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Sample records for adsorbed polymer layer

  1. Structure of polymer layers adsorbed from concentrated solutions

    NASA Astrophysics Data System (ADS)

    Auvray, Loïc; Auroy, Philippe; Cruz, Margarida

    1992-06-01

    We study by neutron scattering the interfacial strucuture of poly(dimethylsiloxane) layers irreversibly adsorbed from concentrated solutions or melts. We first measure the thickness h of the layers swollen by a good solvent as a function of the chain polymerisation index N and of the polymer volume fraction in the initial solution Φ. The relation h ≈ N^{0.8}Φ^{0.3}, recently predicted from an analogy between irreversibly adsorbed layers and grafted polymer brushes, describes well our results. We can therefore deduce that there is at least one large loop of about N monomers per adsorbed chain. We also study the shape of the polymer concentration profile in the layers by measuring on two samples the polymer-solid partial structure factor, that is proportional to the Fourier transform of the profile. The model of pseudobrushes predicts a concentration decay varying with the distance of the wall z as z^{-2/5}. This power law profile accounts quantitatively for the angular variation of the polymer-solid cross structure factor but it is difficult to distinguish it without anbiguity from less singular profiles. It implies that the adsorption of PDMS onto silica is sufficiently strong and fast to quench completely the loop distribution in the initial layer. Nous étudions par diffusion de neutrons la structure interfaciale de couches de poly(diméthylsiloxane) irréversiblement adsorbées sur de la silice à partir de solutions semidiluées et de fondus. Nous mesurons d'abord l'épaisseur h des couches gonflées par un bon solvant en fonction du degré de polymérisation des chaînes N et de la fraction volumique dans la solution initiale Φ. La relation h≈ N^{0.8}Φ^{0.3} récemment prédite à partir de l'analogie entre couches irréversiblement adsorbées et brosses de polymères greffés décrit bien nos résultats. Nous en déduisons qu'il existe au moins une grande boucle d'environ N monomères par chaîne adsorbée. Nous étudions aussi la forme du profil de

  2. The origin and characterization of conformational heterogeneity in adsorbed polymer layers

    NASA Astrophysics Data System (ADS)

    Douglas, Jack F.; Schneider, Hildegard M.; Frantz, Peter; Lipman, Robert; Granick, Steve

    1997-09-01

    The equilibration of polymer conformations tends to be sluggish in polymer layers adsorbed onto highly attractive substrates, so the structure of these layers must be understood in terms of the layer growth process rather than equilibrium theory. Initially adsorbed chains adopt a highly flattened configuration while the chains which arrive later must adapt their configurations to the increasingly limited space available for adsorption. Thus, the chains adsorbed in the late stage of deposition are more tenuously attached to the surface. This type of non-equilibrium growth process is studied for polymethylmethacrylate (PMMA) adsorbed on oxidized silicon where the segmental attraction is strong (0953-8984/9/37/005/img7/segment) and for polystyrene (PS) adsorbed on oxidized silicon from a carbon tetrachloride solution where the segmental attraction is relatively weak (0953-8984/9/37/005/img8/segment). Measurements were based on Fourier transform infrared spectroscopy in attenuated total reflection (FTIR - ATR). In both cases, the chains arriving first adsorbed more tightly, became flattened (as measured by the dichroic ratio), and occupied a disproportionately large fraction of the surface. This non-uniform structure persisted indefinitely for the strongly adsorbed PMMA chains, while the PS chains exhibited a gradual evolution, presumably reflecting an equilibration of the adsorbed layer occurring after long times. On the theoretical side, the initial heterogeneity of these adsorbed polymer layers is modelled using a random sequential adsorption (RSA) model where the size of the adsorbing species is allowed to adapt to the surface space available at the time of adsorption. The inhomogeneity in the size of adsorbing species (hemispheres) in this model is similar to the distribution of chain contacts in our measurements on adsorbed polymer layers. Owing to extensive variance around the mean, conformations having the mean number of chain contacts are least probable, which

  3. Conformational properties of an adsorbed charged polymer.

    PubMed

    Cheng, Chi-Ho; Lai, Pik-Yin

    2005-06-01

    The behavior of a strongly charged polymer adsorbed on an oppositely charged surface of a low-dielectric constant is formulated by the functional integral method. By separating the translational, conformational, and fluctuational degrees of freedom, the scaling behaviors for both the height of the polymer and the thickness of the diffusion layer are determined. Unlike the results predicted by scaling theory, we identified the continuous crossover from the weak compression to the compression regime. All the analytical results are found to be consistent with Monte Carlo simulations. Finally, an alternative (operational) definition of a charged polymer adsorption is proposed. PMID:16089715

  4. The persistence length of adsorbed dendronized polymers.

    PubMed

    Grebikova, Lucie; Kozhuharov, Svilen; Maroni, Plinio; Mikhaylov, Andrey; Dietler, Giovanni; Schlüter, A Dieter; Ullner, Magnus; Borkovec, Michal

    2016-07-21

    The persistence length of cationic dendronized polymers adsorbed onto oppositely charged substrates was studied by atomic force microscopy (AFM) and quantitative image analysis. One can find that a decrease in the ionic strength leads to an increase of the persistence length, but the nature of the substrate and of the generation of the side dendrons influence the persistence length substantially. The strongest effects as the ionic strength is being changed are observed for the fourth generation polymer adsorbed on mica, which is a hydrophilic and highly charged substrate. However, the observed dependence on the ionic strength is much weaker than the one predicted by the Odijk, Skolnik, and Fixman (OSF) theory for semi-flexible chains. Low-generation polymers show a variation with the ionic strength that resembles the one observed for simple and flexible polyelectrolytes in solution. For high-generation polymers, this dependence is weaker. Similar dependencies are found for silica and gold substrates. The observed behavior is probably caused by different extents of screening of the charged groups, which is modified by the polymer generation, and to a lesser extent, the nature of the substrate. For highly ordered pyrolytic graphite (HOPG), which is a hydrophobic and weakly charged substrate, the electrostatic contribution to the persistence length is much smaller. In the latter case, we suspect that specific interactions between the polymer and the substrate also play an important role. PMID:27353115

  5. Theory of colloid depletion stabilization by unattached and adsorbed polymers.

    PubMed

    Semenov, A N; Shvets, A A

    2015-12-01

    The polymer-induced forces between colloidal particles in a semidilute or concentrated polymer solution are considered theoretically. This study is focussed on the case of partially adsorbing colloidal surfaces involving some attractive centers able to trap polymer segments. In the presence of free polymers the particles are covered by self-assembled fluffy layers whose structure is elucidated. It is shown that the free-polymer-induced interaction between the particles is repulsive at distances exceeding the polymer correlation length, and that this depletion repulsion can be strongly enhanced due to the presence of fluffy layers. This enhanced depletion stabilization mechanism (which works in tandem with a more short-range steric repulsion of fluffy layers) can serve on its own to stabilize colloidal dispersions. More generally, we identify three main polymer-induced interaction mechanisms: depletion repulsion, depletion attraction, and steric repulsion. Their competition is analyzed both numerically and analytically based on an asymptotically rigorous mean-field theory. It is shown that colloid stabilization can be achieved by simply increasing the molecular weight of polymer additives, or by changing their concentration.

  6. The persistence length of adsorbed dendronized polymers

    NASA Astrophysics Data System (ADS)

    Grebikova, Lucie; Kozhuharov, Svilen; Maroni, Plinio; Mikhaylov, Andrey; Dietler, Giovanni; Schlüter, A. Dieter; Ullner, Magnus; Borkovec, Michal

    2016-07-01

    The persistence length of cationic dendronized polymers adsorbed onto oppositely charged substrates was studied by atomic force microscopy (AFM) and quantitative image analysis. One can find that a decrease in the ionic strength leads to an increase of the persistence length, but the nature of the substrate and of the generation of the side dendrons influence the persistence length substantially. The strongest effects as the ionic strength is being changed are observed for the fourth generation polymer adsorbed on mica, which is a hydrophilic and highly charged substrate. However, the observed dependence on the ionic strength is much weaker than the one predicted by the Odijk, Skolnik, and Fixman (OSF) theory for semi-flexible chains. Low-generation polymers show a variation with the ionic strength that resembles the one observed for simple and flexible polyelectrolytes in solution. For high-generation polymers, this dependence is weaker. Similar dependencies are found for silica and gold substrates. The observed behavior is probably caused by different extents of screening of the charged groups, which is modified by the polymer generation, and to a lesser extent, the nature of the substrate. For highly ordered pyrolytic graphite (HOPG), which is a hydrophobic and weakly charged substrate, the electrostatic contribution to the persistence length is much smaller. In the latter case, we suspect that specific interactions between the polymer and the substrate also play an important role.The persistence length of cationic dendronized polymers adsorbed onto oppositely charged substrates was studied by atomic force microscopy (AFM) and quantitative image analysis. One can find that a decrease in the ionic strength leads to an increase of the persistence length, but the nature of the substrate and of the generation of the side dendrons influence the persistence length substantially. The strongest effects as the ionic strength is being changed are observed for the fourth

  7. Novel adhesion properties of irreversibly adsorbed polymer chains

    NASA Astrophysics Data System (ADS)

    Chen, Zhizhao; Sen, Mani; Cheung, Justin; Barkley, Deborah; Jiang, Naisheng; Zeng, Wenduo; Endoh, Maya K.; Koga, Tadanori

    The stability of thin polymer films on solids is of vital interest in traditional technologies and in new emerging nanotechnologies. We recently found that nanoscale structures of polymer chains adsorbed onto a silicon (Si) substrate (``adsorbed nanolayers'') play a crucial role in the thermal stability of the film. To understand the adhesion mechanism at the adsorbed polymer-free polymer interface, we mimicked the interface by preparing bilayers where a 200 nm-thick polymer film and an adsorbed nanolayer, both prepared on Si, were pressed together at high temperature. The bilayers were then subjected to an adhesion test by measuring the critical normal force required to separate the two films. Polystyrene was used as a model. The results are intriguing as they show an absence of adhesion between the ``flattened'' adsorbed chains, which lie flat on the solid, and the chemically identical free chains. On the other hand, the ``loosely adsorbed'' polymer chains, which are formed as a result of limited adsorption space on the solid surface, do display a degree of adhesion with the bulk polymer. We postulate that the loosely adsorbed chains act as ``connectors'' which promote adhesion effectively across the solid-polymer interface. We acknowledge the financial support from NSF Grant No. CMMI-1332499.

  8. Interlocking order parameter fluctuations in structural transitions between adsorbed polymer phases.

    PubMed

    Martins, Paulo H L; Bachmann, Michael

    2016-01-21

    By means of contact-density chain-growth simulations of a simple coarse-grained lattice model for a polymer grafted at a solid homogeneous substrate, we investigate the complementary behavior of the numbers of surface-monomer and monomer-monomer contacts under various solvent and thermal conditions. This pair of contact numbers represents an appropriate set of order parameters that enables the distinct discrimination of significantly different compact phases of polymer adsorption. Depending on the transition scenario, these order parameters can interlock in perfect cooperation. The analysis helps understand the transitions from compact filmlike adsorbed polymer conformations into layered morphologies and dissolved adsorbed structures, respectively, in more detail.

  9. Layered plasma polymer composite membranes

    DOEpatents

    Babcock, W.C.

    1994-10-11

    Layered plasma polymer composite fluid separation membranes are disclosed, which comprise alternating selective and permeable layers for a total of at least 2n layers, where n is [>=]2 and is the number of selective layers. 2 figs.

  10. Monte Carlo lattice models for adsorbed polymer conformation

    NASA Technical Reports Server (NTRS)

    Good, B. S.

    1985-01-01

    The adhesion between a polymer film and a metal surface is of great technological interest. However, the prediction of adhesion and wear properties of polymer coated metals is quite difficult because a fundamental understanding of the polymer surface interaction does not yet exist. A computer model for the conformation of a polymer molecule adsorbed on a surface is discussed. The chain conformation is assumed to be described by a partially directed random walk on a three dimensional simple cubic lattice. An attractive surface potential is incorporated into the model through the use of a random walk step probability distribution that is anisotropic in the direction normal to the attractive surface. The effects of variations in potential characteristics are qualitatively included by varying both the degree of anisotropy of the step distribution and the range of the anisotropy. Polymer conformation is characterized by the average end to end distance, average radius of gyration, and average number of chain segments adsorbed on the surface.

  11. Secondary polymer layered impregnated tile

    NASA Technical Reports Server (NTRS)

    Tran, Huy K. (Inventor); Rasky, Daniel J. (Inventor); Szalai, Christine E. (Inventor); Carroll, Joseph A. (Inventor); Hsu, Ming-ta S. (Inventor)

    2005-01-01

    A low density organic polymer impregnated preformed fibrous ceramic article includes a plurality of layers. A front layer includes ceramic fibers or carbon fibers or combinations of ceramic fibers and carbon fibers, and is impregnated with an effective amount of at least one organic polymer. A middle layer includes polymer impregnated ceramic fibers. A back layer includes ceramic fibers or carbon fibers or combinations of ceramic fibers and carbon fibers, and is impregnated with an effective amount of at least one low temperature pyrolyzing organic polymer capable of decomposing without depositing residues.

  12. Modeling diffusion of adsorbed polymer with explicit solvent.

    PubMed

    Desai, Tapan G; Keblinski, Pawel; Kumar, Sanat K; Granick, Steve

    2007-05-25

    Computer simulations of a polymer chain of length N strongly adsorbed at the solid-liquid interface in the presence of explicit solvent are used to delineate the factors affecting the N dependence of the polymer lateral diffusion coefficient, D(||). We find that surface roughness has a large influence, and D(||) scales as D(||) approximately N(-x), with x approximately 3/4 and x approximately 1 for ideal smooth and corrugated surfaces, respectively. The first result is consistent with the hydrodynamics of a "particle" of radius of gyration R(G) approximately N(nu) (nu=0.75) translating parallel to a planar interface, while the second implies that the friction of the adsorbed chains dominates. These results are discussed in the context of recent measurements.

  13. Removal of acutely hazardous pharmaceuticals from water using multi-template imprinted polymer adsorbent.

    PubMed

    Venkatesh, Avinash; Chopra, Nikita; Krupadam, Reddithota J

    2014-05-01

    Molecularly imprinted polymer adsorbent has been prepared to remove a group of recalcitrant and acutely hazardous (p-type) chemicals from water and wastewaters. The polymer adsorbent exhibited twofold higher adsorption capacity than the commercially used polystyrene divinylbenzene resin (XAD) and powdered activated carbon adsorbents. Higher adsorption capacity of the polymer adsorbent was explained on the basis of high specific surface area formed during molecular imprinting process. Freundlich isotherms drawn showed that the adsorption of p-type chemicals onto polymer adsorbent was kinetically faster than the other reference adsorbents. Matrix effect on adsorption of p-type chemicals was minimal, and also polymer adsorbent was amenable to regeneration by washing with water/methanol (3:1, v/v) solution. The polymer adsorbent was unaltered in its adsorption capacity up to 10 cycles of adsorption and desorption, which will be more desirable in cost reduction of treatment compared with single-time-use activated carbon. PMID:24499987

  14. Structural features of polymer adsorbent LiChrolut EN and interfacial behavior of water and water/organic mixtures.

    PubMed

    Gun'ko, V M; Turov, V V; Zarko, V I; Nychiporuk, Y M; Goncharuk, E V; Pakhlov, E M; Yurchenko, G R; Kulik, T V; Palyanytsya, B B; Borodavka, T V; Krupskaya, T V; Leboda, R; Skubiszewska-Zieba, J; Osovskii, V D; Ptushinskii, Y G; Turov, A V

    2008-07-01

    The structural and adsorption characteristics of polymer adsorbent LiChrolut EN and the behavior of adsorbed water and water/organic mixtures were studied using adsorption, microcalorimetry, transmission and scanning electron microscopy, mass spectrometry, infrared spectroscopy, 1H NMR spectroscopy with layer-by-layer freezing-out of liquids (190-273 K), and thermally stimulated depolarization current method (90-265 K). This adsorbent is characterized by large specific surface area (approximately 1500 m2/g) and pore volume (0.83 cm3/g) with a major contribution of narrow pores (R<10 nm) of a complicated shape (long hysteresis loop is in nitrogen adsorption-desorption isotherm). The adsorbent includes aromatic and aliphatic structures and oxygen-containing functionalities and can effectively adsorb organics and water/organic mixtures. On co-adsorption of water and organics (dimethyl sulfoxide, chloroform, methane), there is a weak influence of one on another adsorbate due to their poor mixing in pores. Weakly polar chloroform displaces a fraction of water from narrow pores. These effects can explain high efficiency of the adsorbent in solid-phase extraction of organics from aqueous solutions. The influence of structural features of several carbon and polymer adsorbents on adsorbed nitrogen, water and water/organics is compared on the basis of the adsorption and 1H NMR data. PMID:18440015

  15. Reduced colloidal repulsion imparted by adsorbed polymer of particle dimensions.

    PubMed

    Wen, Yu Ho; Lin, Po-Chang; Lee, Chun Yi; Hua, Chi Chung; Lee, Tai-Chou

    2010-09-01

    This work investigated the detailed interparticle interactions in a concentrated polymer-coated colloidal system in which the bare colloidal particles and the adsorbed polymers are of comparable size and, hence, the polymer adsorption cannot be foreseen to induce repulsive or attractive interactions. Specifically, poly(ethylene oxide) (PEO) chains (R(g) approximately 10nm) adsorbed onto fine silica colloidal particles (SAXS-determined radius approximately 7.4nm; width of log-normal size distribution approximately 0.28) were considered as a model system, for which the impact of a small amount of polymer adsorption (0.18mg/m(2)) in controlling the interactions of the PEO-coated silica particles was systematically explored by analyzing the small-angle X-ray scattering (SAXS) data against three interaction potentials-the equivalent hard-sphere (EHS) potential, the Hayter-Penfold-Yukawa (HPY) potential, and the square-well (SW) potential. Moreover, the SAXS analysis was enforced by dynamic light scattering (DLS) for predetermining the adsorption behavior, as well as for evaluating the possibility of polymer bridging. Under a dilute condition, the DLS analysis showed no sign of forming colloidal multiplets. In concentrated dispersions, both the HPY and SW potentials clearly revealed a systematic decrease of colloidal repulsions with increased PEO coverage, ascribed to a partially "screened" electrostatic interaction and/or the formation of PEO-bridged silica doublets. The present findings have interesting implications for controlling the colloidal interactions and microstructures of fine polymer-coated particles in dense or condensed phases.

  16. Untangleing the effects of chain rigidity on the structure and dynamics of strongly adsorbed polymer melts

    SciTech Connect

    Carrillo, Jan-Michael Y.; Cheng, Shiwang; Kumar, Rajeev; Goswami, Monojoy; Sokolov, Alexei P; Sumpter, Bobby G.

    2015-06-11

    Here, we present a detailed analysis of coarse-grained molecular dynamics simulations of semiflexible polymer melts in contact with a strongly adsorbing substrate. We have characterized the segments in the interfacial layer by counting the number of trains, loops, tails and unadsorbed segments. For more rigid chains, a tail and an adsorbed segment (a train) dominate while loops are more prevalent in more flexible chains. The tails exhibit a non-uniformly stretched conformation akin to the polydispersed pseudobrush envisioned by Guiselin. To probe the dynamics of the segments we computed the layer z-resolved intermediate coherent collective dynamics structure factor, S(q, t, z), mean-square displacement of segments, and the 2nd Legendre polynomial of the time-autocorrelation of unit bond vectors, 2[ni(t,z)•ni(0,z)]>. Our results show that segmental dynamics is slower for stiffer chains and there is a strong correlation between the structure and dynamics in the interfacial layer. There is no glassy layer, and the slowing down in dynamics of stiffer chains in the adsorbed region can be attributed to the densification and the more persistent layering of segments.

  17. Untangleing the effects of chain rigidity on the structure and dynamics of strongly adsorbed polymer melts

    DOE PAGES

    Carrillo, Jan-Michael Y.; Cheng, Shiwang; Kumar, Rajeev; Goswami, Monojoy; Sokolov, Alexei P; Sumpter, Bobby G.

    2015-06-11

    Here, we present a detailed analysis of coarse-grained molecular dynamics simulations of semiflexible polymer melts in contact with a strongly adsorbing substrate. We have characterized the segments in the interfacial layer by counting the number of trains, loops, tails and unadsorbed segments. For more rigid chains, a tail and an adsorbed segment (a train) dominate while loops are more prevalent in more flexible chains. The tails exhibit a non-uniformly stretched conformation akin to the polydispersed pseudobrush envisioned by Guiselin. To probe the dynamics of the segments we computed the layer z-resolved intermediate coherent collective dynamics structure factor, S(q, t, z),more » mean-square displacement of segments, and the 2nd Legendre polynomial of the time-autocorrelation of unit bond vectors, 2[ni(t,z)•ni(0,z)]>. Our results show that segmental dynamics is slower for stiffer chains and there is a strong correlation between the structure and dynamics in the interfacial layer. There is no glassy layer, and the slowing down in dynamics of stiffer chains in the adsorbed region can be attributed to the densification and the more persistent layering of segments.« less

  18. Dynamics in Adsorbed Homopolymer Layers: Entanglements and Osmotic Effects

    NASA Astrophysics Data System (ADS)

    Santore, Maria; Mubarekyan, Ervin

    2001-03-01

    This work seeks the dynamic mechanism for the exchange of homopolymer chains between a dilute solution and a layer adsorbed at the solid-liquid interface. With the model system of polyethylene oxide (PEO) adsorbed onto silica from aqueous solution, it is shown that the behavior of saturated interfaces compared to starved layers reveals an interesting trend: The characteristic self exchange time is dependent only on coverage, not molecular weight, for chains of 100K or less. Therefore, it is concluded that classical entanglements do not play a role below 100K. For all molecular weights, when the coverage of 0.2 mg/m2 is exceeded, the interfacial dynamics become slow. At lower coverages, chains lie flat in train, with no loops or tails, and no lateral interactions either. The onset of slow dynamics at higher coverages may be a result of both surface crowding and the resistance of loops and tails to new chains approaching the layer.

  19. Nanorheology of adsorbed polymer chains immersed in pure solvent.

    PubMed

    Lapique, Fabrice; Montfort, Jean Pierre; Derail, Christophe

    2015-06-01

    Long linear chains of polybutadiene are adsorbed on the two surfaces of a surface force apparatus and immersed in pure tetradecane. The hydrodynamic force was measured by drainage experiments and by frequency sweeps at constant distances. We related the hydrodynamic thickness to the chain dimension. The complex modulus encompasses the shear modulus and, at distances lower than the hydrodynamic thickness, a compression modulus. The compression term was related to the static force which appears when the two adsorbed layers are overlapped. The complex shear modulus was interpreted by a two-components hydrodynamic model proposed by P. Sens et al. We first complemented the theoretical model. Then, our experimental data fit the proposed viscoelastic expressions in the entire range of distances. The storage modulus is supposed to be affected by a residue of free chains and by the dispersion of the loop lengths. PMID:26087919

  20. DPPG Liposomes Adsorbed on Polymer Cushions: Effect of Roughness on Amount, Surface Composition and Topography.

    PubMed

    Duarte, Andreia A; Botelho do Rego, Ana M; Salerno, Marco; Ribeiro, Paulo A; El Bari, Nezha; Bouchikhi, Benachir; Raposo, Maria

    2015-07-01

    The adsorption of intact liposomes onto solid supports is a fundamental issue when preparing systems with encapsulated biological molecules. In this work, the adsorption kinetic of 1,2-dipalmitoyl-sn-glycero-3-[phospho-rac-(1-glycerol)] (sodium salt) liposomes onto cushions prepared from commom polyelectrolytes by the layer-by-layer technique was investigated with the main objective of finding the surface conditions leading to the adsorption of intact liposomes. For this purpose, different cushion surface roughnesses were obtained by changing the number of cushion bilayers. The adsorbed amount per unit area was measured through quartz crystal microbalance, surface morphology was characterized by atomic force microscopy, and the surface composition was assessed by X-ray photoelectron spectroscopy. The results show that (1) the amount of adsorbed lipids depends on the number of cushion bilayers, (2) the cushions are uniformly covered by the adsorbed lipids, and (3) the surface morphology of polymer cushions tunes liposome rupture and its adsorption kinetics. The fraction of ruptured liposomes, calculated from the measured amount of adsorbed lipids, is a function of surface roughness together with other surface morphology parameters, namely the dominating in-plane spatial feature size, the fractal dimension, and other textural features as well as amplitude and hybrid parameters. PMID:26076391

  1. Influence of Polymers on the Crystal Growth Rate of Felodipine: Correlating Adsorbed Polymer Surface Coverage to Solution Crystal Growth Inhibition.

    PubMed

    Schram, Caitlin J; Taylor, Lynne S; Beaudoin, Stephen P

    2015-10-20

    The bioavailability of orally administered drugs that exhibit poor aqueous solubility can be enhanced with the use of supersaturating dosage forms. Stabilization of these forms by preventing or inhibiting crystallization in solution is an important area of study. Polymers can be used to stabilize supersaturated systems; however, the properties that impact their effectiveness as crystal growth rate inhibitors are not yet fully understood. In this study, the impact of various polymers on the crystal growth rate of felodipine and the conformation of these polymers adsorbed to crystalline felodipine was investigated in order to gain a mechanistic understanding of crystal growth inhibition. It was determined that polymer hydrophobicity impacted polymer adsorption as well as adsorbed polymer conformation. Polymer conformation impacts its surface coverage, which was shown to directly correlate to the polymer's effectiveness as a growth rate inhibitor. By modeling this correlation, it is possible to predict polymer effectiveness given the surface coverage of the polymer.

  2. Analytical phase diagrams for colloids and non-adsorbing polymer.

    PubMed

    Fleer, Gerard J; Tuinier, Remco

    2008-11-01

    We review the free-volume theory (FVT) of Lekkerkerker et al. [Europhys. Lett. 20 (1992) 559] for the phase behavior of colloids in the presence of non-adsorbing polymer and we extend this theory in several aspects: (i) We take the solvent into account as a separate component and show that the natural thermodynamic parameter for the polymer properties is the insertion work Pi(v), where Pi is the osmotic pressure of the (external) polymer solution and v the volume of a colloid particle. (ii) Curvature effects are included along the lines of Aarts et al. [J. Phys.: Condens. Matt. 14 (2002) 7551] but we find accurate simple power laws which simplify the mathematical procedure considerably. (iii) We find analytical forms for the first, second, and third derivatives of the grand potential, needed for the calculation of the colloid chemical potential, the pressure, gas-liquid critical points and the critical endpoint (cep), where the (stable) critical line ends and then coincides with the triple point. This cep determines the boundary condition for a stable liquid. We first apply these modifications to the so-called colloid limit, where the size ratio q(R)=R/a between the radius of gyration R of the polymer and the particle radius a is small. In this limit the binodal polymer concentrations are below overlap: the depletion thickness delta is nearly equal to R, and Pi can be approximated by the ideal (van't Hoff) law Pi=Pi(0)=phi/N, where phi is the polymer volume fraction and N the number of segments per chain. The results are close to those of the original Lekkerkerker theory. However, our analysis enables very simple analytical expressions for the polymer and colloid concentrations in the critical and triple points and along the binodals as a function of q(R). Also the position of the cep is found analytically. In order to make the model applicable to higher size ratio's q(R) (including the so-called protein limit where q(R)>1) further extensions are needed. We

  3. Concentration and saturation effects of tethered polymer chains on adsorbing surfaces

    NASA Astrophysics Data System (ADS)

    Descas, Radu; Sommer, Jens-Uwe; Blumen, Alexander

    2006-12-01

    We consider end-grafted chains at an adsorbing surface under good solvent conditions using Monte Carlo simulations and scaling arguments. Grafting of chains allows us to fix the surface concentration and to study a wide range of surface concentrations from the undersaturated state of the surface up to the brushlike regime. The average extension of single chains in the direction parallel and perpendicular to the surface is analyzed using scaling arguments for the two-dimensional semidilute surface state according to Bouchaud and Daoud [J. Phys. (Paris) 48, 1991 (1987)]. We find good agreement with the scaling predictions for the scaling in the direction parallel to the surface and for surface concentrations much below the saturation concentration (dense packing of adsorption blobs). Increasing the grafting density we study the saturation effects and the oversaturation of the adsorption layer. In order to account for the effect of excluded volume on the adsorption free energy we introduce a new scaling variable related with the saturation concentration of the adsorption layer (saturation scaling). We show that the decrease of the single chain order parameter (the fraction of adsorbed monomers on the surface) with increasing concentration, being constant in the ideal semidilute surface state, is properly described by saturation scaling only. Furthermore, the simulation results for the chains' extension from higher surface concentrations up to the oversaturated state support the new scaling approach. The oversaturated state can be understood using a geometrical model which assumes a brushlike layer on top of a saturated adsorption layer. We provide evidence that adsorbed polymer layers are very sensitive to saturation effects, which start to influence the semidilute surface scaling even much below the saturation threshold.

  4. Low-Friction Adsorbed Layers of a Triblock Copolymer Additive in Oil-Based Lubrication.

    PubMed

    Yamada, Shinji; Fujihara, Ami; Yusa, Shin-ichi; Tanabe, Tadao; Kurihara, Kazue

    2015-11-10

    The tribological properties of the dilute solution of an ABA triblock copolymer, poly(11-acrylamidoundecanoic acid)-block-poly(stearyl methacrylate)-block-poly(11-acrylamidoundecanoic acid (A5S992A5), in poly(α-olefin) (PAO) confined between mica surfaces were investigated using the surface forces apparatus (SFA). Friction force was measured as a function of applied load and sliding velocity, and the film thickness and contact geometry during sliding were analyzed using the fringes of equal chromatic order (FECO) in the SFA. The results were contrasted with those of confined PAO films; the effects of the addition of A5S992A5 on the tribological properties were discussed. The thickness of the A5S992A5/PAO system varied with time after surface preparation and with repetitive sliding motions. The thickness was within the range from 40 to 70 nm 1 day after preparation (the Day1 film), and was about 20 nm on the following day (the Day2 film). The thickness of the confined PAO film was thinner than 1.4 nm, indicating that the A5S992A5/PAO system formed thick adsorbed layers on mica surfaces. The friction coefficient was about 0.03 to 0.04 for the Day1 film and well below 0.01 for the Day2 film, which were 1 or 2 orders of magnitude lower than the values for the confined PAO films. The time dependent changes of the adsorbed layer thickness and friction properties should be caused by the relatively low solubility of A5S992A5 in PAO. The detailed analysis of the contact geometry and friction behaviors implies that the particularly low friction of the Day2 film originates from the following factors: (i) shrinkage of the A5S992A5 molecules (mainly the poly(stearyl methacrylate) blocks) that leads to a viscoelastic properties of the adsorbed layers; and (ii) the intervening PAO layer between the adsorbed polymer layers that constitutes a high-fluidity sliding interface. Our results suggest that the block copolymer having relatively low solubility in a lubricant base oil is

  5. Adsorbed layers and the origin of Amontons' laws

    NASA Astrophysics Data System (ADS)

    Robbins, Mark

    2000-03-01

    Three hundred years ago, Amontons wrote down phenomenogical friction laws that are still used today. They state that the friction is proportional to load, and independent of the dimensions of the contacting surfaces. The molecular underpinning of these laws has remained unclear. Indeed, exact analytic results and experiments in ultra-high vacuum indicate that the static friction between clean crystalline surfaces almost always vanishes in the thermodynamic limit. Of course any surface exposed to air is typically coated by a thin layer of hydrocarbons, water and other small molecules. Simulations are presented that show that these layers naturally produce static and kinetic friction forces that are consistent with Amontons' laws and other aspects of macroscopic experiments.(G. He, M. H. Muser and M. O. Robbins, Science 284, 1650 (1999).) For example, the friction is only weakly dependent on parameters that are not controlled in most experiments, such as the areal density of adsorbed molecules, their length, the orientation of the surfaces and the direction of sliding. The kinetic friction is of the same order as the static friction and varies only logarithmically with velocity.

  6. Surfactant induced aggregation behavior of Merocyanine-540 adsorbed on polymer coated positively charged gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Das, K.; Uppal, A.; Saini, R. K.

    2016-01-01

    Surfactant induced aggregation behavior of Merocyanine 540 adsorbed on polymer (PDD) coated gold nanoparticles (AuNP) is reported. The absorption band of the dye shifts to higher energy in the presence of free polymer and polymer coated AuNP implying aggregation. Addition of a negatively charged surfactant (SDS) induces multiple bands in the extinction spectrum of the dye adsorbed on nanoparticle surface. The highest (460 nm) and lowest (564 nm) energy bands of the dye become prominent at 10 and >50 μM SDS concentrations respectively (dye: 10 μM; AuNP: 100-200 pM). Based on earlier results the high energy band is likely to originate from dye aggregates and the low energy band is likely to originate from dye monomers. This is attributed to the interplay between polymer-surfactant and polymer-dye interactions at the AuNP surface. The extinction spectra of dye adsorbed at AuNP surface remain unaffected in the presence of a positively charged (CTAB) or a neutral surfactant (Tx-100), at low surfactant concentrations. However at higher surfactant concentrations (>60 μM) dye aggregation takes place which is attributed to dye-surfactant interactions. The fluorescence intensity of the dye quenched significantly but its lifetime increased in the presence of polymer coated AuNP. This is attributed to aggregation and reduction in the photoisomerization rate of the dye adsorbed on AuNP surface.

  7. Towards Understanding KOH Conditioning of Amidoxime-based Polymer Adsorbents for Sequestering Uranium from Seawater

    SciTech Connect

    Pan, Horng-Bin; Kuo, Li-Jung; Wood, Jordana R.; Strivens, Jonathan E.; Gill, Gary A.; Janke, C.; Wai, Chien M.

    2015-11-16

    Conditioning of polymer fiber adsorbents grafted with amidoxime and carboxylic acid groups is necessary to make the materials hydrophilic for sequestering uranium from seawater. Spectroscopic techniques were employed to study the effectiveness of the traditional KOH conditioning method (2.5% KOH at 80 oC) on recently developed high-surface-area amidoxime-based polymer fiber adsorbents developed at Oak Ridge National Laboratory. FTIR spectra reveal that the KOH conditioning process removes the proton from the carboxylic acids and also converts the amidoxime groups to carboxylate groups in the adsorbent. With prolonged KOH treatment (>1 hr) at 80 oC, physical damage to the adsorbent material occurs which can lead to a significant reduction in the adsorbent’s uranium adsorption capability in real seawater during extended exposure times (>21 days). The physical damage to the adsorbent can be minimized by lowering KOH conditioning temperature. For the high-surface-area amidoxime-based adsorbents, 20 min of conditioning in 2.5% KOH at 80 oC or 1 hr of conditioning in 2.5% KOH at 60 oC appears sufficient to achieve de-protonation of the carboxylic acid with minimal harmful effects to the adsorbent material. The use of NaOH instead of KOH can also reduce the cost of the base treatment process required for conditioning the amidoxime-based sorbents with minimal loss of adsorption capacity (≤ 7%).

  8. Activity of lactoperoxidase when adsorbed on protein layers.

    PubMed

    Haberska, Karolina; Svensson, Olof; Shleev, Sergey; Lindh, Liselott; Arnebrant, Thomas; Ruzgas, Tautgirdas

    2008-09-15

    Lactoperoxidase (LPO) is an enzyme, which is used as an antimicrobial agent in a number of applications, e.g., food technology. In the majority of applications LPO is added to a homogeneous product phase or immobilised on product surface. In the latter case, however, the measurements of LPO activity are seldom reported. In this paper we have assessed LPO enzymatic activity on bare and protein modified gold surfaces by means of electrochemistry. It was found that LPO rapidly adsorbs to bare gold surfaces resulting in an amount of LPO adsorbed of 2.9mg/m(2). A lower amount of adsorbed LPO is obtained if the gold surface is exposed to bovine serum albumin, bovine or human mucin prior to LPO adsorption. The enzymatic activity of the adsorbed enzyme is in general preserved at the experimental conditions and varies only moderately when comparing bare gold and gold surface pretreated with the selected proteins. The measurement of LPO specific activity, however, indicate that it is about 1.5 times higher if LPO is adsorbed on gold surfaces containing a small amount of preadsorbed mucin in comparison to the LPO directly adsorbed on bare gold.

  9. Atomic force microscopy study of the interaction between adsorbed poly(ethylene oxide) layers: effects of surface modification and approach velocity.

    PubMed

    McLean, Scott C; Lioe, Hadi; Meagher, Laurence; Craig, Vincent S J; Gee, Michelle L

    2005-03-15

    The interaction forces between layers of the triblock copolymer Pluronic F108 adsorbed onto hydrophobic radio frequency glow discharge (RFGD) thin film surfaces and hydrophilic silica, in polymer-free 0.15 M NaCl solution, have been measured using the atomic force microscope (AFM) colloid probe technique. Compression of Pluronic F108 layers adsorbed on the hydrophobic RFGD surfaces results in a purely repulsive force due to the steric overlap of the layers, the form of which suggests that the PEO chains adopt a brush conformation. Subsequent fitting of these data to the polymer brush models of Alexander-de Gennes and Milner, Witten, and Cates confirms that the adsorbed Pluronic F108 adsorbs onto hydrophobic surfaces as a polymer brush with a parabolic segment density profile. In comparison, the interaction between Pluronic F108 layers adsorbed on silica exhibits a long ranged shallow attractive force and a weaker steric repulsion. The attractive component is reasonably well described by van der Waals forces, but polymer bridging cannot be ruled out. The weaker steric component of the force suggests that the polymer is less densely packed on the surface and is less extended into solution, existing as polymeric isolated mushrooms. When the surfaces are driven together at high piezo ramp velocities, an additional repulsive force is measured, attributable to hydrodynamic drainage forces between the surfaces. In comparing theoretical predictions of the hydrodynamic force to the experimentally obtained data, agreement could only be obtained if the flow profile of the aqueous solution penetrated significantly into the polymer brush. This finding is in line with the theoretical predictions of Milner and provides further evidence that the segment density profile of the adsorbed polymer brush is parabolic. A velocity dependent additional stepped repulsive force, reminiscent of a solvation oscillatory force, is also observed when the adsorbed layers are compressed under high

  10. Polymer composite adsorbents using particles of molecularly imprinted polymers or aluminium oxide nanoparticles for treatment of arsenic contaminated waters.

    PubMed

    Önnby, L; Pakade, V; Mattiasson, B; Kirsebom, H

    2012-09-01

    Removal of As(V) by adsorption from water solutions was studied using three different synthetic adsorbents. The adsorbents, (a) aluminium nanoparticles (Alu-NPs, <50 nm) incorporated in amine rich cryogels (Alu-cryo), (b) molecular imprinted polymers (<38 μm) in polyacrylamide cryogels (MIP-cryo) and (c) thiol functionalised cryogels (SH-cryo) were evaluated regarding material characteristics and arsenic removal in batch test and continuous mode. Results revealed that a composite design with particles incorporated in cryogels was a successful means for applying small particles (nano- and micro- scale) in water solutions with maintained adsorption capacity and kinetics. Low capacity was obtained from SH-cryo and this adsorbent was hence excluded from the study. The adsorption capacities for the composites were 20.3 ± 0.8 mg/g adsorbent (Alu-cryo) and 7.9 ± 0.7 mg/g adsorbent (MIP-cryo) respectively. From SEM images it was seen that particles were homogeneously distributed in Alu-cryo and heterogeneously distributed in MIP-cryo. The particle incorporation increased the mechanical stability and the polymer backbones of pure polyacrylamide (MIP-cryo) were of better stability than the amine containing polymer backbone (Alu-cryo). Both composites worked well in the studied pH range of pH 2-8. Adsorption tested in real wastewater spiked with arsenic showed that co-ions (nitrate, sulphate and phosphate) affected arsenic removal for Alu-cryo more than for MIP-cryo. Both composites still adsorbed well in the presence of counter-ions (copper and zinc) present at low concentrations (μg/l). The unchanged and selective adsorption in realistic water observed for MIP-cryo was concluded to be due to a successful imprinting, here controlled using a non-imprinted polymer (NIP). A development of MIP-cryo is needed, considering its low adsorption capacity.

  11. Analytic liquid-state theory of the interactions between colloids mediated by reversibly adsorbed polymers.

    PubMed

    Chervanyov, A I

    2014-12-28

    We develop an analytic liquid-state theory of the effective interactions induced by reversibly adsorbing polymers, acting between colloids immersed in a polymer melt. This theory is based on the polymer reference interaction site model that has no restrictions with respect to the density of the polymer system and colloid-to-polymer size ratio. By making use of the developed theory, we calculate the potential of the polymer mediated interactions as a function of the colloid radius, strength and range of the adsorption potential, and the polymer density. In addition, we investigate the behavior of the second virial coefficient as a function of the polymer density in both the colloid and nano-particle limits. We found out that the presence of the adsorption interactions significantly changes the polymer mediated forces relative to the case of the pure entropic depletion interactions, showing most pronounced difference in the case of large polymer densities and small colloid-to-polymer size ratios. The significance of the above differences is determined by the relation between the range of the adsorption potential and polymer correlation length.

  12. Analytic liquid-state theory of the interactions between colloids mediated by reversibly adsorbed polymers.

    PubMed

    Chervanyov, A I

    2014-12-28

    We develop an analytic liquid-state theory of the effective interactions induced by reversibly adsorbing polymers, acting between colloids immersed in a polymer melt. This theory is based on the polymer reference interaction site model that has no restrictions with respect to the density of the polymer system and colloid-to-polymer size ratio. By making use of the developed theory, we calculate the potential of the polymer mediated interactions as a function of the colloid radius, strength and range of the adsorption potential, and the polymer density. In addition, we investigate the behavior of the second virial coefficient as a function of the polymer density in both the colloid and nano-particle limits. We found out that the presence of the adsorption interactions significantly changes the polymer mediated forces relative to the case of the pure entropic depletion interactions, showing most pronounced difference in the case of large polymer densities and small colloid-to-polymer size ratios. The significance of the above differences is determined by the relation between the range of the adsorption potential and polymer correlation length. PMID:25554175

  13. Optical sensor based on sensitive polymer layer

    NASA Astrophysics Data System (ADS)

    Will, Matthias; Martan, Tomas; Müller, Ralf; Brodersen, Olaf; Mohr, Gerhard J.

    2008-11-01

    In chemical, oil, and food industries, there are still higher requirements on miniaturization of optical sensors for a concentration measurement of gases e.g. a CO2, O2, and NH3. The paper deals with development of miniaturised optical sensor for an aqueous carbon dioxide measurement using a sensitive polymer layer. The optical sensor module consists of two parts, a remission sensor and a removable layered structure (with incorporated dyed polymer) which is closely placed on the surface of a remission sensor. A dyed polymer film is used as an optical-chemical transducer working on a principle of colour changes caused by a chemical reaction of an analyte and indicator dye. A novel remission sensor module was developed for an evaluation of the spectral absorption changes of sensitive polymer layer. The remission sensor module composed of LED diodes located in a central cavity of the sensor module and PIN diodes situated around the cavity. The LEDs emit light with optimised wavelengths and irradiate the polymer film. Light response (the changes of the spectral absorption) of the irradiated polymer film is detected by PIN diodes. A colour shift is further analyzed and evaluated by electronics without using a photometer.

  14. Synthesis and characterization of macromolecular layers grafted to polymer surfaces

    NASA Astrophysics Data System (ADS)

    Burtovyy, Oleksandr

    The composition and behavior of surfaces and interfaces play a pivotal role in dictating the overall efficiency of the majority of polymeric materials and devices. Surface properties of the materials can be altered using surface modification techniques. It is necessary to highlight that successful methods of surface modification should affect only the upper layer of the polymer material without changing bulk properties. The processes must introduce new functionalities to the surface, optimize surface roughness, lubrication, hydrophobicity, hydrophilicity, adhesion, conductivity, and/or biocompatibility. Research presented in this dissertation is dedicated to the synthesis, characterization, and application of thin macromolecular layers anchored to polymer substrates. Specifically, attachment of functional polymers via a "grafting to" approach has been extensively studied using PET and nylon model substrates. First, poly(glycidyl methacrylate) was used to introduce permanent functionalities to the model substrates by anchoring it to model films. Then, three different functional polymers were grafted on top of the previous layer. As one part of this study, the temperature and time dependence of grafting functional layers were studied. The surface coverage by hydrophobic polymer was determined from experimental data and predicted by a model. In general, the model has a high degree of predictive capability. Next, surface modification of polymeric fibers and membranes is presented as an important application of the polymer thin layers targeted in the study. Specifically, the procedures developed for surface modification of model substrates was employed for modification of PET, nylon, and cotton fabrics as well as PET track-etched membranes. Since epoxy groups are highly reactive in various chemical reactions, the approach becomes virtually universal, allowing both various surfaces and end-functionalized macromolecules to be used in the grafted layer synthesis. PET

  15. Phase transition and winding properties of a flexible polymer adsorbed to a rigid perioidic copolymer.

    PubMed

    Liu, Lei; Schubert, David; Chu, Min; Heermann, Dieter W

    2015-03-01

    Motivated by the noncovalent binding of polypeptides to DNA, the adsorption of a flexible polymer to a rigid periodic copolymer is studied in two dimensions and three dimensions. The fraction of adsorbed monomers, the specific heat, and the Binder cumulant are analyzed and compared with analytical results for an ideal chain. As the interaction strength ε increases, a second-order phase transition occurs from a nonadsorbed state to an adsorbed state, in two dimensions, and a higher-order transition occurs in three dimensions. The transition point is estimated as ε0∼2.2 for d=2 and ε0∼2.1 for d=3, where ε is given in units of kBT. The dependence of the number of adsorbed monomers Nads on the chain length L of the flexible polymer shows a power law scaling relation Nads∼Lϕ, with ϕ∼0.46,0.42 for d=2,3, respectively. We also find an optimal ε∼2.8 for the winding of the flexible polymer around the rigid one in three dimensions. Compared to the adsorbed monomers, the successive nonadsorbed monomers contribute more to the winding. When the interaction is strong, ε>3.5, the winding value or the number of winding turns of the flexible polymer becomes linearly dependent on the chain length. PMID:25871135

  16. Tailoring polymer properties with layered silicates

    NASA Astrophysics Data System (ADS)

    Xu, Liang

    Polymer layered silicate nanocomposites have found widespread applications in areas such as plastics, oil and gas production, biomedical, automotive and information storage, but their successful commercialization critically depends on consistent control over issues such as complete dispersion of layered silicate into the host polymer and optimal interaction between the layered silicates and the polymers. Polypropylene is a commercially important polymer but usually forms intercalated structures with organically modified layered silicate upon mixing, even it is pre-treated with compatibilizing agent such as maleic anhydride. In this work, layered silicate is well dispersed in ammonium modified polypropylene but does not provide sufficient reinforcement to the host polymer due to poor interactions. On the other hand, interactions between maleic anhydride modified polypropylene and layered silicate are fine tuned by using a small amount of maleic anhydride and mechanical strength of the resultant nanocomposites are significantly enhanced. In particular, the melt rheological properties of layered silicate nanocomposites with maleic anhydride functionalized polypropylene are contrasted to those based on ammonium-terminated polypropylene. While the maleic anhydride treated polypropylene based nanocomposites exhibit solid-like linear dynamic behavior, consistent with the formation of a long-lived percolated nanoparticle network, the single-end ammonium functionalized polypropylene based nanocomposites demonstrated liquid-like behavior at comparable montmorillonite concentrations. The differences in the linear viscoelasticity are attributed to the presence of bridging interaction in maleic anhydride functionalized nanocomposites, which facilitates formation of a long-lived silicate network mediated by physisorbed polymer chains. Further, the transient shear stress of the maleic anhydride functionalized nanocomposites in start-up of steady shear is a function of the shear

  17. Mechanism of dialkyl phthalates removal from aqueous solution using γ-cyclodextrin and starch based polyurethane polymer adsorbents.

    PubMed

    Okoli, Chukwunonso Peter; Adewuyi, Gregory Olufemi; Zhang, Qian; Diagboya, Paul N; Guo, Qingjun

    2014-12-19

    Phthalate esters have been known as potent endocrine disruptors and carcinogens; and their removal from water have been of considerable concern recently. In the present study, γ-cyclodextrin polyurethane polymer (GPP), γ-cyclodextrin/starch polyurethane copolymer (GSP), and starch polyurethane polymer (SPP) have been synthesized and characterized. Their adsorption efficiencies for the removal of dimethyl phthalate (DMP) and diethyl phthalate (DEP) from aqueous solutions were investigated. The characterization results showed the success of the synthesis. The isotherms were L-type, and both the Langmuir and Freundlich adsorption isotherm gave good fittings to the adsorption data. Adsorption mechanisms suggested that these adsorbents spontaneously adsorb phthalate molecules driven mainly by enthalpy change, and the adsorption process was attributed to multiple adsorbent-adsorbate interactions such as hydrogen bonding, π-π stacking, and pore filling. The results showed that starch and γ-cyclodextrin polyurethane polymer adsorbents have excellent potential as adsorbent materials for the removal of phthalates from the contaminated water.

  18. Thermoset polymer-layered silicic acid nanocomposites

    NASA Astrophysics Data System (ADS)

    Wang, Zhen

    Nanocomposites are formed when phase mixing occurs on a nanometer length scale. Due to the improved phase morphology and interfacial properties, nanocomposites exhibit mechanical properties superior to conventional composites. Toyota researchers first demonstrated that organoclay could be exfoliated in a nylon-6 matrix to greatly improve the thermal and mechanical properties of the polymer, which has resulted in a practical application in the automobile industry. A great deal of research has been conducted on organic-inorganic hybrid composites in which smectite clays are used as reinforcement agents. However, little work has been devoted to derivatives of other layered inorganic solids. In the present work, the first examples of organic polymer-layered silicic acid nanocomposites have been prepared by formation of a cured epoxy polymer network in the presence of organo cation exchange forms of magadiite. The exfoliation of silicate nanolayers in the epoxy matrix was achieved by in-situ intragallery polymerization during the thermosetting process. In general, the tensile properties, solvent resistance, barrier properties and chemical stability of the polymer matrix are greatly improved by the embedded silicate nanolayers when the matrix is flexible (sub-ambient Tg). The improvement of properties are dependent on the silicate loading, the degree of nanolayer separation and interfacial properties. Interestingly, the exfoliation also affects the polymer elasticity in a favorable way. The mechanism leading to nanocomposite formation is proposed. One exfoliated epoxy-magadiite nanocomposite/composition possessed unique transparent optical properties. The exfoliation chemistry was successfully extended to the other members of the layered silicic acid family. A new approach also was developed to prepare thermoset epoxy polymer-layered silicate nanocomposites in which curing agents can be directly intercalated into the intragallery without the need for alkylammonium ions

  19. Analysis of structure and orientation of adsorbed polymers in solution subject to a dynamic shear stress

    SciTech Connect

    Smith, G.; Baker, S.; Toprakcioglu, C.

    1996-09-01

    This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Polymer-based separation techniques rely on the ability of a binding portion of the polymer to interact with a specific molecule in a solution flowing past the polymer. The location of the binding site within or out of the entangled polymer chains is thus crucial to the effectiveness of these methods. For this reason, the details of flow induced deformation of the polymer chains is important in such applications as exclusion chromatography, waste water treatment, ultrafiltration, enhanced oil recovery and microbial adhesion. Few techniques exist to examine the structure and orientation of polymeric materials, and even fewer to examine systems in a dynamic fluid flow. The goal of this project was to understand the molecular structure and orientation of adsorbed polymers with and without active binding ligands as a function of solvent shear rate, solvent power, polymer molecular weight, surface polymer coverage and heterogeneity of the surface polymer chains by neutron reflectometry in a newly designed shear cell. Geometrical effects on binding of molecules in the flow was also studied subject to the same parameters.

  20. Cellular Responses Modulated by FGF-2 Adsorbed on Albumin/Heparin Layer-by-Layer Assemblies

    PubMed Central

    Kumorek, Marta; Kubies, Dana; Filová, Elena; Houska, Milan; Kasoju, Naresh; Mázl Chánová, Eliška; Matějka, Roman; Krýslová, Markéta; Bačáková, Lucie; Rypáček, František

    2015-01-01

    In a typical cell culture system, growth factors immobilized on the cell culture surfaces can serve as a reservoir of bio-signaling molecules, without the need to supplement them additionally into the culture medium. In this paper, we report on the fabrication of albumin/heparin (Alb/Hep) assemblies for controlled binding of basic fibroblast growth factor (FGF-2). The surfaces were constructed by layer-by-layer adsorption of polyelectrolytes albumin and heparin and were subsequently stabilized by covalent crosslinking with glutaraldehyde. An analysis of the surface morphology by atomic force microscopy showed that two Alb/Hep bilayers are required to cover the surface of substrate. The formation of the Alb/Hep assemblies was monitored by the surface plasmon resonance (SPR), the infrared multiinternal reflection spectroscopy (FTIR MIRS) and UV/VIS spectroscopy. The adsorption of FGF-2 on the cross-linked Alb/Hep was followed by SPR. The results revealed that FGF-2 binds to the Alb/Hep assembly in a dose and time-dependent manner up to the surface concentration of 120 ng/cm2. The bioactivity of the adsorbed FGF-2 was assessed in experiments in vitro, using calf pulmonary arterial endothelial cells (CPAE). CPAE cells could attach and proliferate on Alb/Hep surfaces. The adsorbed FGF-2 was bioactive and stimulated both the proliferation and the differentiation of CPAE cells. The improvement was more pronounced at a lower FGF-2 surface concentration (30 ng/cm2) than on surfaces with a higher concentration of FGF-2 (120 ng/cm2). PMID:25945799

  1. Rupture force of adsorbed self-assembled surfactant layers. Effect of the dielectric exchange force

    NASA Astrophysics Data System (ADS)

    Teschke, O.; Ceotto, G.; de Souza, E. F.

    2001-08-01

    The tip applied force necessary to obtain tip/substrate contact, i.e., rupture force between adsorbed layers of self-assembled surfactant films and atomic force microscope (AFM) tips in water has been measured. A substantial contribution of this rupture force is due to the dielectric exchange force (DEF). The DEF model is in agreement with the observation that the surfactant layer rupture forces are smaller in the thickest layers, where the compactness of the adsorbed film results in the smallest values of the dielectric permittivity. Within experimental accuracy a dielectric permittivity value of ˜4 for bilayers and of ˜36 for monolayers is found.

  2. Inhibition of cell adhesion by a synthetic polymer adsorbed to glass shown under defined hydrodynamic stress.

    PubMed

    Owens, N F; Gingell, D; Rutter, P R

    1987-06-01

    A co-polymer with hydrophobic and hydrophilic segments was allowed to adsorb from aqueous solution onto glass previously made hydrophobic by derivatization with octadecyl dimethylchlorosilane. The polymer is thought to adsorb via its hydrophobic segments, leaving the hydrophilic segments free to extend into the water. After allowing cells to settle on the treated surface, the shear stress at the chamber wall required to remove red blood cells, Dictyostelium discoideum amoebae and Escherichia coli was determined in a calibrated laminar flow chamber. On octadecyl glass a shear stress of 2-3 Nm-2 evicts 50% of adherent red cells and E. coli. No D. discoideum amoebae could be removed at 5Nm-2. In striking contrast, the lowest experimentally obtainable shear stress of 0.03 Nm-2 removes 97.0-99.5% of cells of all three types from the polymer-treated surface, even after a cell residence time of 1 h without flow in the absence of free polymer. The minimum shear stress of 0.03Nm-2 corresponds to only approximately equal to 20 times the force of gravity on a red cell. The mechanism of action of the polymer and the implications of the results are discussed. PMID:3312253

  3. Hybrid layered polymer slot waveguide Young interferometer.

    PubMed

    Ahmadi, Leila; Hiltunen, Marianne; Stenberg, Petri; Hiltunen, Jussi; Aikio, Sanna; Roussey, Matthieu; Saarinen, Jyrki; Honkanen, Seppo

    2016-05-16

    We demonstrate a polymer slot waveguide Young interferometer coated with a bilayer of Al2O3/TiO2. The approach enables relaxed dimensions of the polymer waveguide which simplifies the fabrication of the structure with a resolution of 50 nm. The layers were coated by an atomic layer deposition technique. The feasibility of the device was investigated by exploiting the interferometric structure as a bulk refractive index sensor operating at 975 nm wavelength for detection of an ethanol-water solution. A refractive index change of 1 × 10-6 RIU with a sensing length of only 800 µm was detected. The approach confirms the possibility of realizing a low cost device with a small footprint and enhanced sensitivity by employing the TiO2 rails in the sides of the slot waveguide. PMID:27409852

  4. Theoretical study of line and boundary tension in adsorbed colloid-polymer mixtures.

    PubMed

    Koning, Jesper; Vandecan, Yves; Indekeu, Joseph

    2014-07-28

    An extended theoretical study of interface potentials in adsorbed colloid-polymer mixtures is performed. To describe the colloid-polymer mixture near a hard wall, a simple Cahn-Nakanishi-Fisher free-energy functional is used. The bulk phase behaviour and the substrate-adsorbate interaction are modelled by the free-volume theory for ideal polymers with polymer-to-colloid size ratios q = 0.6 and q = 1. The interface potentials are constructed with help from a Fisher-Jin crossing constraint. By manipulating the crossing density, a complete interface potential can be obtained from natural, single-crossing, profiles. The line tension in the partial wetting regime and the boundary tension along prewetting are computed from the interface potentials. The line tensions are of either sign, and descending with increasing contact angle. The line tension takes a positive value of 10(-14)-10(-12) N near a first-order wetting transition, passes through zero and decreases to minus 10(-14)-10(-12) N away from the first-order transition. The calculations of the boundary tension along prewetting yield values increasing from zero at the prewetting critical point up to the value of the line tension at first-order wetting. PMID:25084953

  5. Theoretical predictions of structures in dispersions containing charged colloidal particles and non-adsorbing polymers.

    PubMed

    Xie, Fei; Turesson, Martin; Woodward, Clifford E; van Gruijthuijsen, Kitty; Stradner, Anna; Forsman, Jan

    2016-04-28

    We develop a theoretical model to describe structural effects on a specific system of charged colloidal polystyrene particles, upon the addition of non-adsorbing PEG polymers. This system has previously been investigated experimentally, by scattering methods, so we are able to quantitatively compare predicted structure factors with corresponding experimental data. Our aim is to construct a model that is coarse-grained enough to be computationally manageable, yet detailed enough to capture the important physics. To this end, we utilize classical polymer density functional theory, wherein all possible polymer configurations are accounted for, subject to a mean-field Boltzmann weight. We make efforts to counteract drawbacks with this mean-field approach, resulting in structural predictions that agree very well with computationally more demanding simulations. Electrostatic interactions are handled at the fully non-linear Poisson-Boltzmann level, and we demonstrate that a linearization leads to less accurate predictions. The particle charge is an experimentally unknown parameter. We define the surface charge such that the experimental and theoretical gel point at equal polymer concentration coincide. Assuming a fixed surface charge for a certain salt concentration, we find very good agreements between measured and predicted structure factors across a wide range of polymer concentrations. We also present predictions for other structural quantities, such as radial distribution functions, and cluster size distributions. Finally, we demonstrate that our model predicts the occurrence of equilibrium clusters at high polymer concentrations, but low particle volume fractions and salt levels. PMID:27056112

  6. Revealed nano-architecture and dynamics of bound polymer layers on nanofillers

    NASA Astrophysics Data System (ADS)

    Koga, Tadanori; Jiang, Naisheng; Endoh, Maya; Masui, Tomomi; Kishimoto, Hiroyuki; Taniguchi, Takashi; Watanabe, Hiroshi; Nagao, Michihiro

    2013-03-01

    It is known that the physical properties of adsorbed polymers on solids are often different from those of bulks. However, the mechanism associated with the structure and dynamics at the polymer/solid interfaces still remains unsolved, primarily due to the lack of suitable experimental tools. Recently, we used small-angle neutron scattering and neutron spin-echo spectroscopy which allow us to highlight adsorbed polymers on nanofillers with deuterated labeling. The system used was polybutadiene (PB) adsorbed on carbon black (CB) fillers in toluene. The CB (80 nm in diameter) was compounded into PB by using a Banbury mixer. The CB/PB compound was then dissolved in toluene, until the weight of the compound remained unchanged. To label the resultant un-dissolved PB layer on CB (i.e., about 3 nm in thickness based on TEM analysis) for the neutron scattering experiments, deuterated toluene, which has the nearly same scattering length density as that of CB, was used. We will highlight the unique structure and dynamics of the bound PB layer by comparing with a PB brush grafted on CB and further discuss geometric effects of solids (curvature or flat) on the nano-architectures at the polymer/solid interfaces. We acknowledge the financial support from NSF Grant No. CMMI-084626.

  7. Identification of polymer surface adsorbed proteins implicated in pluripotent human embryonic stem cell expansion.

    PubMed

    Hammad, Moamen; Rao, Wei; Smith, James G W; Anderson, Daniel G; Langer, Robert; Young, Lorraine E; Barrett, David A; Davies, Martyn C; Denning, Chris; Alexander, Morgan R

    2016-08-16

    Improved biomaterials are required for application in regenerative medicine, biosensing, and as medical devices. The response of cells to the chemistry of polymers cultured in media is generally regarded as being dominated by proteins adsorbed to the surface. Here we use mass spectrometry to identify proteins adsorbed from a complex mouse embryonic fibroblast (MEF) conditioned medium found to support pluripotent human embryonic stem cell (hESC) expansion on a plasma etched tissue culture polystyrene surface. A total of 71 proteins were identified, of which 14 uniquely correlated with the surface on which pluripotent stem cell expansion was achieved. We have developed a microarray combinatorial protein spotting approach to test the potential of these 14 proteins to support expansion of a hESC cell line (HUES-7) and a human induced pluripotent stem cell line (ReBl-PAT) on a novel polymer (N-(4-Hydroxyphenyl) methacrylamide). These proteins were spotted to form a primary array yielding several protein mixture 'hits' that enhanced cell attachment to the polymer. A second array was generated to test the function of a refined set of protein mixtures. We found that a combination of heat shock protein 90 and heat shock protein-1 encourage elevated adherence of pluripotent stem cells at a level comparable to fibronectin pre-treatment. PMID:27466628

  8. Influence of polymer charge on the shear yield stress of silica aggregated with adsorbed cationic polymers.

    PubMed

    Zhou, Ying; Yu, Hai; Wanless, Erica J; Jameson, Graeme J; Franks, George V

    2009-08-15

    Flocs were produced by adding three cationic polymers (10% charge density, 3.0x10(5) g/mol molecular weight; 40% charge density, 1.1x10(5) g/mol molecular weight; and 100% charge density, 1.2x10(5) g/mol molecular weight) to 90 nm diameter silica particles. The shear yield stresses of the consolidated sediment beds from settled and centrifuged flocs were determined via the vane technique. The polymer charge density plays an important role in influencing the shear yield stresses of sediment beds. The shear yield stresses of sediment beds from flocs induced by the 10% charged polymer were observed to increase with an increase in polymer dose, initial solid concentration and background electrolyte concentration at all volume fractions. In comparison, polymer dose has a marginal effect on the shear yield stresses of sediment beds from flocs induced by the 40% and 100% charged polymers. The shear yield stresses of sediments from flocs induced by the 40% charged polymer are independent of salt concentration whereas the addition of salt decreases the shear yield stresses of sediments from flocs induced by the 100% charged polymer. When flocculated at the optimum dose for each polymer (12 mg/g silica for the 10% charged polymer at 0.03 M NaCl, 12 mg/g for 40% and 2 mg/g for 100%), shear yield stress increases as polymer charge increases. The effects observed are related to the flocculation mechanism (bridging, patch attraction or charge neutralisation) and the magnitude of the adhesive force. Comparison of shear and compressive yield stresses show that the network is only slightly weaker in shear than in compression. This is different than many other systems (mainly salt and pH coagulation) which have shear yield stress much less than compressive yield stress. The existing models relating the power law exponent of the volume fraction dependence of the shear yield stress to the network fractal structure are not satisfactory to predict all the experimental behaviour.

  9. Challenges and strategies in the preparation of large-volume polymer-based monolithic chromatography adsorbents.

    PubMed

    Ongkudon, Clarence M; Kansil, Tamar; Wong, Charlotte

    2014-03-01

    To date, the number of published reports on the large-volume preparation of polymer-based monolithic chromatography adsorbents is still lacking and is of great importance. Many critical factors need to be considered when manufacturing a large-volume polymer-based monolith for chromatographic applications. Structural integrity, validity, and repeatability are thought to be the key factors determining the usability of a large-volume monolith in a separation process. In this review, we focus on problems and solutions pertaining to heat dissipation, pore size distribution, "wall channel" effect, and mechanical strength in monolith preparation. A template-based method comprising sacrificial and nonsacrificial techniques is possibly the method of choice due to its precise control over the porous structure. However, additional expensive steps are usually required for the template removal. Other strategies in monolith preparation are also discussed.

  10. Surface rheology of PEO-PPO-PEO triblock copolymers at the air-water interface: comparison of spread and adsorbed layers.

    PubMed

    Blomqvist, B Rippner; Wärnheim, T; Claesson, P M

    2005-07-01

    The dilatational rheological properties of monolayers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)-type block copolymers at the air-water interface have been investigated by employing an oscillating ring trough method. The properties of adsorbed monolayers were compared to spread layers over a range of surface concentrations. The studied polymers were PEO26-PPO39-PEO26 (P85), PEO103-PPO40-PEO103 (F88), and PEO99-PPO65-PEO99 (F127). Thus, two of the polymers have similar PPO block size and two of them have similar PEO block size, which allows us to draw conclusions about the relationship between molecular structure and surface dilatational rheology. The dilatational properties of adsorbed monolayers were investigated as a function of time and bulk solution concentration. The time dependence was found to be rather complex, reflecting structural changes in the layer. When the dilatational modulus measured at different concentrations was replotted as a function of surface pressure, one unique master curve was obtained for each polymer. It was found that the dilatational behavior of spread (Langmuir) and adsorbed (Gibbs) monolayers of the same polymer is close to identical up to surface concentrations of approximately 0.7 mg/m2. At higher coverage, the properties are qualitatively alike with respect to dilatational modulus, although some differences are noticeable. Relaxation processes take place mainly within the interfacial layers by a redistribution of polymer segments. Several conformational transitions were shown to occur as the area per molecule decreased. PEO desorbs significantly from the interface at segmental areas below 20 A(2), while at higher surface coverage, we propose that segments of PPO are forced to leave the interface to form a mixed sublayer in the aqueous region. PMID:15982044

  11. Aminosilane-grafted polymer/silica hollow fiber adsorbents for CO₂ capture from flue gas.

    PubMed

    Rezaei, Fateme; Lively, Ryan P; Labreche, Ying; Chen, Grace; Fan, Yanfang; Koros, William J; Jones, Christopher W

    2013-05-01

    Amine/silica/polymer composite hollow fiber adsorbents are produced using a novel reactive post-spinning infusion technique, and the obtained fibers are shown to capture CO2 from simulated flue gas. The post-spinning infusion technique allows for functionalization of polymer/silica hollow fibers with different types of amines during the solvent exchange step after fiber spinning. The post-spinning infusion of 3-aminopropyltrimethoxysilane (APS) into mesoporous silica/cellulose acetate hollow fibers is demonstrated here, and the materials are compared with hollow fibers infused with poly(ethyleneimine) (PEI). This approach results in silica/polymer composite fibers with good amine distribution and accessibility, as well as adequate porosity retained within the fibers to facilitate rapid mass transfer and adsorption kinetics. The CO2 adsorption capacities for the APS-infused hollow fibers are shown to be comparable to those of amine powders with similar amine loadings. In contrast, fibers that are spun with presynthesized, amine-loaded mesoporous silica powders show negligible CO2 uptake and low amine loadings because of loss of amines from the silica materials during the fiber spinning process. Aminosilica powders are shown to be more hydrophilic than the corresponding amine containing composite hollow fibers, the bare polymer as well as silica support. Both the PEI-infused and APS-infused fibers demonstrate reduced CO2 adsorption upon elevating the temperature from 35 to 80 °C, in accordance with thermodynamics, whereas PEI-infused powders show increased CO2 uptake over that temperature range because of competing diffusional and thermodynamic effects. The CO2 adsorption kinetics as probed via TGA show that the APS-infused hollow fiber adsorbents have more rapid uptake kinetics than their aminosilica powder analogues. The adsorption performance of the functionalized hollow fibers is also assessed in CO2 breakthrough experiments. The breakthrough results show a

  12. Analytic theory of the adsorption-desorption transition of Gaussian polymers interacting with a periodic lattice of adsorbing centers.

    PubMed

    Chervanyov, A I; Heinrich, G

    2008-08-21

    Based on the obtained exact analytic solution, we calculate the adsorption-desorption diagram that describes the adsorption of Gaussian polymers onto a rigid surface that bears a periodic array of the adsorbing centers. It is shown that the polymer adsorption onto this substrate is fully governed by a delicate balance between the entropic depletion repulsion of polymers from the rigid surface and their attraction to the adsorbing centers. Magnitudes of these competitive effects are calculated in terms of the reduced overall affinity of the substrate eta(-1) and the reduced separation between the adsorbing centers d. The calculated exact adsorption-desorption diagram eta(d) that describes the equilibrium between the above depletion and adsorption interactions, is shown to obey the scaling law eta approximately d(-1.17).

  13. Adsorbed polymer and NOM limits adhesion and toxicity of nano scale zerovalent iron to E. coli.

    PubMed

    Li, Zhiqiang; Greden, Karl; Alvarez, Pedro J J; Gregory, Kelvin B; Lowry, Gregory V

    2010-05-01

    Nanoscale zerovalent iron (NZVI) is used for groundwater remediation. Freshly synthesized bare, i.e. uncoated NZVI is bactericidal at low mg/L concentration, but the impact of surface modifiers and aging (partial oxidation) on its bactericidal properties have not been determined. Here we assess the effect that adsorbed synthetic polymers and natural organic matter (NOM) and aging (partial oxidation) have on the bactericidal properties of NZVI to the gram-negative bacterium, Escherichia coli. Exposure to 100 mg/L of bare NZVI with 28% Fe(0) content resulted in a 2.2-log inactivation after 10 min and a 5.2-log inactivation after 60 min. Adsorbed poly(styrene sulfonate) (PSS), poly(aspartate) (PAP), or NOM on NZVI with the same Fe(0) content significantly decreased its toxicity, causing less than 0.2-log inactivation after 60 min. TEM images and heteroaggregation studies indicate that bare NZVI adheres significantly to cells and that the adsorbed polyelectrolyte or NOM prevents adhesion, thereby decreasing NZVI toxicity. The 1.8-log inactivation observed for bare NZVI with 7% Fe(0) content was lower than the 5.2-log inactivation using NZVI with 28% Fe(0) after 1 h; however, the minimum inhibitory concentration (MIC) after 24 h was 5 mg/L regardless of Fe(0) content. The MIC of PSS, PAP, and NOM coated NZVI were much higher: 500 mg/L, 100 mg/L, and 100 mg/L, respectively. But the MIC was much lower than the typical injection concentration used in remediation (10 g/L). Complete oxidation of Fe(0) in NZVI under aerobic conditions eliminated its bactericidal effects. This study indicates that polyelectrolyte coatings and NOM will mitigate the toxicity of NZVI for exposure concentrations below 0.1 to 0.5 g/L depending on the coating and that aged NZVI without Fe(0) is relatively benign to bacteria.

  14. Molecular Insights into the pH-Dependent Adsorption and Removal of Ionizable Antibiotic Oxytetracycline by Adsorbent Cyclodextrin Polymers

    PubMed Central

    Zhang, Yu; Cai, Xiyun; Xiong, Weina; Jiang, Hao; Zhao, Haitong; Yang, Xianhai; Li, Chao; Fu, Zhiqiang; Chen, Jingwen

    2014-01-01

    Effects of pH on adsorption and removal efficiency of ionizable organic compounds (IOCs) by environmental adsorbents are an area of debate, because of its dual mediation towards adsorbents and adsorbate. Here, we probe the pH-dependent adsorption of ionizable antibiotic oxytetracycline (comprising OTCH2+, OTCH±, OTC−, and OTC2−) onto cyclodextrin polymers (CDPs) with the nature of molecular recognition and pH inertness. OTCH± commonly has high adsorption affinity, OTC− exhibits moderate affinity, and the other two species have negligible affinity. These species are evidenced to selectively interact with structural units (e.g., CD cavity, pore channel, and network) of the polymers and thus immobilized onto the adsorbents to different extents. The differences in adsorption affinity and mechanisms of the species account for the pH-dependent adsorption of OTC. The mathematical equations are derived from the multiple linear regression (MLR) analysis of quantitatively relating adsorption affinity of OTC at varying pH to adsorbent properties. A combination of the MLR analysis for OTC and molecular recognition of adsorption of the species illustrates the nature of the pH-dependent adsorption of OTC. Based on this finding, γ-HP-CDP is chosen to adsorb and remove OTC at pH 5.0 and 7.0, showing high removal efficiency and strong resistance to the interference of coexisting components. PMID:24465975

  15. The role of adsorbed water on the friction of a layer of submicron particles

    USGS Publications Warehouse

    Sammis, Charles G.; Lockner, David A.; Reches, Ze’ev

    2011-01-01

    Anomalously low values of friction observed in layers of submicron particles deformed in simple shear at high slip velocities are explained as the consequence of a one nanometer thick layer of water adsorbed on the particles. The observed transition from normal friction with an apparent coefficient near μ = 0.6 at low slip speeds to a coefficient near μ = 0.3 at higher slip speeds is attributed to competition between the time required to extrude the water layer from between neighboring particles in a force chain and the average lifetime of the chain. At low slip speeds the time required for extrusion is less than the average lifetime of a chain so the particles make contact and lock. As slip speed increases, the average lifetime of a chain decreases until it is less than the extrusion time and the particles in a force chain never come into direct contact. If the adsorbed water layer enables the otherwise rough particles to rotate, the coefficient of friction will drop to μ = 0.3, appropriate for rotating spheres. At the highest slip speeds particle temperatures rise above 100°C, the water layer vaporizes, the particles contact and lock, and the coefficient of friction rises to μ = 0.6. The observed onset of weakening at slip speeds near 0.001 m/s is consistent with the measured viscosity of a 1 nm thick layer of adsorbed water, with a minimum particle radius of approximately 20 nm, and with reasonable assumptions about the distribution of force chains guided by experimental observation. The reduction of friction and the range of velocities over which it occurs decrease with increasing normal stress, as predicted by the model. Moreover, the analysis predicts that this high-speed weakening mechanism should operate only for particles with radii smaller than approximately 1 μm. For larger particles the slip speed required for weakening is so large that frictional heating will evaporate the adsorbed water and weakening will not occur.

  16. Polymer melt droplets adsorbed on a solid wall: A Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Milchev, Andrey; Binder, Kurt

    2001-05-01

    Using a coarse-grained bead-spring model of flexible polymers, we study the contact angle of polymer melt droplets sitting at a flat structureless wall, when the strength ɛ of the adsorption potential Vwall(z)=ɛ/z3 is varied. For this purpose, droplets containing 2048 or 4096 monomers for chain lengths N=16 and N=32 were carefully equilibrated at temperatures in the range from 74% to 82% of the Theta temperature, and the density profile of these droplets both in the z direction perpendicular to the substrate surface and in the radial direction was obtained. Beyond a critical value of ɛ we find that the contact angle vanishes, i.e., the droplets spread out and form a flat film. Such flat polymer films are also studied with considerably more polymers (up to 24 576 monomers contained in the simulation box). It is shown that the density profile ρ(z) is affected by the hard wall (exhibiting the characteristic layering oscillations) up to about z=5 (measuring lengths in units of the length of an effective bond), while at larger z the profile is flat and has the melt density at that temperature, with an interface to the "gas" at about z=20. Analyzing the capillary wave spectrum of the interfacial fluctuations, the surface tension of the polymer melt is extracted. Via the anisotropy of the local pressure near the wall, the wall excess free energy of the polymer melt is found as well, and the Young equation is tested. Thus methods have been developed that allow a systematic study of polymer-wall interactions and wetting vs dewetting behavior.

  17. Statistical mechanics of polymer chains grafted to adsorbing boundaries of fractal lattices embedded in three-dimensional space

    NASA Astrophysics Data System (ADS)

    Živić, I.; Elezović-Hadžić, S.; Milošević, S.

    2014-11-01

    We study the adsorption problem of linear polymers, immersed in a good solvent, when the container of the polymer-solvent system is taken to be a member of the Sierpinski gasket (SG) family of fractals, embedded in the three-dimensional Euclidean space. Members of the SG family are enumerated by an integer b (2≤b<∞), and it is assumed that one side of each SG fractal is impenetrable adsorbing boundary. We calculate the surface critical exponents γ11,γ1, and γs which, within the self-avoiding walk model (SAW) of polymer chain, are associated with the numbers of all possible SAWs with both, one, and no ends grafted to the adsorbing surface (adsorbing boundary), respectively. By applying the exact renormalization group method, for 2≤b≤4, we have obtained specific values for these exponents, for various types of polymer conformations. To extend the obtained sequences of exact values for surface critical exponents, we have applied the Monte Carlo renormalization group method for fractals with 2≤b≤40. The obtained results show that all studied exponents are monotonically increasing functions of the parameter b, for all possible polymer states. We discuss mutual relations between the studied critical exponents, and compare their values with those found for other types of lattices, in order to attain a unified picture of the attacked problem.

  18. Partially exposed polymer dispersed liquid crystals for boundary layer investigations

    NASA Technical Reports Server (NTRS)

    Parmar, Devendra S.; Singh, Jag J.

    1992-01-01

    A new configuration termed partially exposed polymer dispersed liquid crystal in which the liquid crystal microdroplets dispersed in a rigid polymer matrix are partially entrapped on the free surface of the thin film deposited on a glass substrate is reported. Optical transmission characteristics of the partially exposed polymer dispersed liquid crystal thin film in response to an air flow induced shear stress field reveal its potential as a sensor for gas flow and boundary layer investigations.

  19. Fabrication of Micro-Lens Array using a Chemically Adsorbed Monomolecular Layer

    NASA Astrophysics Data System (ADS)

    Okada, Kazushi; Oohira, Fumikazu; Hosogi, Maho; Hashiguchi, Gen; Mihara, Yutaka; Ogawa, Kazufumi; Shiwaku, Kazuya

    We proposed a new method of patterning a chemically adsorbed monomolecular layer on the substrate and then dropping UV cure material to form a lens shape using oil repellent effect of this film. The curvature radius of the lens was controlled by the amount of the dropped UV cure material. Using this method, a micro-lens array of various radiuses was fabricated. The formed micro-lens array shapes are transferred by the electro-plating and then the micro dies are fabricated, which are used for molding the plastic lens array. The optical characteristic of the molded micro-lens was evaluated.

  20. High basicity adsorbents from solid residue of cellulose and synthetic polymer co-pyrolysis for phenol removal: Kinetics and mechanism

    NASA Astrophysics Data System (ADS)

    Lorenc-Grabowska, Ewa; Rutkowski, Piotr

    2014-10-01

    The activated carbons (ACs) produced from solid residue of cellulose and synthetic polymer co-pyrolysis (CACs) and commercial activated carbon from coconut shell (GC) were used for phenol removal. The adsorption kinetics and mechanism were investigated. All studied activated carbons are predominantly microporous and are characterized by basic surface characteristics. Surface area SBET varies between 1235 and 1499 m2/g, whereas the pHPZC changes from 7.70 to 10.63. The bath adsorption of phenol (P) was carried out at ambient temperature. The equilibrium time and equilibrium sorption capacity were determined. It was found that the boundary layer effect is bigger in AC with high basic characteristics of the surface. The rate controlling step is the intraparticle diffusion in CACs only, whereas in ACs with higher amount of acidic functionalities the adsorbate-surface interaction influences the rate of kinetic as well. The equilibrium isotherms are L2 type for commercial AC and L4 for CACs. The CACs are characterized by very high adsorption capacity that vary between 312 and 417 mg/g. The main mechanism of phenol adsorption is micropore filling within pores smaller than 1.4 nm. In the absence of solvent effect further adsorption of phenol on CACs takes place. The enhanced adsorption is due to dispersive/repulsive interaction induced by oxygen functionalities.

  1. Synthetic polymer-layer silicate clay composites

    SciTech Connect

    Carrado, K.A.; Elder, D.L.; Thiyagarajan, P.

    1995-07-01

    Synthetic hectorites were hydrothermally crystallized with direct incorporation of water-soluble polyvinyl alcohol (PVA), a cationic polymer poly(dimethyl diallyl ammonium chloride) (PDDA), and two cellulosic polymers: hydroxypropyl methylcellulose (HPMC) and hydroxyethyl cellulose (HEC). The molecular weight of polyvinyl alcohols had little effect on the success of hydrothermal hectorite synthesis, d-spacing, or amount of polymer incorporated; the basal spacings range from 19.5 {angstrom} to 20.8 {angstrom} and the percent of polymer incorporated ranges from 20.4 wt% to 23.0 wt%. Synthetic PDDA-hectorite displays the lowest d-spacing at 15.8 {angstrom}, and less cationic PDDA is incorporated into hectorite (7.8 wt% organic) than the other neutral polymers (17.8-23.0 wt% organic). The basal spacing for synthetic HPMC-hectorite is the largest at 25.2 {angstrom}. Small angle neutron scattering was used to further examine the PVA-clay systems.

  2. Adsorbate-catalyzed layer-by-layer metal dissolution in inert electrolyte: Pd(100)-c(2 × 2)-I

    NASA Astrophysics Data System (ADS)

    Schimpf, Jane A.; Abreu, Juan B.; Carrasquillo, Arnaldo; Soriaga, Manuel P.

    1994-08-01

    Studies on the corrosion of Pd in inert ( halide-free) H 2SO 4 solution, catalyzed by a single adsorbed layer of iodine, have been extended to a Pd(100) single-crystal electrode that contained an ordered c(2 × 2) adlattice of iodine. Experimental measurements were based upon a combination of linear-sweep voltammetry, potential-step coulometry, low-energy electron diffraction, and Auger electron spectroscopy. As was earlier noted with polycrystalline electrodes, Pd dissolution occurred only when iodine was present on the surface. More significantly, neither the coverage nor the ordered structure of the iodine adlattice was affected by the dissolution process. These observations strongly suggest that the iodine-catalyzed corrosion occurs one layer at a time.

  3. Effect of the interplay between protein and surface on the properties of adsorbed protein layers.

    PubMed

    Ouberai, Myriam M; Xu, Kairuo; Welland, Mark E

    2014-08-01

    Although protein adsorption to surface is a common phenomenon, investigation of the process is challenging due to the complexity of the interplay between external factors, protein and surface properties. Therefore experimental approaches have to measure the properties of adsorbed protein layers with high accuracy in order to achieve a comprehensive description of the process. To this end, we used a combination of two biosensing techniques, dual polarization interferometry and quartz crystal microbalance with dissipation. From this, we are able to extract surface coverage values, layer structural parameters, water content and viscoelastic properties to examine the properties of protein layers formed at the liquid/solid interface. Layer parameters were examined upon adsorption of proteins of varying size and structural properties, on surfaces with opposite polarity. We show that "soft" proteins such as unfolded α-synuclein and high molecular weight albumin are highly influenced by the surface polarity, as they form a highly diffuse and hydrated layer on the hydrophilic silica surface as opposed to the denser, less hydrated layer formed on a hydrophobic methylated surface. These layer properties are a result of different orientations and packing of the proteins. By contrast, lysozyme is barely influenced by the surface polarity due to its intrinsic structural stability. Interestingly, we show that for a similar molecular weight, the unfolded α-synuclein forms a layer with the highest percentage of solvation not related to surface coverage but resulting from the highest water content trapped within the protein. Together, these data reveal a trend in layer properties highlighting the importance of the interplay between protein and surface for the design of biomaterials. PMID:24780165

  4. The recognition of biomaterials: pattern recognition of medical polymers and their adsorbed biomolecules.

    PubMed

    Love, Ryan J; Jones, Kim S

    2013-09-01

    All biomedical materials are recognized as foreign entities by the host immune system despite the substantial range of different materials that have been developed by material scientists and engineers. Hydrophobic biomaterials, hydrogels, biomaterials with low protein binding surfaces, and those that readily adsorb a protein layer all seem to incite similar host responses in vivo that may differ in magnitude, but ultimately result in encapsulation by fibrotic tissue. The recognition of medical materials by the host is explained by the very intricate pattern recognition system made up of integrins, toll-like receptors, scavenger receptors, and other surface proteins that enable leukocytes to perceive almost any foreign body. In this review, we describe the various pattern recognition receptors and processes that occur on biomedical material surfaces that permit detection of a range of materials within the host.

  5. Understanding Molecular Interactions within Chemically Selective Layered Polymer Assemblies

    SciTech Connect

    Gary J. Blanchard

    2009-06-30

    This work focuses on two broad issues. These are (1) the molecular origin of the chemical selectivity achieved with ultrathin polymer multilayers, and (2) how the viscoelastic properties of the polymer layers are affected by exposure to solvent and analytes. These issues are inter-related, and to understand them we need to design experiments that probe both the energetic and kinetic aspects of interfacial adsorption processes. This project focuses on controling the chemical structure, thickness, morphology and sequential ordering of polymer layers bound to interfaces using maleimide-vinyl ether and closely related alternating copolymerization chemistry and efficient covalent cross-linking reactions that allow for layer-by-layer polymer deposition. This chemistry has been developed during the funding cycle of this Grant. We have measure the equilibrium constants for interactions between specific layers within the polymer interfaces and size-controlled, surface-functionalized gold nanoparticles. The ability to control both size and functionality of gold nanoparticle model analytes allows us to evaluate the average “pore size” that characterizes our polymer films. We have measured the “bulk” viscosity and shear modulus of the ultrathin polymer films as a function of solvent overlayer identity using quartz crystal microbalance complex impedance measurements. We have measured microscopic viscosity at specific locations within the layered polymer interfaces with time-resolved fluorescence lifetime and depolarization techniques. We combine polymer, cross-linking and nanoparticle synthetic expertise with a host of characterization techniques, including QCM gravimetry and complex impedance analysis, steady state and time-resolved spectroscopies.

  6. Coalescence behavior of oil droplets coated in irreversibly-adsorbed surfactant layers.

    PubMed

    Reichert, Matthew D; Walker, Lynn M

    2015-07-01

    Coalescence between oil caps with irreversibly adsorbed layers of nonionic surfactant is characterized in deionized water and electrolyte solution. The coalescence is characterized using a modified capillary tensiometer allowing for accurate measurement of the coalescence time. Results suggest two types of coalescence behavior, fast coalescence at low surface coverages that are independent of ionic strength and slow coalescence at high coverage. These slow coalescence events (orders of magnitude slower) are argued to be due to electric double layer forces or more complicated stabilization mechanisms arising from interfacial deformation and surface forces. A simple film drainage model is used in combination with measured values for interfacial properties to quantify the interaction potential between the two interfaces. Since this approach allows the two caps to have the same history, interfacial coverage and curvature, the results offer a tool to better understand a mechanism that is important to emulsion stability.

  7. Layered double hydroxide-based nanomaterials as highly efficient catalysts and adsorbents.

    PubMed

    Li, Changming; Wei, Min; Evans, David G; Duan, Xue

    2014-11-01

    Layered double hydroxides (LDHs) are a class of anion clays consisting of brucite-like host layers and interlayer anions, which have attracted increasing interest in the fields of catalysis/adsorption. By virtue of the versatility in composition, morphology, and architecture of LDH materials, as well as their unique structural properties (intercalation, topological transformation, and self-assembly with other functional materials), LDHs display great potential in the design and fabrication of nanomaterials applied in photocatalysis, heterogeneous catalysis, and adsorption/separation processes. Taking advantage of the structural merits and various control synthesis strategies of LDHs, the active center structure (e.g., crystal facets, defects, geometric and electronic states, etc.) and macro-nano morphology can be facilely manipulated for specific catalytic/adsorbent processes with largely enhanced performances. In this review, the latest advancements in the design and preparation of LDH-based functional nanomaterials for sustainable development in catalysis and adsorption are summarized.

  8. Method for Controlling Electrical Properties of Single-Layer Graphene Nanoribbons via Adsorbed Planar Molecular Nanoparticles

    NASA Astrophysics Data System (ADS)

    Tanaka, Hirofumi; Arima, Ryo; Fukumori, Minoru; Tanaka, Daisuke; Negishi, Ryota; Kobayashi, Yoshihiro; Kasai, Seiya; Yamada, Toyo Kazu; Ogawa, Takuji

    2015-07-01

    A simple method for fabricating single-layer graphene nanoribbons (sGNRs) from double-walled carbon nanotubes (DWNTs) was developed. A sonication treatment was employed to unzip the DWNTs by inducing defects in them through annealing at 500 °C. The unzipped DWNTs yielded double-layered GNRs (dGNRs). Further sonication allowed each dGNR to be unpeeled into two sGNRs. Purification performed using a high-speed centrifuge ensured that more than 99% of the formed GNRs were sGNRs. The changes induced in the electrical properties of the obtained sGNR by the absorption of nanoparticles of planar molecule, naphthalenediimide (NDI), were investigated. The shape of the I-V curve of the sGNRs varied with the number of NDI nanoparticles adsorbed. This was suggestive of the existence of a band gap at the narrow-necked part near the NDI-adsorbing area of the sGNRs.

  9. Cooperation between adsorbates accounts for the activation of atomic layer deposition reactions.

    PubMed

    Shirazi, Mahdi; Elliott, Simon D

    2015-04-14

    Atomic layer deposition (ALD) is a technique for producing conformal layers of nanometre-scale thickness, used commercially in non-planar electronics and increasingly in other high-tech industries. ALD depends on self-limiting surface chemistry but the mechanistic reasons for this are not understood in detail. Here we demonstrate, by first-principle calculations of growth of HfO2 from Hf(N(CH3)2)4-H2O and HfCl4-H2O and growth of Al2O3 from Al(CH3)3-H2O, that, for all these precursors, co-adsorption plays an important role in ALD. By this we mean that previously-inert adsorbed fragments can become reactive once sufficient numbers of molecules adsorb in their neighbourhood during either precursor pulse. Through the calculated activation energies, this 'cooperative' mechanism is shown to have a profound influence on proton transfer and ligand desorption, which are crucial steps in the ALD cycle. Depletion of reactive species and increasing coordination cause these reactions to self-limit during one precursor pulse, but to be re-activated via the cooperative effect in the next pulse. This explains the self-limiting nature of ALD.

  10. Method for Controlling Electrical Properties of Single-Layer Graphene Nanoribbons via Adsorbed Planar Molecular Nanoparticles

    PubMed Central

    Tanaka, Hirofumi; Arima, Ryo; Fukumori, Minoru; Tanaka, Daisuke; Negishi, Ryota; Kobayashi, Yoshihiro; Kasai, Seiya; Yamada, Toyo Kazu; Ogawa, Takuji

    2015-01-01

    A simple method for fabricating single-layer graphene nanoribbons (sGNRs) from double-walled carbon nanotubes (DWNTs) was developed. A sonication treatment was employed to unzip the DWNTs by inducing defects in them through annealing at 500 °C. The unzipped DWNTs yielded double-layered GNRs (dGNRs). Further sonication allowed each dGNR to be unpeeled into two sGNRs. Purification performed using a high-speed centrifuge ensured that more than 99% of the formed GNRs were sGNRs. The changes induced in the electrical properties of the obtained sGNR by the absorption of nanoparticles of planar molecule, naphthalenediimide (NDI), were investigated. The shape of the I-V curve of the sGNRs varied with the number of NDI nanoparticles adsorbed. This was suggestive of the existence of a band gap at the narrow-necked part near the NDI-adsorbing area of the sGNRs. PMID:26205209

  11. Method for Controlling Electrical Properties of Single-Layer Graphene Nanoribbons via Adsorbed Planar Molecular Nanoparticles.

    PubMed

    Tanaka, Hirofumi; Arima, Ryo; Fukumori, Minoru; Tanaka, Daisuke; Negishi, Ryota; Kobayashi, Yoshihiro; Kasai, Seiya; Yamada, Toyo Kazu; Ogawa, Takuji

    2015-01-01

    A simple method for fabricating single-layer graphene nanoribbons (sGNRs) from double-walled carbon nanotubes (DWNTs) was developed. A sonication treatment was employed to unzip the DWNTs by inducing defects in them through annealing at 500 °C. The unzipped DWNTs yielded double-layered GNRs (dGNRs). Further sonication allowed each dGNR to be unpeeled into two sGNRs. Purification performed using a high-speed centrifuge ensured that more than 99% of the formed GNRs were sGNRs. The changes induced in the electrical properties of the obtained sGNR by the absorption of nanoparticles of planar molecule, naphthalenediimide (NDI), were investigated. The shape of the I-V curve of the sGNRs varied with the number of NDI nanoparticles adsorbed. This was suggestive of the existence of a band gap at the narrow-necked part near the NDI-adsorbing area of the sGNRs. PMID:26205209

  12. A Highly Water-Tolerant Magnesium(II) Coordination Polymer Derived from a Flexible Layered Structure.

    PubMed

    Ochi, Rika; Noro, Shin-Ichiro; Kamiya, Yuichi; Kubo, Kazuya; Nakamura, Takayoshi

    2016-07-25

    A two-dimensional (2D) layered Mg(II) coordination polymer (CP) with a high tolerance for H2 O was designed, synthesised, and crystallographically characterised. The synthesis was achieved by the introduction of a flexible 2D layered structure composed of Mg(II) ions and isonicotinate N-oxide ligands. Owing to its high H2 O tolerance, the obtained 2D layered structure has the flexibility to repeatedly adsorb a large amount of H2 O associated with interlayer expansion and enable the removal of H2 O from a H2 O/2-propanol mixed vapour. These results indicate that the CP could be an excellent dehydrating agent. PMID:27373696

  13. Brownian dynamics simulation of peeling a strongly-adsorbed polymer molecule from a frictionless substrate.

    PubMed

    Iliafar, Sara; Vezenov, Dmitri; Jagota, Anand

    2013-02-01

    We used brownian dynamics to study the peeling of a polymer molecule, represented by a freely jointed chain, from a frictionless surface in an implicit solvent with parameters representative of single-stranded DNA adsorbed on graphite. For slow peeling rates, simulations match the predictions of an equilibrium statistical thermodynamic model. We show that deviations from equilibrium peeling forces are dominated by a combination of Stokes (viscous) drag forces acting on the desorbed section of the chain and a finite rate of hopping over a desorption barrier. Characteristic velocities separating equilibrium and nonequilibrium regimes are many orders of magnitude higher than values accessible in force spectroscopy experiments. Finite probe stiffness resulted in disappearance of force spikes due to desorption of individual links predicted by the statistical thermodynamic model under displacement control. Probe fluctuations also masked sharp transitions in peeling force between blocks of distinct sequences, indicating limitation in the ability of single-molecule force spectroscopy to distinguish small differences in homologous molecular structures.

  14. Path-integral Monte Carlo simulation of the second layer of 4He adsorbed on graphite

    NASA Astrophysics Data System (ADS)

    Pierce, Marlon; Manousakis, Efstratios

    1999-02-01

    We have developed a path-integral Monte Carlo method for simulating helium films and apply it to the second layer of helium adsorbed on graphite. We use helium-helium and helium-graphite interactions that are found from potentials which realistically describe the interatomic interactions. The Monte Carlo sampling is over both particle positions and permutations of particle labels. From the particle configurations and static structure factor calculations, we find that this layer possesses, in order of increasing density, a superfluid liquid phase, a 7×7 commensurate solid phase that is registered with respect to the first layer, and an incommensurate solid phase. By applying the Maxwell construction to the dependence of the low-temperature total energy on the coverage, we are able to identify coexistence regions between the phases. From these, we deduce an effectively zero-temperature phase diagram. Our phase boundaries are in agreement with heat capacity and torsional oscillator measurements, and demonstrate that the experimentally observed disruption of the superfluid phase is caused by the growth of the commensurate phase. We further observe that the superfluid phase has a transition temperature consistent with the two-dimensional value. Promotion to the third layer occurs for densities above 0.212 atom/Å 2, in good agreement with experiment. Finally, we calculate the specific heat for each phase and obtain peaks at temperatures in general agreement with experiment.

  15. Elution of uranium and transition metals from amidoxime-based polymer adsorbents for sequestering uranium from seawater

    DOE PAGES

    Pan, Horng-Bin; Kuo, Li-Jung; Miyamoto, Naomi; Wood, Jordana; Strivens, Jonathan E.; Gill, Gary; Janke, Christopher James; Wai, Chien

    2015-11-30

    High-surface-area amidoxime and carboxylic acid grafted polymer adsorbents developed at Oak Ridge National Laboratory were tested for sequestering uranium in a flowing seawater flume system at the PNNL-Marine Sciences Laboratory. FTIR spectra indicate that a KOH conditioning process is necessary to remove the proton from the carboxylic acid and make the sorbent effective for sequestering uranium from seawater. The alkaline conditioning process also converts the amidoxime groups to carboxylate groups in the adsorbent. Both Na2CO3 H2O2 and hydrochloric acid elution methods can remove ~95% of the uranium sequestered by the adsorbent after 42 days of exposure in real seawater. Themore » Na2CO3 H2O2 elution method is more selective for uranium than conventional acid elution. Iron and vanadium are the two major transition metals competing with uranium for adsorption to the amidoxime-based adsorbents in real seawater. Tiron (4,5-Dihydroxy-1,3-benzenedisulfonic acid disodium salt, 1 M) can remove iron from the adsorbent very effectively at pH around 7. The coordination between vanadium (V) and amidoxime is also discussed based on our 51V NMR data.« less

  16. Elution of uranium and transition metals from amidoxime-based polymer adsorbents for sequestering uranium from seawater

    SciTech Connect

    Pan, Horng-Bin; Kuo, Li-Jung; Miyamoto, Naomi; Wood, Jordana; Strivens, Jonathan E.; Gill, Gary; Janke, Christopher James; Wai, Chien

    2015-11-30

    High-surface-area amidoxime and carboxylic acid grafted polymer adsorbents developed at Oak Ridge National Laboratory were tested for sequestering uranium in a flowing seawater flume system at the PNNL-Marine Sciences Laboratory. FTIR spectra indicate that a KOH conditioning process is necessary to remove the proton from the carboxylic acid and make the sorbent effective for sequestering uranium from seawater. The alkaline conditioning process also converts the amidoxime groups to carboxylate groups in the adsorbent. Both Na2CO3 H2O2 and hydrochloric acid elution methods can remove ~95% of the uranium sequestered by the adsorbent after 42 days of exposure in real seawater. The Na2CO3 H2O2 elution method is more selective for uranium than conventional acid elution. Iron and vanadium are the two major transition metals competing with uranium for adsorption to the amidoxime-based adsorbents in real seawater. Tiron (4,5-Dihydroxy-1,3-benzenedisulfonic acid disodium salt, 1 M) can remove iron from the adsorbent very effectively at pH around 7. The coordination between vanadium (V) and amidoxime is also discussed based on our 51V NMR data.

  17. Free energy of electrical double layers: Entropy of adsorbed ions and the binding polynomial

    SciTech Connect

    Stigter, D.; Dill, K.A. )

    1989-09-07

    The authors adapt the method of binding polynomials to general problems of binding equilibria of ions to polybases, polyacids, and mixed polyelectrolytes, such as proteins and other colloids. For spherical particles with a smeared charge the interaction effects are taken into account using the Poisson-Boltzmann equation, which is shown to differ little from the Debye-Hueckel approximation under conditions met in most protein solutions. Examples are given of the salt dependence of pH titration equilibria. Binding polynomials produce an extra term in the free energy of the electrical double layer, which arises from the entropy of the adsorbed ions. The maximum term method applied to the binding polynominal yields an expression which is similar to that derived by the charging process of Chan and Mitchell. Applications to monolayers and to polyelectrolyte gels are also discussed.

  18. Ultra-Thin Optically Transparent Carbon Electrodes Produced from Layers of Adsorbed Proteins

    PubMed Central

    Alharthi, Sarah A.; Benavidez, Tomas E.; Garcia, Carlos D.

    2013-01-01

    This work describes a simple, versatile, and inexpensive procedure to prepare optically transparent carbon electrodes, using proteins as precursors. Upon adsorption, the protein-coated substrates were pyrolyzed under reductive conditions (5% H2) to form ultra-thin, conductive electrodes. Because proteins spontaneously adsorb to interfaces forming uniform layers, the proposed method does not require a precise control of the preparation conditions, specialized instrumentation, or expensive precursors. The resulting electrodes were characterized by a combination of electrochemical, optical, and spectroscopic means. As a proof-of-concept, the optically-transparent electrodes were also used as substrate for the development of an electrochemical glucose biosensor. The proposed films represent a convenient alternative to more sophisticated, and less available, carbon-based nanomaterials. Furthermore, these films could be formed on a variety of substrates, without classical limitations of size or shape. PMID:23421732

  19. Effect of nanoconfinement on polymer dynamics: surface layers and interphases.

    PubMed

    Krutyeva, M; Wischnewski, A; Monkenbusch, M; Willner, L; Maiz, J; Mijangos, C; Arbe, A; Colmenero, J; Radulescu, A; Holderer, O; Ohl, M; Richter, D

    2013-03-01

    We present neutron spin echo experiments that address the much debated topic of dynamic phenomena in polymer melts that are induced by interacting with a confining surface. We find an anchored surface layer that internally is highly mobile and not glassy as heavily promoted in the literature. The polymer dynamics in confinement is, rather, determined by two phases, one fully equal to the bulk polymer and another that is partly anchored at the surface. By strong topological interaction, this phase confines further chains with no direct contact to the surface. These form the often invoked interphase, where the full chain relaxation is impeded through the interaction with the anchored chains. PMID:23521308

  20. Electrical conductivity of insulating polymer nanoscale layers: environmental effects.

    PubMed

    Bliznyuk, Valery; Galabura, Yuriy; Burtovyy, Ruslan; Karagani, Pranay; Lavrik, Nickolay; Luzinov, Igor

    2014-02-01

    As electronic devices are scaled down to submicron sizes, it has become critical to obtain uniform and robust insulating nanoscale polymer films. For that reason, we address the electrical properties of grafted polymer layers made of poly(glycidyl methacrylate), polyacrylic acid, poly(2-vinylpyridine), and polystyrene with thicknesses of 10-20 nm. It was found that layers insulating under normal ambient conditions can display a significant increase in conductivity as the environment changes. Namely, we demonstrated that the in-plane electrical conductivity of the polymer grafted layers can be changed by at least two orders of magnitude upon exposure to water or organic solvent vapors. Conductive properties of all polymer grafted films under study could also be significantly enhanced with an increase in temperature. The observed phenomenon makes possible the chemical design of polymer nanoscale layers with reduced or enhanced sensitivity to the anticipated change in environmental conditions. Finally, we demonstrated that the observed effects could be used in a micron-sized conductometric transducing scheme for the detection of volatile organic solvents.

  1. Template-free synthesis and encapsulation technique for layer-by-layer polymer nanocarrier fabrication.

    PubMed

    Qi, Aisha; Chan, Peggy; Ho, Jenny; Rajapaksa, Anushi; Friend, James; Yeo, Leslie

    2011-12-27

    The encapsulation of therapeutic molecules within multiple layers of biocompatible and biodegradable polymeric excipients allows exquisite design of their release profile, to the extent the drug can be selectively delivered to a specific target location in vivo. Here, we develop a novel technique for the assembly of multilayer polyelectrolyte nanocarriers based on surface acoustic wave atomization as a rapid and efficient alternative to conventional layer-by-layer assembly, which requires the use of a sacrificial colloidal template over which consecutive polyelectrolyte layers are deposited. Polymer nanocarriers are synthesized by atomizing a polymer solution and suspending them within a complementary polymer solution of opposite charge subsequent to their solidification in-flight as the solvent evaporates; reatomizing this suspension produces nanocarriers with a layer of the second polymer deposited over the initial polymer core. Successive atomization-suspension layering steps can then be repeated to produce as many additional layers as desired. Specifically, we synthesize nanocarriers comprising two and three, and up to eight, alternating layers of chitosan (or polyethyleneimine) and carboxymethyl cellulose within which plasmid DNA is encapsulated and show in vitro DNA release profiles over several days. Evidence that the plasmid's viability is preserved and hence the potential of the technique for gene delivery is illustrated through efficient in vitro transfection of the encapsulated plasmid in human mesenchymal progenitor and COS-7 cells.

  2. Trypsin immobilization on to polymer surface through grafted layer and its reaction with inhibitors.

    PubMed

    Kulik, E A; Kato, K; Ivanchenko, M I; Ikada, Y

    1993-08-01

    Trypsin was covalently immobilized and physically adsorbed on to the surface of poly(ethylene terephthalate) fibres using poly(acrylic acid) (PAAc) chains grafted on to the ozonized fibres. The covalent immobilization was accomplished through amide formation between amino groups of trypsin and carboxyl groups of grafted PAAc chains, with the use of water-soluble carbodiimide. A set of samples with surface concentrations of grafted polymer ranging from 0.03 to 2.5 micrograms/cm2 was used to study the effects of grafted layer on the enzymatic activity of immobilized trypsin and its inhibition by trypsin inhibitors of different molecular sizes. The amount of immobilized trypsin increased linearly with an increase in graft yield of fibres, but the activity of immobilized enzyme reached saturation at a certain graft yield, probably because of diffusion limitation for the transport of enzyme substrate molecules into the grafted PAAc layer. The reduction of inhibition with an increase in graft yield and in molecular weight of inhibitors was attributed to enhancement of steric hindrance and enzyme inactivation in the dense grafted layer. We also found that the adsorbed trypsin was inhibited more easily than the covalently immobilized at any concentration of the grafted PAAc and for any type of inhibitor used.

  3. Polymer adsorption

    NASA Astrophysics Data System (ADS)

    Joanny, Jean-Francois

    2008-03-01

    The aim of this talk is to review Pierre-Gilles deGennes' work on polymer adsorption and the impact that it has now in our understanding of this problem. We will first present the self-consistent mean-field theory and its applications to adsorption and depletion. De Gennes most important contribution is probably the derivation of the self-similar power law density profile for adsorbed polymer layers that we will present next, emphasizing the differences between the tail sections and the loop sections of the adsorbed polymers. We will then discuss the kinetics of polymer adsorption and the penetration of a new polymer chain in an adsobed layer that DeGennes described very elegantly in analogy with a quantum tunneling problem. Finally, we will discuss the role of polymer adsorption for colloid stabilization.

  4. Adsorption of enzymes to stimuli-responsive polymer brushes: Influence of brush conformation on adsorbed amount and biocatalytic activity.

    PubMed

    Koenig, Meike; Bittrich, Eva; König, Ulla; Rajeev, Bhadra Lakshmi; Müller, Martin; Eichhorn, Klaus-Jochen; Thomas, Sabu; Stamm, Manfred; Uhlmann, Petra

    2016-10-01

    Polyelectrolyte brushes can be utilized to immobilize enzymes on macroscopic surfaces. This report investigates the influence of the pH value of the surrounding medium on the amount and the activity of enzymes adsorbed to poly(2-vinylpyridine) and poly(acrylic acid) brushes, as well as the creation of thermoresponsive biocatalytically active coatings via the adsorption of enzymes onto a mixed brush consisting of a polyelectrolyte and temperature-sensitive poly(N-isopropylacryl amide). Spectroscopic ellipsometry and attenuated total reflection-Fourier transform infrared spectroscopy are used to monitor the adsorption process. Additionally, infrared spectra are evaluated in terms of the secondary structure of the enzymes. Glucose oxidase is used as a model enzyme, where the enzymatic activity is measured after different adsorption conditions. Poly(acrylic acid) brushes generally adsorb larger amounts of enzyme, while less glucose oxidase is found on poly(2-vinylpyridine), which however exhibits higher specific activity. This difference in activity could be attributed to a difference in secondary structure of the adsorbed enzyme. For glucose oxidase adsorbed to mixed brushes, switching of enzymatic activity between an active state at 20°C and a less active state at 40°C as compared to the free enzyme in solution is observed. However, this switching is strongly depending on pH in mixed brushes of poly(acrylic acid) and poly(N-isopropylacryl amide) due to interactions between the polymers.

  5. Elution of Uranium and Transition Metals from Amidoxime-Based Polymer Adsorbents for Sequestering Uranium from Seawater

    SciTech Connect

    Pan, Horng-Bin; Kuo, Li-Jung; Wai, Chien M.; Miyamoto, Naomi; Joshi, Ruma; Wood, Jordana R.; Strivens, Jonathan E.; Janke, Christopher J.; Oyola, Yatsandra; Das, Sadananda; Mayes, Richard T.; Gill, Gary A.

    2015-11-30

    High-surface-area amidoxime and carboxylic acid grafted polymer adsorbents developed at Oak Ridge National Laboratory were tested for sequestering uranium in a flowing seawater flume system at the PNNL-Marine Sciences Laboratory. FTIR spectra indicate that a KOH conditioning process is necessary to remove the proton from the carboxylic acid and make the sorbent effective for sequestering uranium from seawater. The alkaline conditioning process also converts the amidoxime groups to carboxylate groups in the adsorbent. Both Na2CO3-H2O2 and hydrochloric acid elution methods can remove ~95% of the uranium sequestered by the adsorbent after 42 days of exposure in real seawater. The Na2CO3-H2O2 elution method is more selective for uranium than conventional acid elution. Iron and vanadium are the two major transition metals competing with uranium for adsorption to the amidoxime-based adsorbents in real seawater.

  6. Adsorption of enzymes to stimuli-responsive polymer brushes: Influence of brush conformation on adsorbed amount and biocatalytic activity.

    PubMed

    Koenig, Meike; Bittrich, Eva; König, Ulla; Rajeev, Bhadra Lakshmi; Müller, Martin; Eichhorn, Klaus-Jochen; Thomas, Sabu; Stamm, Manfred; Uhlmann, Petra

    2016-10-01

    Polyelectrolyte brushes can be utilized to immobilize enzymes on macroscopic surfaces. This report investigates the influence of the pH value of the surrounding medium on the amount and the activity of enzymes adsorbed to poly(2-vinylpyridine) and poly(acrylic acid) brushes, as well as the creation of thermoresponsive biocatalytically active coatings via the adsorption of enzymes onto a mixed brush consisting of a polyelectrolyte and temperature-sensitive poly(N-isopropylacryl amide). Spectroscopic ellipsometry and attenuated total reflection-Fourier transform infrared spectroscopy are used to monitor the adsorption process. Additionally, infrared spectra are evaluated in terms of the secondary structure of the enzymes. Glucose oxidase is used as a model enzyme, where the enzymatic activity is measured after different adsorption conditions. Poly(acrylic acid) brushes generally adsorb larger amounts of enzyme, while less glucose oxidase is found on poly(2-vinylpyridine), which however exhibits higher specific activity. This difference in activity could be attributed to a difference in secondary structure of the adsorbed enzyme. For glucose oxidase adsorbed to mixed brushes, switching of enzymatic activity between an active state at 20°C and a less active state at 40°C as compared to the free enzyme in solution is observed. However, this switching is strongly depending on pH in mixed brushes of poly(acrylic acid) and poly(N-isopropylacryl amide) due to interactions between the polymers. PMID:27447452

  7. Kinetics of protein adsorption/desorption mediated by pH-responsive polymer layer

    NASA Astrophysics Data System (ADS)

    Su, Xiao-Hang; Lei, Qun-Li; Ren, Chun-Lai

    2015-11-01

    We propose a new way of regulating protein adsorption by using a pH-responsive polymer. According to the theoretical results obtained from the molecular theory and kinetic approaches, both thermodynamics and kinetics of protein adsorption are verified to be well controlled by the solution pH. The kinetics and the amount of adsorbed proteins at equilibrium are greatly increased when the solution environment changes from acid to neutral. The reason is that the increased pH promotes the dissociation of the weak polyelectrolyte, resulting in more charged monomers and more stretched chains. Thus the steric repulsion within the polymer layer is weakened, which effectively lowers the barrier felt by the protein during the process of adsorption. Interestingly, we also find that the kinetics of protein desorption is almost unchanged with the variation of pH. It is because although the barrier formed by the polymer layer changes along with the change of pH, the potential at contact with the surface varies equally. Our results may provide useful insights into controllable protein adsorption/desorption in practical applications. Project supported by the National Natural Science Foundation of China (Grant Nos. 21274062, 11474155, and 91027040).

  8. Characterization of the surface-active components of sugar beet pectin and the hydrodynamic thickness of the adsorbed pectin layer.

    PubMed

    Siew, Chee Kiong; Williams, Peter A; Cui, Steve W; Wang, Qi

    2008-09-10

    The fraction of sugar beet pectin (SBP) adsorbed onto limonene oil droplets during emulsification has been isolated, and its chemical and physicochemical characteristics have been determined. While the SBP sample itself was found to contain 2.67 and 1.06% protein and ferulic acid, respectively, the adsorbed fraction contained 11.10% protein and 2.16% ferulic acid. The adsorbed fraction was also found to have a higher degree of acetylation, notably at the C2 position on the galacturonic acid residues, and was also found to contain a higher proportion of neutral sugars, which are present in the ramified side chains of the pectin molecules. The thickness of the layer of SBP adsorbed onto polystyrene latex particles was studied by dynamic light scattering and was found to increase with increasing surface coverage. It was found to have a value of approximately 140 nm at plateau coverage, which closely corresponded to the hydrodynamic diameter of the pectin chains. The adsorbed layer thickness was found to be sensitive to pH and the presence of electrolyte. The thickness at a surface coverage of approximately 20 mg/m(2) in the absence of electrolyte at pH approximately 4 was 107 nm and at pH 8.8 was 70 nm, while at pH approximately 4 in the presence of 10 mM NaCl the thickness was found to be 70 nm. It was concluded that the SBP molecules form multilayers at the surface due to electrostatic interaction between the positively charged protein moieties and the galacturonic acid residues. The removal of calcium from the SBP had no effect on the adsorbed layer thickness; hence, multilayer formation due to calcium ion cross-linking was considered unlikely.

  9. Programmable light-controlled shape changes in layered polymer nanocomposites.

    PubMed

    Zhu, Zhichen; Senses, Erkan; Akcora, Pinar; Sukhishvili, Svetlana A

    2012-04-24

    We present soft, layered nanocomposites that exhibit controlled swelling anisotropy and spatially specific shape reconfigurations in response to light irradiation. The use of gold nanoparticles grafted with a temperature-responsive polymer (poly(N-isopropylacrylamide), PNIPAM) with layer-by-layer (LbL) assembly allowed placement of plasmonic structures within specific regions in the film, while exposure to light caused localized material deswelling by a photothermal mechanism. By layering PNIPAM-grafted gold nanoparticles in between nonresponsive polymer stacks, we have achieved zero Poisson's ratio materials that exhibit reversible, light-induced unidirectional shape changes. In addition, we report rheological properties of these LbL assemblies in their equilibrium swollen states. Moreover, incorporation of dissimilar plasmonic nanostructures (solid gold nanoparticles and nanoshells) within different material strata enabled controlled shrinkage of specific regions of hydrogels at specific excitation wavelengths. The approach is applicable to a wide range of metal nanoparticles and temperature-responsive polymers and affords many advanced build-in options useful in optically manipulated functional devices, including precise control of plasmonic layer thickness, tunability of shape variations to the excitation wavelength, and programmable spatial control of optical response. PMID:22452351

  10. Hypersonic properties of polymer films and multi-layers

    NASA Astrophysics Data System (ADS)

    Sharp, James; Walker, Paul; Young, Eric; Goussev, Vitali; Akimov, Andrey; Kent, Anthony

    2012-02-01

    Picosecond acoustic measurements were performed on ultrathin films of polymers and thin film polymer multilayers supported on silicon (Si) substrates using a state of the art THz acoustic technique. In these experiments, a high power laser is used to excite picosecond duration strain pulses in an aluminium film evaporated on the reverse side of the Si substrate. These strain pulses then propagate through the substrate and interact with the polymer film/multi-layer. Vibrations in the film are detected optically using the same (pump-probe) beam which is passed through an optical delay line and reflected from the surface of the polymer film/multi-layer. Ultrathin films of polystyrene and a styrene-butadiene-styrene block copolymer were found to exhibit quantized closed-pipe organ like modes in the 0- 50 GHz regime that were attributed to vibrations of the entire polymer film. Thin film polystyrene/polyvinylpyrrolidone multilayer structures were found to display folded phonon dispersion curves that are characteristic of super-lattice structures. These structures have potential applications in GHz and THz optical switching and biosensing applications.

  11. Measuring sub-nm adsorbed water layer thickness and desorption rate using a fused-silica whispering-gallery microresonator

    NASA Astrophysics Data System (ADS)

    Ganta, D.; Dale, E. B.; Rosenberger, A. T.

    2014-05-01

    We report an optical method for measuring the thickness of the water layer adsorbed onto the surface of a high-Q fused-silica microresonator. Light from a tunable diode laser operating near 1550 nm is coupled into the microresonator to excite whispering-gallery modes (WGMs). By observing thermal distortion or even bistability of the WGM resonances caused by absorption in the water layer, the contribution of that absorption to the total loss is determined. Thereby, the thickness of the water layer is found to be ˜0.1 nm (approximately one monolayer). This method is further extended to measure the desorption rate of the adsorbed water, which is roughly exponential with a decay time of ˜40 h when the fused-silica microresonator is held in a vacuum chamber at low pressure.

  12. Particle Restabilization in Silica/PEG/Ethanol Suspensions: How Strongly do Polymers Need To Adsorb To Stabilize Against Aggregation?

    SciTech Connect

    Kim, So Youn; Zukoski, Charles F.

    2014-09-24

    We study the effects of increasing the concentration of a low molecular weight polyethylene glycol on the stability of 44 nm diameter silica nanoparticles suspended in ethanol. Polymer concentration, c{sub p}, is increased from zero to that characterizing the polymer melt. Particle stability is accessed through measurement of the particle second-virial coefficient, B{sub -2}, performed by light scattering and ultrasmall angle X-ray scattering (USAXS). The results show that at low polymer concentration, c{sub p} < 3 wt %, B{sub -2} values are positive, indicating repulsive interactions between particles. B{sub -2} decreases at intermediate concentrations (3 wt % < c{sub p} < 50 wt %), and particles aggregates are formed. At high concentrations (50 wt % < c{sub p}) B{sub -2} increases and stabilizes at a value expected for hard spheres with a diameter near 44 nm, indicating the particles are thermodynamically stable. At intermediate polymer concentrations, rates of aggregation are determined by measuring time-dependent changes in the suspension turbidity, revealing that aggregation is slowed by the necessity of the particles diffusing over a repulsive barrier in the pair potential. The magnitude of the barrier passes through a minimum at c{sub p} {approx} 12 wt % where it has a value of {approx}12kT. These results are understood in terms of a reduction of electrostatic repulsion and van der Waals attractions with increasing c{sub p}. Depletion attractions are found to play a minor role in particle stability. A model is presented suggesting displacement of weakly adsorbed polymer leads to slow aggregation at intermediate concentration, and we conclude that a general model of depletion restabilization may involve increased strength of polymer adsorption with increasing polymer concentration.

  13. Viscoelastic properties of adsorbed and cross-linked polypeptide and protein layers at a solid-liquid interface.

    PubMed

    Dutta, Amit K; Nayak, Arpan; Belfort, Georges

    2008-08-01

    The real-time changes in viscoelasticity of adsorbed poly(L-lysine) (PLL) and adsorbed histone (lysine rich fraction) due to cross-linking by glutaraldehyde and corresponding release of associated water were investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D) and attenuated total reflection Fourier transform infrared spectroscopy (ATR/FTIR). The kinetics of PLL and histone adsorption were measured through changes in mass adsorbed onto a gold-coated quartz surface from changes in frequency and dissipation and using the Voigt viscoelastic model. Prior to cross-linking, the shear viscosity and shear modulus of the adsorbed PLL layer were approximately 3.0 x 10(-3) Pas and approximately 2.5 x 10(5) Pa, respectively, while after cross-linking, they increased to approximately 17.5 x 10(-3) Pas and approximately 2.5 x 10(6) Pa, respectively. For the adsorbed histone layer, shear viscosity and shear modulus increased modestly from approximately 1.3 x 10(-3) to approximately 2.0 x 10(-3) Pas and from approximately 1.2 x 10(4) to approximately 1.6 x 10(4) Pa, respectively. The adsorbed mass estimated from the Sauerbrey equation (perfectly elastic) and the Voigt viscoelastic model differ appreciably prior to cross-linking whereas after cross-linking they converged. This is because trapped water molecules were released during cross-linking. This was confirmed experimentally via ATR/FTIR measurements. The variation in viscoelastic properties increased substantially after cross-linking presumably due to fluctuation of the randomly cross-linked network structure. An increase in fluctuation of the viscoelastic properties and the loss of imbibed water could be used as a signature of the formation of a cross-linked network and the amount of cross-linking, respectively. PMID:18508070

  14. Thermally Induced Charge Reversal of Layer-by-Layer Assembled Single-Component Polymer Films.

    PubMed

    Richardson, Joseph J; Tardy, Blaise L; Ejima, Hirotaka; Guo, Junling; Cui, Jiwei; Liang, Kang; Choi, Gwan H; Yoo, Pil J; De Geest, Bruno G; Caruso, Frank

    2016-03-23

    Temperature can be harnessed to engineer unique properties for materials useful in various contexts and has been shown to affect the layer-by-layer (LbL) assembly of polymer thin films and cause physical changes in preassembled polymer thin films. Herein we demonstrate that exposure to relatively low temperatures (≤ 100 °C) can induce physicochemical changes in cationic polymer thin films. The surface charge of polymer films containing primary and secondary amines reverses after heating (from positive to negative), and different characterization techniques are used to show that the change in surface charge is related to oxidation of the polymer that specifically occurs in the thin film state. This charge reversal allows for single-polymer LbL assembly to be performed with poly(allylamine) hydrochloride (PAH) through alternating heat/deposition steps. Furthermore, the negative charge induced by heating reduces the fouling and cell-association of PAH-coated planar and particulate substrates, respectively. This study highlights a unique property of thin films which is relevant to LbL assembly and biofouling and is of interest for the future development of thin polymer films for biomedical systems. PMID:26953514

  15. High-productivity membrane adsorbers: Polymer surface-modification studies for ion-exchange and affinity bioseparations

    NASA Astrophysics Data System (ADS)

    Chenette, Heather C. S.

    This dissertation centers on the surface-modification of macroporous membranes to make them selective adsorbers for different proteins, and the analysis of the performance of these membranes relative to existing technology. The common approach used in these studies, which is using membrane technology for chromatographic applications and using atom transfer radical polymerization (ATRP) as a surface modification technique, will be introduced and supported by a brief review in Chapter 1. The specific approaches to address the unique challenges and motivations of each study system are given in the introduction sections of the respective dissertation chapters. Chapter 2 describes my work to develop cation-exchange membranes. I discuss the polymer growth kinetics and characterization of the membrane surface. I also present an analysis of productivity, which measures the mass of protein that can bind to the stationary phase per volume of stationary phase adsorbing material per time. Surprisingly and despite its importance, this performance measure was not described in previous literature. Because of the significantly shorter residence time necessary for binding to occur, the productivity of these cation-exchange membrane adsorbers (300 mg/mL/min) is nearly two orders of magnitude higher than the productivity of a commercial resin product (4 mg/mL/min). My work studying membrane adsorbers for affinity separations was built on the productivity potential of this approach, as articulated in the conclusion of Chapter 2. Chapter 3 focuses on the chemical formulation work to incorporate glycoligands into the backbone of polymer tentacles grown from the surface of the same membrane stationary phase. Emphasis is given to characterizing and testing the working formulation for ligand incorporation, and details about how I arrived at this formulation are given in Appendix B. The plant protein, or lectin, Concanavalin A (conA) was used as the target protein. The carbohydrate affinity

  16. Slow process in confined polymer melts: Layer exchange dynamics at a polymer solid interface

    NASA Astrophysics Data System (ADS)

    Yelash, L.; Virnau, P.; Binder, K.; Paul, W.

    2010-11-01

    Employing Molecular Dynamics simulations of a chemically realistic model of 1,4-polybutadiene between graphite walls we show that the mass exchange between layers close to the walls is a slow process already in the melt state. For the glass transition of confined polymers this process competes with the slowing down due to packing effects and intramolecular rotation barriers.

  17. Relationship between the amount of bitter substances adsorbed onto lipid/polymer membrane and the electric response of taste sensors.

    PubMed

    Toko, Kiyoshi; Hara, Daichi; Tahara, Yusuke; Yasuura, Masato; Ikezaki, Hidekazu

    2014-01-01

    The bitterness of bitter substances can be measured by the change in the membrane electric potential caused by adsorption (CPA) using a taste sensor (electronic tongue). In this study, we examined the relationship between the CPA value due to an acidic bitter substance and the amount of the bitter substance adsorbed onto lipid/polymer membranes, which contain different lipid contents, used in the taste sensor. We used iso-α-acid which is an acidic bitter substance found in several foods and beverages. The amount of adsorbed iso-α-acid, which was determined by spectroscopy, showed a maximum at the lipid concentration 0.1 wt % of the membrane, and the same phenomenon was observed for the CPA value. At the higher lipid concentration, however, the amount adsorbed decreased and then remained constant, while the CPA value decreased monotonically to zero. This constant adsorption amount was observed when the membrane potential in the reference solution did not change with increasing lipid concentration. The decrease in CPA value in spite of the constant adsorption amount is caused by a decrease in the sensitivity of the membrane as the surface charge density increases. The reason why the peaks appeared in both the CPA value and adsorption amount is based on the contradictory adsorption properties of iso-α-acid. The increasing charged lipid concentration of the membrane causes an increasing electrostatic attractive interaction between iso-α-acid and the membrane, but simultaneously causes a decreasing hydrophobic interaction that results in decreasing adsorption of iso-α-acid, which also has hydrophobic properties, onto the membrane. Estimates of the amount of adsorption suggest that iso-α-acid molecules are adsorbed onto both the surface and interior of the membrane. PMID:25184491

  18. Dilatational rheology of beta-casein adsorbed layers at liquid-fluid interfaces.

    PubMed

    Maldonado-Valderrama, Julia; Fainerman, Valentin B; Galvez-Ruiz, M José; Martín-Rodriguez, Antonio; Cabrerizo-Vílchez, Miguel A; Miller, Reinhard

    2005-09-22

    The rheological behavior of beta-casein adsorption layers formed at the air-water and tetradecane-water interfaces is studied in detail by means of pendant drop tensiometry. First, its adsorption behavior is briefly summarized at both interfaces, experimentally and also theoretically. Subsequently, the experimental dilatational results obtained for a wide range of frequencies are presented for both interfaces. An interesting dependence with the oscillation frequency is observed via the comparative analysis of the interfacial elasticity (storage part) and the interfacial viscosity (loss part) for the two interfaces. The analysis of the interfacial elasticities provides information on the conformational transitions undergone by the protein upon adsorption at both interfaces. The air-water interface shows a complex behavior in which two maxima merge into one as the frequency increases, whereas only a single maximum is found at the tetradecane interface within the range of frequencies studied. This is interpreted in terms of a decisive interaction between the oil and the protein molecules. Furthermore, the analysis of the interfacial viscosities provides information on the relaxation processes occurring at both interfaces. Similarly, substantial differences arise between the gaseous and liquid interfaces and various possible relaxation mechanisms are discussed. Finally, the experimental elasticities obtained for frequencies higher than 0.1 Hz are further analyzed on the basis of a thermodynamic model. Accordingly, the nature of the conformational transition given by the maximum at these frequencies is discussed in terms of different theoretical considerations. The formation of a protein bilayer at the interface or the limited compressibility of the protein in the adsorbed state are regarded as possible explanations of the maximum.

  19. Configuration of bovine serum albumin adsorbed on polymer particles with grafted dextran corona.

    PubMed

    Vauthier, Christine; Lindner, Peter; Cabane, Bernard

    2009-03-01

    The configuration of BSA macromolecules adsorbed on the surfaces of poly(alkylcyanoacrylate) nanoparticles has been determined using small angle neutron scattering (SANS). The nanoparticles were made by anionic emulsion polymerization (AEP) and self-assembly of dextran-poly(isobutylcyanoacrylate) (PICBA) copolymers. They have a hydrophobic PICBA core and a hydrophilic dextran corona. In vivo, they are recognized by the macrophages of the mononuclear phagocyte system. The amount of BSA bound to the particles, at adsorption equilibrium, has been determined through immunodiffusion, immunoelectrophoresis, and SANS. For particles with a radius of 25.3nm, the adsorption was found to saturate at 64 adsorbed BSA molecules per particle. The configuration of the adsorbed BSA molecules was determined from the SANS scattering curves, first at full contrast, and then at contrast match. Both experiments indicate that the BSA molecules are adsorbed on the PICBA core, in a flat configuration. This result may be important for understanding the in vivo opsonization mechanisms of nanoparticles and their resulting biodistribution.

  20. High-Performance Carbon Nanotube/Polymer Composite Fiber from Layer-by-Layer Deposition.

    PubMed

    Wu, Min Le; Chen, Yun; Zhang, Liang; Zhan, Hang; Qiang, Lei; Wang, Jian Nong

    2016-03-01

    So far, preparation of high-performance carbon nanotube (CNT)/polymer composites still faces big challenges mainly due to the limited control of CNT dispersion, fraction, and alignment in polymers. Here, a new "layer-by-layer deposition" method is put forward for preparing CNT/polymer composite fibers using poly(vinyl alcohol) (PVA) as an exemplary polymer. This is based on the continuous production of a hollow cylindrical CNT assembly from a high temperature reactor and its shrinking by a PVA-containing solution and deposition on a removable substrate wire. The in situ mixing of the two composite components at the molecular level allows CNTs to disperse and PVA to infiltrate into the fiber efficiently. As a result, remarkable effects of the CNT reinforcement on the PVA matrix are observed, including a strength improvement from ∼50 to 1255 MPa and electrical conductivity from ∼0 to 1948 S cm(-1). The new method offers good controllability of CNT dispersion and fraction in the polymer matrix, variability for making composite fibers using different polymers, and suitability for scaled up production. This study thus provides a new research direction for preparing CNT-reinforced composites and future performance maximization.

  1. High-Performance Carbon Nanotube/Polymer Composite Fiber from Layer-by-Layer Deposition.

    PubMed

    Wu, Min Le; Chen, Yun; Zhang, Liang; Zhan, Hang; Qiang, Lei; Wang, Jian Nong

    2016-03-01

    So far, preparation of high-performance carbon nanotube (CNT)/polymer composites still faces big challenges mainly due to the limited control of CNT dispersion, fraction, and alignment in polymers. Here, a new "layer-by-layer deposition" method is put forward for preparing CNT/polymer composite fibers using poly(vinyl alcohol) (PVA) as an exemplary polymer. This is based on the continuous production of a hollow cylindrical CNT assembly from a high temperature reactor and its shrinking by a PVA-containing solution and deposition on a removable substrate wire. The in situ mixing of the two composite components at the molecular level allows CNTs to disperse and PVA to infiltrate into the fiber efficiently. As a result, remarkable effects of the CNT reinforcement on the PVA matrix are observed, including a strength improvement from ∼50 to 1255 MPa and electrical conductivity from ∼0 to 1948 S cm(-1). The new method offers good controllability of CNT dispersion and fraction in the polymer matrix, variability for making composite fibers using different polymers, and suitability for scaled up production. This study thus provides a new research direction for preparing CNT-reinforced composites and future performance maximization. PMID:26959406

  2. Bioorthogonal layer-by-layer encapsulation of pancreatic islets via hyperbranched polymers

    PubMed Central

    Gattás-Asfura, Kerim M.; Stabler, Cherie L.

    2013-01-01

    The encapsulation of viable tissues via layer-by-layer polymer assembly provides a versatile platform for cell surface engineering, with nanoscale control over capsule properties. Herein, we report the development of a hyperbranched polymer-based, ultrathin capsule architecture expressing bioorthogonal functionality and tailored physiochemical properties. Random carbodiimide-based condensation of 3,5-dicarboxyphenyl glycineamide on alginate yielded a highly branched polysaccharide with multiple, spatially restricted, and readily functionalizable terminal carboxylate moieties. Poly(ethylene glycol) (PEG) was utilized to link azido end groups to the structured alginate. Together with phosphine functionalized poly(amido amine) (PAMAM) dendrimer, nanoscale layer-by-layer coatings, covalently stabilized via Staudinger ligation, were assembled onto solid surfaces and pancreatic islets. The effects of electrostatic and/or bioorthogonal covalent interlayer interactions on the resulting coating efficiency and stability, as well as pancreatic islet viability and function, were studied. These hyperbranched polymers provide a flexible platform for the formation of covalently stabilized ultrathin coatings on viable cells and tissues. In addition, the hyperbranched nature of the polymers presents a highly functionalized surface capable of bioorthogonal conjugation of additional bioactive or labeling motifs. PMID:24063764

  3. Solid-phase microextraction of phthalate esters in water sample using different activated carbon-polymer monoliths as adsorbents.

    PubMed

    Lirio, Stephen; Fu, Chung-Wei; Lin, Jhih-Yun; Hsu, Meng-Ju; Huang, Hsi-Ya

    2016-07-13

    In this study, the application of different activated carbon-polymer (AC-polymer) monoliths as adsorbents for the solid-phase microextraction (SPME) of phthalate esters (PAEs) in water sample were investigated. The activated carbon (AC) was embedded in organic polymers, poly(butyl methacrylate-co-ethylene dimethacrylate) (poly(BMA-EDMA)) or poly(styrene-co-divinylbenzene) (poly(STY-DVB)), via a 5-min microwave-assisted or a 15-min water bath heating polymerization. Preliminary investigation on the performance of the native poly(BMA-EDMA) and poly(STY-DVB) demonstrated remarkable adsorption efficiencies for PAEs. However, due to the strong hydrophobic, π-π, and hydrogen bonding interactions between the analytes and polymers, low extraction recoveries were achieved. In contrast, the presence of AC in native polymers not only enhanced the adsorption efficiencies but also assisted the PAE desorption, especially for AC-poly(STY-DVB) with extraction recovery ranged of 76.2-99.3%. Under the optimized conditions, the extraction recoveries for intra-, inter-day and column-to-column were in the range of 76.5-100.8% (<3.7% RSDs), 77.2-97.6% (<5.6% RSDs) and 75.5-99.7% (<6.2% RSDs), respectively. The developed AC-poly(STY-DVB) monolithic column showed good mechanical stability, which can be reused for more than 30 extraction times without any significant loss in the extraction recoveries of PAEs. The AC-poly(STY-DVB) monolithic column was successfully applied in SPME of PAEs in water sample with extraction recovery ranged of 78.8%-104.6% (<5.5% RSDs). PMID:27237837

  4. Forced desorption of semiflexible polymers, adsorbed and driven by molecular motors.

    PubMed

    Chaudhuri, Abhishek; Chaudhuri, Debasish

    2016-02-21

    We formulate and characterize a model to describe the dynamics of semiflexible polymers in the presence of activity due to motor proteins attached irreversibly to a substrate, and a transverse pulling force acting on one end of the filament. The stochastic binding-unbinding of the motor proteins and their ability to move along the polymer generate active forces. As the pulling force reaches a threshold value, the polymer eventually desorbs from the substrate. Performing underdamped Langevin dynamics simulation of the polymer, and with stochastic motor activity, we obtain desorption phase diagrams. The correlation time for fluctuations in the desorbed fraction increases as one approaches complete desorption, captured quantitatively by a power law spectral density. We present theoretical analysis of the phase diagram using mean field approximations in the weakly bending limit of the polymer and performing linear stability analysis. This predicts an increase in the desorption force with the polymer bending rigidity, active velocity and processivity of the motor proteins to capture the main features of the simulation results. PMID:26750537

  5. Adsorbed serum albumin is permissive to macrophage attachment to perfluorocarbon polymer surfaces in culture

    PubMed Central

    Godek, M.L.; Michel, R.; Chamberlain, L. M.; Castner, D. G.; Grainger, D.W.

    2013-01-01

    Monocyte/macrophage adhesion to biomaterials, correlated with foreign body response, occurs through protein-mediated surface interactions. Albumin-selective perfluorocarbon (FC) biomaterials are generally poorly cell-conducive due to insufficient receptor-mediated surface interactions, but macrophages bind to albumin-coated substrates and also preferentially to highly hydrophobic fluorinated surfaces. Bone marrow macrophages (BMMO) and IC-21, RAW 264.7 and J774A.1 monocyte/macrophage cells were cultured on FC surfaces. Protein deposition onto two distinct FC surfaces from complex and single-component solutions was tracked using fluorescence and time-of-flight secondary ion mass spectrometry (ToF-SIMS) methods. Cell adhesion and growth on protein pre-treated substrates were compared by light microscopy. Flow cytometry and integrin-directed antibody receptor blocking assessed integrins critical for monocyte/macrophage adhesion in vitro. Albumin predominantly adsorbs onto both FC surfaces from 10% serum. In cultures pre-adsorbed with albumin or serum-dilutions, BMMO responded similar to IC-21 at early time points. Compared to Teflon® AF, plasma-polymerized FC was less permissive to extended cell proliferation. The β2 integrins play major roles in macrophage adhesion to FC surfaces: antibody blocking significantly disrupted cell adhesion. Albumin-mediated cell adhesion mechanisms to FC surfaces could not be clarified. Primary BMMO and secondary IC-21 macrophages behave similarly on FC surfaces, regardless of pre-adsorbed protein biasing, with respect to adhesion, cell morphology, motility and proliferation. PMID:18306309

  6. Arsenate removal by layered double hydroxides embedded into spherical polymer beads: Batch and column studies.

    PubMed

    Nhat Ha, Ho Nguyen; Kim Phuong, Nguyen Thi; Boi An, Tran; Mai Tho, Nguyen Thi; Ngoc Thang, Tran; Quang Minh, Bui; Van Du, Cao

    2016-01-01

    In this study, the performance of poly(layered double hydroxides) [poly(LDHs)] beads as an adsorbent for arsenate removal from aqueous solution was investigated. The poly(LDHs) beads were prepared by immobilizing LDHs into spherical alginate/polyvinyl alcohol (PVA)-glutaraldehyde beads (spherical polymer beads). Batch adsorption studies were conducted to assess the effect of contact time, solution pH, initial arsenate concentrations and co-existing anions on arsenate removal performance. The potential reuse of these poly(LDHs) beads was also investigated. Approximately 79.1 to 91.2% of arsenic was removed from an arsenate solution (50 mg As L(-1)) by poly(LDHs). The adsorption data were well described by the pseudo-second-order kinetics model and the Langmuir isotherm model, and the adsorption capacities of these poly(LDHs) beads at pH 8 were from 1.64 to 1.73 mg As g(-1), as calculated from the Langmuir adsorption isotherm. The adsorption ability of the poly(LDHs) beads decreased by approximately 5-6% after 5 adsorption-desorption cycles. Phosphates markedly decreased arsenate removal. The effect of co-existing anions on the adsorption capacity declined in the following order: HPO4 (2-) > HCO3 (-) > SO4 (2-) > Cl(-). A fixed-bed column study was conducted with real-life arsenic-containing water. The breakthrough time was found to be from 7 to 10 h. Under optimized conditions, the poly(LDHs) removed more than 82% of total arsenic. The results obtained in this study will be useful for further extending the adsorbents to the field scale or for designing pilot plants in future studies. From the viewpoint of environmental friendliness, the poly(LDHs) beads are a potential cost-effective adsorbent for arsenate removal in water treatment. PMID:26818806

  7. Arsenate removal by layered double hydroxides embedded into spherical polymer beads: Batch and column studies.

    PubMed

    Nhat Ha, Ho Nguyen; Kim Phuong, Nguyen Thi; Boi An, Tran; Mai Tho, Nguyen Thi; Ngoc Thang, Tran; Quang Minh, Bui; Van Du, Cao

    2016-01-01

    In this study, the performance of poly(layered double hydroxides) [poly(LDHs)] beads as an adsorbent for arsenate removal from aqueous solution was investigated. The poly(LDHs) beads were prepared by immobilizing LDHs into spherical alginate/polyvinyl alcohol (PVA)-glutaraldehyde beads (spherical polymer beads). Batch adsorption studies were conducted to assess the effect of contact time, solution pH, initial arsenate concentrations and co-existing anions on arsenate removal performance. The potential reuse of these poly(LDHs) beads was also investigated. Approximately 79.1 to 91.2% of arsenic was removed from an arsenate solution (50 mg As L(-1)) by poly(LDHs). The adsorption data were well described by the pseudo-second-order kinetics model and the Langmuir isotherm model, and the adsorption capacities of these poly(LDHs) beads at pH 8 were from 1.64 to 1.73 mg As g(-1), as calculated from the Langmuir adsorption isotherm. The adsorption ability of the poly(LDHs) beads decreased by approximately 5-6% after 5 adsorption-desorption cycles. Phosphates markedly decreased arsenate removal. The effect of co-existing anions on the adsorption capacity declined in the following order: HPO4 (2-) > HCO3 (-) > SO4 (2-) > Cl(-). A fixed-bed column study was conducted with real-life arsenic-containing water. The breakthrough time was found to be from 7 to 10 h. Under optimized conditions, the poly(LDHs) removed more than 82% of total arsenic. The results obtained in this study will be useful for further extending the adsorbents to the field scale or for designing pilot plants in future studies. From the viewpoint of environmental friendliness, the poly(LDHs) beads are a potential cost-effective adsorbent for arsenate removal in water treatment.

  8. Optical activity of transparent polymer layers characterized by spectral means

    NASA Astrophysics Data System (ADS)

    Cosutchi, Andreea Irina; Dimitriu, Dan Gheorghe; Zelinschi, Carmen Beatrice; Breaban, Iuliana; Dorohoi, Dana Ortansa

    2015-06-01

    The method based on the channeled spectrum, validated for inorganic optical active layers, is used now to determine the optical activity of some transparent polymer solutions in different solvents. The circular birefringence, the dispersion parameter and the specific rotation were estimated in the visible range by using the measurements of wavelengths in the channeled spectra of Hydroxypropyl cellulose in water, methanol and acetic acid. The experiments showed the specific rotation dependence on the polymer concentration and also on the solvent nature. The decrease of the specific rotation in the visible range with the increase in wavelength was evidenced. The method has some advantages as the rapidity of the experiments and the large spectral range in which it can be applied. One disadvantage is the fact that the channeled spectrum does not allow to establish the rotation sense of the electric field intensity.

  9. Electrodeposited cobalt sulfide hole collecting layer for polymer solar cells

    SciTech Connect

    Zampetti, Andrea; De Rossi, Francesca; Brunetti, Francesca; Reale, Andrea; Di Carlo, Aldo; Brown, Thomas M.

    2014-08-11

    In polymer solar cells based on the blend of regioregular poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester, the hole collecting layer has to be endowed with its ionization potential close to or greater than that of P3HT (∼5 eV). Conductive polymer blends such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and metal oxides such as vanadium pentoxide (V{sub 2}O{sub 5}) and molybdenum trioxide (MoO{sub 3}) satisfy this requirement and have been the most common materials used so far in bulk heterojunction structures. We report here cobalt sulfide (CoS) to be a promising hole collecting material deposited by convenient and room temperature electrodeposition. By simply tuning the CoS electrodeposition parameters, power conversion efficiencies similar (within 15%) to a reference structure with PEDOT:PSS were obtained.

  10. Study of the Relationship between Taste Sensor Response and the Amount of Epigallocatechin Gallate Adsorbed Onto a Lipid-Polymer Membrane

    PubMed Central

    Harada, Yuhei; Tahara, Yusuke; Toko, Kiyoshi

    2015-01-01

    A taste sensor using lipid-polymer membranes has been developed to evaluate the taste of foods, beverages and medicines. The response of the taste sensor, measured as a change in the membrane potential caused by adsorption (CPA), corresponds to the aftertaste felt by humans. The relationships between the CPA value and the amount of adsorbed taste substances, quinine and iso-α acid (bitterness), and tannic acid (astringency), have been studied so far. However, that of epigallocatechin gallate (EGCg) has not been clarified, although EGCg is abundantly present in green tea as one of its astringent substances. This study aimed at clarifying the response of the taste sensor to EGCg and its relationship with the amount of EGCg adsorbed onto lipid-polymer membranes. The lipid concentration dependence of the CPA value was similar to that of the amount of adsorbed EGCg, indicating a high correlation between the CPA value and the amount of adsorbed EGCg. The CPA value increased with increasing amount of adsorbed EGCg; however, the CPA value showed a tendency of leveling off when the amount of adsorbed EGCg further increased. PMID:25781512

  11. Study of the relationship between taste sensor response and the amount of epigallocatechin gallate adsorbed onto a lipid-polymer membrane.

    PubMed

    Harada, Yuhei; Tahara, Yusuke; Toko, Kiyoshi

    2015-01-01

    A taste sensor using lipid-polymer membranes has been developed to evaluate the taste of foods, beverages and medicines. The response of the taste sensor, measured as a change in the membrane potential caused by adsorption (CPA), corresponds to the aftertaste felt by humans. The relationships between the CPA value and the amount of adsorbed taste substances, quinine and iso-α acid (bitterness), and tannic acid (astringency), have been studied so far. However, that of epigallocatechin gallate (EGCg) has not been clarified, although EGCg is abundantly present in green tea as one of its astringent substances. This study aimed at clarifying the response of the taste sensor to EGCg and its relationship with the amount of EGCg adsorbed onto lipid-polymer membranes. The lipid concentration dependence of the CPA value was similar to that of the amount of adsorbed EGCg, indicating a high correlation between the CPA value and the amount of adsorbed EGCg. The CPA value increased with increasing amount of adsorbed EGCg; however, the CPA value showed a tendency of leveling off when the amount of adsorbed EGCg further increased. PMID:25781512

  12. Multi-layer graphene oxide alone and in a composite with nanosilica: Preparation and interactions with polar and nonpolar adsorbates

    NASA Astrophysics Data System (ADS)

    Gun'ko, V. M.; Turov, V. V.; Zarko, V. I.; Goncharuk, O. V.; Matkovsky, A. K.; Prykhod'ko, G. P.; Nychiporuk, Yu. M.; Pakhlov, E. M.; Krupska, T. V.; Balakin, D. Yu.; Charmas, B.; Andriyko, L. S.; Skubiszewska-Zięba, J.; Marynin, A. I.; Ukrainets, A. I.; Kartel, M. T.

    2016-11-01

    Freeze-dried multi-layer graphene oxide (MLGO), produced from natural flake graphite using ionic hydration method, demonstrates strong interactions of functionalized carbon sheets with polar or nonpolar adsorbates or co-adsorbates depending on the characteristics of dispersion media. Interactions of MLGO with a mixture of water and n-decane in chloroform media provide specific surface area (Su) in contact with unfrozen liquids greater than 1000 m2/g corresponding to stacks with 3-5 carbon layers. Electrostatic interactions between functionalized carbon sheets in dried MLGO are very strong. Therefore, nonpolar molecules (benzene, decane, nitrogen) cannot penetrate between the sheets. Water molecules can effectively penetrate between the sheets, especially if MLGO is located in weakly polar CDCl3 medium. In this case, n-decane molecules (co-adsorbate) can also penetrate into the sheet stacks and locate around nonpolar fragments of the sheets. The Su value of MLGO being in contact with unfrozen water can reach 360 m2/g, but upon co-adsorption of water with decane Su = 930 m2/g, i.e., hydrophobic interactions of the mentioned fragments with decane are stronger that with co-adsorbed water. Water alone (0.25 or 0.5 g/g) bound to MLGO in a mixture with fumed silica A-300 in air or CDCl3 media can provide Su = 30-50 m2/g. Pores in wetted MLGO or MLGO/A-300 mainly correspond to mesopores. Nanosilica does not provide significant opening of the MLGO sheet stacks during their mechanical mixing.

  13. Synthesis and characterization of thermally responsive polymer layers

    NASA Astrophysics Data System (ADS)

    Seeber, Michael

    Future devices such as biomedical and microfluidic devices, to a large extent, will depend on the interactions between the device surfaces and the contacting liquid. Further, biological liquids containing proteins call for controllable interactions between devices and such proteins, however the bulk material must retain the inherent mechanical properties from which the device was fabricated from. It is well known that surface modification is a suitable technique to tune the surface properties without sacrificing the bulk properties of the substrate. In the present study, surface properties were modified through temperature responsive polymer layers. After the modification, the surfaces gained switchability toward protein interaction as well as surface wettability properties. Poly(N-isopropylacrylamide) (PNIPAM), a well studied thermo-responsive polymer was utilized in the subsequent work. Firstly, thermally responsive brushes made from well defined block copolymers incorporating NIPAM and the surface reactive monomer, glycidyl methacrylate (GMA) were fabricated in a single step process. Reaction of the PGMA block with surface hydroxyl groups anchors the polymers to the surface yet allows PNIPAM to assemble at the interface at high enough concentration to exhibit thermally responsive properties in aqueous solutions. Surface properties of the resulting brushes prepared the 1-step process are compared to characteristics of PNIPAM brushes synthesized by already established methods. The thickness, swelling, and protein adsorption of the PNIPAM films were studied by ellipsometry. Chemical composition of the layer was studied by angle-resolved x-ray photoelectron spectroscopy. Film morphologies and forces of adhesion to fibrinogen were examined using atomic force microscopy (AFM) tapping mode and colloidal probe technique. Block copolymer (BCP) and conventional brush films were abraded and subsequently examined for changes in thermally responsive behavior. The results

  14. Polymer coatings as separator layers for microbial fuel cell cathodes

    NASA Astrophysics Data System (ADS)

    Watson, Valerie J.; Saito, Tomonori; Hickner, Michael A.; Logan, Bruce E.

    2011-03-01

    Membrane separators reduce oxygen flux from the cathode into the anolyte in microbial fuel cells (MFCs), but water accumulation and pH gradients between the separator and cathode reduces performance. Air cathodes were spray-coated (water-facing side) with anion exchange, cation exchange, and neutral polymer coatings of different thicknesses to incorporate the separator into the cathode. The anion exchange polymer coating resulted in greater power density (1167 ± 135 mW m-2) than a cation exchange coating (439 ± 2 mW m-2). This power output was similar to that produced by a Nafion-coated cathode (1114 ± 174 mW m-2), and slightly lower than the uncoated cathode (1384 ± 82 mW m-2). Thicker coatings reduced oxygen diffusion into the electrolyte and increased coulombic efficiency (CE = 56-64%) relative to an uncoated cathode (29 ± 8%), but decreased power production (255-574 mW m-2). Electrochemical characterization of the cathodes ex situ to the MFC showed that the cathodes with the lowest charge transfer resistance and the highest oxygen reduction activity produced the most power in MFC tests. The results on hydrophilic cathode separator layers revealed a trade off between power and CE. Cathodes coated with a thin coating of anion exchange polymer show promise for controlling oxygen transfer while minimally affecting power production.

  15. Enhanced physical stabilization of fenofibrate nanosuspensions via wet co-milling with a superdisintegrant and an adsorbing polymer.

    PubMed

    Azad, Mohammad; Afolabi, Afolawemi; Bhakay, Anagha; Leonardi, Jonathan; Davé, Rajesh; Bilgili, Ecevit

    2015-08-01

    Drug nanoparticles in suspensions can form aggregates leading to physical instability, which is traditionally mitigated using soluble polymers and surfactants. The aim of this paper was to explore common superdisintegrants, i.e., sodium starch glycolate (SSG), croscarmellose sodium (CCS), and crospovidone (CP), as novel class of dispersants for enhanced stabilization of fenofibrate (FNB), a model BCS Class II drug, suspensions. FNB was wet-milled with superdisintegrants along with hydroxypropyl methylcellulose (HPMC), a soluble adsorbing polymer, in a stirred media mill. For comparison, FNB was also milled in the presence of HPMC and/or SDS (sodium dodecyl sulfate) without superdisintegrants. Laser diffraction, scanning electron microscopy, viscometry, differential scanning calorimetry, and powder X-ray diffraction were used to characterize the suspensions. The results show that 2% HPMC along with 1% SSG or 1% CCS mitigated the aggregation of FNB nanoparticles significantly similar to the use of either 5% HPMC or 1% HPMC-0.075% SDS, whereas CP was not effective due to its low swelling capacity. CCS/SSG enhanced steric-kinetic stabilization of the FNB suspensions owing to their high swelling capacity, viscosity enhancement, and physical barrier action. Overall, this study provides a mechanistic basis for a novel method of formulating surfactant-free drug nanosuspensions with co-milled superdisintegrants. PMID:26079832

  16. Protein interactions with bottle-brush polymer layers: Effect of side chain and charge density ratio probed by QCM-D and AFM.

    PubMed

    Olanya, Geoffrey; Thormann, Esben; Varga, Imre; Makuska, Ricardas; Claesson, Per M

    2010-09-01

    Silica surfaces were coated with a range of cationic bottle-brush polymers with 45 units long poly(ethylene oxide) side chains, and their efficiency in reducing protein adsorption was probed by QCM-D, reflectometry and AFM. Preadsorbed layers formed by bottle-brush polymers with different side chain to charge ratio was exposed to two proteins with different net charge, lysozyme and BSA. The reduction in protein adsorption was found to depend on both the type of protein and on the nature of the polyelectrolyte layer. The most pronounced reduction in protein adsorption was achieved when the fraction of charged backbone segments was in the range 0.25-0.5 equivalent to a fraction of poly(ethylene oxide) side chains of 0.75-0.5. It was concluded that these polymers have enough electrostatic attachment points to ensure a strong binding to the surface, and at the same time a sufficient amount of poly(ethylene oxide) side chains to counteract protein adsorption. In contrast, a layer formed by a highly charged polyelectrolyte without side chains was unable to resists protein adsorption. On such a layer the adsorption of negatively charged BSA was strongly enhanced, and positively charged lysozyme adsorbed to a similar extent as to bare silica. AFM colloidal probe force measurement between silica surfaces with preadsorbed layers of bottle-brush polymers were conducted before and after exposure to BSA and lysozyme to gain insight into how proteins were incorporated in the bottle-brush polymer layers.

  17. Phase transfer of citrate stabilized gold nanoparticles using nonspecifically adsorbed polymers.

    PubMed

    Alkilany, Alaaldin M; Caravana, Aidan C; Hamaly, Majd A; Lerner, Kevin T; Thompson, Lucas B

    2016-01-01

    Many synthetic approaches for gold nanoparticles rely on an aqueous media, resulting in water-soluble nanoparticles, which limits the ability to incorporate gold nanoparticles into other organic solvents or hydrophobic polymeric composites. Surface functionalization and phase transfer approaches using alkylthiols or alkylamines, which strongly bind the gold surface, are common routes to overcome this limitation, however they are typically challenging methods. In this paper we report an approach to transport citrate capped gold nanoparticles into a variety of solvents, including ones that are hydrophobic and not miscible with water without the need for phase transfer agents. We suspend gold nanoparticles in a water-miscible polar organic solvent that also is a solvent for a hydrophobic polymer. After drying, polymer-stabilized gold nanoparticles were found to be dispersible in various hydrophobic solvents with maintained colloidal stability. This work investigates two hydrophobic polymers, namely (polymethylmethacrylate and polyvinylacetate), which share common chemical motifs but have significantly different physiochemical properties. Interestingly, a significant difference in their ability to stabilize the transferred gold nanoparticles is observed and discussed. PMID:26397907

  18. Phase transfer of citrate stabilized gold nanoparticles using nonspecifically adsorbed polymers.

    PubMed

    Alkilany, Alaaldin M; Caravana, Aidan C; Hamaly, Majd A; Lerner, Kevin T; Thompson, Lucas B

    2016-01-01

    Many synthetic approaches for gold nanoparticles rely on an aqueous media, resulting in water-soluble nanoparticles, which limits the ability to incorporate gold nanoparticles into other organic solvents or hydrophobic polymeric composites. Surface functionalization and phase transfer approaches using alkylthiols or alkylamines, which strongly bind the gold surface, are common routes to overcome this limitation, however they are typically challenging methods. In this paper we report an approach to transport citrate capped gold nanoparticles into a variety of solvents, including ones that are hydrophobic and not miscible with water without the need for phase transfer agents. We suspend gold nanoparticles in a water-miscible polar organic solvent that also is a solvent for a hydrophobic polymer. After drying, polymer-stabilized gold nanoparticles were found to be dispersible in various hydrophobic solvents with maintained colloidal stability. This work investigates two hydrophobic polymers, namely (polymethylmethacrylate and polyvinylacetate), which share common chemical motifs but have significantly different physiochemical properties. Interestingly, a significant difference in their ability to stabilize the transferred gold nanoparticles is observed and discussed.

  19. A new generation of electrochemical supercapacitors based on layer-by-layer polymer films

    NASA Astrophysics Data System (ADS)

    Christinelli, Wania Ap.; Gonçalves, Roger; Pereira, Ernesto C.

    2016-01-01

    Here we report supercapacitors fabricated with the layer-by-layer (LBL) technique using two polymers, namely poly(o-methoxyaniline) (POMA) and poly(3-thiophene acetic acid) (PTAA). The electrochemical performances of POMA/PTAA supercapacitors were characterized by cyclic voltammetry and electrochemical impedance spectroscopy. The results were compared with POMA casting film. The specific capacitance of LBL films increases almost linearly with a number of bilayers which were not observed for POMA casting films. The results of this investigation demonstrate that the self-doping effect between POMA and PTAA can change the properties on films and can be successfully used as a supercapacitor technology.

  20. Polymer-Layered Silicate Nanocomposites for Cryotank Applications

    NASA Technical Reports Server (NTRS)

    Miller, Sandi G.; Meador, Michael A.

    2007-01-01

    Previous composite cryotank designs have relied on the use of conventional composite materials to reduce microcracking and permeability. However, revolutionary advances in nanotechnology derived materials may enable the production of ultra-lightweight cryotanks with significantly enhanced durability and damage tolerance, as well as reduced propellant permeability. Layered silicate nanocomposites are especially attractive in cryogenic storage tanks based on results that have been reported for epoxy nanocomposite systems. These materials often exhibit an order of magnitude reduction in gas permeability when compared to the base resin. In addition, polymer-silicate nanocomposites have been shown to yield improved dimensional stability, strength, and toughness. The enhancement in material performance of these systems occurs without property trade-offs which are often observed in conventionally filled polymer composites. Research efforts at NASA Glenn Research Center have led to the development of epoxy-clay nanocomposites with 70% lower hydrogen permeability than the base epoxy resin. Filament wound carbon fiber reinforced tanks made with this nanocomposite had a five-fold lower helium leak rate than the corresponding tanks made without clay. The pronounced reduction observed with the tank may be due to flow induced alignment of the clay layers during processing. Additionally, the nanocomposites showed CTE reductions of up to 30%, as well as a 100% increase in toughness.

  1. Investigation of thin polymer layers for biosensor applications

    NASA Astrophysics Data System (ADS)

    Saftics, András; Agócs, Emil; Fodor, Bálint; Patkó, Dániel; Petrik, Péter; Kolari, Kai; Aalto, Timo; Fürjes, Péter; Horvath, Robert; Kurunczi, Sándor

    2013-09-01

    Novel biosensors made of polymers may offer advantages over conventional technology such as possibility of mass production and tunability of the material properties. With the ongoing work on the polymer photonic chip fabrication in our project, simple model samples were tested parallel for future immobilization and accessing conditions for applications in typical aqueous buffers. The model samples consist of a thin, high refractive index polyimide film on top of TEOS on Si wafer. These model samples were measured by in situ spectroscopic ellipsometry using different aqueous buffers. The experiments revealed a high drift in aqueous solutions; the drift in the ellipsometric parameters (delta, psi) can be evaluated and presented as changes in thickness and refractive index of the polyimide layer. The first molecular layer of immobilization is based on polyethyleneimine (PEI). The signal for the PEI adsorption was detected on a stable baseline, only after a long conditioning. The stability of polyimide films in aqueous buffer solutions should be improved toward the real biosensor application. Preliminary results are shown on the possibilities to protect the polyimide. Optical Waveguide Lightmode Spectroscopy (OWLS) has been used to demonstrate the shielding effect of the thin TiO2 adlayer in biosensor applications.

  2. Influence of the bound polymer layer on nanoparticle diffusion in polymer melts

    DOE PAGES

    Griffin, Philip J.; Bocharova, Vera; Middleton, L. Robert; Composto, Russell J.; Clarke, Nigel; Schweizer, Kenneth S.; Winey, Karen I.

    2016-09-23

    We measure the center-of-mass diffusion of silica nanoparticles (NPs) in entangled poly(2-vinylpyridine) (P2VP) melts using Rutherford backscattering spectrometry. While these NPs are well within the size regime where enhanced, nonhydrodynamic NP transport is theoretically predicted and has been observed experimentally (2RNP/dtube ≈ 3, where 2RNP is the NP diameter and dtube is the tube diameter), we find that the diffusion of these NPs in P2VP is in fact well-described by the hydrodynamic Stokes–Einstein relation. The effective NP diameter 2Reff is significantly larger than 2RNP and strongly dependent on P2VP molecular weight, consistent with the presence of a bound polymer layermore » on the NP surface with thickness heff ≈ 1.1Rg. Our results show that the bound polymer layer significantly augments the NP hydrodynamic size in polymer melts with attractive polymer–NP interactions and effectively transitions the mechanism of NP diffusion from the nonhydrodynamic to hydrodynamic regime, particularly at high molecular weights where NP transport is expected to be notably enhanced. Lastly, these results provide the first experimental demonstration that hydrodynamic NP transport in polymer melts requires particles of size ≳5dtube, consistent with recent theoretical predictions.« less

  3. 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.

  4. FTIR spectroscopy and thermodynamics of hydrogen adsorbed in a cross-linked polymer.

    PubMed

    Spoto, Giuseppe; Vitillo, Jenny G; Cocina, Donato; Damin, Alessandro; Bonino, Francesca; Zecchina, Adriano

    2007-09-28

    The adsorption of H(2) in a cross-linked poly(styrene-co-divinylbenzene) (St-DVB) microporous polymer (BET surface area 920 m(2) g(-1)) is studied by volumetric and gravimetric methods, FTIR spectroscopy at variable temperature (300-14 K) and ab initio calculations. At 77 K the polymer reversibly stores up to 1.3 mass% H(2) at a pressure of 1 bar and 1.8 mass% at 10 bar. The adsorption process involves the specific interaction of H(2) with the structural phenyl rings through weak dispersive forces. The interacting molecules become IR active and give rise to vibrational and rotational-vibrational manifestations which are affected by the temperature, the contact time and the H(2) equilibrium pressure. The spectra of the H(2)/St-DVB system reported here represent the first IR evidence of the adsorption of hydrogen on unsaturated molecules. The adsorption enthalpy is evaluated by the VTIR (variable temperature IR spectroscopy) method (C. Otero Areán et al., Phys. Chem. Chem. Phys., 2007, DOI: 10.1039/b615535a) and compared with the results of ab initio calculations for the H(2)/benzene interaction and with literature data.

  5. Adsorbed serum albumin is permissive to macrophage attachment to perfluorocarbon polymer surfaces in culture.

    PubMed

    Godek, M L; Michel, R; Chamberlain, L M; Castner, D G; Grainger, D W

    2009-02-01

    Monocyte/macrophage adhesion to biomaterials, correlated with foreign body response, occurs through protein-mediated surface interactions. Albumin-selective perfluorocarbon (FC) biomaterials are generally poorly cell-conducive because of insufficient receptor-mediated surface interactions, but macrophages bind to albumin-coated substrates and also preferentially to highly hydrophobic fluorinated surfaces. Bone marrow macrophages (BMMO) and IC-21, RAW 264.7, and J774A.1 monocyte/macrophage cells were cultured on FC surfaces. Protein deposition onto two distinct FC surfaces from complex and single-component solutions was tracked using fluorescence and time-of-flight secondary ion mass spectrometry (ToF-SIMS) methods. Cell adhesion and growth on protein pretreated substrates were compared by light microscopy. Flow cytometry and integrin-directed antibody receptor blocking were used to assess integrins critical for monocyte/macrophage adhesion in vitro. Albumin predominantly adsorbs onto both FC surfaces from 10% serum. In cultures preadsorbed with albumin or serum-dilutions, BMMO responded similar to IC-21 at early time points. Compared with Teflon AF, plasma-polymerized FC was less permissive to extended cell proliferation. The beta(2) integrins play major roles in macrophage adhesion to FC surfaces: antibody blocking significantly disrupted cell adhesion. Albumin-mediated cell adhesion mechanisms to FC surfaces could not be clarified. Primary BMMO and secondary IC-21 macrophages behave similarly on FC surfaces, regardless of preadsorbed protein biasing, with respect to adhesion, cell morphology, motility, and proliferation. PMID:18306309

  6. Photoinduced Reconfiguration Cycle in a Molecular Adsorbate Layer Studied by Femtosecond Inner-Shell Photoelectron Spectroscopy

    SciTech Connect

    Dachraoui, H.; Michelswirth, M.; Bartz, P.; Pfeiffer, W.; Heinzmann, U.; Siffalovic, P.; Schaefer, C.; Schnatwinkel, B.; Mattay, J.; Drescher, M.

    2011-03-11

    A time-resolved study of core-level chemical shifts in a monolayer of aromatic molecules reveals complex photoinduced reaction dynamics. The combination of electron spectroscopy for chemical analysis and ultrashort pulse excitation in the extreme ultraviolet allows performing time-correlated 4d-core-level spectroscopy of iodine atoms that probe the local chemical environment in the adsorbate molecule. The selectivity of the method unveils metastable molecular configurations that appear about 50 ps after the excitation and are efficiently quenched back to the ground state.

  7. Subharmonic excitation in amplitude modulation atomic force microscopy in the presence of adsorbed water layers

    SciTech Connect

    Santos, Sergio; Barcons, Victor; Verdaguer, Albert; Chiesa, Matteo

    2011-12-01

    In ambient conditions, nanometric water layers form on hydrophilic surfaces covering them and significantly changing their properties and characteristics. Here we report the excitation of subharmonics in amplitude modulation atomic force microscopy induced by intermittent water contacts. Our simulations show that there are several regimes of operation depending on whether there is perturbation of water layers. Single period orbitals, where subharmonics are never induced, follow only when the tip is either in permanent contact with the water layers or in pure noncontact where the water layers are never perturbed. When the water layers are perturbed subharmonic excitation increases with decreasing oscillation amplitude. We derive an analytical expression which establishes whether water perturbations compromise harmonic motion and show that the predictions are in agreement with numerical simulations. Empirical validation of our interpretation is provided by the observation of a range of values for apparent height of water layers when subharmonic excitation is predicted.

  8. Observation of spin-glass behavior in nickel adsorbed few layer graphene

    SciTech Connect

    Mitra, Sreemanta; Mondal, Oindrila; Banerjee, Sourish; Chakravorty, Dipankar

    2013-01-14

    Nickel-adsorbed graphene was prepared by first synthesizing graphite oxide (GO) by modified Hummers' method and then reducing a solution containing both GO and Ni{sup 2+}. Energy dispersive X-ray spectroscopy analysis showed 31 at. % nickel was present. Magnetization measurements under both dc and ac magnetic fields were carried out in the temperature range 2 K to 300 K. The zero field cooled and field cooled magnetization data showed a pronounced irreversibility at a temperature around 20 K. The analysis of the ac susceptibility data was carried out by both Vogel-Fulcher as well as power law. From dynamic scaling analysis, the microscopic flipping time {tau}{sub 0}{approx}10{sup -13}s and critical exponent z{nu}=5.9{+-}0.1 were found, indicating the presence of conventional spin glass in the system. The spin glass transition temperature was estimated as 19.5 K. Decay of thermoremanent magnetization was explained by stretched exponential function with a value of the exponent as 0.6. From the results, it is concluded that nickel adsorbed graphene behaves like a spin-glass.

  9. Performance of electric double layer capacitors with polymer gel electrolytes

    SciTech Connect

    Ishikawa, Masashi; Kishino, Takahiro; Katada, Naoji; Morita, Masayuki

    2000-07-01

    Polymer gel electrolytes consisting of poly(vinylidene fluoride) (PVdF), tetraethylammonium tetrafluoroborate (TEABF{sub 4}), and propylene carbonate (PC) as a plasticizer have been investigated for electric double layer capacitors. The PVdF gel electrolytes showed high ionic conductivity (ca. 6 mS/cm at 298 K). To assemble model capacitors with the PVdF gel electrolytes and activated carbon fiber cloth electrodes, a pair of the fixed electrodes was soaked in a precursor solution containing PC, PVdF, and TEABF{sub 4}, followed by evaporation of the PC solvent in a vacuum oven. The resulting gel electrolytes were in good contact with the electrodes. The model capacitors with the PVdF gel electrolytes showed a large value of capacitance and high coulombic efficiency in operation voltage ranges of 1--2 and 1--3 V. It is worth noting that the capacitors with the PVdF electrolytes showed long voltage retention in a self-discharge test. These good characteristics of the gel capacitors were comparable to those of typical double layer capacitors with a liquid organic electrolyte containing PC and TEABF{sub 4}; rather, the voltage retentivity of the PVdF gel capacitors was much superior to that of the capacitors with the organic electrolyte.

  10. Synthesis, Development, and Testing of High-Surface-Area Polymer-Based Adsorbents for the Selective Recovery of Uranium from Seawater

    DOE PAGES

    Oyola, Yatsandra; Janke, Christopher J.; Dai, Sheng

    2016-02-29

    The ocean contains uranium with an approximate concentration of 3.34 ppb, which can serve as an incredible supply source to sustain nuclear energy in the United States. Unfortunately, technology currently available to recover uranium from seawater is not efficient enough and mining uranium on land is still more economical. For this study, we have developed polymer-based adsorbents with high uranium adsorption capacities by grafting amidoxime onto high-surface-area polyethylene (PE) fibers. Various process conditions have been screened, in combination with developing a rapid testing protocol (<24 h), to optimize the process. These adsorbents are synthesized through radiation-induced grafting of acrylonitrile (AN)more » and methacrylic acid (MAA) onto PE fibers, followed by the conversion of nitriles to amidoximes and basic conditioning. In addition, the uranium adsorption capacity, measured in units of gU/kgads, is greatly increased by reducing the diameter of the PE fiber or changing its morphology. An increase in the surface area of the PE polymer fiber allows for more grafting sites that are positioned in more-accessible locations, thereby increasing access to grafted molecules that would normally be located in the interior of a fiber with a larger diameter. Polymer fibers with hollow morphologies are able to adsorb beyond 1 order of magnitude more uranium from simulated seawater than current commercially available adsorbents. Finally, several high-surface-area fibers were tested in natural seawater and were able to extract 5–7 times more uranium than any adsorbent reported to date.« less

  11. High-performance polymer/layered silicate nanocomposites

    NASA Astrophysics Data System (ADS)

    Heidecker, Matthew J.

    High-performance layered-silicate nanocomposites of Polycarbonate (PC), poly(ethylene terephthalate) (PET), and their blends were produced via conventional melt-blending techniques. The focus of this thesis was on the fundamentals of dispersion, control of thermal stability, maintenance of melt-blending processing conditions, and on optimization of the composites' mechanical properties via the design of controlled and thermodynamically favorable nano-filler dispersions within the polymer matrices. PET and PC require high temperatures for melt-processing, rendering impractical the use of conventional/commercial organically-modified layered-silicates, since the thermal degradation temperatures of their ammonium surfactants lies below the typical processing temperatures. Thus, different surfactant chemistries must be employed in order to develop melt-processable nanocomposites, also accounting for polymer matrix degradation due to water (PET) or amine compounds (PC). Novel high thermal-stability surfactants were developed and employed in montmorillonite nanocomposites of PET, PC, and PC/PET blends, and were compared to the respective nanocomposites based on conventional quaternary-ammonium modified montmorillonites. Favorable dispersion was achieved in all cases, however, the overall material behavior -- i.e., the combination of crystallization, mechanical properties, and thermal degradation -- was better for the nanocomposites based on the thermally-stable surfactant fillers. Studies were also done to trace, and ultimately limit, the matrix degradation of Polycarbonate/montmorillonite nanocomposites, through varying the montmorillonite surfactant chemistry, processing conditions, and processing additives. Molecular weight degradation was, maybe surprisingly, better controlled in the conventional quaternary ammonium based nanocomposites -- even though the thermal stability of the organically modified montmorillonites was in most cases the lowest. Dependence of the

  12. Layer-by-layer assembly of ferrocene-modified linear polyethylenimine redox polymer films.

    PubMed

    DeLuca, Jared L; Hickey, David P; Bamper, Daniel A; Glatzhofer, Daniel T; Johnson, Matthew B; Schmidtke, David W

    2013-07-22

    Herein, both electrostatic and covalent layer-by-layer assembly were used for the construction of multicomposite thin films using a ferrocene-modified linear poly(ethylenimine) redox polymer (Fc-C6-LPEI) as the cationic polyelectrolye, and poly(acrylic acid) (PAA), poly(glutamic acid) (PGA), or glucose oxidase (GOX) as the negative polyelectrolyte. The assembly of the multilayer films was characterized by cyclic voltammetry (CV), UV/Vis spectroscopy, and ellipsometry with the enzymatic response of the films containing GOX being characterized via constant potential amperometry. CV measurements suggested that the successful buildup of multilayer films was dependent upon the nature of the anionic polyelectrolyte used. Electrostatic assembly of films composed of Fc-C6-LPEI and either PAA or PGA produced large oxidation peak current densities of 630 and 670 μA cm(-2), respectively, during cyclic voltammetry. Increased measured absorbance by UV/Vis spectroscopy and increased measured film thicknesses (400-600 nm) by ellipsometry provided additional evidence of successful film formation. In contrast, the films incorporating GOX that were electrostatically assembled surprisingly produced significantly lower electrochemical responses (12 μA cm(-2)), low absorbance values, and reduced film thicknesses (~15 nm), and glucose electro-oxidation current densities less than 1 μA cm(-2), which all suggested unstable or minimal film formation. Subsequently, we developed a covalent layer-by-layer approach to fabricate films of Fc-C6-LPEI/GOX by covalently linking the amine groups of Fc-C6-LPEI to the aldehyde groups of periodate-oxidized glucose oxidase. Covalent assembly of the Fc-C6-LPEI/GOX films produced oxidation peak current densities during cyclic voltammetry of 40 μA cm(-2) and glucose electro-oxidation current densities of 220 μA cm(-2). These films also showed an increase in their thicknesses (~140 nm) relative to the electrostatic GOX films. For the films containing

  13. X-ray Reflectivity Studies of Adsorbed Proteins on Langmuir Layers

    NASA Astrophysics Data System (ADS)

    Málková, Šárka; Pingali, Sai V.; Long, Fei; Cho, Wonhwa; Schlossman, Mark L.

    2002-03-01

    Synchrotron X-ray reflectivity is used to study the interaction of the C2 domain of cytosolic phospholipase A2 (cPLA_2-C2) with a phospholipid membrane. SOPC (1-steraoyl-2-oleoyl-sn-glycero-3-phosphocholine) monolayer has been chosen as our model membrane. SOPC monolayer is supported on a buffered, Ca^2+ containing aqueous solution. The original phospholipid layer, which can be described by a two layer model roughened by capillary wave theory, is modified and a three layer model is necessary to fit the data after the protein is injected. The data analysis indicates that a third layer attached to the phospholipid headgroup region is formed. This additional layer corresponds to proteins bound to the phospholipid. The mechanism of the protein binding to the lipid depends on the initial lipid pressure with adsorption being less pronounced at higher pressures. Two control experiments are performed. Buffer containing no Ca^2+ is used in the first and F35/L39A mutant of cPLA_2-C2 (the mutation is in the region containing ligands for multiple Ca^2+ ions) is used in the second. Reflectivity curves do not show any evidence of protein adsorption to the phospholipid monolayer in any of our two control experiments. Our results thus support the idea that the initial pressure of the lipid, Ca^2+ ions and Ca^2+ binding sites of cPLA_2-C2 are important factors for the membrane binding of this protein.

  14. Bionanocomposites based on layered silicates and cationic starch as eco-friendly adsorbents for hexavalent chromium removal.

    PubMed

    Koriche, Yamina; Darder, Margarita; Aranda, Pilar; Semsari, Saida; Ruiz-Hitzky, Eduardo

    2014-07-21

    Functional bionanocomposites based on two layered silicates, the commercial montmorillonite known as Cloisite®Na and a natural bentonite from Algeria, were prepared by intercalation of cationic starch, synthesized with two different degrees of substitution, 0.85 and 0.55. After characterization of the prepared bionanocomposites by XRD and zeta potential measurements, batch studies were conducted to evaluate the adsorption capacity of hexavalent chromium anions from aqueous solution. The adsorption isotherms, adsorption kinetics, and the effect of pH on the process were studied. The removal efficiency was evaluated in the presence of competing anions such as NO3(-), ClO4(-), SO4(2-) and Cl(-). In order to regenerate the adsorbent for its repeated use, the regeneration process was studied in two different extractant solutions, 0.1 M NaCl at pH 10 and 0.28 M Na2CO3 at pH 12. PMID:24658793

  15. Immobilization of DNA at Glassy Ccarbon Electrodes: A Critical Study of Adsorbed Layer

    PubMed Central

    Pedano, M. L.; Rivas, G. A.

    2005-01-01

    In this work we present a critical study of the nucleic acid layer immobilized at glassy carbon electrodes. Different studies were performed in order to assess the nature of the interaction between DNA and the electrode surface. The adsorption and electrooxidation of DNA demonstrated to be highly dependent on the surface and nature of the glassy carbon electrode. The DNA layer immobilized at a freshly polished glassy carbon electrode was very stable even after applying highly negative potentials. The electron transfer of potassium ferricyanide, catechol and dopamine at glassy carbon surfaces modified with thin (obtained by adsorption under controlled potential conditions) and thick (obtained by casting the glassy carbon surface with highly concentrated DNA solutions) DNA layers was slower than that at the bare glassy carbon electrode, although this effect was dependent on the thickness of the layer and was not charge selective. Raman experiments showed an important decrease of the vibrational modes assigned to the nucleobases residues, suggesting a strong interaction of these residues with the electrode surface. The hybridization of oligo(dG)21 and oligo(dC)21 was evaluated from the guanine oxidation signal and the reduction of the redox indicator Co(phen)33+. In both cases the chronopotentiometric response indicated that the compromise of the bases in the interaction of DNA with the electrode surface is too strong, preventing further hybridization. In summary, glassy carbon is a useful electrode material to detect DNA in a direct and very sensitive way, but not to be used for the preparation of biorecognition layers by direct adsorption of the probe sequence on the electrode surface for detecting the hybridization event.

  16. Influence of carboxylic ion-pairing reagents on retention of peptides in thin-layer chromatography systems with C18 silica-based adsorbents.

    PubMed

    Gwarda, Radosław Ł; Aletańska-Kozak, Monika; Klimek-Turek, Anna; Ziajko-Jankowska, Agnieszka; Matosiuk, Dariusz; Dzido, Tadeusz H

    2016-04-01

    One of the main problems related to chromatography of peptides concerns adverse interactions of their strong basic groups with free silanol groups of the silica based stationary phase. Influence of type and concentration of ion-pairing regents on peptide retention in reversed-phase high-performance liquid chromatography (RP-HPLC) systems has been discussed before. Here we present influence of these mobile phase additives on retention of some peptide standards in high-performance thin-layer chromatography (HPTLC) systems with C18 silica-based adsorbents. We prove, that due to different characteristic of adsorbents used in both techniques (RP HPLC and HPTLC), influence of ion-pairing reagents on retention of basic and/or amphoteric compounds also may be quite different. C18 silica-based HPTLC adsorbents provide more complex mechanism of retention and should be rather considered as mixed-mode adsorbents.

  17. Layer structured graphite oxide as a novel adsorbent for humic acid removal from aqueous solution.

    PubMed

    Hartono, Tri; Wang, Shaobin; Ma, Qing; Zhu, Zhonghua

    2009-05-01

    Layer structured graphite oxide (GO) was prepared from graphite using the Hummers-Offeman method, characterised using N(2) adsorption, XRD, XPS, SEM(TEM), and FT-IR, and tested for humic acid (HA) adsorption in aqueous solution. XRD, XPS, and FT-IR measurements indicate the formation of layered structure with strong functional groups of GO. It is also found that the GO exhibits strong and much higher adsorption capacity of HA than graphite. The maximum adsorption capacity of the GO from the Langmuir isotherm is 190 mg/g, higher than activated carbon. For the adsorption, several parameters will affect the adsorption such as solid loading and pH. HA adsorption will decrease with increasing pH and an optimum GO loading is required for maximum adsorption. PMID:19233379

  18. Layered polymer: inorganic composite waveguides for biosensor applications

    NASA Astrophysics Data System (ADS)

    Hiltunen, Jussi; Wang, Meng; Liedert, Christina; Aikio, Sanna; Masuda, Noriyuki; Pearce, Stuart; Charlton, Martin; Karioja, Pentti

    2012-06-01

    In this work, we investigate the usability of layered polymer - inorganic composite waveguides for label-free sensing of surface bound bioreactions in an aqueous environment. The waveguide structure consists of a nanoimprint fabricated polymeric inverted rib waveguide with a sputtered Ta2O5 thin film on top. The interaction of the optical field with the surface is increased as a consequence of the mode profile localization near the surface, when high-index coating is deposited on a low-index waveguide. Young interferometer configuration with reference and sensors waveguide arms was utilized in sensor chips. Light from a laser source was end-fire coupled into the chips and interference pattern produced by the outcoupled light was investigated. External μ-fluidic pump was used to produce the analyte flow. Ambient refractive index change was characterized by applying DI-water with varying glucose concentration on waveguides. With the waveguide length of 1 cm a detection limit in the order of 10-7 - 10-6 refractive index unit (RIU) was achieved. Specific binding reactions on the surface were investigated with C - reactive protein (CRP) antibodies and antigens.

  19. Extended triple layer modeling of arsenate and phosphate adsorption on a goethite-based granular porous adsorbent.

    PubMed

    Kanematsu, Masakazu; Young, Thomas M; Fukushi, Keisuke; Green, Peter G; Darby, Jeannie L

    2010-05-01

    The extended triple layer model (ETLM), which is consistent with spectroscopic and theoretical molecular evidence, is first systematically tested for its capability to model adsorption of arsenate and phosphate, a strong competitor, on a common goethite-based granular porous adsorptive media (Bayoxide E33 (E33)) in water treatment systems under a wide range of solution conditions. Deprotonated bidentate-binuclear, protonated bidentate-binuclear, and deprotonated monodentate complexes are chosen as surface species for both arsenate and phosphate. The estimated values of the ETLM parameters of arsenate for the adsorbent are close to those for pure goethite minerals previously determined by others. The ETLM predictions for arsenate and phosphate adsorption basically agree with experimental results over a wide range of pH, surface coverage, and solid concentrations. High background electrolyte concentration (i.e., I = 0.1 M), however, was found to strongly impact arsenate and phosphate adsorption on E33 probably because of the porous structure of the adsorbent, which cannot be observed for pure goethite minerals and could not be completely modeled by the ETLM. Prediction of phosphate adsorption isotherms at higher pH were relatively poor, and this may suggest searching for alternative surface species for phosphate. Since adsorption equilibrium constants of major coexisting ions encountered in water treatment systems for goethite minerals have been estimated by others, the application of ETLM theory to this common goethite-based adsorptive media will enable us to understand how those coexisting ions macroscopically and thermodynamically interact with arsenate and phosphate in the environment of adsorptive water treatment system in a way consistent with molecular and spectroscopic evidence.

  20. Hybrid polymer networks as ultra low `k` dielectric layers

    DOEpatents

    Lewicki, James; Worsley, Marcus A.

    2016-02-16

    According to one embodiment, a polymeric material includes at least one polydimethylsiloxane (PDMS) polymer, and at least one polyhedral oligomericsilsequioxane (POSS) molecule. According to another embodiment, a method includes providing at least one polydimethylsiloxane (PDMS) polymer, providing at least one polyhedral oligomericsilsequioxane (POSS) molecule, and coupling the at least one PDSM polymer to the at least one POSS molecule to form a hybrid polymeric material.

  1. MAPLE prepared heterostructures with arylene based polymer active layer for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Stanculescu, F.; Rasoga, O.; Catargiu, A. M.; Vacareanu, L.; Socol, M.; Breazu, C.; Preda, N.; Socol, G.; Stanculescu, A.

    2015-05-01

    This paper presents some studies about the preparation by matrix-assisted pulsed laser evaporation (MAPLE) technique of heterostructures with single layer of arylene based polymer, poly[N-(2-ethylhexyl)2.7-carbazolyl vinylene]/AMC16 and poly[N-(2-ethylhexyl)2.7-carbazolyl 1.4-phenylene ethynylene]/AMC22, and with layers of these polymers mixed with Buckminsterfullerene/C60 in the weight ratio of 1:2 (AMC16:C60) and 1:3 (AMC22:C60). The deposited layers have been characterized by spectroscopic (UV-Vis-NIR, PL, FTIR) and microscopic (SEM, AFM) methods. The effect of the polymer particularities on the optical and electrical properties of the structures based on polymer and polymer:C60 mixed layer has been analyzed. The study of the electrical properties has revealed typical solar cell behavior for the heterostructure prepared by MAPLE on glass/ITO/PEDOT-PSS with AMC16, AMC22 and AMC22:C60 layer, confirming that this method is adequate for the preparation of polymeric and mixed active layers for solar cells applications. The highest photovoltaic effect was shown by the solar cell structure realized with single layer of AMC16 polymer: glass/ITO/PEDOT-PSS/AMC16/Al.

  2. Speciation of trace metals in natural waters: the influence of an adsorbed layer of natural organic matter (NOM) on voltammetric behaviour of copper.

    PubMed

    Louis, Yoann; Cmuk, Petra; Omanović, Dario; Garnier, Cédric; Lenoble, Véronique; Mounier, Stéphane; Pizeta, Ivanka

    2008-01-01

    The influence of an adsorbed layer of the natural organic matter (NOM) on voltammetric behaviour of copper on a mercury drop electrode in natural water samples was studied. The adsorption of NOM strongly affects the differential pulse anodic stripping voltammogram (DPASV) of copper, leading to its distortion. Phase sensitive ac voltammetry confirmed that desorption of adsorbed NOM occurs in general at accumulation potentials more negative than -1.4V. Accordingly, an application of negative potential (-1.6V) for a very short time at the end of the accumulation time (1% of total accumulation time) to remove the adsorbed NOM was introduced in the measuring procedure. Using this protocol, a well-resolved peak without interferences was obtained. It was shown that stripping chronopotentiogram of copper (SCP) in the depletive mode is influenced by the adsorbed layer in the same manner as DPASV. The influence of the adsorbed NOM on pseudopolarographic measurements of copper and on determination of copper complexing capacity (CuCC) was demonstrated. A shift of the peak potential and the change of the half-peak width on the accumulation potential (for pseudopolarography) and on copper concentration in solution (for CuCC) were observed. By applying a desorption step these effects vanished, yielding different final results.

  3. Enhanced humoral and cell-mediated immune responses generated by cationic polymer-coated PLA microspheres with adsorbed HBsAg.

    PubMed

    Chen, Xiaoming; Liu, Yuying; Wang, Lianyan; Liu, Yuan; Zhang, Weifeng; Fan, Bei; Ma, Xiaowei; Yuan, Qipeng; Ma, Guanghui; Su, Zhiguo

    2014-06-01

    Surface-engineered particulate delivery systems for vaccine administration have been widely investigated in experimental and clinical studies. However, little is known about charge-coated microspheres as potential recombinant subunit protein antigen delivery systems in terms of adsorption and related immune responses. In the present study, cationic polymers, including chitosan (CS), chitosan chloride (CSC), and polyethylenimine (PEI), were used to coat PLA microspheres to build positively charged surfaces. Antigen adsorption capacity was enhanced with increased surface charge of coated microspheres. In macrophages, HBsAg adsorbed on the surface of cationic microspheres specifically enhanced antigen uptake and augmented CD86, MHC I, and MHC II expression and IL-1β, IL-6, TNF-α, and IL-12 release. Antigens were more likely to localize independent of lysosomes after phagocytosis in antigen-attached cationic microsphere formulations. After intraperitoneal immunization, cationic microsphere-based vaccine formulations generated a rapid and efficient humoral immune response and cytokine release as compared with aluminum-adsorbed vaccine and free antigens in vivo. Moreover, microspheres coated with cationic polymers with relatively high positive charges and higher antigen adsorption exhibited strong stimulation of the Th1 response. In conclusion, PLA microspheres coated with cationic polymers may be a potential recombinant antigen delivery system to induce strong cell and humoral immune responses.

  4. Determination of imidazole derivatives by micellar electrokinetic chromatography combined with solid-phase microextraction using activated carbon-polymer monolith as adsorbent.

    PubMed

    Shih, Yung-Han; Lirio, Stephen; Li, Chih-Keng; Liu, Wan-Ling; Huang, Hsi-Ya

    2016-01-01

    In this study, an effective method for the separation of imidazole derivatives 2-methylimidazole (2-MEI), 4- methylimidazole (4-MEI) and 2-acetyl-4-tetrahydroxybutylimidazole (THI) in caramel colors using cation-selective exhaustive injection and sweeping micellar electrokinetic chromatography (CSEI-sweeping-MEKC) was developed. The limits of detection (LOD) and quantitation (LOQ) for the CSEI-sweeping-MEKC method were in the range of 4.3-80μgL(-1) and 14-270μgL(-1), respectively. Meanwhile, a rapid fabrication activated carbon-polymer (AC-polymer) monolithic column as adsorbent for solid-phase microextraction (SPME) of imidazole colors was developed. Under the optimized SPME condition, the extraction recoveries for intra-day, inter-day and column-to-column were in the range of 84.5-95.1% (<6.3% RSDs), 85.6-96.1% (<4.9% RSDs), and 81.3-96.1% (<7.1% RSDs), respectively. The LODs and LOQs of AC-polymer monolithic column combined with CSEI-sweeping-MEKC method were in the range of 33.4-60.4μgL(-1) and 111.7-201.2μgL(-1), respectively. The use of AC-polymer as SPME adsorbent demonstrated the reduction of matrix effect in food samples such as soft drink and alcoholic beverage thereby benefiting successful determination of trace-level caramel colors residues using CSEI-sweeping-MEKC method. The developed AC-polymer monolithic column can be reused for more than 30 times without any significant loss in the extraction recovery for imidazole derivatives.

  5. Synthesis and characterization of low flammability polymer/layered silicate nanocomposites

    NASA Astrophysics Data System (ADS)

    Zhang, Xin

    There has been significant interest in the applications of polymer nanocomposites in a variety of areas. Polymer/layered silicate nanocomposites have been of interest because of relatively low raw material cost and improved materials properties such as higher Young's modulus, higher thermal deformation temperature, lower small molecule permeability, lower density (compared to metals and traditional glass fiber reinforced composites) as well as low flammability. The relationships between the flammability and the dispersion of the layered silicate platelets inside the polymer matrix is just being established. The complete set of factors that affect the flammability of polymer/layered nanocomposites are not fully identified. In this thesis polymer/layered silicate nanocomposites with different degrees of platelet dispersion were synthesized. The structure of the nanocomposites was characterized by X-ray diffraction (XRD), small angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). The flammability of these nanocomposites was characterized by TGA, cone calorimetry and gasification. By coupling the structural and flammability data it has been concluded that forming a nanometer scale dispersed structure significantly improves the flammability but the details of the degree of dispersion are not critical. The improvement in the flammability arises from the formation of a residue or char layer at the surface of the nanocomposite. This residue layer acts as a radiation shield and as a physical barrier preventing the polymer degradation products from escaping and acting as fuel. It is observed that the stability of the residue layer formed during combustion has major impact on the flammability. This thesis also describes work to improve the flammability of the polymer/layered silicate nanocomposites by enhancing char/residue formation in order to improve the residue layer stability.

  6. Adsorption isotherms and structure of cationic surfactants adsorbed on mineral oxide surfaces prepared by atomic layer deposition.

    PubMed

    Wangchareansak, Thipvaree; Craig, Vincent S J; Notley, Shannon M

    2013-12-01

    The adsorption isotherms and aggregate structures of adsorbed surfactants on smooth thin-film surfaces of mineral oxides have been studied by optical reflectometry and atomic force microscopy (AFM). Films of the mineral oxides of titania, alumina, hafnia, and zirconia were produced by atomic layer deposition (ALD) with low roughness. We find that the surface strongly influences the admicelle organization on the surface. At high concentrations (2 × cmc) of cetyltrimethylammonium bromide (CTAB), the surfactant aggregates on a titania surface exhibit a flattened admicelle structure with an average repeat distance of 8.0 ± 1.0 nm whereas aggregates on alumina substrates exhibit a larger admicelle with an average separation distance of 10.5 ± 1.0 nm. A wormlike admicelle structure with an average separation distance of 7.0 ± 1.0 nm can be observed on zirconia substrates whereas a bilayered aggregate structure on hafnia substrates was observed. The change in the surface aggregate structure can be related to an increase in the critical packing parameter through a reduction in the effective headgroup area of the surfactant. The templating strength of the surfaces are found to be hafnia > alumina > zirconia > titania. Weakly templating surfaces are expected to have superior biocompatibility.

  7. Preparation of amino acid-based polymer functionalized magnetic nanoparticles as adsorbents for analysis of plant growth regulators in bean sprouts.

    PubMed

    Ji, Shilei; Qi, Li; Li, Nan; Wang, Minglin

    2016-09-01

    A novel magnetic solid phase extraction (MSPE) adsorbent has been developed for enriching two plant growth regulators, including 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chlorophenoxyacetic acid (4-CPA), in bean sprouts. For preparing the MSPE adsorbent, poly(N-methacryloyl-L-phenylalanine methyl ester (P(MA-L-Phe-OMe)), amino acid-based polymer, was modified onto the magnetic nanoparticles via "grafting to" method by free radical polymerization. The resultant P(MA-L-Phe-OMe)-functionalized magnetic nanoparticles (Fe3O4@P(MA-L-Phe-OMe)) were characterized by Fourier transform infrared (FT-IR) spectroscopy and elemental analysis. The adsorption amount of Fe3O4@P(MA-L-Phe-OMe) nanoparticles to 2,4-D and 4-CPA were 39.82mgg(-1) and 29.02mgg(-1), respectively. Moreover, the prepared MSPE adsorbents showed good selectivity towards 2,4-D and 4-CPA due to the hydrophobic interactions and electrostatic forces between the target analytes and Fe3O4@P(MA-L-Phe-OMe). The results demonstrated that the proposed MSPE adsorbents have high affinity to the targets 2,4-D and 4-CPA. Under the optimized conditions, the proposed materials were successfully applied to enrich 2,4-D and 4-CPA in bean sprouts samples. The recovery values of the bean sprouts solution spiked the targets were from 90.9% to 96.4% with the relative standard deviations of 2.3-3.9%. Our work proved that the novel Fe3O4@P(MA-L-Phe-OMe) nanoparticles were the good adsorbents of magnetic solid phase extraction (MSPE) and have good potential for the analysis of trace compound in real samples.

  8. Preparation of amino acid-based polymer functionalized magnetic nanoparticles as adsorbents for analysis of plant growth regulators in bean sprouts.

    PubMed

    Ji, Shilei; Qi, Li; Li, Nan; Wang, Minglin

    2016-09-01

    A novel magnetic solid phase extraction (MSPE) adsorbent has been developed for enriching two plant growth regulators, including 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chlorophenoxyacetic acid (4-CPA), in bean sprouts. For preparing the MSPE adsorbent, poly(N-methacryloyl-L-phenylalanine methyl ester (P(MA-L-Phe-OMe)), amino acid-based polymer, was modified onto the magnetic nanoparticles via "grafting to" method by free radical polymerization. The resultant P(MA-L-Phe-OMe)-functionalized magnetic nanoparticles (Fe3O4@P(MA-L-Phe-OMe)) were characterized by Fourier transform infrared (FT-IR) spectroscopy and elemental analysis. The adsorption amount of Fe3O4@P(MA-L-Phe-OMe) nanoparticles to 2,4-D and 4-CPA were 39.82mgg(-1) and 29.02mgg(-1), respectively. Moreover, the prepared MSPE adsorbents showed good selectivity towards 2,4-D and 4-CPA due to the hydrophobic interactions and electrostatic forces between the target analytes and Fe3O4@P(MA-L-Phe-OMe). The results demonstrated that the proposed MSPE adsorbents have high affinity to the targets 2,4-D and 4-CPA. Under the optimized conditions, the proposed materials were successfully applied to enrich 2,4-D and 4-CPA in bean sprouts samples. The recovery values of the bean sprouts solution spiked the targets were from 90.9% to 96.4% with the relative standard deviations of 2.3-3.9%. Our work proved that the novel Fe3O4@P(MA-L-Phe-OMe) nanoparticles were the good adsorbents of magnetic solid phase extraction (MSPE) and have good potential for the analysis of trace compound in real samples. PMID:27343600

  9. Buckling instabilities of nanoscale polymer films and colloidal particle layers

    NASA Astrophysics Data System (ADS)

    Gurmessa, Bekele Jemama

    Nanoscale polymer films have numerous potential applications such as protective coatings, flexible electronics, energy harvesting devices, and drug delivery systems. For realization of these potential applications, the mechanical properties of these materials and the underlying physics need to be understood. This dissertation focuses on understanding the responses of nanoscale films to mechanical deformations. In this regard, an elastic instability was exploited to locally bend and impart a local tensile stress in a nanoscale polystyrene film, and directly measure the resulting residual stress caused by the bending. Our results indicate that the onset of permanent deformation for thin polystyrene films is an order of magnitude smaller than what has been reported for the bulk value. In addition, not only is the onset of failure strain found to be small but also it increases with increased confinement. Using similar processing techniques, the yield strain of a more complex material---poly(styrene-b-divinylpyridine)---was studied. Similar to the polystyrene films, failure in polystyrene-b-poly(2-vinylpyridine) is also initiated at extremely low strain and is influenced by thin film confinement effects. In addition, we have demonstrated that internal nanostructure of self-assembled polystyrene-b-poly(2-vinylpyridine) affects the onset of failure strain. Having introduced an idealized heterogeneity to a sample through ultraviolet/ozone treatment, we have created samples ranging from continuous thin films to sets of isolated plates. We demonstrated that, when subjected to mechanical deformation, the unbounded plates form isotropic undulations that persist even beyond high strain. In contrast, isolated plates undergo non-isotropic undulations in the range of high strains. The non-isotropic undulation shape has been described through a simple numerical modeling subjected to controlled boundary conditions. The agreement between experiment and numerical modeling is

  10. Polymer chains grafted "to" and "from" layered silicate clay platelets.

    PubMed

    Mittal, V

    2007-10-01

    Polymerization of lauryl methacrylate "to" and "from" the surface of montmorillonite platelets was studied under a range of different reaction conditions. The polymerization was performed in order to achieve better organic coverage of the platelets, thus facilitating their exfoliation in the polymer matrices. For polymerization "to" the surface, a methacrylic functionality was first generated on the clay surface which was subsequently polymerized with the external lauryl methacrylate monomer. Substantial amounts of the polymer could be attached to the surface when lower polymerization temperatures and longer reaction times were used. Bulk polymerization was more effective in increasing the amount of polymer mass on the surface. In order to achieve polymerization "from" the surface, a bicationic initiator was first ionically bound on the surface followed by polymerization with lauryl methacrylate. Under the nonliving conditions, however, no significant amount of polymer could be grown from the surface. Nitroxide-mediated living polymerization was successful in eliminating suspected termination reactions leading to substantial gains in the organic mass bound to clay surfaces. Care was taken to avoid the presence of excess of unbound ammonium ions which can interfere in the grafting of polymer chains on the surface. X-ray diffraction and transmission electron microscopy in conjunction with thermogravimetric analysis confirmed the grafting of the polymer chains on the surface. PMID:17586519

  11. Sheet shape-controlling method for hundreds-of-nanometer-thick polymer film using soluble polymer layer

    NASA Astrophysics Data System (ADS)

    Shimbo, Sota; Fujie, Toshinori; Iwase, Eiji

    2016-06-01

    We proposed a sheet shape-controlling method for a hundreds-of-nanometers-thick polymeric ultrathin film (referred to as a “nanosheet”) for folding the film into a cylindrical shape and unfolding the film into a flat shape. To control the shape of the nanosheet, we used a triple-layered structure, which included a nanosheet and additional two layers of a water-soluble polymer. The additional two layers are thicker than the nanosheet, and one of the two layers was loaded to prestretch that layer. Therefore, the triple-layered structure was folded into a cylindrical shape owing to strain mismatch between the two layers and unfolded into a flat shape after the dissolution of the two layers. In this study, we could successfully estimate the radius of curvature of the triple-layered structure by considering the strain mismatch between the two layers. In addition, we confirmed that the triple-layered structure unfolded into a flat shape by the dissolution of the two layers.

  12. Numerical Well Testing Interpretation Model and Applications in Crossflow Double-Layer Reservoirs by Polymer Flooding

    PubMed Central

    Guo, Hui; He, Youwei; Li, Lei; Du, Song; Cheng, Shiqing

    2014-01-01

    This work presents numerical well testing interpretation model and analysis techniques to evaluate formation by using pressure transient data acquired with logging tools in crossflow double-layer reservoirs by polymer flooding. A well testing model is established based on rheology experiments and by considering shear, diffusion, convection, inaccessible pore volume (IPV), permeability reduction, wellbore storage effect, and skin factors. The type curves were then developed based on this model, and parameter sensitivity is analyzed. Our research shows that the type curves have five segments with different flow status: (I) wellbore storage section, (II) intermediate flow section (transient section), (III) mid-radial flow section, (IV) crossflow section (from low permeability layer to high permeability layer), and (V) systematic radial flow section. The polymer flooding field tests prove that our model can accurately determine formation parameters in crossflow double-layer reservoirs by polymer flooding. Moreover, formation damage caused by polymer flooding can also be evaluated by comparison of the interpreted permeability with initial layered permeability before polymer flooding. Comparison of the analysis of numerical solution based on flow mechanism with observed polymer flooding field test data highlights the potential for the application of this interpretation method in formation evaluation and enhanced oil recovery (EOR). PMID:25302335

  13. Tandem Solar Cells from Accessible Low Band-Gap Polymers Using an Efficient Interconnecting Layer.

    PubMed

    Bag, Santanu; Patel, Romesh J; Bunha, Ajaykumar; Grand, Caroline; Berrigan, J Daniel; Dalton, Matthew J; Leever, Benjamin J; Reynolds, John R; Durstock, Michael F

    2016-01-13

    Tandem solar cell architectures are designed to improve device photoresponse by enabling the capture of wider range of solar spectrum as compared to single-junction device. However, the practical realization of this concept in bulk-heterojunction polymer systems requires the judicious design of a transparent interconnecting layer compatible with both polymers. Moreover, the polymers selected should be readily synthesized at large scale (>1 kg) and high performance. In this work, we demonstrate a novel tandem polymer solar cell that combines low band gap poly isoindigo [P(T3-iI)-2], which is easily synthesized in kilogram quantities, with a novel Cr/MoO3 interconnecting layer. Cr/MoO3 is shown to be greater than 80% transparent above 375 nm and an efficient interconnecting layer for P(T3-iI)-2 and PCDTBT, leading to 6% power conversion efficiencies under AM 1.5G illumination. These results serve to extend the range of interconnecting layer materials for tandem cell fabrication by establishing, for the first time, that a thin, evaporated layer of Cr/MoO3 can work as an effective interconnecting layer in a tandem polymer solar cells made with scalable photoactive materials.

  14. Tandem Solar Cells from Accessible Low Band-Gap Polymers Using an Efficient Interconnecting Layer.

    PubMed

    Bag, Santanu; Patel, Romesh J; Bunha, Ajaykumar; Grand, Caroline; Berrigan, J Daniel; Dalton, Matthew J; Leever, Benjamin J; Reynolds, John R; Durstock, Michael F

    2016-01-13

    Tandem solar cell architectures are designed to improve device photoresponse by enabling the capture of wider range of solar spectrum as compared to single-junction device. However, the practical realization of this concept in bulk-heterojunction polymer systems requires the judicious design of a transparent interconnecting layer compatible with both polymers. Moreover, the polymers selected should be readily synthesized at large scale (>1 kg) and high performance. In this work, we demonstrate a novel tandem polymer solar cell that combines low band gap poly isoindigo [P(T3-iI)-2], which is easily synthesized in kilogram quantities, with a novel Cr/MoO3 interconnecting layer. Cr/MoO3 is shown to be greater than 80% transparent above 375 nm and an efficient interconnecting layer for P(T3-iI)-2 and PCDTBT, leading to 6% power conversion efficiencies under AM 1.5G illumination. These results serve to extend the range of interconnecting layer materials for tandem cell fabrication by establishing, for the first time, that a thin, evaporated layer of Cr/MoO3 can work as an effective interconnecting layer in a tandem polymer solar cells made with scalable photoactive materials. PMID:26699653

  15. Bonding technique of polymer layer with ceramic elements of analytical microsystems

    NASA Astrophysics Data System (ADS)

    Chudy, Michał; Malecha, Karol; Golonka, Leszek; Sosicki, Adam; Roguszczak, Henryk; Jakubowska, Małgorzata; Dybko, Artur; Brzózka, Zbigniew

    2006-10-01

    The possibilities of the construction of microsystems using ceramics and polymers are presented in the paper. The technology of irreversible and reversible bonding of ceramic and polymer microsystems' layers was developed. The irreversible bonding is required only for microfluidic structures, in which samples and reagents are introduced into the system using pressure methods. For the systems with an electroosmotic reagents dosing adhesion forces between particular layers are enough to seal the microchannels. In both cases a glaze layer was screen-printed on ceramic plates to eliminate their surface roughness.

  16. Amino-functionalized alkaline clay with cationic star-shaped polymer as adsorbents for removal of Cr(VI) in aqueous solution

    NASA Astrophysics Data System (ADS)

    Pan, Yuanfeng; Cai, Pingxiong; Farmahini-Farahani, Madjid; Li, Yiduo; Hou, Xiaobang; Xiao, Huining

    2016-11-01

    Pentaerythritol (PER) was esterified with 2-bromoisobutyryl bromide to synthesize a four-arm initiator 4Br-PER for atom transfer radical polymerization (ATRP). Star-shaped copolymers (P(AM-co-DMAEMA)4, CSP) were prepared via ATRP using dimethyl aminoethyl methacrylate (DMAEMA) and acrylamide (AM) as comonomers, while Br-PER and CuBr/2,2‧-bipyridine (BPY) as the initiator and the catalyst, respectively. The resulting four-arm initiator and star-shaped polymer (CSP) were characterized with FT-IR, 1H NMR and Ubbelohde viscometry. Alkaline clay (AC) was immobilized with CSPs to yield amino groups, and the cationic star polymer-immobilized alkaline clay (CSP-AC) was applied to remove Cr(VI) from the aqueous solution in batch experiments. Various influencing factors, including pH, contact time and immobilization amount of CSP on adsorption capacity of CSP-AC for Cr(VI) were also investigated. The results demonstrated that Cr(VI) adsorption was highly pH dependent. The optimized pH value was 4.0. The adsorption isotherms of the adsorbent fit the Langmuir model well, with the maximum adsorption capacity of 137.9 mg/g at 30 °C. The material should be a promising adsorbent for Cr(VI) removal, with the advantages of high adsorption capacity.

  17. Surface Smoothing Effect and Characteristics of New 1,4-Phenylenediamine Polymer as Anode Buffer Layer

    NASA Astrophysics Data System (ADS)

    Iida, Koichiro; Ogata, Tomoyuki; Okabe, Kazuki; Tanaka, Futoshi; Hara, Masahiko

    2007-11-01

    We have developed a new 1,4-phenylenediamine polymer with suitable properties for the anode buffer layer of organic devices. The anode buffer layer composed of a polymer doped with an electron acceptor [tris(4-bromophenyl)aminium hexachloroantimonate] was found to improve the surface roughness of the anode, particularly when the layer was sufficiently baked at a high temperature to transform it into the glass phase. The phase transition of the layer into the glass phase also affected its electric properties. Despite that the baking temperature was higher than the decomposition temperature of the electron acceptor, the resistivity of the layer with a smooth surface was one order of magnitude lower than that of the undoped layer.

  18. Understanding the interfacial layer dynamics of polymer nanocomposites from broadband dielectric spectroscopy

    NASA Astrophysics Data System (ADS)

    Carroll, Robert; Cheng, Shiwang; Sokolov, Alexei

    Polymer nanocomposites show many advanced mechanical, thermal, optical, and transport properties mainly due to the vast interfacial area between the polymer matrix and nanoparticles. Recent studies show that there is an interfacial polymer layer with structure and dynamics that are different from the bulk polymer, and that contributes to the advanced macroscopic properties. It has been shown that broadband dielectric spectroscopy provides good method to study the interfacial dynamics in nanocomposites. However, current dielectric spectroscopy studies ignore the heterogeneous nature of polymer nanocomposites. Models based on a simple superposition of bulk polymer and interfacial layer spectra, or those that assume the interfacial layer is dynamically ``dead'' are inaccurate. In this talk, the prevailing methods in the literature will be compared with an accurate method accounting for the heterogeneity of the nanocomposites. Different nanocomposites with well-dispersed nanoparticles will be used as examples. The analysis clearly shows that the width and the amplitude of the relaxation peaks are affected by the data analysis. Thus accurate quantitative conclusions on properties and thickness of the interfacial layer can be achieved only using heterogeneous models.

  19. Surface plasmon resonance image sensor module of spin-coated silver film with polymer layer.

    PubMed

    Son, Jung-Han; Lee, Dong Hun; Cho, Yong-Jin; Lee, Myung-Hyun

    2013-11-01

    Prism modules of 20 nm-, 40 nm-, and 60 nm-thick spin-coated silver films both without and with an upper 100 nm-thick spin-coated polymer layer were fabricated for surface plasmon resonance (SPR) image sensor applications. The prism modules were applied to an SPR image sensor system. The coefficients of determination (R2s) for the 20 nm-, 40 nm- and 60 nm-thick silver films without the polymer layer were 0.9231, 0.9901, and 0.9889, respectively, and with the polymer layer 0.9228, 0.9951, and 0.9880, respectively when standard ethanol solutions with 0.1% intervals in the range of 20.0% to 20.5% were applied. The upper polymer layer has no effect on the R2. The prism modules of the 40-nm-thick spin-coated silver films had the highest R2 value of approximately 0.99. The durability of the 40 nm-thick spin-coated silver film with the 100 nm-thick polymer layer is much better than that without the upper low-loss polymer layer. The developed SPR image sensor module of the 40 nm-thick spin-coated silver film with the upper 100 nm-thick low-loss polymer film is expected to be a very cost-effective and robust solution because the films are formed at low temperatures in a short period of time without requiring a vacuum system and are very durable.

  20. Changes in the adsorbate dipole layer with changing d-filling of the metal (II) (Co, Ni, Cu) phthalocyanines on Au(111).

    PubMed

    Xiao, Jie; Dowben, Peter A

    2009-02-01

    In combined photoemission and inverse photoemission spectroscopy studies, we observe changes in the metal phthalocyanine molecular orbital offsets with respect to the conducting gold substrate Fermi level, with the changing d-electron filling of the metal (II) (Co, Ni, Cu) phthalocyanines. The implication is that the interfacial dipole layer depends upon the choice of metal (Co, Ni, Cu) centers within the metal (II) phthalocyanines adsorbed on Au(111).

  1. Effect of electron collecting metal oxide layer in normal and inverted structure polymer solar cells

    SciTech Connect

    Ng, A.; Liu, X.; Sun, Y. C.; Djurišić, A. B.; Ng, A. M. C.; Chan, W. K.

    2013-12-04

    We performed a systematic study of the effect of electron collecting metal oxide layer on the performance of P3HT: PCBM solar cells. Zinc oxide (ZnO) or titanium dioxide (TiO{sub 2}) buffer layers were prepared by either e-beam evaporation or solution processing method. We also compared the photovoltaic performance of inserting the buffer layer between indium tin oxide (ITO) and the polymer layer for the inverted structure (ITO/ ZnO or TiO{sub 2}/P3HT:PCBM/V{sub 2}O{sub 5}/Au) as well as inserting the buffers layers between the polymer and the aluminum electrode for the conventional structure (ITO/V{sub 2}O{sub 5}/P3HT:PCBM/ZnO or TiO{sub 2}/Al). The results are shown in detail.

  2. Adsorption of peptides and small proteins with control access polymer permeation to affinity binding sites. Part I: Polymer permeation-immobilized metal ion affinity chromatography separation adsorbents with polyethylene glycol and immobilized metal ions.

    PubMed

    González-Ortega, Omar; Porath, Jerker; Guzmán, Roberto

    2012-03-01

    Despite the many efforts to develop efficient protein purification techniques, the isolation of peptides and small proteins on a larger than analytical scale remains a significant challenge. Recovery of small biomolecules from diluted complex biological mixtures, such as human serum, employing porous adsorbents is a difficult task mainly due to the presence of concentrated large biomolecules that can add undesired effects in the system such as blocking of adsorbent pores, impairing diffusion of small molecules, or competition for adsorption sites. Adsorption and size exclusion chromatography (AdSEC) controlled access media, using polyethylene glycol (PEG) as a semi-permeable barrier on a polysaccharide matrix, have been developed and explored in this work to overcome such effects and to preferentially adsorb small molecules while rejecting large ones. In the first part of this work, adsorption studies were performed with small peptides and proteins from synthetic mixtures using controlled access polymer permeation adsorption (CAPPA) media created by effectively grafting PEG on an immobilized metal affinity chromatography (IMAC) agarose resin, where chelating agents and immobilized metal ions were used as the primary affinity binding sites. Synthetic mixtures consisted of bovine serum albumin (BSA) with small proteins, peptides, amino acids (such as histidine or Val⁴-Angiotensin III), and small molecules-spiked human serum. The synthesized hybrid adsorbent consisted of agarose beads modified with iminodiacetic (IDA) groups, loaded with immobilized Cu(II) ions, and PEG. These CAPPA media with grafted PEG on the interior and exterior surfaces of the agarose matrix were effective in rejecting high molecular weight proteins. Different PEG grafting densities and PEG of different molecular weight were tested to determine their effect in rejecting and controlling adsorbent permeation properties. Low grafting density of high molecular weight PEG was found to be as

  3. Polymer/graphite oxide composites as high-performance materials for electric double layer capacitors

    NASA Astrophysics Data System (ADS)

    Tien, Chien-Pin; Teng, Hsisheng

    A single graphene sheet represents a carbon material with the highest surface area available to accommodating molecules or ions for physical and chemical interactions. Here we demonstrate in an electric double layer capacitor the outstanding performance of graphite oxide for providing a platform for double layer formation. Graphite oxide is generally the intermediate compound for obtaining separated graphene sheets. Instead of reduction with hydrazine, we incorporate graphite oxide with a poly(ethylene oxide)-based polymer and anchor the graphene oxide sheets with poly(propylene oxide) diamines. This polymer/graphite oxide composite shows in a "dry" gel-electrolyte system a double layer capacitance as high as 130 F g -1. The polymer incorporation developed here can significantly diversify the application of graphene-based materials in energy storage devices.

  4. Fabrication of multi-layered polymer LEDs by resonant infrared pulsed-laser deposition

    NASA Astrophysics Data System (ADS)

    Johnson, S. L.; Park, H. K.; Haglund, R. F., Jr.

    2007-09-01

    Multi-layered polymer light-emitting diodes (PLEDs) have been fabricated in a vacuum environment by resonant infrared pulsed-laser deposition of the polymer layers. The light emitter used was poly[2-methoxy-5-(2- ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), and in some cases a layer of the hole-transport polymer poly(3,4 etylenedioxythiophene:polystyrenesulfonate) (PEDOT:PSS) was also laser deposited, resulting in a device structure of ITO/PEDOT:PSS/MEH-PPV/Al. Fourier transform infrared (FTIR) spectroscopy confirmed that neither of the laser-deposited polymers was significantly altered by the deposition process. Laser-fabricated devices displayed electroluminescent spectra similar to those of conventional spin-coated devices, but the differences in electrical characteristics and device efficiency were substantial. These discrepancies can probably be attributed to surface roughness of the deposited polymer layers. With the appropriate refinement of the deposition protocols, however, we believe that this process can be improved to a level that is suitable for routine fabrication of organic electronic components.

  5. Electron-collecting oxide layers in inverted polymer solar cells via oxidation of thermally evaporated titanium

    NASA Astrophysics Data System (ADS)

    Zampetti, A.; Salamandra, L.; Brunetti, F.; Reale, A.; Di Carlo, A.; Brown, T. M.

    2016-10-01

    A simple and intuitive deposition technique is discussed to obtain titanium oxide used as an electron collecting layer in polymer solar cells based on the thermal evaporation of pristine titanium and further thermal treatment to convert the metal in oxide. Since the degradation of indium-doped tin oxide at high temperatures is an issue, we demonstrate that the combination of glass/fluorine tin oxide and high temperatures represents a promising approach in the fabrication of inverted polymer solar cells with such a titanium oxide electron collecting layer.

  6. Polymer solar cells with gold nanoclusters decorated multi-layer graphene as transparent electrode

    NASA Astrophysics Data System (ADS)

    Zhang, Di; Choy, Wallace C. H.; Wang, Charlie C. D.; Li, Xiao; Fan, Lili; Wang, Kunlin; Zhu, Hongwei

    2011-11-01

    A thin layer of ultraviolet-ozone (UVO) treated gold (Au) is introduced on multi-layer graphene (MLG) to enable the MLG as an effective anode for polymer solar cells (PSCs). By optimizing the Au thickness and the durations of the UVO treatments at different stages, MLG PSCs with enhanced fill factor and power conversion efficiency are obtained, exhibiting better performance compared with MLG devices directly modified with UVO and poly(3,4-ethylenedioythiophene):poly(styrenesulfonate). Further analysis shows that UVO treated Au provides favorable band alignment at the MLG/polymer interface. Moreover, the improved interfacial contact and shortened UVO durations reduce the series resistance of PSCs significantly.

  7. An automated spin-assisted approach for molecular layer-by-layer assembly of crosslinked polymer thin films

    SciTech Connect

    Chan, Edwin P.; Chung, Jun Young; Stafford, Christopher M.; Lee, Jung-Hyun

    2012-11-15

    We present the design of an automated spin-coater that facilitates fabrication of polymer films based on molecular layer-by-layer (mLbL) assembly. Specifically, we demonstrate the synthesis of ultrathin crosslinked fully-aromatic polyamide (PA) films that are chemically identical to polymer membranes used in water desalination applications as measured by X-ray photoelectron spectroscopy. X-ray reflectivity measurements indicate that the automated mLbL assembly creates films with a constant film growth rate and minimal roughness compared with the traditional interfacial polymerization of PA. This automated spin-coater improves the scalability and sample-to-sample consistency by reducing human involvement in the mLbL assembly.

  8. An automated spin-assisted approach for molecular layer-by-layer assembly of crosslinked polymer thin films.

    PubMed

    Chan, Edwin P; Lee, Jung-Hyun; Chung, Jun Young; Stafford, Christopher M

    2012-11-01

    We present the design of an automated spin-coater that facilitates fabrication of polymer films based on molecular layer-by-layer (mLbL) assembly. Specifically, we demonstrate the synthesis of ultrathin crosslinked fully-aromatic polyamide (PA) films that are chemically identical to polymer membranes used in water desalination applications as measured by X-ray photoelectron spectroscopy. X-ray reflectivity measurements indicate that the automated mLbL assembly creates films with a constant film growth rate and minimal roughness compared with the traditional interfacial polymerization of PA. This automated spin-coater improves the scalability and sample-to-sample consistency by reducing human involvement in the mLbL assembly.

  9. Efficient removal of dyes by a novel magnetic Fe3O4/ZnCr-layered double hydroxide adsorbent from heavy metal wastewater.

    PubMed

    Chen, Dan; Li, Yang; Zhang, Jia; Li, Wenhui; Zhou, Jizhi; Shao, Li; Qian, Guangren

    2012-12-01

    A novel magnetic Fe(3)O(4)/ZnCr-layered double hydroxide adsorbent was produced from electroplating wastewater and pickling waste liquor via a two-step microwave hydrothermal method. Adsorption of methyl orange (MO) from water was studied using this material. The effects of three variables have been investigated by a single-factor method. The response surface methodology (RSM) based on Box-Behnken design was successfully applied to the optimization of the preparation conditions. The maximum adsorption capacity of MO was found to be 240.16 mg/g, indicating that this material may be an effective adsorbent. It was shown that 99% of heavy metal ions (Fe(2+), Fe(3+), Cr(3+), and Zn(2+)) can be effectively removed into precipitates and released far less in the adsorption process. In addition, this material with adsorbed dye can be easily separated by a magnetic field and recycled after catalytic regeneration with advanced oxidation technology. Meanwhile, kinetic models, FTIR spectra and X-ray diffraction pattern were applied to the experimental data to examine uptake mechanism. The boundary layer and intra-particle diffusion played important roles in the adsorption mechanisms. PMID:23122732

  10. Tension amplification in tethered layers of bottle-brush polymers

    DOE PAGES

    Leuty, Gary M.; Tsige, Mesfin; Grest, Gary S.; Rubinstein, Michael

    2016-02-26

    In this paper, molecular dynamics simulations of a coarse-grained bead–spring model have been used to study the effects of molecular crowding on the accumulation of tension in the backbone of bottle-brush polymers tethered to a flat substrate. The number of bottle-brushes per unit surface area, Σ, as well as the lengths of the bottle-brush backbones Nbb (50 ≤ Nbb ≤ 200) and side chains Nsc (50 ≤ Nsc ≤ 200) were varied to determine how the dimensions and degree of crowding of bottle-brushes give rise to bond tension amplification along the backbone, especially near the substrate. From these simulations, wemore » have identified three separate regimes of tension. For low Σ, the tension is due solely to intramolecular interactions and is dominated by the side chain repulsion that governs the lateral brush dimensions. With increasing Σ, the interactions between bottle-brush polymers induce compression of the side chains, transmitting increasing tension to the backbone. For large Σ, intermolecular side chain repulsion increases, forcing side chain extension and reorientation in the direction normal to the surface and transmitting considerable tension to the backbone.« less

  11. Recent trends in electrospinning of polymer nanofibers and their applications in ultra thin layer chromatography.

    PubMed

    Moheman, Abdul; Alam, Mohammad Sarwar; Mohammad, Ali

    2016-03-01

    Fabrication of polymer derived electrospun nanofibers by electrospinning as chromatographic sorbent bed for ultra-thin layer chromatography (UTLC) is a very demanding topic in analytical chemistry. This review presents an overview of recent development in the fabrication of polymer derived electrospun nanofibers and their applications to design UTLC plates as stationary phases for on-plate identification and separation of analytes from their mixture solutions. It has been reported that electrospun fiber based stationary phases in UTLC have enhanced separation efficiency to provide separation of analyte mixture in a shorter development time than those of traditional particle-based TLC stationary phases. In addition, electrospun UTLC is cost effective and can be modified for obtaining different surface selectivities by changing the polymer materials to electrospun devices. Electrospun UTLC plates are not available commercially till date and efforts are being rendered for their commercialization. The morphology and diameter of electrospun nanofibers are highly dependent on several parameters such as type of polymer, polymer molecular weight, solvent, viscosity, conductivity, surface tension, applied voltage, collector distance and flow rate of the polymer solution during electrospinning process. Among the aforementioned parameters, solution viscosity is an important parameter which is mainly influenced by polymer concentration. This review provides evidence for the fabrication of UTLC plates containing electrospun polymer nanofibers. Furthermore, the future prospects related to electrospinning and its application in obtaining of different types of electrospun nanofibers are discussed. The present communication is aimed to review the work which appeared during 2009-2014 on the application of polymer derived electrospun nanofibers in ultra thin layer chromatography.

  12. Structural studies of polymer-cushioned lipid bilayers.

    PubMed

    Majewski, J; Wong, J Y; Park, C K; Seitz, M; Israelachvili, J N; Smith, G S

    1998-11-01

    The structure of softly supported polymer-cushioned lipid bilayers, prepared in two different ways at the quartz-solution interface, were determined using neutron reflectometry. The polymer cushion consisted of a thin layer of branched, cationic polyethyleneimine (PEI), and the bilayers were formed by adsorption of small unilamellar dimyristoylphosphatidylcholine (DMPC) vesicles. When vesicles were first allowed to adsorb to a bare quartz substrate, an almost perfect bilayer formed. When the polymer was then added to the aqueous solution, it appeared to diffuse beneath this bilayer, effectively lifting it from the substrate. In contrast, if the polymer layer is adsorbed first to the bare quartz substrate followed by addition of vesicles to the solution, there is very little interaction of the vesicles with the polymer layer, and the result is a complex structure most likely consisting of patchy multilayers or adsorbed vesicles.

  13. Synthesis of Au-CeO 2/SiO 2 catalyst via adsorbed-layer reactor technique combined with alcohol-thermal treatment

    NASA Astrophysics Data System (ADS)

    Jiang, Xin; Deng, Hui

    2011-10-01

    Au-CeO 2/SiO 2 was prepared via adsorbed-layer reactor technique combined with alcohol-thermal treatment. The catalytic performance in complete oxidation of benzene was investigated. TEM, Raman characterization showed that Au particles grew up obviously during alcohol-thermal process, while CeO 2 particles maintained 4 nm in diameter. The content of oxygen vacancies and adsorbed oxygen species on catalysts surface increased apparently. Alcohol-thermally treated Au-CeO 2/SiO 2 and CeO 2/SiO 2 showed similar change in catalytic performance, and were much superior to calcined CeO 2/SiO 2. Of alcohol-thermally treated and calcined CeO 2/SiO 2, initial temperatures of the reaction were 80 °C and 150 °C, respectively. The benzene conversions reached 85% and 40% at 300 °C.

  14. Surface-Engineered Graphene Quantum Dots Incorporated into Polymer Layers for High Performance Organic Photovoltaics

    PubMed Central

    Kim, Jung Kyu; Kim, Sang Jin; Park, Myung Jin; Bae, Sukang; Cho, Sung-Pyo; Du, Qing Guo; Wang, Dong Hwan; Park, Jong Hyeok; Hong, Byung Hee

    2015-01-01

    Graphene quantum dots (GQDs), a newly emerging 0-dimensional graphene based material, have been widely exploited in optoelectronic devices due to their tunable optical and electronic properties depending on their functional groups. Moreover, the dispersibility of GQDs in common solvents depending on hydrophobicity or hydrophilicity can be controlled by chemical functionalization, which is particularly important for homogeneous incorporation into various polymer layers. Here we report that a surface-engineered GQD-incorporated polymer photovoltaic device shows enhanced power conversion efficiency (PCE), where the oxygen-related functionalization of GQDs enabled good dispersity in a PEDOT:PSS hole extraction layer, leading to significantly improved short circuit current density (Jsc) value. To maximize the PCE of the device, hydrophobic GQDs that are hydrothermally reduced (rGQD) were additionally incorporated in a bulk-heterojunction layer, which is found to promote a synergistic effect with the GQD-incorporated hole extraction layer. PMID:26392211

  15. Initiation of atomic layer deposition of metal oxides on polymer substrates by water plasma pretreatment

    SciTech Connect

    Steven Brandt, E.; Grace, Jeremy M.

    2012-01-15

    The role of surface hydroxyl content in atomic layer deposition (ALD) of aluminum oxide (AO) on polymers is demonstrated by performing an atomic layer deposition of AO onto a variety of polymer types, before and after pretreatment in a plasma struck in water vapor. The treatment and deposition reactions are performed in situ in a high vacuum chamber that is interfaced to an x-ray photoelectron spectrometer to prevent adventitious exposure to atmospheric contaminants. X-ray photoelectron spectroscopy is used to follow the surface chemistries of the polymers, including theformation of surface hydroxyls and subsequent growth of AO by ALD. Using dimethyl aluminum isopropoxide and water as reactants, ALD is obtained for water-plasma-treated poly(styrene) (PS), poly(propylene) (PP), poly(vinyl alcohol) (PVA), and poly(ethylene naphthalate) (PEN). For PS, PP, and PEN, initial growth rates of AO on the native (untreated) polymers are at least an order of magnitude lower than on the same polymer surface following the plasma treatment. By contrast, native PVA is shown to initiate ALD of AO as a result of the presence of intrinsic surface hydroxyls that are derived from the repeat unit of this polymer.

  16. Ultrathin Polyaniline-based Buffer Layer for Highly Efficient Polymer Solar Cells with Wide Applicability

    PubMed Central

    Zhao, Wenchao; Ye, Long; Zhang, Shaoqing; Fan, Bin; Sun, Mingliang; Hou, Jianhui

    2014-01-01

    Interfacial buffer layers often attribute the improved device performance in organic optoelectronic device. Herein, a water-soluble hydrochloric acid doped polyanilines (HAPAN) were utilized as p-type electrode buffer layer in highly efficient polymer solar cells (PSC) based on PBDTTT-EFT and several representative polymers. The PBDTTT-EFT-based conventional PSC featuring ultrathin HAPAN (1.3 nm) delivered high PCE approximately 9%, which is one of the highest values among conventional PSC devices. Moreover, ultrathin HAPAN also exhibited wide applicability in a variety of efficient photovoltaic polymers including PBDTTT-C-T, PTB7, PBDTBDD, PBTTDPP-T, PDPP3T and P3HT. The excellent performances were originated from the high transparency, small film roughness and suitable work function. PMID:25300365

  17. Study of Organosilicon Plasma Polymer Used in Composite Layers with Biomedical Application

    NASA Astrophysics Data System (ADS)

    Radeva, E.; Pramatarova, L.; Pecheva, E.; Hikov, T.; Iacob, E.; Vanzetti, L.; Dimitrova, R.; Krasteva, N.; Spassov, T.; Fingarova, D.

    2010-01-01

    In this work we study the ability of plasma polymer (PP) films obtained from hexamethyldisiloxane (HMDS) on silica glass (SG) to induce hydroxyapatite (HA)-based composite layers from a mixture of simulated body fluid (SBF) and clear solution of detonation nanodiamond (DND) by a biomimetic process. The grown composites (PPHMDS/HADND) were studied by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and Rutherford backscattering (RBS) techniques. FTIR spectra of the PPHMDS indicated diminishing of the polymer characteristic bands when the polymer is immersed in DND clear solution. Furthermore, after sample immersion in the SBF-DND mixture, the FTIR spectra showed the presence of carbonate-containing HA through the characteristic vibration modes of P-O in the phosphate group and C-O in the carbonate group. The formation of HA layers, rich in silica and/or carbon was confirmed by RBS and SEM. The cell viability measured after 7 days on the polymer surface is more then 95% for all samples. The results show that the PPHMDS is promising as a substrate for growing HA/DND layers and that the materials obtained are biocompatible. The variations of plasma polymerization conditions and modification of the composite layers will aid in using such materials for biomedical applications.

  18. Study of Organosilicon Plasma Polymer Used in Composite Layers with Biomedical Application

    SciTech Connect

    Radeva, E.; Pramatarova, L.; Pecheva, E.; Hikov, T.; Fingarova, D.; Iacob, E.; Vanzetti, L.; Dimitrova, R.; Krasteva, N.; Spassov, T.

    2010-01-21

    In this work we study the ability of plasma polymer (PP) films obtained from hexamethyldisiloxane (HMDS) on silica glass (SG) to induce hydroxyapatite (HA)-based composite layers from a mixture of simulated body fluid (SBF) and clear solution of detonation nanodiamond (DND) by a biomimetic process. The grown composites (PPHMDS/HADND) were studied by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and Rutherford backscattering (RBS) techniques. FTIR spectra of the PPHMDS indicated diminishing of the polymer characteristic bands when the polymer is immersed in DND clear solution. Furthermore, after sample immersion in the SBF-DND mixture, the FTIR spectra showed the presence of carbonate-containing HA through the characteristic vibration modes of P-O in the phosphate group and C-O in the carbonate group. The formation of HA layers, rich in silica and/or carbon was confirmed by RBS and SEM. The cell viability measured after 7 days on the polymer surface is more then 95% for all samples. The results show that the PPHMDS is promising as a substrate for growing HA/DND layers and that the materials obtained are biocompatible. The variations of plasma polymerization conditions and modification of the composite layers will aid in using such materials for biomedical applications.

  19. 3D Printing of Human Tissue Mimics via Layer-by-Layer Assembly of Polymer/Hydrogel Biopapers

    NASA Astrophysics Data System (ADS)

    Ringeisen, Bradley

    2015-03-01

    The foundations of tissue engineering were built on two fundamental areas of research: cells and scaffolds. Multipotent cells and their derivatives are traditionally randomly seeded into sophisticated polymer or hydrogel scaffolds, ultimately with the goal of forming a tissue-like material through cell differentiation and cell-material interactions. One problem with this approach is that no matter how complex or biomimetic the scaffold is, the cells are still homogeneously distributed throughout this three dimensional (3D) material. Natural tissue is inherently heterogeneous on both a microscopic and macroscopic level. It also contains different types of cells in close proximity, extracellular matrix, voids, and a complex vascularized network. Recently developed 3D cell and organ printers may be able to enhance traditional tissue engineering experiments by building scaffolds layer-by-layer that are crafted to mimic the microscopic and macroscopic structure of natural tissue or organs. Over the past decade, my laboratory has developed a capillary-free, live cell printer termed biological laser printing, or BioLP. We find that printed cells do not express heat shock protein and retain >99% viability. Printed cells also incur no DNA strand fracture and preserve their ability to differentiate. Recent work has used a layer-by-layer approach, stacking sheets of hybrid polymer/hydrogel biopapers in conjunction with live cell printing to create 3D tissue structures. Our specific work is now focused on the blood-brain-barrier and air-lung interface and will be described during the presentation.

  20. Water Transport in the Micro Porous Layer and Gas Diffusion Layer of a Polymer Electrolyte Fuel Cell

    NASA Astrophysics Data System (ADS)

    Qin, C.; Hassanizadeh, S. M.

    2015-12-01

    In this work, a recently developed dynamic pore-network model is presented [1]. The model explicitly solves for both water pressure and capillary pressure. A semi-implicit scheme is used in updating water saturation in each pore body, which considerably increases the numerical stability at low capillary number values. Furthermore, a multiple-time-step algorithm is introduced to reduce the computational effort. A number of case studies of water transport in the micro porous layer (MPL) and gas diffusion layer (GDL) are conducted. We illustrate the role of MPL in reducing water flooding in the GDL. Also, the dynamic water transport through the MPL-GDL interface is explored in detail. This information is essential to the reduced continua model (RCM), which was developed for multiphase flow through thin porous layers [2, 3]. C.Z. Qin, Water transport in the gas diffusion layer of a polymer electrolyte fuel cell: dynamic pore-network modeling, J Electrochimical. Soci., 162, F1036-F1046, 2015. C.Z. Qin and S.M. Hassanizadeh, Multiphase flow through multilayers of thin porous media: general balance equations and constitutive relationships for a solid-gas-liquid three-phase system, Int. J. Heat Mass Transfer, 70, 693-708, 2014. C.Z. Qin and S.M. Hassanizadeh, A new approach to modeling water flooding in a polymer electrolyte fuel cell, Int. J. Hydrogen Energy, 40, 3348-3358, 2015.

  1. Layer-by-layer synthesis of metal-containing conducting polymers: caged metal centers for interlayer charge transport.

    PubMed

    Liu, Wenjun; Huang, Weijie; Pink, Maren; Lee, Dongwhan

    2010-09-01

    Metal-templated [2 + 3]-type cocondensation of a pi-extended boronic acid and nioxime furnished a series of cage molecules, which were electropolymerized to prepare metal-containing conducting polymers (MCPs). Despite sharing essentially isostructural organic scaffolds, these materials display metal-dependent electrochemical properties as evidenced by different redox windows observed for M = Co, Fe, Ru. Consecutive electropolymerization using two different monomers furnished bilayer MCPs having different metals in each layer. In addition to functioning as heavy atom markers in cross-sectional analysis by FIB and EDX, redox-active metal centers participate in voltage-dependent interlayer electron transport to give rise to cyclic voltammograms that are distinctively different from those of each layer alone or random copolymers. A simple electrochemical technique can thus be used as a straightforward diagnostic tool to investigate the structural ordering of electrically conductive layered materials. PMID:20690667

  2. Layer-by-Layer Deposition with Polymers Containing Nitrilotriacetate, A Convenient Route to Fabricate Metal- and Protein-Binding Films.

    PubMed

    Wijeratne, Salinda; Liu, Weijing; Dong, Jinlan; Ning, Wenjing; Ratnayake, Nishanka Dilini; Walker, Kevin D; Bruening, Merlin L

    2016-04-27

    This paper describes a convenient synthesis of nitrilotriacetate (NTA)-containing polymers and subsequent layer-by-layer adsorption of these polymers on flat surfaces and in membrane pores. The resulting films form NTA-metal-ion complexes and capture 2-3 mmol of metal ions per mL of film. Moreover, these coatings bind multilayers of polyhistidine-tagged proteins through association with NTA-metal-ion complexes. Inclusion of acrylic acid repeat units in NTA-containing copolymers promotes swelling to increase protein binding in films on Au-coated wafers. Adsorption of NTA-containing films in porous nylon membranes gives materials that capture ∼46 mg of His-tagged ubiquitin per mL. However, the binding capacity decreases with the protein molecular weight. Due to the high affinity of NTA for metal ions, the modified membranes show modest leaching of Ni(2+) in binding and rinsing buffers. Adsorption of NTA-containing polymers is a simple method to create metal- and protein-binding films and may, with future enhancement of stability, facilitate development of disposable membranes that rapidly purify tagged proteins. PMID:27042860

  3. Shear-induced surface alignment of polymer dispersed liquid crystal microdroplets on the boundary layer

    NASA Technical Reports Server (NTRS)

    Parmar, D. S.; Singh, J. J.

    1993-01-01

    Polymer dispersed liquid crystal thin films have been deposited on a glass substrate, utilizing the processes of polymerization and solvent evaporation induced phase separation. Liquid crystal microdroplets trapped on the upper surface of the thin film respond to the shear stress due to air or gas flow on the surface layer. Response to an applied step shear stress input on the surface layer has been measured by measuring the time response of the transmitted light intensity. Initial results on the measurements of the light transmission as a function of the air flow differential pressure indicate that these systems offer features suitable for boundary layer and gas flow sensors.

  4. Adsorbent and adsorbent bed for materials capture and separation processes

    SciTech Connect

    Liu, Wei

    2011-01-25

    A method device and material for performing adsorption wherein a fluid mixture is passed through a channel in a structured adsorbent bed having a solid adsorbent comprised of adsorbent particles having a general diameter less than 100 um, loaded in a porous support matrix defining at least one straight flow channel. The adsorbent bed is configured to allow passage of a fluid through said channel and diffusion of a target material into said adsorbent under a pressure gradient driving force. The targeted molecular species in the fluid mixture diffuses across the porous support retaining layer, contacts the adsorbent, and adsorbs on the adsorbent, while the remaining species in the fluid mixture flows out of the channel.

  5. Modification of conductive polymer PEDOT:PSS layer by SWCNT

    NASA Astrophysics Data System (ADS)

    Araźna, Aneta; Janeczek, Kamil; Futera, Konrad; Koziol, Andrzej

    2016-01-01

    In this study, the effect of addition of single-walled carbon nanotubes (SWCNTs) on the morphological properties of poly(3,4-ethylenedioxythiophene/poly(4-styrenesulfonate) (PEDOT:PSS) has been investigated using scanning electron microscope (SEM) as well as the surface roughness evaluation by atomic force microscopy (AFM). The spin-coated films of PEDOT:PSS and PEDOT:PSS with addition of SWNTs (0.5 % by wt.) on glass were compared in our study. Experimental results show that surface roughness of PEDOT:PSS layers increases after addition SWNTs to the solution - from 3.50 nm for the samples without SWNTs to 4.65 nm for the samples with SWNTs. The analysis of SEM images showed that there are some agglomerations of SWNTs on the surface of PEDOT:PSS/SWCNT composite film.

  6. Preparation of a thick polymer brush layer composed of poly(2-methacryloyloxyethyl phosphorylcholine) by surface-initiated atom transfer radical polymerization and analysis of protein adsorption resistance.

    PubMed

    Inoue, Yuuki; Onodera, Yuya; Ishihara, Kazuhiko

    2016-05-01

    The purpose of this study was to prepare a thick polymer brush layer composed of poly(2-methacryloyloxyethyl phosphorylcholine (MPC)) and assess its resistance to protein adsorption from the dissolved state of poly(MPC) chains in an aqueous condition. The thick poly(MPC) brush layer was prepared through the surface-initiated atom transfer radical polymerization (SI-ATRP) of MPC with a free initiator from an initiator-immobilized substrate at given [Monomer]/[Free initiator] ratios. The ellipsometric thickness of the poly(MPC) brush layers could be controlled by the polymerization degree of the poly(MPC) chains. The thickness of the poly(MPC) brush layer in an aqueous medium was larger than that in air, and this tendency became clearer when the polymerization degree of the poly(MPC) increased. The maximum thickness of the poly(MPC) brush layer in an aqueous medium was around 110 nm. The static air contact angle of the poly(MPC) brush layer in water indicated a reasonably hydrophilic nature, which was independent of the thickness of the poly(MPC) brush layer at the surface. This result occurred because the hydrated state of the poly(MPC) chains is not influenced by the environment surrounding them. Finally, as measured with a quartz crystal microbalance, the amount of protein adsorbed from a fetal bovine serum solution (10% in phosphate-buffered saline) on the original substrate was 420 ng/cm(2). However, the poly(MPC) brush layer reduced this value dramatically to less than 50 ng/cm(2). This effect was independent of the thickness of the poly(MPC) brush layer for thicknesses between 20 nm and about 110 nm. These results indicated that the surface covered with a poly(MPC) brush layer is a promising platform to avoid biofouling and could also be applied to analyze the reactions of biological molecules with a high signal/noise ratio.

  7. Sensing skin for strain monitoring made of PC-CNT conductive polymer nanocomposite sprayed layer by layer.

    PubMed

    Robert, Colin; Feller, Jean François; Castro, Mickaël

    2012-07-25

    Sensing skins about 1.5 μm thick made of 40 nanolayers of conductive polymer nanocomposites (CPC) were sprayed layer by layer (sLbL) directly on a PET woven textile to demonstrate their versatility to monitor the deformation of a flexible, rigid and rough substrate such as a commercial boat sail. CPC sensing skins were developed by structuring a 3D carbon nanotubes network into three kinds of amorphous thermoplastic matrices (PMMA, aPS, PC). Adjustable parameters such as the thickness (number of sprayed layers) and the initial resistance of CPC transducers (CNT content relatively to percolation threshold) enabled to tailor both sensitivity and stability of the piezo-resistive responses, so that it was possible to monitor the strain evolution in the elastic domain and damage accumulation over this limit. Polymer matrices were selected after calculation of their χ Flory-Huggins parameters to evaluate their interactions with the PET substrate and solvent of dispersion, and after the comparison of their stress/strain characteristics, particularly their elastic limit. PC-1%CNT was found to be the best candidate satisfying both chemical and physical criteria. Finally, the exponential evolution of the piezo-resistive response of CPC sensing skins on a wide range of deformation (until breakage at ε = 27%), was well fitted with a model based on quantum tunnelling conduction inducing an exponential evolution of resistance with variations of CNT/CNT junction gap from 0.5 to 0.625 nm. PMID:22704247

  8. Polymer layer ordering of polyaniline derivatives in PLED devices: Surface adsorption and characterization[Polymer Light Emitting Diodes

    SciTech Connect

    Advincula, R.C.; Knoll, W.; Frank, C.W.; Roitman, D.; Moon, R.; Sheats, J.

    1998-07-01

    The fabrication and characterization of polyaniline (PANI) derivatives deposited on ITO coated glass is investigated as possible hole injection layers for MEH-PPV based polymer light emitting diode (PLED) devices. This involved multilayer ordering by the alternate polyelectrolyte adsorption of polyaniline and sulfonated polyaniline with an oppositely charged polyelectrolyte from solution. A combination of spectroscopic and microscopic techniques was utilized to determine the layer ordering, film structure, morphology, and homogeneity. The deposition process generally showed a linear behavior for all pairs as shown by ellipsometry and UV-vis spectroscopy. However, surface plasmon spectroscopy (SPS) and AFM revealed that thicker films are accompanied by increased surface roughness regardless of concentration. Comparison in performance was made between bare ITO and PANI or SPANI coated devices. Initial investigations of PLED performance showed significant improvements in lifetime and efficiency compared to bare ITO.

  9. Molecular layer-by-layer self-assembly and mercury sensing characteristics of novel brush polymers bearing thymine moieties.

    PubMed

    Jung, Jungwoon; Kim, Jin Chul; Rho, Yecheol; Kim, Mihee; Kwon, Wonsang; Kim, Heesoo; Ree, Moonhor

    2011-07-01

    Two new brush polyoxyethylenes bearing thymine moieties at the bristle ends have been synthesized as model polymers in which the chemical loading of the thymine functional group into the polymer is maximized: poly(oxy(11-thyminoacetyloxyundecylthiomethyl)ethylene) (PECH(S)-T) and poly(oxy(11-thyminoacetyloxyundecylsulfonylmethyl)ethylene) (PECH(SO(2))-T). These brush polymers are thermally stable up to around 225 °C, and their glass transitions occur in the range 23-27 °C, but they have significantly different properties despite the similarity of their chemical structures. In particular, PECH(SO(2))-T films exhibit better performance in sensing mercury ions than PECH(S)-T films. These differences were found to originate in the differences between their morphological structures. The PECH(SO(2))-T film has a multi-bilayer structure without interdigitation, in which the layers stack along the out-of-plane of the film and provide a thymine-rich surface. In contrast, the PECH(S)-T film is amorphous with a relatively low population of thymine moieties at the surface. This study demonstrated that a thymine-rich surface is required for recyclable thymine-based polymers to provide highly improved sensitivity and selectivity as well as full reversibility in the sensing of mercury ions. A thymine-rich surface can be achieved with a brush polymer bearing thymine moieties that can self-assemble into a multi-bilayer structure. Because of the thymine-rich surface, the PECH(SO(2))-T thin films even in only 6 nm thickness demonstrate the detection of mercury ions in aqueous solutions with a detection limit of 10(-6) M. PMID:21650219

  10. Multi-layer beam with variable stiffness based on electroactive polymers

    NASA Astrophysics Data System (ADS)

    Henke, Markus; Sorber, Jörg; Gerlach, Gerald

    2012-04-01

    The contribution describes a new kind of multi-layer beam with a variable stiffness based on electroactive polymers (EAP). These structures are supposed to be components of new smart, self-sensing and -controlling composite materials for lightweight constructions. Dielectric Elastomer foils from Danfoss PolyPower are used to control the beam's stiffness. The basic idea is to change the area moment of inertia of bending beams. These beams are built up as multi-layer stacks of thin metal or PMMA plates. Its internal structure can be changed by the use of the electroactive polymers for controlling the area moment of inertia. So it is possible to strongly change the stiffness of bending beams up to two orders of magnitude. Thereby, the magnitude of varying the stiffness can be scaled by the number of layers and the number and type of electroactive polymer elements used within the bending beam. The mechanisms for controlling the area moment of inertia are described in detail. Modeling of the mechanical structure including the EAP uses a pseudo rigid-body model, a strain energy model as well as a finite element analysis. The theoretical calculations are verified by experiments. The prototype described here consists of two structural layers. First results show the feasibility of the proposed structure for mechanical components with stiffness control.

  11. Layered protonated titanate nanosheets synthesized with a simple one-step, low-temperature, urea-modulated method as an effective pollutant adsorbent.

    PubMed

    Lin, Cheng-Hsien; Wong, David Shan-Hill; Lu, Shih-Yuan

    2014-10-01

    A simple one-step, low-temperature, urea-modulated method is developed for the synthesis of layered protonated titanate nanosheets (LPTNs). Urea serves as an indirect ammonium ion source, and the controlled supply of the ammonium ion slows the crystalline formation process and enables the production of the LPTNs from amorphous intermediate through aging-induced restructuring. The resulting LPTNs exhibit excellent adsorption capacities for methylene blue and Pb(2+) because of their high specific surface areas and excellent ion-exchange capability. Intercalation of Pb(2+) into the interlayer space of the LPTNs is evidenced by the relevant X-ray diffraction patterns on perturbation of the layered structure. The LPTNs prove to be a promising adsorbent in wastewater treatment for adsorption removal of metal ions or cationic organic dyes. PMID:25198517

  12. High efficiency polymer light-emitting diodes using ternary electron injection layers

    NASA Astrophysics Data System (ADS)

    Wen, Ten-Chin; Tsai, Kai-Wei; Jan, Jiun-Yun; Guo, Tzung-Fang

    2016-02-01

    The high efficiency of polymer light-emitting diodes (PLED) with ternary electron injection layers (EILs) including tetraoctylammonium bromide (TOAB), poly (vinylpyrrolidone) (PVP) and polyethylenimine (PEIE) to comprise PEIE-PVP-TOAB (E-P-T) EIL that has been achieved and well-studied via mixture design. In the unary system, TOAB can construct interfacial dipole via self-assembly crystallization atop various conjugated polymer surfaces to elevate the vacuum level of cathode. When employing three EILs as ternary system, the electrical property of PLED was further improved. The optimum luminescence efficiency respectively are 13.4 cd/A and 13.5 cd/A for T-P-D and E-P-T based PLED. In the ternary system (E-P-T), PEIE , PVP, and TOAB respectively provides electron injection, hole blocking, and polymer intersecting in the ternary based devices. The intersecting between PEIE and PVP by TOAB was evidenced by roughness change from AFM images.

  13. Electric Double Layer Capacitors with Carbon Nanotubes Electrodes and Gel Polymer/polyacid Electrolytes

    NASA Astrophysics Data System (ADS)

    Zhang, Yanping; Pan, Likun; Gao, Yang; Zhang, Zhejuan; Sun, Zhuo

    Electric double layer capacitors (EDLCs) with carbon nanotubes (CNTs) film electrodes and gel polymer/polyacid electrolytes have been demonstrated. The low-cost CNTs film is directly grown on Cu-Ni current collector by low pressure and low temperature thermal chemical vapor deposition. The electrolytes consist of gel polymer poly(vinyl alcohol), polyacid phosphomolybdic acid (PMA) with different concentrations from 10 to 40 wt.% and KCl. The electrochemical measurement of the EDLCs by cyclic voltammetry and chronopotentiometry shows that gel polymer/polyacid electrolytes can work stable at a wide potential range of -1.5 to 1.5 V and EDLCs with electrolytes containing 30 wt.% PMA exhibit optimum capacitive behavior with 8.09 F/g specific capacitance.

  14. Biocompatible interface films deposited within porous polymers by Atomic Layer Deposition (ALD).

    PubMed

    Liang, Xinhua; Lynn, Aaron D; King, David M; Bryant, Stephanie J; Weimer, Alan W

    2009-09-01

    Ultrathin ceramic films were deposited throughout highly porous poly(styrene-divinylbenzene) (PS-DVB) particles using a low-temperature atomic layer deposition (ALD) process. Alumina and titania films were deposited by alternating reactions of trimethylaluminum and H2O at 33 degrees C and of titanium tetrachloride and H2O2 (50 wt % in H2O) at 100 degrees C, respectively. Analytical characterization revealed that conformal alumina and titania films were grown on internal and external polymer surfaces. The improved bioactivity of the polymer substrates was revealed on the basis of the formation of hydroxyapatite (HA) in simulated body fluid. The accelerated formation of HA on the ALD-modified polymer surface was caused by the negatively charged surface provided by the ultrathin ceramic interface. The potential for ALD films to support cell attachment was demonstrated.

  15. Molecular simulation of dispersion and mechanical stability of organically modified layered silicates in polymer matrices

    NASA Astrophysics Data System (ADS)

    Fu, Yao-Tsung

    The experimental analysis of nanometer-scale separation processes and mechanical properties at buried interfaces in nanocomposites has remained difficult. We have employed molecular dynamics simulation in relation to available experimental data to alleviate such limitations and gain insight into the dispersion and mechanical stability of organically modified layered silicates in hydrophobic polymer matrices. We analyzed cleavage energies of various organically modified silicates as a function of the cation exchange capacity, surfactant head group chemistry, and chain length using MD simulations with the PCFF-PHYLLOSILICATE force field. The range of the cleavage energy is between 25 and 210 mJ/m2 upon the molecular structures and packing of surfactants. As a function of chain length, the cleavage energy indicates local minima for interlayer structures comprised of loosely packed layers of alkyl chains and local maxima for interlayer structures comprised of densely packed layers of alkyl chains between the layers. In addition, the distribution of cationic head groups between the layers in the equilibrium state determines whether large increases in cleavage energy due to Coulomb attraction. We have also examined mechanical bending and failure mechanisms of layered silicates on the nanometer scale using molecular dynamics simulation in comparison to a library of TEM data of polymer nanocomposites. We investigated the energy of single clay lamellae as a function of bending radius and different cation density. The layer energy increases particularly for bending radii below 20 nm and is largely independent of cation exchange capacity. The analysis of TEM images of agglomerated and exfoliated aluminosilicates of different CEC in polymer matrices at small volume fractions showed bending radii in excess of 100 nm due to free volumes in the polymer matrix. At a volume fraction >5%, however, bent clay layers were found with bending radii <20 nm and kinks as a failure mechanism

  16. Two-step adsorption on jungle-gym-type porous coordination polymers: dependence on hydrogen-bonding capability of adsorbates, ligand-substituent effect, and temperature.

    PubMed

    Uemura, Kazuhiro; Yamasaki, Yukari; Onishi, Fumiaki; Kita, Hidetoshi; Ebihara, Masahiro

    2010-11-01

    A preliminary study of isopropanol (IPA) adsorption/desorption isotherms on a jungle-gym-type porous coordination polymer, [Zn(2)(bdc)(2)(dabco)](n) (1, H(2)bdc = 1,4-benzenedicarboxylic acid, dabco =1,4-diazabicyclo[2.2.2]octane), showed unambiguous two-step profiles via a highly shrunk intermediate framework. The results of adsorption measurements on 1, using probing gas molecules of alcohol (MeOH and EtOH) for the size effect and Me(2)CO for the influence of hydrogen bonding, show that alcohol adsorption isotherms are gradual two-step profiles, whereas the Me(2)CO isotherm is a typical type-I isotherm, indicating that a two-step adsorption/desorption is involved with hydrogen bonds. To further clarify these characteristic adsorption/desorption behaviors, selecting nitroterephthalate (bdc-NO(2)), bromoterephthalate (bdc-Br), and 2,5-dichloroterephthalate (bdc-Cl(2)) as substituted dicarboxylate ligands, isomorphous jungle-gym-type porous coordination polymers, {[Zn(2)(bdc-NO(2))(2)(dabco)]·solvents}(n) (2 ⊃ solvents), {[Zn(2)(bdc-Br)(2)(dabco)]·solvents}(n) (3 ⊃ solvents), and {[Zn(2)(bdc-Cl(2))(2)(dabco)]·solvents}(n) (4 ⊃ solvents), were synthesized and characterized by single-crystal X-ray analyses. Thermal gravimetry, X-ray powder diffraction, and N(2) adsorption at 77 K measurements reveal that [Zn(2)(bdc-NO(2))(2)(dabco)](n) (2), [Zn(2)(bdc-Br)(2)(dabco)](n) (3), and [Zn(2)(bdc-Cl(2))(2)(dabco)](n) (4) maintain their frameworks without guest molecules with Brunauer-Emmett-Teller (BET) surface areas of 1568 (2), 1292 (3), and 1216 (4) m(2) g(-1). As found in results of MeOH, EtOH, IPA, and Me(2)CO adsorption/desorption on 2-4, only MeOH adsorption on 2 shows an obvious two-step profile. Considering the substituent effects and adsorbate sizes, the hydrogen bonds, which are triggers for two-step adsorption, are formed between adsorbates and carboxylate groups at the corners in the pores, inducing wide pores to become narrow pores. Interestingly, such

  17. Numerical simulation of viscoelastic layer rearrangement in polymer melts using OpenFOAM®

    SciTech Connect

    Köpplmayr, Thomas Mayrhofer, Elias

    2015-05-22

    In addition to their shear-thinning behavior, polymer melts are characterized by first and second normal stress differences, which cause secondary motions. Polymer coextrusion processes involve viscoelastic two-phase flows that influence layer formation. Using polymer melts with different pigmentation makes visible the layers deformed by second normal stress differences. We used a new solver for the OpenFOAM CFD toolbox which handles viscoelastic two-phase flows. A derivative of the volume-of-fluid (VoF) methodology was employed to describe the interface. Different types of polymer melt, such as polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET) were investigated. In a coextrusion process, the less viscous phase usually tends to encapsulate the more viscous one. However, the different viscoelastic properties of the melts also influence interface deformation. The materials were characterized by small-amplitude oscillatory-shear rheometry, and a multimode Giesekus model was used to fit shear viscosity, storage and loss modulus. Our simulations also took interfacial tension into account. Experimental observations and corresponding numerical simulations were found to be in good accordance.

  18. High Efficiency Tandem Thin-Perovskite/Polymer Solar Cells with a Graded Recombination Layer.

    PubMed

    Liu, Yao; Renna, Lawrence A; Bag, Monojit; Page, Zachariah A; Kim, Paul; Choi, Jaewon; Emrick, Todd; Venkataraman, D; Russell, Thomas P

    2016-03-23

    Perovskite-containing tandem solar cells are attracting attention for their potential to achieve high efficiencies. We demonstrate a series connection of a ∼ 90 nm thick perovskite front subcell and a ∼ 100 nm thick polymer:fullerene blend back subcell that benefits from an efficient graded recombination layer containing a zwitterionic fullerene, silver (Ag), and molybdenum trioxide (MoO3). This methodology eliminates the adverse effects of thermal annealing or chemical treatment that occurs during perovskite fabrication on polymer-based front subcells. The record tandem perovskite/polymer solar cell efficiency of 16.0%, with low hysteresis, is 75% greater than that of the corresponding ∼ 90 nm thick perovskite single-junction device and 65% greater than that of the polymer single-junction device. The high efficiency of this hybrid tandem device, achieved using only a ∼ 90 nm thick perovskite layer, provides an opportunity to substantially reduce the lead content in the device, while maintaining the high performance derived from perovskites. PMID:26918708

  19. High Efficiency Tandem Thin-Perovskite/Polymer Solar Cells with a Graded Recombination Layer.

    PubMed

    Liu, Yao; Renna, Lawrence A; Bag, Monojit; Page, Zachariah A; Kim, Paul; Choi, Jaewon; Emrick, Todd; Venkataraman, D; Russell, Thomas P

    2016-03-23

    Perovskite-containing tandem solar cells are attracting attention for their potential to achieve high efficiencies. We demonstrate a series connection of a ∼ 90 nm thick perovskite front subcell and a ∼ 100 nm thick polymer:fullerene blend back subcell that benefits from an efficient graded recombination layer containing a zwitterionic fullerene, silver (Ag), and molybdenum trioxide (MoO3). This methodology eliminates the adverse effects of thermal annealing or chemical treatment that occurs during perovskite fabrication on polymer-based front subcells. The record tandem perovskite/polymer solar cell efficiency of 16.0%, with low hysteresis, is 75% greater than that of the corresponding ∼ 90 nm thick perovskite single-junction device and 65% greater than that of the polymer single-junction device. The high efficiency of this hybrid tandem device, achieved using only a ∼ 90 nm thick perovskite layer, provides an opportunity to substantially reduce the lead content in the device, while maintaining the high performance derived from perovskites.

  20. Numerical simulation of viscoelastic layer rearrangement in polymer melts using OpenFOAM®

    NASA Astrophysics Data System (ADS)

    Köpplmayr, Thomas; Mayrhofer, Elias

    2015-05-01

    In addition to their shear-thinning behavior, polymer melts are characterized by first and second normal stress differences, which cause secondary motions. Polymer coextrusion processes involve viscoelastic two-phase flows that influence layer formation. Using polymer melts with different pigmentation makes visible the layers deformed by second normal stress differences. We used a new solver for the OpenFOAM CFD toolbox which handles viscoelastic two-phase flows. A derivative of the volume-of-fluid (VoF) methodology was employed to describe the interface. Different types of polymer melt, such as polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET) were investigated. In a coextrusion process, the less viscous phase usually tends to encapsulate the more viscous one. However, the different viscoelastic properties of the melts also influence interface deformation. The materials were characterized by small-amplitude oscillatory-shear rheometry, and a multimode Giesekus model was used to fit shear viscosity, storage and loss modulus. Our simulations also took interfacial tension into account. Experimental observations and corresponding numerical simulations were found to be in good accordance.

  1. Confinement Effects on the Structure and Dynamics in Intercalated Polymer / Layered Silicates Nanohybrids

    SciTech Connect

    Chrissopoulou, K.; Afratis, A.; Fotiadou, S.; Frick, B.; Anastasiadis, S. H.

    2010-06-02

    The structure and dynamics of PEO/Na{sup +} MMT nanocomposites are investigated by XRD, DSC, and quasielastic neutron scattering (QENS). For concentrations up to 20 wt% the PEO chains within the galleries form either a single- or a double-layered structure of intercalated chains; at higher PEO content only double layers of intercalated PEO chains are formed within the 0.9 nm galleries. Moreover, it is only for polymer content above 70 wt% that peaks corresponding to crystalline PEO and DSC melting transition are observed, indicating that the confined chains remain liquid-like and only the excess polymer outside the completely full galleries can crystallize. QENS investigated the dynamics of PEO in bulk and in confinement. A jump of the bulk PEO dynamics at T{sub m} is observed whereas the dynamics of confined PEO shows only weak wavevector and temperature dependence and goes smoothly through the bulk T{sub m}.

  2. Adsorptive selenite removal from water using a nano-hydrated ferric oxides (HFOs)/polymer hybrid adsorbent.

    PubMed

    Pan, Bingjun; Xiao, Lili; Nie, Guangze; Pan, Bingcai; Wu, Jun; Lv, Lu; Zhang, Weiming; Zheng, Shourong

    2010-01-01

    Selenite (SeO(3)(2-)) is an oxyanion of environmental significance due to its toxicity when taken in excess. In the present study, a hybrid adsorbent (HFO-201) was prepared by irreversibly impregnating hydrated ferric oxide (HFO) nanoparticles within a commercial available anion-exchange resin (D-201), and its adsorption towards selenite from water was investigated in batch and column tests. HFO-201 exhibited improved sorption selectivity toward selenite as compared to the polymeric anion exchanger D-201. Two possible adsorption interactions were responsible for selenite removal by HFO-201, the electrostatic interaction from the ammonium groups bound to the D-201 matrix, and the formation of inner-sphere complexes between the loaded HFO nanoparticles and selenite. In a wide pH range (i.e., 3-8), increasing solution pH was found to result in a decrease of selenite removal on HFO-201. Adsorption isotherms fit the Freundlich model well, and selenite adsorption increased with increasing ambient temperature, indicating its endothermic nature. Column adsorption tests suggested that satisfactory removal of selenite from 2 mg/L to less than 0.01 mg/L could be achieved by HFO-201 even in the presence of the commonly encountered anionic competition at greater concentration, with the treatment capacity of approximately 1200 bed volume (BV) per run, while that for D-201 was only less than 30 BV under otherwise identical conditions. Furthermore, the exhausted HFO-201 was amenable to efficient in situ regeneration with a binary NaOH-NaCl solution.

  3. Polymer-Layer-Free Alignment for Fast Switching Nematic Liquid Crystals by Multifunctional Nanostructured Substrate.

    PubMed

    Jung, Woo-Bin; Jeong, Hyeon Su; Jeon, Hwan-Jin; Kim, Yun Ho; Hwang, Jeong Yeon; Kim, Jae-Hoon; Jung, Hee-Tae

    2015-11-01

    A novel polymer-layer-free system for liquid-crystal alignment is demonstrated by various shaped indium tin oxide (ITO) patterns. Liquid crystals are aligned along the ITO line pattern and secondary sputtering lithography can change the shape of the ITO line pattern. Different shapes can control the direction and size of the pretilt angle. This effect eliminates defects and reduces the response time.

  4. Improved performance of polymer solar cells by using inorganic, organic, and doped cathode buffer layers

    NASA Astrophysics Data System (ADS)

    Taohong, Wang; Changbo, Chen; Kunping, Guo; Guo, Chen; Tao, Xu; Bin, Wei

    2016-03-01

    The interface between the active layer and the electrode is one of the most critical factors that could affect the device performance of polymer solar cells. In this work, based on the typical poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester (P3HT:PCBM) polymer solar cell, we studied the effect of the cathode buffer layer (CBL) between the top metal electrode and the active layer on the device performance. Several inorganic and organic materials commonly used as the electron injection layer in an organic light-emitting diode (OLED) were employed as the CBL in the P3HT:PCBM polymer solar cells. Our results demonstrate that the inorganic and organic materials like Cs2CO3, bathophenanthroline (Bphen), and 8-hydroxyquinolatolithium (Liq) can be used as CBL to efficiently improve the device performance of the P3HT:PCBM polymer solar cells. The P3HT:PCBM devices employed various CBLs possess power conversion efficiencies (PCEs) of 3.0%-3.3%, which are ca. 50% improved compared to that of the device without CBL. Furthermore, by using the doped organic materials Bphen:Cs2CO3 and Bphen:Liq as the CBL, the PCE of the P3HT:PCBM device will be further improved to 3.5%, which is ca. 70% higher than that of the device without a CBL and ca. 10% increased compared with that of the devices with a neat inorganic or organic CBL. Project supported by the National Natural Science Foundation of China (Grant No. 61204014), the “Chenguang” Project (13CG42) supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation, China, and the Shanghai University Young Teacher Training Program of Shanghai Municipality, China.

  5. Development of a silver/polymer nanocomposite interconnection layer for organic tandem solar cells

    NASA Astrophysics Data System (ADS)

    Torabi, Naeimeh; Behjat, Abbas; Shahpari, Mahboobeh; Edalati, Shadi

    2015-01-01

    Interconnecting layers (ICL) play an important role in regulating the performance of tandem devices. We report the design of a solution-processed ICL that consists of a silver/polymer nanocomposite deposited on the top of a TiO2 layer. This nanocomposite contains modified poly (3,4-ethylenedioxythiophene) polystyrene sulfonic acid (PEDOT:PSS), and silver nanoparticles (Ag NPs) synthesized by the chemical reduction of silver nitrate in the presence of PEDOT:PSS. Formation of Ag NPs was confirmed by monitoring the plasmon absorption peak characteristics in the UV-visible spectrum of the synthesized nanocomposite. Transmission electron microscopy analysis indicated the presence of spherical silver NPs in a polymer matrix with a mean size of around 20 nm. The sheet resistance of PEDOT:PSS was found to be 2474±35 Ω/sq. It was changed to 445±28 Ω/sq after solvent modification and decreased to 53.31±3.59 Ω/sq after synthesizing silver NPs in the polymer medium. Meanwhile, the transparency of the nanocomposite film deposited on TiO2 was 89.6%, which is considered appropriate for an interconnecting electrode. We demonstrated that by incorporating a silver/polymer nanocomposite as a hole-transporting layer in contact with TiO2 as an electron-transporting layer, the ohmic behavior of ICL is enhanced with respect to pristine PEDOT:PSS. P3HT:PCBM-based tandem solar cells based on this solution-processed intermediate electrode represent significantly increased open-circuit voltage (Voc), reaching close to the sum of the single cells. By incorporating the nanocomposite in the tandem structure, a Voc of 1.1 V was obtained. This value was almost the sum of the Voc of two single cells, which was 1.18 V.

  6. On Theory of Dispersive Transport in a Two-Layer Polymer Structure

    NASA Astrophysics Data System (ADS)

    Sibatov, R. T.; Morozova, E. V.

    2016-09-01

    Dispersive transport of charge carriers in a two-layer polymer structure is modeled on the basis of the integrodifferential equation of hereditary diffusion. The model of multiple trapping in a bilayer is generalized to the case of an arbitrary density of localized states. With the help of an efficient Monte Carlo algorithm, curves of the transient current are calculated and their features are explained within the framework of a stochastic interpretation of the process.

  7. Tuning the Microcavity of Organic Light Emitting Diodes by Solution Processable Polymer-Nanoparticle Composite Layers.

    PubMed

    Preinfalk, Jan B; Schackmar, Fabian R; Lampe, Thomas; Egel, Amos; Schmidt, Tobias D; Brütting, Wolfgang; Gomard, Guillaume; Lemmer, Uli

    2016-02-01

    In this study, we present a simple method to tune and take advantage of microcavity effects for an increased fraction of outcoupled light in solution-processed organic light emitting diodes. This is achieved by incorporating nonscattering polymer-nanoparticle composite layers. These tunable layers allow the optimization of the device architecture even for high film thicknesses on a single substrate by gradually altering the film thickness using a horizontal dipping technique. Moreover, it is shown that the optoelectronic device parameters are in good agreement with transfer matrix simulations of the corresponding layer stack, which offers the possibility to numerically design devices based on such composite layers. Lastly, it could be shown that the introduction of nanoparticles leads to an improved charge injection, which combined with an optimized microcavity resulted in a maximum luminous efficacy increase of 85% compared to a nanoparticle-free reference device.

  8. Benzocyclobutene (BCB) Polymer as Amphibious Buffer Layer for Graphene Field-Effect Transistor.

    PubMed

    Wu, Yun; Zou, Jianjun; Huo, Shuai; Lu, Haiyan; Kong, Yuecan; Chen, Tangshen; Wu, Wei; Xu, Jingxia

    2015-08-01

    Owing to the scattering and trapping effects, the interfaces of dielectric/graphene or substrate/graphene can tailor the performance of field-effect transistor (FET). In this letter, the polymer of benzocyclobutene (BCB) was used as an amphibious buffer layer and located at between the layers of substrate and graphene and between the layers of dielectric and graphene. Interestingly, with the help of nonpolar and hydrophobic BCB buffer layer, the large-scale top-gated, chemical vapor deposited (CVD) graphene transistors was prepared on Si/SiO2 substrate, its cutoff frequency (fT) and the maximum cutoff frequency (fmax) of the graphene field-effect transistor (GFET) can be reached at 12 GHz and 11 GHz, respectively. PMID:26369142

  9. Graphene oxide-based carbon interconnecting layer for polymer tandem solar cells.

    PubMed

    Chen, Yonghua; Lin, Wei-Chun; Liu, Jun; Dai, Liming

    2014-03-12

    Tandem polymer solar cells (PSCs), consisting of more than one (normally two) subcells connected by a charge recombination layer (i.e., interconnecting layer), hold great promise for enhancing the performance of PSCs. For an ideal tandem solar cell, the open circuit voltage (Voc) equals to the sum of those of the subcells while keeping the short circuit current the same as the lower one, leading to an increased overall power conversion efficiency. The interconnecting layer plays an important role in regulating the tandem device performance. Here, we report that graphene oxide (GO)/GO-Cs (cesium neutralized GO) bilayer modified with ultrathin Al and MoO3 can act as an efficient interconnecting layer in tandem PSCs to achieve a significantly increased Voc, reaching almost 100% of the sum of the subcell V(oc)s under standard AM 1.5 conditions. PMID:24521516

  10. Polymer adsorption from the melts - In-situ x-ray/neutron reflectivity studies on the chain conformations at the polymer/solid interfaces

    NASA Astrophysics Data System (ADS)

    Jiang, Naisheng; Shang, Jun; Endoh, Maya; Akgun, Bulent; Satija, Sushil; Koga, Tadanori

    2013-03-01

    Adsorbed polymer layers formed on flat solid substrates have recently been the subject of extensive studies due to their strong influence on the physical properties of polymeric materials confined at the nanometer scale. Such adsorbed layers are stable against temperature and solvents and can be formed even onto weakly attractive substrate surfaces. In this study, we aim to clarify the detailed structures and thermal properties by the combined use of in-situ x-ray/neutron reflectivity and atomic force microscopy techniques. Various polymers including polystyrene, polybutadiene, poly (2-vinylpyridine), polycarbonate, and poly(methyl methacrylate) were used to prepare equilibrium adsorbed polymer layers on silicon substrates. We report the effects of the intramolecular architectures, molecular weight, and polymer/substrate interactions on the structures, leading to a better understanding of the thermodynamics at the polymer melt/solid interfaces. We acknowledges the financial support from NSF Grant No. CMMI-084626.

  11. Highly efficient inverted polymer light-emitting diodes using surface modifications of ZnO layer.

    PubMed

    Lee, Bo Ram; Jung, Eui Dae; Park, Ji Sun; Nam, Yun Seok; Min, Sa Hoon; Kim, Byeong-Su; Lee, Kyung-Min; Jeong, Jong-Ryul; Friend, Richard H; Kim, Ji-Seon; Kim, Sang Ouk; Song, Myoung Hoon

    2014-01-01

    Organic light-emitting diodes have been recently focused for flexible display and solid-state lighting applications and so much effort has been devoted to achieve highly efficient organic light-emitting diodes. Here, we improve the efficiency of inverted polymer light-emitting diodes by introducing a spontaneously formed ripple-shaped nanostructure of ZnO and applying an amine-based polar solvent treatment to the nanostructure of ZnO. The nanostructure of the ZnO layer improves the extraction of the waveguide modes inside the device structure, and a 2-ME+EA interlayer enhances the electron injection and hole blocking in addition to reducing exciton quenching between the polar-solvent-treated ZnO and the emissive layer. Therefore, our optimized inverted polymer light-emitting diodes have a luminous efficiency of 61.6 cd A(-1) and an external quantum efficiency of 17.8%, which are the highest efficiency values among polymer-based fluorescent light-emitting diodes that contain a single emissive layer.

  12. The mechanical robustness of atomic-layer- and molecular-layer-deposited coatings on polymer substrates

    NASA Astrophysics Data System (ADS)

    Miller, David C.; Foster, Ross R.; Zhang, Yadong; Jen, Shih-Hui; Bertrand, Jacob A.; Lu, Zhixing; Seghete, Dragos; O'Patchen, Jennifer L.; Yang, Ronggui; Lee, Yung-Cheng; George, Steven M.; Dunn, Martin L.

    2009-05-01

    The mechanical robustness of atomic layer deposited alumina and recently developed molecular layer deposited aluminum alkoxide ("alucone") films, as well as laminated composite films composed of both materials, was characterized using mechanical tensile tests along with a recently developed fluorescent tag to visualize channel cracks in the transparent films. All coatings were deposited on polyethylene naphthalate substrates and demonstrated a similar evolution of damage morphology according to applied strain, including channel crack initiation, crack propagation at the critical strain, crack densification up to saturation, and transverse crack formation associated with buckling and delamination. From measurements of crack density versus applied tensile strain coupled with a fracture mechanics model, the mode I fracture toughness of alumina and alucone films was determined to be KIC=1.89±0.10 and 0.17±0.02 MPa m0.5, respectively. From measurements of the saturated crack density, the critical interfacial shear stress was estimated to be τc=39.5±8.3 and 66.6±6.1 MPa, respectively. The toughness of nanometer-scale alumina was comparable to that of alumina thin films grown using other techniques, whereas alucone was quite brittle. The use of alucone as a spacer layer between alumina films was not found to increase the critical strain at fracture for the composite films. This performance is attributed to the low toughness of alucone. The experimental results were supported by companion simulations using fracture mechanics formalism for multilayer films. To aid future development, the modeling method was used to study the increase in the toughness and elastic modulus of the spacer layer required to render improved critical strain at fracture. These results may be applied to a broad variety of multilayer material systems composed of ceramic and spacer layers to yield robust coatings for use in chemical barrier and other applications.

  13. An Adsorbate Discriminatory Gate Effect in a Flexible Porous Coordination Polymer for Selective Adsorption of CO2 over C2H2.

    PubMed

    Foo, Maw Lin; Matsuda, Ryotaro; Hijikata, Yuh; Krishna, Rajamani; Sato, Hiroshi; Horike, Satoshi; Hori, Akihiro; Duan, Jingui; Sato, Yohei; Kubota, Yoshiki; Takata, Masaki; Kitagawa, Susumu

    2016-03-01

    The adsorptive separation of C2H2 and CO2 via porous materials is nontrivial due to the close similarities of their boiling points and kinetic diameters. In this work, we describe a new flexible porous coordination polymer (PCP) [Mn(bdc)(dpe)] (H2bdc = 1,4-benzenedicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene) having zero-dimensional pores, which shows an adsorbate discriminatory gate effect. The compound shows gate opening type abrupt adsorption for C2H2 but not for CO2, leading to an appreciable selective adsorption of CO2 over C2H2 at near ambient temperature (273 K). The origin of this unique selectivity, as unveiled by in situ adsorption-X-ray diffraction experiments and density functional theory calculations, is due to vastly different orientations between the phenylene ring of bdc and each gas in the nanopores. The structural change by photochemical transformation of this PCP via [2 + 2] photodimerization leads to the removal of inverse CO2/C2H2 selectivity, verifying the mechanism of the guest discriminatory gate effect. PMID:26876504

  14. An Adsorbate Discriminatory Gate Effect in a Flexible Porous Coordination Polymer for Selective Adsorption of CO2 over C2H2.

    PubMed

    Foo, Maw Lin; Matsuda, Ryotaro; Hijikata, Yuh; Krishna, Rajamani; Sato, Hiroshi; Horike, Satoshi; Hori, Akihiro; Duan, Jingui; Sato, Yohei; Kubota, Yoshiki; Takata, Masaki; Kitagawa, Susumu

    2016-03-01

    The adsorptive separation of C2H2 and CO2 via porous materials is nontrivial due to the close similarities of their boiling points and kinetic diameters. In this work, we describe a new flexible porous coordination polymer (PCP) [Mn(bdc)(dpe)] (H2bdc = 1,4-benzenedicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene) having zero-dimensional pores, which shows an adsorbate discriminatory gate effect. The compound shows gate opening type abrupt adsorption for C2H2 but not for CO2, leading to an appreciable selective adsorption of CO2 over C2H2 at near ambient temperature (273 K). The origin of this unique selectivity, as unveiled by in situ adsorption-X-ray diffraction experiments and density functional theory calculations, is due to vastly different orientations between the phenylene ring of bdc and each gas in the nanopores. The structural change by photochemical transformation of this PCP via [2 + 2] photodimerization leads to the removal of inverse CO2/C2H2 selectivity, verifying the mechanism of the guest discriminatory gate effect.

  15. Efficient, Air-Stable Bulk Heterojunction Polymer Solar Cells Using MoOx as the Anode Interfacial Layer

    SciTech Connect

    Sun, Yanming; Takacs, Christopher J.; Cowan, Sarah R.; Seo, Jung Hwa; Gong, Xiong; Roy, Anshuman; Heeger, Alan J.

    2011-04-05

    The use of molybdenum oxide as the anode interfacial layer in conventional bulk heterojunction polymer solar cells leads to an improved power conversion efficiency and also dramatically increases the device stability. This indicates that the engineering of improved anode interface materials is an important method by which to fabricate efficient and stable polymer solar cells.

  16. A membrane-less enzymatic fuel cell with layer-by-layer assembly of redox polymer and enzyme over graphite electrodes.

    PubMed

    Rengaraj, Saravanan; Mani, Vigneshwaran; Kavanagh, Paul; Rusling, James; Leech, Dónal

    2011-11-21

    Layer-by-layer (LBL) assembly of alternate osmium redox polymers and glucose oxidase, at anode, and laccase, at cathode, using graphite electrodes form a membrane-less glucose/O(2) enzymatic fuel cell providing a power density of 103 μW cm(-2) at pH 5.5. PMID:21975371

  17. Flame retardant polymer-clay nanocoatings on cotton textile substrates using a newly developed, continuous layer-by-layer deposition process

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cotton’s exceptional softness, breathability, and absorbency have made it America’s best selling textile fiber; however, cotton textiles are generally more combustible than most synthetic fabrics. In this study, a continuous layer-by-layer self-assembly technique was used to deposit polymer-clay nan...

  18. Magnetized graphene layers synthesized on the carbon nanofibers as novel adsorbent for the extraction of polycyclic aromatic hydrocarbons from environmental water samples.

    PubMed

    Rezvani-Eivari, Mostafa; Amiri, Amirhassan; Baghayeri, Mehdi; Ghaemi, Ferial

    2016-09-23

    The application of magnetized graphene (G) layers synthesized on the carbon nanofibers (CNFs) (m-G/CNF) was investigated as novel adsorbent for the magnetic solid-phase extraction (MSPE) of polycyclic aromatic hydrocarbons (PAHs) in water samples followed by gas chromatography-flame ionization detector (GC-FID). Six important parameters, affecting the extraction efficiency of PAHs, including: amount of adsorbent, adsorption and desorption times, type and volume of the eluent solvent and salt content of the sample were evaluated. The optimum extraction conditions were obtained as: 5min for extraction time, 20mg for sorbent amount, dichloromethane as desorption solvent, 1mL for desorption solvent volume, 5min for desorption time and 15% (w/v) for NaCl concentration. Good performance data were obtained at the optimized conditions. The calibration curves were linear over the concentration ranges from 0.012 to 100ngmL(-1) with correlation coefficients (r) between 0.9950 and 0.9967 for all the analytes. The limits of detection (LODs, S/N=3) of the proposed method for the studied PAHs were 0.004-0.03ngmL(-1). The relative standard deviations (RSDs) for five replicates at two concentration levels (0.1 and 50ngmL(-1)) of PAHs were ranged from 3.4 to 5.7%. Appropriate relative recovery values, in the range of 95.5-99.9%, were also obtained for the real water sample analysis. PMID:27578405

  19. Flexible inverted polymer solar cells with an indium-free tri-layer cathode

    SciTech Connect

    El Hajj, Ahmad; Lucas, Bruno Schirr-Bonnans, Martin; Ratier, Bernard; Kraft, Thomas M.; Torchio, Philippe

    2014-01-21

    Indium tin oxide (ITO)-free inverted polymer solar cells (PSCs) have been fabricated without the need of an additional electron transport layer. The indium-free transparent electrode consists of a tri-layer stack ZnO (30 nm)/Ag (14 nm)/ZnO (30 nm) deposited on glass and plastic substrates via ion-beam sputtering. The tri-layer electrodes exhibit similar physical properties to its ITO counterpart, specifically yielding high transmittance and low resistivity (76.5% T at 550 nm, R{sub sq} of 8 Ω/◻) on plastic substrates. The novel tri-layer electrode allows for the fabrication of inverted PSCs without the additional ZnO interfacial layer commonly deposited between ITO and the photoactive layer. This allows for the preparation of thinner plastic solar cells using less material than conventional architectures. Initial studies involving the newly realized architecture (tri-layer electrode/P3HT:PCBM/PEDOT:PSS/Ag) have shown great promise for the transition from ITO to other viable electrodes in organic electronics.

  20. Transparent actuators and robots based on single-layer superaligned carbon nanotube sheet and polymer composites.

    PubMed

    Chen, Luzhuo; Weng, Mingcen; Zhang, Wei; Zhou, Zhiwei; Zhou, Yi; Xia, Dan; Li, Jiaxin; Huang, Zhigao; Liu, Changhong; Fan, Shoushan

    2016-03-28

    Transparent actuators have been attracting emerging interest recently, as they demonstrate potential applications in the fields of invisible robots, tactical displays, variable-focus lenses, and flexible cellular phones. However, previous technologies did not simultaneously realize macroscopic transparent actuators with advantages of large-shape deformation, low-voltage-driven actuation and fast fabrication. Here, we develop a fast approach to fabricate a high-performance transparent actuator based on single-layer superaligned carbon nanotube sheet and polymer composites. Various advantages of single-layer nanotube sheets including high transparency, considerable conductivity, and ultra-thin dimensions together with selected polymer materials completely realize all the above required advantages. Also, this is the first time that a single-layer nanotube sheet has been used to fabricate actuators with high transparency, avoiding the structural damage to the single-layer nanotube sheet. The transparent actuator shows a transmittance of 72% at the wavelength of 550 nm and bends remarkably with a curvature of 0.41 cm(-1) under a DC voltage for 5 s, demonstrating a significant advance in technological performances compared to previous conventional actuators. To illustrate their great potential usage, a transparent wiper and a humanoid robot "hand" were elaborately designed and fabricated, which initiate a new direction in the development of high-performance invisible robotics and other intelligent applications with transparency.

  1. Polymer-layered silicate nanocomposite materials: Morphological studies and potential applications

    NASA Astrophysics Data System (ADS)

    Kurian, Mary

    Polymer-layered silicate nanocomposites, materials where layered silicates are molecularly dispersed in suitable polymer matrices, are of both scientific and commercial significance. The dramatic enhancements in tensile strength, heat and solvent resistance, as well as the decrease in gas permeability of the neat polymer matrix that can be achieved through the incorporation of small amounts of a suitable layered silicate are intricately linked to the nanocomposite morphology. In the current work, the morphological behavior of nanocomposite materials has been investigated by the fabrication and extensive characterization of a series of model experimental systems. The results from the experimental systems that were developed based on one of the theoretical models for morphology prediction in nanocomposites, provide useful insight into controlling nanocomposite morphology by tailoring various system parameters. The unique properties of nanocomposites also make them promising materials for use as electrolytes in lithium polymer batteries. Though an all-solid-state lithium polymer battery is attractive due to characteristics such as low safety risks in comparison with the conventional systems that contain liquid electrolytes, several challenges related to materials design have to be overcome in order to create materials that have good mechanical properties. Our work focuses on the development of a new class of nanocomposite electrolytes where the incorporation of lithium cation-exchanged nanoscale clay sheets into a suitable polymer matrix is expected to impart the inherent favorable characteristics of nanocomposites to the electrolyte. Additionally, this modification is expected to substantially eliminate the need for lithium salt dopants that are currently used to achieve significant conductivities and form what are essentially single-ion conductors. Extensive characterization of these electrolytes showed that properties were strongly dependent on nanocomposite

  2. Novel Polymer Nanocomposites Resulted from Melt Processing of Polystyrene-Based Substrates Coated with Layer-by-Layer Assemblies

    NASA Astrophysics Data System (ADS)

    Soltani, Iman; Spontak, Richard J.

    The novel polymer nanocomposites (PNCs) prepared through two steps of coating polystyrene-based substrates with layer-by-layer (LBL) deposition of montmorillonite and alternative polyelectrolyte layers of polyethyleneimine and polyethylene terephthalate ionomer, followed by their cyclic melt pressing, demonstrated particular morphologies. Transmission electron microscopy images at high magnification scales showed the occurrence of swollen intercalation and flocculated exfoliations of clay platelets, down to a few nanometer thickness, inside and sometimes out of LBL assemblies crushed portions. In fact, intercalation and exfoliation of clay platelets, established in LBL assemblies, increased by shear applied through their repetitive melt pressing. Additionally, x-ray diffractometry traces confirmed the aforementioned increase in clay intercalation. These high aspect ratio LBL assemblies portions formed highly tortuous labyrinths, which may work as scavenging centers to promote barrier properties of the PNCs against transport of gases like oxygen and carbon dioxide. It is despite spontaneously low interaction between hydrophobic styrenic groups and almost hydrophilic natural clay and moderate efficiency of cyclic pressing for providing intensive shear stress on samples.

  3. Redox responsive nanotubes from organometallic polymers by template assisted layer by layer fabrication

    NASA Astrophysics Data System (ADS)

    Song, Jing; Jańczewski, Dominik; Guo, Yuanyuan; Xu, Jianwei; Vancso, G. Julius

    2013-11-01

    Redox responsive nanotubes were fabricated by the template assisted layer-by-layer (LbL) assembly method and employed as platforms for molecular payload release. Positively and negatively charged organometallic poly(ferrocenylsilane)s (PFS) were used to construct the nanotubes, in combination with other polyions. During fabrication, multilayers of these polyions were deposited onto the inner pores of template porous membranes, followed by subsequent removal of the template. Anodized porous alumina and track-etched polycarbonate membranes were used as templates. The morphology, electrochemistry, composition and other properties of the obtained tubular structure were characterized by fluorescence microscopy, scanning (SEM) and transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) spectroscopy. Composite nanotubes, consisting of poly(acrylic acid) anions with PFS+ and nanoparticles including fluorophore labelled dextran and decorated quantum dots, with PFS polyelectrolytes were also fabricated, broadening the scope of the structures. Cyclic voltammograms of PFS containing nanotubes showed similar redox responsive behaviour to thin LbL assembled films. Redox triggered release of labelled macromolecules from these tubular structures demonstrated application potential in controlled molecular delivery.Redox responsive nanotubes were fabricated by the template assisted layer-by-layer (LbL) assembly method and employed as platforms for molecular payload release. Positively and negatively charged organometallic poly(ferrocenylsilane)s (PFS) were used to construct the nanotubes, in combination with other polyions. During fabrication, multilayers of these polyions were deposited onto the inner pores of template porous membranes, followed by subsequent removal of the template. Anodized porous alumina and track-etched polycarbonate membranes were used as templates. The morphology, electrochemistry, composition and other properties of the obtained tubular

  4. Strengthening of polymer ordered porous materials based on a layered nanocomposite internal structure.

    PubMed

    Heng, Liping; Guo, Xieyou; Guo, Tianqi; Wang, Bin; Jiang, Lei

    2016-07-21

    Ordered porous polymeric films attract more and more attention because they have many advantages and broad application prospects in many fields. But because of their large flexibility and poor mechanical properties, some of the scope for application is greatly limited. Inspired by the ordered pore structure of the honeycomb and the layered structure of natural nacre, we prepared an ordered porous polymer film with a layered structure in the pore wall by the solvent-evaporation-restriction assisted hard template method. Compared with other samples, this kind of film with the layered structure showed both excellent mechanical properties and good stability. This kind of film with high mechanical strength, is considered to have wide applications in the areas of separation, biomedicine, precision instruments, aerospace, environmental protection and so on. PMID:27355160

  5. Interaction of polymer with clays.

    SciTech Connect

    Auvray, L.; Lal, J.

    1999-07-02

    Normally synthetic well defined monodisperse discotic laponite clays are known to form a gel phase at mass concentrations as low as a few percent in distilled water. Hydrosoluble polymer polyethylene oxide was added to this intriguing clay system, it was observed that it either prevents gelation or slows it down extremely depending on the polymer weight, concentration or the laponite concentration. Small Angle Neutron scattering (SANS) was used to study these systems because only by isotopic labelling can the structure of the adsorbed polymer layers be determined. The contrast variation technique is specifically used to determine separately the different partial structure factors of the clay and polymer. In this way the signal of the adsorbed chains is separated from the signal of the free chains.

  6. 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.

  7. In situ prepared polymer films as alignment layers for nematic liquid crystals

    SciTech Connect

    Pires, David; Galerne, Yves

    2006-12-15

    By means of UV-visible irradiations and convenient photoinitiators, we realize the cross-linked polymerization of a triacrylate monomer in solution in a nematic liquid crystal (p-pentyl-p{sup '}-cyanobiphenyl) at low concentrations (a few wt %), i.e., under conditions opposite to the synthesis of polymer-dispersed liquid crystals. As atomic force microscope measurements show, when operating close to, but below, the percolation transition, a thin polymer layer is synthesized in situ, directly covering and coating all the substrate. These observations therefore confirm that the properties of anchoring and of alignment memory previously observed in such nematic cells effectively originate from the synthesized polymer film. According to the photoinitiator used, bulk or surface polymerizations dominate and respectively produce continuous or discontinuous films (i.e., with separate clusters). In the former case, polymer aggregates are first synthesized. They then diffuse in the volume until they meet a surface, where they definitely stick if they are large enough. An estimate of the entropy and interaction energy differences between the two states, stuck or free, shows that the aggregates stick on the substrates if their size exceeds the length of about three monomers, i.e., if they contain more than 20-30 monomers. Interestingly, these films may be used to replicate nonuniform alignment patterns that are difficult to realize otherwise. The method may be considered as an imprinting method.

  8. Strengthening of polymer ordered porous materials based on a layered nanocomposite internal structure

    NASA Astrophysics Data System (ADS)

    Heng, Liping; Guo, Xieyou; Guo, Tianqi; Wang, Bin; Jiang, Lei

    2016-07-01

    Ordered porous polymeric films attract more and more attention because they have many advantages and broad application prospects in many fields. But because of their large flexibility and poor mechanical properties, some of the scope for application is greatly limited. Inspired by the ordered pore structure of the honeycomb and the layered structure of natural nacre, we prepared an ordered porous polymer film with a layered structure in the pore wall by the solvent-evaporation-restriction assisted hard template method. Compared with other samples, this kind of film with the layered structure showed both excellent mechanical properties and good stability. This kind of film with high mechanical strength, is considered to have wide applications in the areas of separation, biomedicine, precision instruments, aerospace, environmental protection and so on.Ordered porous polymeric films attract more and more attention because they have many advantages and broad application prospects in many fields. But because of their large flexibility and poor mechanical properties, some of the scope for application is greatly limited. Inspired by the ordered pore structure of the honeycomb and the layered structure of natural nacre, we prepared an ordered porous polymer film with a layered structure in the pore wall by the solvent-evaporation-restriction assisted hard template method. Compared with other samples, this kind of film with the layered structure showed both excellent mechanical properties and good stability. This kind of film with high mechanical strength, is considered to have wide applications in the areas of separation, biomedicine, precision instruments, aerospace, environmental protection and so on. Electronic supplementary information (ESI) available: SEM image of hexagonal silicon pillar templates, AFM images of clay platelets on a silicon substrate, photographs of free-standing gels, X-ray diffraction profiles for dried materials, FTIR and TGA of the samples, and

  9. Tailored porosities of the cathode layer for improved polymer electrolyte fuel cell performance

    NASA Astrophysics Data System (ADS)

    Zlotorowicz, A.; Jayasayee, K.; Dahl, P. I.; Thomassen, M. S.; Kjelstrup, S.

    2015-08-01

    We show experimentally for the first time that the introduction of macro-pores in the nanoporous catalyst layer of a polymer electrolyte membrane fuel cell can improve its performance. We have achieved a Pt utilization of about 0.23 mg W-1 at 0.6 V which is twice the value of the DOE target for 2020, and three times (0.60 mg W-1) smaller than the value of a fully nanoporous reference layer at a catalyst loading of 0.11 mg cm-2. In this work, monodispersed polystyrene particles with diameters of 0.5 and 1 μm were used as pore formers. Cathode catalyst layers with macroporous volume fractions between 0 and 0.58 were investigated. Maximum performance was observed for fuel cells with a macroporous volume fraction of about 0.52 for a 1 μm thick catalyst layer. The results, which were obtained for the cathode layer, support earlier theoretical predictions that gas access to and water escape from the catalyst can be facilitated by introduction of macropores in the nanoporous layer.

  10. Layer-by-layer films assembled from natural polymers for sustained release of neurotrophin.

    PubMed

    Zhang, Zhiling; Li, Qianqi; Han, Lin; Zhong, Yinghui

    2015-09-01

    Cortical neural prostheses (CNPs) hold great promise for paralyzed patients by recording neural signals from the brain and translating them into movement commands. However, these electrodes normally fail to record neural signals weeks to months after implantation due to inflammation and neuronal loss around the implanted neural electrodes. Sustained local delivery of neurotrophins from biocompatible coatings on CNPs can potentially promote neuron survival and attract the nearby neurons to migrate toward the electrodes to increase neuron density at the electrode/brain interface, which is important for maintaining the recording quality and long-term performance of the implanted CNPs. However, sustained release of neurotrophins from biocompatible ultrathin coatings is very difficult to achieve. In this study, we investigated the potential of several biocompatible natural polyanions including heparin, dextran sulfate, and gelatin to form layer-by-layer (LbL) assembly with positively charged neurotrophin nerve growth factor (NGF) and its model protein lysozyme, and whether sustained release of NGF and lysozyme can be achieved from the nanoscale thin LbL coatings. We found that gelatin, which is less negatively charged than heparin and dextran sulfate, showed the highest efficacy in loading proteins into the LbL films because other interactions in addition to electrostatic interactions were involved in LbL assembly. Sustained release of NGF and lysozymes for approximately 2 weeks was achieved from the gelatin-based LbL coatings. Released NGF maintained the bioactivity to stimulate neurite outgrowth from PC12 cells. Gelatin is generally recognized as safe by the FDA. Thus, the biocompatible LbL coating developed in this study is highly promising to be used for implanted CNPs to improve their long-term performance in human patients. PMID:26358683

  11. Layered conductive polymer on nylon membrane templates for high performance, thin-film supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Shi, HaoTian Harvey; Naguib, Hani E.

    2016-04-01

    Flexible Thin-film Electrochemical Capacitors (ECs) are emerging technology that plays an important role as energy supply for various electronics system for both present era and the future. Intrinsically conductive polymers (ICPs) are promising pseudo-capacitive materials as they feature both good electrical conductivity and high specific capacitance. This study focuses on the construction and characterization of ultra-high surface area porous electrodes based on coating of nano-sized conductive polymer materials on nylon membrane templates. Herein, a novel nano-engineered electrode material based on nylon membranes was presented, which allows the creation of super-capacitor devices that is capable of delivering competitive performance, while maintaining desirable mechanical characteristics. With the formation of a highly conductive network with the polyaniline nano-layer, the electrical conductivity was also increased dramatically to facilitate the charge transfer process. Cyclic voltammetry and specific capacitance results showed promising application of this type of composite materials for future smart textile applications.

  12. Prevention of the water flooding by micronizing the pore structure of gas diffusion layer for polymer electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Hiramitsu, Yusuke; Sato, Hitoshi; Hori, Michio

    In polymer electrolyte fuel cells, high humidity must be established to maintain high proton conductivity in the polymer electrolyte. However, the water that is produced electrochemically at the cathode catalyst layer can condense in the cell and cause an obstruction to the diffusion of reaction gas in the gas diffusion layer and the gas channel. This leads to a sudden decrease of the cell voltage. To combat this, strict water management techniques are required, which usually focus on the gas diffusion layer. In this study, the use of specially treated carbon paper as a flood-proof gas diffusion layer under extremely high humidity conditions was investigated experimentally. The results indicated that flooding originates at the interface between the gas diffusion layer and the catalyst layer, and that such flooding could be eliminated by control of the pore size in the gas diffusion layer at this interface.

  13. Protection of Polymers from the Space Environment by Atomic Layer Deposition

    NASA Astrophysics Data System (ADS)

    Lindholm, Ned F.; Zhang, Jianming; Minton, Timothy K.; O'Patchen, Jennifer; George, Steven M.; Groner, Markus D.

    2009-01-01

    Polymers in space may be subjected to a barrage of incident atoms, photons, and/or ions. For example, oxygen atoms can etch and oxidize these materials. Photons may act either alone or in combination with oxygen atoms to degrade polymers and paints and thus limit their usefulness. Colors fade under the intense vacuum ultraviolet (VUV) solar radiation. Ions can lead to the build-up of static charge on polymers. Atomic layer deposition (ALD) techniques can provide coatings that could mitigate many challenges for polymers in space. ALD is a gas-phase technique based on two sequential, self-limiting surface reactions, and it can deposit very uniform, conformal, and pinhole-free films with atomic layer control. We have studied the efficacy of various ALD coatings to protect Kapton® polyimide, FEP Teflon®, and poly(methyl methacrylate) films from atomic-oxygen and VUV attack. Atomic-oxygen and VUV studies were conducted with the use of a laser-breakdown source for hyperthermal O atoms and a D2 lamp as a source of VUV light. These studies used a quartz crystal microbalance (QCM) to monitor mass loss in situ, as well as surface profilometry and scanning electron microscopy to study the surface recession and morphology changes ex situ. Al2O3 ALD coatings applied to polyimide and FEP Teflon® films protected the underlying substrates from O-atom attack, and ZnO coatings protected the poly(methyl methacrylate) substrate from VUV-induced damage.

  14. Modeling approach for tensile strength of interphase layers in polymer nanocomposites.

    PubMed

    Zare, Yasser

    2016-06-01

    At the first step, this paper describes a developed model for tensile strength of interphase layers (σ(k)) in polymer nanocomposites. The "σ(k)" is expressed as linear, exponential and power functions of the distance between nanoparticles and polymer matrix (x(k)). Afterwards, the predictions of these equations at the central layer of interphase (the average strength) are compared to the calculations of interphase strength (σ(i)) by several micromechanical models including the developed Leidner-Woodhams and Pukanszky models to choose the best equation which expresses "σ(k)". The calculations are carried out for several reported samples. The equation which expresses the "σ(k)" as a power function of "xk" shows the best results compared to others. Also, its predictions significantly depend to an exponent as "Z" which demonstrates the level of interphase properties. According to the chosen equation, the "σ(m)" and "σ(p)" play positive roles in "σ(i)" predictions at low "Z" value, but a high "Z" eliminates the effect of "σ(m)" on the tensile strength of interphase layers. PMID:26990956

  15. An Alkane-Soluble Dendrimer as Electron-Transport Layer in Polymer Light-Emitting Diodes.

    PubMed

    Zhong, Zhiming; Zhao, Sen; Pei, Jian; Wang, Jian; Ying, Lei; Peng, Junbiao; Cao, Yong

    2016-08-10

    Polymer light-emitting diodes (PLEDs) have attracted broad interest due to their solution-processable properties. It is well-known that to achieve better performance, organic light-emitting diodes require multilayer device structures. However, it is difficult to realize multilayer device structures by solution processing for PLEDs. Because most semiconducting polymers have similar solubility in common organic solvents, such as toluene, xylene, chloroform, and chlorobenzene, the deposition of multilayers can cause layers to mix together and damage each layer. Herein, a novel semiorthogonal solubility relationship was developed and demonstrated. For the first time, an alkane-soluble dendrimer is utilized as the electron-transport layer (ETL) in PLEDs via a solution-based process. With the dendrimer ETL, the external quantum efficiency increases more than threefold. This improvement in the device performance is attributed to better exciton confinement, improved exciton energy transfer, and better charge carrier balance. The semiorthogonal solubility provided by alkane offers another process dimension in PLEDs. By combining them with water/alcohol-soluble polyelectrolytes, more exquisite multilayer devices can be fabricated to achieve high device performance, and new device structures can be designed and realized.

  16. Modification of inkjet printer for polymer sensitive layer preparation on silicon-based gas sensors

    NASA Astrophysics Data System (ADS)

    Li, Tianjian; Dong, Ying; Yuan, Dengpeng; Liu, Yujin

    2015-04-01

    Inkjet printing is a versatile, low cost deposition technology with the capabilities for the localized deposition of high precision, patterned deposition in a programmable way, and the parallel deposition of a variety of materials. This paper demonstrates a new method of modifying the consumer inkjet printer to prepare polymer-sensitive layers on silicon wafer for gas sensor applications. A special printing tray for the modified inkjet printer to support a 4-inch silicon wafer is designed. The positioning accuracy of the deposition system is tested, based on the newly modified printer. The experimental data show that the positioning errors in the horizontal direction are negligibly small, while the positioning errors in the vertical direction rise with the increase of the printing distance of the wafer. The method for making suitable ink to be deposited to form the polymer-sensitive layer is also discussed. In the testing, a solution of 0.1 wt% polyvinyl alcohol (PVA) was used as ink to prepare a sensitive layer with certain dimensions at a specific location on the surface of the silicon wafer, and the results prove the feasibility of the methods presented in this article.

  17. High performance polymer solar cells with as-prepared zirconium acetylacetonate film as cathode buffer layer.

    PubMed

    Tan, Zhan'ao; Li, Shusheng; Wang, Fuzhi; Qian, Deping; Lin, Jun; Hou, Jianhui; Li, Yongfang

    2014-01-01

    Low-work-function active metals are commonly used as cathode in polymer solar cells (PSCs), but sensitivity of the active metals towards moisture and oxygen results in poor stability of the devices. Therefore, solution-proceessable and stable cathode buffer layer is of great importance for the application of PSCs. Here we demonstrate high performance PSCs by employing as-prepared zirconium acetylacetonate (a-ZrAcac) film spin-cast from its ethanol solution as cathode buffer layer. The PSCs based on a low bandgap polymer PBDTBDD as donor and PC60BM as acceptor with a-ZrAcac/Al cathode demonstrated an average power conversion efficiency (PCE) of 8.75% which is significantly improved than that of the devices with traditional Ca/Al cathode. The improved photovoltaic performance is benefitted from the decreased series resistance and enhanced light harvest of the PSCs with the a-ZrAcac/Al cathode. The results indicate that a-ZrAcac is a promising high performance cathode buffer layer for fabricating large area flexible PSCs. PMID:24732976

  18. An Alkane-Soluble Dendrimer as Electron-Transport Layer in Polymer Light-Emitting Diodes.

    PubMed

    Zhong, Zhiming; Zhao, Sen; Pei, Jian; Wang, Jian; Ying, Lei; Peng, Junbiao; Cao, Yong

    2016-08-10

    Polymer light-emitting diodes (PLEDs) have attracted broad interest due to their solution-processable properties. It is well-known that to achieve better performance, organic light-emitting diodes require multilayer device structures. However, it is difficult to realize multilayer device structures by solution processing for PLEDs. Because most semiconducting polymers have similar solubility in common organic solvents, such as toluene, xylene, chloroform, and chlorobenzene, the deposition of multilayers can cause layers to mix together and damage each layer. Herein, a novel semiorthogonal solubility relationship was developed and demonstrated. For the first time, an alkane-soluble dendrimer is utilized as the electron-transport layer (ETL) in PLEDs via a solution-based process. With the dendrimer ETL, the external quantum efficiency increases more than threefold. This improvement in the device performance is attributed to better exciton confinement, improved exciton energy transfer, and better charge carrier balance. The semiorthogonal solubility provided by alkane offers another process dimension in PLEDs. By combining them with water/alcohol-soluble polyelectrolytes, more exquisite multilayer devices can be fabricated to achieve high device performance, and new device structures can be designed and realized. PMID:27435357

  19. Driving mechanisms of ionic polymer actuators having electric double layer capacitor structures.

    PubMed

    Imaizumi, Satoru; Kato, Yuichi; Kokubo, Hisashi; Watanabe, Masayoshi

    2012-04-26

    Two solid polymer electrolytes, composed of a polyether-segmented polyurethaneurea (PEUU) and either a lithium salt (lithium bis(trifluoromethanesulfonyl)amide: Li[NTf2]) or a nonvolatile ionic liquid (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide: [C2mim][NTf2]), were prepared in order to utilize them as ionic polymer actuators. These salts were preferentially dissolved in the polyether phases. The ionic transport mechanism of the polyethers was discussed in terms of the diffusion coefficients and ionic transference numbers of the incorporated ions, which were estimated by means of pulsed-field gradient spin-echo (PGSE) NMR. There was a distinct difference in the ionic transport properties of each polymer electrolyte owing to the difference in the magnitude of interactions between the cations and the polyether. The anionic diffusion coefficient was much faster than that of the cation in the polyether/Li[NTf2] electrolyte, whereas the cation diffused faster than the anion in the polyether/[C2mim][NTf2] electrolyte. Ionic polymer actuators, which have a solid-state electric-double-layer-capacitor (EDLC) structure, were prepared using these polymer electrolyte membranes and ubiquitous carbon materials such as activated carbon and acetylene black. On the basis of the difference in the motional direction of each actuator against applied voltages, a simple model of the actuation mechanisms was proposed by taking the difference in ionic transport properties into consideration. This model discriminated the behavior of the actuators in terms of the products of transference numbers and ionic volumes. The experimentally observed behavior of the actuators was successfully explained by this model. PMID:22489566

  20. Synthesis and characterization of polymer layers for control of fluid transport

    NASA Astrophysics Data System (ADS)

    Vatansever, Fehime

    The level of wetting of fiber surface with liquids is an important characteristic of fibrous materials. It is related to fiber surface energy and the structure of the material. Surface energy can be changed by surface modification via the grafting methodologies that have been reported for introducing new and stable functionality to fibrous substrates without changing bulk properties. Present work is dedicated to synthesis and characterization of macromolecular layers grafted to fiber surface in order to achieve directional liquid transport for the modified fabric. Modification technique used here is based on formation of stable polymer layer on fabric surface using "grafting to" technique. Specifically, modification of fabric with wettability gradient for facilitated one way-liquid transport, and pointed modification of yarn-based channels on textile microfluidic device for directional liquid transport are reported here. First, fabric was activated with alkali (NaOH) solution. Second, poly (glycidyl methacrylate) (PGMA) was deposited on fabric as an anchoring layer. Finally, polymers of interest were grafted to surface through the epoxy functionality of PGMA. Effect of polymer grafting on the wicking property of the fabric has been evaluated by vertical wicking technique at the each step of surface modification. The results shows that wicking performance of fabric can be altered by grafting of a thin nanoscale polymeric film. For the facilitated liquid transport, the gradient polymer coating was created using "grafting to" technique and its dependence on the grafting temperature. Wettability gradient from hydrophilic to hydrophobic (change in water contact angle from 0 to 140 degrees on fabric) was achieved by grafting of polystyrene (PS) and polyacrylic acid (PAA) sequentially with concentration gradient. This study proposes that fabric with wettability gradient property can be used to transfer sweat from skin and support moisture management when it is used in a

  1. Adsorbed polyelectrolyte coatings decrease Fe(0) nanoparticle reactivity with TCE in water: conceptual model and mechanisms.

    PubMed

    Phenrat, Tanapon; Liu, Yueqiang; Tilton, Robert D; Lowry, Gregory V

    2009-03-01

    The surfaces of reactive nanoscale zerovalent iron (NZVI) particles used for in situ groundwater remediation are modified with polymers or polyelectrolytes to enhance colloidal stability and mobility in the subsurface. However, surface modification decreases NZVI reactivity. Here, the TCE dechlorination rate and reaction products are measured as a function of adsorbed polyelectrolyte mass for three commercially available polyelectrolytes used for NZVI surface modification including poly(styrene sulfonate) (PSS), carboxymethyl cellulose (CMC), and polyaspartate (PAP). The adsorbed mass, extended layer thickness, and TCE-polyelectrolyte partition coefficient are measured and used to explain the effect of adsorbed polyelectrolyte on NZVI reactivity. For all modifiers, the dechlorination rate constant decreased nonlinearly with increasing surface excess, with a maximum of a 24-fold decrease in reactivity. The TCE dechlorination pathways were not affected. Consistent with Scheutjens-Fleer theory for homopolymer adsorption, the nonlinear relationship between the dechlorination rate and the surface excess of adsorbed polyelectrolyte suggests that adsorbed polyelectrolyte decreases reactivity primarily by blocking reactive surface sites at low surface excess where they adsorb relatively flat onto the NZVI surface, and by a combination of site blocking and decreasing the aqueous TCE concentration at the NZVI surface due to partitioning of TCE to adsorbed polyelectrolytes. This explanation is also consistent with the effect of adsorbed polyelectrolyte on acetylene formation. This conceptual model should apply to other medium and high molecular weight polymeric surface modifiers on nanoparticles, and potentially to adsorbed natural organic matter.

  2. In-syringe extraction using dissolvable layered double hydroxide-polymer sponges templated from hierarchically porous coordination polymers.

    PubMed

    Ghani, Milad; Frizzarin, Rejane M; Maya, Fernando; Cerdà, Víctor

    2016-07-01

    Herein we report the use of cobalt porous coordination polymers (PCP) as intermediates to prepare advanced extraction media based on layered double hydroxides (LDH) supported on melamine polymer foam. The obtained dissolvable Ni-Co LDH composite sponges can be molded and used as sorbent for the in-syringe solid-phase extraction (SPE) of phenolic acids from fruit juices. The proposed sorbent is obtained due to the surfactant-assisted self-assembly of Co(II)/imidazolate PCPs on commercially available melamine foam, followed by the in situ conversion of the PCP into the final dissolvable LDH coating. Advantageous features for SPE are obtained by using PCPs with hierarchical porosity (HPCPs). The LDH-sponge prepared using intermediate HPCPs (HLDH-sponge) is placed in the headspace of a glass syringe, enabling flow-through extraction followed by analyte elution by the dissolution of the LDH coating in acidic conditions. Three phenolic acids (gallic acid, p-hydroxybenzoic acid and caffeic acid) were extracted and quantified using high performance liquid chromatography. Using a 5mL sample volume, the obtained detection limits were 0.15-0.35μgL(-1). The proposed method for the preparation of HLDH-sponges showed a good reproducibility as observed from the intra- and inter-day RSD's, which were <10% for all analytes. The batch-to-batch reproducibility for three different batches of HLDH-sponges was 10.6-11.2%. Enrichment factors of 15-21 were obtained. The HLDH-sponges were applied satisfactorily to the determination of phenolic acids in natural and commercial fruit juices, obtaining relative recoveries among 89.7-95.3%.

  3. Effects of surface water on gas sorption capacities of gravimetric sensing layers analyzed by molecular descriptors of organic adsorbates.

    PubMed

    Sugimoto, Iwao; Mitsui, Kouta; Nakamura, Masayuki; Seyama, Michiko

    2011-02-01

    The gas sorption capacities of sputtered carbonaceous films are evaluated with quartz crystal resonators. These films are sensitive to 20 ppm organic vapors and exhibit structure-dependent responses. Films derived from synthetic polymers are hydrophobic, whereas films derived from biomaterials are amphiphilic or hydrophilic. Polyethylene (PE) film has an extremely high sorption capacity for a wide range of vapors. Transient sorption responses are investigated using a humidified carrier by employing carboxylic acid esters, whose aliphatic groups are systematically changed. Small esters with a higher affinity to water induce negative U-shaped responses from amphiphilic films derived from biomaterials. On the other hand, polymeric films exhibit positive exponential response curves. Even if the concentrations are decreased, the response intensities are enhanced with the incremental expansion of carbon chains of aliphatic groups. Only fluoropolymer film shows the opposite tendency. The modeling of quantitative structure property relationships has indicated that the sorption capacities of the PE film to the carboxylic acid esters are fundamentally governed by electrostatic interactions. The intermolecular attractive forces are basically attributable to interactions between the positively polarized sites in esters and the negatively polarized/charged sites in PE film.

  4. A novel (ex situ) method to quantify oxygen diffusion coefficient of polymer fuel cells backing and catalyst layers

    NASA Astrophysics Data System (ADS)

    Baricci, Andrea; Casalegno, Andrea

    2016-09-01

    Limiting current density of oxygen reduction reaction in polymer electrolyte fuel cells is determined by several mass transport resistances that lower the concentration of oxygen on the catalyst active site. Among them, diffusion across porous media plays a significant role. Despite the extensive experimental activity documented in PEMFC literature, only few efforts have been dedicated to the measurement of the effective transport properties in porous layers. In the present work, a methodology for ex situ measurement of the effective diffusion coefficient and Knudsen radius of porous layers for polymer electrolyte fuel cells (gas diffusion layer, micro porous layer and catalyst layer) is described and applied to high temperature polymer fuel cells State of Art materials. Regression of the measured quantities by means of a quasi 2D physical model is performed to quantify the Knudsen effect, which is reported to account, respectively, for 30% and 50% of the mass transport resistance in micro porous layer and catalyst layer. On the other side, the model reveals that pressure gradient consequent to permeation in porous layers of high temperature polymer fuel cells has a negligible effect on oxygen concentration in relevant operating conditions.

  5. Electrically tunable liquid-crystal wave plate using quadripolar electrode configuration and transparent conductive polymer layers.

    PubMed

    Fraval, Nicolas; Joffre, Pascal; Formont, Stéphane; Chazelas, Jean

    2009-10-01

    We present the realization of an electrically tunable wave plate, which uses a nematic liquid-crystal (LC) phase retarder that allows fast and continuous control of the polarization state. This device is built using a quadripolar electrode design and transparent conductive polymer layers in order to obtain a uniform electric field distribution in the interelectrode area. With this realization, we obtain a high degree of control of the orientation of the electric field and, consequently, of the LC director. Indeed, this modulator outperforms classical bipolar LC cells in both optical path variation (>4 microm) and LC rotation speed (0.4 degrees/micros). PMID:19798369

  6. Amine-pillared Nanosheet Adsorbents for CO2 Capture Applications

    NASA Astrophysics Data System (ADS)

    Jiang, Hui

    3D microporous layers with 8 MB openings in the plane of the layers, as well as perpendicular to the layers, which are larger than CO2 molecules. Based on the structure differences between nanosheets precursor material MCM-22(P) and nanoporous layered silicate material AMH-3, the latter might be more suitable for CO 2 capturer application as an APN candidate material. However, none of the assumptions above have been approved experimentally. In this study, the influence of the amine loading on adsorption capacity and kinetics of adsorption for the mixed porosity material pillared MCM-22 (P) (also called MCM-36) is studied systematically, in order to determine a potential route to achieve a final material with both high amine loading and high adsorption capacity. We first synthesized MCM-22(P), followed by swelling and pillaring to create MCM-36. Polymeric amines such as polyethylenimine (PEI) are used as an organic component of the supported amine adsorbents, with varying polymer loadings within the adsorbents used. The kinetics and diffusion properties of carbon dioxide capture on a MCM-36 pillared material impregnated with amine containing Polyethylenimine polymers has been investigated. It was determined that the introduction of amine polymer cannot be used to improve the capture capacity of the support over that of the bare material, due to the fact that with the addition of a high loading of amine polymer the large pore diffusion channels become impossible for carbon dioxide molecules to diffuse through. This sets an upper limit to the capture capacity of polymer impregnated MCM-36 for carbon dioxide which does not surpass that for the initial bare material, and greatly reduces the utility of using this sort of amine-solid adsorbent for carbon capture plans in the future.

  7. Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer

    DOE PAGES

    Dell'Angela, M.; Anniyev, T.; Beye, M.; Coffee, R.; Föhlisch, A.; Gladh, J.; Kaya, S.; Katayama, T.; Krupin, O.; Nilsson, A.; et al

    2015-03-01

    Vacuum space charge-induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400 nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse.

  8. Fullerenes as adhesive layers for mechanical peeling of metallic, molecular and polymer thin films.

    PubMed

    Wieland, Maria B; Slater, Anna G; Mangham, Barry; Champness, Neil R; Beton, Peter H

    2014-01-01

    We show that thin films of C60 with a thickness ranging from 10 to 100 nm can promote adhesion between a Au thin film deposited on mica and a solution-deposited layer of the elastomer polymethyldisolaxane (PDMS). This molecular adhesion facilitates the removal of the gold film from the mica support by peeling and provides a new approach to template stripping which avoids the use of conventional adhesive layers. The fullerene adhesion layers may also be used to remove organic monolayers and thin films as well as two-dimensional polymers which are pre-formed on the gold surface and have monolayer thickness. Following the removal from the mica support the monolayers may be isolated and transferred to a dielectric surface by etching of the gold thin film, mechanical transfer and removal of the fullerene layer by annealing/dissolution. The use of this molecular adhesive layer provides a new route to transfer polymeric films from metal substrates to other surfaces as we demonstrate for an assembly of covalently-coupled porphyrins.

  9. Polymer-surfactant layered heterostructures by electropolymerization of phenosafranine in Langmuir-Blodgett films.

    PubMed

    Sawant, Shilpa N; Doble, Mukesh; Yakhmi, J V; Kulshreshtha, S K; Miyazaki, Akira; Enoki, Toshiaki

    2006-12-01

    Langmuir-Blodgett (LB) films of the water-soluble dye phenosafranine (PS) have been prepared by its adsorption from aqueous dye solution to an arachidic acid (AA) monolayer at the air-water interface. Atomic force microscopy (AFM) images of the LB films revealed the effect of change in pH of deposition on the degree of complexation of AA with the PS dye. Well-defined circular islands and holes were observed which disappeared with the increase in pH. Polarized absorption studies indicated that the dye molecules are oriented uniaxially with their long axis titled at a constant angle to the surface normal of the LB film. Within the restricted geometry of the LB film, the PS dye was electropolymerized to form a two-dimensional film of poly(phenosafranine) sandwiched between arachidic acid layers. The film was characterized by IR spectroscopy, cyclic voltammetry, and AFM. X-ray diffraction studies reveal the presence of a layer structure in the AA-PS LB film before and after polymerization. The polymer film showed highly anisotropic electrical conductivity of ca. 10 orders of magnitude. This indicates the formation of two-dimensional polyPS layers between arachidic acid layers resulting in a layered heterostructure film having alternate conducting and insulating regions. Also, the conductivity of the polyPS prepared from LB film was found to be approximately 2.5 times higher than the conductivity of polyPS prepared by solution polymerization method. PMID:17134212

  10. Efficient inverted polymer solar cells integrated with a compound electron extraction layer

    NASA Astrophysics Data System (ADS)

    Ma, Zhong-Sheng; Wang, Qian-Kun; Li, Chi; Li, Yan-Qing; Zhang, Dan-Dan; Liu, Weimin; Wang, Pengfei; Tang, Jian-Xin

    2015-12-01

    We constructed an effective electron extraction layer (EEL) used for polymer solar cells by integrating one new kind of organic material of 4,4‧-(1,4-phenylene) bis(2-phenyl-6-p-tolylnicotinonitrile) (p-PPtNT) and cesium carbonate (Cs2CO3) used as a compound EEL (CEEL). The CEEL based device exhibits an ideal PCE of 4.15%, corresponding to an enhancement 220% in contrast to that of control device without EEL, which is also comparable to that of ZnO based device. Our analyses indicated that the remarkably improved PCE for CEEL based device is mainly ascribed to the Ohmic contact and the negligible electron extraction barrier at cathode/active layer by inserting CEEL.

  11. Transparent actuators and robots based on single-layer superaligned carbon nanotube sheet and polymer composites

    NASA Astrophysics Data System (ADS)

    Chen, Luzhuo; Weng, Mingcen; Zhang, Wei; Zhou, Zhiwei; Zhou, Yi; Xia, Dan; Li, Jiaxin; Huang, Zhigao; Liu, Changhong; Fan, Shoushan

    2016-03-01

    Transparent actuators have been attracting emerging interest recently, as they demonstrate potential applications in the fields of invisible robots, tactical displays, variable-focus lenses, and flexible cellular phones. However, previous technologies did not simultaneously realize macroscopic transparent actuators with advantages of large-shape deformation, low-voltage-driven actuation and fast fabrication. Here, we develop a fast approach to fabricate a high-performance transparent actuator based on single-layer superaligned carbon nanotube sheet and polymer composites. Various advantages of single-layer nanotube sheets including high transparency, considerable conductivity, and ultra-thin dimensions together with selected polymer materials completely realize all the above required advantages. Also, this is the first time that a single-layer nanotube sheet has been used to fabricate actuators with high transparency, avoiding the structural damage to the single-layer nanotube sheet. The transparent actuator shows a transmittance of 72% at the wavelength of 550 nm and bends remarkably with a curvature of 0.41 cm-1 under a DC voltage for 5 s, demonstrating a significant advance in technological performances compared to previous conventional actuators. To illustrate their great potential usage, a transparent wiper and a humanoid robot ``hand'' were elaborately designed and fabricated, which initiate a new direction in the development of high-performance invisible robotics and other intelligent applications with transparency.Transparent actuators have been attracting emerging interest recently, as they demonstrate potential applications in the fields of invisible robots, tactical displays, variable-focus lenses, and flexible cellular phones. However, previous technologies did not simultaneously realize macroscopic transparent actuators with advantages of large-shape deformation, low-voltage-driven actuation and fast fabrication. Here, we develop a fast approach to

  12. Impact of polymer electrolyte membrane fuel cell microporous layer nano-scale features on thermal conductance

    NASA Astrophysics Data System (ADS)

    Botelho, S. J.; Bazylak, A.

    2015-04-01

    In this study, the microporous layer (MPL) of the polymer electrolyte membrane (PEM) fuel cell was analysed at the nano-scale. Atomic force microscopy (AFM) was utilized to image the top layer of MPL particles, and a curve fitting algorithm was used to determine the particle size and filling radius distributions for SGL-10BB and SGL-10BC. The particles in SGL-10BC (approximately 60 nm in diameter) have been found to be larger than those in SGL-10BB (approximately 40 nm in diameter), highlighting structural variability between the two materials. The impact of the MPL particle interactions on the effective thermal conductivity of the bulk MPL was analysed using a discretization of the Fourier equation with the Gauss-Seidel iterative method. It was found that the particle spacing and filling radius dominates the effective thermal conductivity, a result which provides valuable insight for future MPL design.

  13. Inverted polymer solar cells with enhanced fill factor by inserting the potassium stearate interfacial modification layer

    NASA Astrophysics Data System (ADS)

    Li, Jiangsheng; Jiu, Tonggang; Li, Bairu; Kuang, Chaoyang; Chen, Qiushan; Ma, Sushuang; Shu, Jie; Fang, Junfeng

    2016-05-01

    A thin potassium stearate (KSt) film combined with an optimized ZnO film was introduced to improve the fill factor (FF) of highly efficient inverted polymer solar cells (PSCs). Atomic force microscopy and contact angle measurements were used to show that the introduction of KSt did not change the morphology of interlayer. On the contrary, it is beneficial for the spread of the active layer on the interlayer. The origin of enhanced FF was systematically studied by the ideal current-voltage model for a single heterojunction solar cell and electrochemical impedance spectroscopy. On the basis of the data analysis, the reduced charge recombination loss was responsible for this improved FF. At last, when KSt was replaced by sodium stearate (NaSt), the similar experiment phenomenon was observed. This indicates that inserting a metallic stearate modified layer is a promising strategy to enhance inverted PSCs performance.

  14. Interaction of polymer with discotic clay particles.

    SciTech Connect

    Auvray, L.; Lal, J.

    1999-08-04

    Normally synthetic well defined monodisperse discotic laponite clays are known to form a gel phase at mass concentrations as low as a few percent in distilled water. Hydrosoluble polymer polyethylene oxide was added to this intriguing clay system, it was observed that it either prevents gelation or slows it down extremely depending on the polymer weight, concentration or the laponite concentration. Small Angle Neutron scattering (SANS) was used to study these systems because only by isotopic labeling can the structure of the adsorbed polymer layers be determined. The contrast variation technique is specifically used to determine separately the different partial structure factors of the clay and polymer. In this way the signal of the adsorbed chains is separated from the signal of the free chains in the dilute regime. Attempts have also been made to characterize the structure in the concentrated regime of laponite with polymer.

  15. Broadband All-Polymer Phototransistors with Nanostructured Bulk Heterojunction Layers of NIR-Sensing n-Type and Visible Light-Sensing p-Type Polymers.

    PubMed

    Han, Hyemi; Nam, Sungho; Seo, Jooyeok; Lee, Chulyeon; Kim, Hwajeong; Bradley, Donal D C; Ha, Chang-Sik; Kim, Youngkyoo

    2015-11-13

    We report 'broadband light-sensing' all-polymer phototransistors with the nanostructured bulk heterojunction (BHJ) layers of visible (VIS) light-sensing electron-donating (p-type) polymer and near infrared (NIR) light-sensing electron-accepting (n-type) polymer. Poly[{2,5-bis-(2-ethylhexyl)-3,6-bis-(thien-2-yl)-pyrrolo[3,4-c]pyrrole-1,4-diyl}-co-{2,2'-(2,1,3-benzothiadiazole)]-5,5'-diyl}] (PEHTPPD-BT), which is synthesized via Suzuki coupling and employed as the n-type polymer, shows strong optical absorption in the NIR region (up to 1100 nm) in the presence of weak absorption in the VIS range (400~600 nm). To strengthen the VIS absorption, poly(3-hexylthiophene) (P3HT) is introduced as the p-type polymer. All-polymer phototransistors with the BHJ (P3HT:PEHTPPD-BT) layers, featuring a peculiar nano-domain morphology, exhibit typical p-type transistor characteristics and efficiently detect broadband (VIS~NIR) lights. The maximum corrected responsivity (without contribution of dark current) reaches up to 85~88% (VIS) and 26~40% (NIR) of theoretical responsivity. The charge separation process between P3HT and PEHTPPD-BT components in the highest occupied molecular orbital is proposed as a major working mechanism for the effective NIR sensing.

  16. Broadband All-Polymer Phototransistors with Nanostructured Bulk Heterojunction Layers of NIR-Sensing n-Type and Visible Light-Sensing p-Type Polymers

    PubMed Central

    Han, Hyemi; Nam, Sungho; Seo, Jooyeok; Lee, Chulyeon; Kim, Hwajeong; Bradley, Donal D. C.; Ha, Chang-Sik; Kim, Youngkyoo

    2015-01-01

    We report ‘broadband light-sensing’ all-polymer phototransistors with the nanostructured bulk heterojunction (BHJ) layers of visible (VIS) light-sensing electron-donating (p-type) polymer and near infrared (NIR) light-sensing electron-accepting (n-type) polymer. Poly[{2,5-bis-(2-ethylhexyl)-3,6-bis-(thien-2-yl)-pyrrolo[3,4-c]pyrrole-1,4-diyl}-co-{2,2′-(2,1,3-benzothiadiazole)]-5,5′-diyl}] (PEHTPPD-BT), which is synthesized via Suzuki coupling and employed as the n-type polymer, shows strong optical absorption in the NIR region (up to 1100 nm) in the presence of weak absorption in the VIS range (400 ~ 600 nm). To strengthen the VIS absorption, poly(3-hexylthiophene) (P3HT) is introduced as the p-type polymer. All-polymer phototransistors with the BHJ (P3HT:PEHTPPD-BT) layers, featuring a peculiar nano-domain morphology, exhibit typical p-type transistor characteristics and efficiently detect broadband (VIS ~ NIR) lights. The maximum corrected responsivity (without contribution of dark current) reaches up to 85 ~ 88% (VIS) and 26 ~ 40% (NIR) of theoretical responsivity. The charge separation process between P3HT and PEHTPPD-BT components in the highest occupied molecular orbital is proposed as a major working mechanism for the effective NIR sensing. PMID:26563576

  17. Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer.

    PubMed

    Dell'Angela, M; Anniyev, T; Beye, M; Coffee, R; Föhlisch, A; Gladh, J; Kaya, S; Katayama, T; Krupin, O; Nilsson, A; Nordlund, D; Schlotter, W F; Sellberg, J A; Sorgenfrei, F; Turner, J J; Öström, H; Ogasawara, H; Wolf, M; Wurth, W

    2015-03-01

    Vacuum space charge induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400 nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse.

  18. Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer.

    PubMed

    Dell'Angela, M; Anniyev, T; Beye, M; Coffee, R; Föhlisch, A; Gladh, J; Kaya, S; Katayama, T; Krupin, O; Nilsson, A; Nordlund, D; Schlotter, W F; Sellberg, J A; Sorgenfrei, F; Turner, J J; Öström, H; Ogasawara, H; Wolf, M; Wurth, W

    2015-03-01

    Vacuum space charge induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400 nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse. PMID:26798795

  19. High voltage electric double layer capacitor using a novel solid-state polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Sato, Takaya; Marukane, Shoko; Morinaga, Takashi; Kamijo, Toshio; Arafune, Hiroyuki; Tsujii, Yoshinobu

    2015-11-01

    We designed and fabricated a bipolar-type electric double layer capacitor (EDLC) with a maximum 7.5 V operating voltage using a new concept in solid electrolytes. A cell having a high operating voltage, that is free from liquid leakage and is non-flammable is achieved by a bipolar design utilizing a solid polymer electrolyte made up of particles in a three-dimensional array, such as crystals composed of 75 wt% of hybrid particles decorated with a concentrated ionic liquid polymer brush (PSiP) and 25wt% of an ionic liquid (IL). The resulting solid film had sufficient physical strength and a high enough ionic conductivity to function as an electrolyte. Solidification as well as ionic conduction is due to the regular array of PSiPs, thereby producing a high ion-conductivity from a networked path between cores containing an appropriate amount of IL as a plasticizer. The demonstration cell shows a relatively good cycle durability and rate properties up to a 10C discharge process. It also has a very small leakage current in continuous charging and better self-discharge properties, even at 60 °C, compared with conventional cells. This paper demonstrates the first successful fabrication of a bipolar EDLC in a simple structure using this novel polymer solid electrolyte.

  20. Laser-Induced Forward Transfer Using Triazene Polymer Dynamic Releaser Layer

    SciTech Connect

    Stewart, James Shaw; Lippert, Thomas; Wokaun, Alexander; Nagel, Matthias; Nueesch, Frank

    2010-10-08

    This article presents a short review of the use of triazene polymer as a dynamic release layer (DRL) for laser-induced forward transfer (LIFT), before looking at the latest research in more detail. The field of triazene polymer ablation only started around 20 years ago and has grown rapidly into a number of different application areas. Most promisingly, triazene ablation has been refined as a method for propulsion, bringing the benefits of LIFT to the deposition of sensitive transfer materials. The key to understanding LIFT with a triazene DRL is to understand the more fundamental nature of triazene polymer ablation in both frontside and backside orientations. This article focuses on the most recent experimental results on LIFT with a triazene DRL: the effect of picosecond pulse lengths compared with nanosecond pulse lengths; the effect of reduced air pressure; and the improvements in transfer in terms of range of transfer materials, and transfer across a gap. The results all help improve fundamental understanding of triazene-based LIFT, and the transfer of functioning OLEDs demonstrates the capability of the technique.

  1. Polymer Coated CaAl-Layered Double Hydroxide Nanomaterials for Potential Calcium Supplement

    PubMed Central

    Kim, Tae-Hyun; Lee, Jeong-A; Choi, Soo-Jin; Oh, Jae-Min

    2014-01-01

    We have successfully prepared layered double hydroxide (LDH) nanomaterials containing calcium and aluminum ions in the framework (CaAl-LDH). The surface of CaAl-LDH was coated with enteric polymer, Eudragit®L 100 in order to protect nanomaterials from fast dissolution under gastric condition of pH 1.2. The X-ray diffraction patterns, Fourier transform infrared spectroscopy, scanning electron and transmission electron microscopy revealed that the pristine LDH was well prepared having hydrocalumite structure, and that the polymer effectively coated the surface of LDH without disturbing structure. From thermal analysis, it was determined that only a small amount (less than 1%) of polymer was coated on the LDH surface. Metal dissolution from LDH nanomaterials was significantly reduced upon Eudragit®L 100 coating at pH 1.2, 6.8 and 7.4, which simulates gastric, enteric and plasma conditions, respectively, and the dissolution effect was the most suppressed at pH 1.2. The LDH nanomaterials did not exhibit any significant cytotoxicity up to 1000 μg/mL and intracellular calcium concentration significantly increased in LDH-treated human intestinal cells. Pharmacokinetic study demonstrated absorption efficiency of Eudragit®L 100 coated LDH following oral administration to rats. Moreover, the LDH nanomaterials did not cause acute toxic effect in vivo. All the results suggest the great potential of CaAl-LDH nanomaterials as a calcium supplement. PMID:25490138

  2. Imaging Fourier transform spectroscopy of the boundary layer plume from laser irradiated polymers and carbon materials

    NASA Astrophysics Data System (ADS)

    Acosta, Roberto I.

    The high-energy laser (HEL) lethality community needs for enhanced laser weapons systems requires a better understanding of a wide variety of emerging threats. In order to reduce the dimensionality of laser-materials interaction it is necessary to develop novel predictive capabilities of these events. The objective is to better understand the fundamentals of laser lethality testing by developing empirical models from hyperspectral imagery, enabling a robust library of experiments for vulnerability assessments. Emissive plumes from laser irradiated fiberglass reinforced polymers (FRP), poly(methyl methacrylate) (PMMA) and porous graphite targets were investigated primarily using a mid-wave infrared (MWIR) imaging Fourier transform spectrometer (FTS). Polymer and graphite targets were irradiated with a continuous wave (cw) fiber lasers. Data was acquired with a spectral resolution of 2 cm-1 and spatial resolution as high as 0.52 mm2 per pixel. Strong emission from H2O, CO, CO2 and hydrocarbons were observed in the MWIR between 1900-4000 cm-1. A single-layer radiative transfer model was developed to estimate spatial maps of temperature and column densities of CO and CO2 from the hyperspectral imagery of the boundary layer plume. The spectral model was used to compute the absorption cross sections of CO and CO2, using spectral line parameters from the high temperature extension of the HITRAN. Also, spatial maps of gas-phase temperature and methyl methacrylate (MMA) concentration were developed from laser irradiated carbon black-pigmented PMMA at irradiances of 4-22 W/cm2. Global kinetics interplay between heterogeneous and homogeneous combustion kinetics are shown from experimental observations at high spatial resolutions. Overall the boundary layer profile at steady-state is consistent with CO being mainly produced at the surface by heterogeneous reactions followed by a rapid homogeneous combustion in the boundary layer towards buoyancy.

  3. Nanocomposites of polymers with layered inorganic nanofillers: Antimicrobial activity, thermo-mechanical properties, morphology, and dispersion

    NASA Astrophysics Data System (ADS)

    Songtipya, Ponusa

    In the first part of the thesis, polyethylene/layered silicate nanocomposites that exhibit an antimicrobial activity were synthesized and studied. Their antimicrobial activity was designed to originate from non-leaching, novel cationic modifiers---amine-based surfactants---used as the organic-modification of the fillers. Specifically, PE/organically-modified montmorillonite ( mmt) nanocomposites were prepared via melt-processing, and simultaneous dispersion and antimicrobial activity was designed by proper choice of the fillers' organic modification. The antimicrobial activity was measured against three micotoxinogen fungal strains (Penicillium roqueforti and claviforme, and Fusarium graminearum ). Various mmt-based organofillers, which only differ in the type or amount of their organic modification, were used to exemplify how these surfactants can be designed to render antifungal activity to the fillers themselves and the respective nanocomposites. A comparative discussion of the growth of fungi on unfilled PE and nanocomposite PE films is used to demonstrate how the antimicrobial efficacy is dictated by the surfactant chemistry and, further, how the nanocomposites' inhibitory activity compares to that of the organo-fillers and the surfactants. An attempt to improve the thermomechanical reinforcement of PE/mmt nanocomposites while maintaining their antimicrobial activity, was also carried out by combining two different organically modified montmorillonites. However, a uniform microscopic dispersion could not be achieved through this approach. In the second part of this thesis, a number of fundamental studies relating to structure-property relations in nanocomposites were carried out, towards unveiling strategies that can concurrently optimize selected properties of polymers by the addition of nanofillers. Specifically, the dispersion-crystallinity-reinforcement relations in HDPE/mmt nanocomposites was investigated. The influence of a functional HDPE compatibilizer

  4. 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

  5. Effect of catalyst layer defects on local membrane degradation in polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Tavassoli, Arash; Lim, Chan; Kolodziej, Joanna; Lauritzen, Michael; Knights, Shanna; Wang, G. Gary; Kjeang, Erik

    2016-08-01

    Aiming at durability issues of fuel cells, this research is dedicated to a novel experimental approach in the analysis of local membrane degradation phenomena in polymer electrolyte fuel cells, shedding light on the potential effects of manufacturing imperfections on this process. With a comprehensive review on historical failure analysis data from field operated fuel cells, local sources of iron oxide contaminants, catalyst layer cracks, and catalyst layer delamination are considered as potential candidates for initiating or accelerating the local membrane degradation phenomena. Customized membrane electrode assemblies with artificial defects are designed, fabricated, and subjected to membrane accelerated stress tests followed by extensive post-mortem analysis. The results reveal a significant accelerating effect of iron oxide contamination on the global chemical degradation of the membrane, but dismiss local traces of iron oxide as a potential stressor for local membrane degradation. Anode and cathode catalyst layer cracks are observed to have negligible impact on the membrane degradation phenomena. Notably however, distinct evidence is found that anode catalyst layer delamination can accelerate local membrane thinning, while cathode delamination has no apparent effect. Moreover, a substantial mitigating effect for platinum residuals on the site of delamination is observed.

  6. Polymer bulk heterojunction solar cells with PEDOT:PSS bilayer structure as hole extraction layer.

    PubMed

    Kim, Wanjung; Kim, Namhun; Kim, Jung Kyu; Park, Insun; Choi, Yeong Suk; Wang, Dong Hwan; Chae, Heeyeop; Park, Jong Hyeok

    2013-06-01

    A high current density obtained in a limited, nanometer-thick region is important for high efficiency polymer solar cells (PSCs). The conversion of incident photons to charge carriers only occurs in confined active layers; therefore, charge-carrier extraction from the active layer within the device by using solar light has an important impact on the current density and the related to power conversion efficiency. In this study, we observed a surprising result, that is, extracting the charge carrier generated in the active layer of a PSC device, with a thickness-controlled PEDOT:PSS bilayer that acted as a hole extraction layer (HEL), yielded a dramatically improved power conversion efficiency in two different model systems (P3HT:PC₆₀BM and PCDTBT:PC₇₀BM). To understand this phenomenon, we conducted optical strength simulation, photocurrent-voltage measurements, incident photon to charge carrier efficiency measurements, ultraviolet photoelectron spectroscopy, and AFM studies. The results revealed that approximately 60 nm was the optimum PEDOT:PSS bilayer HEL thickness in PSCs for producing the maximum power conversion efficiency.

  7. On-line thickness measurement for two-layer systems on polymer electronic devices.

    PubMed

    Grassi, Ana Perez; Tremmel, Anton J; Koch, Alexander W; El-Khozondar, Hala J

    2013-11-18

    During the manufacturing of printed electronic circuits, different layers of coatings are applied successively on a substrate. The correct thickness of such layers is essential for guaranteeing the electronic behavior of the final product and must therefore be controlled thoroughly. This paper presents a model for measuring two-layer systems through thin film reflectometry (TFR). The model considers irregular interfaces and distortions introduced by the setup and the vertical vibration movements caused by the production process. The results show that the introduction of these latter variables is indispensable to obtain correct thickness values. The proposed approach is applied to a typical configuration of polymer electronics on transparent and non-transparent substrates. We compare our results to those obtained using a profilometer. The high degree of agreement between both measurements validates the model and suggests that the proposed measurement method can be used in industrial applications requiring fast and non-contact inspection of two-layer systems. Moreover, this approach can be used for other kinds of materials with known optical parameters.

  8. Quantitative characterization of water transport and flooding in the diffusion layers of polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Casalegno, A.; Colombo, L.; Galbiati, S.; Marchesi, R.

    Optimization of water management in polymer electrolyte membrane fuel cells (PEMFC) and in direct methanol fuel cells (DMFC) is a very important factor for the achievement of high performances and long lifetime. A good hydration of the electrolyte membrane is essential for high proton conductivity; on the contrary water in excess may lead to electrode flooding and severe reduction in performances. Many studies on water transport across the gas diffusion layer (GDL) have been carried out to improve these components; anyway efforts in this field are affected by lack of effective experimental methods. The present work reports an experimental investigation with the purpose to determine the global coefficient of water transport across different diffusion layers under real operating conditions. An appropriate and accurate experimental apparatus has been designed and built to test the single GDL under a wide range of operating conditions. Data analysis has allowed quantification of both the water vapor transport across different diffusion layers, and the effects of micro-porous layers; furthermore flooding onset and its consequences on the mass transport coefficient have been characterized by means of suitably defined parameters.

  9. Interphase and particle dispersion correlations in polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Senses, Erkan

    Particle dispersion in polymer matrices is a major parameter governing the mechanical performance of polymer nanocomposites. Controlling particle dispersion and understanding aging of composites under large shear and temperature variations determine the processing conditions and lifetime of composites which are very important for diverse applications in biomedicine, highly reinforced materials and more importantly for the polymer composites with adaptive mechanical responses. This thesis investigates the role of interphase layers between particles and polymer matrices in two bulk systems where particle dispersion is altered upon deformation in repulsive composites, and good-dispersion of particles is retained after multiple oscillatory shearing and aging cycles in attractive composites. We demonstrate that chain desorption and re-adsorption processes in attractive composites under shear can effectively enhance the bulk microscopic mechanical properties, and long chains of adsorbed layers lead to a denser entangled interphase layer. We further designed experiments where particles are physically adsorbed with bimodal lengths of homopolymer chains to underpin the entanglement effect in interphases. Bimodal adsorbed chains are shown to improve the interfacial strength and used to modulate the elastic properties of composites without changing the particle loading, dispersion state or polymer conformation. Finally, the role of dynamic asymmetry (different mobilities in polymer blends) and chemical heterogeneity in the interphase layer are explored in systems of poly(methyl methacrylate) adsorbed silica nanoparticles dispersed in poly(ethylene oxide) matrix. Such nanocomposites are shown to exhibit unique thermal-stiffening behavior at temperatures above glass transitions of both polymers. These interesting findings suggest that the mobility of the surface-bound polymer is essential for reinforcement in polymer nanocomposites, contrary to existing glassy layer theories

  10. Gas Diffusion Barriers Using Atomic Layer Deposition: A New Calcium Test and Polymer Substrate Effects

    NASA Astrophysics Data System (ADS)

    Bertrand, Jacob Andrew

    The increasing demand on available energy resources has led to a desire for more energy efficient devices. The wide use of displays in consumer electronics, such as televisions, cell phones, cameras and computers makes them an ideal target for improvement. Organic light-emitting diodes (OLEDs) are a good candidate to replace traditional Si based devices. However, the low work function metals typically used as electrodes in OLEDs are very reactive with water and oxygen. Ultralow permeability gas diffusion barriers with water vapor transmission rates (WVTRs) as low as <10-6g/(m2*day) are required on the polymers used to fabricate organic electronic and thin film photovoltaic devices. Atomic Layer Deposition (ALD) uses self-limiting surface reactions to deposit thin conformal films. ALD is capable of depositing thin, conformal, high quality barriers. WVTR values as low as ˜5 x 10-5 g/(m2*day) have been measured for Al2O3 ALD films at 38 °C/85% RH using the Ca test with optical transmission probing. The Ca test is a technique with very high sensitivity to measure ultralow WVTRs. This test relies on measuring the oxidation of a Ca metal film by monitoring the change in its optical or electrical properties. However, glass lid control experiments have indicated that the WVTRs measured by the Ca test are limited by H2O permeability through the epoxy seals. Varying results have been reported in the literature using the electrical conductance of Ca to measure permeation. In this work, two approaches were applied to overcome the epoxy edge seal limitations. The first approach was to deposit Al2O 3 ALD barriers directly on Ca metal. While the Al 2O3 ALD barriers were successfully deposited, the measurement of an accurate WVTR was limited by barrier pinholes. The presence of pinholes in the Al2O3 ALD barrier on Ca results in the localized oxidation of the Ca sensor. Heterogeneous degradation of the Ca causes inaccuracies in the conductance of the film. As oxidation regions

  11. Reflectivity studies on adsorbed block copolymers under shear

    SciTech Connect

    Smith, G.S.; Wages, S.; Baker, S.M.; Toprakcioglu, C.; Hadziioannou, G.

    1994-12-01

    The authors report neutron reflectivity data on (poly)styrene-(poly)ethylene oxide (PS-PEO) diblock copolymers adsorbed onto quartz from the selective solvent cyclohexane (a non-solvent for PEO and a poor solvent for PS). The PEO ``anchor block`` adsorbs strongly to form a thin layer on the quartz substrate, while the deuterated PS chains dangle into the solvent. They find that under static conditions the density profile of the PS block in a poor solvent can be well described by a Schultz function which is indicative of a polymer ``mushroom.`` Furthermore, they have studied the same system under shear at shear rates from 0--400s{sup {minus}1}. They find that there is a dramatic increase in the thickness of the PS layer under shear in cyclohexane and that the relaxation time from the shear-on profile back to the static profile is on the order of several days.

  12. Controlled release from triple layer, donut-shaped tablets with enteric polymers.

    PubMed

    Kim, Cherng-ju

    2005-10-22

    The purpose of this research was to evaluate triple layer, donut-shaped tablets (TLDSTs) for extended release dosage forms. TLDSTs were prepared by layering 3 powders sequentially after pressing them with a punch. The core tablet consisted of enteric polymers, mainly hydroxypropyl methylcellulose acetate succinate, and the bottom and top layers were made of a water-insoluble polymer, ethyl cellulose. Drug release kinetics were dependent on the pH of the dissolution medium and the drug properties, such as solubility, salt forms of weak acid and weak base drugs, and drug loading. At a 10% drug loading level, all drugs, regardless of their type or solubility, yielded the same release profiles within an acceptable level of experimental error. As drug loading increased from 10% to 30%, the drug release rate of neutral drugs increased for all except sulfathiazole, which retained the same kinetics as at 10% loading. HCl salts of weak base drugs had much slower release rates than did those of neutral drugs (eg, theophylline) as drug loading increased. The release of labetalol HCl retarded as drug loading increased from 10% to 30%. On the other hand, Na salts of weak acid drugs had much higher release rates than did those of neutral drugs (eg, theophylline). Drug release kinetics were governed by the ionization/erosion process with slight drug diffusion, observing no perfect straight line. A mathematical expression for drug release kinetics (erosion-controlled system) of TLDSTs is presented. In summary, a TLDST is a good design to obtain zero-order or nearly zero-order release kinetics for a wide range of drug solubilities.

  13. Identification of polymer surface adsorbed proteins implicated in pluripotent human embryonic stem cell expansion† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6bm00214e Click here for additional data file.

    PubMed Central

    Hammad, Moamen; Rao, Wei; Smith, James G. W.; Anderson, Daniel G.; Langer, Robert; Young, Lorraine E.; Barrett, David A.; Davies, Martyn C.; Denning, Chris

    2016-01-01

    Improved biomaterials are required for application in regenerative medicine, biosensing, and as medical devices. The response of cells to the chemistry of polymers cultured in media is generally regarded as being dominated by proteins adsorbed to the surface. Here we use mass spectrometry to identify proteins adsorbed from a complex mouse embryonic fibroblast (MEF) conditioned medium found to support pluripotent human embryonic stem cell (hESC) expansion on a plasma etched tissue culture polystyrene surface. A total of 71 proteins were identified, of which 14 uniquely correlated with the surface on which pluripotent stem cell expansion was achieved. We have developed a microarray combinatorial protein spotting approach to test the potential of these 14 proteins to support expansion of a hESC cell line (HUES-7) and a human induced pluripotent stem cell line (ReBl-PAT) on a novel polymer (N-(4-Hydroxyphenyl) methacrylamide). These proteins were spotted to form a primary array yielding several protein mixture ‘hits’ that enhanced cell attachment to the polymer. A second array was generated to test the function of a refined set of protein mixtures. We found that a combination of heat shock protein 90 and heat shock protein-1 encourage elevated adherence of pluripotent stem cells at a level comparable to fibronectin pre-treatment. PMID:27466628

  14. Reduction of birefringence in a skin-layer of injection molded polymer strips using CO{sub 2} laser irradiation

    SciTech Connect

    Kurosaki, Yasuo; Satoh, Isao; Saito, Takushi

    1995-12-31

    Injection molding of polymers is currently utilized for numerous industrial applications. Because of high productivity and stable quality of molded products, the injection-molding process makes the production costs lower, and therefore, is expected to spread more widely in the future. This paper deals with a technique for improving the optical quality of injection molded polymer products using radiative heating. The birefringence frozen in a skin-layer of the molded part was reduced by CO{sub 2} laser heating, and the efficiency of this technique was investigated experimentally. Namely, a simple numerical calculation was performed to estimate the heating efficiency of CO{sub 2} laser in the polymer, effects of radiation heating on the skin-layer of the molded polymer were observed by using a mold with transparent windows, and the residual birefringence frozen in the final molded specimen was measured. The results clearly showed that the birefringence in the skin-layer of injection molded polymer strips was reduced with CO{sub 2} laser heating. The authors believe that the proposed method for reducing the birefringence frozen in injection-molded polymer products is suitable for practical molding, because process time required for the injection-molding is only slightly increased with this method.

  15. Bubble-surface interactions with graphite in the presence of adsorbed carboxymethylcellulose.

    PubMed

    Wu, Jueying; Delcheva, Iliana; Ngothai, Yung; Krasowska, Marta; Beattie, David A

    2015-01-21

    The adsorption of carboxymethylcellulose (CMC), and the subsequent effect on bubble-surface interactions, has been studied for a graphite surface. CMC adsorbs on highly oriented pyrolytic graphite (HOPG) in specific patterns: when adsorbed from a solution of low concentration it forms stretched, isolated and sparsely distributed chains, while upon adsorption from a solution of higher concentration, it forms an interconnected network of multilayer features. The amount and topography of the adsorbed CMC affect the electrical properties as well as the wettability of the polymer-modified HOPG surface. Adsorption of CMC onto the HOPG surface causes the zeta potential to be more negative and the modified surface becomes more hydrophilic. This increase in both the absolute value of zeta potential and the surface hydrophilicity originates from the carboxymethyl groups of the CMC polymer. The effect of the adsorbed polymer layer on wetting film drainage and bubble-surface/particle attachment was determined using high speed video microscopy to monitor single bubble-surface collision, and single bubble Hallimond tube flotation experiments. The time of wetting film drainage and the time of three-phase contact line spreading gets significantly longer for polymer-modified HOPG surfaces, indicating that the film rupture and three-phase contact line expansion were inhibited by the presence of polymer. The effect of longer drainage times and slower dewetting correlated with reduced flotation recovery. The molecular kinetic (MK) model was used to quantify the effect of the polymer on dewetting dynamics, and showed an increase in the jump frequency for the polymer adsorbed at the higher concentration.

  16. Freestanding and Reactive Thin Films Fabricated by Covalent Layer-by-Layer Assembly and Subsequent Lift-Off of Azlactone-Containing Polymer Multilayers

    PubMed Central

    Buck, Maren E.

    2010-01-01

    We report an approach to the fabrication of freestanding and amine-reactive thin films that is based on the reactive layer-by-layer assembly and subsequent lift-off of azlactone-containing polymer multilayers. We demonstrate that covalently crosslinked multilayers fabricated using the azlactone-functionalized polymer poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) and a primary amine-containing polymer [poly(ethyleneimine) (PEI)] can be delaminated from planar glass and silicon surfaces by immersion in mildly acidic aqueous environments to yield flexible freestanding membranes. These freestanding membranes are robust and can withstand exposure to strong acid, strong base, or incubation in high ionic strength solutions that typically lead to the disruption and erosion of polymer multilayers assembled by reversible weak interactions (e.g., ‘polyelectrolyte multilayers’ assembled by electrostatic interactions or hydrogen bonding). We demonstrate further that these PEI/PVDMA assemblies contain residual reactive azlactone functionality that can be exploited to chemically modify the films (either directly after fabrication or after they have been lifted off of the substrates on which they were fabricated) using a variety of amine-functionalized small molecules. These freestanding membranes can also be transferred readily onto other objects (for example, onto the surfaces of planar substrates containing holes or pores) to fabricate suspended polymer membranes and other film-functionalized interfaces. In addition to planar, two-dimensional freestanding films, this approach can be used to fabricate and isolate three-dimensional freestanding membranes (e.g., curved films or tubes) by layer-by-layer assembly on, and subsequent lift-off from, the surfaces of topologically complex substrates (e.g., the curved ends of glass tubing, etc.). The results of this investigation, when combined, suggest the basis of methods for the fabrication of stable, chemically-reactive, and

  17. Molecular interaction forces generated during protein adsorption to well-defined polymer brush surfaces.

    PubMed

    Sakata, Sho; Inoue, Yuuki; Ishihara, Kazuhiko

    2015-03-17

    The molecular interaction forces generated during the adsorption of proteins to surfaces were examined by the force-versus-distance (f-d) curve measurements of atomic force microscopy using probes modified with appropriate molecules. Various substrates with polymer brush layers bearing zwitterionic, cationic, anionic, and hydrophobic groups were systematically prepared by surface-initiated atom transfer radical polymerization. Surface interaction forces on these substrates were analyzed by the f-d curve measurements using probes with the same polymer brush layer as the substrate. Repulsive forces, which decreased depending on the ionic strength, were generated between cationic or anionic polyelectrolyte brush layers; these were considered to be electrostatic interaction forces. A strong adhesive force was detected between hydrophobic polymer brush layers during retraction; this corresponded to the hydrophobic interaction between two hydrophobic polymer layers. In contrast, no significant interaction forces were detected between zwitterionic polymer brush layers. Direct interaction forces between proteins and polymer brush layers were then quantitatively evaluated by the f-d curve measurements using protein-immobilized probes consisting of negatively charged albumin and positively charged lysozyme under physiological conditions. In addition, the amount of protein adsorbed on the polymer brush layer was quantified by surface plasmon resonance measurements. Relatively large amounts of protein adsorbed to the polyelectrolyte brush layers with opposite charges. It was considered that the detachment of the protein after contact with the polymer brush layer hardly occurred due to salt formation at the interface. Both proteins adsorbed significantly on the hydrophobic polymer brush layer, which was due to hydrophobic interactions at the interface. In contrast, the zwitterionic polymer brush layer exhibited no significant interaction force with proteins and suppressed

  18. Enhanced Lifetime of Polymer Solar Cells by Surface Passivation of Metal Oxide Buffer Layers.

    PubMed

    Venkatesan, Swaminathan; Ngo, Evan; Khatiwada, Devendra; Zhang, Cheng; Qiao, Qiquan

    2015-07-29

    The role of electron selective interfaces on the performance and lifetime of polymer solar cells were compared and analyzed. Bilayer interfaces consisting of metal oxide films with cationic polymer modification namely poly ethylenimine ethoxylated (PEIE) were found to enhance device lifetime compared to bare metal oxide films when used as an electron selective cathode interface. Devices utilizing surface-modified metal oxide layers showed enhanced lifetimes, retaining up to 85% of their original efficiency when stored in ambient atmosphere for 180 days without any encapsulation. The work function and surface potential of zinc oxide (ZnO) and ZnO/PEIE interlayers were evaluated using Kelvin probe and Kelvin probe force microscopy (KPFM) respectively. Kelvin probe measurements showed a smaller reduction in work function of ZnO/PEIE films compared to bare ZnO films when aged in atmospheric conditions. KPFM measurements showed that the surface potential of the ZnO surface drastically reduces when stored in ambient air for 7 days because of surface oxidation. Surface oxidation of the interface led to a substantial decrease in the performance in aged devices. The enhancement in the lifetime of devices with a bilayer interface was correlated to the suppressed surface oxidation of the metal oxide layers. The PEIE passivated surface retained a lower Fermi level when aged, which led to lower trap-assisted recombination at the polymer-cathode interface. Further photocharge extraction by linearly increasing voltage (Photo-CELIV) measurements were performed on fresh and aged samples to evaluate the field required to extract maximum charges. Fresh devices with a bare ZnO cathode interlayer required a lower field than devices with ZnO/PEIE cathode interface. However, aged devices with ZnO required a much higher field to extract charges while aged devices with ZnO/PEIE showed a minor increase compared to the fresh devices. Results indicate that surface modification can act as a

  19. Divergent layer topologies in divalent metal aliphatic dicarboxylate coordination polymers containing 3-pyridylmethylnicotinamide

    NASA Astrophysics Data System (ADS)

    White, Charmaine L.; Torres Salgado, Maria D.; Mizzi, Jessica E.; LaDuca, Robert L.

    2015-12-01

    Hydrothermal reaction of the requisite metal salt, an aliphatic dicarboxylic acid, and the hydrogen-bonding capable dipyridylamide ligand 3-pyridylmethylnicotinamide (3-pmna) resulted in four coordination polymers whose connectedness and layer topology depend on the metal coordination environment and dicarboxylate binding mode. These new crystalline phases were characterized by single crystal X-ray diffraction. [Cu(ox)(3-pmna)]n (1, ox = oxalate) manifests stacked 3-connected (6,3) herringbone layer motifs. {[Cd(mal)(3-pmna)(H2O)]·3H2O}n (2, mal = malonate) shows a 4-connected (4,4) grid topology with entrained water molecule trimeric chains in the interlamellar regions. {[Cd2(suc)2(3-pmna)(H2O)2]·3H2O}n (3, suc = succinate) possesses {Cd2O2} dimer-based [Cd(suc)]n layers pillared by 3-pmna ligands into a 5-connected sandwich motif with 4862 topology. {[Cd(glu)(3-pmna)(H2O)]·3H2O}n (4, glu = glutarate) manifests a rippled (4,4) grid topology. Luminescent behavior in the cadmium complexes is ascribed to intra-ligand molecular orbital transitions. Thermal decomposition behavior is also discussed herein.

  20. Development and characterization of high refractive index and high scattering acrylate polymer layers

    NASA Astrophysics Data System (ADS)

    Eiselt, Thomas; Gomard, Guillaume; Preinfalk, Jan; Gleissner, Uwe; Lemmer, Uli; Hanemann, Thomas

    2016-04-01

    The aim is to develop a polymer layer which has the ability to diffuse light homogeneously and exhibit a high refractive index. The mixtures are containing an acrylate casting resin, benzylmethacrylate, phenanthrene and other additives. Phenanthrene is employed to increase the refractive index. The mixtures are first rheologically characterized and then polymerized with heat and UV radiation. For the refractive index measurements the polymerized samples require a planar surface without air bubbles. To produce flat samples a special construction consisting of a glass plate, a teflon sheet, a silicone ring (PDMS mold), another teflon sheet and another glass plate is developed. Glue clamps are used to fix this construction together. Selected samples have a refractive index of 1.585 at 20°C at a wavelength of 589nm. A master mixture with a high refractive index is taken for further experiments. Nano scaled titanium dioxide is added and dispersed into the master mixture and then spin coated on a glass substrate. These layers are optically characterized. The specular transmission and the overall transmission are measured to investigate the degree of scattering, which is defined as the haze. Most of the presented layers express the expected haze of over 50%.

  1. Determination of the emission zone in a single-layer polymer light-emitting diode through optical measurements

    SciTech Connect

    Granlund, Thomas; Pettersson, Leif A. A.; Inganas, Olle

    2001-06-01

    We study the emission zone in a single-layer polymer light-emitting diode. The emission zone is found by studying the angular distribution of the electroluminescence. The emission is modeled by accounting for optical interference. We account for birefringence of the anode layer in our model. The active polymer was, however, found to be isotropic. The anode consists of a single-layer of the conducting polymer complex poly(3,4-ethylenedioxythiophene) and poly(styrene sulfonate) (PEDOT-PSS), with enhanced conductivity. As a cathode we use plain aluminum. By using only PEDOT-PSS we avoid having a thin metal layer or indium-tin-oxide as the anode in the path of the escaping light. The active material is a substituted polythiophene with excellent film forming properties. A comparison between the experimental and calculated angular distribution of light emission from a single-layered polymer light-emitting diode was shown to be in good agreement for the spectral region studied. By assuming a distribution of the emission zone, we deduce the position as well as the width of the zone. {copyright} 2001 American Institute of Physics.

  2. AFM, ellipsometry, XPS and TEM on ultra-thin oxide/polymer nanocomposite layers in organic thin film transistors.

    PubMed

    Fian, A; Haase, A; Stadlober, B; Jakopic, G; Matsko, N B; Grogger, W; Leising, G

    2008-03-01

    Here we report on the fabrication and characterization of ultra-thin nanocomposite layers used as gate dielectric in low-voltage and high-performance flexible organic thin film transistors (oTFTs). Reactive sputtered zirconia layers were deposited with low thermal exposure of the substrate and the resulting porous oxide films with high leakage currents were spin-coated with an additional layer of poly-alpha-methylstyrene (P alphaMS). After this treatment a strong improvement of the oTFT performance could be observed; leakage currents could be eliminated almost completely. In ellipsometric studies a higher refractive index of the ZrO(2)/P alphaMS layers compared to the "as sputtered" zirconia films could be detected without a significant enhancement of the film thickness. Atomic force microscopy (AFM) measurements of the surface topography clearly showed a surface smoothing after the P alphaMS coating. Further studies with X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) also indicated that the polymer definitely did not form an extra layer. The polymer chains rather (self-)assemble in the nano-scaled interspaces of the porous oxide film giving an oxide-polymer "nanocomposite" with a high oxide filling grade resulting in high dielectric constants larger than 15. The dielectric strength of more than 1 MV cm(-1) is in good accordance with the polymer-filled interspaces. PMID:17952415

  3. Biomimetic piezoelectric quartz crystal sensor with chloramphenicol-imprinted polymer sensing layer.

    PubMed

    Ebarvia, Benilda S; Ubando, Isaiah E; Sevilla, Fortunato B

    2015-11-01

    The measurement of banned antibiotic like chloramphenicol is significant for customer protection and safety. The presence of residual antibiotics in foods and food products of animal origin could pose as health hazards and affect food quality for global acceptance. In this study, the potential of a chloramphenicol sensor based on molecularly imprinted polymer (MIP) coupled with a piezoelectric quartz crystal was explored. The MIP was prepared by precipitation polymerization at 60 °C. Methacrylic acid was used as monomer, trimethylolpropane trimethacrylate (TRIM) as crosslinker, and chloramphenicol as the template. Template removal on the resulting polymer was done by extraction using methanol-acetic acid. Characterization of the MIP and NIP were conducted by spectroscopic and microscopic methods. These further supported the imprinting and rebinding process of chloramphenicol to the polymer matrix. The chloramphenicol sensor was devised by spin-coating onto one side of the 10 MHz AT-cut quartz crystal the MIP suspension in polyvinylchloride-tetrahydrofuran (6:2:1 w/w/v) solution. Optimization of sensor response was performed by varying the type of cross-linker, amount of MIP sensing layer, curing time, and pH. The sensor exhibited good sensitivity of about 73 Hz/log (conc., µg mL(-1)) and good repeatability (rsd<10%). A linear relationship (r(2)=0.9901) between frequency shift and chloramphenicol concentration in the range of 1×10(-6) up to 1×10(-1) µg/mL was obtained. The sensor response was highly selective to chloramphenicol than with other compounds of similar chemical structures. Acceptable percent recovery was obtained for real sample analysis using the sensor. The proposed sensor could be a promising low cost and highly sensitive approach for residual chloramphenicol quantification in food products. PMID:26452956

  4. Biomimetic piezoelectric quartz crystal sensor with chloramphenicol-imprinted polymer sensing layer.

    PubMed

    Ebarvia, Benilda S; Ubando, Isaiah E; Sevilla, Fortunato B

    2015-11-01

    The measurement of banned antibiotic like chloramphenicol is significant for customer protection and safety. The presence of residual antibiotics in foods and food products of animal origin could pose as health hazards and affect food quality for global acceptance. In this study, the potential of a chloramphenicol sensor based on molecularly imprinted polymer (MIP) coupled with a piezoelectric quartz crystal was explored. The MIP was prepared by precipitation polymerization at 60 °C. Methacrylic acid was used as monomer, trimethylolpropane trimethacrylate (TRIM) as crosslinker, and chloramphenicol as the template. Template removal on the resulting polymer was done by extraction using methanol-acetic acid. Characterization of the MIP and NIP were conducted by spectroscopic and microscopic methods. These further supported the imprinting and rebinding process of chloramphenicol to the polymer matrix. The chloramphenicol sensor was devised by spin-coating onto one side of the 10 MHz AT-cut quartz crystal the MIP suspension in polyvinylchloride-tetrahydrofuran (6:2:1 w/w/v) solution. Optimization of sensor response was performed by varying the type of cross-linker, amount of MIP sensing layer, curing time, and pH. The sensor exhibited good sensitivity of about 73 Hz/log (conc., µg mL(-1)) and good repeatability (rsd<10%). A linear relationship (r(2)=0.9901) between frequency shift and chloramphenicol concentration in the range of 1×10(-6) up to 1×10(-1) µg/mL was obtained. The sensor response was highly selective to chloramphenicol than with other compounds of similar chemical structures. Acceptable percent recovery was obtained for real sample analysis using the sensor. The proposed sensor could be a promising low cost and highly sensitive approach for residual chloramphenicol quantification in food products.

  5. Film bulk acoustic resonators integrated on arbitrary substrates using a polymer support layer

    PubMed Central

    Chen, Guohao; Zhao, Xinru; Wang, Xiaozhi; Jin, Hao; Li, Shijian; Dong, Shurong; Flewitt, A. J.; Milne, W. I.; Luo, J. K.

    2015-01-01

    The film bulk acoustic resonator (FBAR) is a widely-used MEMS device which can be used as a filter, or as a gravimetric sensor for biochemical or physical sensing. Current device architectures require the use of an acoustic mirror or a freestanding membrane and are fabricated as discrete components. A new architecture is demonstrated which permits fabrication and integration of FBARs on arbitrary substrates. Wave confinement is achieved by fabricating the resonator on a polyimide support layer. Results show when the polymer thickness is greater than a critical value, d, the FBARs have similar performance to devices using alternative architectures. For ZnO FBARs operating at 1.3–2.2 GHz, d is ~9 μm, and the devices have a Q-factor of 470, comparable to 493 for the membrane architecture devices. The polymer support makes the resonators insensitive to the underlying substrate. Yields over 95% have been achieved on roughened silicon, copper and glass. PMID:25824706

  6. Film bulk acoustic resonators integrated on arbitrary substrates using a polymer support layer.

    PubMed

    Chen, Guohao; Zhao, Xinru; Wang, Xiaozhi; Jin, Hao; Li, Shijian; Dong, Shurong; Flewitt, A J; Milne, W I; Luo, J K

    2015-01-01

    The film bulk acoustic resonator (FBAR) is a widely-used MEMS device which can be used as a filter, or as a gravimetric sensor for biochemical or physical sensing. Current device architectures require the use of an acoustic mirror or a freestanding membrane and are fabricated as discrete components. A new architecture is demonstrated which permits fabrication and integration of FBARs on arbitrary substrates. Wave confinement is achieved by fabricating the resonator on a polyimide support layer. Results show when the polymer thickness is greater than a critical value, d, the FBARs have similar performance to devices using alternative architectures. For ZnO FBARs operating at 1.3-2.2 GHz, d is ~9 μm, and the devices have a Q-factor of 470, comparable to 493 for the membrane architecture devices. The polymer support makes the resonators insensitive to the underlying substrate. Yields over 95% have been achieved on roughened silicon, copper and glass. PMID:25824706

  7. Engineering of a polymer layered bio-hybrid heart valve scaffold.

    PubMed

    Jahnavi, S; Kumary, T V; Bhuvaneshwar, G S; Natarajan, T S; Verma, R S

    2015-06-01

    Current treatment strategy for end stage valve disease involves either valvular repair or replacement with homograft/mechanical/bioprosthetic valves. In cases of recurrent stenosis/ regurgitation, valve replacement is preferred choice of treatment over valvular repair. Currently available mechanical valves primarily provide durability whereas bioprosthetic valves have superior tissue compatibility but both lack remodelling and regenerative properties making their utility limited in paediatric patients. With advances in tissue engineering, attempts have been made to fabricate valves with regenerative potential using various polymers, decellularized tissues and hybrid scaffolds. To engineer an ideal heart valve, decellularized bovine pericardium extracellular matrix (DBPECM) is an attractive biocompatible scaffold but has weak mechanical properties and rapid degradation. However, DBPECM can be modified with synthetic polymers to enhance its mechanical properties. In this study, we developed a Bio-Hybrid scaffold with non-cross linked DBPECM in its native structure coated with a layer of Polycaprolactone-Chitosan (PCL-CH) nanofibers that displayed superior mechanical properties. Surface and functional studies demonstrated integration of PCL-CH to the DBPECM with enhanced bio and hemocompatibility. This engineered Bio-Hybrid scaffold exhibited most of the physical, biochemical and functional properties of the native valve that makes it an ideal scaffold for fabrication of cardiac valve with regenerative potential. PMID:25842134

  8. Engineering of a polymer layered bio-hybrid heart valve scaffold.

    PubMed

    Jahnavi, S; Kumary, T V; Bhuvaneshwar, G S; Natarajan, T S; Verma, R S

    2015-06-01

    Current treatment strategy for end stage valve disease involves either valvular repair or replacement with homograft/mechanical/bioprosthetic valves. In cases of recurrent stenosis/ regurgitation, valve replacement is preferred choice of treatment over valvular repair. Currently available mechanical valves primarily provide durability whereas bioprosthetic valves have superior tissue compatibility but both lack remodelling and regenerative properties making their utility limited in paediatric patients. With advances in tissue engineering, attempts have been made to fabricate valves with regenerative potential using various polymers, decellularized tissues and hybrid scaffolds. To engineer an ideal heart valve, decellularized bovine pericardium extracellular matrix (DBPECM) is an attractive biocompatible scaffold but has weak mechanical properties and rapid degradation. However, DBPECM can be modified with synthetic polymers to enhance its mechanical properties. In this study, we developed a Bio-Hybrid scaffold with non-cross linked DBPECM in its native structure coated with a layer of Polycaprolactone-Chitosan (PCL-CH) nanofibers that displayed superior mechanical properties. Surface and functional studies demonstrated integration of PCL-CH to the DBPECM with enhanced bio and hemocompatibility. This engineered Bio-Hybrid scaffold exhibited most of the physical, biochemical and functional properties of the native valve that makes it an ideal scaffold for fabrication of cardiac valve with regenerative potential.

  9. Imprinted nonoxidized graphene sheets as an efficient hole transport layer in polymer light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Huang, Chun-Yuan; Peter Chen, I.-Wen; Chen, Chih-Jung; Chiang, Ray-Kuang; Vu, Hoang-Tuan

    2014-02-01

    Nonoxidized graphene sheets (NGSs) with single- and multilayered structures were generated by direct exfoliation of highly oriented pyrolytic graphite in a water-ethanol mixture with the assistances of pyridinium salt (Py+Br3-) and sonication. Raman spectrum exhibited a low intensity ratio (0.055) of D and G bands, indicating that the NGSs were nearly defect-free. Their application for the fabrication of polymer light-emitting diodes (PLEDs) was also demonstrated. The PLEDs that used an imprinted NGS film as a hole transport layer show a luminance exceeding 13000 cd/m2, which was comparable to that of devices using the typical hole transport material: poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid.

  10. Modeling of the polymer solar cell with a P3HT:PCBM active layer

    NASA Astrophysics Data System (ADS)

    Jelić, Ž.; Petrović, J.; Matavulj, P.; Melancon, J.; Sharma, A.; Zellhofer, C.; Živanović, S.

    2014-09-01

    In this paper we present a theoretical model for simulating the behavior of a polymer solar cell with a poly(3-hexylthiophene):1-(3-methoxycarbonyl) propyl-1-phenyl-[6, 6]-methanofullerene (P3HT:PCBM) active layer. Two different types of boundary conditions were considered, Dirichlet’s and mixed. For Dirichlet’s boundary conditions we have achieved an excellent agreement with the experiment. The influence of boundary conditions on the appearance of the s-shaped current-voltage characteristic (sometimes observed in experiments) has been investigated. When mixed boundary conditions are applied, calculated current-voltage characteristics are inevitably s-shaped. By altering the boundary carrier concentration, an s-shaped deformation in current-voltage characteristics is numerically simulated by using Dirichlet’s boundary conditions.

  11. Structural optimization of interpenetrated pillared-layer coordination polymers for ethylene/ethane separation.

    PubMed

    Kishida, Keisuke; Horike, Satoshi; Watanabe, Yoshihiro; Tahara, Mina; Inubushi, Yasutaka; Kitagawa, Susumu

    2014-06-01

    With the goal of achieving effective ethylene/ethane separation, we evaluated the gas sorption properties of four pillared-layer-type porous coordination polymers with double interpenetration, [Zn2(tp)2(bpy)]n (1), [Zn2(fm)2(bpe)]n (2), [Zn2(fm)2(bpa)]n (3), and [Zn2(fm)2(bpy)]n (4) (tp = terephthalate, bpy = 4,4'-bipyridyl, fm = fumarate, bpe = 1,2-di(4-pyridyl)ethylene and bpa = 1,2-di(4-pyridyl)ethane). It was found that 4, which contains the narrowest pores of all of these compounds, exhibited ethylene-selective sorption profiles. The ethylene selectivity of 4 was estimated to be 4.6 at 298 K based on breakthrough experiments using ethylene/ethane gas mixtures. In addition, 4 exhibited a good regeneration ability compared with a conventional porous material.

  12. A polarization-independent liquid crystal phase modulation using polymer-network liquid crystal with orthogonal alignment layers

    NASA Astrophysics Data System (ADS)

    Chen, Ming-Syuan; Lin, Wei-Chih; Tsou, Yu-Shih; Lin, Yi-Hsin

    2012-10-01

    A polarization-independent liquid crystal (LC) phase modulation using polymer-network liquid crystals with orthogonal alignments layers (T-PNLC) is demonstrated. T-PNLC consists of three layers. LC directors in the two layers near glass substrates are orthogonal to each other. In the middle layer, LC directors are perpendicular to the glass substrate. The advantages of such T-PNLC include polarizer-free, larger phase shift (~0.4π rad) than the residual phase type (<0.05π rad), and low operating voltage (< 30Vrms). It does not require bias voltage for avoiding scattering because the refractive index of liquid crystals matches that of polymers. The phase shift of T-PNLC is affected by the cell gap and the curing voltages. The potential applications are laser beam steering, spatial light modulators and electrically tunable micro-lens arrays.

  13. Recent advances in polymer solar cells: realization of high device performance by incorporating water/alcohol-soluble conjugated polymers as electrode buffer layer.

    PubMed

    He, Zhicai; Wu, Hongbin; Cao, Yong

    2014-02-01

    This Progress Report highlights recent advances in polymer solar cells with special attention focused on the recent rapid-growing progress in methods that use a thin layer of alcohol/water-soluble conjugated polymers as key component to obtain optimized device performance, but also discusses novel materials and device architectures made by major prestigious institutions in this field. We anticipate that due to drastic improvements in efficiency and easy utilization, this method opens up new opportunities for PSCs from various material systems to improve towards 10% efficiency, and many novel device structures will emerge as suitable architectures for developing the ideal roll-to-roll type processing of polymer-based solar cells.

  14. Photoinduced Charge Carrier Generation and Decay in Sequentially Deposited Polymer/Fullerene Layers: Bulk Heterojunction vs. Planar Interface

    SciTech Connect

    Nardes, A.; Ayzner, A.; Hammond, S.; Ferguson, A.; Schwartz, B.; Kopidakis, N.

    2012-04-05

    In this work, we use the time-resolved microwave conductivity (TRMC) technique to study the dynamics of charge carrier generation in sequentially deposited conjugated polymer/fullerene layers. These layers are either fully solution-processed, using orthogonal solvents for the layers of the polymer poly(3-hexylthiophene) (P3HT) and the fullerene phenyl-C{sup 61}-butyric acid methyl ester (PCBM), or prepared by thermally evaporating a C{sup 60} layer onto P3HT films. Our work is motivated by the remarkable efficiency of organic photovoltaic (OPV) devices using a sequentially processed P3HT/PCBM active layer. Here we use an electrodeless photoconductivity probe, so we can photoexcite the sample either through the polymer or the fullerene layer. We use samples with extremely thick P3HT films (2.4 {micro}m) and show that excitation from either side of both as-cast and thermally annealed sample yields virtually identical results, consistent with mixing of the PCBM into the polymer film. We also compare solution-deposited samples to samples made by thermally evaporating C{sup 60} on P3HT, and find that we can distinguish between charge generation in bulk-P3HT and at the polymer/fullerene interface. We show that, despite their morphological differences, the carrier dynamics in the sequentially processed samples resemble those of mixed, bulk heterojunction (BHJ) systems. All of this is consistent with the idea that PCBM readily mixes into the P3HT film in sequentially deposited P3HT/PCBM samples, although the total amount of fullerene mixed into the P3HT appears to be less than that typically used in an optimized BHJ. Finally, we discuss the implications for OPV device architectures prepared by sequential deposition from solution.

  15. Free Surface Command Layer for Photoswitchable Out-of-Plane Alignment Control in Liquid Crystalline Polymer Films.

    PubMed

    Nakai, Takashi; Tanaka, Daisuke; Hara, Mitsuo; Nagano, Shusaku; Seki, Takahiro

    2016-01-26

    To date, reversible alignment controls of liquid crystalline materials have widely been achieved by photoreactive layers on solid substrates. In contrast, this work demonstrates the reversible out-of-plane photocontrols of liquid crystalline polymer films by using a photoresponsive skin layer existing at the free surface. A polymethacrylate containing a cyanobiphenyl side-chain mesogen adopts the planar orientation. Upon blending a small amount of azobenzene-containing side-chain polymer followed by successive annealing, segregation of the azobenzene polymer at the free surface occurs and induces a planar to homeotropic orientation transition of cyanobiphenyl mesogens underneath. By irradiation with UV light, the mesogen orientation turns into the planar orientation. The orientation reverts to the homeotropic state upon visible light irradiation or thermally, and such cyclic processes can be repeated many times. On the basis of this principle, erasable optical patterning is performed by irradiating UV light through a photomask. PMID:26734930

  16. Free Surface Command Layer for Photoswitchable Out-of-Plane Alignment Control in Liquid Crystalline Polymer Films.

    PubMed

    Nakai, Takashi; Tanaka, Daisuke; Hara, Mitsuo; Nagano, Shusaku; Seki, Takahiro

    2016-01-26

    To date, reversible alignment controls of liquid crystalline materials have widely been achieved by photoreactive layers on solid substrates. In contrast, this work demonstrates the reversible out-of-plane photocontrols of liquid crystalline polymer films by using a photoresponsive skin layer existing at the free surface. A polymethacrylate containing a cyanobiphenyl side-chain mesogen adopts the planar orientation. Upon blending a small amount of azobenzene-containing side-chain polymer followed by successive annealing, segregation of the azobenzene polymer at the free surface occurs and induces a planar to homeotropic orientation transition of cyanobiphenyl mesogens underneath. By irradiation with UV light, the mesogen orientation turns into the planar orientation. The orientation reverts to the homeotropic state upon visible light irradiation or thermally, and such cyclic processes can be repeated many times. On the basis of this principle, erasable optical patterning is performed by irradiating UV light through a photomask.

  17. Phase Diagram and Transformations of Iron Pentacarbonyl to nm Layered Hematite and Carbon-Oxygen Polymer under Pressure

    NASA Astrophysics Data System (ADS)

    Ryu, Young Jay; Kim, Minseob; Yoo, Choong-Shik

    2015-10-01

    We present the phase diagram of Fe(CO)5, consisting of three molecular polymorphs (phase I, II and III) and an extended polymeric phase that can be recovered at ambient condition. The phase diagram indicates a limited stability of Fe(CO)5 within a pressure-temperature dome formed below the liquid- phase II- polymer triple point at 4.2 GPa and 580 K. The limited stability, in turn, signifies the temperature-induced weakening of Fe-CO back bonds, which eventually leads to the dissociation of Fe-CO at the onset of the polymerization of CO. The recovered polymer is a composite of novel nm-lamellar layers of crystalline hematite Fe2O3 and amorphous carbon-oxygen polymers. These results, therefore, demonstrate the synthesis of carbon-oxygen polymer by compressing Fe(CO)5, which advocates a novel synthetic route to develop atomistic composite materials by compressing organometallic compounds.

  18. Fabrication and independent control of patterned polymer gate for a few-layer WSe2 field-effect transistor

    NASA Astrophysics Data System (ADS)

    Hong, Sung Ju; Park, Min; Kang, Hojin; Lee, Minwoo; Jeong, Dae Hong; Park, Yung Woo

    2016-08-01

    We report the fabrication of a patterned polymer electrolyte for a two-dimensional (2D) semiconductor, few-layer tungsten diselenide (WSe2) field-effect transistor (FET). We expose an electron-beam in a desirable region to form the patterned structure. The WSe2 FET acts as a p-type semiconductor in both bare and polymer-covered devices. We observe a highly efficient gating effect in the polymer-patterned device with independent gate control. The patterned polymer gate operates successfully in a molybdenum disulfide (MoS2) FET, indicating the potential for general applications to 2D semiconductors. The results of this study can contribute to large-scale integration and better flexibility in transition metal dichalcogenide (TMD)-based electronics.

  19. Deformation sensor based on polymer-supported discontinuous graphene multi-layer coatings

    NASA Astrophysics Data System (ADS)

    Carotenuto, G.; Schiavo, L.; Romeo, V.; Nicolais, L.

    2014-05-01

    Graphene can be conveniently used in the modification of polymer surfaces. Graphene macromolecules are perfectly transparent to the visible light and electrically conductive, consequently these two properties can be simultaneously provided to polymeric substrates by surface coating with thin graphene layers. In addition, such coating process provides the substrates of: water-repellence, higher surface hardness, low-friction, self-lubrication, gas-barrier properties, and many other functionalities. Polyolefins have a non-polar nature and therefore graphene strongly sticks on their surface. Nano-crystalline graphite can be used as graphene precursor in some chemical processes (e.g., graphite oxide synthesis by the Hummer method), in addition it can be directly applied to the surface of a polyolefin substrate (e.g., polyethylene) to cover it by a thin graphene multilayer. In particular, the nano-crystalline graphite perfectly exfoliate under the application of a combination of shear and friction forces and the produced graphene single-layers perfectly spread and adhere on the polyethylene substrate surface. Such polymeric materials can be used as ITO (indium-tin oxide) substitute and in the fabrication of different electronic devices. Here the fabrication of transparent resistive deformation sensors based on low-density polyethylene films coated by graphene multilayers is described. Such devices are very sensible and show a high reversible and reproducible behavior.

  20. Solution-processed nickel compound as hole collection layer for efficient polymer solar cells

    NASA Astrophysics Data System (ADS)

    He, Shaojian; Li, Shusheng; Tan, Zhan'ao; Zheng, Hua; Lin, Jun; Hu, Siqian; Liu, Jiyan; Li, Yongfang

    2014-12-01

    We demonstrated efficient bulk heterojunction polymer solar cells (PSCs) by inserting a solution-processable hole collection layer (HCL) between the indium tin oxide (ITO) electrode and photoactive layer. The HCL was prepared by spin-coating nickel acetylacetonate (Ni(acac)2) isopropanol solution on ITO, and then baking in air at 180 °C for 10 min followed by UV ozone treatment, which was marked as a-Ni(acac)2. The a-Ni(acac)2 HCL shows suitable energy levels, high hole mobility of 4.09  ×  10-3 cm2 V-1·s-1, and high transparency with light transmittance better than poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) in the wavelength range 550-800 nm. The PSCs with a-Ni(acac)2 HCL showed improved performance compared with the PSCs without or with traditional PEDOT:PSS HCL. The power conversion efficiency of the PSC based on PBDTTT-C-T:PC70BM with a-Ni(acac)2 HCL reached 7.84% under the illumination of AM 1.5 G, 100 mW cm-2.

  1. Deformation sensor based on polymer-supported discontinuous graphene multi-layer coatings

    SciTech Connect

    Carotenuto, G.; Schiavo, L.; Romeo, V.; Nicolais, L.

    2014-05-15

    Graphene can be conveniently used in the modification of polymer surfaces. Graphene macromolecules are perfectly transparent to the visible light and electrically conductive, consequently these two properties can be simultaneously provided to polymeric substrates by surface coating with thin graphene layers. In addition, such coating process provides the substrates of: water-repellence, higher surface hardness, low-friction, self-lubrication, gas-barrier properties, and many other functionalities. Polyolefins have a non-polar nature and therefore graphene strongly sticks on their surface. Nano-crystalline graphite can be used as graphene precursor in some chemical processes (e.g., graphite oxide synthesis by the Hummer method), in addition it can be directly applied to the surface of a polyolefin substrate (e.g., polyethylene) to cover it by a thin graphene multilayer. In particular, the nano-crystalline graphite perfectly exfoliate under the application of a combination of shear and friction forces and the produced graphene single-layers perfectly spread and adhere on the polyethylene substrate surface. Such polymeric materials can be used as ITO (indium-tin oxide) substitute and in the fabrication of different electronic devices. Here the fabrication of transparent resistive deformation sensors based on low-density polyethylene films coated by graphene multilayers is described. Such devices are very sensible and show a high reversible and reproducible behavior.

  2. Biodegradable polymer for sealing porous PEO layer on pure magnesium: An in vitro degradation study

    NASA Astrophysics Data System (ADS)

    Alabbasi, Alyaa; Mehjabeen, Afrin; Kannan, M. Bobby; Ye, Qingsong; Blawert, Carsten

    2014-05-01

    An attempt was made to seal the porous silicate-based plasma electrolytic oxidation (PEO) layer on pure magnesium (Mg) with a biodegradable polymer, poly(L-lactide) (PLLA), to delay the localized degradation of magnesium-based implants in body fluid for better in-service mechanical integrity. Firstly, a silicate-based PEO coating on pure magnesium was performed using a pulsed constant current method. In order to seal the pores in the PEO layer, PLLA was coated using a two-step spin coating method. The performance of the PEO-PLLA Mg was evaluated using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The EIS results showed that the polarization resistance (Rp) of the PEO-PLLA Mg was close to two orders of magnitude higher than that of the PEO Mg. While the corrosion current density (icorr) of the pure Mg was reduced by 65% with the PEO coating, the PEO-PLLA coating reduced the icorr by almost 100%. As expected, the Rp of the PEO-PLLA Mg decreased with increase in exposure time. However, it was noted that the Rp of the PEO-PLLA Mg even after 100 h was six times higher than that of the PEO Mg after 48 h exposure, and did not show any visible localized attack.

  3. Influence of emissive layer thickness on electrical characteristics of polyfluorene copolymer based polymer light emitting diodes

    NASA Astrophysics Data System (ADS)

    Das, D.; Gopikrishna, P.; Singh, A.; Dey, A.; Iyer, P. K.

    2016-04-01

    Polymer light emitting diodes (PLEDs) with a device configuration of ITO/PEDOT:PSS/PFONPN01 [Poly [2,7-(9,9’-dioctylfluorene)-co-N-phenyl-1,8-naphthalimide (99:01)]/LiF/Al have been fabricated by varying the emissive layer (EML) thickness (40/65/80/130 nm) and the influence of EML thickness on the electrical characteristics of PLED has been studied. PLED can be modelled as a simple combination of resistors and capacitors. The impedance spectroscopy analysis showed that the devices with different EML thickness had different values of parallel resistance (RP) and the parallel capacitance (CP). The impedance of the devices is found to increase with increasing EML thickness resulting in an increase in the driving voltage. The device with an emissive layer thickness of 80nm, spin coated from a solution of concentration 15 mg/mL is found to give the best device performance with a maximum brightness value of 5226 cd/m2.

  4. A new 68Ge/68Ga generator system using an organic polymer containing N-methylglucamine groups as adsorbent for 68Ge.

    PubMed

    Nakayama, M; Haratake, M; Ono, M; Koiso, T; Harada, K; Nakayama, H; Yahara, S; Ohmomo, Y; Arano, Y

    2003-01-01

    A macroporous styrene-divinylbenzene copolymer containing N-methylglucamine groups was selected for a new 68Ge/68Ga generator system. This resin packed into a column effectively adsorbed the parent nuclide 68Ge. The daughter 68Ga was eluted from the resin with a solution of a low-affinity gallium chelating ligand such as citric or phosphoric acid. The 68Ge leakage was less than 0.0004% of the 68Ge adsorbed on the resin. By simple mixing of transferrin and desferoxamine conjugated HSA and IgG with the eluate from the column, 68Ga-labeling was completed in high yield. PMID:12485657

  5. Sodium bromide electron-extraction layers for polymer bulk-heterojunction solar cells

    SciTech Connect

    Gao, Zhi; Qu, Bo Xiao, Lixin; Chen, Zhijian; Zhang, Lipei; Gong, Qihuang

    2014-03-10

    Inexpensive and non-toxic sodium bromide (NaBr) was introduced into polymer solar cells (PSCs) as the cathode buffer layer (CBL) and the electron extraction characteristics of the NaBr CBL were investigated in detail. The PSCs based on NaBr CBL with different thicknesses (i.e., 0 nm, 0.5 nm, 1 nm, and 1.5 nm) were prepared and studied. The optimal thickness of NaBr was 1 nm according to the photovoltaic data of PSCs. The open-circuit voltage (V{sub oc}), short-circuit current density (J{sub sc}), fill factor (FF), and power conversion efficiency (PCE) of the PSC with 1 nm NaBr were evaluated to be 0.58 V, 7.36 mA/cm{sup 2}, 0.63, and 2.70%, respectively, which were comparable to those of the reference device with the commonly used LiF. The optimized photovoltaic performance of PSC with 1 nm NaBr was ascribed to the improved electron transport and extraction capability of 1 nm NaBr in PSCs. In addition, the NaBr CBL could prevent the diffusion of oxygen and water vapor into the active layer and prolong the lifetime of the devices to some extent. Therefore, NaBr layer could be considered as a promising non-toxic CBL for PSCs in future.

  6. MULPEX: a compact multi-layered polymer foil collector for micrometeoroids and orbital debris.

    NASA Astrophysics Data System (ADS)

    Kearsley, A. T.; Graham, G. A.; Burchell, M. J.; Taylor, E. A.; Drolshagen, G.; Chater, R. J.; McPhail, D.

    Detailed studies of preserved hypervelocity impact residues on spacecraft multi-layer insulation foils have yielded important information about the flux of small particles from different sources in low-Earth orbit (LEO). We have extended our earlier research on impacts occurring in LEO to design and testing of a compact capture device. MULPEX (MUlti-Layer Polymer EXperiment) is simple, cheap to build, lightweight, of no power demand, easy to deploy, and optimised for the efficient collection of impact residue for analysis on return to Earth. The capture medium is a stack of very thin (8 micron and 40 micron) polyimide foils, supported on poly-tetrafluoroethylene sheet frames, surrounded by a protective aluminium casing. The uppermost foil has a very thin metallic coating for thermal protection and resistance to atomic oxygen and ultra-violet exposure. The casing provides a simple detachable interface for deployment on the spacecraft, facing into the desired direction for particle collection. On return to the laboratory, the stacked foils are separated for examination in a variable pressure scanning electron microscope, without need for surface coating. Analysis of impact residue is performed using energy dispersive X-ray spectrometers. Our laboratory experiments, utilising buck-shot firings of analogues to micrometeoroids (35-38 micron olivine) and space debris (4 micron alumina and 1mm stainless steel) in a light gas gun, have shown that impact residue is abundant within the foil layers, and preserves a record of the impacting particle, whether of micrometer or millimetre dimensions. Penetrations of the top foil are easily recognised, and act as a proxy for dimensions of the penetrating particle. Impact may cause disruption and melting, but some residue retains sufficient crystallographic structure to show clear Raman lines, diagnostic of the original mineral.

  7. MULPEX: A compact multi-layered polymer foil collector for micrometeoroids and orbital debris

    NASA Astrophysics Data System (ADS)

    Kearsley, A. T.; Graham, G. A.; Burchell, M. J.; Taylor, E. A.; Drolshagen, G.; Chater, R. J.; McPhail, D.

    Detailed studies of preserved hypervelocity impact residues on spacecraft multi-layer insulation foils have yielded important information about the flux of small particles from different sources in low-Earth orbit (LEO). We have extended our earlier research on impacts occurring in LEO to design and testing of a compact capture device. MUlti- Layer Polymer EXperiment (MULPEX) is simple, cheap to build, lightweight, of no power demand, easy to deploy, and optimised for the efficient collection of impact residue for analysis on return to Earth. The capture medium is a stack of very thin (8 and 40 μm) polyimide foils, supported on poly-tetrafluoroethylene sheet frames, surrounded by a protective aluminium casing. The uppermost foil has a very thin metallic coating for thermal protection and resistance to atomic oxygen and ultra-violet exposure. The casing provides a simple detachable interface for deployment on the spacecraft, facing into the desired direction for particle collection. On return to the laboratory, the stacked foils are separated for examination in a variable pressure scanning electron microscope, without need for surface coating. Analysis of impact residue is performed using energy dispersive X-ray spectrometers. Our laboratory experiments, utilising buck-shot firings of analogues to micrometeoroids (35-38 μm olivine) and space debris (4 μm alumina and 1 mm stainless steel) in a light gas gun, have shown that impact residue is abundant within the foil layers, and preserves a record of the impacting particle, whether of micrometer or millimetre dimensions. Penetrations of the top foil are easily recognised, and act as a proxy for dimensions of the penetrating particle. Impact may cause disruption and melting, but some residue retains sufficient crystallographic structure to show clear Raman lines, diagnostic of the original mineral.

  8. MUPLEX: a compact multi-layered polymer foil collector for micrometeoroids and orbital debris

    SciTech Connect

    Kearsley, A T; Graham, G A; Burchell, M J; Taylor, E A; Drolshagen, G; Chater, R J; McPhail, D

    2004-10-04

    Detailed studies of preserved hypervelocity impact residues on spacecraft multi-layer insulation foils have yielded important information about the flux of small particles from different sources in low-Earth orbit. We have extended our earlier research on impacts occurring in LEO to design and testing of a compact capture device. MULPEX (MUlti-Layer Polymer EXperiment) is simple, cheap to build, lightweight, of no power demand, easy to deploy, and optimized for the efficient collection of impact residue for analysis on return to Earth. The capture medium is a stack of very thin (8 micron and 40 micron) polyimide foils, supported on poly-tetrafluoroethylene sheet frames, surrounded by a protective aluminum casing. The uppermost foil has a very thin metallic coating for thermal protection and resistance to atomic oxygen and ultra-violet exposure. The casing provides a simple detachable interface for deployment on the spacecraft, facing into the desired direction for particle collection. On return to the laboratory, the stacked foils are separated for examination in a variable pressure scanning electron microscope, without need for surface coating. Analysis of impact residue is performed using energy dispersive X-ray spectrometers. Our laboratory experiments, utilizing buck-shot firings of analogues to micrometeoroids (35-38 micron olivine) and space debris (4 micron alumina and 1mm stainless steel) in a light gas gun, have shown that impact residue is abundant within the foil layers, and preserves a record of the impacting particle, whether of micrometer or millimeter dimensions. Penetrations of the top foil are easily recognized, and act as a proxy for dimensions of the penetrating particle. Impact may cause disruption and melting, but some residue retains sufficient crystallographic structure to show clear Raman lines, diagnostic of the original mineral.

  9. Influence of Irreversible Adsorption on the Glass Transition Temperature of Polymer Thin Films as Measured by Fluorescence

    NASA Astrophysics Data System (ADS)

    Burroughs, Mary; Priestley, Rodney

    2014-03-01

    Polymers confined to the nanometer length scale have been shown to exhibit deviations in the glass transition temperature (Tg) from the bulk. With the increasing use of confined polymers in nanotechnology, understanding and predicting this behavior is extremely relevant to industries ranging from pharmaceuticals to organic electronics. Recent work (Napolitano, Wübbenhorst, Nature Communications, 2, 260 (2011)) has connected deviations in Tg under confinement with irreversible physical adsorption of polymer chains at substrate interfaces. Here we investigate the influence of irreversibly adsorbed layers on the Tg of polystyrene (PS) thin films supported on silica via fluorescence. We examine the Tg of the brushes as a function of annealing time and irreversibly adsorbed layer thickness. By incorporating fluorescently labeled polymer layers into multilayered films of unlabeled polymer, we will examine the influence of brushes on adjacent layers dynamics. Finally, we will compare the results on PS with those of poly(methyl methacrylate).

  10. Reversible Thermal-Stiffening in Polymer Nanocomposites

    NASA Astrophysics Data System (ADS)

    Senses, Erkan; Akcora, Pinar

    2015-03-01

    Silica nanoparticles adsorbed with a high glass-transition temperature polymer, PMMA (Tg: 130 °C) are shown to uniformly disperse in a low-Tg polymer matrix, PEO (Tg: -60 °C). These nanocomposites exhibit an unusual reversible liquid-to-solid transition at temperatures above Tg's of both polymers. Mechanical adaptivity of PEO nanocomposites to temperatures underlies the existence of dynamically asymmetric bound layers on particles, and more importantly their impact on mechanical behavior, which sets these materials apart from conventional polymer composites that soften upon heating. Moreover, the growth rate of elastic moduli at temperatures above Tg of PMMA presents an Arrhenius-type relaxation with activation energy well-matching with the α- β merging region of PMMA. These results suggest that the mobility of the surface-bound polymer is essential for reinforcement contrary to commonly accepted glassy-layer hypothesis.

  11. Heat transfer to the adsorbent in solar adsorption cooling device

    NASA Astrophysics Data System (ADS)

    Pilat, Peter; Patsch, Marek; Papucik, Stefan; Vantuch, Martin

    2014-08-01

    The article deals with design and construction of solar adsorption cooling device and with heat transfer problem in adsorber. The most important part of adsorption cooling system is adsorber/desorber containing adsorbent. Zeolith (adsorbent) type was chosen for its high adsorption capacity, like a coolant was used water. In adsorber/desorber occur, at heating of adsorbent, to heat transfer from heat change medium to the adsorbent. The time required for heating of adsorber filling is very important, because on it depend flexibility of cooling system. Zeolith has a large thermal resistance, therefore it had to be adapted the design and construction of adsorber. As the best shows the tube type of adsorber with double coat construction. By this construction is ensured thin layer of adsorbent and heating is quick in all volume of adsorbent. The process of heat transfer was experimentally measured, but for comparison simulated in ANSYS, too.

  12. Polymers.

    ERIC Educational Resources Information Center

    Tucker, David C.

    1986-01-01

    Presents an open-ended experiment which has students exploring polymer chemistry and reverse osmosis. This activity involves construction of a polymer membrane, use of it in a simple osmosis experiment, and application of its principles in solving a science-technology-society problem. (ML)

  13. Drug release from hydrophilic matrices. 1. New scaling laws for predicting polymer and drug release based on the polymer disentanglement concentration and the diffusion layer.

    PubMed

    Ju, R T; Nixon, P R; Patel, M V

    1995-12-01

    Two scaling laws for predicting polymer and drug release profiles from hydrophilic matrices were developed. They were developed on the basis of the diffusion layer and the polymer disentanglement concentration, rho p,dis, the critical polymer concentration below which polymer chains detach off a gelled matrix that is undergoing simultaneous swelling and dissolution. The relation between rho p,dis and molecular weight, M1 for (hydroxypropyl)methylcellulose (HPMC) in water was established as rho p,dis (g/mL) varies M-0.8. This power-law relationship for rho p,dis, along with the diffusion layer adjacent to the gelled matrix, leads to the scaling law of mp(t)/mp(infinity) varies Meq-1.15, where mp(t)/mp(infinity) is the fractional HPMC release. The scaling law explains the observation that polymer and drug release rates decreased sharply with M at low M and approach limiting values at high M. Experimentally, mp(t)/mp(infinity) was found to scale with Meq as mp(t)/mp(infinity) varies Meq-0.93, where Meq is the equivalent matrix molecular weight. Moreover, fractional drug release, md(t)/md(infinity), followed Meq as md(t)/md(infinity) varies Meq-0.48. These two scaling laws imply that, if the release profiles are known for one composition, release profiles for other compositions can be predicted. The above two power laws lead to two master curves for mp(t)/mp(infinity) and md(t)/md(infinity), suggesting that the release mechanism for soluble drugs from HPMC matrices is independent of matrix compositions, presumably via a diffusion-controlled process. Limitations of the power laws are discussed. PMID:8748329

  14. Intricacies of Polymer Dewetting: Nanoscaled Architectures for the Tailored Control of Polystyrene Thin Film Stability

    NASA Astrophysics Data System (ADS)

    Cheung, Justin; Sen, Mani; Chen, Zhizhao; Jiang, Naisheng; Endoh, Maya; Koga, Tadanori; Satija, Sushil

    Recently, structural properties of polymer thin films have garnered attention for their relevance in the fields of organic photovoltaics and biosensors. The dewetting of polymer films poses an obstacle in the face of widespread implementation. For this study, we show that adsorbed polymer chains on a substrate surface play crucial roles in film stability. Polystyrene (PS) thin films (20 nm in thickness) with different molecular weights (Mw) on silicon (Si) substrates were used as a model. The PS films were annealed at high temperatures for several days, and Mw dependence on film stability was evidenced. At the same time, the annealed PS films were leached with a good solvent and the residue films (i.e., irreversibly adsorbed layers) were characterized by x-ray reflectivity (XR). We reveal strong correlation between film stability and two different interfacial structures of the adsorbed polymer chains: their opposing wettability against chemically identical free polymer chains results in a wetting-dewetting transition at the adsorbed polymer-free polymer interface. This is a unique aspect of polymer thin film stability and may be generalizable to other polymer systems regardless of the magnitude of solid-polymer attractive interactions. We acknowledge the financial support of NSF Grant (CMMI-1332499).

  15. Covalent deposition of zwitterionic polymer and citric acid by click chemistry-enabled layer-by-layer assembly for improving the blood compatibility of polysulfone membrane.

    PubMed

    Xiang, Tao; Wang, Rui; Zhao, Wei-Feng; Sun, Shu-Dong; Zhao, Chang-Sheng

    2014-05-13

    Development of blood compatible membranes is critical for biomedical applications. Zwitterionic polymers have been proved to be resistant to nonspecific protein adsorption and platelet adhesion. In this work, two kinds of zwitterionic copolymers bearing alkynyl and azide groups are synthesized by atom transfer radical polymerization (ATRP) and subsequent reactions, namely alkynyl-poly(sulfobetaine methacrylate) (alkynyl-PSBMA) and azide-poly(sulfobetaine methacrylate) (azide-PSBMA). The copolymers are directly used to modify azido-functionalized polysulfone (PSf-N3) membrane via click chemistry-enabled layer-by-layer (LBL) assembly. Alkynyl-citric acid is then clicked onto the membrane when the outermost layer was azide-PSBMA. The chemical compositions, surface morphologies, and hydrophilicity of the zwitterionic polymer and citric acid multilayer modified membranes are characterized. The composite multilayer is resistant to protein adsorption and platelet adhesion and also prolongs clotting times, indicating that the blood compatibility is improved. Moreover, after clicking the small molecule anticoagulant alkynyl-citric acid onto the outermost of the zwitterionic multilayer, the membrane shows further improved anticoagulant property. The deposition of zwitterionic polymer and citric acid via click chemistry-enabled LBL assembly can improve the blood compatibility of the PSf membrane. PMID:24754639

  16. Covalent deposition of zwitterionic polymer and citric acid by click chemistry-enabled layer-by-layer assembly for improving the blood compatibility of polysulfone membrane.

    PubMed

    Xiang, Tao; Wang, Rui; Zhao, Wei-Feng; Sun, Shu-Dong; Zhao, Chang-Sheng

    2014-05-13

    Development of blood compatible membranes is critical for biomedical applications. Zwitterionic polymers have been proved to be resistant to nonspecific protein adsorption and platelet adhesion. In this work, two kinds of zwitterionic copolymers bearing alkynyl and azide groups are synthesized by atom transfer radical polymerization (ATRP) and subsequent reactions, namely alkynyl-poly(sulfobetaine methacrylate) (alkynyl-PSBMA) and azide-poly(sulfobetaine methacrylate) (azide-PSBMA). The copolymers are directly used to modify azido-functionalized polysulfone (PSf-N3) membrane via click chemistry-enabled layer-by-layer (LBL) assembly. Alkynyl-citric acid is then clicked onto the membrane when the outermost layer was azide-PSBMA. The chemical compositions, surface morphologies, and hydrophilicity of the zwitterionic polymer and citric acid multilayer modified membranes are characterized. The composite multilayer is resistant to protein adsorption and platelet adhesion and also prolongs clotting times, indicating that the blood compatibility is improved. Moreover, after clicking the small molecule anticoagulant alkynyl-citric acid onto the outermost of the zwitterionic multilayer, the membrane shows further improved anticoagulant property. The deposition of zwitterionic polymer and citric acid via click chemistry-enabled LBL assembly can improve the blood compatibility of the PSf membrane.

  17. Three-dimensional bioprinting of cell-laden constructs with polycaprolactone protective layers for using various thermoplastic polymers.

    PubMed

    Kim, Byoung Soo; Jang, Jinah; Chae, Suhun; Gao, Ge; Kong, Jeong-Sik; Ahn, Minjun; Cho, Dong-Woo

    2016-01-01

    Three-dimensional (3D) cell-printed constructs have been recognized as promising biological substitutes for tissue/organ regeneration. They provide tailored physical properties and biological cues via multi-material printing process. In particular, hybrid bioprinting, enabling to use biodegradable synthetic polymers as framework, has been an attractive method to support weak hydrogels. The constructs with controlled architecture and high shape fidelity were fabricated through this method, depositing spatial arrangement of multi-cell types into microscale constructs. Among biodegradable synthetic polymers, polycaprolactone (PCL) has been commonly chosen in fabrication of cell-printed constructs because of its low melting temperature of 60 °C to be dispensed with extrusion-based bioprinting system. However, in addition to PCL, various synthetic polymers have been widely applied for tissue regeneration. These polymers have distinctive characteristics essential for tissue/organ regeneration. Nevertheless, it is difficult to use some polymers, such as poly (lactic-co-glycolic acid) (PLGA) and polylactic acid (PLA) with 3D bioprinting technology because of their high melting temperature to be dispensed, which can result in thermal damage to the cells in the printed constructs during the fabrication process. We present a novel bioprinting method to use various synthetic polymers in fabrication of cell-printed constructs. PCL was introduced as a protective layer to prevent thermal damage caused by high temperature of polymers during fabrication. Remarkable improvement in cellular activities in the printed constructs with PCL layers was observed compared with the construct without PCL. This bioprinting method can be applied to fabricate more tissue-like constructs through the use of various biomaterials. PMID:27550946

  18. Boundary layer charge dynamics in ionic liquid-ionic polymer transducers

    NASA Astrophysics Data System (ADS)

    Davidson, Jacob D.; Goulbourne, N. C.

    2011-01-01

    Ionic polymer transducers (IPTs), also known as ionic polymer-metal composites, are soft sensors and actuators which operate through a coupling of microscale chemical, electrical, and mechanical interactions. The use of an ionic liquid as solvent for an IPT has been shown to dramatically increase transducer lifetime in free-air use, while also allowing for higher applied voltages without electrolysis. In this work, we apply Nernst-Planck/Poisson theory to model charge transport in an ionic liquid IPT by considering a certain fraction of the ionic liquid ions as mobile charge carriers, a phenomenon which is unique to ionic liquid IPTs compared to their water-based counterparts. Numerical simulations are performed using the finite element method to examine how the introduction of another pair of mobile ions affects boundary layer charge dynamics, concentration, and charge density distributions in the electric double layer, and the overall charge transferred and current response of the IPT. Due to interactions with the Nafion ionomer, not all of the ionic liquid ions will function as mobile charge carriers; only a certain fraction will exist as "free" ions. The presence of mobile ionic liquid ions in the transducer will increase the overall charge transferred when a voltage is applied, and cause the current in the transducer to decay more slowly. The additional mobile ions also cause the ionic concentration profiles to exhibit a nonlinear dynamic response, characterized by nonmonotonic ionic concentration profiles in space and time. Although the presence of mobile ionic liquid ions increases the overall amount of charge transferred, this additional charge transfer occurs in a somewhat symmetric manner. Therefore, the additional charge transferred due to the ionic liquid ions does not greatly increase the net bending moment of the transducer; in fact, it is possible that ionic liquid ion movement actually decreases the observed bending response. This suggests that an

  19. Reversible Thermal Stiffening in Polymer Nanocomposites.

    PubMed

    Senses, Erkan; Isherwood, Andrew; Akcora, Pinar

    2015-07-15

    Miscible polymer blends with different glass transition temperatures (Tg) are known to create confined interphases between glassy and mobile chains. Here, we show that nanoparticles adsorbed with a high-Tg polymer, poly(methyl methacrylate), and dispersed in a low-Tg matrix polymer, poly(ethylene oxide), exhibit a liquid-to-solid transition at temperatures above Tg's of both polymers. The mechanical adaptivity of nanocomposites to temperature underlies the existence of dynamically asymmetric bound layers on nanoparticles and more importantly reveals their impact on macroscopic mechanical response of composites. The unusual reversible stiffening behavior sets these materials apart from conventional polymer composites that soften upon heating. The presented stiffening mechanism in polymer nanocomposites can be used in applications for flexible electronics or mechanically induced actuators responding to environmental changes like temperature or magnetic fields.

  20. Protein Adsorption on Surfaces with Grafted Polymers

    PubMed Central

    Szleifer, I.

    1997-01-01

    A general theoretical framework for studying the adsorption of protein molecules on surfaces with grafted polymers is presented. The approach is a generalization of the single-chain mean-field theory, in which the grafted polymer-protein-solvent layer is assumed to be inhomogeneous in the direction perpendicular to the grafting surface. The theory enables the calculation of the adsorption isotherms of the protein as a function of the surface coverage of grafted polymers, concentration of protein in bulk, and type of solvent molecules. The potentials of mean force of the protein with the surface are calculated as a function of polymer surface coverage and amount of protein adsorbed. The theory is applied to model lysozyme on surfaces with grafted polyethylene oxide. The protein is modeled as spherical in solution, and it is assumed that the protein-polymer, protein-solvent, and polymer-solvent attractive interactions are all equal. Therefore, the interactions determining the structure of the layer (beyond the bare polymer-surface and protein-surface interactions) are purely repulsive. The bare surface-protein interaction is taken from atomistic calculations by Lee and Park. For surfaces that do not have preferential attractions with the grafted polymer segments, the adsorption isotherms of lysozyme are independent of the polymer length for chains with more than 50 ethylene oxide units. However, the potentials of mean force show strong variations with grafted polymer molecular weight. The competition between different conformations of the adsorbed protein is studied in detail. The adsorption isotherms change qualitatively for surfaces with attractive interactions with ethylene oxide monomers. The protein adsorption is a function of chain length—the longer the polymer the more effective it is in preventing protein adsorption. The structure of the layer and its deformation upon protein adsorption are very important in determining the adsorption isotherms and the

  1. Threshold improvement in uniformly lying helix cholesteric liquid crystal laser using auxiliary π-conjugated polymer active layer

    NASA Astrophysics Data System (ADS)

    Yoshida, Hiroyuki; Shiozaki, Yusuke; Inoue, Yo; Takahashi, Masaya; Ogawa, Yasuhiro; Fujii, Akihiko; Ozaki, Masanori

    2013-05-01

    We propose a device structure to lower the lasing threshold of a uniformly lying helix cholesteric liquid crystal (ChLC) laser. We place a π-conjugated polymer active layer beneath the ChLC layer to provide auxiliary gain, and demonstrate an improvement in the lasing threshold by a factor of 2.3. We also perform finite difference time domain calculations coupled with rate equations for a four-level system, and clarify the effect of the additional active layer on both the photonic density of states and the inversion population density. Although the addition of an extra layer lowers the photonic density of states, the gain provided by the auxiliary layer is sufficient to overcome the losses and decrease the lasing threshold. Our concept is useful for obtaining high-performance ChLC lasers.

  2. Fabrication of Covalently Crosslinked and Amine-Reactive Microcapsules by Reactive Layer-by-Layer Assembly of Azlactone-Containing Polymer Multilayers on Sacrificial Microparticle Templates.

    PubMed

    Saurer, Eric M; Flessner, Ryan M; Buck, Maren E; Lynn, David M

    2011-02-14

    We report on the fabrication of covalently crosslinked and amine-reactive hollow microcapsules using 'reactive' layer-by-layer assembly to deposit thin polymer films on sacrificial microparticle templates. Our approach is based on the alternating deposition of layers of a synthetic polyamine and a polymer containing reactive azlactone functionality. Multilayered films composed of branched poly(ethylene imine) (BPEI) and poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) were fabricated layer-by-layer on the surfaces of calcium carbonate and glass microparticle templates. After fabrication, these films contained residual azlactone functionality that was accessible for reaction with amine-containing molecules. Dissolution of the calcium carbonate or glass cores using aqueous ethylenediamine tetraacetic acid (EDTA) or hydrofluoric acid (HF), respectively, led to the formation of hollow polymer microcapsules. These microcapsules were robust enough to encapsulate and retain a model macromolecule (FITC-dextran) and were stable for at least 22 hours in high ionic strength environments, in low and high pH solutions, and in several common organic solvents. Significant differences in the behaviors of capsules fabricated on CaCO(3) and glass cores were observed and characterized using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Whereas capsules fabricated on CaCO(3) templates collapsed upon drying, capsules fabricated on glass templates remained rigid and spherical. Characterization using EDS suggested that this latter behavior results, at least in part, from the presence of insoluble metal fluoride salts that are trapped or precipitate within the walls of capsules after etching of the glass cores using HF. Our results demonstrate that the assembly of BPEI/PVDMA films on sacrificial templates can be used to fabricate reactive microcapsules of potential use in a wide range of fields, including catalysis, drug and gene delivery, imaging, and

  3. Synthesis, characterization, and application of novel microporous mixed metal oxides, and nanostructured layered material-polymer films

    NASA Astrophysics Data System (ADS)

    Jeong, Hae-Kwon

    Zeolites are microporous crystalline aluminosilicates with pores and cavities of molecular dimension. They consist of interconnected aluminum and silicon tetrahedra to build a variety of 3D open framework structures. Due to their structure, stability, and activity, zeolites have been widely used in a broad variety of applications in industry. It is, therefore, of great interest to make new structures with potentially novel properties. In this regard, there has recently been a growing interest in the synthesis of novel mixed metal oxides with octahedral and tetrahedral units owing to the possibility to find unique electronic and optical properties. Hence, these materials can find advanced applications as well as conventional applications, just like zeolites. Research efforts have led to the discovery of several mixed octahedral and tetrahedral metal oxides with novel crystal structures including titanium silicates and cerium silicate. Layered materials with transport paths along the thickness of the layers are of particular interest due to potential usage as selective layers of nanometer scale in nanocomposite membranes. A new layered silicate (we call AMH-3) has been synthesized under hydrothermal conditions. The crystal structure solution via powder X-ray diffraction has revealed its unique layer structure of three dimensional microporosity within layers. Layered materials with porous layers will open up new areas of applications, such as selective nanocomposite separation membranes. Polymer/selective-flake nanocomposite membranes have been fabricated for the first time, which can, in principle, be scaled down to submicrometer structures. A layered aluminophosphate with a porous net layer is used as a selective phase and a polyimide as a continuous phase. The microstructures of the nanocomposite membranes were investigated using various characterization techniques. Nanocomposite membranes with 10 wt% layered aluminophosphate show substantial enhancement in

  4. Interactions between liquid-water and gas-diffusion layers in polymer-electrolyte fuel cells

    DOE PAGES

    Das, Prodip K.; Santamaria, Anthony D.; Weber, Adam Z.

    2015-06-11

    Over the past few decades, a significant amount of research on polymer-electrolyte fuel cells (PEFCs) has been conducted to improve performance and durability while reducing the cost of fuel cell systems. However, the cost associated with the platinum (Pt) catalyst remains a barrier to their commercialization and PEFC durability standards have yet to be established. An effective path toward reducing PEFC cost is making the catalyst layers (CLs) thinner thus reducing expensive Pt content. The limit of thin CLs is high gas-transport resistance and the performance of these CLs is sensitive to the operating temperature due to their inherent lowmore » water uptake capacity, which results in higher sensitivity to liquid-water flooding and reduced durability. Therefore, reducing PEFC's cost by decreasing Pt content and improving PEFC's performance and durability by managing liquid-water are still challenging and open topics of research. An overlooked aspect nowadays of PEFC water management is the gas-diffusion layer (GDL). While it is known that GDL's properties can impact performance, typically it is not seen as a critical component. In this work, we present data showing the importance of GDLs in terms of water removal and management while also exploring the interactions between liquid-water and GDL surfaces. The critical interface of GDL and gas-flow-channel in the presence of liquid-water was examined through systematic studies of adhesion forces as a function of water-injection rate for various GDLs of varying thickness. GDL properties (breakthrough pressure and adhesion force) were measured experimentally under a host of test conditions. Specifically, the effects of GDL hydrophobic (PTFE) content, thickness, and water-injection rate were examined to identify trends that may be beneficial to the design of liquid-water management strategies and next-generation GDL materials for PEFCs.« less

  5. Interactions between liquid-water and gas-diffusion layers in polymer-electrolyte fuel cells

    SciTech Connect

    Das, Prodip K.; Santamaria, Anthony D.; Weber, Adam Z.

    2015-06-11

    Over the past few decades, a significant amount of research on polymer-electrolyte fuel cells (PEFCs) has been conducted to improve performance and durability while reducing the cost of fuel cell systems. However, the cost associated with the platinum (Pt) catalyst remains a barrier to their commercialization and PEFC durability standards have yet to be established. An effective path toward reducing PEFC cost is making the catalyst layers (CLs) thinner thus reducing expensive Pt content. The limit of thin CLs is high gas-transport resistance and the performance of these CLs is sensitive to the operating temperature due to their inherent low water uptake capacity, which results in higher sensitivity to liquid-water flooding and reduced durability. Therefore, reducing PEFC's cost by decreasing Pt content and improving PEFC's performance and durability by managing liquid-water are still challenging and open topics of research. An overlooked aspect nowadays of PEFC water management is the gas-diffusion layer (GDL). While it is known that GDL's properties can impact performance, typically it is not seen as a critical component. In this work, we present data showing the importance of GDLs in terms of water removal and management while also exploring the interactions between liquid-water and GDL surfaces. The critical interface of GDL and gas-flow-channel in the presence of liquid-water was examined through systematic studies of adhesion forces as a function of water-injection rate for various GDLs of varying thickness. GDL properties (breakthrough pressure and adhesion force) were measured experimentally under a host of test conditions. Specifically, the effects of GDL hydrophobic (PTFE) content, thickness, and water-injection rate were examined to identify trends that may be beneficial to the design of liquid-water management strategies and next-generation GDL materials for PEFCs.

  6. Nanoparticle surface modification by amphiphilic polymers in aqueous media: role of polar organic solvents.

    PubMed

    Sarkar, Biswajit; Venugopal, Vinithra; Bodratti, Andrew M; Tsianou, Marina; Alexandridis, Paschalis

    2013-05-01

    We investigate the role of three polar organic solvents (dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), and glycerol) on the interfacial behavior of Pluronic P105 poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers on protonated silica nanoparticles in an aqueous dispersion. The polymer adsorption and self-assembly have been assessed from critical surface micelle concentration (csmc, measured by pyrene fluorescence spectroscopy) and adsorbed layer thickness (measured by capillary viscometry) data. Above its csmc, PEO-PPO-PEO block copolymers form hydrophobic domains on the nanoparticle surface. Below a critical concentration in water (known as critical displacer concentration, cdc), organic solvents act as displacers (molecules that can displace adsorbed polymer from a solid surface). The critical displacer concentration is obtained from the csmc and the polymer adsorbed layer thickness data. The cdc is found to be dependent on both the amount of nanoparticles present in the system as well as the nature of the displacer. Below the cdc, the csmc increases and the adsorbed polymer layer thickness decreases with increasing organic solvent concentration. Interfacial free energy calculations suggest that DMF, DMSO, and glycerol can adsorb onto the silica particles by displacing adsorbed PEO. These calculations are consistent with the experimental results in that, as a displacer, glycerol is the most effective and DMF is the least effective. Above the cdc, the influence of glycerol or DMSO on csmc is opposite to that of DMF which is attributed to the cosolvent effect.

  7. A bioactive polymer grafted on titanium oxide layer obtained by electrochemical oxidation. Improvement of cell response.

    PubMed

    Hélary, Gérard; Noirclère, Flavie; Mayingi, Josselin; Bacroix, Brigitte; Migonney, Véronique

    2010-02-01

    The anchorage failure of titanium implants in human body is mainly due to biointegration problem. The proposed solution is to graft a bioactive polymer at the surface of the implant in order to improve and control the interactions with the living system. In this paper, we describe the grafting of poly sodium styrene sulfonate on titanium surface by using a silanization reaction. The key point is to increase the TiOH content at the surface of the implant which can react with methoxy silane groups of 3-methacryloxypropyltrimethoxysilane (MPS). Two procedures were used: chemical oxidation and electrochemical oxidation. The last oxidation procedure was carried out in two different electrolytes: oxalic acid and methanol. These different oxidation methods allow controlling the roughness and the depth of the oxide layer. The methacryloyl group of MPS grafted at the titanium surface by silanization reaction is copolymerized with sodium styrene sulfonate using a thermal initiator able to produce radicals by heating. Colorimetric method, ATR-FTIR, XPS techniques and contact angle measurements were applied to characterize the surfaces. MG63 osteoblastic cell response was studied on polished, oxidized and grafted titanium samples. Cell adhesion, Alkaline Phosphatase activity and calcium nodules formation were significantly enhanced on grafted titanium surfaces compared to un-modified surfaces.

  8. Polymer-Based Mesh as Supports for Multi-layered 3D Cell Culture and Assays

    PubMed Central

    Simon, Karen A.; Park, Kyeng Min; Mosadegh, Bobak; Subramaniam, Anand Bala; Mazzeo, Aaron; Ngo, Phil M.; Whitesides, George M.

    2013-01-01

    Three-dimensional (3D) culture systems can mimic certain aspects of the cellular microenvironment found in vivo, but generation, analysis and imaging of current model systems for 3D cellular constructs and tissues remain challenging. This work demonstrates a 3D culture system – Cells-in-Gels-in-Mesh (CiGiM) – that uses stacked sheets of polymer-based mesh to support cells embedded in gels to form tissue-like constructs; the stacked sheets can be disassembled by peeling the sheets apart to analyze cultured cells—layer-by-layer—within the construct. The mesh sheets leave openings large enough for light to pass through with minimal scattering, and thus allowing multiple options for analysis—(i) using straightforward analysis by optical light microscopy, (ii) by high-resolution analysis with fluorescence microscopy, or (iii) with a fluorescence gel scanner. The sheets can be patterned into separate zones with paraffin film-based decals, in order to conduct multiple experiments in parallel; the paraffin-based decal films also block lateral diffusion of oxygen effectively. CiGiM simplifies the generation and analysis of 3D culture without compromising throughput, and quality of the data collected: it is especially useful in experiments that require control of oxygen levels, and isolation of adjacent wells in a multi-zone format. PMID:24095253

  9. Feasibility of atomic layer etching of polymer material based on sequential O{sub 2} exposure and Ar low-pressure plasma-etching

    SciTech Connect

    Vogli, Evelina; Metzler, Dominik; Oehrlein, Gottlieb S.

    2013-06-24

    We describe controlled, self-limited etching of a polystyrene polymer using a composite etching cycle consisting of sequential deposition of a thin reactive layer from precursors produced from a polymer-coated electrode within the etching chamber, modification using O{sub 2} exposure, and subsequent low-pressure Ar plasma etching, which removes the oxygen-modified deposited reactive layer along with Almost-Equal-To 0.1 nm unmodified polymer. Deposition prevents net etching of the unmodified polymer during the etching step and enables self-limited etch rates of 0.1 nm/cycle.

  10. The first biantennary bacterial secondary cell wall polymer and its influence on S-layer glycoprotein assembly.

    PubMed Central

    Steindl, Christian; Schäffer, Christina; Wugeditsch, Thomas; Graninger, Michael; Matecko, Irena; Müller, Norbert; Messner, Paul

    2002-01-01

    The cell surface of Aneurinibacillus thermoaerophilus DSM 10155 is covered with a square surface (S)-layer glycoprotein lattice. This S-layer glycoprotein, which was extracted with aqueous buffers after a freeze-thaw cycle of the bacterial cells, is the only completely water-soluble S-layer glycoprotein to be reported to date. The purified S-layer glycoprotein preparation had an overall carbohydrate content of 19%. Detailed chemical investigations indicated that the S-layer O-glycans of previously established structure accounted for 13% of total glycosylation. The remainder could be attributed to a peptidoglycan-associated secondary cell wall polymer. Structure analysis was performed using purified secondary cell wall polymer-peptidoglycan complexes. NMR spectroscopy revealed the first biantennary secondary cell wall polymer from the domain Bacteria, with the structure alpha-L-Glc p NAc-(1-->3)-beta-L-Man p NAc-(1-->4)-beta-L-Gal p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->3)-beta-L-Man p NAc-(1-->4)-beta-L-Gal p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->4)-[alpha-L-Glc p NAc-(1-->3)-beta-L-Man p NAc-(1-->4)-beta-L-Gal p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->3)-beta-L-Man p NAc-(1-->4)-beta-L-Gal p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->3)]-beta-L-Man p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->3)-beta-L-Man p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->3)-alpha-L-Glc p NAc-(1-->O)-PO(2)(-)-O-PO(2)(-)-(O-->6)-MurNAc- (where MurNAc is N -acetylmuramic acid). The neutral polysaccharide is linked via a pyrophosphate bond to the C-6 atom of every fourth N -acetylmuramic acid residue, in average, of the A1gamma-type peptidoglycan. In vivo, the biantennary polymer anchored the S-layer glycoprotein very effectively to the cell wall, probably due to the doubling of motifs for a proposed lectin-like binding between the polymer and the N-terminus of the S-layer protein. When the cellular support was removed during S-layer glycoprotein isolation, the co-purified polymer mediated the solubility of the S-layer

  11. Optimization of the Energy Level Alignment between the Photoactive Layer and the Cathode Contact Utilizing Solution-Processed Hafnium Acetylacetonate as Buffer Layer for Efficient Polymer Solar Cells.

    PubMed

    Yu, Lu; Li, Qiuxiang; Shi, Zhenzhen; Liu, Hao; Wang, Yaping; Wang, Fuzhi; Zhang, Bing; Dai, Songyuan; Lin, Jun; Tan, Zhan'ao

    2016-01-13

    The insertion of an appropriate interfacial buffer layer between the photoactive layer and the contact electrodes makes a great impact on the performance of polymer solar cells (PSCs). Ideal interfacial buffer layers could minimize the interfacial traps and the interfacial barriers caused by the incompatibility between the photoactive layer and the electrodes. In this work, we utilized solution-processed hafnium(IV) acetylacetonate (Hf(acac)4) as an effective cathode buffer layer (CBL) in PSCs to optimize the energy level alignment between the photoactive layer and the cathode contact, with the short-circuit current density (Jsc), open-circuit voltage (Voc), and fill factor (FF) all simultaneously improved with Hf(acac)4 CBL, leading to enhanced power conversion efficiencies (PCEs). Ultraviolet photoemission spectroscopy (UPS) and scanning Kelvin probe microscopy (SKPM) were performed to confirm that the interfacial dipoles were formed with the same orientation direction as the built-in potential between the photoactive layer and Hf(acac)4 CBL, benefiting the exciton separation and electron transport/extraction. In addition, the optical characteristics and surface morphology of the Hf(acac)4 CBL were also investigated.

  12. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells.

    PubMed

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-01-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials. PMID:27411487

  13. Polymer ferroelectric field-effect memory device with SnO channel layer exhibits record hole mobility

    NASA Astrophysics Data System (ADS)

    Caraveo-Frescas, J. A.; Khan, M. A.; Alshareef, H. N.

    2014-06-01

    Here we report for the first time a hybrid p-channel polymer ferroelectric field-effect transistor memory device with record mobility. The memory device, fabricated at 200°C on both plastic polyimide and glass substrates, uses ferroelectric polymer P(VDF-TrFE) as the gate dielectric and transparent p-type oxide (SnO) as the active channel layer. A record mobility of 3.3 cm2V-1s-1, large memory window (~16 V), low read voltages (~-1 V), and excellent retention characteristics up to 5000 sec have been achieved. The mobility achieved in our devices is over 10 times higher than previously reported polymer ferroelectric field-effect transistor memory with p-type channel. This demonstration opens the door for the development of non-volatile memory devices based on dual channel for emerging transparent and flexible electronic devices.

  14. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells

    NASA Astrophysics Data System (ADS)

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-07-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials.

  15. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells

    PubMed Central

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-01-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials. PMID:27411487

  16. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells.

    PubMed

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-01-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials.

  17. Negative chromatography of hepatitis B virus-like particle: Comparative study of different adsorbent designs.

    PubMed

    Lee, Micky Fu Xiang; Chan, Eng Seng; Tan, Wen Siang; Tam, Kam Chiu; Tey, Beng Ti

    2016-05-01

    Purification of virus-like particles (VLPs) in bind-and-elute mode has reached a bottleneck. Negative chromatography has emerged as the alternative solution; however, benchmark of negative chromatography media and their respective optimized conditions are absent. Hence, this study was carried out to compare the performance of different negative chromatography media for the purification of hepatitis B VLPs (HB-VLPs) from clarified Escherichia coli feedstock. The modified anion exchange media, core-shell adsorbents (InertShell and InertLayer 1000) and polymer grafted adsorbents (SQ) were compared. The results of chromatography from packed bed column of core-shell adsorbents showed that there is a trade-off between the purity and recovery of HB-VLPs in the flowthrough fraction due to the shell thickness. Atomic force microscopic analysis revealed funnel-shaped pore channels in the shell layer which may contribute to the entrapment of HB-VLPs. A longer residence time at a lower feed flow rate (0.5ml/min) improved slightly the HB-VLPs purity in all modified adsorbents, but the recovery in InertShell reduced substantially. The preheat-treatment is not recommended for the negative chromatography as the thermal-induced co-aggregation of HCPs and HB-VLPs would flow along with HB-VLPs and thus reduced the HB-VLPs purity in the flowthrough. Further reduction in the feedstock concentration enhanced the purity of HB-VLPs especially in InertLayer 1000 but reduced substantially the recovery of HB-VLPs. In general, the polymer grafted adsorbent, SQ, performed better than the core-shell adsorbents in handling a higher feedstock concentration.

  18. Negative chromatography of hepatitis B virus-like particle: Comparative study of different adsorbent designs.

    PubMed

    Lee, Micky Fu Xiang; Chan, Eng Seng; Tan, Wen Siang; Tam, Kam Chiu; Tey, Beng Ti

    2016-05-01

    Purification of virus-like particles (VLPs) in bind-and-elute mode has reached a bottleneck. Negative chromatography has emerged as the alternative solution; however, benchmark of negative chromatography media and their respective optimized conditions are absent. Hence, this study was carried out to compare the performance of different negative chromatography media for the purification of hepatitis B VLPs (HB-VLPs) from clarified Escherichia coli feedstock. The modified anion exchange media, core-shell adsorbents (InertShell and InertLayer 1000) and polymer grafted adsorbents (SQ) were compared. The results of chromatography from packed bed column of core-shell adsorbents showed that there is a trade-off between the purity and recovery of HB-VLPs in the flowthrough fraction due to the shell thickness. Atomic force microscopic analysis revealed funnel-shaped pore channels in the shell layer which may contribute to the entrapment of HB-VLPs. A longer residence time at a lower feed flow rate (0.5ml/min) improved slightly the HB-VLPs purity in all modified adsorbents, but the recovery in InertShell reduced substantially. The preheat-treatment is not recommended for the negative chromatography as the thermal-induced co-aggregation of HCPs and HB-VLPs would flow along with HB-VLPs and thus reduced the HB-VLPs purity in the flowthrough. Further reduction in the feedstock concentration enhanced the purity of HB-VLPs especially in InertLayer 1000 but reduced substantially the recovery of HB-VLPs. In general, the polymer grafted adsorbent, SQ, performed better than the core-shell adsorbents in handling a higher feedstock concentration. PMID:27059397

  19. Generation of conducting polymer-based heterojunctions, diodes, and capacitors using an intermediate-layer lithography method

    NASA Astrophysics Data System (ADS)

    Liu, Xinchuan; Chakraborty, Anirban; Parthasarathi, Ganga; Luo, Cheng

    2007-04-01

    In this work, conducting polymer-based heterojunctions, diodes and capacitors have been generated using an intermediate-layer lithography (ILL) approach which has been recently developed in our group. Polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), Poly(methyl methacrylate) (PMMA) and aluminum were used as component materials in these devices. Compared with Si-based devices, conducting polymerbased devices have distinctive advantages of low weight and good flexibility, and may potentially replace the corresponding Si-based devices. A challenge is how to fabricate the conducting polymer-based microsystems. Most conducting polymers are sensitive to the environment, and their electrical properties tend to deteriorate over time due to overoxidation (air), moisture, high temperature and chemical alteration. The current fabrication techniques (e.g. lift-off, dry and wet etching processes) used in lithographic approaches involve ultra-violet, electron-beam, x-ray, gases (e.g., oxygen and nitrogen), DI water, and/or chemical solution (e.g. photoresist and acetone), making them improper to pattern conducting polymers. Since the ILL method does not involve aggressive chemistry in generation of patterns, it has been employed in this work to fabricate conducting polymer-based microdevices, particularly diodes and capacitors. In fabrication of the devices, multiple layers of polymers (e.g., PPy and PEDOT) and metals (e.g., Al) are coated on a PMMA sheet followed by the patterning with the insertion of Si molds. The detailed fabrication procedure and testing results are given in this paper.

  20. Extending microcontact printing for patterning of thick polymer layers: semi-drying of inks and contact mechanisms

    NASA Astrophysics Data System (ADS)

    Kusaka, Yasuyuki; Miyashita, Kaori; Ushijima, Hirobumi

    2014-12-01

    We investigate the applicability of the microcontact printing technique for the patterning of polymeric etch-resistant layers with thicknesses in the order of micrometers. In contrast to small molecular materials such as thiols and silane coupling agents typically used in microcontact printing, the patterning of thick layers requires tuning of the rheological properties of an ink film to prevent pattern deformation and attain high-quality transfer. By evaluating the swelling rate of a microcontact stamp material (i.e. poly(dimethylsiloxane) (PDMS)) and the evaporation rate of solvents, we find an optimal ink formulation to attain the desired semi-dried state for the printing of polymer layers. In polymer films with solid content below the optimal limit, split- or wrinkle-type deformations were found depending on the adhesion force and deformability of ink films, while overly-dried polymer films failed to be transferred. These phenomena are in qualitative agreement with deformation curves obtained from colloidal probe microscopy measurements that successfully revealed the deformability and adhesion of semi-dried polymer films. Further investigation of the effects of stamp stiffness on pattern formation reveals that a pattern region in which the thickness profile has a small curvature radius failed to be transferred when a stiffer PDMS stamp was used. This type of defect is thought to be caused by incomplete contact between the film and substrate due to a semi-circular cap structure of the polymer film and insufficient deformation of the stamp. Herein, a detailed contacting mechanism for high-quality patterning is discussed on the basis of the Hertz contact model. Using the developed etch-resistant ink and optimized printing process conditions, a finely defined etched structure for a silicon substrate is obtained.

  1. The influence of few-layer graphene on the gas permeability of the high-free-volume polymer PIM-1

    PubMed Central

    Althumayri, Khalid; Harrison, Wayne J.; Shin, Yuyoung; Gardiner, John M.; Casiraghi, Cinzia; Bernardo, Paola; Clarizia, Gabriele

    2016-01-01

    Gas permeability data are presented for mixed matrix membranes (MMMs) of few-layer graphene in the polymer of intrinsic microporosity PIM-1, and the results compared with previously reported data for two other nanofillers in PIM-1: multiwalled carbon nanotubes functionalized with poly(ethylene glycol) (f-MWCNTs) and fused silica. For few-layer graphene, a significant enhancement in permeability is observed at very low graphene content (0.05 vol.%), which may be attributed to the effect of the nanofiller on the packing of the polymer chains. At higher graphene content permeability decreases, as expected for the addition of an impermeable filler. Other nanofillers, reported in the literature, also give rise to enhancements in permeability, but at substantially higher loadings, the highest measured permeabilities being at 1 vol.% for f-MWCNTs and 24 vol.% for fused silica. These results are consistent with the hypothesis that packing of the polymer chains is influenced by the curvature of the nanofiller surface at the nanoscale, with an increasingly pronounced effect on moving from a more-or-less spherical nanoparticle morphology (fused silica) to a cylindrical morphology (f-MWCNT) to a planar morphology (graphene). While the permeability of a high-free-volume polymer such as PIM-1 decreases over time through physical ageing, for the PIM-1/graphene MMMs a significant permeability enhancement was retained after eight months storage. PMID:26712643

  2. The influence of few-layer graphene on the gas permeability of the high-free-volume polymer PIM-1.

    PubMed

    Althumayri, Khalid; Harrison, Wayne J; Shin, Yuyoung; Gardiner, John M; Casiraghi, Cinzia; Budd, Peter M; Bernardo, Paola; Clarizia, Gabriele; Jansen, Johannes C

    2016-02-13

    Gas permeability data are presented for mixed matrix membranes (MMMs) of few-layer graphene in the polymer of intrinsic microporosity PIM-1, and the results compared with previously reported data for two other nanofillers in PIM-1: multiwalled carbon nanotubes functionalized with poly(ethylene glycol) (f-MWCNTs) and fused silica. For few-layer graphene, a significant enhancement in permeability is observed at very low graphene content (0.05 vol.%), which may be attributed to the effect of the nanofiller on the packing of the polymer chains. At higher graphene content permeability decreases, as expected for the addition of an impermeable filler. Other nanofillers, reported in the literature, also give rise to enhancements in permeability, but at substantially higher loadings, the highest measured permeabilities being at 1 vol.% for f-MWCNTs and 24 vol.% for fused silica. These results are consistent with the hypothesis that packing of the polymer chains is influenced by the curvature of the nanofiller surface at the nanoscale, with an increasingly pronounced effect on moving from a more-or-less spherical nanoparticle morphology (fused silica) to a cylindrical morphology (f-MWCNT) to a planar morphology (graphene). While the permeability of a high-free-volume polymer such as PIM-1 decreases over time through physical ageing, for the PIM-1/graphene MMMs a significant permeability enhancement was retained after eight months storage. PMID:26712643

  3. Scattering-layer-induced energy storage function in polymer-based quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Zhang, Xi; Jiang, Hongrui

    2015-03-01

    Photo-self-charging cells (PSCs) are compact devices with dual functions of photoelectric conversion and energy storage. By introducing a scattering layer in polymer-based quasi-solid-state dye-sensitized solar cells, two-electrode PSCs with highly compact structure were obtained. The charge storage function stems from the formed ion channel network in the scattering layer/polymer electrolyte system. Both the photoelectric conversion and the energy storage functions are integrated in only the photoelectrode of such PSCs. This design of PSC could continuously output power as a solar cell with considerable efficiency after being photo-charged. Such PSCs could be applied in highly-compact mini power devices.

  4. Gradient polymer-disposed liquid crystal single layer of large nematic droplets for modulation of laser light.

    PubMed

    Hadjichristov, Georgi B; Marinov, Yordan G; Petrov, Alexander G

    2011-06-01

    The light modulating ability of gradient polymer-disposed liquid crystal (PDLC) single layer of large droplets formed by nematic E7 in UV-cured polymer NOA65 is studied. Operating at relatively low voltages, such PDLC film with a of thickness 10-25 μm and droplet size up to 50 μm exhibits a good contrast ratio and is capable of producing a large phase shift for the propagating coherent light. For a linearly polarized He-Ne laser (λ=633 nm), an electrically commanded phase shift as large as π/2 can be obtained by the large-droplet region of the film. The electrically produced phase shift and its spatial profile controlled by the thickness of the gradient PDLC single layers of large nematic droplets can be useful for tunable spatial light modulators and other devices for active control of laser light. PMID:21629309

  5. Study and modeling of the ironing process on a multi-layered polymer coated low-carbon steel

    NASA Astrophysics Data System (ADS)

    Selles Canto, Miguel Angel

    The ironing process is the most crucial step in the manufacture of cans. Sheet steel covered by three polymer layers can be used as the starting material, but this coating must neither break nor fail in any manner in order to be considered as a viable and effective alternative to traditional practice. During ironing, the deformations are severe and high pressures exist at the tool-workpiece interface. Thickness reductions inherent in ironing require a large amount of surface generation. Deterioration of the coating in this delicate operation might enable direct contact of the stored food or drink with the metal. As can be appreciated, the key to the use of polymer-coated steel sheets in the manufacture of cans lies in the survival of these layers during the ironing process. Another important issue is the roughness of the newly-generated surface, because it should be possible to decorate the can without any difficulty. Changing the traditional manufacture of metallic containers such as cans and using this new coated material permits great reduction in environmental contaminants produced as a result of avoiding the formation of Volatile Organic Compounds (VOCs) during the manufacture of the polymer layers. This reduction is even greater because of not using additional lubricants due to the self-lubricanting property of the solid polymer coating layers during the drawing process. These objectives, together with the improvement of the mechanical characteristics and the adhesion of the painting or decorative priming, are realized by the use of the proposed material. In the existing bibliography about ironing processes on coated materials, some authors propose the use of the Upper Bound Theorem for modeling the material behavior. The present research shows for the first time the modeling of the ironing process on a three-layer polymer coated material. In addition, it takes into account the cases in which successful ironing is produced and those in which ones the ironing

  6. Synthesis of metronidazole-imprinted molecularly imprinted polymers by distillation precipitation polymerization and their use as a solid-phase adsorbent and chromatographic filler.

    PubMed

    Liu, Jiang; Zhang, Lu; Li Han Song, Le; Liu, Yuan; Tang, Hui; Li, Yingchun

    2015-04-01

    Metronidazole-imprinted polymers with superior recognition properties were prepared by a novel strategy called distillation-precipitation polymerization. The as-obtained polymers were characterized by Fourier-transform infrared spectroscopy, laser particle size determination and scanning electron microscopy, and their binding performances were evaluated in detail by static, kinetic and dynamic rebinding tests, and Scatchard analysis. The results showed that when the fraction of the monomers was 5 vol% in the whole reaction system, the prepared polymers afforded good morphology, monodispersity, and high adsorption capacity and excellent selectivity to the target molecule, metronidazole. The optimal binding performance is 12.41 mg/g for metronidazole just before leakage occurred and 38.51 mg/g at saturation in dynamic rebinding tests. Metronidazole-imprinted polymers were further applied as packing agents in solid-phase extraction and as chromatographic filler, both of which served for the detection of metronidazole in fish tissue. The results illustrated the recoveries of spiked samples ranged from 82.97 to 87.83% by using molecularly imprinted solid-phase extraction combined with a C18 commercial column and 93.7 to 101.2% by directly using the polymer-packed chromatographic column. The relative standard deviation of both methods was less than 6%. PMID:25594306

  7. Properties of poly(ethylene terephthalate) track membranes with a polymer layer obtained by plasma polymerization of pyrrole vapors

    NASA Astrophysics Data System (ADS)

    Kravets, L.; Dmitriev, S.; Lizunov, N.; Satulu, V.; Mitu, B.; Dinescu, G.

    2010-03-01

    The structure and the charge transport properties of poly(ethylene terephthalate) track membrane modified by pyrrole plasma were studied. It was found that polymer deposition on the surface of a track membrane via plasma polymerization of pyrrole results in the creation of composite nanomembranes that, in the case of the formation of a semipermeable layer, possess asymmetric conductivity in electrolyte solutions - a rectification effect similar to that of a p-n junction in semiconductors. It is caused by presence in the membranes of two layers with different functional groups and also by the pore geometry. Such membranes can be used to create chemical and biochemical sensors.

  8. Anode modification of polymer light-emitting diode using graphene oxide interfacial layer: The role of ultraviolet-ozone treatment

    NASA Astrophysics Data System (ADS)

    Jiang, Xiao-Chen; Li, Yan-Qing; Deng, Yan-Hong; Zhuo, Qi-Qi; Lee, Shuit-Tong; Tang, Jian-Xin

    2013-08-01

    A simple and efficient method has been developed to modify the anode interface of polymer light-emitting diode by incorporating solution-processable graphene oxide as hole transport layer. Interface engineering of ultraviolet-ozone treatment on graphene oxide is demonstrated to dramatically enhance the electrical properties, leading to 15% increase in efficiency compared to that with a traditionally used poly(styrenesulfonate)-doped poly(3,4-ethylenedioxythiophene) layer. As determined by photoelectron spectroscopy and impedance spectroscopy, an optimized ultraviolet-ozone treatment results in a more favorable energy level alignment and a decrease in series resistance, which can subsequently facilitate charge injection at the anodic interface.

  9. Deuterium-Tritium Beta-Layering Within a National Ignition Facility Scale Polymer Target in the LANL Cryogenic Pressure Loader

    SciTech Connect

    Ebey, Peter S.; Dole, James M.; Geller, Drew A.; Hoffer, James K.; Nobile, Arthur; Sheliak, John D.

    2005-11-15

    Beta-layering, the process of beta-decay heat-driven mass redistribution, has been demonstrated in a deuterium-tritium (D-T)-filled polymer sphere of the type required for fusion ignition experiments at the National Ignition Facility. This is the first report, to the best of the authors' knowledge, of a D-T layer formed in a permeation-filled sphere. The 2-mm-diam sphere was filled with D-T by permeation; cooled to cryogenic temperatures while in the high-pressure permeation vessel; and, while cold, removed to an optical axis where the D-T was frozen, melted, and beta-layered in a series of experiments over several weeks' time. This work was performed in the Los Alamos National Laboratory cryogenic pressure loader system. The beta-layering time constant was 24.0 {+-} 2.5 min, less than the theoretical value of 26.8 min, and not showing the significant increase due to build-up of {sup 3}He often observed in beta-layered samples. Supercooling of the liquid D-T was observed. Neither the polymer target nor its tenting material showed visual signs of degradation after 5 weeks of exposure to D-T. Small external thermal gradients were used to shift the D-T material back and forth within the sphere.

  10. Enhanced performance of polymer solar cell with ZnO nanoparticle electron transporting layer passivated by in situ cross-linked three-dimensional polymer network

    NASA Astrophysics Data System (ADS)

    Wu, Zhongwei; Song, Tao; Xia, Zhouhui; Wei, Huaixin; Sun, Baoquan

    2013-12-01

    An in situ cross-linked three-dimensional polymer network has been developed to passivate ZnO nanoparticles as an electron transporting layer (ETL) to improve the performance of inverted organic solar cells. The passivated ZnO ETL-based devices achieve efficiencies of 3.26% for poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and 7.37% for poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b‧]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl

  11. Comparison of precursor infiltration into polymer thin films via atomic layer deposition and sequential vapor infiltration using in-situ quartz crystal microgravimetry

    SciTech Connect

    Padbury, Richard P.; Jur, Jesse S.

    2014-07-01

    Previous research exploring inorganic materials nucleation behavior on polymers via atomic layer deposition indicates the formation of hybrid organic–inorganic materials that form within the subsurface of the polymer. This has inspired adaptations to the process, such as sequential vapor infiltration, which enhances the diffusion of organometallic precursors into the subsurface of the polymer to promote the formation of a hybrid organic–inorganic coating. This work highlights the fundamental difference in mass uptake behavior between atomic layer deposition and sequential vapor infiltration using in-situ methods. In particular, in-situ quartz crystal microgravimetry is used to compare the mass uptake behavior of trimethyl aluminum in poly(butylene terephthalate) and polyamide-6 polymer thin films. The importance of trimethyl aluminum diffusion into the polymer subsurface and the subsequent chemical reactions with polymer functional groups are discussed.

  12. Selective adsorption of modified nucleoside cancer biomarkers by hybrid molecularly imprinted adsorbents.

    PubMed

    Iwanowska, Agnieszka; Yusa, Shin-Ichi; Nowakowska, Maria; Szczubiałka, Krzysztof

    2016-08-01

    Modified adenosine nucleosides have been proposed to be potential DNA-based biomarkers for early diagnosis of tumor and a promising tool for the development of noninvasive prediction systems. However, the low concentration of modified adenosine nucleosides in physiological fluids makes them challenging for both quantitative and qualitative determination. Therefore, materials, which are potentially useful for selective adsorption of nucleobase-containing compounds, were obtained. To obtain the adsorbents, the silica gel particles were coated layer-by-layer with films of the polymers with different combinations of polymers containing thymine groups. Next, the microspheres were irradiated with UV light in the presence of 2'-deoxyadenosine or 5'-deoxy-5'-(methylthio)adenosine, as template molecules, which resulted in the photodimerization of thymine moieties and molecular imprinting of adsorbed modified adenosine compounds. The selectivity of the adsorption was significantly enhanced by the photoimprinting process. Eventually, the imprinted particles have shown an improved ability to recognize mainly 2'-deoxyadenosine and 5'-deoxy-5'-(methylthio)adenosine molecules. The best performing adsorbent was obtained using modified natural polysaccharides. The studied materials could serve as promising adsorbents of biomarkers for tumor diagnostics. PMID:27296785

  13. Mechanistic Insights to the Influence of Adsorbed Organic Macromolecules on Nanoparticle Attachment Efficiency in Porous Media

    NASA Astrophysics Data System (ADS)

    Phenrat, T.; Song, J.; Cisneros, C. M.; Schoenfelder, D. P.; Illangasekare, T. H.; Tilton, R. D.; Lowry, G. V.

    2009-12-01

    Assessing the potential risks of natural or engineered nanoparticles to the environment and human health requires the ability to predict their mobility in porous media such as groundwater aquifers or sand filters used in water treatment. Semi-empirical correlations to predict the collision efficiency of electrostatically stabilized nanoparticles are available; however, they are not applicable to nanoparticles coated with natural organic matter (NOM) or polymeric surface coatings because the existing correlations do not account the electrosteric repulsions and lubrication afforded by coatings that inhibit or reverse nanoparticle attachment to surfaces. Regression analysis of published data on the collision efficiency of NOM-coated latex and hematite particles, and on new data collected for poly(styrene sulfonate)-, carboxy methyl cellulose, and polyaspartate-coated hematite and titanium dioxide nanoparticles was used to develop an empirical correlation of the collision efficiency of NOM- and polymer-coated nanomaterials and dimensionless parameters including the adsorbed layer-electrokinetic parameter (NLEK) representing electrosteric repulsions and lubrication afforded by adsorbed NOM or polyelectrolyte. An empirical correlation with three dimensionless parameters can predict the measured collision efficiency on coated metal oxide nanoparticles over a wide dynamic range in particle type, coating type, and solution conditions (~80 data points). This study indicates that including the adsorbed NOM and polymer layer properties of the properties is essential for understanding the transport and fate of NOM- and polymer-coated natural and manufactured nanomaterials in porous media.

  14. Optical behavior of the conjugated polymer MEH-PPV thin films stretched in bi-layer dwetting by an unstable layer

    NASA Astrophysics Data System (ADS)

    Chen, Po-Tsun; Yang, Arnold C.-M.

    2012-02-01

    Molecular packing and chain conformation play important roles in the optoelectronic performance of conjugated polymer thin films. It has been shown that by virtue of stretching via dewetting, the photoluminescence (PL) efficiencies of rarefied MEH-PPV thin films may be dramatically enhanced. To result similar effects in the stable non-diluted pristine MEH-PPV thin films, bi-layer dewetting was attempted in samples of MEH-PPV thin films (˜7nm) covered by one layer of polystyrene (PS) (˜40nm) that dewetted in toluene vapor to form droplets (height ˜300 nm) and ultrathin residual layer (˜3nm) on the substrate. The instability was initiated from the PS layer in which small pinholes first emerged upon the intake of the solvent vapor. The pinholes then expanded and deepened into the underlying MEH-PPV, forcing the conjugated film to dewet. As a result of the stretching induced by the dewetting, the PL peak blue-shifted 20 nm to 540 nm and the intensity was enhanced around 10 times. Revealed by the position-sensitive confocal PL data, the huge enhancement came from both the droplet and residual layer, caused by molecular separation and stretching. Electroluminescence devices are being made based on these stretched MEH-PPV films.

  15. Direct Evidence for Percolation of Immobilized Polymer Layer around Nanoparticles Accounting for Sol-Gel Transition in Fumed Silica Dispersions.

    PubMed

    Zheng, Zhong; Song, Yihu; Yang, Ruiquan; Zheng, Qiang

    2015-12-22

    Immobilized polymer fractions have been claimed to be of vital importance for sol-gel transitions generally observed in nanoparticle dispersions but remain a matter of debate regarding mechanism and difficulty for prediction. Here we investigate the immobilized layer structures of trifunctionality polyether polyol (PPG) near the surfaces of hydrophilic and hydrophobic fumed silica (FS) nanoparticles to reveal the role of surface chemistry on the molecular dynamics and sol-gel transitions of the dispersions. Using modulated differential scanning calorimetry, we measure the specific heat capacity during glass transition and the enthalpy during cold-crystallization. Comparing with hydrophobic FS that forms a fully immobilized (glassy) layer, we find that hydrophilic FS immobilizes more PPG, forming a partially immobilized outer layer being unable to crystallize next to the inner glassy layer. By correlating the thickness of the glassy layer with half of the minimum spacing between nanoparticles, we directly evidence the percolation of this layer along the nearest neighbor nanoparticles responsible for the sol-gel transition. Using effective volume fraction including the glassy layer, we successfully construct master curves of relative viscosity of both hydrophilic and hydrophobic FS dispersions, pointing to a common sol-gel transition mechanism mediated by the surface chemistry.

  16. Enhancing the performance of polymer photovoltaic cells by using an alcohol soluble fullerene derivative as the interfacial layer.

    PubMed

    Mei, Qiang; Li, Cuihong; Gong, Xue; Lu, Heng; Jin, Enquan; Du, Chun; Lu, Zhen; Jiang, Li; Meng, Xiangyue; Wang, Chunru; Bo, Zhishan

    2013-08-28

    Alcohol soluble fullerene derivative (FN-C60) has been synthesized and used as a cathode interfacial layer for high-efficiency polymer solar cells (PSCs). To examine the function of the FN-C60 interfacial layer, polymer solar cells were fabricated with blends of P3:PC71BM, HXS-1:PC71BM, PDFCDTBT:PC71BM, and PDPQTBT:PC71BM as the active layer. In comparison to the bare Al electrode, power conversion efficiencies (PCEs) of P3:PC71BM, HXS-1:PC71BM, PDFCDTBT:PC71BM, and PDPQTBT:PC71BM based PSCs were increased from 3.50 to 4.64%, 4.69 to 5.25%, 2.70 to 4.60%, and 1.52 to 2.29%, respectively, when FN-C60/Al was used as the electrode. Moreover, the overall photovoltaic performances of PSCs with the FN-C60/Al electrode were better than those of cells with LiF/Al electrode, indicating that FN-C60 is a potential interfacial layer material to replace LiF.

  17. Improved performance of polymer solar cells using PBDTT-F-TT:PC71BM blend film as active layer

    NASA Astrophysics Data System (ADS)

    Zang, Yue; Gao, Xiumin; Lu, Xinmiao; Xin, Qing; Lin, Jun; Zhao, Jufeng

    2016-07-01

    A detailed study of high-efficiency polymer solar cells (PSCs) based on a low bandgap polymer PBDTT-F-TT and PC71BM as the bulk heterojunction (BHJ) layer is carried out. By using 1,8-diiodooctane (DIO) as solvent additive to control the morphology of active layer and comparing different device architecture to optimize the optical field distribution, the power conversion efficiency (PCE) of the resulted devices can be reached as high as 9.34%. Comprehensive characterization and optical modeling of the resulting devices is performed to understand the effect of DIO and device geometry on photovoltaic performance. It was found that the addition of DIO can significantly improve the nanoscale morphology and increased electron mobility in the BHJ layer. The inverted device architecture was chosen because the results from optical modeling shows that it offers better optical field distribution and exciton generation profile. Based on these results, a low-temperature processed ZnO was finally introduced as an electron transport layer to facility the fabrication on flexible substrates and showed comparable performance with the device based on conventional ZnO interlayer prepared by sol-gel process.

  18. Effectiveness of the statistical potential in the description of fermions in a worm-algorithm path-integral Monte Carlo simulation of 3He atoms placed on a 4He layer adsorbed on graphite.

    PubMed

    Ghassib, Humam B; Sakhel, Asaad R; Obeidat, Omar; Al-Oqali, Amer; Sakhel, Roger R

    2012-01-01

    We demonstrate the effectiveness of a statistical potential (SP) in the description of fermions in a worm-algorithm path-integral Monte Carlo simulation of a few 3He atoms floating on a 4He layer adsorbed on graphite. The SP in this work yields successful results, as manifested by the clusterization of 3He, and by the observation that the 3He atoms float on the surface of 4He. We display the positions of the particles in 3D coordinate space, which reveal clusterization of the 3He component. The correlation functions are also presented, which give further evidence for the clusterization.

  19. Using Zn/Al layered double hydroxide as a novel solid-phase extraction adsorbent to extract polycyclic aromatic hydrocarbons at trace levels in water samples prior to the determination of gas chromatography-mass spectrometry.

    PubMed

    Liu, Yan-Long; Zhou, Jia-Bin; Zhao, Ru-Song; Chen, Xiang-Feng

    2012-09-01

    This paper demonstrates, for the first time, the great potential of using Zn/Al layered double hydroxide intercalated sodium dodecyl benzene sulfonate (Zn/Al-SDBS-LDH) as a solid-phase extraction (SPE) material in the extraction of persistent organic pollutants prior to the determination of gas chromatography-mass spectrometry in environmental water samples. Zn/Al-SDBS-LDH, a relatively inexpensive and simply prepared material, was synthesized and used as a SPE adsorbent to quantitatively determine the concentration of five polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Factors affecting extraction efficiency, such as, eluent type, eluent volume, flow rate of sample, sample volume, and amount of adsorbent, were investigated and optimized in detail. Experimental results indicate that there is an excellent linear relationship between peak area and the concentration of PAHs over the range of 5-500 ng L(-1), and the precisions (relative standard deviation (RSD)) were 2.5-6.3% under the optimum conditions. Based on the ratio of chromatographic signal-to-base line noise (S/N = 3), the limits of detection could reach 1.2-3.2 ng L(-1). This novel method was successfully applied to the analysis of PAHs in environmental water samples. As such, we show here that the use of Zn/Al-SDBS-LDH as SPE adsorbent materials, coupled with gas chromatography-mass spectrometry, is an excellent improvement in the routine analysis of PAHs at trace levels in the environment.

  20. Structure and mechanical effects of random copolymer layers at polymer interfaces

    SciTech Connect

    Brown, H.R.; Russell, T.P.; Hawker, C.J.; Bernard, B.

    1996-12-31

    Chemically different polymers are frequently immiscible in each other because the large size of the individual molecules causes the mixing entropy to be low. The interfaces between polymers are normally relatively sharp ({approximately}20-30{Angstrom}) on the scale of a polymer chain. However polymer materials gain their mechanical strength from the entanglement between chains. Significant entanglement at an interface can only occur if the interface width is greater that the distance between entanglements which is typically 40-80{Angstrom}. It is therefore not surprising that polymer interfaces are frequently weak. The most common way to increase the strength or toughness of a polymer interface is to use some specific polymer chains that can connect across the interface. These connecting chains can be formed using one of a number of techniques. Sometimes they are formed in-situ by an interfacial chemical reaction that connects a chain of one of the materials to a chain of the other. Alternatively the connecting chains can be preformed copolymers which are placed at the interface or allowed to diffuse to the interface during processing. The aim of the work presented here is to examine the effects of composition of a P(S{sub f}-MMA{sub 1{minus}f}) copolymer, where f refers to the fraction of PS, on its effectiveness as a coupling agent between PS and PMMA homopolymers. The mechanical results are compared with neutron reflection measurements of the width of the interfaces between the copolymers and the two homopolymers.

  1. Polymer network/carbon layer on monolith support and monolith catalytic reactor

    DOEpatents

    Nordquist, Andrew Francis; Wilhelm, Frederick Carl; Waller, Francis Joseph; Machado, Reinaldo Mario

    2003-08-26

    The present invention relates to an improved monolith catalytic reactor and a monolith support. The improvement in the support resides in a polymer network/carbon coating applied to the surface of a porous substrate and a catalytic metal, preferably a transition metal catalyst applied to the surface of the polymer network/carbon coating. The monolith support has from 100 to 800 cells per square inch and a polymer network/carbon coating with surface area of from 0.1 to 15 m.sup.2 /gram as measured by adsorption of N.sub.2 or Kr using the BET method.

  2. A low-temperature processed environment-friendly full-organic carrier collection layer for polymer solar cells

    SciTech Connect

    Shi, Ai-Li; Li, Yan-Qing E-mail: zhangdd@suda.edu.cn Jiang, Xiao-Chen; Ma, Zhong-Sheng; Wang, Qian-Kun; Guo, Zhen-Yu; Zhang, Dan-Dan E-mail: zhangdd@suda.edu.cn Lee, Shuit-Tong; Tang, Jian-Xin E-mail: zhangdd@suda.edu.cn

    2014-08-04

    We constructed a concept of the full-organic carrier collection layer (CCL) used for polymer solar cells. The CCL is composed of dipyrazino[2,3-f:2′,3′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile as hole collection layer (HCL) and chlorine-free solvents (formic acid (FA)) processed 4,7-Diphenyl-1,10-phenanthroline (Bphen) as electron collection layer, exhibiting good solubility, and environmental protection. The FA based device shows ideal power conversion efficiency (3.75%), which is higher than that of control device (3.6%). Besides, the HCL shows a different mechanism in hole extraction by functioning as a charge recombination zone for electrons injected from anode and holes extracted from the donor materials.

  3. Effects of hydrophobicity of diffusion layer on the electroreduction of biomass derivatives in polymer electrolyte membrane reactors.

    PubMed

    Chen, Wei; He, Gaohong; Ge, Feilong; Xiao, Wu; Benziger, Jay; Wu, Xuemei

    2015-01-01

    For the first time, the hydrophobicity design of a diffusion layer based on the volatility of hydrogenation reactants in aqueous solutions is reported. The hydrophobicity of the diffusion layer greatly influences the hydrogenation performance of two model biomass derivatives, namely, butanone and maleic acid, in polymer electrolyte membrane reactors operated at atmospheric pressure. Hydrophobic carbon paper repels aqueous solutions, but highly volatile butanone can permeate in vapor form and achieve a high hydrogenation rate, whereas, for nonvolatile maleic acid, great mass transfer resistance prevents hydrogenation. With a hydrophilic stainless-steel welded mesh diffusion layer, aqueous solutions of both butanone and maleic acid permeate in liquid form. Hydrogenation of maleic acid reaches a similar level as that of butanone. The maximum reaction rate is 340 nmol cm(-2)  s(-1) for both hydrogenation systems and the current efficiency reaches 70 %. These results are better than those reported in the literature. PMID:25319718

  4. A low-temperature processed environment-friendly full-organic carrier collection layer for polymer solar cells

    NASA Astrophysics Data System (ADS)

    Shi, Ai-Li; Li, Yan-Qing; Jiang, Xiao-Chen; Ma, Zhong-Sheng; Wang, Qian-Kun; Guo, Zhen-Yu; Zhang, Dan-Dan; Lee, Shuit-Tong; Tang, Jian-Xin

    2014-08-01

    We constructed a concept of the full-organic carrier collection layer (CCL) used for polymer solar cells. The CCL is composed of dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile as hole collection layer (HCL) and chlorine-free solvents (formic acid (FA)) processed 4,7-Diphenyl-1,10-phenanthroline (Bphen) as electron collection layer, exhibiting good solubility, and environmental protection. The FA based device shows ideal power conversion efficiency (3.75%), which is higher than that of control device (3.6%). Besides, the HCL shows a different mechanism in hole extraction by functioning as a charge recombination zone for electrons injected from anode and holes extracted from the donor materials.

  5. Effects of hydrophobicity of diffusion layer on the electroreduction of biomass derivatives in polymer electrolyte membrane reactors.

    PubMed

    Chen, Wei; He, Gaohong; Ge, Feilong; Xiao, Wu; Benziger, Jay; Wu, Xuemei

    2015-01-01

    For the first time, the hydrophobicity design of a diffusion layer based on the volatility of hydrogenation reactants in aqueous solutions is reported. The hydrophobicity of the diffusion layer greatly influences the hydrogenation performance of two model biomass derivatives, namely, butanone and maleic acid, in polymer electrolyte membrane reactors operated at atmospheric pressure. Hydrophobic carbon paper repels aqueous solutions, but highly volatile butanone can permeate in vapor form and achieve a high hydrogenation rate, whereas, for nonvolatile maleic acid, great mass transfer resistance prevents hydrogenation. With a hydrophilic stainless-steel welded mesh diffusion layer, aqueous solutions of both butanone and maleic acid permeate in liquid form. Hydrogenation of maleic acid reaches a similar level as that of butanone. The maximum reaction rate is 340 nmol cm(-2)  s(-1) for both hydrogenation systems and the current efficiency reaches 70 %. These results are better than those reported in the literature.

  6. Conformal organic-inorganic hybrid network polymer thin films by molecular layer deposition using trimethylaluminum and glycidol.

    PubMed

    Gong, Bo; Peng, Qing; Parsons, Gregory N

    2011-05-19

    Growing interest in nanoscale organic-inorganic hybrid network polymer materials is driving exploration of new bulk and thin film synthesis reaction mechanisms. Molecular layer deposition (MLD) is a vapor-phase deposition process, based on atomic layer deposition (ALD) which proceeds by exposing a surface to an alternating sequence of two or more reactant species, where each surface half-reaction goes to completion before the next reactant exposure. This work describes film growth using trimethyl aluminum and heterobifunctional glycidol at moderate temperatures (90-150 °C), producing a relatively stable organic-inorganic network polymer of the form (-Al-O-(C(4)H(8))-O-)(n). Film growth rate and in situ reaction analysis indicate that film growth does not initially follow a steady-state rate, but increases rapidly during early film growth. The mechanism is consistent with subsurface species transport and trapping, previously documented during MLD and ALD on polymers. A water exposure step after the TMA produces a more linear growth rate, likely by blocking TMA subsurface diffusion. Uniform and conformal films are formed on complex nonplanar substrates. Upon postdeposition annealing, films transform into microporous metal oxides with ∼5 Å pore size and surface area as high as ∼327 m(2)/g, and the resulting structures duplicate the shape of the original substrate. These hybrid films and porous materials could find uses in several research fields including gas separations and diffusion barriers, biomedical scaffolds, high surface area coatings, and others.

  7. Phase Diagram and Transformations of Iron Pentacarbonyl to nm Layered Hematite and Carbon-Oxygen Polymer under Pressure

    PubMed Central

    Ryu, Young Jay; Kim, Minseob; Yoo, Choong-Shik

    2015-01-01

    We present the phase diagram of Fe(CO)5, consisting of three molecular polymorphs (phase I, II and III) and an extended polymeric phase that can be recovered at ambient condition. The phase diagram indicates a limited stability of Fe(CO)5 within a pressure-temperature dome formed below the liquid- phase II- polymer triple point at 4.2 GPa and 580 K. The limited stability, in turn, signifies the temperature-induced weakening of Fe-CO back bonds, which eventually leads to the dissociation of Fe-CO at the onset of the polymerization of CO. The recovered polymer is a composite of novel nm-lamellar layers of crystalline hematite Fe2O3 and amorphous carbon-oxygen polymers. These results, therefore, demonstrate the synthesis of carbon-oxygen polymer by compressing Fe(CO)5, which advocates a novel synthetic route to develop atomistic composite materials by compressing organometallic compounds. PMID:26456761

  8. Phase diagram and transformations of iron pentacarbonyl to nm layered hematite and carbon-oxygen polymer under pressure

    DOE PAGES

    Ryu, Young Jay; Kim, Minseob; Yoo, Choong -Shik

    2015-10-12

    In this study, we present the phase diagram of Fe(CO)5, consisting of three molecular polymorphs (phase I, II and III) and an extended polymeric phase that can be recovered at ambient condition. The phase diagram indicates a limited stability of Fe(CO)5 within a pressure-temperature dome formed below the liquid- phase II- polymer triple point at 4.2 GPa and 580 K. The limited stability, in turn, signifies the temperature-induced weakening of Fe-CO back bonds, which eventually leads to the dissociation of Fe-CO at the onset of the polymerization of CO. The recovered polymer is a composite of novel nm-lamellar layers ofmore » crystalline hematite Fe2O3 and amorphous carbon-oxygen polymers. These results, therefore, demonstrate the synthesis of carbon-oxygen polymer by compressing Fe(CO)5, which advocates a novel synthetic route to develop atomistic composite materials by compressing organometallic compounds.« less

  9. Phase diagram and transformations of iron pentacarbonyl to nm layered hematite and carbon-oxygen polymer under pressure

    SciTech Connect

    Ryu, Young Jay; Kim, Minseob; Yoo, Choong -Shik

    2015-10-12

    In this study, we present the phase diagram of Fe(CO)5, consisting of three molecular polymorphs (phase I, II and III) and an extended polymeric phase that can be recovered at ambient condition. The phase diagram indicates a limited stability of Fe(CO)5 within a pressure-temperature dome formed below the liquid- phase II- polymer triple point at 4.2 GPa and 580 K. The limited stability, in turn, signifies the temperature-induced weakening of Fe-CO back bonds, which eventually leads to the dissociation of Fe-CO at the onset of the polymerization of CO. The recovered polymer is a composite of novel nm-lamellar layers of crystalline hematite Fe2O3 and amorphous carbon-oxygen polymers. These results, therefore, demonstrate the synthesis of carbon-oxygen polymer by compressing Fe(CO)5, which advocates a novel synthetic route to develop atomistic composite materials by compressing organometallic compounds.

  10. Submicroporous/microporous and compatible/incompatible multi-functional dual-layer polymer electrolytes and their interfacial characteristics with lithium metal anode

    NASA Astrophysics Data System (ADS)

    Lee, Young-Gi; Kyhm, Kwangseuk; Choi, Nam-Soon; Ryu, Kwang Sun

    A novel multi-functional dual-layer polymer electrolyte was prepared by impregnating the interconnected pores with an ethylene carbonate (EC)/dimethyl carbonate (DMC)/lithium hexafluorophosphate (LiPF 6) solution. An incompatible layer is based on a microporous polyethylene (PE) and a compatible layer, based on a poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) is sub-microporous and compatible with an electrolyte solution. The Li electrode/the dual-layer polymer electrolyte/Li[Ni 0.15Li 0.23M n0.62]O 2 cell showed stable cycle performance under prolonged cycle number. This behavior is due to the enhanced compatibility between the matrix polymer and the liquid electrolytes within the submicroporous compatible layer, which could lead to a controlled Li + deposition on the Li anode surface by forming homegeneous electrolyte zone near the anode.

  11. Layer-by-Layer Assembly of Metal-Organic Frameworks in Macroporous Polymer Monolith and Their Use for Enzyme Immobilization.

    PubMed

    Wen, Liyin; Gao, Aicong; Cao, Yao; Svec, Frantisek; Tan, Tianwei; Lv, Yongqin

    2016-03-01

    New monolithic materials comprising zeolitic imidazolate framework (ZIF-8) located on the pore surface of poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith previously functionalized with N-(3-aminopropyl)-imidazole have been prepared via a layer-by-layer self-assembly strategy. These new ZIF-8@monolith hybrids are used as solid-phase carriers for enzyme immobilization. Their performance is demonstrated with immobilization of a model proteolytic enzyme trypsin. The best of the conjugates enable very efficient digestion of proteins that can be achieved in mere 43 s. PMID:26806691

  12. Layer-by-Layer Assembly of Metal-Organic Frameworks in Macroporous Polymer Monolith and Their Use for Enzyme Immobilization.

    PubMed

    Wen, Liyin; Gao, Aicong; Cao, Yao; Svec, Frantisek; Tan, Tianwei; Lv, Yongqin

    2016-03-01

    New monolithic materials comprising zeolitic imidazolate framework (ZIF-8) located on the pore surface of poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith previously functionalized with N-(3-aminopropyl)-imidazole have been prepared via a layer-by-layer self-assembly strategy. These new ZIF-8@monolith hybrids are used as solid-phase carriers for enzyme immobilization. Their performance is demonstrated with immobilization of a model proteolytic enzyme trypsin. The best of the conjugates enable very efficient digestion of proteins that can be achieved in mere 43 s.

  13. Molecular layer deposition of aluminum alkoxide polymer films using trimethylaluminum and glycidol.

    PubMed

    Lee, Younghee; Yoon, Byunghoon; Cavanagh, Andrew S; George, Steven M

    2011-12-20

    Molecular layer deposition (MLD) of aluminum alkoxide polymer films was examined using trimethlyaluminum (TMA) and glycidol (GLY) as the reactants. Glycidol is a high vapor pressure heterobifunctional reactant with both hydroxyl and epoxy chemical functionalites. These two different functionalities help avoid "double reactions" that are common with homobifuctional reactants. A variety of techniques, including in situ Fourier transform infrared (FTIR) spectroscopy and quartz crystal microbalance (QCM) measurements, were employed to study the film growth. FTIR measurements at 100 and 125 °C observed the selective reaction of the GLY hydroxyl group with the AlCH(3) surface species during GLY exposure. Epoxy ring-opening and methyl transfer from TMA to the surface epoxy species were then monitored during TMA exposure. This epoxy ring-opening reaction is dependent on strong Lewis acid-base interactions between aluminum and oxygen. The QCM experiments observed linear growth with self-limiting surface reactions at 100-175 °C under certain growth conditions. With a sufficient purge time of 20 s after TMA and GLY exposures at 125 °C, the mass gain per cycle (MGPC) was 19.8 ng/cm(2)-cycle. The individual mass gains after the TMA and GLY exposures were also consistent with a TMA/GLY stoichiometry of 4:3 in the MLD film. This TMA/GLY stoichiometry suggests the presence of Al(2)O(2) dimeric core species. The MLD films resulting from these TMA and GLY exposures also evolved with annealing temperature to form thinner conformal porous films with increased density. Non-self-limiting growth was a problem at shorter purge times and lower temperatures. With shorter purge times of 10 s at 125 °C, the MPGC increased dramatically to 134 ng/cm(2)-cycle. The individual mass gains after the TMA and GLY exposures in the CVD regime were consistent with a TMA/GLY stoichiometry of 1:1. The MGPC decreased progressively versus purge time. This behavior was attributed to the removal of

  14. Layer-by-layer self-assembled osmium polymer-mediated laccase oxygen cathodes for biofuel cells: the role of hydrogen peroxide.

    PubMed

    Scodeller, Pablo; Carballo, Romina; Szamocki, Rafael; Levin, Laura; Forchiassin, Flavia; Calvo, Ernesto J

    2010-08-18

    High potential purified Trametes trogii laccase has been studied as a biocatalyst for oxygen cathodes composed of layer-by-layer self-assembled thin films by sequential immersion of mercaptopropane sulfonate-modified Au electrode surfaces in solutions containing laccase and osmium-complex bound to poly(allylamine), (PAH-Os). The polycation backbone carries the Os redox relay, and the polyanion is the enzyme adsorbed from a solution of a suitable pH so that the protein carries a net negative charge. Enzyme thin films were characterized by quartz crystal microbalance, ellipsometry, cyclic voltammetry, and oxygen reduction electrocatalysis under variable oxygen partial pressures with a rotating disk electrode. New kinetic evidence relevant to biofuel cells is presented on the detection of traces of H(2)O(2), intermediate in the O(2) reduction, with scanning electrochemical microscopy (SECM). Furthermore the inhibitory effect of peroxide on the biocatalytic current resulted in abnormal current dependence on the O(2) partial pressure and peak shape with hysteresis in the polarization curves under stagnant conditions, which is offset upon stirring with the RDE. The new kinetic evidence reported in the present work is very relevant for the operation of biofuel cells under stagnant conditions of O(2) mass transport.

  15. Impact of micro-porous layer on liquid water distribution at the catalyst layer interface and cell performance in a polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Tabe, Yutaka; Aoyama, Yusuke; Kadowaki, Kazumasa; Suzuki, Kengo; Chikahisa, Takemi

    2015-08-01

    In polymer electrolyte membrane fuel cells, a gas diffusion layer (GDL) with a micro-porous layer (MPL) gives better anti-flooding performance than GDLs without an MPL. To investigate the function and mechanism of the MPL to suppress water flooding, the liquid water distribution at the cathode catalyst layer (CL) surface are observed by a freezing method; in the method liquid water is immobilized in ice form by rapid freezing, followed by disassembling the cell for observations. The ice covered area is quantified by image processing and cells with and without an MPL are compared. The results show that the MPL suppresses water accumulation at the interface due to smaller pore size and finer contact with the CL, and this results in less water flooding. Investigation of ice formed after -10 °C cold start shutdowns and the temporary performance deterioration at ordinary temperatures also indicates a significant influence of the liquid water accumulating at the interface. The importance of the fine contact between CL and MPL, the relative absence of gaps, is demonstrated by a gas diffusion electrode (GDE) which is directly coated with catalyst ink on the surface of the MPL achieving finer contact of the layers.

  16. Electron transport through a diazonium-based initiator layer to covalently attached polymer brushes of ferrocenylmethyl methacrylate.

    PubMed

    Lillethorup, Mie; Torbensen, Kristian; Ceccato, Marcel; Pedersen, Steen Uttrup; Daasbjerg, Kim

    2013-11-01

    A versatile method based on electrografting of aryldiazonium salts was used to introduce covalently attached initiators for atom transfer radical polymerization (ATRP) on glassy carbon surfaces. Polymer brushes of ferrocenylmethyl methacrylate were prepared from the surface-attached initiators, and these films were thoroughly analyzed using various techniques, including X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IRRAS), ellipsometry, and electrochemistry. Of particular interest was the electrochemical characterization of the electron transfer through the diazonium-based initiator layer to the redox centers in the polymer brush films. It was found that the apparent rate constant of electron transfer decreases exponentially with the dry-state thickness of this layer. To investigate the electron transfer in the brushes themselves, scanning electrochemical microscopy (SECM) was applied, thereby allowing the effect from the initiator layer to be excluded. The unusual transition feature of the approach curves recorded suggests that an initial fast charge transfer to the outermost-situated ferrocenyl groups is followed by a slower electron transport involving the neighboring redox units. PMID:24144237

  17. Determination of Optimal Parameters for Dual-Layer Cathode of Polymer Electrolyte Fuel Cell Using Computational Intelligence-Aided Design

    PubMed Central

    Chen, Yi; Huang, Weina; Peng, Bei

    2014-01-01

    Because of the demands for sustainable and renewable energy, fuel cells have become increasingly popular, particularly the polymer electrolyte fuel cell (PEFC). Among the various components, the cathode plays a key role in the operation of a PEFC. In this study, a quantitative dual-layer cathode model was proposed for determining the optimal parameters that minimize the over-potential difference and improve the efficiency using a newly developed bat swarm algorithm with a variable population embedded in the computational intelligence-aided design. The simulation results were in agreement with previously reported results, suggesting that the proposed technique has potential applications for automating and optimizing the design of PEFCs. PMID:25490761

  18. Investigation of gas diffusion layer compression by electrochemical impedance spectroscopy on running polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Dotelli, Giovanni; Omati, Luca; Gallo Stampino, Paola; Grassini, Paolo; Brivio, Davide

    Two gas diffusion layers based on the same carbon cloth substrate, produced by an Italian Company (SAATI), and coated with microporous layers of different hydrophobicities, were assembled in a polymer electrolyte membrane fuel cell and its performances assessed. For comparison the cell mounting the carbon cloth without microporous layer was also tested. The membrane electrode assembly was made of Nafion ® 212 with Pt load 0.3/0.6 mg cm -2 (anode/cathode). The cell testing was run at 60 °C and 80 °C with fully humidified air (100%RH) and 80%RH hydrogen feedings. The assembly of gas diffusion layers and membrane with electrodes was compressed to 30% and 50% of its initial thickness. For each configuration polarization and power curves were recorded; in order to evaluate the role of different GDLs, AC impedance spectroscopy of the running cell was also performed. The higher compression ratio caused the worsening of cell performances, partially mitigated when the operating temperature was raised to 80 °C. The presence of the microporous layer onto the carbon cloth resulted extremely beneficial for the operations especially at high current density; moreover, it sensibly reduces the high frequency resistance of the overall assembly.

  19. Tailoring dispersion and aggregation of Au nanoparticles in the BHJ layer of polymer solar cells: plasmon effects versus electrical effects.

    PubMed

    Kim, Wanjung; Cha, Bong Geun; Kim, Jung Kyu; Kang, Woonggi; Kim, Eunchul; Ahn, Tae Kyu; Wang, Dong Hwan; Du, Qing Guo; Cho, Jeong Ho; Kim, Jaeyun; Park, Jong Hyeok

    2014-12-01

    Plasmonic effects that arise from embedding metallic nanoparticles (NPs) in polymer solar cells (PSCs) have been extensively studied. Many researchers have utilized metallic NPs in PSCs by either incorporating them into the PSC interlayers (e.g., the hole extraction and electron extraction layers) or blending them into the bulk heterojunction (BHJ) active layer. In such studies, the dispersity of the metallic NPs in each layer may vary due to both the different nature of the ligands and the amount of ligands on the metallic NPs. This in turn can produce different PSC performance parameters. Here, we systematically control the amount of attached organic ligands on Au NPs to control their dispersion behavior in the BHJ active layer of PSCs. By controlling the number of capping organic ligands on the Au NPs, the dispersity of the NPs in the BHJ layer is also controlled and the positive effects (particularly the plasmonic and electrical effects) of the Au NPs in the PSCs are investigated. From the obtained results, we find that the electrical contribution of the Au NPs is a more dominant factor for enhancing cell efficiency when compared to the plasmonic effect.

  20. Photovoltaic response and values of state dipole moments in single-layered pyrazoloquinoline/polymer composites

    NASA Astrophysics Data System (ADS)

    Gondek, E.; Kityk, I. V.; Danel, A.; Sanetra, J.

    2008-06-01

    We report the photovoltaic response of composite films formed by polymer transport matrices poly(3-octylthiophene) (P3OT) and poly(3-decylthiophene) (PDT) with incorporated 1 H-pyrazolo[3,4- b]quinoline (PAQ) chromophore (see the first figure). The photovoltage (PV) data were obtained for different substituted PAQ possessing different state dipole moments. The photovoltaic cells were formed between ITO and aluminum electrodes. We found that the PV signal of polymer/PAQ substantially depends on the state dipole moments of the pyrazoloquinoline chromophore. This fact indicates on a possibility of significant enhancement of PV efficiency by appropriate variations of the state dipole moments of chromophore. This results in photoinduced electron transfer from polymer serving as donors to PAQ being the electron acceptor. Despite an efficiency of the PV devices is below 1%, however, it may be substantially enhanced in future varying the chromophore state dipole moments appropriately.

  1. Impact of compression on gas transport in non-woven gas diffusion layers of high temperature polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Froning, Dieter; Yu, Junliang; Gaiselmann, Gerd; Reimer, Uwe; Manke, Ingo; Schmidt, Volker; Lehnert, Werner

    2016-06-01

    Gas transport in non-woven gas diffusion layers of a high-temperature polymer electrolyte fuel cell was calculated with the Lattice Boltzmann method. The underlying micro structure was taken from two sources. A real micro structure was analyzed in the synchrotron under the impact of a compression mask mimicking the channel/rib structure of a flow field. Furthermore a stochastic geometry model based on synchrotron X-ray tomography studies was applied. The effect of compression is included in the stochastic model. Gas transport in these micro structures was simulated and the impact of compression was analyzed. Fiber bundles overlaying the micro structure were identified which affect the homogeneity of the gas flow. There are significant deviations between the impact of compression on effective material properties for this type of gas diffusion layers and the Kozeny-Carman equation.

  2. Gas diffusion layers coated with a microporous layer containing hydrophilic carbon nanotubes for performance enhancement of polymer electrolyte fuel cells under both low and high humidity conditions

    NASA Astrophysics Data System (ADS)

    Kitahara, Tatsumi; Nakajima, Hironori; Okamura, Kosuke

    2015-06-01

    Gas diffusion layers (GDLs) coated with a hydrophobic microporous layer (MPL) composed of carbon black and polytetrafluoroethylene (PTFE) have been commonly used to improve the water management characteristics of polymer electrolyte fuel cells (PEFCs). However, the hydrophobic MPL coated GDL designed to prevent dehydration of the membrane under low humidity conditions is generally inferior at reducing flooding under high humidity conditions. It is therefore important to develop a robust MPL coated GDL that can enhance the PEFC performance regardless of the humidity conditions. In the present study, a GDL coated with an MPL containing hydrophilic carbon nanotubes (CNTs) was developed. The less hydrophobic pores incorporating CNTs are effective at conserving the membrane humidity under low humidity conditions. The MPL with CNTs is also effective at expelling excess water from the catalyst layer while maintaining oxygen flow pathways from the GDL substrate, allowing the mean flow pore diameter to be decreased to 2 μm without reducing the ability of the MPL to prevent flooding under high humidity conditions. An MPL coated GDL with a CNT content of 4 mass% exhibits significantly higher performance under both low and high humidity conditions than a hydrophobic MPL coated GDL.

  3. Morphology and Transport Properties of Novel Polymer Nanocomposites Resulted from Melt Processing of Polyvinylacetate Substrates Coated with Layer-by-Layer Assemblies

    NASA Astrophysics Data System (ADS)

    Soltani, Iman; Spontak, Richard J.

    Novel polymer nanocomposites (PNCs) were processed through layer-by-layer (LBL) deposition of clay and polyethylene terephthalate ionomer layers on polyvinylacetate (PVAc) substrates, followed by repetitive melt pressing of coated samples to crush LBL assemblies into the polymeric matrix. The increase in the clay content in resulted PNCs prepared through similar LBL coatings, relative to previously studied hydrophobic polystyrene-based nanocomposites, postulated superiority of PVAc, with relatively higher hydrophilicity, to interact with LBL assemblies. Also, these PNCs showed relatively good barrier improvement against transport of oxygen and carbon dioxide gases, proposing the scavenging effect of LBL assemblies crushed portions as highly tortuous labyrinths with high aspect ratios, comprising edge-edge flocculated exfoliated clay platelets, observed through transmission electron micrographs. However, combinative morphological investigations through optical microscopy, x-ray diffractometry, and transmission electron microscopy proposed low global dispersion of clay throughout polymeric matrix, conjecturing insufficient intensity of stress applied through cyclic melt pressing, and/or slight thermal degradation of samples via extended times of processing at high temperatures.

  4. Device performance and lifetime of polymer:fullerene solar cells with UV-ozone-irradiated hole-collecting buffer layers.

    PubMed

    Lee, Seungsoo; Nam, Sungho; Lee, Hyena; Kim, Hwajeong; Kim, Youngkyoo

    2011-11-18

    We report the influence of UV-ozone irradiation of the hole-collecting buffer layers on the performance and lifetime of polymer:fullerene solar cells. UV-ozone irradiation was targeted at the surface of the poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) layers by varying the irradiation time up to 600 s. The change of the surface characteristics in the PEDOT:PSS after UV-ozone irradiation was measured by employing optical absorption spectroscopy, photoelectron yield spectroscopy, and contact angle measurements, while Raman and X-ray photoelectron spectroscopy techniques were introduced for more microscopic analysis. Results showed that the UV-ozone irradiation changed the chemical structure/composition of the surface of the PEDOT:PSS layers leading to the gradual increase of ionization potential with irradiation time in the presence of up-and-down variations in the contact angle (polarity). This surface property change was attributed to the formation of oxidative components, as evidenced by XPS and Auger electron images, which affected the sheet resistance of the PEDOT:PSS layers. Interestingly, device performance was slightly improved by short irradiation (up to 10 s), whereas it was gradually decreased by further irradiation. The short-duration illumination test showed that the lifetime of solar cells with the UV-ozone irradiated PEDOT:PSS layer was improved due to the protective role of the oxidative components formed upon UV-ozone irradiation against the attack of sulfonic acid groups in the PEDOT:PSS layer to the active layer.

  5. Device performance and lifetime of polymer:fullerene solar cells with UV-ozone-irradiated hole-collecting buffer layers.

    PubMed

    Lee, Seungsoo; Nam, Sungho; Lee, Hyena; Kim, Hwajeong; Kim, Youngkyoo

    2011-11-18

    We report the influence of UV-ozone irradiation of the hole-collecting buffer layers on the performance and lifetime of polymer:fullerene solar cells. UV-ozone irradiation was targeted at the surface of the poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) layers by varying the irradiation time up to 600 s. The change of the surface characteristics in the PEDOT:PSS after UV-ozone irradiation was measured by employing optical absorption spectroscopy, photoelectron yield spectroscopy, and contact angle measurements, while Raman and X-ray photoelectron spectroscopy techniques were introduced for more microscopic analysis. Results showed that the UV-ozone irradiation changed the chemical structure/composition of the surface of the PEDOT:PSS layers leading to the gradual increase of ionization potential with irradiation time in the presence of up-and-down variations in the contact angle (polarity). This surface property change was attributed to the formation of oxidative components, as evidenced by XPS and Auger electron images, which affected the sheet resistance of the PEDOT:PSS layers. Interestingly, device performance was slightly improved by short irradiation (up to 10 s), whereas it was gradually decreased by further irradiation. The short-duration illumination test showed that the lifetime of solar cells with the UV-ozone irradiated PEDOT:PSS layer was improved due to the protective role of the oxidative components formed upon UV-ozone irradiation against the attack of sulfonic acid groups in the PEDOT:PSS layer to the active layer. PMID:22038984

  6. Polymer composite electrolytes having core-shell silica fillers with anion-trapping boron moiety in the shell layer for all-solid-state lithium-ion batteries.

    PubMed

    Shim, Jimin; Kim, Dong-Gyun; Kim, Hee Joong; Lee, Jin Hong; Lee, Jong-Chan

    2015-04-15

    Core-shell silica particles with ion-conducting poly(ethylene glycol) and anion-trapping boron moiety in the shell layer were prepared to be used as fillers for polymer composite electrolytes based on organic/inorganic hybrid branched copolymer as polymer matrix for all-solid-state lithium-ion battery applications. The core-shell silica particles were found to improve mechanical strength and thermal stability of the polymer matrix and poly(ethylene glycol) and boron moiety in the shell layer increase compatibility between filler and polymer matrix. Furthermore, boron moiety in the shell layer increases both ionic conductivity and lithium transference number of the polymer matrix because lithium salt can be more easily dissociated by the anion-trapping boron. Interfacial compatibility with lithium metal anode is also improved because well-dispersed silica particles serve as protective layer against interfacial side reactions. As a result, all-solid-state battery performance was found to be enhanced when the copolymer having core-shell silica particles with the boron moiety was used as solid polymer electrolyte.

  7. Epitaxial Growth of Thin Ferroelectric Polymer Films on Graphene Layer for Fully Transparent and Flexible Nonvolatile Memory.

    PubMed

    Kim, Kang Lib; Lee, Wonho; Hwang, Sun Kak; Joo, Se Hun; Cho, Suk Man; Song, Giyoung; Cho, Sung Hwan; Jeong, Beomjin; Hwang, Ihn; Ahn, Jong-Hyun; Yu, Young-Jun; Shin, Tae Joo; Kwak, Sang Kyu; Kang, Seok Ju; Park, Cheolmin

    2016-01-13

    Enhancing the device performance of organic memory devices while providing high optical transparency and mechanical flexibility requires an optimized combination of functional materials and smart device architecture design. However, it remains a great challenge to realize fully functional transparent and mechanically durable nonvolatile memory because of the limitations of conventional rigid, opaque metal electrodes. Here, we demonstrate ferroelectric nonvolatile memory devices that use graphene electrodes as the epitaxial growth substrate for crystalline poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE) polymer. The strong crystallographic interaction between PVDF-TrFE and graphene results in the orientation of the crystals with distinct symmetry, which is favorable for polarization switching upon the electric field. The epitaxial growth of PVDF-TrFE on a graphene layer thus provides excellent ferroelectric performance with high remnant polarization in metal/ferroelectric polymer/metal devices. Furthermore, a fully transparent and flexible array of ferroelectric field effect transistors was successfully realized by adopting transparent poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] semiconducting polymer.

  8. Polymer ferroelectric field-effect memory device with SnO channel layer exhibits record hole mobility

    PubMed Central

    Caraveo-Frescas, J. A.; Khan, M. A.; Alshareef, H. N.

    2014-01-01

    Here we report for the first time a hybrid p-channel polymer ferroelectric field-effect transistor memory device with record mobility. The memory device, fabricated at 200°C on both plastic polyimide and glass substrates, uses ferroelectric polymer P(VDF-TrFE) as the gate dielectric and transparent p-type oxide (SnO) as the active channel layer. A record mobility of 3.3 cm2V−1s−1, large memory window (∼16 V), low read voltages (∼−1 V), and excellent retention characteristics up to 5000 sec have been achieved. The mobility achieved in our devices is over 10 times higher than previously reported polymer ferroelectric field-effect transistor memory with p-type channel. This demonstration opens the door for the development of non-volatile memory devices based on dual channel for emerging transparent and flexible electronic devices. PMID:24912617

  9. Electric double-layer capacitors with tea waste derived activated carbon electrodes and plastic crystal based flexible gel polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Suleman, M.; Deraman, M.; Othman, M. A. R.; Omar, R.; Hashim, M. A.; Basri, N. H.; Nor, N. S. M.; Dolah, B. N. M.; Hanappi, M. F. Y. M.; Hamdan, E.; Sazali, N. E. S.; Tajuddin, N. S. M.; Jasni, M. R. M.

    2016-08-01

    We report a novel configuration of symmetrical electric double-layer capacitors (EDLCs) comprising a plastic crystalline succinonitrile (SN) based flexible polymer gel electrolyte, incorporated with sodium trifluoromethane sulfonate (NaTf) immobilised in a host polymer poly (vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP). The cost-effective activated carbon powder possessing a specific surface area (SSA) of ~ 1700 m2g-1 containing a large proportion of meso-porosity has been derived from tea waste to use as supercapacitor electrodes. The high ionic conductivity (~3.6×10-3 S cm-1 at room temperature) and good electrochemical stability render the gel polymer electrolyte film a suitable candidate for the fabrication of EDLCs. The performance of the EDLCs has been tested by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge-discharge studies. The performance of the EDLC cell is found to be promising in terms of high values of specific capacitance (~270 F g-1), specific energy (~ 36 Wh kg-1), and power density (~ 33 kW kg-1).

  10. Unprecedented layered coordination polymers of dithiolene group 10 metals: magnetic and electrical properties.

    PubMed

    Delgado, Esther; Gómez-García, Carlos J; Hernández, Diego; Hernández, Elisa; Martín, Avelino; Zamora, Félix

    2016-04-21

    One-pot reactions between Ni(ii), Pd(ii) or Pt(ii) salts and 3,6-dichloro-1,2-benzenedithiol (HSC6H2Cl2SH) in KOH medium under argon lead to a series of bis-dithiolene coordination polymers. X-ray analysis shows the presence of a common square planar complex [M(SC6H2Cl2S)2](2-) linked to potassium cations forming either a two-dimensional coordination polymer network for {[K2(μ-H2O)2(μ-thf)(thf)2][M(SC6H2Cl2S)2]}n [M = Ni () and Pd ()] or a one-dimensional coordination polymer for {[K2(μ-H2O)2(thf)6][Pt(SC6H2Cl2S)2]}n (). In the coordination environment of the potassium ions may slightly change leading to the two-dimensional coordination polymer {[K2(μ-H2O)(μ-thf)2][Pt(SC6H2Cl2S)2]}n () that crystallizes together with . The physical characterization of compounds show similar trends, they are diamagnetic and behave as semiconductors. PMID:26974399

  11. Evidence that the N-terminal part of the S-layer protein from Bacillus stearothermophilus PV72/p2 recognizes a secondary cell wall polymer.

    PubMed Central

    Ries, W; Hotzy, C; Schocher, I; Sleytr, U B; Sára, M

    1997-01-01

    The S-layer of Bacillus stearothermophilus PV72/p2 shows oblique lattice symmetry and is composed of identical protein subunits with a molecular weight of 97,000. The isolated S-layer subunits could bind and recrystallize into the oblique lattice on native peptidoglycan-containing sacculi which consist of peptidoglycan of the A1gamma chemotype and a secondary cell wall polymer with an estimated molecular weight of 24,000. The secondary cell wall polymer could be completely extracted from peptidoglycan-containing sacculi with 48% HF, indicating the presence of phosphodiester linkages between the polymer chains and the peptidoglycan backbone. The cell wall polymer was composed mainly of GlcNAc and ManNAc in a molar ratio of 4:1, constituted about 20% of the peptidoglycan-containing sacculus dry weight, and was also detected in the fraction of the S-layer self-assembly products. Extraction experiments and recrystallization of the whole S-layer protein and proteolytic cleavage fragments confirmed that the secondary cell wall polymer is responsible for anchoring the S-layer subunits by the N-terminal part to the peptidoglycan-containing sacculi. In addition to this binding function, the cell wall polymer was found to influence the in vitro self-assembly of the guanidinium hydrochloride-extracted S-layer protein. Chemical modification studies further showed that the secondary cell wall polymer does not contribute significant free amino or carboxylate groups to the peptidoglycan-containing sacculi. PMID:9190804

  12. Evidence that the N-terminal part of the S-layer protein from Bacillus stearothermophilus PV72/p2 recognizes a secondary cell wall polymer.

    PubMed

    Ries, W; Hotzy, C; Schocher, I; Sleytr, U B; Sára, M

    1997-06-01

    The S-layer of Bacillus stearothermophilus PV72/p2 shows oblique lattice symmetry and is composed of identical protein subunits with a molecular weight of 97,000. The isolated S-layer subunits could bind and recrystallize into the oblique lattice on native peptidoglycan-containing sacculi which consist of peptidoglycan of the A1gamma chemotype and a secondary cell wall polymer with an estimated molecular weight of 24,000. The secondary cell wall polymer could be completely extracted from peptidoglycan-containing sacculi with 48% HF, indicating the presence of phosphodiester linkages between the polymer chains and the peptidoglycan backbone. The cell wall polymer was composed mainly of GlcNAc and ManNAc in a molar ratio of 4:1, constituted about 20% of the peptidoglycan-containing sacculus dry weight, and was also detected in the fraction of the S-layer self-assembly products. Extraction experiments and recrystallization of the whole S-layer protein and proteolytic cleavage fragments confirmed that the secondary cell wall polymer is responsible for anchoring the S-layer subunits by the N-terminal part to the peptidoglycan-containing sacculi. In addition to this binding function, the cell wall polymer was found to influence the in vitro self-assembly of the guanidinium hydrochloride-extracted S-layer protein. Chemical modification studies further showed that the secondary cell wall polymer does not contribute significant free amino or carboxylate groups to the peptidoglycan-containing sacculi. PMID:9190804

  13. Bifunctional Polymer Nanocomposites as Hole-Transport Layers for Efficient Light Harvesting: Application to Perovskite Solar Cells.

    PubMed

    Wang, Jhong-Yao; Hsu, Fang-Chi; Huang, Jeng-Yeh; Wang, Leeyih; Chen, Yang-Fang

    2015-12-23

    A new approach to largely enhancing light harvesting of solar cells by employing bifunctional polymer nanocomposites as hole-transport layers (HTLs) is proposed. To illustrate our working principle, CH3NH3PbI3-xClx perovskite solar cells are used as examples. Gold nanoparticles (Au-NPs) are added into a conjugated poly(3-hexylthiophene-2,5-diyl) (P3HT) matrix, resulting in a ∼4-fold enhancement in the electrical conductivity and carrier mobility of the native P3HT film. The improved electrical properties are attributed to enhanced polymer chain ordering caused by Au-NPs. By integration of those P3HT:Au-NP films with an optimum loading concentration of 20% into perovskite solar cells as HTLs, this leads to a more than 25% enhancement in the power conversion efficiency (PCE) compared with that of the NP-free one. In addition to the modulated electrical properties of the HTL, the improved performance can also be attributed to the scattering effect from the incorporated Au-NPs, which effectively extends the optical pathway to amplify photon absorption of the photoactive layer. The design principle shown here can be generalized to other organic materials as well, which should be very useful for the further development of high-performance optoelectronic devices.

  14. Highly Crystalline Low Band Gap Polymer Based on Thieno[3,4-c]pyrrole-4,6-dione for High-Performance Polymer Solar Cells with a >400 nm Thick Active Layer.

    PubMed

    Jung, Jae Woong; Russell, Thomas P; Jo, Won Ho

    2015-06-24

    Two thieno[3,4-c]pyrrole-4,6-dione (TPD)-based copolymers combined with 2,2'-bithiophene (BT) or (E)-2-(2-(thiophen-2-yl)vinyl)thiophene (TV) have been designed and synthesized to investigate the effect of the introduction of a vinylene group in the polymer backbone on the optical, electrochemical, and photovoltaic properties of the polymers. Although both polymers have shown similar optical band gaps and frontier energy levels, regardless of the introduction of vinylene bridge, the introduction of a π-extended vinylene group in the polymer backbone substantially enhances the charge transport characteristics of the resulting polymer due to its strong tendency to self-assemble and thus to enhance the crystallinity. An analysis on charge recombination in the active layer of a solar cell device indicates that the outstanding charge transport (μ = 1.90 cm(2)·V(-1)·s(-1)) of PTVTPD with a vinylene group effectively suppresses the bimolecular recombination, leading to a high power conversion efficiency (PCE) up to 7.16%, which is 20% higher than that (5.98%) of the counterpart polymer without a vinylene group (PBTTPD). More importantly, PTVTPD-based devices do not show a large variation of photovoltaic performance with the active layer thickness; that is, the PCE remains at 6% as the active layer thickness increases up to 450 nm, demonstrating that the PTVTPD-based solar cell is very compatible with industrial processing.

  15. Development of advanced catalytic layer based on vertically aligned conductive polymer arrays for thin-film fuel cell electrodes

    NASA Astrophysics Data System (ADS)

    Jiang, Shangfeng; Yi, Baolian; Cao, Longsheng; Song, Wei; Zhao, Qing; Yu, Hongmei; Shao, Zhigang

    2016-10-01

    The degradation of carbon supports significantly influences the performance of proton exchange membrane fuel cells (PEMFCs), particularly in the cathode, which must be overcome for the wide application of fuel cells. In this study, advanced catalytic layer with electronic conductive polymer-polypyrrole (PPy) nanowire as ordered catalyst supports for PEMFCs is prepared. A platinum-palladium (PtPd) catalyst thin layer with whiskerette shapes forms along the long axis of the PPy nanowires. The resulting arrays are hot-pressed on both sides of a Nafion® membrane to construct a membrane electrode assembly (without additional ionomer). The ordered thin catalyst layer (approximately 1.1 μm) is applied in a single cell as the anode and the cathode without additional Nafion® ionomer. The single cell yields a maximum performance of 762.1 mW cm-2 with a low Pt loading (0.241 mg Pt cm-2, anode + cathode). The advanced catalyst layer indicates better mass transfer in high current density than that of commercial Pt/C-based electrode. The mass activity is 1.08-fold greater than that of DOE 2017 target. Thus, the as-prepared electrodes have the potential for application in fuel cells.

  16. Simplified tandem polymer solar cells with an ideal self-organized recombination layer.

    PubMed

    Kang, Hongkyu; Kee, Seyoung; Yu, Kilho; Lee, Jinho; Kim, Geunjin; Kim, Junghwan; Kim, Jae-Ryoung; Kong, Jaemin; Lee, Kwanghee

    2015-02-25

    A new tandem architecture for printable photovoltaics using a versatile organic nanocomposite containing photoactive and interfacial materials is demonstrated. The nanocomposite forms an ideal self-organized recombination layer via a spontaneous vertical phase separation, which yields a simplified tandem structure fabricated with only four component layers and a high tandem efficiency of 10.8%. PMID:25449142

  17. Simplified tandem polymer solar cells with an ideal self-organized recombination layer.

    PubMed

    Kang, Hongkyu; Kee, Seyoung; Yu, Kilho; Lee, Jinho; Kim, Geunjin; Kim, Junghwan; Kim, Jae-Ryoung; Kong, Jaemin; Lee, Kwanghee

    2015-02-25

    A new tandem architecture for printable photovoltaics using a versatile organic nanocomposite containing photoactive and interfacial materials is demonstrated. The nanocomposite forms an ideal self-organized recombination layer via a spontaneous vertical phase separation, which yields a simplified tandem structure fabricated with only four component layers and a high tandem efficiency of 10.8%.

  18. Facile Isolation of Adsorbent-Free Long and Highly-Pure Chirality-Selected Semiconducting Single-Walled Carbon Nanotubes Using A Hydrogen-bonding Supramolecular Polymer

    PubMed Central

    Toshimitsu, Fumiyuki; Nakashima, Naotoshi

    2015-01-01

    The ideal form of semiconducting-single-walled carbon nanotubes (sem-SWNTs) for science and technology is long, defect-free, chirality pure and chemically pure isolated narrow diameter tubes. While various techniques to solubilize and purify sem-SWNTs have been developed, many of them targeted only the chiral- or chemically-purity while sacrificing the sem-SWNT intrinsic structural identities by applying strong ultra-sonication and/or chemical modifications. Toward the ultimate purification of the sem-SWNTs, here we report a mild-conditioned extraction of the sem-SWNTs using removable supramolecular hydrogen-bonding polymers (HBPs) that are composed of dicarboxylic- or diaminopyridyl-fluorenes with ~70%-(8,6)SWNT selective extraction. Replacing conventional strong sonication techniques by a simple shaking using HPBs was found to provide long sem-SWNTs (>2.0 μm) with a very high D/G ratio, which was determined by atomic force microscopy observations. The HBPs were readily removed from the nanotube surfaces by an outer stimulus, such as a change in the solvent polarities, to provide chemically pure (8,6)-enriched sem-SWNTs. We also describe molecular mechanics calculations to propose possible structures for the HBP-wrapped sem-SWNTs, furthermore, the mechanism of the chiral selectivity for the sorted sem-SWNTs is well explained by the relationship between the molecular surface area and mass of the HBP/SWNT composites. PMID:26658356

  19. Facile Isolation of Adsorbent-Free Long and Highly-Pure Chirality-Selected Semiconducting Single-Walled Carbon Nanotubes Using A Hydrogen-bonding Supramolecular Polymer

    NASA Astrophysics Data System (ADS)

    Toshimitsu, Fumiyuki; Nakashima, Naotoshi

    2015-12-01

    The ideal form of semiconducting-single-walled carbon nanotubes (sem-SWNTs) for science and technology is long, defect-free, chirality pure and chemically pure isolated narrow diameter tubes. While various techniques to solubilize and purify sem-SWNTs have been developed, many of them targeted only the chiral- or chemically-purity while sacrificing the sem-SWNT intrinsic structural identities by applying strong ultra-sonication and/or chemical modifications. Toward the ultimate purification of the sem-SWNTs, here we report a mild-conditioned extraction of the sem-SWNTs using removable supramolecular hydrogen-bonding polymers (HBPs) that are composed of dicarboxylic- or diaminopyridyl-fluorenes with ~70%-(8,6)SWNT selective extraction. Replacing conventional strong sonication techniques by a simple shaking using HPBs was found to provide long sem-SWNTs (>2.0 μm) with a very high D/G ratio, which was determined by atomic force microscopy observations. The HBPs were readily removed from the nanotube surfaces by an outer stimulus, such as a change in the solvent polarities, to provide chemically pure (8,6)-enriched sem-SWNTs. We also describe molecular mechanics calculations to propose possible structures for the HBP-wrapped sem-SWNTs, furthermore, the mechanism of the chiral selectivity for the sorted sem-SWNTs is well explained by the relationship between the molecular surface area and mass of the HBP/SWNT composites.

  20. Facile Isolation of Adsorbent-Free Long and Highly-Pure Chirality-Selected Semiconducting Single-Walled Carbon Nanotubes Using A Hydrogen-bonding Supramolecular Polymer.

    PubMed

    Toshimitsu, Fumiyuki; Nakashima, Naotoshi

    2015-01-01

    The ideal form of semiconducting-single-walled carbon nanotubes (sem-SWNTs) for science and technology is long, defect-free, chirality pure and chemically pure isolated narrow diameter tubes. While various techniques to solubilize and purify sem-SWNTs have been developed, many of them targeted only the chiral- or chemically-purity while sacrificing the sem-SWNT intrinsic structural identities by applying strong ultra-sonication and/or chemical modifications. Toward the ultimate purification of the sem-SWNTs, here we report a mild-conditioned extraction of the sem-SWNTs using removable supramolecular hydrogen-bonding polymers (HBPs) that are composed of dicarboxylic- or diaminopyridyl-fluorenes with ~70%-(8,6)SWNT selective extraction. Replacing conventional strong sonication techniques by a simple shaking using HPBs was found to provide long sem-SWNTs (>2.0 μm) with a very high D/G ratio, which was determined by atomic force microscopy observations. The HBPs were readily removed from the nanotube surfaces by an outer stimulus, such as a change in the solvent polarities, to provide chemically pure (8,6)-enriched sem-SWNTs. We also describe molecular mechanics calculations to propose possible structures for the HBP-wrapped sem-SWNTs, furthermore, the mechanism of the chiral selectivity for the sorted sem-SWNTs is well explained by the relationship between the molecular surface area and mass of the HBP/SWNT composites.

  1. Facile Isolation of Adsorbent-Free Long and Highly-Pure Chirality-Selected Semiconducting Single-Walled Carbon Nanotubes Using A Hydrogen-bonding Supramolecular Polymer.

    PubMed

    Toshimitsu, Fumiyuki; Nakashima, Naotoshi

    2015-01-01

    The ideal form of semiconducting-single-walled carbon nanotubes (sem-SWNTs) for science and technology is long, defect-free, chirality pure and chemically pure isolated narrow diameter tubes. While various techniques to solubilize and purify sem-SWNTs have been developed, many of them targeted only the chiral- or chemically-purity while sacrificing the sem-SWNT intrinsic structural identities by applying strong ultra-sonication and/or chemical modifications. Toward the ultimate purification of the sem-SWNTs, here we report a mild-conditioned extraction of the sem-SWNTs using removable supramolecular hydrogen-bonding polymers (HBPs) that are composed of dicarboxylic- or diaminopyridyl-fluorenes with ~70%-(8,6)SWNT selective extraction. Replacing conventional strong sonication techniques by a simple shaking using HPBs was found to provide long sem-SWNTs (>2.0 μm) with a very high D/G ratio, which was determined by atomic force microscopy observations. The HBPs were readily removed from the nanotube surfaces by an outer stimulus, such as a change in the solvent polarities, to provide chemically pure (8,6)-enriched sem-SWNTs. We also describe molecular mechanics calculations to propose possible structures for the HBP-wrapped sem-SWNTs, furthermore, the mechanism of the chiral selectivity for the sorted sem-SWNTs is well explained by the relationship between the molecular surface area and mass of the HBP/SWNT composites. PMID:26658356

  2. New development of large-area direct conversion detector for digital radiography using amorphous selenium with a C60-doped polymer layer

    NASA Astrophysics Data System (ADS)

    Nariyuki, F.; Imai, S.; Watano, H.; Nabeta, T.; Hosoi, Y.

    2010-04-01

    We have developed a novel direct conversion detector for digital radiography by using a fullerene (C60)-doped polymer layer added on a thick amorphous selenium (a-Se) layer coupled to an amorphous silicon thin-film transistor (a-Si TFT) array. This detector exhibits considerable improvement in the lag characteristics and durability in high ambient temperatures. The C60-doped polymer layer, which is directly and uniformly solution cast on the a-Se layer and followed by an inorganic electron-transporting layer, smoothly changes the electronic junction between the a-Se layer and the inorganic layer. It lubricates the emission of photocurrents from the a-Se photo-conversion layer and leads to the improved lag characteristics. Another merit of using a C60-doped polymer is that it is stabile in high-temperature ambient conditions and is not degraded by humidity or a large amount of X-ray exposure. The polymer layer prevents the crystallization of a-Se, which otherwise occurs on exposure of a-Se to high temperature not only during the deposition of the inorganic layer or the metal electrode layer in the manufacturing process but also in actual use. A prototype detector, with a size of 17 in × 17 in and a pixel pitch of 150 μm, exhibited a good resolution; its DQE is approximately 48% at 1 cy/mm in 258 μC/kg (RQA5). This new development can simplify cooling apparatus and detector modules and also make a wide range of operational environments available. In addition, the improved lag characteristics make it possible to reduce the exposure intervals for static imaging, tomosynthesis, and other various exposure techniques.

  3. Silica-Polymer Dual Layer-Encapsulated Quantum Dots with Remarkable Stability

    PubMed Central

    Hu, Xiaoge; Gao, Xiaohu

    2010-01-01

    Semiconductor quantum dots (QDs) are important fluorescent probes due to their high brightness, multiplexing capability, and photostability. However, applications in quantitative and in vivo imaging are hampered by their sensitivity to chemical environments and potential toxicity. Here we report a surprising finding that the combination of silica and amphiphilic polymer can stabilize CdSe/ZnS QDs in a broad range of chemical conditions including strong acidic solutions, which is unavailable for any of the current encapsulation technologies (e.g., mercapto compounds, silica, and amphiphilic polymers) used alone. We further demonstrate the use of these ultrastable QDs as internal references in pH sensing applications. We expect this work will open exciting opportunities for in vivo and quantitative applications, and may help solve the toxicity problem of QDs. PMID:20863118

  4. Volumetric Interpretation of Protein Adsorption: Capacity Scaling with Adsorbate Molecular Weight and Adsorbent Surface Energy

    PubMed Central

    Parhi, Purnendu; Golas, Avantika; Barnthip, Naris; Noh, Hyeran; Vogler, Erwin A.

    2009-01-01

    Silanized-glass-particle adsorbent capacities are extracted from adsorption isotherms of human serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa) for adsorbent surface energies sampling the observable range of water wettability. Adsorbent capacity expressed as either mass-or-moles per-unit-adsorbent-area increases with protein molecular weight (MW) in a manner that is quantitatively inconsistent with the idea that proteins adsorb as a monolayer at the solution-material interface in any physically-realizable configuration or state of denaturation. Capacity decreases monotonically with increasing adsorbent hydrophilicity to the limit-of-detection (LOD) near τo = 30 dyne/cm (θ~65o) for all protein/surface combinations studied (where τo≡γlvocosθ is the water adhesion tension, γlvo is the interfacial tension of pure-buffer solution, and θ is the buffer advancing contact angle). Experimental evidence thus shows that adsorbent capacity depends on both adsorbent surface energy and adsorbate size. Comparison of theory to experiment implies that proteins do not adsorb onto a two-dimensional (2D) interfacial plane as frequently depicted in the literature but rather partition from solution into a three-dimensional (3D) interphase region that separates the physical surface from bulk solution. This interphase has a finite volume related to the dimensions of hydrated protein in the adsorbed state (defining “layer” thickness). The interphase can be comprised of a number of adsorbed-protein layers depending on the solution concentration in which adsorbent is immersed, molecular volume of the adsorbing protein (proportional to MW), and adsorbent hydrophilicity. Multilayer adsorption accounts for adsorbent capacity over-and-above monolayer and is inconsistent with the idea that protein adsorbs to surfaces primarily through protein/surface interactions because proteins within second (or higher

  5. Integrated optics ring-resonator chemical sensor with polymer transduction layer

    NASA Technical Reports Server (NTRS)

    Ksendzov, A.; Homer, M. L.; Manfreda, A. M.

    2004-01-01

    An integrated optics chemical sensor based on a ring resonator with an ethyl cellulose polymer coating has been demonstrated. The measured sensitivity to isopropanol in air is 50 ppm-the level immediately useful for health-related air quality monitoring. The resonator was fabricated using SiO2 and SixNy materials. The signal readout is based on tracking the wavelength of a resonance peak. The resonator layout optimisation for sensing applications is discussed.

  6. Viscoelastic properties and efficient acoustic damping in confined polymer nano-layers at GHz frequencies.

    PubMed

    Hettich, Mike; Jacob, Karl; Ristow, Oliver; Schubert, Martin; Bruchhausen, Axel; Gusev, Vitalyi; Dekorsy, Thomas

    2016-09-16

    We investigate the viscoelastic properties of confined molecular nano-layers by time resolved optical pump-probe measurements. Access to the elastic properties is provided by the damping time of acoustic eigenmodes of thin metal films deposited on the molecular nano-layers which show a strong dependence on the molecular layer thickness and on the acoustic eigen-mode frequencies. An analytical model including the viscoelastic properties of the molecular layer allows us to obtain the longitudinal sound velocity as well as the acoustic absorption coefficient of the layer. Our experiments and theoretical analysis indicate for the first time that the molecular nano-layers are much more viscous than elastic in the investigated frequency range from 50 to 120 GHz and thus show pronounced acoustic absorption. The longitudinal acoustic wavenumber has nearly equal real and imaginary parts, both increasing proportional to the square root of the frequency. Thus, both acoustic velocity and acoustic absorption are proportional to the square root of frequency and the propagation of compressional/dilatational acoustic waves in the investigated nano-layers is of the diffusional type, similar to the propagation of shear waves in viscous liquids and thermal waves in solids.

  7. Viscoelastic properties and efficient acoustic damping in confined polymer nano-layers at GHz frequencies

    PubMed Central

    Hettich, Mike; Jacob, Karl; Ristow, Oliver; Schubert, Martin; Bruchhausen, Axel; Gusev, Vitalyi; Dekorsy, Thomas

    2016-01-01

    We investigate the viscoelastic properties of confined molecular nano-layers by time resolved optical pump-probe measurements. Access to the elastic properties is provided by the damping time of acoustic eigenmodes of thin metal films deposited on the molecular nano-layers which show a strong dependence on the molecular layer thickness and on the acoustic eigen-mode frequencies. An analytical model including the viscoelastic properties of the molecular layer allows us to obtain the longitudinal sound velocity as well as the acoustic absorption coefficient of the layer. Our experiments and theoretical analysis indicate for the first time that the molecular nano-layers are much more viscous than elastic in the investigated frequency range from 50 to 120 GHz and thus show pronounced acoustic absorption. The longitudinal acoustic wavenumber has nearly equal real and imaginary parts, both increasing proportional to the square root of the frequency. Thus, both acoustic velocity and acoustic absorption are proportional to the square root of frequency and the propagation of compressional/dilatational acoustic waves in the investigated nano-layers is of the diffusional type, similar to the propagation of shear waves in viscous liquids and thermal waves in solids. PMID:27633351

  8. Viscoelastic properties and efficient acoustic damping in confined polymer nano-layers at GHz frequencies.

    PubMed

    Hettich, Mike; Jacob, Karl; Ristow, Oliver; Schubert, Martin; Bruchhausen, Axel; Gusev, Vitalyi; Dekorsy, Thomas

    2016-01-01

    We investigate the viscoelastic properties of confined molecular nano-layers by time resolved optical pump-probe measurements. Access to the elastic properties is provided by the damping time of acoustic eigenmodes of thin metal films deposited on the molecular nano-layers which show a strong dependence on the molecular layer thickness and on the acoustic eigen-mode frequencies. An analytical model including the viscoelastic properties of the molecular layer allows us to obtain the longitudinal sound velocity as well as the acoustic absorption coefficient of the layer. Our experiments and theoretical analysis indicate for the first time that the molecular nano-layers are much more viscous than elastic in the investigated frequency range from 50 to 120 GHz and thus show pronounced acoustic absorption. The longitudinal acoustic wavenumber has nearly equal real and imaginary parts, both increasing proportional to the square root of the frequency. Thus, both acoustic velocity and acoustic absorption are proportional to the square root of frequency and the propagation of compressional/dilatational acoustic waves in the investigated nano-layers is of the diffusional type, similar to the propagation of shear waves in viscous liquids and thermal waves in solids. PMID:27633351

  9. Viscoelastic properties and efficient acoustic damping in confined polymer nano-layers at GHz frequencies

    NASA Astrophysics Data System (ADS)

    Hettich, Mike; Jacob, Karl; Ristow, Oliver; Schubert, Martin; Bruchhausen, Axel; Gusev, Vitalyi; Dekorsy, Thomas

    2016-09-01

    We investigate the viscoelastic properties of confined molecular nano-layers by time resolved optical pump-probe measurements. Access to the elastic properties is provided by the damping time of acoustic eigenmodes of thin metal films deposited on the molecular nano-layers which show a strong dependence on the molecular layer thickness and on the acoustic eigen-mode frequencies. An analytical model including the viscoelastic properties of the molecular layer allows us to obtain the longitudinal sound velocity as well as the acoustic absorption coefficient of the layer. Our experiments and theoretical analysis indicate for the first time that the molecular nano-layers are much more viscous than elastic in the investigated frequency range from 50 to 120 GHz and thus show pronounced acoustic absorption. The longitudinal acoustic wavenumber has nearly equal real and imaginary parts, both increasing proportional to the square root of the frequency. Thus, both acoustic velocity and acoustic absorption are proportional to the square root of frequency and the propagation of compressional/dilatational acoustic waves in the investigated nano-layers is of the diffusional type, similar to the propagation of shear waves in viscous liquids and thermal waves in solids.

  10. Rechargeable solid polymer electrolyte battery cell

    DOEpatents

    Skotheim, Terji

    1985-01-01

    A rechargeable battery cell comprising first and second electrodes sandwiching a solid polymer electrolyte comprising a layer of a polymer blend of a highly conductive polymer and a solid polymer electrolyte adjacent said polymer blend and a layer of dry solid polymer electrolyte adjacent said layer of polymer blend and said second electrode.

  11. Effects of microstructure on carbon support in the catalyst layer on the performance of polymer electrolyte fuel cells

    SciTech Connect

    Uchida, Makoto; Fukuoka, Yuko; Sugawara, Yasushi

    1996-12-31

    In the case of the Polymer-electrolyte fuel cells (PEFCs), the reaction sites exist on the platinum (Pt) surface covered with PFSI. Though PFSI membrane is used as an electrolyte of the PEFC, the membrane does not soak deeply into the electrodes as a liquid electrolyte does. Therefore, PFSI solution was impregnated into the catalyst layers to increase the contact areas between Pt and PFSI. In our previous work we proposed a new preparation method of the M&E assembly which emphasized the colloid formation of the PFSI to optimize the network of PFSIs in the catalyst layer and also to simplify the fabrication process of the M&E assembly. Following this work, we focused on the microstructure of the catalyst layer. The importance of the morphological properties of the gas-diffusion electrodes on performance has been reported in several papers. The catalyst layer was claimed to have had two distinctive pore distributions with a boundary of ca. 0.1 {mu}m. The smaller pore (primary pore) was identified with the space in and between the primary particles in the agglomerate of the carbon support and the larger one (secondary pore) was that between the agglomerates. In our recent work, we reported that the PFSI was distributed only in the secondary pores, and the reaction sites were therefore limited to that location. The results indicated that the PEFC system required a particular design rather than a conventional one for the fuel cells with liquid electrolytes. We proposed that novel structure and/or preparation methods of the catalyst layer were keys to higher utilization of Pt.

  12. Bulk-heterojunction polymer solar cells with polyaniline-silica nanocomposites as an efficient hole-collecting layer

    NASA Astrophysics Data System (ADS)

    Mohsennia, Mohsen; Bidgoli, Maryam Massah; Khoddami, Mohammad Hossein; Salehi, Alireza; Boroumand, Farhad Akbari

    2016-01-01

    At first, bulk-heterojunction polymer solar cells (PSCs) with conventional configuration: ITO/PEDOT:PSS/P3HT:C60/Al, containing different blend ratios of poly(3-hexylthiophene):fullerene, (P3HT):C60 as active layer have been fabricated. The effect of replacement of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) by the prepared polyaniline-fumed silica (PANI-SiO2) nanocomposites as the hole-collecting layer (HCL) on the performance of the fabricated PSC with the optimized blending ratio of P3HT:C60 was examined in detail. According to the obtained results, it was found that the fabricated PSC with PANI-SiO2 nanocomposite containing 10% SiO2 (PANI-10% SiO2) as the HCL and P3HT:C60 with the optimized blending ratio (P3HT:33% C60) as active layer exhibited best performance with a fill factor (FF) of 0.35, compared to the PSC containing conventional PEDOT:PSS HCL with an FF of 0.32. Our demonstration suggests that PANI-SiO2 nanocomposites could be promising HCL replacing PEDOT:PSS in PSCs as well as other organic electronic devices.

  13. Interface investigation of the alcohol-/water-soluble conjugated polymer PFN as cathode interfacial layer in organic solar cells

    NASA Astrophysics Data System (ADS)

    Zhong, Shu; Wang, Rui; Ying Mao, Hong; He, Zhicai; Wu, Hongbin; Chen, Wei; Cao, Yong

    2013-09-01

    In this work, in situ ultraviolet photoelectron spectroscopy measurements were used to investigate the working mechanism of an alcohol-/water-soluble conjugated polymer poly [(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) as the cathode interfacial layer in organic solar cells from the view of interfacial energy level alignment. Fullerene (C60) was chosen as the model acceptor material in contact with PFN as well as two other cathode interfacial layers ZnO and TiO2 in the configuration of an inverted solar cell structure. Significant charge transfer between PFN modified ITO (indium tin oxide) electrode and C60 is observed due to the low work function of PFN. This results in the Fermi level of the substrate pinned very close to the lowest unoccupied molecular orbital of C60 as well as an additional electric field at the cathode/acceptor interface. Both of them facilitate the electron extraction from the acceptor C60 to the ITO cathode, as confirmed by the electrical measurements of the electron-only devices with PFN modification. The better electron extraction originated from the Fermi level pinning and the additional interface electric field are believed to contribute to the efficiency enhancement of the inverted organic solar cells employing PFN as cathode interfacial layer.

  14. A data-driven approach to establishing microstructure-property relationships in porous transport layers of polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Çeçen, A.; Fast, T.; Kumbur, E. C.; Kalidindi, S. R.

    2014-01-01

    The diffusion media (DM) has been shown to be a vital component for performance of polymer electrolyte fuel cells (PEFCs). The DM has a dual-layer structure composed of a macro-substrate referred to as the gas diffusion layer (GDL) coated with a micro-porous layer (MPL). Efficient prediction of the effective transport properties of the DM from its internal structure is essential to optimizing the multifunctional characteristics of this critical component. In this work, a unique data-driven approach to establishing structure-property correlations is introduced and applied to the case of gas diffusion in the GDL and MPL. This new approach provides an automated process to produce unbiased estimators to microstructural variance, in contrast to many process-related (hence biased) parameters employed by prominent correlations in the field. The present approach starts with a rigorous quantification of microstructure in the form of n-point statistics. It is followed by the identification of the key aspects of the internal structure through the use of principle component analysis. A data-driven correlation is established when the principal components are related to effective diffusivity by multivariate linear regression. This data-driven approach is compared to the conventional correlations and shown to achieve a very high accuracy for capturing the diffusive transport in the tested PEFC components.

  15. Effect of the solvent used to prepare the photoactive layer on the performance of inverted bulk heterojunction polymer solar cells

    NASA Astrophysics Data System (ADS)

    Kuwabara, Takayuki; Kuzuba, Mitsuhiro; Emoto, Natsumi; Yamaguchi, Takahiro; Taima, Tetsuya; Takahashi, Kohshin

    2014-02-01

    The initial performance and subsequent degradation of inverted polymer solar cells [indium-tin oxide/titanium oxide (TiOx)/[6,6]-phenyl C61 butyric acid methyl ester (PCBM): regioregular poly(3-hexylthiophene) (P3HT)/poly(3,4-ethylenedioxylenethiophene):poly(4-styrene sulfonic acid)/Au, TiOx cell] are studied by photocurrent-voltage measurements as well as ac impedance spectroscopy (IS) and carrier mobility measurements. The TiOx cells containing a P3HT:PCBM layer prepared from a solution of chlorobenzene (CB) showed a maximum power conversion efficiency (PCE) of 2.23%. In contrast, the TiOx cells containing a P3HT:PCBM layer prepared from a solution of 1,2,3,4-tetrahydronaphthalene (tetralin) containing 2 vol % 1,8-octanedithiol (ODT) exhibited a maximum PCE of 2.92%. However, after exposure to light irradiation for 100 h, the maximum PCE of the tetralin:ODT cell decreased to 68% of its initial value. On the other hand, over 96% of the maximum PCE was maintained in the CB cell after 100 h of irradiation. The IS measurement results suggest that the degradation of the Tetralin:ODT cell was caused by a morphological change of the P3HT:PCBM layer that made efficient photoinduced charge separation difficult.

  16. Application of the design of experiments in optimization of drug layering of pellets with an insight into drug polymer interactions.

    PubMed

    Kovacevic, Jovana; Ibric, Svetlana; Djuris, Jelena; Kleinebudde, Peter

    2016-06-15

    This study consists of two experimental designs. Within the first one, suitable technique for application of model drug onto inactive pellets was evaluated and formulation and process parameters with greatest impact to process efficency and useful yield were determined. Results of experiments showed that formulation characteristics were the ones with the greatest impact on coating efficiency and that suspension layering technique was significantly better for drug application onto inactive pellets in comparison to solution layering during which pronounced agglomeration of pellets occurred. Analysis of drug-polymer interactions by differential scanning calorimetry was performed to explain the results of experiments. The reason for agglomeration of pellets during solution layering was formation of low Tg amorphous form of model drug. The second set of experiments was performed according to central composite design experimental plan in order to optimize level of binder and concentration of solids in the coating liquid which were found to have greatest positive impact on process efficiency and useful yield in the screening study. Statistically significant models were obtained by response surface methodology and it was possible to use them to define optimal levels of excipients in the formulation. PMID:27094356

  17. Process For Cutting Polymers Electrolyte Multi-Layer Batteries And Batteries Obtained Thereby

    DOEpatents

    Gauthier, Michel; Lessard, Ginette; Dussault, Gaston; Rouillard, Roger; Simoneau, Martin; Miller, Alan Paul

    2003-09-09

    A stacking of battery laminate is prepared, each battery consisting of anode, polymer electrolyte, cathode films and possibly an insulating film, under conditions suitable to constitute a rigid monoblock assembly, in which the films are unitary with one another. The assembly obtained is thereafter cut in predetermined shape by using a mechanical device without macroscopic deformation of the films constituting the assembly and without inducing permanent short circuits. The battery which is obtained after cutting includes at least one end which appears as a uniform cut, the various films constituting the assembly having undergone no macroscopic deformation, the edges of the films of the anode including an electronically insulating passivation film.

  18. Enzyme and Mediator-coadsorbed Carbon Felt Electrode for Electrochemical Detection of Glucose Covered with Polymer Layers Based on Layer-by-Layer Technique.

    PubMed

    Yabuki, Soichi; Hirata, Yoshiki

    2015-01-01

    Glucose dehydrogenase (GlDH) and ferrocene were coadsorbed on a carbon felt (CF) sheet (5 × 10 mm, 2 mm thickness), which was used to construct an electrode for the electrochemical detection of glucose. A potential of +0.3 V vs. Ag/AgCl was applied on the base CF, and the current was measured. After the addition of glucose, the current increased and reached a steady state within 50 s. The current response was proportional to the glucose concentration up to 20 μM, with a lower detection limit of 1 μM. The surface of the CF electrode was covered by layers of polystyrene sulfonate and poly-L-lysine using layer-by-layer technique. Again the current response was proportional to glucose concentration up to 20 μM, with a lower detection limit of 2 μM. The oxidation current owing to electrochemical interferents such as L-ascorbate and acetaminophen was 1/8 times of the current observed on the unprotected electrode. In addition, the protection imparted stability to the electrode. Our work demonstrates that a GlDH/ferrocene CF electrode, protected with polystyrene sulfonate and poly-L-lysine, could be used for the electrochemical detection of glucose. PMID:26165293

  19. Modeling adsorption: Investigating adsorbate and adsorbent properties

    NASA Astrophysics Data System (ADS)

    Webster, Charles Edwin

    1999-12-01

    Surface catalyzed reactions play a major role in current chemical production technology. Currently, 90% of all chemicals are produced by heterogeneously catalyzed reactions. Most of these catalyzed reactions involve adsorption, concentrating the substrate(s) (the adsorbate) on the surface of the solid (the adsorbent). Pore volumes, accessible surface areas, and the thermodynamics of adsorption are essential in the understanding of solid surface characteristics fundamental to catalyst and adsorbent screening and selection. Molecular properties such as molecular volumes and projected molecular areas are needed in order to convert moles adsorbed to surface volumes and areas. Generally, these molecular properties have been estimated from bulk properties, but many assumptions are required. As a result, different literature values are employed for these essential molecular properties. Calculated molar volumes and excluded molecular areas are determined and tabulated for a variety of molecules. Molecular dimensions of molecules are important in the understanding of molecular exclusion as well as size and shape selectivity, diffusion, and adsorbent selection. Molecular dimensions can also be used in the determination of the effective catalytic pore size of a catalyst. Adsorption isotherms, on zeolites, (crystalline mineral oxides) and amorphous solids, can be analyzed with the Multiple Equilibrium Analysis (MEA) description of adsorption. The MEA produces equilibrium constants (Ki), capacities (ni), and thermodynamic parameters (enthalpies, ΔHi, and entropies, ΔSi) of adsorption for each process. Pore volumes and accessible surface areas are calculated from the process capacities. Adsorption isotherms can also be predicted for existing and new adsorbate-adsorbent systems with the MEA. The results show that MEA has the potential of becoming a standard characterization method for microporous solids that will lead to an increased understanding of their behavior in gas

  20. Deposition of functionalized polymer layers in surface plasmon resonance immunosensors by in-situ polymerization in the evanescent wave field.

    PubMed

    Chegel, Vladimir; Whitcombe, Michael J; Turner, Nicholas W; Piletsky, Sergey A

    2009-01-01

    Traditionally, the integration of sensing gel layers in surface plasmon resonance (SPR) is achieved via "bulk" methods, such as precipitation, spin-coating or in-situ polymerization onto the total surface of the sensor chip, combined with covalent attachment of the antibody or receptor to the gel surface. This is wasteful in terms of materials as the sensing only occurs at the point of resonance interrogated by the laser. By isolating the sensing materials (antibodies, enzymes, aptamers, polymers, MIPs, etc.) to this exact spot a more efficient use of these recognition elements will be achieved. Here we present a method for the in-situ formation of polymers, using the energy of the evanescent wave field on the surface of an SPR device, specifically localized at the point of interrogation. Using the photo-initiator couple of methylene blue (sensitizing dye) and sodium p-toluenesulfinate (reducing agent) we polymerized a mixture of N,N-methylene-bis-acrylamide and methacrylic acid in water at the focal point of SPR. No polymerization was seen in solution or at any other sites on the sensor surface. Varying parameters such as monomer concentration and exposure time allowed precise control over the polymer thickness (from 20-200 nm). Standard coupling with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide was used for the immobilization of protein G which was used to bind IgG in a typical biosensor format. This model system demonstrated the characteristic performance for this type of immunosensor, validating our deposition method. PMID:18789676

  1. Dynamics of various polymer-graphene interfacial systems through atomistic molecular dynamics simulations.

    PubMed

    Rissanou, Anastassia N; Harmandaris, Vagelis

    2014-04-28

    The current work refers to a simulation study on hybrid polymer-graphene interfacial systems. We explore the effect of graphene on the mobility of polymers, by studying three well known and widely used polymers, polyethylene (PE), polystyrene (PS) and poly(methyl-methacrylate) (PMMA). Qualitative and quantitative differences in the dynamical properties of the polymer chains in particular at the polymer-graphene interface are detected. Results concerning both the segmental and the terminal dynamics render PE much faster than the other two polymers; PS follows, while PMMA is the slowest one. Clear spatial dynamic heterogeneity has been observed for all model systems, with different dynamical behavior of the adsorbed polymer segments. The segmental relaxation time of the polymer (τseg) as a function of the distance from graphene shows an abrupt decrease beyond the first adsorption layer for PE, as a result of its well-ordered layered structure close to graphene, though a more gradual decay is observed for PS and PMMA. The distribution of the relaxation times of adsorbed segments was also found to be broader than those of the bulk ones for all three polymer-graphene systems. PMID:24667937

  2. Localized removal of layers of metal, polymer, or biomaterial by ultrasound cavitation bubbles.

    PubMed

    Fernandez Rivas, David; Verhaagen, Bram; Seddon, James R T; Zijlstra, Aaldert G; Jiang, Lei-Meng; van der Sluis, Luc W M; Versluis, Michel; Lohse, Detlef; Gardeniers, Han J G E

    2012-09-01

    We present an ultrasonic device with the ability to locally remove deposited layers from a glass slide in a controlled and rapid manner. The cleaning takes place as the result of cavitating bubbles near the deposited layers and not due to acoustic streaming. The bubbles are ejected from air-filled cavities micromachined in a silicon surface, which, when vibrated ultrasonically at a frequency of 200 kHz, generate a stream of bubbles that travel to the layer deposited on an opposing glass slide. Depending on the pressure amplitude, the bubble clouds ejected from the micropits attain different shapes as a result of complex bubble interaction forces, leading to distinct shapes of the cleaned areas. We have determined the removal rates for several inorganic and organic materials and obtained an improved efficiency in cleaning when compared to conventional cleaning equipment. We also provide values of the force the bubbles are able to exert on an atomic force microscope tip.

  3. Charge transfer from an adsorbed ruthenium-based photosensitizer through an ultra-thin aluminium oxide layer and into a metallic substrate

    SciTech Connect

    Gibson, Andrew J.; Temperton, Robert H.; Handrup, Karsten; Weston, Matthew; Mayor, Louise C.; O’Shea, James N.

    2014-06-21

    The interaction of the dye molecule N3 (cis-bis(isothiocyanato)bis(2,2-bipyridyl-4,4′-dicarbo-xylato) -ruthenium(II)) with the ultra-thin oxide layer on a AlNi(110) substrate, has been studied using synchrotron radiation based photoelectron spectroscopy, resonant photoemission spectroscopy, and near edge X-ray absorption fine structure spectroscopy. Calibrated X-ray absorption and valence band spectra of the monolayer and multilayer coverages reveal that charge transfer is possible from the molecule to the AlNi(110) substrate via tunnelling through the ultra-thin oxide layer and into the conduction band edge of the substrate. This charge transfer mechanism is possible from the LUMO+2 and 3 in the excited state but not from the LUMO, therefore enabling core-hole clock analysis, which gives an upper limit of 6.0 ± 2.5 fs for the transfer time. This indicates that ultra-thin oxide layers are a viable material for use in dye-sensitized solar cells, which may lead to reduced recombination effects and improved efficiencies of future devices.

  4. Structure, scattering patterns and phase behavior of polymer nanocomposites with nonspherical fillers

    SciTech Connect

    Hall, Lisa M; Schweizer, Kenneth S

    2010-01-01

    Polymer nanocomposites made with carbon nanotubes, clay platelets, laponite disks and other novel nonspherical fillers have been the focus of many recent experiments. However, the effects of nanoparticle shape on statistical structure, polymer-mediated effective interactions, scattering patterns, and phase diagrams are not well understood. We extend and apply the polymer reference interaction site model liquid state theory to study the equilibrium properties of pseudo one-, two- and threedimensional particles (rod, disk, cube) of modest steric anisotropy and fixed space-filling volume in a dense adsorbing homopolymer melt up to relatively high volume fractions. The second virial coefficient, nanoparticle potential-of-mean force, osmotic compressibilities, and isotropic spinodal demixing boundaries have been determined. The entropic depletion attraction between nanoparticles is dominant for weakly adsorbing polymer, while strongly adsorbing chains induce a bridging attraction. Intermediate interfacial cohesion results in the formation of a steric stabilizing adsorbed polymer layer around each nanoparticle, which can partially damp inter-filler collective order on various length scales and increase order on an averaged length scale. The details of depletion, stabilization, or bridging behavior are shape-dependent and often, but not always, trends are monotonic with increasing filler dimensionality. Distinctive nanoparticle shape-dependent low angle features are predicted for the collective polymer structure factor associated with competing macrophase fluctuations and microphase-like ordering. The influence of nonzero mixture compressibility on the scattering profiles is established.

  5. Ultrastable BSA-capped gold nanoclusters with a polymer-like shielding layer against reactive oxygen species in living cells.

    PubMed

    Zhou, Wenjuan; Cao, Yuqing; Sui, Dandan; Guan, Weijiang; Lu, Chao; Xie, Jianping

    2016-05-01

    The prevalence of reactive oxygen species (ROS) production and the enzyme-containing intracellular environment could lead to the fluorescence quenching of bovine serum albumin (BSA)-capped gold nanoclusters (AuNCs). Here we report an efficient strategy to address this issue, where a polymer-like shielding layer is designed to wrap around the Au core to significantly improve the stability of AuNCs against ROS and protease degradation. The key of our design is to covalently incorporate a thiolated AuNC into the BSA-AuNC via carbodiimide-activated coupling, leading to the formation of a AuNC pair inside the cross-linked BSA molecule. The as-designed paired AuNCs in BSA (or BSA-p-AuNCs for short) show improved performances in living cells.

  6. Performance of electrical double layer capacitors fabricated with gel polymer electrolytes containing Li+ and K+-salts: A comparison

    NASA Astrophysics Data System (ADS)

    Singh, Manoj K.; Hashmi, S. A.

    2015-06-01

    The comparative performance of the solid-state electrical double layer capacitors (EDLCs) based on the multiwalled carbon nanotube (MWCNT) electrodes and poly (vinaylidinefluoride-co-hexafluoropropyline) (PVdF-HFP) based gel polymer electrolytes (GPEs) containing potassium and lithium salts have been studied. The room temperature ionic conductivity of the GPEs have been found to be ˜3.8×10-3 and 5.9×10-3 S cm-1 for lithium and potassium based systems. The performance of EDLC cells studied by impedance spectroscopy, cyclic voltammetry and constant current charge-discharge techniques, indicate that the EDLC with potassium salt containing GPE shows excellent performance almost equivalent to the EDLC with Li-salt-based GPE.

  7. Conformal coating of thin polymer electrolyte layer on nanostructured electrode materials for three-dimensional battery applications.

    PubMed

    Gowda, Sanketh R; Reddy, Arava Leela Mohana; Shaijumon, Manikoth M; Zhan, Xiaobo; Ci, Lijie; Ajayan, Pulickel M

    2011-01-12

    Various three-dimensional (3D) battery architectures have been proposed to address effective power delivery in micro/nanoscale devices and for increasing the stored energy per electrode footprint area. One step toward obtaining 3D configurations in batteries is the formation of core-shell nanowires that combines electrode and electrolyte materials. One of the major challenges however in creating such architectures has been the coating of conformal thin nanolayers of polymer electrolytes around nanostructured electrodes. Here we show conformal coatings of 25-30 nm poly(methyl methacralate) electrolyte layers around individual Ni-Sn nanowires used as anodes for Li ion battery. This configuration shows high discharge capacity and excellent capacity retention even at high rates over extended cycling, allowing for scalable increase in areal capacity with electrode thickness. Our results demonstrate conformal nanoscale anode-electrolyte architectures for an efficient Li ion battery system.

  8. Effects of Membrane- and Catalyst-layer-thickness Nonuniformitiesin Polymer-electrolyte Fuel Cells

    SciTech Connect

    Weber, Adam Z.; Newman, John

    2006-09-01

    In this paper, results from mathematical, pseudo 2-D simulations are shown for four different along-the-channel thickness distributions of both the membrane and cathode catalyst layer. The results and subsequent analysis clearly demonstrate that for the membrane thickness distributions, cell performance is affected a few percent under low relative-humidity conditions and that the position along the gas channel is more important than the local thickness variations. However, for the catalyst-layer thickness distributions, global performance is not impacted, although for saturated conditions there is a large variability in the local temperature and performance depending on the thickness.

  9. Two-layer flow of polymer melts in extruder die channel

    NASA Astrophysics Data System (ADS)

    Sharafutdinov, R. F.; Snigerev, B. A.; Galimov, E. R.; Galimova, N. Ya

    2016-06-01

    The paper discusses numerical modeling of two-layer flow of viscous non-Newtonian fluids in extruder die channels. Fluid motion is described by mass and momentum conservation equations supplemented by the rheological equation of state of a viscous non-Newtonian fluid according to the Carreau model. Technique of numerical solution of the problem based on the finite element method is presented. Distribution pattern of fluid velocities, pressure, stresses, positions of the interface in the two-layer flow depending on the rheological properties of a fluid and flow regimes is investigated.

  10. Ultrastable BSA-capped gold nanoclusters with a polymer-like shielding layer against reactive oxygen species in living cells

    NASA Astrophysics Data System (ADS)

    Zhou, Wenjuan; Cao, Yuqing; Sui, Dandan; Guan, Weijiang; Lu, Chao; Xie, Jianping

    2016-05-01

    The prevalence of reactive oxygen species (ROS) production and the enzyme-containing intracellular environment could lead to the fluorescence quenching of bovine serum albumin (BSA)-capped gold nanoclusters (AuNCs). Here we report an efficient strategy to address this issue, where a polymer-like shielding layer is designed to wrap around the Au core to significantly improve the stability of AuNCs against ROS and protease degradation. The key of our design is to covalently incorporate a thiolated AuNC into the BSA-AuNC via carbodiimide-activated coupling, leading to the formation of a AuNC pair inside the cross-linked BSA molecule. The as-designed paired AuNCs in BSA (or BSA-p-AuNCs for short) show improved performances in living cells.The prevalence of reactive oxygen species (ROS) production and the enzyme-containing intracellular environment could lead to the fluorescence quenching of bovine serum albumin (BSA)-capped gold nanoclusters (AuNCs). Here we report an efficient strategy to address this issue, where a polymer-like shielding layer is designed to wrap around the Au core to significantly improve the stability of AuNCs against ROS and protease degradation. The key of our design is to covalently incorporate a thiolated AuNC into the BSA-AuNC via carbodiimide-activated coupling, leading to the formation of a AuNC pair inside the cross-linked BSA molecule. The as-designed paired AuNCs in BSA (or BSA-p-AuNCs for short) show improved performances in living cells. Electronic supplementary information (ESI) available: Detailed experimental materials, apparatus, experimental procedures and characterization data. See DOI: 10.1039/c6nr02178f

  11. Polyfluorene Electrolytes Interfacial Layer for Efficient Polymer Solar Cells: Controllably Interfacial Dipoles by Regulation of Polar Groups.

    PubMed

    Liu, Huimin; Hu, Lin; Wu, Feiyan; Chen, Lie; Chen, Yiwang

    2016-04-20

    The polar groups in the conjugated polyelectrolytes (CPEs) can create the favorable dipoles at the electrode/active layer interface, which is critical for the CPEs to minimize the interfacial energy barrier in polymer solar cells (PSCs). Herein, a series of CPEs based on poly [(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-co-2,7-(9,9-dioctylfluorene)] derivates (PFNs) (PFN30, PFN50, PFN70, and PFN100) with different mole ratio of polar groups (-N(C2H5)2) were designed and synthesized to investigate the effect of the numbers of polar groups on the interfacial dipoles. Controllably interfacial dipoles could be readily achieved by only tuning the numbers of -N(C2H5)2 in PFNs, as revealed by the work function of the PFNs modified ITO gradually reduced as the loadings of the -N(C2H5)2 increased. In addition, increasing the numbers of -N(C2H5)2 in PFNs were also favorable for developing the smooth and homogeneous morphology of the active layer. As a result, the content of the polar amine in the PFNs exerted great influence on the performance of polymer solar cells. Increasing the numbers of the pendent -N(C2H5)2 could effectively improve the power conversion efficiency (PCE) of the devices. Among these PFNs, PFN100 with the highest content of -N(C2H5)2 polar groups delivered the device with the best PCE of 3.27%. It indicates tailoring the content of the polar groups in the CPEs interlayer is a facial and promising approach for interfacial engineering to developing high performance PSCs.

  12. Influence of polymeric electron injection layers on the electrical properties of solution-processed multilayered polymer light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Itoh, Eiji; Kurami, Kazuhiko

    2016-02-01

    In this study, we fabricated multilayered polymer-based light-emitting diodes (pLEDs) with various solution-processed electron-injection layers (EILs), and investigated the influence of the EILs on the electrical properties of pLEDs in indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonic acid) (PEDOT:PSS)/poly[(9,9-dioctylfluorene-alt-(1,4-phenylene((4-sec-butylphenyl)amino)-1,4-phenylene))] (TFB) (HTL)/poly(9,9-dioctylfluorene-alt-1,4-benzothiadiazole) (F8BT) (EML)/EIL/Al structures. We have used the quaternized ammonium π-conjugated polyelectrolyte derivative (poly[(9,9-di(3,3‧-N,N‧-trimethylammonium)propylfluorenyl-2,7-diyl)-co-(1,4-phenylene)]diiodide salt) (PF-PDTA), a mixture of PF-PDTA and CS2CO3, and the aliphatic-amine-based polymer poly(ethylene imine) (PEI) as solution-processed EILs, and compared them with LiF as a solvent-free EIL. The EILs enhanced the electron injection and improve the pLED performance. High external quantum efficiencies of nearly 4% were obtained in the pLEDs with the combination of a multilayered structure fabricated by a transfer printing technique and EILs of a PF-PDTA:CS2CO3 mixture and PEI. On the other hand, the device with PF-PDTA exhibited lower efficiency, higher driving voltage, and larger leakage current at lower voltage. The migration of ionic charges was suggested from the abnormal dielectric behaviors, and serious damage on the electrode material occurred when both an acid hole-injection layer (PEDOT:PSS) and PF-PDTA were used. On the other hand, the pLEDs with ultrathin PEI showed high performance and stable device operation in terms of the influence of ionic charges.

  13. Molecular Structure and Equilibrium Forces of Bovine Submaxillary Mucin Adsorbed at a Solid-Liquid Interface.

    PubMed

    Zappone, Bruno; Patil, Navinkumar J; Madsen, Jan B; Pakkanen, Kirsi I; Lee, Seunghwan

    2015-04-21

    By combining dynamic light scattering, circular dichroism spectroscopy, atomic force microscopy, and surface force apparatus, the conformation of bovine submaxillary mucin in dilute solution and nanomechanical properties of mucin layers adsorbed on mica have been investigated. The samples were prepared by additional chromatographic purification of commercially available products. The mucin molecule was found to have a z-average hydrodynamic diameter of ca. 35 nm in phosphate buffered solution, without any particular secondary or tertiary structure. The contour length of the mucin is larger than, yet of the same order of magnitude as the diameter, indicating that the molecule can be modeled as a relatively rigid polymeric chain due to the large persistence length of the central glycosylated domain. Mucin molecules adsorbed abundantly onto mica from saline buffer, generating polymer-like, long-ranged, repulsive, and nonhysteretic forces upon compression of the adsorbed layers. Detailed analysis of such forces suggests that adsorbed mucins had an elongated conformation favored by the stiffness of the central domain. Acidification of aqueous media was chosen as means to reduce mucin-mucin and mucin-substrate electrostatic interactions. The hydrodynamic diameter in solution did not significantly change when the pH was lowered, showing that the large persistence length of the mucin molecule is due to steric hindrance between sugar chains, rather than electrostatic interactions. Remarkably, the force generated by an adsorbed layer with a fixed surface coverage also remained unaltered upon acidification. This observation can be linked to the surface-protective, pH-resistant role of bovine submaxillary mucin in the variable environmental conditions of the oral cavity. PMID:25806669

  14. Measuring drug saturation solubility in thin polymer films: use of a thin acceptor layer.

    PubMed

    Kunst, Anders; Lee, Geoffrey

    2015-03-15

    The saturation solubility of scopolamine base in two pressure sensitive adhesive DURO-TAKs has been determined using the 5-layer laminate technique. The acceptor layer had a thickness of less than 25 μm to promote a rapid partitioning equilibrium. With DURO-TAK 87-2510 the saturation solubility is 5.2 ± 0.6% w/w when measured after 7 days. With DURO-TAK 87-4098 the saturation solubility is slightly higher, 7.9 ± 0.7% w/w after 7 days. These values remained constant up to approximately 30 days' experimental time. In both cases the acceptor was free of crystalline material at the end of the experiment. This strongly suggests that that equilibrium had been reached between the saturated solution in the acceptor layer and the crystalline drug still present in the donor layer. The addition of light liquid paraffin to the acceptor produced a solubilizing effect with 87-4098 but not 87-2510. We recommend some experimental conditions that we consider to be necessary to achieve a reliable and accurate result with this technique. If performed correctly, it can give a feasible result.

  15. Dynamic Ellipsometric Porosimetry Investigation of Permeation Pathways in Moisture Barrier Layers on Polymers.

    PubMed

    Perrotta, Alberto; Kessels, Wilhelmus M M; Creatore, Mariadriana

    2016-09-28

    The quality assessment of moisture permeation barrier layers needs to include both water permeation pathways, namely through bulk nanoporosity and local macroscale defects. Ellipsometric porosimetry (EP) has been already demonstrated a valuable tool for the identification of nanoporosity in inorganic thin film barriers, but the intrinsic lack of sensitivity toward the detection of macroscale defects prevents the overall barrier characterization. In this contribution, dynamic EP measurements are reported and shown to be sensitive to the detection of macroscale defects in SiO2 layers on polyethylene naphthalate substrate. In detail, the infiltration of probe molecules, leading to changes in optical properties of the polymeric substrate, is followed in time and related to permeation through macroscale defects. PMID:27618251

  16. Powder-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

    DOEpatents

    Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

    2016-05-03

    A powder-based adsorbent and a related method of manufacture are provided. The powder-based adsorbent includes polymer powder with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the powder-based adsorbent includes irradiating polymer powder, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Powder-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

  17. Foam-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

    DOEpatents

    Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

    2015-06-02

    Foam-based adsorbents and a related method of manufacture are provided. The foam-based adsorbents include polymer foam with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the foam-based adsorbents includes irradiating polymer foam, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Foam-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

  18. 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

  19. Crystal-to-crystal transformation from a chain compound to a layered coordination polymer.

    PubMed

    Shi, Jinbiao; Zhang, Yan; Zhang, Bin; Zhu, Daoben

    2016-01-01

    A crystal-to-crystal transformation was observed from a green chain compound CuBr2(1,4-dioxane)2(H2O)2 (1) to a brown layered compound (CuBr2)3(1,4-dioxane)2 (2). The hydrogen bond connecting chains in were replaced by a μ-Br bridge in and the antiferromagnetic interaction between the metal atoms in became stronger than in 1. PMID:26600206

  20. Hydration and dynamic state of nanoconfined polymer layers govern toughness in nacre-mimetic nanocomposites.

    PubMed

    Verho, Tuukka; Karesoja, Mikko; Das, Paramita; Martikainen, Lahja; Lund, Reidar; Alegría, Angel; Walther, Andreas; Ikkala, Olli

    2013-09-25

    Biological high-performance composites inspire to create new tough, strong, and stiff structural materials. We show a brittle-to-ductile transition in a self-assembled nacre-inspired poly(vinyl alcohol)/nanoclay composite based on a hydration-induced glass-to-rubber transition in the 2D-nanoconfined poly(vinyl alcohol) layers. The findings open routes to design dissipative toughening mechanisms to combine stiffness and strength in nanocomposites. PMID:23913740

  1. Origin of photogenerated carrier recombination at the metal-active layer interface in polymer solar cells.

    PubMed

    Kumar, Mukesh; Dubey, Ashish; Reza, Khan Mamun; Adhikari, Nirmal; Qiao, Qiquan; Bommisetty, Venkat

    2015-11-01

    The role of the metal-active layer interface in photogenerated recombination has been investigated using nanoscale current sensing atomic force microscopy (CS-AFM) and intensity modulated photocurrent spectroscopy (IMPS) in as-deposited, pre-annealed and post-annealed bulk heterojunction (BHJ) solar cells. Aluminum (Al) confined post-annealed BHJ solar cells exhibited a significantly improved device efficiency compared to pre-annealed BHJ solar cells having similar photocarrier harvesting ability in the active layer. The nanoscale topography and CS-AFM results indicate a uniform PCBM rich phase at the metal-active layer interface in the post-annealed cells, but PCBM segregation in the pre-annealed cells. These two different annealing processes showed different carrier dynamics revealed using IMPS under various light intensities. The IMPS results suggest reduced photo generated carrier recombination in uniform PCBM rich post-annealed BHJ solar cells. This study reveals the importance of the metal-bend interface in BHJ solar cells in order to obtain efficient charge carrier extraction for high efficiency. PMID:26431263

  2. In situ monitoring of structure formation in the active layer of polymer solar cells during roll-to-roll coating

    NASA Astrophysics Data System (ADS)

    Rossander, Lea H.; Zawacka, Natalia K.; Dam, Henrik F.; Krebs, Frederik C.; Andreasen, Jens W.

    2014-08-01

    The active layer crystallization during roll-to-roll coating of organic solar cells is studied in situ. We developed an X-ray setup where the coater unit is an integrated part of the small angle X-ray scattering instrument, making it possible to control the coating process while recording scattering measurements in situ, enabling us to follow the crystal formation during drying. By varying the distance between the coating head and the point where the X-ray beam hits the film, we obtained measurements of 4 different stages of drying. For each of those stages, the scattering from as long a foil as possible is summed together, with the distance from coating head to scattering point kept constant. The results are average crystallographic properties for the active layer coated on a 30 m long foil. With this insight into the dynamics of crystallization in a roll-coated polymer film, we find that the formation of textured and untextured crystallites seems uncorrelated, and happens at widely different rates. Untextured P3HT crystallites form later in the drying process than expected which may explain previous studies speculating that untextured crystallization depends on concentration. Textured crystallites, however, begin forming much earlier and steadily increases as the film dries, showing a development similar to other in situ studies of these materials.

  3. In situ monitoring of structure formation in the active layer of polymer solar cells during roll-to-roll coating

    SciTech Connect

    Rossander, Lea H.; Zawacka, Natalia K.; Dam, Henrik F.; Krebs, Frederik C.; Andreasen, Jens W.

    2014-08-15

    The active layer crystallization during roll-to-roll coating of organic solar cells is studied in situ. We developed an X-ray setup where the coater unit is an integrated part of the small angle X-ray scattering instrument, making it possible to control the coating process while recording scattering measurements in situ, enabling us to follow the crystal formation during drying. By varying the distance between the coating head and the point where the X-ray beam hits the film, we obtained measurements of 4 different stages of drying. For each of those stages, the scattering from as long a foil as possible is summed together, with the distance from coating head to scattering point kept constant. The results are average crystallographic properties for the active layer coated on a 30 m long foil. With this insight into the dynamics of crystallization in a roll-coated polymer film, we find that the formation of textured and untextured crystallites seems uncorrelated, and happens at widely different rates. Untextured P3HT crystallites form later in the drying process than expected which may explain previous studies speculating that untextured crystallization depends on concentration. Textured crystallites, however, begin forming much earlier and steadily increases as the film dries, showing a development similar to other in situ studies of these materials.

  4. Highly reliable top-gated thin-film transistor memory with semiconducting, tunneling, charge-trapping, and blocking layers all of flexible polymers.

    PubMed

    Wang, Wei; Hwang, Sun Kak; Kim, Kang Lib; Lee, Ju Han; Cho, Suk Man; Park, Cheolmin

    2015-05-27

    The core components of a floating-gate organic thin-film transistor nonvolatile memory (OTFT-NVM) include the semiconducting channel layer, tunneling layer, floating-gate layer, and blocking layer, besides three terminal electrodes. In this study, we demonstrated OTFT-NVMs with all four constituent layers made of polymers based on consecutive spin-coating. Ambipolar charges injected and trapped in a polymer electret charge-controlling layer upon gate program and erase field successfully allowed for reliable bistable channel current levels at zero gate voltage. We have observed that the memory performance, in particular the reliability of a device, significantly depends upon the thickness of both blocking and tunneling layers, and with an optimized layer thickness and materials selection, our device exhibits a memory window of 15.4 V, on/off current ratio of 2 × 10(4), read and write endurance cycles over 100, and time-dependent data retention of 10(8) s, even when fabricated on a mechanically flexible plastic substrate.

  5. Precise control of surface electrostatic forces on polymer brush layers with opposite charges for resistance to protein adsorption.

    PubMed

    Sakata, Sho; Inoue, Yuuki; Ishihara, Kazuhiko

    2016-10-01

    Various molecular interaction forces are generated during protein adsorption process on material surfaces. Thus, it is necessary to control them to suppress protein adsorption and the subsequent cell and tissue responses. A series of binary copolymer brush layers were prepared via surface-initiated atom transfer radical polymerization, by mixing the cationic monomer unit and anionic monomer unit randomly in various ratios. Surface characterization revealed that the constructed copolymer brush layers exhibited an uniform super-hydrophilic nature and different surface potentials. The strength of the electrostatic interaction forces operating on these mixed-charge copolymer brush surfaces was evaluated quantitatively using force-versus-distance (f-d) curve measurements by atomic force microscopy (AFM) and probes modified by negatively charged carboxyl groups or positively charged amino groups. The electrostatic interaction forces were determined based on the charge ratios of the copolymer brush layers. Notably, the surface containing equivalent cationic/anionic monomer units hardly interacted with both the charged groups. Furthermore, the protein adsorption force and the protein adsorption mass on these surfaces were examined by AFM f-d curve measurement and surface plasmon resonance measurement, respectively. To clarify the influence of the electrostatic interaction on the protein adsorption behavior on the surface, three kinds of proteins having negative, positive, and relatively neutral net charges under physiological conditions were used in this study. We quantitatively demonstrated that the amount of adsorbed proteins on the surfaces would have a strong correlation with the strength of surface-protein interaction forces, and that the strength of surface-protein interaction forces would be determined from the combination between the properties of the electrostatic interaction forces on the surfaces and the charge properties of the proteins. Especially, the

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

    PubMed

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

    2015-09-14

    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. PMID:26374054

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

    PubMed

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

    2015-09-14

    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.

  8. Force control of a tri-layer conducting polymer actuator using optimized fuzzy logic control

    NASA Astrophysics Data System (ADS)

    Itik, Mehmet; Sabetghadam, Mohammadreza; Alici, Gursel

    2014-12-01

    Conducting polymers actuators (CPAs) are potential candidates for replacing conventional actuators in various fields, such as robotics and biomedical engineering, due to their advantageous properties, which includes their low cost, light weight, low actuation voltage and biocompatibility. As these actuators are very suitable for use in micro-nano manipulation and in injection devices in which the magnitude of the force applied to the target is of crucial importance, the force generated by CPAs needs to be accurately controlled. In this paper, a fuzzy logic (FL) controller with a Mamdani inference system is designed to control the blocking force of a trilayer CPA with polypyrrole electrodes, which operates in air. The particle swarm optimization (PSO) method is employed to optimize the controller’s membership function parameters and therefore enhance the performance of the FL controller. An adaptive neuro-fuzzy inference system model, which can capture the nonlinear dynamics of the actuator, is utilized in the optimization process. The optimized Mamdani FL controller is then implemented on the CPA experimentally, and its performance is compared with a non-optimized fuzzy controller as well as with those obtained from a conventional PID controller. The results presented indicate that the blocking force at the tip of the CPA can be effectively controlled by the optimized FL controller, which shows excellent transient and steady state characteristics but increases the control voltage compared to the non-optimized fuzzy controllers.

  9. Control of Pre-Tilt Angles of Liquid Crystal Molecules Using a Chemically Adsorbed Monomolecular Layer as an Alignment Film in Liquid Crystal Cells

    NASA Astrophysics Data System (ADS)

    Ogawa, Kazufumi; Ohtake, Tadashi; Nomura, Takaiki

    2002-11-01

    Photoaligned monomolecular layers containing two materials were formed to control pre-tilt angles (θp) of liquid crystal molecules for twisted nematic (TN) type liquid crystal displays (LCDs) by a chemical adsorption (CA) technique and a photoalignment technique. One was a new chlorosilane type surfactant, 4‧-(6-trichlorosilyloxyhexyloxy) chalcone (CO), having photopolymerizablity, and the other was a surfactant having a straight carbon chain (SC). Although we tried screening six different surfectants as an additive to CO, a surfactant having a long straight hydrocarbon chain (octadecyl-trichlorosilane: C18) was the most suitable for the TN type LCDs. By changing the molecular ratio of CO and C18, pre-tilt angles of liquid crystal molecules in a test liquid crystal (LC) cell could be controlled from 0 to 8° with perfect mono-domain alignment. When surfactants having short hydrocarbon chains and those having fluorocarbon chains were used, the quality of the TN type LC cells obtained was not good.

  10. Bimodal Latex Effect on Spin-Coated Thin Conductive Polymer-Single-Walled Carbon Nanotube Layers.

    PubMed

    Moradi, Mohammad-Amin; Larrakoetxea Angoitia, Katalin; van Berkel, Stefan; Gnanasekaran, Karthikeyan; Friedrich, Heiner; Heuts, Johan P A; van der Schoot, Paul; van Herk, Alex M

    2015-11-10

    We synthesize two differently sized poly(methyl methacrylate-co-tert-butyl acrylate) latexes by emulsion polymerization and mix these with a sonicated single-walled carbon nanotube (SWCNT) dispersion, in order to prepare 3% SWCNT composite mixtures. We spin-coat these mixtures at various spin-speed rates and spin times over a glass substrate, producing a thin, transparent, solid, conductive layer. Keeping the amount of SWCNTs constant, we vary the weight fraction of our smaller 30-nm latex particles relative to the larger 70-nm-sized ones. We find a maximum in the electrical conductivity up to 370 S/m as a function of the weight fraction of smaller particles, depending on the overall solid content, the spin speed, and the spin time. This maximum occurs at 3-5% of the smaller latex particles. We also find a more than 2-fold increase in conductivity parallel to the radius of spin-coating than perpendicular to it. Atomic force microscopy points at the existence of lanes of latex particles in the spin-coated thin layer, while large-area transmission electron microscopy demonstrates that the SWCNTs are aligned over a grid fixed on the glass substrate during the spin-coating process. We extract the conductivity distribution on the surface of the thin film and translate this into the direction of the SWCNTs in it. PMID:26491888

  11. Bimodal Latex Effect on Spin-Coated Thin Conductive Polymer-Single-Walled Carbon Nanotube Layers.

    PubMed

    Moradi, Mohammad-Amin; Larrakoetxea Angoitia, Katalin; van Berkel, Stefan; Gnanasekaran, Karthikeyan; Friedrich, Heiner; Heuts, Johan P A; van der Schoot, Paul; van Herk, Alex M

    2015-11-10

    We synthesize two differently sized poly(methyl methacrylate-co-tert-butyl acrylate) latexes by emulsion polymerization and mix these with a sonicated single-walled carbon nanotube (SWCNT) dispersion, in order to prepare 3% SWCNT composite mixtures. We spin-coat these mixtures at various spin-speed rates and spin times over a glass substrate, producing a thin, transparent, solid, conductive layer. Keeping the amount of SWCNTs constant, we vary the weight fraction of our smaller 30-nm latex particles relative to the larger 70-nm-sized ones. We find a maximum in the electrical conductivity up to 370 S/m as a function of the weight fraction of smaller particles, depending on the overall solid content, the spin speed, and the spin time. This maximum occurs at 3-5% of the smaller latex particles. We also find a more than 2-fold increase in conductivity parallel to the radius of spin-coating than perpendicular to it. Atomic force microscopy points at the existence of lanes of latex particles in the spin-coated thin layer, while large-area transmission electron microscopy demonstrates that the SWCNTs are aligned over a grid fixed on the glass substrate during the spin-coating process. We extract the conductivity distribution on the surface of the thin film and translate this into the direction of the SWCNTs in it.

  12. Effect of Ag doping and insulator buffer layer on the memory mechanism of polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Kaur, Ramneek; Kaur, Jagdish; Tripathi, S. K.

    2015-07-01

    Resistive memory devices based on nanocomposites have attracted great potential for future applications in electronic and optoelectronic devices. The successful synthesis of aqueous CdSe nanoparticles has been provided with UV-Vis and Photoluminescence spectroscopy. The two terminal planar devices of CdSe nanocomposite have been fabricated. The effect of Ag doping and additional dielectric buffer layers on the memory devices have been studied by current-voltage (I-V) and capacitance-voltage (C-V) measurements. The devices show hysteresis loops in both positive and negative bias directions. The memory window has been found to be increased with both Ag doping and PVA layer addition. The charge carrier transport mechanism in the memory devices has been studied by fitting the I-V characteristics with the theoretical model, Space charge conduction model (SCLC). C-V hysteresis loop in both positive and negative bias directions indicate that both the electrons and holes are responsible for memory mechanism of the devices. The switching mechanism of the memory devices has been explained by charge trapping/detrapping model. The retention characteristics show good stability and reliability of the devices.

  13. Inverted polymer fullerene solar cells exceeding 10% efficiency with poly(2-ethyl-2-oxazoline) nanodots on electron-collecting buffer layers

    PubMed Central

    Nam, Sungho; Seo, Jooyeok; Woo, Sungho; Kim, Wook Hyun; Kim, Hwajeong; Bradley, Donal D. C.; Kim, Youngkyoo

    2015-01-01

    Polymer solar cells have been spotlighted due to their potential for low-cost manufacturing but their efficiency is still less than required for commercial application as lightweight/flexible modules. Forming a dipole layer at the electron-collecting interface has been suggested as one of the more attractive approaches for efficiency enhancement. However, only a few dipole layer material types have been reported so far, including only one non-ionic (charge neutral) polymer. Here we show that a further neutral polymer, namely poly(2-ethyl-2-oxazoline) (PEOz) can be successfully used as a dipole layer. Inclusion of a PEOz layer, in particular with a nanodot morphology, increases the effective work function at the electron-collecting interface within inverted solar cells and thermal annealing of PEOz layer leads to a state-of-the-art 10.74% efficiency for single-stack bulk heterojunction blend structures comprising poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene-alt-3-fluorothieno[3,4-b]thiophene-2-carboxylate] as donor and [6,6]-phenyl-C71-butyric acid methyl ester as acceptor. PMID:26656447

  14. Inverted polymer fullerene solar cells exceeding 10% efficiency with poly(2-ethyl-2-oxazoline) nanodots on electron-collecting buffer layers

    NASA Astrophysics Data System (ADS)

    Nam, Sungho; Seo, Jooyeok; Woo, Sungho; Kim, Wook Hyun; Kim, Hwajeong; Bradley, Donal D. C.; Kim, Youngkyoo

    2015-12-01

    Polymer solar cells have been spotlighted due to their potential for low-cost manufacturing but their efficiency is still less than required for commercial application as lightweight/flexible modules. Forming a dipole layer at the electron-collecting interface has been suggested as one of the more attractive approaches for efficiency enhancement. However, only a few dipole layer material types have been reported so far, including only one non-ionic (charge neutral) polymer. Here we show that a further neutral polymer, namely poly(2-ethyl-2-oxazoline) (PEOz) can be successfully used as a dipole layer. Inclusion of a PEOz layer, in particular with a nanodot morphology, increases the effective work function at the electron-collecting interface within inverted solar cells and thermal annealing of PEOz layer leads to a state-of-the-art 10.74% efficiency for single-stack bulk heterojunction blend structures comprising poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-alt-3-fluorothieno[3,4-b]thiophene-2-carboxylate] as donor and [6,6]-phenyl-C71-butyric acid methyl ester as acceptor.

  15. Transparent polymer solar cells employing a layered light-trapping architecture

    NASA Astrophysics Data System (ADS)

    Betancur, Rafael; Romero-Gomez, Pablo; Martinez-Otero, Alberto; Elias, Xavier; Maymó, Marc; Martorell, Jordi

    2013-12-01

    Organic solar cells have unique properties that make them very attractive as a renewable energy source. Of particular interest are semi-transparent cells, which have the potential to be integrated into building façades yet not completely block light. However, making organic cells transparent limits the metal electrode thickness to a few nanometres, drastically reducing its reflectivity and the device photon-harvesting capacity. Here, we propose and implement an ad hoc path for light-harvesting recovery to bring the photon-to-charge conversion up to almost 80% that of its opaque counterpart. We report semi-transparent PTB7:PC71BM cells that exhibit 30% visible light transmission and 5.6% power conversion efficiency. Non-periodic photonic crystals are used to trap near-infrared and near-ultraviolet photons. By modifying the layer structure it is possible to tune the device colour without significantly altering cell performance.

  16. Effect of cyclic outer and inner bending on the fatigue behavior of a multi-layer metal film on a polymer substrate

    NASA Astrophysics Data System (ADS)

    Kim, Byoung-Joon; Shin, Hae-A.-Seul; Lee, Ji-Hoon; Joo, Young-Chang

    2016-06-01

    The electrical reliability of a multi-layer metal film on a polymer substrate during cyclic inner bending and outer bending is investigated using a bending fatigue system. The electrical resistance of a Cu film on a polymer substrate during cyclic outer bending increases due to fatigue damage formation, such as cracks and extrusion. Cyclic inner bending also leads to fatigue damage and a similar increase in the electrical resistance. In a sample having a NiCr under-layer, however, the electrical resistance increases significantly during outer bending but not during inner bending mode. Cross-sectional observations reveal that brittle cracking in the hard under-layer results in different fatigue behaviors according to the stress mode. By applying an Al over-layer, the fatigue resistance is improved during both outer bending and inner bending by suppressing fatigue damage formation. The effects of the position, materials, and thickness of the inter-layer on the electrical reliability of a multi-layer sample are also investigated. This study can provide meaningful information for designing a multi-layer structure under various mechanical deformations including tensile and compressive stress.

  17. Improvement of Performance and Stability of Polymer Photovoltaic Cells by WO3/CUPC as Anode Buffer Layers

    NASA Astrophysics Data System (ADS)

    Varnamkhasti, M. G.; Shahriaria, E.

    2015-05-01

    In this work, bulk-hetrojunction polymer photovoltaic cells based on poly-(3-hexylthiophene) (P3HT): [6,6]-phenyl C61 butyric acid methyl ester (PCBM) were fabricated with tungsten oxide (WO3) and copper phthalocyanine (CuPc) as anodic buffer layers. The WO3 plays an important role in reducing the interfacial resistance, efficiently extracting holes and good band structure matching between the work function of the anode and the highest occupied molecular orbital of the organic material. The insertion of CuPc improves the device In this work, bulk-hetrojunction polymer photovoltaic cells based on poly-(3-hexylthiophene) (P3HT): [6, 6]-phenyl C61 butyric acid methylester (PCBM) were fabricated with tungsten oxide (WO3) and copper phthalocyanine (CuPc) as anodic buffer layers. The WO3 plays animportant role in reducing the interfacial resistance, efficiently extracting holes and good band structure matching between the workfunction of the anode and the highest occupied molecular orbital of the organic material. The insertion of CuPc improves the device performance and expands the absorption spectra range of the photovoltaic devices. The effects of WO3 and CuPc thickness on the performance of the photovoltaic devices were investigated. The optimum thicknesses of WO3 and CuPc were 10 nm and 8 nm, respectively. The obtained power conversion efficiency of optimized cell was about 4.21%. Also, the device performance was analyzed based on thesurface roughness of bare ITO and ITO that was covered with poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonate) (PEDOT:PSS) or WO3/CuPc. The device stability in an ambient atmosphere without encapsulation under continuous light irradiation was also investigated.For the cell with PEDOT:PSS, the power conversion efficiency reduced down to 50% of the maximum value (half-life) after light irradiation for 12 h, while the half-life of device for WO3/CuPc was about 120 h. Therefore, the lifetime of unpackaged devices was improved with

  18. Adsorption of polymer chains at penetrable interfaces

    SciTech Connect

    Gerasimchuk, I. V.; Sommer, J.-U.; Gerasimchuk, V. S.

    2011-03-15

    We investigate the problem of adsorption (localization) of polymer chains in the system of two penetrable interfaces within the mean-field approximation. The saturation of the polymer system in the limit case of zero bulk concentration is studied. We find the exact solution of this mean-field polymer adsorption problem that opens the possibility to treat various localization problems for polymer chains in such environments using appropriate boundary conditions. The exact solution is controlled by a single scaling variable that describes the coupling between the interfaces due to the polymer chains. We obtain a nonmonotonic behavior of the amount of adsorbed polymers as a function of the distance between the interfaces. This leads to a high-energy and a low-energy phase for the double layer with respect to the amount of polymers localized. At the saturation point, we find the total energy of the system and determine the force acting between the interfaces to be strictly attractive and to monotonically decay to zero when the interface distance increases.

  19. Properties of electric double-layer capacitors with various polymer gel electrolytes

    SciTech Connect

    Liu, X.; Osaka, Tetsuya

    1997-09-01

    Polyethylene oxide (PEO), polymethyl methacrylate (PMMA), and polyacrylonitrile (PAN) based gel electrolytes with a mixture of ethylene carbonate and propylene carbonate as plasticizer and lithium perchlorate were used to fabricate an electric double-layer capacitor (EDLC). The performance of EDLCs with these gel electrolytes was investigated by using isotropic high-density graphite electrodes. The ion conductivities of various gel electrolytes were of the order of 10{sup {minus}4} to 10{sup {minus}3} S/cm, and they decreased in the order PAN > PEO > PMMA at ambient temperature. Capacitances approaching the value of EDLCs using organic liquid electrolyte, 20 mF/cm{sup 2}, with an isotropic high-density graphite electrode were obtained in PAN and PMMA gel electrolytes. The EDLC with PMMA-based gel electrolyte showed good charge-discharge behavior over 10{sup 4} cycles at a charge potential of 3.0 V. The rapid progress in the development of electric vehicles and electronic devices has placed increased demand on high-power capacitors. The EDLC is attractive as a rechargeable pulse power source or backup power supply for such applications.

  20. Morphology of Organically-Modified Layered Silicates (ols) in Binary Solvents: Model System for Polymer Nanocomposites

    NASA Astrophysics Data System (ADS)

    Vaia, Richard; Farmer, Barry; Lui, Weidong; Bharadwaj, Rishi

    2001-03-01

    Critical to forwarding nanocomposite technology is development of a detailed understanding of the spatial distribution of the various constituents (inorganic, polymeric and additives) and associated influence on thermodynamic and kinetic (rheological) aspects of the system. With regard to these issues, in-situ small angle x-ray scattering, associated scattering models, coarse grain simulations, and rheology have been used to examine the phase behavior of organically modified layered silicates (OLS) suspended in pure and binary solvent mixtures. These serve as model systems for examining aspects of morphology development and phase behavior in thermoset and thermoplastic nanocomposites. The phase structure of solvent - OLS system is qualitatively described by Onsager arguments modified to include a crystal-solvate (intercalated phase) and a gelation point. Ternary behavior (binary solvent mixtures) provides evidence for preferential segregation of the polar component to the inorganic surface. The chemical structure of the organic surfactant modifier has a negligible influence on the structure of the intercalated phase, but has a marked effect on the extent and concentration of the dispersed phase. These studies provide insight into the use of polar activators for organosilicate rheolgical control agents and additives to enhance nanocomposite formation (e.g. H20 addition for optimal exfoliated PDMS nanocomposites and incorporation of malic anhydride to produce polypropylene nanocomposites).

  1. Adsorption and flocculation by polymers and polymer mixtures.

    PubMed

    Gregory, John; Barany, Sandor

    2011-11-14

    Polymers of various types are in widespread use as flocculants in several industries. In most cases, polymer adsorption is an essential prerequisite for flocculation and kinetic aspects are very important. The rates of polymer adsorption and of re-conformation (relaxation) of adsorbed chains are key factors that influence the performance of flocculants and their mode of action. Polyelectrolytes often tend to adopt a rather flat adsorbed configuration and in this state their action is mainly through charge effects, including 'electrostatic patch' attraction. When the relaxation rate is quite low, particle collisions may occur while the adsorbed chains are still in an extended state and flocculation by polymer bridging may occur. These effects are now well understood and supported by much experimental evidence. In recent years there has been considerable interest in the use of multi-component flocculants, especially dual-polymer systems. In the latter case, there can be significant advantages over the use of single polymers. Despite some complications, there is a broad understanding of the action of dual polymer systems. In many cases the sequence of addition of the polymers is important and the pre-adsorbed polymer can have two important effects: providing adsorption sites for the second polymer or causing a more extended adsorbed conformation as a result of 'site blocking'.

  2. Laser-induced nondestructive patterning of a thin ferroelectric polymer film with controlled crystals using Ge8Sb2Te11 alloy layer for nonvolatile memory.

    PubMed

    Bae, Insung; Kim, Richard Hahnkee; Hwang, Sun Kak; Kang, Seok Ju; Park, Cheolmin

    2014-09-10

    We present a simple but robust nondestructive process for fabricating micropatterns of thin ferroelectric polymer films with controlled crystals. Our method is based on utilization of localized heat arising from thin Ge(8)Sb(2)Te(11) (GST) alloy layer upon exposure of 650 nm laser. The heat was generated on GST layer within a few hundred of nanosecond exposure and subsequently transferred to a thin poly(vinylidene fluoride-co-trifluoroethylene) film deposited on GST layer. By controlling exposure time and power of the scanned laser, ferroelectric patterns of one or two microns in size are fabricated with various shape. In the micropatterned regions, ferroelectric polymer crystals were efficiently controlled in both degree of the crystallinity and the molecular orientations. Nonvolatile memory devices with laser scanned ferroelectric polymer layers exhibited excellent device performance of large remnant polarization, ON/OFF current ratio and data retention. The results are comparable with devices containing ferroelectric films thermally annealed at least for 2 h, making our process extremely efficient for saving time. Furthermore, our approach can be conveniently combined with a number of other functional organic materials for the future electronic applications.

  3. Laser-induced nondestructive patterning of a thin ferroelectric polymer film with controlled crystals using Ge8Sb2Te11 alloy layer for nonvolatile memory.

    PubMed

    Bae, Insung; Kim, Richard Hahnkee; Hwang, Sun Kak; Kang, Seok Ju; Park, Cheolmin

    2014-09-10

    We present a simple but robust nondestructive process for fabricating micropatterns of thin ferroelectric polymer films with controlled crystals. Our method is based on utilization of localized heat arising from thin Ge(8)Sb(2)Te(11) (GST) alloy layer upon exposure of 650 nm laser. The heat was generated on GST layer within a few hundred of nanosecond exposure and subsequently transferred to a thin poly(vinylidene fluoride-co-trifluoroethylene) film deposited on GST layer. By controlling exposure time and power of the scanned laser, ferroelectric patterns of one or two microns in size are fabricated with various shape. In the micropatterned regions, ferroelectric polymer crystals were efficiently controlled in both degree of the crystallinity and the molecular orientations. Nonvolatile memory devices with laser scanned ferroelectric polymer layers exhibited excellent device performance of large remnant polarization, ON/OFF current ratio and data retention. The results are comparable with devices containing ferroelectric films thermally annealed at least for 2 h, making our process extremely efficient for saving time. Furthermore, our approach can be conveniently combined with a number of other functional organic materials for the future electronic applications. PMID:25127181

  4. In Situ Conductance Analysis of Zinc Oxide Nucleation and Coalescence during Atomic Layer Deposition on Metal Oxides and Polymers.

    PubMed

    Sweet, William J; Parsons, Gregory N

    2015-07-01

    Real time in situ conductance is collected continuously during atomic layer deposition (ALD) of zinc oxide films, and trends are used to study ALD nucleation on polypropylene, nylon-6, SiO2, TiO2, and Al2O3 substrates. The detailed conductance change during the ALD cycle is ascribed to changes in surface band bending upon precursor/reactant exposure. Conductive pathways form earlier on the inorganic surfaces than on the polymers, with Al2O3 substrates showing more rapid nucleation than SiO2 or TiO2, consistent with the expected density of nucleation sites (e.g., hydroxyl groups) on these different materials. The measured conductance is ohmic, and both two- and four-electrode configurations show the same data trends. Detailed analysis of conductivity at deposition temperatures between 100 and 175 °C shows faster conductivity decay at higher temperature during the water purge step, ascribed to thermally activated water desorption kinetics. Analysis of real-time conductivity during ALD of other material systems could provide further insight into key aspects of film nucleation and nuclei coalescence.

  5. Experimental studies on poly methyl methacrylate based gel polymer electrolytes for application in electrical double layer capacitors

    NASA Astrophysics Data System (ADS)

    Hashmi, S. A.; Kumar, Ashok; Tripathi, S. K.

    2007-11-01

    Studies have been carried out on gel polymer electrolytes comprising poly methyl methacrylate (PMMA)-ethylene carbonate (EC)-propylene carbonate (PC)-salts, LiClO4, NaClO4 and (C2H5)4NClO4 (TEAClO4) with a view to using them as electrolytes in electrical double layer capacitors (EDLCs) based on activated charcoal powder electrodes. The optimum composition of gel electrolytes, PMMA (20 wt%)-EC : PC (1 : 1 v/v)-1.0 M salts exhibit high ionic conductivity of the order of ~10-3 S cm-1 at room temperature with good mechanical/dimensional stability, suitable for their application in EDLCs. The EDLCs have been characterized using linear sweep cyclic voltammetry, galvanostatic charge-discharge tests and ac impedance spectroscopy. The values of capacitance of 68-151 mF cm-2 (equivalent to single electrode specific capacitance of 38-78 Fg-1 of activated charcoal powder) have been observed. These values correspond to a specific energy of 5.3-10.8 Wh kg-1 and a power density of 0.19-0.22 kW kg-1. The capacitance values have been observed to be stable up to 5000 voltammetric cycles or even more. A comparison of studies shows the predominant role of anions of the gel electrolytes in the capacitive behaviour of EDLCs.

  6. Effect of acid dopants in biodegradable gel polymer electrolyte and the performance in an electrochemical double layer capacitor

    NASA Astrophysics Data System (ADS)

    Sudhakar, Y. N.; Selvakumar, M.; Krishna Bhat, D.

    2015-09-01

    Proton-conducting biodegradable gellan gum gel polymer electrolytes (GPEs) have been prepared using three different dopants, namely ortho-phosphoric (o-H3PO4), sulfuric (H2SO4) and hydrochloric acids (HCl). The GPEs were cross-linked using borax. The polymeric gels were characterized by spectroscopic, thermal, ionic conductivities and dielectric measurements. Proton conductivity was in the range of 5.1 × 10-3 to 3.7 × 10-4 s cm-1 and activation energies were between 0.14 meV and 0.19 meV, at different temperatures. Among the doped acids, the H3PO4 doped GPE exhibited thermal stability at varying temperature. Electrochemical double layer capacitors (EDLCs) were fabricated using activated carbon as electrode material and GPEs. The EDLCs were tested using cyclic voltammetry, ac impedance spectroscopic and galvanostatic charge-discharge techniques. The maximum specific capacitance value was 146 F g-1 at a scan rate of 2 mV s-1. Quite stable values were obtained at a constant current density up to 1000 cycles.

  7. Improvement of oxygen diffusion characteristic in gas diffusion layer with planar-distributed wettability for polymer electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Koresawa, Ryo; Utaka, Yoshio

    2014-12-01

    Mass transfer characteristics of gas diffusion layer (GDL) are closely related to performance of polymer electrolyte fuel cells. Therefore, it is necessary to clarify the characteristics of water distribution relating to the microscopic conformation and oxygen diffusivity of GDL. A hybrid type carbon paper GDL with planar-distributed wettability is investigated for control of liquid water movement and distribution due to hydrophobic to hydrophilic areas that provide wettability differences in GDL and to achieve enhancement of both oxygen diffusion and moisture retention. Hybrid GDLs with different PTFE content were fabricated in an attempt to improve the oxygen diffusion characteristics. The effects of different PTFE contents on the oxygen diffusivity and water distribution were simultaneously measured and observed using galvanic cell oxygen absorber and X-ray radiography. The PTFE distribution was observed using scanning electron microscopy. The formation of oxygen diffusion paths was confirmed by X-ray radiography, where voids in the hybrid GDL were first formed in the hydrophobic regions and then spread to the untreated wetting region. Thus, the formation of oxygen diffusion paths enhanced the oxygen diffusion. In addition, the effects of local PTFE content in the hydrophobic region and the optimal amount of PTFE for hybrid GDL were elucidated.

  8. Syntheses, structure and properties of three-dimensional pillared-layer Ag(I)-Ln(III) heterometallic coordination polymers based on mixed isonicotinate and hemimellitate ligands

    SciTech Connect

    Li, Xinfa; Cao, Rong

    2012-12-15

    Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers (HCPs), formulated as [Ln{sub 2}Ag(hma){sub 2}(ina)(H{sub 2}O){sub 2}]{sub n} nH{sub 2}O [Ln=La(1), Pr(2), Nd(3); Hina=isonicotinic acid, H{sub 3}hma=hemimellitic acid], have been synthesized under hydrothermal conditions. Single-crystal and powder X-ray diffractions confirm that they are isostructural, which features a three-dimensional (3D) pillared-layer heterometallic structure built upon the strictly alternate arrangement of lanthanide-organic layers and [Ag(ina)] pillars. The layers and pillars are connected to each other by Ln-O and Ag-O coordination bonds. The photoluminescent property of the Nd derivative (3) has also been investigated. - Graphical abstract: Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers have been synthesized and structurally characterized. Highlights: Black-Right-Pointing-Pointer Three 3D pillared-layer 4d-4f HCPs were synthesized by hydrothermal reactions. Black-Right-Pointing-Pointer The synergistic coordination strategy was employed. Black-Right-Pointing-Pointer It opens new perspective for the construction of structurally diversified 4d-4f HCPs.

  9. 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.

  10. Étude thermodynamique du polymère super absorbant X10 vis à vis de l'eau vapeur

    NASA Astrophysics Data System (ADS)

    Bakass, M.; Bellat, J. P.; Mokhlisse, A.; Bertrand, G.

    2004-12-01

    The organic polymers super absorbents present values of specific surface lower than 2m2/g. The isobars of adsorption of water vapor on studied polymer are of type III at ambient temperature with the hysterisis phenomena. For temperatures lower than ambient, the isobars become deformed because of an effect of chains. This type of polymer is characterized by a multi-layer adsorption which occurs before the full-course one is complete. During reactions of adsorption, the polymer undergoes rearrangement polymeric network which results from a co-operative diffusion of the water molecules and from a spacing of chain followed by an expansion of the polymeric network. Three types of water molecules adsorbed on polymer were identified: strongly dependent water, adsorbed water and the water only trapped between the macromolecular chains.

  11. Molecular Adsorber Coating

    NASA Technical Reports Server (NTRS)

    Straka, Sharon; Peters, Wanda; Hasegawa, Mark; Hedgeland, Randy; Petro, John; Novo-Gradac, Kevin; Wong, Alfred; Triolo, Jack; Miller, Cory

    2011-01-01

    A document discusses a zeolite-based sprayable molecular adsorber coating that has been developed to alleviate the size and weight issues of current ceramic puck-based technology, while providing a configuration that more projects can use to protect against degradation from outgassed materials within a spacecraft, particularly contamination-sensitive instruments. This coating system demonstrates five times the adsorption capacity of previously developed adsorber coating slurries. The molecular adsorber formulation was developed and refined, and a procedure for spray application was developed. Samples were spray-coated and tested for capacity, thermal optical/radiative properties, coating adhesion, and thermal cycling. Work performed during this study indicates that the molecular adsorber formulation can be applied to aluminum, stainless steel, or other metal substrates that can accept silicate-based coatings. The coating can also function as a thermal- control coating. This adsorber will dramatically reduce the mass and volume restrictions, and is less expensive than the currently used molecular adsorber puck design.

  12. Modulating Electro-osmotic Flow with Polymer Coatings

    NASA Astrophysics Data System (ADS)

    Hickey, Owen A.

    Micro- and nano-fluidic devices represent an exciting field with a wide range of possible applications. These devices, typically made of either silica or glass, ionize when placed in contact with water. Upon the application of an electric field parallel to the wall, a flow is produced by the charged walls called the electro-osmotic flow (EOF). Since electric fields are so often used as the driving force in these devices, EOF is an extremely common phenomenon. For this reason it is highly desirable to be able to control EOF in order to optimize the functioning of these devices. One method which is quite common experimentally is the modification of the surface using polymer coatings. These coatings can be either adsorbed or grafted, and charged or neutral. The first part of this thesis looks at the role of neutral adsorbed polymer coatings for the modulation of EOF. Specifically our simulation results show that for adsorbed coatings made from a dilute polymer solution the strongest quenching of EOF is found for an adsorption strength at the phase transition for adsorption of the polymers. Further evidence is presented that shows that by using a high density of polymer solution and a polymer which has a strong attraction to the surface a very thick polymer layer can be created. Next the case of charged grafted polymer coatings is examined. The variation of the EOF with respect to several key parameters which characterize the polymer coating is investigated and compared to theory. The prediction that the electrophoretic velocity of the polymers is the same as the EOF generated by a coating made up of the same polymers is found to be false though the two values are quite close. The last section presents results which show how hydrodynamic interactions in charged polymer systems can be modeled mesoscopically without the use of explicit charges by forcing a slip between monomers and the surrounding fluid. This model is validated by simulating some surprising predictions

  13. Electrochemical Analysis of Conducting Polymer Thin Films

    PubMed Central

    Vyas, Ritesh N.; Wang, Bin

    2010-01-01

    Polyelectrolyte multilayers built via the layer-by-layer (LbL) method has been one of the most promising systems in the field of materials science. Layered structures can be constructed by the adsorption of various polyelectrolyte species onto the surface of a solid or liquid material by means of electrostatic interaction. The thickness of the adsorbed layers can be tuned precisely in the nanometer range. Stable, semiconducting thin films are interesting research subjects. We use a conducting polymer, poly(p-phenylene vinylene) (PPV), in the preparation of a stable thin film via the LbL method. Cyclic voltammetry and electrochemical impedance spectroscopy have been used to characterize the ionic conductivity of the PPV multilayer films. The ionic conductivity of the films has been found to be dependent on the polymerization temperature. The film conductivity can be fitted to a modified Randle’s circuit. The circuit equivalent calculations are performed to provide the diffusion coefficient values. PMID:20480052

  14. Dual phase polymer gel electrolyte based on non-woven poly(vinylidenefluoride-co-hexafluoropropylene)–layered clay nanocomposite fibrous membranes for lithium ion batteries

    SciTech Connect

    Shubha, Nageswaran; Prasanth, Raghavan; Hoon, Hng Huey; Srinivasan, Madhavi

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► P(VdF-co-HFP)–clay nanocomposite based electrospun membranes are prepared. ► The membranes are used as polymer gel electrolyte (PGE) in lithium ion batteries. ► The composite PGE shows ionic conductivity of 5.5 mS cm{sup −1} at room temperature. ► Li/PGE/LiFePO{sub 4} cell delivers initial discharge capacity of 160 mAh g{sup −1}. ► The use of prepared electrolyte significantly improved the cell performance. -- Abstract: A new approach for fabricating polymer gel electrolytes (PGEs) based on electrospun poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) incorporated with layered nanoclay has been employed to enhance the ionic conductivity and electrochemical properties of P(VdF-co-HFP) without compromising its mechanical strength. The effect of layered nanoclay on properties of membranes has been evaluated by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Surface morphology of the membranes has been studied using field-emission scanning electron microscopy (FE-SEM). Polymer gel electrolytes are prepared by soaking the fibrous membrane into 1 M LiPF{sub 6} in EC/DEC. The electrochemical studies show that incorporation of layered nanoclay into the polymer matrix greatly enhanced the ionic conductivity and compatibility with lithium electrodes. The charge–discharge properties and cycling performance of Li/LiFePO{sub 4} cells comprising nanocomposite polymer gel electrolytes have been evaluated at room temperature.

  15. Large and Reversible Plasmon Tuning using Ultrathin Responsive Polymer film

    NASA Astrophysics Data System (ADS)

    Singamaneni, Srikanth; Nergiz, Saide

    2011-03-01

    We demonstrate reversible linear and branched aggregation of gold nanoparticles adsorbed on an ultrathin responsive polymer ((poly(4-vinyl pyridine), P4VP) film. P4VP is a weak cationic polymer, which exhibits a reversible coil to globule transition with change in external pH. Atomic force microscopy revealed that in the coiled state (below the isoelectric point of the polymer) of the polymer chains, gold nanoparticles adsorbed on the polymer layer existed as primarily individual nanoparticles. On the other hand, lowering the pH caused the polymer chains to transition from coil to globule state, resulting in aggregation of the nanoparticles into linear and branched chains. Reversible aggregation of the nanoparticles results in a dramatic change in the optical properties of the metal nanostructures. Apart from the large redistribution of the intensity between the individual (530 nm) and coupled (650 nm) plasmon bands, the coupled plasmon band exhibits a shift of nearly 60 nm with change in external pH. The pH triggered aggregation of the nanoparticles and the dramatic change in the optical properties associated with the same can form an excellent platform for colorimetric sensing. The work reported here is supported by the Siteman Cancer Center at Barnes-Jewish Hospital and Washington University School of Medicine.

  16. Durable metallized polymer mirror

    DOEpatents

    Schissel, Paul O.; Kennedy, Cheryl E.; Jorgensen, Gary J.; Shinton, Yvonne D.; Goggin, Rita M.

    1994-01-01

    A metallized polymer mirror construction having improved durability against delamination and tunneling, comprising: an outer layer of polymeric material; a metal oxide layer underlying the outer layer of polymeric material; a silver reflective layer underneath the metal oxide layer; and a layer of adhesive attaching the silver layer to a substrate.

  17. Durable metallized polymer mirror

    DOEpatents

    Schissel, P.O.; Kennedy, C.E.; Jorgensen, G.J.; Shinton, Y.D.; Goggin, R.M.

    1994-11-01

    A metallized polymer mirror construction is disclosed having improved durability against delamination and tunneling, comprising: an outer layer of polymeric material; a metal oxide layer underlying the outer layer of polymeric material; a silver reflective layer underneath the metal oxide layer; and a layer of adhesive attaching the silver layer to a substrate. 6 figs.

  18. Correlation to Predict Collision Efficiency of Natural Organic Matter (NOM)- and Polymer- coated Nanoparticles in Porous Media

    NASA Astrophysics Data System (ADS)

    Lowry, G. V.; Phenrat, T.; Cisneros, C. M.; Schoenfelder, D. P.; Fagerlund, F.; Kim, H.; Illangasekare, T.; Tilton, R. D.

    2008-12-01

    The fate of manufactured nanoparticles released to the environment is of great interest due to their increasing use in consumer products and their potential risk to the environment and human health. Manufactured nanomaterials typically have a polymeric surface coating to provide specific functionality, or will adsorb natural organic matter (NOM) once released into the environment. Adsorbed polymer and NOM can provide electrosteic repulsions that enhance the migration of nanoparticles in porous media. Semi-empirical correlations to predict the collision efficiency of electrostatically stabilized (uncoated) colloids are available, however, they are not applicable to nanomaterials coated with polymeric or NOM layers. We present a semi- empirical correlation to predict the collision efficiency of NOM and polymer-coated nanomaterials in saturated porous media. The adsorbed mass and adsorbed layer properties (including thickness) are determined and particle breakthrough curves are generated for a number of particle and coating types. Regression analysis is then used to develop a semi-empirical correlation that includes a parameter (NLEK) representing electrosteric repulsions afforded by adsorbed NOM or polymer. The correlation appears robust over a range of four particle and four coating types and should be a valuable tool for predicting the relative mobility of different manufactured and natural nanomaterials based on a few measurable properties.

  19. Single-layer electroluminescent devices based on fluorene-1H-pyrazolo[3,4-b]quinoxaline co-polymers

    NASA Astrophysics Data System (ADS)

    Pokladko-Kowar, Monika; Danel, Andrzej; Chacaga, Łukasz

    2013-11-01

    A fluorene based copolymer was synthesized for electroluminescent application. To the main chain of polymer the nitrogen heterocyclic, 1H-pyrazolo[3,4-b]quinoxaline, unit was introduced. The incorporation of this derivative tuned the emission from the blue to yellow-green one. A simple, single layered device was fabricated with the configuration ITO/PEDOT/co-poly-FLU-PQX/Ca/Mg.

  20. Adsorption properties of the nanozirconia/anionic polyacrylamide system-Effects of surfactant presence, solution pH and polymer carboxyl groups content

    NASA Astrophysics Data System (ADS)

    Wiśniewska, Małgorzata; Chibowski, Stanisław; Urban, Teresa

    2016-05-01

    The adsorption mechanism of anionic polyacrylamide (PAM) on the nanozirconia surface was examined. The effects of solution pH, carboxyl groups content in macromolecules and anionic surfactant (sodium dodecyl sulfate-SDS) addition were determined. The more probable structure of polymer adsorption layer was characterized based on the data obtained from spectrophotometry, viscosimetry and potentiometric titration methods. The adsorbed amount of polymer, size of macromolecules in the solution and surface charge density of ZrO2 particles in the absence and presence of PAM were assessed, respectively. Analysis of these results indicated that the increase of solution pH and content of carboxyl groups in the polymeric chains lead to more expanded conformations of adsorbing macromolecules. As a result, the adsorption of anionic polyacrylamide decreased. The SDS presence caused the significant increase of PAM adsorbed amount at pH 3, whereas at pH 6 and 9 the surfactant addition resulted in reduction of polymer adsorption level.

  1. Using specialized adsorbents for remediation

    SciTech Connect

    Hochmuth, D.P.; Grant, A.

    1995-11-01

    This paper describes two remediation case studies in which specialized adsorbents were used. In one case, the adsorbents were used to treat effluent from a soil vapor extraction system. In the other case, the adsorbents were used to treat air from a groundwater air stripper. The specialized adsorbents effectively removed volatile organic compounds from each air stream.

  2. A two-dimensional layered Cd(II) coordination polymer with a three-dimensional supramolecular architecture incorporating mixed multidentate N- and O-donor ligands.

    PubMed

    Huang, Qiu-Ying; Su, Ming-Yang; Meng, Xiang-Ru

    2015-06-01

    The combination of N-heterocyclic and multicarboxylate ligands is a good choice for the construction of metal-organic frameworks. In the title coordination polymer, poly[bis{μ2-1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole-κ(2)N(3):N(4)}(μ4-butanedioato-κ(4)O(1):O(1'):O(4):O(4'))(μ2-butanedioato-κ(2)O(1):O(4))dicadmium], [Cd(C4H4O4)(C9H8N6)]n, each Cd(II) ion exhibits an irregular octahedral CdO4N2 coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole (bimt) ligands. Cd(II) ions are connected by two kinds of crystallographically independent succinate ligands to generate a two-dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three-dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.

  3. Influence of the Secondary Cell Wall Polymer on the Reassembly, Recrystallization, and Stability Properties of the S-Layer Protein from Bacillus stearothermophilus PV72/p2

    PubMed Central

    Sára, Margit; Dekitsch, Christine; Mayer, Harald F.; Egelseer, Eva M.; Sleytr, Uwe B.

    1998-01-01

    The high-molecular-weight secondary cell wall polymer (SCWP) from Bacillus stearothermophilus PV72/p2 is mainly composed of N-acetylglucosamine (GlcNAc) and N-acetylmannosamine (ManNAc) and is involved in anchoring the S-layer protein via its N-terminal region to the rigid cell wall layer. In addition to this binding function, the SCWP was found to inhibit the formation of self-assembly products during dialysis of the guanidine hydrochloride (GHCl)-extracted S-layer protein. The degree of assembly (DA; percent assembled from total S-layer protein) that could be achieved strongly depended on the amount of SCWP added to the GHCl-extracted S-layer protein and decreased from 90 to 10% when the concentration of the SCWP was increased from 10 to 120 μg/mg of S-layer protein. The SCWP kept the S-layer protein in the water-soluble state and favored its recrystallization on solid supports such as poly-l-lysine-coated electron microscopy grids. Derived from the orientation of the base vectors of the oblique S-layer lattice, the subunits had bound with their charge-neutral outer face, leaving the N-terminal region with the polymer binding domain exposed to the ambient environment. From cell wall fragments about half of the S-layer protein could be extracted with 1 M GlcNAc, indicating that the linkage type between the S-layer protein and the SCWP could be related to that of the lectin-polysaccharide type. Interestingly, GlcNAc had an effect on the in vitro self-assembly and recrystallization properties of the S-layer protein that was similar to that of the isolated SCWP. The SCWP generally enhanced the stability of the S-layer protein against endoproteinase Glu-C attack and specifically protected a potential cleavage site in position 138 of the mature S-layer protein. PMID:9696762

  4. Restricted access molecularly imprinted polymers obtained by bovine serum albumin and/or hydrophilic monomers' external layers: a comparison related to physical and chemical properties.

    PubMed

    Santos, Mariane Gonçalves; Moraes, Gabriel de Oliveira Isac; Nakamura, Maurício Gustavo; dos Santos-Neto, Álvaro José; Figueiredo, Eduardo Costa

    2015-11-21

    Molecularly imprinting polymers (MIPs) can be modified with external layers in order to obtain restricted access molecularly imprinted polymers (RAMIPs) able to exclude macromolecules and retain low weight compounds. These modifications have been frequently achieved using hydrophilic monomers, chemically bound on the MIP surface. Recently, our group proposed a new biocompatible RAMIP based on the formation of a bovine serum albumin coating on the surface of MIP particles. This material has been used to extract drugs directly from untreated human plasma samples, but its physicochemical evaluation has not been carried out yet, mainly in comparison with RAMIPs obtained by hydrophilic monomers. Thus, we proposed in this paper a comparative study involving the surface composition, microscopic aspect, selectivity, binding kinetics, adsorption and macromolecule elimination ability of these different materials. We concluded that the synthesis procedure influences the size and shape of particles and that hydrophilic co-monomer addition as well as coating with BSA do not alter the chemical recognition ability of the material. The difference between imprinted and non-imprinted polymers' adsorption was evident (suggesting that imprinted polymers have a better capacity to bind the template than the non-imprinted ones). The Langmuir model presents the best fit to describe the materials' adsorption profile. The polymer covered with hydrophilic monomers presented the best adsorption for the template in an aqueous medium, probably due to a hydrophilic layer on its surface. We also concluded that an association of the hydrophilic monomers with the bovine serum albumin coating is important to obtain materials with higher capacity of macromolecule exclusion.

  5. Restricted access molecularly imprinted polymers obtained by bovine serum albumin and/or hydrophilic monomers' external layers: a comparison related to physical and chemical properties.

    PubMed

    Santos, Mariane Gonçalves; Moraes, Gabriel de Oliveira Isac; Nakamura, Maurício Gustavo; dos Santos-Neto, Álvaro José; Figueiredo, Eduardo Costa

    2015-11-21

    Molecularly imprinting polymers (MIPs) can be modified with external layers in order to obtain restricted access molecularly imprinted polymers (RAMIPs) able to exclude macromolecules and retain low weight compounds. These modifications have been frequently achieved using hydrophilic monomers, chemically bound on the MIP surface. Recently, our group proposed a new biocompatible RAMIP based on the formation of a bovine serum albumin coating on the surface of MIP particles. This material has been used to extract drugs directly from untreated human plasma samples, but its physicochemical evaluation has not been carried out yet, mainly in comparison with RAMIPs obtained by hydrophilic monomers. Thus, we proposed in this paper a comparative study involving the surface composition, microscopic aspect, selectivity, binding kinetics, adsorption and macromolecule elimination ability of these different materials. We concluded that the synthesis procedure influences the size and shape of particles and that hydrophilic co-monomer addition as well as coating with BSA do not alter the chemical recognition ability of the material. The difference between imprinted and non-imprinted polymers' adsorption was evident (suggesting that imprinted polymers have a better capacity to bind the template than the non-imprinted ones). The Langmuir model presents the best fit to describe the materials' adsorption profile. The polymer covered with hydrophilic monomers presented the best adsorption for the template in an aqueous medium, probably due to a hydrophilic layer on its surface. We also concluded that an association of the hydrophilic monomers with the bovine serum albumin coating is important to obtain materials with higher capacity of macromolecule exclusion. PMID:26460233

  6. Layers

    NASA Astrophysics Data System (ADS)

    Hong, K. J.; Jeong, T. S.; Youn, C. J.

    2014-09-01

    The temperature-dependent photoresponse characteristics of MnAl2S4 layers have been investigated, for the first time, by use of photocurrent (PC) spectroscopy. Three peaks were observed at all temperatures. The electronic origin of these peaks was associated with band-to-band transitions from the valence-band states Γ4( z), Γ5( x), and Γ5( y) to the conduction-band state Γ1( s). On the basis of the relationship between PC-peak energy and temperature, the optical band gap could be well expressed by the expression E g( T) = E g(0) - 2.80 × 10-4 T 2/(287 + T), where E g(0) was estimated to be 3.7920 eV, 3.7955 eV, and 3.8354 eV for the valence-band states Γ4( z), Γ5( x), and Γ5( y), respectively. Results from PC spectroscopy revealed the crystal-field and spin-orbit splitting were 3.5 meV and 39.9 meV. The gradual decrease of PC intensity with decreasing temperature can be explained on the basis of trapping centers associated with native defects in the MnAl2S4 layers. Plots of log J ph, the PC current density, against 1/ T, revealed a dominant trap level in the high-temperature region. By comparing PC and the Hall effect results, we confirmed that this trap level is a shallow donor 18.9 meV below the conduction band.

  7. Regenerative adsorbent heat pump

    NASA Technical Reports Server (NTRS)

    Jones, Jack A. (Inventor)

    1991-01-01

    A regenerative adsorbent heat pump process and system is provided which can regenerate a high percentage of the sensible heat of the system and at least a portion of the heat of adsorption. A series of at least four compressors containing an adsorbent is provided. A large amount of heat is transferred from compressor to compressor so that heat is regenerated. The process and system are useful for air conditioning rooms, providing room heat in the winter or for hot water heating throughout the year, and, in general, for pumping heat from a lower temperature to a higher temperature.

  8. Comparison of light out-coupling enhancements in single-layer blue-phosphorescent organic light emitting diodes using small-molecule or polymer hosts

    SciTech Connect

    Chang, Yung-Ting; Liu, Shun-Wei; Yuan, Chih-Hsien; Lee, Chih-Chien; Ho, Yu-Hsuan; Wei, Pei-Kuen; Chen, Kuan-Yu; Lee, Yi-Ting; Wu, Min-Fei; Chen, Chin-Ti E-mail: chihiwu@cc.ee.ntu.edu.tw; Wu, Chih-I E-mail: chihiwu@cc.ee.ntu.edu.tw

    2013-11-07

    Single-layer blue phosphorescence organic light emitting diodes (OLEDs) with either small-molecule or polymer hosts are fabricated using solution process and the performances of devices with different hosts are investigated. The small-molecule device exhibits luminous efficiency of 14.7 cd/A and maximum power efficiency of 8.39 lm/W, which is the highest among blue phosphorescence OLEDs with single-layer solution process and small molecular hosts. Using the same solution process for all devices, comparison of light out-coupling enhancement, with brightness enhancement film (BEF), between small-molecule and polymer based OLEDs is realized. Due to different dipole orientation and anisotropic refractive index, polymer-based OLEDs would trap less light than small molecule-based OLEDs internally, about 37% better based simulation results. In spite of better electrical and spectroscopic characteristics, including ambipolar characteristics, higher carrier mobility, higher photoluminescence quantum yield, and larger triplet state energy, the overall light out-coupling efficiency of small molecule-based devices is worse than that of polymer-based devices without BEF. However, with BEF for light out-coupling enhancement, the improved ratio in luminous flux and luminous efficiency for small molecule based device is 1.64 and 1.57, respectively, which are significantly better than those of PVK (poly-9-vinylcarbazole) devices. In addition to the theoretical optical simulation, the experimental data also confirm the origins of differential light-outcoupling enhancement. The maximum luminous efficiency and power efficiency are enhanced from 14.7 cd/A and 8.39 lm/W to 23 cd/A and 13.2 lm/W, respectively, with laminated BEF, which are both the highest so far for single-layer solution-process blue phosphorescence OLEDs with small molecule hosts.

  9. Finding the lost open-circuit voltage in polymer solar cells by UV-ozone treatment of the nickel acetate anode buffer layer.

    PubMed

    Wang, Fuzhi; Sun, Gang; Li, Cong; Liu, Jiyan; Hu, Siqian; Zheng, Hua; Tan, Zhan'ao; Li, Yongfang

    2014-06-25

    Efficient polymer solar cells (PSCs) with enhanced open-circuit voltage (Voc) are fabricated by introducing solution-processed and UV-ozone (UVO)-treated nickel acetate (O-NiAc) as an anode buffer layer. According to X-ray photoelectron spectroscopy data, NiAc partially decomposed to NiOOH during the UVO treatment. NiOOH is a dipole species, which leads to an increase in the work function (as confirmed by ultraviolet photoemission spectroscopy), thus benefitting the formation of ohmic contact between the anode and photoactive layer and leading to increased Voc. In addition, the UVO treatment improves the wettability between the substrate and solvent of the active layer, which facilitates the formation of an upper photoactive layer with better morphology. Further, the O-NiAc layer can decrease the series resistance (Rs) and increase the parallel resistance (Rp) of the devices, inducing enhanced Voc in comparison with the as-prepared NiAc-buffered control devices without UVO treatment. For PSCs based on the P3HT:PCBM system, Voc increases from 0.50 to 0.60 V after the NiAc buffer layer undergoes UVO treatment. Similarly, in the P3HT:ICBA system, the Voc value of the device with a UVO-treated NiAc buffer layer increases from 0.78 to 0.88 V, showing an enhanced power conversion efficiency of 6.64%.

  10. Finding the lost open-circuit voltage in polymer solar cells by UV-ozone treatment of the nickel acetate anode buffer layer.

    PubMed

    Wang, Fuzhi; Sun, Gang; Li, Cong; Liu, Jiyan; Hu, Siqian; Zheng, Hua; Tan, Zhan'ao; Li, Yongfang

    2014-06-25

    Efficient polymer solar cells (PSCs) with enhanced open-circuit voltage (Voc) are fabricated by introducing solution-processed and UV-ozone (UVO)-treated nickel acetate (O-NiAc) as an anode buffer layer. According to X-ray photoelectron spectroscopy data, NiAc partially decomposed to NiOOH during the UVO treatment. NiOOH is a dipol