and ~ 3.9 nm, respectively. More importantly, the novel activated BN exhibits an excellent adsorption performance for various metal ions (Cr3+, Co2+, Ni2+, Ce3+, Pb2+) and organic pollutants (tetracycline, methyl orange and congo red) in water, as well as volatile organic compounds (benzene) in air. The excellent reusability of the activated BN has also been confirmed. All the features render the activated BN a promising material suitable for environmental remediation.

  20. Activated boron nitride as an effective adsorbent for metal ions and organic pollutants.

    PubMed

    Li, Jie; Xiao, Xing; Xu, Xuewen; Lin, Jing; Huang, Yang; Xue, Yanming; Jin, Peng; Zou, Jin; Tang, Chengchun

    2013-01-01

    Novel activated boron nitride (BN) as an effective adsorbent for pollutants in water and air has been reported in the present work. The activated BN was synthesized by a simple structure-directed method that enabled us to control the surface area, pore volume, crystal defects and surface groups. The obtained BN exhibits an super high surface area of 2078 m(2)/g, a large pore volume of 1.66 cm(3)/g and a special multimodal microporous/mesoporous structure located at ~ 1.3, ~ 2.7, and ~ 3.9 nm, respectively. More importantly, the novel activated BN exhibits an excellent adsorption performance for various metal ions (Cr(3+), Co(2+), Ni(2+), Ce(3+), Pb(2+)) and organic pollutants (tetracycline, methyl orange and congo red) in water, as well as volatile organic compounds (benzene) in air. The excellent reusability of the activated BN has also been confirmed. All the features render the activated BN a promising material suitable for environmental remediation. PMID:24220570

  1. Activated boron nitride as an effective adsorbent for metal ions and organic pollutants

    PubMed Central

    Li, Jie; Xiao, Xing; Xu, Xuewen; Lin, Jing; Huang, Yang; Xue, Yanming; Jin, Peng; Zou, Jin; Tang, Chengchun

    2013-01-01

    Novel activated boron nitride (BN) as an effective adsorbent for pollutants in water and air has been reported in the present work. The activated BN was synthesized by a simple structure-directed method that enabled us to control the surface area, pore volume, crystal defects and surface groups. The obtained BN exhibits an super high surface area of 2078 m2/g, a large pore volume of 1.66 cm3/g and a special multimodal microporous/mesoporous structure located at ~ 1.3, ~ 2.7, and ~ 3.9 nm, respectively. More importantly, the novel activated BN exhibits an excellent adsorption performance for various metal ions (Cr3+, Co2+, Ni2+, Ce3+, Pb2+) and organic pollutants (tetracycline, methyl orange and congo red) in water, as well as volatile organic compounds (benzene) in air. The excellent reusability of the activated BN has also been confirmed. All the features render the activated BN a promising material suitable for environmental remediation. PMID:24220570

  2. Effect of alkane chain length and counterion on the freezing transition of cationic surfactant adsorbed film at alkane mixture - water interfaces.

    PubMed

    Tokiwa, Yuhei; Sakamoto, Hiroyasu; Takiue, Takanori; Aratono, Makoto; Matsubara, Hiroki

    2015-05-21

    Penetration of alkane molecules into the adsorbed film gives rise to a surface freezing transition of cationic surfactant at the alkane-water interface. To examine the effect of the alkane chain length and counterion on the surface freezing, we employed interfacial tensiometry and ellipsometry to study the interface of cetyltrimethylammonium bromide and cetyltrimethylammonium chloride aqueous solutions against dodecane, tetradecane, hexadecane, and their mixtures. Applying theoretical equations to the experimental results obtained, we found that the alkane molecules that have the same chain length as the surfactant adsorb preferentially into the surface freezing film. Furthermore, we demonstrated that the freezing transition temperature of cationic surfactant adsorbed film was independent of the kind of counterion. PMID:25932500

  3. Use of layered double hydroxides and their derivatives as adsorbents for inorganic and organic pollutants

    NASA Astrophysics Data System (ADS)

    You, Youwen

    Contamination of surface and groundwaters by hazardous inorganic and organic pollutants has become an increasing threat to the safety of drinking waters. Cleanup of contaminated surface and groundwaters has, therefore, become a major focus of environmental research. Primary objectives of this dissertation study were to examine the adsorption properties of layered double hydroxides (LDHs) and their derivatives for inorganic and organic contaminants and to identify potential technologies that utilize LDHs and their derivatives for environment remediation. Studies examined the adsorption characteristics of anionic selenium, arsenic and dicamba (3,6 dichloro-2-methoxy benzoic acid) on original LDHs and calcined-LDHs. Adsorption of selenium and arsenic on LDHs was a function of pH. Competing anions in solution strongly affected adsorption of all three contaminants, with divalent anions decreasing adsorption more intensely than monovalent anions. Adsorbed selenium, arsenic and dicamba could be released from LDHs in anion solutions. Adsorption isotherms for selenium and arsenic retention could be fitted to a simple Langmuir equation. Calcination processes significantly increased adsorption capacities of LDHs. Because of adsorption-desorpion characteristics, LDHs could be recycled. X-ray diffraction patterns revealed an increase of d-spacing coupling with adsorption of contaminants, verifying the intercalation of contaminants into layer structure of LDHs. Long chain anionic surfactants intercalated into LDHs modified their surface properties, resulting in organo-LDHs with hydrophobic surface properties. Various organo-LDHs were developed by incorporating different surfactants into LDHs via different synthesis methods. Surfactant intercalation properties were examined and the geometrical arrangements of the intercalated surfactants were characterized. Results revealed that surfactant molecules could adopt various configurations within the LDH interlayer space. Intercalation

  4. Optical and electrical characterizations of nanocomposite film of titania adsorbed onto oxidized multiwalled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Feng, Wei; Feng, Yiyu; Wu, Zigang; Fujii, Akihiko; Ozaki, Masanori; Yoshino, Katsumi

    2005-07-01

    Composite film containing titania electrostatically linked to oxidized multiwalled carbon nanotubes (TiO2-s-MWNTs) was prepared from a suspension of TiO2 nanoparticles in soluble carbon nanotubes. The structure of the film was analysed principally by Fourier transform infrared spectroscopy, scanning electron micrography and x-ray diffraction. The optical and electrical characterizations of the film were investigated by UV-vis spectrum, photoluminescence and photoconductivity. The enhancement of photocurrent in the TiO2-s-MWNT film is discussed by taking the photoinduced charge transfer between the MWNT and TiO2 into consideration.

  5. NMR Study of Phase Transitions in Pure Water and Binary H(2)O/HNO(3) Films Adsorbed on Surface of Pyrogenic Silica.

    PubMed

    Bogdan; Kulmala; Gorbunov; Kruppa

    1996-01-15

    Pyrogenic silica (aerosil) was employed as host within which the phase transitions in the adsorbed pure water and binary H(2)O/HNO(3) films have been studied with NMR spectroscopy. The median freezing temperature and freezing temperature region were shown to be highly sensitive both to the average thickness of the adsorbed films and to the amount of adsorbed nitric acid. The molar concentration of nitric acid in the adsorbed films was found to be very small, on the order of 10(-3)-10(-2) (M/liter). The concentration was found to be greater in the layers adjacent to the surface of silica and sharply decreases with distance from the surface. The difference between the median freezing temperatures for adsorbed pure water and for the binary system was found to be about 9 K for films of equal thickness. This is about 150 times greater than the difference between the freezing temperatures of bulk pure water and a solution with the same concentration of nitric acid. PMID:10479419

  6. Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

    USGS Publications Warehouse

    Goldberg, M.C.; Cunningham, K.M.; Weiner, Eugene R.

    1993-01-01

    Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

  7. Adsorbable organic halogens (AOXs) in solid residues from hazardous and clinical waste incineration.

    PubMed

    Durmusoglu, Ertan; Bakoglu, Mithat; Karademir, Aykan; Kirli, Lale

    2006-01-01

    Trace concentrations of a variety of chemicals remain in solid residues following combustion even in properly designed and operated incinerators. In the present study, the adsorbable organic halogen (AOX) levels of the solid residues, i.e., bottom ash, fly ash, and filter cake, were investigated during a 82-day of continuous operation of a Hazardous and Clinical Waste Incinerator. The distribution of halogens in the waste input prior to the incineration was also determined. The AOX levels measured in bottom ash, fly ash and filter cake were in the range of 0.014-1.879, 0.012-0.263, and 0.004-0.062 mg-Cl(-)/kg, respectively. The AOX levels are significantly low in the fly ash and filter cake due to the post-combustion process in the incinerator. At the end of the 82 days, the total AOX output in the bottom ash, fly ash, and filter cake were 571, 3.71, and 6.26 g, respectively. The partitioning of the total AOX in solid residues was 98.28, 0.64, and 1.08% for the bottom ash, fly ash and filter cake, respectively. This shows that the bottom ash is more contaminated with AOX than the other two residues. PMID:16835121

  8. Organic silicon compounds anf hydrogen sulfide removal from biogas by mineral and adsorbent

    NASA Astrophysics Data System (ADS)

    Choi, J.

    2015-12-01

    Biogas utilized for energy production needs to be free from organic silicon compounds and hydrogen sulfide , as their burning has damaging effects on utilities and humans; organic silicon compounds and hydrogen sulfide can be found in biogas produced from biomass wastes, due to their massive industrial use in synthetic product,such as cosmetics, detergents and paints.Siloxanes and hydrogen sulfide removal from biogas can be carried out by various methods (Ajhar et al., 2010); aim of the present work is to find a single practical andeconomic way to drastically and simultaneously reduce both hydrogen sulfide and the siloxanes concentration to less than 1 ppm. Some commercial activated carbons previously selected (Monteleoneet al., 2011) as being effective in hydrogen sulfide up taking have been tested in an adsorption measurement apparatus, by flowing both hydrogen sulphide and volatile siloxane (Decamethycyclopentasiloxane or D5) in a nitrogen stream,typically 25-300 ppm D5 over N2, through an clay minerals, Fe oxides and Silica; the adsorption process was analyzed by varying some experimental parameters (concentration, grain size, bed height). The best silica shows an adsorption capacity of 0.2 g D5 per gram of silica. The next thermo gravimetric analysis (TGA) confirms the capacity data obtained experimentally by the breakthrough curve tests.The capacity results depend on D5 and hydrogen sulphide concentrations. A regenerative silica process is then carried out byheating the silica bed up to 200 ° C and flushing out the adsorbed D5 and hydrogen sulphide samples in a nitrogen stream in athree step heating procedure up to 200 ° C. The adsorption capacity is observed to degrade after cyclingthe samples through several adsorption-desorption cycles.

  9. Analysis of Chemical Reactions between Radical Growth Precursors Adsorbed on Plasma-Deposited Silicon Thin-Film Surfaces

    NASA Astrophysics Data System (ADS)

    Bakos, Tamas; Valipa, Mayur; Maroudas, Dimitrios

    2006-03-01

    The dominant precursor in the plasma deposition of hydrogenated amorphous silicon (a-Si:H) thin films is the SiH3 radical. In this presentation, we report results of first-principles density functional theory calculations on the crystalline Si(001)-(2x1):H surface and molecular-dynamics simulations on a-Si:H surfaces for the interactions between SiH3 radicals adsorbed on Si thin-film surfaces. The analysis reveals that two SiH3 radicals may either form disilane (Si2H6) that desorbs from the surface or undergo a disproportionation reaction producing an SiH2 radical that is incorporated in the film and a silane molecule that is released in the gas phase. The corresponding activation barriers depend on the local atomic coordination of the surface Si atoms; Si2H6 formation is barrierless if both radicals are bonded to overcoordinated surface Si atoms and exhibits barriers in excess of 1 eV for two chemisorbed SiH3 radicals.

  10. Fluorescence and photoelectrochemical behavior of chlorophyll {ital a} adsorbed on a nanocrystalline SnO{sub 2} film

    SciTech Connect

    Bedja, I.; Kamat, P.V.; Hotchandani, S.

    1996-10-01

    Fluorescence and photoelectrochemical studies of chlorophyll {ital a} (Chl {ital a}) adsorbed on nanocrystalline SnO{sub 2} film were carried out. The results of fluorescence and incident photon to current conversion efficiency (IPCE) as a function of applied bias suggest that the fluorescence quenching and the photocarrier generation are interrelated. Fluorescence quenching has thus been utilized to determine the photogeneration efficiency, {eta}({ital e}), of charges in a SnO{sub 2}/Chl {ital a} based photoelectrochemical cell. A value of 0.75 was obtained for {eta}({ital e}) for unbiased cells. With an IPCE of 13{percent}, {eta}({ital e}) of 75{percent}, and a light harvesting efficiency of 70{percent}, the charge collection efficiency of {approximately}23{percent} was evaluated. These results suggest that the losses due to the charge recombination are a major factor that limit the efficiency of the cells. {copyright} {ital 1996 American Institute of Physics.}

  11. EPR studies on the organization of self-assembled spin-labeled organic monolayers adsorbed on GaAs.

    PubMed

    Ruthstein, Sharon; Artzi, Reit; Goldfarb, Daniella; Naaman, Ron

    2005-02-01

    Characterizing the structure and dynamic properties of a single monolayer is a challenge due to the minute amount of material that is probed. Here, EPR spectroscopy is used for investigating the spatial and temporal organization of self-assembled monolayers of 5- and 16-doxyl stearic acid (5 DSA and 16 DSA, respectively) adsorbed on a GaAs substrate. The results are complemented with FTIR and ellipsometery measurements, which provide the evidence for the formation of monolayers. Moreover, a comparison with the FTIR spectrum of a monolayer of stearic acid shows that the monolayers of the spin labeled molecules are less packed due to the hindrance introduced by the labeling group. The EPR spectra provide a new insight on the ordering in the layer and more interestingly, it reveals the time dependence of the organization. For 5DSA, with the spin-label group situated close to the substrate, the EPR spectrum immediately after adsorption is poorly resolved and dominated by the spin-exchange interaction between neighboring molecules. As time increases (up to 1 week) the resolution of the 14N hyperfine coupling increases, revealing a better organized monolayer where the molecules are more homogenously spaced. Moreover, the spectrum of the layer, after reaching equilibrium, shows that there is no motional freedom near the GaAs surface. Orientation dependence measurements on the equilibrated sample show the presence of a preferred orientation of the molecules, although with a wide distribution. The spectrum of the 16DSA monolayer, where the nitroxide spin label is situated at the end of the chain, far from the surface, also showed a poorly resolved spectrum at short times, but unlike 5DSA, it did not exhibit any time dependence. Through EPR line-shape simulations and by comparison with FTIR results, the differences between 5DSA and 16DSA were attributed to difference in coverage caused by the bulky spin label near the surface in the case of 5DSA. PMID:19785139

  12. Relationship between surface viscosity and surface composition of adsorbed surfactant films

    SciTech Connect

    Djabbarah, N.F.; Wasan, D.T.

    1982-02-01

    The single-bubble foaming technique was used to determine the surface excess concentrations of aqueous solutions of sodium lauryl sulfate (SLS) and lauryl alcohol (LOH). The excess concentrations of sodium lauryl sulfate-lauryl alcohol showed that lauryl alcohol is preferentially adsorbed at the surface, but only partially displaces sodium lauryl sulfate. This causes a higher total surface concentration and, consequently, a closer packing of surfactant molecules. The total surface excess concentration increases with an increase in the bulk concentration of the 2 surfactants until the critical micelle concentration (CMC) is reached. At concentrations exceeding the CMC, the surface excess concentration of LOH remains virtually constant, while that of SLS declines. This is due to the formation of SLS micelles. The surface excess concentration data have been used to estimate the extent of molecular packing at the gas/liquid interface and to assess interactions among surfactant molecules in order to explain trends in surface viscosity of a mixed surfactant system adsorbed from an aqueous solution. 30 references.

  13. Nonequilibrium Molecular Dynamics Simulations of Organic Friction Modifiers Adsorbed on Iron Oxide Surfaces.

    PubMed

    Ewen, James P; Gattinoni, Chiara; Morgan, Neal; Spikes, Hugh A; Dini, Daniele

    2016-05-10

    For the successful development and application of lubricants, a full understanding of the nanoscale behavior of complex tribological systems is required, but this is difficult to obtain experimentally. In this study, we use nonequilibrium molecular dynamics (NEMD) simulations to examine the atomistic structure and friction properties of commercially relevant organic friction modifier (OFM) monolayers adsorbed on iron oxide surfaces and lubricated by a thin, separating layer of hexadecane. Specifically, acid, amide, and glyceride OFMs, with saturated and Z-unsaturated hydrocarbon tail groups, are simulated at various surface coverages and sliding velocities. At low and medium coverage, the OFMs form liquidlike and amorphous monolayers, respectively, which are significantly interdigitated with the hexadecane lubricant, resulting in relatively high friction coefficients. At high coverage, solidlike monolayers are formed for all of the OFMs, which, during sliding, results in slip planes between well-defined OFM and hexadecane layers, yielding a marked reduction in the friction coefficient. When present at equal surface coverage, OFMs with saturated and Z-unsaturated tail groups are found to yield similar structure and friction behavior. OFMs with glyceride head groups yield significantly lower friction coefficients than amide and particularly carboxylic acid head groups. For all of the OFMs and coverages simulated, the friction coefficient is found to increase linearly with the logarithm of sliding velocity; however, the gradient of this increase depends on the coverage. The structure and friction details obtained from these simulations agree well with experimental results and also shed light on the relative tribological performance of these OFMs through nanoscale structural variations. This has important implications in terms of the applicability of NEMD to aid the development of new formulations to control friction. PMID:27064962

  14. Screening Metal-Organic Frameworks by Analysis of Transient Breakthrough of Gas Mixtures in a Fixed Bed Adsorber

    SciTech Connect

    Krishna, Rajamani; Long, Jeffrey R.

    2011-07-07

    Metal–organic frameworks (MOFs) offer considerable potential for separating a variety of mixtures that are important in applications such as CO₂ capture and H₂ purification. In view of the vast number of MOFs that have been synthesized, there is a need for a reliable procedure for comparing screening and ranking MOFs with regard to their anticipated performance in pressure swing adsorption (PSA) units. For this purpose, the most commonly used metrics are the adsorption selectivity and the working capacity. Here, we suggest an additional metric for comparing MOFs that is based on the analysis of the transient response of an adsorber to a step input of a gaseous mixture. For a chosen purity of the gaseous mixture exiting from the adsorber, a dimensionless breakthrough time τ{sub break} can be defined and determined; this metric determines the frequency of required regeneration and influences the productivity of a PSA unit. The values of τ{sub break} are dictated both by selectivity and by capacity metrics .By performing transient adsorber calculations for separation of CO₂/H₂, CO₂/CH₄, CH₄/H₂, and CO₂/CH₄/H₂ mixtures, we compare the values of τbreak to highlight some important advantages of MOFs over conventionally used adsorbents such as zeolite NaX. For a given separation duty, such comparisons provide a more realistic ranking of MOFs than afforded by either selectivity or capacity metrics alone. We conclude that breakthrough calculations can provide an essential tool for screening MOFs.

  15. Preface: Thin films of molecular organic materials

    NASA Astrophysics Data System (ADS)

    Fraxedas, J.

    2008-03-01

    This special issue is devoted to thin films of molecular organic materials and its aim is to assemble numerous different aspects of this topic in order to reach a wide scientific audience. Under the term 'thin films', structures with thicknesses spanning from one monolayer or less up to several micrometers are included. In order to narrow down this relaxed definition (how thin is thin?) I suggest joining the stream that makes a distinction according to the length scale involved, separating nanometer-thick films from micrometer-thick films. While the physical properties of micrometer-thick films tend to mimic those of bulk materials, in the low nanometer regime new structures (e.g., crystallographic and substrate-induced phases) and properties are found. However, one has to bear in mind that some properties of micrometer-thick films are really confined to the film/substrate interface (e.g. charge injection), and are thus of nanometer nature. Supported in this dimensionality framework, this issue covers the most ideal and model 0D case, a single molecule on a surface, through to the more application-oriented 3D case, placing special emphasis on the fascinating 2D domain that is monolayer assembly. Thus, many aspects will be reviewed, such as single molecules, self-organization, monolayer regime, chirality, growth, physical properties and applications. This issue has been intentionally restricted to small molecules, thus leaving out polymers and biomolecules, because for small molecules it is easier to establish structure--property relationships. Traditionally, the preparation of thin films of molecular organic materials has been considered as a secondary, lower-ranked part of the more general field of this class of materials. The coating of diverse surfaces such as silicon, inorganic and organic single crystals, chemically modified substrates, polymers, etc., with interesting molecules was driven by the potential applications of such molecular materials

  16. Development and characterization of activated hydrochars from orange peels as potential adsorbents for emerging organic contaminants.

    PubMed

    Fernandez, M E; Ledesma, B; Román, S; Bonelli, P R; Cukierman, A L

    2015-05-01

    Activated hydrochars obtained from the hydrothermal carbonization of orange peels (Citrus sinensis) followed by various thermochemical processing were assessed as adsorbents for emerging contaminants in water. Thermal activation under flows of CO2 or air as well as chemical activation with phosphoric acid were applied to the hydrochars. Their characteristics were analyzed and related to their ability to uptake three pharmaceuticals (diclofenac sodium, salicylic acid and flurbiprofen) considered as emerging contaminants. The hydrothermal carbonization and subsequent activations promoted substantial chemical transformations which affected the surface properties of the activated hydrochars; they exhibited specific surface areas ranging from 300 to ∼620 m(2)/g. Morphological characterization showed the development of coral-like microspheres dominating the surface of most hydrochars. Their ability to adsorb the three pharmaceuticals selected was found largely dependent on whether the molecules were ionized or in their neutral form and on the porosity developed by the new adsorbents. PMID:25742754

  17. Surface-sensitive UHV dielectric studies of nanoscale organic thin films: Adsorption, crystallization, and sublimation

    NASA Astrophysics Data System (ADS)

    Underwood, Jason M.

    Nanoscale systems are small collections of atoms or molecules, which as a result of their limited extent, show measurable thermodynamic deviations from bulk samples of the same species. The deviations may result from purely finite-size effects, or may be due to an increased significance of the interaction between the nanoscale system and its container. Ultra-thin (<100 nm) films of organic molecules adsorbed on surfaces afford unique opportunities to study the interplay of forces relevant to nanoscale physics. This thesis describes the development of a novel ultra-high vacuum apparatus to study the behavior of adsorbed polar molecules via dielectric spectroscopy (UHV-DS). Ultra-thin films are grown and characterized in-situ. The use of interdigitated electrode capacitors and a ratio-transformer bridge technique yields resolutions of ˜1 aF and ˜10-5 ppm in the capacitance and loss tangent, respectively. Typical sensitivity is 10 aF per monolayer at 80 K. Results are given for studies on water, methanol, and Cp* (a synthetic molecular rotor). The desorption event in the dielectric spectra is correlated with thermal desorption spectroscopy. During growth of methanol films, we observe partial crystallization for temperatures above ≳ 100 K. Crystallization is also observed upon heating glassy films grown at 80 K. Finally, we discuss UHV-DS as a probe for solid thin-film vapor pressure measurements, and show that our data on methanol compare favorably with those in the literature.

  18. Entropy-Driven Conformational Control of α,ω-Difunctional Bidentate-Dithiol Azo-Based Adsorbates Enables the Fabrication of Thermally Stable Surface-Grafted Polymer Films.

    PubMed

    Lee, Han Ju; Jamison, Andrew C; Lee, T Randall

    2016-06-22

    Thermally stable radical initiator monolayers were prepared from uniquely designed α,ω-difunctional adsorbates with bidentate headgroups for the growth of nanoscale polymer films on metal surfaces. The length of the spacer separating the bidentate headgroups was varied to afford 4,4'-(diazene-1,2-diyl)bis(N-(16-(3,5-bis(mercaptomethyl)phenoxy)hexadecyl)-4-cyanopentanamide) (B16), 4,4'-(diazene-1,2-diyl)bis(N-(16-(3,5-bis(mercapto-methyl)phenoxy)decyl)-4-cyanopentanamide) (B10), and 4,4'-(diazene-1,2-diyl)bis(N-(4-(3,5-bis(mercaptomethyl)phenoxy)butyl)-4-cyanopentanamide) (B4). The structural features of the self-assembled monolayers (SAMs) derived from B16, B10, and B4 were characterized by X-ray photoelectron spectroscopy (XPS), ellipsometry, and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and compared to those derived from an analogous α,ω-difunctional adsorbate with monodentate headgroups, 4,4'-(diazene-1,2-diyl)bis(4-cyano-N-(16-mercaptohexadecyl)pentanamide (M). These studies demonstrate that the conformation (i.e., hairpin vs standing up) of the bidentate initiator adsorbates on gold surfaces was easily controlled by adjusting the concentration of the adsorbates in solution. The results of solution-phase thermal desorption tests revealed that the radical initiator monolayers generated from B16, B10, and B4 exhibit an enhanced thermal stability when compared to those generated from M. Furthermore, a study of the growth of polymer films was performed to evaluate the utility of these new bidentate adsorbate SAMs as film-development platforms for new functional materials and devices. Specifically, surface-grafted polystyrene films were successfully generated from SAMs derived from B16. In contrast, attempts to grow polystyrene films from SAMs derived from M under a variety of analogous conditions were unsuccessful. PMID:27219525

  19. Organic thin films. Rational synthesis of organic thin films with exceptional long-range structural integrity.

    PubMed

    Seiki, Noriya; Shoji, Yoshiaki; Kajitani, Takashi; Ishiwari, Fumitaka; Kosaka, Atsuko; Hikima, Takaaki; Takata, Masaki; Someya, Takao; Fukushima, Takanori

    2015-06-01

    Highly oriented, domain-boundary-free organic thin films could find use in various high-performance organic materials and devices. However, even with state-of-the-art supramolecular chemistry, it is difficult to construct organic thin films with structural integrity in a size regime beyond the micrometer length scale. We show that a space-filling design, relying on the two-dimensional (2D) nested hexagonal packing of a particular type of triptycene, enables the formation of large-area molecular films with long-range 2D structural integrity up to the centimeter length scale by vacuum evaporation, spin-coating, and cooling from the isotropic liquid of the triptycene. X-ray diffraction analysis and microscopic observations reveal that triptycene molecules form a completely oriented 2D (hexagonal triptycene array) + 1D (layer stacking) structure, which is key for the long-range propagation of structural order. PMID:26045433

  20. Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates

    PubMed Central

    Behm, R Jürgen

    2014-01-01

    Summary As part of a mechanistic study of the electrooxidation of C1 molecules we have systematically investigated the dissociative adsorption/oxidation of formaldehyde on a polycrystalline Pt film electrode under experimental conditions optimizing the chance for detecting weakly adsorbed reaction intermediates. Employing in situ IR spectroscopy in an attenuated total reflection configuration (ATR-FTIRS) with p-polarized IR radiation to further improve the signal-to-noise ratio, and using low reaction temperatures (3 °C) and deuterium substitution to slow down the reaction kinetics and to stabilize weakly adsorbed reaction intermediates, we could detect an IR absorption band at 1660 cm−1 characteristic for adsorbed formyl intermediates. This assignment is supported by an isotope shift in wave number. Effects of temperature, potential and deuterium substitution on the formation and disappearance of different adsorbed species (COad, adsorbed formate, adsorbed formyl), are monitored and quantified. Consequences on the mechanism for dissociative adsorption and oxidation of formaldehyde are discussed. PMID:24991512

  1. Effect of adsorbed films on friction of Al2O3-metal systems

    NASA Technical Reports Server (NTRS)

    Pepper, S. V.

    1976-01-01

    The kinetic friction of polycrystalline Al2O3 sliding on Cu, Ni, and Fe in ultrahigh vacuum was studied as a function of the surface chemistry of the metal. Clean metal surfaces were exposed to O2, Cl2, C2H4, and C2H3Cl, and the change in friction due to the adsorbed species was observed. Auger electron spectroscopy assessed the elemental composition of the metal surface. It was found that the systems exposed to Cl2 exhibited low friction, interpreted as the van der Waals force between the Al2O3 and metal chloride. The generation of metal oxide by oxygen exposures resulted in an increase in friction, interpreted as due to strong interfacial bonds established by reaction of metal oxide with Al2O3 to form the complex oxide (spinel). The only effect of C2H4 was to increase the friction of the Fe system, but C2H3Cl exposures decreases friction in both Ni and Fe systems, indicating the dominance of the chlorine over the ethylene complex on the surface

  2. The analysis of surface-adsorbed organic molecules by alkali-assisted MIES combined with UPS(He I)

    NASA Astrophysics Data System (ADS)

    Günster, J.; Ochs, D.; Dieckhoff, S.; Kempter, V.

    1996-12-01

    Metastable impact electron spectroscopy (MIES) in combination with UPS(He I) is applied to the study of s-triazine and triethoxytriazine molecules adsorbed on Si(100) either alone or in combination with cesium atoms. It is demonstrated that the presence of the Cs atoms facilitates the identification of the adsorbed species considerably. It is concluded that (i) non-dissociative adsorption of the studied organic molecules occurs whereby the basal rings of the molecules lie flat on the silicon surface, in accordance with previous studies by Bu and Lin, (ii) the binding of the molecules to the surface is mainly via the lone pair orbitals of the nitrogen in the ring, and (iii) s-triazine reacts strongly with oxygen which bonds to the carbon atoms of the triazine ring.

  3. Thick-Film Carbon Dioxide Sensor via Anodic Adsorbate Stripping Technique and Its Structural Dependence

    PubMed Central

    Photinon, Kanokorn; Wang, Shih-Han; Liu, Chung-Chiun

    2009-01-01

    A three-electrode based CO2 sensor was fabricated using thick-film technology. The performance of this sensor was further enhanced by incorporating platinum nanoparticles onto the working electrode surface. An eight-fold increase in the signal output was obtained from the electrode with the platinum nanoparticles. The sensing output was linearly related to the CO2 presented. Stability measurements demonstrated that the decline of the active surface area and the sensitivity of the sensor were 8% and 13%, respectively, over a two week period of time. The sensor response appeared to be a structural dependence of the crystallographic orientation of platinum electrode. PMID:22399993

  4. Kosterlitz-Thouless Transition in 4He Films Adsorbed to Rough Calcium Fluoride

    SciTech Connect

    Luhman, D. R.; Hallock, R. B.

    2006-09-07

    Previous measurements in our lab have shown that the onset of superfluidity at the KT transition, typically seen as a sharp change in the frequency of a smooth-surface quartz crystal microbalance, becomes less identifiable in the presence of increasing surface roughness or disorder, while the peak in the dissipation is unchanged. Using a series of microbalances coated with increasingly rough CaF2, we have extended our measurements to lower 4He film coverages and thus lower temperatures. We find at lower 4He coverages that the presence of disorder on the substrate has a diminished effect on the frequency shift.

  5. Third Sound Generation in Superfluid 4He Films Adsorbed on Multiwall Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Iaia, Vito; Menachekanian, Emin; Williams, Gary

    2014-03-01

    A technique is developed for generating third sound in superfluid 4He films coating the surface of multiwall carbon nanotubes. Third sound is a thickness and temperature wave of the helium film, and in our case we detect the temperature oscillations with a carbon resistance bolometer. The nanotubes are packed in an annular resonator that is vibrated with a mechanical shaker assembly consisting of a permanent magnet mounted on springs, and surrounded by a superconducting coil. The coil is driven with an oscillating current, vibrating the cell at that frequency. Sweeping the drive frequency over the range 100-200 Hz excites the resonant third sound mode of the cell, seen as a high-Q signal in the FFT analysis of the bolometer signal. A problem with our original cell was that the mechanical drive would also shake the dilution refrigerator cooling the cell to low temperatures, and increasing the drive would start to heat up the refrigerator and the cell, which were rigidly coupled together. A new configuration now suspends the cell as a pendulum on a string, with thermal contact made by copper wires. Piezo sensor measurements show this reduces the vibration reaching the refrigerator by two orders of magnitude, which should allow measurements at lower temperatures.

  6. Infrared spectroscopy of water clusters co-adsorbed with hydrogen molecules on a sodium chloride film

    NASA Astrophysics Data System (ADS)

    Yamakawa, Koichiro; Fukutani, Katsuyuki

    2016-06-01

    Hydrogen gas containing a trace of water vapor was dosed on a vacuum-evaporated sodium chloride film at 13 K, and water clusters formed on the substrate were investigated by infrared absorption spectroscopy. Absorption bands due to (H2O)n clusters with n = 3-6 and an induced absorption band due to hydrogen were clearly observed. With increasing gas dosage, the intensities of the cluster bands increased linearly while the intensity of the hydrogen band was constant. This suggests that the water clusters were formed in two-dimensional matrices of hydrogen. We found that the water clusters did exist on the surface upon heating even after the hydrogen molecules had desorbed. A further rise of the substrate temperature up to 27 K yielded the formation of larger clusters, (H2O)n with n > 6 . We also discuss the origins of the two bands of the trimer in terms of pseudorotation and a metastable isomer.

  7. Dynamic interfaces in an organic thin film

    PubMed Central

    Tao, Chenggang; Liu, Qiang; Riddick, Blake C.; Cullen, William G.; Reutt-Robey, Janice; Weeks, John D.; Williams, Ellen D.

    2008-01-01

    Low-dimensional boundaries between phases and domains in organic thin films are important in charge transport and recombination. Here, fluctuations of interfacial boundaries in an organic thin film, acridine-9-carboxylic acid on Ag(111), have been visualized in real time and measured quantitatively using scanning tunneling microscopy. The boundaries fluctuate via molecular exchange with exchange time constants of 10–30 ms at room temperature, with length-mode fluctuations that should yield characteristic f−1/2 signatures for frequencies less than ≈100 Hz. Although acridine-9-carboxylic acid has highly anisotropic intermolecular interactions, it forms islands that are compact in shape with crystallographically distinct boundaries that have essentially identical thermodynamic and kinetic properties. The physical basis of the modified symmetry is shown to arise from significantly different substrate interactions induced by alternating orientations of successive molecules in the condensed phase. Incorporating this additional set of interactions in a lattice–gas model leads to effective multicomponent behavior, as in the Blume–Emery–Griffiths model, and can straightforwardly reproduce the experimentally observed isotropic behavior. The general multicomponent description allows the domain shapes and boundary fluctuations to be tuned from isotropic to highly anisotropic in terms of the balance between intermolecular interactions and molecule–substrate interactions. PMID:18765797

  8. Comparison between the adsorption behaviors of an organic cation and an organic anion on several reversed-phase liquid chromatography adsorbents.

    PubMed

    Gritti, Fabrice; Guiochon, Georges

    2004-09-01

    Adsorption data of an organic cation (propranololium chloride) and an organic anion (sodium 1-naphthalene sulfonate) were measured by frontal analysis on two RPLC adsorbents, Symmetry-C18 and XTerra-C18, with aqueous solutions of methanol as the mobile phases. The influence of supporting neutral salts on the adsorption behavior of these two ions are compared. The Henry constants are close (H approximately 5). The four sets of isotherm data are all well accounted for using the bi-Moreau model. However, the isotherms of the two ions behave differently at high concentrations. The initial behaviors of all the isotherms are antilangmuirian but remain so in a much wider concentration range for the cation than for the anion, due to its stronger adsorbate-adsorbate interactions on the low-energy adsorption sites. The retention times of both ions increase with increasing concentration of neutral salt in the mobile phase, suggesting the formation of ion-pair complexes, with Cl- for the cation and with Na+ for the anion. The adsorbate-adsorbate interactions vanish in the presence of salt and the bi-Moreau isotherm model tends toward a bi-Langmuir model. Differences in adsorption behavior are also observed between the cation and the anion when bivalent inorganic anions and cations, respectively, are dissolved in the mobile phase. High concentration band profiles of 1-naphthalene sulfonic acid are langmuirian, except in the presence of a trivalent cation, while those of propranolol are antilangmuirian under certain conditions even with uni- or divalent cations. PMID:15453413

  9. Hybrid inorganic-organic adsorbents Part 1: Synthesis and characterization of mesoporous zirconium titanate frameworks containing coordinating organic functionalities.

    PubMed

    Griffith, Christopher S; De Los Reyes, Massey; Scales, Nicholas; Hanna, John V; Luca, Vittorio

    2010-12-01

    A series of functional hybrid inorganic-organic adsorbent materials have been prepared through postsynthetic grafting of mesoporous zirconium titanate xerogel powders using a range of synthesized and commercial mono-, bis-, and tris-phosphonic acids, many of which have never before been investigated for the preparation of hybrid phases. The hybrid materials have been characterized using thermogravimetric analysis, diffuse reflectance infrared (DRIFT) and 31P MAS NMR spectroscopic techniques and their adsorption properties studied using a 153Gd radiotracer. The highest level of surface functionalization (molecules/nm2) was observed for methylphosphonic acid (∼3 molecules/nm2). The level of functionalization decreased with an increase in the number of potential surface coordinating groups of the phosphonic acids. Spectral decomposition of the DRIFT and 31P MAS NMR spectra showed that each of the phosphonic acid molecules coordinated strongly to the metal oxide surface but that for the 1,1-bis-phosphonic acids and tris-phosphonic acids the coordination was highly variable resulting in a proportion of free or loosely coordinated phosphonic acid groups. Functionalization of a porous mixed metal oxide framework with the tris-methylenephosphonic acid (ATMP-ZrTi-0.33) resulted in a hybrid with the highest affinity for 153Gd3+ in nitric acid solutions across a wide range of acid concentrations. The ATMP-ZrTi-0.33 hybrid material extracted 153Gd3+ with a Kd value of 1×10(4) in 0.01 M HNO3 far exceeding that of the other hybrid phases. The unfunctionalized mesoporous mixed metal oxide had negligible affinity for Gd3+ (Kd<100) under identical experimental conditions. It has been shown that the presence of free or loosely coordinated phosphonic acid groups does not necessarily translate to affinity for 153Gd3+. The theoretical cation exchange capacity of the ATMP-ZrTi-0.33 hybrid phase for Gd3+ has been determined to be about 0.005 mmol/g in 0.01 M HNO3. This behavior and

  10. David Adler Lectureship Award Talk: Friction and energy dissipation mechanisms in adsorbed molecules and molecularly thin films

    NASA Astrophysics Data System (ADS)

    Krim, Jacqueline

    2015-03-01

    Studies of the fundamental origins of friction have undergone rapid progress in recent years, with the development of new experimental and computational techniques for measuring and simulating friction at atomic length and time scales. The increased interest has sparked a variety of discussions and debates concerning the nature of the atomic-scale and quantum mechanisms that dominate the dissipative process by which mechanical energy is transformed into heat. Measurements of the sliding friction of physisorbed monolayers and bilayers can provide information on the relative contributions of these various dissipative mechanisms. Adsorbed films, whether intentionally applied or present as trace levels of physisorbed contaminants, moreover are ubiquitous at virtually all surfaces. As such, they impact a wide range of applications whose progress depends on precise control and/or knowledge of surface diffusion processes. Examples include nanoscale assembly, directed transport of Brownian particles, material flow through restricted geometries such as graphene membranes and molecular sieves, passivation and edge effects in carbon-based lubricants, and the stability of granular materials associated with frictional and frictionless contacts. Work supported by NSFDMR1310456.

  11. Tribochemical synthesis of nano-lubricant films from adsorbed molecules at sliding solid interface: Tribo-polymers from α-pinene, pinane, and n-decane

    NASA Astrophysics Data System (ADS)

    He, Xin; Barthel, Anthony J.; Kim, Seong H.

    2016-06-01

    The mechanochemical reactions of adsorbed molecules at sliding interfaces were studied for α-pinene (C10H16), pinane (C10H18), and n-decane (C10H22) on a stainless steel substrate surface. During vapor phase lubrication, molecules adsorbed at the sliding interface could be activated by mechanical shear. Under the equilibrium adsorption condition of these molecules, the friction coefficient of sliding steel surfaces was about 0.2 and a polymeric film was tribochemically produced. The synthesis yield of α-pinene tribo-polymers was about twice as much as pinane tribo-polymers. In contrast to these strained bicyclic hydrocarbons, n-decane showed much weaker activity for tribo-polymerization at the same mechanical shear condition. These results suggested that the mechanical shear at tribological interfaces could induce the opening of the strained ring structure of α-pinene and pinane, which leads to polymerization of adsorbed molecules at the sliding track. On a stainless steel surface, such polymerization reactions of adsorbed molecules do not occur under typical surface reaction conditions. The mechanical properties and boundary lubrication efficiency of the produced tribo-polymer films are discussed.

  12. Structural studies of ultrathin organic films

    NASA Astrophysics Data System (ADS)

    Yim, Hyun

    1998-11-01

    Ultrathin organic films have been a focus of research due to the growing interest in optoelectronics and molecular electronics. In both areas, it is believed that self-assembled (SA) films and Langmuir-Blodgett (LB) films may provide the desired control of order at the molecular level. The tethering of polyglutamate molecules to surfaces is of special interest due to nonlinear optical properties which can be achieved when the molecules are oriented. The tethering of poly(benzyl-L-glutamate) to silicon has been done by polymerization of benzyl-L-glutamate-N-carboxyanhydride using self-assembled monolayers with various concentrations of amino end groups as initiating layers. X-ray reflectivity results show that a minimum concentration of initiator sites on the surface is required. The second tethering system is a polystyrene brush. The polystyrene brush is expected to give strong sensitivity to solvent swelling. The structure of the polystyrene brush, which was chemically grafted to a substrate, in poor solvent and its change at different temperatures were investigated by neutron reflectometry. When temperature increases up to 30sp°C, both the thickness and roughness increase greatly, which indicates that the polystyrene brush changes from a collapsed state to a theta state. Hairy-rod polyimide molecules are of interest due to their interesting physical properties. Multilayer films of preformed polyimide molecules (6FDA-C18) have been obtained for the first time by the LB technique. The multilayer films do not display a distinctively periodic structure. Upon annealing for a few hours at 180sp°C, the structure relaxes slightly. The alkyl side chain substituted polyimides (BACBF/BPDA) can form metastable monolayers for which the pressure-area isotherms vary markedly with side chain length. For the polyimide with octadecyl side chains, a sharp reduction in zero pressure area occurs between 20 and 24sp°C, suggesting an important change in side chain mobility

  13. Effects of molecule-insulator interaction on geometric property of a single phthalocyanine molecule adsorbed on an ultrathin NaCl film

    NASA Astrophysics Data System (ADS)

    Miwa, Kuniyuki; Imada, Hiroshi; Kawahara, Shota; Kim, Yousoo

    2016-04-01

    The adsorption structure and orientation of a metal-free phthalocyanine (H2Pc ) and a magnesium phthalocyanine (MgPc) on a bilayer of NaCl films were investigated both theoretically and experimentally by means of first-principles calculations based on density functional theory and by scanning tunneling microscopy. H2Pc is adsorbed with its center over the sodium cation, and H-N bonds in the molecule are aligned with the [100] or [010] surface direction of a bilayer (001)-terminated NaCl film. The most stable structures of MgPc on the NaCl film show two kinds of orientations corresponding to the molecule rotated by ±7∘ relative to the [110] surface direction, with the Mg cation positioned over the chlorine anion in both cases. The energetic barrier for switching between these orientations is as low as 9.0 meV, and during an STM measurement, an orientational change of MgPc can be observed. The interaction between the adsorbed molecule and the NaCl film were analyzed in terms of dispersion interaction, Mg-Cl chemical bonding, and electrostatic interaction. It is found that the small electrostatic interaction between the molecule and the film gives a dominant contribution to determining the molecular orientation. Our detailed and comprehensive studies of the molecule-insulator interaction will provide knowledge to understand and control the properties of molecules on an insulating material.

  14. Ultrathin organic semiconductor films--soft matter effect.

    PubMed

    Wang, Tong; Yan, Donghang

    2014-05-01

    The growth of organic semiconductor thin films has been a crucial issue in organic electronics, especially the growth at the early stages. The thin-film phase has been found to be a common phenomenon in many organic semiconductor thin films, which is closely related with the weak van der Waals interaction between organic molecules, the long-range interaction between organic molecules and the substrate, as well as the soft matter characteristics of ultrathin films. The growth behavior and soft matter characteristics of the thin-film phase have great effects on thin film morphology and structure, for example, the formation and coalescence of grain boundaries, which further influences the performance of organic electronic devices. The understanding of thin-film phase and its intrinsic quality is necessary for fabricating large-size, highly ordered, continuous and defect-free ultrathin films. This review will focus on the growth behavior of organic ultrathin films, i.e., the level of the first several molecular layers, and provide an overview of the soft matter characteristics. PMID:24548597

  15. Effect of the adsorbate kinetic diameter on the accuracy of the Dubinin-Radushkevich equation for modeling adsorption of organic vapors on activated carbon.

    PubMed

    Jahandar Lashaki, Masoud; Fayaz, Mohammadreza; Niknaddaf, Saeid; Hashisho, Zaher

    2012-11-30

    This paper investigates the effect of the kinetic diameter (KD) of the reference adsorbate on the accuracy of the Dubinin-Radushkevich (D-R) equation for predicting the adsorption isotherms of organic vapors on microporous activated carbon. Adsorption isotherms for 13 organic compounds on microporous beaded activated carbon were experimentally measured, and predicted using the D-R model and affinity coefficients. The affinity coefficients calculated based on molar volumes, molecular polarizabilities, and molecular parachors were used to predict the isotherms based on four reference compounds (4.3≤KD≤6.8 Å). The results show that the affinity coefficients are independent of the calculation method if the reference and test adsorbates are from the same organic group. Choosing a reference adsorbate with a KD similar to that of the test adsorbate results in better prediction of the adsorption isotherm. The relative error between the predicted and the measured adsorption isotherms increases as the absolute difference in the kinetic diameters of the reference and test adsorbates increases. Finally, the proposed hypothesis was used to explain reports of inconsistent findings among published articles. The results from this study are important because they allow a more accurate prediction of adsorption capacities of adsorbents which allow for better design of adsorption systems. PMID:23044198

  16. Difference in Surface Properties between Insoluble Monolayer and Adsorbed Film from Kinetics of Water Evaporation and BAM Image.

    PubMed

    Moroi, Yoshikiyo; Rusdi, Muhammad; Kubo, Izumi

    2004-05-20

    The evaporation rate of water molecules across three kinds of interfaces (air/water interface (1), air/surfactant solution interface (2), and air/water interface covered by insoluble monolayer (3)) was examined using a remodeled thermogravimetric balance. There was no difference in both the evaporation rate and the activation energy for the first two interfaces for three types of surfactant solutions below and above the critical micelle concentration (cmc). This means that the molecular surface area from the Gibbs surface excess has nothing to do with the evaporation rate. In the third case, the insoluble monolayer of 1-heptadecanol decreased the evaporation rate and increased the activation energy, indicating a clear difference between an insoluble monolayer and an adsorbed film of soluble surfactant. This difference was substantiated by BAM images, too. The images of three surfactant solution interfaces were similar to that of just the water surface, while distinct structures of molecular assemblies were observed for the insoluble monolayer. The concentration profile of water molecules in an air/liquid interfacial region was derived by Fix's second law. The profile indicates that a definite layer just beneath the air/liquid interface of the surfactant solution is made mostly of water molecules and that the layer thickness is a few times the root-mean-square displacement %@mt;sys@%%@rl;;@%2%@ital@%Dt%@rsf@%%@rlx@%%@mx@% of the water molecules. The thickness was found to be more than a few nanometers, as estimated from several relaxation times derived from the other kinetics than evaporation of amphiphilic molecules in aqueous systems and a maximum evaporation rate of purified water. PMID:18950121

  17. Influence of molecular structure and adsorbent properties on sorption of organic compounds to a temperature series of wood chars.

    PubMed

    Lattao, Charisma; Cao, Xiaoyan; Mao, Jingdong; Schmidt-Rohr, Klaus; Pignatello, Joseph J

    2014-05-01

    Chars from wildfires and soil amendments (biochars) are strong adsorbents that can impact the fate of organic compounds in soil, yet the effects of solute and adsorbent properties on sorption are poorly understood. We studied sorption of benzene, naphthalene, and 1,4-dinitrobenzene from water to a series of wood chars made anaerobically at different heat treatment temperatures (HTT) from 300 to 700 °C, and to graphite as a nonporous, unfunctionalized reference adsorbent. Peak suppression in the NMR spectrum by sorption of the paramagnetic relaxation probe TEMPO indicated that only a small fraction of char C atoms lie near sorption sites. Sorption intensity for all solutes maximized with the 500 °C char, but failed to trend regularly with N2 or CO2 surface area, micropore volume, mesopore volume, H/C ratio, O/C ratio, aromatic fused ring size, or HTT. A model relating sorption intensity to a weighted sum of microporosity and mesoporosity was more successful. Sorption isotherm linearity declined progressively with carbonization of the char. Application of a thermodynamic model incorporating solvent-water and char-graphite partition coefficients permitted for the first time quantification of steric (size exclusion in pores) and π-π electron donor-acceptor (EDA) free energy contributions, relative to benzene. Steric hindrance for naphthalene increases exponentially from 9 to 16 kJ/mol (∼ 1.6-2.9 log units of sorption coefficient) with the fraction of porosity in small micropores. π-π EDA interactions of dinitrobenzene contribute -17 to -19 kJ/mol (3-3.4 log units of sorption coefficient) to sorption on graphite, but less on chars. π-π EDA interaction of naphthalene on graphite is small (-2 to 2 kJ/mol). The results show that sorption is a complex function of char properties and solute molecular structure, and not very predictable on the basis of readily determined char properties. PMID:24758543

  18. CORRELATIONS FOR THE DETERMINATION OF SURFACE DIFFUSIVITIES OF ORGANIC CHEMICALS ADSORBED ONTO GRANULAR ACTIVATED CARBON

    EPA Science Inventory

    Differential column batch reactor (DCBR) experiments in organic-free water were conducted for the following volatile organic compounds (VOCs): trichloroethene, tetrachloroethene, cis-1,2 dichlorethene, and toluene. Surface diffusion was required to explain the rate of uptake for ...

  19. In-plane conductance of thin films as a probe of surface chemical environment: Adsorbate effects on film electronic properties of indium tin oxide and gold

    NASA Astrophysics Data System (ADS)

    Swint, Amy Lynn

    Changes in the in-plane conductance of conductive thin films are observed as a result of chemical adsorption at the surface. Reaction of the indium tin oxide (ITO) surface with Bronsted acids (bases) leads to increases (decreases) in its in-plane conductance as measured by a four-point probe configuration. The conductance varies monotonically with pH suggesting that the degree of surface protonation or hydroxylation controls the surface charge density, which in turn affects the width of the n-type depletion layer, and ultimately the in-plane conductance. Measurements at constant pH with a series of tetraalkylammonium hydroxide species of varying cation size indicate that surface dipoles also affect ITO conductance by modulating the magnitude of the surface polarization. Modulating the double layer with varying aqueous salt solutions also affects ITO conductance, though not to the same degree as strong Bronsted acids and bases. Solvents of varying dielectric constant and proton donating ability (ethanol, dimethylformamide) decrease ITO conductance relative to H2O. In addition, changing solvent gives rise to thermally-derived conductance transients, which result from exothermic solvent mixing. The self-assembly of alkanethiols at the surface increases the conductance of ITO films, most likely through carrier population effects. In all cases examined the combined effects of surface charge, adsorbed dipole layer magnitude and carrier injection are responsible for altering the ITO conductance. Besides being directly applicable to the control of electronic properties, these results also point to the use of four-point probe resistance measurements in condensed phase sensing applications. Ultrasensitive conductance-based gas phase sensing of organothiol adsorption to gold nanowires is accomplished with a limit of detection in the 105 molecule range. Further refinement of the inherently low noise resistance measurement may lead to observation of single adsorption events at

  20. Removing organic contaminants with bifunctional iron modified rectorite as efficient adsorbent and visible light photo-Fenton catalyst.

    PubMed

    Zhao, Xiaorong; Zhu, Lihua; Zhang, Yingying; Yan, Jingchun; Lu, Xiaohua; Huang, Yingping; Tang, Heqing

    2012-05-15

    Iron-modified rectorite (FeR) was prepared as both adsorbent and catalyst. The iron modification increased layer-to-layer spacing and surface area of rectorite, leading to much increased adsorption of Rhodamine B (RhB) on rectorite. The maximum adsorption capacity of RhB on FeR reached 101mgg(-1) at pH 4.5, being 11 folds of that on the unmodified one. The iron modification also enabled rectorite to have efficient visible light photocatalytic ability. The apparent rate constant for the degradation of RhB (80μM) at 298K and pH 4.5 in the presence of H(2)O(2) (6.0mM) and FeR (0.4gL(-1)) was evaluated to be 0.0413min(-1) under visible light and 0.122min(-1) under sunlight, respectively. The analysis with electron spin resonance spin-trapping technique supported that the iron modified rectorite effectively catalyzed the decomposition of H(2)O(2) into hydroxyl radicals. On the basis of the characterization and analysis, the new bifunctional material was well clarified as both adsorbent and photocatalyst in the removing of organic pollutants. PMID:22410720

  1. A model to predict the adsorber thermal behavior during treatment of volatile organic compounds onto wet activated carbon.

    PubMed

    Pré, P; Delage, F; Le Cloirec, P

    2002-11-01

    A model for adsorption of volatile organic compounds (VOCs) onto a wet activated carbon bed was proposed in this study. This model accounts for temperature changes induced by the reversed and coupled mass-transfer processes of both organic species adsorption and water desorption. Indeed, it was experimentally pointed out that temperature rises, which result from the exothermal nature of the energetic interactions between the organic molecule and the activated carbon surface, are notably reduced when the adsorbent contains an initial moisture of approximately 10% in weight. Moreover, it was shown that water rate desorption was enhanced in the presence of organic vapor. This phenomenon may be explained by the displacement of sorbed water bythe organic molecules, owing to more intensive interactions with the activated carbon surface. The model proposed was elaborated from a previous comprehensive analysis of the diffusion mechanisms governing VOC adsorption at high concentrations onto a dry activated carbon bed. In a similar way, a theoretical approach was developed to model water desorption during drying of a wet activated carbon bed under pure flowing air. At last, a theoretical depiction of both competitive and reverse processes was outlined. The final model fits reasonably with experimental data relative to both breakthrough curves and thermal wave shape along the bed, even if local temperature change calculation may require some further improvement. PMID:12433182

  2. Resin pellets from beaches of the Portuguese coast and adsorbed persistent organic pollutants

    NASA Astrophysics Data System (ADS)

    Antunes, J. C.; Frias, J. G. L.; Micaelo, A. C.; Sobral, P.

    2013-09-01

    The occurrence of stranded plastic marine debris along the Portuguese coastline was investigated. Number of items m-2 and size range of resin pellets were recorded, corresponding to 53% of total marine debris collected items. In addition, concentrations of adsorbed persistent bioaccumulative and toxic chemicals (PBTC) were determined, PAH - polycyclic aromatic hydrocarbons; PCB - polychlorinated biphenyls and DDT - dichlorodiphenyltrichloroethane. Matosinhos (Mt) and Vieira de Leiria (VL) presented the highest number of items m-2 (362 and 332, respectively). Resin pellets with 4 mm diameter were the most abundant (50%). Contaminants concentration was variable. PAH concentrations recorded values between 53 and 44800 ng g-1, PCB ranged from 2 to 223 ng g-1 and DDT between 0.42 and 41 ng g-1. In general, aged and black pellets recorded higher concentrations for all contaminants. Matosinhos (Mt), Vieira de Leiria (VL) and Sines (Si), near industrial areas and port facilities, were the most contaminated beaches. Research efforts are needed to assess the points of entry of industrial plastic pellets in order to take action and minimize impacts on the ecosystems, in particular, points of transfer during transportation from plastic manufacturers to plastic converters should be identified and controlled so that virgin pellets are contained and will not enter rivers and be carried to the oceans where they can remain for a long time and travel great distances.

  3. Comparison of nutshell granular activated carbons to commercial adsorbents for the purge-and-trap gas chromatographic analysis of volatile organic compounds.

    PubMed

    Wartelle, L H; Marshall, W E; Toles, C A; Johns, M M

    2000-05-26

    Granular activated carbons (GACs) made from agricultural by-products were investigated as adsorbents for short path thermal desorption gas chromatographic analysis of selected polar and nonpolar organic compounds. GACs made from macadamia nut, black walnut and hazelnut shells were compared to four commercially available adsorbents, namely, Tenax TA, Carboxen 569, Carbosieve SIII and coconut charcoal for their properties in purge-and-trap analysis. Adsorption values and breakthrough volumes were calculated for compounds from C3 and C6-C10. GACs derived from macadamia nut shells were found to adsorb and desorb between 80% (benzene) and 277% (ethylbenzene) more acetone (C3), benzene (C6), toluene (C7), ethyl- (C8), n-propyl- (C9), or sec.-butylbenzenes (C10) purged from water at the 100 ppb level than the commercial adsorbents tested. PMID:10893033

  4. [Melting in adsorbed films

    SciTech Connect

    Simon, M.I.

    1992-01-01

    Over the past several years we have been developing a new approach to cloning large fragments of mammalian DNA in E. coli. which will permit detailed analysis of complex genomes. In January 1992 we began construction of an arrayed total human genomic library prepared in our BAC vector. Our goal is to create a 4-5X library which will be accessible for screening both by colony hybridization and by PCR. Our efforts in 1992 have been focused on expanding this library, characterizing specific clones isolated from the library, and demonstrating the use of BACs and Fosmids in creating physical maps. As a Model for the use of BACs in physical mapping, we have begun mapping human chromosome 22. In addition to their stability and ease of handling, BACs and Fosniids offer the advantage of permitting isolation of relatively large amounts of pure DNA which should greatly facilitate contig construction. We have created a 7X chromosome 22-specific Fosmid library consisting of clones obtained from DNA from a hybrid cell line.

  5. Removal of hexenuronic acid by xylanase to reduce adsorbable organic halides formation in chlorine dioxide bleaching of bagasse pulp.

    PubMed

    Nie, Shuangxi; Wang, Shuangfei; Qin, Chengrong; Yao, Shuangquan; Ebonka, Johnbull Friday; Song, Xueping; Li, Kecheng

    2015-11-01

    Xylanase-aided chlorine dioxide bleaching of bagasse pulp was investigated. The pulp was pretreated with xylanase and followed a chlorine dioxide bleaching stage. The ATR-FTIR and XPS were employed to determine the surface chemistry of the control pulp, xylanase treated and chlorine dioxide treated pulps. The hexenuronic acid (HexA) could obviously be reduced after xylanase pretreatment, and the adsorbable organic halides (AOX) were reduced after chlorine dioxide bleaching. Compared to the control pulp, AOX could be reduced by 21.4-26.6% with xylanase treatment. Chlorine dioxide demand could be reduced by 12.5-22% to achieve the same brightness. The ATR-FTIR and XPS results showed that lignin and hemicellulose (mainly HexA) were the main source for AOX formation. Xylanase pretreatment could remove HexA and expose more lignin, which decreased the chlorine dioxide demand and thus reduced formation of AOX. PMID:26263004

  6. Fluorescent thin gel films using organic dyes and pigments

    NASA Astrophysics Data System (ADS)

    Nakazumi, Hiroyuki; Takashi, Tarao; Taniguchi, Shin-ichi; Nanto, Hidehito

    1997-10-01

    New organic-inorganic fluorescent thin gel films included with laser dyes or fluorescent organic pigments have been prepared for display application. The florescent dyes (benzoxazolium, pyrromethene, and rhodamine dyes) and super-fine particles of fluorescent pigments (coumarin and perylene) were successfully incorporated into thin silicate gel films prepared from tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), and methoxysilane oligomer (MTSO) under acid catalyzed hydrolysis. The blue, green, and red luminescence were observed from these thin films (thickness: 100 - 400 nm), respectively. Fluorescence spectra, fluorescent quantum yield and lifetime of thin gel films are examined. Fluorescent peaks for most of dyes and pigments used in gel films were similar to those in solution, and fluorescent lifetime for dyes and pigments used in gel films were 2.9 - 4.5 ns. Photostability of fluorescent gel films is dependent on fluorescent organic dyes and pigments used and/or silicate gel matrixes. Coumarin and perylene pigments have higher fluorescent quantum yield in gel film prepared from MTSO. The large Stokes shift was observed in fluorescent gel film using coumarin and benzoxazolium dyes. The coumarin and perylene pigments are significantly photo- stable in gel film prepared from MTSO, and photodegradation of perylene red after irradiation of 500 W Xi-lamp for 30 min is below 20%.

  7. Binding energy and work function of organic electrode materials phenanthraquinone, pyromellitic dianhydride and their derivatives adsorbed on graphene.

    PubMed

    Yu, Yang-Xin

    2014-09-24

    Electroactive organic compounds are a novel group of green cathode materials for rechargeable metal-ion batteries. However, the organic battery life is short because the organic compounds can be dissolved by nonaqueous electrolytes. Here a comparative investigation of phenanthraquinone (PQ), pyromellitic dianhydride (PMDA) and their derivatives, i.e., benzo[1,2-b:4,3-b']difuran-4,5-dione (BDFD), benzo[1,2-b:4,3-b']dithiophene-4,5-quinone (BDTQ), 3,8-phenanthroline-5,6-dione (PAD), pyromellitic dithioanhydride (PMDT), pyromellitic diimide (PMDI) and 1,4,5,8-anthracenetetrone (ATO), adsorbed on graphene is performed using a density functional theory (DFT) with a van der Waals (vdW) dispersion-correction. The computed results show a strong physisorption with the binding energies between 1.10 and 1.56 eV. A sequence of the calculated binding energies from weak to strong is found to be BDFD < BDTQ < PMDA ≤ PMDI < PMDT < PQ < PAD < ATO. The formation of stable organic molecule-graphene nanocomposites can prevent the dissolution of the eight organic compounds in nonaqueous electrolyte and hence improve cycling performance of batteries. In addition, the work functions for the nanocomposites are found to be strongly affected by the work function of each organic compound. To understand the DFT results, a novel simple expression is proposed to predict the work function of the nanocomposites from the interfacial dipole and the work functions of the isolated graphene nanosheet and organic molecules. The predicted work functions for the nanocomposites from the new equation agree quite well with the values calculated from the vdW dispersion-corrected DFT. PMID:25216389

  8. Prediction of capacity factors for aqueous organic solutes adsorbed on a porous acrylic resin

    USGS Publications Warehouse

    Thurman, E.M.

    1978-01-01

    The capacity factors of 20 aromatic, allphatic, and allcycllc organic solutes with carboxyl, hydroxyl, amine, and methyl functional groups were determined on Amberlite XAD-8, a porous acrylic resin. The logarithm of the capacity factor, k???, correlated inversely with the logarithm of the aqueous molar solubility with significance of less than 0.001. The log k???-log solubility relationship may be used to predict the capacity of any organic solute for XAD-8 using only the solubility of the solute. The prediction is useful as a guide for determining the proper ratio of sample to column size In the preconcentration of organic solutes from water. The inverse relationship of solubility and capacity is due to the unfavorable entropy of solution of organic solutes which affects both solubility and sorption.

  9. Porous Organic Cage Thin Films and Molecular-Sieving Membranes.

    PubMed

    Song, Qilei; Jiang, Shan; Hasell, Tom; Liu, Ming; Sun, Shijing; Cheetham, Anthony K; Sivaniah, Easan; Cooper, Andrew I

    2016-04-01

    Porous organic cage molecules are fabricated into thin films and molecular-sieving membranes. Cage molecules are solution cast on various substrates to form amorphous thin films, with the structures tuned by tailoring the cage chemistry and processing conditions. For the first time, uniform and pinhole-free microporous cage thin films are formed and demonstrated as molecular-sieving membranes for selective gas separation. PMID:26800019

  10. Growth and physical properties of molecular organic thin films

    NASA Astrophysics Data System (ADS)

    Fraxedas, J.

    2004-04-01

    Highly-oriented polycrystalline thin films of molecular organic materials consisting of small molecules can be easily obtained by physical and chemical vapour deposition methods. The crystallographic phase, orientation and morphology of the films critically depend on the interface and on the kinetics of growth and can be controlled, to a certain extent, by a judicious selection of the substrates and of the growth parameters. This article shortly explores the formation of organic-inorganic heterostructures as a function of coverage: from the most fundamental case, a single molecule on a surface, to thick films (thickness ˜ 1 μ m). The case of high-quality thick TTF-TCNQ films exemplifies the fact that the derived physical properties are essentially identical to those obtained from single crystals. Key words. Molecular organic materials thin films interfaces.

  11. Understanding organic film behavior on alloy and metal oxides.

    PubMed

    Raman, Aparna; Quiñones, Rosalynn; Barriger, Lisa; Eastman, Rachel; Parsi, Arash; Gawalt, Ellen S

    2010-02-01

    Native oxide surfaces of stainless steel 316L and Nitinol alloys and their constituent metal oxides, namely nickel, chromium, molybdenum, manganese, iron, and titanium, were modified with long chain organic acids to better understand organic film formation. The adhesion and stability of films of octadecylphosphonic acid, octadecylhydroxamic acid, octadecylcarboxylic acid, and octadecylsulfonic acid on these substrates were examined in this study. The films formed on these surfaces were analyzed by diffuse reflectance infrared Fourier transform spectroscopy, contact angle goniometry, atomic force microscopy, and matrix-assisted laser desorption ionization mass spectrometry. The effect of the acidity of the organic moiety and substrate composition on the film characteristics and stability is discussed. Interestingly, on the alloy surfaces, the presence of less reactive metal sites does not inhibit film formation. PMID:20039608

  12. Understanding Organic Film Behavior on Alloy and Metal Oxides

    PubMed Central

    Raman, Aparna; Quiñones, Rosalynn; Barriger, Lisa; Eastman, Rachel; Parsi, Arash

    2010-01-01

    Native oxide surfaces of stainless steel 316L and Nitinol alloys and their constituent metal oxides namely, nickel, chromium, molybdenum, manganese, iron and titanium were modified with long chain organic acids to better understand organic film formation. The adhesion and stability of films of octadecylphosphonic acid, octadecylhydroxamic acid, octadecylcarboxylic acid and octadecylsulfonic acid on these substrates was examined in this study. The films formed on these surfaces were analyzed by diffuse reflectance infrared Fourier transform spectroscopy, contact angle goniometry, atomic force microscopy and matrix assisted laser desorption ionization mass spectrometry. The effect of the acidity of the organic moiety and substrate composition on the film characteristics and stability is discussed. Interestingly, on the alloy surfaces, the presence of less reactive metal sites does not inhibit film formation. PMID:20039608

  13. Organic conductive films for semiconductor electrodes

    DOEpatents

    Frank, A.J.

    1984-01-01

    According to the present invention, improved electrodes overcoated with conductive polymer films and preselected catalysts are provided. The electrodes typically comprise an inorganic semiconductor over-coated with a charge conductive polymer film comprising a charge conductive polymer in or on which is a catalyst or charge-relaying agent.

  14. Organic conductive films for semiconductor electrodes

    DOEpatents

    Frank, Arthur J.

    1984-01-01

    According to the present invention, improved electrodes overcoated with conductive polymer films and preselected catalysts are provided. The electrodes typically comprise an inorganic semiconductor overcoated with a charge conductive polymer film comprising a charge conductive polymer in or on which is a catalyst or charge-relaying agent.

  15. Uptake of organic trace gases by organic films

    NASA Astrophysics Data System (ADS)

    Donaldson, D. James

    2004-03-01

    Surfaces exposed to the atmosphere, particularly in urban environments, become coated with a film whose chemical composition is similar to that of urban aerosol particles. Such films can act as reservoirs for gas phase pollutants and as media for chemical reactions (much as aerosols do). We have constructed a Knudsen effusion cell apparatus to study the non-reactive and reactive uptake of trace atmospheric gases by such urban films. We report here our first results of the uptake of three classes of compound: polycyclic aromatic hydrocarbons (PAHs), chlorinated aromatics and carboxylic acids, by films composed of fatty acids and high molecular weight hydrocarbons.

  16. Composition of Organic Compounds Adsorbed on PM10 in the Air Above Maribor.

    PubMed

    Miuc, Alen; Vončina, Ernest; Lečnik, Uroš

    2015-01-01

    Organic compounds in atmospheric particulate matterabove Maribor were analysed in 120 samples of PM10 sampled according to the EN 12341:2014 reference method. Organic compounds compositions were investigated together with the primary and secondary sources of air pollution. Silylation as derivatisation method was used for the GC/MS determination of volatile and semi-volatile polar organic compounds. Distribution of fatty acids, n-alkanes and iso-alkanes, phthalate esters, siloxanes, different sterols, various sugars and sugar alcohols, compounds of lignin and resin acids, dicarboxylic acids from photochemical reactions, PAHs, organic nitrogen compounds and products from secondary oxidation of monoterpenes were determined. The use of silicone grease for the purpose of lubricating the impact surface of the air sampler caused higher values of gravimetric determination. Solid particles may have been bounced from the surface of a greasy impact plate and re-entrained within the air stream and then collected on a sample filter. The carryover of siloxanes was at least from 5% up to 15% of the accumulated particles weight, depending on ambient temperature. This was the reason that the gravimetric results for determination of PM10 according to the standard EN 12341:2014 were overestimated. PMID:26680711

  17. Design of hydrophilic metal organic framework water adsorbents for heat reallocation.

    PubMed

    Cadiau, Amandine; Lee, Ji Sun; Damasceno Borges, Daiane; Fabry, Paul; Devic, Thomas; Wharmby, Michael T; Martineau, Charlotte; Foucher, Damien; Taulelle, Francis; Jun, Chul-Ho; Hwang, Young Kyu; Stock, Norbert; De Lange, Martijn F; Kapteijn, Freek; Gascon, Jorge; Maurin, Guillaume; Chang, Jong-San; Serre, Christian

    2015-08-26

    A new hydrothermally stable Al polycarboxylate metal-organic framework (MOF) based on a heteroatom bio-derived aromatic spacer is designed through a template-free green synthesis process. It appears that in some test conditions this MOF outperforms the heat reallocation performances of commercial SAPO-34. PMID:26193346

  18. AMBIENT LEVEL VOLATILE ORGANIC COMPOUND (VOC) MONITORING USING SOLID ADSORBANTS - RECENT U.S. EPA STUDIES

    EPA Science Inventory

    Ambient air spiked with 1-10 ppbv concentrations of 41 toxic volatile organic compounds (VOCs) listed in U.S. Environmental Protection Agency (EPA) Compendium Method TO-14A was monitored using solid sorbents for sample collection and a Varian Saturn 2000 ion trap mass spectrome...

  19. Fluorous Metal Organic Frameworks as Superhydrophobic Adsorbents for Oil Spill Cleanup and Hydrocarbons Storage

    SciTech Connect

    Yang, Chi; Mather, Qian; Wang, Xiaoping; Kaipa, Ushasree; Nesterov, Vladimir; Venero, Augustin; Omary, Mohammad A

    2011-01-01

    We demonstrate that fluorous metal-organic frameworks (FMOFs) are highly hydrophobic porous materials with a high capacity and affinity to C{sub 6}-C{sub 8} hydrocarbons of oil components. FMOF-1 exhibits reversible adsorption with a high capacity for n-hexane, cyclohexane, benzene, toluene, and p-xylene, with no detectable water adsorption even at near 100% relative humidity, drastically outperforming activated carbon and zeolite porous materials. FMOF-2, obtained from annealing FMOF-1, shows enlarged cages and channels with double toluene adsorption vs FMOF-1 based on crystal structures. The results suggest great promise for FMOFs in applications such as removal of organic pollutants from oil spills or ambient humid air, hydrocarbon storage and transportation, water purification, etc. under practical working conditions.

  20. Reduction of ferrihydrite with adsorbed and coprecipitated organic matter: microbial reduction by Geobacter bremensis vs. abiotic reduction by Na-dithionite

    NASA Astrophysics Data System (ADS)

    Eusterhues, K.; Hädrich, A.; Neidhardt, J.; Küsel, K.; Keller, T. F.; Jandt, K. D.; Totsche, K. U.

    2014-09-01

    Ferrihydrite is a widespread poorly crystalline Fe oxide which becomes easily coated by natural organic matter in the environment. This mineral-bound organic matter entirely changes the mineral surface properties and therefore the reactivity of the original mineral. Here, we investigated 2-line ferrihydrite, ferrihydrite with adsorbed organic matter, and ferrihydrite coprecipitated with organic matter for microbial and abiotic reduction of Fe(III). Ferrihydrite-organic matter associations with different organic matter loadings were reduced either by Geobacter bremensis or abiotically by Na-dithionite. Both types of experiments showed decreasing initial Fe-reduction rates and decreasing degrees of reduction with increasing amounts of mineral-bound organic matter. At similar organic matter loadings, coprecipitated ferrihydrites were more reactive than ferrihydrites with adsorbed organic matter. The difference can be explained by the smaller crystal size and poor crystallinity of such coprecipitates. At small organic matter loadings the poor crystallinity of coprecipitates led to even faster Fe-reduction rates than found for pure ferrihydrite. The amount of mineral-bound organic matter also affected the formation of secondary minerals: goethite was only found after reduction of organic matter-free ferrihydrite and siderite was only detected when ferrihydrites with relatively low amounts of mineral-bound organic matter were reduced. We conclude that direct contact of G. bremensis to the Fe oxide mineral surface was inhibited by attached organic matter. Consequently, mineral-bound organic matter shall be taken into account as a factor in slowing down reductive dissolution.

  1. Recycling of Organic Waste Sludge by Hydrothermal Dry Steam Aiming for Adsorbent

    NASA Astrophysics Data System (ADS)

    Hoshikawa, Hisahiro; Hayakawa, Tomoki; Yamasaki, Nakamichi

    2006-05-01

    Global warming becomes more serious problem today. We have to develop new technology for new energy or fixation of carbon dioxide. Biomass is considered to be one of new energies. Methane fermentation is a method to make methane from biomass, such as garbage and fecal of farm animals, by methane fermentation bacteria. It has a problem, however, that bacteria are deactivated due to ammonia, which is made by itself. And much methane fermentation residue is incinerated. Therefore recycling methane fermentation residue is important for effective use of biomass. We research hydrothermal process. Dry steam means unsaturated vapor, we call. It demands a temperature less than 400 °C. And it is expected to accelerate dehydration effect, decompose and extract the organic matter, and make porous material. Thus, we try to apply the dry steam to recycling of organic waste sludge aiming for absorbent. Experiments were conducted at 250-350 °C in nitrogen atmosphere. The carbon products are analyzed by CHNS elemental analysis, and Thermogravimetry. The extractives are analyzed by gas chromatograph.

  2. Femtomagnetism in graphene induced by core level excitation of organic adsorbates

    PubMed Central

    Ravikumar, Abhilash; Baby, Anu; Lin, He; Brivio, Gian Paolo; Fratesi, Guido

    2016-01-01

    We predict the induction or suppression of magnetism in the valence shell of physisorbed and chemisorbed organic molecules on graphene occurring on the femtosecond time scale as a result of core level excitations. For physisorbed molecules, where the interaction with graphene is dominated by van der Waals forces and the system is non-magnetic in the ground state, numerical simulations based on density functional theory show that the valence electrons relax towards a spin polarized configuration upon excitation of a core-level electron. The magnetism depends on efficient electron transfer from graphene on the femtosecond time scale. On the other hand, when graphene is covalently functionalized, the system is magnetic in the ground state showing two spin dependent mid gap states localized around the adsorption site. At variance with the physisorbed case upon core-level excitation, the LUMO of the molecule and the mid gap states of graphene hybridize and the relaxed valence shell is not magnetic anymore. PMID:27089847

  3. Mechanisms of Heat Transfer in Porous Crystals Containing Adsorbed Gases: Applications to Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Babaei, Hasan; Wilmer, Christopher E.

    2016-01-01

    We have studied the mechanisms of heat transfer in a porous crystal-gas mixture system, motivated by the not insignificant challenge of quickly dissipating heat generated in metal-organic frameworks (MOFs) due to gas adsorption. Our study reveals that the thermal conductance of the system (crystal and gas) is dominated by lattice thermal conductivity in the crystal, and that conductance is reduced as the concentration of gas in the pores increases. This mechanism was observed from classical molecular simulations of a monatomic gas in an idealized porous crystal structure. We show that the decreased conductivity associated with increased gas concentration is due to phonon scattering in the crystal due to interactions with gas molecules. Calculations of scattering rates for two phonon modes reveal that scattering of the lowest frequency mode scales linearly with gas density. This result suggests that the probability of a phonon-gas collision is simply proportional to the number of gas molecules in the pore.

  4. Femtomagnetism in graphene induced by core level excitation of organic adsorbates

    NASA Astrophysics Data System (ADS)

    Ravikumar, Abhilash; Baby, Anu; Lin, He; Brivio, Gian Paolo; Fratesi, Guido

    2016-04-01

    We predict the induction or suppression of magnetism in the valence shell of physisorbed and chemisorbed organic molecules on graphene occurring on the femtosecond time scale as a result of core level excitations. For physisorbed molecules, where the interaction with graphene is dominated by van der Waals forces and the system is non-magnetic in the ground state, numerical simulations based on density functional theory show that the valence electrons relax towards a spin polarized configuration upon excitation of a core-level electron. The magnetism depends on efficient electron transfer from graphene on the femtosecond time scale. On the other hand, when graphene is covalently functionalized, the system is magnetic in the ground state showing two spin dependent mid gap states localized around the adsorption site. At variance with the physisorbed case upon core-level excitation, the LUMO of the molecule and the mid gap states of graphene hybridize and the relaxed valence shell is not magnetic anymore.

  5. Femtomagnetism in graphene induced by core level excitation of organic adsorbates.

    PubMed

    Ravikumar, Abhilash; Baby, Anu; Lin, He; Brivio, Gian Paolo; Fratesi, Guido

    2016-01-01

    We predict the induction or suppression of magnetism in the valence shell of physisorbed and chemisorbed organic molecules on graphene occurring on the femtosecond time scale as a result of core level excitations. For physisorbed molecules, where the interaction with graphene is dominated by van der Waals forces and the system is non-magnetic in the ground state, numerical simulations based on density functional theory show that the valence electrons relax towards a spin polarized configuration upon excitation of a core-level electron. The magnetism depends on efficient electron transfer from graphene on the femtosecond time scale. On the other hand, when graphene is covalently functionalized, the system is magnetic in the ground state showing two spin dependent mid gap states localized around the adsorption site. At variance with the physisorbed case upon core-level excitation, the LUMO of the molecule and the mid gap states of graphene hybridize and the relaxed valence shell is not magnetic anymore. PMID:27089847

  6. A Water-Stable Cationic Metal-Organic Framework as a Dual Adsorbent of Oxoanion Pollutants.

    PubMed

    Desai, Aamod V; Manna, Biplab; Karmakar, Avishek; Sahu, Amit; Ghosh, Sujit K

    2016-06-27

    A three-dimensional water-stable cationic metal-organic framework (MOF) pillared by a neutral ligand and with Ni(II)  metal nodes has been synthesized employing a rational design approach. Owing to the ordered arrangement of the uncoordinated tetrahedral sulfate (SO4 (2-) ) ions in the channels, the compound has been employed for aqueous-phase ion-exchange applications. The compound exhibits rapid and colorimetric aqueous-phase capture of environmentally toxic oxoanions (with similar geometries) in a selective manner. This system is the first example of a MOF-based system which absorbs both dichromate (Cr2 O7 (2-) ) and permanganate (MnO4 (-) ) ions, with the latter acting as a model for the radioactive contaminant pertechnetate (TcO4 (-) ). PMID:26855323

  7. In situ x-ray photoelectron spectroscopic and density-functional studies of Si atoms adsorbed on a C60 film.

    PubMed

    Onoe, Jun; Nakao, Aiko; Hara, Toshiki

    2004-12-01

    The interaction between C(60) and Si atoms has been investigated for Si atoms adsorbed on a C(60) film using in situ x-ray photoelectron spectroscopy (XPS) and density-functional (DFT) calculations. Analysis of the Si 2p core peak identified three kinds of Si atoms adsorbed on the film: silicon suboxides (SiO(x)), bulk Si crystal, and silicon atoms bound to C(60). Based on the atomic percent ratio of silicon to carbon, we estimated that there was approximately one Si atom bound to each C(60) molecule. The Si 2p peak due to the Si-C(60) interaction demonstrated that a charge transfer from the Si atom to the C(60) molecule takes place at room temperature, which is much lower than the temperature of 670 K at which the charge transfer was observed for C(60) adsorbed on Si(001) and (111) clean surfaces [Sakamoto et al., Phys. Rev. B 60, 2579 (1999)]. The number of electrons transferred between the C(60) molecule and Si atom was estimated to be 0.59 based on XPS results, which is in good agreement with the DFT result of 0.63 for a C(60)Si with C(2v) symmetry used as a model cluster. Furthermore, the shift in binding energy of both the Si 2p and C 1s core peaks before and after Si-atom deposition was experimentally obtained to be +2.0 and -0.4 eV, respectively. The C(60)Si model cluster provides the shift of +2.13 eV for the Si 2p core peak and of -0.28 eV for the C 1s core peak, which are well corresponding to those experimental results. The covalency of the Si-C(60) interaction was also discussed in terms of Mulliken overlap population between them. PMID:15634092

  8. Effective anchoring energy in dipolar organic film on metals surfaces

    NASA Astrophysics Data System (ADS)

    Iwamoto, Mitsumasa; Zakharov, A. V.

    2007-04-01

    The influence of electron injection from the metal electrode into organic liquid crystal dipolar film on the effective anchoring energy (EAE) of the polar organic film is discussed from the energy point of view. It is shown that the accounting for the injected carrier in organic film results in a polynomial function for the EAE expanded up to the fourth order in cos θs, where θs is the polar angle of the director nˆ at the film/metal interface. It is also shown that in a certain range of the location of centroid of the injected carrier z¯ the destabilizing surface polarization mechanism may lead to destruction of the linear anchoring strength coefficient w1. The strong influence of z¯ on the quadratic term w2 also has been demonstrated.

  9. Aluminium fumarate metal-organic framework: A super adsorbent for fluoride from water.

    PubMed

    Karmakar, Sankha; Dechnik, Janina; Janiak, Christoph; De, Sirshendu

    2016-02-13

    Potential of aluminium fumarate metal organic framework (MOF) for fluoride removal from groundwater has been explored in this work. The laboratory produced MOF exhibited characteristics similar to the commercial version. MOF was found to be micro-porous with surface area of 1156 m(2)/g and average pore size 17Å. Scanning electron micrograph of the AlFu MOF showed minute pores and texture was completely different from either of the parent materials. Change in the composition of AlFu MOF after fluoride adsorption was evident from powder X-ray diffraction analysis. Thermal stability of the AlFu MOF up to 700K was established by thermo-gravimetric analysis. Incorporation of fluoride phase after adsorption was confirmed by X-ray fluorescence analysis. As observed from FTIR study, hydroxyl ions in AlFu MOF were substituted by fluoride. 0.75 g/l AlFu MOF was good enough for complete removal of 30 mg/l fluoride concentration in feed solution. The maximum adsorption capacity for fluoride was 600, 550, 504 and 431 mg/g, respectively, at 293, 303, 313 and 333K. PMID:26513559

  10. Adsorbent phosphates

    NASA Technical Reports Server (NTRS)

    Watanabe, S.

    1983-01-01

    An adsorbent which uses as its primary ingredient phosphoric acid salts of zirconium or titanium is presented. Production methods are discussed and several examples are detailed. Measurements of separating characteristics of some gases using the salts are given.

  11. Preparation of a new adsorbent from activated carbon and carbon nanofiber (AC/CNF) for manufacturing organic-vacbpour respirator cartridge

    PubMed Central

    2013-01-01

    In this study a composite of activated carbon and carbon nanofiber (AC/CNF) was prepared to improve the performance of activated carbon (AC) for adsorption of volatile organic compounds (VOCs) and its utilization for respirator cartridges. Activated carbon was impregnated with a nickel nitrate catalyst precursor and carbon nanofibers (CNF) were deposited directly on the AC surface using catalytic chemical vapor deposition. Deposited CNFs on catalyst particles in AC micropores, were activated by CO2 to recover the surface area and micropores. Surface and textural characterizations of the prepared composites were investigated using Brunauer, Emmett and Teller’s (BET) technique and electron microscopy respectively. Prepared composite adsorbent was tested for benzene, toluene and xylene (BTX) adsorption and then employed in an organic respirator cartridge in granular form. Adsorption studies were conducted by passing air samples through the adsorbents in a glass column at an adjustable flow rate. Finally, any adsorbed species not retained by the adsorbents in the column were trapped in a charcoal sorbent tube and analyzed by gas chromatography. CNFs with a very thin diameter of about 10-20 nm were formed uniformly on the AC/CNF. The breakthrough time for cartridges prepared with CO2 activated AC/CNF was 117 minutes which are significantly longer than for those cartridges prepared with walnut shell- based activated carbon with the same weight of adsorbents. This study showed that a granular form CO2 activated AC/CNF composite could be a very effective alternate adsorbent for respirator cartridges due to its larger adsorption capacities and lower weight. PMID:23369424

  12. EFFECTS OF COVAPORS ON ADSORPTION RATE COEFFICIENTS OF ORGANIC VAPORS ADSORBED ONTO ACTIVATED CARBON FROM FLOWING AIR

    SciTech Connect

    G. WOOD

    2000-12-01

    Published breakthrough time, adsorption rate, and capacity data for components of organic vapor mixtures adsorbed from flows through fixed activated carbon beds have been analyzed. Capacities (as stoichiometric centers of constant pattern breakthrough curves) yielded stoichiometric times {tau}, which are useful for determining elution orders of mixture components. We also calculated adsorption rate coefficients k{sub v} of the Wheeler (or, more general Reaction Kinetic) breakthrough curve equation, when not reported, from breakthrough times and {tau}. Ninety-five k{sub v} (in mixture)/ k{sub v} (single vapor) ratios at similar vapor concentrations were calculated and averaged for elution order categories. For 43 first-eluting vapors the average ratio (1.07) was statistically no different (0.21 standard deviation) than unity, so that we recommend using the single-vapor k{sub v} for such. Forty-seven second-eluting vapor ratios averaged 0.85 (0.24 standard deviation), also not significantly different from unity; however, other evidence and considerations lead us recommend using k{sub v} (in mixture) = 0.85 k{sub v} (single vapor). Five third- and fourth-eluting vapors gave an average of 0.56 (0.16 standard deviation) for a recommended k{sub v} (in mixture) = 0.56 k{sub v} (single vapor) for such.

  13. Preparation and characterization of humic acid-carbon hybrid materials as adsorbents for organic micro-pollutants.

    PubMed

    Radwan, Emad K; Abdel Ghafar, Hany H; Moursy, Ahmed S; Langford, Cooper H; Bedair, Ahmed H; Achari, Gopal

    2015-08-01

    The present work involves the preparation of novel adsorbent materials by the insolubilization and hybridization of humic acid (HA) with carbon. The prepared materials were characterized by N2 adsorption, elemental analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, solid-state (13)C cross polarization magic angle spinning nuclear magnetic resonance, and low-field nuclear magnetic resonance (NMR) relaxometry on wetted samples. The water solubility of these materials and the lack of effect of oxidants were also confirmed. With this background, the adsorption capacities toward phenol, 2,4,6-tricholrophenol, and atrazine were evaluated, using these as model compounds for organic micropollutants of concern in water. Experimental results show that the prepared materials are mesoporous and have a higher surface area than humic acid and even than the porous carbon in the case of carbon coating. They retain the basic features of the starting materials with lowered functional group content. Moreover, there are interesting new features. NMR relaxometry shows that equilibration of water uptake is very fast, making use in water simple. They have higher adsorption capacities than the pure materials, and they can be applied under a wide range of environmental conditions. PMID:25874433

  14. Use of industrial by-products and natural media to adsorb nutrients, metals and organic carbon from drinking water.

    PubMed

    Grace, Maebh A; Healy, Mark G; Clifford, Eoghan

    2015-06-15

    Filtration technology is well established in the water sector but is limited by inability to remove targeted contaminants, found in surface and groundwater, which can be damaging to human health. This study optimises the design of filters by examining the efficacy of seven media (fly ash, bottom ash, Bayer residue, granular blast furnace slag (GBS), pyritic fill, granular activated carbon (GAC) and zeolite), to adsorb nitrate, ammonium, total organic carbon (TOC), aluminium, copper (Cu) and phosphorus. Each medium and contaminant was modelled to a Langmuir, Freundlich or Temkin adsorption isotherm, and the impact of pH and temperature (ranging from 10 °C to 29 °C) on their performance was quantified. As retention time within water filters is important in contaminant removal, kinetic studies were carried out to observe the adsorption behaviour over a 24h period. Fly ash and Bayer residue had good TOC, nutrient and Cu adsorption capacity. Granular blast furnace slag and pyritic fill, previously un-investigated in water treatment, showed adsorption potential for all contaminants. In general, pH or temperature adjustment was not necessary to achieve effective adsorption. Kinetic studies showed that at least 60% of adsorption had occurred after 8h for all media. These media show potential for use in a multifunctional water treatment unit for the targeted treatment of specific contaminants. PMID:25777954

  15. Organic thin film transistors: from active materials to novel applications

    NASA Astrophysics Data System (ADS)

    Torsi, L.; Cioffi, N.; Di Franco, C.; Sabbatini, L.; Zambonin, P. G.; Bleve-Zacheo, T.

    2001-08-01

    In this paper, a bird's eye view of most of the organic materials employed as n-channel and p-channel transistor active layers is given along with the relevant device performances; organic thin film transistors (OTFT) operation regimes are discussed and an interesting perspective application of OTFT as multi-parameter gas sensor is proposed.

  16. Reversible CO Scavenging via Adsorbate-Dependent Spin State Transitions in an Iron(II)-Triazolate Metal-Organic Framework.

    PubMed

    Reed, Douglas A; Xiao, Dianne J; Gonzalez, Miguel I; Darago, Lucy E; Herm, Zoey R; Grandjean, Fernande; Long, Jeffrey R

    2016-05-01

    A new metal-organic framework, Fe-BTTri (Fe3[(Fe4Cl)3(BTTri)8]2·18CH3OH, H3BTTri =1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene)), is found to be highly selective in the adsorption of CO over a variety of other gas molecules, making it extremely effective, for example, in the removal of trace CO from mixtures with H2, N2, and CH4. This framework not only displays significant CO adsorption capacity at very low pressures (1.45 mmol/g at just 100 μbar), but, importantly, also exhibits readily reversible CO binding. Fe-BTTri utilizes a unique spin state change mechanism to bind CO in which the coordinatively unsaturated, high-spin Fe(II) centers of the framework convert to octahedral, low-spin Fe(II) centers upon CO coordination. Desorption of CO converts the Fe(II) sites back to a high-spin ground state, enabling the facile regeneration and recyclability of the material. This spin state change is supported by characterization via infrared spectroscopy, single crystal X-ray analysis, Mössbauer spectroscopy, and magnetic susceptibility measurements. Importantly, the spin state change is selective for CO and is not observed in the presence of other gases, such as H2, N2, CO2, CH4, or other hydrocarbons, resulting in unprecedentedly high selectivities for CO adsorption for use in CO/H2, CO/N2, and CO/CH4 separations and in preferential CO adsorption over typical strongly adsorbing gases like CO2 and ethylene. While adsorbate-induced spin state transitions are well-known in molecular chemistry, particularly for CO, to our knowledge this is the first time such behavior has been observed in a porous material suitable for use in a gas separation process. Potentially, this effect can be extended to selective separations involving other π-acids. PMID:27097297

  17. Mechanism of formation of humus coatings on mineral surfaces 3. Composition of adsorbed organic acids from compost leachate on alumina by solid-state 13C NMR

    USGS Publications Warehouse

    Wershaw, R. L.; Llaguno, E.C.; Leenheer, J.A.

    1996-01-01

    The adsorption of compost leachate DOC on alumina is used as a model for elucidation of the mechanism of formation of natural organic coatings on hydrous metal oxide surfaces in soils and sediments. Compost leachate DOC is composed mainly of organic acid molecules. The solid-state 13C NMR spectra of these organic acids indicate that they are very similar in composition to aquatic humic substances. Changes in the solid-state 13C NMR spectra of compost leachate DOC fractions adsorbed on alumina indicate that the DOC molecules are most likely adsorbed on metal oxide surfaces through a combination of polar and hydrophobic interaction mechanisms. This combination of polar and hydrophobic mechanism leads to the formation of bilayer coatings of the leachate molecules on the oxide surfaces.

  18. The effects of framework dynamics on the behavior of water adsorbed in the [Zn(l-L)(Cl)] and Co-MOF-74 metal-organic frameworks.

    PubMed

    Terranova, Zachary L; Paesani, Francesco

    2016-03-21

    The effects of framework flexibility on the structural and dynamical properties of water adsorbed in two prototypical metal-organic frameworks are investigated through molecular dynamics simulations. It is found that water molecules in the pores of a flexible model of [Zn(l-L)(Cl)] exhibit slower dynamics than when the framework is artificially held rigid in the simulations. In contrast, the water dynamics in Co-MOF-74 is predicted to be accelerated by the framework vibrations. The origin of this different behavior directly relates to how water interacts with the two frameworks, which, in turn, determines different hydrogen-bond patterns in the pores. While the first water molecules adsorbed in [Zn(l-L)(Cl)] donate a single hydrogen bond to the Zn-Cl groups and point the other hydrogen atom towards the center of the pore, water molecules adsorbed in Co-MOF-74 initially bind to the cobalt atoms of the framework via their oxygen atoms, thus leaving each molecule free to form two hydrogen bonds with additional molecules adsorbed at higher loading. The simulation results indicate that taking into account the framework flexibility in computer simulations is necessary for a quantitative modeling of adsorption and transport processes in metal-organic frameworks. PMID:26928975

  19. High Performance Airbrushed Organic Thin Film Transistors

    SciTech Connect

    Chan, C.; Richter, L; Dinardo, B; Jaye, C; Conrad, B; Ro, H; Germack, D; Fischer, D; DeLongchamp, D; Gunlach, D

    2010-01-01

    Spray-deposited poly-3-hexylthiophene (P3HT) transistors were characterized using electrical and structural methods. Thin-film transistors with octyltrichlorosilane treated gate dielectrics and spray-deposited P3HT active layers exhibited a saturation regime mobility as high as 0.1 cm{sup 2} V{sup -1} s{sup -1}, which is comparable to the best mobilities observed in high molecular mass P3HT transistors prepared using other methods. Optical and atomic force microscopy showed the presence of individual droplets with an average diameter of 20 {micro}m and appreciable large-scale film inhomogeneities. Despite these inhomogeneities, near-edge x-ray absorption fine structure spectroscopy of the device-relevant channel interface indicated excellent orientation of the P3HT.

  20. Growth and nonlinear optical characterization of organic single crystal films

    NASA Astrophysics Data System (ADS)

    Zhou, Ligui

    1997-12-01

    Organic single crystal films are important for various future applications in photonics and integrated optics. The conventional method for inorganic crystal growth is not suitable for organic materials, and the high temperature melting method is not good for most organic materials due to decomposition problems. We developed a new method-modified shear method-to grow large area organic single crystal thin films which have exceptional nonlinear optical properties and high quality surfaces. Several organic materials (NPP, PNP and DAST) were synthesized and purified before the thin film crystal growth. Organic single crystal thin films were grown from saturated organic solutions using modified shear method. The area of single crystal films were about 1.5 cm2 for PNP, 1 cm2 for NPP and 5 mm2 for DAST. The thickness of the thin films which could be controlled by the applied pressure ranged from 1μm to 10 μm. The single crystal thin films of organic materials were characterized by polarized microscopy, x-ray diffraction, polarized UV-Visible and polarized micro-FTIR spectroscopy. Polarized microscopy showed uniform birefringence and complete extinction with the rotation of the single crystal thin films under crossed- polarization, which indicated high quality single crystals with no scattering. The surface orientation of single crystal thin films was characterized by x-ray diffraction. The molecular orientation within the crystal was further studied by the polarized UV-Visible and Polarized micro-FTIR techniques combined with the x-ray and polarized microscopy results. A Nd:YAG laser with 35 picosecond pulses at 1064nm wavelength was employed to perform the nonlinear optical characterization of the organic single crystal thin films. Two measurement techniques were used to study the crystal films: second harmonic generation (SHG) and electro-optic (EO) effect. SHG results showed that the nonlinear optical coefficient of NPP was 18 times that of LiNbO3, a standard

  1. Electrical and Optical Properties of Organic Thin Films

    NASA Astrophysics Data System (ADS)

    Buckner, Spencer Lewis

    The purpose of this research was to examine the applicability of organic thin films as electrical insulators in metal-insulator-semiconductor (MIS) and metal-insulator -metal (MIM) devices and an anti-reflective (A-R) coatings for solar cells. Films of anthracene, stearic acid and diacetylene alcohol were examined for their electrical and optical properties. Two techniques were used to deposit the films for these studies. Thermal evaporation in vacuum was used to deposit aluminum as electrodes and contacts in MIS and MIM devices. The organic films were deposited by either thermal evaporation or the Langmuir-Blodgett (L-B) dipping technique. Several vacuum systems and an L-B trough were fabricated for these studies and their design and construction are outlined. Several types of measurements were used to examine the properties of the organic films. Optical reflectance measurements of the diacetylene alcohol and stearic acid, both deposited by the L-B technique, on commercial silicon solar cells were used to study the potential use of these types of films as A-R and protective coatings. Electrical breakdown studies of the MIM devices were conducted to determine the maximum electric fields the insulators could withstand without destruction. Capacitance versus voltage (C-V) measurements of the organic films in MIS devices were used to determine surface defect densities at the semicondcutor/insulator interface. For each type of measurements made on the devices, theories are outlined to analyze the data obtained. The optical reflectance data are analyzed using standard electromagnetic theory. The electrical breakdown data are examined using the theories of Forlani and Minnaja (F-M) and Klein. The C-V data are examined using several different theories to determine charge and defect densities and to analyze the effects of thermal stressing and annealing. Finally, conclusions are drawn as to the applicability of these types of organic materials as insulators and coatings

  2. New diffusive gradients in a thin film technique for measuring inorganic arsenic and selenium(IV) using a titanium dioxide based adsorbent.

    PubMed

    Bennett, William W; Teasdale, Peter R; Panther, Jared G; Welsh, David T; Jolley, Dianne F

    2010-09-01

    A new diffusive gradients in a thin film (DGT) technique, using a titanium dioxide based adsorbent (Metsorb), has been developed and evaluated for the determination of dissolved inorganic arsenic and selenium. As(III), As(V), and Se(IV) were found to be quantitatively accumulated by the adsorbent (uptake efficiencies of 96.5-100%) and eluted in 1 M NaOH (elution efficiencies of 81.2%, 75.2%, and 88.7%). Se(VI) was not quantitatively accumulated by the adsorbent (<20%). Laboratory DGT validation experiments gave linear mass uptake over time (R(2) >or= 0.998) for As(III), As(V), and Se(IV). Consistent uptake occurred over pH (3.5-8.5) and ionic strength (0.0001-0.75 mol L(-1) NaNO(3)) ranges typical of natural waters, including seawater. Field deployments of DGT probes with various diffusive layer thicknesses confirmed the use of the technique in situ, allowing calculation of the diffusive boundary layers and an accurate measurement of inorganic arsenic. Reproducibility of the technique in field deployments was good (relative standard deviation <8%). Limits of detection (4 day deployments) were 0.01 microg L(-1) for inorganic arsenic and 0.05 microg L(-1) for Se(IV). The results of this study confirmed that DGT with Metsorb was a reliable and robust method for the measurement of inorganic arsenic and the selective measurement of Se(IV) within useful limits of accuracy. PMID:20695441

  3. Evaluation and Application of a Solid Adsorbent Method for Monitoring Exposure to Volatile Organic Compounds from Oil and Gas Operations.

    NASA Astrophysics Data System (ADS)

    Smith, K. R.; Helmig, D.; Thompson, C. R.; Wang, W.; Terrell, R. M.; Lewis, A. C.

    2014-12-01

    Residential communities are being increasingly impacted by emissions from oil and gas development and this has driven the need for simple, effective, and low-cost methods for air quality monitoring. Primary emissions from oil and gas production consist of volatile organic compounds (VOCs) ranging from the short chain alkanes and alkenes to aromatic and semi-volatile species; many of these are a concern from both an air quality and public health viewpoint, as they can lead to local ozone pollution and increased risk of cancer or respiratory illness. The fate of hydrocarbons once in the atmosphere is ultimately oxidation through to CO2 and water, adding to the greenhouse gas burden. Measurement techniques that are capable of identifying and quantifying the full range of primary emissions of concern are required to assess community exposure to air toxics and to better inform residents, as well as local and state legislators. Here, we present evaluation of a low-cost air monitoring technique using stainless steel diffusion cartridges containing multiple solid adsorbents. Over the course of a three-month period in summer of 2014, cartridges were deployed at five monitoring sites located around Boulder County in the Northern Colorado Front Range, and exposed to ambient air for periods of up to four days along with concurrent sampling using stainless steel SUMMA canisters. Samples collected with both methods were subsequently analyzed for VOCs by GC-FID and the results were compared to determine the accuracy and precision of the diffusion cartridge method. Results of this evaluation show that the diffusion cartridge method has the potential to be a simple and low-cost solution for widespread exposure monitoring in communities near oil and gas development regions. Such measurements may also provide supporting evidence on wider effects on greenhouse gas emissions from oil and gas development operations.

  4. 3He Bilayer Film Adsorbed on Graphite Plated with a Bilayer of 4He: a New Frustrated 2D Magnetic System

    NASA Astrophysics Data System (ADS)

    Neumann, Michael; Nyéki, Ján; Cowan, Brian; Saunders, John

    2006-09-01

    The heat capacity and NMR response of a 3He bilayer adsorbed on graphite plated with a bilayer of 4He have been measured over the temperature range 1-80 mK. We find that the first 3He layer requires the presence of a 3He fluid overlayer before it solidifies. Solidification is completed at a total coverage close to 9.85 nm-2, On further increasing the coverage the heat capacity maximum grows from `antiferromagnetic-like' (AFM-like) to `ferromagnetic-like' (FM-like). On the other hand, when the 3He layer first solidifies, it has a low temperature saturation magnetisation corresponding to a significant fraction of full polarisation, and this increases with increasing coverage. Furthermore the effective exchange constant inferred from the high temperature magnetisation data is always ferromagnetic. The effective exchange constants inferred from the heat capacity and magnetisation are significantly larger than those observed in the second layer of pure 3He films adsorbed on bare graphite. Otherwise there are strong similarities in the coverage dependence of the heat capacity and magnetisation, providing fresh insights into how the magnetic ground state of such 2D magnets evolves as the frustration is tuned with increasing coverage.

  5. Nanoscale confinement and interfacial effects on the dynamics and glass transition/crystallinity of thin adsorbed films on silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Madathingal, Rajesh Raman

    The research investigated in this dissertation has focused on understanding the structure-property-function relationships of polymer nanocomposites. The properties of composite systems are dictated by the properties of their components, typically fillers in a polymer matrix. In nanocomposites, the polymer near an interface has significantly different properties compared with the bulk polymer, and the contribution of the adsorbed polymer to composite properties becomes increasingly important as the filler size decreases. Despite many reports of highly favorable properties, the behavior of polymer nanocomposites is not generally predictable, and thus requires a better understanding of the interfacial region. The ability to tailor the filler/matrix interaction and an understanding of the impact of the interface on macroscopic properties are keys in the design of nanocomposite properties. In this original work the surface of silica nanoparticles was tailored by: (a) Changing the number of sites for polymer attachment by varying the surface silanols and, (b) By varying the size/curvature of nanoparticles. The effect of surface tailoring on the dynamic properties after the adsorption of two model polymers, amorphous polymethyl methacrylate (PMMA) and semicrystalline polyethylene oxide (PEO) was observed. The interphase layer of polymers adsorbed to silica surfaces is affected by the surface silanol density as well as the relative size of the polymer compared with the size of the adsorbing substrate. The non-equilibrium adsorption of PMMA onto individual colloidal Stober silica (SiO2) particles, where Rparticle (100nm) > RPMMA (˜6.5nm) was compared with the adsorption onto fumed silica, where Rparticle (7nm) ˜ RPMMA (6.5nm) < Raggregate (˜1000nm), both as a function of silanol density [SiOH] and hydrophobility. In the former case, TEM images showed that the PMMA adsorbed onto individual nanoparticles, so that the number of PMMA chains/bead could be calculated, whereas

  6. Measuring Thicknesses Of Vacuum-Deposited Organic Thin Films

    NASA Technical Reports Server (NTRS)

    David, Carey E.

    1996-01-01

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

  7. Metal-organic frameworks: A thin film opening

    NASA Astrophysics Data System (ADS)

    Sumby, Christopher J.

    2016-04-01

    The properties of metal-organic frameworks -- promising for a myriad of applications -- can be commonly tuned by judicious choice of the building blocks used to prepare the material. Now, simply downsizing a rigid, non-porous MOF to a thin film has been shown to endow it with dynamic, gate-opening-type guest uptake behaviour.

  8. Remediation of Organic and Inorganic Arsenic Contaminated Groundwater using a Nonocrystalline TiO2 Based Adsorbent

    SciTech Connect

    Jing, C.; Meng, X; Calvache, E; Jiang, G

    2009-01-01

    A nanocrystalline TiO2-based adsorbent was evaluated for the simultaneous removal of As(V), As(III), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in contaminated groundwater. Batch experimental results show that As adsorption followed pseudo-second order rate kinetics. The competitive adsorption was described with the charge distribution multi-site surface complexation model (CD-MUSIC). The groundwater containing an average of 329 ?g L-1 As(III), 246 ?g L-1 As(V), 151 ?g L-1 MMA, and 202 ?g L-1 DMA was continuously passed through a TiO2 filter at an empty bed contact time of 6 min for 4 months. Approximately 11 000, 14 000, and 9900 bed volumes of water had been treated before the As(III), As(V), and MMA concentration in the effluent increased to 10 ?g L-1. However, very little DMA was removed. The EXAFS results demonstrate the existence of a bidentate binuclear As(V) surface complex on spent adsorbent, indicating the oxidation of adsorbed As(III). A nanocrystalline TiO2-based adsorbent could be used for the simultaneous removal of As(V), As(III), MMA, and DMA in contaminated groundwater.

  9. Sample water removal method in volatile organic compound analysis based on diffusion through poly(vinyl fluoride) film.

    PubMed

    Beghi, Sandra; Guillot, Jean-Michel

    2006-09-15

    The humidity caught during air sampling or sample storage causes various problems during volatile organic compound (VOC) analysis and gives unreliable results. In this study, water vapour diffusion capacities through poly(vinyl fluoride) Tedlar, fluoroethylene propylene Teflon and Flex foil film were compared. A new approach to humidity removal has been tested for moderately polluted atmospheres. This approach consists in using the water vapour diffusion property of Tedlar film to remove humidity from bag samples containing a mixture of ten VOCs at 500 ppbv each in a 70% relative humidity atmosphere. The sampling bags were placed in a chamber flushed by a dry air stream at less than 5% relative humidity. After a few hours in the chamber, the samples in the Tedlar bags were dry (relative humidity <5%) and did not show significant VOC loss. This sample water removal (SWR) method is especially interesting as a pretreatment before air sampling on water sensitive adsorbents. PMID:16828784

  10. Thin-film transistors based on organic conjugated semiconductors

    NASA Astrophysics Data System (ADS)

    Garnier, Francis

    1998-02-01

    The use of organic semiconductors as active layers in thin-film transistors has raised in the recent years a large interest, both for the fundamental understanding of the charge transport processes in organic materials, and also for the potential applications of these devices in the new field of flexible electronics. Short conjugated oligomers have been shown to possess much higher field-effect mobilities than their parent conjugated polymers. The origin of such increase in the efficiency of charge transport is mainly attributed to the close-packing and long-range structural organization displayed in thin films of conjugated oligomers. The various routes for controlling this organization are described, which allow to realize liquid crystal-like two-dimensional structures for these semiconductors, whose carrier mobility has now become equivalent to that of amorphous silicon. It is also shown that the effect of conjugation length on carrier mobility is not as critical as previously thought, but the associated increase of the band gap energy effects the efficiency of charge injection at the metal/semiconductor interface. This problem can be answered by realizing a local doping of the semiconductor, which allows the injection of charge to operate through an efficient tunneling mechanism. Organic-based thin-film transistors have now become viable devices.

  11. Exploration of exciton delocalization in organic crystalline thin films

    NASA Astrophysics Data System (ADS)

    Hua, Kim; Manning, Lane; Rawat, Naveen; Ainsworth, Victoria; Furis, Madalina

    The electronic properties of organic semiconductors play a crucial role in designing new materials for specific applications. Our group recently found evidence for a rotation of molecular planes in phthalocyanines that is responsible for the disappearance of a delocalized exciton in these systems for T >150K.................()().......1 In this study, we attempt to tune the exciton delocalization of small organic molecules using strain effects and alloying different molecules in the same family. The exciton behavior is monitored using time- and polarization resolved photolumniscence (PL) spectroscopy as a function of temperature. Specifically, organic crystalline thin films of octabutoxy phthalocyanine (H2OBPc), octyloxy phthalocyanines and H-bonded semiconductors such as the quinacridone and indigo derivatives are deposited on flexible substrates (i.e. Kapton and PEN) using an in-house developed pen-writing method.........2 that results in crystalline films with macroscopic long range order. The room temperature PL studies show redshift and changes in polarization upon bending of the film. Crystalline thin films of alloyed H2OBPc and octabutoxy naphthalocyanine with ratios ranging from 1:1 to 100:1 fabricated on both sapphire and flexible substrates are also explored using the same PL spectroscopy to elucidate the behaviors of delocalized excitons. .1N. Rawat, et al., J Phys Chem Lett 6, 1834 (2015). 2R. L. Headrick, et al., Applied Physics Letters 92, 063302 (2008). NSF DMR-1056589, NSF DMR-1062966.

  12. Thin films by metal-organic precursor plasma spray

    SciTech Connect

    Schulz, Douglas L.; Sailer, Robert A.; Payne, Scott; Leach, James; Molz, Ronald J.

    2009-07-15

    While most plasma spray routes to coatings utilize solids as the precursor feedstock, metal-organic precursor plasma spray (MOPPS) is an area that the authors have investigated recently as a novel route to thin film materials. Very thin films are possible via MOPPS and the technology offers the possibility of forming graded structures by metering the liquid feed. The current work employs metal-organic compounds that are liquids at standard temperature-pressure conditions. In addition, these complexes contain chemical functionality that allows straightforward thermolytic transformation to targeted phases of interest. Toward that end, aluminum 3,5-heptanedionate (Al(hd){sub 3}), triethylsilane (HSi(C{sub 2}H{sub 5}){sub 3} or HSiEt{sub 3}), and titanium tetrakisdiethylamide (Ti(N(C{sub 2}H{sub 5}){sub 2}){sub 4} or Ti(NEt{sub 2}){sub 4}) were employed as precursors to aluminum oxide, silicon carbide, and titanium nitride, respectively. In all instances, the liquids contain metal-heteroatom bonds envisioned to provide atomic concentrations of the appropriate reagents at the film growth surface, thus promoting phase formation (e.g., Si-C bond in triethylsilane, Ti-N bond in titanium amide, etc.). Films were deposited using a Sulzer Metco TriplexPro-200 plasma spray system under various experimental conditions using design of experiment principles. Film compositions were analyzed by glazing incidence x-ray diffraction and elemental determination by x-ray spectroscopy. MOPPS films from HSiEt{sub 3} showed the formation of SiC phase but Al(hd){sub 3}-derived films were amorphous. The Ti(NEt{sub 2}){sub 4} precursor gave MOPPS films that appear to consist of nanosized splats of TiOCN with spheres of TiO{sub 2} anatase. While all films in this study suffered from poor adhesion, it is anticipated that the use of heated substrates will aid in the formation of dense, adherent films.

  13. Determination of adsorbable organic fluorine from aqueous environmental samples by adsorption to polystyrene-divinylbenzene based activated carbon and combustion ion chromatography.

    PubMed

    Wagner, Andrea; Raue, Brigitte; Brauch, Heinz-Jürgen; Worch, Eckhard; Lange, Frank T

    2013-06-21

    A new method for the determination of trace levels of adsorbable organic fluorine (AOF) in water is presented. Even if the individual contributing target compounds are widely unknown, this surrogate parameter is suited to identify typical organofluorine contaminations, such as with polyfluorinated chemicals (PFCs), and represents a lower boundary of the organofluorine concentration in water bodies. It consists of the adsorption of organofluorine chemicals on a commercially available synthetic polystyrene-divinylbenzene based activated carbon (AC) followed by analysis of the loaded AC by hydropyrolysis combustion ion chromatography (CIC). Inorganic fluorine is displaced by excess nitrate during the extraction step and by washing the loaded activated carbon with an acidic sodium nitrate solution. Due to its high purity the synthetic AC had a very low and reproducible fluorine blank (0.3 μg/g) compared to natural ACs (up to approximately 9 μg/g). Using this AC, fluoride and the internal standard phosphate could be detected free of chromatographic interferences. With a sample volume of 100 mL and 2× 100 mg of AC packed into two extraction columns combined in series, a limit of quantification (LOQ), derived according to the German standard method DIN 32645, of 0.3 μg/L was achieved. The recoveries of six model PFCs were determined from tap water and a municipal wastewater treatment plant (WWTP) effluent. Except for the extremely polar perfluoroacetic acid (recovery of approximately 10%) the model substances showed fairly good (50% for perfluorobutanoic acid (PFBA)) to very good fluorine recoveries (100±20% for perfluorooctanoic acid (PFOA), perfluorobutanesulfonate (PFBS), 6:2 fluorotelomersulfonate (6:2 FTS)), both from tap water and wastewater matrix. This new analytical protocol was exemplarily applied to several surface water and groundwater samples. The obtained AOF values were compared to the fluorine content of 19 target PFCs analyzed by high performance

  14. Reference spectra of important adsorbed organic and inorganic phosphate binding forms for soil P speciation using synchrotron-based K-edge XANES spectroscopy.

    PubMed

    Prietzel, Jörg; Harrington, Gertraud; Häusler, Werner; Heister, Katja; Werner, Florian; Klysubun, Wantana

    2016-03-01

    Direct speciation of soil phosphorus (P) by linear combination fitting (LCF) of P K-edge XANES spectra requires a standard set of spectra representing all major P species supposed to be present in the investigated soil. Here, available spectra of free- and cation-bound inositol hexakisphosphate (IHP), representing organic P, and of Fe, Al and Ca phosphate minerals are supplemented with spectra of adsorbed P binding forms. First, various soil constituents assumed to be potentially relevant for P sorption were compared with respect to their retention efficiency for orthophosphate and IHP at P levels typical for soils. Then, P K-edge XANES spectra for orthophosphate and IHP retained by the most relevant constituents were acquired. The spectra were compared with each other as well as with spectra of Ca, Al or Fe orthophosphate and IHP precipitates. Orthophosphate and IHP were retained particularly efficiently by ferrihydrite, boehmite, Al-saturated montmorillonite and Al-saturated soil organic matter (SOM), but far less efficiently by hematite, Ca-saturated montmorillonite and Ca-saturated SOM. P retention by dolomite was negligible. Calcite retained a large portion of the applied IHP, but no orthophosphate. The respective P K-edge XANES spectra of orthophosphate and IHP adsorbed to ferrihydrite, boehmite, Al-saturated montmorillonite and Al-saturated SOM differ from each other. They also are different from the spectra of amorphous FePO4, amorphous or crystalline AlPO4, Ca phosphates and free IHP. Inclusion of reference spectra of orthophosphate as well as IHP adsorbed to P-retaining soil minerals in addition to spectra of free or cation-bound IHP, AlPO4, FePO4 and Ca phosphate minerals in linear combination fitting exercises results in improved fit quality and a more realistic soil P speciation. A standard set of P K-edge XANES spectra of the most relevant adsorbed P binding forms in soils is presented. PMID:26917141

  15. Direct observation of epitaxial organic film growth: temperature-dependent growth mechanisms and metastability.

    PubMed

    Marchetto, Helder; Schmidt, Thomas; Groh, Ullrich; Maier, Florian C; Lévesque, Pierre L; Fink, Rainer H; Freund, Hans-Joachim; Umbach, Eberhard

    2015-11-21

    The growth of the first ten layers of organic thin films on a smooth metallic substrate has been investigated in real-time using the model system PTCDA on Ag(111). The complex behaviour is comprehensively studied by electron microscopy, spectroscopy and diffraction in a combined PEEM/LEEM instrument revealing several new phenomena and yielding a consistent picture of this layer growth. PTCDA grows above room temperature in a Stranski-Krastanov mode, forming three-dimensional islands on a stable bi-layer, in competition with metastable 3rd and 4th layers. Around room temperature this growth mode changes into a quasi layer-by-layer growth, while at temperatures below about 250 K a Vollmer-Weber-like behaviour is observed. By means of laterally resolved soft X-ray absorption spectroscopy the orientation of all adsorbed molecules is found to be homogeneously flat lying on the surface, even during the growth process. The films grow epitaxially, showing long-range order with rotational domains. For the monolayer these domains could be directly analysed, showing an average size of several micrometers extending over substrate steps. PMID:26462749

  16. Graphene nanosheets as novel adsorbents in adsorption, preconcentration and removal of gases, organic compounds and metal ions.

    PubMed

    Yu, Jin-Gang; Yu, Lin-Yan; Yang, Hua; Liu, Qi; Chen, Xiao-Hong; Jiang, Xin-Yu; Chen, Xiao-Qing; Jiao, Fei-Peng

    2015-01-01

    Due to their high adsorption capacities, carbon-based nanomaterials such as carbon nanotubes, activated carbons, fullerene and graphene are widely used as the currently most promising functional materials. Since its discovery in 2004, graphene has exhibited great potential in many technological fields, such as energy storage materials, supercapacitors, resonators, quantum dots, solar cells, electronics, and sensors. The large theoretical specific surface area of graphene nanosheets (2630 m(2)·g(-1)) makes them excellent candidates for adsorption technologies. Further, graphene nanosheets could be used as substrates for decorating the surfaces of nanoparticles, and the corresponding nanocomposites could be applied as novel adsorbents for the removal of low concentrated contaminants from aqueous solutions. Therefore, graphene nanosheets will challenge the current existing adsorbents, including other types of carbon-based nanomaterials. PMID:25244035

  17. Temperature and layer thickness dependent in situ investigations on epindolidione organic thin-film transistors

    PubMed Central

    Lassnig, R.; Striedinger, B.; Jones, A.O.F.; Scherwitzl, B.; Fian, A.; Głowacl, E.D.; Stadlober, B.; Winkler, A.

    2016-01-01

    We report on in situ performance evaluations as a function of layer thickness and substrate temperature for bottom-gate, bottom-gold contact epindolidione organic thin-film transistors on various gate dielectrics. Experiments were carried out under ultra-high vacuum conditions, enabling quasi-simultaneous electrical and surface analysis. Auger electron spectroscopy and thermal desorption spectroscopy (TDS) were applied to characterize the quality of the substrate surface and the thermal stability of the organic films. Ex situ atomic force microscopy (AFM) was used to gain additional information on the layer formation and surface morphology of the hydrogen-bonded organic pigment. The examined gate dielectrics included SiO2, in its untreated and sputtered forms, as well as the spin-coated organic capping layers poly(vinyl-cinnamate) (PVCi) and poly((±)endo,exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, diphenylester) (PNDPE, from the class of polynorbornenes). TDS and AFM revealed Volmer-Weber island growth dominated film formation with no evidence of a subjacent wetting layer. This growth mode is responsible for the comparably high coverage required for transistor behavior at 90–95% of a monolayer composed of standing molecules. Surface sputtering and an increased sample temperature during epindolidione deposition augmented the surface diffusion of adsorbing molecules and therefore led to a lower number of better-ordered islands. Consequently, while the onset of charge transport was delayed, higher saturation mobility was obtained. The highest, bottom-contact configuration, mobilities of approximately 2.5 × 10−3cm2/Vs were found for high coverages (50 nm) on sputtered samples. The coverage dependence of the mobility showed very different characteristics for the different gate dielectrics, while the change of the threshold voltage with coverage was approximately the same for all systems. An apparent decrease of the mobility with increasing coverage on the

  18. Remediation of organic and inorganic arsenic contaminated groundwater using a nanocrystalline TiO2-based adsorbent.

    PubMed

    Jing, Chuanyong; Meng, Xiaoguang; Calvache, Edwin; Jiang, Guibin

    2009-01-01

    A nanocrystalline TiO2-based adsorbent was evaluated for the simultaneous removal of As(V), As(III), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in contaminated groundwater. Batch experimental results show that As adsorption followed pseudo-second order rate kinetics. The competitive adsorption was described with the charge distribution multi-site surface complexation model (CD-MUSIC). The groundwater containing an average of 329 microg L(-1) As(III), 246 microg L(-1) As(V), 151 microg L(-1) MMA, and 202 microg L(-1) DMA was continuously passed through a TiO2 filter at an empty bed contact time of 6 min for 4 months. Approximately 11,000, 14,000, and 9900 bed volumes of water had been treated before the As(III), As(V), and MMA concentration in the effluent increased to 10 microg L(-1). However, very little DMA was removed. The EXAFS results demonstrate the existence of a bidentate binuclear As(V) surface complex on spent adsorbent, indicating the oxidation of adsorbed As(III). PMID:19339086

  19. Liquid crystals for organic thin-film transistors

    NASA Astrophysics Data System (ADS)

    Iino, Hiroaki; Usui, Takayuki; Hanna, Jun-Ichi

    2015-04-01

    Crystalline thin films of organic semiconductors are a good candidate for field effect transistor (FET) materials in printed electronics. However, there are currently two main problems, which are associated with inhomogeneity and poor thermal durability of these films. Here we report that liquid crystalline materials exhibiting a highly ordered liquid crystal phase of smectic E (SmE) can solve both these problems. We design a SmE liquid crystalline material, 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10), for FETs and synthesize it. This material provides uniform and molecularly flat polycrystalline thin films reproducibly when SmE precursor thin films are crystallized, and also exhibits high durability of films up to 200 °C. In addition, the mobility of FETs is dramatically enhanced by about one order of magnitude (over 10 cm2 V-1 s-1) after thermal annealing at 120 °C in bottom-gate-bottom-contact FETs. We anticipate the use of SmE liquid crystals in solution-processed FETs may help overcome upcoming difficulties with novel technologies for printed electronics.

  20. Effects of dissolved organic matter on adsorbed Fe(II) reactivity for the reduction of 2-nitrophenol in TiO2 suspensions.

    PubMed

    Zhu, Zhenke; Tao, Liang; Li, Fangbai

    2013-09-01

    Dissolved organic matter (DOM) is widespread in aquatic and terrestrial environments. Iron is the most abundant transition metal in the Earth's crust. The biogeochemistry of iron and the strength of Fe(II) as a reducing agent while adsorbed on minerals are affected by DOM. This study investigated the effects of Fe(II)/DOM interactions on the reduction of 2-nitrophenol (2-NP) in TiO2 suspensions. Kinetic measurements demonstrated that rates (k) of 2-NP reduction by adsorbed Fe(II) species are affected by adding DOM (denoted O-DOM), and the obtained k values under the impact of the Fe(II)/DOM interaction with different molecular weight DOM fractions [including MW<3500Da (L-DOM), 350014000Da (H-DOM)] showed significant differences. The enhanced rates of 2-NP reduction contributed to increases in the amount of adsorbed Fe(II) species and negative shifts in peak oxidation potential values (EP) in CV tests. For different molecular weight DOM fractions, increases in k (O-DOMadsorbed Fe(II) and the lower EP values. In addition, the ETC values were slightly higher in the TiO2 suspension containing the H-DOM fraction as compared the other two DOM fractions, which would further enhance the reduction rate of 2-NP. These findings promote a general understanding of Fe(II)/DOM interactions and their impact on the fate of contaminants in actual subsurface environments. PMID:23796307

  1. Polycrystalline organic thin film transistors for advanced chemical sensing

    NASA Astrophysics Data System (ADS)

    Torsi, Luisa; Tanese, Maria C.; Cioffi, Nicola; Sabbatini, Luigia; Zambonin, Pier G.

    2003-11-01

    Organic thin-film transistors have seen a dramatic improvement of their performance in the last decade. They have been also proposed as gas sensors. This paper deals with the interesting new aspects that polycrystalline based conducting polymer transistors present when operated as chemical sensors. Such devices are capable to deliver multi-parameter responses that are also extremely repeatable and fast at room temperature. Interesting are also the perspectives for their use as chemically selective devices in array type sensing systems.

  2. Magnetic field effect in organic films and devices

    NASA Astrophysics Data System (ADS)

    Gautam, Bhoj Raj

    In this work, we focused on the magnetic field effect in organic films and devices, including organic light emitting diodes (OLEDs) and organic photovoltaic (OPV) cells. We measured magnetic field effect (MFE) such as magnetoconductance (MC) and magneto-electroluminescence (MEL) in OLEDs based on several pi- conjugated polymers and small molecules for fields |B|<100 mT. We found that both MC(B) and MEL(B) responses in bipolar devices and MC(B) response in unipolar devices are composed of two B-regions: (i) an 'ultra-small' region at |B| < 1-2 mT, and (ii) a monotonic response region at |B| >˜2mT. Magnetic field effect (MFE) measured on three isotopes of Poly (dioctyloxy) phenylenevinylene (DOO-PPV) showed that both regular and ultra-small effects are isotope dependent. This indicates that MFE response in OLED is mainly due to the hyperfine interaction (HFI). We also performed spectroscopy of the MFE including magneto-photoinduced absorption (MPA) and magneto-photoluminescence (MPL) at steady state conditions in several systems. This includes pristine Poly[2-methoxy-5-(2-ethylhexyl-oxy)-1,4-phenylene-vinylene] (MEH-PPV) films, MEH-PPV films subjected to prolonged illumination, and MEH-PPV/[6,6]-Phenyl C61 butyric acid methyl ester (PCBM) blend, as well as annealed and pristine C60 thin films. For comparison, we also measured MC and MEL in organic diodes based on the same materials. By directly comparing the MPA and MPL responses in films to MC and MEL in organic diodes based on the same active layers, we are able to relate the MFE in organic diodes to the spin densities of the excitations formed in the device, regardless of whether they are formed by photon absorption or carrier injection from the electrodes. We also studied magneto-photocurrent (MPC) and power conversion efficiency (PCE) of a 'standard' Poly (3-hexylthiophene)/PCBM device at various Galvinoxyl radical wt%. We found that the MPC reduction with Galvinoxyl wt% follows the same trend as that of the

  3. Rate of organic film formation and oxidation on aqueous drops

    NASA Astrophysics Data System (ADS)

    Aumann, E.; Tabazadeh, A.

    2008-12-01

    Previous studies suggest that saturated fatty acids or other lipids, which are known to be strong film-forming agents, form condensed films on aqueous drops. Specifically, stearic acid (SA) has been used in laboratory and modeling studies to mimic the surface composition of some particles in the atmosphere. In this study, laboratory measurements were used to determine the rate of SA spreading from a solid on aqueous surfaces,ranging in composition from ammonium sulfate to highly acidic sulfuric acid. Maximum spreading rates were measured on neutral electrolyte solutions, while spreading was not observed on aqueous sulfuric and hydrochloric acids (pH < 0). Also, the spreading rates on water and electrolyte surfaces declined sharply as the solution pH was lowered from 7 to 3. Spreading rates are reported with a dependence on the length of solid-aqueous-air boundary (triple interface perimeter). Spreading rates measured on bulk solutions were modeled on atmospheric particles to determine the time constant of organic film formation on aqueous drops. The time required for a saturated fatty acid to spread and coat a submicron salt particle or a cloud drop is on the order of seconds to minutes or minutes to hours, respectively. In conclusion, lipid coatings can form quickly on neutral or slightly acidic salt drops if a sufficient amount of lipid is present in the drop and the lipid is in direct contact with the aqueous solution surface. Rapid film formation and fast heterogeneous oxidation can provide an efficient way of converting water-insoluble organic films into more water-soluble components in aerosols or cloud drops.

  4. Organic thin-film transistors for chemical and biological sensing.

    PubMed

    Lin, Peng; Yan, Feng

    2012-01-01

    Organic thin-film transistors (OTFTs) show promising applications in various chemical and biological sensors. The advantages of OTFT-based sensors include high sensitivity, low cost, easy fabrication, flexibility and biocompatibility. In this paper, we review the chemical sensors and biosensors based on two types of OTFTs, including organic field-effect transistors (OFETs) and organic electrochemical transistors (OECTs), mainly focusing on the papers published in the past 10 years. Various types of OTFT-based sensors, including pH, ion, glucose, DNA, enzyme, antibody-antigen, cell-based sensors, dopamine sensor, etc., are classified and described in the paper in sequence. The sensing mechanisms and the detection limits of the devices are described in details. It is expected that OTFTs may have more important applications in chemical and biological sensing with the development of organic electronics. PMID:22102447

  5. Novel solutions for thin film layer deposition for organic materials

    NASA Astrophysics Data System (ADS)

    Keiper, Dietmar; Long, Michael; Schwambera, Markus; Gersdorff, Markus; Kreis, Juergen; Heuken, Michael

    2011-03-01

    Innovative systems for carrier-gas enhanced vapor phase deposition of organic layers offer advanced methods for the precise deposition of complex thin-film layer stacks. The approach inherently avoids potential short-comings from solvent-based polymer deposition and offers new opportunities. The process operates at low pressure (thus avoiding complex vacuum setups), and, by employing AIXTRON's extensive experience in freely scalable solutions, can be adapted to virtually any production process and allows for R&D and production systems alike. Deposition of organic layers and stacks recommends the approach for a wide range of organic small molecule and polymer materials (including layers with gradual change of the composition), for conductive layers, for dielectric layers, for barrier systems, for OLED materials, and surface treatments such as oleophobic / hydrophobic coatings. With the combination of other vapor phase deposition solutions, hybrid systems combining organic and inorganic materials and other advanced stacks can be realized.

  6. Printed organic thin-film transistor-based integrated circuits

    NASA Astrophysics Data System (ADS)

    Mandal, Saumen; Noh, Yong-Young

    2015-06-01

    Organic electronics is moving ahead on its journey towards reality. However, this technology will only be possible when it is able to meet specific criteria including flexibility, transparency, disposability and low cost. Printing is one of the conventional techniques to deposit thin films from solution-based ink. It is used worldwide for visual modes of information, and it is now poised to enter into the manufacturing processes of various consumer electronics. The continuous progress made in the field of functional organic semiconductors has achieved high solubility in common solvents as well as high charge carrier mobility, which offers ample opportunity for organic-based printed integrated circuits. In this paper, we present a comprehensive review of all-printed organic thin-film transistor-based integrated circuits, mainly ring oscillators. First, the necessity of all-printed organic integrated circuits is discussed; we consider how the gap between printed electronics and real applications can be bridged. Next, various materials for printed organic integrated circuits are discussed. The features of these circuits and their suitability for electronics using different printing and coating techniques follow. Interconnection technology is equally important to make this product industrially viable; much attention in this review is placed here. For high-frequency operation, channel length should be sufficiently small; this could be achievable with a combination of surface treatment-assisted printing or laser writing. Registration is also an important issue related to printing; the printed gate should be perfectly aligned with the source and drain to minimize parasitic capacitances. All-printed organic inverters and ring oscillators are discussed here, along with their importance. Finally, future applications of all-printed organic integrated circuits are highlighted.

  7. Oriented Thin Films of a Benzodithiophene Covalent Organic Framework

    PubMed Central

    2014-01-01

    A mesoporous electron-donor covalent organic framework based on a benzodithiophene core, BDT-COF, was obtained through condensation of a benzodithiophene-containing diboronic acid and hexahydroxytriphenylene (HHTP). BDT-COF is a highly porous, crystalline, and thermally stable material, which can be handled in air. Highly porous, crystalline oriented thin BDT-COF films were synthesized from solution on different polycrystalline surfaces, indicating the generality of the synthetic strategy. The favorable orientation, crystallinity, porosity, and the growth mode of the thin BDT-COF films were studied by means of X-ray diffraction (XRD), 2D grazing incidence diffraction (GID), transmission and scanning electron microscopy (TEM, SEM), and krypton sorption. The highly porous thin BDT-COF films were infiltrated with soluble fullerene derivatives, such as [6,6]-phenyl C61 butyric acid methyl ester (PCBM), to obtain an interpenetrated electron-donor/acceptor host–guest system. Light-induced charge transfer from the BDT-framework to PCBM acceptor molecules was indicated by efficient photoluminescence quenching. Moreover, we monitored the dynamics of photogenerated hole-polarons via transient absorption spectroscopy. This work represents a combined study of the structural and optical properties of highly oriented mesoporous thin COF films serving as host for the generation of periodic interpenetrated electron-donor and electron-acceptor systems. PMID:24559375

  8. Effects of feed-borne Fusarium mycotoxins with or without yeast cell wall adsorbent on organ weight, serum biochemistry, and immunological parameters of broiler chickens.

    PubMed

    Li, Z; Yang, Z B; Yang, W R; Wang, S J; Jiang, S Z; Wu, Y B

    2012-10-01

    The objectives of the present study were to investigate the toxicity of feed-borne Fusarium mycotoxins on organ weight, serum biochemistry, and immunological parameters of broiler chickens and to evaluate the efficacy of yeast cell wall adsorbent in preventing mycotoxin-induced adverse effects. In total, 300 one-day-old vaccinated (Marek's disease and infectious bronchitis) Arbor Acres broiler chickens (mixed sex) were randomly divided into 3 treatments (5 repetitions per treatment) and fed basal diet and naturally contaminated diets with or without yeast cell wall adsorbent. Treatments were control, naturally contaminated diet (NCD; aflatoxin, 102.08 mg/kg; zearalenone, 281.92 mg/kg; fumonisin, 5,874.38 mg/kg; deoxynivalenol, 2,038.96 mg/kg), and NCD + 2 g/kg of yeast cell wall adsorbent (NCDD). The test included 2 phases: d 0-21 and d 22-42. At 42 d, broilers fed contaminated diets without yeast cell wall adsorbent had higher (P < 0.05) serum albumin and higher relative weight of liver, bursa of Fabricius, and thymus, and greater splenic mRNA expression of IL-1β and IL-6 at 42 d compared with the control, but lower (P < 0.05) serum globulin at 42 d, IgA at 21 d, relative weight of spleen at 21 d, antibody titers of Newcastle disease at both 28 d and 42 d, and splenic mRNA expression of IFN-γ at 42 d were observed in the NCD treatment compared with control. Dietary addition of yeast cell wall adsorbent in the NCD treatment showed a positive protection effect on the relative weight of the liver and spleen at 21 d, relative weight of the bursa of Fabricius and thymus at 42 d, antibody titers of Newcastle disease at both 28 d and 42 d, and splenic mRNA expression of IL-1β, IL-6, and IFN-γ at 42 d. It is suggested that feeding a naturally contaminated diet for 42 d might result in a deleterious effect in broiler chickens, and addition of 2 g/kg of yeast cell wall enterosorbent can partly neutralize the detrimental effects of the naturally contaminated feed. PMID

  9. Ion-imprinted silica adsorbent modified diffusive gradients in thin films technique: Tool for speciation analysis of free lead species.

    PubMed

    Sui, Dian-Peng; Chen, Hua-Xia; Liu, Lin; Liu, Ming-Xuan; Huang, Cong-Cong; Fan, Hong-Tao

    2016-02-01

    A new diffusive gradients in thin films (DGT) device, using Pb(II) ion-imprinted silica (IIS) as the binding agents and commercial cellulose acetate dialysis (CAD) membrane as the diffusion layer (CAD/IIS-DGT), has been developed and evaluated for sampling and measurement of free Pb(II) species. The CAD/IIS-DGT devices were successfully applied to the measurement of free Pb(II) species in synthetic solutions, in natural freshwaters and in industrial wastewaters. The CAD/IIS-DGT provides reliable results over pH range of 4.5-6.5 and a wide range of ionic strength from 1.0×10(-3) to 0.7 mol L(-1). The concentrations of the free Pb(II) species in synthetic solution containing different concentrations of ligands measured by CAD/IIS-DGT showed a good agreement with the value measured by Pb-ion selective electrode. Field deployments of the CAD/IIS-DGT devices allowed accurate measurements of the concentrations of free Pb(II) species. PMID:26653451

  10. Robust absolute magnetometry with organic thin-film devices

    PubMed Central

    Baker, W.J.; Ambal, K.; Waters, D.P.; Baarda, R.; Morishita, H.; van Schooten, K.; McCamey, D.R.; Lupton, J.M.; Boehme, C.

    2012-01-01

    Magnetic field sensors based on organic thin-film materials have attracted considerable interest in recent years as they can be manufactured at very low cost and on flexible substrates. However, the technological relevance of such magnetoresistive sensors is limited owing to their narrow magnetic field ranges (∼30 mT) and the continuous calibration required to compensate temperature fluctuations and material degradation. Conversely, magnetic resonance (MR)-based sensors, which utilize fundamental physical relationships for extremely precise measurements of fields, are usually large and expensive. Here we demonstrate an organic magnetic resonance-based magnetometer, employing spin-dependent electronic transitions in an organic diode, which combines the low-cost thin-film fabrication and integration properties of organic electronics with the precision of a MR-based sensor. We show that the device never requires calibration, operates over large temperature and magnetic field ranges, is robust against materials degradation and allows for absolute sensitivities of <50 nT Hz−1/2. PMID:22692541

  11. Electric Transport Phenomena of Nanocomposite Organic Polymer Thin Films

    NASA Astrophysics Data System (ADS)

    Jira, Nicholas C.; Sabirianov, Ildar; Ilie, Carolina C.

    We discuss herein the nanocomposite organic thin film diodes for the use of plasmonic solar cells. This experimental work follows the theoretical calculations done for plasmonic solar cells using the MNPBEM toolbox for MatLab. These calculations include dispersion curves and amount of light scattering cross sections for different metallic nanoparticles. This study gives us clear ideas on what to expect from different metals, allowing us to make the best choice on what to use to obtain the best results. One specific technique for light trapping in thin films solar cells utilizes metal nanoparticles on the surface of the semiconductor. The characteristics of the metal, semiconductor interface allows for light to be guided in between them causing it to be scattered, allowing for more chances of absorption. The samples were fabricated using organic thin films made from polymers and metallic nanoparticles, more specifically Poly(1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate) copolymer and silver or gold nanoparticles. The two fabrication methods applied include spin coating and Langmuir-Blodgett technique. The transport properties are obtained by analyzing the I-V curves. We will also discuss the resistance, resistivity, conductance, density of charge carriers. SUNY Oswego SCAC Grant.

  12. Multifunctional organic thin films and their electronic/optical properties

    NASA Astrophysics Data System (ADS)

    Shao, Yan

    The concept of multifunctional organic thin films and their electronic/optical properties has been applied to organic functional device design, fabrication, and characterization. The organic devices involve organic light-emitting diodes (OLEDs) and organic photovoltaic devices (OPV) in this dissertation. In the research of graded junction structure of OLEDs, two kinds of naturally-formed graded junction (NFGJ) structures, sharp and shallow graded junctions, can be formed using single thermal evaporation boat loaded with uniformly mixed charge transport and light-emitting materials. OLEDs with NFGJ have been demonstrated in Chapter 3; the performance is comparable to the heterojunction OLEDs, but with better device lifetime. A novel method to prepare highly uniform mixed organic solid solutions through a high temperature and high-pressure fusion process has been demonstrated in Chapter 4. A series of fused organic solid solution (FOSS) compounds with NPD doped with different organic emitting dopants were prepared and DSC technique was utilized to determine the thermal characteristics. For the first time, the schematic phase diagram for this binary system has been obtained. High performance OLEDs of single color and white emission were fabricated and the device properties were characterized. In Chapter 5, an efficient photovoltaic heterojunction of tetracene and fullerene has been investigated and high performance organic solar cells have been demonstrated by thermal deposition and successive heat treatment. The preliminary conclusion for this enhancement is discussed and supported by atomic force microscopy images, absorption spectra and x-ray diffraction analysis. Additionally, an effective organic photovoltaic heterojunction based on the typical triplet material PtOEP was demonstrated. It is believed that introducing appropriate organic materials with long exciton lifetime is a very promising way to improve photovoltaic performance.

  13. Thin film solar cells grown by organic vapor phase deposition

    NASA Astrophysics Data System (ADS)

    Yang, Fan

    Organic solar cells have the potential to provide low-cost photovoltaic devices as a clean and renewable energy resource. In this thesis, we focus on understanding the energy conversion process in organic solar cells, and improving the power conversion efficiencies via controlled growth of organic nanostructures. First, we explain the unique optical and electrical properties of organic materials used for photovoltaics, and the excitonic energy conversion process in donor-acceptor heterojunction solar cells that place several limiting factors of their power conversion efficiency. Then, strategies for improving exciton diffusion and carrier collection are analyzed using dynamical Monte Carlo models for several nanostructure morphologies. Organic vapor phase deposition is used for controlling materials crystallization and film morphology. We improve the exciton diffusion efficiency while maintaining good carrier conduction in a bulk heterojunction solar cell. Further efficiency improvement is obtained in a novel nanocrystalline network structure with a thick absorbing layer, leading to the demonstration of an organic solar cell with 4.6% efficiency. In addition, solar cells using simultaneously active heterojunctions with broad spectral response are presented. We also analyze the efficiency limits of single and multiple junction organic solar cells, and discuss the challenges facing their practical implementations.

  14. Sense or no-sense of the sum parameter for water soluble "adsorbable organic halogens" (AOX) and "absorbed organic halogens" (AOX-S18) for the assessment of organohalogens in sludges and sediments.

    PubMed

    Müller, German

    2003-07-01

    "AOX" is the abbreviation of the sum parameter for water soluble "adsorbable organic halogens" in which 'A' stands for adsorbable, 'O' for organic and 'X' for the halogens chlorine, bromine and iodine. After the introduction of the AOX in 1976, this parameter has been correctly used for "real" AOX constituents (DDT and its metabolites, PCBs, etc.) but also misused for non-adsorbable adsorbed OX-compounds, mostly high molecular organohalogens in plants and even to inorganic compounds being neither organic nor adsorbable. The question of natural "Adsorbable Organic Halogens" (AOX) formed by living organisms and/or during natural abiogenic processes has been definitively solved by the known existence of already more than 3650 organohalogen compounds, amongst them the highly reactive, cancerogenic vinyl chloride (VC). The extension of the AOX to AOX-S18 for Sludges and Sediments, in which A stands for adsorbed (not for adsorbable) is questionable. It includes the most important water insoluble technical organochlorine product: polyvinyl chloride, PVC. In addition to organic halogens it also includes inorganic, mineralogenic halides, incorporated mainly in the crystal lattice of fine grained phyllosilicates, the typical clay minerals (kaolinite, montmorillonite, illite and chlorite) which are main constituents of sediments and sedimentary rocks representing the major part of the sedimentary cover of the earth. Other phyllosilicates, biotite and muscovite, major constituents of granites and many metamorphic rocks (gneiss and mica schist) will also contribute to the AOX-S18 especially in soils as result of weathering processes. Since chlorine is incorporated into the mineral structure and, as a consequence, not soluble by the nitric acid analytical step (pH 0.5) of the S18 determination, it will account to the AOX-S18 in the final charcoal combustion step at temperatures >950 degrees C. After heavy rainfalls sewage sludge composition is strongly influenced by

  15. Two-Dimensional Organic-Inorganic Hybrid Perovskite Photonic Films.

    PubMed

    Meng, Ke; Gao, Shanshan; Wu, Longlong; Wang, Geng; Liu, Xin; Chen, Gang; Liu, Zhou; Chen, Gang

    2016-07-13

    Organic-inorganic hybrid perovskites have created enormous expectations for low-cost and high-performance optoelectronic devices. In prospect, future advancements may derive from reaping novel electrical and optical properties beyond pristine perovskites through microscopic structure design and engineering. Herein, we report the successful preparation of two-dimensional inverse-opal perovskite (IOP) photonic films, featuring unique nanostructures and vivid colors. Further compositional and structural managements promise optical property and energy level tunability of the IOP films. They are further functionalized in solar cells, resulting in colorful devices with respectable power conversion efficiency. Such concept has not been previously applied for perovskite-based solar cells, which could open a route for more versatile optoelectronic devices. PMID:27267266

  16. Surface vibrational spectroscopy. A comparison of the EELS spectra of organic adsorbates at Pt(111) with IR and Raman spectra of the unadsorbed organics

    NASA Astrophysics Data System (ADS)

    Kahn, Bruce E.; Chaffins, Scott A.; Gui, John Y.; Lu, Frank; Stern, Donald A.; Hubbard, Arthur T.

    1990-02-01

    In this study EELS spectra obtained for the adsorbed species formed from aqueous electrolytes at Pt(111) electrode surfaces are compared with the IR and Raman spectra of the unadsorbed compounds in order to reveal the changes in vibrational spectra resulting from chemisorption of various important functional groups, and to explore the differences in vibrational absorptivities between EELS spectra of adsorbed species and IR and Raman spectra of the corresponding unadsorbed compounds. Of particular interest are the variations in EELS vibrational frequency, bandwidth and absorptivity due to bonding with the surface, intermolecular interactions of adsorbed molecules and changes in adsorbate molecular orientation. The influence of surface bonding on the EELS spectrum of a functional group was explored through studies of phenol (PL), phenol- d6 (PLD6), benzyl alcohol (BZOH), catechol (CT), benzoic acid (BA), 2-picolinic acid (PA), 2,6-pyridine dicarboxylic acid (26PDCA), and propenoic acid (PPEA). The aromatic ring of adsorbed PL, PLD6, BZA, CT, BA, PA and 26PDCA is oriented parallel to the Pt(111) surface. The resulting strong interactions affect the frequencies and relative intensities of the EELS bands: weak CH stretching modes; a large CC stretching band (1600-1650 cm -1), and weak CH bending (700-800 cm -1). The carboxylic acid moieties of BA and PA interact strongly with the Pt surface, while those of 26PDCA do so only when adsorbed at relatively positive electrode potentials. OH stretching and bending are absent from the EELS spectra of adsorbed PL, BZOH and CT, perhaps due to dissociation of the hydroxyl hydrogen during adsorption of the molecule. Adsorption of alkenes at Pt(111) from solution preserves the characteristic CC stretching band near 1650 cm -1; examples are: PPEA; 1-hexene (HXE); propenol (PPEOH); 4-pentenol (PTEOH); and cis-2-butene-1,4-diol (CBED); adsorption of ethene, propene and butene from vacuum at room temperature has been reported to

  17. Orbital tomography for highly symmetric adsorbate systems

    NASA Astrophysics Data System (ADS)

    Stadtmüller, B.; Willenbockel, M.; Reinisch, E. M.; Ules, T.; Bocquet, F. C.; Soubatch, S.; Puschnig, P.; Koller, G.; Ramsey, M. G.; Tautz, F. S.; Kumpf, C.

    2012-10-01

    Orbital tomography is a new and very powerful tool to analyze the angular distribution of a photoemission spectroscopy experiment. It was successfully used for organic adsorbate systems to identify (and consequently deconvolute) the contributions of specific molecular orbitals to the photoemission data. The technique was so far limited to surfaces with low symmetry like fcc(110) oriented surfaces, owing to the small number of rotational domains that occur on such surfaces. In this letter we overcome this limitation and present an orbital tomography study of a 3,4,9,10-perylene-tetra-carboxylic-dianhydride (PTCDA) monolayer film adsorbed on Ag(111). Although this system exhibits twelve differently oriented molecules, the angular resolved photoemission data still allow a meaningful analysis of the different local density of states and reveal different electronic structures for symmetrically inequivalent molecules. We also discuss the precision of the orbital tomography technique in terms of counting statistics and linear regression fitting algorithm. Our results demonstrate that orbital tomography is not limited to low-symmetry surfaces, a finding which makes a broad field of complex adsorbate systems accessible to this powerful technique.

  18. A rapid microwave-assisted synthesis of a sodium-cadmium metal-organic framework having improved performance as a CO2 adsorbent for CCS.

    PubMed

    Palomino Cabello, Carlos; Arean, Carlos Otero; Parra, José B; Ania, Conchi O; Rumori, P; Turnes Palomino, G

    2015-06-01

    We report on a facile and rapid microwave-assisted method for preparing a sodium-cadmium metal-organic framework (having coordinatively unsaturated sodium ions) that considerably shortens the conventional synthesis time from 5 days to 1 hour. The obtained (Na,Cd)-MOF showed an excellent volumetric CO2 adsorption capacity (5.2 mmol cm(-3) at 298 K and 1 bar) and better CO2 adsorption properties than those shown by the same metal-organic framework when synthesized following a more conventional procedure. Moreover, the newly prepared material was found to display high selectivity for adsorption of carbon dioxide over nitrogen, and good regenerability and stability during repeated CO2 adsorption-desorption cycles, which are the required properties for any adsorbent intended for carbon dioxide capture and sequestration (CSS) from the post-combustion flue gas of fossil fuelled power stations. PMID:25939594

  19. Thin Film Solar Cells: Organic, Inorganic and Hybrid

    NASA Technical Reports Server (NTRS)

    Dankovich, John

    2004-01-01

    Thin film solar cells are an important developing resource for hundreds of applications including space travel. In addition to being more cost effective than traditional single crystal silicon cells, thin film multi-crystaline cells are plastic and light weight. The plasticity of the cells allows for whole solar panels to be rolled out from reams. Organic layers are being investigated in order to increase the efficiency of the cells to create an organic / inorganic hybrid cell. The main focus of the group is a thin film inorganic cell made with the absorber CuInS2. So far the group has been successful in creating the layer from a single-source precursor. They also use a unique method of film deposition called chemical vapor deposition for this. The general makeup of the cell is a molybdenum back contact with the CuInS2 layer, then CdS, ZnO and aluminum top contacts. While working cells have been produced, the efficiency so far has been low. Along with quantum dot fabrication the side project of this that is currently being studied is adding a polymer layer to increase efficiency. The polymer that we are using is P3OT (Poly(3-octylthiopene-2,5-diyll), retroregular). Before (and if) it is added to the cell, it must be understood in itself. To do this simple diodes are being constructed to begin to look at its behavior. The P3OT is spin coated onto indium tin oxide and silver or aluminum contacts are added. This method is being studied in order to find the optimal thickness of the layer as well as other important considerations that may later affect the composition of the finished solar cell. Because the sun is the most abundant renewable, energy source that we have, it is important to learn how to harness that energy and begin to move away from our other depleted non-renewable energy sources. While traditional silicon cells currently create electricity at relatively high efficiencies, they have drawbacks such as weight and rigidness that make them unattractive

  20. Controlled Growth of Ultrathin Film of Organic Semiconductors by Balancing the Competitive Processes in Dip-Coating for Organic Transistors.

    PubMed

    Wu, Kunjie; Li, Hongwei; Li, Liqiang; Zhang, Suna; Chen, Xiaosong; Xu, Zeyang; Zhang, Xi; Hu, Wenping; Chi, Lifeng; Gao, Xike; Meng, Yancheng

    2016-06-28

    Ultrathin film with thickness below 15 nm of organic semiconductors provides excellent platform for some fundamental research and practical applications in the field of organic electronics. However, it is quite challenging to develop a general principle for the growth of uniform and continuous ultrathin film over large area. Dip-coating is a useful technique to prepare diverse structures of organic semiconductors, but the assembly of organic semiconductors in dip-coating is quite complicated, and there are no reports about the core rules for the growth of ultrathin film via dip-coating until now. In this work, we develop a general strategy for the growth of ultrathin film of organic semiconductor via dip-coating, which provides a relatively facile model to analyze the growth behavior. The balance between the three direct factors (nucleation rate, assembly rate, and recession rate) is the key to determine the growth of ultrathin film. Under the direction of this rule, ultrathin films of four organic semiconductors are obtained. The field-effect transistors constructed on the ultrathin film show good field-effect property. This work provides a general principle and systematic guideline to prepare ultrathin film of organic semiconductors via dip-coating, which would be highly meaningful for organic electronics as well as for the assembly of other materials via solution processes. PMID:27267545

  1. High performance small-molecule organic thin film transistors

    NASA Astrophysics Data System (ADS)

    Kuo, Chung-Chen

    The roadmap of developing microelectronics has a new branch: organic electronics. Organic electronics, which utilizes the electrical properties of organic materials in the active or passive layers, is an emerging technology that has received much attention. In conjunction with today's demands for new materials and devices, many technologies have emerged for developing organic electronics and consolidating applications and markets. An organic thin-film transistor is the essential device in this paradigm in addition to organic photodiodes and organic light emitting diodes. This thesis presents advances made in design and fabrication of organic thin-film transistors (OTFTs) using small-molecule organic semiconductors (pentacene, anthradithiophene, and their derivatives) as the active layer with record device performance. In this work OTFT test structures fabricated on oxidized silicon substrates were utilized to provide a convenient substrate, gate contact, and gate insulator for the processing and characterization of vapor-deposited organic materials and their transistors. By developing a gate dielectric treatment using silane coupling agents the performance and yield of pentacene OTFTs was improved and a field-effect mobility of larger than 2 cm2/V-s was achieved. Such device performance is comparable to a-Si:H TFTs and have the potential for electronic applications. In addition, the first direct photolithographic process for top contacts to pentacene OTFTs on oxidized silicon with an acceptable performance (a field-effect mobility of 0.3 cm2/V-s, an on/off current ratio of 10 7, and a subthreshold slope of 1 V/decade) was developed. The multiple layer photoresist process demonstrated the feasibility of creating source and drain metallic electrodes on vapor-deposited pentacene thin films with a resolution less than 10 mum. Subsequently, solution-processed OTFTs were then investigated and high performance transistors, with field-effect mobilities > 1 cm2/V-s and an

  2. Quantitation of persistent organic pollutants adsorbed on plastic debris from the Northern Pacific Gyre's "eastern garbage patch".

    PubMed

    Rios, Lorena M; Jones, Patrick R; Moore, Charles; Narayan, Urja V

    2010-12-01

    Floating marine plastic debris was found to function as solid-phase extraction media, adsorbing and concentrating pollutants out of the water column. Plastic debris was collected in the North Pacific Gyre, extracted, and analyzed for 36 individual PCB congeners, 17 organochlorine pesticides, and 16 EPA priority PAHs. Over 50% contained PCBs, 40% contained pesticides, and nearly 80% contained PAHs. The PAHs included 2, 3 and 4 ring congeners. The PCBs were primarily CB-11, 28, 44, 52, 66, and 101. The pesticides detected were primarily p,p-DDTs and its metabolite, o,p-DDD, as well as BHC (a,b,g and d). The concentrations of pollutants found ranged from a few ppb to thousands of ppb. The types of PCBs and PAHs found were similar to those found in marine sediments. However, these plastic particles were mostly polyethylene which is resistant to degradation and although functioning similarly to sediments in accumulating pollutants, these had remained on or near the ocean surface. Particles collected included intact plastic items as well as many pieces less than 5 mm in size. PMID:21042605

  3. A novel photoelectrochromic device with dual application based on poly(3,4-alkylenedioxythiophene) thin film and an organic dye

    NASA Astrophysics Data System (ADS)

    Hsu, Chih-Yu; Lee, Kun-Mu; Huang, Jen-Hsien; Justin Thomas, K. R.; Lin, Jiann T.; Ho, Kuo-Chuan

    A novel photoelectrochromic device (PECD) with dual application was studied using an electrochromic polymer thin film, poly(3,3-diethyl-3,4-dihydro-2 H-thieno-[3,4- b][1,4]dioxepine) (PProDot-Et 2), and an organic photosensitive dye, FL dye1, which was adsorbed on a TiO 2 electrode. In the presence of the redox couple, the electron transfer reaction at the electrolyte/PProDot-Et 2 conducting polymer interface was found to determine the electrochromism of the PECD. The rate constants of the electron transfer (k 0) for different redox couples at the PProDot-Et 2 film were obtained by using electrochemical impedance spectroscopy (EIS) and were correlated with the coloration depth of the thin film. Since I -/I 3 - and Br -/Br 3 - couples possess the highest and the lowest k 0 value, respectively, the PECD was investigated using these two redox couples under constant light illumination of 50 mW cm -2. The I -/I 3 - couple provided a higher short circuit current density (J SC) when acting as a dye-sensitized solar cell (DSSC), thus the switching response upon coloration (ca. 3 s) was much faster than that of the PECD using the Br -/Br 3 - couple (ca. 2 min). On the contrary, the PECD using Br -/Br 3 - exhibited a larger transmittance attenuation of ca. 33.7%, in comparison to that using I -/I 3 - (ca. 14.1%).

  4. Mutagenicity of organic pollutants adsorbed on suspended particulate matter in the center of Wrocław (Poland)

    NASA Astrophysics Data System (ADS)

    Bełcik, Maciej; Trusz-Zdybek, Agnieszka; Galas, Ewa; Piekarska, Katarzyna

    2014-10-01

    Mutagenicity of pollutants adsorbed on suspended dust of the PM10 fraction, collected in winter and summer season alike over the Wrocław city centre (Poland) was studied using the standard Salmonella assay (plate-incorporation) and the Kado modified assay (microsuspension method). The dust was collected using Staplex high volume air sampler. Further on it was extracted with dichloromethane in a Soxhlet apparatus. PAH content in extracts was determined by the high performance liquid chromatography technique using fluorescence detection, whereas the nitro-PAH content- by the gas chromatography using mass detection. Two Salmonella typhimurium strains, TA98 and YG1041, were used in the assays. The assays were conducted with and without a metabolic activation. Investigated air pollution extracts differed against each other with regard to a total content as well as to a percentage of individual compounds, depending on the sampling season. Both the total PAH content and the nitro-PAH content in the tested samples, and their spectrum as well, were found the highest in winter season. Higher mutagenic effect was noted for the dust extract from samples collected in wintertime than from those collected in summer. Pollutants directly affecting the genetic material and those showing such indirect action were present in the examined samples. The YG1041 strain turned out to be the most sensitive, which was the sign that large amounts of nitro-aromatic compounds were present in the tested samples. Obtained results proved that the Kado modified Salmonella assay would be useful for the atmospheric air pollution monitoring in urban agglomerations. Mutagenic effect in assays conducted according to the Kado procedure was obtained by using in the assays lower concentrations of tested extracts, compared to the classical assay.

  5. Light amplification device using organic electroluminescent diode coupled with photoresponsive organic pigment film

    NASA Astrophysics Data System (ADS)

    Katsume, Tadashi; Hiramoto, Masahiro; Yokoyama, Masaaki

    1995-05-01

    An all-organic light amplification device was successfully constructed using the organic electroluminescent diode coupled with photoresponsive perylene pigment film. Light amplification gain, such as the quantum efficiency of photon conversion, reached as large as 25-folds. Optical switching behavior caused by the feedback of output light to the photoresponsive perylene layer was noted. Because the spatial pattern of light was verified to be conserved precisely, the current device had the potential to evolve into the light amplification device, optical switching device, and optical memory device for two-dimensional parallel image processing.

  6. Organic and inorganic-organic thin film structures by molecular layer deposition: A review.

    PubMed

    Sundberg, Pia; Karppinen, Maarit

    2014-01-01

    The possibility to deposit purely organic and hybrid inorganic-organic materials in a way parallel to the state-of-the-art gas-phase deposition method of inorganic thin films, i.e., atomic layer deposition (ALD), is currently experiencing a strongly growing interest. Like ALD in case of the inorganics, the emerging molecular layer deposition (MLD) technique for organic constituents can be employed to fabricate high-quality thin films and coatings with thickness and composition control on the molecular scale, even on complex three-dimensional structures. Moreover, by combining the two techniques, ALD and MLD, fundamentally new types of inorganic-organic hybrid materials can be produced. In this review article, we first describe the basic concepts regarding the MLD and ALD/MLD processes, followed by a comprehensive review of the various precursors and precursor pairs so far employed in these processes. Finally, we discuss the first proof-of-concept experiments in which the newly developed MLD and ALD/MLD processes are exploited to fabricate novel multilayer and nanostructure architectures by combining different inorganic, organic and hybrid material layers into on-demand designed mixtures, superlattices and nanolaminates, and employing new innovative nanotemplates or post-deposition treatments to, e.g., selectively decompose parts of the structure. Such layer-engineered and/or nanostructured hybrid materials with exciting combinations of functional properties hold great promise for high-end technological applications. PMID:25161845

  7. Organic and inorganic–organic thin film structures by molecular layer deposition: A review

    PubMed Central

    Sundberg, Pia

    2014-01-01

    Summary The possibility to deposit purely organic and hybrid inorganic–organic materials in a way parallel to the state-of-the-art gas-phase deposition method of inorganic thin films, i.e., atomic layer deposition (ALD), is currently experiencing a strongly growing interest. Like ALD in case of the inorganics, the emerging molecular layer deposition (MLD) technique for organic constituents can be employed to fabricate high-quality thin films and coatings with thickness and composition control on the molecular scale, even on complex three-dimensional structures. Moreover, by combining the two techniques, ALD and MLD, fundamentally new types of inorganic–organic hybrid materials can be produced. In this review article, we first describe the basic concepts regarding the MLD and ALD/MLD processes, followed by a comprehensive review of the various precursors and precursor pairs so far employed in these processes. Finally, we discuss the first proof-of-concept experiments in which the newly developed MLD and ALD/MLD processes are exploited to fabricate novel multilayer and nanostructure architectures by combining different inorganic, organic and hybrid material layers into on-demand designed mixtures, superlattices and nanolaminates, and employing new innovative nanotemplates or post-deposition treatments to, e.g., selectively decompose parts of the structure. Such layer-engineered and/or nanostructured hybrid materials with exciting combinations of functional properties hold great promise for high-end technological applications. PMID:25161845

  8. Adsorbed Water Illustration

    NASA Technical Reports Server (NTRS)

    2008-01-01

    The Thermal and Electrical Conductivity Probe on NASA's Phoenix Mars Lander detected small and variable amounts of water in the Martian soil.

    In this schematic illustration, water molecules are represented in red and white; soil minerals are represented in green and blue. The water, neither liquid, vapor, nor solid, adheres in very thin films of molecules to the surfaces of soil minerals. The left half illustrates an interpretation of less water being adsorbed onto the soil-particle surface during a period when the tilt, or obliquity, of Mars' rotation axis is small, as it is in the present. The right half illustrates a thicker film of water during a time when the obliquity is greater, as it is during cycles on time scales of hundreds of thousands of years. As the humidity of the atmosphere increases, more water accumulates on mineral surfaces. Thicker films behave increasingly like liquid water.

    The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

  9. Method for measurement of the density of thin films of small organic molecules

    SciTech Connect

    Xiang Haifeng; Xu Zongxiang; Roy, V. A. L.; Che Chiming; Lai, P. T.

    2007-03-15

    An accurate and sensitive method is reported to measure the thin-film density of vacuum-deposited, small-molecular organic semiconductor materials. A spectrophotometer and surface profiler had been used to determine the mass and thickness of organic thin film, respectively. The calculated density of tris-(8-hydroxyquinolato) aluminum (Alq{sub 3}) thin film was 1.31{+-}0.01 g/cm{sup 3}. Vacuum pressures and thin-film growth rates are found to have less impact on the thin-film density of organic material. However, the thin-film density of organic material strongly depends on its chemical structure and molecular weight. Specifically, the chemical structure determines the density of organic material that affects the molecular volume and intermolecular stacking.

  10. Influence of organic acids on kinetic release of chromium in soil contaminated with leather factory waste in the presence of some adsorbents.

    PubMed

    Taghipour, Marzieh; Jalali, Mohsen

    2016-07-01

    In this study, batch experiments were conducted to investigate the effects of nanoparticles (NPs) (MgO, ZnO, TiO2) and clay minerals (bentonite, zeolite) on the release of chromium (Cr) from leather factory waste (LFW) and LFW treated soil using organic acids. Chromium release from all treatments was studied in the presence of citric acid, oxalic acid and CaCl2 solutions. The results showed that, in all treatments, organic acids released more Cr than inorganic salt (CaCl2). The release of Cr by citric acid was higher than that by oxalic acid. In LFW treated soil and LFW, the release of Cr from the all treatments with NPs was less than that from the clay mineral treatments. On the other hand, in the presence of organic acids, Cr release by NPs and clay minerals decreased. Two kinetic models including pseudo-first- and pseudo-second-order model were tested to describe the time dependent Cr release data. Among the kinetic models used, the pseudo-second-order model generally gave the best fits to experimental data. Before and after release experiments, Cr in LFW, treated LFW, control soil and LFW treated soils were fractionated. In all treatments, the greatest amounts of Cr were found in the residual fraction (RES). The organic acids were effective in reducing the exchangeable (EXC), bound to organic matter (OM) and bound to carbonate (CAR) fractions of Cr in all treatments, whereas, after release of Cr from treated soils, Cr remained mainly in the RES fraction. The application of NPs and clay minerals in soil led to a significant transformation of Cr from mobile fractions to the RES fraction. Therefore, organic ligands played a dominant role in mobility and bioavailability of Cr and the removal of Cr by adsorbents. PMID:27139119

  11. Molecular assembly and organic film growth on complex intermetallic surfaces

    NASA Astrophysics Data System (ADS)

    Al-Mahboob, Abdullah; Sharma, Hem Raj; Sadowski, Jerzy T.; Ledieu, Julian; Fournée, Vincent; McGrath, Ronan

    We extensively studied the role of molecular symmetry and symmetry/structures of wide ranges of substrate-surfaces from non-periodic to periodic to quasi-crystalline in nucleation, growth and phase transition in films made of organic molecular materials. Recently, most interest in quasicrystals is due to the generalization of aperiodic ordering to several classes of systems. Compared to periodic materials, these provide a closer approximation to an isotropic first Brillouin zone, which is of great importance to the design of new functional materials. Here, we present results obtained from our ongoing study of interface mediated molecular assembly extended on complex intermetallic surfaces with specific examples of C60 and Zn-phthalocyanine on quasicrystalline and approximant surfaces. We employed in-situ real-time low-energy electron microscopy (LEEM) for investigation of the processes in assembly and film growth and post-growth STM study and DFT calculations to understand structural details and growth mechanism. Research were carried out in part at the Center for Functional Nanomaterials, Brookhaven National Lab, USA; partly at Institut Jean Lamour, Université de Lorraine, France; and partly at the Surface Science Research Centre, University of Liverpool, UK.

  12. QSAR models for removal rates of organic pollutants adsorbed by in situ formed manganese dioxide under acid condition.

    PubMed

    Su, Pingru; Zhu, Huicen; Shen, Zhemin

    2016-02-01

    Manganese dioxide formed in oxidation process by potassium permanganate exhibits promising adsorptive capacity which can be utilized to remove organic pollutants in wastewater. However, the structure variances of organic molecules lead to wide difference of adsorption efficiency. Therefore, it is of great significance to find a general relationship between removal rate of organic compounds and their quantum parameters. This study focused on building up quantitative structure activity relationship (QSAR) models based on experimental removal rate (r(exp)) of 25 organic compounds and 17 quantum parameters of each organic compounds computed by Gaussian 09 and Material Studio 6.1. The recommended model is rpre = -0.502-7.742 f(+)x + 0.107 E HOMO + 0.959 q(H(+)) + 1.388 BOx. Both internal and external validations of the recommended model are satisfied, suggesting optimum stability and predictive ability. The definition of applicability domain and the Y-randomization test indicate all the prediction is reliable and no possibility of chance correlation. The recommended model contains four variables, which are closely related to adsorption mechanism. f(+)x reveals the degree of affinity for nucleophilic attack. E HOMO represents the difficulty of electron loss. q(H(+)) reflect the distribution of partial charge between carbon and hydrogen atom. BO x shows the stability of a molecule. PMID:26490942

  13. Organic Thin Film Devices for Displays and Lighting

    NASA Astrophysics Data System (ADS)

    Weiss, Oliver J.; Krause, Ralf; Paetzold, Ralph

    Organic materials can be used for fabrication of, e.g., electronic circuits, solar cells, light sensors, memory cells and light emitting diodes. Especially organic light emitting diodes (OLEDs) are increasingly attractive because of their huge market potential. The feasibility of efficient OLEDs was first shown in 1987 [3]. Only about ten years later the first product, a display for car radios, entered the market. Today monochrome and full colour OLED-displays can be found in many applications replacing established flat panel display technologies like TFT-LCDs. This substitution is a consequence of the outstanding attributes of OLED technology: Organic light emitting displays are self-emissive, thin, video capable and in addition they show a wide temperature operation range and allow a viewing angle of nearly 180 degree in conjunction with a low power consumption. As performance has steadily increased over the last years, today OLEDs are also under investigation as next generation light source. In contrast to inorganic LEDs, they can be built as flat 2-dimensional light sources that are lightweight, colour tunable, and potentially cheap. This will open up new degrees of freedom in design leading also to completely new applications. In this contribution we will have a brief view on the history of organic electroluminescent materials before we introduce the basic principles of OLEDs with a focus on the physical processes leading to light generation in thin organic films. Along with an overview of different concepts and technologies used to build OLEDs, the current status of OLED development will be illustrated. The last part focuses on the challenges that have to be overcome to enable a sustainable success in the display and lighting markets.

  14. Simultaneous removal of multiple pesticides from water: effect of organically modified clays as coagulant aid and adsorbent in coagulation-flocculation process.

    PubMed

    Shabeer, T P Ahammed; Saha, Ajoy; Gajbhiye, V T; Gupta, Suman; Manjaiah, K M; Varghese, Eldho

    2014-01-01

    Contamination of drinking water sources with agrochemical residues became a major concern in the twenty-first century. Coagulation-flocculation is the most widely used water-treatment process, but the efficiency to remove pesticides and other organic pollutants are limited compared to adsorption process. Thus, simultaneous action of adsorption on normal bentonite or organo-modified montmorillonite clays [modified with octadecylamine (ODA-M) and octadecylamine + amino-propyltriethoxysilane (ODAAPS-M)] followed by coagulation-flocculation by alum and poly aluminium chloride has been evaluated for removal of 10 different pesticides, namely atrazine, lindane, metribuzin, aldrin, chlorpyriphos, pendimethalin, alpha-endosulphan, beta-endosulphan, p,p'-DDT, cypermethrin and two of its metabolites, endosulphan sulphate and p,p'-DDE, from water. The coagulation without integration of adsorption was less effective (removal % varies from 12 to 49) than the adsorption-coagulation integrated system (removal % varies from 71 to 100). Further, coagulation integrated with adsorption was more effective when organically modified montmorillonite was used as adsorbent compared to normal bentonite. The removal efficiency of organic clay depends upon the concentration of pesticides, doses of clay minerals, and efficiency was more for ODAAPS-M as compared to ODA-M. The combination of ODAAPS-M-clay with coagulants was also used efficiently for the removal of pesticides from natural and fortified natural water collected and the results exhibit the usefulness of this remediation technique for application in water decontamination and in treatment of industrial and agricultural waste waters. PMID:25145219

  15. Inorganic-organic composite nanoengineered films using self-assembled monolayers for directed zeolite film growth

    SciTech Connect

    Dye, R.C.; Hermes, R.E.; Martinez, M.G.; Peachey, N.M.

    1997-10-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Zeolites, or molecular sieves, are aluminosilicate cage structures that are typically grown from a heterogeneous mixture of organic template molecules, inorganic salts of alumina and silica, and water. These zeolites are used in industry for catalytic cracking of hydrocarbons (gasoline manufacture from oil), and contaminant removal from chemical production processes. Within one year, we developed a viable method for the deposition of a quaternary ammonium salt amphiphile onto silicon wafer substrates. Using a biomimetic growth process, we were also able to demonstrate the first thin-film formation of a zeolite structure from such an organic template. Additionally, we synthesized the precursor to another amphiphile which was to be for further studies.

  16. Organically Modified Nanoclay-Reinforced Rigid Polyurethane Films

    NASA Astrophysics Data System (ADS)

    Park, Yong Tae; Qian, Yuqiang; Lindsay, Chris; Stein, Andreas; Macosko, Christopher

    2012-02-01

    The nanodispersion of vermiculite in polyurethanes was investigated to produce organoclay-reinforced rigid gas barrier films. Reducing gas transport can improve the insulation performance of closed cell polyurethane foam. In a previous study, the dispersion of vermiculite in polyurethanes without organic modification was not sufficient due to the non-uniform dispersion morphology. When vermiculite was modified by cation exchange with long-chain quaternary ammonium cations, the dispersion in methylene diphenyl diisocyanate (MDI) was significantly improved. Dispersion was improved by combining high intensity dispersive mixing with efficient distributive mixing. Polymerization conditions were also optimized in order to provide a high state of nanodispersion in the polyurethane nanocomposite. The dispersions were characterized using rheological, microscopic and scattering/diffraction techniques. The final nanocomposites showed enhancement of mechanical properties and reduction in permeability to carbon dioxide at low clay concentration (around 2 wt percent).

  17. REUSABLE ADSORBENTS FOR DILUTE SOLUTIONS SEPARATION. 5: PHOTODEGRADATION OF ORGANIC COMPOUNDS ON SURFACTANT-MODIFIED TITANIA. (R828598C753)

    EPA Science Inventory

    A semiconductor titania (TiO2) surface was modified by surfactant adsorption to make it more hydrophobic and to increase the adsorption of hydrophobic organic compounds (HOCs) and their photodegradation rates under UV irradiation. Photocatalytic experiments using Ti...

  18. Optical properties of organic films, multilayers and plasmonic metal-organic waveguides fabricated by organic molecular beam deposition

    NASA Astrophysics Data System (ADS)

    Wickremasinghe, Niranjala D.

    In this thesis, the optical properties of tris (8-hydroxyquinoline) aluminum (Alq3) and 3,5,9,10-perylentetracarboxylic dianhydride (PTCDA) organic films, PTCDA/ Alq3 multilayers and plasmonic Alq3 -metal waveguides are investigated. The organic films and heterostructures used for this work were fabricated by organic molecular beam deposition (OMBD). We investigated the quenching of the light emission in Alq3 films grown on a Si substrate as a function of cw laser excitation intensity at varying temperatures from 15 to 300 K. The saturation of the singlet-singlet annihilation coefficient was measured with spectrally-integrated (SI) photoluminescence (PL) using a photodiode. The bimolecular quenching coefficient was further studied with time-resolved (TR) PL as a function of 100 fs pulse fluences. The PL quenching is attributed to the annihilation of trapped excitons at Alq3 nanocrystal grain boundaries. The saturation is explained by the limited density of available trapping states at the grain boundaries. Our interpretation is supported by structural investigations of ultrathin Alq3 films with atomic force microscopy (AFM), scanning electron microscopy (SEM) and by comparing the experimental data with calculations using a coupled rate equation model. The wavelength dispersion of the refractive indices of PTCDA and Alq 3 layers and of PTCDA/Alq3 multilayer waveguides grown on Pyrex substrates was investigated. The m-line technique, an evanescent prism coupling technique, was used to determine the layers' thickness and the in-plane (TE modes) and normal (TM modes) refractive indices. The potential for controlling the refractive index dispersion and anisotropy by tailored organic multilayer waveguides is discussed.

  19. Organic crystalline films for optical applications and related methods of fabrication

    NASA Technical Reports Server (NTRS)

    Leyderman, Alexander (Inventor); Cui, Yunlong (Inventor)

    2003-01-01

    The present invention provides organic single crystal films of less than 20 .mu.m, and devices and methods of making such films. The crystal films are useful in electro-optical applications and can be provided as part of an electro-optical device which provides strength, durability, and relative ease of manipulation of the mono-crystalline films during and after crystal growth.

  20. Reduction of ferrihydrite with adsorbed and coprecipitated organic matter: microbial reduction by Geobacter bremensis vs. abiotic reduction by Na-dithionite

    NASA Astrophysics Data System (ADS)

    Eusterhues, K.; Hädrich, A.; Neidhardt, J.; Küsel, K.; Keller, T. F.; Jandt, K. D.; Totsche, K. U.

    2014-04-01

    Ferrihydrite (Fh) is a widespread poorly crystalline Fe oxide which becomes easily coated by natural organic matter (OM) in the environment. This mineral-bound OM entirely changes the mineral surface properties and therefore the reactivity of the original mineral. Here, we investigated the reactivity of 2-line Fh, Fh with adsorbed OM and Fh coprecipitated with OM towards microbial and abiotic reduction of Fe(III). As a surrogate for dissolved soil OM we used a water extract of a Podzol forest floor. Fh-OM associations with different OM-loadings were reduced either by Geobacter bremensis or abiotically by Na-dithionite. Both types of experiments showed decreasing initial Fe reduction rates and decreasing degrees of reduction with increasing amounts of mineral-bound OM. At similar OM-loadings, coprecipitated Fhs were more reactive than Fhs with adsorbed OM. The difference can be explained by the smaller crystal size and poor crystallinity of such coprecipitates. At small OM loadings this led to even faster Fe reduction rates than found for pure Fh. The amount of mineral-bound OM also affected the formation of secondary minerals: goethite was only found after reduction of OM-free Fh and siderite was only detected when Fhs with relatively low amounts of mineral-bound OM were reduced. We conclude that direct contact of G. bremensis to the Fe oxide mineral surface was inhibited when blocked by OM. Consequently, mineral-bound OM shall be taken into account besides Fe(II) accumulation as a further widespread mechanism to slow down reductive dissolution.

  1. Organic and inorganic contaminants removal from water with biochar, a renewable, low cost and sustainable adsorbent--a critical review.

    PubMed

    Mohan, Dinesh; Sarswat, Ankur; Ok, Yong Sik; Pittman, Charles U

    2014-05-01

    Biochar is used for soil conditioning, remediation, carbon sequestration and water remediation. Biochar application to water and wastewater has never been reviewed previously. This review focuses on recent applications of biochars, produced from biomass pyrolysis (slow and fast), in water and wastewater treatment. Slow and fast pyrolysis biochar production is briefly discussed. The literature on sorption of organic and inorganic contaminants by biochars is surveyed and reviewed. Adsorption capacities for organic and inorganic contaminants by different biochars under different operating conditions are summarized and, where possible, compared. Mechanisms responsible for contaminant remediation are briefly discussed. Finally, a few recommendations for further research have been made in the area of biochar development for application to water filtration. PMID:24636918

  2. Organic Single-Crystal Semiconductor Films on a Millimeter Domain Scale.

    PubMed

    Kwon, Sooncheol; Kim, Jehan; Kim, Geunjin; Yu, Kilho; Jo, Yong-Ryun; Kim, Bong-Joong; Kim, Junghwan; Kang, Hongkyu; Park, Byoungwook; Lee, Kwanghee

    2015-11-18

    Nucleation and growth processes can be effectively controlled in organic semiconductor films through a new concept of template-mediated molecular crystal seeds during the phase transition; the effective control of these processes ensures millimeter-scale crystal domains, as well as the performance of the resulting organic films with intrinsic hole mobility of 18 cm(2) V(-1) s(-1). PMID:26425962

  3. Organic thin film devices with stabilized threshold voltage and mobility, and method for preparing the devices

    DOEpatents

    Nastasi, Michael Anthony; Wang, Yongqiang; Fraboni, Beatrice; Cosseddu, Piero; Bonfiglio, Annalisa

    2013-06-11

    Organic thin film devices that included an organic thin film subjected to a selected dose of a selected energy of ions exhibited a stabilized mobility (.mu.) and threshold voltage (VT), a decrease in contact resistance R.sub.C, and an extended operational lifetime that did not degrade after 2000 hours of operation in the air.

  4. Low resistance thin film organic solar cell electrodes

    SciTech Connect

    Forrest, Stephen; Xue, Jiangeng

    2008-01-01

    A method which lower the series resistance of photosensitive devices includes providing a transparent film of a first electrically conductive material arranged on a transparent substrate; depositing and patterning a mask over the first electrically conductive material, such that openings in the mask have sloping sides which narrow approaching the substrate; depositing a second electrically conductive material directly onto the first electrically conductive material exposed in the openings of the mask, at least partially filling the openings; stripping the mask, leaving behind reentrant structures of the second electrically conductive material which were formed by the deposits in the openings of the mask; after stripping the mask, depositing a first organic material onto the first electrically conductive material in between the reentrant structures; and directionally depositing a third electrically conductive material over the first organic material deposited in between the reentrant structures, edges of the reentrant structures aligning deposition so that the third electrically conductive material does not directly contact the first electrically conductive material, and does not directly contact the second electrically conductive material.

  5. Clean graphene electrodes on organic thin-film devices via orthogonal fluorinated chemistry.

    PubMed

    Beck, Jonathan H; Barton, Robert A; Cox, Marshall P; Alexandrou, Konstantinos; Petrone, Nicholas; Olivieri, Giorgia; Yang, Shyuan; Hone, James; Kymissis, Ioannis

    2015-04-01

    Graphene is a promising flexible, highly transparent, and elementally abundant electrode for organic electronics. Typical methods utilized to transfer large-area films of graphene synthesized by chemical vapor deposition on metal catalysts are not compatible with organic thin-films, limiting the integration of graphene into organic optoelectronic devices. This article describes a graphene transfer process onto chemically sensitive organic semiconductor thin-films. The process incorporates an elastomeric stamp with a fluorinated polymer release layer that can be removed, post-transfer, via a fluorinated solvent; neither fluorinated material adversely affects the organic semiconductor materials. We used Raman spectroscopy, atomic force microscopy, and scanning electron microscopy to show that chemical vapor deposition graphene can be successfully transferred without inducing defects in the graphene film. To demonstrate our transfer method's compatibility with organic semiconductors, we fabricate three classes of organic thin-film devices: graphene field effect transistors without additional cleaning processes, transparent organic light-emitting diodes, and transparent small-molecule organic photovoltaic devices. These experiments demonstrate the potential of hybrid graphene/organic devices in which graphene is deposited directly onto underlying organic thin-film structures. PMID:25774924

  6. Fabrication of Isolated Metal-Organic Polyhedra in Confined Cavities: Adsorbents/Catalysts with Unusual Dispersity and Activity.

    PubMed

    Kang, Ying-Hu; Liu, Xiao-Dan; Yan, Ni; Jiang, Yao; Liu, Xiao-Qin; Sun, Lin-Bing; Li, Jian-Rong

    2016-05-18

    Metal-organic polyhedra (MOPs) have attracted great attention due to their intriguing structure. However, the applications of MOPs are severely hindered by two shortcomings, namely low dispersity and poor stability. Here we report the introduction of four MOPs (constructed from dicopper and carboxylates) to cavity-structured mesoporous silica SBA-16 via a double-solvent strategy to overcome both shortcomings simultaneously. By judicious design, the dimension of MOPs is just between the size of cavities and entrances of SBA-16, MOP molecules are thus confined in the cavities. This leads to the formation of isolated MOPs with unusual dispersion, making the active sites highly accessible. Hence, the adsorption capacity on carbon dioxide and propene as well as catalytic performance on ring opening are much superior to bulk MOPs. More importantly, the structure and catalytic activity of MOPs in confined cavities are well preserved after exposure to humid atmosphere, whereas those of bulk MOPs are degraded seriously. PMID:27049737

  7. Conductance Thin Film Model of Flexible Organic Thin Film Device using COMSOL Multiphysics

    NASA Astrophysics Data System (ADS)

    Carradero-Santiago, Carolyn; Vedrine-Pauléus, Josee

    We developed a virtual model to analyze the electrical conductivity of multilayered thin films placed above a graphene conducting and flexible polyethylene terephthalate (PET) substrate. The organic layers of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) as a hole conducting layer, poly(3-hexylthiophene-2,5-diyl) (P3HT), as a p-type, phenyl-C61-butyric acid methyl ester (PCBM) and as n-type, with aluminum as a top conductor. COMSOL Multiphysics was the software we used to develop the virtual model to analyze potential variations and conductivity through the thin-film layers. COMSOL Multiphysics software allows simulation and modeling of physical phenomena represented by differential equations such as heat transfer, fluid flow, electromagnetism, and structural mechanics. In this work, using the AC/DC, electric currents module we defined the geometry of the model and properties for each of the six layers: PET/graphene/PEDOT:PSS/P3HT/PCBM/aluminum. We analyzed the model with varying thicknesses of graphene and active layers (P3HT/PCBM). This simulation allowed us to analyze the electrical conductivity, and visualize the model with varying voltage potential, or bias across the plates, useful for applications in solar cell devices.

  8. EMERGING TECHNOLOGY SUMMARY: DEMONSTRATION OF AMBERSORB 563 ADSORBENT TECHNOLOGY

    EPA Science Inventory

    A field pilot study was conducted to demonstrate the technical feasibility and cost-effectiveness of Ambersorb® 5631 carbonaceous adsorbent for remediating groundwater contaminated with volatile organic compounds (VOCs). The Ambersorb adsorbent technology demonstration consist...

  9. Combined optical and acoustical method for determination of thickness and porosity of transparent organic layers below the ultra-thin film limit

    NASA Astrophysics Data System (ADS)

    Rodenhausen, K. B.; Kasputis, T.; Pannier, A. K.; Gerasimov, J. Y.; Lai, R. Y.; Solinsky, M.; Tiwald, T. E.; Wang, H.; Sarkar, A.; Hofmann, T.; Ianno, N.; Schubert, M.

    2011-10-01

    Analysis techniques are needed to determine the quantity and structure of materials composing an organic layer that is below an ultra-thin film limit and in a liquid environment. Neither optical nor acoustical techniques can independently distinguish between thickness and porosity of ultra-thin films due to parameter correlation. A combined optical and acoustical approach yields sufficient information to determine both thickness and porosity. We describe application of the combinatorial approach to measure single or multiple organic layers when the total layer thickness is small compared to the wavelength of the probing light. The instrumental setup allows for simultaneous in situ spectroscopic ellipsometry and quartz crystal microbalance dynamic measurements, and it is combined with a multiple-inlet fluid control system for different liquid solutions to be introduced during experiments. A virtual separation approach is implemented into our analysis scheme, differentiated by whether or not the organic adsorbate and liquid ambient densities are equal. The analysis scheme requires that the film be assumed transparent and rigid (non-viscoelastic). We present and discuss applications of our approach to studies of organic surfactant adsorption, self-assembled monolayer chemisorption, and multiple-layer target DNA sensor preparation and performance testing.

  10. Combined optical and acoustical method for determination of thickness and porosity of transparent organic layers below the ultra-thin film limit.

    PubMed

    Rodenhausen, K B; Kasputis, T; Pannier, A K; Gerasimov, J Y; Lai, R Y; Solinsky, M; Tiwald, T E; Wang, H; Sarkar, A; Hofmann, T; Ianno, N; Schubert, M

    2011-10-01

    Analysis techniques are needed to determine the quantity and structure of materials composing an organic layer that is below an ultra-thin film limit and in a liquid environment. Neither optical nor acoustical techniques can independently distinguish between thickness and porosity of ultra-thin films due to parameter correlation. A combined optical and acoustical approach yields sufficient information to determine both thickness and porosity. We describe application of the combinatorial approach to measure single or multiple organic layers when the total layer thickness is small compared to the wavelength of the probing light. The instrumental setup allows for simultaneous in situ spectroscopic ellipsometry and quartz crystal microbalance dynamic measurements, and it is combined with a multiple-inlet fluid control system for different liquid solutions to be introduced during experiments. A virtual separation approach is implemented into our analysis scheme, differentiated by whether or not the organic adsorbate and liquid ambient densities are equal. The analysis scheme requires that the film be assumed transparent and rigid (non-viscoelastic). We present and discuss applications of our approach to studies of organic surfactant adsorption, self-assembled monolayer chemisorption, and multiple-layer target DNA sensor preparation and performance testing. PMID:22047284

  11. Influence of surface chemistry on the structural organization of monomolecular protein layers adsorbed to functionalized aqueous interfaces.

    PubMed Central

    Lösche, M; Piepenstock, M; Diederich, A; Grünewald, T; Kjaer, K; Vaknin, D

    1993-01-01

    The molecular organization of streptavidin (SA) bound to aqueous surface monolayers of biotin-functionalized lipids and binary lipid mixtures has been investigated with neutron reflectivity and electron and fluorescence microscopy. The substitution of deuterons (2H) for protons (1H), both in subphase water molecules and in the alkyl chains of the lipid surface monolayer, was utilized to determine the interface structure on the molecular length scale. In all cases studied, the protein forms monomolecular layers underneath the interface with thickness values of approximately 40 A. A systematic dependence of the structural properties of such self-assembled SA monolayers on the surface chemistry was observed: the lateral protein density depends on the length of the spacer connecting the biotin moiety and its hydrophobic anchor. The hydration of the lipid head groups in the protein-bound state depends on the dipole moment density at the interface. Images FIGURE 1 FIGURE 2 FIGURE 3 FIGURE 5 FIGURE 11 FIGURE 12 FIGURE A1 PMID:8298041

  12. A Multi-technique Characterization of Adsorbed Protein Films: Orientation and Structure by ToF-SIMS, NEXAFS, SFG, and XPS

    NASA Astrophysics Data System (ADS)

    Baio, Joseph E.

    immobilization schemes. This protein contained both a hexahistidine tag and a cysteine residue, introduced at opposite ends of the HuLys Fv, for immobilization onto nitrilotriacetic acid (NTA) and maleimide oligo- (ethylene glycol) (MEG)-terminated substrates. The thiol group on the cysteine residue selectively binds to the MEG groups, while the his-tag selectively binds to the Ni-loaded NTA groups. XPS was used to monitor protein coverage on both surfaces by following the change in the nitrogen atomic %. The ToF-SIMS data provided a clear differentiation between the two samples due to the intensity differences of secondary ions originating from asymmetrically located amino acids in HuLys Fv. Indicating that the HuLys Fv fragment when adsorbed into the NTA and MEG substrates will be induced into two different orientations. On the NTA substrate the protein's binding site is accessible, while on the MEG substrate the binding site is oriented towards the surface. By taking advantage of the electron pathway through the heme group in cytochrome c (CytoC) electrochemists have built sensors based upon CytoC immobilized onto functionalized metal electrodes. When immobilized onto a charged surface, CytoC, with its distribution of lysine and glutamate residues around its surface, should orient and form a well-ordered protein film. Here a detailed examination of CytoC orientation when electrostatically immobilized onto both amine (NH 3+) and carboxyl (COO-) functionalized gold is presented. Again, protein coverage, on both surfaces, was monitored by the change in the atomic % N, as determined by XPS. ToF-SIMS data demonstrated a clear separation between the two samples based on the intensity differences of secondary ions stemming from amino acids located asymmetrically within CytoC, indicating opposite orientations of the protein on the two different surfaces. Spectral features within the in situ sum frequency generation vibrational spectra, acquired for the protein interacting with

  13. Heterogeneous Reactions of Surface-Adsorbed Catechol: A Comparison of Tropospheric Aerosol Surrogates

    NASA Astrophysics Data System (ADS)

    Hinrichs, R. Z.; Woodill, L. A.

    2009-12-01

    Surface-adsorbed organics can alter the chemistry of tropospheric solid-air interfaces, such as aerosol and ground level surfaces, thereby impacting photochemical cycles and altering aerosol properties. The nature of the surface can also influence the chemistry of the surface-adsorbed organic. We employed diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to monitor the adsorption of gaseous catechol on several tropospheric aerosol surrogates and to investigate the subsequent reactivity of adsorbed-catechol with nitrogen dioxide and, in separate preliminary experiments, ozone. Graphite, kaolinite, and sodium halide (NaF, NaCl, NaBr) powders served as carbonaceous, mineral and sea salt aerosol surrogates, respectively. Broad OH stretching bands for adsorbed catechol shifted to lower wavenumber with peak frequencies following the trend NaBr > NaCl > NaF ≈ kaolinite, consistent with the increasing basicity of the halide anions and basic Brønsted sites on kaolinite. The dark heterogeneous reaction of NO2 with NaCl-adsorbed catechol at relative humidity (RH) <2% promoted nitration forming 4-nitrocatechol and oxidation forming 1,2-benzoquinone and the ring cleavage product muconic acid, with product yields of 88%, 8%, and 4%, respectively. 4-Nitrocatechol was the dominant product for catechol adsorbed on NaF and kaolinite, while NaBr-adsorbed catechol produced less 4-nitrocatechol and more 1,2-benzoquinone and muconic acid. For all three sodium halides, the reactions of NO2 with adsorbed catechol were orders of magnitude faster than between NO2 and each NaX substrate. 4-Nitrocatechol rates and product yields were consistent with the relative ability of each substrate to enhance the deprotonated nature of adsorbed-catechol. Increasing the relative humidity caused the rate of each product channel to decrease and also altered the product branching ratios. Most notably, 1,2-benzoquinone formation decreased significantly even at 13% RH. The dramatic

  14. Doped thin films of two organic molecules for light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Giovanella, Umberto; Botta, Chiara; Pasini, Mariacecilia; Porzio, William; Destri, Silvia

    2003-11-01

    The photoluminescence and electroluminescence of doped organic materials are reported for thin films prepared by ultrahigh-vacuum coevaporation and by spin coating from solution of two emitting molecules. For both films, efficient energy transfer from the donor to the acceptor molecules is observed without relevant dopant segregation for molar concentrations up to 10%. In spin-coated films the energy transfer from the matrix to the dopant is due to purely resonant energy transfer processes while the cosublimated films show the presence of additional thermally activated hopping processes. Light-emitting diodes fabricated with coevaporated films yield electroluminescence with higher efficiency and stability.

  15. Electroless plating of honeycomb and pincushion polymer films prepared by self-organization.

    PubMed

    Yabu, Hiroshi; Hirai, Yuji; Shimomura, Masatsugu

    2006-11-01

    This report describes the fabrication and electroless plating of regular porous and pincushion-like polymer structures prepared by self-organization. Honeycomb-patterned films were prepared by simple casting of polymer solution under applied humid air and pincushion structures by peeling off the top layer of the former films. Silver-deposited honeycomb-patterned films and pincushion films were obtained by simple electroless plating of the respective original structures. XPS revealed Ag deposition on the honeycomb-patterned film. After thermal decomposition or solvent elution of the template polymer, unique metal mesoscopic structures were obtained. PMID:17073508

  16. Adsorption mechanism of ester phosphate on baryum titanate in organic medium. Preliminary results on the structure of the adsorbed layer

    NASA Astrophysics Data System (ADS)

    Le Bars, N.; Tinet, D.; Faugère, A. M.; van Damme, H.; Levitz, P.

    1991-05-01

    The purpose of this work is to evidence the adsorption mechanism and the structure of commercial phosphate ester surfactant stabilized BaTiO3 in organic suspension, and to relate these characteristics to rheological behaviour. Binders and plasticizers are omitted to reduce the number of system components. Firstly adsorption isotherm were determined by inductively coupled argon plasma technique and interpretated based on transmission electron microscopy and ^{31}P nuclear magnetic resonance studies. Preliminary rheological measurements were then performed and related to suspension structure. Structure of the adsorption layer is critically discussed. L'objectif de cette étude est la compréhension du mécanisme d'adsorption d'agents dispersants phosphatés dans des suspensions organiques de BaTiO3, ainsi que la caractérisation de la structure, et du comportement rhéologique de ces suspensions. Liants et plastifiants ne sont pas utilisés, afin de réduire le nombre de composants dans le système. Dans un premier temps, l'isotherme d'adsorption est établie par dosage en émission plasma, puis interprétée sur la base de résultats de Microscopie Eloctronique à Transmission, et de spectroscopie par Résonance Magnétique Nucléaire du ^{31}P. Des mesures rhéologiques préliminaires sont effectuées pour caractériser la structure des suspensions.

  17. Fabrication and Performance of Organic Thin Film Solar Cells Using the Brush Painting Method

    NASA Astrophysics Data System (ADS)

    Ishihara, Hirohumi; Kojima, Kenzo; Mizutani, Teruyoshi; Ochiai, Shizuyasu

    As organic solar thin films fabricated by an active layer of organic materials are economical, lightweight, and flexible, as well as facilitating processing, organic solar cells have attracted considerable attention within the past few decades as a clean energy source. With this in mind, there have been global investigations and studies of the power conversion efficiency (PCE) within organic solar cells. In organic thin-film solar cells, the effect of the performance is not only dependent on an adopted active material but also the molecular orientation on the electrode. Using the mixed solution of Poly (3-hexylthiophene) and PCBM, both dissolved by solvent, an organic thin film is fabricated using the paint method (The conceptual diagram of the paint method is shown in Fig. 1) The form of the thin film was evaluated, an organic thin-film solar cell using the paint method for the active layer was made, and its performance was evaluated and examined. Using the mixed solution of Poly(3-hexylthiophene) and PCBM, both dissolved by solvent, an organic thin film is fabricated using the paint method (The conceptual diagram of the paint method is shown in Fig. 1) The morphology of the thin film was evaluated using an AFM image, UV/vis spectra, and so forth. Based on these data, an organic thin-film solar cell that used the paint method for the active layer was fabricated, and the performance was evaluated and examined. For the organic thin film solar cell fabricated using the brush painting method, the open-circuit voltage (Voc) is 0.41 V, the short circuit current density (Jsc) is 2.07 mA/cm2, and the fill factor is 0.34. The efficiency η of PCE becomes 0.29%.

  18. Simulation study of twisted crystal growth in organic thin films

    NASA Astrophysics Data System (ADS)

    Fang, Alta; Haataja, Mikko

    2015-10-01

    Many polymer and organic small-molecule thin films crystallize with microstructures that twist or curve in a regular manner as crystal growth proceeds. Here we present a phase-field model that energetically favors twisting of the three-dimensional crystalline orientation about and along particular axes, allowing morphologies such as banded spherulites, curved dendrites, and "s"- or "c"-shaped needle crystals to be simulated. When twisting about the fast-growing crystalline axis is energetically favored and spherulitic growth conditions are imposed, crystallization occurs in the form of banded spherulites composed of radially oriented twisted crystalline fibers. Due to the lack of symmetry, twisting along the normal growth direction leads to heterochiral banded spherulites with opposite twist handedness in each half of the spherulite. When twisting is instead favored about the axis perpendicular to the plane of the substrate and along the normal growth direction under diffusion-limited single-crystalline growth conditions, crystallization occurs in the form of curved dendrites with uniformly rotating branches. We show that the rate at which the branches curve affects not only the morphology but also the overall kinetics of crystallization, as the total crystallized area at a given time is maximized for a finite turning rate.

  19. Simulation study of twisted crystal growth in organic thin films.

    PubMed

    Fang, Alta; Haataja, Mikko

    2015-10-01

    Many polymer and organic small-molecule thin films crystallize with microstructures that twist or curve in a regular manner as crystal growth proceeds. Here we present a phase-field model that energetically favors twisting of the three-dimensional crystalline orientation about and along particular axes, allowing morphologies such as banded spherulites, curved dendrites, and "s"- or "c"-shaped needle crystals to be simulated. When twisting about the fast-growing crystalline axis is energetically favored and spherulitic growth conditions are imposed, crystallization occurs in the form of banded spherulites composed of radially oriented twisted crystalline fibers. Due to the lack of symmetry, twisting along the normal growth direction leads to heterochiral banded spherulites with opposite twist handedness in each half of the spherulite. When twisting is instead favored about the axis perpendicular to the plane of the substrate and along the normal growth direction under diffusion-limited single-crystalline growth conditions, crystallization occurs in the form of curved dendrites with uniformly rotating branches. We show that the rate at which the branches curve affects not only the morphology but also the overall kinetics of crystallization, as the total crystallized area at a given time is maximized for a finite turning rate. PMID:26565254

  20. Perylene Diimide Based ``Nanofabric'' Thin Films for Organic Photovoltaic Cells

    NASA Astrophysics Data System (ADS)

    Carter, Austin; Park, June Hyoung; Min, Yong; Epstein, Arthur

    2011-03-01

    We report progress in using a perylene diimide (PDI) nanofabric as an effective electron accepting nanostructure for organic photovoltaics (OPV). A key challenge in OPV continues to be the recovery of electrons after charge separation due to the relatively poor mobility of C60 and related materials. A series of PDI compounds and complexes have been synthesized and used to fabricate nanofibers and thin films using solution and vacuum deposition techniques. Overlaping PDI-based nanofibers form a fast electron-transporting ``nanofabric'' that has been characterized (AFM, PL, UV-vis, etc.) and can be blended with electron donating materials. A solution-processible OPV configuration containing a nanofabric heterojunction (FHJ) of poly(3-hexylthiophene) and the PDI nanofabric was investigated. We observed a significant improvement in power-conversion efficiency due in part to expansion of the interfacial area and the presence of high mobility electron pathways to the LiF/Al electrode. This work is supported by the Wright Center for Photovoltaic Innovation and Commercialization, the Institute for Materials Research and the Center for Affordable Nanoengineering of Polymeric Biomedical Devices.

  1. Hysteresis in pentacene-based organic thin-film transistors

    NASA Astrophysics Data System (ADS)

    Gu, Gong; Kane, Michael G.

    2006-08-01

    Memory effects are commonly seen in organic thin-film transistor (OTFT) characteristics. In the absence of memory effects associated with the gate dielectric, the hysteresis in p-channel pentacene-based OTFTs, as measured in air and under illumination, was found to be dominated by trapped electrons, rather than trapped holes, in the semiconductor. The responsible acceptor type traps have very long lifetime. The immobile, previously stored negative charge requires extra holes to balance it, resulting in early establishment of the channel and extra drain current. This model is unique in that it discusses the majority carrier population influenced by trapped charge opposite in sign to the majority carriers in a simple electrostatic manner, to explain history dependence. The model was supported by drain current transient decay data. This memory effect is ambient and illumination sensitive. We studied the presence or absence of this effect under various ambient and illumination conditions, and found the responsible acceptor type traps mostly extrinsic and their formation reversible. Efforts were taken in the quantitative analysis to exclude the bias stress effect from the memory effect due to the charged acceptors.

  2. A novel dispersive solid-phase extraction method using metal-organic framework MIL-101 as the adsorbent for the analysis of benzophenones in toner.

    PubMed

    Li, Ning; Zhu, Quanfei; Yang, Yang; Huang, Jianlin; Dang, Xueping; Chen, Huaixia

    2015-01-01

    Metal-organic frameworks (MOFs) have been paid widespread attention in the field of adsorption and separation materials due to its porosity, large specific surface area, unsaturated metal-ligand sites and structural diversity. In this study, the green powder MIL-101 was synthesized and used for the extraction of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone from toner samples for the first time. The synthesized MIL-101 was characterized by X-ray diffraction, scanning electron microscopy, thermogravimetry and nitrogen adsorption porosimetry. The MIL-101 was applied as the dispersive solid phase extraction (DSPE) adsorbent for the extraction and preconcentration of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone from toner samples. The extraction conditions were investigated. Under the optimized conditions, a DSPE-HPLC method for the determination of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone was developed. The method yielded a linear calibration curve in the concentration ranges from 4.0 to 3500 μg L(-1) for the three analytes in toner samples with regression coefficients (r(2)) of 0.9992, 0.9999 and 0.9990, respectively. Limits of detection were 1.2, 1.2 and 0.9 μg L(-1), respectively. Both the intra-day and inter-day precisions (RSDs) were <10%. PMID:25476369

  3. Effect of the adsorbate (Bromacil) equilibrium concentration in water on its adsorption on powdered activated carbon. Part 3: Competition with natural organic matter.

    PubMed

    Al Mardini, Fadi; Legube, Bernard

    2010-10-15

    This study (part 3) was carried out to investigate the effect of the natural organic matter (NOM) concentration on Bromacil (pesticide) adsorption on powdered activated carbon (PAC) in the same experimental conditions as in our previous studies (parts 1 and 2). Our previous findings showed that Bromacil adsorption in buffered pure water (pH 7.8) occurred at two types of site. In the presence of NOM (three kinds), we noted a significant reduction in Bromacil adsorption capacities due to the competitive effects exerted by NOM. Highly reactive sites (or pores) in PAC appeared to be blocked by NOM adsorption, as demonstrated by the application of a pseudo-single solute isotherm and of the simplified ideal adsorbed solution theory (IAST), regardless of the initial Bromacil and NOM concentrations. The competing effect of low-molecular weight NOM was found to be greater than the competing effect of high-molecular weight NOM. The pseudo-second order surface-reaction model fitted Bromacil adsorption particularly well, even in the presence of NOM. However, the adsorption-kinetic constant values were found to be independent of the aqueous equilibrium concentration of the target compound, contrary to that observed in pure water. The kinetic data thus confirmed that high reactivity PAC sites were blocked by NOM adsorption. A practical approach concluded this work. PMID:20619963

  4. Magnetic metal-organic nanotubes: An adsorbent for magnetic solid-phase extraction of polychlorinated biphenyls from environmental and biological samples.

    PubMed

    Li, Qiu-Lin; Wang, Lei-Lei; Wang, Xia; Wang, Ming-Lin; Zhao, Ru-Song

    2016-06-01

    A new type of three-dimensional, echinus-like magnetic Fe3O4 @ cobalt(Ⅱ)-based metal-organic nanotube (Fe3O4 @ Co-MONT) yolk-shell microspheres, have been designed and synthesized for the first time. Fe3O4 @ Co-MONTs yolk-shell microspheres were characterized by scanning electron micrographs, transmission electron microscopy, Fourier transform infrared spectra, X-ray diffraction, and vibrating sample magnetometry. The feasibility of the new material for use as an absorbent was investigated for magnetic solid phase-extraction (MSPE) of polychlorinated biphenyls (PCBs) from environmental water samples and biological samples. The Plackett-Burman design and Box-Behnken design were used to determine and optimize the extraction parameters influencing the extraction efficiency through response surface methodology. Under the optimized conditions, the developed method showed good linearity within the range of 5-1000ngL(-1), low limits of detection (0.31-0.49ngL(-1)), and good reproducibility (RSD<10%). The proposed method was successfully applied for the analysis of PCBs in real environmental water samples. These results demonstrated that Fe3O4 @ Co-MONTs is a promising adsorbent material for the MSPE of PCBs at trace levels from environmental water samples and biological samples. PMID:27156750

  5. Magnetic porous carbon derived from a Zn/Co bimetallic metal-organic framework as an adsorbent for the extraction of chlorophenols from water and honey tea samples.

    PubMed

    Li, Menghua; Wang, Junmin; Jiao, Caina; Wang, Chun; Wu, Qiuhua; Wang, Zhi

    2016-05-01

    A novel magnetic porous carbon derived from a bimetallic metal-organic framework, Zn/Co-MPC, was prepared by introducing cobalt into ZIF-8. Magnetic porous carbon that possesses magnetic properties and a large specific surface area was firstly fabricated by the direct carbonization of Zn/Co-ZIF-8. The prepared magnetic porous carbon material was characterized by scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, N2 adsorption, and vibrating sample magnetometry. The prepared magnetic porous carbon was used as a magnetic solid-phase extraction adsorbent for the enrichment of chlorophenols from water and honey tea samples before high-performance liquid chromatography analysis. Several experimental parameters that could influence the extraction efficiency were investigated and optimized. Under the optimum conditions, good linearities (r > 0.9957) for all calibration curves were obtained with low limits of detection, which are in the range of 0.1-0.2 ng mL(-1) for all the analytes. The results showed that the prepared magnetic porous carbon had an excellent adsorption capability toward the target analytes. PMID:26991637

  6. Adsorption of Polyethylene from Solution onto Starch Film Surfaces

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Since starch adsorbs onto polyethylene (PE) surfaces from cooled solutions of jet cooked starch, this study was carried out to determine whether adsorption of PE onto hydrophilic starch film surfaces would also take place if starch films were placed in hot solutions of PE in organic solvents, and th...

  7. Organic Solar Cells Based on Electrodeposited Polyaniline Films

    NASA Astrophysics Data System (ADS)

    Inoue, Kei; Akiyama, Tsuyoshi; Suzuki, Atsushi; Oku, Takeo

    2012-04-01

    Polyaniline thin films as hole transporting layers were fabricated on transparent indium-tin-oxide electrodes by electrodeposition of aniline in an aqueous H2SO4 electrolyte solution. Emerald-green polyaniline films were obtained, which showed stable redox waves. A mixed solution of polythiophene and fullerene derivative was spin-coated onto the electrodeposited polyaniline film. After the modification of titanium oxide film on the surface of the polythiophene/fullerene layer, an aluminum electrode was fabricated by vacuum deposition. The obtained solar cells generated stable photocurrent and photovoltage under light illumination.

  8. Chemical and biological sensing with organic thin-film transistors

    NASA Astrophysics Data System (ADS)

    Mabeck, Jeffrey Todd

    Organic thin-film transistors (OTFTs) offer a great deal of promise for applications in chemical and biological sensing where there is a demand for small, portable, and inexpensive sensors. OTFTs have many advantages over other types of sensors, including low-cost fabrication, straightforward miniaturization, simple instrumentation, and inherent signal amplification. This dissertation examines two distinct types of OTFTs: organic field-effect transistors (OFETs) based on pentacene, and organic electrochemical transistors (OECTs) based on poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). The bulk of the previous work on sensing with OFETs has focused on gas sensing, and this dissertation contributes to this body of work by briefly treating the large, reversible response of pentacene OFETs to humidity. However, there are many applications where the analyte of interest must be detected in an aqueous environment rather than a gaseous environment, and very little work has been done in this area for OFETs. Therefore, the integration of pentacene OFETs with microfluidics is treated in detail. Using poly(dimethylsiloxane) (PDMS) microfluidic channels to confine aqueous solutions over the active region of pentacene transistors, it is demonstrated that the current-voltage characteristics remain stable under aqueous flow with a decrease in mobility of ˜30% compared to its value when dry. The operation of PEDOT:PSS transistors is also treated in detail. It is demonstrated that their transistor behavior cannot be attributed solely to a field effect and that ion motion is key to the switching mechanism. It is also demonstrated that simple glucose sensors based on PEDOT:PSS OECTs are sensitive to low glucose concentrations below 1 mM, therefore showing promise for potential application in the field of noninvasive glucose monitoring for diabetic patients using saliva rather than blood samples. Furthermore, a novel microfluidic gating technique has been

  9. High flux thin film nanocomposite membranes based on metal-organic frameworks for organic solvent nanofiltration.

    PubMed

    Sorribas, Sara; Gorgojo, Patricia; Téllez, Carlos; Coronas, Joaquín; Livingston, Andrew G

    2013-10-01

    Thin-film nanocomposite membranes containing a range of 50-150 nm metal-organic framework (MOF) nanoparticles [ZIF-8, MIL-53(Al), NH2-MIL-53(Al) and MIL-101(Cr)] in a polyamide (PA) thin film layer were synthesized via in situ interfacial polymerization on top of cross-linked polyimide porous supports. MOF nanoparticles were homogeneously dispersed in the organic phase containing trimesoyl chloride prior to the interfacial reaction, and their subsequent presence in the PA layer formed was inferred by a combination of contact angle measurements, FT-IR spectroscopy, SEM, EDX, XPS, and TEM. Membrane performance in organic solvent nanofiltration was evaluated on the basis of methanol (MeOH) and tetrahydrofuran (THF) permeances and rejection of styrene oligomers (PS). The effect of different post-treatments and MOF loadings on the membrane performance was also investigated. MeOH and THF permeance increased when MOFs were embedded into the PA layer, whereas the rejection remained higher than 90% (molecular weight cutoff of less than 232 and 295 g·mol(-1) for MeOH and THF, respectively) in all membranes. Moreover, permeance enhancement increased with increasing pore size and porosity of the MOF used as filler. The incorporation of nanosized MIL-101(Cr), with the largest pore size of 3.4 nm, led to an exceptional increase in permeance, from 1.5 to 3.9 and from 1.7 to 11.1 L·m(-2)·h(-1)·bar(-1) for MeOH/PS and THF/PS, respectively. PMID:24044635

  10. Protection of MoO{sub 3} high work function by organic thin film

    SciTech Connect

    Wang, Chenggong; Irfan, Irfan; Gao, Yongli

    2014-11-03

    The effects of air exposure are investigated for molybdenum trioxide (MoO{sub 3}) covered with organic thin films using ultraviolet photoemission spectroscopy. It is found that the severe drop of the work function of MoO{sub 3} by air exposure is substantially reduced by the organic thin films. Both CuPc and C{sub 60} are used for the investigations. The results indicate that the MoO{sub 3} surface can be passivated by approximately two monolayers of organic thin films against exposure to air.