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Sample records for adsorbed polymer layer

  1. Structure of Non-Equilibrium Adsorbed Polymer Layers

    NASA Astrophysics Data System (ADS)

    O'Shaughnessy, Ben; Vavylonis, Dimitrios

    2004-03-01

    Equilibrium polymer adsorption has been widely studied theoretically. Many experiments however implicate strong non-equilibrium effects for monomer sticking energies somewhat larger than kT, the most common case. The structure and slow dynamics in these layers is not understood. We analyze theoretically non-equilibrium layers from dilute solutions in the limit of irreversible monomer adsorption. We find the density profile ˜ z-4/3 and loop distribution ˜ s-11/5 of the resulting layer are no different to equilibrium. However, single chain statistics are radically different: the layer consists of a flat inner portion of fully collapsed chains plus an outer part whose chains make only fN surface contacts where N is chain length. The contact fractions f follow a broad distribution, P(f) ˜ f-4/5, consistent with experiment [H. M. Schneider et al, Langmuir 12, 994 (1996)], and the lateral size R of adsorbed chains is of order the bulk coil size, R ˜ N^3/5. For equilibrium layers, by contrast, P has a unique peak at a value of f of order unity, while R ˜ N^1/2 is significantly less. The relaxation of a non-equilibrium layer towards equilibrium thus entails chain shrinkage and tighter binding. We speculate that the observed decrease of bulk-layer chain exchange rates with increasing aging reflects these internal layer dynamics.

  2. 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

  3. Examining Adsorbed Polymer Conformations with Fluorescence Imaging

    NASA Astrophysics Data System (ADS)

    Parkes, Maria; Chennaoui, Mourad; Wong, Janet; Tribology Group, Dept. of Mechanical Engineering Team

    2011-03-01

    The conformation of adsorbed polymers can have significant impact on their properties such as dynamics and elasticity as well as their ability to take part in reactions with other molecules. Experimental research to determine adsorbed polymer conformation has relied mainly on atomic force microscopy (AFM) studies. During an AFM scan, the contact between the scanning probe and the polymer could affect the polymer conformation, particularly where parts of the polymer might have formed projected loops and tails. In this work, conformations of model polymers are examined with total internal reflection fluorescence microscopy (TIRFM). The advantage of TIRFM over AFM is that TIRFM is a non contact technique. Lambda DNA labelled along its length with fluorescent probes was adsorbed in a projected 2D -- 3D state. With TIRFM, the relationship between intensity and depth was used as a basis to determine how the conformation of the adsorbed polymers evolved with time using our custom algorithm.

  4. Block copolymer adsorbed layers on solids

    NASA Astrophysics Data System (ADS)

    Sen, Mani; Jiang, Naisheng; Gowd, Bhoje; Endoh, Maya; Koga, Tadanori

    Block copolymer thin films offer a simple and effective route to fabricate highly ordered periodic microdomain structures. The fundamental, yet unsolved question is whether these highly oriented microdomain structures persist even near an impenetrable solid wall. We here report the adsorbed structures of polystyrene-block-poly (4-vinylpyridine) (PS-block-P4VP, Mw = 41,000, PS (weight fraction =0.81) formed on planar silicon substrates. Perpendicularly aligned cylindrical microdomains were created by solvent vapor annealing (Gowd et al., Soft Matter, 2014, 10, 7753), and the adsorbed layer was derived by solvent leaching with chloroform, a good solvent for the polymers and thereafter characterized by using atomic force microscopy, scanning electron microscopy, grazing incidence small angle x-ray scattering, and x-ray reflectivity. The results showed that both PS and P4VP chains lie flat on the substrate, forming a microphase-separated structure (MSS) without long-range order. Moreover, a spin-coated PS-block-P4VP thin film annealed under vacuum at 190 °C showed similar MSS on the substrate, indicating the generality of the interfacial polymer structure. Details will be discussed in the presentation. NSF Grant No. CMMI-1332499.

  5. 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

  6. 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. PMID:26400677

  7. 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

  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. PMID:26690091

  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. 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

  13. The density and refractive index of adsorbing protein layers.

    PubMed

    Vörös, Janos

    2004-07-01

    The structure of the adsorbing layers of native and denatured proteins (fibrinogen, gamma-immunoglobulin, albumin, and lysozyme) was studied on hydrophilic TiO(2) and hydrophobic Teflon-AF surfaces using the quartz crystal microbalance with dissipation and optical waveguide lightmode spectroscopy techniques. The density and the refractive index of the adsorbing protein layers could be determined from the complementary information provided by the two in situ instruments. The observed density and refractive index changes during the protein-adsorption process indicated the presence of conformational changes (e.g., partial unfolding) in general, especially upon contact with the hydrophobic surface. The structure of the formed layers was found to depend on the size of the proteins and on the experimental conditions. On the TiO(2) surface smaller proteins formed a denser layer than larger ones and the layer of unfolded proteins was less dense than that adsorbed from the native conformation. The hydrophobic surface induced denaturation and resulted in the formation of thin compact protein films of albumin and lysozyme. A linear correlation was found between the quartz crystal microbalance measured dissipation factor and the total water content of the layer, suggesting the existence of a dissipative process that is related to the solvent molecules present inside the adsorbed protein layer. Our measurements indicated that water and solvent molecules not only influence the 3D structure of proteins in solution but also play a crucial role in their adsorption onto surfaces. PMID:15240488

  14. 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.

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

    DOE PAGESBeta

    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

  16. Dynamics of Confined Flexible and Unentangled Polymer Melts in Highly Adsorbing Cylindrical Pores

    SciTech Connect

    Carrillo, Jan-Michael Y; Sumpter, Bobby G

    2014-01-01

    Inspired by the recent neutron spin echo experiments (NSE) designed to address the dynamic phenomena in polymer melts that are induced by interactions with a confining surface, we performed coarse-grained molecular dynamics simulations to replicate the experimental results in order to provide new molecular insight for the observations. The results show excellent agreement in the values obtained for the normalized coherent single chain dynamic structure factor, S(Q;Dt)/S(Q;0) , between experiments and simulations. The simulations indicate that using different chain molecular weights that are used to achieve scattering contrast results in the uneven distribution of scatterers in the radial direction because lower molecular weight chains prefer to adsorb in the confining surface. In the bulk configuration, both simulations and experiments confirm that the polymer chains follow Rouse dynamics. However, under confinement, the Rouse modes are suppressed. The mean-squared radius of gyration, R2g, and the average relative shape anisotropy k2 of the conformation of the polymer chains indicate a pancake-like conformation near the surface and a bulk-like conformation near the center of the confining cylinder. Direct visualization of the polymers in the simulation confirm the pancake-like conformation of the adsorbed chains and the presence of trains, loops and tails in the region between the adsorbed chains and the chains not in contact with the surface. Despite the presence of these different conformations, the average form factor of the confined chains still follows the Debye function which describes linear ideal chains, which is in agreement with small angle neutron scattering (SANS) experiments. The experimentally inaccessible mean squared displacement of the confined monomers, calculated as a function of radial distance from the pore surface, was obtained in the simulations. The simulation shows a gradual increase of the MSD from the adsorbed, but mobile layer, to that

  17. 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

  18. Plasma protein adsorbed biomedical polymers: activation of human monocytes and induction of interleukin 1.

    PubMed

    Bonfield, T L; Colton, E; Anderson, J M

    1989-06-01

    These studies involved the evaluation of human monocyte/macrophage activation by biomedical polymers coated with human blood proteins. The biomedical polymers were polyethylene, polydimethylsiloxane, woven Dacron fabric, expanded polytetrafluoroethylene, Biomer, and tissue culture treated polystyrene as the control. They were adsorbed with human blood proteins: albumin, fibrinogen, fibronectin, hemoglobin, and gamma globulin. The protein adsorbed polymers were evaluated for their potential to activate the monocyte/macrophage cellular population in vitro as assessed by the induction of the monocyte/macrophage inflammatory mediator, Interleukin 1 (IL1). Suppression of IL1 was observed when protein adsorbed polymers were compared to the appropriate protein adsorbed control. Protein adsorbed polymers, when compared to polymers without protein adsorption, stimulated IL1 production. The data presented in this manuscript show the level of induction and secretion of IL1 was dependent on the biomedical polymer and the protein adsorbed, as well as the requirement of lipopolysaccharide. These results show differential interactions occur between the proteins, monocytes/macrophages, and biomedical polymers which alter activation and induction of IL1. PMID:2786877

  19. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  1. Stabilization of nanorods in polymer melts by end-adsorbed chains

    NASA Astrophysics Data System (ADS)

    Frischknecht, Amalie L.

    2007-03-01

    Adsorbed or grafted polymers are often used to provide steric stabilization of colloidal particles. When the particle size approaches the nanoscale, the curvature of the particles becomes relevant, and rules of thumb based on the behavior of polymers attached to flat surfaces may no longer apply. To investigate this effect for the case of cylindrical symmetry, I use a classical density functional theory applied to a coarse-grained model to study the polymer-mediated interactions between two nanorods. The rods are immersed in a polymer melt consisting of two kinds of chains: 1) a small fraction of chains of length N with ends that are attracted to the rods so that they form a polymer brush on the rods; and 2) a matrix of chains of length P which have no interactions with the rods. Calculations of the density profiles and potential of mean force reveal the effects of curvature compared to similar calculations for chains adsorbed to flat planar surfaces.

  2. 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.

  3. 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%).

  4. 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. PMID:22687522

  5. 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

  6. 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

  7. Immobilized Polymer Layers on Spherical Nanoparticles

    SciTech Connect

    Harton, S.; Kumar, S; Yang, H; Koga, T; Hicks, K; Lee, H; Mijovic, J; Liu, M; Vallery, R; Gidley, D

    2010-01-01

    Polymer properties, such as their mechanical strength, barrier properties, and dielectric response, can be dramatically improved by the addition of nanoparticles. This improvement is thought to be because the surface area per unit mass of particles increases with decreasing particle size, R, as 1/R. This favorable effect has to be reconciled with the expectation that at small enough R the nanoparticles must behave akin to a solvent and cause a deterioration of properties. How does this transition in behavior from large solutes to the solvent limit occur? We conjecture that for small enough particles the layer of polymer affected by the particles ('bound' polymer layer) must be much smaller than that for large particles: the favorable effect of increasing particle surface area can thus be overcome and lead to the small solvent limit with unfavorable mechanical properties, for example. To substantiate this picture requires that we measure and compare the 'bound polymer layer' formed on nanoparticles with those near large particles with equivalent chemistry. We have implemented a novel strategy to obtain uniform nanoparticle dispersion in polymers, a problem for many previous works. Then, by combining theory and a suite of experimental techniques, including differential scanning calorimetry and positron annihilation lifetime spectroscopy, we show that the immobilized poly(2-vinylpyridine) layer near 15 nm diameter silica particles ({approx}1 nm) is considerably thinner than that at flat silica surfaces ({approx}4 to 5 nm), which is the limit of an infinitely large particle. We have also determined that the changes in the polymer's glass-transition temperature due to the presence of this strongly interacting surface are very small in both well-dispersed nanocomposites and thin films (<100 nm). Similarly, the polymer's fragility, as determined by dielectric spectroscopy, is also found to be little affected in the nanocomposites relative to the pure polymer. While a

  8. 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

  9. Fluorescence Correlation Spectroscopy to Study Diffusion of Polymer Chains within Layered Hydrogen-Bonded Polymer Films

    NASA Astrophysics Data System (ADS)

    Pristinski, Denis; Kharlampieva, Evguenia; Sukhishvili, Svetlana

    2002-03-01

    Fluorescence Correlation Spectroscopy (FCS) has been used to probe molecular motions within polymer multilayers formed by hydrogen-bonding sequential self-assembly. Polyethylene glycol (PEG) molecules were end-labeled with the fluorescent tags, and self-assembled with polymethacrylic acid (PMAA) using layer-by-layer deposition. We have found that molecules included in the top adsorbed layer have significant mobility at the millisecond time scale, probably due to translational diffusion. However, their dynamics deviate from classical Brownian motion with a single diffusion time. Possible reasons for the deviation are discussed. We found that motions were significantly slowed with increasing depth within the PEG/PMAA multilayer. This phenomena occured in a narrow pH range around 4.0 in which intermolecular interactions were relatively weak.

  10. 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.

  11. 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

  12. Adsorption of phenolic compounds from aqueous solutions using carbon nanoporous adsorbent coated with polymer

    NASA Astrophysics Data System (ADS)

    Anbia, Mansoor; Ghaffari, Arezoo

    2009-09-01

    Phenolic compounds are a widespread class of water pollutants that are known to cause serious human health problems; and the demand for effective adsorbents for the removal of toxic compounds is increasing. In this work adsorption of phenol, resorcinol and p-cresol on mesoporous carbon material (CMK-1) and modified with polyaniline polymer (CMK-1/PANI) has been investigated in attempt to explore the possibility of using nanoporous carbon as an efficient adsorbent for pollutants. It was found that CMK-1/PANI exhibits significant adsorption for phenolic derivatives. Batch adsorption studies were carried out to study the effect of various parameters like adsorbent dose, pH, initial concentration and contact time. From the sorption studies it was observed that the uptake of resorcinol was higher than other phenolic derivatives. Freundlich and Langmuir adsorption isotherms were used to model the equilibrium adsorption data for phenolic compounds.

  13. 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.

  14. Imparting Nonfouling Properties to Chemically Distinct Surfaces with a Single Adsorbing Polymer: A Multimodal Binding Approach.

    PubMed

    Serrano, Ângela; Zürcher, Stefan; Tosatti, Samuele; Spencer, Nicholas D

    2016-04-01

    Surface-active polymers that display nonfouling properties and carry binding groups that can adsorb onto different substrates are highly desirable. We present a postmodification protocol of an active-ester-containing polymer that allows the creation of such a versatile platform. Poly(pentafluorophenyl acrylate) has been postmodified with a fixed grafting ratio of a nonfouling function (mPEG) and various combinations of functional groups, such as amine, silane and catechol, which can provide strong affinity to two model substrates: SiO2 and TiO2 . Adsorption, stability and resistance to nonspecific protein adsorption of the polymer films were studied. A polymer was obtained that maintained its surface functionality under a variety of harsh conditions. EG surface-density calculations show that this strategy generates a denser packing when both negatively and positively charged groups are present within the backbone, and readily allows the fabrication of a broad combinatorial matrix. PMID:26858017

  15. Identification of vitronectin as a major plasma protein adsorbed on polymer surfaces of different copolymer composition.

    PubMed

    Bale, M D; Wohlfahrt, L A; Mosher, D F; Tomasini, B; Sutton, R C

    1989-12-01

    The arrays of proteins adsorbed from plasma onto a series of polystyrene copolymeric latexes were analyzed by enzyme-linked immunosorbent assay (ELISA) of washed beads and immunoblotting of proteins desorbed from the beads and separated by polyacrylamide gel electrophoresis (PAGE). Beads were prepared by continuous emulsion polymerization in the absence of surfactant. Coomassie brilliant blue staining of gel electropherograms of desorbed proteins indicated that the presence of small amounts of comonomers (1 to 10 mole %) significantly influenced the composition of the adsorbed protein layer. Immunoblotting revealed that fibrinogen, fibronectin, and vitronectin were adsorbed by all surfaces investigated. C3 and Clq adsorption varied significantly with copolymer composition. The ELISAs revealed that although the concentrations of vitronectin and fibronectin in plasma are similar, the extent of vitronectin adsorption from 70% to 85% plasma was greater by two orders of magnitude than fibronectin adsorption. Vitronectin adsorbed on carboxylic acid-containing copolymers reacted more strongly with a conformationally sensitive antivitronectin monoclonal antibody (MoAb) than vitronectin adsorbed to polystyrene and was more susceptible to cleavage by plasma proteases(s). The results show that vitronectin is a major protein adsorbed from concentrated plasma and that small changes in the chemical composition of a copolymer profoundly affects the extent and nature of protein adsorption from complex mixtures such as plasma. PMID:2479428

  16. 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

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

    NASA Astrophysics Data System (ADS)

    Koning, Jesper; Vandecan, Yves; Indekeu, Joseph

    2014-07-01

    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.

  18. 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

  19. Photostability enhancement of azoic dyes adsorbed and intercalated into Mg-Al-layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Liu, Pengfei; Liu, Pei; Zhao, Kongcao; Li, Lei

    2015-11-01

    Two azoic dyes 4-aminoazobenzene-4-sulfonic (AS) and ethyl orange (EO) were adsorbed on or intercalated into Mg-Al-CO3 layered double hydroxide (LDH) for photostability enhancement. Fluorescence analysis results showed that the photostability of two dyes could be greatly improved after being adsorbed on the surface of Mg-Al-CO3-LDH matrix. Furthermore, photostability of adsorbed dyes was superior to that of intercalated dyes. It was suggested that AS or EO was adsorbed on LDHs surface through a strong chemisorption interaction, resulting in the enhancement of photostability. After the UV irradiation under N2 atmosphere, the absorbed dyes not only show great increase of fluorescence intensity but also exhibited high stability against UV irradiation. This work provides a feasible approach to enhance the photostability of azoic dye confined in an inorganic two-dimensional (2D) matrix via changing the microenvironment, which may be considered to be a promising method of improving photostability of solid fluorescent materials.

  20. The Effect of Acid-Base Interactions on Conformation of Adsorbed Polymer Chains

    NASA Astrophysics Data System (ADS)

    Dhopatkar, Nishad; Zhu, He; Dhinojwala, Ali

    Adsorption of polymer chains from solutions is of fundamental interest in polymer science. This absorption process is governed by the complex interplay between the solvent-polymer, polymer-substrate, and solvent-substrate interaction energies. In early 1970's, Fowkes and his coworkers have introduced the concept of acid base interactions in explaining why PMMA (basic) adsorption was extremely low on acidic substrates from acidic solvents. The acidic solvent molecules compete with the surface for binding with the basic polymer sites and this reduces the adsorption of PMMA. Here, by using interface-selective sum frequency generation spectroscopy (SFG) and attenuated-total-reflectance (ATR)-FTIR spectroscopy we directly measure whether the solvent or polymer molecules interact with the substrate in acidic, basic, and neutral solvents. Surprisingly, we find that the surface acidic site (hydroxyl) groups are still covered with PMMA chains in acidic solvent. The PMMA chains in acidic solvent adsorb with much higher fraction of chains as trains in comparison to loops and tails. Such differences in the static and dynamic conformations have consequences in understanding the exchange kinetics, colloidal stabilization, chromatographic separations, adhesion and friction, and stabilization of nanocomposites.

  1. Kinetic Assembly of Near-IR Active Gold Nanoclusters using Weakly Adsorbing Polymers to Control Size

    PubMed Central

    Tam, Jasmine M.; Murthy, Avinash K.; Ingram, Davis R.; Nguyen, Robin; Sokolov, Konstantin V.; Johnston, Keith P.

    2013-01-01

    Clusters of metal nanoparticles with an overall size less than 100 nm and high metal loadings for strong optical functionality, are of interest in various fields including microelectronics, sensors, optoelectronics and biomedical imaging and therapeutics. Herein we assemble ~5 nm gold particles into clusters with controlled size, as small as 30 nm and up to 100 nm, which contain only small amounts of polymeric stabilizers. The assembly is kinetically controlled with weakly adsorbing polymers, PLA(2K)-b-PEG(10K)-b-PLA(2K) or PEG (MW = 3350), by manipulating electrostatic, van der Waals (VDW), steric, and depletion forces. The cluster size and optical properties are tuned as a function of particle volume fractions and polymer/gold ratios to modulate the interparticle interactions. The close spacing between the constituent gold nanoparticles and high gold loadings (80–85% w/w gold) produce a strong absorbance cross section of ~9×10−15 m2 in the NIR at 700 nm. This morphology results from VDW and depletion attractive interactions that exclude the weakly adsorbed polymeric stabilizer from the cluster interior. The generality of this kinetic assembly platform is demonstrated for gold nanoparticles with a range of surface charges from highly negative to neutral, with the two different polymers. PMID:20361735

  2. 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

  3. Contact line of adsorbed colloid-polymer droplets in theory and experiment.

    PubMed

    Koning, Jesper; Hennequin, Yves; Bonn, Daniel; Indekeu, Joseph O

    2016-05-01

    The contact line between the colloid-rich bulk liquid and an adsorbed thin film in colloid-polymer mixtures (CPM) is studied by means of an interface displacement model. The interface displacement profiles are compared to laser scanning confocal microscopy (LSCM) images. The mixtures consist of poly(methylmetacrylate) (PMMA) colloids and polystyrene (PS) polymers with polymer-to-colloid size ratio q = 1.18. Based on the experimental parameters, the theoretical model predicts a contact angle for colloid-rich liquid droplets adsorbed on glass of θ∞ = 59°, assuming a contact line with infinite radius, R = ∞. When a contact-line curvature correction and a correction for the protein-limit character of the CPM are taken into account, a modest shift is obtained. The refined theory predicts θ≈ 56°. The contact angle determined visually from the LSCM images is θ≈ 30°. The model predicts a three-phase contact-line tension of τ = -1.2 × 10(-12) N (uncorrected) and τ = -2.3 × 10(-13) N (with protein-limit correction), which is physically sound both in sign and magnitude. The line tension influences the contact angle to a small extent due to the contact line curvature. The predicted width of the transition zone between the thin film and the droplet is about 2 μm. The effect of gravity is noticeable as a deformation near the middle of the droplet. PMID:27029605

  4. Excitation energy migration in yellow fluorescent protein (citrine) layers adsorbed on modified gold surfaces

    NASA Astrophysics Data System (ADS)

    Yusoff, Hanis Mohd; Rzeźnicka, Izabela I.; Hoshi, Hirotaka; Kajimoto, Shinji; Horimoto, Noriko Nishizawa; Sogawa, Kazuhiro; Fukumura, Hiroshi

    2013-09-01

    The nature of functional proteins adsorbed on solid surfaces is interesting from the perspective of developing of bioelectronics and biomaterials. Here we present evidence that citrine (one of yellow fluorescent protein variants) adsorbed on modified gold surfaces would not undergo denaturation and energy transfer among the adsorbed citrine molecules would occur. Gold substrates were chemically modified with 3-mercaptopropionic acid and tert-butyl mercaptan for the preparation of hydrophilic and hydrophobic surfaces, respectively. A pure solution of citrine was dropped and dried on the modified gold substrates and their surface morphology was studied with scanning tunnelling microscopy (STM). The obtained STM images showed multilayers of citrine adsorbed on the modified surfaces. On hydrophobic surfaces, citrine was adsorbed more randomly, formed various non-uniform aggregates, while on hydrophilic surfaces, citrine appeared more aligned and isolated uniform protein clusters were observed. Fluorescence lifetime and anisotropy decay of these dried citrine layers were also measured using the time correlated single photon counting method. Fluorescence anisotropy of citrine on the hydrophobic surface decayed faster than citrine on the hydrophilic surface. From these results we concluded that fluorescence energy migration occurred faster among citrine molecules which were randomly adsorbed on the hydrophobic surface to compare with the hydrophilic surface.

  5. Stability, structural and electronic properties of benzene molecule adsorbed on free standing Au layer

    NASA Astrophysics Data System (ADS)

    Katoch, Neha; Kapoor, Pooja; Sharma, Munish; Kumar, Ashok; Ahluwalia, P. K.

    2016-05-01

    We report stability and electronic properties of benzene molecule adsorbed on the Au atomic layer within the framework of density function theory (DFT). Horizontal configuration of benzene on the top site of Au monolayer prefers energetically over other studied configurations. On the adsorption of benzene, the ballistic conductance of Au monolayer is found to decrease from 4G0 to 2G0 suggesting its applications for the fabrications of organic sensor devices based on the Au atomic layers.

  6. Graphene-enhanced Raman spectroscopy of thymine adsorbed on single-layer graphene

    NASA Astrophysics Data System (ADS)

    Fesenko, Olena; Dovbeshko, Galyna; Dementjev, Andrej; Karpicz, Renata; Kaplas, Tommi; Svirko, Yuri

    2015-04-01

    Graphene-enhanced Raman scattering (GERS) spectra and coherent anti-Stokes Raman scattering (CARS) of thymine molecules adsorbed on a single-layer graphene were studied. The enhancement factor was shown to depend on the molecular groups of thymine. In the GERS spectra of thymine, the main bands are shifted with respect to those for molecules adsorbed on a glass surface, indicating charge transfer for thymine on graphene. The probable mechanism of the GERS enhancement is discussed. CARS spectra are in accord with the GERS results, which indicates similar benefit from the chemical enhancement.

  7. Molecular Orientation of Hydroquinone Adsorbed at a Platinum(111) Thin-Layer Electrode.

    PubMed

    Ren; Hubbard

    1999-01-15

    Reported are new findings regarding the molecular orientation of hydroquinone (HQ) adsorbed on Pt surfaces. The packing density of hydroquinone adsorbed from 1 M HClO4 supporting electrolyte has been measured by use of a Pt(111) thin-layer electrode. The packing-density-vs-concentration profiles for hydroquinone, measured by a differential thin-layer electrode method at an ordered Pt(111) surface and at an electrochemically disordered Pt(111) surface, are identical within an experimental error of about 8%. The profiles from this study are similar to the ones obtained previously at an ordered Pt(111) surface by Auger spectroscopy, but they are significantly different from those reported previously for polycrystalline Pt thin-layer electrodes. A procedure based upon displacement of HQ by thiocyanate has been developed as an alternative method for determining the packing density of adsorbed HQ. Both methods afford information regarding the molecular state of HQ adsorbed at the Pt(111) surface. Copyright 1999 Academic Press. PMID:9885274

  8. Nanostructured Membranes from Triblock Polymer Precursors as High Capacity Copper Adsorbents.

    PubMed

    Weidman, Jacob L; Mulvenna, Ryan A; Boudouris, Bryan W; Phillip, William A

    2015-10-13

    Membrane adsorbers are a proposed alternative to packed beds for chromatographic separations. To date, membrane adsorbers have suffered from low binding capacities and/or complex processing methodologies. In this work, a polyisoprene-b-polystyrene-b-poly(N,N-dimethylacrylamide) (PI-PS-PDMA) triblock polymer is cast into an asymmetric membrane that possesses a high density of nanopores (d ∼ 38 nm) at the upper surface of the membrane. Exposing the membrane to a 6 M aqueous hydrochloric acid solution converts the PDMA brushes that line the pore walls to poly(acrylic acid) (PAA) brushes, which are capable of binding metal ions (e.g., copper ions). Using mass transport tests and static binding experiments, the saturation capacity of the PI-PS-PAA membrane was determined to be 4.1 ± 0.3 mmol Cu(2+) g(-1). This experimental value is consistent with the theoretical binding capacity of the membranes, which is based on the initial PDMA content of the triblock polymer precursor and assumes a 1:1 stoichiometry for the binding interaction. The uniformly sized nanoscale pores provide a short diffusion length to the binding sites, resulting in a sharp breakthrough curve. Furthermore, the membrane is selective for copper ions over nickel ions, which permeate through the membrane over 10 times more rapidly than copper during the loading stage. This selectivity is present despite the fact that the sizes of these two ions are nearly identical and speaks to the chemical selectivity of the triblock polymer-based membrane. Furthermore, addition of a pH 1 solution releases the bound copper rapidly, allowing the membrane to be regenerated and reused with a negligible loss in binding capacity. Because of the high binding capacities, facile processing method implemented, and ability to tailor further the polymer brushes lining the pore walls using straightforward coupling reactions, these membrane adsorbers based on block polymer precursors have potential as a separation media that can

  9. 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. PMID:25263912

  10. Study of the adsorbed layer on a solid electrode surface by specular reflection measurement

    NASA Astrophysics Data System (ADS)

    Kusu, Fumiyo; Takamura, Kiyoko

    1985-07-01

    Specular reflection measurements were carried out to study the adsorbed layers of certain heterocyclic compounds such as adenine, barbital, 2'-deoxyadenosine, phenobarbital, pyridine and thymine. When pyridine was present in 0.1M NaClO 4, a marked decrease in the reflectivity of a gold electrode was observed. In the potential range near the point of zero charge on the reflectivity-potential curve, the decrease was due to the adsorption of pyridine. Assuming the reflectivity change to be proportional to the surface coverage, the potential and concentration dependence of pyridine adsorption was determined and analysed on the basis of a Langmuir-type adsorption isotherm. The refractive indices and extinction coefficients for the adsorbed layers of the compounds investigated were evaluated using the observed reflectivity change, according to relations proposed by McIntyre and Aspnes.

  11. Hydrodynamic thickness of petroleum oil adsorbed layers in the pores of reservoir rocks.

    PubMed

    Alkafeef, Saad F; Algharaib, Meshal K; Alajmi, Abdullah F

    2006-06-01

    The hydrodynamic thickness delta of adsorbed petroleum (crude) oil layers into the pores of sandstone rocks, through which the liquid flows, has been studied by Poiseuille's flow law and the evolution of (electrical) streaming current. The adsorption of petroleum oil is accompanied by a numerical reduction in the (negative) surface potential of the pore walls, eventually stabilizing at a small positive potential, attributed to the oil macromolecules themselves. After increasing to around 30% of the pore radius, the adsorbed layer thickness delta stopped growing either with time or with concentrations of asphaltene in the flowing liquid. The adsorption thickness is confirmed with the blockage value of the rock pores' area determined by the combination of streaming current and streaming potential measurements. This behavior is attributed to the effect on the disjoining pressure across the adsorbed layer, as described by Derjaguin and Churaev, of which the polymolecular adsorption films lose their stability long before their thickness has approached the radius of the rock pore. PMID:16414057

  12. Site blocking effects on adsorbed polyacrylamide conformation

    NASA Astrophysics Data System (ADS)

    Brotherson, Brett A.

    ionic strength, and an adsorbed polymer on a surface functionalized with site blocking additives. This work investigated these scenarios using a low charge density high molecular weight cationic polyacrylamide. Three different substrates, for polymer adsorption were analyzed: mica, anionic latex, and glass. It was determined that, similar to previous studies, the adsorbed polymer layer thickness in water is relatively small even for high molecular weight polymers, on the order of tens of nanometers. The loop length distribution of a single polymer, experimentally verified for the first time, revealed a broad span of loop lengths as high as 1.5 microns. However, the bulk of the distribution was found between 40 and 260 nanometers. For the first time, previous theoretical predictions regarding the salt effect on adsorbed polymer conformation were confirmed experimentally. It was determined that the adsorbed polymer layer thickness expanded with increasing ionic strength of the solvent. Using atomic force microscopy, it was determined that the adsorbed polymer loop lengths and tail lengths increased with increasing ionic strength, supporting the results found using dynamic light scattering. The effect of the addition of site blocking additives on a single polymer's conformation was investigated for the first time. It was determined that the addition of site blocking additives caused strikingly similar results as the addition of salt to the medium. The changes in adsorbed polymer's loop lengths was found to be inconsistent and minimal. However, the changes in an adsorbed polymer's free tail length was found to increase with increasing site blocking additive levels. These results were obtained using either PDADMAC or cationic nanosilica as site blocking additives.

  13. 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

  14. Modeling colloid deposition on a protein layer adsorbed to iron-oxide-coated sand

    NASA Astrophysics Data System (ADS)

    Yang, X.; Flynn, R.; von der Kammer, F.; Hofmann, T.

    2012-11-01

    Our recent study reported that conformation change of granule-associated Bovine Serum Albumin (BSA) may influence the role of the protein controlling colloid deposition in porous media (Flynn et al., 2012). The present study conceptualized the observed phenomena with an ellipsoid morphology model, describing BSA as an ellipsoid taking a side-on or end-on conformation on granular surface, and identified the following processes: (1) at low adsorbed concentrations, BSA exhibited a side-on conformation blocking colloid deposition; (2) at high adsorbed concentrations, BSA adapted to an end-on conformation promoted colloid deposition; and (3) colloid deposition on the BSA layer may progressively generate end-on molecules (sites) by conformation change of side-on BSA, resulting in sustained increasing deposition rates. Generally, the protein layer lowered colloid attenuation by the porous medium, suggesting the overall effect of BSA was inhibitory at the experimental time scale. A mathematical model was developed to interpret the ripening curves. Modeling analysis identified the site generation efficiency of colloid as a control on the ripening rate (declining rate in colloid concentrations), and this efficiency was higher for BSA adsorbed from a more dilute BSA solution.

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

    NASA Astrophysics Data System (ADS)

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

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

  17. The role of hydrogen bonding in tethered polymer layers

    PubMed Central

    Ren, C.; Nap, R. J.; Szleifer, I.

    2009-01-01

    A molecular theory to study the properties of end tethered polymer layers, in which the polymers have the ability to form hydrogen bonds with water is presented. The approach combines the ideas of the single-chain mean-field theory to treat tethered layers with the approach of Dormidontova (Macromolecules, 2002 35,987) to include hydrogen bonds. The generalization includes the consideration of position dependent polymer-water and water-water hydrogen bonds. The theory is applied to model poly ethylene oxide (PEO) and the predictions are compared with equivalent polymer layers that do not form hydrogen bonds. It is found that increasing the temperature lowers the solubility of the PEO and results in a collapse of the layer at high enough temperatures. The properties of the layer and their temperature dependence are shown to be the result of the coupling between the conformational entropy of the chains, the ability of the polymer to form hydrogen bonds, and the intermolecular interactions. The structural and thermodynamic properties of the PEO layers, such as the lateral pressure-area isotherms and polymer chemical potentials, are studied as a function of temperature and type of tethering surface. The possibility of phase separation of the PEO layer at high enough temperature is predicted, due to the reduced solubility induced by breaking of polymer-water hydrogen bonds. A discussion of the advantages and limitations of the theory, together with how to apply the approach to different hydrogen bonding polymers is presented. PMID:19367906

  18. 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.

  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. Phase behaviour of a dispersion of charge-stabilised colloidal spheres with added non-adsorbing interacting polymer chains.

    PubMed

    Gögelein, C; Tuinier, R

    2008-10-01

    We present a theory for the phase behaviour of mixtures of charge-stabilised colloidal spheres plus interacting polymer chains in good and theta -solvents within the framework of free-volume theory. We use simple but accurate combination rules for the depletion thickness around a colloidal particle and for the osmotic pressure up to the semi-dilute concentration regime. Hence, we obtain expressions for the free energy for mixtures of charged colloidal particles and non-adsorbing interacting polymers. From that, we calculate the phase behaviour, and discuss its topology in dependence on the competition between the charge-induced repulsion and the polymer-induced attraction. The homogeneous mixture of colloids and polymers becomes more stabilised against demixing when increasing the electrostatic repulsion. This charge-induced stabilisation is strongest for small polymer-to-colloid size ratios and is more pronounced for charged colloids mixed with polymers in a good solvent than for polymers in a theta -solvent. For the weakly charged regime we find that the phase diagram becomes salt-concentration-independent in the protein limit for charged colloids plus polymers in a theta -solvent. The liquid window, i.e., the concentration regimes where a colloidal liquid exists, is narrowed down upon increasing the charge-induced repulsion. Also this effect is more pronounced when charged colloids are mixed with polymer chains in a good solvent. In summary, we demonstrate that the solvent quality significantly influences the phase behaviour of mixtures of charged colloids plus non-adsorbing polymers if the range of the screened electrostatic repulsion becomes of the order of the range of the depletion-induced attraction. PMID:18791755

  2. 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

  3. Pyrocarbons prepared by carbonisation of polymers adsorbed or synthesised on a surface of silica and mixed oxides

    NASA Astrophysics Data System (ADS)

    Gun'ko, V. M.; Skubiszewska-Zi ęba, J.; Leboda, R.; Voronin, E. F.; Zarko, V. I.; Levitskaya, S. I.; Brei, V. V.; Guzenko, N. V.; Kazakova, O. A.; Seledets, O.; Janusz, W.; Chibowski, S.

    2004-04-01

    Initial oxides fumed silica, alumina/silica and titania/silica and silica gel and hybrid adsorbents with pyrocarbon formed on these oxide substrates by carbonisation of immobilised (adsorbed or synthesised) polymers such as starch, methyl cellulose, polyvinylpyrrolidone, polystyrene, and polybutylvinyl ether were studied by adsorption, AFM, TEM, and FTIR methods. Polymer/oxide materials were investigated by nitrogen and Pb(II) adsorption, FTIR, and potentiometric titration methods. Analysis of nitrogen adsorption-desorption isotherms by different methods, FTIR spectra, AFM and TEM images of the initial and hybrid adsorbents reveals that the morphology of the substrates significantly changes on carbonisation of oxygen-containing polymers because of hydrothermal treatment of them by water eliminated as a product of pyrolysis. Contribution of own microporosity of pyrocarbon deposits formed on carbonisation of immobilised polymers is greater (dependent on reaction conditions) than that on pyrolysis of low-molecular compounds at the same oxide substrates. Pyrocarbon particles formed on silica gel are larger than those formed on fumed oxides and larger than those formed on silica gel on pyrolysis of low-molecular compounds.

  4. 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.

  5. 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

  6. 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

  7. 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. PMID:25786200

  8. 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. PMID:25766654

  9. 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.

  10. Equilibrium flattening process of irreversibly adsorbed polymer chains on a solid

    NASA Astrophysics Data System (ADS)

    Sen, Mani; Jiang, Naisheng; Endoh, Maya; Koga, Tadanori; Kawaguchi, Daisuke; Tanaka, Keiji

    We here report the equilibrium process of adsorbed polymer chains on a solid by sum frequency generation (SFG) spectroscopy. Polystyrene (PS,Mw = 290 kDa) thin films prepared onto quartz prisms (a weakly attractive system) were used as a model system. Spin-cast PS 50 nm films on quartz surface (QS) were annealed at 150 °C >Tg for up to 100 h and subsequently rinsed with chloroform to derive the ``flattened chains'' that lie flat onto the substrate surface. The SFG results for the ``matured'' flattened chains after annealing for 96 h revealed the strong interfacial orientation of the backbone chains and weak orientation of PS phenyl rings at the QS which is in contrast to a PS spin-cast film annealed at 150 °C for 1 h: the phenyl rings were strongly directed toward the QS, while the backbone chains were weakly orientated at the QS. We postulate that the increase in the number of solid/segment contacts of the backbone chains is the driving force for this equilibrium flattening process. We will also discuss the generality of this flattening process by using solvent-cast PS thin films where the chains are randomly oriented near the QS. Acknowledgement: NSF Grant No. CMMI-1332499.

  11. 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.

  12. Thrombocyte adhesion and release of extracellular microvesicles correlate with surface morphology of adsorbent polymers for lipid apheresis.

    PubMed

    Weiss, René; Spittler, Andreas; Schmitz, Gerd; Fischer, Michael B; Weber, Viktoria

    2014-07-14

    Whole blood lipid apheresis is clinically applied to reduce low density lipoprotein cholesterol in patients with homozygous familial hypercholesterolemia. Here, we studied the correlation between physicochemical parameters, in particular, surface roughness and blood compatibility, of two polyacrylate-based and a dextran sulfate-based polymer for lipid apheresis. The adsorbent surface roughness was assessed by atomic force microscopy. Freshly isolated human thrombocytes were circulated over adsorbent columns downscaled equivalent to clinical use to study thrombocyte adhesion and microvesicle generation. Quantification of thrombocytes and microvesicles in the flow-through of the columns revealed that both thrombocyte adhesion and microvesicle generation increased with increasing adsorbent surface roughness. Activation of thrombocytes with thrombin receptor-activating peptide-6 favored their adhesion to the adsorbents, as demonstrated by preferential depletion of CD62(+) and PAC-1(+) thrombocytes. Taken together, enhanced polymer surface roughness fostered cell adhesion and microvesicle release, underscoring the role of extracellular microvesicles as markers of cellular activation and of blood compatibility. PMID:24844344

  13. Novel negatively charged hybrids. 3. Removal of Pb2+ from aqueous solution using zwitterionic hybrid polymers as adsorbent.

    PubMed

    Liu, Junsheng; Ma, Yue; Zhang, Yaping; Shao, Guoquan

    2010-01-15

    Using zwitterionic hybrid polymers as adsorbent, the adsorption kinetics and isotherm, thermodynamic parameters of Delta G, Delta H and DeltaS for the removal of Pb(2+) from aqueous solution were investigated. It is indicated that the adsorption of Pb(2+) ions on these zwitterionic hybrid polymers followed the Lagergren second-order kinetic model and Freundlich isotherm model, demonstrating that the adsorption process might be Langmuir monolayer adsorption. The negative values of Delta G and the positive values of Delta H evidence that Pb(2+) adsorption on these zwitterionic hybrid polymers is spontaneous and endothermic process in nature. Moreover, the zwitterionic hybrid polymers produced reveal relatively higher desorption efficiency in 2 mol dm(-3) aqueous HNO(3) solution, indicating that they can be recycled in industrial processes. These findings suggest that these zwitterionic hybrid polymers are the promising adsorbents for Pb(2+) removal and can be potentially applied in the separation and recovery of Pb(2+) ions from the waste chemicals and contaminated water of lead-acid rechargeable battery. PMID:19744785

  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 PAGESBeta

    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. Grafted polymers inside cylindrical tubes: Chain stretching vs layer thickness

    NASA Astrophysics Data System (ADS)

    Suo, Tongchuan; Whitmore, Mark D.

    2013-04-01

    We present a study of the detailed structure of grafted polymer chains and the layers they form inside cylindrical tubes, using the finitely extensible nonlinear elastic chain model and numerical self-consistent field theory. For very large tube radius, the chain stretching and layer thicknesses are the same as for polymers grafted to a planar surface. For decreasing radius, our calculations indicate that the layer almost always gets thinner, although there can be situations where it is very slightly thicker. However, we find that this thinning is not necessarily due to changes to the polymers: in fact, the root-mean-squared layer thickness would decrease even if the polymers themselves are completely unchanged. Furthermore, we find that the polymer stretching can increase at the same time that the layer thickness decreases. These apparent paradoxes are resolved by analyzing and distinguishing between the volume fraction profiles and monomer number distributions in these systems, including how they change and why. We also find that, in a given system, parts of each polymer move towards the curved surface and parts away from it, and that these differences are key to understanding the behavior.

  18. 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

  19. Optical anisotropy of flagellin layers: in situ and label-free measurement of adsorbed protein orientation using OWLS.

    PubMed

    Kovacs, Noemi; Patko, Daniel; Orgovan, Norbert; Kurunczi, Sandor; Ramsden, Jeremy J; Vonderviszt, Ferenc; Horvath, Robert

    2013-06-01

    The surface adsorption of the protein flagellin was followed in situ using optical waveguide lightmode spectroscopy (OWLS). Flagellin did not show significant adsorption on a hydrophilic waveguide, but very rapidly formed a dense monolayer on a hydrophobic (silanized) surface. The homogeneous and isotropic optical layer model, which has hitherto been generally applied in OWLS data interpretation for adsorbed protein films, failed to characterize the flagellin layer, but it could be successfully modeled as an uniaxial thin film. This anisotropic modeling revealed a significant positive birefringence in the layer, suggesting oriented protein adsorption. The adsorbed flagellin orientation was further evidenced by monitoring the surface adsorption of truncated flagellin variants, in which the terminal protein regions or the central (D3) domain were removed. Without the terminal regions the protein adsorption was much slower and the resulting films were significantly less birefringent, implying that intact flagellin adsorbs on the hydrophobic surface via its terminal regions. PMID:23631669

  20. 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.

  1. 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

  2. Poly(ethylene oxide) Mushrooms Adsorbed at Silica-Ionic Liquid Interfaces Reduce Friction.

    PubMed

    Sweeney, James; Webber, Grant B; Atkin, Rob

    2016-03-01

    The adsorbed layer conformation and lubricity of 35, 100, and 300 kDa PEO adsorbed to ionic liquid (IL)-silica interfaces from 0.01 wt % solutions have been investigated using colloid probe atomic force microscopy. The ILs used were propylammonium nitrate (PAN) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), which are protic and aprotic ILs, respectively. Normal force curves reveal steric interactions consistent with adsorbed polymer layers which are best fit using the mushroom model. Friction measurements show that the adsorbed polymer layer markedly reduces friction compared to surfaces sliding in the pure ILs and that lubricity increases with polymer length. When polymer is adsorbed to the sliding surfaces, friction is controlled by the creation and disruption of intermolecular interactions between entangled chains and the dragging of polymer chains through the interpenetration region. These experiments show that added polymer can reduce friction while maintaining the useful properties of ILs as lubricants. PMID:26844589

  3. Polymer layered silicate nanocomposites: Structure, morphology, and properties

    NASA Astrophysics Data System (ADS)

    Nawani, Pranav

    Layered silicates are important fillers for improving various mechanical, flame retardant, and barrier properties of polymers, which can be attributed to their sheet-like morphology. Layered silicates can be modified with organic surfactants to render them compatible with polymer matrices. Organically modified silicates (organoclays) having large surface areas are very cost-efficient non-toxic nanofillers effective at very low loads and are readily available. Upon amalgamation of organoclays with polymer matrix nanocomposites, polymer chains can penetrate in between the silicate layers and result in an intercalated structure where the clay stack remains intact but the interlayer spacing is increased. When penetration becomes more severe, disintegration of clay stacks can occur, resulting in an exfoliated structure. It has often been observed that exfoliation is not complete down to the level of isolated silicate layers; rather, the large clay stacks are broken up into shorter stacks termed 'tactoids' together with a few individual silicate layers, resulting in a kind of mixed intercalated-exfoliated structure. Organoclay particles are mostly intercalated, having a preferred orientation with the clay gallery planes being preferentially parallel to the plane of the pressed film. Preferential orientation of organoclays affects the barrier properties of polymer membranes. Additional fillers like carbon black can induce a change in the orientation of organoclays. The effect of carbon black on the orientation of organoclays was elucidated and a relationship between orientation and permeability of air through such membranes was established. We have also investigated the flammability properties of a series of polymer nanocomposites, containing various Transition Metal Ion (TMI) modified organoclays. The improved fire retardation in nanocomposites with TMI-modified organoclays can be attributed to enhanced carbonaceous char formation during combustion, i.e., charring

  4. Theoretical study of the three-phase contact line and its tension in adsorbed colloid-polymer mixtures.

    PubMed

    Vandecan, Yves; Indekeu, Joseph O

    2008-03-14

    We perform a theoretical study of the three-phase contact line and the line tension in an adsorbed colloid-polymer mixture near a first-order wetting transition, employing an interface displacement model. We use a simple free-energy functional to describe a colloid-polymer mixture near a hard wall. The bulk phase behavior and the substrate-adsorbate interaction are modeled by the free-volume theory for ideal polymers. The large size of the colloidal particles and the suppression of the van der Waals interaction by optical matching of colloid and solvent justify the planar hard wall model for the substrate. Following the Fisher-Jin scheme, we derive from the free-energy functional an interface potential V(l) for these mixtures. For a particle diameter of 10-100 nm, the calculations indicate a line tension tau approximately 10(-12)-10(-13) N at room temperature. In view of the ultralow interfacial tension in colloid-polymer mixtures, gamma approximately 10(-7) Nm, this leads to a rather large characteristic length scale taugamma in the micrometer range for the three-phase contact zone width. In contrast with molecular fluids, this zone could be studied directly with optical techniques such as confocal scanning laser microscopy. PMID:18345923

  5. Fabrication and Theoretical Evaluation of Microlens Arrays on Layered Polymers

    NASA Astrophysics Data System (ADS)

    Oder, Tom; McMaster, Michael; Merlo, Corey; Bagheri, Camron; Reakes, Clayton; Petrus, Joshua; Li, Dingqiang; Crescimanno, Michael; Andrews, James

    2014-03-01

    Arrays of microlens were fabricated on nano-layered polymers using reactive ion etching. Semi hemispherical patterns with diameters ranging from 20 to 80 micrometers were first formed on a thick photoresist film that was spin-coated on the layered polymers using standard photolithographic process employing a gray scale glass mask. These patterns were then transferred to the polymers using dry etching in a reactive ion etching system. The optimized etch condition included a mixture of sulfur hexafluoride and oxygen, which resulted in an etch depth of 5 micrometers and successfully exposed the individual sub-micron thick layers in the polymers. Physical characterization of the microlens arrays was done using atomic force microscope and scanning electron microscope. We combine basic physical optics theory with the transfer matrix analysis of optical transport in nano-layered polymers to address subtleties in the chromatic response of microlenses made from these materials. In particular this method explains the len's behavior in and around the reflection band of the materials. We wish to acknowledge support of funds from NSF through its Center for Layered Polymeric Systems (CLiPS) at Case Western Reserve University.

  6. 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.

  7. 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

  8. 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).

  9. 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.

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

    NASA Astrophysics Data System (ADS)

    You, Youwen

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

  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. Layered structures and nanosheets of pyrimidinethiolate coordination polymers.

    PubMed

    Beldon, P J; Tominaka, S; Singh, P; Saha Dasgupta, T; Bithell, E G; Cheetham, A K

    2014-04-18

    We report the synthesis, crystal structure and exfoliation of a new member of an important family of layered compounds: lamellar pyrimidinethiolate coordination polymers. Conductivity measurements and DFT calculations of iron(II) pyrimidine-2-thiolate show that this material and a related compound are insulators. PMID:24599380

  13. Elastic repulsion from polymer brush layers exhibiting high protein repellency.

    PubMed

    Inoue, Yuuki; Nakanishi, Tomoaki; Ishihara, Kazuhiko

    2013-08-27

    Hydrophilic poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) and poly(2-hydroxyethyl methacrylate) (PHEMA) brush layers with different thicknesses and graft densities were prepared to construct a model surface to elucidate protein-surface interactions. In particular, we focused on the steric repulsion of hydrophilic polymer layers as one of the surface properties that strongly influence protein adsorption and employed force-versus-distance (f-d) curve measurements obtained via atomic force microscopy to quantitatively evaluate the steric repulsion force, which is also referred to as the "elastic repulsion energy." We also analyzed direct interactions between the surface and proteins via the f-d curve, because these interactions trigger the protein-adsorption phenomenon. Protein-surface interactions were extremely suppressed at surfaces with high elastic repulsion energies and highly dense polymer brush structures, which is in contrast to those at surfaces with low elastic repulsion energies and low density of the grafted polymer layers. These results indicate that the elastic repulsion from the grafted polymer layer at the surface is an important parameter for controlling protein-surface interactions and protein adsorption phenomenon. PMID:23898820

  14. 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

  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. Thermoplastic polymer patterning without residual layer by advanced nanoimprinting schemes

    NASA Astrophysics Data System (ADS)

    Park, Hyunsoo; Cheng, Xing

    2009-06-01

    Nanoimprinting is a fast-growing technique for nanoscale patterning. One of the remaining issues in nanoimprinting is the removal of the residual layer after nanoimprinting. Traditionally the residual layer is removed by an oxygen reactive-ion etching (RIE) step. The need for a vacuum environment and dedicated equipment in this step lowers the throughput and increases the cost of the nanoimprinting process. It also prevents the possibility of patterning isolated functional polymers because oxygen RIE destroys the functional materials. In this work, novel nanoimprinting schemes are developed to nondestructively remove the residual layer in thermal nanoimprinting by solvent developing and dewetting. Combined with a transfer-bonding technique, three-dimensional polymer scaffolds are achieved. The techniques developed here eliminate the RIE step in thermal nanoimprinting and are compatible with roller nanoimprinting for large-scale patterning of polymer micro- or nanostructures. The technique also opens up new applications for nanoimprinting in patterning isolated conjugated polymers for organic electronic devices and circuits.

  17. Thermoplastic polymer patterning without residual layer by advanced nanoimprinting schemes.

    PubMed

    Park, Hyunsoo; Cheng, Xing

    2009-06-17

    Nanoimprinting is a fast-growing technique for nanoscale patterning. One of the remaining issues in nanoimprinting is the removal of the residual layer after nanoimprinting. Traditionally the residual layer is removed by an oxygen reactive-ion etching (RIE) step. The need for a vacuum environment and dedicated equipment in this step lowers the throughput and increases the cost of the nanoimprinting process. It also prevents the possibility of patterning isolated functional polymers because oxygen RIE destroys the functional materials. In this work, novel nanoimprinting schemes are developed to nondestructively remove the residual layer in thermal nanoimprinting by solvent developing and dewetting. Combined with a transfer-bonding technique, three-dimensional polymer scaffolds are achieved. The techniques developed here eliminate the RIE step in thermal nanoimprinting and are compatible with roller nanoimprinting for large-scale patterning of polymer micro- or nanostructures. The technique also opens up new applications for nanoimprinting in patterning isolated conjugated polymers for organic electronic devices and circuits. PMID:19468173

  18. 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

  19. 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

  20. 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

  1. 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

  2. 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

    2016-03-30

    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

  3. Ammonium-Functionalized Hollow Polymer Particles As a pH-Responsive Adsorbent for Selective Removal of Acid Dye.

    PubMed

    Qin, Yan; Wang, Li; Zhao, Changwen; Chen, Dong; Ma, Yuhong; Yang, Wantai

    2016-07-01

    In this work, a novel type of ammonium-functionalized hollow polymer particles (HPP-NH3(+)) with a high density of ammonium groups in the shell has been specially designed and synthesized. Benefiting from both the high surface area and from the high density of positively charged ammonium groups, the as-prepared HPP-NH3(+) can serve as a selective adsorbent for the removal of negatively charged acid dye (e.g., methyl blue a-MB). The equilibrium adsorption data of a-MB on the HPP-NH3(+) were evaluated using Freundlich and Langmuir isotherm models, and Langmuir isotherm exhibited a better fit with a maximum adsorption capacity of 406 mg/g. Most importantly, because of the presence of dual functional groups (ammonium and carboxyl groups), the HPP-NH3(+) showed a significant pH-dependent equilibrium adsorption capacity, which increased dramatically from 59 mg/g to 449 mg/g as the solution pH decreased from 9 to 2. This uniqueness makes the dye-adsorbed HPP-NH3(+) can be facilely regenerated under mild condition (in weak alkaline solution, pH 10) to recover both a-MB and the HPP-NH3(+), whereas the recovery of conventional adsorbents is commonly performed under particularly severe conditions. The regenerated HPP-NH3(+) can be reused for dye removal and the dye removal efficiency remained above 98% even after five adsorption-desorption cycles. Because of its high adsorption capacity, pH-sensitivity, easy regeneration, and good reusability, the HPP-NH3(+) has great potential for the application in the field of water treatment, controlled drug release, and pH-responsive delivery. PMID:27302068

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

    PubMed

    Gattás-Asfura, Kerim M; Stabler, Cherie L

    2013-10-23

    Encapsulation of viable tissues via layer-by-layer polymer assembly provides a versatile platform for cell surface engineering, with nanoscale control over the 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 a phosphine-functionalized poly(amidoamine) 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

  5. Design of bending multi-layer electroactive polymer actuators

    NASA Astrophysics Data System (ADS)

    Balakrisnan, Bavani; Nacev, Alek; Smela, Elisabeth

    2015-04-01

    The effects of layer thickness and stiffness on multilayer bending actuator performance were investigated with an analytical mechanical model. Performance was evaluated in terms of curvature, blocked force, and work. Multilayer device designs corresponding to dielectric elastomer actuator, ionic polymer metal composite, and conjugated polymer structures were examined. Normalized plots of the performance metrics as functions of relative layer thickness and stiffness are presented that should allow initial, starting-point estimates for designs for particular applications. The results show that to achieve high curvature, layer thickness and stiffness may need to be set above or below particular bounds, or varied together, depending on the device configuration; often there is a broad plateau of combinations that work equally well. There is a conflict between achieving high bending and high force: the former requires the device to behave as much as possible like a simple bilayer with optimal ratios of thickness and modulus, while the latter requires thicker layers and shows little dependence on their moduli. Finally, to maximize work there are areas in the thickness-modulus plane that should be avoided, these areas varying with the configuration in sometimes surprising ways.

  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. Novel adhesive properties of poly(ethylene-oxide) adsorbed nanolayers

    NASA Astrophysics Data System (ADS)

    Zeng, Wenduo

    Solid-polymer interfaces play crucial roles in the multidisciplinary field of nanotechnology and are the confluence of physics, chemistry, biology, and engineering. There is now growing evidence that polymer chains irreversibly adsorb even onto weakly attractive solid surfaces, forming a nanometer-thick adsorbed polymer layer ("adsorbed polymer nanolayers"). It has also been reported that the adsorbed layers greatly impact on local structures and properties of supported polymer thin films. In this thesis, I aim to clarify adhesive and tribological properties of adsorbed poly(ethylene-oxide) (PEO) nanolayers onto silicon (Si) substrates, which remain unsolved so far. The adsorbed nanolayers were prepared by the established protocol: one has to equilibrate the melt or dense solution against a solid surface; the unadsorbed chains can be then removed by a good solvent, while the adsorbed chains are assumed to maintain the same conformation due to the irreversible freezing through many physical solid-segment contacts. I firstly characterized the formation process and the surface/film structures of the adsorbed nanolayers by using X-ray reflectivity, grazing incidence X-ray diffraction, and atomic force microscopy. Secondly, to compare the surface energy of the adsorbed layers with the bulk, static contact angle measurements with two liquids (water and glycerol) were carried out using a optical contact angle meter equipped with a video camera. Thirdly, I designed and constructed a custom-built adhesion-testing device to quantify the adhesive property. The experimental results provide new insight into the microscopic structure - macroscopic property relationship at the solid-polymer interface.

  8. 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

  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. Electrodeposited cobalt sulfide hole collecting layer for polymer solar cells

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

    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 (V2O5) and molybdenum trioxide (MoO3) 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.

  11. Determination of ractopamine in pork using a magnetic molecularly imprinted polymer as adsorbent followed by HPLC.

    PubMed

    Tang, Yiwei; Gao, Jingwen; Liu, Xiuying; Lan, Jianxing; Gao, Xue; Ma, Yong; Li, Min; Li, Jianrong

    2016-06-15

    A new magnetic molecularly imprinted polymers (MMIPs) for separation and concentration of ractopamine (RAC) were prepared using surface molecular imprinting technique with methacryloyl chloride as functional monomer and RAC as template. The MMIPs were characterized using transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and vibrating sample magnetometer. The results of re-binding experiments indicated that the MMIPs had fast adsorption kinetics and could reach binding equilibrium within 20 min, and the adsorption capacity of the MMIPs was 2.87-fold higher than that of the corresponding non-imprinted polymer. The selectivity of the MMIPs was evaluated according to its recognition to RAC and its analogues. The synthesized MMIPs were successfully applied to extraction, followed by high performance liquid chromatography to determine RAC in real food samples. Spiked recoveries ranged from 73.60% to 94.5%, with relative standard deviations of <11.17%. PMID:26868550

  12. 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

  13. Incorporating microorganisms into polymer layers provides bioinspired functional living materials

    PubMed Central

    Gerber, Lukas C.; Koehler, Fabian M.; Grass, Robert N.; Stark, Wendelin J.

    2012-01-01

    Artificial two-dimensional biological habitats were prepared from porous polymer layers and inoculated with the fungus Penicillium roqueforti to provide a living material. Such composites of classical industrial ingredients and living microorganisms can provide a novel form of functional or smart materials with capability for evolutionary adaptation. This allows realization of most complex responses to environmental stimuli. As a conceptual design, we prepared a material surface with self-cleaning capability when subjected to standardized food spill. Fungal growth and reproduction were observed in between two specifically adapted polymer layers. Gas exchange for breathing and transport of nutrient through a nano-porous top layer allowed selective intake of food whilst limiting the microorganism to dwell exclusively in between a confined, well-enclosed area of the material. We demonstrated a design of such living materials and showed both active (eating) and waiting (dormant, hibernation) states with additional recovery for reinitiation of a new active state by observing the metabolic activity over two full nutrition cycles of the living material (active, hibernation, reactivation). This novel class of living materials can be expected to provide nonclassical solutions in consumer goods such as packaging, indoor surfaces, and in biotechnology. PMID:22198770

  14. Biocompatible two-layer tantalum/titania-polymer hybrid coating.

    PubMed

    Cortecchia, Elisa; Pacilli, Annalisa; Pasquinelli, Gianandrea; Scandola, Mariastella

    2010-09-13

    Using a two-step procedure, radiopaque and biocompatible coatings were obtained, consisting of a tantalum layer deposited by sputtering technique and of an upper organic-inorganic hybrid layer synthesized via sol-gel. As shown by radiographic images, tantalum confers to plastic substrates good X-ray visibility, adjustable via control of deposition time, but its adhesion to the substrate is poor and manipulation easily damages the metal layer. Polymer-titania hybrid coatings, synthesized using poly-ε-caprolactone (PCL) or carboxy-terminated polydimethylsiloxane (PDMS) as organic precursors, were applied on the metal layer as biocompatible protective coatings. Biocompatibility is demonstrated by cytotoxicity tests conducted using vascular wall resident-mesenchymal stem cells (VW-MSCs). Both coatings show very good adhesion to the substrate, showing no sign of detachment upon large substrate deformations. Under such conditions, SEM observations show that the PCL-containing hybrid forms cracks, whereas the PDMS-based hybrid does not crack, suggesting possible applications of the latter material as a protective layer of sputtered tantalum radiopaque markers for flexible medical devices. PMID:20831278

  15. 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.

  16. 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

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. C,N-bipyrazole receptor grafted onto a porous silica surface as a novel adsorbent based polymer hybrid.

    PubMed

    Radi, Smaail; Attayibat, Ahmed; El-Massaoudi, Mohamed; Bacquet, Maryse; Jodeh, Shehdeh; Warad, Ismail; Al-Showiman, Salim S; Mabkhot, Yahia N

    2015-10-01

    A simple heterogeneous synthesis of pure adsorbent based polymer hybrid made by condensing a functionalized C,N-bipyrazole with a 3-glycidoxypropyl-trimethoxysilane silylant agent, previously anchored on a silica surface was developed. The formed material (SG2P) was characterized through elemental analysis, FT-IR spectroscopy, (13)C NMR of solid state, scanning electron microscope (SEM), and was studied and evaluated by determination of the surface area using the BET equation, the adsorption and desorption capability using the isotherm of nitrogen and B.J.H. pore sizes. The new material exhibits good thermal stability determined by thermogravimetry curves and good chemical stability was examined in various acidic and buffer solutions (pH 1-7). The binding and adsorption abilities of SG2P were investigated for Hg(2+), Cd(2+), Pb(2+), Zn(2+), K(+), Na(+) and Li(+) cations and compared to the results of classical liquid-liquid extraction with the unbound C,N-bipyrazole compound. The grafting at the surface of silica does not affect complexing properties of the ligand and the SG2P exhibits a high selectivity toward Hg(2+) ion with no complexation being observed towards zinc and alkali metals. The extracted and the complexing cation percentages were determined by atomic absorption measurements. PMID:26078121

  5. Capillary electrophoresis-mass spectrometry of basic proteins using a new physically adsorbed polymer coating. Some applications in food analysis.

    PubMed

    Simó, Carolina; Elvira, Carlos; González, Nieves; San Román, J; Barbas, Coral; Cifuentes, Alejandro

    2004-07-01

    A new physically adsorbed capillary coating for capillary electrophoresis-mass spectrometry (CE-MS) of basic proteins is presented, which is easily obtained by flushing the capillary with a polymer aqueous solution for two min. This coating significantly reduces the electrostatic adsorption of a group of basic proteins (i.e., cytochrome c, lysozyme, and ribonuclease A) onto the capillary wall allowing their analysis by CE-MS. The coating protocol is compatible with electrospray inonization (ESI)-MS via the reproducible separation of the standard basic proteins (%RSD values (n = 5) < 1% for analysis time reproducibility and < 5% for peak heights, measured from the total ion electropherograms (TIEs) within the same day). The LODs determined using cytochrome c with total ion current and extracted ion current defection were 24.5 and 2.9 fmol, respectively. Using this new coating lysozymes from chicken and turkey egg white could be easily distinguished by CE-MS, demonstrating the usefulness of this method to differentiate animal species. Even after sterilization at 120 degrees C for 30 min, lysozyme could be detected, as well as in wines at concentrations much lower than the limit marked by the EC Commission Regulation. Adulteration of minced meat with 5% of egg-white could also be analysed by our CE-MS protocol. PMID:15237406

  6. Polymer Thin Films and Interfaces; a Layer-by-Layer Approach

    NASA Astrophysics Data System (ADS)

    White, Ronald; Lipson, Jane

    2013-03-01

    In this talk we discuss new ways to model polymer films and interfaces, including properties such as density and concentration gradients, interfacial tension, and surface enrichment. We build on recent work where we developed a very simple equation of state approach for polymer thin films, and successfully applied it to determine thermodynamic properties and even to make predictions for the thickness-dependent depression of the thin film glass transition temperature. In that very simplified mean field model, the film properties across the entire interface region were treated as a ``whole sample'' average. Here, we take the next step, and develop a layer-by-layer equation of state model wherein details of the interface region are captured by allowing properties to vary from one discretized layer (within which properties are uniform) to the next. The model can be solved by imposing hydrostatic equilibrium in each layer, which then leads to predictions for the corresponding density gradient and other key interface properties. Work supported by the National Science Foundation.

  7. Interrogating protonated/deuterated fibronectin fragment layers adsorbed to titania by neutron reflectivity and their concomitant control over cell adhesion

    PubMed Central

    McIntosh, Lisa; Whitelaw, Christine; Rekas, Agata; Holt, Stephen A.; van der Walle, Christopher F.

    2015-01-01

    The fibronectin fragment, 9th–10th-type III domains (FIII9–10), mediates cell attachment and spreading and is commonly investigated as a bioadhesive interface for implant materials such as titania (TiO2). How the extent of the cell attachment–spreading response is related to the nature of the adsorbed protein layer is largely unknown. Here, the layer thickness and surface fraction of two FIII9–10 mutants (both protonated and deuterated) adsorbed to TiO2 were determined over concentrations used in cell adhesion assays. Unexpectedly, the isotopic forms had different adsorption behaviours. At solution concentrations of 10 mg l−1, the surface fraction of the less conformationally stable mutant (FIII9′10) was 42% for the deuterated form and 19% for the protonated form (fitted to the same monolayer thickness). Similarly, the surface fraction of the more stable mutant (FIII9′10–H2P) was 34% and 18% for the deuterated and protonated forms, respectively. All proteins showed a transition from monolayer to bilayer between 30 and 100 mg l−1, with the protein longitudinal orientation moving away from the plane of the TiO2 surface at high concentrations. Baby hamster kidney cells adherent to TiO2 surfaces coated with the proteins (100 mg l−1) showed a strong spreading response, irrespective of protein conformational stability. After surface washing, FIII9′10 and FIII9′10–H2P bilayer surface fractions were 30/25% and 42/39% for the lower/upper layers, respectively, implying that the cell spreading response requires only a partial protein surface fraction. Thus, we can use neutron reflectivity to inform the coating process for generating bioadhesive TiO2 surfaces. PMID:25926699

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

    DOE PAGESBeta

    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

  9. Development and application of thin-layer spectroelectrochemical techniques for the study of organosulfur monolayers adsorbed at gold

    SciTech Connect

    Simmons, N.

    1997-10-08

    A main research interest is the characterization of monolayers formed by the spontaneous adsorption of organosulfur compounds at gold. This dissertation describes the development and application of long optical pathlength thin-layer spectroelectrochemistry in an attempt to address key issues regarding the reactivity of surface-immobilized molecules. The first section of this introductory chapter briefly describes the general approach to the preparation and characterization of these films. The last section provides an overview of the main principles and advantages of thin-layer spectroelectrochemistry for studying surface-adsorbed species. The body of this dissertation is divided into four chapters. Chapter 2 consists of a paper describing the design, construction, and characterization of a cuvette-based LOPTLC. Chapter 3 is a paper which examines the reductive desorption process using thin-layer spectroelectrochemistry to monitor and identify the desorption product. Chapter 4 is a paper describing the characterization of monolayers functionalized with a catechol terminal group which serves as a redox transformable coordination site for metal ion binding. Chapter 5 discusses the application of thin-layer spectroelectrochemistry to acid-base reactivity studies of surface-immobilized molecules. The final section provides some general conclusions and a prospectus for future studies. These chapters have been processed separately for inclusion on the data base. This report contains the introduction, references, and general conclusions. 78 refs.

  10. Strength improvement via coating of a cylindrical hole by layer-by-layer assembled polymer particles.

    PubMed

    Wu, Shuqing; Garfield, Lucas B; Rupert, Nicholas E; Grady, Brian P; Funkhouser, Gary P

    2010-04-01

    Negatively charged colloidal poly(methyl methacrylate-co-butyl acrylate) (P(MMA-BA)) particles and positively charged dissolved poly(ethyleneimine) (PEI) were adsorbed onto a cement block using a layer-by-layer (LBL) assembly technique. The block was fashioned so as to have a cylindrical hole running from one face to another along the long axis of the rectangular block, and a fluid containing either of the two charged materials was pumped through the block. The result was a film tens of micrometers thick, and the pressure required to crack the cement block was measured after one end of the hole was sealed. Latex particles with a T(g) near the use temperature showed the maximum improvement in the cracking stress of the blocks. In a multilayer coating with identically sized particles, the cracking stress of the blocks increased to an improvement of 25% and then dropped off with increasing number of layers, even though the relationship between film thickness and the number of layers was linear. An improvement of about 30% in the cracking stress of the coated blocks was obtained when using multiple layers with different particle sizes. The effects of the number of layers and particle size on the cracking stress suggest that both the morphology and the thickness of the film play a role in performance. Tests done under confinement, e.g., with an external stress applied to the outside of the blocks, suggest that not only does a film-forming mechanism contribute to performance but that filling of microcracks in the rock may also play a role. PMID:20423142

  11. Contact Forces between TiO2 Nanoparticles Governed by an Interplay of Adsorbed Water Layers and Roughness.

    PubMed

    Laube, Jens; Salameh, Samir; Kappl, Michael; Mädler, Lutz; Colombi Ciacchi, Lucio

    2015-10-20

    Interparticle forces govern the mechanical behavior of granular matter and direct the hierarchical assembling of nanoparticles into supramolecular structures. Understanding how these forces change under different ambient conditions would directly benefit industrial-scale nanoparticle processing units such as filtering and fluidization. Here we rationalize and quantify the contributions of dispersion, capillary, and solvation forces between hydrophilic TiO2 nanoparticles with sub-10 nm diameter and show that the humidity dependence of the interparticle forces is governed by a delicate interplay between the structure of adsorbed water layers and the surface roughness. All-atom molecular dynamics modeling supported by force-spectroscopy experiments reveals an unexpected decrease in the contact forces at increasing humidity for nearly spherical particles, while the forces between rough particles are insensitive to strong humidity changes. Our results also frame the limits of applicability of discrete solvation and continuum capillary theories in a regime where interparticle forces are dominated by the molecular nature of surface adsorbates. PMID:26414448

  12. 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

  13. Superhydrophobic Thin Films Fabricated by Reactive Layer-by-Layer Assembly of Azlactone-Functionalized Polymers

    PubMed Central

    Buck, Maren E.; Schwartz, Sarina C.

    2010-01-01

    We report an approach to the fabrication of superhydrophobic thin films that is based on the ‘reactive’ layer-by-layer assembly of azlactone-containing polymer multilayers. We demonstrate that films fabricated from alternating layers of the azlactone functionalized polymer poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) and poly(ethyleneimine) (PEI) exhibit micro- and nanoscale surface features that result in water contact angles in excess of 150º. Our results reveal that the formation of these surface features is (i) dependent upon film thickness (i.e., the number of layers of PEI and PVDMA deposited) and (ii) that it is influenced strongly by the presence (or absence) of cyclic azlactone-functionalized oligomers that can form upon storage of the 2-vinyl-4,4-dimethylazlactone (VDMA) used to synthesize PVDMA. For example, films fabricated using polymers synthesized in the presence of these oligomers exhibited rough, textured surfaces and superhydrophobic behavior (i.e., advancing contact angles in excess of 150º). In contrast, films fabricated from PVDMA polymerized in the absence of this oligomer (e.g., using freshly distilled monomer) were smooth and only moderately hydrophobic (i.e., advancing contact angles of ~75º). The addition of authentic, independently synthesized oligomer to samples of distilled VDMA at specified and controlled concentrations permitted reproducible fabrication of superhydrophobic thin films on the surfaces of a variety of different substrates. The surfaces of these films were demonstrated to be superhydrophobic immediately after fabrication, but they became hydrophilic after exposure to water for six days. Additional experiments demonstrated that it was possible to stabilize and prolong the superhydrophobic properties of these films (e.g., advancing contact angles in excess of 150° even after complete submersion in water for at least six weeks) by exploiting the reactivity of residual azlactones to functionalize the surfaces of the

  14. 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.

  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. Covalent layer-by-layer assembly of hyperbranched polymers on alginate microcapsulesto impart stability and permselectivity.

    PubMed

    Gattás-Asfura, Km; Valdes, M; Celik, E; Stabler, Cl

    2014-12-14

    The microencapsulation of cells has shown promise as a therapeutic vehicle for the treatment of a wide variety of diseases. While alginate microcapsules provide an ideal cell encapsulation material, polycations coatings are commonly employed to enhance stability and impart permselectivity. In this study, functionalized hyperbranched alginate and dendrimer polymers were used to generate discreet nanoscale coatings onto alginate microbeads via covalent layer-by-layer assembly. The bioorthogonal Staudinger ligation scheme was used to chemoselectively crosslink azide functionalized hyperbranched alginate (alginate-hN3) to methyl-2-diphenylphosphino-terephthalate (MDT) linked PAMAM dendrimer (PAMAM-MDT). Covalent layer-by-layer deposition of PAMAM-MDT/alginate-hN3 coatings onto alginate microbeads resulted in highly stable coatings, even after the inner alginate gel was liquefied to form microcapsules. The permselectivity of the coated microcapsules could be manipulated via the charge density of the PAMAM, the number of layers deposited, and the length of the functional arms. The cytocompatibility of the resulting PAMAM-MDT/alginate-hN3 coating was evaluated using a beta cell line, with no significant detrimental response observed. The biocompatibility of the coatings in vivo was also found comparable to uncoated alginate beads. The remarkable stability and versatile nature of these coatings provides an appealing option for bioencapsulation and the release of therapeutic agents. PMID:25478165

  17. 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

  18. 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. PMID:26944833

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

    PubMed

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

    2016-06-22

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

  20. Tunable photochemical properties of a covalently anchored and spatially confined organic polymer in a layered compound

    NASA Astrophysics Data System (ADS)

    Matsui, Hiroshi; Oaki, Yuya; Imai, Hiroaki

    2016-05-01

    A covalently anchored and spatially confined organic polymer was formed in a layered compound with a surface-modified layer. The resultant anchored and confined polymer showed tunable photochemical properties with the incorporation of a variety of guest molecules originating from the specific incorporation states. The layer surface of an inorganic layered compound was modified by an organic molecule with vinyl groups. The precursor layered composite accommodated N-vinylcarbazole (VCz), a vinyl monomer, in the hydrophobic interlayer space. The introduction of VCz induced the simultaneous exfoliation of the layered structures and copolymerization with vinyl groups on the layer surface. The covalently anchored and spatially confined poly(N-vinylcarbazole) (PVCz) with tunable photochemical properties was formed in a layered structure. The present study shows the versatile potential of polymers with anchored and confined states in surface-functionalized layered composites.A covalently anchored and spatially confined organic polymer was formed in a layered compound with a surface-modified layer. The resultant anchored and confined polymer showed tunable photochemical properties with the incorporation of a variety of guest molecules originating from the specific incorporation states. The layer surface of an inorganic layered compound was modified by an organic molecule with vinyl groups. The precursor layered composite accommodated N-vinylcarbazole (VCz), a vinyl monomer, in the hydrophobic interlayer space. The introduction of VCz induced the simultaneous exfoliation of the layered structures and copolymerization with vinyl groups on the layer surface. The covalently anchored and spatially confined poly(N-vinylcarbazole) (PVCz) with tunable photochemical properties was formed in a layered structure. The present study shows the versatile potential of polymers with anchored and confined states in surface-functionalized layered composites. Electronic supplementary

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

    PubMed

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

    2010-05-01

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

  2. 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.

  3. 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. PMID:26363948

  4. 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.

  5. Characteristics of resistivity log response of oil layers under polymer flooding

    NASA Astrophysics Data System (ADS)

    Yu, Jun; Pan, Bao-Zhi; Yang, Qing-Shan

    2012-06-01

    Resistivity log responses are different when the oil layers is filled by a polymer solution or water and it seriously affects the log interpretation of the water flooded layer. In this paper, we first analyze the electrical properties of the polymer solution. Then, according to the different processes for polymer flooding the reservoir, we perform rock resistivity experiments and analyze the rock resistivity variations in different displacement phases. We also compare the resistivity log responses of oil layers filled with the polymer solution to those filled with water. The results show that when displacing the oil-bearing core by different polymers, the resistivity changes monotonously decrease and show either "W" type or "S" type. The resistivity log responses are weak when displacing water and there is no flooded show if the oil layer is injected by a fresh water polymer solution. If the oil layer is injected by a sewage polymer solution, the resistivity log response has similar characteristic as a polluted water flooded layer.

  6. 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

  7. 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. PMID:24224944

  8. 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.

  9. The effect of chain rigidity on the interfacial layer thickness and dynamics of polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Cheng, Shiwang; Carrillo, Jan-Michael Y.; Carroll, Bobby; Sumpter, Bobby G.; Sokolov, Alexei P.

    There are growing experimental evidences showing the existence of an interfacial layer that has a finite thickness with slowing down dynamics in polymer nanocomposites (PNCs). Moreover, it is believed that the interfacial layer plays a significant role on various macroscopic properties of PNCs. A thicker interfacial layer is found to have more pronounced effect on the macroscopic properties such as the mechanical enhancement. However, it is not clear what molecular parameter controls the interfacial layer thickness. Inspired by our recent computer simulations that showed the chain rigidity correlated well with the interfacial layer thickness, we performed systematic experimental studies on different polymer nanocomposites by varying the chain stiffness. Combining small-angle X-ray scattering, broadband dielectric spectroscopy and temperature modulated differential scanning calorimetry, we find a good correlation between the polymer Kuhn length and the thickness of the interfacial layer, confirming the earlier computer simulations results. Our findings provide a direct guidance for the design of new PNCs with desired properties.

  10. Uniform-sized molecularly imprinted polymer for (S)-naproxen selectively modified with hydrophilic external layer.

    PubMed

    Haginaka, J; Takehira, H; Hosoya, K; Tanaka, N

    1999-07-23

    A uniform-sized molecularly imprinted polymer (MIP) for (S)-naproxen selectively modified with hydrophilic external layer has been prepared. First, the molecularly imprinted polymer for (S)-naproxen was prepared using 4-vinylpyridine and ethylene glycol dimethacrylate (EDMA) as a functional monomer and cross-linker, respectively, by a multi-step swelling and thermal polymerization method. Next, a 1:1 mixture of glycerol monomethacrylate (GMMA) and glycerol dimethacrylate (GDMA) was used for hydrophilic surface modification, and it was added directly to the molecularly imprinted polymer for (S)-naproxen 4 h after the start of molecular imprinting. The retention factors of all solutes tested were decreased with the surface modified molecularly imprinted polymer, compared with the unmodified molecularly imprinted polymer. However, chiral recognition of racemic naproxen was attained with the surface modified molecularly imprinted polymer as well as the unmodified molecularly imprinted polymer. Further, bovine serum albumin was completely recovered from the surface modified molecularly imprinted polymer. These results revealed that the chiral recognition sites of (S)-naproxen remained unchanged with hydrophilic surface modification, and that the molecularly imprinted polymer for (S)-naproxen was selectively modified with hydrophilic external layer. Preliminary results reveal that the surface modified molecularly imprinted polymer could be applicable to direct serum injection assays of (S)-naproxen. PMID:10457431

  11. Innovative Nano-Layered Solid Sorbents for CO{sub 2} Capture

    SciTech Connect

    Li, Bengyun; Jiang, Bingbing; Fauth, Daniel J; Gray, McMahan L; Pennline, Henry W; Richards, George A

    2011-01-01

    Nano-layered sorbents for CO{sub 2} capture, for the first time, were developed using layer-by-layer nanoassembly. A CO{sub 2}-adsorbing polymer and a strong polyelectrolyte were alternately immobilized within porous particles. The developed sorbents had fast CO{sub 2} adsorption and desorption properties and their CO{sub 2} capture capacity increased with increasing nano-layers of the CO{sub 2}-adsorbing polymer.

  12. Solution-processed amorphous niobium oxide as a novel electron collection layer for inverted polymer solar cells

    NASA Astrophysics Data System (ADS)

    Hamada, Keisuke; Murakami, Naoya; Tsubota, Toshiki; Ohno, Teruhisa

    2013-10-01

    Amorphous niobium oxide (NbOx) as an electron collection layer in inverted polymer solar cells was prepared by a solution process. The power conversion efficiency of inverted polymer solar cells based on a blend of poly(3-hexylthiophene) and [6,6]-phenyl C61 butyric acid methyl ester was improved to 2.22% by inserting an NbOx layer between the active layer and indium tin oxide electrode. An energy level diagram of component materials in the inverted polymer solar cell indicated that the NbOx layer works as both an electron collection layer and hole blocking layer in polymer solar cells.

  13. 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.

  14. 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

  15. Polymer films as planarization and sacrificial layers for uncooled infrared focal plane arrays

    NASA Astrophysics Data System (ADS)

    Liu, Huan; Liu, Weiguo; Cai, Changlong; Zhou, Shun

    2010-10-01

    This paper presents a planarization procedure using polymer films to achieve a flat CMOS surface of Readout Integrated Circuit (ROIC) for the integration between uncooled infrared focal plane arrays and ROIC. At the same time, the polymer film is also used as the sacrificial layers. After amorphous Silicon (a-Si) film was deposited using plasma enhanced chemical vapor deposition (PECVD), and patterned using inductively coupled plasma (ICP), the polymer sacrificial layer should be removed to form a-Si self-supporting micro-bridge structure. So the thickness of polymer film determine the height of the micro-bridge; the soft curing temperature determines if the contact hole can be etched by developer during the first photolithography; and the rate of dry etching determines whether the sacrificial layers of the structure can be released successfully. In this paper, the curing temperature, surface roughness, etching process of polymer films are systematically researched. On this basis, polymer film as planarization successfully reduces the 2μm height of the bumps on ROIC to less than 83 nm, over the planarized polymer mesas, bolometer arrays are fabricated. Then the polymer film as sacrificial are removed by ICP and 160x120 self-supporting micro-bridge structure arrays are successfully fabricated.

  16. Polymer films as planarization and sacrificial layers for uncooled infrared focal plane arrays

    NASA Astrophysics Data System (ADS)

    Liu, Huan; Liu, Weiguo; Cai, Changlong; Zhou, Shun

    2011-02-01

    This paper presents a planarization procedure using polymer films to achieve a flat CMOS surface of Readout Integrated Circuit (ROIC) for the integration between uncooled infrared focal plane arrays and ROIC. At the same time, the polymer film is also used as the sacrificial layers. After amorphous Silicon (a-Si) film was deposited using plasma enhanced chemical vapor deposition (PECVD), and patterned using inductively coupled plasma (ICP), the polymer sacrificial layer should be removed to form a-Si self-supporting micro-bridge structure. So the thickness of polymer film determine the height of the micro-bridge; the soft curing temperature determines if the contact hole can be etched by developer during the first photolithography; and the rate of dry etching determines whether the sacrificial layers of the structure can be released successfully. In this paper, the curing temperature, surface roughness, etching process of polymer films are systematically researched. On this basis, polymer film as planarization successfully reduces the 2μm height of the bumps on ROIC to less than 83 nm, over the planarized polymer mesas, bolometer arrays are fabricated. Then the polymer film as sacrificial are removed by ICP and 160x120 self-supporting micro-bridge structure arrays are successfully fabricated.

  17. 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

  18. Numerical well testing interpretation model and applications in crossflow double-layer reservoirs by polymer flooding.

    PubMed

    Yu, Haiyang; Guo, Hui; He, Youwei; Xu, Hainan; Li, Lei; Zhang, Tiantian; Xian, Bo; 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

  19. 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

  20. 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.

  1. Patterned colloid assembly by grafted photochromic polymer layers.

    SciTech Connect

    Piech, Marcin; Braun, Paul; Bell, Nelson Simmons; George, Matt

    2005-06-01

    Quartz surfaces and colloidal silica particles were derivatized with a poly(methyl methacrylate) copolymer containing spirobenzopyran (SP) photochromic molecules in the pendant groups at a concentration of 20 mol %. Two-photon near-IR excitation ({approx}780 nm) was then used to create chemically distinct patterns on the modified surfaces through a photochromic process of SP transformation to the zwitterionic merocyanine (MC) isomer. The derivatized colloids were approximately 10 times more likely to adsorb onto the photoswitched, MC regions. Surface coverage and adsorption kinetics have been compared to the mean-field model of irreversible monolayer adsorption.

  2. Effect of surface alignment layer and polymer network on the Helfrich deformation in cholesteric liquid crystals

    NASA Astrophysics Data System (ADS)

    Nemati, H.; Yang, D.-K.; Cheng, K.-L.; Liang, C.-C.; Shiu, J.-W.; Tsai, C.-C.; Zola, R. S.

    2012-12-01

    We show that the Helfrich deformation can be used for fast response time, low driving voltage reflective displays by using cholesteric liquid crystals under short voltage pulses (˜10 ms). Rather than turning planar domains into focal conic domains through a nucleation process, as used in bistable modes, the fast voltage pulse only deforms the cholesteric planar layers to form wrinkled layers. Since the deformed state is formed through a homogeneous process, quick response times and low operating voltage can be achieved. We studied the effects of alignment layer and dispersed polymer on the stability of the Helfrich deformed cholesteric layers, and found that homogeneous alignment layer and polymer network can inhibit the nucleation process responsible for breaking the layers.

  3. 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.

  4. Adsorbing a PVDF polymer via noncovalent interactions to effectively tune the electronic and magnetic properties of zigzag SiC nanoribbons.

    PubMed

    Li, Hui; Chen, Wei; Sun, Yuanhui; Huang, Xuri; Yu, Guangtao

    2015-10-01

    On the basis of first-principle computations, we first propose a simple and effective strategy through surface-adsorbing a poly(vinylidene fluoride) (PVDF) polymer via noncovalent interactions to tune the electronic and magnetic behaviors of zigzag SiC nanoribbons (zSiCNRs). It is revealed that depositing the strong electron-withdrawing PVDF polymer with a permanent dipole moment can induce the evident change of the electrostatic potential in the substrate zSiCNRs, like applying an electric field. As a result, this kind of noncovalent surface-modification by a polymer can break the magnetic degeneracy of zSiCNRs independent of the adsorption type and position, and sole ferromagnetic metallicity and even antiferromagnetic half-metallicity can be achieved. Moreover, all PVDF-modified zSiCNR systems can exhibit considerable adsorption energies in the range of -0.436 to -1.315 eV, indicating that these joint systems possess high structural stabilities. These intriguing findings will be advantageous for promoting excellent SiC-based nanomaterials in the applications of spintronics and multifunctional nanodevices in the near future. PMID:26312553

  5. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    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 (TiO2) 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 TiO2/P3HT:PCBM/V2O5/Au) as well as inserting the buffers layers between the polymer and the aluminum electrode for the conventional structure (ITO/V2O5/P3HT:PCBM/ZnO or TiO2/Al). The results are shown in detail.

  7. 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.

  8. Modeling of Electro Optic Polymer Electrical Characteristics in a 3 layer Optical Waveguide Modulator

    NASA Technical Reports Server (NTRS)

    Watson, Michael D.; Ashley, Paul R.; Guenthner, Andrew J.; Abushagur, Mustafa

    2004-01-01

    The electrical characteristics of electro optic polymer waveguide modulators are often described by the bulk reactance of the individual layers. However, the resistance and capacitance between the layers can significantly alter the electrical performance of a waveguide modulator. These interface characteristics are related to the boundary charge density and are strongly affected by the adhesion of the layers in the waveguide stack. An electrical reactance model has been derived to investigate this phenomenon at low frequencies. The model shows the waveguide stack frequency response has no limiting effects below the microwave range and that a true DC response requires a stable voltage for over 1000 hours. Thus, reactance of the layers is the key characteristic of optimizing the voltage across the core layer, even at very low frequencies (> 10(exp -6) Hz). The results of the model are compared with experimental data for two polymer systems and show quite good correlation.

  9. Effects of polymer sidebranching in double- and single-layer polyfluorene light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Nakazawa, Y. K.; Carter, S. A.; Nothofer, H.-G.; Scherf, U.; Lee, V. Y.; Miller, R. D.; Scott, J. C.

    2002-05-01

    We study how changes in sidebranching in electroluminescent polymers affect the performance of polyfluorene-based light-emitting diodes with and without additional hole transport materials. We observe that light emission and device efficiency are determined more by the position of the exciton recombination zone than by changes in the polymer morphology induced by sidebranching. Consequently, we find that sidebranching mainly controls the relative emission between vibrational energy levels and has a minimal effect on polymer charge transport properties. Light outputs of 10 000 cd/m2 and device efficiencies of 0.85 and 1.8 cd/A are obtained for single- and double-layer devices, respectively.

  10. Measurement of the skin layer in the drying process of a polymer solution.

    PubMed

    Shimokawa, Yuji; Kajiya, Tadashi; Sakai, Keiji; Doi, Masao

    2011-11-01

    When a polymer solution is dried in air, a polymer-concentrated region, called a "skin" layer, often appears near the surface. In this paper, an experimental method is proposed for detecting the initial process of the formation of the skin layer. An electric field is applied on the surface of polymer solutions by a wedge-type "electric field tweezers," and the dynamic response of the surface profile is measured by an optical lever technique. Our experiments and theory indicate that when a skin layer is formed, (i) the slow relaxation process appears in the time domain and (ii) the long-persisting dip region appears in the surface profile. A parameter to quantify the difference of the surface response is proposed in this paper. PMID:22181435

  11. Ionic polymer-metal composite actuators based on triple-layered polyelectrolytes composed of individually functionalized layers.

    PubMed

    Lee, Jang-Woo; Yoo, Young-Tai; Lee, Jae Yeol

    2014-01-22

    Ionic polymer-metal composite (IPMC) actuators based on two types of triple-layered Nafion composite membranes were prepared via consecutive solution recasting and electroless plating methods. The triple-layered membranes are composed of a Nafion layer containing an amphiphilic organic molecule (10-camphorsulfonic acid; CSA) in the middle section (for fast and large ion conduction) and two Nafion/modified inorganic composite layers in the outer sections (for large accumulation/retention of mobile ions). For construction of the two types of IPMCs, sulfonated montmorillonite (MMT) and polypyrrole (PPy)-coated alumina fillers were incorporated into the outer layers. Both the triple-layered IPMCs exhibited 42% higher tip displacements at the maximum deflections with a negligible back-relaxation, 50-74% higher blocking forces, and more rapid responses under 3 V dc, compared with conventional single-layered Nafion-IPMCs. Improvements in cyclic displacement under a rectangular voltage input of 3 V at 1 Hz were also made in the triple-layered configurations. Compared with single-layered IPMCs consisting of the identical compositions with the respective outer composite layers, the bending rates and energy efficiencies of both the triple-layered IPMCs were significantly higher, although the blocking forces were a bit lower. These remarkable improvements were attributed to higher capacitances and Young's moduli as well as a more efficient transport of mobile ions and water through the middle layer (Nafion/CSA) and a larger accumulation/retention of the mobile species in the outer functionalized inorganic composite layers. Especially, the triple-layered IPMC with the PPy-modified alumina registered the best actuation performance among all the samples, including a viable actuation even at a low voltage of 1.5 V due to involving efficient redox reactions of PPy with the aid of hygroscopic alumina. PMID:24383744

  12. 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.

  13. Semiconducting Polymer Photodetectors with Electron and Hole Blocking Layers: High Detectivity in the Near-Infrared

    PubMed Central

    Gong, Xiong; Tong, Ming-Hong; Park, Sung Heum; Liu, Michelle; Jen, Alex; Heeger, Alan J.

    2010-01-01

    Sensing from the ultraviolet-visible to the infrared is critical for a variety of industrial and scientific applications. Photodetectors with broad spectral response, from 300 nm to 1,100 nm, were fabricated using a narrow-band gap semiconducting polymer blended with a fullerene derivative. By using both an electron-blocking layer and a hole-blocking layer, the polymer photodetectors, operating at room temperature, exhibited calculated detectivities greater than 1013 cm Hz1/2/W over entire spectral range with linear dynamic range approximately 130 dB. The performance is comparable to or even better than Si photodetectors. PMID:22163562

  14. Entropic elasticity of end adsorbed polymer chains: The spectrin network of red blood cells as C*-gel

    NASA Astrophysics Data System (ADS)

    Everaers, Ralf; Graham, Ian S.; Zuckermann, Martin J.; Sackmann, Erich

    1996-03-01

    We use Monte Carlo methods to investigate the end-to-end distance distribution and entropic elasticity of self-avoiding walks in a three-dimensional half-space with both ends adsorbed on the limiting surface. The obtained distributions are well described by the Redner-des Cloizeaux (RdC) ansatz q(x)=Cxθ exp(-(Kx)t), x being the rescaled length. Using the recent solution of the junction affine model for networks of RdC springs we apply the results to the cytoskeleton of the red blood cell (RBC), a two-dimensional network of spectrin molecules which is attached to the inner surface of the erythrocyte membrane. The shear moduli predicted for a noninteracting surface are in close agreement with simulation results by Boal for a bead-spring model of the spectrin network. Moreover, we calculate stress-strain relations for finite deformations. In particular for a network which is fully adsorbed on the bilayer we find a strongly nonlinear elastic response. Our results suggest that the elastic properties of RBCs cannot be obtained within the usual Gaussian models and depend sensitively on the degree of adsorption of the spectrin network.

  15. Recent Advances in Gas Barrier Thin Films via Layer-by-Layer Assembly of Polymers and Platelets.

    PubMed

    Priolo, Morgan A; Holder, Kevin M; Guin, Tyler; Grunlan, Jaime C

    2015-05-01

    Layer-by-layer (LbL) assembly has emerged as the leading non-vacuum technology for the fabrication of transparent, super gas barrier films. The super gas barrier performance of LbL deposited films has been demonstrated in numerous studies, with a variety of polyelectrolytes, to rival that of metal and metal oxide-based barrier films. This Feature Article is a mini-review of LbL-based multilayer thin films with a 'nanobrick wall' microstructure comprising polymeric mortar and nano-platelet bricks that impart high gas barrier to otherwise permeable polymer substrates. These transparent, water-based thin films exhibit oxygen transmission rates below 5 × 10(-3) cm(3) m(-2) day(-1) atm(-1) and lower permeability than any other barrier material reported. In an effort to put this technology in the proper context, incumbent technologies such as metallized plastics, metal oxides, and flake-filled polymers are briefly reviewed. PMID:25800245

  16. Stimuli-Responsive Layer-by-Layer Tellurium-Containing Polymer Films for the Combination of Chemotherapy and Photodynamic Therapy.

    PubMed

    Fan, Fuqiang; Wang, Lu; Li, Feng; Fu, Yu; Xu, Huaping

    2016-07-01

    Tellurium-containing photoresponsive polyelectrolyte multilayer films were fabricated by layer-by-layer assembly of a tellurium-containing polymer, photosensitizer, and poly(styrenesulfonate). The resulting films were investigated by UV/vis spectroscopy, XPS, EPR, and fluorescence spectroscopy. Under visible light, the photosensitizer in the film is excited and transforms triplet oxygen into singlet oxygen in aqueous solution. Singlet oxygen oxidizes -Te- to high valence state (Te═O) on the polymer backbone. The generated (Te═O) group makes the micelles more hydrophilic and looser, thereby facilitating the controlled release of the loaded cargo of micelles. These results show that the film has the potential to be used for cargo loading and controlled release, thus may provide a new way to combine photodynamic therapy and chemotherapy. PMID:27301845

  17. 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.

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

    DOE PAGESBeta

    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

  19. Interfacial interactions in polymer-layered silicate nanocomposites.

    PubMed

    Kato, Ryo; Liauw, Christopher M; Allen, Norman S; Irure, Ainhoa; Wilkinson, Arthur N; Stanford, John L; Fithriyah, Nurul H

    2008-03-01

    Interactions between sodium montmorillonite (Na-MMT) and a variety of probes, some of which are intended to model components of a polyurethane system, have been studied. Particular attention was given to the effect of preadsorbed water on the adsorption behavior of the probes. Flow microcalorimetry (FMC), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), and wide-angle X-ray scattering (WAXS) were used to monitor the adsorption process. The probe set included alcohols, amines, ethers, poly(propylene glycol) monobutyl ethers (PPG), and 4-ethylphenyl isocyanate (4-EPI). FMC revealed that the preadsorbed water molecules on undried Na-MMT hindered the adsorption of alcohol and ether probes, but had little effect on the adsorption of amines. Drying of Na-MMT to less than 0.3% w/w H2O led to an increase in heat of adsorption and generally greater retention of the probes. PPG showed strong interaction with Na-MMT due to multipoint adsorption. With dried Na-MMT, WAXS revealed that PPG of molecular weight (MW) 1000 was partly intercalated into the gallery while lower molecular weight PPG (MW 340) did not intercalate the Na-MMT. DRIFTS spectra of 4-EPI adsorbed on undried Na-MMT revealed urea linkages, indicating formation of N,N'-bis(4-ethylphenyl) urea. In contrast, with dried Na-MMT the 4-EPI formed a urethane linkage with hydroxyl groups present at the edges of the silicate platelets. PMID:18205417

  20. Measurement of the electrical properties of ultrathin polymer layers

    SciTech Connect

    Erikolopyan, N.S.; Galashina, N.M.; Grigorov, L.N.; Gruzdeva, S.G.; Shklyarova, E.I.

    1986-02-01

    A hypothesis is tested that consists of the following: thin layers of polypropylene ca 0.1 um thick can have elevated conducting properties at a low pressure, significantly lower than the creep limit. The authors measured the electrical properties of ultrathin polymeric layers, with a significant difference in the local thickness and through openings, by using a microelectrode whose diameter at the point of contact with the film is less than the average distance between the openings in the film. The microelectrode for the electrical measurements was a steel sewing needle with an indium tip with a radius of curvature of approximately 25 um soldered on the end. The results of use of the indium tip on the needle with a yield point of 4.5 MPa are presented. They indicate that ultra thin layers of polypropylene exhibit elevated conductivity at a low pressure of 4.5 MPa.

  1. 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. PMID:26792019

  2. 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.

  3. Super-adhesive polymer-silica nanocomposite layers.

    PubMed

    Wood, T J; Ward, L J; Badyal, J P S

    2013-10-01

    Atomized spray plasma deposition (ASPD) using a precursor mixture of 2-hydroxyethyl methacrylate and methacryloyl-functionalized 15 nm silica nanoparticles leads to the formation of poly(2-hydroxyethyl methacrylate)-silica nanocomposite layers. The direct application of these coatings to overlapping glass-glass joints gives rise to excellent in situ adhesion reaching 84 MPa shear bond strength and 6 GPa shear modulus prior to the onset of adherent (bulk glass) failure. This significant enhancement in interfacial adhesion arises due to the silica nanoparticle surface methacryloyl groups enhancing cross-linking throughout the nanocomposite layer. PMID:24079883

  4. Orientation Difference of Chemically Immobilized and Physically Adsorbed Biological Molecules on Polymers Detected at the Solid/Liquid Interfaces in Situ

    PubMed Central

    Ye, Shuji; Nguyen, Khoi Tan; Boughton, Andrew P.; Mello, Charlene M.; Chen, Zhan

    2009-01-01

    A surface sensitive second order nonlinear optical technique, sum frequency generation (SFG) vibrational spectroscopy, was applied to study peptide orientation on polymer surfaces, supplemented by a linear vibrational spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). Using the antimicrobial peptide Cecropin P1 as a model system, we have quantitatively demonstrated that chemically immobilized peptides on polymers adopt a more ordered orientation than less tightly bound physically adsorbed peptides. These differences were also observed in different chemical environments, e.g., air versus water. Although numerous studies have reported a direct correlation between the choice of immobilization method and the performance of an attached biological molecule, the lack of direct biomolecular structure and orientation data has made it difficult to elucidate the relationship between structure, orientation and function at a surface. In this work, we directly studied the effect of chemical immobilization method on biomolecular orientation/ordering, an important step for future studies of biomolecular activity. The methods for orientation analysis described within are also of relevance to understanding biosensors, biocompatibility, marine-antifouling, membrane protein functions, and antimicrobial peptide activities. PMID:19961170

  5. 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

  6. 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.

  7. Novel processing to produce polymer/ceramic nanocomposites by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Liang, Xinhua

    Polymeric materials can be greatly influenced by nanoscale inclusions of inorganic materials. The main goal of this thesis is to fabricate novel polymer/ceramic composite materials for two different applications using atomic layer deposition (ALD) or molecular layer deposition (MLD) methods. One is to produce well-dispersed polymer/ceramic nanocomposites with improved barrier properties for packaging applications. The other is to produce porous polymer/ceramic composites with improved bioactivity for tissue engineering applications. ALD has been successfully utilized for the conformal and uniform deposition of ultra-thin alumina and titania films on primary micron-sized polymer particles. The mechanism to initiate alumina and titania ALD on polymer particles without chemical functional groups was confirmed. A nucleation period was needed for both alumina and titania ALD on high density polyethylene (HDPE) particles and no nucleation period was needed for alumina ALD on polymethyl methacrylate particles. Titania ALD films deposited at low temperatures had an amorphous structure and showed much weaker photoactivity than common pigment-grade anatase TiO2 particles. Highly uniform and conformal ultra-thin aluminum alkoxide (alucone) polymer films were deposited on primary silica and titania nanoparticles using MLD in a fluidized bed reactor. The deposition chemistry and properties of alucone MLD films were investigated. The photoactivity of pigment-grade TiO2 particles was quenched after 20 cycles of an alucone MLD film, but the films shrank and decomposed in the presence of water, which decreased the passivation effect of the photoactivity of TiO2 particles. Well-dispersed polymer/ceramic nanocomposites were obtained by extruding alumina ALD coated HDPE particles. The diffusion coefficient of the fabricated nanocomposite membranes can be reduced by half with the inclusion of 7.3 vol.% alumina flakes. However, a corresponding increase in permeability was also observed

  8. 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

  9. Zinc oxide nanowire-poly(methyl methacrylate) dielectric layers for polymer capacitive pressure sensors.

    PubMed

    Chen, Yan-Sheng; Hsieh, Gen-Wen; Chen, Shih-Ping; Tseng, Pin-Yen; Wang, Cheng-Wei

    2015-01-14

    Polymer capacitive pressure sensors based on a dielectric composite layer of zinc oxide nanowire and poly(methyl methacrylate) show pressure sensitivity in the range of 2.63 × 10(-3) to 9.95 × 10(-3) cm(2) gf(-1). This represents an increase of capacitance change by as much as a factor of 23 over pristine polymer devices. An ultralight load of only 10 mg (corresponding to an applied pressure of ∼0.01 gf cm(-2)) can be clearly recognized, demonstrating remarkable characteristics of these nanowire-polymer capacitive pressure sensors. In addition, optical transmittance of the dielectric composite layer is approximately 90% in the visible wavelength region. Their low processing temperature, transparency, and flexible dielectric film makes them a highly promising means for flexible touching and pressure-sensing applications. PMID:25494204

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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

  16. 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.

  17. Organic field-effect transistors based on a crosslinkable polymer blend as the semiconducting layer

    NASA Astrophysics Data System (ADS)

    Yan, He; Yoon, Myung-Han; Facchetti, Antonio; Marks, Tobin J.

    2005-10-01

    For fabrication of top-gate polymer-based organic field-effect transistors (OFETs), it is essential that the semiconducting layer remain intact during spin coating of the overlying dielectric layer. This requirement severely limits the applicable solvent and materials combinations. We show here that a crosslinkable polymer blend consisting of a p-type semiconducting polymer {e.g., TFB; poly[9,9-dioctyl-fluorene-co-N-(4-butylphenyl)-diphenylamine]} and an electroactive crosslinkable silyl reagent {e.g., TPDSi2; 4,4'-bis[(p-trichloro-silylpropylphenyl)phenylamino]biphenyl} is effective as the semiconducting layer in a top-gate bottom-contact OFET device. The TFB +TPDSi2 semiconducting blend is prepared by spin-coating in ambient. The crosslinking process occurs during spin-coating in air and is completed by curing at 90 °C, which renders the resulting film insoluble in common organic solvents and allows subsequent deposition of dielectric layers from a wide range of organic solvents. We also show that the presence of TPDSi2 in the semiconductor layer significantly reduces typical TFB-source-drain threshold voltages in bottom-contact devices, likely due to favorable interfacial TPDSi2-gold electrode interactions.

  18. 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

  19. Exploiting cellular convection in a thick liquid layer to pattern a thin polymer film

    NASA Astrophysics Data System (ADS)

    Nejati, Iman; Dietzel, Mathias; Hardt, Steffen

    2016-02-01

    A method to shape thin polymer films into periodic array of lenses is presented. A liquid layer placed on top of a much thinner polymer film is exposed to a transverse temperature gradient. The upper liquid layer undergoes the short-wavelength Bénard-Marangoni instability, which leads to periodic shear stresses at the liquid-liquid interface and corresponding interfacial deformations. The structures formed are solidified by curing with ultraviolet light. In comparison to previously reported single-layer patterning techniques, the presented method achieves structures of very high horizontal planform symmetry (highly ordered structures). Furthermore, other shapes of technical interest can be easily fabricated by engineering the temperature distribution at the liquid-gas interface.

  20. Polymer Solar Cell Device Characteristics Are Independent of Vertical Phase Separation in Active Layers

    NASA Astrophysics Data System (ADS)

    Loo, Yueh-Lin

    2013-03-01

    Preferential segregation of organic semiconductor constituents in multicomponent thin-film active layers has long been speculated to affect the characteristics of bulk-heterojunction polymer solar cells. Using soft-contact lamination and delamination schemes - with which we have been able to remove compositionally well characterized polymer thin films, flip them over so as to reverse their composition profiles, and then transfer them onto existing device platforms - we showed unambiguously that the device performance of P3HT:PCBM solar cells are independent of the interfacial segregation characteristics of the active layers. Temperature-dependent single-carrier diode measurements of the organic semiconductor constituents suggest that the origin of this invariance stems from the fact that P3HT comprises a high density of mid-gap states. Hole carriers in these mid-gap states can in turn recombine with electrons at the electron-collecting interface, effectively promoting electron transfer from the cathode to the active layer.

  1. 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.

  2. 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 110nm. 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 420ng/cm(2). However, the poly(MPC) brush layer reduced this value dramatically to less than 50ng/cm(2). This effect was independent of the thickness of the poly(MPC) brush layer for thicknesses between 20nm and about 110nm. 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. PMID:26896657

  3. Dynamic charge-carrier-mobility-mediated holography in thin layers of photoconducting polymers

    NASA Astrophysics Data System (ADS)

    Bartkiewicz, S.; Miniewicz, A.; Sahraoui, B.; Kajzar, F.

    2002-11-01

    The dynamic holography technique is proposed for the measurement of the charge-carrier-mobility in thin layers of a photoconducting polymer, used in optically addressed liquid-crystal spatial light modulators. The photorefractive properties of these modulators are studied under short-pulse (20 ps, 532 nm) laser illumination conditions and the charge mobility in the photoconducting polymer (muh=10-7 cm2/V s) is obtained from the temporal evolution of intensity of the first-order diffracted beam. A mechanism responsible for the grating formation is proposed and discussed.

  4. 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

  5. Effect of tethering on the surface dynamics of a thin polymer melt layer.

    PubMed

    Uğur, Gökçe; Akgun, Bulent; Jiang, Zhang; Narayanan, Suresh; Satija, Sushil; Foster, Mark D

    2016-06-28

    The surface height fluctuations of a layer of low molecular weight (2.2k) untethered perdeuterated polystyrene (dPS) chains adjacent to a densely grafted polystyrene brush are slowed dramatically. Due to the interpenetration of the brush with the layer of "untethered chains" a hydrodynamic continuum theory can only describe the fluctuations when the effective thickness of the film is taken to be that which remains above the swollen brush. The portion of the film of initially untethered chains that interpenetrates with the brush becomes so viscous as to effectively play the role of a rigid substrate. Since these hybrid samples containing a covalently tethered layer at the bottom do not readily dewet, and are more robust than thin layers of untethered short chains on rigid substrates, they provide a route for tailoring polymer layer surface properties such as wetting, adhesion and friction. PMID:27222250

  6. Wettability of terminally anchored polymer brush layers on a polyamide surface.

    PubMed

    Varin, Kari J Moses; Cohen, Yoram

    2014-12-15

    Surface wettability of terminally anchored hydrophilic polymer brush layers on polyamide-silicon (PA-Si) surfaces was evaluated with respect to surface topography at the nanoscale. Hydrophilic polyvinylpyrrolidone (PVP) and polyacrylamide (PAAm) brush layers were synthesized via graft polymerization onto a PA-Si surface previously activated by surface treatment with atmospheric pressure plasma. Hydrophilicity (or wettability) of the PA substrate, as quantified by the free energy of hydration, was increased upon surface coverage with the PVP and PAAm brush layers by 13-24% (-101.4 to -111.3 mJ/m(2)) and 19-37% (-106.1 to -122.4 mJ/m(2)), respectively. Surface hydrophilicity increased with both increasing surface roughness (0.55-2.89 nm and 1.54-5.84 nm for PVP and PAAm, respectively) and polymer volume (1.3×10(6)-7.3×10(6) nm(3)/μm(2) and 3.3×10(6)-2.8×10(7) nm(3)/μm(2) for PVP and PAAm surfaces, respectively). The present study suggests that a specific level of surface wettability can be attained by tailor-designing the polymer brush layer's physicochemical characteristics (e.g., surface roughness, wettability, and polymer water affinity) by adjusting surface topography and surface chemistry, which are controlled by surface activation and polymerization conditions. The above indicates that there is merit in structuring various surfaces with hydrophilic brush layers to increase surface wettability in membrane filtration, biomedical devices, and lubrication applications. PMID:25305445

  7. Density functional theory study of epoxy polymer chains adsorbing onto single-walled carbon nanotubes: electronic and mechanical properties.

    PubMed

    Ahangari, Morteza Ghorbanzadeh; Fereidoon, Abdolhosein; Ganji, Masoud Darvish

    2013-08-01

    We performed first principles calculations based on density functional theory (DFT) to investigate the effect of epoxy monomer content on the electronic and mechanical properties of single-walled carbon nanotubes (SWCNTs). Our calculation results reveal that interfacial interaction increases with increasing numbers of epoxy monomers on the surface of SWCNTs. Furthermore, density of states (DOS) results showed no orbital hybridization between the epoxy monomers and nanotubes. Mulliken charge analysis shows that the epoxy polymer carries a positive charge that is directly proportional to the number of monomers. The Young's modulus of the nanotubes was also studied as a function of monomer content. It was found that, with increasing number of monomers on the nanotubes, the Young's modulus first decreases and then approaches a constant value. The results of a SWCNT pullout simulation suggest that the interfacial shear stress of the epoxy/SWCNT complex is approximately 68 MPa. These results agreed well with experimental results, thus proving that the simulation methods used in this study are viable. PMID:23609226

  8. 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

  9. Adaptive sliding mode control of tri-layer conjugated polymer actuators

    NASA Astrophysics Data System (ADS)

    Wang, Xiangjiang; Alici, Gursel; Nguyen, Chuc Huu

    2013-02-01

    This paper proposes an adaptive sliding mode control methodology to enhance the positioning ability of conducting polymer actuators typified by tri-layer conjugated polymer actuators. This is motivated by the search for an effective control strategy to command such actuators to a desired configuration in the presence of parametric uncertainties and unmodeled disturbances. After analyzing the stability of the adaptive sliding mode control system, experiments were conducted to demonstrate its satisfactory tracking ability, based on a series of experimental results. Implementation of the control law requires a valid model of the conducting polymer actuator and boundaries of the uncertainties and disturbances. Based on the theoretical and experimental results presented, the adaptive sliding mode control methodology is very attractive in the field of smart actuators which contain significant uncertainties and disturbances.

  10. 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

  11. Flooding of the diffusion layer in a polymer electrolyte fuel cell: Experimental and modelling analysis

    NASA Astrophysics Data System (ADS)

    Casalegno, A.; Bresciani, F.; Groppi, G.; Marchesi, R.

    Water management is widely investigated because it affects both the performance and the lifetime of polymer electrolyte fuel cells. Membrane hydration is necessary to ensure the high proton conductivity, but too much water can cause flooding and pore obstruction within the cathode gas diffusion layer and the electrode. Experimental studies prove that the characteristics of the diffusion layer have great influence on water transport; the introduction of a micro-porous layer between the gas diffusion layer and the electrode reduces flooding and stabilizes the performance of the fuel cell, although the reason is not fully explained. A quantitative method to characterize water transport through the diffusion layers was proposed in our previous work, and the present work aims to further understand the flooding phenomenon and the role of the micro-porous layer. The improved experimental setup and methodology allow an accurate and reliable evaluation of water transport through the diffusion layer in a wide range of operating conditions. The proposed 1D + 1D model faithfully reproduces the experimental data adopting effective diffusivity values in agreement with literature. The presented experimental and modelling analysis allows us to evaluate the influence of pore obstruction on the effective diffusivity, the overall transport coefficient and water flow through the diffusion layer, elucidating the effect of the micro-porous layer on fuel cell performance and operation stability.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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}.

  17. Layer-by-layer polymer coated gold nanoparticles for topical delivery of imatinib mesylate to treat melanoma.

    PubMed

    Labala, Suman; Mandapalli, Praveen Kumar; Kurumaddali, Abhinav; Venuganti, Venkata Vamsi Krishna

    2015-03-01

    The aim of this study was to investigate the feasibility of using layer-by-layer polymer coated gold nanoparticles (AuNP) as a carrier for topical iontophoretic delivery of imatinib mesylate (IM). AuNP were prepared by the Turkevich method and were stabilized and functionalized using polyvinylpyrrolidone and polyethylene imine. The functionalized AuNP were then sequentially coated with anionic poly(styrenesulfonate) and cationic polyethylene imine and loaded with IM. The layer-by-layer polymer coated AuNP (LbL-AuNP) showed average particle size and zeta-potential of 98.5 ± 4.3 nm and 32.3 ± 1.3 mV respectively. After LbL coating of AuNP, the surface plasmon resonance wavelength shifted from 518 to 530 nm. The loading efficiency of IM in LbL-AuNP was found to be 28.3 ± 2.3%, which was greatest for any small molecule loaded in AuNP. In vitro skin penetration studies in excised porcine ear skin showed that iontophoresis (0.47 mA/cm(2)) application enhanced the skin penetration of IM loaded AuNP by 6.2-fold compared to passive application. Tape stripping studies showed that iontophoresis of IM loaded LbL-AuNP retained 7.8- and 4.9-fold greater IM in stratum corneum and viable skin respectively compared with iontophoresis of free IM. LbL-AuNP were taken up rapidly (15 min) by B16F10 murine melanoma cells. Furthermore, IM loaded LbL-AuNP significantly (p < 0.001) decreased B16F10 cell viability compared to free IM. We have shown for the first time that IM can be delivered by topical application using LbL coated gold nanoparticles to treat melanoma. PMID:25587849

  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. 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.

  20. 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.

  1. 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. PMID:26418973

  2. A new pillared-layer 3D coordination polymer involving in situ generated formate

    NASA Astrophysics Data System (ADS)

    Xia, Yu-Pei; Li, Yun-Wu; Li, Da-Cheng; Du, Yu-Chang; Yao, Qing-Xia; Dou, Jian-Min

    2015-02-01

    A new Cd-based coordination polymer, [Cd(cpt)(HCOO)]n (1), has been synthesized from 1-(4-carboxyphenyl)-1,2,4-triazole) ligand (Hcpt). The structure was characterized through X-ray crystallography, elemental analysis, and IR spectrum. Compound 1 presents a three-dimensional (3D) pillared-layer structure constructed by metal-formate layers and cpt- ligands. Moreover, the unusual formate anions are generated in situ from the decomposition of DMF precursors. The fluorescence property of 1 in solid state was also researched.

  3. 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

  4. 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. PMID:26744904

  5. Controlling gas diffusion layer oxidation by homogeneous hydrophobic coating for polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Hiramitsu, Yusuke; Sato, Hitoshi; Kobayashi, Kenji; Hori, Michio

    Reduced production costs and enhanced durability are necessary for practical application of polymer electrolyte fuel cells. There has been a great deal of concern about degradation of the gas diffusion layer located outside the membrane electrode assembly. However, very few studies have been carried out on the degradation process, and no suitable methods for improving the durability of the cell have been found. In this work, the influence on the cell performance and factors involved in the degradation of the gas diffusion layer has been clarified through power generation tests. Long-term power generation tests on single cells for 6000 h were carried out under high humidity conditions with homogeneous and inhomogeneous hydrophobic coating gas diffusion layers. The results showed that the increase in the diffusion overvoltage from the gas diffusion layer could be controlled by the use of a homogeneous coating. Post-analyses indicated that this occurred by controlling oxidation of the carbon fiber.

  6. Order parameters of the liquid crystal interface layer at a rubbed polymer surface

    NASA Astrophysics Data System (ADS)

    Xuan, Li; Tohyama, Takeshi; Miyashita, Tetsuya; Uchida, Tatsuo

    2004-08-01

    In this paper, the liquid crystal (LC) order parameters of the interface layers at rubbed polymer surfaces were studied. The LC films in this study were made with either polyvinyl alcohol or polyimide and the test LCs were filled into wedge-shaped cells for various measurements. The real distribution of order parameters from LC bulk to the interface was obtained by measuring the anisotropic infrared absorbance of sample films. It was found that the order parameters start to decrease where the LC layer thickness is smaller than 10nm, and the order parameter of LC monolayer at the rubbed polymer surface is only 1/3-1/2 of that of the LC bulk even in a strong rubbing condition. When the temperature was increased to the transition point, the LC interface layer (excluding the adsorption monolayer) completed the phase transition while the bulk layer remained in LC phase. This was a further evidence that the order parameter of the interface layer is lower than that of the bulk.

  7. 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.

  8. 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...

  9. Layer-by-layer electrodeposition of redox polymers and enzymes on screen-printed carbon electrodes for the preparation of reagentless biosensors.

    PubMed

    Gao, Qiang; Yang, Xiurong

    2004-01-01

    Layer-by-layer electrodeposition of redox polymer/enzyme composition films on screen-printed carbon electrodes for fabrication of reagentless enzyme biosensors has been proposed and the resulting films were found to be very stable and rigid. PMID:14737317

  10. 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.

  11. 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. PMID:26959343

  12. 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

  13. Thickness dependence of curvature, strain, and response time in ionic electroactive polymer actuators fabricated via layer-by-layer assembly

    NASA Astrophysics Data System (ADS)

    Montazami, Reza; Liu, Sheng; Liu, Yang; Wang, Dong; Zhang, Qiming; Heflin, James R.

    2011-05-01

    Ionic electroactive polymer (IEAP) actuators containing porous conductive network composites (CNCs) and ionic liquids can result in high strain and fast response times. Incorporation of spherical gold nanoparticles in the CNC enhances conductivity and porosity, while maintaining relatively small thickness. This leads to improved mechanical strain and bending curvature of the actuators. We have employed the layer-by-layer self-assembly technique to fabricate a CNC with enhanced curvature (0.43 mm-1) and large net intrinsic strain (6.1%). The results demonstrate that curvature and net strain of IEAP actuators due to motion of the anions increase linearly with the thickness of the CNC as a result of the increased volume in which the anions can be stored. In addition, after subtracting the curvature of a bare Nafion actuator without a CNC, it is found that the net intrinsic strain of the CNC layer is independent of thickness for the range of 20-80 nm, indicating that the entire CNC volume contributes equivalently to the actuator motion. Furthermore, the response time of the actuator due to anion motion is independent of CNC thickness, suggesting that traversal through the Nafion membrane is the limiting factor in the anion motion.

  14. 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.

  15. High performance of inverted polymer solar cells with cobalt oxide as hole-transporting layer

    NASA Astrophysics Data System (ADS)

    Wang, Xiangdong; Peng, Qing; Zhu, Weiguo; Lei, Gangtie

    2015-05-01

    Cobalt oxide (II, III) (CoOx) was inserted as efficient hole-transporting interlayer between the active layer and top electrode in inverted polymer solar cells (PSCs) with titanium (diisopropoxide) bis(2, 4-pentanedionate) (TIPD) as an electron selective layer. The work function of CoOx was measured by Kelvin probe and the device performances with different thicknesses of cobalt oxide were studied. The device with CoOx exhibited a remarkable improvement in power conversion efficiency compared with that without CoOx, which indicated that CoOx efficiently prevented the recombination of charge carriers at the organic/top electrode interface. The performance improvement was attributed to the fact that the CoOx thin film can module the Schottky barrier and form an ohmic contact at the organic/metal interface, which makes it a promising hole-transporting layer.

  16. 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

  17. 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.

  18. The Effect of Layer Orientation on the Mechanical Properties and Microstructure of a Polymer

    NASA Astrophysics Data System (ADS)

    Vega, V.; Clements, J.; Lam, T.; Abad, A.; Fritz, B.; Ula, N.; Es-Said, O. S.

    2011-08-01

    Rapid Prototyping (RP) is a method used everywhere from the entertainment industry to healthcare. Layer orientation is an important aspect of the final product. The objective of this research was to evaluate the effect of layer orientation on the mechanical strength and toughness of a polymer. The polymer used was a combination of two materials, ZP 130 and ZB 58, fused together in the Z Corporation Spectrum Z510 Rapid Prototyping Machine. ZP 130 is a powder composed of vinyl polymer (2-20%), sulfate salt (0-5%), and plaster that contains <1% crystalline silica (50-95%). ZB 58 is a liquid composed of glycerol (1-10%), preservative (sorbic acid salt) (0-2%), surfactant (<1%), pigment (<1%), and water (85-95%). After removal from the machine the samples were sealed with Z bond 101 which is Beta-methoxyethyl cyanoacrylate (60-100%). The layer orientations studied were the crack arrestor, crack divider, and short transverse with various combinations of the three, for a total of seven orientations. The mechanical strength was evaluated using tensile testing and three-point bend testing. The toughness was evaluated by Izod impact testing. Five samples for tensile testing and three-point bend testing as well as 15 samples for the Izod impact test for each of the seven orientations were made. The total number of samples was 175. The crack arrestor orientation was the strongest main orientation for the tensile and three-point bend test. Weibull analysis was done on the Izod impact testing due to high variation in the results for the crack arrestor and short transverse directions. It was found that the layer orientation and surface roughness played a significant role in the penetration of the Z bond 101 coating and in the overall strength of the samples.

  19. Light transmission of polymer-dispersed liquid crystal layer composed of droplets with inhomogeneous surface anchoring

    NASA Astrophysics Data System (ADS)

    Loiko, V. A.; Zyryanov, V. Ya.; Konkolovich, A. V.; Miskevich, A. A.

    2016-01-01

    We have developed a model and realized an algorithm for the calculation of the coefficient of coherent (direct) transmission of light through a layer of liquid crystal (LC) droplets in a polymer matrix. The model is based on the Hulst anomalous diffraction approximation for describing the scattering by an individual particle and the Foldy-Twersky approximation for a coherent field. It allows one to investigate polymer dispersed LC (PDLC) materials with homogeneous and inhomogeneous interphase surface anchoring on the droplet surface. In order to calculate the configuration of the field of the local director in the droplet, the relaxation method of solving the problem of minimization of the free energy volume density has been used. We have verified the model by comparison with experiment under the inverse regime of the ionic modification of the LC-polymer interphase boundary. The model makes it possible to solve problems of optimization of the optical response of PDLC films in relation to their thickness and optical characteristics of the polymer matrix, sizes, polydispersity, concentration, and anisometry parameters of droplets. Based on this model, we have proposed a technique for estimating the size of LC droplets from the data on the dependence of the transmission coefficient on the applied voltage.

  20. 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.

  1. Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes.

    PubMed

    Lindemann, Peter; Träutlein, Yannick; Wöll, Christof; Tsotsalas, Manuel

    2015-01-01

    CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in combination with their outstanding thermal and chemical stability, and low densities. However, their insoluble nature causes problems in their processing since usually applied techniques such as spin coating are not available. Especially for membrane applications, where the processing of CMP as thin films is desirable, the processing problems have hindered their commercial application. Here we describe the interfacial synthesis of CMP thin films on functionalized substrates via molecular layer-by-layer (l-b-l) synthesis. This process allows the preparation of films with desired thickness and composition and even desired composition gradients. The use of sacrificial supports allows the preparation of freestanding membranes by dissolution of the support after the synthesis. To handle such ultra-thin freestanding membranes the protection with sacrificial coatings showed great promise, to avoid rupture of the nanomembranes. To transfer the nanomembranes to the desired substrate, the coated membranes are upfloated at the air-liquid interface and then transferred via dip coating. PMID:26710232

  2. 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

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

    DOE PAGESBeta

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    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.

  5. 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.

  6. 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.

  7. 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 (σk) in polymer nanocomposites. The "σk" is expressed as linear, exponential and power functions of the distance between nanoparticles and polymer matrix (xk). Afterwards, the predictions of these equations at the central layer of interphase (the average strength) are compared to the calculations of interphase strength (σi) by several micromechanical models including the developed Leidner-Woodhams and Pukanszky models to choose the best equation which expresses "σk". The calculations are carried out for several reported samples. The equation which expresses the "σk" 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 "σm" and "σp" play positive roles in "σi" predictions at low "Z" value, but a high "Z" eliminates the effect of "σm" on the tensile strength of interphase layers. PMID:26990956

  8. A Love Wave Reflective Delay Line with Polymer Guiding Layer for Wireless Sensor Application

    PubMed Central

    Wang, Wen; He, Shitang

    2008-01-01

    This paper presents an optimal design for a Love wave reflective delay line on 41° YX LiNbO3 with a polymer guiding layer for wireless sensor applications. A theoretical model was established to describe the Love wave propagation along the larger piezoelectric substrate with polymer waveguide, and the lossy mechanism from the viscoelastic waveguide was discussed, which results in the optimal guiding layer thickness. Coupling of modes (COM) was used to determine the optimal design parameters of the reflective delay line structured by single phase unidirectional transducers (SPUDTs) and shorted grating reflectors. Using the network analyzer, the fabricated Love wave reflective delay line was characterized, high signal noise ratio (S/N), sharp reflection peaks, and few spurious noise between the peaks were found, and the measured result agrees well with the simulated one. Also, the optimal guiding layer thickness of 1.5∼1.8µm was extracted experimentally, and it is consistent with the theoretical analysis.

  9. Numerical simulations of the role of a ferroelectric polymer interfacial layer in organic solar cells.

    PubMed

    Liu, Bo; Xu, Feng; Zhang, Xinghua; Yan, Dadong; Lu, Dan

    2016-02-21

    A Pauli master equation method is adopted for the simulation of polymer bulk heterojunction (BHJ) solar cells with vinylidene fluoride-trifluoroethylene copolymer (P(VDF-TrFE)) films as interfacial layers. According to previous reports, using highly crystalline P(VDF-TrFE) films as interfacial layers can highly enhance the efficiency of polymer BHJ solar cells, and possible mechanisms for the enhancement by two different groups were given as the dipole induced permanent internal electric field or simply the electrode improvement which implied that the origin is the barrier lowering effect. The correlation between the appearance of S-shaped current density-voltage (J-V) characteristics and the energy barrier is studied first, and then further results indicate that the previous electrode improvement model provides a consistent explanation for the origin of performance enhancement due to the insertion of polarized P(VDF-TrFE) interfacial layers. Moreover, the phenomenon of an increase of the internal electric field observed before can be attributed to better contact conditions which help reduce the bimolecular recombination rate. Comparatively speaking, the electrode improvement model can give a more rational explanation for the origin of performance enhancement experimentally found. In contrast, the dipole induced permanent internal electric field model was not complete enough. PMID:26822850

  10. 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

  11. 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

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

    PubMed Central

    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.

    2015-01-01

    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

  13. 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

  14. 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

  15. Characterization of polymer adsorption onto drug nanoparticles using depletion measurements and small-angle neutron scattering.

    PubMed

    Goodwin, Daniel J; Sepassi, Shadi; King, Stephen M; Holland, Simon J; Martini, Luigi G; Lawrence, M Jayne

    2013-11-01

    Production of polymer and/or surfactant-coated crystalline nanoparticles of water-insoluble drugs (nanosuspensions) using wet bead milling is an important formulation approach to improve the bioavailability of said compounds. Despite the fact that there are a number of nanosuspensions on the market, there is still a deficiency in the characterization of these nanoparticles where further understanding may lead to the rational selection of polymer/surfactant. To this end small-angle neutron scattering (SANS) measurements were performed on drug nanoparticles milled in the presence of a range of polymers of varying molecular weight. Isotopic substitution of the aqueous solvent to match the scattering length density of the drug nanoparticles (i.e., the technique of contrast matching) meant that neutron scattering resulted only from the adsorbed polymer layer. The layer thickness and amount of hydroxypropylcellulose adsorbed on nabumetone nanoparticles derived from fitting the SANS data to both model-independent and model dependent volume fraction profiles were insensitive to polymer molecular weight over the range Mv = 47-112 kg/mol, indicating that the adsorbed layer is relatively flat but with tails extending up to approximately 23 nm. The constancy of the absorbed amount is in agreement with the adsorption isotherm determined by measuring polymer depletion from solution in the presence of the nanoparticles. Insensitivity to polymer molecular weight was similarly determined using SANS measurements of nabumetone or halofantrine nanoparticles stabilized with hydroxypropylmethylcellulose or poly(vinylpyrrolidone). Additionally SANS studies revealed the amount adsorbed, and the thickness of the polymer layer was dependent on both the nature of the polymer and drug particle surface. The insensitivity of the adsorbed polymer layer to polymer molecular weight has important implications for the production of nanoparticles, suggesting that lower molecular weight polymers

  16. 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%. PMID:27247213

  17. 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.

  18. 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

  19. Ultrasound-driven preparation and pair distribution function-assisted structure solution of a copper-based layered coordination polymer.

    PubMed

    Mohideen, M Infas; Allan, Phoebe K; Chapman, Karena W; Hriljac, Joseph A; Morris, Russell E

    2014-07-21

    Nanoparticles of a copper-based layered coordination polymer, STAM-2, have been prepared via an ultrasound mediated transformation from a layered metal-organic framework, STAM-1. The structure of the material was then solved using pair distribution function analysis to identify the structural units present and the final structural model refined against the pair distribution function data. PMID:24310447

  20. 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.

  1. 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.

  2. 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

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

    NASA Astrophysics Data System (ADS)

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

    1991-05-01

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

  4. 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.

  5. Biopolymer as an electron selective layer for inverted polymer solar cells

    NASA Astrophysics Data System (ADS)

    Jin Tan, Mein; Zhong, Shu; Wang, Rui; Zhang, Zhongxing; Chellappan, Vijila; Chen, Wei

    2013-08-01

    In this work, a solution-processable electron selective layer is introduced for inverted polymer solar cells (PSCs). Cationic biopolymer poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) is used as a solution-processable work function modifier of indium-tin-oxide transparent conducting electrode to yield efficient inverted PSCs of 3.3% under AM1.5G illumination, with poly(3-hexylthiophene) and [6,6]-phenyl-C61-butyric acid methyl ester as the active layer. Devices using PDMAEMA exhibit greater stability in ambient "working conditions" as compared to devices using ZnO, retaining 90% of peak power conversion efficiency after 8 weeks. Therefore, PDMAEMA has great potential as a universal work function modifier material with high robustness.

  6. 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.

  7. 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

  8. 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

  9. Diffusion of prodan on self-assembled monolayers and grafted polymer layers

    NASA Astrophysics Data System (ADS)

    Heitzman, Carla Ellen

    2005-11-01

    This thesis explores 2-D, solid state diffusion of small organic molecules, both on several chemically functionalized surfaces and through thin layers of polymer grafted to a surface, as a means for directed molecular transport. Toward this end diffusion rates of a dye molecule, prodan, were quantified for naked glass, three surfaces chemistries and two different polymer brushes; additionally, surfaces and brushes were patterned. Fluorescence recovery after photobleaching (FRAP) was the primary experimental technique. Circular areas were bleached with multi-photon IR utilizing an electo-optical modulator (EOM) and the region of interest (ROI) capabilities of a commercial confocal microscope. Diffusion constants were extracted by comparing FRAP data to curves generated from Fick's second law and from linear fits of variance verses time plots. Diffusion constants from the two methods generally agreed well. Prodan diffusion rates were quantified for clean glass, SAMs formed from chlorotrimethyl silane (CTS) and octadecyltrichlorosilane (OTS), and poly(ethylene glycol) (PEG) grafted to silica. Similar diffusion constants, ˜1--3 x 10-7 cm2/s, were found for the CTS and PEG layers; this is thought to be due to the intermediate surface polarity and the ability of prodan to partially intercalate. Very little fluorescence recovery is observed on the OTS SAM or on the clean silica surface; dye is thought to aggregate on the former and form hydrogen bonds with the latter. Two grafted polymer layers were synthesized, for diffusion studies, with surface-initiated polymerization (SIP). The results suggest that there is very little bulk translational diffusion in first layer, poly (N-isopropylacrylamide) (PNIPAM). Rather, fluorescence recovery is thought to be due to either rotational diffusion or a combination of fast surface diffusion and slow bulk diffusion. Increasing relative humidity enhanced recovery. FRAP results for prodan on the second grafted layer, poly

  10. 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

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

    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.

  13. 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

  14. 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.

  15. 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

  16. From carbon nanotubes and silicate layers to graphene platelets for polymer nanocomposites.

    PubMed

    Zaman, Izzuddin; Kuan, Hsu-Chiang; Dai, Jingfei; Kawashima, Nobuyuki; Michelmore, Andrew; Sovi, Alex; Dong, Songyi; Luong, Lee; Ma, Jun

    2012-08-01

    In spite of extensive studies conducted on carbon nanotubes and silicate layers for their polymer-based nanocomposites, the rise of graphene now provides a more promising candidate due to its exceptionally high mechanical performance and electrical and thermal conductivities. The present study developed a facile approach to fabricate epoxy-graphene nanocomposites by thermally expanding a commercial product followed by ultrasonication and solution-compounding with epoxy, and investigated their morphologies, mechanical properties, electrical conductivity and thermal mechanical behaviour. Graphene platelets (GnPs) of 3.57 ± 0.50 nm in thickness were created after the expanded product was dispersed in tetrahydrofuran using 60 min ultrasonication. Since epoxy resins cured by various hardeners are widely used in industries, we chose two common hardeners: polyoxypropylene (J230) and 4,4'-diaminodiphenylsulfone (DDS). DDS-cured nanocomposites showed a better dispersion and exfoliation of GnPs, a higher improvement (573%) in fracture energy release rate and a lower percolation threshold (0.612 vol%) for electrical conductivity, because DDS contains benzene groups which create π-π interactions with GnPs promoting a higher degree of dispersion and exfoliation of GnPs during curing. This research pointed out a potential trend where GnPs would replace carbon nanotubes and silicate layers for many applications of polymer nanocomposites. PMID:22706725

  17. Construction of a functional S-layer fusion protein comprising an immunoglobulin G-binding domain for development of specific adsorbents for extracorporeal blood purification.

    PubMed

    Völlenkle, Christine; Weigert, Stefan; Ilk, Nicola; Egelseer, Eva; Weber, Viktoria; Loth, Fritz; Falkenhagen, Dieter; Sleytr, Uwe B; Sára, Margit

    2004-03-01

    The chimeric gene encoding a C-terminally-truncated form of the S-layer protein SbpA from Bacillus sphaericus CCM 2177 and two copies of the Fc-binding Z-domain was constructed, cloned, and heterologously expressed in Escherichia coli HMS174(DE3). The Z-domain is a synthetic analogue of the B-domain of protein A, capable of binding the Fc part of immunoglobulin G (IgG). The S-layer fusion protein rSbpA(31-1068)/ZZ retained the specific properties of the S-layer protein moiety to self-assemble in suspension and to recrystallize on supports precoated with secondary cell wall polymer (SCWP), which is the natural anchoring molecule for the S-layer protein in the bacterial cell wall. Due to the construction principle of the S-layer fusion protein, the ZZ-domains remained exposed on the outermost surface of the protein lattice. The binding capacity of the native or cross-linked monolayer for human IgG was determined by surface plasmon resonance measurements. For batch adsorption experiments, 3-microm-diameter, biocompatible cellulose-based, SCWP-coated microbeads were used for recrystallization of the S-layer fusion protein. In the case of the native monolayer, the binding capacity for human IgG was 5.1 ng/mm(2), whereas after cross-linking with dimethyl pimelimidate, 4.4 ng of IgG/mm(2) was bound. This corresponded to 78 and 65% of the theoretical saturation capacity of a planar surface for IgGs aligned in the upright position, respectively. Compared to commercial particles used as immunoadsorbents to remove autoantibodies from sera of patients suffering from an autoimmune disease, the IgG binding capacity of the S-layer fusion protein-coated microbeads was at least 20 times higher. For that reason, this novel type of microbeads should find application in the microsphere-based detoxification system. PMID:15006773

  18. 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.

  19. On-Line Thickness Measurement for Two-Layer Systems on Polymer Electronic Devices

    PubMed Central

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

    2013-01-01

    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. PMID:24253192

  20. 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.

  1. 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

  2. Bridging in grafted layers : Statics and kinetics

    NASA Astrophysics Data System (ADS)

    Johner, A.

    We discuss bridging between a grafted layer and an opposing plate which adsorbs the polymer. The case of end adsorption is considered, as well as the case where all monomers adsorb. We predict that with increasing adsorption an exclusion zone grows in the vicinity of the adsorbing plate, this slows down the kinetics. For end adsorption we study the kinetics and argue that two main processes are involved: the exploration of the brush by a free end and its adsorption through the exclusion zone.

  3. 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

  4. Metal dicyanamide layered coordination polymers with cyanopyridine co-ligands: Synthesis, crystal structures and magnetism

    SciTech Connect

    Du Miao . E-mail: dumiao@public.tpt.tj.cn; Wang Qian; Wang Ying; Zhao Xiaojun; Ribas, Joan

    2006-12-15

    A series of metal dicyanamide (dca) coordination polymers combined with cyanopyridine (cypy) terminal co-ligands, namely, [Co{sub 2}(dca){sub 4}(4-cypy){sub 4}] {sub n} (1), [Cd(dca){sub 2}(4-cypy){sub 2}] {sub n} (2), [Fe(dca){sub 2}(3-cypy){sub 2}] {sub n} (3) and [Co(dca){sub 2}(3-cypy){sub 2}] {sub n} (4), have been synthesized at the ambient conditions. X-ray single crystal diffraction reveals that complexes 1-4 have similar metal-dca coordination layers in which the octahedral metal centers are connected by {mu} {sub 1,5}-dca linkers. Notably, three types of 3-D packing lattices are observed for these layered arrays. The thermal stabilities of such new crystalline materials have been studied by thermogravimetric analysis of mass loss. The magnetic properties of the Co{sup II} and Fe{sup II} complexes have been investigated and discussed in detail. A discrete mononuclear molecule [Cd(dca){sub 2}(pyom){sub 2}] (5) is also described, in which the chelated ligand O-methyl picolinimidate (pyom) arises from the addition of methanol solvent across the C{identical_to}N bond of 2-cypy. - Graphical abstract: A series of new metal dicyanamide complexes with cyanopyridine terminal co-ligands have been prepared and structurally determined by X-ray single-crystal diffraction. The magnetic properties of the Co{sup II} and Fe{sup II} layered coordination polymers are also discussed.

  5. Polymer/Perovskite-type nanoparticle multilayers with multielectric properties prepared from ligand addition-induced layer-by-layer assembly.

    PubMed

    Kim, Younghoon; Kook, Kyungyun; Hwang, Sun Kak; Park, Cheolmin; Cho, Jinhan

    2014-03-25

    We introduce an adsorption mechanism for a layer-by-layer (LbL) assembly (i.e., a ligand addition-induced LbL assembly) and demonstrate that the (polymer/perovskite nanoparticle (NP))n nanocomposite films based on the ligand addition LbL exhibit ferroelectric and resistive switching properties. Oleic acid (OA)-stabilized BaTiO3 NPs (OA-BTO NPs) with a size of approximately 8 nm were LbL-assembled with amine-functionalized dendrimers (NH2-dendrimers) using the high affinity between NH2 moieties and Ti ions. The ferroelectric properties of the (NH2-dendrimer/OA-BTO NP)n multilayers were generated by the Ti disorder in the OA-BTO NP unit cell despite the use of sub-10 nm OA-BTO NPs (i.e., OA-BTO NPs), which are near the critical size for ferroelectric properties. Additionally, the (NH2-dendrimer/OA-BTO NP)n multilayers sandwiched between the bottom (platinum) and top (silver or tungsten) electrodes exhibited a resistive switching memory at a relatively low operating voltage below 2 V with a switching speed of approximately 100 ns and an ON/OFF current ratio of approximately 10(4). Furthermore, the ferroelectric and resistive switching properties could be further improved by controlling the bilayer number (n). We believe that our approach can provide a basis for designing and exploiting multifunctional memory electronics based on a variety of perovskite NPs with ferroelectric properties. PMID:24571293

  6. Modeling of Multiphase Flow through Thin Porous Layers: Application to a Polymer Electrolyte Fuel Cell (PEFC)

    NASA Astrophysics Data System (ADS)

    Qin, C.; Hassanizadeh, S.

    2013-12-01

    Multiphase flow and species transport though thin porous layers are encountered in a number of industrial applications, such as fuel cells, filters, and hygiene products. Based on some macroscale models like the Darcy's law, to date, the modeling of flow and transport through such thin layers has been mostly performed in 3D discretized domains with many computational cells. But, there are a number of problems with this approach. First, a proper representative elementary volume (REV) is not defined. Second, one needs to discretize a thin porous medium into computational cells whose size may be comparable to the pore sizes. This suggests that the traditional models are not applicable to such thin domains. Third, the interfacial conditions between neighboring layers are usually not well defined. Last, 3D modeling of a number of interacting thin porous layers often requires heavy computational efforts. So, to eliminate the drawbacks mentioned above, we propose a new approach to modeling multilayers of thin porous media as 2D interacting continua (see Fig. 1). Macroscale 2D governing equations are formulated in terms of thickness-averaged material properties. Also, the exchange of thermodynamic properties between neighboring layers is described by thickness-averaged quantities. In Comparison to previous macroscale models, our model has the distinctive advantages of: (1) it is rigorous thermodynamics-based model; (2) it is formulated in terms of thickness-averaged material properties which are easily measureable; and (3) it reduces 3D modeling to 2D leading to a very significant reduction of computation efforts. As an application, we employ the new approach in the study of liquid water flooding in the cathode of a polymer electrolyte fuel cell (PEFC). To highlight the advantages of the present model, we compare the results of water distribution with those obtained from the traditional 3D Darcy-based modeling. Finally, it is worth noting that, for specific case studies, a

  7. 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.

  8. A poly(phenyleneethynylene) polymer bearing amino acid substituents as active layer in enantioselective solid-state sensors

    NASA Astrophysics Data System (ADS)

    Tanese, M. C.; Hassan Omar, O.; Torsi, L.; Marinelli, F.; Colangiuli, D.; Farinola, G. M.; Babudri, F.; Naso, F.; Sabbatini, L.; Zambonin, P. G.

    2006-04-01

    A poly(phenyleneethynylene) polymer bearing amino acid pendant groups is used as enantioselective active layer in solid-state sensing devices. The chiral analyte in the present study is menthol in both the natural (-) and synthetic (+) enantiomers. The polymer bearing amino acid chiral sites is demonstrated to interact more favorably with the natural menthol than the synthetic one in a quartz crystal microbalance revealing system. Promising perspectives are seen for the use of such polymers in chiral discriminating, chemically sensitive resistors or even transistors.

  9. 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

  10. New paradigm for stabilization of liquid polymer films on solids

    NASA Astrophysics Data System (ADS)

    Koga, Tad; Jiang, Naisheng; Wang, Jiaxun; di, Xiaoyu; Cheung, Justin; Endoh, Maya

    2015-03-01

    We report that wetting/dewetting behavior of liquid polymer films on solids can be controlled by nanoscale architectures of polymer chains irreversibly adsorbed on the impenetrable surfaces. Monodisperse polystyrene (PS) ultrathin films (20 nm in thickness) with different molecular weights on silicon (Si) substrates with a natural amorphous Si dioxide layer were used as models. The PS thin films were annealed at high temperatures at T>Tg (Tg is the bulk glass transition temperature) for several days, and the surface structures were studied by using optical and atomic force microscopes. At the same time, the annealed PS films were further leached with a good solvent and the residue films (i.e., irreversibly adsorbed layers) were characterized by x-ray reflectivity. The experimental data reveals a strong correlation between the conformations of the adsorbed polymer chains and the stability of the liquid films on top. T. K. acknowledges the partial financial support from NSF Grant No. CMMI-1332499.

  11. High-performance hole transport layers for polymer light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Yan, He

    One key component in more advanced multilayer polymer light-emitting diode (PLED) structures is the hole transport layer (HTL). Conventional PLED conductive polymer HTLs exhibit serious drawbacks such as corrosion of anodes, significant absorption in visible region, and mediating oxidative doping of polyfluorene emissive layers (EMLs). In addition, the question still remains as to whether conventional PLED HTLs have the electron-blocking capacity required to achieve high-performance PLEDs. If not, the question arises as to how a PLED structure can be modified to afford greater electron-blocking at the HTL/EML interface. In the present thesis work, three generations of PLED HTLs were developed based on a siloxane-derivatized, crosslinkable, hole-transporting material, 4,4'-bis[(p-trichlorosilylpropylphenyl)phenylamino]biphenyl, TPDSi2. The first generation is the self-assembled monolayer (SAM) of TPDSi2, which can increase the work function of indium tin oxide (ITO) anode, enhance ITO anode hole injection, and hence improve PLED performance. The second generation is the spin-coated blend of TPDSi2 and a hole transporting polymer TFB on ITO, which forms an insoluble crosslinked network that can be used as a PLED HTL. The third generation is a double-layer HTL with the TPDSi2 + TFB on top of a conventional PLED HTL, which combines the hole injection capacity of conventional PLED HTLs and the electron-blocking capacity of the TPDSi2 + TFB blend. PLED devices based on these new HTLs exhibit comparable or superior performance compared to those based on conventional HTLs; high current efficiencies of ˜17 cd/A and maximum luminance of ˜140,000 cd/m2 have been achieved. These siloxane-based HTLs not only enhance PLED anode hole-injection by chemically bonding the HTL to the ITO anode, they also exhibit great electron-blocking capacity. The present organosiloxane HTL approach offers many other attractions such as convenience of fabrication, flexibility in choosing HTL

  12. 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

  13. 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.

  14. A Simple Nanoscale Interface Directs Alignment of a Confluent Cell Layer on Oxide and Polymer Surfaces

    PubMed Central

    Donnelly, Patrick E.; Jones, Casey M.; Bandini, Stephen B.; Singh, Shivani; Schwartz, Jeffrey; Schwarzbauer, Jean E.

    2013-01-01

    Templating of cell spreading and proliferation is described that yields confluent layers of cells aligned across an entire two-dimensional surface. The template is a reactive, two-component interface that is synthesized in three steps in nanometer thick, micron-scaled patterns on silicon and on several biomaterial polymers. In this method, a volatile zirconium alkoxide complex is first deposited at reduced pressure onto a surface pattern that is prepared by photolithography; the substrate is then heated to thermolyze the organic ligands to form surface-bound zirconium oxide patterns. The thickness of this oxide layer ranges from 10 to 70 nanometers, which is controlled by alkoxide complex deposition time. The oxide layer is treated with 1,4-butanediphosphonic acid to give a monolayer pattern whose composition and spatial conformity to the photolithographic mask are determined spectroscopically. NIH 3T3 fibroblasts and human bone marrow-derived mesenchymal stem cells attach and spread in alignment with the pattern without constraint by physical means or by arrays of cytophilic and cytophobic molecules. Cell alignment with the pattern is maintained as cells grow to form a confluent monolayer across the entire substrate surface. PMID:23936630

  15. 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.

  16. 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

  17. 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

  18. 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

  19. 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

  20. 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

  1. 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

  2. A copper-based layered coordination polymer: synthesis, magnetic properties and electrochemical performance in supercapacitors.

    PubMed

    Liu, Qi; Liu, Xiuxiu; Shi, Changdong; Zhang, Yanpeng; Feng, Xuejun; Cheng, Mei-Ling; Su, Seng; Gu, Jiande

    2015-11-28

    A copper-based layered coordination polymer ([Cu(hmt)(tfbdc)(H2O)]; hmt = hexamethylenetetramine, tfbdc = 2,3,5,6-tetrafluoroterephthalate; Cu-LCP) has been synthesized, and it has been structurally and magnetically characterized. The Cu-LCP shows ferromagnetic interactions between the adjacent copper(II) ions. Density functional theory calculations on the special model of Cu-LCP support the occurrence of ferromagnetic interactions. As an electrode material for supercapacitors, Cu-LCP exhibits a high specific capacitance of 1274 F g(-1) at a current density of 1 A g(-1) in 1 M LiOH electrolyte, and the capacitance retention is about 88% after 2000 cycles. PMID:26487265

  3. From carbon nanotubes and silicate layers to graphene platelets for polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Zaman, Izzuddin; Kuan, Hsu-Chiang; Dai, Jingfei; Kawashima, Nobuyuki; Michelmore, Andrew; Sovi, Alex; Dong, Songyi; Luong, Lee; Ma, Jun

    2012-07-01

    In spite of extensive studies conducted on carbon nanotubes and silicate layers for their polymer-based nanocomposites, the rise of graphene now provides a more promising candidate due to its exceptionally high mechanical performance and electrical and thermal conductivities. The present study developed a facile approach to fabricate epoxy-graphene nanocomposites by thermally expanding a commercial product followed by ultrasonication and solution-compounding with epoxy, and investigated their morphologies, mechanical properties, electrical conductivity and thermal mechanical behaviour. Graphene platelets (GnPs) of 3.57 +/- 0.50 nm in thickness were created after the expanded product was dispersed in tetrahydrofuran using 60 min ultrasonication. Since epoxy resins cured by various hardeners are widely used in industries, we chose two common hardeners: polyoxypropylene (J230) and 4,4'-diaminodiphenylsulfone (DDS). DDS-cured nanocomposites showed a better dispersion and exfoliation of GnPs, a higher improvement (573%) in fracture energy release rate and a lower percolation threshold (0.612 vol%) for electrical conductivity, because DDS contains benzene groups which create π-π interactions with GnPs promoting a higher degree of dispersion and exfoliation of GnPs during curing. This research pointed out a potential trend where GnPs would replace carbon nanotubes and silicate layers for many applications of polymer nanocomposites.In spite of extensive studies conducted on carbon nanotubes and silicate layers for their polymer-based nanocomposites, the rise of graphene now provides a more promising candidate due to its exceptionally high mechanical performance and electrical and thermal conductivities. The present study developed a facile approach to fabricate epoxy-graphene nanocomposites by thermally expanding a commercial product followed by ultrasonication and solution-compounding with epoxy, and investigated their morphologies, mechanical properties, electrical

  4. 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.

  5. Fabrication of nanofluidic diodes with polymer nanopores modified by atomic layer deposition

    PubMed Central

    Sheng, Qian; Wang, Lin; Wang, Ceming; Wang, Xinwei; Xue, Jianming

    2014-01-01

    Surface charge distribution is a crucial factor for the ionic transport properties inside nanopores. Modifying the surface charge inside a single conical nanopore can greatly affect the rectification behavior of the ionic current through the nanopore and afford nanofluidic diodes. In this work, we describe a new method to fabricate nanofluidic diodes by atomic layer deposition (ALD) on conical track-etched nanopores. Thorough investigation of the ionic transport behavior through ALD-modified polyethylene terephthalate (PET) nanopores is carried out. Our results demonstrate that ALD is a simple and effective method to modify the inner surface of the polymer nanopores for fabricating nanofluidic devices. In addition, we also investigate the stability of the ALD-modified nanopores, and the results suggest that the long-time stability could be compromised by high voltage applied along the nanopore. PMID:25332737

  6. Highly efficient polymer-based optoelectronic devices using PEDOT:PSS and a GO composite layer as a hole transport layer.

    PubMed

    Yu, Jae Choul; Jang, Jeong In; Lee, Bo Ram; Lee, Geon-Woong; Han, Joong Tark; Song, Myoung Hoon

    2014-02-12

    We demonstrate highly efficient polymer light-emitting diodes (PLEDs), as well as polymer solar cells (PSCs), using a solution-processable poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS):graphene oxide (GO) (PEDOT:GO) composite layer as hole transport layers (HTLs). The PEDOT:GO composite HTL layer shows enhanced charge carrier transport due to improved conductivity by benzoid-quinoid transitions with a well-matched work function between GO (4.89 eV) and PEDOT:PSS (4.95 eV). Moreover, it reduces remarkably exciton quenching and suppresses recombinations that bring higher charge extraction in PSCs and increases the recombinations of holes and electrons within the active layer by the blocking behavior of the electrons from a fluorescent semiconductor due to the existence of GO with large bandgap (∼3.6 eV) in the PEDOT:GO composite layer, therefore leading to an enhancement of device efficiency in PLEDs and PSCs. The optimized PLEDs and PSCs with a PEDOT:GO composite HTL layer shows the maximum luminous efficiency of 21.74 cd/A (at 6.4 V) for PLEDs, as well as the power conversion efficiency of 8.21% for PSCs, which were improved by ∼220 and 12%, respectively, compared to reference PLEDs and PSCs with a PEDOT:PSS layer. PMID:24433032

  7. 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.

  8. 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.

  9. 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

  10. Performance enhancement of low temperature polymer electrolyte membrane fuel cells by catalyst and support layer modifications

    NASA Astrophysics Data System (ADS)

    Hall, Timothy David

    Possible enhancement of low temperature polymer electrolyte membrane fuel cells (PEMFC) or direct methanol fuel cells (DMFC) was investigated by modifying catalyst and support layers. Platinum (Pt) and platinum cobalt (Pt xCo1-x) alloys were prepared by pulsed electrodeposition onto Toray carbon paper. Composite supports composed of either commercial multi-walled nanofiber (MWNF) mats or MWNF layers on a commercial backing were also investigated. X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma-optical emission spectroscopy (ICP-OES), and energy dispersive x-ray (EDX) were used to characterize the surface structure, composition, and catalyst loading. Various electrochemical techniques with a wet electrochemical cell, a Nuvant multi-array system, and a Scribner fuel cell system were used to study and rank the effectiveness of the catalysts and supports toward both the methanol oxidation reaction and the oxygen reduction reaction. The activity toward methanol oxidation of the electrodeposited Pt catalyst was found to be dependent on the deposited mass. Further comparisons between commercial electrodes in the Nuvant system showed these deposits can yield activities comparable to those of commercially available electrodes. The structure of the Pt electrodeposits was highly non-uniform due to the H2 evolution during the deposition process blocking the cathodes surface. The activities of the planar structured PtxCo1-x deposits were insignificant for both oxygen reduction and methanol oxidation. The composition of the deposits ranged from 5 to 15 at% Pt. It was found by both the Nuvant and Scribner systems that the addition of a thin hydrophilic MWNF layer to a hydrophobic electrode would enhance the performance of a DMFC anode. In the Nuvant system, the addition of a thin hydrophilic MWNF layer to a hydrophobic electrode also enhanced the PEM cathode activity. This however was not corroborated by Scribner analysis, showing a

  11. 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).

  12. 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.

  13. 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.

  14. Cathodes incorporating thin fluoride layers for efficient injection in blue polymer light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Brown, Thomas M.; Millard, Ian S.; Lacey, David; Burroughes, Jeremy H.; Friend, Richard H.; Cacialli, Franco

    2002-02-01

    Efficient blue Polymer Light-Emitting Diodes (PLEDs) were fabricated by evaporating thin LiF layers between Al or Ca cathodes. Electroabsorption measurements of the built-in potential across the diodes show that devices fabricated with LiF/Ca/Al cathodes exhibit the smallest average barrier height and operating voltage (compared to both Ca and LiF/Al currently amongst the most efficient electron injectors). The turn-on bias is essentially equivalent to the built-in potential (~2.7 V), indicating an effective minimisation of the barrier to electron injection. Results are also compared with devices incorporating CsF layers and are correlated with the electroluminescent characteristics of the LEDs. A very strong dependence (~ exponential) between the built-in potential and the current and luminance at a fixed electric field (0.5MV/cm) is observed and is explained with the reduction of the cathodic barrier height brought about by the different cathode multilayers.

  15. 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.

  16. 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.

  17. 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.

  18. Inorganic solution-processed hole-injecting and electron-blocking layers in polymer light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Reynolds, K. J.; Barker, J. A.; Greenham, N. C.; Friend, R. H.; Frey, G. L.

    2002-12-01

    The use of the solution-processed layered transition metal dichalcogenide (LTMDC) MoS2 as a hole-injecting electrode in polymer light-emitting diodes (LEDs) is reported. MoS2 functions as a very high work function metal and, in combination with an electron-blocking layer in the form of MoO3, provides good LED performance. In this study we investigated model LED devices with a single semiconductor layer, namely, the electron transporting polymer poly-[2,7-(9,9'-di-n-octylfluorene)-3,6-benzothiadiazole]. LED operation was successfully modeled using experimentally determined work functions, carrier mobilities, and barrier properties. Good agreement between experiment and model allows us to demonstrate that the MoS2 and the MoO3 layers act as a high work function hole-injection layer (MoS2) and an electron extraction barrier layer (MoO3), respectively. They improve device performance by allowing the buildup of electron density at the oxide/emissive layer interface which generates a local field, enhancing hole injection and recombination. Furthermore, the model shows the importance of controlling the thickness of the blocking layer to optimize device performance. The wide variety of polymeric emitters available and the range of electronic properties displayed by the LTMDC family and their corresponding oxides, provides the potential to tailor device performance through the selection of suitable organic and inorganic components.

  19. Solution-processed high-LUMO-level polymers in n-type organic field-effect transistors: a comparative study as a semiconducting layer, dielectric layer, or charge injection layer

    NASA Astrophysics Data System (ADS)

    Liu, Chuan; Xu, Yong; Liu, Xuying; Minari, Takeo; Sirringhaus, Henning; Noh, Yong-Young

    2015-04-01

    In solution-processed organic field-effect transistors (OFETs), the polymers with high level of lowest unoccupied molecular orbitals (LUMOs, > -3.5 eV) are especially susceptible to electron-trapping that causes low electron mobility and strong instability in successive operation. However, the role of high-LUMO-level polymers could be different depending on their locations relative to the semiconductor/insulator interface, or could even possibly benefit the device in some cases. We constructed unconventional polymer heterojunction n-type OFETs to control the location of the same polymer with a high LUMO level, to be in, under, or above the accumulation channel. We found that although the devices with the polymer in the channel suffer from dramatic instability, the same polymer causes much less instability when it acts as a dielectric modification layer or charge injection layer. Especially, it may even improve the device performance in the latter case. This result helps to improve our understanding of the electron-trapping and explore the value of these polymers in OFETs.

  20. 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).

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Novel routes for direct preparation of surface-modifying polyelectrolyte layers and patterned polymer surfaces

    NASA Astrophysics Data System (ADS)

    Sankhe, Amit Y.

    The focus of this research was on the use of surface-confined atom transfer radical polymerization (SC-ATRP) for growing surface-tethered brushes of electrolytic or charged monomers on solid substrates. The use of SC-ATRP to produce well-defined polymer brushes from monomers with non-ionic functionalities in aprotic solvents has been well documented. Although it is possible to produce PE brushes by postpolymerization chemical conversion of some neutral brushes, this approach limits the types of PE brushes that can be produced and uses organic solvents. Thus, to more widely open the design envelope in terms of types of PE brushes that can be made and to reduce the use of organic solvents, it would be beneficial to directly synthesize PE brushes using more environmentally friendly, "green" solvents, such as water, for the reaction media. But the direct ATRP of hydrophilic monomers with ionic groups presents new challenges due to the complex interactions of the charged monomers and water with the ATRP catalyst. In this dissertation, I report findings on SC-ATRP of charged monomers such as itaconic acid (IA), methacrylic acid (MAA) and sodium 4-styrenesulfonate (SS) in aqueous solutions. Surface-tethered polyelectrolyte brushes comprised of poly(itaconic acid) (PIA), poly(methacrylic acid) (PMAA) and poly(4-styrenesulfonate) (PSS) were grown using surface-confined atom transfer radical polymerization (ATRP). The surface-tethered initiator monolayer was formed by self-assembling 2-bromoisobutyryl bromide terminated thiol molecules on gold coated silicon substrates. This polymerization initiator molecule and a copper-based organometallic catalyst allowed tethered polyelectrolyte chains to be grown via radical polymerization at room temperature in aqueous solutions. To suppress consumption of the ATRP deactivator, a halide salt was added to the reaction mixture, which enabled controlled growth of the polyelectrolyte layers. Phase-modulated ellipsometry was used to follow

  6. 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)

  7. 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

  8. Ordered conducting polymer multilayer films and its application for hole injection layers in organic light-emitting devices

    NASA Astrophysics Data System (ADS)

    Xu, Jianhua; Yang, Yajie; Yu, Junsheng; Jiang, Yadong

    2009-01-01

    We reported a controlled architecture growth of layer-ordered multilayer film of poly(3,4-ethylene dioxythiophene) (PEDOT) via a modified Langmuir-Blodgett (LB) method. An in situ polymerization of 3,4-ethylene dioxythiophene (EDOT) monomer in multilayer LB film occurred for the formation of ordered conducting polymer embedded multilayer film. The well-distribution of conducting polymer particles was characterized by secondary-ion mass spectrometry (SIMS). The conducting film consisting of ordered PEDOT ultrathin layers was investigated as a hole injection layer for organic light-emitting diodes (OLEDs). The results showed that, compared to conventional spin-coating PEDOT film and electrostatic self-assembly (ESA) film, the improved performance of OLEDs was obtained after using ordered PEDOT LB film as hole injection layer. It also indicated that well-ordered structure of hole injection layer was attributed to the improvement of OLED performance, leading to the increase of charged carrier mobility in hole injection layer and the recombination rate of electrons and holes in the electroluminescent layer.

  9. Electrical and Optical Properties of ZnO Processed by Atomic Layer Deposition in Inverted Polymer Solar Cells

    SciTech Connect

    Cheun, Hyeunseok; Fuentes-Hernandez, Canek; Zhou, Yinhua; Potscavage, William J.; Kim, Sung-Jin; Shim, Jae Won; Dindar, Amir; Kippelen, Bernard

    2010-12-09

    We report on the photovoltaic properties of inverted polymer solar cells where the transparent electron-collecting electrode is formed by a ZnO-modified indium-tin oxide (ITO) electrode. The ZnO layers were deposited by atomic layer deposition (ALD) with varying thicknesses from 0.1 to 100 nm. The work function, surface roughness, and morphology of ITO/ZnO were found to be independent of the ZnO thickness. However, the device performance was found to be strongly dependent on a critical ZnO thickness, around 10 nm. Below the critical thickness the device performance was degraded because of the appearance of a “kink” in the current-voltage characteristics. The kink features became less pronounced after ultraviolet (UV) exposure. This was attributed to oxygen desorption, leading to an increased conductivity of the ZnO layer. At and above this critical thickness, the device performance significantly improved and no longer depended strongly on the thickness of the ZnO layer, in agreement with optical simulations. Instead, these optical simulations showed that the thickness of the active layer plays a more important role than the thickness of the ZnO layer in optimizing the photovoltaic properties of inverted solar cells. Inverted polymer solar cells with an increased thickness of the active layer showed a power conversion efficiency (PCE) of 3.06% estimated for AM1.5G, a 100 mW cm-2 illumination.

  10. 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

  11. 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

  12. Water/alcohol soluble conjugated polymers as highly efficient electron transporting/injection layer in optoelectronic devices.

    PubMed

    Huang, Fei; Wu, Hongbin; Cao, Yong

    2010-07-01

    Water/alcohol soluble conjugated polymers (WSCPs) can be processed from water or other polar solvents, which offer good opportunities to avoid interfacial mixing upon fabrication of multilayer polymer optoelectronic devices by solution processing, and can dramatically improve charge injection from high work-function metal cathode resulting in greatly enhancement of the device performance. In this critical review, the authors provide a brief review of recent developments in this field, including the materials design, functional principles, and their unique applications as interface modification layer in solution-processable multilayer optoelectronic devices (135 references). PMID:20571672

  13. Enhanced Electron Extraction Capability of Polymer Solar Cells via Employing Electrostatically Self-Assembled Molecule on Cathode Interfacial Layer.

    PubMed

    Li, Zhiqi; Zhang, Xinyuan; Liu, Chunyu; Zhang, Zhihui; Li, Jinfeng; Shen, Liang; Guo, Wenbin; Ruan, Shengping

    2016-03-01

    In this paper, high-performance inverted polymer solar cells (PSCs) with a modified cathode buffer layer, titanium dioxide:polyethylenimine (TiO2:PEI), are demonstrated. The TiO2-O-PEI transport layer was fabricated by electrostatically self-assembled monolayers (ESAM) of PEI molecules. Protonated amine functional groups of PEI can combine protons (H(+)) hydrolyzing from its aqueous solution. Also, PEI could produce ESAM on the surface of hydroxylated TiO2 because of its cationic characteristics. The incorporation of the TiO2-O-PEI layer enhances the photocurrent and power conversion efficiency (PCE) due to the improved interfacial electron transport and extraction of the TiO2-O-PEI surface and the increased light absorption of the active layer. The enhanced PCE, low-cost materials, and solution process of TiO2-O-PEI buffer layers provide a promising method for highly efficient PSCs. PMID:26955888

  14. Performance improvement of polymer solar cells by using a solution processible titanium chelate as cathode buffer layer

    NASA Astrophysics Data System (ADS)

    Tan, Zhan'ao; Yang, Chunhe; Zhou, Erjun; Wang, Xiang; Li, Yongfang

    2007-07-01

    A solution processible titanium chelate, titanium (diisopropoxide) bis (2,4-pentanedionate) (TIPD), was used as the cathode buffer layer in the polymer solar cells (PSCs) based on the blend of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] and [6,6]-phenyl-C61-butyric acid methyl ester. Introducing TIPD buffer layer reduced the interface resistance between the active layer and Al electrode, leading to a lower device resistance. The power conversion efficiency of the PSC with TIPD buffer layer reached 2.52% under the illumination of AM1.5, 100mW/cm2, which is increased by 51.8% in comparison with that (1.66%) of the device without TIPD buffer layer under the same experimental conditions.

  15. 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

  16. 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

  17. Fabrication of Covalently Crosslinked and Amine-Reactive Microcapsules by Reactive Layer-by-Layer Assembly of Azlactone-Containing Polymer Multilayers on Sacrificial Microparticle Templates

    PubMed Central

    Saurer, Eric M.; Flessner, Ryan M.; Buck, Maren E.; Lynn, David M.

    2011-01-01

    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 CaCO3 and glass cores were observed and characterized using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Whereas capsules fabricated on CaCO3 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

  18. 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.

  19. Nanotube liquid crystal elastomers: photomechanical response and flexible energy conversion of layered polymer composites

    NASA Astrophysics Data System (ADS)

    Fan, Xiaoming; King, Benjamin C.; Loomis, James; Campo, Eva M.; Hegseth, John; Cohn, Robert W.; Terentjev, Eugene; Panchapakesan, Balaji

    2014-09-01

    Elastomeric composites based on nanotube liquid crystals (LCs) that preserve the internal orientation of nanotubes could lead to anisotropic physical properties and flexible energy conversion. Using a simple vacuum filtration technique of fabricating nanotube LC films and utilizing a transfer process to poly (dimethyl) siloxane wherein the LC arrangement is preserved, here we demonstrate unique and reversible photomechanical response of this layered composite to excitation by near infra-red (NIR) light at ultra-low nanotube mass fractions. On excitation by NIR photons, with application of small or large pre-strains, significant expansion or contraction of the sample occurs, respectively, that is continuously reversible and three orders of magnitude larger than in pristine polymer. Schlieren textures were noted in these LC composites confirming long range macroscopic nematic order of nanotubes within the composites. Order parameters of LC films ranged from Soptical = 0.51-0.58 from dichroic measurements. Film concentrations, elastic modulus and photomechanical stress were all seen to be related to the nematic order parameter. For the same nanotube concentration, the photomechanical stress was almost three times larger for the self-assembled LC nanotube actuator compared to actuator based on randomly oriented carbon nanotubes. Investigation into the kinetics of photomechanical actuation showed variation in stretching exponent β with pre-strains, concentration and orientation of nanotubes. Maximum photomechanical stress of ˜0.5 MPa W-1 and energy conversion of ˜0.0045% was achieved for these layered composites. The combination of properties, namely, optical anisotropy, reversible mechanical response to NIR excitation and flexible energy conversion all in one system accompanied with low cost makes nanotube LC elastomers important for soft photochromic actuation, energy conversion and photo-origami applications.

  20. Interactions between liquid-water and gas-diffusion layers in polymer-electrolyte fuel cells

    DOE PAGESBeta

    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

  1. Generalized flooded agglomerate model for the cathode catalyst layer of a polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Kamarajugadda, Sai; Mazumder, Sandip

    2012-06-01

    The flooded agglomerate model has found prolific usage in modeling the oxygen reduction reaction within the cathode catalyst layer of a polymer electrolyte membrane fuel cell (PEMFC). The assumption made in this model is that the ionomer-coated carbon-platinum agglomerate is spherical in shape and that the spheres are non-overlapping. This assumption is convenient because the governing equations lend themselves to closed-form analytical solution when a spherical shape is assumed. In reality, micrographs of the catalyst layer show that the agglomerates are best represented by sets of overlapping spheres of unequal radii. In this article, the flooded agglomerate is generalized by considering overlapping spheres of unequal radii. As a first cut, only two overlapping spheres are considered. The governing reaction-diffusion equations are solved numerically using the unstructured finite-volume method. The volumetric current density is extracted for various parametric variations, and tabulated. This sub-grid-scale generalized flooded agglomerate model is first validated and finally coupled to a computational fluid dynamics (CFD) code for predicting the performance of the PEMFC. Results show that when the agglomerates are small (<200 nm equivalent radius), the effect of agglomerate shape on the overall PEMFC performance is insignificant. For large agglomerates, on the other hand, the effect of agglomerate shape was found to be critical, especially for high current densities for which the mass transport resistance within the agglomerate is strongly dependent on the shape of the agglomerate, and was found to correlate well with the surface-to-volume ratio of the agglomerate.

  2. Surface Plasmon Resonance Enhanced Polymer Solar Cells by Thermally Evaporating Au into Buffer Layer.

    PubMed

    Yao, Mengnan; Jia, Xu; Liu, Yan; Guo, Wenbin; Shen, Liang; Ruan, Shengping

    2015-08-26

    Generally, the surface plasmon resonance (SPR) effect of metal nanoparticles is widely applied on polymer solar cells (PSCs) to improve device performance by doping method into solution. Herein, a diameter-controlled thermally evaporation method was used to realize Au nanoparticles (Au NPs) doping into WO3 anode buffer layer in inverted PSCs. The surface energy differences between Au and WO3 inevitably lead to Au growing up through the process from nucleation, isolated island, aggregation of metal islands to continuous films along with the process of evaporation. The atom force microscopy (AFM) images indicate that critical thickness of Au film formation is 8 nm, which is in accordance with current density-voltage (J-V) and incident photon-to-electron conversion efficiency (IPCE) measurement results of optimal device performance. The power conversion efficiency (PCE) with 8 nm Au is dramatically improved from 4.67 ± 0.13% to 6.63 ± 0.17% compared to the one without Au. Moreover, the optical absorption enhancement is demonstrated by steady state photoluminescence (PL), which agrees well with transmission spectrum. The optical and electrical improvement all suggest that thermal evaporation is the appropriate method to further enhance device performance. PMID:26230868

  3. 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

  4. Effect of gaseous void on bipolar charge transport in layered polymer film

    NASA Astrophysics Data System (ADS)

    Lean, Meng H.; Chu, Wei-Ping L.

    2014-02-01

    This paper describes a hybrid algorithm to study the effect of a gaseous void on bipolar charge transport in layered polymer film. This hybrid algorithm uses a source distribution technique based on an axisymmetric boundary integral equation method to solve the Poisson equation and a fourth order Runge-Kutta (RK4) method with an upwind scheme for time integration. Iterative stability is assured by satisfying the Courant-Friedrichs-Levy stability criterion. Dynamic charge mapping is achieved by allowing conducting and insulating boundaries and material interfaces to be represented by equivalent free and bound charge distributions that collectively satisfy all local and far-field conditions. This hybrid technique caters to bipolar charge injection, field-dependent mobility transport, recombination, and trapping/de-trapping in the bulk and at material and physical interfaces. The resulting charge map is the taxonomy of the different charge types and their abundance, and presents a dynamic view of the temporal and spatial distributions. The paper is motivated by images of breakdown experiments that point to the role of gaseous void in delamination growth. For the test configuration, the high field at the edge of the gaseous void act as a sink first for positive and then negative charge. The net effect is to increase delamination stress at the edge leading to further growth of the defect and increasing the potential for partial discharge within the void.

  5. Low-temperature photo-activated inorganic electron transport layers for flexible inverted polymer solar cells

    NASA Astrophysics Data System (ADS)

    Lee, Jung-Wook; Lee, Soo-Hyoung; Kim, Yong-Hoon; Park, Sung Kyu

    2014-09-01

    A simple and versatile route of forming sol-gel-derived metal oxide n-type electron transport layers (ETLs) for flexible inverted polymer solar cells (PSCs) is proposed using low-temperature photochemical activation process. The photochemical activation, which is induced by deep ultraviolet irradiation on sol-gel films, allows formation of metal oxide n-type ETLs such as zinc oxide (ZnO) and indium gallium zinc oxide films at a low temperature. Compared to poly(3-hexylthiophene)/phenyl-C61-butyric acid methyl ester inverted PSCs with thermally annealed ZnO ETLs (optimized efficiency of 3.26 ± 0.03 %), the inverted PSCs with photo-activated ZnO ETLs showed an improved efficiency of 3.60 ± 0.02 %. The enhanced photovoltaic property is attributed to efficient charge collection from low overall series resistance and high surface area-to-geometric area ratio by the photo-activated ZnO ETLs.

  6. 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.

  7. 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

  8. 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. PMID:26684416

  9. 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.

  10. 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

  11. 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

  12. 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.

  13. 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.

  14. 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

  15. 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

  16. 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.

  17. Scattering-layer-induced energy storage function in polymer-based quasi-solid-state dye-sensitized solar cells

    PubMed Central

    Zhang, Xi; Jiang, Hongrui

    2015-01-01

    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. PMID:25829547

  18. 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

  19. 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

  20. 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.

  1. 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.

  2. Inverted polymer solar cells with Nafion® as the hole extraction layer: efficiency and lifetime studies

    NASA Astrophysics Data System (ADS)

    Manceau, Matthieu; Berson, Solenn

    2014-01-01

    The use of Nafion® as the hole extraction layer in polymer solar cells is demonstrated in this work. Inverted devices were built on plastic foil with the following architecture: PET/ITO/ZnO/P3HT:PCBM/Nafion®/Ag. The Nafion® was processed from a surfactant-free solution in alcoholic solvents on top of the active layer. Optimization of film thickness and annealing yielded fully functional devices with power conversion efficiency similar to others referenced, along with good operational stability.

  3. Flexible multilayer inverted polymer light-emitting diodes with a gravure contact printed Cs2CO3 electron injection layer

    NASA Astrophysics Data System (ADS)

    Chung, Dae-Young; Leem, Dong-Seok; Bradley, Donal D. C.; Campbell, Alasdair J.

    2011-03-01

    Here we demonstrate high efficiency, flexible inverted polymer light-emitting diodes in which the bottom-contact cesium carbonate electron injection layer is gravure contact printed. The poly(9,9-dioctylfluorene-alt-benzothiadiazole) emissive/electron transport layer, the poly(9,9-dioctylfluorene-alt-N-(4-butylphenyl)-diphenylamine) hole transport/electron blocking layer and the poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) hole injection layer were sequentially spin-coated from solution using orthogonal solvent formulations with appropriate wetting properties. By switching from indium-tin-oxide (ITO) on glass to ITO on poly(ethylene terephthalate) and using gravure contact printing instead of spin-coating, Cs2CO3 smoothness and morphology was optimized, resulting in an approximately fivefold increase in current efficiency and power efficiency at 100 cd/m2.

  4. 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.

  5. Functionalization of Fibers Using Azlactone-Containing Polymers: Layer-by-Layer Fabrication of Reactive Thin Films on the Surfaces of Hair and Cellulose-Based Materials

    PubMed Central

    Buck, Maren E.

    2010-01-01

    We report an approach to the functionalization of fibers and fiber-based materials that is based on the deposition of reactive azlactone-functionalized polymers and the ‘reactive’ layer-by-layer assembly of azlactone-containing thin films. We demonstrate (i) that the azlactone-functionalized polymer poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) can be used to modify the surfaces of a model protein-based fiber (horsehair) and cellulose-based materials (e.g., cotton and paper), and (ii) that fibers functionalized in this manner can be used to support the fabrication of covalently crosslinked and reactive polymer multilayers assembled using PVDMA and poly(ethyleneimine) (PEI). The growth, chemical reactivity, and uniformity of films deposited on these substrates were characterized using fluorescence microscopy, confocal microscopy, and scanning electron microscopy (SEM). In addition to the direct functionalization of fibers, we demonstrate that the residual azlactone functionality in PVDMA-treated or film-coated fibers can be exploited to chemically modify the surface chemistry and physicochemical properties of fiber-based materials post-fabrication using amine functionalized molecules. For example, we demonstrate that this approach permits control over the surface properties of paper (e.g., absorption of water) by simple post-fabrication treatment of film-coated paper with the hydrophobic amine n-decylamine. The azlactone functionality present in these materials provides a platform for the modification of polymer-treated and film-coated fibers with a broad range of other chemical and biological species (e.g., enzymes, peptides, catalysts, etc.). The results of this investigation thus provide a basis for the functionalization of fibers and fiber-based materials (e.g., textile fabrics or non-woven mats) of potential utility in a broad range of consumer, industrial, and biomedical contexts. PMID:20402471

  6. Effect of polyelectrolyte electron collection layer counteranion on the properties of polymer solar cells.

    PubMed

    Do, Thu Trang; Hong, Hee Seob; Ha, Ye Eun; Park, Juyun; Kang, Yong-Cheol; Kim, Joo Hyun

    2015-02-11

    Polyviologen (PV) derivatives are known materials used for adjusting the work function (WF) of cathodes by reducing the electron injection/collection barrier at the cathode interface. To tune and improve device performance, we introduce different types of counteranions (CAs), such as bromide, tetrafluoroborate, and tetraphenylborate, to a PV derivative. The effective WF of the Al cathode is shown to depend on the size of the CA, indicating that a Schottky barrier can be modulated by the size of the CA. Through the increased size of the CA from bromide to tetraphenylborate, the effective WF of the Al cathode is gradually decreased, indicating a decreased Schottky barrier at the cathode interface. In addition, the change of the power conversion efficiency (PCE) and the short circuit current (Jsc) value show good correlation with the change of the WF of the cathode, signifying the typical transition from a Schottky to an Ohmic contact. The turn-on electric field of the electron-only device without PV was 0.21 MV/cm, which is dramatically higher than those of devices with PV-X (0.07 MV/cm for PV-Br, 0.06 MV/cm for PV-BF4, and 0.05 MV/cm for PV-BPh4) This is also coincident with a decrease in the Schottky barrier at the cathode interface. The device ITO/PEDOT/P3HT:PCBM/PV/Al, with a thin layer of PV derivative and tetraphenylborate CA as the cathode buffer layer, has the highest PCE of 4.02%, an open circuit voltage of 0.64 V, a Jsc of 11.6 mA/cm2, and a fill factor of 53.0%. Our results show that it is possible to improve the performance of polymer solar cells by choosing different types of CAs in PV derivatives without complicated synthesis and to refine the electron injection/collection barrier height at the cathode interface. PMID:25611078

  7. Graphene oxide nanoribbon as hole extraction layer to enhance efficiency and stability of polymer solar cells.

    PubMed

    Liu, Jun; Kim, Gi-Hwan; Xue, Yuhua; Kim, Jin Young; Baek, Jong-Beom; Durstock, Michael; Dai, Liming

    2014-02-01

    Graphene oxide nanoribbons for efficient and stable polymer solar cells are discussed. With controllable bandgap, good solubility and film forming property, graphene oxide nanoribbons serve as a new class of excellent hole extraction materials for efficient and stable polymer solar cells outperforming their counterparts based on conventional hole extraction materials, including PEDOT:PSS. PMID:24167012

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. Comparative study of hole transport in polyspirobifluorene polymers measured by the charge-generation layer time-of-flight technique

    NASA Astrophysics Data System (ADS)

    Laquai, Frédéric; Wegner, Gerhard; Im, Chan; Bässler, Heinz; Heun, Susanne

    2006-01-01

    Hole transport in a polyspirobifluorene homopolymer and a statistical polyspirobifluorene-triarylamine copolymer has been studied in detail employing the charge-generation layer time-of-flight (TOF) technique over a wide range of electric fields and temperatures. Both materials exhibit nondispersive TOF signals after injection of a sheet of charge carriers from a thin (10 nm) perylene-diimide charge-carrier generation layer into a relatively thick (d>1 μm) polymer film. Results were analyzed within the framework of the Gaussian disorder model and the charge transport parameters were extracted for both polymers. The zero-field hole mobility of the spirohomopolymer was found to be on the order of 10-6 cm2/V s, whereas the copolymer showed a considerably lower hole mobility of 6×10-8 cm2/V s. The width of the density of states σ was determined to be 86 meV for the homopolymer and 107 meV for the copolymer. The latter polymer also showed an increased positional disorder due to the statistically incorporated triarylamine units.

  15. 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.

  16. Phase diagram and transformations of iron pentacarbonyl to nm layered hematite and carbon-oxygen polymer under pressure

    DOE PAGESBeta

    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

  17. 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

  18. 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. PMID:20698679

  19. 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

  20. Thick polymer light-emitting diodes with very high power efficiency using Ohmic charge-injection layers

    NASA Astrophysics Data System (ADS)

    Lu, Li Ping; Finlayson, Chris E.; Friend, Richard H.

    2014-02-01

    We demonstrate the optimization of single-layer polymer LED structures with active layers with thicknesses of the order of 1 micron. By using a combined approach of the addition of MoO3, as a bottom hole-injection layer, and the incorporation of such thick active layers, exceptionally high performance metrics are achieved. In particular, brightnesses of 1000 cd m-2 at driving voltages of only 6.8 V, corresponding to a power efficiency of 7.8 lm W-1, a current efficiency of 17.2 cd A-1, and external quantum efficiency of 5.6%, are reported for devices based on F8BT (Poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)]). A side-by-side comparison, between the standard LED structure and hybrid structures, demonstrates that with MoO3 as bottom hole-injection layer, the electron and hole charge carriers are both giving space-charge limited current for both carriers due to the Ohmic contacts. The devices hence show improved charge carrier balance, and, most importantly, high brightness at low operational voltage. Such thick active-layer devices with high performance metrics, in addition to improved engineering and processing tolerances, are thus especially important for application to high-throughput device fabrication methods.

  1. 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.

  2. Selective identification of macrophages and cancer cells based on thermal transport through surface-imprinted polymer layers.

    PubMed

    Eersels, Kasper; van Grinsven, Bart; Ethirajan, Anitha; Timmermans, Silke; Jiménez Monroy, Kathia L; Bogie, Jeroen F J; Punniyakoti, Sathya; Vandenryt, Thijs; Hendriks, Jerome J A; Cleij, Thomas J; Daemen, Mat J A P; Somers, Veerle; De Ceuninck, Ward; Wagner, Patrick

    2013-08-14

    In this article, we describe a novel straightforward method for the specific identification of viable cells (macrophages and cancer cell lines MCF-7 and Jurkat) in a buffer solution. The detection of the various cell types is based on changes of the heat transfer resistance at the solid-liquid interface of a thermal sensor device induced by binding of the cells to a surface-imprinted polymer layer covering an aluminum chip. We observed that the binding of cells to the polymer layer results in a measurable increase of heat transfer resistance, meaning that the cells act as a thermally insulating layer. The detection limit was found to be on the order of 10(4) cells/mL, and mutual cross-selectivity effects between the cells and different types of imprints were carefully characterized. Finally, a rinsing method was applied, allowing for the specific detection of cancer cells with their respective imprints while the cross-selectivity toward peripheral blood mononuclear cells was negligible. The concept of the sensor platform is fast and low-cost while allowing also for repetitive measurements. PMID:23820628

  3. New polymer for 157-nm single-layer resist based on fluorine-containing acryl copolymer

    NASA Astrophysics Data System (ADS)

    Ogata, Toshiyuki; Endo, Koutaro; Komano, Hiroshi; Nakayama, Toshimasa

    2001-08-01

    We are reporting on the development of acryl polymer based on novel methacrylate and acrylate monomers with various trifluoromethyl groups for the application to 157nm chemically amplified positive-tone resists. The (alpha) - trifluoromethylation of the alkyl ester in methacrylate or acrylate could employ the reduction of acrylpolymer absorbance at 157nm by spectra analysis with the VUV-200 spectrophotometer by JASCO. Although the trifluoromethyl groups could employ the reduction of base polymer absorbance at 157nm, the homopolymers have issued weak etch resistance as a photoresist base polymer. To take account of this issue, we have developed a novel monomer, trifluoromethyl- iso-adamantylmethacrylate (TFIAdMA) and a new co-polymer system with the combination of fluorinated methacrylate derivatives and substituted p-hydroxystyrene. The absorption coefficient of poly(p-tert-butoxystyren-co- hexafluoro-tert-butyl methacrylate-co-methacrylic acid) incicated to be less than 3 micrometers -1 at 157nm. Patterning results were obtained with a 157nm contact exposure system of VUVES-4500 by LTJ. One of the experimental resists, based on a particular polymer ratio and photo acid generator, has clearly achieved 180nm line and space pattern resolution. At 140nm resist film thickness, the sensitivity was 31 mJ/cm2 when using 0,26N tetrametylammonium hydroxide surfactant type developer.

  4. 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

  5. A liquid crystalline polymer microlens array with tunable focal intensity by the polarization control of a liquid crystal layer

    NASA Astrophysics Data System (ADS)

    Choi, Yoonseuk; Kim, Hak-Rin; Lee, Kwang-Ho; Lee, Yong-Min; Kim, Jae-Hoon

    2007-11-01

    We propose a focal intensity tunable microlens array by using a birefringent liquid crystalline polymer for lensing action. Due to the difference of effective refractive indices, it acts as a positive or negative microlens with respect to the polarization state. As we control the incident polarization by adding a liquid crystal layer, the focal intensity can be tuned by an applied voltage. Twisted nematic and bistable ferroelectric liquid crystal modes were applied to demonstrate the possibility of various driving features such as a continuously tunable focal intensity or fast switching with memory effect.

  6. 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

  7. Photon recycling across a ultraviolet-blocking layer by luminescence in polymer solar cells

    NASA Astrophysics Data System (ADS)

    Engmann, Sebastian; Machalett, Marie; Turkovic, Vida; Rösch, Roland; Rädlein, Edda; Gobsch, Gerhard; Hoppe, Harald

    2012-08-01

    UV-blocking layers can increase the long term stability of organic solar cell devices; however, they limit the amount of light that can be utilized for energy conversion. We present photon recycling and down-conversion via a luminescent layer across a UV-blocking TiO2 layer. Our results show that the use of an additional UV-blocking layer does not necessarily reduce the overall efficiency of organic solar cells, since the loss in photocurrent due to the UV-absorption loss can be partially compensated using high energy photon down-conversion via luminescence layers.

  8. 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. PMID:25333870

  9. 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.

  10. Use of two-phase aqueous systems based on water-soluble polymers in thin-layer and extraction chromatography for recovery and separtion of actinides

    SciTech Connect

    Molochnikova, N.P.; Shkinev, V.M.; Myasoedov, B.F.

    1995-11-01

    The feasibility has been demonstrated of using two-phase aqueous systems based on water-soluble polymers, polyethylene glycol and dextran sulfate, in thin-layer and extraction chromatography for recovery and separation of actinides. A convenient method has been proposed for continuous recovery of {sup 239}Np from {sup 243}Am, originating from differences in sorption of tri- and pentavalent actinides from sulfate solutions containing potassium phosphotungstate by silica gel impregnated with polyethylene glycol. New plates for thin-layer chromatography using water-soluble polymers have been developed. These plates were used to study behavior of americium in various oxidation states in thin sorbent layers.

  11. 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

  12. 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.

  13. 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

  14. Determination of ibuprofen, naproxen and diclofenac in aqueous samples using a multi-template molecularly imprinted polymer as selective adsorbent for solid-phase extraction.

    PubMed

    Madikizela, Lawrence Mzukisi; Chimuka, Luke

    2016-09-01

    This study describes the application of multi-template molecularly imprinted polymer (MIP) as selective sorbent in the solid-phase extraction (SPE) of naproxen, ibuprofen and diclofenac from wastewater and river water. MIP was synthesized at 70°C by employing naproxen, ibuprofen and diclofenac as multi-templates, ethylene glycol dimethacrylate, 2-vinyl pyridine and toluene as cross-linker, functional monomer and porogen, respectively. Wastewater and river water samples (pH 2.5) were percolated through SPE cartridge packed with 50mg of the MIP. The cartridge was washed with 2mL of methanol-water 10:90% (v:v) prior to elution with 2mL of acetic acid-acetonitrile 20:80% (v:v). Quantification of eluted compounds was performed with high performance liquid chromatography equipped with photo diode array detection. The detection limits were 0.15, 1.00 and 0.63μgL(-1) for naproxen, ibuprofen and diclofenac, respectively. Recoveries for naproxen, ibuprofen and diclofenac in deionized water spiked at 5 and 50μgL(-1) were greater than 80%. Ibuprofen was the most frequently detected compound with maximum concentrations of 221, 67.9 and 11.4μgL(-1) in wastewater influent, effluent and river water, respectively. PMID:27268945

  15. Coordination polymer adsorbent for matrix solid-phase dispersion extraction of pesticides during analysis of dehydrated Hyptis pectinata medicinal plant by GC/MS.

    PubMed

    Aquino, Adriano; Wanderley, Kaline A; Paiva-Santos, Carlos de Oliveira; de Sá, Gilberto F; Alexandre, Marcelo da R; Júnior, Severino A; Navickiene, Sandro

    2010-12-15

    The coordination polymer [Zn(BDC)(H(2)O)(2)](n) was tested for extraction of pyrimethanil, ametryn, dichlofluanid, tetraconazole, flumetralin, kresoxim-methyl and tebuconazole from the medicinal plant Hyptis pectinata, with analysis using gas chromatography-mass spectrometry in selected ion monitoring mode (GC/MS, SIM). Experiments carried out at different fortification levels (0.1, 0.5 and 1.0 μg g(-1)) resulted in recoveries in the range 73-97%, and RSD values were between 5 and 12% for the [Zn(BDC)(H(2)O)(2)](n) sorbent. Detection and quantification limits ranged from 0.02 to 0.07 μg g(-1) and from 0.05 to 0.1 μg g(-1), respectively, for the different pesticides studied. The method developed was linear over the range tested (0.04-14.0 μg g(-1)), with correlation coefficients ranging from 0.9987 to 0.9998. Comparison between [Zn(BDC)(H(2)O)(2)](n) and the commercial phase C(18)-bonded silica showed good performance of the [Zn(BDC)(H(2)O)(2)](n) polymeric sorbent for the pesticides tested. PMID:21111184

  16. Kinetic regimes of polyelectrolyte exchange between the adsorbed state and free solution

    NASA Astrophysics Data System (ADS)

    Sukhishvili, Svetlana A.; Granick, Steve

    1998-10-01

    We studied the exchange between the adsorbed state and free solution when polyelectrolyte chains, adsorbed to a solid surface of opposite charge, were displaced by chains of higher charge density. Metastable states of surface composition were extremely long-lived (>2-3 days). The system was a family of poly(1,4 vinyl)pyridines (PVP) with different fractions of charged segments (14%, 48%, and 98% quaternized and the same degree of polymerization); samples were exposed sequentially from aqueous D2O solution to a single silicon oxide substrate at pH where the surface carried a large negative charge (pH=9.2 or 10.5). Measurements were based on Fourier transform infrared spectroscopy in attenuated total reflection (FTIR-ATR). As a first conclusion, we found charge of adsorbed polymer to be conserved during extended exchange times, suggesting that charge at the surface (not mass adsorbed) regulated the dynamics of adsorption and desorption. Except at the highest ionic strength charge of polymer at the surface during the displacement process considerably exceeded that for the initially-adsorbed layer, suggesting an intermediate state in which newly-adsorbed chains were more extended from the surface and not yet equilibrated in their conformations. Second, we concluded that desorption was the rate-limiting step in adsorption-desorption, since the desorption rate responded more to changes of ionic strength than did the adsorption rate onto previously-adsorbed polymer. Ionic strength appeared to modulate the intensity of sticking to the surface. Third, we found that the initial stages of desorption obeyed a simple functional form, exponential in the square root of elapsed time. This is conclusively slower than a first-order kinetic process and suggests that desorption in this polyelectrolyte system was diffusion-controlled during the initial stages. It is the same functional form observed for flexible polymers in nonpolar solvents. Fourth, we concluded that at relatively low

  17. Development and characterization of a layer by layer ultrasound assisted spray deposition process for thin polymer films

    NASA Astrophysics Data System (ADS)

    Balakrishnan, Anandh

    An Ultrasound assisted Atomization (UA) system has been developed and investigated to synthesize ˜20microm polyurethane thin films with uniform, repeatable thickness and microstructure. The UA system comprised a 20 kHz atomizer probe mounted on 750 W/cm2 transducer, a heated glass chamber and a rotating substrate. The rationale for the work has been built through a careful Design of Experiments (DoE) that sought to answer questions regarding the process-microstructure relationships from both the spray and material points of view. The independent variables chosen were the polymer solution weight percentage (0.2%, 2%, and 4%), power amplitude (energy) percentage supplied to the nozzle (23%, 29%, 37%, and 46%),the temperature of deposition (45°C, 80°C) and flow rate (50microL/min, 150microL/min). The research questions focused on influence of the process parameters on the microstructure and properties of the film. One of the problems involved fixing the trajectory of the spray and also making use of the droplet surfaces created by the spray. To achieve this, a simple air-draft attachment was devised and the influence of the same was evaluated through process and film characterization experiments. A mechanism for the draft has been schematically provided. The use of such a draft to fabricate thin polymer films via ultrasound atomization has not been achieved before and represents a 'first step' in advancing this ultrasound technology. The primary findings of the work were that the film microstructure and properties were heavily influenced by the flow rate, energy of atomization, and test temperature. In addition, the droplet diameters seemed to be readily amenable to change for the 0.2 and 2% solutions and the use of the air-draft made the process feasible, repeatable and accurate. For the 4% solutions, viscosity seemed to stabilize the liquid solution film at the tip requiring larger energies of atomization. In all, relative to the 0.2% films the fracture strengths

  18. Role of ultrathin Alq3 and LiF layers in conjugated polymer light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Deng, X. Y.; Tong, S. W.; Hung, L. S.; Mo, Y. Q.; Cao, Y.

    2003-05-01

    We report that an ultrathin layer of tris-(8-hydroxyquinoline) aluminum (Alq3) interposed between a bilayer cathode of LiF/Al and an emissive layer can significantly improve electroluminescence efficiency in a polymer light-emitting device (PLED). At a current density of 35 mA/cm2, a poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenyl-enevinylene] (MEH-PPV)-based PLED with a cathode of Alq3/LiF/Al has a quantum efficiency of 2.5%, considerably higher than that of a MEH-PPV-based PLED with a bare Al or a LiF/Al cathode. Interfacial characteristics of MEH-PPV/LiF/Al and MEH-PPV/Alq3/LiF/Al were investigated by photoelectron spectroscopy, and the results were used to explain the difference in device performance.

  19. 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.

  20. 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.

  1. 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.

  2. Corrugated mesh flow channel and novel microporous layers for reducing flooding and resistance in gas diffusion layer-less polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Tanaka, Shiro; Shudo, Toshio

    2014-12-01

    Electrode flooding at the cathode impedes the increase in power density of polymer electrolyte fuel cells (PEFCs), limiting their use at high current densities. Liquid water can accumulate in the pores of the gas-diffusion layer (GDL), deteriorating performances significantly. This paper reports a novel fuel-cell structure for the reduction of electrode flooding utilizing corrugated mesh as gas-flow channels and gas diffusers placed directly onto the microporous layer (MPL) without a conventional GDL in between. The polarization curve of the corrugated-mesh fuel cell shows a lower flooding tendency at a high current density; however, the high-frequency resistance (HFR) of this fuel cell increases significantly as a result of fewer contact points between the corrugated mesh and MPL. In addition, MPL conductivity and rigidity are investigated in efforts to reduce the flow-channel pattern resistance. The rigidity of the MPL has a small effect on the reduction in HFR, which may be caused by an improved pressure distribution on the catalyst layer.

  3. 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

  4. 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. PMID:26618802

  5. Temperature and exposure dependence of hybrid organic-inorganic layer formation by sequential vapor infiltration into polymer fibers.

    PubMed

    Akyildiz, Halil I; Padbury, Richard P; Parsons, Gregory N; Jur, Jesse S

    2012-11-01

    The characteristic processing behavior for growth of a conformal nanoscale hybrid organic-inorganic modification to polyamide 6 (PA6) by sequential vapor infiltration (SVI) is demonstrated. The SVI process is a materials growth technique by which exposure of organometallic vapors to a polymeric material promotes the formation of a hybrid organic-inorganic modification at the near surface region of the polymer. This work investigates the SVI exposure temperature and cycling times of sequential exposures of trimethylaluminum (TMA) on PA6 fiber mats. The result of TMA exposure is the preferential subsurface organic-inorganic growth by diffusion into the polymer and reaction with the carbonyl in PA6. Mass gain, infrared spectroscopy, and transmission electron microscopy analysis indicate enhanced materials growth and uniformity at lower processing temperatures. The inverse relationship between mass gain and exposure temperature is explained by the formation of a hybrid layer that prevents the diffusion of TMA into the polymer to react with the PA6 upon subsequent exposure cycles. As few as 10 SVI exposure cycles are observed to saturate the growth, yielding a modified thickness of ∼75 nm and mass increase of ∼14 wt %. Removal of the inherent PA6 moisture content reduces the mass gain by ∼4 wt % at low temperature exposures. The ability to understand the characteristic growth process is critical for the development of the hybrid materials fabrication and modification techniques. PMID:23050951

  6. 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

  7. Layer-by-layer coated lipid-polymer hybrid nanoparticles designed for use in anticancer drug delivery.

    PubMed

    Ramasamy, Thiruganesh; Tran, Tuan Hiep; Choi, Ju Yeon; Cho, Hyuk Jun; Kim, Jeong Hwan; Yong, Chul Soon; Choi, Han-Gon; Kim, Jong Oh

    2014-02-15

    Polyelectrolyte multilayers created via sequential adsorption of complimentary materials may be useful in the delivery of small molecules such as anti-cancer drugs. In this study, layer-by-layer (LbL) nanoarchitectures were prepared by step-wise deposition of naturally derived chitosan and hyaluronic acid on negatively charged hybrid solid lipid nanoparticles (SLNs). A doxorubicin/dextran sulfate complex was incorporated into the SLNs. This resulted in the production of spherical nanoparticles ∼ 265 nm in diameter, with a zeta potential of approximately -12 mV. The nanoparticles were physically stable and exhibited controlled doxorubicin (DOX) release kinetics. Further pharmacokinetic manipulations revealed that in comparison with both free DOX and uncoated DOX-loaded SLNs, LbL-functionalized SLNs remarkably enhanced the circulation half-life and decreased the elimination rate of the drug. Cumulatively, our results suggest that this novel LbL-coated system, with a pH-responsive shell and molecularly targeted entities, has the potential to act as a vehicle to deliver medication to targeted tumor regions. PMID:24507332

  8. Inhibition of platelet spreading from plasma onto glass by an adsorbed layer of a novel fluorescent-labeled poly(ethylene oxide)/poly(butylene oxide) block copolymer: characteristics of the exclusion zone probed by means of polystyrene beads and macromolecules.

    PubMed

    Gingell, D; Owens, N

    1994-04-01

    We have investigated the anti-adhesive properties of a newly synthesized fluorescent triblock copolymer containing poly(ethylene oxide). This adsorbs from aqueous solution onto glass that has been rendered hydrophobic. When the polymer-treated surface was exposed to human platelet-rich plasma (PRP) or whole blood at 37 degrees C, platelet adhesion and spreading were prevented. Avid adhesion and rapid platelet spreading occurred along tracks scraped in the adsorbed polymer coating, as seen by video-enhanced interference reflection microscopy. Leukocytes from whole blood are eventually able to adhere to the polymer-treated surface and were seen to remove labeled polymer from their vicinity and accumulate it at the cell body. Interferometry using polystyrene spheres showed that they do not adhere to polymer-coated glass and are unable to approach closer than 70-95 nm. On scraped tracks, beads make molecular contacts with the glass. Because the fully extended solvated (EO)400 arms may extend up to 100 nm from the glass, this suggests that the polymer forms a monolayer with the hydrophilic arms projecting into the water, whereas the hydrophobic (BO)55 segment binds the molecule to the hydrophobic surface. Another tri-bloc copolymer with shorter hydrophilic arms allows particles to approach more closely. PMID:7516339

  9. 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

  10. A novel double-layer molecularly imprinted polymer film based surface plasmon resonance for determination of testosterone in aqueous media

    NASA Astrophysics Data System (ADS)

    Tan, Yuan; Jing, Lijing; Ding, Yonghong; Wei, Tianxin

    2015-07-01

    This work aimed to prepare a novel double-layer structure molecularly imprinted polymer film (MIF) on the surface plasmon resonance (SPR) sensor chips for detection of testosterone in aqueous media. The film was synthesized by in-situ UV photo polymerization. Firstly, the modification of gold surface of SPR chip was performed by 1-dodecanethiol. Then double-layer MIF was generated on the 1-dodecanethiol modified gold surface. The non-modified and imprinted surfaces were characterized by atomic force microscopy (AFM), fourier transform infrared (FTIR) spectroscopy and contact angle measurements. Analysis of SPR spectroscopy showed that the imprinted sensing film displayed good selectivity for testosterone compared to other analogues and the non-imprinted polymer film (NIF). Within the concentrations range of 1 × 10-12-1 × 10-8 mol/L, the coupling angle changes of SPR were linear with the negative logarithm of testosterone concentrations (R2 = 0.993). Based on a signal/noise ratio of three, the detection limit was estimated to be 10-12 mol/L. Finally, the developed MIF was successfully applied to the seawater detection of testosterone. The results in the experiments suggested that a combination of SPR sensing with MIF was a promising alternative method for detection of testosterone in aqueous media.

  11. Fluorescence studies of polymer surfactant association

    NASA Astrophysics Data System (ADS)

    Miguel, M. da G.; Burrows, H. D.; Formosinho, S. J.; Lindman, B.

    2001-05-01

    Fluorescence spectroscopy has been successfully used for the study of central issues of solutions of surfactants and associating polymers. Different fluorescence techniques and methods are uniquely adapted to investigate problems in this field and can, by using extrinsic or intrinsic probes, provide information on molecular association, microstructure and molecular dynamics. This constitutes an important contribution to the understanding and control of macroscopic properties, as well as to their biological functions and technical applications. Important aspects of these mixed systems, related to their self-assembly, are: formation of micelles and hydrophobic microdomains in general; size and shape of surfactant molecular aggregates; formation and stability of vesicles; intra- vs. intermolecular association in polymers; conformational changes in polymers as affected by polymer-surfactant association; surfactant organization in adsorbed layers; kinetic aspects of the formation and disintegration of self-assembly structures; residence times of molecules in microdomains and migration of active molecules. Some of these issues will be addressed in this paper.

  12. The influence of polymer content on early gel-layer formation in HPMC matrices: The use of CLSM visualisation to identify the percolation threshold.

    PubMed

    Mason, Laura Michelle; Campiñez, María Dolores; Pygall, Samuel R; Burley, Jonathan C; Gupta, Pranav; Storey, David E; Caraballo, Isidoro; Melia, Colin D

    2015-08-01

    Percolation theory has been used for several years in the design of HPMC hydrophilic matrices. This theory predicts that a minimum threshold content of polymer is required to provide extended release of drug, and that matrices with a lower polymer content will exhibit more rapid drug release as a result of percolation pathways facilitating the faster penetration of the aqueous medium. At present, percolation thresholds in HPMC matrices have been estimated solely through the mathematical modelling of dissolution data. This paper examines whether they can be also identified in a novel way: through the use of confocal laser scanning fluorescence microscopy (CLSM) to observe the morphology of the emerging gel layer during the initial period of polymer hydration and early gel formation at the matrix surface. In this study, matrices have been prepared with a polymer content of 5-30% w/w HPMC 2208 (Methocel K4M), with a mix of other excipients (a soluble drug (caffeine), lactose, microcrystalline cellulose and magnesium stearate) to provide a typical industrially realistic formulation. Dissolution studies, undertaken in water using USP apparatus 2 (paddle) at 50rpm, provided data for the calculation of the percolation threshold through relating dissolution kinetic parameters to the excipient volumetric fraction of the dry matrix. The HPMC percolation threshold estimated this way was found to be 12.8% v/v, which was equivalent to a matrix polymer content of 11.5% w/w. The pattern of polymer hydration and gel layer growth during early gel layer formation was examined by confocal laser scanning fluorescence microscopy (CLSM). Clear differences in gel layer formation were observed. At polymer contents above the estimated threshold a continuous gel layer was formed within 15min, whereas matrices with polymer contents below the threshold were characterised by irregular gel layer formation with little evidence of HPMC particle coalescence. According to percolation theory, this

  13. Water balance model for polymer electrolyte fuel cells with ultrathin catalyst layers.

    PubMed

    Chan, Karen; Eikerling, Michael

    2014-02-01

    We present a water balance model of membrane electrode assemblies (MEAs) with ultrathin catalyst layers (UTCLs). The model treats the catalyst layers in an interface approximation and the gas diffusion layers as linear transmission lines of water fluxes. It relates current density, pressure distribution, and water fluxes in the different functional layers of the assembly. The optimal mode of operation of UTCLs is in a fully flooded state. The main challenge for MEAs with UTCLs is efficient liquid water removal, to avoid flooding of the gas diffusion layers. The model provides strategies for increasing the critical current density for the onset of flooding, via liquid permeabilities, vaporization areas, and gas pressure differentials. Finally, we discuss methods to identify regimes of transport via water flux measurements. PMID:24343559

  14. Frictional properties of the end-grafted polymer layer in presence of salt solution

    NASA Astrophysics Data System (ADS)

    Raftari, Maryam; Zhang, Zhenyu; Leggett, Graham J.; Geoghegan, Mark

    2012-02-01

    We have studied the frictional behaviour of grafted poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) films using friction force microscopy (FFM). The films were prepared on native oxide-terminated silicon substrates using the technique of atom transfer radical polymerization (ATRP). These brushes had constant grafting density (1.18 nm2), and of a thickness of ˜66 nm, as measured by ellipsometry. We show that single asperity contact mechanics (Johnson-Kendall-Roberts (JKR) and Derjaguin-M"uller-Toporov (DMT) models) as well as a linear (Amontons) relation between applied load and frictional load all apply to these systems depending on the concentration of salt and the nature of the FFM probe. Measurements were made using gold-coating and polymer functionalized silicon nitride triangular probes. Polymer functionalized probe included growth the PDMAEMA with same method on tips. The frictional behaviour are investigated between PDMAEMA and gold coated and PDMAEMA tips immersed in different concentrations of KCl, KBr and KI.

  15. Translational Diffusion in Supported Rubberly Polymer Films at Different Layer Thicknesses

    NASA Astrophysics Data System (ADS)

    Pak, Hunkyun; Ellingson, Peter Christopher; Yu, Hyuk

    2002-03-01

    Translational diffusion of an organic dye with C18 hydrocarbon tail (4-octadecylamino-NBD) is examined in thin films of poly(isoprene) and poly(dimethylsiloxane) spincast on substrates. Surface functionalized silicon wafers were used as the substrates. Two kinds of surface functionalized wafers, one with predominantly methyl group and the other with primary amine group, were examined with respect to the diffusion as a function of film thickness over a range of 10-2000 nm. The diffusion coefficient was determined by the technique of fluorescence recovery after photobleaching and the film thickness by ellipsometry. The diffusion coefficient is found to reduce substantially from that in bulk polymers, vary by an order of magnitude over the thickness range, and its dependence is analyzed in terms of a simple model that takes into account of polymer interactions with the functionalized surfaces.

  16. 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.

  17. 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.

  18. Highly efficient hybrid light-emitting device using complex of CdSe/ZnS quantum dots embedded in co-polymer as an active layer.

    PubMed

    Kang, Byoung-Ho; Seo, Jun-Seon; Jeong, Sohee; Lee, Jihye; Han, Chang-Soo; Kim, Do-Eok; Kim, Kyu-Jin; Yeom, Se-Hyuk; Kwon, Dae-Hyuk; Kim, Hak-Rin; Kang, Shin-Won

    2010-08-16

    We propose a highly efficient hybrid light-emitting device (LED) with a single active layer where CdSe/ZnS quantum dots (QDs) are dispersed as a guest material in a conjugated polymer (co-polymer) matrix used for a host material. In our structure, the QDs act on light-emitting chromophores by trapping the migrating excitons in the co-polymer matrix via Förster energy transfer, and improve the charge balance within the co-polymer by trapping the injected electron carriers. Experimental results show that the electroluminescent properties highly depend on the doping density of the QDs within the co-polymer matrix, where the luminance as well as the external current efficiency are initially enhanced with increasing the concentration of the dispersed QDs in the co-polymer solution, and then such properties are degraded due to aggregation of the QDs. We can get the maximum brightness of 9,088 cd/m(2) and the maximum external current efficiency of 7.5 cd/A in mixing ratio of the QDs by 1.0 wt%. The external current efficiency is enhanced by over 15 times and the turn-on voltage is reduced in comparison with the corresponding values for a reference device that uses only a co-polymer as an active layer. PMID:20721223

  19. A small angle neutron scattering study of the adsorbed asphaltene layer in water-in-hydrocarbon emulsions: structural description related to stability.

    PubMed

    Jestin, Jacques; Simon, Sébastien; Zupancic, Lina; Barré, Loïc

    2007-10-01

    We have developed a specific protocol to study with SANS measurements, the structure of the interfacial film layer in water-in-oil emulsions stabilized by asphaltene. Using the contrast matching technique available for neutron scattering, we have access to both the composition and the quantity of interface. The results obtained give us a view of the asphaltene aggregates in the interfacial film, which are structured as a monolayer and show a direct correlation between the size of asphaltene aggregates in solution and the thickness of the film layer. The organization of the interface has been studied as a function of several parameters such as the quantity of resins, i.e., the size of aggregates, the pH of the aqueous phase, and the aging time of the emulsions and the consequences of these variations on the macroscopic stability of these emulsions. We show that the key parameter for the stability is the inter-asphaltene aggregate interaction inside the film layer. Changing the attractive/repulsive balance between the aggregates in the film at the microscopic scale, by changing the aggregate's size or the aggregate's ionization, has a direct incidence on the quantity of water recovered after centrifugation: the stronger the attraction between aggregates in the film, the more stable the emulsion is. PMID:17867712

  20. 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.

  1. Charge transfer from an adsorbed ruthenium-based photosensitizer through an ultra-thin aluminium oxide layer and into a metallic substrate

    NASA Astrophysics Data System (ADS)

    Gibson, Andrew J.; Temperton, Robert H.; Handrup, Karsten; Weston, Matthew; Mayor, Louise C.; O'Shea, James N.

    2014-06-01

    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.

  2. Water vapor exchange system using a hydrophilic microporous layer coated gas diffusion layer to enhance performance of polymer electrolyte fuel cells without cathode humidification

    NASA Astrophysics Data System (ADS)

    Kitahara, Tatsumi; Nakajima, Hironori; Morishita, Masashi

    2012-09-01

    Polymer electrolyte fuel cells (PEFCs) generally have external humidifiers to supply humidified hydrogen and oxidant gases, which prevents dehydration of the membrane. If a PEFC could be operated without humidification, then external humidifiers could be removed, which would result in a simplified PEFC system with increased total efficiency and reduced cost. A water vapor exchange system installed in the PEFC was developed to enhance the performance without cathode humidification. A gas diffusion layer (GDL) coated with a hydrophobic microporous layer (MPL) was used at the active reaction area. A GDL coated with a hydrophilic MPL consisting of polyvinyl alcohol (PVA) and carbon black was used at the cathode water vapor exchange area to promote water transport from the cathode outlet wet gas to the anode inlet dry gas. This is effective for reducing the IR overpotential, which enhances the PEFC performance. Appropriate enhancement of hydrophilicity by increasing the PVA content in the MPL to 20 mass% is effective to increase water transport from the cathode to anode. At the anode water exchange area, a GDL without the hydrophilic MPL is effective to promote water transport from the water exchange area to the active reaction area, which enhances the PEFC performance.

  3. Equilibrium chain conformations of bound polymers at the polymer melt/solid interface

    NASA Astrophysics Data System (ADS)

    Sen, Mani; Jiang, Naisheng; Sendogdular, Levent; Endoh, Maya; Koga, Tadanori

    2014-03-01

    We report the equilibrium conformations of bound polymer chains formed on planar solids. In this study, bound polystyrene (PS) layers onto silicon (Si) substrates were used as a model system. Three 50 nm-thick PS thin films were prepared by using different film processes (i.e., spin coating, dip coating, and floating) following prolonged thermal annealing and subsequent solvent leaching. The structures of the bound layers on Si were then characterized by using x-ray reflectivity and atomic force microscopy. We found that the adsorption kinetics for the dip coating film is much longer than that for the spun cast film or the floating film. It was also found that all the bound PS layers are composed of two different nanoarchitectures: flattened chains that constitute the inner higher density region of the bound layers and loosely adsorbed polymer chains that form the outer bulk-like density region. We acknowledge the financial support from NSF Grant No. CMMI-084626.

  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. Separation of the attractive and repulsive contributions to the adsorbate-adsorbate interactions of polar adsorbates on Si(100)

    NASA Astrophysics Data System (ADS)

    Lin, Ying-Hsiu; Jeng, Horng-Tay; Lin, Deng-Sung

    2015-11-01

    Dissociative adsorption of H2O, NH3, CH3OH and CH3NH2 polar molecules on the Si(100) surface results in a 1:1 mixture of two adsorbates (H and multi-atomic fragment A = OH, NH2, CH3O, CH3NH, respectively) on the surface. By using density functional theory (DFT) calculations, the adsorption geometry, the total energies and the charge densities for various possible ordered structures of the mixed adsorbate layer have been found. Analyzing the systematic trends in the total energies unveils concurrently the nearest-neighbor interactions ENN and the next nearest-neighbor interactions ENNN between two polar adsorbates A. In going from small to large polar adsorbates, ENN's exhibit an attractive-to-repulsive crossover behavior, indicating that they include competing attractive and repulsive contributions. Exploration of the charge density distributions allows the estimation of the degree of charge overlapping between immediately neighboring A's, the resulting contribution of the steric repulsions, and that of the attractive interactions to the corresponding ENN's. The attractive contributions to nearest neighboring adsorbate-adsorbate interactions between the polar adsorbates under study are shown to result from hydrogen bonds or dipole-dipole interactions.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. Investigation of the microstructure in the catalyst layer and effects of both perfluorosulfonate ionomer and PTFE-loaded carbon on the catalyst layer of polymer electrolyte fuel cells

    SciTech Connect

    Uchida, Makoto; Aoyama, Yuko; Eda, Nobuo; Ohta, Akira

    1995-12-01

    Effects of a perfluorosulfonate ionomer (PFSI) and of a polytetrafluoroethylene (PTFE) loaded carbon (PTFE-C) on the catalyst layer in the electrode of a polymer electrolyte fuel cell (PEFC) prepared by a new method based on the process of PFSI-colloid formation were investigated by electrochemical techniques and a mercury pore sizer. The microstructure of the catalyst layer and its effect on the PEFC performance were affected by the contents of both PFSI and PTFE-C. The catalyst layer has two distinctive pore distributions with a boundary of ca. 0.04 {micro}m. The volume of larger pore (secondary pore) decreased with an increase of the PFSI content and increased with an increase of the PTFE-C content. The volume of the smaller pore (primary pore) was independent of the content of both PFSI and PTFE-C. The PFSI as well as the PTFE existed only in the secondary pore. The content of PFSI affected the performance of PEFC in the whole current density range. On the other hand, the content of PTFE-C influenced it greatly at high current density due to its gas feeding faculty. In the PEFC, reaction sites were found to exist in the secondary pore coated with the macromolecule PFSI. The hydrophobic PTFE-C works to supply the reaction gas to the reaction sites covered with the PFSI in the secondary pore, and to exhaust the product water from there. The high performance of PEFC at high current density was achieved with the best mixture of the PFSI and the PTFE-C.

  11. Power conversion efficiency enhancement of polymer solar cells using MoO3/TFB as hole transport layer

    NASA Astrophysics Data System (ADS)

    Zheng, Qiao; Sun, Jianbin; Cheng, Shuying; Lai, Yunfeng; Zhou, Haifang; Yu, Jinling

    2015-09-01

    In this paper, we report a simple method to increase the power conversion efficiency (PCE) of the polymer solar cells based on poly(3-hexylthiophene) and [6, 6]-phenyl-C61-butyric acid methyl ester derivatives blended active layer. The approach includes using a molybdenum oxide (MoO3) and Poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4-( N-(4-sec-butylphenyl))diphenylamine)] (TFB) composites as the hole transport layer (HTL). Compared with that of the device with bare MoO3 HTL, the maximum 39 % increased of PCE is obtained when MoO3/TFB composites as the HTL in the devices. The device with MoO3/TFB shows the best performance with a PCE of 3.70 %, an open-circuit voltage of 0.58 V, and a short-circuit current density of 11.39 mA/cm2. The intrinsically mechanisms behind PCE increased are due to the improvement in the interface layer morphology and the more appropriately energy level of the cells.

  12. 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.

  13. 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.

  14. Bifunctional polymer hydrogel layers as forward osmosis draw agents for continuous production of fresh water using solar energy.

    PubMed

    Razmjou, Amir; Liu, Qi; Simon, George P; Wang, Huanting

    2013-11-19

    The feasibility of bilayer polymer hydrogels as draw agent in forward osmosis process has been investigated. The dual-functionality hydrogels consist of a water-absorptive layer (particles of a copolymer of sodium acrylate and N-isopropylacrylamide) to provide osmotic pressure, and a dewatering layer (particles of N-isopropylacrylamide) to allow the ready release of the water absorbed during the FO drawing process at lower critical solution temperature (32 °C). The use of solar concentrated energy as the source of heat resulted in a significant increase in the dewatering rate as the temperature of dewatering layer increased to its LSCT more rapidly. Dewatering flux rose from 10 to 25 LMH when the solar concentrator increased the input energy from 0.5 to 2 kW/m(2). Thermodynamic analysis was also performed to find out the minimum energy requirement of such a bilayer hydrogel-driven FO process. This study represents a significant step forward toward the commercial implementation of hydrogel-driven FO system for continuous production of fresh water from saline water or wastewaters. PMID:24144265

  15. 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

  16. Modulated ionomer distribution in the catalyst layer of polymer electrolyte membrane fuel cells for high temperature operation.

    PubMed

    Choo, Min-Ju; Oh, Keun-Hwan; Kim, Hee-Tak; Park, Jung-Ki

    2014-08-01

    Ionomer distribution is an important design parameter for high performance polymer electrolyte membrane fuel cells (PEMFCs); however, the nano-scale modulation of the ionomer morphology has not been intensively explored. Here, we propose a new route to modulate the ionomer distribution that features the introduction of poly(ethylene glycol) (PEG) to the cathode catalyst layer and the leaching the PEG phase from the catalyst layer using a water effluent during operation. The key concept in the approach is the expansion of the ionomer thin film through the PEG addition. We demonstrate that the modulated ionomer distribution increases the electrochemical active area and proton transport property, without loss in oxygen transport, at a fixed ionomer content. At a high temperature of 120 °C, the power performance at 0.6 V is increased by 1.73-fold with the modulated ionomer distribution as a result of 1.25-fold increase in the electrochemical active area and two-fold increase in the proton transport rate in the catalyst layer. PMID:24777945

  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. Polymers encapsulated in short single wall carbon nanotubes: pseudo-1D morphologies and induced chirality.

    PubMed

    Kumar, Sunil; Pattanayek, Sudip K; Pereira, Gerald G

    2015-03-21

    Molecular dynamics simulations are performed to investigate the stable morphologies of semi-flexible polymer chains within a single wall carbon nanotube (CNT). We characterize these morphologies with a variety of measures. Due to the different curvature inside the CNT to outside, there are increased numbers of polymer-CNT bead contacts for polymers which reside inside the CNT. A sufficiently long polymer chain first adsorbs on the exterior of the nanotube and subsequently moves inside the cavity of the nanotube. At equilibrium, the polymer configuration consists of a central stem surrounded by helically wrapped layers. Sections of the polymer outside the CNT have helical conformations (for CNTs of small radius) or circular arrangements (for CNTs of larger radius). Polymers encapsulated within the CNT have an increased chirality due to packing of the beads and this chirality is further enhanced for moderately stiff chains. PMID:25796260

  19. 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

  20. Carbon nanotube/polymer composites as a highly stable hole collection layer in perovskite solar cells.

    PubMed

    Habisreutinger, Severin N; Leijtens, Tomas; Eperon, Giles E; Stranks, Samuel D; Nicholas, Robin J; Snaith, Henry J

    2014-10-01

    Organic-inorganic perovskite solar cells have recently emerged at the forefront of photovoltaics research. Power conversion efficiencies have experienced an unprecedented increase to reported values exceeding 19% within just four years. With the focus mainly on efficiency, the aspect of stability has so far not been thoroughly addressed. In this paper, we identify thermal stability as a fundamental weak point of perovskite solar cells, and demonstrate an elegant approach to mitigating thermal degradation by replacing the organic hole transport material with polymer-functionalized single-walled carbon nanotubes (SWNTs) embedded in an insulating polymer matrix. With this composite structure, we achieve JV scanned power-conversion efficiencies of up to 15.3% with an average efficiency of 10 ± 2%. Moreover, we observe strong retardation in thermal degradation as compared to cells employing state-of-the-art organic hole-transporting materials. In addition, the resistance to water ingress is remarkably enhanced. These are critical developments for achieving long-term stability of high-efficiency perovskite solar cells. PMID:25226226

  1. Localized removal of layers of metal, polymer, or biomaterial by ultrasound cavitation bubbles

    PubMed Central

    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.

    2012-01-01

    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. PMID:23964308

  2. 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. PMID:27102116

  3. Enhanced electron extraction capability of polymer solar cells via modifying the cathode buffer layer with inorganic quantum dots.

    PubMed

    Li, Zhiqi; Li, Shujun; Zhang, Zhihui; Zhang, Xinyuan; Li, Jingfeng; Liu, Chunyu; Shen, Liang; Guo, Wenbin; Ruan, Shengping

    2016-04-20

    Enhanced performance of polymer solar cells (PSCs) based on the blend of poly[N-9''-hepta-decanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT):[6,6]-phenyl-C70-butyric acid methyl ester (PC71BM) is demonstrated by titanium dioxide (TiO2) interface modification via CuInS2/ZnS quantum dots (CZdots). Devices with a TiO2/CZdots composite buffer layer exhibit both a high short-circuit current density (Jsc) and fill factor (FF), leading to a power conversion efficiency (PCE) up to 7.01%. The charge transport recombination mechanisms are investigated by an impedance behavior model, which indicates that TiO2 interfacial modification results in not only increasing the electron extraction but also reducing impedance. This study provides an important and beneficial approach to develop high efficiency PSCs. PMID:27055908

  4. Surface Modification of ZnO Layers via Hydrogen Plasma Treatment for Efficient Inverted Polymer Solar Cells.

    PubMed

    Papamakarios, Vasilis; Polydorou, Ermioni; Soultati, Anastasia; Droseros, Nikos; Tsikritzis, Dimitris; Douvas, Antonios M; Palilis, Leonidas; Fakis, Mihalis; Kennou, Stella; Argitis, Panagiotis; Vasilopoulou, Maria

    2016-01-20

    Modifications of the ZnO electron extraction layer with low-pressure H plasma treatment increased the efficiency of inverted polymer solar cells (PSCs) based on four different photoactive blends, namely, poly(3-hexylthiophene):[6,6]-phenyl C71 butyric acid methyl ester (P3HT:PC71BM), P3HT:1',1″,4',4″-tetrahydro-di[1,4]methanonaphthaleno-[5,6]ullerene-C60 (P3HT:IC60BA), poly[(9-(1-octylnonyl)-9H-carbazole-2,7-diyl)-2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]:PC71BM (PCDTBT:PC71BM), and (poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-(2-ethylhexy)carbonyl]thieno[3,4-b]thiophenediyl

  5. 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.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  8. 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

  9. 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.

  10. 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. PMID:27028166

  11. Ultra-fast photo-patterning of hydroxamic acid layers adsorbed on TiAlN: The challenge of modeling thermally induced desorption

    NASA Astrophysics Data System (ADS)

    Hemgesberg, Maximilian; Schütz, Simon; Müller, Christine; Schlörholz, Matthias; Latzel, Harald; Sun, Yu; Ziegler, Christiane; Thiel, Werner R.

    2012-10-01

    Long-chain n-alkyl terminated hydroxamic acids (HA) are used for the modification of titanium aluminum nitride (TiAlN) surfaces. HA coatings improve the hydrophobicity of this wear resistant and industrially relevant ceramic. Therefore, HAs with different structural properties are evaluated with respect to their wear resistance and their thermal desorption properties. In order to find new coatings for rewritable offset printing plates, the changes in the surface polarity, composition, and morphology are analyzed by contact angle measurements, X-ray photoemission spectroscopy (XPS), and scanning force microscopy (SFM), respectively. The results are referenced to the strongly bonding molecule n-dodecyl phosphonate (PO11M), which has been used for surface hydrophobization before but proved difficult to remove due to the high laser outputs required for thermal desorption. It is found that for certain HAs, an equally good hydrophobization compared to PO11M can be achieved. Contact angles obtained for different hydroxamic acid coatings can be correlated to their modes of adsorption. Only for selected HA species, resistance to mechanical wear is sufficient for further investigations. Photo-patterning of these hydroxamic acid layers is achieved using a high energy IR laser beam at different energy inputs. Fitting of the obtained data and further evaluation using finite element analysis (FEM) calculations reveal significantly reduced energy consumption of about 20% for the removal of a specific hydroxamic acid coating from the ceramic surface compared to PO11M.

  12. Theoretical analysis on polarization-induced resistance switching effects of polymer thin films including dead layers

    NASA Astrophysics Data System (ADS)

    Honmi, Hitoshi; Hashizume, Yoichiro; Nakajima, Takashi; Okamura, Soichiro

    2015-10-01

    Polarization-induced resistance switching effects are analytically investigated. The electrostatic potential profile in metal is expressed by the Thomas-Fermi screening theory at the metal/ferroelectric interface. We estimate the current density using an assumed effective potential in metal/ferroelectric/metal junctions. Furthermore, we focus on the existence of a lower permittivity region such as a “dead layer” located at the boundary between the metal electrode and the ferroelectric material. In order to explain the ON/OFF ratio obtained in the experiment, we suggest that the dead layer near the smaller-work-function electrode side should be thicker by 2-3 Å than another electrode. Consequently, we propose a new hypothesis, that is, the thickness of the dead layer controls the ratio of resistance switching.

  13. 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

  14. 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

  15. 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.

  16. 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

  17. Preparation and characterization of ultrathin layers of substituted oligo- and poly(p-phenylene)s and mixed layers with octadecanethiol on gold and copper

    SciTech Connect

    Brunner, S.; Caseri, W.R.; Suter, U.W.

    1999-09-14

    Substituted poly(p-phenylene)s were adsorbed from solution onto gold and copper and oligo(p-phenylene)s onto gold. The layers were investigated with IR spectroscopy at grazing incidence reflection, XPS, NEXAFS, ToF-SIMS, surface profilometry, AFM, SEM, optical microscopy, ellipsometry, and contact angle measurements to examine their formation and structure. The structure and the properties of the investigated layers depend not only on the chemical structure of the polymer but also on the type of substrate. On gold, the polymers form layers of 15--25 {angstrom} in thickness and the oligomers of ca. 5 {angstrom} in thickness. On copper, thick layers of up to 900 {angstrom} were also observed. The oligomers have a lower affinity to gold than the polymers. Mixed octadecanethiol-polymer layers were prepared by immersion of polymer-coated substrates in an octadecanethiol solution or by exposure of self-assembled monolayers of octadecanethiol to polymer solutions. The structure of the mixed layers depends on the sequence of the exposure of the two components and on the chemical structure of the polymer. In the mixed layers, structures that protrude above the surroundings were frequently detected at the surface.

  18. 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.

  19. Effects of operating conditions on durability of polymer electrolyte membrane fuel cell Pt cathode catalyst layer

    NASA Astrophysics Data System (ADS)

    Ohyagi, Shinsuke; Matsuda, Toshihiko; Iseki, Yohei; Sasaki, Tatsuyoshi; Kaito, Chihiro

    In this study, we investigated the effects of humidity and oxygen reduction on the degradation of the catalyst of a polymer electrolyte membrane fuel cell (PEMFC) in a voltage cycling test. To elucidate the effect of humidity on the voltage cycling corrosion of a carbon-supported Pt catalyst with 3 nm Pt particles, voltage cycling tests based on 10,000 cycles were conducted using 100% relative humidity (RH) hydrogen as anode gas and nitrogen of varying humidities as cathode gas. The degradation rate of an electrochemical surface area (ECSA) was almost 50% under 189% RH nitrogen atmosphere and the Pt average particle diameter after 10,000 cycles under these conditions was about 2.3 times that of a particle of fresh catalyst because of the agglomeration of Pt particles. The oxygen reduction reaction (ORR) that facilitated Pt catalyst agglomeration when oxygen was employed as the cathode gas also demonstrated that Pt agglomeration was prominent in higher concentrations of oxygen. The ECSA degradation figure in 100% RH oxygen was similar to that in 189% RH nitrogen. It was concluded that liquid water, which was dropped under a supersaturated condition or generated by ORR, accelerated Pt agglomeration. In this paper, we suggest that the Pt agglomeration degradation occurs in a flooding area in a cell plane.

  20. The Characteristics Improvement of Ozone Water Production by Multi-layer Electrodes at Water Electrolysis Cell by Solid Polymer Electrolyte

    NASA Astrophysics Data System (ADS)

    Ohba, Takahiro; Kusunoki, Hironobu; Sunakawa, Daisuke; Araki, Takuto; Onda, Kazuo

    Ozone is recently used for many purposes as an environmental friendly oxidant, so the ozone production device with high ozone concentration and low production energy is desired. One of the candidates for such device is the ozone water production by water electrolysis cell using the solid polymer electrolyte with PbO2 anode catalyst, which has merits to be compact and to produce high-concentration ozone water directly by the deionized water electrolysis. In this study, we have tested ozone water production by changing electrodes and electrolytes constitution in order to improve the ozone production performance. Tested two electrolytes are Nafion117 and a membrane-electrode assembly (MEA) with Pt catalyst on cathode side of Nafion117. Tested two electrodes are mono-layer of Ti expanded metal and four different mesh layers of Ti expanded metal. Ozone water production tests are performed under long-term operations changing temperature and flow rate to optimize experimental conditions. The voltage-current characteristic for electrolysis cell have been improved significantly, when the electrode is four layers of Ti metal and the electrolyte is the MEA with Pt catalyst. The stable ozone water concentration has been obtained by operating the cell for about 8 hours. The optimum temperature and water flow rate for ozone water production are 25˜30° and 33L/h, respectively. Furthermore, the optimum overpotential was measured by a reference electrode at the cathode-side MEA, and the anode catalyst suitable for ozone water production was identified to be βPbO2 by the X ray diffraction pattern.

  1. Flexible polymer optical layer for board-level optical interconnects by highly durable metal imprinting method

    NASA Astrophysics Data System (ADS)

    Wang, Xiaolong; Dou, Xinyuan; Lin, Xiaohui; Chen, Ray T.

    2010-02-01

    In this paper, we presented fabrication of nickel based metal mold with 45° tilted surfaces on both ends of the channel waveguide through electroplating process. To obtain a precise 45° tilted angle, a 50μm thick SU-8 layer was UV exposed under de-ionized water, with repeatable error control of 0.5°. The polymeric waveguide array with 45° micromirrors, which is formed by a UV imprinting method with the fabricated metallic mold, shows total insertion losses around 4dB, propagation loss around 0.18dB/cm and 75% coupling efficiency.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. Inverted polymer fullerene solar cells exceeding 10% efficiency with poly(2-ethyl-2-oxazoline) nanodots on electron-collecting buffer layers.

    PubMed

    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

  7. 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.

  8. 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

  9. Nanoporous Gyroid-Structured Epoxy from Block Copolymer Templates for High Protein Adsorbability.

    PubMed

    Wang, Xin-Bo; Lin, Tze-Chung; Hsueh, Han-Yu; Lin, Shih-Chieh; He, Xiao-Dong; Ho, Rong-Ming

    2016-06-28

    Nanoporous epoxy with gyroid texture is fabricated by using a nanoporous polymer with gyroid-forming nanochannels as a template for polymerization of epoxy. The nanoporous polymer template is obtained from the self-assembly of degradable block copolymer, polystyrene-b-poly(l-lactide) (PS-PLLA), followed by hydrolysis of PLLA blocks. Templated polymerization can be conducted under ambient conditions to create well-defined, bicontinuous epoxy networks in a PS matrix. By taking advantage of multistep curing of epoxy, well-ordered robust nanoporous epoxy can be obtained after removal of PS template, giving robust porous materials. The through-hole nanoporous epoxy in the film state can be used as a coated layer to enhance the adsorbability for both lysozyme and bovine serum albumin. PMID:27245380

  10. Dynamics of layer-by-layer growth of a polyelectrolyte multilayer studied in situ using attenuated total reflectance infrared spectroscopy.

    PubMed

    Owusu-Nkwantabisah, Silas; Gammana, Madhira; Tripp, Carl P

    2014-10-01

    Attenuated total reflectance infrared spectroscopy (ATR-IR) was used to study the dynamic layer-by-layer (LBL) growth of a sodium polyacrylate (NaPA)/poly(diallydimethylammonium) chloride (PDADMAC) multilayer on TiO2 particles. Molecular weights (Mw) used were 30 and 60 kDa for NaPA and 8.5 and 150 kDa for PDADMAC. IR spectra were recorded in situ as a function of time and were used to obtain the dynamic mass adsorbed and bound fraction of the polymers during each deposition step. For 30 kDa NaPA layers, the dynamics of adsorption show an initial rapid rise in mass followed by a slow increase toward a plateau value upon LBL with 150 kDa PDADMAC. In contrast, the 60 kDa NaPA layers achieve a plateau quickly and do not show a slow increase toward a plateau. In the case of LBL with 150 kDa PDADMAC, the dynamics of the bound fraction of polymer per layer suggest that polymer diffusion and conformational rearrangement occur for the layers of 30 kDa NaPA but not for the 60 kDa NaPA layers. Furthermore, PDADMAC adsorption profiles show that there is no diffusion of the PDADMAC layers and that PDADMAC flattens onto the underlying layer. A linear growth in the mass adsorbed per layer was observed for 150 kDa PDADMAC with both molecular weights of NaPA. In the case of 8.5 kDa PDADMAC, smaller growth increments and the desorption of underlying layers were observed. This work demonstrates the use of ATR-IR in obtaining the dynamics of LBL multilayer formation. Furthermore, it provides an example in which polymer diffusion during LBL film formation does not lead to exponential growth. PMID:25203136

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. Shape-responsive actuator from a single layer of a liquid-crystal polymer.

    PubMed

    Kamal, Tahseen; Park, Soo-young

    2014-10-22

    Actuation of various shape changes, including bending, helical twisting, and reversible hinging, has been achieved from a single-layer sheet of poly(1,4-di(4-(3-acryloyloxypropyloxy)benzoyloxy)-2-methylbenzene) [poly(RM257)]. This actuator was developed through photopolymerization of a reactive liquid-crystal (LC) monomer (RM257) mixed with 4-pentyl-4'-cyanobiphenyl (5CB, nematic LC at room temperature) in a planar polyimide-coated LC cell. The UV beam perpendicular to one side of the LC cell produced an asymmetric phase separation between the poly(RM257) network and 5CB that resulted in an asymmetric porous structure along the thickness direction when the 5CB was extracted, in which the UV-exposed surface was pore-free and compact while the opposite surface was highly porous. As a result of this structure, the dry and curled poly(RM257) film exhibits actuation behavior when placed in acetone because of a difference in swelling between the two morphologically different sides, the film UV-exposed and nonexposed sides. The actuation of a three-dimensional tetrahedron (pyramidal) structure is also demonstrated for the first time by using a simple photopatterning technique to selectively control its asymmetric morphology at specific locations. PMID:25243321

  16. Interface-engineering additives of poly(oxyethylene tridecyl ether) for low-band gap polymer solar cells consisting of PCDTBT:PCBM₇₀ bulk-heterojunction layers.

    PubMed

    Huh, Yoon Ho; Park, Byoungchoo

    2013-01-14

    We herein report on the improved photovoltaic (PV) effects of using a polymer bulk-heterojunction (BHJ) layer that consists of a low-band gap electron donor polymer of poly(N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)) (PCDTBT) and an acceptor of [6,6]-phenyl C₇₁ butyric acid methyl ester (PCBM₇₀), doped with an interface-engineering surfactant additive of poly(oxyethylene tridecyl ether) (PTE). The presence of an interface-engineering additive in the PV layer results in excellent performance; the addition of PTE to a PCDTBT:PCBM₇₀ system produces a power conversion efficiency (PCE) of 6.0%, which is much higher than that of a reference device without the additive (4.9%). We attribute this improvement to an increased charge carrier lifetime, which is likely to be the result of the presence of PTE molecules oriented at the interfaces between the BHJ PV layer and the anode and cathode, as well as at the interfaces between the phase-separated BHJ domains. Our results suggest that the incorporation of the PTE interface-engineering additive in the PCDTBT:PCBM₇₀ PV layer results in a functional composite system that shows considerable promise for use in efficient polymer BHJ PV cells. PMID:23389265

  17. 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

  18. 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.

  19. 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. PMID:26018196

  20. 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.

  1. Effect of the PTFE content in the gas diffusion layer on water transport in polymer electrolyte fuel cells (PEFCs)

    NASA Astrophysics Data System (ADS)

    Mortazavi, Mehdi; Tajiri, Kazuya

    2014-01-01

    The dynamic behavior of a liquid water droplet emerging and detaching from the surface of the gas diffusion layer (GDL) is investigated. The droplet growth and detachment are studied for different polytetrafluoroethylene (PTFE) contents within the GDL and for different superficial gas velocities flowing in the gas channel. To simulate the droplet behavior in the cathode and anode of an operating polymer electrolyte fuel cell, separate experiments are conducted with air and hydrogen being supplied in the gas channel, respectively. Both the superficial gas velocity and the PTFE content within the GDL are found to impact the droplet detachment diameter. Increasing the superficial gas velocity increases the drag force applied on the droplet sitting on the GDL surface. It is observed that the droplet detaches at a smaller diameter for higher superficial gas velocities. The droplets also detach at smaller diameters from GDLs with a higher amount of PTFE. Such observation is justified according to two different points of view: (1) heterogeneous through-plane PTFE distribution through the GDL and (2) reduced GDL surface roughness caused by PTFE loading.

  2. Three novel electrochemical electrodes for the fabrication of conducting polymer/SWCNTs layered nanostructures and their thermoelectric performance

    NASA Astrophysics Data System (ADS)

    Shi, Hui; Liu, Congcong; Jiang, Qinglin; Xu, Jingkun; Lu, Baoyang; Jiang, Fengxing; Zhu, Zhengyou

    2015-06-01

    Single-walled carbon nanotubes (SWCNTs), PEDOT:PSS/SWCNTs, and SWCNTs/PEDOT:PSS nanofilms were used as working electrodes to electrodeposit polyaniline (PANI) in a mixed alcohol solution of isopropyl alcohol (IPA), boron trifluoride ethyl ether (BFEE), and polyethylene glycol (PEG). The thermoelectric (TE) performances of the resulting nanofilms were systematically investigated. SWCNTs/PEDOT:PSS/PANI nanofilms showed a relatively high electrical conductivity value of 232.0 S cm-1. The Seebeck coefficient was enhanced and exhibited the values of 33.8, 25.6, and 23.0 μV K-1 for the SWCNTs/PANI, PEDOT:PSS/SWCNTs/PANI, and SWCNTs/PEDOT:PSS/PANI films, respectively. The maximum power factor achieved was 12.3 μW m-1 K-2. This technique offers a facile and versatile approach to a class of layered nanostructures, and it may provide a general strategy for fabricating a new generation of conducting polymer/SWCNTs materials for further practical applications.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Syntheses, crystal structures and properties of two unusual pillared-layer 3d-4f Ln-Cu heterometallic coordination polymers

    SciTech Connect

    Fan Leqing; Wu Jihuai; Huang Yunfang

    2011-09-15

    Two unusual pillared-layer 3d-4f Ln-Cu heterometallic coordination polymers, {l_brace}[Ln{sub 2}Cu{sub 5}Br{sub 4}(IN){sub 7}(H{sub 2}O){sub 6}].H{sub 2}O{r_brace}{sub n} (Ln=Eu (1) and Gd (2), HIN=isonicotinic acid), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, thermal analysis and single-crystal X-ray diffraction. The structure determination reveals that 1 and 2 are isostructural and feature a novel three-dimensional pillared-layer hetrometallic structure built upon the linkages of one-dimensional (1D) linear Ln-carboxylate chains, zero-dimensional (0D) Ln-carboxylate Ln{sub 2}(IN){sub 8} dimers, rare 1D zigzag [Cu{sub 5}Br{sub 4}]{sub n} inorganic chains and IN{sup -} pillars. In both 3D structures, there are Ln-carboxylate layers resulted from the connections of 1D Ln-carboxylate chains and 0D Ln{sub 2}(IN){sub 8} dimers through O-H...O hydrogen bondings. The luminescent properties of 1 have been investigated. The magnetic properties of 1 and 2 have also been studied. - Graphical abstract: Two unusual pillared-layer Eu (Gd)-Cu heterometallic coordination polymers have been hydrothermally synthesized. The luminescent properties of Eu-Cu compound and magnetic properties of both compounds are investigated. Highlights: > Two unusual 3D pillared-layer Eu (Gd)-Cu heterometallic coordination polymers have been synthesized. > 1D and 0D Ln-carboxylate motifs construct layers by O-H...O hydrogen bondings. > In both the structures, there are rare 1D zigzag Cu/Br inorganic chains. > Luminescent properties of Eu-Cu compound and magnetic properties of both the compounds are investigated.

  11. A nano-grid structure made of perovskite SrTiO3 nanowires for efficient electron transport layers in inverted polymer solar cells.

    PubMed

    Kim, Jeong Won; Suh, Yo-han; Lee, Chang-Lyoul; Kim, Yong Seok; Kim, Won Bae

    2015-03-14

    A nano-grid structure of perovskite SrTiO3 NWs is developed for a novel electron transport layer in inverted polymer solar cells. Due to the excellent charge transporting properties of the SrTiO3 nano-grid structure, the device employing this nanostructure showed ∼32% enhanced photovoltaic performance, compared to the solar cell using a TiO2 thin film. PMID:25684116

  12. 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.

  13. Effect of ageing of gas diffusion layers on the water distribution in flow field channels of polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Kätzel, Juliane; Markötter, Henning; Arlt, Tobias; Klages, Merle; Haußmann, Jan; Messerschmidt, Matthias; Kardjilov, Nikolay; Scholta, Joachim; Banhart, John; Manke, Ingo

    2016-01-01

    We present a quantitative analysis of the influence of artificial ageing of gas diffusion layers (GDL) on the water distribution and transport in polymer electrolyte membrane fuel cells (PEMFCs) during cell operation. Water droplet size distributions are measured by means of in-operando neutron radiography. We find a strong correlation between droplet size distribution and GDL ageing time: With increasing GDL ageing, water droplet sizes in the flow field channels strongly decrease, indicating an ineffective water transport that leads to a reduced cell performance. This effect can be assigned to water accumulations on the GDL surface that block the gas supply towards the catalyst layer.

  14. Enhanced performance and stability in PBDTTT-C-T : PC70 BM polymer solar cells by optimizing thickness of NiOx buffer layers

    NASA Astrophysics Data System (ADS)

    Fan, Xi; Fang, Guojia; Cheng, Fei; Qin, Pingli; Huang, Huihui; Li, Yongfang

    2013-07-01

    We report efficient polymer solar cells (PSCs) based on PBDTTT-C-T : PC70BM with a NiOx anode buffer layer (thickness of 3-15 nm) prepared by radio-frequency magnetron sputtering deposition. The PSC with the optimum NiOx buffer layer thickness of 9 nm showed the highest power conversion efficiency of 7.42% with Voc of 0.75 V, Jsc of 15.82 mA cm-2 and FF of 62.5%, which was higher than that of the PSCs with a PEDOT : PSS buffer layer. Moreover, compared with the PSCs with a PEDOT : PSS buffer layer, the PSCs with the optimum NiOx buffer layer exhibited a better stability under N2 atmosphere. The results indicate that the sputtered 9 nm thick NiOx buffer layer is superior to the PEDOT : PSS buffer layer not only for better performance but also for improved long-term stability. The optimized NiOx buffer layer thickness possesses an appropriate energy level matching with PBDTTT-C-T, which results in effective hole collection and improved photovoltaic performance.

  15. New Insights into the Microvascular Mechanisms of Drag Reducing Polymers: Effect on the Cell-Free Layer

    PubMed Central

    Brands, Judith; Kliner, Dustin; Lipowsky, Herbert H.; Kameneva, Marina V.; Villanueva, Flordeliza S.; Pacella, John J.

    2013-01-01

    Drag-reducing polymers (DRPs) significantly increase blood flow, tissue perfusion, and tissue oxygenation in various animal models. In rectangular channel microfluidic systems, DRPs were found to significantly reduce the near-wall cell-free layer (CFL) as well as modify traffic of red blood cells (RBC) into microchannel branches. In the current stu