WorldWideScience

Sample records for added polymer chains

  1. Phase behaviour of charged colloidal sphere dispersions with added polymer chains

    International Nuclear Information System (INIS)

    Fortini, Andrea; Dijkstra, Marjolein; Tuinier, Remco

    2005-01-01

    We study the stability of mixtures of highly screened repulsive charged spheres and non-adsorbing ideal polymer chains in a common solvent using free volume theory. The effective interaction between charged colloids in an aqueous salt solution is described by a screened Coulomb pair potential, which supplements the pure hard-sphere interaction. The ideal polymer chains are treated as spheres that are excluded from the colloids by a hard-core interaction, whereas the interaction between two ideal chains is set to zero. In addition, we investigate the phase behaviour of charged colloid-polymer mixtures in computer simulations, using the two-body (Asakura-Oosawa pair potential) approximation to the effective one-component Hamiltonian of the charged colloids. Both our results obtained from simulations and from free volume theory show similar trends. We find that the screened Coulomb repulsion counteracts the effect of the effective polymer-mediated attraction. For mixtures of small polymers and relatively large charged colloidal spheres, the fluid-crystal transition shifts to significantly larger polymer concentrations with increasing range of the screened Coulomb repulsion. For relatively large polymers, the effect of the screened Coulomb repulsion is weaker. The resulting fluid-fluid binodal is only slightly shifted towards larger polymer concentrations upon increasing the range of the screened Coulomb repulsion. In conclusion, our results show that the miscibility of dispersions containing charged colloids and neutral non-adsorbing polymers increases upon increasing the range of the screened Coulomb repulsion, or upon lowering the salt concentration, especially when the polymers are small compared to the colloids

  2. Liquid crystal polymers: evidence of hairpin defects in nematic main chains, comparison with side chain polymers

    Science.gov (United States)

    Li, M. H.; Brûlet, A.; Keller, P.; Cotton, J. P.

    1996-09-01

    This article describes the conformation of two species of liquid crystalline polymers as revealed by small angle neutron scattering. The results obtained with side chain polymers are recalled. The procedure used to analyze the scattering data of main chains in the nematic phase is reported in this paper. It permits a demonstration of the existence of hairpins. Comparison of both polymer species shows that in the isotropic phase, the two polymers adopt a random coil conformation. In the nematic phase, the conformations are very different; the side chains behave as a melt of penetrable random coils whereas the main chains behave as a nematic phase of non penetrable cylinders.

  3. Side Chain Engineering in Solution-Processable Conjugated Polymers

    KAUST Repository

    Mei, Jianguo; Bao, Zhenan

    2014-01-01

    Side chains in conjugated polymers have been primarily utilized as solubilizing groups. However, these side chains have roles that are far beyond. We advocate using side chain engineering to tune a polymer's physical properties, including absorption

  4. Adsorption of polymer chains at penetrable interfaces

    International Nuclear Information System (INIS)

    Gerasimchuk, I. V.; Sommer, J.-U.; Gerasimchuk, V. S.

    2011-01-01

    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.

  5. Buckling a Semiflexible Polymer Chain under Compression

    Directory of Open Access Journals (Sweden)

    Ekaterina Pilyugina

    2017-03-01

    Full Text Available Instability and structural transitions arise in many important problems involving dynamics at molecular length scales. Buckling of an elastic rod under a compressive load offers a useful general picture of such a transition. However, the existing theoretical description of buckling is applicable in the load response of macroscopic structures, only when fluctuations can be neglected, whereas membranes, polymer brushes, filaments, and macromolecular chains undergo considerable Brownian fluctuations. We analyze here the buckling of a fluctuating semiflexible polymer experiencing a compressive load. Previous works rely on approximations to the polymer statistics, resulting in a range of predictions for the buckling transition that disagree on whether fluctuations elevate or depress the critical buckling force. In contrast, our theory exploits exact results for the statistical behavior of the worm-like chain model yielding unambiguous predictions about the buckling conditions and nature of the buckling transition. We find that a fluctuating polymer under compressive load requires a larger force to buckle than an elastic rod in the absence of fluctuations. The nature of the buckling transition exhibits a marked change from being distinctly second order in the absence of fluctuations to being a more gradual, compliant transition in the presence of fluctuations. We analyze the thermodynamic contributions throughout the buckling transition to demonstrate that the chain entropy favors the extended state over the buckled state, providing a thermodynamic justification of the elevated buckling force.

  6. Added clinical value of the inferior temporal EEG electrode chain

    DEFF Research Database (Denmark)

    Bach Justesen, Anders; Eskelund Johansen, Ann Berit; Martinussen, Noomi Ida

    2018-01-01

    Objective To investigate the diagnostic added value of supplementing the 10–20 EEG array with six electrodes in the inferior temporal chain. Methods EEGs were recorded with 25 electrodes: 19 positions of the 10–20 system, and six additional electrodes in the inferior temporal chain (F9/10, T9/10, P...... in the inferior chain) and 6% (only seen at the inferior chain). Conclusions Adding six electrodes in the inferior temporal electrode chain to the 10–20 array improves the localization and identification of EEG abnormalities, especially those located in the temporal region. Significance Our results suggest...

  7. Topology of polymer chains under nanoscale confinement.

    Science.gov (United States)

    Satarifard, Vahid; Heidari, Maziar; Mashaghi, Samaneh; Tans, Sander J; Ejtehadi, Mohammad Reza; Mashaghi, Alireza

    2017-08-24

    Spatial confinement limits the conformational space accessible to biomolecules but the implications for bimolecular topology are not yet known. Folded linear biopolymers can be seen as molecular circuits formed by intramolecular contacts. The pairwise arrangement of intra-chain contacts can be categorized as parallel, series or cross, and has been identified as a topological property. Using molecular dynamics simulations, we determine the contact order distributions and topological circuits of short semi-flexible linear and ring polymer chains with a persistence length of l p under a spherical confinement of radius R c . At low values of l p /R c , the entropy of the linear chain leads to the formation of independent contacts along the chain and accordingly, increases the fraction of series topology with respect to other topologies. However, at high l p /R c , the fraction of cross and parallel topologies are enhanced in the chain topological circuits with cross becoming predominant. At an intermediate confining regime, we identify a critical value of l p /R c , at which all topological states have equal probability. Confinement thus equalizes the probability of more complex cross and parallel topologies to the level of the more simple, non-cooperative series topology. Moreover, our topology analysis reveals distinct behaviours for ring- and linear polymers under weak confinement; however, we find no difference between ring- and linear polymers under strong confinement. Under weak confinement, ring polymers adopt parallel and series topologies with equal likelihood, while linear polymers show a higher tendency for series arrangement. The radial distribution analysis of the topology reveals a non-uniform effect of confinement on the topology of polymer chains, thereby imposing more pronounced effects on the core region than on the confinement surface. Additionally, our results reveal that over a wide range of confining radii, loops arranged in parallel and cross

  8. Elastic properties of a polymer chain

    International Nuclear Information System (INIS)

    Webman, I.; Lebowitz, J.L.; Kalos, M.H.

    1981-01-01

    We describe the results of computer simulations on a model polymer chain with excluded volume interactions in the presence of an external stretching force. For weak and moderate forces the response is linear while for strong forces the behavior is nonlinear, consistent with the non-Gaussian nature of the end-to-end vector R distribution for large R. In the vicinity of the THETA temperature the onset of nonlinearity occurs at larger forces

  9. Added sugars in kids' meals from chain restaurants

    OpenAIRE

    Scourboutakos, Mary J.; Semnani-Azad, Zhila; L'Abbé, Mary R.

    2016-01-01

    Objective To analyze the added sugars in kids' meals from Canadian chain restaurants in relation to the World Health Organization's proposed sugar recommendation (less than 5% of total daily calories should come from added sugars) and current recommendation (less than 10% of total daily calories should come from added sugars). Methods Total sugar levels were retrieved from the websites of 10 fast-food and 7 sit-down restaurants in 2010. The added sugar levels in 3178 kids' meals from Canadian...

  10. The effect of chain flexibility and chain mobility on radiation crosslinking reactions of polymers

    International Nuclear Information System (INIS)

    Sun Jiazhen

    2003-01-01

    Flexibility of polymer chains is an important factor to effects of radiation crosslinking of the polymer. Polymers with flexible chains are easier to be crosslinked, with lower dose of gelation, than polymers with more rigid chains. And it is known that most polymers with abnormal rigidity can be radiation-crosslinked only at high temperatures when the molecular chains get enough mobility. The flexibility of polymer chains also influences the relationship between degree of degradation and radiation dose. A chain flexibility factor β has been introduced to modify the Charlesby-Pinner equation of sol-fraction and radiation dose. The new relationship equation applies to a wider range of polymers in radiation crosslinking. Studies also show that for flexible polymers with lower T g and molecular internal rotating factor, mechanism of radiation crosslinking is mainly in H type, whereas for rigid polymers with higher T g and molecular internal rotating factor, mechanism of radiation crosslinking is mainly in T type

  11. Side Chain Engineering in Solution-Processable Conjugated Polymers

    KAUST Repository

    Mei, Jianguo

    2014-01-14

    Side chains in conjugated polymers have been primarily utilized as solubilizing groups. However, these side chains have roles that are far beyond. We advocate using side chain engineering to tune a polymer\\'s physical properties, including absorption, emission, energy level, molecular packing, and charge transport. To date, numerous flexible substituents suitable for constructing side chains have been reported. In this Perspective article, we advocate that the side chain engineering approach can advance better designs for next-generation conjugated polymers. © 2013 American Chemical Society.

  12. Critical Casimir effect in a polymer chain in supercritical solvents.

    Science.gov (United States)

    Sumi, Tomonari; Imazaki, Nobuyuki; Sekino, Hideo

    2009-03-01

    Density fluctuation effects on the conformation of a polymer chain in a supercritical solvent were investigated by performing a multiscale simulation based on the density-functional theory. We found (a) a universal swelling of the polymer chain near the critical point, irrespective of whether the polymer chain is solvophilic or solvophobic, and (b) a characteristic collapse of the polymer chain having a strong solvophilicity at a temperature slightly higher than the critical point, where the isothermal compressibility becomes less than the ideal one.

  13. Competing irreversible cooperative reactions on polymer chains

    International Nuclear Information System (INIS)

    Evans, J.W.; Hoffman, D.K.; Burgess, D.R.

    1984-01-01

    We analyze model processes involving competition between several irreversible reactions at the sites of a 1D, infinite, uniform polymer chain. These reactions can be cooperative, i.e., the corresponding rates depend on the state of the surrounding sites. An infinite hierarchy of rate equations is readily derived for the probabilities of various subconfigurations. By exploiting a shielding property of suitable blocks of unreacted sites, we show how exact hierarchy truncation and solution is sometimes possible. The behavior of solutions is illustrated in several cases by plotting families of ''reaction trajectories'' for varying ratios of reactant concentrations. As a specific application, we consider competition between coordination of ZnCl 2 to pairs of oxygen atoms and to single oxygen atoms in poly(propylene oxide). The observed glass transition temperature behavior is eludicated

  14. Added clinical value of the inferior temporal EEG electrode chain.

    Science.gov (United States)

    Bach Justesen, Anders; Eskelund Johansen, Ann Berit; Martinussen, Noomi Ida; Wasserman, Danielle; Terney, Daniella; Meritam, Pirgit; Gardella, Elena; Beniczky, Sándor

    2018-01-01

    To investigate the diagnostic added value of supplementing the 10-20 EEG array with six electrodes in the inferior temporal chain. EEGs were recorded with 25 electrodes: 19 positions of the 10-20 system, and six additional electrodes in the inferior temporal chain (F9/10, T9/10, P9/10). Five-hundred consecutive standard and sleep EEG recordings were reviewed using the 10-20 array and the extended array. We identified the recordings with EEG abnormalities that had peak negativities at the inferior temporal electrodes, and those that only were visible at the inferior temporal electrodes. From the 286 abnormal recordings, the peak negativity was at the inferior temporal electrodes in 81 cases (28.3%) and only visible at the inferior temporal electrodes in eight cases (2.8%). In the sub-group of patients with temporal abnormalities (n = 134), these represented 59% (peak in the inferior chain) and 6% (only seen at the inferior chain). Adding six electrodes in the inferior temporal electrode chain to the 10-20 array improves the localization and identification of EEG abnormalities, especially those located in the temporal region. Our results suggest that inferior temporal electrodes should be added to the EEG array, to increase the diagnostic yield of the recordings. Copyright © 2017 International Federation of Clinical Neurophysiology. Published by Elsevier B.V. All rights reserved.

  15. Suspensions of polymer-grafted nanoparticles with added polymers-Structure and effective pair-interactions.

    Science.gov (United States)

    Chandran, Sivasurender; Saw, Shibu; Kandar, A K; Dasgupta, C; Sprung, M; Basu, J K

    2015-08-28

    We present the results of combined experimental and theoretical (molecular dynamics simulations and integral equation theory) studies of the structure and effective interactions of suspensions of polymer grafted nanoparticles (PGNPs) in the presence of linear polymers. Due to the absence of systematic experimental and theoretical studies of PGNPs, it is widely believed that the structure and effective interactions in such binary mixtures would be very similar to those of an analogous soft colloidal material-star polymers. In our study, polystyrene-grafted gold nanoparticles with functionality f = 70 were mixed with linear polystyrene (PS) of two different molecular weights for obtaining two PGNP:PS size ratios, ξ = 0.14 and 2.76 (where, ξ = Mg/Mm, Mg and Mm being the molecular weights of grafting and matrix polymers, respectively). The experimental structure factor of PGNPs could be modeled with an effective potential (Model-X), which has been found to be widely applicable for star polymers. Similarly, the structure factor of the blends with ξ = 0.14 could be modeled reasonably well, while the structure of blends with ξ = 2.76 could not be captured, especially for high density of added polymers. A model (Model-Y) for effective interactions between PGNPs in a melt of matrix polymers also failed to provide good agreement with the experimental data for samples with ξ = 2.76 and high density of added polymers. We tentatively attribute this anomaly in modeling the structure factor of blends with ξ = 2.76 to the questionable assumption of Model-X in describing the added polymers as star polymers with functionality 2, which gets manifested in both polymer-polymer and polymer-PGNP interactions especially at higher fractions of added polymers. The failure of Model-Y may be due to the neglect of possible many-body interactions among PGNPs mediated by matrix polymers when the fraction of added polymers is high. These observations point to the need for a new framework to

  16. Added sugars in kids' meals from chain restaurants.

    Science.gov (United States)

    Scourboutakos, Mary J; Semnani-Azad, Zhila; L'Abbé, Mary R

    2016-06-01

    To analyze the added sugars in kids' meals from Canadian chain restaurants in relation to the World Health Organization's proposed sugar recommendation (less than 5% of total daily calories should come from added sugars) and current recommendation (less than 10% of total daily calories should come from added sugars). Total sugar levels were retrieved from the websites of 10 fast-food and 7 sit-down restaurants in 2010. The added sugar levels in 3178 kids' meals from Canadian chain restaurants were calculated in 2014 (in Toronto, Canada) by subtracting all naturally occurring sugars from the total sugar level. The average amount of added sugars in restaurant kids' meals (25 ± 0.36 g) exceeded the WHO's proposed daily recommendation for sugar intake. There was a wide range of added sugar levels in kids' meals ranging from 0 g to 114 g. 50% of meals exceeded the WHO's proposed daily sugar recommendation, and 19% exceeded the WHO's current daily sugar recommendation. There is a wide range of sugar levels in kids' meals from restaurants, and many contain more than a day's worth of sugar.

  17. General approach to polymer chains confined by interacting boundaries.

    Science.gov (United States)

    Freed, Karl F; Dudowicz, Jacek; Stukalin, Evgeny B; Douglas, Jack F

    2010-09-07

    Polymer chains, confined to cavities or polymer layers with dimensions less than the chain radius of gyration, appear in many phenomena, such as gel chromatography, rubber elasticity, viscolelasticity of high molar mass polymer melts, the translocation of polymers through nanopores and nanotubes, polymer adsorption, etc. Thus, the description of how the constraints alter polymer thermodynamic properties is a recurrent theoretical problem. A realistic treatment requires the incorporation of impenetrable interacting (attractive or repulsive) boundaries, a process that introduces significant mathematical complications. The standard approach involves developing the generalized diffusion equation description of the interaction of flexible polymers with impenetrable confining surfaces into a discrete eigenfunction expansion, where the solutions are normally truncated at the first mode (the "ground state dominance" approximation). This approximation is mathematically well justified under conditions of strong confinement, i.e., a confinement length scale much smaller than the chain radius of gyration, but becomes unreliable when the polymers are confined to dimensions comparable to their typically nanoscale size. We extend a general approach to describe polymers under conditions of weak to moderate confinement and apply this semianalytic method specifically to determine the thermodynamics and static structure factor for a flexible polymer confined between impenetrable interacting parallel plate boundaries. The method is first illustrated by analyzing chain partitioning between a pore and a large external reservoir, a model system with application to chromatography. Improved agreement is found for the partition coefficients of a polymer chain in the pore geometry. An expression is derived for the structure factor S(k) in a slit geometry to assist in more accurately estimating chain dimensions from scattering measurements for thin polymer films.

  18. ''adding'' algorithm for the Markov chain formalism for radiation transfer

    International Nuclear Information System (INIS)

    Esposito, L.W.

    1979-01-01

    The Markov chain radiative transfer method of Esposito and House has been shown to be both efficient and accurate for calculation of the diffuse reflection from a homogeneous scattering planetary atmosphere. The use of a new algorithm similar to the ''adding'' formula of Hansen and Travis extends the application of this formalism to an arbitrarily deep atmosphere. The basic idea for this algorithm is to consider a preceding calculation as a single state of a new Markov chain. Successive application of this procedure makes calculation possible for any optical depth without increasing the size of the linear system used. The time required for the algorithm is comparable to that for a doubling calculation for a homogeneous atmosphere, but for a non-homogeneous atmosphere the new method is considerably faster than the standard ''adding'' routine. As with he standard ''adding'' method, the information on the internal radiation field is lost during the calculation. This method retains the advantage of the earlier Markov chain method that the time required is relatively insensitive to the number of illumination angles or observation angles for which the diffuse reflection is calculated. A technical write-up giving fuller details of the algorithm and a sample code are available from the author

  19. Stochastic entangled chain dynamics of dense polymer solutions.

    Science.gov (United States)

    Kivotides, Demosthenes; Wilkin, S Louise; Theofanous, Theo G

    2010-10-14

    We propose an adjustable-parameter-free, entangled chain dynamics model of dense polymer solutions. The model includes the self-consistent dynamics of molecular chains and solvent by describing the former via coarse-grained polymer dynamics that incorporate hydrodynamic interaction effects, and the latter via the forced Stokes equation. Real chain elasticity is modeled via the inclusion of a Pincus regime in the polymer's force-extension curve. Excluded volume effects are taken into account via the combined action of coarse-grained intermolecular potentials and explicit geometric tracking of chain entanglements. We demonstrate that entanglements are responsible for a new (compared to phantom chain dynamics), slow relaxation mode whose characteristic time scale agrees very well with experiment. Similarly good agreement between theory and experiment is also obtained for the equilibrium chain size. We develop methods for the solution of the model in periodic flow domains and apply them to the computation of entangled polymer solutions in equilibrium. We show that the number of entanglements Π agrees well with the number of entanglements expected on the basis of tube theory, satisfactorily reproducing the latter's scaling of Π with the polymer volume fraction φ. Our model predicts diminishing chain size with concentration, thus vindicating Flory's suggestion of excluded volume effects screening in dense solutions. The predicted scaling of chain size with φ is consistent with the heuristic, Flory theory based value.

  20. Relaxation Dynamics of Nanoparticle-Tethered Polymer Chains

    KAUST Repository

    Kim, Sung A; Mangal, Rahul; Archer, Lynden A.

    2015-01-01

    © 2015 American Chemical Society. Relaxation dynamics of nanoparticle-tethered cis-1,4-polyisoprene (PI) are investigated using dielectric spectroscopy and rheometry. A model system composed of polymer chains densely grafted to spherical SiO2

  1. Nitroxide radicals formed in situ as polymer chain growth regulators

    International Nuclear Information System (INIS)

    Kolyakina, Elena V; Grishin, Dmitry F

    2009-01-01

    Published data on controlled synthesis of macromolecules using nitroxide radicals, formed in situ during polymerization, as polymer chain growth regulators are systematized and generalized. The attention is focused on the mechanism of polymer chain growth control during reversibly inhibited radical homopolymerization and the effect of structure of precursors and regulating additives on the polymerization kinetics of monomers of different nature and the molecular-mass characteristics of the polymers thus formed. The key methods for generation of nitroxide radicals directly during polymerization are considered. The prospects for development and practical use of these approaches for the synthesis of new polymeric materials are evaluated.

  2. Dynamics of dissolved polymer chains in isotropic turbulence

    International Nuclear Information System (INIS)

    Jin Shi; Collins, Lance R

    2007-01-01

    Polymers are remarkable molecules that have relaxation times that can span 15 orders of magnitude. The very longest of the relaxation times for high molecular weight polymers are sufficiently long to overlap with fluid mechanical times scales; under those circumstances, polymers can influence the flow. A well-known example that is still not fully understood is polymer drag reduction. It has been known since Toms (1949 Proc. 1st Int. Congress on Rheology 2 135-41) that parts per million (mass basis) concentrations of polymers can reduce the drag on a solid surface by as much as 80%. Understanding the mechanism of drag reduction requires an understanding of the dynamics of the dissolved polymer chain in response to local fluctuations in the turbulent flow field. We investigate this by using Brownian dynamics simulations of bead-spring models of polymers immersed in a turbulent solvent that is separately computed using direct numerical simulations. We observe that polymer chains with parameters that are effective for drag reduction generally remain stretched for long periods of time and only occasionally relax. The relatively restricted configuration space they sample makes it reasonable to represent their behavior with simpler dumbbell models. We also study the spatial structure of the polymer stresses using a Lagrangian strategy. The results explain the need for relatively high spatial resolution for numerical simulations of polymer flows

  3. Specific Interaction between Redox Phospholipid Polymers and Plastoquinone in Photosynthetic Electron Transport Chain.

    Science.gov (United States)

    Tanaka, Kenya; Kaneko, Masahiro; Ishikawa, Masahito; Kato, Souichiro; Ito, Hidehiro; Kamachi, Toshiaki; Kamiya, Kazuhide; Nakanishi, Shuji

    2017-04-19

    Redox phospholipid polymers added in culture media are known to be capable of extracting electrons from living photosynthetic cells across bacterial cell membranes with high cytocompatibility. In the present study, we identify the intracellular redox species that transfers electrons to the polymers. The open-circuit electrochemical potential of an electrolyte containing the redox polymer and extracted thylakoid membranes shift to positive (or negative) under light irradiation, when an electron transport inhibitor specific to plastoquinone is added upstream (or downstream) in the photosynthetic electron transport chain. The same trend is also observed for a medium containing living photosynthetic cells of Synechococcus elongatus PCC7942. These results clearly indicate that the phospholipid redox polymers extract photosynthetic electrons mainly from plastoquinone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Relaxation Dynamics of Nanoparticle-Tethered Polymer Chains

    KAUST Repository

    Kim, Sung A

    2015-09-08

    © 2015 American Chemical Society. Relaxation dynamics of nanoparticle-tethered cis-1,4-polyisoprene (PI) are investigated using dielectric spectroscopy and rheometry. A model system composed of polymer chains densely grafted to spherical SiO2 nanoparticles to form self-suspended suspensions facilitates detailed studies of slow global chain and fast segmental mode dynamics under surface and geometrical confinement-from experiments performed in bulk materials. We report that unentangled polymer molecules tethered to nanoparticles relax far more slowly than their tethered entangled counterparts. Specifically, at fixed grafting density we find, counterintuitively, that increasing the tethered polymer molecular weight up to values close to the entanglement molecular weight speeds up chain relaxation dynamics. Decreasing the polymer grafting density for a fixed molecular weight has the opposite effect: it dramatically slows down chain relaxation, increases interchain coupling, and leads to a transition in rheological response from simple fluid behavior to viscoelastic fluid behavior for tethered PI chains that are unentangled by conventional measures. Increasing the measurement temperature produces an even stronger elastic response and speeds up molecular relaxation at a rate that decreases with grafting density and molecular weight. These observations are discussed in terms of chain confinement driven by crowding between particles and by the existence of an entropic attractive force produced by the space-filling constraint on individual chains in a self-suspended material. Our results indicate that the entropic force between densely grafted polymer molecules couples motions of individual chains in an analogous manner to reversible cross-links in associating polymers.

  5. Polymer ultrapermeability from the inefficient packing of 2D chains

    Science.gov (United States)

    Rose, Ian; Bezzu, C. Grazia; Carta, Mariolino; Comesaña-Gándara, Bibiana; Lasseuguette, Elsa; Ferrari, M. Chiara; Bernardo, Paola; Clarizia, Gabriele; Fuoco, Alessio; Jansen, Johannes C.; Hart, Kyle E.; Liyana-Arachchi, Thilanga P.; Colina, Coray M.; McKeown, Neil B.

    2017-09-01

    The promise of ultrapermeable polymers, such as poly(trimethylsilylpropyne) (PTMSP), for reducing the size and increasing the efficiency of membranes for gas separations remains unfulfilled due to their poor selectivity. We report an ultrapermeable polymer of intrinsic microporosity (PIM-TMN-Trip) that is substantially more selective than PTMSP. From molecular simulations and experimental measurement we find that the inefficient packing of the two-dimensional (2D) chains of PIM-TMN-Trip generates a high concentration of both small (Gas permeability data for PIM-TMN-Trip surpass the 2008 Robeson upper bounds for O2/N2, H2/N2, CO2/N2, H2/CH4 and CO2/CH4, with the potential for biogas purification and carbon capture demonstrated for relevant gas mixtures. Comparisons between PIM-TMN-Trip and structurally similar polymers with three-dimensional (3D) contorted chains confirm that its additional intrinsic microporosity is generated from the awkward packing of its 2D polymer chains in a 3D amorphous solid. This strategy of shape-directed packing of chains of microporous polymers may be applied to other rigid polymers for gas separations.

  6. Quantum criticality and duality in the Sachdev-Ye-Kitaev/AdS2 chain

    Science.gov (United States)

    Jian, Shao-Kai; Xian, Zhuo-Yu; Yao, Hong

    2018-05-01

    We show that the quantum critical point (QCP) between a diffusive metal and ferromagnetic (or antiferromagnetic) phases in the SYK chain has a gravitational description corresponding to the double-trace deformation in an AdS2 chain. Specifically, by studying a double-trace deformation of a Z2 scalar in an AdS2 chain where the Z2 scalar is dual to the order parameter in the SYK chain, we find that the susceptibility and renormalization group equation describing the QCP in the SYK chain can be exactly reproduced in the holographic model. Our results suggest that the infrared geometry in the gravity theory dual to the diffusive metal of the SYK chain is also an AdS2 chain. We further show that the transition in SYK model captures universal information about double-trace deformation in generic black holes with near horizon AdS2 space-time.

  7. Chain confinement, phase transitions, and lamellar structure in semicrystalline polymers, polymer blends and polymer nanocomposites

    Science.gov (United States)

    Chen, Huipeng

    and is applied to the iPS/atactic polystyrene, aPS, blends. The fractions of MAF inside and outside the lamellar stacks were quantified for the first time. For A/B binary polymer blends, it has been reported that if B is already crystalline, the crystalline fraction would serve as a restriction on the subsequent growth of the crystallizable partner A, while amorphous fraction could be diffused from the crystalline growth front of the crystallizing A component. Considering the effect of RAF on binary blends, a new concept is provided: like the crystals, the RAF of one polymer component may inhibit the growth of crystals of the other blend partner. The non-isothermal crystallization of PET/poly(lactic acid), PLA, blends were investigated and the results confirmed the new concept is correct: PET forms a large amount of RAF and inhibits crystal formation in PLA. Then, we broadened the concept of RAF and investigated the RAF in recent 'hot' materials, polymer nanocomposites. It was found the fraction of RAF greatly increased with a small amount of multi-wall carbon nanotubes, MWCNT, loading in PET electrospun, ES, fibers. A general model is given for polymer ES fibers with MWCNTs: the addition of MWCNTs causes polymer chains in the ES fibers to become more extended, (ie, more stretched), resulting in more confinement of PET chains and an increase in the RAF.

  8. New polymer systems: Chain extension by dianhydrides

    Science.gov (United States)

    Rhein, R. A.; Ingham, J. D.

    1974-01-01

    Three anhydrides provide effective chain extension of hydroxy-terminated polyalkylene oxides and polybutadienes. Novel feature of these anhydride reactants is that they are difunctional as anhydrides, but they are tetrafunctional if conditions are selected that lead to total esterification or reaction of all carboxyl groups.

  9. Rouse mode analysis of chain relaxation in polymer nanocomposites.

    Science.gov (United States)

    Kalathi, Jagannathan T; Kumar, Sanat K; Rubinstein, Michael; Grest, Gary S

    2015-05-28

    Large-scale molecular dynamics simulations are used to study the internal relaxations of chains in nanoparticle (NP)/polymer composites. We examine the Rouse modes of the chains, a quantity that is closest in spirit to the self-intermediate scattering function, typically determined in an (incoherent) inelastic neutron scattering experiment. Our simulations show that for weakly interacting mixtures of NPs and polymers, the effective monomeric relaxation rates are faster than in a neat melt when the NPs are smaller than the entanglement mesh size. In this case, the NPs serve to reduce both the monomeric friction and the entanglements in the polymer melt, as in the case of a polymer-solvent system. However, for NPs larger than half the entanglement mesh size, the effective monomer relaxation is essentially unaffected for low NP concentrations. Even in this case, we observe a strong reduction in chain entanglements for larger NP loadings. Thus, the role of NPs is to always reduce the number of entanglements, with this effect only becoming pronounced for small NPs or for high concentrations of large NPs. Our studies of the relaxation of single chains resonate with recent neutron spin echo (NSE) experiments, which deduce a similar entanglement dilution effect.

  10. Statistical properties of multi-theta polymer chains

    Science.gov (United States)

    Uehara, Erica; Deguchi, Tetsuo

    2018-04-01

    We study statistical properties of polymer chains with complex structures whose chemical connectivities are expressed by graphs. The multi-theta curve of m subchains with two branch points connected by them is one of the simplest graphs among those graphs having closed paths, i.e. loops. We denoted it by θm , and for m  =  2 it is given by a ring. We derive analytically the pair distribution function and the scattering function for the θm -shaped polymer chains consisting of m Gaussian random walks of n steps. Surprisingly, it is shown rigorously that the mean-square radius of gyration for the Gaussian θm -shaped polymer chain does not depend on the number m of subchains if each subchain has the same fixed number of steps. For m  =  3 we show the Kratky plot for the theta-shaped polymer chain consisting of hard cylindrical segments by the Monte-Carlo method including reflection at trivalent vertices.

  11. Single-Chain Folding of Synthetic Polymers: A Critical Update.

    Science.gov (United States)

    Altintas, Ozcan; Barner-Kowollik, Christopher

    2015-11-23

    The current contribution serves as a critical update to a previous feature article from us (Macromol. Rapid Commun. 2012, 33, 958-971), and highlights the latest advances in the preparation of single chain polymeric nanoparticles and initial-yet promising-attempts towards mimicking the structure of natural biomacromolecules via single-chain folding of well-defined linear polymers via so-called single chain selective point folding and repeat unit folding. The contribution covers selected examples from the literature published up to ca. September 2015. Our aim is not to provide an exhaustive review but rather highlight a selection of new and exciting examples for single-chain folding based on advanced macromolecular precision chemistry. Initially, the discussion focuses on the synthesis and characterization of single-chain folded structures via selective point folding. The second part of the feature article addresses the folding of well-defined single-chain polymers by means of repeat unit folding. The current state of the art in the field of single-chain folding indicates that repeat unit folding-driven nanoparticle preparation is well-advanced, while initial encouraging steps towards building selective point folding systems have been taken. In addition, a summary of the-in our view-open key questions is provided that may guide future biomimetic design efforts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. The influence of polymer architectures on the dewetting behavior of thin polymer films: from linear chains to ring chains.

    Science.gov (United States)

    Wang, Lina; Xu, Lin; Liu, Binyuan; Shi, Tongfei; Jiang, Shichun; An, Lijia

    2017-05-03

    The dewetting behavior of ring polystyrene (RPS) film and linear polystyrene (LPS) film on silanized Si substrates with different grafting densities and PDMS substrate was investigated. Results showed that polymer architectures greatly influenced the dewetting behavior of the thin polymer film. On the silanized Si substrate with 69% grafting density, RPS chains exhibited stronger adsorption compared with LPS chains, and as a result the wetting layer formed more easily. For LPS films, with a decreased annealing temperature, the stability of the polymer film changed from non-slip dewetting via apparent slip dewetting to apparently stable. However, for RPS films, the polymer film stability switched from apparent slip dewetting to apparently stable. On the silanized Si substrate with 94% grafting density, the chain adsorption became weaker and the dewetting processes were faster than that on the substrate with 69% grafting density at the same experimental temperature for both the LPS and RPS films. Moreover, on the PDMS substrate, LPS films always showed non-slip dewetting, while the dewetting kinetics of RPS films switched from non-slip dewetting to slip dewetting behaviour. Forming the wetting layer strongly influenced the stability and dewetting behavior of the thin polymer films.

  13. Controlling photophysical properties of ultrasmall conjugated polymer nanoparticles through polymer chain packing

    KAUST Repository

    Piwonski, Hubert Marek

    2017-05-16

    Applications of conjugated polymer nanoparticles (Pdots) for imaging and sensing depend on their size, fluorescence brightness and intraparticle energy transfer. The molecular design of conjugated polymers (CPs) has been the main focus of the development of Pdots. Here we demonstrate that proper control of the physical interactions between the chains is as critical as the molecular design. The unique design of twisted CPs and fine-tuning of the reprecipitation conditions allow us to fabricate ultrasmall (3.0–4.5 nm) Pdots with excellent photostability. Extensive photophysical and structural characterization reveals the essential role played by the packing of the polymer chains in the particles in the intraparticle spatial alignment of the emitting sites, which regulate the fluorescence brightness and the intraparticle energy migration efficiency. Our findings enhance understanding of the relationship between chain interactions and the photophysical properties of CP nanomaterials, providing a framework for designing and fabricating functional Pdots for imaging applications.

  14. Unconventional phase transitions in a constrained single polymer chain

    International Nuclear Information System (INIS)

    Klushin, L I; Skvortsov, A M

    2011-01-01

    Phase transitions were recognized among the most fascinating phenomena in physics. Exactly solved models are especially important in the theory of phase transitions. A number of exactly solved models of phase transitions in a single polymer chain are discussed in this review. These are three models demonstrating the second order phase transitions with some unusual features: two-dimensional model of β-structure formation, the model of coil–globule transition and adsorption of a polymer chain grafted on the solid surface. We also discuss models with first order phase transitions in a single macromolecule which admit not only exact analytical solutions for the partition function with explicit finite-size effects but also the non-equilibrium free energy as a function of the order parameter (Landau function) in closed analytical form. One of them is a model of mechanical desorption of a macromolecule, which demonstrates an unusual first order phase transition with phase coexistence within a single chain. Features of first and second order transitions become mixed here due to phase coexistence which is not accompanied by additional interfacial free energy. Apart from that, there exist several single-chain models belonging to the same class (adsorption of a polymer chain tethered near the solid surface or liquid–liquid interface, and escape transition upon compressing a polymer between small pistons) that represent examples of a highly unconventional first order phase transition with several inter-related unusual features: no simultaneous phase coexistence, and hence no phase boundary, non-concave thermodynamic potential and non-equivalence of conjugate ensembles. An analysis of complex zeros of partition functions upon approaching the thermodynamic limit is presented for models with and without phase coexistence. (topical review)

  15. Communication: Polarizable polymer chain under external electric field in a dilute polymer solution.

    Science.gov (United States)

    Budkov, Yu A; Kolesnikov, A L; Kiselev, M G

    2015-11-28

    We study the conformational behavior of polarizable polymer chain under an external homogeneous electric field within the Flory type self-consistent field theory. We consider the influence of electric field on the polymer coil as well as on the polymer globule. We show that when the polymer chain conformation is a coil, application of external electric field leads to its additional swelling. However, when the polymer conformation is a globule, a sufficiently strong field can induce a globule-coil transition. We show that such "field-induced" globule-coil transition at the sufficiently small monomer polarizabilities goes quite smoothly. On the contrary, when the monomer polarizability exceeds a certain threshold value, the globule-coil transition occurs as a dramatic expansion in the regime of first-order phase transition. The developed theoretical model can be applied to predicting polymer globule density change under external electric field in order to provide more efficient processes of polymer functionalization, such as sorption, dyeing, and chemical modification.

  16. Dynamical behavior of a single polymer chain under nanometric confinement

    Science.gov (United States)

    Lagrené, K.; Zanotti, J.-M.; Daoud, M.; Farago, B.; Judeinstein, P.

    2010-10-01

    We address the dynamical behavior of a single polymer chain under nanometric confinement. We consider a polymer melt made of a mixture of hydrogenated and deuterated high molecular mass Poly(Ethylene Oxide) (PEO). The confining material is a membrane of Anodic Aluminum Oxide (AAO), a macroscopically highly ordered confining system made of parallel cylindrical channels. We use Neutron Spin-Echo (NSE) under the Zero Average Contrast (ZAC) condition to, all at once, i) match the intense porous AAO detrimental elastic SANS (Small Angle Neutron Scattering) contribution to the total intermediate scattering function I(Q,t) and ii) measure the Q dependence of the dynamical modes of a single chain under confinement. The polymer dynamics is probed on an extremely broad spacial ([2.2 10-2 Å-1, 0.2 Å-1]) and temporal ([0.1 ns, 600 ns]) ranges. We do not detect any influence of confinement on the polymer dynamics. This result is discussed in the framework of the debate on the existence of a "corset effect" recently suggested by NMR relaxometry data.

  17. Investigations of model polymers: Dynamics of melts and statics of a long chain in a dilute melt of shorter chains

    International Nuclear Information System (INIS)

    Bishop, M.; Ceperley, D.; Frisch, H.L.; Kalos, M.H.

    1982-01-01

    We report additional results on a simple model of polymers, namely the diffusion in concentrated polymer systems and the static properties of one long chain in a dilute melt of shorter chains. It is found, for the polymer sizes and time scales amenable to our computer calculations, that there is as yet no evidence for a ''reptation'' regime in a melt. There is some indication of reptation in the case of a single chain moving through fixed obstacles. No statistically significant effect of the change, from excluded volume behavior of the long chain to ideal behavior as the shorter chains grow, is observed

  18. Application of dimensional regularization to single chain polymer static properties: Conformational space renormalization of polymers. III

    International Nuclear Information System (INIS)

    Oono, Y.; Ohta, T.; Freed, K.F.

    1981-01-01

    A dimensional regularization approach to the renormalization group treatment of polymer excluded volume is formulated in chain conformation space where monomers are specified by their spatial positions and their positions along the chain and the polymers may be taken to be monodisperse. The method utilizes basic scale invariance considerations. First, it is recognized that long wavelength macroscopic descriptions must be well defined in the limit that the minimum atomic or molecular scale L is set to zero. Secondly, the microscopic theory is independent of the conveniently chosen macroscopic scale of length k. The freedom of choice of k is exploited along with the assumed renormalizability of the theory to provide the renormalization group equations which directly imply the universal scaling laws for macroscopic properties. The renormalizability of the model implies the existence of the general relations between the basic macroparameters, such as chain length, excluded volume, etc., and their microscopic counterparts in the microscopic model for the system. These macro--micro relations are defined through the condition that macroscopic quantities be well defined for polymer chains for any spatial dimensionality. The method is illustrated by calculating the end vector distribution function for all values of end vectors R. The evaluation of this distribution function currently requires the use of expansions in e = 4-d. In this case our distribution reduces to known limits for R→0 or infinity. Subsequent papers will present calculations of the polymer coherent scattering function, the monomer spatial distribution function, and concentration dependent properties

  19. The added value of 3D polymer deposition on textiles

    NARCIS (Netherlands)

    Brinks, G.J. (Ger); Warmoeskerken, M.M.C.G. (Marijn)

    2013-01-01

    The working hypothesis for this research project is that it is possible to develop a new functional polymer printing process for the direct application of conductive polymer onto textiles. We will use the basic extrusion technology that is currently applied in 3D printing. Thus the aim is also

  20. Folding of polymer chains with short-range binormal interactions

    International Nuclear Information System (INIS)

    Craig, A; Terentjev, E M

    2006-01-01

    We study the structure of chains which have anisotropic short-range contact interactions that depend on the alignment of the binormal vectors of chain segments. This represents a crude model of hydrogen bonding or 'stacking' interactions out of the plane of curvature. The polymers are treated as ribbon-like semi-flexible chains, where the plane of the ribbon is determined by the local binormal. We show that with dipole-dipole interactions between the binormals of contacting chain segments, mean-field theory predicts a first-order transition to a binormally aligned state. We describe the onset of this transition as a function of the temperature-dependent parameters that govern the chain stiffness and the strength of the binormal interaction, as well as the binormal alignment's coupling to chain collapse. We also examine a metastable state governing the folding kinetics. Finally, we discuss the possible mesoscopic structure of the aligned phase, and application of our model to secondary structure motifs like β-sheets and α-helices, as well as composite structures like β-(amyloid) fibrils

  1. Charge photogeneration and transport in side-chain carbazole polymers and co-polymers

    KAUST Repository

    Li, Huawei; Termine, Roberto; Godbert, Nicolas; Angiolini, Luigi; Giorgini, Loris; Golemme, Attilio

    2011-01-01

    The photoconductivity, hole mobility and charge photogeneration efficiency of a series of side-chain carbazole homopolymers and copolymers (with azo side-chains) have been investigated. Cyclic voltammetry measurement of frontier orbitals energies show that the HOMO energy is determined by the nature and the position of attachment of the linker between the main chain and the carbazole, the azo-moiety being not relevant in this respect. Hole mobility is not influenced by the HOMO energy but seems to depend on the degree of conformational mobility of the side-chains, reaching values of the order of 10-3cm2V-1s-1 in the best cases. The HOMO energy is instead extremely important when considering photogeneration efficiency, that can change by 10 orders of magnitude depending on the density of the carbazole side-chains in co-polymers and on the linker nature and attachment position. © 2011 Elsevier B.V. All rights reserved.

  2. Charge photogeneration and transport in side-chain carbazole polymers and co-polymers

    KAUST Repository

    Li, Huawei

    2011-07-01

    The photoconductivity, hole mobility and charge photogeneration efficiency of a series of side-chain carbazole homopolymers and copolymers (with azo side-chains) have been investigated. Cyclic voltammetry measurement of frontier orbitals energies show that the HOMO energy is determined by the nature and the position of attachment of the linker between the main chain and the carbazole, the azo-moiety being not relevant in this respect. Hole mobility is not influenced by the HOMO energy but seems to depend on the degree of conformational mobility of the side-chains, reaching values of the order of 10-3cm2V-1s-1 in the best cases. The HOMO energy is instead extremely important when considering photogeneration efficiency, that can change by 10 orders of magnitude depending on the density of the carbazole side-chains in co-polymers and on the linker nature and attachment position. © 2011 Elsevier B.V. All rights reserved.

  3. Segregation of chain ends to polymer melt surfaces and interfaces

    International Nuclear Information System (INIS)

    Zhao, W.; Zhao, X.; Rafailovich, M.H.; Sokolov, J.; Composto, R.J.; Smith, S.D.; Satkowski, M.; Russell, T.P.; Dozier, W.D.; Mansfield, T.

    1993-01-01

    The conformation of polymer chains in the melt near an impenetrable boundary has recently been studied by molecular dynamics and off-lattice Monte Carlo simulations. Both types of calculations show an enhancement of the chain end density within a distance of approximately two polymer segment lengths of the interface relative to the bulk. In the absence of preferential interactions between monomers and the interface, the segregation arises from minimizing the loss of conformational entropy near an impenetrable boundary; i.e., by positioning an end near the surface, only one unit rather than two is reflected. In order to obtain an experimental measure of this effect, monodisperse polystyrene (PS) chains of molecular weight 63 000 with short blocks of deuterated polystyrene (dPS) at each end were prepared. The block length was kept as short as possible, while yet producing sufficient neutron scattering contrast in order to minimize any preferential surface segregation due to isotopic effects. The synthesis was carried out via living anionic polymerization of a purified styrene monomer in cyclohexane at 60 C, utilizing sec-butyllithium as the initiator. The process was terminated using degassed methanol

  4. SANS study of polymer chains in confined space

    International Nuclear Information System (INIS)

    Hasegawa, Hirokazu; Tanaka, Hideaki; Hashimoto, Takeji; Han, C.C.

    1993-01-01

    The lateral and vertical components of the radius of gyration for a single block copolymer chain in the lamellar microdomain space formed by a mixture of diblock copolymers and homopolymers were investigated by means of small-angle neutron scattering (SANS), and the microdomain structures by small-angle X-ray scattering (SAXS). We used the homopolymers whose molecular weights are much smaller than that of the corresponding chains of the block copolymers so that the homopolymers are uniformly solubilized in the corresponding microdomains. The SANS result suggests that the block copolymer chains in the microdomain space are more compressed in the direction parallel to the interface and more stretched in the direction perpendicular to the interface than the corresponding unperturbed polymer chains with the same molecular weight. With increasing the volume fraction of the homopolymers the thickness of the lamellar microdomains increases. The block copolymer chains were found to undergo an isochoric affine deformation on addition of the homopolymers or with the change of the thickness of the lamellar microdomains. (author)

  5. Flow boundary conditions for chain-end adsorbing polymer blends.

    Science.gov (United States)

    Zhou, Xin; Andrienko, Denis; Delle Site, Luigi; Kremer, Kurt

    2005-09-08

    Using the phenol-terminated polycarbonate blend as an example, we demonstrate that the hydrodynamic boundary conditions for a flow of an adsorbing polymer melt are extremely sensitive to the structure of the epitaxial layer. Under shear, the adsorbed parts (chain ends) of the polymer melt move along the equipotential lines of the surface potential whereas the adsorbed additives serve as the surface defects. In response to the increase of the number of the adsorbed additives the surface layer becomes thinner and solidifies. This results in a gradual transition from the slip to the no-slip boundary condition for the melt flow, with a nonmonotonic dependence of the slip length on the surface concentration of the adsorbed ends.

  6. Polymer Chain Dynamics in a Random Environment: Heterogeneous Mobilities

    International Nuclear Information System (INIS)

    Niedzwiedz, K.; Wischnewski, A.; Monkenbusch, M.; Richter, D.; Strauch, M.; Straube, E.; Genix, A.-C.; Arbe, A.; Colmenero, J.

    2007-01-01

    We present a neutron scattering investigation on a miscible blend of two polymers with greatly different glass-transition temperatures T g . Under such conditions, the nearly frozen high-T g component imposes a random environment on the mobile chain. The results demand the consideration of a distribution of heterogeneous mobilities in the material and demonstrate that the larger scale dynamics of the fast component is not determined by the average local environment alone. This distribution of mobilities can be mapped quantitatively on the spectrum of local relaxation rates measured at high momentum transfers

  7. Value-Added Taxes, Chain Effects, and Informality

    OpenAIRE

    Áureo de Paula; Jose A. Scheinkman

    2010-01-01

    This paper investigates determinants of informal economic activity. We present an equilibrium model of informality and test its implications using a survey of 48,000+ small firms in Brazil. We define informality as tax avoidance; firms in the informal sector avoid tax payments but suffer other limitations. A novel theoretical contribution in this model is the role of value added taxes in transmitting informality. It predicts that the informality of a firm is correlated to the informality of f...

  8. Theoretical predictions for side-chain liquid-crystal polymers and comparison to experiment

    International Nuclear Information System (INIS)

    Dowell, F.

    1988-01-01

    This paper presents results from a new unique microscopic molecular theory for side-chain liquid-crystalline polymers (LCPs) in the nematic (N) and multiple smectic-A (SA) LC phases and the isotropic (I) liquid phase. There are no ad hoc or arbitrarily adjustable parameters in this theory. The agreement between the theoretical and experimental values for various properties (including transition temperatures and quadratic characteristic radii) is very good (relative deviations between 0% and less than 6.2%). The theoretical results also show--for the first time--that the N and I phases for these LCPs involve the packing of plate-like sections of backbones and side chains and that the local bilayer SA phase involves packing of side-chains within a plate-like section. This type of packing is predicted to be typical for side-chain LCPs. This theory can predict--for the first time--whether the side chains of a molecule pack on the same or alternating opposite sides of the backbone and whether side chains on different molecules interdigitate (overlap) with each other. 13 refs., 1 fig., 4 tabs

  9. Effect of chain stiffness on the structure of single-chain polymer nanoparticles

    Science.gov (United States)

    Moreno, Angel J.; Bacova, Petra; Lo Verso, Federica; Arbe, Arantxa; Colmenero, Juan; Pomposo, José A.

    2018-01-01

    Polymeric single-chain nanoparticles (SCNPs) are soft nano-objects synthesized by purely intramolecular cross-linking of single polymer chains. By means of computer simulations, we investigate the conformational properties of SCNPs as a function of the bending stiffness of their linear polymer precursors. We investigate a broad range of characteristic ratios from the fully flexible case to those typical of bulky synthetic polymers. Increasing stiffness hinders bonding of groups separated by short contour distances and increases looping over longer distances, leading to more compact nanoparticles with a structure of highly interconnected loops. This feature is reflected in a crossover in the scaling behaviour of several structural observables. The scaling exponents change from those characteristic for Gaussian chains or rings in θ-solvents in the fully flexible limit, to values resembling fractal or ‘crumpled’ globular behaviour for very stiff SCNPs. We characterize domains in the SCNPs. These are weakly deformable regions that can be seen as disordered analogues of domains in disordered proteins. Increasing stiffness leads to bigger and less deformable domains. Surprisingly, the scaling behaviour of the domains is in all cases similar to that of Gaussian chains or rings, irrespective of the stiffness and degree of cross-linking. It is the spatial arrangement of the domains which determines the global structure of the SCNP (sparse Gaussian-like object or crumpled globule). Since intramolecular stiffness can be varied through the specific chemistry of the precursor or by introducing bulky side groups in its backbone, our results propose a new strategy to tune the global structure of SCNPs.

  10. Identifying hubs and spokes in global supply chains using redirected trade in value added

    NARCIS (Netherlands)

    Lejour, Arjan; Rojas-Romagosa, Hugo; Veenendaal, Paul

    2017-01-01

    The increasing importance of global supply chains has prompted the use of analytical tools based on trade in value added - instead of traditional measures in gross value. We use this analytical framework to develop indicators that identify production hubs and supply spokes in global supply chains.

  11. Phase transitions of single polymer chains and of polymer solutions: insights from Monte Carlo simulations

    International Nuclear Information System (INIS)

    Binder, K; Paul, W; Strauch, T; Rampf, F; Ivanov, V; Luettmer-Strathmann, J

    2008-01-01

    The statistical mechanics of flexible and semiflexible macromolecules is distinct from that of small molecule systems, since the thermodynamic limit can also be approached when the number of (effective) monomers of a single chain (realizable by a polymer solution in the dilute limit) is approaching infinity. One can introduce effective attractive interactions into a simulation model for a single chain such that a swollen coil contracts when the temperature is reduced, until excluded volume interactions are effectively canceled by attractive forces, and the chain conformation becomes almost Gaussian at the theta point. This state corresponds to a tricritical point, as the renormalization group theory shows. Below the theta temperature a fluid globule is predicted (at nonzero concentration then phase separation between dilute and semidilute solutions occurs), while at still lower temperature a transition to a solid phase (crystal or glass) occurs. Monte Carlo simulations have shown, however, that the fluid globule phase may become suppressed, when the range of the effective attractive forces becomes too short, with the result that a direct (ultimately first-order) transition from the swollen coil to the solid occurs. This behavior is analogous to the behavior of colloidal particles with a very short range of attractive forces, where liquid-vapor-type phase separation may be suppressed. Analogous first-order transitions from swollen coils to dense rodlike or toroidal structures occur for semiflexible polymers. Finally, the modifications of the behavior discussed when the polymers are adsorbed at surfaces are also mentioned, and possible relations to wetting behavior of polymer solutions are addressed.

  12. Reduced viscosity for flagella moving in a solution of long polymer chains

    Science.gov (United States)

    Zhang, Yuchen; Li, Gaojin; Ardekani, Arezoo M.

    2018-02-01

    The bacterial flagellum thickness is smaller than the radius of gyration of long polymer chain molecules. The flow velocity gradient over the length of polymer chains can be nonuniform and continuum models of polymeric liquids break in this limit. In this work, we use Brownian dynamics simulations to study a rotating helical flagellum in a polymer solution and overcome this limitation. As the polymer size increases, the viscosity experienced by the flagellum asymptotically reduces to the solvent viscosity. The contribution of polymer molecules to the local viscosity in a solution of long polymer chains decreases with the inverse of polymer size to the power 1/2. The difference in viscosity experienced by the bacterial cell body and flagella can predict the nonmonotonic swimming speed of bacteria in polymer solutions.

  13. High Performance All-Polymer Solar Cell via Polymer Side-Chain Engineering

    KAUST Repository

    Zhou, Yan; Kurosawa, Tadanori; Ma, Wei; Guo, Yikun; Fang, Lei; Vandewal, Koen; Diao, Ying; Wang, Chenggong; Yan, Qifan; Reinspach, Julia; Mei, Jianguo; Appleton, Anthony Lucas; Koleilat, Ghada I.; Gao, Yongli; Mannsfeld, Stefan C. B.; Salleo, Alberto; Ade, Harald; Zhao, Dahui; Bao, Zhenan

    2014-01-01

    An average PCE of 4.2% for all-polymer solar cells from 20 devices with an average J SC of 8.8 mA cm-2 are obtained with a donor-acceptor pair despite a low LUMO-LUMO energy offset of less than 0.1 eV. Incorporation of polystyrene side chains into the donor polymer is found to assist in reducing the phase separation domain length scale, and results in more than 20% enhancement of PCE. We observe a direct correlation between the short circuit current (J SC) and the length scale of BHJ phase separation, which is obtained by resonance soft X-ray scattering. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. High Performance All-Polymer Solar Cell via Polymer Side-Chain Engineering

    KAUST Repository

    Zhou, Yan

    2014-03-24

    An average PCE of 4.2% for all-polymer solar cells from 20 devices with an average J SC of 8.8 mA cm-2 are obtained with a donor-acceptor pair despite a low LUMO-LUMO energy offset of less than 0.1 eV. Incorporation of polystyrene side chains into the donor polymer is found to assist in reducing the phase separation domain length scale, and results in more than 20% enhancement of PCE. We observe a direct correlation between the short circuit current (J SC) and the length scale of BHJ phase separation, which is obtained by resonance soft X-ray scattering. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Stretching of a polymer chain anchored to a surface: the massive field theory approach

    International Nuclear Information System (INIS)

    Usatenko, Zoryana

    2014-01-01

    Taking into account the well-known correspondence between the field theoretical φ 4 O(n)-vector model in the limit n → 0 and the behaviour of long-flexible polymer chains, the investigation of stretching of an ideal and a real polymer chain with excluded volume interactions in a good solvent anchored to repulsive and inert surfaces is performed. The calculations of the average stretching force which arises when the free end of a polymer chain moves away from a repulsive or inert surface are performed up to one-loop order of the massive field theory approach in fixed space dimensions d = 3. The analysis of the obtained results indicates that the average stretching force for a real polymer chain anchored to a repulsive surface demonstrates different behaviour for the cases z-tilde ≪1 and z-tilde ≫1, where z-tilde =z ′ /R z . Besides, the results obtained in the framework of the massive field theory approach are in good agreement with previous theoretical results for an ideal polymer chain and results of a density functional theory approach for the region of small applied forces when deformation of a polymer chain in the direction of the applied force is not bigger than the linear extension of a polymer chain in this direction. The better agreement between these two methods is observed in the case where the number of monomers increases and the polymer chain becomes longer. (paper)

  16. Improved power conversion efficiency of dye-sensitized solar cells using side chain liquid crystal polymer embedded in polymer electrolytes

    International Nuclear Information System (INIS)

    Cho, Woosum; Lee, Jae Wook; Gal, Yeong-Soon; Kim, Mi-Ra; Jin, Sung Ho

    2014-01-01

    Side chain liquid crystal polymer (SCLCP) embedded in poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-co-HFP)-based polymer electrolytes (PVdF-co-HFP:side chain liquid crystal polymer (SCLCP)) was prepared for dye-sensitized solar cell (DSSC) application. The polymer electrolytes contained tetrabutylammonium iodide (TBAI), iodine (I 2 ), and 8 wt% PVdF-co-HFP in acetonitrile. DSSCs comprised of PVdF-co-HFP:SCLCP-based polymer electrolytes displayed enhanced redox couple reduction and reduced charge recombination in comparison to those of the conventional PVdF-co-HFP-based polymer electrolyte. The significantly increased short-circuit current density (J sc , 10.75 mA cm −2 ) of the DSSCs with PVdF-co-HFP:SCLCP-based polymer electrolytes afforded a high power conversion efficiency (PCE) of 5.32% and a fill factor (FF) of 0.64 under standard light intensity of 100 mW cm −2 irradiation of AM 1.5 sunlight. - Highlights: • We developed the liquid crystal polymer embedded on polymer electrolyte for DSSCs. • We fabricated the highly efficient DSSCs using polymer electrolyte. • The best PCE achieved for P1 is 5.32% using polymer electrolyte

  17. Improved power conversion efficiency of dye-sensitized solar cells using side chain liquid crystal polymer embedded in polymer electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Woosum [Department of Chemistry Education, and Department of Frontier Materials Chemistry, and Institute for Plastic Information and Energy Materials, Pusan National University, Busan 609-735 (Korea, Republic of); Lee, Jae Wook, E-mail: jlee@donga.ac.kr [Department of Chemistry, Dong-A University, Busan 604-714 (Korea, Republic of); Gal, Yeong-Soon [Polymer Chemistry Lab, College of General Education, Kyungil University, Hayang 712-701 (Korea, Republic of); Kim, Mi-Ra, E-mail: mrkim2@pusan.ac.kr [Department of Polymer Science and Engineering, Pusan National University, Busan 609-735 (Korea, Republic of); Jin, Sung Ho, E-mail: shjin@pusan.ac.kr [Department of Chemistry Education, and Department of Frontier Materials Chemistry, and Institute for Plastic Information and Energy Materials, Pusan National University, Busan 609-735 (Korea, Republic of)

    2014-02-14

    Side chain liquid crystal polymer (SCLCP) embedded in poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-co-HFP)-based polymer electrolytes (PVdF-co-HFP:side chain liquid crystal polymer (SCLCP)) was prepared for dye-sensitized solar cell (DSSC) application. The polymer electrolytes contained tetrabutylammonium iodide (TBAI), iodine (I{sub 2}), and 8 wt% PVdF-co-HFP in acetonitrile. DSSCs comprised of PVdF-co-HFP:SCLCP-based polymer electrolytes displayed enhanced redox couple reduction and reduced charge recombination in comparison to those of the conventional PVdF-co-HFP-based polymer electrolyte. The significantly increased short-circuit current density (J{sub sc}, 10.75 mA cm{sup −2}) of the DSSCs with PVdF-co-HFP:SCLCP-based polymer electrolytes afforded a high power conversion efficiency (PCE) of 5.32% and a fill factor (FF) of 0.64 under standard light intensity of 100 mW cm{sup −2} irradiation of AM 1.5 sunlight. - Highlights: • We developed the liquid crystal polymer embedded on polymer electrolyte for DSSCs. • We fabricated the highly efficient DSSCs using polymer electrolyte. • The best PCE achieved for P1 is 5.32% using polymer electrolyte.

  18. Fluorocarbon polymer formation, characterization, and reduction in polycrystalline-silicon etching with CF4-added plasma

    International Nuclear Information System (INIS)

    Xu Songlin; Sun Zhiwen; Chen Arthur; Qian Xueyu; Podlesnik, Dragan

    2001-01-01

    Addition of CF 4 into HBr-based plasma for polycrystalline-silicon gate etching reduces the deposition of an etch byproduct, silicon oxide, onto the chamber wall but tends to generate organic polymer. In this work, a detailed study has been carried out to analyze the mechanism of polymerization and to characterize the polymer composition and quantity. The study has shown that the polymer formation is due to the F-radical depletion by H atoms dissociated from HBr. The composition of the polymer changes significantly with CF 4 concentration in the gas feed, and the polymer deposition rate depends on CF 4 % and other process conditions such as source power, bias power, and pressure. Surface temperature also affects the polymer deposition rate. Adding O 2 into the plasma can clean the organic polymer, but the O 2 amount has to be well controlled in order to prevent the formation of silicon oxide. Based on a series of tests to evaluate polymer deposition and oxide cleaning with O 2 addition, an optimized process regime in terms of O 2 -to-CF 4 ratio has been identified to simultaneously suppress the polymer and oxide deposition so that the etch process becomes self-cleaning

  19. Equivalence of chain conformations in the surface region of a polymer melt and a single Gaussian chain nder critical conditions

    NARCIS (Netherlands)

    Skvortsov, A.M.; Leermakers, F.A.M.; Fleer, G.J.

    2013-01-01

    In the melt polymer conformations are nearly ideal according to Flory's ideality hypothesis. Silberberg generalized this statement for chains in the interfacial region. We check the Silberberg argument by analyzing the conformations of a probe chain end-grafted at a solid surface in a sea of

  20. Flory-type theories of polymer chains under different external stimuli

    Science.gov (United States)

    Budkov, Yu A.; Kiselev, M. G.

    2018-01-01

    In this Review, we present a critical analysis of various applications of the Flory-type theories to a theoretical description of the conformational behavior of single polymer chains in dilute polymer solutions under a few external stimuli. Different theoretical models of flexible polymer chains in the supercritical fluid are discussed and analysed. Different points of view on the conformational behavior of the polymer chain near the liquid-gas transition critical point of the solvent are presented. A theoretical description of the co-solvent-induced coil-globule transitions within the implicit-solvent-explicit-co-solvent models is discussed. Several explicit-solvent-explicit-co-solvent theoretical models of the coil-to-globule-to-coil transition of the polymer chain in a mixture of good solvents (co-nonsolvency) are analysed and compared with each other. Finally, a new theoretical model of the conformational behavior of the dielectric polymer chain under the external constant electric field in the dilute polymer solution with an explicit account for the many-body dipole correlations is discussed. The polymer chain collapse induced by many-body dipole correlations of monomers in the context of statistical thermodynamics of dielectric polymers is analysed.

  1. Equivalence of chain conformations in the surface region of a polymer melt and a single Gaussian chain under critical conditions.

    Science.gov (United States)

    Skvortsov, A M; Leermakers, F A M; Fleer, G J

    2013-08-07

    In the melt polymer conformations are nearly ideal according to Flory's ideality hypothesis. Silberberg generalized this statement for chains in the interfacial region. We check the Silberberg argument by analyzing the conformations of a probe chain end-grafted at a solid surface in a sea of floating free chains of concentration φ by the self-consistent field (SCF) method. Apart from the grafting, probe chain and floating chains are identical. Most of the results were obtained for a standard SCF model with freely jointed chains on a six-choice lattice, where immediate step reversals are allowed. A few data were generated for a five-choice lattice, where such step reversals are forbidden. These coarse-grained models describe the equilibrium properties of flexible atactic polymer chains at the scale of the segment length. The concentration was varied over the whole range from φ = 0 (single grafted chain) to φ = 1 (probe chain in the melt). The number of contacts with the surface, average height of the free end and its dispersion, average loop and train length, tail size distribution, end-point and overall segment distributions were calculated for a grafted probe chain as a function of φ, for several chain lengths and substrate∕polymer interactions, which were varied from strong repulsion to strong adsorption. The computations show that the conformations of the probe chain in the melt do not depend on substrate∕polymer interactions and are very similar to the conformations of a single end-grafted chain under critical conditions, and can thus be described analytically. When the substrate∕polymer interaction is fixed at the value corresponding to critical conditions, all equilibrium properties of a probe chain are independent of φ, over the whole range from a dilute solution to the melt. We believe that the conformations of all flexible chains in the surface region of the melt are close to those of an appropriate single chain in critical conditions, provided

  2. Effect of backbone structure on charge transport along isolated conjugated polymer chains

    International Nuclear Information System (INIS)

    Siebbeles, Laurens D.A.; Grozema, Ferdinand C.; Haas, Matthijs P. de; Warman, John M.

    2005-01-01

    Fast charge transport in conjugated polymers is essential for their application in opto-electronic devices. In the present paper, measurements and theoretical modeling of the mobility of excess charges along isolated chains of conjugated polymers in dilute solution are presented. Charge carriers were produced by irradiation of the polymer solution with 3-MeV electrons from a Van de Graaff accelerator. The mobilities of the charges along the polymer chains were obtained from time-resolved microwave conductivity measurements. The mobilities are strongly dependent on the chemical nature of the polymer backbone. Comparison of the experimental data with results from ab initio quantum mechanical calculations shows that the measured mobilities are strongly limited by torsional disorder, chemical defects and chain ends. Improvement of the structure of polymer backbones is therefore expected to significantly enhance the performance of these materials in 'plastic electronics'

  3. Polymer chain alignment and transistor properties of nanochannel-templated poly(3-hexylthiophene) nanowires

    Science.gov (United States)

    Oh, Seungjun; Hayakawa, Ryoma; Pan, Chengjun; Sugiyasu, Kazunori; Wakayama, Yutaka

    2016-08-01

    Nanowires of semiconducting poly(3-hexylthiophene) (P3HT) were produced by a nanochannel-template technique. Polymer chain alignment in P3HT nanowires was investigated as a function of nanochannel widths (W) and polymer chain lengths (L). We found that the ratio between chain length and channel width (L/W) was a key parameter as regards promoting polymer chain alignment. Clear dichroism was observed in polarized ultraviolet-visible (UV-Vis) absorption spectra only at a ratio of approximately L/W = 2, indicating that the L/W ratio must be optimized to achieve uniaxial chain alignment in the nanochannel direction. We speculate that an appropriate L/W ratio is effective in confining the geometries and conformations of polymer chains. This discussion was supported by theoretical simulations based on molecular dynamics. That is, the geometry of the polymer chains, including the distance and tilting angles of the chains in relation to the nanochannel surface, was dominant in determining the longitudinal alignment along the nanochannels. Thus prepared highly aligned polymer nanowire is advantageous for electrical carrier transport and has great potential for improving the device performance of field-effect transistors. In fact, a one-order improvement in carrier mobility was observed in a P3HT nanowire transistor.

  4. Molecular dynamics simulation of AFM studies of a single polymer chain

    International Nuclear Information System (INIS)

    Wang Wenhai; Kistler, Kurt A.; Sadeghipour, Keya; Baran, George

    2008-01-01

    Single polymer chain force-extension behavior measured by Atomic Force Microscopy (AFM) was interpreted by molecular dynamics (MD) simulation performed by applying a bead-spring (coarse-graining) model in which the bond potential function between adjacent beads is described by a worm-like chain (WLC) model. Simulation results indicate that caution should be applied when interpreting experimental AFM data, because the data vary depending on the point of AFM tip-polymer chain attachment. This approach offers an effective way for eventual analysis of the mechanical behavior of complex polymer networks

  5. Molecular dynamics simulation of AFM studies of a single polymer chain

    Energy Technology Data Exchange (ETDEWEB)

    Wang Wenhai [Center for Bioengineering and Biomaterials, College of Engineering, Temple University, 1947 N. 12th Street, Philadelphia, PA 19122 (United States); Kistler, Kurt A. [Department of Chemistry, Temple University, 1901 N. 13th Street, Philadelphia, PA 19122 (United States); Sadeghipour, Keya [Center for Bioengineering and Biomaterials, College of Engineering, Temple University, 1947 N. 12th Street, Philadelphia, PA 19122 (United States); Baran, George [Center for Bioengineering and Biomaterials, College of Engineering, Temple University, 1947 N. 12th Street, Philadelphia, PA 19122 (United States)], E-mail: grbaran@temple.edu

    2008-11-24

    Single polymer chain force-extension behavior measured by Atomic Force Microscopy (AFM) was interpreted by molecular dynamics (MD) simulation performed by applying a bead-spring (coarse-graining) model in which the bond potential function between adjacent beads is described by a worm-like chain (WLC) model. Simulation results indicate that caution should be applied when interpreting experimental AFM data, because the data vary depending on the point of AFM tip-polymer chain attachment. This approach offers an effective way for eventual analysis of the mechanical behavior of complex polymer networks.

  6. Single-molecule study on polymer diffusion in a melt state: Effect of chain topology

    KAUST Repository

    Habuchi, Satoshi; Fujiwara, Susumu; Yamamoto, Takuya; Vá cha, Martin; Tezuka, Yasuyuki

    2013-01-01

    We report a new methodology for studying diffusion of individual polymer chains in a melt state, with special emphasis on the effect of chain topology. A perylene diimide fluorophore was incorporated into the linear and cyclic poly(THF)s, and real-time diffusion behavior of individual chains in a melt of linear poly(THF) was measured by means of a single-molecule fluorescence imaging technique. The combination of mean squared displacement (MSD) and cumulative distribution function (CDF) analysis demonstrated the broad distribution of diffusion coefficient of both the linear and cyclic polymer chains in the melt state. This indicates the presence of spatiotemporal heterogeneity of the polymer diffusion which occurs at much larger time and length scales than those expected from the current polymer physics theory. We further demonstrated that the cyclic chains showed marginally slower diffusion in comparison with the linear counterparts, to suggest the effective suppression of the translocation through the threading-entanglement with the linear matrix chains. This coincides with the higher activation energy for the diffusion of the cyclic chains than of the linear chains. These results suggest that the single-molecule imaging technique provides a powerful tool to analyze complicated polymer dynamics and contributes to the molecular level understanding of the chain interaction. © 2013 American Chemical Society.

  7. Single-molecule study on polymer diffusion in a melt state: Effect of chain topology

    KAUST Repository

    Habuchi, Satoshi

    2013-08-06

    We report a new methodology for studying diffusion of individual polymer chains in a melt state, with special emphasis on the effect of chain topology. A perylene diimide fluorophore was incorporated into the linear and cyclic poly(THF)s, and real-time diffusion behavior of individual chains in a melt of linear poly(THF) was measured by means of a single-molecule fluorescence imaging technique. The combination of mean squared displacement (MSD) and cumulative distribution function (CDF) analysis demonstrated the broad distribution of diffusion coefficient of both the linear and cyclic polymer chains in the melt state. This indicates the presence of spatiotemporal heterogeneity of the polymer diffusion which occurs at much larger time and length scales than those expected from the current polymer physics theory. We further demonstrated that the cyclic chains showed marginally slower diffusion in comparison with the linear counterparts, to suggest the effective suppression of the translocation through the threading-entanglement with the linear matrix chains. This coincides with the higher activation energy for the diffusion of the cyclic chains than of the linear chains. These results suggest that the single-molecule imaging technique provides a powerful tool to analyze complicated polymer dynamics and contributes to the molecular level understanding of the chain interaction. © 2013 American Chemical Society.

  8. Specific heat study of quasi-one-dimensional antiferromagnetic model for an organic polymer chain

    International Nuclear Information System (INIS)

    Qu Shaohua; Zhu Lin

    2008-01-01

    The specific heat of an infinite one-dimensional polymer chain bearing periodically arranged side radicals connected to the even sites is studied by means of quantum transfer-matrix method based on a Ising-Heisenberg model. In the absence of the exchange interactions between side radicals and the main chain, the curves of specific heat show a round peak due to the antiferromagnetic excitations for the all antiferromagnetic interactions along the polymer chain. Considering the exchange interactions between the side radicals and the main chain, the curves of the specific heat show double-peak structure for ferromagnetic interactions between the radicals and main chain, indicating that a competition between ferromagnetic and antiferromagnetic interactions and the possibility of the occurrence of the stable ferrimagnetic state along the polymer chain

  9. Evolution of Value Added Chains in Asia Pacific Region and Opportunities for Russia

    Directory of Open Access Journals (Sweden)

    Igor Alekseevich Makarov

    2018-03-01

    Full Text Available This paper examines the changing patterns of transnational value chains in the Asia-Pacific region. The methodology is based on the analysis of data extracted from the OECD – WTO Trade in Value Added Database (2016. The study demonstrates that 1 Asia-Pacific countries show extremely high involvement in the global value chains; 2 intra-Asian value chains develop at a fast pace, reflecting the trend towards regiona-lization of economic ties in Asia-Pacific (caused by the processes of transformation within China, the growing income divergence in the region and the development of regional integration mechanisms; 3 the level of participation in global value chains differs across countries and is subject to constant changes. In particular, Chinese manufacturers are moving to the processes with higher value added, and the role of an ‘assembly shop’ in the region is shifting to the ASEAN countries. Russia’s participation in the value chains in the Asia-Pacific region is currently limited to its role as a supplier of raw materials. High tariffs make manufacturing oriented towards Asia less viable, especially considering that most of Asia-Pacific countries have free trade agreements with each other. However, favorable rules of origin in Asian RTAs as well as good political relations with leading Asian countries in conditions of tensions between them still create some opportunities for involving Russia in regional value chains at the more advanced stages

  10. Effect of short-chain branching on interfacial polymer structure and dynamics under shear flow.

    Science.gov (United States)

    Jeong, Sohdam; Kim, Jun Mo; Cho, Soowon; Baig, Chunggi

    2017-11-22

    We present a detailed analysis on the effect of short-chain branches on the structure and dynamics of interfacial chains using atomistic nonequilibrium molecular dynamics simulations of confined polyethylene melts in a wide range of shear rates. The intrinsically fast random motions of the short branches constantly disturb the overall chain conformation, leading to a more compact and less deformed chain structure of the short-chain branched (SCB) polymer against the imposed flow field in comparison with the corresponding linear polymer. Moreover, such highly mobile short branches along the backbone of the SCB polymer lead to relatively weaker out-of-plane wagging dynamics of interfacial chains, with highly curvy backbone structures in the intermediate flow regime. In conjunction with the contribution of short branches (as opposed to that of the backbone) to the total interfacial friction between the chains and the wall, the SCB polymer shows a nearly constant behavior in the degree of slip (d s ) with respect to shear rate in the weak-to-intermediate flow regimes. On the contrary, in the strong flow regime where irregular chain rotation and tumbling dynamics occur via intensive dynamical collisions between interfacial chains and the wall, an enhancement effect on the chain detachment from the wall, caused by short branches, leads to a steeper increase in d s for the SCB polymer than for the linear polymer. Remarkably, the SCB chains at the interface exhibit two distinct types of rolling mechanisms along the backbone, with a half-dumbbell mesoscopic structure at strong flow fields, in addition to the typical hairpin-like tumbling behavior displayed by the linear chains.

  11. Record high hole mobility in polymer semiconductors via side-chain engineering.

    Science.gov (United States)

    Kang, Il; Yun, Hui-Jun; Chung, Dae Sung; Kwon, Soon-Ki; Kim, Yun-Hi

    2013-10-09

    Charge carrier mobility is still the most challenging issue that should be overcome to realize everyday organic electronics in the near future. In this Communication, we show that introducing smart side-chain engineering to polymer semiconductors can facilitate intermolecular electronic communication. Two new polymers, P-29-DPPDBTE and P-29-DPPDTSE, which consist of a highly conductive diketopyrrolopyrrole backbone and an extended branching-position-adjusted side chain, showed unprecedented record high hole mobility of 12 cm(2)/(V·s). From photophysical and structural studies, we found that moving the branching position of the side chain away from the backbone of these polymers resulted in increased intermolecular interactions with extremely short π-π stacking distances, without compromising solubility of the polymers. As a result, high hole mobility could be achieved even in devices fabricated using the polymers at room temperature.

  12. Cylindrical polymer brushes with dendritic side chains by iterative anionic reactions

    KAUST Repository

    Zhang, Hefeng; Qu, Chengke; He, Junpo

    2015-01-01

    We report in this paper an easy method for the synthesis of cylindrical polymer brushes with dendritic side chains through anionic reaction. The synthesis is accomplished by iteratively grafting a living block copolymer, polyisoprene-. b

  13. Grafted polymers layers: neutral chains to charged chains; Couches de polymeres greffes: des chaines neutres aux chaines chargees

    Energy Technology Data Exchange (ETDEWEB)

    Mir, Y

    1995-09-29

    This work concerns an experimental study, by small angle neutrons scattering, of neutral or charged grafted polymers layers structures. The method consisted in exploiting the acknowledges got on neutral brushes, to reach the problem of grafted polyelectrolyte layers. The difficulty of charged layers making has been, until this day, an important obstacle to the experimental study of these systems. It has been partially resolved in the case of sodium sulfonate polystyrene layers, and allowed to study their structure. (N.C.). 72 refs., 74 figs., 24 tabs.

  14. Surface functionalization of quantum dots with fine-structured pH-sensitive phospholipid polymer chains.

    Science.gov (United States)

    Liu, Yihua; Inoue, Yuuki; Ishihara, Kazuhiko

    2015-11-01

    To add novel functionality to quantum dots (QDs), we synthesized water-soluble and pH-responsive block-type polymers by reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were composed of cytocompatible 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer segments, which contain a small fraction of active ester groups and can be used to conjugate biologically active compounds to the polymer, and pH-responsive poly(2-(N,N-diethylamino) ethyl methacrylate (DEAEMA)) segments. One terminal of the polymer chain had a hydrophobic alkyl group that originated from the RAFT initiator. This hydrophobic group can bind to the hydrophobic layer on the QD surface. A fluorescent dye was conjugated to the polymer chains via the active ester group. The block-type polymers have an amphiphilic nature in aqueous medium. The polymers were thus easily bound to the QD surface upon evaporation of the solvent from a solution containing the block-type polymer and QDs, yielding QD/fluorescence dye-conjugated polymer hybrid nanoparticles. Fluorescence resonance energy transfer (FRET) between the QDs (donors) and the fluorescent dye molecules (acceptors) was used to obtain information on the conformational dynamics of the immobilized polymers. Higher FRET efficiency of the QD/fluorescent dye-conjugated polymer hybrid nanoparticles was observed at pH 7.4 as compared to pH 5.0 due to a stretching-shrinking conformational motion of the poly(DEAEMA) segments in response to changes in pH. We concluded that the block-type MPC polymer-modified nanoparticles could be used to evaluate the pH of cells via FRET fluorescence based on the cytocompatibility of the MPC polymer. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Lattice cluster theory of associating polymers. I. Solutions of linear telechelic polymer chains.

    Science.gov (United States)

    Dudowicz, Jacek; Freed, Karl F

    2012-02-14

    The lattice cluster theory (LCT) for the thermodynamics of a wide array of polymer systems has been developed by using an analogy to Mayer's virial expansions for non-ideal gases. However, the high-temperature expansion inherent to the LCT has heretofore precluded its application to systems exhibiting strong, specific "sticky" interactions. The present paper describes a reformulation of the LCT necessary to treat systems with both weak and strong, "sticky" interactions. This initial study concerns solutions of linear telechelic chains (with stickers at the chain ends) as the self-assembling system. The main idea behind this extension of the LCT lies in the extraction of terms associated with the strong interactions from the cluster expansion. The generalized LCT for sticky systems reduces to the quasi-chemical theory of hydrogen bonding of Panyioutou and Sanchez when correlation corrections are neglected in the LCT. A diagrammatic representation is employed to facilitate the evaluation of the corrections to the zeroth-order approximation from short range correlations. © 2012 American Institute of Physics

  16. Only adding stationary storage to vaccine supply chains may create and worsen transport bottlenecks.

    Science.gov (United States)

    Haidari, Leila A; Connor, Diana L; Wateska, Angela R; Brown, Shawn T; Mueller, Leslie E; Norman, Bryan A; Schmitz, Michelle M; Paul, Proma; Rajgopal, Jayant; Welling, Joel S; Leonard, Jim; Claypool, Erin G; Weng, Yu-Ting; Chen, Sheng-I; Lee, Bruce Y

    2013-01-01

    Although vaccine supply chains in many countries require additional stationary storage and transport capacity to meet current and future needs, international donors tend to donate stationary storage devices far more often than transport equipment. To investigate the impact of only adding stationary storage equipment on the capacity requirements of transport devices and vehicles, we used HERMES (Highly Extensible Resource for Modeling Supply Chains) to construct a discrete event simulation model of the Niger vaccine supply chain. We measured the transport capacity requirement for each mode of transport used in the Niger vaccine cold chain, both before and after adding cold rooms and refrigerators to relieve all stationary storage constraints in the system. With the addition of necessary stationary storage, the average transport capacity requirement increased from 88% to 144% for cold trucks, from 101% to 197% for pickup trucks, and from 366% to 420% for vaccine carriers. Therefore, adding stationary storage alone may worsen or create new transport bottlenecks as more vaccines flow through the system, preventing many vaccines from reaching their target populations. Dynamic modeling can reveal such relationships between stationary storage capacity and transport constraints.

  17. A possibility for generation of two species of charge carriers along main-chain and side-chains for a π-conjugated polymer

    International Nuclear Information System (INIS)

    Kudo, Yuki; Kawabata, Kohsuke; Goto, Hiromasa

    2013-01-01

    Iodide doping produces charge carriers in π-conjugated polymers. Solitons can be generated in the case of polyacetylene, and polarons in the case of aromatic-type conjugated polymers. We synthesized a conjugated main-chain/side-chain polymer, which consists of polyene in the main-chain and aromatic-type conjugated units in the side-chains. Based on the SSH (Su, Schrieffer, Heeger) theoretical model of solitons in one-dimensional conjugated polymers, we experimentally carried out chemical doping to the main-chain/side-chains conjugated polymer. Generation of the charge carriers was examined by electron spin resonance spectroscopy. This study may lead to realization of a dual doping system of solitons and polarons in π-conjugation expanded to two-dimensional directions in polymers.

  18. Synthesis of Main-Chain Chiral Quaternary Ammonium Polymers for Asymmetric Catalysis Using Quaternization Polymerization

    Directory of Open Access Journals (Sweden)

    Md. Masud Parvez

    2012-06-01

    Full Text Available Main-chain chiral quaternary ammonium polymers were successfully synthesized by the quaternization polymerization of cinchonidine dimer with dihalides. The polymerization occurred smoothly under optimized conditions to give novel type of main-chain chiral quaternary ammonium polymers. The catalytic activity of the polymeric chiral organocatalysts was investigated on the asymmetric benzylation of N-(diphenylmethylideneglycine tert-butyl ester.

  19. Brownian dynamics of a protein-polymer chain complex in a solid-state nanopore

    Science.gov (United States)

    Wells, Craig C.; Melnikov, Dmitriy V.; Gracheva, Maria E.

    2017-08-01

    We study the movement of a polymer attached to a large protein inside a nanopore in a thin silicon dioxide membrane submerged in an electrolyte solution. We use Brownian dynamics to describe the motion of a negatively charged polymer chain of varying lengths attached to a neutral protein modeled as a spherical bead with a radius larger than that of the nanopore, allowing the chain to thread the nanopore but preventing it from translocating. The motion of the protein-polymer complex within the pore is also compared to that of a freely translocating polymer. Our results show that the free polymer's standard deviations in the direction normal to the pore axis is greater than that of the protein-polymer complex. We find that restrictions imposed by the protein, bias, and neighboring chain segments aid in controlling the position of the chain in the pore. Understanding the behavior of the protein-polymer chain complex may lead to methods that improve molecule identification by increasing the resolution of ionic current measurements.

  20. Well-defined single-chain polymer nanoparticles via thiol-Michael addition

    NARCIS (Netherlands)

    Kröger, A. Pia P.; Boonen, Roy J.E.A.; Paulusse, Jos M.J.

    2017-01-01

    A synthetic strategy has been developed giving facile access to well-defined single-chain polymer nanoparticles (SCNPs) from styrene-, acrylate- and methacrylate-based polymers. Random copolymers (polydispersity indices 1.10–1.15) of methyl (meth)acrylate, benzyl methacrylate or styrene containing

  1. Influence of polymer chain architecture of poly(vinyl alcohol) on the inhibition of ice recrystallization

    NARCIS (Netherlands)

    Olijve, L.L.C.; Hendrix, M.M.R.M.; Voets, I.K.

    2016-01-01

    Poly(vinyl alcohol) (PVA) is a water-soluble synthetic polymer well-known to effectively block the recrystallization of ice. The effect of polymer chain architecture on the ice recrystallization inhibition (IRI) by PVA remains unexplored. In this work, the synthesis of PVA molecular bottlebrushes is

  2. REGIONAL CHAINS OF ADDED VALUE AS A TOOL OF INDUSTRIAL COOPERATION- COMPETITIVENESS

    Directory of Open Access Journals (Sweden)

    M. E. Guliyev

    2017-01-01

    Full Text Available Objectives. The infrastructural aspects of integrated interaction and factors impacting on the efficiency increase of regional participation  in the creation of added value chains on the example of cooperation  between developed and developing countries during the  implementation of joint production projects are considered.Methods. A factor analysis of the degree of various countries’ involvement into global added value chains is carried out,  taking into account their geographical location, natural resources and openness of markets, as well as the infrastructure, professional knowledge of the workforce, practice of cooperation of  domestic firms with foreign partners and the attractiveness of their investment climate.Results. An evaluation of the integrated potential of individual countries, which could undertake the functions of  integrators and mediators within the implementation of regional  programmes of social and economic development, is presented. The  growth potential is estimated and the role of global creation chains  of added value (AVC revealed as a tool for increasing the  competitiveness of national trade policies. It is determined that,  when adopting the latest technologies, companies strive to geographically approximate the placement of the middle links of added value chains to specialised suppliers, “smart” consumers and scientific centres as a means of maintaining innovation continuity.Conclusion. The countries of the EEU and the CIS have significant potential for developing cooperation in the field of  transition to a model of new economic growth, as well as in the  development and application of regional added value chains. As well  as the extractive sector of the economy of the EEU and CIS  countries, included in the regional added value chains, agriculture, chemical and textile industries, metallurgy, transport  engineering, and services sector have the potential to be key

  3. Real-time observation of conformational switching in single conjugated polymer chains.

    Science.gov (United States)

    Tenopala-Carmona, Francisco; Fronk, Stephanie; Bazan, Guillermo C; Samuel, Ifor D W; Penedo, J Carlos

    2018-02-01

    Conjugated polymers (CPs) are an important class of organic semiconductors that combine novel optoelectronic properties with simple processing from organic solvents. It is important to study CP conformation in solution to understand the physics of these materials and because it affects the properties of solution-processed films. Single-molecule techniques are unique in their ability to extract information on a chain-to-chain basis; however, in the context of CPs, technical challenges have limited their general application to host matrices or semiliquid environments that constrain the conformational dynamics of the polymer. We introduce a conceptually different methodology that enables measurements in organic solvents using the single-end anchoring of polymer chains to avoid diffusion while preserving polymer flexibility. We explore the effect of organic solvents and show that, in addition to chain-to-chain conformational heterogeneity, collapsed and extended polymer segments can coexist within the same chain. The technique enables real-time solvent-exchange measurements, which show that anchored CP chains respond to sudden changes in solvent conditions on a subsecond time scale. Our results give an unprecedented glimpse into the mechanism of solvent-induced reorganization of CPs and can be expected to lead to a new range of techniques to investigate and conformationally manipulate CPs.

  4. Method for conversion of carbohydrate polymers to value-added chemical products

    Science.gov (United States)

    Zhang, Zongchao C [Norwood, NJ; Brown, Heather M [Kennewick, WA; Su, Yu [Richland, WA

    2012-02-07

    Methods are described for conversion of carbohydrate polymers in ionic liquids, including cellulose, that yield value-added chemicals including, e.g., glucose and 5-hydroxylmethylfurfural (HMF) at temperatures below 120.degree. C. Catalyst compositions that include various mixed metal halides are described that are selective for specified products with yields, e.g., of up to about 56% in a single step process.

  5. Flow-induced correlation effects within a linear chain in a polymer melt

    NARCIS (Netherlands)

    Stepanyan, R.; Slot, J.J.M.; Molenaar, J.; Tchesnokov, M.A.

    2005-01-01

    A framework for a consistent description of the flow-induced correlation effects within a linear polymer chain in a melt is proposed. The formalism shows how correlations between chain segments in the flow can be incorporated into a hierarchy of distribution functions for tangent vectors. The

  6. Rational Design of Coordination Polymers with Flexible Oxyethylene Side Chains

    International Nuclear Information System (INIS)

    Choi, Eun Young; Gao, Chunji; Lee, Suck Hyun; Kwon, O Pil

    2012-01-01

    We rationally designed and synthesized metallopolymers with organic 1,4-benzenedicarboxylic acid (BDC) linkers with different lengths of oxyethylene side chains in order to examine the influence of side chains on the coordination characteristics. While in a previous report the BDC linkers with alkyl side chains were found to form three-dimensional (3D) isoreticular metal-organic framework (IRMOF) structures or one-dimensional (1D) coordination polymeric structures with short -O(CH 2 ) 6 CH 3 or long -O(CH 2 ) 9 CH 3 side chains, respectively, new BDC linkers with oxyethylene side chains of the same lengths, -(OCH 2 CH 2 ) 2 CH 3 and -(OCH 2 CH 2 ) 3 CH 3 , form only 3D IRMOF structures. This result is attributed to the higher flexibility and smaller volume of oxyethylene side chains compared to alkyl side chains

  7. New theories for smectic and nematic liquid-crystal polymers: Backbone LCPs [liquid crystalline polymers] and their mixtures and side-chain LCPs

    International Nuclear Information System (INIS)

    Dowell, F.

    1987-01-01

    A summary of predictions and explanations from statistical-physics theories for both backbone and side-chain liquid crystalline polymers (LCPs) and for mixtures with backbone LCPs are presented. Trends in the thermodynamic and molecular ordering properties have been calculated as a function of pressure, density, temperature, and molecule chemical structures (including degree of polymerization and the following properties of the chemical structures of the repeat units: lengths and shapes, intra-chain rotation energies, dipole moments, site-site polarizabilities and Lennard-Jones potentials, etc.) in nematic and multiple smectic-A LC phases and in the isotropic liquid phase. The theoretical results are found to be in good agreement with existing experimental data. These theories can also be applied to combined LCPs. Since these theories have no ad hoc or arbitrarily adjustable parameters, these theories can be used to design new LCPs and new solvents as well as to predict and explain properties. 27 refs., 4 tabs

  8. Restrictions in Model Reduction for Polymer Chain Models in Dissipative Particle Dynamics

    KAUST Repository

    Moreno Chaparro, Nicolas

    2014-06-06

    We model high molecular weight homopolymers in semidilute concentration via Dissipative Particle Dynamics (DPD). We show that in model reduction methodologies for polymers it is not enough to preserve system properties (i.e., density ρ, pressure p, temperature T, radial distribution function g(r)) but preserving also the characteristic shape and length scale of the polymer chain model is necessary. In this work we apply a DPD-model-reduction methodology for linear polymers recently proposed; and demonstrate why the applicability of this methodology is limited upto certain maximum polymer length, and not suitable for solvent coarse graining.

  9. Restrictions in Model Reduction for Polymer Chain Models in Dissipative Particle Dynamics

    KAUST Repository

    Moreno Chaparro, Nicolas; Nunes, Suzana Pereira; Calo, Victor M.

    2014-01-01

    We model high molecular weight homopolymers in semidilute concentration via Dissipative Particle Dynamics (DPD). We show that in model reduction methodologies for polymers it is not enough to preserve system properties (i.e., density ρ, pressure p, temperature T, radial distribution function g(r)) but preserving also the characteristic shape and length scale of the polymer chain model is necessary. In this work we apply a DPD-model-reduction methodology for linear polymers recently proposed; and demonstrate why the applicability of this methodology is limited upto certain maximum polymer length, and not suitable for solvent coarse graining.

  10. A stability study of polymer solar cells using conjugated polymers with different donor or acceptor side chain patterns

    DEFF Research Database (Denmark)

    Heckler, Ilona Maria; Kesters, Jurgen; Defour, Maxime

    2016-01-01

    -phenylethyl group. It is shown that the exchange of the hexyl chain on the DTBT moiety has a negative impact on the stability of the polymer as well as on the performance of the resulting PSCs. On the other hand, partial exchange of the 2-hexyldecyl side chain of the BDT unit by a 2-hydroxyethyl group results......)benzo[c][1,2,5]thiadiazole (DTBT), specifically selected because of its suitability for roll-coating in the ambient environment, is investigated in terms of operational stability via partial exchange (5 or 10%) of the alkyl side chain on either the donor or the acceptor monomer with a 2-hydroxyethyl or 2...

  11. The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells

    DEFF Research Database (Denmark)

    Heckler, Ilona Maria; Kesters, Jurgen; Defour, Maxime

    2016-01-01

    ]thiazole (TzTz) acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10%) of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio...... studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable) TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear......The stability of polymer solar cells (PSCs) can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyl)dialkoxybenzene donor and benzo[c][1,2,5]thiadiazole (BT) or thiazolo[5,4-d...

  12. Effect of Chain Conformation on the Single-Molecule Melting Force in Polymer Single Crystals: Steered Molecular Dynamics Simulations Study.

    Science.gov (United States)

    Feng, Wei; Wang, Zhigang; Zhang, Wenke

    2017-02-28

    Understanding the relationship between polymer chain conformation as well as the chain composition within the single crystal and the mechanical properties of the corresponding single polymer chain will facilitate the rational design of high performance polymer materials. Here three model systems of polymer single crystals, namely poly(ethylene oxide) (PEO), polyethylene (PE), and nylon-66 (PA66) have been chosen to study the effects of chain conformation, helical (PEO) versus planar zigzag conformation (PE, PA66), and chain composition (PE versus PA66) on the mechanical properties of a single polymer chain. To do that, steered molecular dynamics simulations were performed on those polymer single crystals by pulling individual polymer chains out of the crystals. Our results show that the patterns of force-extension curve as well as the chain moving mode are closely related to the conformation of the polymer chain in the single crystal. In addition, hydrogen bonds can enhance greatly the force required to stretch the polymer chain out of the single crystal. The dynamic breaking and reformation of multivalent hydrogen bonds have been observed for the first time in PA66 at the single molecule level.

  13. Nature of the Binding Interactions between Conjugated Polymer Chains and Fullerenes in Bulk Heterojunction Organic Solar Cells

    KAUST Repository

    Ravva, Mahesh Kumar; Wang, Tonghui; Bredas, Jean-Luc

    2016-01-01

    Blends of π-conjugated polymers and fullerene derivatives are ubiquitous as the active layers of organic solar cells. However, a detailed understanding of the weak noncovalent interactions at the molecular level between the polymer chains

  14. State of mixing of deuterated and non-deuterated block polymer chains

    International Nuclear Information System (INIS)

    Hasegawa, Hirokazu; Hashimoto, Takeji

    1984-01-01

    Prior to the small-angle neutron scattering study on the conformation of block polymer chains in the domain space, the state of mixing of two block polymers, an ordinary polystyrene-polyisoprene diblock polymer and a poly(deuterated styrene)-polyisoprene diblock polymer with a different molecular weight and composition, was investigated by a small-angle X-ray scattering (SAXS) technique. Only one kind of domain structure was observed for each blend, and the domain spacings obtained by SAXS were proportional to the two-thirds power of the number-average molecular weight of the blends (reduced to non-deuterated block polymer). The volume fractions of polystyrene domain in the blends evaluated by computer simulation of SAXS profiles well agreed with the values estimated from blend composition. All these facts suggest the molecular mixing of the two block polymers in the domain space. (author)

  15. Parallelized event chain algorithm for dense hard sphere and polymer systems

    International Nuclear Information System (INIS)

    Kampmann, Tobias A.; Boltz, Horst-Holger; Kierfeld, Jan

    2015-01-01

    We combine parallelization and cluster Monte Carlo for hard sphere systems and present a parallelized event chain algorithm for the hard disk system in two dimensions. For parallelization we use a spatial partitioning approach into simulation cells. We find that it is crucial for correctness to ensure detailed balance on the level of Monte Carlo sweeps by drawing the starting sphere of event chains within each simulation cell with replacement. We analyze the performance gains for the parallelized event chain and find a criterion for an optimal degree of parallelization. Because of the cluster nature of event chain moves massive parallelization will not be optimal. Finally, we discuss first applications of the event chain algorithm to dense polymer systems, i.e., bundle-forming solutions of attractive semiflexible polymers

  16. a European Global Navigation Satellite System — the German Market and Value Adding Chain Effects

    Science.gov (United States)

    Vollerthun, A.; Wieser, M.

    2002-03-01

    Since Europe is considering to establish a "market-driven" European Global Navigation Satellite System, the German Center of Aerospace initiated a market research to justify a German investment in such a European project. The market research performed included the following market segments: aviation, railway, road traffic, shipping, surveying, farming, military, space applications, leisure, and sport. In these market segments, the forementioned inputs were determined for satellite navigation hardware (receivers) as well as satellite navigation services. The forecast period was from year 2007 to 2017. For the considered period, the market amounts to a total of DM 83.0 billion (approx. US $50 billion), whereas the satellite navigation equipment market makes up DM 39.8 billion, and charges for value-added-services amount to DM 43.2 billion. On closer examination road traffic can be identified as the dominant market share, both in the receiver-market and service-market. With a share of 96% for receivers and 73% for services the significance of the road traffic segment becomes obvious. The second part of this paper investigates the effects the market potential has on the Value-Adding-Chain. Therefore, all participants in the Value-Adding-Chain are identified, using industrial cost structure models the employment effect is analyzed, and possible tax revenues for the state are examined.

  17. The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells.

    Science.gov (United States)

    Heckler, Ilona M; Kesters, Jurgen; Defour, Maxime; Madsen, Morten V; Penxten, Huguette; D'Haen, Jan; Van Mele, Bruno; Maes, Wouter; Bundgaard, Eva

    2016-03-09

    The stability of polymer solar cells (PSCs) can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyl)dialkoxybenzene donor and benzo[ c ][1,2,5]thiadiazole (BT) or thiazolo[5,4- d ]thiazole (TzTz) acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10%) of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio, a decrease in solar cell efficiency was observed for the BT-based series, whereas the efficiencies for the devices based on the TzTz polymers remained approximately the same. The photochemical degradation rate for PSCs based on the TzTz polymers decreased with an increasing 2-phenylethoxy ratio. Lifetime studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable) TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear trends in the degradation behavior, linked to the copolymer structural changes, could be established at this point, evidencing the complex interplay of events determining PSCs' lifetime.

  18. The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells

    Directory of Open Access Journals (Sweden)

    Ilona M. Heckler

    2016-03-01

    Full Text Available The stability of polymer solar cells (PSCs can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyldialkoxybenzene donor and benzo[c][1,2,5]thiadiazole (BT or thiazolo[5,4-d]thiazole (TzTz acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10% of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio, a decrease in solar cell efficiency was observed for the BT-based series, whereas the efficiencies for the devices based on the TzTz polymers remained approximately the same. The photochemical degradation rate for PSCs based on the TzTz polymers decreased with an increasing 2-phenylethoxy ratio. Lifetime studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear trends in the degradation behavior, linked to the copolymer structural changes, could be established at this point, evidencing the complex interplay of events determining PSCs’ lifetime.

  19. Mechanisms of chain adsorption on porous substrates and critical conditions of polymer chromatography.

    Science.gov (United States)

    Cimino, Richard T; Rasmussen, Christopher J; Brun, Yefim; Neimark, Alexander V

    2016-11-01

    Polymer adsorption is a ubiquitous phenomenon with numerous technological and healthcare applications. The mechanisms of polymer adsorption on surfaces and in pores are complex owing to a competition between various entropic and enthalpic factors. Due to adsorption of monomers to the surface, the chain gains in enthalpy yet loses in entropy because of confining effects. This competition leads to the existence of critical conditions of adsorption when enthalpy gain and entropy loss are in balance. The critical conditions are controlled by the confining geometry and effective adsorption energy, which depends on the solvent composition and temperature. This phenomenon has important implications in polymer chromatography, since the retention at the critical point of adsorption (CPA) is chain length independent. However, the mechanisms of polymer adsorption in pores are poorly understood and there is an ongoing discussion in the theoretical literature about the very existence of CPA for polymer adsorption on porous substrates. In this work, we examine the mechanisms of chain adsorption on a model porous substrate using Monte Carlo (MC) simulations. We distinguish three adsorption mechanisms depending on the chain location: on external surface, completely confined in pores, and also partially confined in pores in so-called "flower" conformations. The free energies of different conformations of adsorbed chains are calculated by the incremental gauge cell MC method that allows one to determine the partition coefficient as a function of the adsorption potential, pore size, and chain length. We confirm the existence of the CPA for chain length independent separation on porous substrates, which is explained by the dominant contributions of the chain adsorption at the external surface, in particular in flower conformations. Moreover, we show that the critical conditions for porous and nonporous substrates are identical and depend only on the surface chemistry. The theoretical

  20. Experimental studies of the dynamic mechanical response of a single polymer chain

    DEFF Research Database (Denmark)

    Thormann, Esben; Evans, Drew R.; Craig, Vincent S. J.

    2006-01-01

    The high-frequency and low-amplitude dynamic mechanical response from a single poly(vinyl alcohol) chain was investigated. Modification of a commercial atomic force microscope enabled high-frequency and low-amplitude periodic deformations of polymer chains during extension to be performed...... mechanical response from poly(vinyl alcohol) does not differ from its static response. This result is not unexpected as poly(vinyl alcohol) is a highly flexible polymer with intramolecular relaxation processes taking place on a short time scale. The choice of a polymer with a fast relaxation allows its...... static properties to be recovered from the dynamic measurements and enables the method suggested in this paper for decoupling the polymer response from the hydrodynamic response to be validated....

  1. Configurational statistics of a polymer chain with random sequence of elements

    International Nuclear Information System (INIS)

    Obukhov, S.P.

    1984-10-01

    It is shown that for a disordered polymer chain the upper critical dimension is d c =3. At d≤3 the effect of randomness increases on large scales due to the space correlations of attractive and repulsive monomers, but it can also be screened by repulsive two- or three-body interaction. The renorm group equations indicate that near the theta point it can be the large dispersion of sizes of polymers which differ only in sequences of elements. (orig.)

  2. Molecular dynamics simulation aiming at interfacial characteristics of polymer chains on nanotubes with different layers

    Science.gov (United States)

    Li, Kun; Gu, Boqin; Zhu, Wanfu

    2017-03-01

    A molecular dynamics (MD) simulations study is performed on multiwalled carbon nanotubes (MWNTs)/acrylonitrile-butadiene rubber (NBR) composites. The physisorption and interfacial characteristics between the various MWNTs and polymer macromolecular chains are identified. The effects of nanotube layers on the nanotubes/polymer interactions are examined. Each of the situation result and surface features is characterized by binding energy (Eb). It is shown that the binding energy (Eb) increase with the number of layers.

  3. Dependence of crystallite formation and preferential backbone orientations on the side chain pattern in PBDTTPD polymers

    KAUST Repository

    El Labban, Abdulrahman

    2014-11-26

    (Figure Presented) Alkyl substituents appended to the π-conjugated main chain account for the solution-processability and film-forming properties of most π-conjugated polymers for organic electronic device applications, including field-effect transistors (FETs) and bulk-heterojunction (BHJ) solar cells. Beyond film-forming properties, recent work has emphasized the determining role that side-chain substituents play on polymer self-assembly and thin-film nanostructural order, and, in turn, on device performance. However, the factors that determine polymer crystallite orientation in thin-films, implying preferential backbone orientation relative to the device substrate, are a matter of some debate, and these structural changes remain difficult to anticipate. In this report, we show how systematic changes in the side-chain pattern of poly(benzo[1,2-b:4,5-b′]dithiophene-alt-thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers can (i) influence the propensity of the polymer to order in the π-stacking direction, and (ii) direct the preferential orientation of the polymer crystallites in thin films (e.g., "face-on" vs "edge-on"). Oriented crystallites, specifically crystallites that are well-ordered in the π-stacking direction, are believed to be a key contributor to improved thin-film device performance in both FETs and BHJ solar cells.

  4. Investigation of the adsorption of polymer chains on amine-functionalized double-walled carbon nanotubes.

    Science.gov (United States)

    Ansari, R; Ajori, S; Rouhi, S

    2015-12-01

    Molecular dynamics (MD) simulations were used to study the adsorption of different polymer chains on functionalized double-walled carbon nanotubes (DWCNTs). The nanotubes were functionalized with two different amines: NH2 (a small amine) and CH2-NH2 (a large amine). Considering three different polymer chains, all with the same number of atoms, the effect of polymer type on the polymer-nanotube interaction was studied. In general, it was found that covalent functionalization considerably improved the polymer-DWCNT interaction. By comparing the results obtained with different polymer chains, it was observed that, unlike polyethylene and polyketone, poly(styrene sulfonate) only weakly interacts with the functionalized DWCNTs. Accordingly, the smallest radius of gyration was obtained with adsorbed poly(styrene sulfonate). It was also observed that the DWCNTs functionalized with the large amine presented more stable interactions with polyketone and poly(styrene sulfonate) than with polyethylene, whereas the DWCNTs functionalized with the small amine showed better interfacial noncovalent bonding with polyethylene.

  5. Synthesis and characterisation of new types of side chain cholesteryl polymers.

    Science.gov (United States)

    Wang, Bin; Du, Haiyan; Zhang, Junhua

    2011-01-01

    A series of cholesterol derivatives have been synthesised via the alkylation reaction of the 3-hydroxyl group with the aliphatic bromide compounds with different chain lengths, namely 3β-alkyloxy-cholesterol. The double bond between the C5 and C6 positions in these cholesterol derivatives was oxidised into epoxy, followed by an epoxy-ring-opening reaction with the treatment with acrylic acid, resulting in a series of 3β-alkyloxy-5α-hydroxy-6β-acryloyloxycholesterol, C(n)OCh (n=1, 2, 4, 6, 8, 10, 12), The acrylate group is connected to the C6 position, which is confirmed by the single crystal structure analysis. The corresponding polymers, PC(n)OCh, were prepared via free radical polymerisation. The structure of monomers and the resulting polymers were characterised with nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). The thermal properties of PC(n)OCh were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). To determine the secondary structure of polymers, circular dichroism (CD) spectra were performed. It was found that not all monomers produce high-molecular-weight polymers because of steric hindrance. However, all polymers have a helical structure, which can be enhanced by increasing the alkoxy chain length. In addition, increasing the alkoxy chain length decreases the glass transition temperature and increases the decomposition temperature of the polymers. Copyright © 2010 Elsevier Inc. All rights reserved.

  6. Covalent bond force profile and cleavage in a single polymer chain

    Science.gov (United States)

    Garnier, Lionel; Gauthier-Manuel, Bernard; van der Vegte, Eric W.; Snijders, Jaap; Hadziioannou, Georges

    2000-08-01

    We present here the measurement of the single-polymer entropic elasticity and the single covalent bond force profile, probed with two types of atomic force microscopes (AFM) on a synthetic polymer molecule: polymethacrylic acid in water. The conventional AFM allowed us to distinguish two types of interactions present in this system when doing force spectroscopic measurements: the first interaction is associated with adsorption sites of the polymer chains onto a bare gold surface, the second interaction is directly correlated to the rupture process of a single covalent bond. All these bridging interactions allowed us to stretch the single polymer chain and to determine the various factors playing a role in the elasticity of these molecules. To obtain a closer insight into the bond rupture process, we moved to a force sensor stable in position when measuring attractive forces. By optimizing the polymer length so as to fulfill the elastic stability conditions, we were able for the first time to map out the entire force profile associated with the cleavage of a single covalent bond. Experimental data coupled with molecular quantum mechanical calculations strongly suggest that the breaking bond is located at one end of the polymer chain.

  7. Abnormal viscoelastic behavior of side-chain liquid-crystal polymers

    Science.gov (United States)

    Gallani, J. L.; Hilliou, L.; Martinoty, P.; Keller, P.

    1994-03-01

    We show that, contrary to what is commonly believed, the isotropic phase of side-chain liquid-crystal polymers has viscoelastic properties which are totally different from those of ordinary flexible melt polymers. The results can be explained by the existence of a transient network created by the dynamic association of mesogenic groups belonging to different chains. The extremely high sensitivity of the compound to the state of the surfaces with which it is in contact offers us an unexpected method of studying surface states.

  8. Effects of alkyl chain positioning on conjugated polymer microstructure and field-effect mobilities

    KAUST Repository

    Schroeder, Bob C.

    2015-07-02

    Solubilizing alkyl chains play a crucial role in the design of semiconducting polymers because they define the materials solubility and processability as well as both the crystallinity and solid-state microstructure. In this paper, we present a scarcely explored design approach by attaching the alkyl side chains on one side (cis-) or on both sides (trans-) of the conjugated backbone. We further investigate the effects of this structural modification on the solid-state properties of the polymers and on the charge-carrier mobilities in organic thin-film transistors. Copyright © Materials Research Society 2015

  9. Effects of alkyl chain positioning on conjugated polymer microstructure and field-effect mobilities

    KAUST Repository

    Schroeder, Bob C.; Nielsen, Christian B.; Westacott, Paul; Smith, Jeremy; Rossbauer, Stephan; Anthopoulos, Thomas D.; Stingelin, Natalie; McCulloch, Iain

    2015-01-01

    Solubilizing alkyl chains play a crucial role in the design of semiconducting polymers because they define the materials solubility and processability as well as both the crystallinity and solid-state microstructure. In this paper, we present a scarcely explored design approach by attaching the alkyl side chains on one side (cis-) or on both sides (trans-) of the conjugated backbone. We further investigate the effects of this structural modification on the solid-state properties of the polymers and on the charge-carrier mobilities in organic thin-film transistors. Copyright © Materials Research Society 2015

  10. Chain propagator, mass, and universality in polymer solutions from Brownian relativity

    International Nuclear Information System (INIS)

    Mezzasalma, Stefano A.

    2005-01-01

    A Lagrangian theory for single chains in polymer solutions is addressed via a recent Brownian relativity. By employing generalized diffusive coordinates, statements of covariance and diffusivity invariance result into free particle Lagrangians, where mass turns out to rise as a universal spacetime property. It descends from lowering diffusivity (or curving spacetime), so identifying a mechanism which conceptually resemble those ruling macromolecular scaling laws. An extended chain propagator recovers the Gaussian end-to-end distribution and, in the limits of time-like and space-like orbits, the dualism for diffusive paths and polymer random-walks

  11. Primitive-path statistics of entangled polymers: mapping multi-chain simulations onto single-chain mean-field models

    International Nuclear Information System (INIS)

    Steenbakkers, Rudi J A; Schieber, Jay D; Tzoumanekas, Christos; Li, Ying; Liu, Wing Kam; Kröger, Martin

    2014-01-01

    We present a method to map the full equilibrium distribution of the primitive-path (PP) length, obtained from multi-chain simulations of polymer melts, onto a single-chain mean-field ‘target’ model. Most previous works used the Doi–Edwards tube model as a target. However, the average number of monomers per PP segment, obtained from multi-chain PP networks, has consistently shown a discrepancy of a factor of two with respect to tube-model estimates. Part of the problem is that the tube model neglects fluctuations in the lengths of PP segments, the number of entanglements per chain and the distribution of monomers among PP segments, while all these fluctuations are observed in multi-chain simulations. Here we use a recently proposed slip-link model, which includes fluctuations in all these variables as well as in the spatial positions of the entanglements. This turns out to be essential to obtain qualitative and quantitative agreement with the equilibrium PP-length distribution obtained from multi-chain simulations. By fitting this distribution, we are able to determine two of the three parameters of the model, which govern its equilibrium properties. This mapping is executed for four different linear polymers and for different molecular weights. The two parameters are found to depend on chemistry, but not on molecular weight. The model predicts a constant plateau modulus minus a correction inversely proportional to molecular weight. The value for well-entangled chains, with the parameters determined ab initio, lies in the range of experimental data for the materials investigated. (paper)

  12. Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

    KAUST Repository

    Abadi, Maram

    2015-08-24

    The motion and relaxation of linear and cyclic polymers under entangled conditions are investigated by means of a newly developed single-molecule tracking technique, cumulative-area (CA) tracking. CA tracking enables simultaneous quantitative characterization of the diffusion mode, diffusion rate, and relaxation time that have been impossible with a widely used conventional single-molecule localization and tracking method, by analyzing cumulative areas occupied by the moving molecule. Using the novel approach, we investigate the motion and relaxation of entangled cyclic polymers, which have been an important but poorly understood question. Fluorescently labeled 42 kbp linear or cyclic tracer dsDNAs in concentrated solutions of unlabeled linear or cyclic DNAs are used as model systems. We show that CA tracking can explicitly distinguish topology-dependent diffusion mode, rate, and relaxation time, demonstrating that the method provides an invaluable tool for characterizing topological interaction between the entangled chains. We further demonstrate that the current models proposed for the entanglement between cyclic polymers which are based on cyclic chains moving through an array of fixed obstacles cannot correctly describe the motion of the cyclic chain under the entangled conditions. Our results rather suggest the mutual relaxation of the cyclic chains, which underscore the necessity of developing a new model to describe the motion of cyclic polymer under the entangled conditions based on the mutual interaction of the chains.

  13. Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

    KAUST Repository

    Abadi, Maram; Serag, Maged F.; Habuchi, Satoshi

    2015-01-01

    The motion and relaxation of linear and cyclic polymers under entangled conditions are investigated by means of a newly developed single-molecule tracking technique, cumulative-area (CA) tracking. CA tracking enables simultaneous quantitative characterization of the diffusion mode, diffusion rate, and relaxation time that have been impossible with a widely used conventional single-molecule localization and tracking method, by analyzing cumulative areas occupied by the moving molecule. Using the novel approach, we investigate the motion and relaxation of entangled cyclic polymers, which have been an important but poorly understood question. Fluorescently labeled 42 kbp linear or cyclic tracer dsDNAs in concentrated solutions of unlabeled linear or cyclic DNAs are used as model systems. We show that CA tracking can explicitly distinguish topology-dependent diffusion mode, rate, and relaxation time, demonstrating that the method provides an invaluable tool for characterizing topological interaction between the entangled chains. We further demonstrate that the current models proposed for the entanglement between cyclic polymers which are based on cyclic chains moving through an array of fixed obstacles cannot correctly describe the motion of the cyclic chain under the entangled conditions. Our results rather suggest the mutual relaxation of the cyclic chains, which underscore the necessity of developing a new model to describe the motion of cyclic polymer under the entangled conditions based on the mutual interaction of the chains.

  14. Effects of supercritical carbon dioxide on immobile bound polymer chains on solid substrates

    Science.gov (United States)

    Sen, Mani; Asada, Mitsunori; Jiang, Naisheng; Endoh, Maya K.; Akgun, Bulent; Satija, Sushil; Koga, Tadanori

    2013-03-01

    Adsorbed polymer layers formed on flat solid substrates have recently been the subject of extensive studies because it is postulated to control the dynamics of technologically relevant polymer thin films, for example, in lithography. Such adsorbed layers have been reported to hinder the mobility of polymer chains in thin films even at a large length scale. Consequently, this bound layer remains immobile regardless of processing techniques (i.e. thermal annealing, solvent dissolution, etc). Here, we investigate the use of supercritical carbon dioxide (scCO2) as a novel plasticizer for bound polystyrene layers formed on silicon substrates. In-situ swelling and interdiffusion experiments using neutron reflectivity were performed. As a result, we found the anomalous plasticization effects of scCO2 on the bound polymer layers near the critical point where the anomalous adsorption of CO2 molecules in polymer thin films has been reported previously. Acknowledgement: We acknowledge the financial support from NSF Grant No. CMMI-084626.

  15. Efficient Synthesis of Single-Chain Polymer Nanoparticles via Amide Formation

    Directory of Open Access Journals (Sweden)

    Ana Sanchez-Sanchez

    2015-01-01

    Full Text Available Single-chain technology (SCT allows the transformation of individual polymer chains to folded/collapsed unimolecular soft nanoparticles. In this work we contribute to the enlargement of the SCT toolbox by demonstrating the efficient synthesis of single-chain polymer nanoparticles (SCNPs via intrachain amide formation. In particular, we exploit cross-linking between active methylene groups and isocyanate moieties as powerful “click” chemistry driving force for SCNP construction. By employing poly(methyl methacrylate- (PMMA- based copolymers bearing β-ketoester units distributed randomly along the copolymer chains and bifunctional isocyanate cross-linkers, SCNPs were successfully synthesized at r.t. under appropriate reaction conditions. Characterization of the resulting SCNPs was carried out by means of a combination of techniques including size exclusion chromatography (SEC, infrared (IR spectroscopy, proton nuclear magnetic resonance (1H NMR spectroscopy, dynamic light scattering (DLS, and elemental analysis (EA.

  16. Distortion of chain conformation and reduced entanglement in polymer-graphene oxide nanocomposites

    Science.gov (United States)

    Weir, Michael; Boothroyd, Stephen; Johnson, David; Thompson, Richard; Coleman, Karl; Clarke, Nigel

    Graphene and related two-dimensional materials are excellent candidates as filler materials in polymer nanocomposites due to their extraordinary physical properties and high aspect ratio. To explore the mechanism by which the filler affects the bulk properties of these unique systems, and to build understanding from the macromolecular level upwards, we use a combination of small-angle neutron scattering (SANS) and oscillatory rheology. Where a good dispersion is achieved in poly(methyl methacrylate)-graphene oxide (PMMA-GO) nanocomposites, we observe a reduction in the polymer radius of gyration with increasing GO concentration that is consistent with the predicted behavior of polymer melt chains at a solid interface. We use concepts from thin-film polymer physics to formulate a scaling relation for the reduction in entanglements caused by the GO interfaces. Using these scaling arguments, we utilize SANS results to directly estimate the changes to the elastic plateau modulus of the network of entangled polymer chains, and find a correlation with the measured bulk rheology. We present a direct link between interfacial confinement effects and the bulk polymer nanocomposite properties, whilst demonstrating a model system for measuring thin film polymer physics in the bulk.

  17. Synthesis and property characterization of two novel side-chain isoindigo copolymers for polymer solar cells

    Directory of Open Access Journals (Sweden)

    X. Liu

    2015-11-01

    Full Text Available Two novel side-chain conjugated polymers, PTBT-TID and PTBT-TTID, based on the new synthetic thiophene-benzne-thiophene (TBT unit, side-chain isoindigo (ID unit, and the introduced thiophene π-bridge, have been designed and synthesized. The photophysical, electrochemical and photovoltaic properties of the two polymers have been systematically investigated. The two polymers possess relatively good solubility as well as excellent thermal stability up to 380°C, and all of the polymer solar cell (PSC devices based on the two polymers obtain high open circuit voltage (Voc of about 0.8 V. The polymer solar cells based on the polymer PTBT-TID show relatively higher efficiencies than the PTBT-TTID-based ones, due to the broader absorption spectrum, a relatively higher hole mobility, a lower HOMO (the highest occupied molecular orbital energy level, a stronger IPCE (the incident photon to current conversion efficiency response and a better microphase separation, Consequently, the device based on PTBT-TID:PC61BM (1:2, by weight gives the best power conversion efficiency (PCE of 2.04%, with a short-circuit current density (Jsc of 5.39 mA·cm–2, an open-circuit voltage (Voc of 0.83 V, and a fill factor (FF of 0.45.

  18. Impedance study of tea with added taste compounds using conducting polymer and metal electrodes.

    Science.gov (United States)

    Dhiman, Mopsy; Kapur, Pawan; Ganguli, Abhijit; Singla, Madan Lal

    2012-09-01

    In this study the sensing capabilities of a combination of metals and conducting polymer sensing/working electrodes for tea liquor prepared by addition of different compounds using an impedance mode in frequency range 1 Hz-100 KHz at 0.1 V potential has been carried out. Classification of six different tea liquor samples made by dissolving various compounds (black tea liquor + raw milk from milkman), (black tea liquor + sweetened clove syrup), (black tea liquor + sweetened ginger syrup), (black tea liquor + sweetened cardamom syrup), (black tea liquor + sweet chocolate syrup) and (black tea liquor + vanilla flavoured milk without sugar) using six different working electrodes in a multi electrode setup has been studied using impedance and further its PCA has been carried out. Working electrodes of Platinum (Pt), Gold (Au), Silver (Ag), Glassy Carbon (GC) and conducting polymer electrodes of Polyaniline (PANI) and Polypyrrole (PPY) grown on an ITO surface potentiostatically have been deployed in a three electrode set up. The impedance response of these tea liquor samples using number of working electrodes shows a decrease in the real and imaginary impedance values presented on nyquist plots depending upon the nature of the electrode and amount of dissolved salts present in compounds added to tea liquor/solution. The different sensing surfaces allowed a high cross-selectivity in response to the same analyte. From Principal Component Analysis (PCA) plots it was possible to classify tea liquor in 3-4 classes using conducting polymer electrodes; however tea liquors were well separated from the PCA plots employing the impedance data of both conducting polymer and metal electrodes.

  19. Spatial Rearrangement and Mobility Heterogeneity of an Anionic Lipid Monolayer Induced by the Anchoring of Cationic Semiflexible Polymer Chains

    Directory of Open Access Journals (Sweden)

    Xiaozheng Duan

    2016-06-01

    Full Text Available We use Monte Carlo simulations to investigate the interactions between cationic semiflexible polymer chains and a model fluid lipid monolayer composed of charge-neutral phosphatidyl-choline (PC, tetravalent anionic phosphatidylinositol 4,5-bisphosphate (PIP2, and univalent anionic phosphatidylserine (PS lipids. In particular, we explore how chain rigidity and polymer concentration influence the spatial rearrangement and mobility heterogeneity of the monolayer under the conditions where the cationic polymers anchor on the monolayer. We find that the anchored cationic polymers only sequester the tetravalent PIP2 lipids at low polymer concentrations, where the interaction strength between the polymers and the monolayer exhibits a non-monotonic dependence on the degree of chain rigidity. Specifically, maximal anchoring occurs at low polymer concentrations, when the polymer chains have an intermediate degree of rigidity, for which the PIP2 clustering becomes most enhanced and the mobility of the polymer/PIP2 complexes becomes most reduced. On the other hand, at sufficiently high polymer concentrations, the anchoring strength decreases monotonically as the chains stiffen—a result that arises from the pronounced competitions among polymer chains. In this case, the flexible polymers can confine all PIP2 lipids and further sequester the univalent PS lipids, whereas the stiffer polymers tend to partially dissociate from the monolayer and only sequester smaller PIP2 clusters with greater mobilities. We further illustrate that the mobility gradient of the single PIP2 lipids in the sequestered clusters is sensitively modulated by the cooperative effects between anchored segments of the polymers with different rigidities. Our work thus demonstrates that the rigidity and concentration of anchored polymers are both important parameters for tuning the regulation of anionic lipids.

  20. Effect of side chain length on charge transport, morphology, and photovoltaic performance of conjugated polymers in bulk heterojunction solar cells

    NARCIS (Netherlands)

    Duan, C.; Willems, R.E.M.; van Franeker, J.J.; Bruijnaers, B.J.; Wienk, M.M.; Janssen, R.A.J.

    2016-01-01

    The effect of side chain length on the photovoltaic properties of conjugated polymers is systematically investigated with two sets of polymers that bear different alkyl side chain lengths based on benzodithiophene and benzo[2,1,3]thiadiazole or 5,6-difluorobenzo[2,1,3]thiadiazole. Characterization

  1. Adsorption of charged and neutral polymer chains on silica surfaces: The role of electrostatics, volume exclusion, and hydrogen bonding

    NARCIS (Netherlands)

    Spruijt, Evan; Biesheuvel, P.M.; de Vos, Wiebe Matthijs

    2015-01-01

    We develop an off-lattice (continuum) model to describe the adsorption of neutral polymer chains and polyelectrolytes to surfaces. Our continuum description allows taking excluded volume interactions between polymer chains and ions directly into account. To implement those interactions, we use a

  2. Beyond the Born approximation. The case of very long polymer chains adsorbed at an interface

    International Nuclear Information System (INIS)

    Guiselin, O.; Jannink, G.; Cloizeaux, J. des

    1991-01-01

    Two experimental evidences are discussed of the reflectance discontinuity associated with very long adsorbed polymer chains. It is shown that the Born approximation is not valid in this case. The anomalous low reflectivity is compared to the Ramsauer-Townsend effect in the scattering of slow electrons by rare-gas atoms. (author) 15 refs.; 6 figs

  3. Adsorption of flexible polymer chains on a surface: Effects of different solvent conditions

    Science.gov (United States)

    Martins, P. H. L.; Plascak, J. A.; Bachmann, M.

    2018-05-01

    Polymer chains undergoing a continuous adsorption-desorption transition are studied through extensive computer simulations. A three-dimensional self-avoiding walk lattice model of a polymer chain grafted onto a surface has been treated for different solvent conditions. We have used an advanced contact-density chain-growth algorithm, in which the density of contacts can be directly obtained. From this quantity, the order parameter and its fourth-order Binder cumulant are computed, as well as the corresponding critical exponents and the adsorption-desorption transition temperature. As the number of configurations with a given number of surface contacts and monomer-monomer contacts is independent of the temperature and solvent conditions, it can be easily applied to get results for different solvent parameter values without the need of any extra simulations. In analogy to continuous magnetic phase transitions, finite-size-scaling methods have been employed. Quite good results for the critical properties and phase diagram of very long single polymer chains have been obtained by properly taking into account the effects of corrections to scaling. The study covers all solvent effects, going from the limit of super-self-avoiding walks, characterized by effective monomer-monomer repulsion, to poor solvent conditions that enable the formation of compact polymer structures.

  4. Influence of structures of polymer backbones on cooperative photoreorientation behavior of p-cyanoazobenzene side chains

    DEFF Research Database (Denmark)

    Han, Mina; Kidowaki, Masatoshi; Ichimura, Kunihiro

    2001-01-01

    Photoinduced orientational behavior of a polymethacrylate (CN6) and a polyester (p6a12) with p-cyanoazobenzene side chains was studied to reveal the structural effect of the liquid crystalline polymer backbones. Irradiation with linearly polarized W light resulted in the reorientation of the azob...

  5. Chain length distribution and kinetic characteristics of an enzymatically produced polymer

    NARCIS (Netherlands)

    Mulders, K.J.M.; Beeftink, H.H.

    2013-01-01

    Non-processive enzymatic polymerization leads to a distribution of polymer chain lengths. A polymerization model was developed to investigate the relation between the extent of this distribution on one hand, and the polymerization start conditions and reaction kinetics on the other hand. The model

  6. Dependence of crystallite formation and preferential backbone orientations on the side chain pattern in PBDTTPD polymers

    KAUST Repository

    El Labban, Abdulrahman; Warnan, Julien; Cabanetos, Clement; Ratel, Olivier; Tassone, Christopher J.; Toney, Michael F.; Beaujuge, Pierre

    2014-01-01

    -effect transistors (FETs) and bulk-heterojunction (BHJ) solar cells. Beyond film-forming properties, recent work has emphasized the determining role that side-chain substituents play on polymer self-assembly and thin-film nanostructural order, and, in turn, on device

  7. Nanoparticle amount, and not size, determines chain alignment and nonlinear hardening in polymer nanocomposites

    Science.gov (United States)

    Varol, H. Samet; Meng, Fanlong; Hosseinkhani, Babak; Malm, Christian; Bonn, Daniel; Bonn, Mischa; Zaccone, Alessio

    2017-01-01

    Polymer nanocomposites—materials in which a polymer matrix is blended with nanoparticles (or fillers)—strengthen under sufficiently large strains. Such strain hardening is critical to their function, especially for materials that bear large cyclic loads such as car tires or bearing sealants. Although the reinforcement (i.e., the increase in the linear elasticity) by the addition of filler particles is phenomenologically understood, considerably less is known about strain hardening (the nonlinear elasticity). Here, we elucidate the molecular origin of strain hardening using uniaxial tensile loading, microspectroscopy of polymer chain alignment, and theory. The strain-hardening behavior and chain alignment are found to depend on the volume fraction, but not on the size of nanofillers. This contrasts with reinforcement, which depends on both volume fraction and size of nanofillers, potentially allowing linear and nonlinear elasticity of nanocomposites to be tuned independently. PMID:28377517

  8. Self-interacting polymer chains terminally anchored to adsorbing surfaces of three-dimensional fractal lattices

    Science.gov (United States)

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

    2018-01-01

    We have studied the adsorption problem of self-attracting linear polymers, modeled by self-avoiding walks (SAWs), situated on three-dimensional fractal structures, exemplified by 3d Sierpinski gasket (SG) family of fractals as containers of a poor solvent. Members of SG family are enumerated by an integer b (b ≥ 2), and it is assumed that one side of each SG fractal is an impenetrable adsorbing surface. We calculate the critical exponents γ1 ,γ11, and γs, which are related to the numbers of all possible SAWs with one, both, and no ends anchored to the adsorbing boundary, respectively. By applying the exact renormalization group (RG) method (for the first three members of the SG fractal family, b = 2 , 3, and 4), we have obtained specific values of these exponents, for θ-chain and globular polymer phase. We discuss their mutual relations and relations with corresponding values pertinent to extended polymer chain phase.

  9. Main chain acid-degradable polymers for the delivery of bioactive materials

    Science.gov (United States)

    Frechet, Jean M. J. [Oakland, CA; Standley, Stephany M [Evanston, IL; Jain, Rachna [Milpitas, CA; Lee, Cameron C [Cambridge, MA

    2012-03-20

    Novel main chain acid degradable polymer backbones and drug delivery systems comprised of materials capable of delivering bioactive materials to cells for use as vaccines or other therapeutic agents are described. The polymers are synthesized using monomers that contain acid-degradable linkages cleavable under mild acidic conditions. The main chain of the resulting polymers readily degrade into many small molecules at low pH, but remain relatively stable and intact at physiological pH. The new materials have the common characteristic of being able to degrade by acid hydrolysis under conditions commonly found within the endosomal or lysosomal compartments of cells thereby releasing their payload within the cell. The materials can also be used for the delivery of therapeutics to the acidic regions of tumors and other sites of inflammation.

  10. Semi-crystalline photovoltaic polymers with siloxane-terminated hybrid side-chains

    Institute of Scientific and Technical Information of China (English)

    Yuxiang Li; Seyeong Song; Song Yi Park; Jin Young Kim; Han Young Woo

    2017-01-01

    Three types of semi-cry stalline photovoltaic polymers were synthesized by incorporating a siloxane-terminated organic/inorganic hybrid side-chain and changing the number of fluorine substituents.A branch point away from a polymer main backbone in the siloxane-containing side-chains and the intra-and/or interchain noncovalent coulombic interactions enhance a chain planarity and facile interchain organization.The resulting polymers formed strongly agglomerated films with high roughness,suggesting strong intermolecular interactions.The optical band gap of ca.1.7 eV was measured for all polymers with a pronounced shoulder peak due to tight π-π stacking.With increasing the fluorine substituents,the frontier energy levels decreased and preferential face-on orientation was observed.The siloxane-terminated side-chains and fluorine substitution promoted the intermolecular packing,showing well resolved lamellar scatterings up to(300) for this series of polymers in the grazing incidence wide angle X-ray scattering measurements.The PPsiDTBT,PPsiDTFBT and PPsiDT2 FBT devices showed a power conversion efficiency of 3.16%,4.40%and 5.65%,respectively,by blending with PC71BM.Langevin-type bimolecular charge recombination was similar for three polymeric solar cells.The main loss in the photocurrent generation for PPsiDTBT:PC71BM was interpreted to originate from the trap assisted charge recombination by measuring light-intensity dependent short-circuit current density(JSC) and open-circuit voltage(VOc).Our results provide a new insight into the rational selection of solubilizing substituents for optimizing crystalline interchain packing with appropriate miscibility with PC71 BM for further optimizing polymer solar cells.

  11. Semi-crystalline photovoltaic polymers with siloxane-terminated hybrid side-chains

    Institute of Scientific and Technical Information of China (English)

    Yuxiang Li; Seyeong Song; Song Yi Park; Jin Young Kim; Han Young Woo

    2017-01-01

    Three types of semi-crystalline photovoltaic polymers were synthesized by incorporating a siloxane-terminated organic/inorganic hybrid side-chain and changing the number of fluorine substituents.A branch point away from a polymer main backbone in the siloxane-containing side-chains and the intra-and/or interchain noncovalent coulombic interactions enhance a chain planarity and facile interchain organization.The resulting polymers formed strongly agglomerated films with high roughness,suggesting strong intermolecular interactions.The optical band gap of ca.1.7 eV was measured for all polymers with a pronounced shoulder peak due to tight π-π stacking.With increasing the fluorine substituents,the frontier energy levels decreased and preferential face-on orientation was observed.The siloxane-terminated side-chains and fluorine substitution promoted the intermolecular packing,showing well resolved lamellar scatterings up to (300) for this series of polymers in the grazing incidence wide angle X-ray scattering measurements.The PPsiDTBT,PPsiDTFBT and PPsiDT2FBT devices showed a power conversion efficiency of 3.16%,4.40% and 5.65%,respectively,by blending with PC71BM.Langevin-type bimolecular charge recombination was similar for three polymeric solar cells.The main loss in the photocurrent generation for PPsiDTBT:PC71BM was interpreted to originate from the trap assisted charge recombination by measuring light-intensity dependent short-circuit current density (Jsc) and open-circuit voltage (Voc).Our results provide a new insight into the rational selection of solubilizing substituents for optimizing crystalline interchain packing with appropriate miscibility with PC71BM for further optimizing polymer solar cells.

  12. On the chain length dependence of local correlations in polymer melts and a perturbation theory of symmetric polymer blends.

    Science.gov (United States)

    Morse, David C; Chung, Jun Kyung

    2009-06-14

    The self-consistent field (SCF) approach to the thermodynamics of dense polymer liquids is based on the idea that short-range correlations in a polymer liquid are almost independent of how monomers are connected into polymers over larger scales. Some limits of this idea are explored in the context of a perturbation theory for symmetric polymer blends. We consider mixtures of two structurally identical polymers, A and B, in which the AB monomer pair interaction differs slightly from the AA and BB interactions by an amount proportional to a parameter alpha. An expansion of the free energy to first order in alpha yields an excess free energy of mixing per monomer of the form alphaz(N)phi(A)phi(B) in both lattice and continuum models, where z(N) is a measure of the number of intermolecular near neighbors per monomer in a one-component (alpha=0) reference liquid with chains of length N. The quantity z(N) decreases slightly with increasing N because the concentration of intramolecular near neighbors is slightly higher for longer chains, creating a slightly deeper intermolecular correlation hole. We predict that z(N)=z(infinity)[1+betaN(-1/2)], where N is an invariant degree of polymerization and beta=(6/pi)(3/2) is a universal coefficient. This and related predictions about the slight N dependence of local correlations are confirmed by comparison to simulations of a continuum bead-spring model and to published lattice Monte Carlo simulations. We show that a renormalized one-loop theory for blends correctly describes this N dependence of local liquid structure. We also propose a way to estimate the effective interaction parameter appropriate for comparisons of simulation data to SCF theory and to coarse-grained theories of corrections to SCF theory, which is based on an extrapolation of perturbation theory to the limit N-->infinity.

  13. Modelling the effect of nonplanarity on charge transport along conjugated polymer chains

    International Nuclear Information System (INIS)

    Correia, Helena M.G.; Ramos, Marta M.D.

    2007-01-01

    Conjugated polymers show interesting properties that make them appropriated for nanoelectronics. Several studies of poly(p-phenylene vinylene) (PPV) have suggested that each polymer chain consists of several planar segments, with conjugation length of nanoscale dimension, linked by twists or kinks. A pronounced twist between two planar segments in a PPV chain not only causes loss of main-chain conjugation but it may also alter electron and hole mobility along the chain, which has further implications for the percolation of charge through the polymer film. We used self-consistent quantum molecular dynamics calculations to provide information on the electric field needed to move the injected charges (either electrons or holes) along the planar segments of PPV and to cross the twist between two planar segments perpendicular to each other. Field-dependent charge mobility was also estimated for conjugated segments of various lengths. Our results suggest that electrons can cross the twist between adjacent planar segments for lower applied electric fields than holes if there is no more than one electronic charge (electron or hole) on the PPV chain, otherwise similar fields are needed

  14. Brownian dynamics simulations of a flexible polymer chain which includes continuous resistance and multibody hydrodynamic interactions

    Science.gov (United States)

    Butler, Jason E.; Shaqfeh, Eric S. G.

    2005-01-01

    Using methods adapted from the simulation of suspension dynamics, we have developed a Brownian dynamics algorithm with multibody hydrodynamic interactions for simulating the dynamics of polymer molecules. The polymer molecule is modeled as a chain composed of a series of inextensible, rigid rods with constraints at each joint to ensure continuity of the chain. The linear and rotational velocities of each segment of the polymer chain are described by the slender-body theory of Batchelor [J. Fluid Mech. 44, 419 (1970)]. To include hydrodynamic interactions between the segments of the chain, the line distribution of forces on each segment is approximated by making a Legendre polynomial expansion of the disturbance velocity on the segment, where the first two terms of the expansion are retained in the calculation. Thus, the resulting linear force distribution is specified by a center of mass force, couple, and stresslet on each segment. This method for calculating the hydrodynamic interactions has been successfully used to simulate the dynamics of noncolloidal suspensions of rigid fibers [O. G. Harlen, R. R. Sundararajakumar, and D. L. Koch, J. Fluid Mech. 388, 355 (1999); J. E. Butler and E. S. G. Shaqfeh, J. Fluid Mech. 468, 204 (2002)]. The longest relaxation time and center of mass diffusivity are among the quantities calculated with the simulation technique. Comparisons are made for different levels of approximation of the hydrodynamic interactions, including multibody interactions, two-body interactions, and the "freely draining" case with no interactions. For the short polymer chains studied in this paper, the results indicate a difference in the apparent scaling of diffusivity with polymer length for the multibody versus two-body level of approximation for the hydrodynamic interactions.

  15. Opportunity for high value-added chemicals from food supply chain wastes.

    Science.gov (United States)

    Matharu, Avtar S; de Melo, Eduardo M; Houghton, Joseph A

    2016-09-01

    With approximately 1.3 billion tonnes of food wasted per annum, food supply chain wastes (FSCWs) may be viewed as the contemporary Periodic Table of biobased feedstock chemicals (platform molecules) and functional materials. Herein, the global drivers and case for food waste valorisation within the context of global sustainability, sustainable development goals and the bioeconomy are discussed. The emerging potential of high value added chemicals from certain tropical FSCW is considered as these are grown in three major geographical areas: Brazil, India and China, and likely to increase in volume. FSCW in the context of biorefineries is discussed and two case studies are reported, namely: waste potato, and; orange peel waste. Interestingly, both waste feedstocks, like many others, produce proteins and with the global demand for vegetable proteins on the rise then proteins from FSCW may become a dominant area. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Intra-chain organisation of hydrophobic residues controls inter-chain aggregation rates of amphiphilic polymers

    Science.gov (United States)

    Varilly, Patrick; Willard, Adam P.; Kirkegaard, Julius B.; Knowles, Tuomas P. J.; Chandler, David

    2017-04-01

    Aggregation of amphiphiles through the action of hydrophobic interactions is a common feature in soft condensed matter systems and is of particular importance in the context of biophysics as it underlies both the generation of functional biological machinery as well as the formation of pathological misassembled states of proteins. Here we explore the aggregation behaviour of amphiphilic polymers using lattice Monte Carlo calculations and show that the distribution of hydrophobic residues within the polymer sequence determines the facility with which dry/wet interfaces can be created and that such interfaces drive the aggregation process.

  17. Bis(thienothiophenyl) diketopyrrolopyrrole-based conjugated polymers with various branched alkyl side chains and their applications in thin-film transistors and polymer solar cells.

    Science.gov (United States)

    Shin, Jicheol; Park, Gi Eun; Lee, Dae Hee; Um, Hyun Ah; Lee, Tae Wan; Cho, Min Ju; Choi, Dong Hoon

    2015-02-11

    New thienothiophene-flanked diketopyrrolopyrrole and thiophene-containing π-extended conjugated polymers with various branched alkyl side-chains were successfully synthesized. 2-Octyldodecyl, 2-decyltetradecyl, 2-tetradecylhexadecyl, 2-hexadecyloctadecyl, and 2-octadecyldocosyl groups were selected as the side-chain moieties and were anchored to the N-positions of the thienothiophene-flanked diketopyrrolopyrrole unit. All five polymers were found to be soluble owing to the bulkiness of the side chains. The thin-film transistor based on the 2-tetradecylhexadecyl-substituted polymer showed the highest hole mobility of 1.92 cm2 V(-1) s(-1) due to it having the smallest π-π stacking distance between the polymer chains, which was determined by grazing incidence X-ray diffraction. Bulk heterojunction polymer solar cells incorporating [6,6]-phenyl-C71-butyric acid methyl ester as the n-type molecule and the additive 1,8-diiodooctane (1 vol %) were also constructed from the synthesized polymers without thermal annealing; the device containing the 2-octyldodecyl-substituted polymer exhibited the highest power conversion efficiency of 5.8%. Although all the polymers showed similar physical properties, their device performance was clearly influenced by the sizes of the branched alkyl side-chain groups.

  18. Brownian dynamics simulation of a polymer chain in a solid-state nanopore attached to a molecular stop

    Science.gov (United States)

    Wells, Craig; Hulings, Zachery; Melnikov, Dmitriy; Gracheva, Maria

    We study a nanopore inside a silicon dioxide membrane submerged in a KCl solution with a negatively charged polymer chain of varying lengths whose movement is described using Brownian dynamics. The polymer is attached to a molecule with a radius larger than that of the nanopore's which acts as a molecular stop, allowing the chain to thread the nanopore but preventing it from translocating. We found that the polymer chain's variation of movement along the nanopore decreased when increasing applied biases and chain lengths for portions of the chain closest to the molecular stop. The chain displacement within the pore is also compared to a freely translocating polymer where preliminary results show the free polymer having a greater variation in the radial direction. Overall, our preliminary results indicate that the radial direction of the polymer chain is dominated by the confinement in the narrow nanopore with restrictions imposed by the molecular stop and bias playing a lesser role. Understanding the interaction behavior of the polymer chain-stop molecule may lead to methods that decrease movement variation, facilitating an improvement on characterizing and identification of molecules. NSF DMR and CBET Grant No. 1352218.

  19. Pruned-enriched Rosenbluth method: Simulations of θ polymers of chain length up to 1000000

    International Nuclear Information System (INIS)

    Grassberger, P.

    1997-01-01

    We present an algorithm for simulating flexible chain polymers. It combines the Rosenbluth-Rosenbluth method with recursive enrichment. Although it can be applied also in more general situations, it is most efficient for three-dimensional θ polymers on the simple-cubic lattice. There it allows high statistics simulations of chains of length up to N=10 6 . For storage reasons, this is feasable only for polymers in a finite volume. For free θ polymers in infinite volume, we present very high statistics runs with N=10000. These simulations fully agree with previous simulations made by Hegger and Grassberger [J. Chem. Phys. 102, 6681 (1995)] with a similar but less efficient algorithm, showing that logarithmic corrections to mean field behavior are much stronger than predicted by field theory. But the finite volume simulations show that the density inside a collapsed globule scales with the distance from the θ point as predicted by mean field theory, in contrast to claims in the work mentioned above. In addition to the simple-cubic lattice, we also studied two versions of the bond fluctuation model, but with much shorter chains. Finally, we show that our method can be applied also to off-lattice models, and illustrate this with simulations of a model studied in detail by Freire et al. [Macromolecules 19, 452 (1986) and later work]. copyright 1997 The American Physical Society

  20. Boosting the ambipolar performance of solution-processable polymer semiconductors via hybrid side-chain engineering.

    Science.gov (United States)

    Lee, Junghoon; Han, A-Reum; Yu, Hojeong; Shin, Tae Joo; Yang, Changduk; Oh, Joon Hak

    2013-06-26

    Ambipolar polymer semiconductors are highly suited for use in flexible, printable, and large-area electronics as they exhibit both n-type (electron-transporting) and p-type (hole-transporting) operations within a single layer. This allows for cost-effective fabrication of complementary circuits with high noise immunity and operational stability. Currently, the performance of ambipolar polymer semiconductors lags behind that of their unipolar counterparts. Here, we report on the side-chain engineering of conjugated, alternating electron donor-acceptor (D-A) polymers using diketopyrrolopyrrole-selenophene copolymers with hybrid siloxane-solubilizing groups (PTDPPSe-Si) to enhance ambipolar performance. The alkyl spacer length of the hybrid side chains was systematically tuned to boost ambipolar performance. The optimized three-dimensional (3-D) charge transport of PTDPPSe-Si with pentyl spacers yielded unprecedentedly high hole and electron mobilities of 8.84 and 4.34 cm(2) V(-1) s(-1), respectively. These results provide guidelines for the molecular design of semiconducting polymers with hybrid side chains.

  1. Large spin limit of AdS5xS5 string theory and low energy expansion of ferromagnetic spin chains

    International Nuclear Information System (INIS)

    Kruczenski, M.; Ryzhov, A.V.; Tseytlin, A.A.

    2004-01-01

    By considering AdS 5 xS 5 string states with large S 5 angular momenta one can provide non-trivial quantitative checks of the AdS/CFT duality. A string rotating in S 5 with two angular momenta J 1 , J 2 is dual to an operator in N=4 SYM theory whose conformal dimension can be computed by diagonalizing a (generalization of) spin 1/2 Heisenberg chain Hamiltonian. It was recently argued and verified to lowest order in a large J=J 1 +J 2 expansion, that the Heisenberg chain can be described using a non-relativistic low energy effective 2d action for a unit vector field n i which exactly matches the corresponding large J limit of the classical AdS 5 xS 5 string action. In this paper we show that this agreement extends to the next order and develop a systematic procedure for computing higher orders in such large angular momentum expansion. This involves several non-trivial steps. On the string side, we need to choose a special gauge with a non-diagonal world-sheet metric which insures that the angular momentum is uniformly distributed along the string, as indeed is the case on the spin chain side. We need also to implement an order by order redefinition of the field n i to get an action linear in the time derivative. On the spin chain side, it turns out to be crucial to include the effects of integrating out short wave-length modes. In this way we gain a better understanding of how (a subsector of) the string sigma model emerges from the dual gauge theory, allowing us to demonstrate the duality beyond comparing particular examples of states with large J

  2. Asymmetric Alkyl Side-Chain Engineering of Naphthalene Diimide-Based n-Type Polymers for Efficient All-Polymer Solar Cells.

    Science.gov (United States)

    Jia, Tao; Li, Zhenye; Ying, Lei; Jia, Jianchao; Fan, Baobing; Zhong, Wenkai; Pan, Feilong; He, Penghui; Chen, Junwu; Huang, Fei; Cao, Yong

    2018-02-13

    The design and synthesis of three n-type conjugated polymers based on a naphthalene diimide-thiophene skeleton are presented. The control polymer, PNDI-2HD, has two identical 2-hexyldecyl side chains, and the other polymers have different alkyl side chains; PNDI-EHDT has a 2-ethylhexyl and a 2-decyltetradecyl side chain, and PNDI-BOOD has a 2-butyloctyl and a 2-octyldodecyl side chain. These copolymers with different alkyl side chains exhibit higher melting and crystallization temperatures, and stronger aggregation in solution, than the control copolymer PNDI-2HD that has the same side chain. Polymer solar cells based on the electron-donating copolymer PTB7-Th and these novel copolymers exhibit nearly the same open-circuit voltage of 0.77 V. Devices based on the copolymer PNDI-BOOD with different side chains have a power-conversion efficiency of up to 6.89%, which is much higher than the 4.30% obtained with the symmetric PNDI-2HD. This improvement can be attributed to the improved charge-carrier mobility and the formation of favorable film morphology. These observations suggest that the molecular design strategy of incorporating different side chains can provide a new and promising approach to developing n-type conjugated polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Cylindrical polymer brushes with dendritic side chains by iterative anionic reactions

    KAUST Repository

    Zhang, Hefeng

    2015-05-01

    We report in this paper an easy method for the synthesis of cylindrical polymer brushes with dendritic side chains through anionic reaction. The synthesis is accomplished by iteratively grafting a living block copolymer, polyisoprene-. b-polystyrenyllithium (PI-. b-PSLi), to the main chain and subsequently to the branches in a divergent way. PI segment is short and serves as a precursor for multifunctional branching unit. The grafting reaction involves two successive steps: i) epoxidation of internal double bonds of PI segments, either in main chain or side chains; ii) ring-opening addition to the resulting epoxy group by the living PI-. b-PSLi. Repeating the two steps affords a series of cylindrical polymer brushes with up to 3rd generation and extremely high molecular weight. The branching multiplicity depends on the average number of oxirane groups per PI segment, usually ca. 8 in the present work. The high branching multiplicity leads to tremendous increase in molecular weights of the cylindrical products with generation growth. Several series of cylindrical polymer brushes with tunable aspect ratios are prepared using backbones and branches with controlled lengths. Shape anisotropy is investigated in dilute solution using light scattering technique. Worm-like single molecular morphology with large persistence length is observed on different substrates by atomic force microscopy.

  4. End-anchored polymers in good solvents from the single chain limit to high anchoring densities.

    Science.gov (United States)

    Whitmore, Mark D; Grest, Gary S; Douglas, Jack F; Kent, Michael S; Suo, Tongchuan

    2016-11-07

    An increasing number of applications utilize grafted polymer layers to alter the interfacial properties of solid substrates, motivating refinement in our theoretical understanding of such layers. To assess existing theoretical models of them, we have investigated end-anchored polymer layers over a wide range of grafting densities, σ, ranging from a single chain to high anchoring density limits, chain lengths ranging over two orders of magnitude, for very good and marginally good solvent conditions. We compare Monte Carlo and molecular dynamics simulations, numerical self-consistent field calculations, and experimental measurements of the average layer thickness, h, with renormalization group theory, the Alexander-de Gennes mushroom theory, and the classical brush theory. Our simulations clearly indicate that appreciable inter-chain interactions exist at all simulated areal anchoring densities so that there is no mushroom regime in which the layer thickness is independent of σ. Moreover, we find that there is no high coverage regime in which h follows the predicted scaling, h ∼ Nσ 1/3 , for classical polymer brushes either. Given that no completely adequate analytic theory seems to exist that spans wide ranges of N and σ, we applied scaling arguments for h as a function of a suitably defined reduced anchoring density, defined in terms of the solution radius of gyration of the polymer chains and N. We find that such a scaling approach enables a smooth, unified description of h in very good solvents over the full range of anchoring density and chain lengths, although this type of data reduction does not apply to marginal solvent quality conditions.

  5. Consistent model reduction of polymer chains in solution in dissipative particle dynamics: Model description

    KAUST Repository

    Moreno Chaparro, Nicolas

    2015-06-30

    We introduce a framework for model reduction of polymer chain models for dissipative particle dynamics (DPD) simulations, where the properties governing the phase equilibria such as the characteristic size of the chain, compressibility, density, and temperature are preserved. The proposed methodology reduces the number of degrees of freedom required in traditional DPD representations to model equilibrium properties of systems with complex molecules (e.g., linear polymers). Based on geometrical considerations we explicitly account for the correlation between beads in fine-grained DPD models and consistently represent the effect of these correlations in a reduced model, in a practical and simple fashion via power laws and the consistent scaling of the simulation parameters. In order to satisfy the geometrical constraints in the reduced model we introduce bond-angle potentials that account for the changes in the chain free energy after the model reduction. Following this coarse-graining process we represent high molecular weight DPD chains (i.e., ≥200≥200 beads per chain) with a significant reduction in the number of particles required (i.e., ≥20≥20 times the original system). We show that our methodology has potential applications modeling systems of high molecular weight molecules at large scales, such as diblock copolymer and DNA.

  6. Unlocking Chain Exchange in Highly Amphiphilic Block Polymer Micellar Systems: Influence of Agitation.

    Science.gov (United States)

    Murphy, Ryan P; Kelley, Elizabeth G; Rogers, Simon A; Sullivan, Millicent O; Epps, Thomas H

    2014-11-18

    Chain exchange between block polymer micelles in highly selective solvents, such as water, is well-known to be arrested under quiescent conditions, yet this work demonstrates that simple agitation methods can induce rapid chain exchange in these solvents. Aqueous solutions containing either pure poly(butadiene- b -ethylene oxide) or pure poly(butadiene- b -ethylene oxide- d 4 ) micelles were combined and then subjected to agitation by vortex mixing, concentric cylinder Couette flow, or nitrogen gas sparging. Subsequently, the extent of chain exchange between micelles was quantified using small angle neutron scattering. Rapid vortex mixing induced chain exchange within minutes, as evidenced by a monotonic decrease in scattered intensity, whereas Couette flow and sparging did not lead to measurable chain exchange over the examined time scale of hours. The linear kinetics with respect to agitation time suggested a surface-limited exchange process at the air-water interface. These findings demonstrate the strong influence of processing conditions on block polymer solution assemblies.

  7. Conformation and elasticity of a charged polymer chain bridging two nanoparticles

    International Nuclear Information System (INIS)

    Nowicki, W.; Nowicka, G.

    2013-01-01

    A complex composed of a charged flexible polymer chain irreversibly attached with its ends to surfaces of two nanoparticles was investigated using the Metropolis Monte Carlo method on a simple cubic lattice. The simulations were performed in the presence of explicit ions. The bridging chain and the nanoparticles bearing the same and the opposite sign charges were considered. Changes in the free energy of the complex upon its stretching or compression, together with the magnitude of the elastic force, were examined. The relative roles of energetic and entropic effects in determining the properties of the complex were identified. Also, the adsorption of charged monomers on the opposite-sign charged nanoparticles and its influence on the examined quantities was studied. Moreover, a simple semi-analytical approach to the thermodynamics of the polymer bridge was derived

  8. Two-Dimensional Nucleation on the Terrace of Colloidal Crystals with Added Polymers.

    Science.gov (United States)

    Nozawa, Jun; Uda, Satoshi; Guo, Suxia; Hu, Sumeng; Toyotama, Akiko; Yamanaka, Junpei; Okada, Junpei; Koizumi, Haruhiko

    2017-04-04

    Understanding nucleation dynamics is important both fundamentally and technologically in materials science and other scientific fields. Two-dimensional (2D) nucleation is the predominant growth mechanism in colloidal crystallization, in which the particle interaction is attractive, and has recently been regarded as a promising method to fabricate varieties of complex nanostructures possessing innovative functionality. Here, polymers are added to a colloidal suspension to generate a depletion attractive force, and the detailed 2D nucleation process on the terrace of the colloidal crystals is investigated. In the system, we first measured the nucleation rate at various area fractions of particles on the terrace, ϕ area . In situ observations at single-particle resolution revealed that nucleation behavior follows the framework of classical nucleation theory (CNT), such as single-step nucleation pathway and existence of critical size. Characteristic nucleation behavior is observed in that the nucleation and growth stage are clearly differentiated. When many nuclei form in a small area of the terrace, a high density of kink sites of once formed islands makes growth more likely to occur than further nucleation because nucleation has a higher energy barrier than growth. The steady-state homogeneous 2D nucleation rate, J, and the critical size of nuclei, r*, are measured by in situ observations based on the CNT, which enable us to obtain the step free energy, γ, which is an important parameter for characterizing the nucleation process. The γ value is found to change according to the strength of attraction, which is tuned by the concentration of the polymer as a depletant.

  9. Solid state nuclear magnetic resonance spectroscopy of polymer thin films: chain conformation, dynamics, and morphology

    International Nuclear Information System (INIS)

    Nasreddine, V.F.

    2003-01-01

    This dissertation presents solid-state NMR studies of the chain conformation, dynamics and morphology of three adsorbed polymer systems: two random semi-crystalline copolymers, poly(ethylene-co-acrylic acid) (PEA) and poly(propylene-co-acrylic acid) (PPA), and an amorphous homopolymer, poly(n-butyl methacrylate) (PnBMA). Zirconia (ZrO 2 ) was chosen as the substrate for all three polymers since the binding of carboxylic acids to this metal oxide is well understood. The choice of polymers was based on their particular bulk conformational and dynamic properties as well as their common use in polymer coatings. These studies are motivated by the general lack of a microscopic picture of adsorbed polymers, which can be provided by NMR, and the relevance of chain conformation and dynamics to important polymer film properties such as adhesion. First the chain conformation and surface binding of adsorbed PEA as a function of acrylic acid content are characterized by 13 C cross polarization - magic angle spinning (CP-MAS), 2D 1 H- 13 C wideline separation (WISE) and 1 H spin diffusion NMR experiments and FTIR-PAS (Fourier transform infrared photoacoustic spectroscopy) measurements. The most important finding is that the chain conformation of adsorbed PEA is determined primarily by the sticker group density rather than the surface coverage. The second study of PEA concerns the chain dynamics in the bulk and adsorbed states. Variable temperature NMR experiments provide evidence that ethylene segments of adsorbed PEA form partially folded loops rather than flat extended trains. Finally 129 Xe NMR studies, used to probe the morphology of adsorbed PEA, show a bulk-like signal only for the highest loadings. The second system investigated, PPA, is another semi-crystalline random copolymer which binds to zirconia via carboxylate linkages. The 13 C CP-MAS NMR spectra of adsorbed PPAC unexpectedly show splittings normally associated with chain-chain packing in the crystalline regions

  10. Crystallization in melts of short, semiflexible hard polymer chains: An interplay of entropies and dimensions

    Science.gov (United States)

    Shakirov, T.; Paul, W.

    2018-04-01

    What is the thermodynamic driving force for the crystallization of melts of semiflexible polymers? We try to answer this question by employing stochastic approximation Monte Carlo simulations to obtain the complete thermodynamic equilibrium information for a melt of short, semiflexible polymer chains with purely repulsive nonbonded interactions. The thermodynamics is obtained based on the density of states of our coarse-grained model, which varies by up to 5600 orders of magnitude. We show that our polymer melt undergoes a first-order crystallization transition upon increasing the chain stiffness at fixed density. This crystallization can be understood by the interplay of the maximization of different entropy contributions in different spatial dimensions. At sufficient stiffness and density, the three-dimensional orientational interactions drive the orientational ordering transition, which is accompanied by a two-dimensional translational ordering transition in the plane perpendicular to the chains resulting in a hexagonal crystal structure. While the three-dimensional ordering can be understood in terms of Onsager theory, the two-dimensional transition can be understood in terms of the liquid-hexatic transition of hard disks. Due to the domination of lateral two-dimensional translational entropy over the one-dimensional translational entropy connected with columnar displacements, the chains form a lamellar phase. Based on this physical understanding, orientational ordering and translational ordering should be separable for polymer melts. A phenomenological theory based on this understanding predicts a qualitative phase diagram as a function of volume fraction and stiffness in good agreement with results from the literature.

  11. Controlling photophysical properties of ultrasmall conjugated polymer nanoparticles through polymer chain packing

    KAUST Repository

    Piwonski, Hubert Marek; Michinobu, Tsuyoshi; Habuchi, Satoshi

    2017-01-01

    of the development of Pdots. Here we demonstrate that proper control of the physical interactions between the chains is as critical as the molecular design. The unique design of twisted CPs and fine-tuning of the reprecipitation conditions allow us to fabricate

  12. Amphiphilic polymer based on fluoroalkyl and PEG side chains for fouling release coating

    Science.gov (United States)

    Cong, W. W.; Wang, K.; Yu, X. Y.; Zhang, H. Q.; Lv, Z.; Gui, T. J.

    2017-12-01

    Under static conditions, fouling release coating could not express good release property to marine organisms. Amphiphilic polymer with mixture of fluorinated monomer and short side group of polyethylene glycol (PEG) was synthesized. And also we studied the ability of amphiphilic polymer to influence the surface properties and how it controlled the adhesion of marine organisms to coated surfaces. By incorporating fluorinated monomer and PEG side chain into the polymer, the effect of incorporating both polar and non-polar groups on fouling-release coating could be studied. The dry surface was characterized by three-dimensional digital microscopy and scanning electron microscopy (SEM), and the morphology of the amphiphilic fouling release coating showed just like flaky petal. The amphiphilic polymer in fouling release coating tended to reconstruct in water, and the ability was examined by static contact angle, which was smaller than the PDMS (polydimethylsiloxane) fouling release coating. Also surface energy was calculated by three solvents, and surface energy of amphiphilic fouling release coating was higher than that of the PDMS fouling release coating. To understand more about its fouling release property, seawater exposure method was adopted in gulf of Qingdao port. Fewer diatoms Navicula were found in biofilm after using amphiphilic fouling release coating. In general, coating containing both PEG and fluorinated side chain possessed certain fouling release property.

  13. Single-chain statistics and the upper wave-vector cutoff in polymer blends

    International Nuclear Information System (INIS)

    Holyst, R.; Vilgis, T.A.

    1994-01-01

    We derive the equation for the single-chain correlation function in polymer blends. The chains in the incompressible blend have a radius of gyration smaller than the radius of gyration for ideal chains. The chains shrink progressively as we approach the critical temperature T c . The correction responsible for shrinking is proportional to 1/ √N , where N is the polymerization index. At T=T c and for N=1000, the size of the chain has been estimated to be 10% smaller than the size of the ideal coil. The estimate relies on the appropriate cutoff. In the limit of N→∞ the chains approach the random walk limit. Additionally, we propose in this paper a self-consistent determination of the radius of gyration and the upper wave-vector cutoff. Our model is free from any divergences such as were encountered in the previous mean-field studies; we make an estimate of the chain size at the true critical temperature and not the mean-field one

  14. Water Sorption and Hindered Diffusion with Different Chain Stiffness of Superabsorbent Polymer

    Energy Technology Data Exchange (ETDEWEB)

    Chun, Myung-Suk; Lee, Dae-Young [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2015-01-15

    Water sorption and diffusion are essential physicochemical properties of a high-performance superabsorbent polymer (SAP). We combine the Park model with the obstruction-scaling model and the water clustering in confined spaces of the polymer hydrogel. Special attention is focused on elucidating the effect of chain stiffness by considering the conformation of the polymer chain. Theoretical model parameters are determined from the best fits by simultaneous nonlinear regressions for both sorption and corrected diffusion data based on previous experiments with poly(acrylamide-co-sodium acrylate) hydrogel. Predictions show that the hindered water diffusivity leads to a sigmoid curve with relative humidity a{sub w}, where it increases monotonically up to aw{sub ≅} 0.6 due to the swelling but decreases at higher a{sub w} caused by water clustering. Water diffusion decreases with increasing chain stiffness, and the larger persistence length provides a smaller opening radius in void spaces regarding the weak elastic deformation of hydrogel under the applied stress.

  15. Microscopic theory of light-induced deformation in amorphous side-chain azobenzene polymers.

    Science.gov (United States)

    Toshchevikov, V; Saphiannikova, M; Heinrich, G

    2009-04-16

    We propose a microscopic theory of light-induced deformation of side-chain azobenzene polymers taking into account the internal structure of polymer chains. Our theory is based on the fact that interaction of chromophores with the polarized light leads to the orientation anisotropy of azobenzene macromolecules which is accompanied by the appearance of mechanical stress. It is the first microscopic theory which provides the value of the light-induced stress larger than the yield stress. This result explains a possibility for the inscription of surface relief gratings in glassy side-chain azobenzene polymers. For some chemical architectures, elongation of a sample demonstrates a nonmonotonic behavior with the light intensity and can change its sign (a stretched sample starts to be uniaxially compressed), in agreement with experiments. Using a viscoplastic approach, we show that the irreversible strain of a sample, which remains after the light is switched off, decreases with increasing temperature and can disappear at certain temperature below the glass transition temperature. This theoretical prediction is also confirmed by recent experiments.

  16. Location of radiation-induced grafted chains in polymers studied by solid-state NMR

    International Nuclear Information System (INIS)

    Whittacker, A.; Liu, H.

    1998-01-01

    In this study styrene and N-phenyl maleimide monomers were grafted onto poly(ethylene) (PE) chains using gamma radiation. Of main interest is the distribution of grafted chains within the polymer matrix, as this will determine the efficacy of mixing with the glassy polymers. It is expected that grafting will occur within the amorphous regions, and especially near the interface of the crystalline and amorphous regions. A suitable method for characterising the location of the grafted chains is solid-state 13 C NMR spectroscopy. The 13 C CPMAS spectrum of the blend of PE and N-phenyl maleimide mixed in the melt at 150 deg C , prior to reaction, is shown above. The spectrum shows the typical peaks for poly(ethylene) due to the amorphous and crystalline phase at 30.5 and 32.5 ppm, respectively. Peaks are also seen in the aromatic and carbonyl region due to the maleimide (not plotted). Experiments will be described where the NMR magnetisation is prepared in either the crystalline and amorphous regions of the poly(ethylene) prior to spin diffusion to the maleimide and styrene fractions. The location of the grafted monomers can then be determined by monitoring the changes in signal of polymer and graft with time

  17. Gamma-radiation induced polymerization of methyl methacrylate in aliphatic hydrocarbons: kinetics and evidence for incorporation of hydrocarbon in the polymer chain

    International Nuclear Information System (INIS)

    Mohan, H.; Iyer, R.M.

    1989-01-01

    On γ-radiolysis, the rate of polymerization of methyl methacrylate in hydrocarbon solvents is observed to decrease. It is explained by hydrocarbon entry into the polymer chains. The hydrocarbon entry into the polymer chains is observed to take place at later stages of polymerization and increases with hydrocarbon chain length. The extent of hydrocarbon entry into the polymer chains is estimated by NMR and GLC analysis. It is observed to be equal to ∼ 12% corresponding to ∼ 97 hexadecane molecules in each polymer chain. The IR, DSC, MW determination and radiation effects on the polymer showed evidences for hydrocarbon entry into the polymer. It is explained by chain transfer from the growing polymer radical to the hydrocarbon molecules. The chain transfer constant is determined to be equal to 1 x 10 -2 . (author)

  18. Synthesis and characterization of associating polymers which contain siloxanes chains; Synthese et caracterisation de polymeres associatifs porteurs de groupes siloxanes

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, V

    1999-01-11

    Polymers that associate via physical interactions in solutions have received much attention as viscosifiers. Such associating polymers are now used in variety of applications due to their unique theological properties coating, food thickeners, paints, enhanced oil recovery, water treatment). They contain a hydrophilic main chain with hydrophobic side chain that is generally constituted of hydrocarbon or fluorocarbon groups. Novel copolymers with sites of association in aqueous solution were prepared by co-polymerizing acrylamide with an hydrophobic monomer containing siloxane parts. Rheological properties were studied as a function of polymer concentration, microstructure, shear rate and frequency in order to show intra intermolecular associations between the hydrophobic parts. The polymer solution viscosity increases as a function of the hydrophobic group content. Tests of adsorption show a high affinity of these copolymers with clay and the amount absorbed increase with the quantity of hydrophobic entities containing in the chain. These properties are enhanced compared to copolymers containing hydrocarbon chains. (authors) 456 refs.

  19. A new series of two-ring-based side chain liquid crystalline polymers: synthesis and mesophase characterization

    CSIR Research Space (South Africa)

    Reddy, GSM

    2013-05-01

    Full Text Available A new series of side chain liquid crystalline polymers containing a core, a butamethylenoxy spacer, ester groups, and terminal alkoxy groups were synthesised and their structures were confirmed. The core was constructed with two phenyl rings...

  20. Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains

    KAUST Repository

    Shivokhin, Maksim E.; Read, Daniel J.; Kouloumasis, Dimitris; Kocen, Rok; Zhuge, Flanco; Bailly, Christian; Hadjichristidis, Nikolaos; Likhtman, Alexei E.

    2017-01-01

    of a linear probe chain. For this purpose we first validate the ability of the model to consistently predict both the viscoelastic and dielectric response of monodisperse and binary mixtures of type A polymers, based on published experimental data. We

  1. Confinement Effects on Host Chain Dynamics in Polymer Nanocomposite Thin Films

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Kyle J. [Department; Glynos, Emmanouil [Department; Maroulas, Serafeim-Dionysios [Department; Narayanan, Suresh [Advanced; Sakellariou, Georgios [Department; Green, Peter F. [Department; National

    2017-09-07

    Incorporating nanoparticles (NPs) within a polymer host to create polymer nanocomposites (PNCs) while having the effect of increasing the functionality (e.g., sensing, energy conversion) of these materials influences other properties. One challenge is to understand the effects of nanoparticles on the viscosity of nanoscale thick polymer films. A new mechanism that contributes to an enhancement of the viscosity of nanoscale thick polymer/nanoparticle films is identified. We show that while the viscosities of neat homopolymer poly(2-vinylpyridine) (P2VP) films as thin as 50 nm remained the same as the bulk, polymer/nanoparticle films containing P2VP brush-coated gold NPs, spaced 50 nm apart, exhibited unprecedented increases in viscosities of over an order of magnitude. For thicker films or more widely separated NPs, the chain dynamics and viscosities were comparable to the bulk values. These results - NP proximities and suppression of their dynamics - suggest a new mechanism by which the viscosities of polymeric liquids could be controlled for nanoscale applications.

  2. Acyclic Diene Metathesis (ADMET Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends

    Directory of Open Access Journals (Sweden)

    Tahmina Haque

    2015-03-01

    Full Text Available This accounts introduces unique characteristics by adopting the acyclic diene metathesis (ADMET polymerization for synthesis of conjugated polymers, poly(arylene vinylenes, known as promising molecular electronics. The method is more suitable than the other methods in terms of atom efficiency affording defect-free, stereo-regular (exclusive trans polymers with well-defined chain ends; the resultant polymers possess better property than those prepared by the conventional methods. The chain ends (vinyl group in the resultant polymer prepared by ruthenium-carbene catalyst(s can be modified by treating with molybdenum-alkylidene complex (olefin metathesis followed by addition of various aldehyde (Wittig type cleavage, affording the end-functionalized polymers exclusively. An introduction of initiating fragment, the other conjugated segment, and one-pot synthesis of end-functionalized block copolymers, star shape polymers can be achieved by adopting this methodology.

  3. Effect of chain rigidity on network architecture and deformation behavior of glassy polymer networks

    Science.gov (United States)

    Knowles, Kyler Reser

    Processing carbon fiber composite laminates creates molecular-level strains in the thermoset matrix upon curing and cooling which can lead to failures such as geometry deformations, micro-cracking, and other issues. It is known strain creation is attributed to the significant volume and physical state changes undergone by the polymer matrix throughout the curing process, though storage and relaxation of cure-induced strains remain poorly understood. This dissertation establishes two approaches to address the issue. The first establishes testing methods to simultaneously measure key volumetric properties of a carbon fiber composite laminate and its polymer matrix. The second approach considers the rigidity of the polymer matrix in regards to strain storage and relaxation mechanisms which ultimately control composite performance throughout manufacturing and use. Through the use of a non-contact, full-field strain measurement technique known as digital image correlation (DIC), we describe and implement useful experiments which quantify matrix and composite parameters necessary for simulation efforts and failure models. The methods are compared to more traditional techniques and show excellent correlation. Further, we established relationships which represent matrix-fiber compatibility in regards to critical processing constraints. The second approach involves a systematic study of epoxy-amine networks which are chemically-similar but differ in chain segment rigidity. Prior research has investigated the isomer effect of glassy polymers, showing sizeable differences in thermal, volumetric, physical, and mechanical properties. This work builds on these themes and shows the apparent isomer effect is rather an effect of chain rigidity. Indeed, it was found that structurally-dissimilar polymer networks exhibit very similar properties as a consequence of their shared average network rigidity. Differences in chain packing, as a consequence of chain rigidity, were shown to

  4. Chain dynamics and nanoparticle motion in attractive polymer nanocomposites subjected to large deformations.

    Science.gov (United States)

    Senses, Erkan; Tyagi, Madhusudan; Natarajan, Bharath; Narayanan, Suresh; Faraone, Antonio

    2017-11-08

    The effect of large deformation on the chain dynamics in attractive polymer nanocomposites was investigated using neutron scattering techniques. Quasi-elastic neutron backscattering measurements reveal a substantial reduction of polymer mobility in the presence of attractive, well-dispersed nanoparticles. In addition, large deformations are observed to cause a further slowing down of the Rouse rates at high particle loadings, where the interparticle spacings are slightly smaller than the chain dimensions, i.e. in the strongly confined state. No noticeable change, however, was observed for a lightly confined system. The reptation tube diameter, measured by neutron spin echo, remained unchanged after shear, suggesting that the level of chain-chain entanglements is not significantly affected. The shear-induced changes in the interparticle bridging reflect the slow nanoparticle motion measured by X-ray photon correlation spectroscopy. These results provide a first step for understanding how large shear can significantly affect the segmental motion in nanocomposites and open up new opportunities for designing mechanically responsive soft materials.

  5. New stochastic treatment of fermions with application to a double-chain polymer

    International Nuclear Information System (INIS)

    Kung, D.; Dahl, D.; Blankenbecler, R.; Deza, R.; Fulco, J.R.

    1985-01-01

    An extension of the stochastic algorithm as applied to Hamiltonian lattice field theories is developed. This new scheme will converge in problems that have intrinsic negative signs in the matrix elements. As an example, this scheme is applied to a two-chain polymer problem with (spinless) fermions that have a pairwise interaction. Because of the multiple connected structure of the double chain, this problem has intrinsic minus signs. It cannot be transformed into a bosonic problem with only positive matrix elements. Numerical results from this application of the new algorithm are presented for the energy and certain correlation functions for moderately long chains. A discussion of a modification of the method which will allow the treatment of much larger systems is discussed

  6. Efficient protein-repelling thin films regulated by chain mobility of low-Tg polymers with increased stability via crosslinking

    Science.gov (United States)

    Zhang, Jinghui; Huang, Zhiwei; Liu, Dan

    2017-12-01

    Polymer thin films are generally employed as coatings on implants to prevent protein adsorption. Polymer chain mobility and surface softness have been found to contribute to the protein resistance, but also bring film instability in a liquid protein medium. We investigated the protein resistance ability of three low-Tg polymers, including hydrophobic polymers polyisoprene (PI), poly(n-butyl methacrylate) (PnBMA) and hydrophilic polyethylene oxide (PEO), by overcoming the instability issue with crosslinking. We found that the Tgs of PI and PEO can be increased to around 0 °C after crosslinking. The remained strong chain mobility of both films can still resist protein adsorption regardless the hydrophobicity, yet greatly increases the film stability under an aqueous circumstance. The PnBMA film increased its Tg to around room temperature after crosslinking, which deteriorated the protein-resistance ability having the surface covered by BSA molecules. Our results support that the chain mobility of a polymer film plays an important role in resisting protein adsorption due to the increased entropy associated with more mobile polymer chains. By tune the degree of crosslinking, the stability of polymer in aqueous environment can be increased while the protein resistant ability can be remained. Our results provide a new strategy to design polymer materials for effective antifouling.

  7. Degradation behavior of polymer blend of isotactic polypropylenes with and without unsaturated chain end group

    International Nuclear Information System (INIS)

    Nakatani, Hisayuki; Kurniawan, Dodik; Taniike, Toshiaki; Terano, Minoru

    2008-01-01

    In this work, the relationship between the unsaturated chain end group content and the thermal oxidative degradation rate was systematically studied with binary polymer blends of isotactic polypropylene (iPP) with and without the unsaturated chain end group. The iPPs with and without the unsaturated chain end group were synthesized by a metallocene catalyst in the absence of hydrogen and by a Ziegler catalyst in the presence of one, respectively. The thermal oxidative degradation rate of the binary iPP blends was estimated from the molecular weight and the apparent activation energy (ΔE), which were obtained through size exclusion chromatography (SEC) and thermogravimetric analysis (TGA) measurements, respectively. These values exhibited a negative correlation against the mole content of the unsaturated chain end group. The thermal oxidative degradation rate apparently depends on the content of the unsaturated chain end group. This tendency suggests that the unsaturated chain end acts as a radical initiator of the iPP degradation reaction.

  8. Effect of chain stiffness on the structure of single-chain polymer nanoparticles

    DEFF Research Database (Denmark)

    Moreno, Angel J; Bacova, Petra; Lo Verso, Federica

    2018-01-01

    of the domains is in all cases similar to that of Gaussian chains or rings, irrespective of the stiffness and degree of cross-linking. It is the spatial arrangement of the domains which determines the global structure of the SCNP (sparse Gaussian-like object or crumpled globule). Since intramolecular stiffness...... or 'crumpled' globular behaviour for very stiff SCNPs. We characterize domains in the SCNPs. These are weakly deformable regions that can be seen as disordered analogues of domains in disordered proteins. Increasing stiffness leads to bigger and less deformable domains. Surprisingly, the scaling behaviour...... can be varied through the specific chemistry of the precursor or by introducing bulky side groups in its backbone, our results propose a new strategy to tune the global structure of SCNPs. ....

  9. Long Range Polymer Chain Dynamics of Highly Flexible Polysiloxane in Solution Probed by Pyrene Excimer Fluorescence

    Directory of Open Access Journals (Sweden)

    Janine L. Thoma

    2018-03-01

    Full Text Available A poly(dimethylsiloxane-co-(3-aminopropylmethylsiloxane polymer (PDMS with 20.3 mol % of (3-aminopropylmethyl siloxane monomer has been labeled randomly with 1-pyreneacetyl groups to generate a series of polysiloxanes (Py-PDMS with pyrenyl contents ranging from 0.7 mol % to 5.2 mol % of the total number of structural units. The remainder of the amino groups were acetylated to avoid intra-chain quenching of the excited singlet states of pyrene via exciplex formation with free amino groups while allowing the formation of excimers to proceed. The fluorescence spectra and temporal decays of the Py-PDMS samples were acquired in tetrahydrofuran (THF, N,N-dimethylformamide (DMF, and dioxane. blob, the average rate constant for intra-chain pyrene excimer formation, was determined from the analysis of the fluorescence decays. blob was found to equal 1.16 (±0.13 × 109, 1.14 (±0.12 × 109, and 0.99 (±0.10 × 109 s−1 in THF, DMF, and dioxane, respectively, at room temperature. They are the largest values found to date for any polymeric backbone in these solvents. The qualitative relationship found here between blob and the chemical structures of the polymers indicates that the luminescence characteristics of randomly labeled polymers is a very useful method to probe the long range dynamics of chains of almost any polymer that is amenable to substitution by a lumophore.

  10. Multi-functionalized side-chain supramolecular polymers: A methodology towards tunable functional materials

    Science.gov (United States)

    Nair, Kamlesh Prabhakaran

    Even as we see a significant growth in the field of supramolecular polymers in the last ten years, multi-functionalized systems have been scarcely studied. Noncovalent multi-functionalization provides unique advantages such as rapid materials optimization via reversible functionalization as well as for the tuning of materials properties by exploiting the differences in the nature of these reversible interactions. This thesis involves the design principles, synthesis & methodology of supramolecular side-chain multi-functionalized polymers. The combination of a functionally tolerant & controlled polymerization technique such as ROMP with multiple noncovalent interactions such as hydrogen bonding, metal coordination and ionic interactions has been successfully used to synthesize these polymers. Furthermore, the orthogonality between the above interactions in block/random copolymers has been studied in detail. It has been found that the studied interactions were orthogonal to each other. To validate the viability of this methodology using multiple orthogonal interactions towards materials design noncovalent crosslinking of polymers has been used as a potential application. Three classes of networks have been studied: complementary multiple hydrogen bonded networks, metal crosslinked networks, & multi-functionalized hydrogen bonded and metal coordinated networks. The first room temperature decrosslinking by exclusive complementary hydrogen bonded interactions has been successfully achieved. Furthermore network properties have been successfully tuned by varying the network micro-structure which in turn was tuned by the hydrogen bonding motifs used for inter-chain crosslinking. By combining two different noncovalent interactions used for inter-chain crosslinking, it was possible to make multi-functionalized materials whose properties could be controlled by varying the crosslinking strategy. Hence by employing multi-functionalization methodology, important materials

  11. Statistical model of a flexible inextensible polymer chain: The effect of kinetic energy

    Science.gov (United States)

    Pergamenshchik, V. M.; Vozniak, A. B.

    2017-01-01

    Because of the holonomic constraints, the kinetic energy contribution in the partition function of an inextensible polymer chain is difficult to find, and it has been systematically ignored. We present the first thermodynamic calculation incorporating the kinetic energy of an inextensible polymer chain with the bending energy. To explore the effect of the translation-rotation degrees of freedom, we propose and solve a statistical model of a fully flexible chain of N +1 linked beads which, in the limit of smooth bending, is equivalent to the well-known wormlike chain model. The partition function with the kinetic and bending energies and correlations between orientations of any pair of links and velocities of any pair of beads are found. This solution is precise in the limits of small and large rigidity-to-temperature ratio b /T . The last exact solution is essential as even very "harmless" approximation results in loss of the important effects when the chain is very rigid. For very high b /T , the orientations of different links become fully correlated. Nevertheless, the chain does not go over into a hard rod even in the limit b /T →∞ : While the velocity correlation length diverges, the correlations themselves remain weak and tend to the value ∝T /(N +1 ). The N dependence of the partition function is essentially determined by the kinetic energy contribution. We demonstrate that to obtain the correct energy and entropy in a constrained system, the T derivative of the partition function has to be applied before integration over the constraint-setting variable.

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

    Science.gov (United States)

    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.

  13. Orientational cross correlations between entangled branch polymers in primitive chain network simulations

    Science.gov (United States)

    Masubuchi, Yuichi; Pandey, Ankita; Amamoto, Yoshifumi; Uneyama, Takashi

    2017-11-01

    Although it has not been frequently discussed, contributions of the orientational cross-correlation (OCC) between entangled polymers are not negligible in the relaxation modulus. In the present study, OCC contributions were investigated for 4- and 6-arm star-branched and H-branched polymers by means of multi-chain slip-link simulations. Owing to the molecular-level description of the simulation, the segment orientation was traced separately for each molecule as well as each subchain composing the molecules. Then, the OCC was calculated between different molecules and different subchains. The results revealed that the amount of OCC between different molecules is virtually identical to that of linear polymers regardless of the branching structure. The OCC between constituent subchains of the same molecule is significantly smaller than the OCC between different molecules, although its intensity and time-dependent behavior depend on the branching structure as well as the molecular weight. These results lend support to the single-chain models given that the OCC effects are embedded into the stress-optical coefficient, which is independent of the branching structure.

  14. Renormalization group for centrosymmetric gauge transformations of the dynamic motion for a Markov-ordered polymer chain

    International Nuclear Information System (INIS)

    Mikhailov, I.D.; Zhuravskii, L.V.

    1987-01-01

    A method is proposed for calculating the vibrational-state density averaged over all configurations for a polymer chain with Markov disorder. The method is based on using a group of centrally symmetric gauge transformations that reduce the dynamic matrix for along polymer chain to renormalized dynamic matrices for short fragments. The short-range order is incorporated exactly in the averaging procedure, while the long-range order is incorporated in the self-consistent field approximation. Results are given for a simple skeletal model for a polymer containing tacticity deviations of Markov type

  15. Entanglement of conjugated polymer chains influences molecular self-assembly and carrier transport

    KAUST Repository

    Zhao, Kui

    2013-06-26

    The influence of polymer entanglement on the self-assembly, molecular packing structure, and microstructure of low-Mw (lightly entangled) and high-Mw (highly entangled) poly (3-hexylthiophene) (P3HT), and the carrier transport in thin-film transistors, are investigated. The polymer chains are gradually disentangled in a marginal solvent via ultrasonication of the polymer solution, and demonstrate improved diffusivity of precursor species (coils, aggregates, and microcrystallites), enhanced nucleation and crystallization of P3HT in solution, and self-assembly of well-ordered and highly textured fibrils at the solid-liquid interface. In low-Mw P3HT, reducing chain entanglement enhances interchain and intrachain ordering, but reduces the interconnectivity of ordered domains (tie molecules) due to the presence of short chains, thus deteriorating carrier transport even in the face of improving crystallinity. Reducing chain entanglement in high-Mw P3HT solutions increases carrier mobility up to ≈20-fold, by enhancing interchain and intrachain ordering while maintaining a sufficiently large number of tie molecules between ordered domains. These results indicate that charge carrier mobility is strongly governed by the balancing of intrachain and interchain ordering, on the one hand, and interconnectivity of ordered domains, on the other hand. In high-Mw P3HT, intrachain and interchain ordering appear to be the key bottlenecks to charge transport, whereas in low-Mw P3HT, the limited interconnectivity of the ordered domains acts as the primary bottleneck to charge transport. Conjugated polymer chains of poly(3-hexylthiophene) (P3HT) are gradually disentangled in solution and trends in carrier transport mechanisms in organic thin film transistors for low- and high-molecular weight P3HT are investigated. While intrachain and interchain ordering within ordered domains are the key bottlenecks to charge transport in high-Mw P3HT films, the limited interconnectivity of ordered

  16. Entanglement of conjugated polymer chains influences molecular self-assembly and carrier transport

    KAUST Repository

    Zhao, Kui; Khan, Hadayat Ullah; Li, Ruipeng; Su, Yisong; Amassian, Aram

    2013-01-01

    The influence of polymer entanglement on the self-assembly, molecular packing structure, and microstructure of low-Mw (lightly entangled) and high-Mw (highly entangled) poly (3-hexylthiophene) (P3HT), and the carrier transport in thin-film transistors, are investigated. The polymer chains are gradually disentangled in a marginal solvent via ultrasonication of the polymer solution, and demonstrate improved diffusivity of precursor species (coils, aggregates, and microcrystallites), enhanced nucleation and crystallization of P3HT in solution, and self-assembly of well-ordered and highly textured fibrils at the solid-liquid interface. In low-Mw P3HT, reducing chain entanglement enhances interchain and intrachain ordering, but reduces the interconnectivity of ordered domains (tie molecules) due to the presence of short chains, thus deteriorating carrier transport even in the face of improving crystallinity. Reducing chain entanglement in high-Mw P3HT solutions increases carrier mobility up to ≈20-fold, by enhancing interchain and intrachain ordering while maintaining a sufficiently large number of tie molecules between ordered domains. These results indicate that charge carrier mobility is strongly governed by the balancing of intrachain and interchain ordering, on the one hand, and interconnectivity of ordered domains, on the other hand. In high-Mw P3HT, intrachain and interchain ordering appear to be the key bottlenecks to charge transport, whereas in low-Mw P3HT, the limited interconnectivity of the ordered domains acts as the primary bottleneck to charge transport. Conjugated polymer chains of poly(3-hexylthiophene) (P3HT) are gradually disentangled in solution and trends in carrier transport mechanisms in organic thin film transistors for low- and high-molecular weight P3HT are investigated. While intrachain and interchain ordering within ordered domains are the key bottlenecks to charge transport in high-Mw P3HT films, the limited interconnectivity of ordered

  17. Polymer Main-Chain Substitution Effects on the Efficiency of Nonfullerene BHJ Solar Cells

    KAUST Repository

    Firdaus, Yuliar; Maffei, Luna Pratali; Cruciani, Federico; Mü ller, Michael A.; Liu, Shengjian; Lopatin, Sergei; Wehbe, Nimer; Ngongang Ndjawa, Guy Olivier; Amassian, Aram; Laquai, Fré dé ric; Beaujuge, Pierre

    2017-01-01

    “Nonfullerene” acceptors are proving effective in bulk heterojunction (BHJ) solar cells when paired with selected polymer donors. However, the principles that guide the selection of adequate polymer donors for high-efficiency BHJ solar cells with nonfullerene acceptors remain a matter of some debate and, while polymer main-chain substitutions may have a direct influence on the donor–acceptor interplay, those effects should be examined and correlated with BHJ device performance patterns. This report examines a set of wide-bandgap polymer donor analogues composed of benzo[1,2-b:4,5-b′]dithiophene (BDT), and thienyl ([2H]T) or 3,4-difluorothiophene ([2F]T) motifs, and their BHJ device performance pattern with the nonfullerene acceptor “ITIC”. Studies show that the fluorine- and ring-substituted derivative PBDT(T)[2F]T largely outperforms its other two polymer donor counterparts, reaching power conversion efficiencies as high as 9.8%. Combining several characterization techniques, the gradual device performance improvements observed on swapping PBDT[2H]T for PBDT[2F]T, and then for PBDT(T)[2F]T, are found to result from (i) notably improved charge generation and collection efficiencies (estimated as ≈60%, 80%, and 90%, respectively), and (ii) reduced geminate recombination (being suppressed from ≈30%, 25% to 10%) and bimolecular recombination (inferred from recombination rate constant comparisons). These examinations will have broader implications for further studies on the optimization of BHJ solar cell efficiencies with polymer donors and a wider range of nonfullerene acceptors.

  18. Polymer Main-Chain Substitution Effects on the Efficiency of Nonfullerene BHJ Solar Cells

    KAUST Repository

    Firdaus, Yuliar

    2017-07-21

    “Nonfullerene” acceptors are proving effective in bulk heterojunction (BHJ) solar cells when paired with selected polymer donors. However, the principles that guide the selection of adequate polymer donors for high-efficiency BHJ solar cells with nonfullerene acceptors remain a matter of some debate and, while polymer main-chain substitutions may have a direct influence on the donor–acceptor interplay, those effects should be examined and correlated with BHJ device performance patterns. This report examines a set of wide-bandgap polymer donor analogues composed of benzo[1,2-b:4,5-b′]dithiophene (BDT), and thienyl ([2H]T) or 3,4-difluorothiophene ([2F]T) motifs, and their BHJ device performance pattern with the nonfullerene acceptor “ITIC”. Studies show that the fluorine- and ring-substituted derivative PBDT(T)[2F]T largely outperforms its other two polymer donor counterparts, reaching power conversion efficiencies as high as 9.8%. Combining several characterization techniques, the gradual device performance improvements observed on swapping PBDT[2H]T for PBDT[2F]T, and then for PBDT(T)[2F]T, are found to result from (i) notably improved charge generation and collection efficiencies (estimated as ≈60%, 80%, and 90%, respectively), and (ii) reduced geminate recombination (being suppressed from ≈30%, 25% to 10%) and bimolecular recombination (inferred from recombination rate constant comparisons). These examinations will have broader implications for further studies on the optimization of BHJ solar cell efficiencies with polymer donors and a wider range of nonfullerene acceptors.

  19. Negative compressibility and non-equivalence of two statistical ensembles in the escape transition of a polymer chain

    NARCIS (Netherlands)

    Skvortsov, A.M.; Klushin, L.I.; Leermakers, F.A.M.

    2007-01-01

    An end-tethered polymer chain compressed between two pistons undergoes an abrupt transition from a confined coil state to an inhomogeneous flowerlike conformation partially escaped from the gap. This phase transition is first order in the thermodynamic limit of infinitely long chains. A rigorous

  20. Tuning the Mechanical Properties of Polymer Nanocomposites Filled with Grafted Nanoparticles by Varying the Grafted Chain Length and Flexibility

    Directory of Open Access Journals (Sweden)

    Zixuan Wang

    2016-08-01

    Full Text Available By employing coarse-grained molecular dynamics simulation, we simulate the spatial organization of the polymer-grafted nanoparticles (NPs in homopolymer matrix and the resulting mechanical performance, by particularly regulating the grafted chain length and flexibility. The morphologies ranging from the agglomerate, cylinder, sheet, and string to full dispersion are observed, by gradually increasing the grafted chain length. The radial distribution function and the total interaction energy between NPs are calculated. Meanwhile, the stress–strain behavior of each morphology and the morphological evolution during the uniaxial tension are simulated. In particular, the sheet structure exhibits the best mechanical reinforcement compared to other morphologies. In addition, the change of the grafted chain flexibility to semi-flexibility leads to the variation of the morphology. We also find that at long grafted chain length, the stress–strain behavior of the system with the semi-flexible grafted chain begins to exceed that of the system with the flexible grafted chain, attributed to the physical inter-locking interaction between the matrix and grafted polymer chains. A similar transition trend is as well found in the presence of the interfacial chemical couplings between grafted and matrix polymer chains. In general, this work is expected to help to design and fabricate high performance polymer nanocomposites filled with grafted NPs with excellent and controllable mechanical properties.

  1. Deformation and concentration fluctuations under stretching in a polymer network with free chains. The ''butterfly'' effect

    International Nuclear Information System (INIS)

    Ramzi, A.

    1994-06-01

    Small Angle Neutron Scattering gives access to concentration fluctuations of mobile labeled polymer chains embedded in a polymer network. At rest they appear progressively larger than for random mixing, with increasing ratio. Under uniaxial stretching, they decrease towards ideal mixing along the direction perpendicular to stretching, and can grow strongly along the parallel one, including the zero scattering vector q limit. This gives rise to intensity contours with double-winged patterns, in the shape of the figure '8', or of 'butterfly'. Random crosslinking and end-linking of monodisperse chains have both been studied. The strength of the 'butterfly' effect increases with the molecular weight of the free chains, the crosslinking ratio, the network heterogeneity, and the elongation ratio. Eventually, the signal collapses on an 'asymptotic' function I(q), of increasing correlation length with the elongation ratio. Deformation appears heterogeneous, maximal for soft areas, where the mobile chains localize preferentially. This could be due to spontaneous fluctuations, or linked to frozen fluctuations of the crosslink density. However, disagreement with the corresponding theoretical expressions makes it necessary to account for the spatial correlations of crosslink density, and their progressive unscreening as displayed by the asymptotic behavior. Networks containing pending labeled chains and free labeled stars lead to more precise understanding of the diffusion of free species and the heterogeneity of the deformation. It seems that the latter occurs even without diffusion for heterogeneous enough networks. In extreme cases (of the crosslinking parameters), the spatial correlations display on apparent fractal behavior, of dimensions 2 to 2.5, which is discussed here in terms of random clusters. 200 refs., 95 figs., 21 tabs., 10 appends

  2. Effect of the alkyl chain length of the ionic liquid anion on polymer electrolytes properties

    International Nuclear Information System (INIS)

    Leones, Rita; Sentanin, Franciani; Nunes, Sílvia Cristina; Esperança, José M.S.S.; Gonçalves, Maria Cristina

    2015-01-01

    New polymer electrolytes (PEs) based on chitosan and three ionic liquid (IL) families ([C 2 mim][C n SO 3 ], [C 2 mim][C n SO 4 ] and [C 2 mim][diC n PO 4 ]) were synthesized by the solvent casting method. The effect of the length of the alkyl chain of the IL anion on the thermal, morphological and electrochemical properties of the PEs was studied. The solid polymer electrolytes SPE membranes were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), polarized optical microscopy (POM), atomic force microscopy (AFM), complex impedance spectroscopy (ionic conductivity) and cyclic voltammetry (CV). The obtained results evidenced an influence of the alkyl chain length of the IL anion on the temperature of degradation, birefringence, surface roughness and ionic conductivity of the membranes. The DSC, XRD and CV results showed independency from the length of the IL-anion-alkyl chain. The PEs displayed an predominantly amorphous morphology, a minimum temperature of degradation of 135 °C, a room temperature (T = 25 °C) ionic conductivity of 7.78 × 10 −4 S cm −1 and a wide electrochemical window of ∼ 4.0 V.

  3. Dynamics of particle chain formation in a liquid polymer under ac electric field: modeling and experiments

    International Nuclear Information System (INIS)

    Belijar, G; Valdez-Nava, Z; Diaham, S; Laudebat, L; Lebey, T; Jones, T B

    2017-01-01

    Polymer/ceramic composite materials are of great interest for their many potential applications because of their ability to combine at least two properties of the constitutive elements: particles and matrix. In most cases, such enhanced properties are required only in one direction. Orthotropic materials can be elaborated by applying an ac electric field to form particle chain structures in the direction of the electric field due to the dielectrophoretic interactions affecting the particles. However, there is still a lack in the understanding of the impact of the structures on the properties of the material. The aim of this study is to propose a predictive model for the evolution of the permittivity during the chain formation, by including micro- and macroscopic phenomena. The chaining model is based on dipole–dipole interactions and the dielectric permittivity is computed through a finite element method. In parallel, an experimental study is performed with online permittivity measurements of composites during chaining. The developed model is able to predict the experimental results from 1 vol% while taking into account parameters such as the resin viscosity and permittivity and the transient evolution of the applied electric field. The formation of particle chains inside a material has applications in many domains such as electrorheological fluids, anisotropic composites, self-recovery materials etc. Such a developed model is a valuable tool for the tailoring of materials. (paper)

  4. A directed walk model of a long chain polymer in a slit with attractive walls

    International Nuclear Information System (INIS)

    Brak, R; Owczarek, A L; Rechnitzer, A; Whittington, S G

    2005-01-01

    We present the exact solutions of various directed walk models of polymers confined to a slit and interacting with the walls of the slit via an attractive potential. We consider three geometric constraints on the ends of the polymer and concentrate on the long chain limit. Apart from the general interest in the effect of geometrical confinement, this can be viewed as a two-dimensional model of steric stabilization and sensitized flocculation of colloidal dispersions. We demonstrate that the large width limit admits a phase diagram that is markedly different from the one found in a half-plane geometry, even when the polymer is constrained to be fixed at both ends on one wall. We are not able to find a closed form solution for the free energy for finite width, at all values of the interaction parameters, but we can calculate the asymptotic behaviour for large widths everywhere in the phase plane. This allows us to find the force between the walls induced by the polymer and hence the regions of the plane where either steric stabilization or sensitized flocculation would occur

  5. Concentration fluctuations in miscible polymer blends: Influence of temperature and chain rigidity

    International Nuclear Information System (INIS)

    Dudowicz, Jacek; Freed, Karl F.; Douglas, Jack F.

    2014-01-01

    In contrast to binary mixtures of small molecule fluids, homogeneous polymer blends exhibit relatively large concentration fluctuations that can strongly affect the transport properties of these complex fluids over wide ranges of temperatures and compositions. The spatial scale and intensity of these compositional fluctuations are studied by applying Kirkwood-Buff theory to model blends of linear semiflexible polymer chains with upper critical solution temperatures. The requisite quantities for determining the Kirkwood-Buff integrals are generated from the lattice cluster theory for the thermodynamics of the blend and from the generalization of the random phase approximation to compressible polymer mixtures. We explore how the scale and intensity of composition fluctuations in binary blends vary with the reduced temperature τ ≡ (T − T c )/T (where T c is the critical temperature) and with the asymmetry in the rigidities of the components. Knowledge of these variations is crucial for understanding the dynamics of materials fabricated from polymer blends, and evidence supporting these expectations is briefly discussed

  6. The Role of Chain Length in Nonergodicity Factor and Fragility of Polymers

    DEFF Research Database (Denmark)

    Dalle-Ferrie, Cecile; Niss, Kristine; Sokolov, Alexei

    2010-01-01

    The mechanism that leads to different fragility values upon approaching the glass transition remains a topic of active discussion. Many researchers are trying to find an answer in the properties of the frozen glassy state. Following this approach, we focus here on a previously proposed relationship...... between the fragility of glass-formers and their nonergodicity factor, determined by inelastic X-ray scattering (IXS) in the glass. We extend this molecular liquid study to two model polymers— polystyrene (PS) and polyisobutylene (PIB)—for which we change the molecular weight. Polymers offer...... the opportunity to change the fragility without altering the chemical structure, just by changing the chain length. Thus, we specifically chose PS and PIB because they exhibit opposite dependences of fragility with molecular weight. Our analysis for these two polymers reveals no unique correlation between...

  7. Surface relief gratings: experiments, physical scenarios, and photoinduced (anomalous) dynamics of functionalized polymer chains

    Science.gov (United States)

    Mitus, A. C.; Radosz, W.; Wysoczanski, T.; Pawlik, G.

    2017-10-01

    Surface Relief Gratings (SRG) were demonstrated experimentally more than 20 years ago. Despite many years of research efforts the underlying physical mechanisms remain unclear. In this paper we present a short overview of the main concepts related to SRG - photofluidization and its counterpart, the orientational approach - based on a seminal paper by Saphiannikova et al. Next, we summarize the derivation of the cos2 θ potential, following the lines of recent paper of this group. Those results validate the generic Monte Carlo model for the photoinduced build-up of the density and SRG gratings in a model polymer matrix functionalized with azo-dyes, presented in another part of the paper. The characterization of the photoinduced motion of polymer chains, based on our recent paper, is briefly discussed in the last part of the paper. This discussion offers a sound insight into the mechanisms responsible for inscription of SRG as well as for single functionalized nanoparticle studies.

  8. Controlled and selective placement of boron subphthalocyanines on either chain end of polymers synthesized by nitroxide mediated polymerization

    Directory of Open Access Journals (Sweden)

    Benoît H. Lessard

    2015-10-01

    Full Text Available In previous studies, we synthesized the first organic light emitting diode (OLED using boron subphthalocyanines (BsubPcs based polymers. When designing new polymer materials for organic electronic applications such as OLEDs or organic photovoltaic (OPV devices it is important to consider not only the contribution of each monomer but also the polymer chain ends. In this paper we establish a post-polymerization strategy to couple BsubPcs onto either the α- or the ω-chain end using chemically selective BsubPc derivatives. We outline how the chain ends of two representative polymers, poly(styrene (PS and poly(n-butylacrylate (BA, synthesized by nitroxide mediated polymerization (NMP, using BlocBuilder-MA as the initiating species, can be chemically modified by the incorporation of BsubPc chromophores. The addition of the BsubPc chromophore was confirmed through the use of a photodiode array detector (PDA connected in-line with a gel permeation chromatography (GPC setup. These findings represent the first reported method for the controlled and selective placement of a BsubPc chromophores on either end of a polymer produced by NMP. This strategy will therefore be utilized to make next generation BsubPc polymers for OLEDs and OPV devices. The extremely high molar extinction coefficient of BsubPc also make these polymers ideally suited for dye-labelling of polymers.

  9. Siloxane-Terminated Solubilizing Side Chains: Bringing Conjugated Polymer Backbones Closer and Boosting Hole Mobilities in Thin-Film Transistors

    KAUST Repository

    Mei, Jianguo

    2011-12-21

    We introduce a novel siloxane-terminated solubilizing group and demonstrate its effectiveness as a side chain in an isoindigo-based conjugated polymer. An average hole mobility of 2.00 cm 2 V -1 s -1 (with a maximum mobility of 2.48 cm 2 V -1 s -1), was obtained from solution-processed thin-film transistors, one of the highest mobilities reported to date. In contrast, the reference polymer with a branched alkyl side chain gave an average hole mobility of 0.30 cm 2 V -1 s -1 and a maximum mobility of 0.57 cm 2 V -1 s -1. This is largely explained by the polymer packing: our new polymer exhibited a π-π stacking distance of 3.58 Å, while the reference polymer showed a distance of 3.76 Å. © 2011 American Chemical Society.

  10. Smectic order and backbone anisotropy of a side-chain liquid crystalline polymer by Small-Angle Neutron Scattering

    Science.gov (United States)

    Noirez, L.; Pépy, G.; Keller, P.; Benguigui, L.

    1991-07-01

    We have simultaneously measured, for the first time, the extension of the polymer backbone of a side-chain liquid crystalline polymer and the intensity of the 001 Bragg reflection, which gives the smectic order parameter Psi as a function of temperature in the smectic phase. We have qualitatively demonstrated that the more the smectic phase is ordered, the more the polymer backbone is localized between the mesogenic layers. It is shown that the Landau theory allows us to relate the radius of gyration parallel to the magnetic field of the polymer backbone to the smectic order parameter. We also show that the Renz-Warner theory is suitable at low temperatures.

  11. A salt water battery with high stability and charging rates made from solution processed conjugated polymers with polar side chains

    OpenAIRE

    Moia, Davide; Giovannitti, Alexander; Szumska, Anna A.; Schnurr, Martin; Rezasoltani, Elham; Maria, Iuliana P.; Barnes, Piers R. F.; McCulloch, Iain; Nelson, Jenny

    2017-01-01

    We report a neutral salt water based battery which uses p-type and n-type solution processed polymer films as the cathode and the anode of the cell. The specific capacity of the electrodes (approximately 30 mAh cm-3) is achieved via formation of bipolarons in both the p-type and n-type polymers. By engineering ethylene glycol and zwitterion based side chains attached to the polymer backbone we facilitate rapid ion transport through the non-porous polymer films. This, combined with efficient t...

  12. Formation of Gd coordination polymer with 1D chains mediated by Bronsted acidic ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Qianqian; Han, Ying [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Lin, Hechun, E-mail: hclin@ee.ecnu.edu.cn [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Zhang, Yuanyuan; Duan, Chungang [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Peng, Hui, E-mail: hpeng@ee.ecnu.edu.cn [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan, Shanxi 030006 (China)

    2017-03-15

    One dimensional coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] (1) is prepared through the mediation of Bronsted acid ionic liquid, which crystallized in the monoclinic space of C2/c. In this polymer, adjacent Gd atoms are linked by two SO{sub 4}{sup 2-} ions to generate a 1-D chain, and all oxygen atoms in SO{sub 4}{sup 2-} groups are connected to three nearest Gd atoms in µ{sup 3}:η{sup 1}:η{sup 1}:η{sup 2} fashion. Gd, S and N from SO{sub 4}{sup 2-} and NO{sub 3}{sup -} are precisely coplanar. The planar is coordinated by a pair of DMSO molecules, which is parallel and linked by hydrogen bonding to form a three-dimensional supramolecular network. Magnetic susceptibility measurement of 1 reveals weak antiferromagnetic interactions between the Gd (III) ions. It exhibits relatively large magneto-caloric effect with –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH=7 T. - Graphical abstract: Coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] was obtained mediated by Bronsted acid Ionic Liquid, which presents a 1-D chains collected by SO{sub 4}{sup 2-} groups. Magnetic susceptibility of the polymer reveals weak antiferromagnetic interactions between the Gd(III) ions with the relatively large magneto-caloric effect of –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH= 7T.

  13. Charge Injection and Transport in Metal/Polymer Chains/Metal Sandwich Structure

    International Nuclear Information System (INIS)

    Hai-Hong, Li; Dong-Mei, Li; Yuan, Li; Kun, Gao; De-Sheng, Liu; Shi-Jie, Xie

    2008-01-01

    Using the tight-binding Su–Schrieffer–Heeger model and a nonadiabatic dynamic evolution method, we study the dynamic processes of the charge injection and transport in a metal/two coupled conjugated polymer chains/metal structure. It is found that the charge interchain transport is determined by the strength of the electric field and the magnitude of the voltage bias applied on the metal electrode. The stronger electric field and the larger voltage bias are both in favour of the charge interchain transport. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  14. Topological derivation of black hole entropy by analogy with a chain polymer

    International Nuclear Information System (INIS)

    Siino, Masaru

    2002-01-01

    The generic crease set of an event horizon possesses anisotropic structure although most black holes are dynamically stable. This fact suggests that a generic almost spherical black hole has a very crumpled crease set on a microscopic scale although the crease set is similar to a pointwise crease set on a macroscopic scale. In the present article, we count the number of such microstates of an almost spherical black hole by analogy with an elastic chain polymer. This estimation of black hole entropy reproduces the well-known Bekenstein-Hawking entropy of a Schwarzschild black hole

  15. Mean-field theory of photoinduced molecular reorientation in azobenzene liquid crystalline side-chain polymers

    DEFF Research Database (Denmark)

    Pedersen, T.G.; Johansen, P.M.

    1997-01-01

    . The theory provides an explanation for the high long-term stability of the photoinduced anisotropy as well as a theoretical prediction of the temporal behavior of photoinduced birefringence. The theoretical results agree favorably with measurements in the entire range of writing intensities used......A novel mean-field theory of photoinduced reorientation and optical anisotropy in liquid crystalline side-chain polymers is presented and compared with experiments, The reorientation mechanism is based on photoinduced trans cis isomerization and a multidomain model of the material is introduced...

  16. Mean-field theory of photoinduced formation of surface reliefs in side-chain azobenzene polymers

    DEFF Research Database (Denmark)

    Pedersen, Thomas Garm; Johansen, Per Michael; Holme, N.C.R.

    1998-01-01

    A mean-field model of photoinduced surface reliefs in dye containing side-chain polymers is presented. It is demonstrated that photoinduced ordering of dye molecules subject to anisotropic intermolecular interactions leads to mass transport even when the intensity of the incident light is spatially...... uniform. Theoretical profiles are obtained using a simple variational method and excellent agreement with experimental surface reliefs recorded under various polarization configurations is found. The polarization dependence of both period and shape of the profiles is correctly reproduced by the model....

  17. Effect of bidispersity in grafted chain length on grafted chain conformations and potential of mean force between polymer grafted nanoparticles in a homopolymer matrix.

    Science.gov (United States)

    Nair, Nitish; Wentzel, Nathaniel; Jayaraman, Arthi

    2011-05-21

    In efforts to produce polymeric materials with tailored physical properties, significant interest has grown around the ability to control the spatial organization of nanoparticles in polymer nanocomposites. One way to achieve controlled particle arrangement is by grafting the nanoparticle surface with polymers that are compatible with the matrix, thus manipulating the interfacial interactions between the nanoparticles and the polymer matrix. Previous work has shown that the molecular weight of the grafted polymer, both at high grafting density and low grafting density, plays a key role in dictating the effective inter-particle interactions in a polymer matrix. At high grafting density nanoparticles disperse (aggregate) if the graft molecular weight is higher (lower) than the matrix molecular weight. At low grafting density the longer grafts can better shield the nanoparticle surface from direct particle-particle contacts than the shorter grafts and lead to the dispersion of the grafted particles in the matrix. Despite the importance of graft molecular weight, and evidence of non-trivial effects of polydispersity of chains grafted on flat surfaces, most theoretical work on polymer grafted nanoparticles has only focused on monodisperse grafted chains. In this paper, we focus on how bidispersity in grafted chain lengths affects the grafted chain conformations and inter-particle interactions in an implicit solvent and in a dense homopolymer polymer matrix. We first present the effects of bidispersity on grafted chain conformations in a single polymer grafted particle using purely Monte Carlo (MC) simulations. This is followed by calculations of the potential of mean force (PMF) between two grafted particles in a polymer matrix using a self-consistent Polymer Reference Interaction Site Model theory-Monte Carlo simulation approach. Monte Carlo simulations of a single polymer grafted particle in an implicit solvent show that in the bidisperse polymer grafted particles

  18. Molecular origin of urea driven hydrophobic polymer collapse and unfolding depending on side chain chemistry.

    Science.gov (United States)

    Nayar, Divya; Folberth, Angelina; van der Vegt, Nico F A

    2017-07-19

    Osmolytes affect hydrophobic collapse and protein folding equilibria. The underlying mechanisms are, however, not well understood. We report large-scale conformational sampling of two hydrophobic polymers with secondary and tertiary amide side chains using extensive molecular dynamics simulations. The calculated free energy of unfolding increases with urea for the secondary amide, yet decreases for the tertiary amide, in agreement with experiment. The underlying mechanism is rooted in opposing entropic driving forces: while urea screens the hydrophobic macromolecular interface and drives unfolding of the tertiary amide, urea's concomitant loss in configurational entropy drives collapse of the secondary amide. Only at sufficiently high urea concentrations bivalent urea hydrogen bonding interactions with the secondary amide lead to further stabilisation of its collapsed state. The observations provide a new angle on the interplay between side chain chemistry, urea hydrogen bonding, and the role of urea in attenuating or strengthening the hydrophobic effect.

  19. Effects of internal friction on contact formation dynamics of polymer chain

    Science.gov (United States)

    Bian, Yukun; Li, Peng; Zhao, Nanrong

    2018-04-01

    A theoretical framework is presented to study the contact formation dynamics of polymer chains, in accompany with an electron-transfer quenching. Based on a non-Markovian Smoluchowski equation supplemented with an exponential sink term, we derive the mean time of contact formation under Wilemski-Fixman approximation. Our particular attentions are paid to the effect of internal friction. We find out that internal friction induces a novel fractional viscosity dependence, which will become more remarkable as internal friction increases. Furthermore, we clarify that internal friction inevitably promotes a diffusion-controlled mechanism by slowing the chain relaxation. Finally, we apply our theory to rationalise the experimental investigation for contact formation of a single-stranded DNA. The theoretical results can reproduce the experimental data very well with quite reasonable estimation for the intrinsic parameters. Such good agreements clearly demonstrate the validity of our theory which has appropriately addressed the very role of internal friction to the relevant dynamics.

  20. Revealing the Supramolecular Nature of Side-Chain Terpyridine-Functionalized Polymer Networks

    Directory of Open Access Journals (Sweden)

    Jérémy Brassinne

    2015-01-01

    Full Text Available Nowadays, finely controlling the mechanical properties of polymeric materials is possible by incorporating supramolecular motifs into their architecture. In this context, the synthesis of a side-chain terpyridine-functionalized poly(2-(dimethylaminoethyl methacrylate is reported via reversible addition-fragmentation chain transfer polymerization. By addition of transition metal ions, concentrated aqueous solutions of this polymer turn into metallo-supramolecular hydrogels whose dynamic mechanical properties are investigated by rotational rheometry. Hence, the possibility for the material to relax mechanical constrains via dissociation of transient cross-links is brought into light. In addition, the complex phenomena occurring under large oscillatory shear are interpreted in the context of transient networks.

  1. Adsorption of a single polymer chain on a surface: effects of the potential range.

    Science.gov (United States)

    Klushin, Leonid I; Polotsky, Alexey A; Hsu, Hsiao-Ping; Markelov, Denis A; Binder, Kurt; Skvortsov, Alexander M

    2013-02-01

    We investigate the effects of the range of adsorption potential on the equilibrium behavior of a single polymer chain end-attached to a solid surface. The exact analytical theory for ideal lattice chains interacting with a planar surface via a box potential of depth U and width W is presented and compared to continuum model results and to Monte Carlo (MC) simulations using the pruned-enriched Rosenbluth method for self-avoiding chains on a simple cubic lattice. We show that the critical value U(c) corresponding to the adsorption transition scales as W(-1/ν), where the exponent ν=1/2 for ideal chains and ν≈3/5 for self-avoiding walks. Lattice corrections for finite W are incorporated in the analytical prediction of the ideal chain theory U(c)≈(π(2)/24)(W+1/2)(-2) and in the best-fit equation for the MC simulation data U(c)=0.585(W+1/2)(-5/3). Tail, loop, and train distributions at the critical point are evaluated by MC simulations for 1≤W≤10 and compared to analytical results for ideal chains and with scaling theory predictions. The behavior of a self-avoiding chain is remarkably close to that of an ideal chain in several aspects. We demonstrate that the bound fraction θ and the related properties of finite ideal and self-avoiding chains can be presented in a universal reduced form: θ(N,U,W)=θ(NU(c),U/U(c)). By utilizing precise estimations of the critical points we investigate the chain length dependence of the ratio of the normal and lateral components of the gyration radius. Contrary to common expectations this ratio attains a limiting universal value /=0.320±0.003 only at N~5000. Finite-N corrections for this ratio turn out to be of the opposite sign for W=1 and for W≥2. We also study the N dependence of the apparent crossover exponent φ(eff)(N). Strong corrections to scaling of order N(-0.5) are observed, and the extrapolated value φ=0.483±0.003 is found for all values of W. The strong correction to scaling effects found here explain why

  2. Chain Gang-The Chemistry of Polymers (edited by Mickey Sarquis)

    Science.gov (United States)

    Collard, David M.

    1999-01-01

    Science in Our World, Vol. 5. Mickey Sarquis, series editor. Terrific Science Press: Middletown, OH, 1995. xiv + 149 pp. ISBN 1-883822-13-0. Spiral-bound, $13.95. Our familiarity with plastics makes polymers ideal examples of chemicals for discussion in K-12 science classes. Most importantly, polymers can be used as examples of chemicals that are safe to handle and of obvious use to society. The structures of polymers are easily represented by a number of models. These simple models go a long way in explaining the familiar physical properties of plastics. However, the introduction of polymers in the classroom relies on the availability of teaching material, experiments, and demonstrations that illustrate concepts in the current science curriculum. Chain Gang-The Chemistry of Polymers, one of the Science in Our World series published by the Center for Chemical Education at Miami University-Middletown (Ohio), will serve as a great resource for teachers interested in providing their students with a series of activities that can be related to their everyday experiences with these ubiquitous chemicals. After a brief introduction to some basic concepts, the book presents a series of 23 experiments. The collection of experiments presented here spans illustrations of chemistry, physical properties, analysis, and processing. Each experiment is recommended as either a hands-on activity or demonstration for various grade levels. A guide for the teacher suggests how the experiment can be used to illustrate topics in the science curriculum. The materials required for each activity are listed in detail, with quantities and sources (all materials are available from Flinn Scientific or hardware stores). There are detailed instructions for preparation of each experiment and how to introduce the experiment to students, and step-by-step instructions for activity. Very importantly, safety and disposal issues are clearly presented. Suggestions for cross-curriculum integration are also

  3. Nanophase separation in side chain polymers: new evidence from structure and dynamics

    International Nuclear Information System (INIS)

    Hiller, S; Pascui, O; Budde, H; Kabisch, O; Reichert, D; Beiner, M

    2004-01-01

    New evidence for a nanophase separation of incompatible main and side chain parts in amorphous poly(n-alkyl methacrylates) with long alkyl groups are presented. Independent indications for the existence of alkyl nanodomains with a typical dimension in the 1 nm range from studies on dynamics and structure are reported. Results from nuclear magnetic resonance (NMR) experiments are compared with data from different relaxation spectroscopy methods on poly(n-decyl methacrylate). The NMR results in combination with relaxation spectroscopy data support the existence of an independent polyethylene-like glass transition, α PE , within the alkyl nanodomains in addition to the conventional glass transition a at higher temperatures. X-ray scattering data show that the situation in homopolymers is similar to that for random poly(n-alkyl methacrylate) copolymers with the same average length of the alkyl group in the side chains. Scattering data for a series of n-butyl methacrylate samples with polymerization degrees reaching from P=1 to 405 indicate that nanophase separation is chain-length independent above P=25, while the nanophase separation tends to disappear below P=6. Insensitivity of structural aspects in nanophase-separated poly(n-alkyl methacrylates) to changes in the molecular microstructure and consistency of NMR results with independent conclusions from relaxation spectroscopy underline the general importance of nanophase separation effects in a broad class of side chain polymers

  4. Confinement Effects on Host Chain Dynamics in Polymer Nanocomposite Thin Films

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Kyle J. [Department; Glynos, Emmanouil [Department; Maroulas, Serafeim-Dionysios [Department; Narayanan, Suresh [Advanced; Sakellariou, Georgios [Department; Green, Peter F. [Department; National

    2017-09-06

    Incorporating nanoparticles (NPs) within a polymer host to create polymer nanocomposites (PNCs) while having the effect of increasing the functionality (e.g.: sensing, energy conversion) of these materials, introduces additional complications with regard to the processing-morphology-function behavior. A primary challenge is to understand and control the viscosity of a PNC with decreasing film thickness confinement for nanoscale applications. Using a combination of X-ray photon correlation spectroscopy (XPCS) and X-ray standing wave based resonance enhanced XPCS to study the dynamics of neat poly-2-vinyl pyridine (P2VP) chains and the nanoparticle dynamics, respectively, we identified a new mechanism that dictates the viscosity of PNC films in the nanoscale regime. We show that while the viscosities of neat P2VP films as thin as 50 nm remained the same as the bulk, PNC films containing P2VP brush-coated gold NPs, spaced 50 nm apart, exhibited unprecedented increases in viscosities of over an order of magnitude. For thicker films or more widely separated NPs, the chain dynamics and viscosities were equal to the bulk values. These results -NP proximities and suppression of their dynamics -suggest a new mechanism by which the viscosities of polymeric liquids could be controlled for 2D and 3D nanoscale applications.

  5. A New 1D Chained Coordination Polymer: Synthesis, Crystal Structure, Antitumor Activity and Luminescent Property

    Directory of Open Access Journals (Sweden)

    Xi-Shi Tai

    2015-11-01

    Full Text Available A new 1D chained coordination polymer of Zn(II, {[Zn(L2(4,4′-bipy]·(H2O}n(1 (HL = N-acetyl-l-phenylalanine; 4,4′-bipy = 4,4′-bipyridine has been synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. Theresults show that each asymmetric unit of Zn(II complex belongs to monoclinic, space group P21 with a = 11.421(2 Å, b = 9.2213(17 Å, c = 15.188(3 Å,β = 106.112(3°, V = 1536.7(5 Å3, Z = 2, Dc = 1.444 g·cm−3, µ = 0.857 mm−1, F(000 = 696, and final R1 = 0.0439, ωR2 = 0.1013. The molecules form one-dimensional chained structure by its the bridging 4,4′-bipyridine ligands. The antitumor activities and luminescent properties of Zn(II coordination polymer have also been investigated.

  6. Detachment of semiflexible polymer chains from a substrate: A molecular dynamics investigation

    Energy Technology Data Exchange (ETDEWEB)

    Paturej, J. [Leibniz-Institut of Poslymer Research Dresden, 01069 Dresden (Germany); Institute of Physics, University of Szczecin, Wielkopolska 15, 70451 Szczecin (Poland); Erbas, A. [Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208 (United States); Milchev, A. [Institute for Physical Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Rostiashvili, V. G. [Max-Planck-Institute for Polymer Research, Ackermannweg 10, 55128 Mainz (Germany)

    2014-12-07

    Using Molecular Dynamics simulations, we study the force-induced detachment of a coarse-grained model polymer chain from an adhesive substrate. One of the chain ends is thereby pulled at constant speed off the attractive substrate and the resulting saw-tooth profile of the measured mean force 〈f〉 vs height D of the end-segment over the plane is analyzed for a broad variety of parameters. It is shown that the observed characteristic oscillations in the 〈f〉-D profile depend on the bending and not on the torsional stiffness of the detached chains. Allowing for the presence of hydrodynamic interactions (HI) in a setup with explicit solvent and dissipative particle dynamics-thermostat, rather than the case of Langevin thermostat, one finds that HI have little effect on the 〈f〉-D profile. Also the change of substrate affinity with respect to the solvent from solvophilic to solvophobic is found to play negligible role in the desorption process. In contrast, a changing ratio ε{sub s}{sup B}/ε{sub s}{sup A} of the binding energies of A- and B-segments in the detachment of an AB-copolymer from adhesive surface strongly changes the 〈f〉-D profile whereby the B-spikes vanish when ε{sub s}{sup B}/ε{sub s}{sup A}<0.15. Eventually, performing an atomistic simulation of (bio)-polymers, we demonstrate that the simulation results, derived from our coarse-grained model, comply favorably with those from the all-atom simulation.

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

    Science.gov (United States)

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

    2006-12-01

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

  8. A salt water battery with high stability and charging rates made from solution processed conjugated polymers with polar side chains

    KAUST Repository

    Moia, Davide; Giovannitti, Alexander; Szumska, Anna A.; Schnurr, Martin; Rezasoltani, Elham; Maria, Iuliana P.; Barnes, Piers R. F.; McCulloch, Iain; Nelson, Jenny

    2017-01-01

    conjugated polymer backbones, allowed the films to maintain constant capacity at high charge and discharge rates (>1000 C-rate). The electrodes also show good stability during electrochemical cycling (less than 30% decrease in capacity over >1000 cycles) and an output voltage up to 1.4 V. The performance of these semiconducting polymers with polar side-chains demonstrates the potential of this material class for fast-charging, water based electrochemical energy storage devices.

  9. Interplay Between Side Chain Pattern, Polymer Aggregation, and Charge Carrier Dynamics in PBDTTPD:PCBM Bulk-Heterojunction Solar Cells

    KAUST Repository

    Dyer-Smith, Clare

    2015-05-01

    Poly(benzo[1,2-b:4,5-b′]dithiophene–alt–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymer donors with linear side-chains yield bulk-heterojunction (BHJ) solar cell power conversion efficiencies (PCEs) of about 4% with phenyl-C71-butyric acid methyl ester (PC71BM) as the acceptor, while a PBDTTPD polymer with a combination of branched and linear substituents yields a doubling of the PCE to 8%. Using transient optical spectroscopy it is shown that while the exciton dissociation and ultrafast charge generation steps are not strongly affected by the side chain modifications, the polymer with branched side chains exhibits a decreased rate of nongeminate recombination and a lower fraction of sub-nanosecond geminate recombination. In turn the yield of long-lived charge carriers increases, resulting in a 33% increase in short circuit current (J sc). In parallel, the two polymers show distinct grazing incidence X-ray scattering spectra indicative of the presence of stacks with different orientation patterns in optimized thin-film BHJ devices. Independent of the packing pattern the spectroscopic data also reveals the existence of polymer aggregates in the pristine polymer films as well as in both blends which trap excitons and hinder their dissociation.

  10. Proof of the identity between the depletion layer thickness and half the average span for an arbitrary polymer chain

    DEFF Research Database (Denmark)

    Wang, Yanwei; Peters, Günther H.J.; Hansen, Flemming Yssing

    2008-01-01

    point in the polymer chain (such as the center of mass, middle segment, and end segments) can be computed as a function of the confinement size solely based on a single sampling of the configuration space of a polymer chain in bulk. Through a simple analysis based on the CABS approach in the case...... of a single wall, we prove rigorously that (i) the depletion layer thickness delta is the same no matter which reference point is used to describe the depletion profile and (ii) the value of delta equals half the average span (the mean projection onto a line) of the macromolecule in free solution. Both...

  11. Factors Governing Intercalation of Fullerenes and Other Small Molecules Between the Side Chains of Semiconducting Polymers Used in Solar Cells

    KAUST Repository

    Miller, Nichole Cates

    2012-08-22

    While recent reports have established signifi cant miscibility in polymer:fullerene blends used in organic solar cells, little is actually known about why polymers and fullerenes mix and how their mixing can be controlled. Here, X-ray diffraction (XRD), differential scanning calorimetry (DSC), and molecular simulations are used to study mixing in a variety of polymer:molecule blends by systematically varying the polymer and smallmolecule properties. It is found that a variety of polymer:fullerene blends mix by forming bimolecular crystals provided there is suffi cient space between the polymer side chains to accommodate a fullerene. Polymer:tetrafl uoro-tetracyanoquinodimethane (F4-TCNQ) bimolecular crystals were also observed, although bimolecular crystals did not form in the other studied polymer:nonfullerene blends, including those with both conjugated and non-conjugated small molecules. DSC and molecular simulations demonstrate that strong polymer-fullerene interactions can exist, and the calculations point to van der Waals interactions as a signifi cant driving force for molecular mixing. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Tunable Crystal-to-Crystal Phase Transition in a Cadmium Halide Chain Polymer

    Directory of Open Access Journals (Sweden)

    Ulli Englert

    2011-07-01

    Full Text Available The chain polymer [{Cd(μ-X2py2}1∞] (X = Cl, Br; py = pyridine undergoes a fully reversible phase transition between a monoclinic low-temperature and an orthorhombic high-temperature phase. The transformation can be directly monitored in single crystals and can be confirmed for the bulk by powder diffraction. The transition temperature can be adjusted by tuning the composition of the mixed-halide phase: Transition temperatures between 175 K up to the decomposition of the material at ca. 350 K are accessible. Elemental analysis, ion chromatography and site occupancy refinements from single-crystal X-ray diffraction agree with respect to the stoichiometric composition of the samples.

  13. Modeling the dynamics of polymer chains in water solution. Application to sensor design

    Science.gov (United States)

    Starovoitov, V. N.; Starovoitova, B. N.

    2017-10-01

    This paper is devoted to a mathematical model of a chaotic dynamics of a polymer chain in water. The model consists of a parabolic equation that is derived according to the self-consistent field approach. This model is employed for the numerical simulation of a biological sensor that detects the presence of a specific protein in the fluid. The sensor is absolutely simple and seems to be new. Besides that, the suggested equation is interesting from the mathematical point of view. It includes a non-local operator of integration not only over the past time interval as in the problems with memory but also over the future time interval. It is unusual for parabolic problems.

  14. Micro tooling technologies for polymer micro replication: direct, indirect and hybrid process chains

    DEFF Research Database (Denmark)

    Tosello, Guido; Hansen, Hans Nørgaard

    2009-01-01

    The increasing employment of micro products, of products containing micro parts and of products with micro-structured surfaces calls for mass fabrication technologies based on replication processes. In many cases, a suitable solution is given by the use of polymer micro products, whose production...... and performance of the corresponding micro mould. Traditional methods of micro tooling, such as various machining processes (e.g. micro milling, micro electrical discharge machining) have already reached their limitations with decreasing dimensions of mould inserts and cavities. To this respect, tooling process...... chains based on combination of micro manufacturing processes (defined as hybrid tooling) have been established in order to obtain further features miniaturization and increased accuracy. In this paper, examples and performance of different hybrid tooling approaches as well as challenges, opportunities...

  15. “Value Added Taxes, Chain Effects and Informality”, Second Version

    OpenAIRE

    Aureo de Paula; Jose A. Scheinkman

    2009-01-01

    This paper investigates determinants of informal economic activity. We present an equilibrium model of informality and test its implications using a survey of 48,000+ small firms in Brazil. We define informality as tax avoidance; firms in the informal sector avoid tax payments but suffer other limitations. A novel theoretical contribution in this model is the role of value added taxes in transmitting informality. It predicts that the informality of a firm is correlated to the informality of f...

  16. Polyurea with luminophor fragments in polymer chain: synthesis and spectral properties

    Science.gov (United States)

    Novikova, Tamara S.; Barashkov, Nikolay N.; Sakhno, Tamara V.

    2003-12-01

    A series of aliphatic polyureas with chromophore moieties in the polymer chain, such as 7-amino-2(4"-aminophenyl)benzoxazole, have been prepared. The absorption and fluorescence spectra of these polymers as well as corresponding chromophore-containing model urea (product of condensation of 7-amino-2(4"-amino-2"-hydroxyphenyl)benzoxazole and phenylisocyanate) were studied and compared. It was found that the special feature of the model compound and polyureas is the large value of Stokes shift due to the presence of a hydroxy group in the ortho-position to the nitrogen atom of the benzoxazole ring. The model of the excited-state proton transfer in molecules containing fragments of 2-(2"-hydroxyphenyl)benzoxazole has been used for the description of bathochromic shift in emission spectra of polymer solutions and films. According to this model, the proton remains predominantly on the phenol oxygen while in the ground state (enol form). Upon UV excitation, in the first excited singlet state, the phenol is a considerably stronger acid and the nitrogen is a stronger base. Thus, the proton is transferred from the oxygen site to the nitrogen site, and the isomer formed (S"1*) is more stable than the isomer before proton transfer (S1*) S"1* can be then regarded as a vibrationally excited form of S1*. Then the molecule de-excites to the ground state, emitting a photon. In the ground state the enol form is again the more stable form and the proton will then transfer back to the oxygen. S"o is also a vibrationally excited state of So. Because of this process the absorption and fluorescence spectra of model urea and polyureas do not intersect and the value of Stokes shift is about 6000 cm-1.

  17. Biogenesis and the growth of DNA-like polymer chains: a computer simulation

    International Nuclear Information System (INIS)

    Herrmann, H.J.; Tsallis, C.

    1987-01-01

    We study, through computer simulation, a crucial step of Biogenesis, namely the growth of self-replicating codified DNA-like polymers starting from a mixture of oligomers. We have adopted the growth scheme that has been recently proposed by Ferreira and Tsallis which incorporates usual ideas of autocatalysis through complementary pairs and within which a central role is played by the hydrogen-like links (characterized by the probabilities p AT and p CG of chemical bonding of the A-T and C-G pairs respectively) between the two chains of the growing polymer. We find that the average equilibrium polymeric length ξ diverges, for any fixed ratio (1-p AT )/(1-p sub (CG)), as ξ ∝ 1/r1-p AT . Selection of patterns may happen at all stages and in particular at chemical equilibrium. Selection occurs via two different mechanisms: (i) away from the critical point p AT = p CG = 1 if p AT ≠ p CG ; (ii) both on and away from the critical point if the initial concentrations of nucleotides (A, T, C and G or their precursors) are different. (author) [pt

  18. Heat conduction in chain polymer liquids: molecular dynamics study on the contributions of inter- and intramolecular energy transfer.

    Science.gov (United States)

    Ohara, Taku; Yuan, Tan Chia; Torii, Daichi; Kikugawa, Gota; Kosugi, Naohiro

    2011-07-21

    In this paper, the molecular mechanisms which determine the thermal conductivity of long chain polymer liquids are discussed, based on the results observed in molecular dynamics simulations. Linear n-alkanes, which are typical polymer molecules, were chosen as the target of our studies. Non-equilibrium molecular dynamics simulations of bulk liquid n-alkanes under a constant temperature gradient were performed. Saturated liquids of n-alkanes with six different chain lengths were examined at the same reduced temperature (0.7T(c)), and the contributions of inter- and intramolecular energy transfer to heat conduction flux, which were identified as components of heat flux by the authors' previous study [J. Chem. Phys. 128, 044504 (2008)], were observed. The present study compared n-alkane liquids with various molecular lengths at the same reduced temperature and corresponding saturated densities, and found that the contribution of intramolecular energy transfer to the total heat flux, relative to that of intermolecular energy transfer, increased with the molecular length. The study revealed that in long chain polymer liquids, thermal energy is mainly transferred in the space along the stiff intramolecular bonds. This finding implies a connection between anisotropic thermal conductivity and the orientation of molecules in various organized structures with long polymer molecules aligned in a certain direction, which includes confined polymer liquids and self-organized structures such as membranes of amphiphilic molecules in water.

  19. Nature of the Binding Interactions between Conjugated Polymer Chains and Fullerenes in Bulk Heterojunction Organic Solar Cells

    KAUST Repository

    Ravva, Mahesh Kumar

    2016-10-24

    Blends of π-conjugated polymers and fullerene derivatives are ubiquitous as the active layers of organic solar cells. However, a detailed understanding of the weak noncovalent interactions at the molecular level between the polymer chains and fullerenes is still lacking and could help in the design of more efficient photoactive layers. Here, using a combination of long-range corrected density functional theory calculations and molecular dynamic simulations, we report a thorough characterization of the nature of binding between fullerenes (C60 and PC61BM) and poly(benzo[1,2-b:4,5-b′]dithiophene–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) chains. We illustrate the variations in binding strength when the fullerenes dock on the electron-rich vs electron-poor units of the polymer as well as the importance of the role played by the polymer and fullerene side chains and the orientations of the PC61BM molecules with respect to the polymer backbones.

  20. DMFC Performance of Polymer Electrolyte Membranes Prepared from a Graft-Copolymer Consisting of a Polysulfone Main Chain and Styrene Sulfonic Acid Side Chains

    Directory of Open Access Journals (Sweden)

    Nobutaka Endo

    2016-08-01

    Full Text Available Polymer electrolyte membranes (PEMs for direct methanol fuel cell (DMFC applications were prepared from a graft-copolymer (PSF-g-PSSA consisting of a polysulfone (PSF main chain and poly(styrene sulfonic acid (PSSA side chains with various average distances between side chains (Lav and side chain lengths (Lsc. The polymers were synthesized by grafting ethyl p-styrenesulfonate (EtSS on macro-initiators of chloromethylated polysulfone with different contents of chloromethyl (CM groups, and by changing EtSS content in the copolymers by using atom transfer radical polymerization (ATRP. The DMFC performance tests using membrane electrode assemblis (MEAs with the three types of the PEMs revealed that: a PSF-g-PSSA PEM (SF-6 prepared from a graft copolymer with short average distances between side chains (Lav and medium Lsc had higher DMFC performance than PEMs with long Lav and long Lsc or with short Lav and short Lsc. SF-6 had about two times higher PDmax (68.4 mW/cm2 than Nafion® 112 at 30 wt % of methanol concentration. Furthermore, it had 58.2 mW/cm2 of PDmax at 50 wt % of methanol concentration because of it has the highest proton selectivity during DMFC operation of all the PSF-g-PSSA PEMs and Nafion® 112.

  1. Free-radical-induced chain scission and cross-linking of polymers in aqueous solution. An overview

    International Nuclear Information System (INIS)

    Von Sonntag, C.

    2002-01-01

    Complete text of publication follows. In the radiolysis of N 2 O-saturated aqueous solutions OH are generated. In their reactions with polymers, they give rise to polymer-derived radicals. The kinetics of the formation and decay of these radicals are reviewed. The rate of reaction of a polymer with a reactive free radical is noticeably lower than that of an equivalent concentration of monomer due to the non-random distribution of the reaction sites. Once a larger number of radicals are formed on one polymer molecule, e.g. upon pulse radiolysis, close-by radicals recombine more rapidly while the more distant ones survive for much longer times than an equivalent concentration of freely diffusing radicals. Intermolecular cross-linking (between two polymer chains, increase in molecular weight) and intramolecular cross-linking (formation of small loops, no increase in polymer weight) are competing processes, and their relative yields thus depend on the dose rate and polymer concentration. Hydrogen-transfer reactions within the polymer, e.g. transformation of a secondary radical into a tertiary one, are common and facilitated by the high local density of reactive sites. Due to repulsive forces, the lifetime of radicals of charged polymers is substantially increased. This enables even relatively slow b-fragmentation reactions to become of importance. In the case of poly(methacrylic acid), where β-fragmentation is comparatively fast, this even leads to an unzipping, and as a consequence of the efficient release of methacrylic acid the situation of equilibrium polymerization is approached. Heterolytic β-fragmentation is possible when adequate leaving groups are available, e.g. in polynucleotides and DNA. In the presence of O 2 , chain scission occurs via oxyl radicals as intermediates. Some implications for technical applications are discussed

  2. Segment-scale, force-level theory of mesoscopic dynamic localization and entropic elasticity in entangled chain polymer liquids

    Science.gov (United States)

    Dell, Zachary E.; Schweizer, Kenneth S.

    2017-04-01

    We develop a segment-scale, force-based theory for the breakdown of the unentangled Rouse model and subsequent emergence of isotropic mesoscopic localization and entropic elasticity in chain polymer liquids in the absence of ergodicity-restoring anisotropic reptation or activated hopping motion. The theory is formulated in terms of a conformational N-dynamic-order-parameter generalized Langevin equation approach. It is implemented using a universal field-theoretic Gaussian thread model of polymer structure and closed at the level of the chain dynamic second moment matrix. The physical idea is that the isotropic Rouse model fails due to the dynamical emergence, with increasing chain length, of time-persistent intermolecular contacts determined by the combined influence of local uncrossability, long range polymer connectivity, and a self-consistent treatment of chain motion and the dynamic forces that hinder it. For long chain melts, the mesoscopic localization length (identified as the tube diameter) and emergent entropic elasticity predictions are in near quantitative agreement with experiment. Moreover, the onset chain length scales with the semi-dilute crossover concentration with a realistic numerical prefactor. Distinctive novel predictions are made for various off-diagonal correlation functions that quantify the full spatial structure of the dynamically localized polymer conformation. As the local excluded volume constraint and/or intrachain bonding spring are softened to allow chain crossability, the tube diameter is predicted to swell until it reaches the radius-of-gyration at which point mesoscopic localization vanishes in a discontinuous manner. A dynamic phase diagram for such a delocalization transition is constructed, which is qualitatively consistent with simulations and the classical concept of a critical entanglement degree of polymerization.

  3. Fine-tuning blend morphology via alkylthio side chain engineering towards high performance non-fullerene polymer solar cells

    Science.gov (United States)

    Li, Ling; Feng, Liuliu; Yuan, Jun; Peng, Hongjian; Zou, Yingping; Li, Yongfang

    2018-03-01

    Two medium bandgap polymers (ffQx-TS1, ffQx-TS2) were designed and synthesized to investigate the influence of different alkylthio side chain on the morphology and photovoltaic performance of non-fullerene polymer solar cells (PSCs). Both polymers exhibit similar molecular weights and comparable the highest occupied molecular orbital (HOMO) energy level. However, the polymer with straight alkylthio chain delivers a root-mean-square (RMS) of 0.86 nm, which is slightly lower than that with branched chain (1.40 nm). The lower RMS benefits the ohmic contact between the active lay and interface layer, thus enhanced short circuit current (Jsc) (from 13.54 mA cm-1 to 15.25 mA cm-1) could be obtained. Due to the enhancement of Jsc, better power conversion efficiency (PCE) of 7.69% for ffQx-TS2 could be realized. These results indicated that alkylthio side chain engineering is a promising method to improve photovoltaic performance.

  4. Development of environmentally friendly coatings and paints using medium-chain-length poly(3-hydroxyalkanoates) as the polymer binder

    NARCIS (Netherlands)

    Walle, van der G.A.M.; Buisman, F.J.H.; Weusthuis, R.A.; Eggink, G.

    1999-01-01

    Unsaturated medium-chain-length poly(3-hydroxyalkanoates) (mcl-PHAs) produced by Pseudomonas putida from linseed oil fatty acids (LOFA) and tall oil fatty acids (TOFA), were used as the polymer binder in the formulation of high solid alkyd-like paints. The relatively high concentration of

  5. Interplay Between Side Chain Pattern, Polymer Aggregation, and Charge Carrier Dynamics in PBDTTPD:PCBM Bulk-Heterojunction Solar Cells

    KAUST Repository

    Dyer-Smith, Clare; Howard, Ian A.; Cabanetos, Clement; El Labban, Abdulrahman; Beaujuge, Pierre; Laquai, Fré dé ric

    2015-01-01

    Poly(benzo[1,2-b:4,5-b′]dithiophene–alt–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymer donors with linear side-chains yield bulk-heterojunction (BHJ) solar cell power conversion efficiencies (PCEs) of about 4% with phenyl-C71-butyric acid methyl

  6. Siloxane-Terminated Solubilizing Side Chains: Bringing Conjugated Polymer Backbones Closer and Boosting Hole Mobilities in Thin-Film Transistors

    KAUST Repository

    Mei, Jianguo; Kim, Do Hwan; Ayzner, Alexander L.; Toney, Michael F.; Bao, Zhenan

    2011-01-01

    We introduce a novel siloxane-terminated solubilizing group and demonstrate its effectiveness as a side chain in an isoindigo-based conjugated polymer. An average hole mobility of 2.00 cm 2 V -1 s -1 (with a maximum mobility of 2.48 cm 2 V -1 s -1

  7. Extensional Strain Hardening Induced by π -π Interactions in Barely Entangled Polymer Chains: The Curious Case of Poly(4-vinylbiphenyl)

    Science.gov (United States)

    López-Barrón, Carlos R.; Zhou, Huaxing

    2017-12-01

    Aromatic π -π interactions between phenyl groups of adjacent chains in poly(4-vinylbiphenyl) (PVBP) have profound effects on the dynamics of this polymer. We report two unexpected nonlinear viscoelastic responses of PVBP when subjected to uniaxial flow. One is the unprecedented observation of extensional strain hardening (SH) in a barely entangled polymer melt. An even more intriguing finding is that SH of lightly (or even barely) entangled melts occurs at strain rates one order of magnitude below the coil-stretch transition predicted by Rouse theory (ɛ˙ H=0.5 /τR ).We postulate that this behavior is due to a molecular rearrangement mechanism (supported by x-ray diffraction measurements) that involves flow-induced π -π stacking of the phenyl groups, which results in an enhancement of the friction coefficient between polymer chains.

  8. A salt water battery with high stability and charging rates made from solution processed conjugated polymers with polar side chains

    KAUST Repository

    Moia, Davide

    2017-11-28

    We report a neutral salt water based battery which uses p-type and n-type solution processed polymer films as the cathode and the anode of the cell. The specific capacity of the electrodes (approximately 30 mAh cm-3) is achieved via formation of bipolarons in both the p-type and n-type polymers. By engineering ethylene glycol and zwitterion based side chains attached to the polymer backbone we facilitate rapid ion transport through the non-porous polymer films. This, combined with efficient transport of electronic charge via the conjugated polymer backbones, allowed the films to maintain constant capacity at high charge and discharge rates (>1000 C-rate). The electrodes also show good stability during electrochemical cycling (less than 30% decrease in capacity over >1000 cycles) and an output voltage up to 1.4 V. The performance of these semiconducting polymers with polar side-chains demonstrates the potential of this material class for fast-charging, water based electrochemical energy storage devices.

  9. Molecular Orientation of Conjugated Polymer Chains in Nanostructures and Thin Films: Review of Processes and Application to Optoelectronics

    Directory of Open Access Journals (Sweden)

    Varun Vohra

    2017-01-01

    Full Text Available Semiconducting polymers are composed of elongated conjugated polymer backbones and side chains with high solubility and mechanical properties. The combination of these two features results in a high processability and a potential to orient the conjugated backbones in thin films and nanofibers. The thin films and nanofibers are usually composed of highly crystalline (high charge transport and amorphous parts. Orientation of conjugated polymer can result in enhanced charge transport or optical properties as it induces increased crystallinity or preferential orientation of the crystallites. After summarizing the potential strategies to exploit molecular order in conjugated polymer based optoelectronic devices, we will review some of the fabrication processes to induce molecular orientation. In particular, we will review the cases involving molecular and interfacial interactions, unidirectional deposition processes, electrospinning, and postdeposition mechanical treatments. The studies presented here clearly demonstrate that process-controlled molecular orientation of the conjugated polymer chains can result in high device performances (mobilities over 40 cm2·V−1·s−1 and solar cells with efficiencies over 10%. Furthermore, the peculiar interactions between molecularly oriented polymers and polarized light have the potential not only to generate low-cost and low energy consumption polarized light sources but also to fabricate innovative devices such as solar cell integrated LCDs or bipolarized LEDs.

  10. Amide side chain amphiphilic polymers disrupt surface established bacterial bio-films and protect mice from chronic Acinetobacter baumannii infection.

    Science.gov (United States)

    Uppu, Divakara S S M; Samaddar, Sandip; Ghosh, Chandradhish; Paramanandham, Krishnamoorthy; Shome, Bibek R; Haldar, Jayanta

    2016-01-01

    Bacterial biofilms represent the root-cause of chronic or persistent infections in humans. Gram-negative bacterial infections due to nosocomial and opportunistic pathogens such as Acinetobacter baumannii are more difficult to treat because of their inherent and rapidly acquiring resistance to antibiotics. Due to biofilm formation, A. baumannii has been noted for its apparent ability to survive on artificial surfaces for an extended period of time, therefore allowing it to persist in the hospital environment. Here we report, maleic anhydride based novel cationic polymers appended with amide side chains that disrupt surface established multi-drug resistant A. baumannii biofilms. More importantly, these polymers significantly (p polymers also show potent antibacterial efficacy against methicillin resistant Staphylococcus aureus (MRSA), vancomycin resistant Enterococci (VRE) and multi-drug resistant clinical isolates of A. baumannii with minimal toxicity to mammalian cells. We observe that optimal hydrophobicity dependent on the side chain chemical structure of these polymers dictate the selective toxicity to bacteria. Polymers interact with the bacterial cell membranes by causing membrane depolarization, permeabilization and energy depletion. Bacteria develop rapid resistance to erythromycin and colistin whereas no detectable development of resistance occurs against these polymers even after several passages. These results suggest the potential use of these polymeric biomaterials in disinfecting biomedical device surfaces after the infection has become established and also for the topical treatment of chronic bacterial infections. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

    KAUST Repository

    Giovannitti, Alexander

    2018-04-24

    We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

  12. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

    KAUST Repository

    Giovannitti, Alexander; Maria, Iuliana P.; Hanifi, David; Donahue, Mary J.; Bryant, Daniel; Barth, Katrina J.; Makdah, Beatrice E.; Savva, Achilleas; Moia, Davide; Zetek, Matyá š; Barnes, Piers R.F.; Reid, Obadiah G.; Inal, Sahika; Rumbles, Garry; Malliaras, George G.; Nelson, Jenny; Rivnay, Jonathan; McCulloch, Iain

    2018-01-01

    We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

  13. THE VALUE ADDED TAX AND THE EVASION CHAIN OF INTRA-COMMUNITARIAN VAT

    Directory of Open Access Journals (Sweden)

    Deliman Eugen

    2011-12-01

    Full Text Available The relationship IRS taxpayer runs the risk of turning into a psychological war in which, however, given the positions held, the IRS is by far on a favorable footing. Between the apparently excessively formal position held by the IRS, which seems to conceal behind the laws, and the sometimes forced interpretation of the laws, by the taxpayer, there are the courts of law, also disturbed by the legislative changes which appear to have entered a perpetual motion. The objective of the fiscal administration regarding the value added tax is to combat tax evasion and fraud. It is very important to combat evasion in the VAT field because it represents the indirect tax of the largest share in the consolidated general budget. VAT evasion represents the intention of not paying the tax, withholding or not declaring it, or requesting its refund which would not be fit, due to the exaggeration of the deductible amount of the VAT. The essential aim of the IRS inspector is to verify the correctness of the declared amount of the value added tax. It should also be observed whether the incorrectness is deliberate or whether it was due to misunderstanding, carelessness or the ignorance of the payer. In all cases judgment is necessary, as for the cases of negligence the amount to be paid must be corrected and accompanied by applying fines and / or penalties, and in the cases of intended fraud legal actions are to be applied in order to obtain a conviction. Deceitful deductions represent other methods for tax evasion and are undertaken based on fake invoices, invoices often used several times for deduction, or invoices related to purchases that have never been made. Thus there are examples of economic agents who have practiced the right to deduct the VAT due to the acquisition of goods which consisted in the property of other economic agents. In other cases noticed was the deduction of VAT on goods or services that were not included in the activities of the economic

  14. Thermoresponsive AuNPs Stabilized by Pillararene-Containing Polymers.

    Science.gov (United States)

    Liao, Xiaojuan; Guo, Lei; Chang, Junxia; Liu, Sha; Xie, Meiran; Chen, Guosong

    2015-08-01

    Pillararene-containing thermoresponsive polymers are synthesized via reversible addition-fragmentation chain transfer polymerization using pillararene derivatives as the effective chain transfer agents for the first time. These polymers can self-assemble into micelles and form vesicles after guest molecules are added. Furthermore, such functional polymers can be further applied to prepare hybrid gold nanoparticles, which integrate the thermoresponsivity of polymers and molecular recognition of pillararenes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Ion solvation in polymer blends and block copolymer melts: effects of chain length and connectivity on the reorganization of dipoles.

    Science.gov (United States)

    Nakamura, Issei

    2014-05-29

    We studied the thermodynamic properties of ion solvation in polymer blends and block copolymer melts and developed a dipolar self-consistent field theory for polymer mixtures. Our theory accounts for the chain connectivity of polymerized monomers, the compressibility of the liquid mixtures under electrostriction, the permanent and induced dipole moments of monomers, and the resultant dielectric contrast among species. In our coarse-grained model, dipoles are attached to the monomers and allowed to rotate freely in response to electrostatic fields. We demonstrate that a strong electrostatic field near an ion reorganizes dipolar monomers, resulting in nonmonotonic changes in the volume fraction profile and the dielectric function of the polymers with respect to those of simple liquid mixtures. For the parameter sets used, the spatial variations near an ion can be in the range of 1 nm or larger, producing significant differences in the solvation energy among simple liquid mixtures, polymer blends, and block copolymers. The solvation energy of an ion depends substantially on the chain length in block copolymers; thus, our theory predicts the preferential solvation of ions arising from differences in chain length.

  16. Self-assembly of the hydrogel polymer chain consisting of chitosan and chondroitin sulphate in the presence of theophylline

    International Nuclear Information System (INIS)

    Lopes, Lais C.; Piai, Juliana F.; Fajardo, Andre R.; Rubira, Adley F.; Muniz, Edvani C.

    2009-01-01

    In this work, polyelectronic complex (PEC) consisting of two polysaccharides were developed. One is chitosan (QT), cationic polymer, produced by the chitin deacetylation and the other is chondroitin sulphate (CS), anionic polymer, extracted from bovine or porcine aorta. The PECs were prepared in the presence of theophylline (TEO) for evaluating the influence of this drug in the polymer chains reorganization, as well as, studying the mechanical properties and release of SC and TEO in aqueous solutions on different pH conditions. By the obtained results, it was observed that the 84QT/15SC/TEO (% in weight) hydrogel is pH responsive because the CS releasing is more effective at pH 8, while the release of the TEO is higher at pH 2. The hydrogel showed mechanical properties more resistant to pH 2, 8 and 10 and this was attributed to interactions between the polymer chains. Finally, the X-rays profile showed the presence of peaks associated to reorganization of the chains in the hydrogel is at times larger than the hydrogel in the absence of solute. (author)

  17. Controlling morphology and chain aggregation in semiconducting conjugated polymers: the role of solvent on optical gain in MEH-PPV.

    Science.gov (United States)

    Lampert, Zach E; Reynolds, C Lewis; Papanikolas, John M; Aboelfotoh, M Osama

    2012-10-25

    We report the results of a detailed investigation that addresses the influence of polymer morphology and chain aggregation, as controlled by the chemical nature of the solvent, on the optical gain properties of the conjugated polymer poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV). Using the variable stripe length technique in the picosecond regime, we have extensively studied the optical gain performance of asymmetric planar waveguides formed with thin MEH-PPV films spin-cast from concentrated chlorobenzene (CB) and tetrahydrofuran (THF) solutions onto thermally oxidized silicon substrates. CB and THF solvents were chosen based on their known ability to promote and effectively limit aggregate formation, respectively. Very large net gain coefficients are demonstrated, reaching values of 330 and 365 cm(-1), respectively, when optically pumping the waveguides with a maximum energy density of 85 μJ/cm(2). Our results clearly demonstrate that polymer morphology, and hence, the chain conformation dependence of the degree of aggregation in the films as controlled by the solvent, has minimal impact on the net gain. Moreover, the waveguides exhibit low loss coefficients of 10-20 cm(-1) at the ASE wavelength. These results question the importance of polymer morphology and aggregate formation in polymer-based optical devices operating at high excitation densities in the stimulated emission regime as would be characteristic of lasers and optical amplifiers.

  18. Polarized Emission from Conjugated Polymer Chains Aligned by Epitaxial Growth during Off-Center Spin-Coating

    Directory of Open Access Journals (Sweden)

    Takuya Anzai

    2017-01-01

    Full Text Available Due to their macromolecular nature, conjugated polymers can be relatively easily aligned by applying a variety of processes resulting in either elongation or ordering of their conjugated backbones. Processes that induce chain alignment include electrospinning, mechanical rubbing, epitaxial growth, and nanoconfinement and unidirectional deposition techniques such as off-center spin-coating. In this study, we compare these deposition techniques by applying them to a green-emitting conjugated polymer material that exhibits liquid crystalline phase behavior. Our study reveals that while methods such as electrospinning and mechanical rubbing can be useful to locally generate polymer chain alignment, the combination of epitaxial growth using 1,3,5-trichlorobenzene as crystallizing agent with off-center spin-coating results in the formation of anisotropic nanofiber-like structures with enhanced crystallinity degree and polarized light-emission properties. The unidirectional epitaxial growth was also applied to a red-emitting polymer that exhibits polarization ratios up to 4.1. Our results emphasize that this simple solution formulation and process can be used for the fabrication of polarized thin films of a variety of conjugated polymers with potential applications in the advanced display technologies or analytical equipment fields.

  19. 乳酸扩链聚合物的降解性能%DEGRADABLE BEHAVIORS OF LACTIDE CHAIN-EXTENED POLYMERS

    Institute of Scientific and Technical Information of China (English)

    封瑞江

    2001-01-01

    In this paper,the effects of change of degradable rate and relative molecular mass on the degradable behaviors of four lactide chain-extened polymers are contrasted with those of lactide polymers.The results indicated that the four lactide chain-extened polymers could degrade in this experiment and their degradable rate were lower than that of P-LA.LA-SDI has the highest degradable rates among the four lactide chain-extened polymers,but there was no significant difference among aromatic and aliphatic lactide chain-extened polymers.The results showed that the degradable rates were dependent on experiment methods and condition and also indicated that the relative molecular mass became smaller and smaller with the progress of degradation time.

  20. Side chain engineering of fused aromatic thienopyrazine based low band-gap polymers for enhanced charge carrier mobility

    KAUST Repository

    Mondal, Rajib

    2011-01-01

    A strategic side-chain engineering approach leads to the two orders of magnitude enhancement of charge carrier mobility in phenanthrene based fused aromatic thienopyrazine polymers. Hole carrier mobility up to 0.012 cm 2/Vs can be obtained in thin film transistor devices. Polymers were also utilized to fabricate bulk heterojunction photovoltaic devices and the maximum PCE obtained in these OPV\\'s was 1.15%. Most importantly, performances of the devices were correlated with thin morphological analysis performed by atomic force microscopy and grazing incidence X-ray scattering. © 2011 The Royal Society of Chemistry.

  1. Influence of chain topology and bond potential on the glass transition of polymer chains simulated with the bond fluctuation model

    International Nuclear Information System (INIS)

    Freire, J J

    2008-01-01

    The bond fluctuation model with a bond potential has been applied to investigation of the glass transition of linear chains and chains with a regular disposition of small branches. Cooling and subsequent heating curves are obtained for the chain energies and also for the mean acceptance probability of a bead jump. In order to mimic different trends to vitrification, a factor B gauging the strength of the bond potential with respect to the long-range potential (i.e. the intramolecular or intermolecular potential between indirectly bonded beads) has been introduced. (A higher value of B leads to a preference for the highest bond lengths and a higher total energy, implying a greater tendency to vitrify.) Different cases have been considered for linear chains: no long-range potential, no bond potential and several choices for B. Furthermore, two distinct values of B have been considered for alternate bonds in linear chains. In the case of the branched chains, mixed models with different values of B for bonds in the main chain and in the branches have also been investigated. The possible presence of ordering or crystallization has been characterized by calculating the collective light scattering function of the different samples after annealing at a convenient temperature below the onset of the abrupt change in the curves associated with a thermodynamic transition. It is concluded that ordering is inherited more efficiently in the systems with branched chains and also for higher values of B. The branched molecules with the highest B values in the main chain bonds exhibit two distinct transitions in the heating curves, which may be associated with two glass transitions. This behavior has been detected experimentally for chains with relatively long flexible branches

  2. Influence of chain topology and bond potential on the glass transition of polymer chains simulated with the bond fluctuation model

    Energy Technology Data Exchange (ETDEWEB)

    Freire, J J [Departamento de Ciencias y Tecnicas FisicoquImicas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), Senda del Rey 9, 28040 Madrid (Spain)], E-mail: jfreire@invi.uned.es

    2008-07-16

    The bond fluctuation model with a bond potential has been applied to investigation of the glass transition of linear chains and chains with a regular disposition of small branches. Cooling and subsequent heating curves are obtained for the chain energies and also for the mean acceptance probability of a bead jump. In order to mimic different trends to vitrification, a factor B gauging the strength of the bond potential with respect to the long-range potential (i.e. the intramolecular or intermolecular potential between indirectly bonded beads) has been introduced. (A higher value of B leads to a preference for the highest bond lengths and a higher total energy, implying a greater tendency to vitrify.) Different cases have been considered for linear chains: no long-range potential, no bond potential and several choices for B. Furthermore, two distinct values of B have been considered for alternate bonds in linear chains. In the case of the branched chains, mixed models with different values of B for bonds in the main chain and in the branches have also been investigated. The possible presence of ordering or crystallization has been characterized by calculating the collective light scattering function of the different samples after annealing at a convenient temperature below the onset of the abrupt change in the curves associated with a thermodynamic transition. It is concluded that ordering is inherited more efficiently in the systems with branched chains and also for higher values of B. The branched molecules with the highest B values in the main chain bonds exhibit two distinct transitions in the heating curves, which may be associated with two glass transitions. This behavior has been detected experimentally for chains with relatively long flexible branches.

  3. Conjugated Polymer Chains Confined in Vertical Nanocylinders of a Block-Copolymer Film: Preparation, Characterization, and Optoelectronic Function

    KAUST Repository

    Dong, Ban Xuan; Honmou, Yoshihiro; Komiyama, Hideaki; Furumaki, Shu; Iyoda, Tomokazu; Vacha, Martin

    2013-01-01

    Hybrid materials composed of phase-separated block copolymer films and conjugated polymers of the phenylenevinylene family (PPV) are prepared. The PPV chains are embedded in vertical cylinders of nanometer diameter in the block-copolymer films. The cylinders span continuously the whole film thickness of 70 nm. Incorporation of the PPV chains into the one-dimensional cylinders leads to modified photoluminescence spectra and to large absorption anisotropy. The hybrid films show electroluminescence from the PPV chains in a simple light-emitting device at minute doping concentrations, and also exhibit a factor of 19 increase in electron transport efficiency along the single PPV chains. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Conjugated Polymer Chains Confined in Vertical Nanocylinders of a Block-Copolymer Film: Preparation, Characterization, and Optoelectronic Function

    KAUST Repository

    Dong, Ban Xuan

    2013-01-15

    Hybrid materials composed of phase-separated block copolymer films and conjugated polymers of the phenylenevinylene family (PPV) are prepared. The PPV chains are embedded in vertical cylinders of nanometer diameter in the block-copolymer films. The cylinders span continuously the whole film thickness of 70 nm. Incorporation of the PPV chains into the one-dimensional cylinders leads to modified photoluminescence spectra and to large absorption anisotropy. The hybrid films show electroluminescence from the PPV chains in a simple light-emitting device at minute doping concentrations, and also exhibit a factor of 19 increase in electron transport efficiency along the single PPV chains. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Impact of charge carrier injection on single-chain photophysics of conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, Felix J.; Vogelsang, Jan, E-mail: jan.vogelsang@physik.uni-regensburg.de; Lupton, John M. [Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstrasse 31, 93053 Regensburg (Germany)

    2016-06-27

    Charges in conjugated polymer materials have a strong impact on the photophysics and their interaction with the primary excited state species has to be taken into account in understanding device properties. Here, we employ single-molecule spectroscopy to unravel the influence of charges on several photoluminescence (PL) observables. The charges are injected either stochastically by a photochemical process or deterministically in a hole-injection sandwich device configuration. We find that upon charge injection, besides a blue-shift of the PL emission and a shortening of the PL lifetime due to quenching and blocking of the lowest-energy chromophores, the non-classical photon arrival time distribution of the multichromophoric chain is modified towards a more classical distribution. Surprisingly, the fidelity of photon antibunching deteriorates upon charging, whereas one would actually expect the opposite: the number of chromophores to be reduced. A qualitative model is presented to explain the observed PL changes. The results are of interest to developing a microscopic understanding of the intrinsic charge-exciton quenching interaction in devices.

  6. Development of environmentally friendly coatings and paints using medium-chain-length poly(3-hydroxyalkanoates) as the polymer binder.

    Science.gov (United States)

    van der Walle, G A; Buisman, G J; Weusthuis, R A; Eggink, G

    1999-01-01

    Unsaturated medium-chain-length poly(3-hydroxyalkanoates) (mcl-PHAs) produced by Pseudomonas putida from linseed oil fatty acids (LOFA) and tall oil fatty acids (TOFA), were used as the polymer binder in the formulation of high solid alkyd-like paints. The relatively high concentration of unsaturated alkyl side chains incorporated into the PHA resins resulted in oxidative drying PHA paints having excellent coating properties. The homogeneously pigmented PHA coatings yielded high-gloss, smooth and strong films upon curing and showed an excellent flexibility, a good adhesion to different substrates, cohesive film properties and resistance to chipping.

  7. Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains

    Energy Technology Data Exchange (ETDEWEB)

    He, Tian [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Yue, Ke-Fen, E-mail: ykflyy@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Zhao, Yi-xing; Chen, San-Ping [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Zhou, Chun-sheng, E-mail: slzhoucs@126.com.cn [Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, College of Chemical Engineering and Modern Materials, Shangluo University, Shangluo 726000 (China); Yan, Ni [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China)

    2016-07-15

    Solvothermal reactions of Zn(II) acetates and four V-shaped carboxylates ligands in the presence of 1,4-Bis(2-methyl-imidazol-1-yl)butane afforded four interesting Zn(II) coordination polymers with helical chains, namely, {[Zn(bib)(atibdc)]·2H_2O}{sub n} (1), {[Zn(bib)(atbip)]·H_2O}{sub n} (2), {[Zn(bib)(2,2′-tda)]}{sub n} (3) and {[Zn(bib)(5-tbipa)]·EtOH}{sub n} (4), (H{sub 2}atibdc=5-amino-2,4,6-triiodoisophthalic acid, H{sub 2}atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2′-H{sub 2}tad=2,2′-thiodiacetic acid, 5-H{sub 2}tbipa=5-tert-butyl-isophthalic acid). 1 reveals a 3D chiral framework with three kinds of helical chains along a, b and c axis. 2 shows a 2D step-type chiral framework with right-handed helical chains. 3 displays a wavelike 2D layer network possessing alternate left- and right-handed helical chains. 4 presents a four-connected 3D framework with zigzag and meso-helical chains. The different spacers and substituent group of carboxylic acid ligands may lead to the diverse network structures of 1–4. The fluorescent properties of complexes 1−4 were studied. In addition, the thermal decompositions properties of 1–4 were investigated by simultaneous TG/DTG–DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1–4 are calculated by the integral Kissinger's method and Ozawa–Doyle's method. The activation energy E (E{sub 1}=209.658 kJ·mol{sup −1}, E{sub 2}=250.037 kJ mol{sup −1}, E{sub 3}=225.300 kJ mol{sup −1}, E{sub 4}=186.529 kJ·mol{sup −1}) demonstrates that the reaction rate of the melting decomposition is slow. The thermodynamic parameters (ΔH{sup ‡}, ΔG{sup ‡} and ΔS{sup ‡}) at the peak temperatures of the DTG curves were also calculated. ΔG{sup ‡}>0 indicates that the skeleton collapse is not spontaneous. ΔH{sub d}>0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC

  8. The Relationship between the Monomer Chain Length and the Electro-Optical Properties of Polymer Dispersed Liquid Crystals

    Directory of Open Access Journals (Sweden)

    Liu J.

    2016-03-01

    Full Text Available Five polymers dispersed liquid crystalline (LC films were fabricated using photo-polymerizable monomers with different lengths of carbon chains. These LC films have shown different electro-optical (EO properties. Through their SEM pictures, the relationship between the linear electro-optical effect and the mesh size of the polymer network was explored. With the increase of number of photo-polymerizable monomers, the mesh size of the polymer network would become larger. So the liquid crystal molecules would be easily oriented in the electric field and therefore, the threshold voltage and saturation voltage would decrease. The open state response times were also reduced and the off state response times would be extended. The DFT simulations have shown principal role of the ground state dipole moments in the observed electro-optical efficiency.

  9. Small-angle x-ray scattering study on conformation of amorphous polymer chain in the bulk

    International Nuclear Information System (INIS)

    Hayashi, Hisao; Hamada, Fumiyuki; Nakajima, Akio

    1975-01-01

    In a previous paper, the new method for the determination of the conformation of polymer chains in concentrated solution and in bulk by small angle X-ray scattering was reported. The purpose of this paper is to estimate the dimension and conformation of polystyrene chains in bulk by this method. The tagged polymer used was the copolymer of styrene and p-iodostyrene. Excess scattering was obtained by subtracting the intensity of polystyrene matrix from that of a mixture containing polystyrene and a small fraction of the tagged polystyrene. Since the excess scattering originates from the group of iodine atoms in the tagged polystyrene, the radius of gyration of the tagged polystyrene is estimated by Guinier plot. Measurement was made with a Kratky camera, and in order to obtain high scattering intensity, the primary beam with line-shaped cross section was used. The intercepts of two limiting curves in the plotted radius of gyration diagram showed good agreement, and the measured molecular dimension agreed with the unperturbed dimension of this polymer. It was concluded that the molecular chains in bulk are mutually penetrable, and the centers of gravity of the molecules distribute almost randomly. It was suggested from the plot of the excess scattering intensity that the conformation of the tagged molecules is a random coil. The present results did not support the ordered structure revealed by bundle model and meander model. (Kako, I.)

  10. Biomedical applications of polymers derived by reversible addition - fragmentation chain-transfer (RAFT).

    Science.gov (United States)

    Fairbanks, Benjamin D; Gunatillake, Pathiraja A; Meagher, Laurence

    2015-08-30

    RAFT- mediated polymerization, providing control over polymer length and architecture as well as facilitating post polymerization modification of end groups, has been applied to virtually every facet of biomedical materials research. RAFT polymers have seen particularly extensive use in drug delivery research. Facile generation of functional and telechelic polymers permits straightforward conjugation to many therapeutic compounds while synthesis of amphiphilic block copolymers via RAFT allows for the generation of self-assembled structures capable of carrying therapeutic payloads. With the large and growing body of literature employing RAFT polymers as drug delivery aids and vehicles, concern over the potential toxicity of RAFT derived polymers has been raised. While literature exploring this complication is relatively limited, the emerging consensus may be summed up in three parts: toxicity of polymers generated with dithiobenzoate RAFT agents is observed at high concentrations but not with polymers generated with trithiocarbonate RAFT agents; even for polymers generated with dithiobenzoate RAFT agents, most reported applications call for concentrations well below the toxicity threshold; and RAFT end-groups may be easily removed via any of a variety of techniques that leave the polymer with no intrinsic toxicity attributable to the mechanism of polymerization. The low toxicity of RAFT-derived polymers and the ability to remove end groups via straightforward and scalable processes make RAFT technology a valuable tool for practically any application in which a polymer of defined molecular weight and architecture is desired. Copyright © 2015. Published by Elsevier B.V.

  11. Enhancing the specificity of polymerase chain reaction by graphene oxide through surface modification: zwitterionic polymer is superior to other polymers with different charges

    Science.gov (United States)

    Zhong, Yong; Huang, Lihong; Zhang, Zhisen; Xiong, Yunjing; Sun, Liping; Weng, Jian

    2016-01-01

    Graphene oxides (GOs) with different surface characteristics, such as size, reduction degree and charge, are prepared, and their effects on the specificity of polymerase chain reaction (PCR) are investigated. In this study, we demonstrate that GO with a large size and high reduction degree is superior to small and nonreduced GO in enhancing the specificity of PCR. Negatively charged polyacrylic acid (PAA), positively charged polyacrylamide (PAM), neutral polyethylene glycol (PEG) and zwitterionic polymer poly(sulfobetaine) (pSB) are used to modify GO. The PCR specificity-enhancing ability increases in the following order: GO-PAA Pfu DNA polymerase. Our data demonstrate that the size, reduction degree and surface charge of GO affect the specificity of PCR. Based on our results, zwitterionic polymer-modified GO may be used as an efficient additive for enhancing the specificity of PCR. PMID:27956830

  12. Phase separation of a Lennard-Jones fluid interacting with a long, condensed polymer chain: implications for the nuclear body formation near chromosomes.

    Science.gov (United States)

    Oh, Inrok; Choi, Saehyun; Jung, YounJoon; Kim, Jun Soo

    2015-08-28

    Phase separation in a biological cell nucleus occurs in a heterogeneous environment filled with a high density of chromatins and thus it is inevitably influenced by interactions with chromatins. As a model system of nuclear body formation in a cell nucleus filled with chromatins, we simulate the phase separation of a low-density Lennard-Jones (LJ) fluid interacting with a long, condensed polymer chain. The influence of the density variation of LJ particles above and below the phase boundary and the role of attractive interactions between LJ particles and polymer segments are investigated at a fixed value of strong self-interaction between LJ particles. For a density of LJ particles above the phase boundary, phase separation occurs and a dense domain of LJ particles forms irrespective of interactions with the condensed polymer chain whereas its localization relative to the polymer chain is determined by the LJ-polymer attraction strength. Especially, in the case of moderately weak attractions, the domain forms separately from the polymer chain and subsequently associates with the polymer chain. When the density is below the phase boundary, however, the formation of a dense domain is possible only when the LJ-polymer attraction is strong enough, for which the domain grows in direct contact with the interacting polymer chain. In this work, different growth behaviors of LJ particles result from the differences in the density of LJ particles and in the LJ-polymer interaction, and this work suggests that the distinct formation of activity-dependent and activity-independent nuclear bodies (NBs) in a cell nucleus may originate from the differences in the concentrations of body-specific NB components and in their interaction with chromatins.

  13. Strain hardening in startup shear of long-chain branched polymer solutions.

    Science.gov (United States)

    Liu, Gengxin; Cheng, Shiwang; Lee, Hyojoon; Ma, Hongwei; Xu, Hongde; Chang, Taihyun; Quirk, Roderic P; Wang, Shi-Qing

    2013-08-09

    We show for the first time that entangled polymeric liquids containing long-chain branching can exhibit strain hardening upon startup shear. As the significant long-chain branching impedes chain disentanglement, Gaussian coils between entanglements can deform to reach the finite extensibility limit where the intrachain retraction force exceeds the value expected from the usual conformational entropy loss evaluated based on Gaussian chain statistics. The phenomenon is expected to lead to further theoretical understanding.

  14. Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains

    KAUST Repository

    Shivokhin, Maksim E.

    2017-05-30

    We propose and verify methods based on the slip-spring (SSp) model [ Macromolecules 2005, 38, 14 ] for predicting the effect of any monodisperse, binary, or ternary environment of topological constraints on the relaxation of the end-to-end vector of a linear probe chain. For this purpose we first validate the ability of the model to consistently predict both the viscoelastic and dielectric response of monodisperse and binary mixtures of type A polymers, based on published experimental data. We also report the synthesis of new binary and ternary polybutadiene systems, the measurement of their linear viscoelastic response, and the prediction of these data by the SSp model. We next clarify the relaxation mechanisms of probe chains in these constraint release (CR) environments by analyzing a set of "toy" SSp models with simplified constraint release rates, by examining fluctuations of the end-to-end vector. In our analysis, the longest relaxation time of the probe chain is determined by a competition between the longest relaxation times of the effective CR motions of the fat and thin tubes and the motion of the chain itself in the thin tube. This picture is tested by the analysis of four model systems designed to separate and estimate every single contribution involved in the relaxation of the probe\\'s end-to-end vector in polydisperse systems. We follow the CR picture of Viovy et al. [ Macromolecules 1991, 24, 3587 ] and refine the effective chain friction in the thin and fat tubes based on Read et al. [ J. Rheol. 2012, 56, 823 ]. The derived analytical equations form a basis for generalizing the proposed methodology to polydisperse mixtures of linear and branched polymers. The consistency between the SSp model and tube model predictions is a strong indicator of the compatibility between these two distinct mesoscopic frameworks.

  15. A Comprehensive study of the Effects of Chain Morphology on the Transport Properties of Amorphous Polymer Films

    Science.gov (United States)

    Mendels, Dan; Tessler, Nir

    2016-07-01

    Organic semiconductors constitute one of the main components underlying present-day paradigm shifting optoelectronic applications. Among them, polymer based semiconductors are deemed particularly favorable due to their natural compatibility with low-cost device fabrication techniques. In light of recent advances in the syntheses of these classes of materials, yielding systems exhibiting charge mobilities comparable with those found in organic crystals, a comprehensive study of their charge transport properties is presented. Among a plethora of effects arising from these systems morphological and non morphological attributes, it is shown that a favorable presence of several of these attributes, including that of rapid on-chain carrier propagation and the presence of elongated conjugation segments, can lead to an enhancement of the system’s mobility by more than 5 orders of magnitude with respect to ‘standard’ amorphous organic semiconductors. New insight for the formulation of new engineering strategies for next generation polymer based semiconductors is thus gathered.

  16. Influence of Side Chain Position on the Electrical Properties of Organic Solar Cells Based on Dithienylbenzothiadiazole-alt-phenylene Conjugated Polymers

    DEFF Research Database (Denmark)

    Livi, Francesco; Zawacka, Natalia Klaudia; Angmo, Dechan

    2015-01-01

    backbone for polymer solar cells. All the polymers were roll slot die coated under ambient conditions on flexible ITO-free plastic substrates to give inverted polymer solar cell devices with an upscaled active area of 1 cm2. The best characteristics were found for the polymer carrying alkoxy side chains...... showed excellent performance under constant illumination and high temperature (exhibiting stable photovoltaic properties even after 670 h under conditions similar to ISOS-L-2 lifetime protocol). This makes P7 a good candidate for further upscaling and device optimization. The photovoltaic performance...

  17. Impact of the Nature of the Side-Chains on the Polymer-Fullerene Packing in the Mixed Regions of Bulk Heterojunction Solar Cells

    KAUST Repository

    Wang, Tonghui; Ravva, Mahesh Kumar; Bredas, Jean-Luc

    2016-01-01

    Polymer-fullerene packing in mixed regions of a bulk heterojunction solar cell is expected to play a major role in exciton-dissociation, charge-separation, and charge-recombination processes. Here, molecular dynamics simulations are combined with density functional theory calculations to examine the impact of nature and location of polymer side-chains on the polymer-fullerene packing in mixed regions. The focus is on poly-benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c]pyrrole-4,6-dione (PBDTTPD) as electron-donating material and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) as electron-accepting material. Three polymer side-chain patterns are considered: i) linear side-chains on both benzodithiophene (BDT) and thienopyrroledione (TPD) moieties; ii) two linear side-chains on BDT and a branched side-chain on TPD; and iii) two branched side-chains on BDT and a linear side-chain on TPD. Increasing the number of branched side-chains is found to decrease the polymer packing density and thereby to enhance PBDTTPD–PC61 BM mixing. The nature and location of side-chains are found to play a determining role in the probability of finding PC61BM molecules close to either BDT or TPD. The electronic couplings relevant for the exciton-dissociation and charge-recombination processes are also evaluated. Overall, the findings are consistent with the experimental evolution of the PBDTTPD–PC61BM solar-cell performance as a function of side-chain patterns. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  18. Impact of the Nature of the Side-Chains on the Polymer-Fullerene Packing in the Mixed Regions of Bulk Heterojunction Solar Cells

    KAUST Repository

    Wang, Tonghui

    2016-06-20

    Polymer-fullerene packing in mixed regions of a bulk heterojunction solar cell is expected to play a major role in exciton-dissociation, charge-separation, and charge-recombination processes. Here, molecular dynamics simulations are combined with density functional theory calculations to examine the impact of nature and location of polymer side-chains on the polymer-fullerene packing in mixed regions. The focus is on poly-benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c]pyrrole-4,6-dione (PBDTTPD) as electron-donating material and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) as electron-accepting material. Three polymer side-chain patterns are considered: i) linear side-chains on both benzodithiophene (BDT) and thienopyrroledione (TPD) moieties; ii) two linear side-chains on BDT and a branched side-chain on TPD; and iii) two branched side-chains on BDT and a linear side-chain on TPD. Increasing the number of branched side-chains is found to decrease the polymer packing density and thereby to enhance PBDTTPD–PC61 BM mixing. The nature and location of side-chains are found to play a determining role in the probability of finding PC61BM molecules close to either BDT or TPD. The electronic couplings relevant for the exciton-dissociation and charge-recombination processes are also evaluated. Overall, the findings are consistent with the experimental evolution of the PBDTTPD–PC61BM solar-cell performance as a function of side-chain patterns. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  19. Simulated glass-forming polymer melts: dynamic scattering functions, chain length effects, and mode-coupling theory analysis.

    Science.gov (United States)

    Frey, S; Weysser, F; Meyer, H; Farago, J; Fuchs, M; Baschnagel, J

    2015-02-01

    We present molecular-dynamics simulations for a fully flexible model of polymer melts with different chain length N ranging from short oligomers (N = 4) to values near the entanglement length (N = 64). For these systems we explore the structural relaxation of the supercooled melt near the critical temperature T c of mode-coupling theory (MCT). Coherent and incoherent scattering functions are analyzed in terms of the idealized MCT. For temperatures T > T c we provide evidence for the space-time factorization property of the β relaxation and for the time-temperature superposition principle (TTSP) of the α relaxation, and we also discuss deviations from these predictions for T ≈ T c. For T larger than the smallest temperature where the TTSP holds we perform a quantitative analysis of the dynamics with the asymptotic MCT predictions for the late β regime. Within MCT a key quantity, in addition to T c, is the exponent parameter λ. For the fully flexible polymer models studied we find that λ is independent of N and has a value (λ = 0.735 ) typical of simple glass-forming liquids. On the other hand, the critical temperature increases with chain length toward an asymptotic value T c (∞) . This increase can be described by T c (∞) - T c(N) ∼ 1/N and may be interpreted in terms of the N dependence of the monomer density ρ, if we assume that the MCT glass transition is ruled by a soft-sphere-like constant coupling parameter Γ c = ρ c T c (-1/4), where ρ c is the monomer density at T c. In addition, we also estimate T c from a Hansen-Verlet-like criterion and MCT calculations based on structural input from the simulation. For our polymer model both the Hansen-Verlet criterion and the MCT calculations suggest T c to decrease with increasing chain length, in contrast to the direct analysis of the simulation data.

  20. A wormlike chain model of forced desorption of a polymer adsorbed on an attractive wall

    International Nuclear Information System (INIS)

    Lam, Pui-Man; Zhen, Yi

    2014-01-01

    Forced desorption of a semiflexible polymer chain on a solid substrate is theoretically investigated. The pulling force versus displacement is studied for varying adsorption energy ε and persistence length P. It is found that the relationships between pulling force and cantilever displacement show a series of characteristic force spikes at different persistence lengths P. These force spikes become more pronounced but the average magnitude of this force decreases as P grows. Our results are of relevance to the forced desorption of DNA on an attractive wall in single-molecule pulling experiments. (paper)

  1. A combined theoretical and experimental study of the polymer inter-chain structure in poly(phenylene vinylene) derivatives

    International Nuclear Information System (INIS)

    Sumpter, B G; Drummond, M L; Shelton, W A; Valeev, E F; Barnes, M D

    2008-01-01

    The structures and photophysical properties of single molecule MEH-PPV (2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylenevinylene) and CN-PPV (2,5,2' ,5'-tetrahexyloxy-7,8'-dicyano-p-phenylenevinylene) nanoparticles are investigated using electronic structure theory and high resolution fluorescence experiments. It is shown that electron withdrawing substituents, such as CN, on the vinyl group of the PPV polymer backbone cause substantial change in the π electronic structure which subsequently decreases the inter-chain distance. Not only does CN-PPV have a smaller inter-chain separation compared to MEH-PPV, but also an increased binding energy and more efficient charge transport (carrier mobility) due to larger electronic coupling (charge transfer integrals). These changes help explain the enhanced luminescence quantum yield, photo-stability, and lifetime for CN-PPV versus MEH-PPV observed in experimental high resolution fluorescence imaging of individual single molecule nanoparticles

  2. Efficient sampling of reversible cross-linking polymers: Self-assembly of single-chain polymeric nanoparticles

    Science.gov (United States)

    Oyarzún, Bernardo; Mognetti, Bortolo Matteo

    2018-03-01

    We present a new simulation technique to study systems of polymers functionalized by reactive sites that bind/unbind forming reversible linkages. Functionalized polymers feature self-assembly and responsive properties that are unmatched by the systems lacking selective interactions. The scales at which the functional properties of these materials emerge are difficult to model, especially in the reversible regime where such properties result from many binding/unbinding events. This difficulty is related to large entropic barriers associated with the formation of intra-molecular loops. In this work, we present a simulation scheme that sidesteps configurational costs by dedicated Monte Carlo moves capable of binding/unbinding reactive sites in a single step. Cross-linking reactions are implemented by trial moves that reconstruct chain sections attempting, at the same time, a dimerization reaction between pairs of reactive sites. The model is parametrized by the reaction equilibrium constant of the reactive species free in solution. This quantity can be obtained by means of experiments or atomistic/quantum simulations. We use the proposed methodology to study the self-assembly of single-chain polymeric nanoparticles, starting from flexible precursors carrying regularly or randomly distributed reactive sites. We focus on understanding differences in the morphology of chain nanoparticles when linkages are reversible as compared to the well-studied case of irreversible reactions. Intriguingly, we find that the size of regularly functionalized chains, in good solvent conditions, is non-monotonous as a function of the degree of functionalization. We clarify how this result follows from excluded volume interactions and is peculiar of reversible linkages and regular functionalizations.

  3. Three dimensional nano-assemblies of noble metal nanoparticle-infinite coordination polymers as specific oxidase mimetics for degradation of methylene blue without adding any cosubstrate.

    Science.gov (United States)

    Wang, Lihua; Zeng, Yi; Shen, Aiguo; Zhou, Xiaodong; Hu, Jiming

    2015-02-07

    Novel three-dimensional (3D) nano-assemblies of noble metal nanoparticle (NP)-infinite coordination polymers (ICPs) are conveniently fabricated through the infiltration of HAuCl4 into hollow Au@Ag@ICPs core-shell nanostructures and its replacement reaction with Au@Ag NPs. The present 3D nano-assemblies exhibit highly efficient and specific intrinsic oxidase-like activity even without adding any cosubstrate.

  4. Two Zn coordination polymers with meso-helical chains based on mononuclear or dinuclear cluster units

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Ling, E-mail: qinling@hfut.edu.cn [Department of Chemical Engineering and Food Processing, Xuancheng Campus, Hefei University of Technology, Xuancheng 242000, Anhui (China); Jiangsu Engineering Technology Research Center of Environmental Cleaning Materials (CEM), School of Environmental Sciences and Engineering, Nanjing University of Information Science and Technology (China); State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093 (China); Qiao, Wen-Cheng; Zuo, Wei-Juan; Zeng, Si-Ying; Mei, Cao; Liu, Chang-Jiang [Department of Chemical Engineering and Food Processing, Xuancheng Campus, Hefei University of Technology, Xuancheng 242000, Anhui (China)

    2016-07-15

    Two zinc coordination polymers {[Zn_2(TPPBDA)(oba)_2]·DMF·1.5H_2O}{sub n} (1), {[Zn(TPPBDA)_1_/_2(tpdc)]·DMF}{sub n} (2) have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. These complexes were characterized by elemental analyses and X-ray single-crystal diffraction analyses. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. These mononuclear or dinuclear cluster units are linked by mix-ligands, resulting in various degrees of interpenetration. In addition, the photoluminescent properties for TPPBDA ligand under different state and coordination polymers have been investigated in detail. - Graphical abstract: Two zinc coordination polymers have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. In addition, the photoluminescent properties for TPPBDA ligand under different status and coordination polymers have been investigated in detail. Display Omitted - Highlights: • Two Zn coordination polymers based on mononuclear or dinuclear cluster units have been synthesized. • Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. • Compound 2 is a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. • The photoluminescent properties for TPPBDA with different state and two coordination polymers have been investigated.

  5. Process chain for fabrication of anisotropic optical functional surfaces on polymer components

    DEFF Research Database (Denmark)

    Li, Dongya; Zhang, Yang; Regi, Francesco

    2017-01-01

    . In order to implement the traceability ofthe manufacturing process, the geometry and dimension of the micro structure on the tool and the replica were assessed viametrological methods. The functionality of the anisotropic surfaces on the polymer replicas were evaluated by a gonioreflectometerand image...

  6. Conformational Behavior of Polymer Chains of Different Architectures in Strongly Endothermic Solvent Mixtures: Specific Solvation Effects.

    Czech Academy of Sciences Publication Activity Database

    Suchá, L.; Limpouchová, Z.; Procházka, Karel

    2017-01-01

    Roč. 295, č. 8 (2017), s. 1391-1403 ISSN 0303-402X R&D Projects: GA ČR GA15-19542S Institutional support: RVO:67985858 Keywords : cononsolvency * preferential solvation * star polymer Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.723, year: 2016

  7. Synthesis and Crosslinking of Polyether-Based Main Chain Benzoxazine Polymers and Their Gas Separation Performance

    Directory of Open Access Journals (Sweden)

    Muntazim Munir Khan

    2018-02-01

    Full Text Available The poly(ethylene glycol-based benzoxazine polymers were synthesized via a polycondensation reaction between Bisphenol-A, paraformaldehyde, and poly(ether diamine/(Jeffamine®. The structures of the polymers were confirmed by proton nuclear magnetic resonance spectroscopy (1H-NMR, indicating the presence of a cyclic benzoxazine ring. The polymer solutions were casted on the glass plate and cross-linked via thermal treatment to produce tough and flexible films without using any external additives. Thermal properties and the crosslinking behaviour of these polymers were studied by thermogravimetric analysis (TGA and differential scanning calorimetry (DSC. Single gas (H2, O2, N2, CO2, and CH4 transport properties of the crosslinked polymeric membranes were measured by the time-lag method. The crosslinked PEG-based polybenzoxazine membranes show improved selectivities for CO2/N2 and CO2/CH4 gas pairs. The good separation selectivities of these PEG-based polybenzoxazine materials suggest their utility as efficient thin film composite membranes for gas and liquid membrane separation technology.

  8. Molecular current modulator consisting of conjugated polymer chain with chemically attached photoactive side groups

    Czech Academy of Sciences Publication Activity Database

    Nešpůrek, Stanislav; Sworakowski, J.

    2001-01-01

    Roč. 393, 1-2 (2001), s. 168-176 ISSN 0040-6090 R&D Projects: GA AV ČR IAA1050901; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : molecular electronics * photoconductivity * polymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.266, year: 2001

  9. Schiff base polymer based on triphenylamine moieties in the main chain. Characterization and studies in solar cells

    International Nuclear Information System (INIS)

    Sánchez, C.O.; Bèrnede, J.C.; Cattin, L.; Makha, M.; Gatica, N.

    2014-01-01

    Polytriphenylamine (PTPA), a Schiff base polymer containing triphenylamine (TPA) segments and whose monomer contains triphenylamine and thiophene end groups, was synthesized. The monomer structure enabled the polymerization to be performed under conditions similar to those of thiophene. Oxidative coupling using FeCl 3 as oxidizing agent in anhydrous CHCl 3 medium was employed for the polymer synthesis. Scanning electron microscopy, fluorescence spectroscopy, and cyclic voltammetry were used to characterize the polymer. PTPA exhibited high thermal stability with a mass loss of 13.3 % at 546.5 °C. The fluorescence spectrum showed emission at 300–550 nm and the optical band gap was found to be 2.6 eV. It was also established that PTPA forms complexes with Lewis acids, e.g. MoO 3 and CuI. Its absorption band widened and extended up to the near-IR. It was seen that PTPA is rich in π-electrons and thus can act as electron donor. The value of the Highest Occupied Molecular Orbital (HOMO) was − 5.35 eV indicating its potential application in optoelectronic devices. An attempt was also made to investigate the photovoltaic potential of PTPA. Organic photovoltaic devices with various buffer layer structures, namely ITO/CuI/PTPA/C 60 /BCP/Al, ITO/MoO 3 /PTPA/C 60 /BCP/Al, and ITO/MoO 3 /CuI/PTPA/C 60 /BCP/Al, where ITO stands for indium tin oxide and BCP for bathocuproine, were utilized for the studies. Power conversion efficiency of these devices ranged between 0.21 and 0.43% under simulated AM 1.5 illumination (100 mW cm −2 ). This result proved that polymers containing TPA in the main chain hold promising properties that would allow their use in photovoltaic devices. - Highlights: • A Schiff base polymer with triphenylamine and thiophene segments was synthesized. • In organic cells, the highest efficiency was obtained in a MoO 3 /CuI double layer. • Polymer exhibited a power conversion efficiency between 0.21 and 0.43 %

  10. Schiff base polymer based on triphenylamine moieties in the main chain. Characterization and studies in solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Sánchez, C.O. [Instituto de Ciencias Químicas, Facultad de Ciencias, Universidad Austral de Chile, Avda. Las Encinas 220, Campus Isla Teja, Valdivia (Chile); Bèrnede, J.C. [L' UNAM, Moltech Anjou, UMR 6200, 2 rue de la Houssinière, BP 92208, Nantes F-44000 (France); Cattin, L. [L' UNAM, Institut Jean Rouxel (IMN), UMR 6502, 2 rue de la Houssinière, BP 92208, Nantes F-44000 (France); Makha, M. [L' UNAM, Moltech Anjou, UMR 6200, 2 rue de la Houssinière, BP 92208, Nantes F-44000 (France); Gatica, N. [Departamento de Polímeros, Facultad de Ciencias, Universidad de Concepción, Avda. Edmundo Larenas 129, Concepción (Chile)

    2014-07-01

    Polytriphenylamine (PTPA), a Schiff base polymer containing triphenylamine (TPA) segments and whose monomer contains triphenylamine and thiophene end groups, was synthesized. The monomer structure enabled the polymerization to be performed under conditions similar to those of thiophene. Oxidative coupling using FeCl{sub 3} as oxidizing agent in anhydrous CHCl{sub 3} medium was employed for the polymer synthesis. Scanning electron microscopy, fluorescence spectroscopy, and cyclic voltammetry were used to characterize the polymer. PTPA exhibited high thermal stability with a mass loss of 13.3 % at 546.5 °C. The fluorescence spectrum showed emission at 300–550 nm and the optical band gap was found to be 2.6 eV. It was also established that PTPA forms complexes with Lewis acids, e.g. MoO{sub 3} and CuI. Its absorption band widened and extended up to the near-IR. It was seen that PTPA is rich in π-electrons and thus can act as electron donor. The value of the Highest Occupied Molecular Orbital (HOMO) was − 5.35 eV indicating its potential application in optoelectronic devices. An attempt was also made to investigate the photovoltaic potential of PTPA. Organic photovoltaic devices with various buffer layer structures, namely ITO/CuI/PTPA/C{sub 60}/BCP/Al, ITO/MoO{sub 3}/PTPA/C{sub 60}/BCP/Al, and ITO/MoO{sub 3}/CuI/PTPA/C{sub 60}/BCP/Al, where ITO stands for indium tin oxide and BCP for bathocuproine, were utilized for the studies. Power conversion efficiency of these devices ranged between 0.21 and 0.43% under simulated AM 1.5 illumination (100 mW cm{sup −2}). This result proved that polymers containing TPA in the main chain hold promising properties that would allow their use in photovoltaic devices. - Highlights: • A Schiff base polymer with triphenylamine and thiophene segments was synthesized. • In organic cells, the highest efficiency was obtained in a MoO{sub 3}/CuI double layer. • Polymer exhibited a power conversion efficiency between 0.21 and 0.43 %.

  11. Self-consistent field theoretic simulations of amphiphilic triblock copolymer solutions: Polymer concentration and chain length effects

    Directory of Open Access Journals (Sweden)

    X.-G. Han

    2014-06-01

    Full Text Available Using the self-consistent field lattice model, polymer concentration φP and chain length N (keeping the length ratio of hydrophobic to hydrophilic blocks constant the effects on temperature-dependent behavior of micelles are studied, in amphiphilic symmetric ABA triblock copolymer solutions. When chain length is increased, at fixed φP, micelles occur at higher temperature. The variations of average volume fraction of stickers φcos and the lattice site numbers Ncols at the micellar cores with temperature are dependent on N and φP, which demonstrates that the aggregation of micelles depends on N and φP. Moreover, when φP is increased, firstly a peak appears on the curve of specific heat CV for unimer-micelle transition, and then in addition a primary peak, the secondary peak, which results from the remicellization, is observed on the curve of CV. For a long chain, in intermediate and high concentration regimes, the shape of specific heat peak markedly changes, and the peak tends to be a more broad peak. Finally, the aggregation behavior of micelles is explained by the aggregation way of amphiphilic triblock copolymer. The obtained results are helpful in understanding the micellar aggregation process.

  12. Construction and Self-Assembly of Single-Chain Polymer Nanoparticles via Coordination Association and Electrostatic Repulsion in Water.

    Science.gov (United States)

    Zhu, Zhengguang; Xu, Na; Yu, Qiuping; Guo, Lei; Cao, Hui; Lu, Xinhua; Cai, Yuanli

    2015-08-01

    Simultaneous coordination-association and electrostatic-repulsion interactions play critical roles in the construction and stabilization of enzymatic function metal centers in water media. These interactions are promising for construction and self-assembly of artificial aqueous polymer single-chain nanoparticles (SCNPs). Herein, the construction and self-assembly of dative-bonded aqueous SCNPs are reported via simultaneous coordination-association and electrostatic-repulsion interactions within single chains of histamine-based hydrophilic block copolymer. The electrostatic-repulsion interactions are tunable through adjusting the imidazolium/imidazole ratio in response to pH, and in situ Cu(II)-coordination leads to the intramolecular association and single-chain collapse in acidic water. SCNPs are stabilized by the electrostatic repulsion of dative-bonded block and steric shielding of nonionic water-soluble block, and have a huge specific surface area of function metal centers accessible to substrates in acidic water. Moreover, SCNPs can assemble into micelles, networks, and large particles programmably in response to the solution pH. These unique media-sensitive phase-transformation behaviors provide a general, facile, and versatile platform for the fabrication of enzyme-inspired smart aqueous catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. On the Wrapping of Polyglycolide, Poly(Ethylene Oxide), and Polyketone Polymer Chains Around Single-Walled Carbon Nanotubes Using Molecular Dynamics Simulations

    Science.gov (United States)

    Rouhi, S.; Alizadeh, Y.; Ansari, R.

    2015-02-01

    By using molecular dynamics simulations, the interaction between a single-walled carbon nanotube and three different polymers has been studied in this work. The effects of various parameters such as the nanotube geometry and temperature on the interaction energy and radius of gyration of polymers have been explored. By studying the snapshots of polymers along the single-walled carbon nanotube, it has been shown that 50 ps can be considered as a suitable time after which the shape of polymer chains around the nanotube remains almost unchanged. It is revealed that the effect of temperature on the interaction energy and radius of gyration of polymers in the range of 250 to 500 K is not significant Also, it is shown that the interaction energy depends on the nanotube diameter.

  14. Molecular weight kinetics and chain scission models for dextran polymers during ultrasonic degradation.

    Science.gov (United States)

    Pu, Yuanyuan; Zou, Qingsong; Hou, Dianzhi; Zhang, Yiping; Chen, Shan

    2017-01-20

    Ultrasonic degradation of six dextran samples with different initial molecular weights (IMW) has been performed to investigate the degradation behavior and chain scission mechanism of dextrans. The weight-average molecular weight (Mw) and polydispersity index (D value) were monitored by High Performance Gel Permeation Chromatography (HPGPC). Results showed that Mw and D value decreased with increasing ultrasonic time, resulting in a more homologous dextran solution with lower molecular weight. A significant degradation occurred in dextrans with higher IMW, particularly at the initial stage of the ultrasonic treatment. The Malhotra model was found to well describe the molecular weight kinetics for all dextran samples. Experimental data was fitted into two chain scission models to study dextran chain scission mechanism and the model performance was compared. Results indicated that the midpoint scission model agreed well with experimental results, with a linear regression factor of R 2 >0.99. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Side-Chain Supramolecular Polymers Employing Conformer Independent Triple Hydrogen Bonding Arrays

    OpenAIRE

    Gooch, Adam; Murphy, Natasha S.; Thomson, Neil H.; Wilson, Andrew J.

    2013-01-01

    Derivatives of thymine have been extensively used to promote supramolecular materials assembly. Such derivatives can be synthetically challenging to access and may be susceptible to degradation. The current article uses a conformer-independent acceptor-donor-acceptor array (ureidopyrimidine) which forms moderate affinity interactions with diamidopyridine derivatives to effect supramolecular blend formation between polystyrene and poly(methyl methacrylate) polymers obtained by RAFT which have ...

  16. Silver-tellurolate polynuclear complexes: from isolated cluster units to extended polymer chains

    International Nuclear Information System (INIS)

    Corrigan, J.F.; Fenske, D.; Power, W.P.

    1997-01-01

    In the presence of tertiary phosphanes, AgCl reacts readily with the reagent Te(Ph)SiMe 3 to yield silver - tellurolate polynuclear complexes. In the case of PMe 3 , the polymer [Ag 10 (μ 3 -TePh) 10 (PMe 3 ) 2 ] ∞ (shown below) is formed, in which the TePh ligands seve as both inter- and intracluster bridges. (orig.)

  17. Self-Assembly of Block Copolymer Chains To Promote the Dispersion of Nanoparticles in Polymer Nanocomposites

    Science.gov (United States)

    2017-01-01

    In this paper we adopt molecular dynamics simulations to study the amphiphilic AB block copolymer (BCP) mediated nanoparticle (NP) dispersion in polymer nanocomposites (PNCs), with the A-block being compatible with the NPs and the B-block being miscible with the polymer matrix. The effects of the number and components of BCP, as well as the interaction strength between A-block and NPs on the spatial organization of NPs, are explored. We find that the increase of the fraction of the A-block brings different dispersion effect to NPs than that of B-block. We also find that the best dispersion state of the NPs occurs in the case of a moderate interaction strength between the A-block and the NPs. Meanwhile, the stress–strain behavior is probed. Our simulation results verify that adopting BCP is an effective way to adjust the dispersion of NPs in the polymer matrix, further to manipulate the mechanical properties. PMID:28892620

  18. Diketopyrrolopyrrole-Based Conjugated Polymer Entailing Triethylene Glycols as Side Chains with High Thin-Film Charge Mobility without Post-Treatments

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Si-Fen [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Liu, Zi-Tong [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Cai, Zheng-Xu [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Dyson, Matthew J. [Department of Materials and Centre for Plastic Electronics, Imperial College London, London SW72AZ UK; Stingelin, Natalie [Department of Materials and Centre for Plastic Electronics, Imperial College London, London SW72AZ UK; Chen, Wei [Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Institute for Molecular Engineering, The University of Chicago, 5640 South Ellis Avenue Chicago IL 60637 USA; Ju, Hua-Jun [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Zhang, Guan-Xin [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Zhang, De-Qing [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China

    2017-04-18

    Side chain engineering of conjugated donor-acceptor polymers is a new way to manipulate their optoelectronic properties. Two new diketopyrrolopyrrole (DPP)-terthiophene-based conjugated polymers PDPP3T-1 and PDPP3T-2, with both hydrophilic triethylene glycol (TEG) and hydrophobic alkyl chains, are reported. It is demonstrated that the incorporation of TEG chains has a significant effect on the interchain packing and thin-film morphology with noticeable effect on charge transport. Polymer chains of PDPP3T-1 in which TEG chains are uniformly distributed can self-assemble spontaneously into a more ordered thin film. As a result, the thin film of PDPP3T-1 exhibits high saturated hole mobility up to 2.6 cm(2) V-1 s(-1) without any post-treatment. This is superior to those of PDPP3T with just alkyl chains and PDPP3T-2. Moreover, the respective field effect transistors made of PDPP3T-1 can be utilized for sensing ethanol vapor with high sensitivity (down to 100 ppb) and good selectivity.

  19. Polymer nanocomposites: polymer and particle dynamics

    KAUST Repository

    Kim, Daniel; Srivastava, Samanvaya; Narayanan, Suresh; Archer, Lynden A.

    2012-01-01

    Polymer nanocomposites containing nanoparticles smaller than the random coil size of their host polymer chains are known to exhibit unique properties, such as lower viscosity and glass transition temperature relative to the neat polymer melt. It has

  20. Silica-filled elastomers polymer chain and filler characterization by a SANS-SAXS approach

    CERN Document Server

    Botti, A; Richter, D; Urban, V; Ipns, A 6 4; Kohlbrecher, J; Straube, E

    2002-01-01

    A study of composites based upon commercially available silica fillers and networks of blends of protonated and deuterated anionically prepared polyisoprene is presented. The extraction of the single chain structure factor for SANS in the polymeric soft phase in isotropic and deformed state has been performed for the first time. The quasi three-component system could not be compositionally matched due to the internal structures of the activated fillers. For this, a parallel SAXS investigation provided the neccessary information on the filler structure which was lacking in the SANS analysis. Whereas mechanically clear reinforcement at low strains and filler-networking can be observed, the microscopic characterization of the chain deformation in the framework of the network tube model agrees with the estimates for hydrodynamic reinforcement of fractal fillers. (orig.)

  1. Silica-filled elastomers: polymer chain and filler characterization by a SANS-SAXS approach

    International Nuclear Information System (INIS)

    Botti, A.; Pyckhout-Hintzen, W.; Richter, D.; Urban, V.; Kohlbrecher, J.; Straube, E.

    2002-01-01

    A study of composites based upon commercially available silica fillers and networks of blends of protonated and deuterated anionically prepared polyisoprene is presented. The extraction of the single chain structure factor for SANS in the polymeric soft phase in isotropic and deformed state has been performed for the first time. The quasi three-component system could not be compositionally matched due to the internal structures of the activated fillers. For this, a parallel SAXS investigation provided the neccessary information on the filler structure which was lacking in the SANS analysis. Whereas mechanically clear reinforcement at low strains and filler-networking can be observed, the microscopic characterization of the chain deformation in the framework of the network tube model agrees with the estimates for hydrodynamic reinforcement of fractal fillers. (orig.)

  2. NOR and nitroxide-based HAS in accelerated photooxidation of carbon-chain polymers; comparison with secondary HAS: an ESRI and ATR FTIR study

    Czech Academy of Sciences Publication Activity Database

    Pilař, Jan; Michálková, Danuše; Šeděnková, Ivana; Pfleger, Jiří; Pospíšil, Jan

    2011-01-01

    Roč. 96, č. 5 (2011), s. 847-862 ISSN 0141-3910 R&D Projects: GA AV ČR IAA400500804 Institutional research plan: CEZ:AV0Z40500505 Keywords : commodity carbon-chain polymers * photodegradation * accelerated weathering Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.769, year: 2011

  3. Pronounced Side Chain Effects in Triple Bond-Conjugated Polymers Containing Naphthalene Diimides for n-Channel Organic Field-Effect Transistors

    KAUST Repository

    Nam, Sungho; Hahm, Suk Gyu; Khim, Dongyoon; Kim, Hwajeong; Sajoto, Tissa; Ree, Moonhor; Marder, Seth R.; Anthopoulos, Thomas D.; Bradley, Donal D.C.; Kim, Youngkyoo

    2018-01-01

    on the surface morphology/nanostructure, thus playing a critical role in charge-transporting properties of the three NDI-based copolymers. Among the polymers, the one with an octyldodecyl (OD) chain at the nitrogen atoms of imide ring and a hexadecyloxy (HO

  4. Molecular Design for Preparation of Hexagonal-Ordered Porous Films Based on Side-chain Type Liquid-Crystalline Star Polymer.

    Science.gov (United States)

    Naka, Yumiko; Takayama, Hiromu; Koyama, Teruhisa; Le, Khoa V; Sasaki, Takeo

    2018-05-02

    Fabrication of regularly porous films by the breath-figure method has attracted much attention. The simple, low-cost technique uses the condensation of water droplets to produce these structures, but the phenomenon itself is complex, requiring control over many interacting parameters that change throughout the process. Developing a unified understanding for the molecular design of polymers to prepare ordered porous films is challenging, but required for further advancements. In this article, the effects of the chemical structure of polymers in the breath-figure technique were systematically explored using side-chain type liquid-crystalline (LC) star polymers. The formation of porous films was affected by the structure of the polymers. Although the entire film surface of poly(11-[4-(4-cyanobiphenyl)oxy]undecyl methacrylate) (P11CB) had a hexagonal ordered porous structure over a certain Mn value, regularly arranged holes did not easily form in poly(methyl methacrylate) (PMMA), even though the main chain of PMMA is similar to that of P11CB. Comparing P11CB and poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11B) (P11CB without cyano groups) showed that the local polar groups in hydrophobic polymers promoted the formation of ordered porous films. No holes formed in poly(4-cyanobiphenyl methacrylate) (P0CB) (P11CB without alkyl spacers) films due to its hydrophilicity. The introduction of alkyl chains in P0CB allowed the preparation of honeycomb-structured films by increasing the internal tension. However, alkyl chains in the side chain alone did not result in a porous structure, as in the case of poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11). Aromatic rings are also required to increase the Tg and improve film formability. In the present study, suitable molecular designs of polymers were found, specifically hydrophobic polymers with local polar groups, to form a regularly porous structure. Development of clear guidelines for the molecular

  5. The Role of Morphology and Electronic Chain Aggregation on the Optical Gain Properties of Semiconducting Conjugated Polymers

    Science.gov (United States)

    Lampert, Zachary Evan

    Conjugated polymers (CPs) are a novel class of materials that exhibit the optical and electrical properties of semiconductors while still retaining the durability and processability of plastics. CPs are also intrinsically 4-level systems with high luminescence quantum efficiencies making them particularly attractive as organic gain media for solid-state laser applications. However, before CPs can emerge as a commercially available laser technology, a more comprehensive understanding of the morphological dependence of the photophysics is required. In this thesis, the morphology and chain conformation dependence of amplified spontaneous emission (ASE) and optical gain in thin films of poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) was investigated. By changing the chemical nature of the solvent from which films were cast, as well as the temperature at which films were annealed, CP films with different morphologies, and hence different degrees of interchain interactions were achieved. Contrary to the common perception that polymer morphology plays a decisive role in determining the ASE behavior of thin CP films, we found that chromophore aggregation and degree of conformational order have minimal impact on optical gain. In fact, experimental results indicated that an extremely large fraction of interchain aggregate species and/or exciton dissociating defects are required to significantly alter the optical properties and suppress stimulated emission. These results are pertinent to the fabrication and optimization of an electrically pumped laser device, as improvements in charge carrier mobility through controlled increases in chain aggregation may provide a viable means of optimizing injection efficiency without significantly degrading optical gain. To offset charge-induced absorption losses under electrical pumping, and to enable the use of more compact and economical sources under optical pumping, conjugated polymers exhibiting low lasing

  6. Size effect of added LaB6 particles on optical properties of LaB6/Polymer composites

    International Nuclear Information System (INIS)

    Yuan Yifei; Zhang Lin; Hu Lijie; Wang Wei; Min Guanghui

    2011-01-01

    Modified LaB 6 particles with sizes ranging from 50 nm to 400 nm were added into polymethyl methacrylate (PMMA) matrix in order to investigate the effect of added LaB 6 particles on optical properties of LaB 6 /PMMA composites. Method of in-situ polymerization was applied to prepare PMMA from raw material—methyl methacrylate (MMA), a process during which LaB 6 particles were dispersed in MMA. Ultraviolet–visible–near infrared (UV–vis–NIR) absorption spectrum was used to study optical properties of the as-prepared materials. The difference in particle size could apparently affect the composites' absorption of visible light around wavelength of 600 nm. Added LaB 6 particles with size of about 70 nm resulted in the best optical properties among these groups of composites. - Graphical abstract: 70 nm LaB 6 particles resulted in the best performance on absorption of VIS and NIR, which could not be apparently achieved by LaB 6 particles beyond nano-scale. Highlights: ► LaB 6 /PMMA composites were prepared using the method of in-situ polymerization. ► LaB 6 particles added in MMA prolonged the time needed for its pre-polymerization. ► Nanosized LaB 6 particles could obviously absorb much NIR but little VIS.

  7. Effects of molecular structure on microscopic heat transport in chain polymer liquids

    International Nuclear Information System (INIS)

    Matsubara, Hiroki; Kikugawa, Gota; Ohara, Taku; Bessho, Takeshi; Yamashita, Seiji

    2015-01-01

    In this paper, we discuss the molecular mechanism of the heat conduction in a liquid, based on nonequilibrium molecular dynamics simulations of a systematic series of linear- and branched alkane liquids, as a continuation of our previous study on linear alkane [T. Ohara et al., J. Chem. Phys. 135, 034507 (2011)]. The thermal conductivities for these alkanes in a saturated liquid state at the same reduced temperature (0.7T c ) obtained from the simulations are compared in relation to the structural difference of the liquids. In order to connect the thermal energy transport characteristics with molecular structures, we introduce the new concept of the interatomic path of heat transfer (atomistic heat path, AHP), which is defined for each type of inter- and intramolecular interaction. It is found that the efficiency of intermolecular AHP is sensitive to the structure of the first neighbor shell, whereas that of intramolecular AHP is similar for different alkane species. The dependence of thermal conductivity on different lengths of the main and side chain can be understood from the natures of these inter- and intramolecular AHPs

  8. Effects of molecular structure on microscopic heat transport in chain polymer liquids

    Energy Technology Data Exchange (ETDEWEB)

    Matsubara, Hiroki, E-mail: matsubara@microheat.ifs.tohoku.ac.jp; Kikugawa, Gota; Ohara, Taku [Institute of Fluid Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Bessho, Takeshi; Yamashita, Seiji [Higashifuji Technical Center, Toyota Motor Corporation, 1200 Mishuku, Susono, Shizuoka 410-1193 (Japan)

    2015-04-28

    In this paper, we discuss the molecular mechanism of the heat conduction in a liquid, based on nonequilibrium molecular dynamics simulations of a systematic series of linear- and branched alkane liquids, as a continuation of our previous study on linear alkane [T. Ohara et al., J. Chem. Phys. 135, 034507 (2011)]. The thermal conductivities for these alkanes in a saturated liquid state at the same reduced temperature (0.7T{sub c}) obtained from the simulations are compared in relation to the structural difference of the liquids. In order to connect the thermal energy transport characteristics with molecular structures, we introduce the new concept of the interatomic path of heat transfer (atomistic heat path, AHP), which is defined for each type of inter- and intramolecular interaction. It is found that the efficiency of intermolecular AHP is sensitive to the structure of the first neighbor shell, whereas that of intramolecular AHP is similar for different alkane species. The dependence of thermal conductivity on different lengths of the main and side chain can be understood from the natures of these inter- and intramolecular AHPs.

  9. Polymer chain dynamics in epoxy based composites as investigated by broadband dielectric spectroscopy

    Directory of Open Access Journals (Sweden)

    Mohammad K. Hassan

    2016-03-01

    Full Text Available Epoxy networks of the diglycidyl ether of bisphenol A (DGEBA were prepared using 3,3′- and 4,4′-diaminodiphenyl sulfone isomer crosslinkers. Secondary relaxations and the glass transitions of resultant networks were probed using broadband dielectric spectroscopy (BDS. A sub-Tg γ relaxation peak for both networks shifts to higher frequencies (f with increasing temperature in Arrhenius fashion, both processes having the same activation energy and being assigned to phenyl ring flipping in DGEBA chains. A β relaxation is assigned to local motions of dipoles that were created during crosslinking reactions. 4,4′-based networks exhibited higher Tg relative to 3,3′-based networks as per dynamic mechanical as well as BDS analyses. The Vogel–Fulcher–Tammann–Hesse equation fitted well to relaxation time vs. temperature data and comparison of Vogel temperatures suggests lower free volume per mass for the 3,3′-based network. The Kramers–Krönig transformation was used to directly calculate dc-free ɛ″ vs. f data from experimental ɛ′ vs. f data. Distribution of relaxation times (DRT curves are bi-modal for the 3,3′-crosslinked resin suggesting large-scale microstructural heterogeneity as opposed to homogeneity for the 4,4′-based network whose DRT consists of a single peak.

  10. Quantum critical scaling for field-induced quantum phase transition in a periodic Anderson-like model polymer chain

    Energy Technology Data Exchange (ETDEWEB)

    Ding, L.J., E-mail: dinglinjie82@126.com; Zhong, Y.

    2017-07-15

    Highlights: • The quantum critical scaling is investigated by Green’s function theory. • The obtained power-law critical exponents (β, δ and α) obey the critical scaling relation α + β(1 + δ) = 2. • The scaling hypothesis equations are proposed to verify the scaling analysis. - Abstract: The quantum phase transition and thermodynamics of a periodic Anderson-like polymer chain in a magnetic field are investigated by Green’s function theory. The T-h phase diagram is explored, wherein a crossover temperature T{sup ∗} denoting the gapless phase crossover into quantum critical regimes, smoothly connects near the critical fields to the universal linear line T{sup ∗} ∼ (h − h{sub c,s}), and ends at h{sub c,s}, providing a new route to capture quantum critical point (QCP). The quantum critical scaling around QCPs is demonstrated by analyzing magnetization, specific heat and Grüneisen parameter Γ{sub h}, which provide direct access to distill the power-law critical exponents (β, δ and α) obeying the critical scaling relation α + β(1 + δ) = 2, analogous to the quantum spin system. Furthermore, scaling hypothesis equations are proposed to check the scaling analysis, for which all the data collapse onto a single curve or two independent branches for the plot against an appropriate scaling variable, indicating the self-consistency and reliability of the obtained critical exponents.

  11. Rod like attapulgite/poly(ethylene terephthalate nanocomposites with chemical bonding between the polymer chain and the filler

    Directory of Open Access Journals (Sweden)

    Q. Fu

    2012-08-01

    Full Text Available Poly(ethylene terephthalate (PET nanocomposites containing rod-like silicate attapulgite (AT were prepared via in situ polymerization. It is presented that PET chains identical to the matrix have been successfully grafted onto simple organically pre-modified AT nanorods (MAT surface during the in situ polymerization process. The covalent bonding at the interface was confirmed by Fourier transform infrared spectroscopy (FTIR and thermogravimetric analysis (TGA. The content of grafted PET polymer on the surface of MAT was about 26 wt%. This high grafting density greatly improved the dispersion of fillers, interfacial adhesion as well as the significant confinement of the segmental motion of PET, as compared to the nanocomposites of PET/pristine AT (PET/AT. Owing to the unique interfacial structure in PET/MAT composites, their thermal and mechanical properties have been greatly improved. Compared with neat PET, the elastic modulus and the yield strength of PET/MAT were significantly improved by about 39.5 and 36.8%, respectively, by incorporating only 2 wt % MAT. Our work provides a novel route to fabricate advanced PET nanocomposites using rod-like attapulgite as fillers, which has great potential for industrial applications.

  12. Future of radiation processing of polymers

    International Nuclear Information System (INIS)

    Chapiro, A.; Tabata, Y.; Stannett, V.; Dole, M.; Dobo, J.; Charlesby, A.

    1990-01-01

    The present development of radiation processing in the polymer field including well established technologies, with large scale productions and substantial markets, such as: crosslinking; curing of monomer-polymer formulations; sterilization of plastic supplies; are discussed. The manufacture of sophisticated devices with low volume production but large added value: electronic devices; resistors and several promising applications for which only small commercial productions are on stream today: chain degradation; polymerization; graft copolymerization, are reviewed. (author)

  13. Factors Governing Intercalation of Fullerenes and Other Small Molecules Between the Side Chains of Semiconducting Polymers Used in Solar Cells

    KAUST Repository

    Miller, Nichole Cates; Cho, Eunkyung; Gysel, Roman; Risko, Chad; Coropceanu, Veaceslav; Miller, Chad E.; Sweetnam, Sean; Sellinger, Alan; Heeney, Martin; McCulloch, Iain; Bré das, Jean-Luc; Toney, Michael F.; McGehee, Michael D.

    2012-01-01

    bimolecular crystals did not form in the other studied polymer:nonfullerene blends, including those with both conjugated and non-conjugated small molecules. DSC and molecular simulations demonstrate that strong polymer-fullerene interactions can exist

  14. Interaction of polymer with discotic clay particles

    International Nuclear Information System (INIS)

    Auvray, L.; Lal, J.

    1999-01-01

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

  15. Comparison of the Photovoltaic Characteristics and Nanostructure of Fullerenes Blended with Conjugated Polymers with Siloxane-Terminated and Branched Aliphatic Side Chains

    KAUST Repository

    Kim, Do Hwan

    2013-02-12

    All-organic bulk heterojunction solar cells based on blends of conjugated polymers with fullerenes have recently surpassed the 8% efficiency mark and are well on their way to the industrially relevant ∼15% threshold. Using a low band-gap conjugated polymer, we have recently shown that polymer side chain engineering can lead to dramatic improvement in the in-plane charge carrier mobility. In this article, we investigate the effectiveness of siloxy side chain derivatization in controlling the photovoltaic performance of polymer:[6,6]-phenyl-C[71]-butyric acid methyl ester (PC71BM) blends and hence its influence on charge transport in the out-of-plane direction relevant for organic solar cells. We find that, in neat blends, the photocurrent of the polymer with siloxy side chains (PII2T-Si) is 4 times greater than that in blends using the polymer with branched aliphatic side chains (PII2T-ref). This difference is due to a larger out-of-plane hole mobility for PII2T-Si brought about by a largely face-on crystallite orientation as well as more optimal nanoscale polymer:PC71BM mixing. However, upon incorporating a common processing additive, 1,8-diiodooctane (DIO), into the spin-casting blend solution and following optimization, the PII2T-ref:PC71BM OPV device performance undergoes a large improvement and becomes the better-performing device, almost independent of DIO concentration (>1%). We find that the precise amount of DIO plays a larger role in determining the efficiency of PII2T-Si:PC71BM, and even at its maximum, the device performance lags behind optimized PII2T-ref:PC71BM blends. Using a combination of atomic force microscopy and small- and wide-angle X-ray scattering, we are able to elucidate the morphological modifications associated with the DIO-induced changes in both the nanoscale morphology and the molecular packing in blend films. © 2012 American Chemical Society.

  16. The effect of side-chain substitution and hot processing on diketopyrrolopyrrole-based polymers for organic solar cells

    NARCIS (Netherlands)

    Heintges, G.H.L.; Leenaers, P.J.; Janssen, R.A.J.

    2017-01-01

    The effects of cold and hot processing on the performance of polymer-fullerene solar cells are investigated for diketopyrrolopyrrole (DPP) based polymers that were specifically designed and synthesized to exhibit a strong temperature-dependent aggregation in solution. The polymers, consisting of

  17. A novel temperature control method for shortening thermal cycling time to achieve rapid polymerase chain reaction (PCR) in a disposable polymer microfluidic device

    DEFF Research Database (Denmark)

    Bu, Minqiang; R. Perch-Nielsen, Ivan; Sørensen, Karen Skotte

    steps to achieve a rapid ramping between the temperature steps for DNA denaturation, annealing and extension. The temperature dynamics within the microfluidic PCR chamber was characterized and the overshooting and undershooting parameters were optimized using the temperature dependent fluorescence......We present a new temperature control method capable of effectively shortening the thermal cycling time of polymerase chain reaction (PCR) in a disposable polymer microfluidic device with external heater and temperature sensor. The method employs optimized temperature overshooting and undershooting...

  18. A temperature control method for shortening thermal cycling time to achieve rapid polymerase chain reaction (PCR) in a disposable polymer microfluidic device

    DEFF Research Database (Denmark)

    Bu, Minqiang; Perch-Nielsen, Ivan R.; Sørensen, Karen Skotte

    2013-01-01

    steps to achieve a rapid ramping between the temperature steps for DNA denaturation, annealing and extension. The temperature dynamics within the microfluidic PCR chamber was characterized and the overshooting and undershooting parameters were optimized using the temperature-dependent fluorescence......We present a temperature control method capable of effectively shortening the thermal cycling time of polymerase chain reaction (PCR) in a disposable polymer microfluidic device with an external heater and a temperature sensor. The method employs optimized temperature overshooting and undershooting...

  19. Side-chain tunability of furan-containing low-band-gap polymers provides control of structural order in efficient solar cells

    KAUST Repository

    Yiu, Alan T.; Beaujuge, Pierre; Lee, Olivia P.; Woo, Claire; Toney, Michael F.; Frechet, Jean

    2012-01-01

    The solution-processability of conjugated polymers in organic solvents has classically been achieved by modulating the size and branching of alkyl substituents appended to the backbone. However, these substituents impact structural order and charge transport properties in thin-film devices. As a result, a trade-off must be found between material solubility and insulating alkyl content. It was recently shown that the substitution of furan for thiophene in the backbone of the polymer PDPP2FT significantly improves polymer solubility, allowing for the use of shorter branched side chains while maintaining high device efficiency. In this report, we use PDPP2FT to demonstrate that linear alkyl side chains can be used to promote thin-film nanostructural order. In particular, linear side chains are shown to shorten π-π stacking distances between backbones and increase the correlation lengths of both π-π stacking and lamellar spacing, leading to a substantial increase in the efficiency of bulk heterojunction solar cells. © 2011 American Chemical Society.

  20. INVERSION SYMMETRY, ARCHITECTURE AND DISPERSITY, AND THEIR EFFECTS ON THERMODYNAMICS IN BULK AND CONFINED REGIONS: FROM RANDOMLY BRANCHED POLYMERS TO LINEAR CHAINS, STARS AND DENDRIMERS

    Directory of Open Access Journals (Sweden)

    P.D.Gujrati

    2002-01-01

    Full Text Available Theoretical evidence is presented in this review that architectural aspects can play an important role, not only in the bulk but also in confined geometries by using our recursive lattice theory, which is equally applicable to fixed architectures (regularly branched polymers, stars, dendrimers, brushes, linear chains, etc. and variable architectures, i.e. randomly branched structures. Linear chains possess an inversion symmetry (IS of a magnetic system (see text, whose presence or absence determines the bulk phase diagram. Fixed architectures possess the IS and yield a standard bulk phase diagram in which there exists a theta point at which two critical lines C and C' meet and the second virial coefficient A2 vanishes. The critical line C appears only for infinitely large polymers, and an order parameter is identified for this criticality. The critical line C' exists for polymers of all sizes and represents phase separation criticality. Variable architectures, which do not possess the IS, give rise to a topologically different phase diagram with no theta point in general. In confined regions next to surfaces, it is not the IS but branching and monodispersity, which becomes important in the surface regions. We show that branching plays no important role for polydisperse systems, but become important for monodisperse systems. Stars and linear chains behave differently near a surface.

  1. Side-chain tunability of furan-containing low-band-gap polymers provides control of structural order in efficient solar cells

    KAUST Repository

    Yiu, Alan T.

    2012-02-01

    The solution-processability of conjugated polymers in organic solvents has classically been achieved by modulating the size and branching of alkyl substituents appended to the backbone. However, these substituents impact structural order and charge transport properties in thin-film devices. As a result, a trade-off must be found between material solubility and insulating alkyl content. It was recently shown that the substitution of furan for thiophene in the backbone of the polymer PDPP2FT significantly improves polymer solubility, allowing for the use of shorter branched side chains while maintaining high device efficiency. In this report, we use PDPP2FT to demonstrate that linear alkyl side chains can be used to promote thin-film nanostructural order. In particular, linear side chains are shown to shorten π-π stacking distances between backbones and increase the correlation lengths of both π-π stacking and lamellar spacing, leading to a substantial increase in the efficiency of bulk heterojunction solar cells. © 2011 American Chemical Society.

  2. Synthesis, structure and optical limiting effect of a novel inorganic-organic hybrid polymer containing mixed chains of copper(I)/iodine

    International Nuclear Information System (INIS)

    Li Haohong; Chen Zhirong; Li Junqian; Zhan Hongbing; Zhang Wenxuan; Huang Changcang; Ma Cheng; Zhao Bin

    2006-01-01

    In this paper, treatment of N-ethyl-benzo[f]quinolium (ebq) iodide and CuI with excess KI afforded an unusual coordination polymer [(ebq) 2 (Cu 3 I 4 )(CuI 2 )] n (1). 1 crystallizes in tetragonal system, space group P4(2)bc with cell parameters of a=23.2040(6)A, c=6.7393(3)A, V=3628.6(2)A 3 , Z=8, D c =2.622g/c 3 , R 1 =0.0447 and wR 2 =0.0974. A highly interesting feature of 1 is its presence of mixed types of chains [(Cu 3 I 4 ) n - and (CuI 2 ) n - chain] in one crystal lattice based on supramolecular self-assembly directed by cations. The infinite chains (Cu 3 I 4 ) n - and (CuI 2 ) n - in 1 could be described as the edge-sharing arrangement of CuI 4 tetrahedron. Furthermore, IR, EA, UV-Vis, thermal analysis and optical limiting measurements were adopted to characterize polymer 1. The optical limiting experiment shows that the present polymer exhibits a large optical limiting capacity

  3. Enhancing the photovoltaic performance of bulk heterojunction polymer solar cells by adding Rhodamine B laser dye as co-sensitizer.

    Science.gov (United States)

    Kazemifard, Sholeh; Naji, Leila; Afshar Taromi, Faramarz

    2018-04-01

    Ternary blend (TB) strategy has been considered as an effective method to enhance the photovoltaic performance of bulk heterojunction (BHJ) polymer solar cells (PSCs). Here, we report on TB-based PSCs containing two donor materials; poly-3-hexylthiophene (P3HT) and Rhodamine B (RhB) laser organic dye, and [6,6]-phenyl C 61 butyric acid methyl ester (PC 61 BM) as an acceptor. The influence of RhB weight percentage and injection volume was extensively studied. To gain insight into the influences of RhB on the photovoltaic performance of PSCs, physicochemical and optical properties of TBs were compared with those of BHJ binary blend as a standard. RhB broadened the light absorption properties of the active layer and played a bridging role between P3HT and PC 61 BM. The PCE and short-circuit current density (Jsc) of the optimized TB-based PSCs comprising of 0.5 wt% RhB reached 5% and 12.12 mA/cm 2 , respectively. Compared to BHJ standard cell, the PCE and the generated current was improved by two orders of magnitude due to higher photon harvest of the active layer, cascade energy level structure of TB components and a considerable decrease in the charge carrier recombination. The results suggest that RhB can be considered as an effective material for application in PSCs to attain high photovoltaic performance. Copyright © 2018 Elsevier Inc. All rights reserved.

  4. Pronounced Side Chain Effects in Triple Bond-Conjugated Polymers Containing Naphthalene Diimides for n-Channel Organic Field-Effect Transistors

    KAUST Repository

    Nam, Sungho

    2018-03-23

    Three triple bond-conjugated naphthalene diimide (NDI) copolymers, poly{[N,N′-bis(2-R1)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-[(2,5-bis(2-R2)-1,4-phenylene)bis(ethyn-2,1-diyl)]} (PNDIR1-R2), were synthesized via Sonogashira coupling polymerization with varying alkyl side chains at the nitrogen atoms of the imide ring and 2,5-positions of the 1,4-diethynylbenzene moiety. Considering their identical polymer backbone structures, the side chains were found to have a strong influence on the surface morphology/nanostructure, thus playing a critical role in charge-transporting properties of the three NDI-based copolymers. Among the polymers, the one with an octyldodecyl (OD) chain at the nitrogen atoms of imide ring and a hexadecyloxy (HO) chain at the 2,5-positions of 1,4-diethynylbenzene, P(NDIOD-HO), exhibited the highest electron mobility of 0.016 cm2 V–1 s–1, as compared to NDI-based copolymers with an ethylhexyl chain at the 2,5-positions of 1,4-diethynylbenzene. The enhanced charge mobility in the P(NDIOD-HO) layers is attributed to the well-aligned nano-fiber-like surface morphology and highly ordered packing structure with a dominant edge-on orientation, thus enabling efficient in-plane charge transport. Our results on the molecular structure–charge transport property relationship in these materials may provide an insight into novel design of n-type conjugated polymers for applications in the organic electronics of the future.

  5. Thermal analysis studies of doping effects on the conformational motions of polymer chains in solid solutions with lasing molecules

    Science.gov (United States)

    Kalogeras, Ioannis M.; Pallikari, Fotini; Vassilikou-Dova, Aglaia; Neagu, Eugen R.

    2007-05-01

    The advancement of the solid-state dye laser performance largely depends on the systematic study of the dye-matrix interactions at the nanoscopic scale. The current work deals with blends of a comparatively inert dye host, poly(methyl methacrylate) (PMMA), with nonionic/apolar (substituted perylenes) and ionic/polar (rhodamine 6G, pyrromethene 567) dyes at ≈10-4 mol L-1 loading. Differential scanning calorimetry (DSC) and thermally stimulated currents (TSC) were used to explore the relative strength of inter- and intramolecular guest-host interactions by monitoring blending-induced modifications of the high-temperature signals: the segmental relaxation, the space-charge relaxation, and the liquid-liquid transition. Both techniques revealed the antiplasticizing role of the oligomeric organics on the relaxation dynamics of polymer segments, evidenced by clear glass-transition temperature upshifts. It becomes apparent that this effect is independent of the size, polarity, and ionicity of the dopant, signifying a common mechanism underway. It is suggested that, at least for the dyes under investigation, the chromophores simply fill the voids within the matrix, imposing strong steric hindrances on the rearrangement of the long-range structure. A comparison between the present results and earlier low-temperature dielectric data reveals that the large-scale relaxation dynamics show stronger perturbations due to blending, in comparison to the localized rotational motion of the pendant groups. DSC provided estimates for the unconverted monomer percentages in the solid blends. These were also determined more accurately by nuclear magnetic resonance (NMR), which additionally confirmed that the tacticity of the chains is not affected by the presence of the dye.

  6. Depleted depletion drives polymer swelling in poor solvent mixtures.

    Science.gov (United States)

    Mukherji, Debashish; Marques, Carlos M; Stuehn, Torsten; Kremer, Kurt

    2017-11-09

    Establishing a link between macromolecular conformation and microscopic interaction is a key to understand properties of polymer solutions and for designing technologically relevant "smart" polymers. Here, polymer solvation in solvent mixtures strike as paradoxical phenomena. For example, when adding polymers to a solvent, such that all particle interactions are repulsive, polymer chains can collapse due to increased monomer-solvent repulsion. This depletion induced monomer-monomer attraction is well known from colloidal stability. A typical example is poly(methyl methacrylate) (PMMA) in water or small alcohols. While polymer collapse in a single poor solvent is well understood, the observed polymer swelling in mixtures of two repulsive solvents is surprising. By combining simulations and theoretical concepts known from polymer physics and colloidal science, we unveil the microscopic, generic origin of this collapse-swelling-collapse behavior. We show that this phenomenon naturally emerges at constant pressure when an appropriate balance of entropically driven depletion interactions is achieved.

  7. Effect of adding Matrix Metallo proteinase inhibitors on the degree of conversion of monomers to polymer an experimental bonding agent

    Directory of Open Access Journals (Sweden)

    Ghavam M.

    2009-11-01

    Full Text Available "nBackground and Aim: In spite of the achievements in the field of dental adhesives, we are facing challenges with dentine bonding resistance, strength and stability. According to recent studies the role of MMP inhibitors in association with bonding,s persistence and leakage reduction and restoration,s persistence is important. The aim of this study was to investigate the effect of doxycycline as a MMP inhibitor on the degree of conversion (DC of an experimental dental adhesive. "nMaterials and Methods: In this experimental study, a new dental adhesive blend was prepared by mixing doxycycline monohydrate (in concentrations of 0.0, 0.25, 0.5, and 1 wt.% with monomers. The monomers were composed of 12% Bis-GMA and 10% TMPTMA, 28% HEMA, and 50% Ethanol by weight for all groups. Comphorquinone and amines were chosen as photo initiator system. Degree of conversion of all adhesives was measured using FTIR spectroscopy. The results were analyzed using one-way ANOVA and Tukey post hoc tests. "nResults: The results showed that addition of 0.25, 0.5, and 1 weight percent doxycycline did not significantly reduce the DC of the adhesives compared to 0.0% control group (p>0.05%. "nConclusion: According to the results of this study, adding doxycycline to the adhesives did not adversely affect the DC.

  8. Deformation and concentration fluctuations under stretching in a polymer network with free chains. The ``butterfly`` effect; Fluctuations de deformation et de concentration sous etirement dans un reseau polymere contenant des chaines libres. L`effet ``papillon``

    Energy Technology Data Exchange (ETDEWEB)

    Ramzi, A

    1994-06-01

    Small Angle Neutron Scattering gives access to concentration fluctuations of mobile labeled polymer chains embedded in a polymer network. At rest they appear progressively larger than for random mixing, with increasing ratio. Under uniaxial stretching, they decrease towards ideal mixing along the direction perpendicular to stretching, and can grow strongly along the parallel one, including the zero scattering vector q limit. This gives rise to intensity contours with double-winged patterns, in the shape of the figure `8`, or of `butterfly`. Random crosslinking and end-linking of monodisperse chains have both been studied. The strength of the `butterfly` effect increases with the molecular weight of the free chains, the crosslinking ratio, the network heterogeneity, and the elongation ratio. Eventually, the signal collapses on an `asymptotic` function I(q), of increasing correlation length with the elongation ratio. Deformation appears heterogeneous, maximal for soft areas, where the mobile chains localize preferentially. This could be due to spontaneous fluctuations, or linked to frozen fluctuations of the crosslink density. However, disagreement with the corresponding theoretical expressions makes it necessary to account for the spatial correlations of crosslink density, and their progressive unscreening as displayed by the asymptotic behavior. Networks containing pending labeled chains and free labeled stars lead to more precise understanding of the diffusion of free species and the heterogeneity of the deformation. It seems that the latter occurs even without diffusion for heterogeneous enough networks. In extreme cases (of the crosslinking parameters), the spatial correlations display on apparent fractal behavior, of dimensions 2 to 2.5, which is discussed here in terms of random clusters. 200 refs., 95 figs., 21 tabs., 10 appends.

  9. Four Novel Zn (II Coordination Polymers Based on 4′-Ferrocenyl-3,2′:6′,3′′-Terpyridine: Engineering a Switch from 1D Helical Polymer Chain to 2D Network by Coordination Anion Modulation

    Directory of Open Access Journals (Sweden)

    Lufei Xiao

    2017-11-01

    Full Text Available Four novel ZnII coordination polymers, [(ZnCl22(L2]n (1, [(ZnBr22(L2]n (2, and [(ZnI22(L2]n (3 and {[Zn(SCN2]1.5(L3}n (4, have been synthesized based on 4′-ferrocenyl-3,2′:6′,3′′-terpyridine with ZnII ions and different coordination anions under similar ambient conditions. Their structures have been confirmed using single crystal X-ray diffraction analysis, showing that complexes 1–3 are one-dimensional (1D double-stranded metal ion helical polymer chains and complex 4 is of a two-dimensional (2D network. The structural transformations of them from a 1D polymer chain to a 2D network under the influence of the coordination anions has been systematic investigated. Furthermore, the optical band gaps have been measured by optical diffuse reflectance spectroscopy, revealing that the ligand and the complexes should have semiconductor properties.

  10. Linear side chains in benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c] pyrrole-4,6-dione polymers direct self-assembly and solar cell performance

    KAUST Repository

    Cabanetos, Clement; El Labban, Abdulrahman; Bartelt, Jonathan A.; Douglas, Jessica D.; Mateker, William R.; Frechet, Jean; McGehee, Michael D.; Beaujuge, Pierre

    2013-01-01

    role that linear side-chain substituents play in poly(benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers for bulk heterojunction (BHJ) solar cell applications. We show that replacing branched side chains by linear ones

  11. Influence of the strength of the smectic order on the backbone anisotropy of side-chain liquid crystal polymers as revealed by SANS

    Science.gov (United States)

    Noirez, L.; Keller, P.; Cotton, J. P.

    1992-06-01

    It is proposed that the strength of the smectic order determines the backbone anisotropy of side-chain liquid crystal polymers. Here this strength increases with the length of the alkyl terminal group of the mesogens. Two liquid crystal polymethacrylates differing only by the mesogenic tails —OCH3 and —OC4H9 are considered. The backbone anisotropy of these polymers is measured by small angle neutron scattering (SANS) whereas the smectic order is evaluated from the intensity of the 001 Bragg peak. Il est proposé que la qualité de l'ordre smectique détermine l'anisotropie du squelette de polymères mésomorphes en peigne confinés dans les lamelles. Ici l'ordre smectique est augmenté en allongeant le groupe alkyl terminal des mésogènes. Nous étudions deux polyméthacrylates cristal liquide qui ne différent que par leurs groupes terminaux : —OCH3 et —OC4H9. L'anisotropie du squellete est mesurée par diffusion de neutrons aux petits angles tandis que l'ordre smectique est évalué à l'aide de l'intensité du pic de Bragg 001.

  12. The Influence of Side-Chain Position on the Optoelectronic Properties of a Red-Emitting Conjugated Polymer

    NARCIS (Netherlands)

    Lu, Li Ping; Finlayson, Chris E.; Kabra, Dinesh; Albert-Seifried, Sebastian; Song, Myoung Hoon; Havenith, Remco W. A.; Tu, Guoli; Huck, Wilhelm T. S.; Friend, Richard H.

    2013-01-01

    A study of the organic semiconductor F8TBT is presented, directly comparing a conventional form (F8TBT-out) with a form with varied alkyl side-chain position (F8TBT-in), in terms of optical properties and device performance in light-emitting-diodes (LEDs). Computational simulations of the side-chain

  13. Liquid crystalline polymers IX Main chain thermotropic poly (azomethine – ethers containing thiazole moiety linked with polymethylene spacers

    Directory of Open Access Journals (Sweden)

    2007-04-01

    Full Text Available A new homologous series of thermally stable thermotropic liquid crystalline poly(azomethine-ethers based on thiazole moiety were synthesized by solution polycondensation of 4,4`-diformyl-α,ω-diphenoxyalkanes, I–IV or 4,4`-diformyl-2,2`-dimethoxy-α,ω-diphenoxyalkanes V–VIII with the new bis(2-aminothiazole monomer X. A model compound XI was synthesized from X with benzaldehyde and characterized by elemental and spectral analyses. The inherent viscosities of the resulting polymers were in the range 0.43–1.34 dI/g. All the poly(azomethine-ethers were insoluble in common organic solvents but dissolved completely in concentrated H2SO4 and formic acid. The mesomorphic properties of these polymers were studied as a function of the diphenoxyalkane space length. Their thermotropic liquid crystalline properties were examined by DSC and optical polarizing microscopy and demonstrated that the resulting polymers form nematic mesophases over wide temperature ranges. The thermogravimetric analyses of those polymers were evaluated by TGA and DSC measurements and correlated to their structural units. X-ray analysis showed that polymers having some degree of crystallinity in the region 2θ = 5–60°. In addition, the morphological properties of selected examples were tested by scanning electron microscopy.

  14. Prognostic and Added Value of Two-Dimensional Global Longitudinal Strain for Prediction of Survival in Patients with Light Chain Amyloidosis Undergoing Autologous Hematopoietic Cell Transplantation.

    Science.gov (United States)

    Pun, Shawn C; Landau, Heather J; Riedel, Elyn R; Jordan, Jonathan; Yu, Anthony F; Hassoun, Hani; Chen, Carol L; Steingart, Richard M; Liu, Jennifer E

    2018-01-01

    Autologous hematopoietic cell transplantation (HCT) is a first-line therapy for prolonging survival in patients with light-chain (AL) amyloidosis. Cardiac involvement is the most important determinant of survival. However, patients with advanced cardiac involvement have often been excluded from HCT because of high risk for transplantation-related mortality and poor overall survival. Whether baseline left ventricular global longitudinal strain (GLS) can provide additional risk stratification and predict survival after HCT in this high-risk population remains unclear. The aim of this study was to evaluate the prognostic implication of baseline GLS and the added value of GLS beyond circulating cardiac biomarkers for risk stratification in patients with AL amyloidosis undergoing HCT. Eighty-two patients with newly diagnosed AL amyloidosis who underwent upfront HCT between January 2007 and April 2014 were included in the study. Clinical, echocardiographic, and serum cardiac biomarker data were collected at baseline and 12 months following HCT. GLS measurements were performed using a vendor-independent offline system. The median follow-up time for survivors was 58 months. Sixty-four percent of patients were in biomarker-based Mayo stage II or III. GLS, brain natriuretic peptide, troponin, and mitral E/A ratio were identified as the strongest predictors of survival (P value that best discriminated survivors from nonsurvivors, and the application of this cutoff value provided further mortality risk stratification within each Mayo stage. GLS is a strong predictor of survival in patients with AL amyloidosis undergoing HCT, potentially providing incremental value over serum cardiac biomarkers for risk stratification. GLS should be considered as a standard parameter along with serum cardiac biomarkers when evaluating eligibility for HCT or other investigational therapies. Copyright © 2017 American Society of Echocardiography. Published by Elsevier Inc. All rights reserved.

  15. Development of a Hydrogen Uptake-Release Mg-Based Alloy by Adding a Polymer CMC (Carboxymethylcellulose, Sodium Salt) via Reaction-Accompanying Milling

    Science.gov (United States)

    Kwak, Young Jun; Choi, Eunho; Song, Myoung Youp

    2018-03-01

    The addition of carboxymethylcellulose, sodium salt (CMC) might improve the hydrogen uptake and release properties of Mg since it has a relatively low melting point and the melting of CMC during milling in hydrogen (reaction-accompanying milling) may make the milled samples be in good states to absorb and release hydrogen rapidly and to have a large hydrogen-storage capacity. Samples with compositions of 95 w/o Mg + 5 w/o CMC (named Mg-5CMC) and 90 w/o Mg + 10 w/o CMC (named Mg-10CMC) were prepared by adding CMC via reaction-accompanying milling. Activation of Mg-10CMC was completed after about 3 hydrogen uptake-release cycles. Mg-10CMC had a higher initial hydrogen uptake rate and a larger amount of hydrogen absorbed in 60 min, U (60 min), than Mg-5CMC before and after activation. At the cycle number of three (CN = 3), Mg-10CMC had a very high initial hydrogen uptake rate (1.56 w/o H/min) and a large U (60 min) (5.57 w/o H) at 593 K in hydrogen of 12 bar, showing that the activated Mg-10CMC has an effective hydrogen-storage capacity of about 5.6 w/o at 593 K in hydrogen of 12 bar at CN = 3. At CN = 2, Mg-10CMC released 1.00 w/o H in 2.5 min, 4.67 w/o H in 10 min, and 4.76 w/o H in 60 min at 648 K in hydrogen of 1.0 bar. The milling in hydrogen of Mg with CMC is believed to generate imperfections and cracks and reduce the particle size. The addition of 10 w/o CMC was more effective on the initial hydrogen uptake rate and U (60 min) compared with the 10 w/o additions of NbF5, TaF5, Fe2O3, and MnO, and the 10 w/o simultaneous addition of Ni, Fe, and Ti. To the best of our knowledge, this study is the first in which a polymer CMC is added to Mg by reaction-accompanying milling to improve the hydrogen storage properties of Mg.

  16. Decades-Scale Degradation of Commercial, Side-Chain, Fluorotelomer-Based Polymers in Soils and Water

    Science.gov (United States)

    Fluorotelomer-based polymers (FTPs) are a primary product of the jluorotelomer industry, yet the role of commercial FTPs in degrading to form perjluorocarboxylic acids (P FCAs), including perjluorooctanoic acid, and P FCA precursors, remains ill-defined. Here we report on a 376-d...

  17. Charge carrier mobility, photovoltaic, and electroluminescent properties of anthracene-based conjugated polymers bearing randomly distributed side chains

    Czech Academy of Sciences Publication Activity Database

    Usluer, Ö.; Kästner, C.; Abbas, M.; Ulbricht, C.; Cimrová, Věra; Wild, A.; Birckner, E.; Tekin, N.; Sariciftci, N. S.; Hoppe, H.; Rathgeber, S.; Egbe, D. A. M.

    2012-01-01

    Roč. 50, č. 16 (2012), s. 3425-3436 ISSN 0887-624X R&D Projects: GA MŠk(CZ) 1M06031 Institutional research plan: CEZ:AV0Z40500505 Keywords : conjugated polymers * organic field-effect transistors * organic solar cells Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.543, year: 2012

  18. A combined semiempirical-DFT study of oligomers within the finite-chain approximation, evolution from oligomers to polymers.

    Science.gov (United States)

    Derosa, Pedro A

    2009-06-01

    A computationally cheap approach combining time-independent density functional theory (TIDFT) and semiempirical methods with an appropriate extrapolation procedure is proposed to accurately estimate geometrical and electronic properties of conjugated polymers using just a small set of oligomers. The highest occupied molecular orbital-lowest unoccupied molecular orbital gap (HLG) obtained at a TIDFT level (B3PW91) for two polymers, trans-polyacetylene--the simplest conjugated polymer, and a much larger poly(2-methoxy-5-(2,9-ethyl-hexyloxy)-1,4-phenylenevinylene (MEH-PPV) polymer converge to virtually the same asymptotic value than the excitation energy obtained with time-dependent DFT (TDDFT) calculations using the same functional. For TIDFT geometries, the HLG is found to converge to a value within the experimentally accepted range for the band gap of these polymers, when an exponential extrapolation is used; however if semiempirical geometries are used, a linear fit of the HLG versus 1/n is found to produce the best results. Geometrical parameters are observed to reach a saturation value in good agreement with experimental information, within the length of oligomers calculated here and no extrapolation was considered necessary. Finally, the performance of three different semiempirical methods (AM1, PM3, and MNDO) and for the TIDFT calculations, the performance of 7 different full electron basis sets (6-311+G**, 6-31+ +G**, 6-311+ +G**, 6-31+G**, 6-31G**, 6-31+G*, and 6-31G) is compared and it is determined that the choice of semiempirical method or the basis set does not significantly affect the results. 2008 Wiley Periodicals, Inc.

  19. Internally plasticised cellulose polymers

    International Nuclear Information System (INIS)

    Burnup, M.; Hayes, G.F.; Fydelor, P.J.

    1981-01-01

    Plasticised cellulose polymers comprise base polymer having a chain of β-anhydroglucose units joined by ether linkages, with at least one of said units carrying at least one chemically unreactive side chain derived from an allylic monomer or a vinyl substituted derivative of ferrocene. The side chains are normally formed by radiation grafting. These internally plasticised celluloses are useful in particular as inhibitor coatings for rocket motor propellants and in general wherever cellulose polymers are employed. (author)

  20. Linear side chains in benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c] pyrrole-4,6-dione polymers direct self-assembly and solar cell performance

    KAUST Repository

    Cabanetos, Clement

    2013-03-27

    While varying the size and branching of solubilizing side chains in π-conjugated polymers impacts their self-assembling properties in thin-film devices, these structural changes remain difficult to anticipate. This report emphasizes the determining role that linear side-chain substituents play in poly(benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers for bulk heterojunction (BHJ) solar cell applications. We show that replacing branched side chains by linear ones in the BDT motifs induces a critical change in polymer self-assembly and backbone orientation in thin films that correlates with a dramatic drop in solar cell efficiency. In contrast, we show that for polymers with branched alkyl-substituted BDT motifs, controlling the number of aliphatic carbons in the linear N-alkyl-substituted TPD motifs is a major contributor to improved material performance. With this approach, PBDTTPD polymers were found to reach power conversion efficiencies of 8.5% and open-circuit voltages of 0.97 V in BHJ devices with PC71BM, making PBDTTPD one of the best polymer donors for use in the high-band-gap cell of tandem solar cells. © 2013 American Chemical Society.

  1. Bioconversion of α-linolenic acid into n-3 long-chain polyunsaturated fatty acid in hepatocytes and ad hoc cell culture optimisation.

    Directory of Open Access Journals (Sweden)

    Ramez Alhazzaa

    Full Text Available This study aimed to establish optimal conditions for a cell culture system that would allow the measurement of 18:3n-3 (ALA bioconversion into n-3 long-chain polyunsaturated fatty acid (n-3 LC-PUFA, and to determine the overall pathway kinetics. Using rat hepatocytes (FaO as model cells, it was established that a maximum 20:5n-3 (EPA production from 50 µM ALA initial concentration was achieved after 3 days of incubation. Next, it was established that a gradual increase in the ALA concentration from 0 up to 125 µM lead to a proportional increase in EPA, without concomitant increase in further elongated or desaturated products, such as 22:5n-3 (DPA and 22:6n-3 (DHA in 3 day incubations. Of interest, ALA bioconversion products were observed in the culture medium. Therefore, in vitro experiments disregarding the medium fatty acid content are underestimating the metabolism efficiency. The novel application of the fatty acid mass balance (FAMB method on cell culture system (cells with medium enabled quantifying the apparent enzymatic activities for the biosynthesis of n-3 LC-PUFA. The activity of the key enzymes was estimated and showed that, under these conditions, 50% (Km of the theoretical maximal (V max = 3654 µmol.g(-1 of cell protein.hour(-1 Fads2 activity on ALA can be achieved with 81 µM initial ALA. Interestingly, the apparent activity of Elovl2 (20:5n-3 elongation was the slowest amongst other biosynthesis steps. Therefore, the possible improvement of Elovl2 activity is suggested toward a more efficient DHA production from ALA. The present study proposed and described an ad hoc optimised cell culture conditions and methodology towards achieving a reliable experimental platform, using FAMB, to assist in studying the efficiency of ALA bioconversion into n-3 LC-PUFA in vitro. The FAMB proved to be a powerful and inexpensive method to generate a detailed description of the kinetics of n-3 LC-PUFA biosynthesis enzymes activities in vitro.

  2. Chain conformations of the component polymers and the microphase separation structures of homopolymer/block coplymer blends

    International Nuclear Information System (INIS)

    Torikai, Naoya; Mogi, Yasuhiro; Matsushita, Yushu; Noda, Ichiro; Han, C.C.

    1993-01-01

    Microdomain spacings of lamellar structures formed by styrene homopolymer/styrene-2-vinylpyridine diblock copolymer/2-vinylpyridine homopolymer blends were measured by small-angle X-ray scattering (SAXS) and single chain conformations of block copolymers in the same blend system were measured by small-angle neutron scattering (SANS). The molecular weight of diblock copolymers is 78K-72K, and three kinds of styrene homopolymer (S H ) and 2-vinylpyridine homopolymer (P H ) pairs were blended, their molecular weight ratios to that of host block chains were 0.17, 0.38, and 0.78, respectively. Two blend ratios of homopolymer (H)/block copolymer (B), i.e. 1/2 and 1/1 were examined. It was found that the domain spacings of all blends are larger than that of pure block copolymer and that they are increasing with increasing the molecular weight of homopolymers and/or with increasing the volume fraction of homopolymers. Further, block chains in the blends were confirmed to have almost the same chain dimension as that of block chain in pure block copolymer system in the direction parallel to the domain interface irrespective of molecular weight and volume fraction of homopolymers. (author)

  3. [Verification of a decrease in the rigidity of the phage lambda DNA polymeric chain in low ionic strength aqueous solutions by testing the polymer-polymer interlink interactions].

    Science.gov (United States)

    Arutiunian, A V; Ivanova, M A; Kurliand, D I; Kapshin, Iu S; Landa, S B; Poshekhonov, S T; Drobchenko, E A; Shevelev, I V

    2011-01-01

    Changes in the rigidity of the polymetric chain of phage lambda double-strand DNA have been studied by laser correlation spectroscopy. It was shown that, as the ionic strength increases, the effect of the screening of the hydrodynamic interaction of the links of the polymeric chain specific for polymeric coils arises in a DNA solution. It is assumed that the screening occurs when the threshold of the overlapping of DNA coils is achieved. The overlapping of coils is the result of a previously observed significant rise of DNA coil size from abnormally small DNA coils in low ionic strength buffers (about 10(-2) M Na+ or less) to maximum possible large coils in the 5SSC and 5SSC-like buffers. Further analysis of the far interlink interactions in linear lambda phage DNA coils in similar buffers at pH 7 and 4 confirms the earlier proposal about the role of H+ ions in the appearance of abnormally small DNA coils. The abnormal decrease in the DNA coil size in low ionic strength buffers is not a specific feature of lambda phage DNA only.

  4. Optimizing the conjugated side chains of quinoxaline based polymers for nonfullerene solar cells with 10.5% efficiency

    Czech Academy of Sciences Publication Activity Database

    Xu, S.; Wang, X.; Feng, L.; He, Z.; Peng, H.; Cimrová, Věra; Yuan, J.; Zhang, Z.-G.; Li, Y.; Zou, Y.

    2018-01-01

    Roč. 6, č. 7 (2018), s. 3074-3083 ISSN 2050-7488 R&D Projects: GA ČR(CZ) GA13-26542S Institutional support: RVO:61389013 Keywords : fluoroquinoxaline * polymer solar cells * high efficiency Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 8.867, year: 2016

  5. Phase transitions in single macromolecules: Loop-stretch transition versus loop adsorption transition in end-grafted polymer chains

    Science.gov (United States)

    Zhang, Shuangshuang; Qi, Shuanhu; Klushin, Leonid I.; Skvortsov, Alexander M.; Yan, Dadong; Schmid, Friederike

    2018-01-01

    We use Brownian dynamics simulations and analytical theory to compare two prominent types of single molecule transitions. One is the adsorption transition of a loop (a chain with two ends bound to an attractive substrate) driven by an attraction parameter ɛ and the other is the loop-stretch transition in a chain with one end attached to a repulsive substrate, driven by an external end-force F applied to the free end. Specifically, we compare the behavior of the respective order parameters of the transitions, i.e., the mean number of surface contacts in the case of the adsorption transition and the mean position of the chain end in the case of the loop-stretch transition. Close to the transition points, both the static behavior and the dynamic behavior of chains with different length N are very well described by a scaling ansatz with the scaling parameters (ɛ - ɛ*)Nϕ (adsorption transition) and (F - F*)Nν (loop-stretch transition), respectively, where ϕ is the crossover exponent of the adsorption transition and ν is the Flory exponent. We show that both the loop-stretch and the loop adsorption transitions provide an exceptional opportunity to construct explicit analytical expressions for the crossover functions which perfectly describe all simulation results on static properties in the finite-size scaling regime. Explicit crossover functions are based on the ansatz for the analytical form of the order parameter distributions at the respective transition points. In contrast to the close similarity in equilibrium static behavior, the dynamic relaxation at the two transitions shows qualitative differences, especially in the strongly ordered regimes. This is attributed to the fact that the surface contact dynamics in a strongly adsorbed chain is governed by local processes, whereas the end height relaxation of a strongly stretched chain involves the full spectrum of Rouse modes.

  6. Highly Grafted Polystyrene/polyvinylpyridine Polymer Gold Nanoparticles in a Good Solvent: Effects of Chain Length and Composition.

    Czech Academy of Sciences Publication Activity Database

    Posel, Zbyšek; Posocco, P.; Lísal, Martin; Fermeglia, M.; Pricl, S.

    2016-01-01

    Roč. 12, č. 15 (2016), s. 3600-3611 ISSN 1744-683X R&D Projects: GA ČR(CZ) GA13-02938S; GA MŠk LH12020 Institutional support: RVO:67985858 Keywords : block copolymers * chains * fiber optic sensors Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.889, year: 2016

  7. Hydrothermal synthesis, crystal structure and properties of a novel chain coordination polymer constructed by tetrafunctional phosphonate anions and cobalt ions

    International Nuclear Information System (INIS)

    Guan, Lei; Wang, Ying

    2015-01-01

    A novel cobalt phosphonate, [Co(HL)(H 2 O) 3 ] n (1) (L=N(CH 2 PO 3 H) 3 3− ) has been synthesized by hydrothermal reaction at 150 °C and structurally characterized by X-ray diffraction, infrared spectroscopy, elemental and thermogravimetric analysis. Complex 1 features a 1D chain structure with double-channel built from CoO 6 octahedra bridged together by the phosphonate groups. Each cobalt ion is octahedrally coordinated by three phosphonate oxygen atoms and three water molecules. The coordinated water molecules can form the hydrogen bonds with the phosphonate oxygen atoms to link the 1D chains, building a 2D layered structure, further resulting in a 3D network. The luminescence spectrum indicates an emission maximum at 435 nm. The magnetic susceptibility curve exhibits a dominant antiferromagnetic behavior with a weakly ferromagnetic component at low temperatures. - Graphical abstract: The connectivity between cobalt ions and the ligands results in a chain structure with a 1D double-channel structure, which is constructed by A-type subrings and B-type subrings. - Highlights: • The tetrafunctional phosphonate ligand was used as the ligand. • A novel chain structure can be formed by A-type rings and B-type rings. • Two types of rings can form a 1D double-channel structure, along the c-axis

  8. Multifunctional chemical additives for hetero chain polymers; Khimikati-dobavki mnogofunkstional'nogo deystviya dlya geterostepnikh polimerov

    Energy Technology Data Exchange (ETDEWEB)

    Niyazi, F. F.; Kalontarov, I. Ya.; Chayko, Yu. V.; Kasimova, E. I. [V.I. Nikitin Institute of Chemistry, Academy of Sciences of the Republic of Tajikistan, Dushanbe, (Tajikistan)

    1994-07-01

    Indane and carbazole derivatives, poly conjugated azomethine, bis-benzimidazole were studied as chemical additives. Photo stabilizing effect was studied as well. It was found that photo stabilizing effect doesn't depend on nature of functional groups of substituent in aromatic nucleus and specified by length and efficiency of conjugation chains.

  9. Influence of the ordered structure of short-chain polymer molecule all-trans-β-carotene on Raman scattering cross section in liquid

    International Nuclear Information System (INIS)

    Qu Guan-Nan; Li Zuo-Wei; Sun Cheng-Lin; Ou Yang Shun-Li; Wang Wei-Wei; Men Zhi-Wei

    2011-01-01

    We measured the resonant Raman spectra of all-trans-β-carotene in solvents with different densities and concentrations at different temperatures. The results demonstrated that the Raman scattering cross section (RSCS) of short-chain polymer all-trans-β-carotene is extremely high in liquid. Resonance and strong coherent weakly damped CC bond vibrating properties play important roles under these conditions. Coherent weakly damped CC bond vibration strength is associated with molecular ordered structure. All-trans-β-carotene has highly ordered structure and strong coherent weakly damped CC bond vibrating properties, which lead to large RSCS in the solvent with large density and low concentration at low temperature. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  10. Star Polymers.

    Science.gov (United States)

    Ren, Jing M; McKenzie, Thomas G; Fu, Qiang; Wong, Edgar H H; Xu, Jiangtao; An, Zesheng; Shanmugam, Sivaprakash; Davis, Thomas P; Boyer, Cyrille; Qiao, Greg G

    2016-06-22

    Recent advances in controlled/living polymerization techniques and highly efficient coupling chemistries have enabled the facile synthesis of complex polymer architectures with controlled dimensions and functionality. As an example, star polymers consist of many linear polymers fused at a central point with a large number of chain end functionalities. Owing to this exclusive structure, star polymers exhibit some remarkable characteristics and properties unattainable by simple linear polymers. Hence, they constitute a unique class of technologically important nanomaterials that have been utilized or are currently under audition for many applications in life sciences and nanotechnologies. This article first provides a comprehensive summary of synthetic strategies towards star polymers, then reviews the latest developments in the synthesis and characterization methods of star macromolecules, and lastly outlines emerging applications and current commercial use of star-shaped polymers. The aim of this work is to promote star polymer research, generate new avenues of scientific investigation, and provide contemporary perspectives on chemical innovation that may expedite the commercialization of new star nanomaterials. We envision in the not-too-distant future star polymers will play an increasingly important role in materials science and nanotechnology in both academic and industrial settings.

  11. Effect of Areal Density of Polymer Chains on Gold Nanoparticles on Nanoparticle Location in a Block Copolymer Template

    Science.gov (United States)

    Kim, B. J.; Bang, J.; Hawker, C. J.; Kramer, E. J.

    2006-03-01

    It is well established that one block of a copolymer can interact preferentially with an inorganic substrate to produce wetting and domain orientation. We take advantage of this preferential interaction to control the location of 2.5 nm diameter Au nanoparticles coated with short thiol-terminated polystyrene (Mn=3.4 kg/mol) chains (PS-SH) in a symmetric poly(styrene-b-2 vinyl-pyridine) (PS-b-P2VP) diblock copolymer (Mn=196 kg/mol) by changing the areal density σ of the PS-SH on the Au. If σ >= 1.6 chains/nm^2, the preferential interaction between the P2VP of the PS-b-P2VP and the Au surface is screened and the Au localizes in the center of the PS domains. If σ <= 1.4 chains/nm^2 , the Au particles are localized at the PS-P2VP interface. Au nanoparticles coated with thiol terminated P2VP (Mn=3 kg/mol) localize in the center of the P2VP domain of the PS-P2VP over the entire range of σ, demonstrating the localization of the PS coated Au nanoparticles at the interface at low values of σ is due to the unscreened Au-P2VP interaction.

  12. Photo-orientation of azobenzene side chain polymers parallel or perpendicular to the polarization of red HeNe light

    International Nuclear Information System (INIS)

    Kempe, Christian; Rutloh, Michael; Stumpe, Joachim

    2003-01-01

    The mechanism of the light-induced orientation process of azobenzene-containing polymers caused by irradiation with linearly polarized red light is investigated. This process is surprising because there is almost no absorption at 633 nm. Depending on the photochemical pre-treatment and the exposure time, the azobenzene moieties can undergo two different orientation processes resulting in either a parallel or a perpendicular orientation with respect to the electric field vector of the incident light. The fast orientation of the photochromic groups with their long axis in the direction of the light polarization requires a photochemical pre-treatment in which non-polarized UV light generates Z-isomers. Due to this procedure the film becomes 'photochemically activated' for the subsequent polarized irradiation with red light. But on continued exposure a second, much slower reorientation process occurs which establishes an orientation of the azobenzene groups perpendicular to the electric field vector. The fast mechanism is probably caused by an angle-selective photo-isomerization of the Z-isomers to the E-isomers, while the subsequent slow reorientation process is caused by the well-known conventional photo-orientation taking place via the accumulation of a number of photoselection steps and the rotational diffusion minimizing the absorbance of the E-isomer. This process occurs in the steady state but at this wavelength with a very small concentration of Z-isomers. The competing mechanisms take place in the same polymer film under almost identical irradiation conditions, differing only in the actual concentration of the Z-isomers

  13. Integration of Fiber-Reinforced Polymers in a Life Cycle Assessment of Injection Molding Process Chains with Additive Manufacturing

    DEFF Research Database (Denmark)

    Hofstätter, Thomas; Bey, Niki; Mischkot, Michael

    2017-01-01

    Additive manufacturing technologies applied to injection molding process chain have acquired an increasingly important role in the context of tool inserts production, especially by vat polymerization. Despite the decreased lifetime during their use in the injection molding process, the inserts come...... with improvements in terms of production time, costs, exibility, as well as potentially improved environmental performance as compared to conventional materials in a life cycle perspective.This contribution supports the development of additively manufactured injection molding inserts with the use of fiber...

  14. Short-chain Acyl-CoA dehydrogenase deficiency: studies in a large family adding to the complexity of the disorder

    NARCIS (Netherlands)

    Bok, Levinus A.; Vreken, Peter; Wijburg, Frits A.; Wanders, Ronald J. A.; Gregersen, Niels; Corydon, Morten J.; Waterham, Hans R.; Duran, Marinus

    2003-01-01

    OBJECTIVE: To understand the expanding clinical and biochemical spectrum of short-chain acyl-CoA dehydrogenase (SCAD) deficiency, the impact of which is not fully understood. STUDY DESIGN: We studied a family with SCAD deficiency and determined urinary ethylmalonic acid excretion, plasma

  15. based gel polymer electrolytes

    Indian Academy of Sciences (India)

    (PVdF) as a host polymer, lithium perchlorate (LiClO4), lithium triflate ... TG/DTA studies showed the thermal stability of the polymer electrolytes. .... are observed while comparing pure XRD spectra with .... batteries as its operating temperature is normally in the .... chain ion movements and the conductivity of the polymer.

  16. Adición de polímeros superabsorbentes en el medio de crecimiento para la producción de plantines de pimiento Hydrophilic polymers added to growing media in pepper transplants production

    Directory of Open Access Journals (Sweden)

    Pablo Adrián Tittonell

    2002-12-01

    Full Text Available Los polímeros sintéticos son aditivos que poseen alta capacidad de retención hídrica y mejoran la eficiencia en el uso del agua por parte de las plántulas. La velocidad con que emergen las plántulas, su uniformidad y su tasa de crecimiento inicial son determinantes para la obtención de plantines de calidad. Existen tres grupos principales de polímeros: co-polímeros de almidón, polivinil alcoholes y poliacrilamidas. Con el objetivo de evaluar la aptitud de los polímeros en la producción de plantines de pimiento, un co-polímero de propenamida-propeonato se adicionó a sustratos preparados con y sin materiales compostados y a un sustrato comercial. Se caracterizó el comportamiento del mismo a través de la tasa de crecimiento y características cualitativas de los plantines. La adición del polímero al sustrato permitió mejorar la precocidad, uniformidad y tamaño de plantines de pimiento, especialmente en las mezclas carentes de compost. En dichos tratamientos, la tasa de crecimiento aumentó en mayor medida como consecuencia de un mejor desarrollo foliar, ya que la tasa de asimilación no fue significativamente afectada en todos los casos. La relación vástago/raíz no fue favorablemente afectada por adición del polímero y dependió más del tipo de sustrato empleado. Mediante la adición del polímero empleado los parámetros de calidad del plantín mejoran, ya sea por una mayor retención hídrica, por una mayor capacidad de intercambio iónico, o por ambas razones.Water-storing synthetic polymers (soil additives designed to improve plant establishment and growth in arid environments has been shown to improve the growth of horticultural plants. Previous research has shown that synthetic polymers are useful when added to low nutrient-holding and water-retaining growing media. There are three groups of polymers used in these applications, some of them added with nutrients and growth starters. A propenamide-propeonate co-polymer

  17. Self-assembly of the hydrogel polymer chain consisting of chitosan and chondroitin sulphate in the presence of theophylline;Propriedades de higrogeis constituidos de quitosana e sulfato decondroitina na presenca de teofilina intumescidos em diferentes pHs

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, Lais C.; Piai, Juliana F.; Fajardo, Andre R.; Rubira, Adley F.; Muniz, Edvani C., E-mail: ecmuniz@uem.b [Universidade Estadual de Maringa (GMPC/UEM), PR (Brazil). Grupo de Materiais Polimericos e Compositos

    2009-07-01

    In this work, polyelectronic complex (PEC) consisting of two polysaccharides were developed. One is chitosan (QT), cationic polymer, produced by the chitin deacetylation and the other is chondroitin sulphate (CS), anionic polymer, extracted from bovine or porcine aorta. The PECs were prepared in the presence of theophylline (TEO) for evaluating the influence of this drug in the polymer chains reorganization, as well as, studying the mechanical properties and release of SC and TEO in aqueous solutions on different pH conditions. By the obtained results, it was observed that the 84QT/15SC/TEO (% in weight) hydrogel is pH responsive because the CS releasing is more effective at pH 8, while the release of the TEO is higher at pH 2. The hydrogel showed mechanical properties more resistant to pH 2, 8 and 10 and this was attributed to interactions between the polymer chains. Finally, the X-rays profile showed the presence of peaks associated to reorganization of the chains in the hydrogel is at times larger than the hydrogel in the absence of solute. (author)

  18. Antimocrobial Polymer

    Science.gov (United States)

    McDonald, William F.; Huang, Zhi-Heng; Wright, Stacy C.

    2005-09-06

    A polymeric composition having antimicrobial properties and a process for rendering the surface of a substrate antimicrobial are disclosed. The composition comprises a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, (ii) an antimicrobial agent selected from quaternary ammonium compounds, gentian violet compounds, substituted or unsubstituted phenols, biguanide compounds, iodine compounds, and mixtures thereof, and (iii) a crosslinking agent containing functional groups capable of reacting with the amino groups. In one embodiment, the polymer is a polyamide formed from a maleic anhydride or maleic acid ester monomer and alkylamines thereby producing a polyamide having amino substituted alkyl chains on one side of the polyamide backbone; the crosslinking agent is a phosphine having the general formula (A)3P wherein A is hydroxyalkyl; and the antimicrobial agent is chlorhexidine, dimethylchlorophenol, cetyl pyridinium chloride, gentian violet, triclosan, thymol, iodine, and mixtures thereof.

  19. Electrospun regenerated cellulose nanofibrous membranes surface-grafted with polymer chains/brushes via the atom transfer radical polymerization method for catalase immobilization.

    Science.gov (United States)

    Feng, Quan; Hou, Dayin; Zhao, Yong; Xu, Tao; Menkhaus, Todd J; Fong, Hao

    2014-12-10

    In this study, an electrospun regenerated cellulose (RC) nanofibrous membrane with fiber diameters of ∼200-400 nm was prepared first; subsequently, 2-hydroxyethyl methacrylate (HEMA), 2-dimethylaminoethyl methacrylate (DMAEMA), and acrylic acid (AA) were selected as the monomers for surface grafting of polymer chains/brushes via the atom transfer radical polymerization (ATRP) method. Thereafter, four nanofibrous membranes (i.e., RC, RC-poly(HEMA), RC-poly(DMAEMA), and RC-poly(AA)) were explored as innovative supports for immobilization of an enzyme of bovine liver catalase (CAT). The amount/capacity, activity, stability, and reusability of immobilized catalase were evaluated, and the kinetic parameters (Vmax and Km) for immobilized and free catalase were determined. The results indicated that the respective amounts/capacities of immobilized catalase on RC-poly(HEMA) and RC-poly(DMAEMA) nanofibrous membranes reached 78 ± 3.5 and 67 ± 2.7 mg g(-1), which were considerably higher than the previously reported values. Meanwhile, compared to that of free CAT (i.e., 18 days), the half-life periods of RC-CAT, RC-poly(HEMA)-CAT, RC-poly(DMAEMA)-CAT, and RC-poly(AA)-CAT were 49, 58, 56, and 60 days, respectively, indicating that the storage stability of immobilized catalase was also significantly improved. Furthermore, the immobilized catalase exhibited substantially higher resistance to temperature variation (tested from 5 to 70 °C) and lower degree of sensitivity to pH value (tested from 4.0 and 10.0) than the free catalase. In particular, according to the kinetic parameters of Vmax and Km, the nanofibrous membranes of RC-poly(HEMA) (i.e., 5102 μmol mg(-1) min(-1) and 44.89 mM) and RC-poly(DMAEMA) (i.e., 4651 μmol mg(-1) min(-1) and 46.98 mM) had the most satisfactory biocompatibility with immobilized catalase. It was therefore concluded that the electrospun RC nanofibrous membranes surface-grafted with 3-dimensional nanolayers of polymer chains/brushes would be

  20. Polymer dynamics: Floored by the rings

    Science.gov (United States)

    McLeish, Tom

    2008-12-01

    The tube model can explain how mutually entangled polymer chains move and interact, but it relies on the loose ends of chains to generate relaxation. Ring polymers have no ends - so how do they relax?

  1. Shape memory polymers

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Thomas S.; Bearinger, Jane P.

    2017-08-29

    New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

  2. Shape memory polymers

    Science.gov (United States)

    Wilson, Thomas S.; Bearinger, Jane P.

    2015-06-09

    New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxyl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

  3. Infrared laser dissociation of single megadalton polymer ions in a gated electrostatic ion trap: the added value of statistical analysis of individual events.

    Science.gov (United States)

    Halim, Mohammad A; Clavier, Christian; Dagany, Xavier; Kerleroux, Michel; Dugourd, Philippe; Dunbar, Robert C; Antoine, Rodolphe

    2018-05-07

    In this study, we report the unimolecular dissociation mechanism of megadalton SO 3 -containing poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) polymer cations and anions with the aid of infrared multiphoton dissociation coupled to charge detection ion trap mass spectrometry. A gated electrostatic ion trap ("Benner trap") is used to store and detect single gaseous polymer ions generated by positive and negative polarity in an electrospray ionization source. The trapped ions are then fragmented due to the sequential absorption of multiple infrared photons produced from a continuous-wave CO 2 laser. Several fragmentation pathways having distinct signatures are observed. Highly charged parent ions characteristically adopt a distinctive "stair-case" pattern (assigned to the "fission" process) whereas low charge species take on a "funnel like" shape (assigned to the "evaporation" process). Also, the log-log plot of the dissociation rate constants as a function of laser intensity between PAMPS positive and negative ions is significantly different.

  4. The Global Value Chain

    DEFF Research Database (Denmark)

    Sørensen, Olav Jull

    The conference paper aims to develop the global value chain concept by including corporate internal value adding activities and competition to the basic framework in order to turn the global value chain into a strategic management tool......The conference paper aims to develop the global value chain concept by including corporate internal value adding activities and competition to the basic framework in order to turn the global value chain into a strategic management tool...

  5. Influence of α-methyl group on molecular aggregation structure and surface physicochemical properties of fluoroalkyl side chain polymers

    International Nuclear Information System (INIS)

    Honda, K; Yamaguchi, H; Takahara, A; Sakata, O; Sasaki, S; Takata, M; Morita, M

    2009-01-01

    Influence of α-methyl group on molecular aggregation states and surface physicochemical properties of poly(fluoroalkyl acrylate)s [PFA-C y , where y is fluoromethylene number in R f group] and poly(fluoroalkykl methacrylate)s [PFMA-C y ] thin films were systematically investigated. Spin-coated PFA-C y and PFMA-C y thin films were characterized by dynamic contact angle measurements and grazing-incidence wide-angle X-ray diffraction (GIWAXD) measurements. GIWAXD data revealed that fluoroalkyl side chains of PFA-C y and PFMA-C y with y≥8 formed regular structures in the surface region as well as bulk one. However, the degree of orientation and ordering of the R f groups of PFMA-C 8 thin films was low. Also, the receding contact angle (θ r ) of PFMA-C 8 thin films was lower than that of PFA-C 8 ones. By annealing treatment, the θ r of PFMA-C 8 was increased. These results suggest that the R f groups of PFMA-C 8 were disordered due to presence of the α-methyl group. The R f groups became ordered to pack closely each other by annealing treatment, so that the water repellency was increased.

  6. Polymer nanocomposites: polymer and particle dynamics

    KAUST Repository

    Kim, Daniel

    2012-01-01

    Polymer nanocomposites containing nanoparticles smaller than the random coil size of their host polymer chains are known to exhibit unique properties, such as lower viscosity and glass transition temperature relative to the neat polymer melt. It has been hypothesized that these unusual properties result from fast diffusion of the nanostructures in the host polymer, which facilitates polymer chain relaxation by constraint release and other processes. In this study, the effects of addition of sterically stabilized inorganic nanoparticles to entangled cis-1,4-polyisoprene and polydimethylsiloxane on the overall rheology of nanocomposites are discussed. In addition, insights about the relaxation of the host polymer chains and transport properties of nanoparticles in entangled polymer nanocomposites are presented. The nanoparticles are found to act as effective plasticizers for their entangled linear hosts, and below a critical, chemistry and molecular-weight dependent particle volume fraction, lead to reduced viscosity, glass transition temperature, number of entanglements, and polymer relaxation time. We also find that the particle motions in the polymer host are hyperdiffusive and at the nanoparticle length scale, the polymer host acts like a simple, ideal fluid and the composites\\' viscosity rises with increasing particle concentration. © 2012 The Royal Society of Chemistry.

  7. The Effects of Adding Whey Protein and Branched-chain Amino Acid to Carbohydrate Beverages on Indices of Muscle Damage after Eccentric Resistance Exercise in Untrained Young Males

    OpenAIRE

    Foad Asjodi; Hamid Mohebi; Ebrahim Mirzajani; Azimeh Izadi

    2017-01-01

    Abstract Background: The aim of this study was to evaluate the effects of supplementation of Branched-Chain Amino Acids (BCAAs) plus carbohydrate (CHO) and whey protein plus CHO on muscle damage indices after eccentric resistant exercise. Materials and Methods: Twenty four untrained healthy males participated in this study. They were randomly divided into three groups, BCAA +glucose (0.1+0.1g/kg) supplement group (n=8), Whey+glucose (0.1+0.1g/kg) supplement group (n=8), and placebo (ma...

  8. The Effects of Adding Whey Protein and Branched-chain Amino Acid to Carbohydrate Beverages on Indices of Muscle Damage after Eccentric Resistance Exercise in Untrained Young Males

    Directory of Open Access Journals (Sweden)

    Foad Asjodi

    2017-07-01

    Full Text Available Abstract Background: The aim of this study was to evaluate the effects of supplementation of Branched-Chain Amino Acids (BCAAs plus carbohydrate (CHO and whey protein plus CHO on muscle damage indices after eccentric resistant exercise. Materials and Methods: Twenty four untrained healthy males participated in this study. They were randomly divided into three groups, BCAA +glucose (0.1+0.1g/kg supplement group (n=8, Whey+glucose (0.1+0.1g/kg supplement group (n=8, and placebo (malto dextrin 0.2g/kg group (n=8. Each subject consumed a carbohydrate beverage with addition of whey protein or branched-chain amino acid or placebo 30 minutes before exercise in a randomized,double-blind fashion. Serum levels of Creatine Kinase (CK, Lactate dehydrogenase (LDH, and muscle pain were measured before, 24, 48, 72 h after exercise. Follow-up analyses included 1-way repeated measures ANOVAs, and Bonferroni post hoc comparisons. Results: 24 h after test, serum levels of CK, LDH and muscle pain in both supplement groups were increased less than placebo group (0.015, 0.001 and 0.001, respectively. Also, the levels of CK and LDH showed significant changes in both intervention groups compared to placebo group at 24 h (0.001, 0. 015, respectively. Similarly, significant differences in the levels of CK and LDH between groups were observed. Conclusion: These data indicate that muscle damage and pain after resistant exercise were reduced by an ingestion of either BCAA drink or whey protein drink.

  9. Mutations Blocking Side Chain Assembly, Polymerization, or Transport of a Wzy-Dependent Streptococcus pneumoniae Capsule Are Lethal in the Absence of Suppressor Mutations and Can Affect Polymer Transfer to the Cell Wall▿

    OpenAIRE

    Xayarath, Bobbi; Yother, Janet

    2007-01-01

    Extracellular polysaccharides of many bacteria are synthesized by the Wzy polymerase-dependent mechanism, where long-chain polymers are assembled from undecaprenyl-phosphate-linked repeat units on the outer face of the cytoplasmic membrane. In gram-positive bacteria, Wzy-dependent capsules remain largely cell associated via membrane and peptidoglycan linkages. Like many Wzy-dependent capsules, the Streptococcus pneumoniae serotype 2 capsule is branched. In this study, we found that deletions ...

  10. Amplification of acid formation from diphenyliodonium salt in γ-irradiated polymers

    International Nuclear Information System (INIS)

    Yamazaki, K.; Iino, K.; Koizumi, H.; Ichikawa, T.

    2006-01-01

    The G values of acid formation from diphenyliodonium salt in γ-irradiated polymers have been measured for developing chemically amplified radiation resists that have abilities of not only amplifying chemical reactions of polymers by the acid as a catalyst but also amplifying the formation of acid itself by a radiation-induced radical chain reaction. Addition of secondary alcohols as amplifiers for acid formation, to poly(alkyl methacrylates) results in the increase of the G value, though the increase is not so significant as that expected from a liquid-phase amplification reaction. The diffusion of free radicals and added molecules is difficult in the polymers due to cage effects by polymer molecules, which causes increases of the radical combination reaction and therefore decrease of the turnover number of the chain reaction. The G values of acid formation for poly(vinyl acetals) are much higher than those for poly(alkyl methacrylates) even the amplifiers are not added in the former polymers. Poly(vinyl acetals) are synthesized by acetalyzation of poly(vinyl alcohol), a polymer composed of secondary alcohol monomer unit, so that the secondary alcohol remaining in the polymer skeleton acts as an efficient amplifier for acid formation. The secondary alcohol acts as stepping-stones for the diffusion of free radical, so that the free radical can encounter a new iodonium salt molecule to continue the radical chain reaction. (authors)

  11. Prognosis of Light Chain Amyloidosis With Preserved LVEF: Added Value of 2D Speckle-Tracking Echocardiography to the Current Prognostic Staging System.

    Science.gov (United States)

    Barros-Gomes, Sergio; Williams, Brittney; Nhola, Lara F; Grogan, Martha; Maalouf, Joseph F; Dispenzieri, Angela; Pellikka, Patricia A; Villarraga, Hector R

    2017-04-01

    This study evaluated whether 2-dimensional speckle-tracking echocardiography (2D-STE) has incremental value for prognosis over traditional clinical, echocardiographic, and serological markers-with main focus on the current prognostic staging system-in light-chain (AL) amyloidosis patients with preserved left ventricular ejection fraction. Cardiac amyloidosis (CA) is the major determinant of outcome in AL amyloidosis. The current prognostic staging system is based primarily on serum levels of cardiac troponin T (cTnT), N-terminal pro-B-type natriuretic peptide (NT-proBNP), and free light chain differential (FLC-diff). Consecutive patients with biopsy-proven AL amyloidosis and left ventricular ejection fraction ≥55% were divided into group 1 with CA (n = 63) and group 2 without CA (n = 87). Global longitudinal strain (GLS) by 2D-STE was performed with Vivid E9 (GE Healthcare Co., Milwaukee, Wisconsin) and syngo Velocity Vector Imaging (VVI) software (Siemens Medical Solutions USA, Inc., Malvern, Pennsylvania) (GLS GE and GLS VVI , respectively). Thirty-two deaths (51%) occurred in group 1 and 13 (15%) in group 2 (p ≤ 0.001). Group 1 had thicker walls, lower early diastolic tissue Doppler velocity at septal mitral annulus, and greater left ventricular mass, left atrial volume, glomerular filtration rate, FLC-diff, cTnT, and NT-proBNP (p value over cTnT, NT-proBNP, and FLC-diff. For survival analysis limited to group 2 (non-CA), GLS GE and GLS VVI both predicted all-cause mortality (GLS GE HR: 1.23; 95% CI: 1.03 to 1.47 [p = 0.02]; GLS VVI HR: 1.22; 95% CI: 1.01 to 1.49 [p = 0.04], respectively). 2D-STE predicted outcome and provided incremental prognostic information over the current prognostic staging system, especially in the group without CA. Copyright © 2017 American College of Cardiology Foundation. Published by Elsevier Inc. All rights reserved.

  12. Extraction and purification of high added value compounds from by-products of the winemaking chain using alternative/nonconventional processes/technologies.

    Science.gov (United States)

    Yammine, Sami; Brianceau, Sylène; Manteau, Sébastien; Turk, Mohammad; Ghidossi, Rémy; Vorobiev, Eugène; Mietton-Peuchot, Martine

    2018-05-24

    Grape byproducts are today considered as a cheap source of valuable compounds since existent technologies allow the recovery of target compounds and their recycling. The goal of the current article is to explore the different recovery stages used by both conventional and alternative techniques and processes. Alternative pre-treatments techniques reviewed are: ultrasounds, pulsed electric fields and high voltage discharges. In addition, nonconventional solvent extraction under high pressure, specifically, supercritical fluid extraction and subcritical water extraction are discussed. Finally alternative purification technologies, for example membrane processing were also examined. The intent is to describe the mechanisms involved by these alternative technologies and to summarize the work done on the improvement of the extraction process of phenolic compounds from winery by-products. With a focus on the developmental stage of each technology, highlighting the research need and challenges to be overcome for an industrial implementation of these unitary operations in the overall extraction process. A critical comparison of conventional and alternative techniques will be reviewed for ethe pre-treatment of raw material, the diffusion of polyphenols and the purification of these high added value compounds. This review intends to give the reader some key answers (costs, advantages, drawbacks) to help in the choice of alternative technologies for extraction purposes.

  13. Hairy AdS solitons

    International Nuclear Information System (INIS)

    Anabalón, Andrés; Astefanesei, Dumitru; Choque, David

    2016-01-01

    We construct exact hairy AdS soliton solutions in Einstein-dilaton gravity theory. We examine their thermodynamic properties and discuss the role of these solutions for the existence of first order phase transitions for hairy black holes. The negative energy density associated to hairy AdS solitons can be interpreted as the Casimir energy that is generated in the dual filed theory when the fermions are antiperiodic on the compact coordinate.

  14. Hairy AdS solitons

    Energy Technology Data Exchange (ETDEWEB)

    Anabalón, Andrés, E-mail: andres.anabalon@uai.cl [Departamento de Ciencias, Facultad de Artes Liberales and Facultad de Ingeniería y Ciencias, Universidad Adolfo Ibáñez, Av. Padre Hurtado 750, Viña del Mar (Chile); Astefanesei, Dumitru, E-mail: dumitru.astefanesei@pucv.cl [Instituto de Física, Pontificia Universidad Católica de Valparaíso, Casilla 4059, Valparaíso (Chile); Choque, David, E-mail: brst1010123@gmail.com [Instituto de Física, Pontificia Universidad Católica de Valparaíso, Casilla 4059, Valparaíso (Chile); Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile)

    2016-11-10

    We construct exact hairy AdS soliton solutions in Einstein-dilaton gravity theory. We examine their thermodynamic properties and discuss the role of these solutions for the existence of first order phase transitions for hairy black holes. The negative energy density associated to hairy AdS solitons can be interpreted as the Casimir energy that is generated in the dual filed theory when the fermions are antiperiodic on the compact coordinate.

  15. Interfacial Friction and Adhesion of Polymer Brushes

    KAUST Repository

    Landherr, Lucas J. T.; Cohen, Claude; Agarwal, Praveen; Archer, Lynden A.

    2011-01-01

    higher molar mass chains exhibit higher friction forces than those created using lower molar mass polymers. Increased grafting density of chains in the brush significantly reduces the COF by creating a uniform surface of stretched chains with a decreased

  16. Polymer friction Molecular Dynamics

    DEFF Research Database (Denmark)

    Sivebæk, Ion Marius; Samoilov, Vladimir N.; Persson, Bo N. J.

    We present molecular dynamics friction calculations for confined hydrocarbon solids with molecular lengths from 20 to 1400 carbon atoms. Two cases are considered: a) polymer sliding against a hard substrate, and b) polymer sliding on polymer. In the first setup the shear stresses are relatively...... independent of molecular length. For polymer sliding on polymer the friction is significantly larger, and dependent on the molecular chain length. In both cases, the shear stresses are proportional to the squeezing pressure and finite at zero load, indicating an adhesional contribution to the friction force....

  17. Effect of waste wax and chain structure on the mechanical and physical properties of polyethylene

    Directory of Open Access Journals (Sweden)

    M.A. AlMaadeed

    2015-05-01

    The wax dispersion in the matrix strongly depends on the percentage of wax added to the polymer and the molecular structure of the polymer. It was found that increasing the wax content enhances the phase separation. LDPE undergoes less phase separation due to its highly branched structure composed of a network of short and long chain branches. The wax has no pronounced plasticising effect on the polymer. This is clearly manifested in LDPE as no change in the melting temperature occurred. LLDPE and HDPE were slightly affected by a high concentration of wax (30% and 40%. This is due to the non-uniform distribution of short chain branching along the LLDPE and HDPE main chains, which can interact with the wax structure.

  18. Polymer deformation in Brownian ratchets: theory and molecular dynamics simulations.

    Science.gov (United States)

    Kenward, Martin; Slater, Gary W

    2008-11-01

    We examine polymers in the presence of an applied asymmetric sawtooth (ratchet) potential which is periodically switched on and off, using molecular dynamics (MD) simulations with an explicit Lennard-Jones solvent. We show that the distribution of the center of mass for a polymer in a ratchet is relatively wide for potential well depths U0 on the order of several kBT. The application of the ratchet potential also deforms the polymer chains. With increasing U0 the Flory exponent varies from that for a free three-dimensional (3D) chain, nu=35 (U0=0), to that corresponding to a 2D compressed (pancake-shaped) polymer with a value of nu=34 for moderate U0. This has the added effect of decreasing a polymer's diffusion coefficient from its 3D value D3D to that of a pancaked-shaped polymer moving parallel to its minor axis D2D. The result is that a polymer then has a time-dependent diffusion coefficient D(t) during the ratchet off time. We further show that this suggests a different method to operate a ratchet, where the off time of the ratchet, toff, is defined in terms of the relaxation time of the polymer, tauR. We also derive a modified version of the Bader ratchet model [Bader, Proc. Natl. Acad. Sci. U.S.A. 96, 13165 (1999)] which accounts for this deformation and we present a simple expression to describe the time dependent diffusion coefficient D(t). Using this model we then illustrate that polymer deformation can be used to modulate polymer migration in a ratchet potential.

  19. Polymer research by neutron scattering

    International Nuclear Information System (INIS)

    Richter, D.

    1993-01-01

    Polymer physics aims on an understanding of the macroscopic behavior of polymer systems on the basis of their molecular structure and dynamics. For this purpose neutrons serve as a unique probe, allowing a simultaneous investigation of polymer structure and dynamics on a molecular scale. Furthermore, hydrogen deuterium exchange facilitates molecular labeling and offers the possibility to observe selected chains or chain parts in dense systems. Neutron small angle scattering reveals information on the conformation and possible aggregation of polymer chains. Data on linear and star like molecules are shown as examples. High resolution neutron spin-echospectroscopy observes the molecular dynamics of long chain molecules. Results on the large scale motion of chins in polymer melts are presented. finally, experiments on chain relaxation close to the glass transition are displayed. Three distinctly different relaxation processes are revealed. (author)

  20. Antiviral Polymer Therapeutics

    DEFF Research Database (Denmark)

    Smith, Anton Allen Abbotsford

    2014-01-01

    polymerized in a controlled manner with carrier monomers of historically proven biocompatible polymers. The carrier polymers, the loading of ribavirin as well as the size of the polymer were varied systematically with the aid of an automated synthesis platform. These polymers were tested in a cellular assay...... of reversible-addition-fragmentation chain transfer polymerization, which not only controls the size of polymer, but also allows the introduction of a terminal amine on the polymer which can be used for further conjugation. This has allowed for not only fluorescent labeling of the polymer, but also protein...... is mediated through specific transporters, it is thought that the accumulation can be alleviated through the attachment of ribavirin to a macromolecule. To this end, ribavirin was enzymatically modified into a monomer compatible with controlled polymerization techniques. The ribavirin monomers were...

  1. SANS studies of polymers

    International Nuclear Information System (INIS)

    Wignall, G.D.

    1984-10-01

    Before small-angle neutron scattering (SANS), chain conformation studies were limited to light and small angle x-ray scattering techniques, usually in dilute solution. SANS from blends of normal and labeled molecules could give direct information on chain conformation in bulk polymers. Water-soluble polymers may be examined in H 2 O/D 2 O mixtures using contrast variation methods to provide further information on polymer structure. This paper reviews some of the information provided by this technique using examples of experiments performed at the National Center for Small-Angle Scattering Research (NCSASR)

  2. Syntheses and Characterization of New Nickel Coordination Polymers with 4,4’-Dipyridylsulfide. Dynamic Rearrangements of One-Dimensional Chains Responding to External Stimuli: Temperature Variation and Guest Releases/Re-Inclusions

    Directory of Open Access Journals (Sweden)

    Hiroyuki Kawaguchi

    2010-08-01

    Full Text Available Crystal structures and dynamic rearrangements of one-dimensional coordination polymers with 4,4'-dipyridylsulfide (dps have been studied. Reaction of Ni(NO32·6H2O with dps in EtOH yielded [Ni(dps2(NO32]·EtOH (1, which had channels filled with guest EtOH molecules among the four Ni(dps2 chains. This coordination polymer reversibly transformed the channel structure responding to temperature variations. Immersion of 1 in m-xylene released guest EtOH molecules to yield a guest-free coordination polymer [Ni(dps2(NO32] (2a, which was also obtained by treatment of Ni(NO32·6H2O with dps in MeOH. On the other hand, removal of the guest molecules from 1 upon heating at 130 °C under reduced pressure produced a guest-free coordination polymer [Ni(dps2(NO32] (2b. Although the 2a and 2b guest-free coordination polymers have the same formula, they showed differences in the assembled structures of the one-dimensional chains. Exposure of 2b to EtOH vapor reproduced 1, while 2a did not convert to 1 in a similar reaction. Reaction of Ni(NO32·6H2O with dps in acetone provided [Ni(dps(NO32(H2O]·Me2CO (4 with no channel structure. When MeOH or acetone was used as a reaction solvent, the [Ni(dps2(NO32]·(guest molecule type coordination polymer ,which was observed in 1, was not formed. Nevertheless, the reaction of Ni(NO32·6H2O with dps in MeOH/acetone mixed solution produced [Ni(dps2(NO32]·0.5(MeOH·acetone (5, which has an isostructural Ni-dps framework to 1.

  3. AFM and SFG studies of pHEMA-based hydrogel contact lens surfaces in saline solution: adhesion, friction, and the presence of non-crosslinked polymer chains at the surface.

    Science.gov (United States)

    Kim, Seong Han; Opdahl, Aric; Marmo, Chris; Somorjai, Gabor A

    2002-04-01

    The surfaces of two types of soft contact lenses neutral and ionic hydrogels--were characterized by atomic force microscopy (AFM) and sum-frequency-generation (SFG) vibrational spectroscopy. AFM measurements in saline solution showed that the presence of ionic functional groups at the surface lowered the friction and adhesion to a hydrophobic polystyrene tip. This was attributed to the specific interactions of water and the molecular orientation of hydrogel chains at the surface. Friction and adhesion behavior also revealed the presence of domains of non-crosslinked polymer chains at the lens surface. SFG showed that the lens surface became partially dehydrated upon exposure to air. On this partially dehydrated lens surface, the non-crosslinked domains exhibited low friction and adhesion in AFM. Fully hydrated in saline solution, the non-crosslinked domains extended more than tens of nanometers into solution and were mobile.

  4. Accessing the dynamics of end-grafted flexible polymer chains by atomic force-electrochemical microscopy. Theoretical modeling of the approach curves by the elastic bounded diffusion model and Monte Carlo simulations. Evidence for compression-induced lateral chain escape.

    Science.gov (United States)

    Abbou, Jeremy; Anne, Agnès; Demaille, Christophe

    2006-11-16

    The dynamics of a molecular layer of linear poly(ethylene glycol) (PEG) chains of molecular weight 3400, bearing at one end a ferrocene (Fc) label and thiol end-grafted at a low surface coverage onto a gold substrate, is probed using combined atomic force-electrochemical microscopy (AFM-SECM), at the scale of approximately 100 molecules. Force and current approach curves are simultaneously recorded as a force-sensing microelectrode (tip) is inserted within the approximately 10 nm thick, redox labeled, PEG chain layer. Whereas the force approach curve gives access to the structure of the compressed PEG layer, the tip-current, resulting from tip-to-substrate redox cycling of the Fc head of the chain, is controlled by chain dynamics. The elastic bounded diffusion model, which considers the motion of the Fc head as diffusion in a conformational field, complemented by Monte Carlo (MC) simulations, from which the chain conformation can be derived for any degree of confinement, allows the theoretical tip-current approach curve to be calculated. The experimental current approach curve can then be very satisfyingly reproduced by theory, down to a tip-substrate separation of approximately 2 nm, using only one adjustable parameter characterizing the chain dynamics: the effective diffusion coefficient of the chain head. At closer tip-substrate separations, an unpredicted peak is observed in the experimental current approach curve, which is shown to find its origin in a compression-induced escape of the chain from within the narrowing tip-substrate gap. MC simulations provide quantitative support for lateral chain elongation as the escape mechanism.

  5. Adding Ajax

    CERN Document Server

    Powers, Shelley

    2007-01-01

    Ajax can bring many advantages to an existing web application without forcing you to redo the whole thing. This book explains how you can add Ajax to enhance, rather than replace, the way your application works. For instance, if you have a traditional web application based on submitting a form to update a table, you can enhance it by adding the capability to update the table with changes to the form fields, without actually having to submit the form. That's just one example.Adding Ajax is for those of you more interested in extending existing applications than in creating Rich Internet Applica

  6. Statistical thermodynamics of equilibrium polymers at interfaces

    NARCIS (Netherlands)

    Gucht, van der J.; Besseling, N.A.M.

    2002-01-01

    The behavior of a solution of equilibrium polymers (or living polymers) at an interface is studied, using a Bethe-Guggenheim lattice model for molecules with orientation dependent interactions. The density profile of polymers and the chain length distribution are calculated. For equilibrium polymers

  7. Mutations blocking side chain assembly, polymerization, or transport of a Wzy-dependent Streptococcus pneumoniae capsule are lethal in the absence of suppressor mutations and can affect polymer transfer to the cell wall.

    Science.gov (United States)

    Xayarath, Bobbi; Yother, Janet

    2007-05-01

    Extracellular polysaccharides of many bacteria are synthesized by the Wzy polymerase-dependent mechanism, where long-chain polymers are assembled from undecaprenyl-phosphate-linked repeat units on the outer face of the cytoplasmic membrane. In gram-positive bacteria, Wzy-dependent capsules remain largely cell associated via membrane and peptidoglycan linkages. Like many Wzy-dependent capsules, the Streptococcus pneumoniae serotype 2 capsule is branched. In this study, we found that deletions of cps2K, cps2J, or cps2H, which encode a UDP-glucose dehydrogenase necessary for side chain synthesis, the putative Wzx transporter (flippase), and the putative Wzy polymerase, respectively, were obtained only in the presence of suppressor mutations. Most of the suppressor mutations were in cps2E, which encodes the initiating glycosyltransferase for capsule synthesis. The cps2K mutants containing the suppressor mutations produced low levels of high-molecular-weight polymer that was detected only in membrane fractions. cps2K-repaired mutants exhibited only modest increases in capsule production due to the effect of the secondary mutation, but capsule was detectable in both membrane and cell wall fractions. Lethality of the cps2K, cps2J, and cps2H mutations was likely due to sequestration of undecaprenyl-phosphate in the capsule pathway and either preclusion of its turnover for utilization in essential pathways or destabilization of the membrane due to an accumulation of lipid-linked intermediates. The results demonstrate that proper polymer assembly requires not only a functional transporter and polymerase but also complete repeat units. A central role for the initiating glycosyltransferase in controlling capsule synthesis is also suggested.

  8. Lagrangian theory with zero component. Application to the study of the polymers in solution (chains with exclued volume) and of the properties of electrons in a random potential

    International Nuclear Information System (INIS)

    Des Cloizeaux, J.

    1976-01-01

    The Lagrangian theory of a field with n components can be generalized for values of n which are not integers and in particular for n=0. This extension is made by introducing ordered Green's functions. It is shown how the zero components Lagrangian theory can be used to describe the behaviour of an isolated polymer or of a solution of polymers with large molecular masses. It is remarked that by analytic continuation with respect to the coupling constant, it should be possible to study the properties of electrons in a random potential and perhaps the nature of the mobility edges [fr

  9. Synthesis of well-defined semitelechelic poly[N-(2-hydroxypropyl)methacrylamide] polymers with functional group at the .alpha.-end of the polymer chain by RAFT polymerization

    Czech Academy of Sciences Publication Activity Database

    Šubr, Vladimír; Kostka, Libor; Strohalm, Jiří; Etrych, Tomáš; Ulbrich, Karel

    2013-01-01

    Roč. 46, č. 6 (2013), s. 2100-2108 ISSN 0024-9297 R&D Projects: GA ČR GAP301/12/1254; GA MŠk EE2.3.30.0029 Institutional support: RVO:61389013 Keywords : RAFT polymerization * N-(2-hydroxypropyl)methacrylamide * semitelechelic polymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 5.927, year: 2013

  10. Mesomorphic structure of poly(styrene)-block-poly(4-vinylpyridine) with oligo(ethylene oxide)sulfonic acid side chains as a model for molecularly reinforced polymer electrolyte

    NARCIS (Netherlands)

    Kosonen, H; Valkama, S; Hartikainen, J; Eerikainen, H; Torkkeli, M; Jokela, K; Serimaa, R; Sundholm, F; ten Brinke, G; Ikkala, O; Eerikäinen, Hannele

    2002-01-01

    We report self-organized polymer electrolytes based on poly(styrene)-block-poly(4-vinylpyridine) (PS-block-P4VP). Liquidlike ethylene oxide (EO) oligomers with sulfonic acid end groups are bonded to the P4VP block, leading to comb-shaped supramolecules with the PS-block-P4VP backbone. Lithium

  11. Chain networking revealed by molecular dynamics simulation

    Science.gov (United States)

    Zheng, Yexin; Tsige, Mesfin; Wang, Shi-Qing

    Based on Kremer-Grest model for entangled polymer melts, we demonstrate how the response of a polymer glass depends critically on the chain length. After quenching two melts of very different chain lengths (350 beads per chain and 30 beads per chain) into deeply glassy states, we subject them to uniaxial extension. Our MD simulations show that the glass of long chains undergoes stable necking after yielding whereas the system of short chains is unable to neck and breaks up after strain localization. During ductile extension of the polymer glass made of long chain significant chain tension builds up in the load-bearing strands (LBSs). Further analysis is expected to reveal evidence of activation of the primary structure during post-yield extension. These results lend support to the recent molecular model 1 and are the simulations to demonstrate the role of chain networking. This work is supported, in part, by a NSF Grant (DMR-EAGER-1444859)

  12. Small angle scattering and polymers

    International Nuclear Information System (INIS)

    Cotton, J.P.

    1996-01-01

    The determination of polymer structure is a problem of interest for both statistical physics and industrial applications. The average polymer structure is defined. Then, it is shown why small angle scattering, associated with isotopic substitution, is very well suited to the measurement of the chain conformation. The corresponding example is the old, but pedagogic, measurement of the chain form factor in the polymer melt. The powerful contrast variation method is illustrated by a recent determination of the concentration profile of a polymer interface. (author) 12 figs., 48 refs

  13. Syntheses and optical properties of triphenylene-containing conjugated polymers

    International Nuclear Information System (INIS)

    Chou, C.-E.; Wang Degang; Bagui, Mahuya; Hsu, Jeffrey; Chakraborty, Sanjiban; Peng Zhonghua

    2010-01-01

    In this paper, we report the detailed synthesis and optical properties of three new conjugated polymers containing triphenylene units in the backbone. Polymer PTPT exhibits strong folding propensity and forms foldamers in both polar and nonpolar solvents. PTPA, with two long alkyl chains attached to the bridging phenyl ring, exhibits mainly as interchain aggregates in 'poor' solvents (DMSO and acetonitrile), but adopts a folding conformation in solvent mixtures with a high poor solvent content. PTPV, on the other hand, adopts a random nonfolding conformation in both polar and nonpolar solvents. The low folding propensity of PTPV is likely due to the added geometrical flexibility of the vinyl bonds. Among the three polymers, PTPV is most fluorescent with a fluorescence quantum yield as high as 0.87, suggesting its potential applications as light-emitting materials or fluorescence-based sensors. PTPT, on the other hand, with its strong folding property, may find applications as efficient charge-transporting materials.

  14. Molecular and supramolecular orientation in conducting polymers

    International Nuclear Information System (INIS)

    Aldissi, M.

    1987-01-01

    Intrinsic anisotropy in electrical and optical properties of conducting polymers constitutes a unique aspect that derives π-electron delocalization along the polymer backbone and from the weak inter-chain interaction. To acquire such an intrinsic property, conducting polymers have to be oriented macroscopically and microscopically (at the chain level). A review of the various techniques, including stretch-alignment of the polymer and of precursor polymers, polymerization in ordered media, i.e., in a liquid crystal solvent, and synthesis of liquid crystalline conducting polymers will be given. 29 refs

  15. Hyperbranched Polymers - Engineering Materials and Degradation Behavior

    National Research Council Canada - National Science Library

    Wooley, Karen

    2000-01-01

    .... In the studies supported under this grant, hyperbranched polycarbonates were designed as analogs to common engineering polymers to investigate the effects of branching upon the chain-chain packing...

  16. Polymer films

    Science.gov (United States)

    Granick, Steve; Sukhishvili, Svetlana A.

    2004-05-25

    A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

  17. Radiation chemistry of polymers

    International Nuclear Information System (INIS)

    Charlesby, A.

    1987-01-01

    There are several and quite distinct major fields of interest discussed in this paper. The first deals with the modification of existing polymers either by main-chain scission or by cross-linking; the theories of these patterns of behavior are summarized here, and typical examples of polymers that show these alternative reactions are given. These are not comprehensive to avoid this presentation becoming a catalog of similar patterns of behavior

  18. Bubbling AdS3

    International Nuclear Information System (INIS)

    Martelli, Dario; Morales, Jose Francisco

    2005-01-01

    In the light of the recent Lin, Lunin, Maldacena (LLM) results, we investigate 1/2-BPS geometries in minimal (and next to minimal) supergravity in D = 6 dimensions. In the case of minimal supergravity, solutions are given by fibrations of a two-torus T 2 specified by two harmonic functions. For a rectangular torus the two functions are related by a non-linear equation with rare solutions: AdS 3 x S 3 , the pp-wave and the multi-center string. 'Bubbling', i.e. superpositions of droplets, is accommodated by allowing the complex structure of the T 2 to vary over the base. The analysis is repeated in the presence of a tensor multiplet and similar conclusions are reached, with generic solutions describing D1D5 (or their dual fundamental string-momentum) systems. In this framework, the profile of the dual fundamental string-momentum system is identified with the boundaries of the droplets in a two-dimensional plane. (author)

  19. New coordination polymers from 1D chain, 2D layer to 3D framework constructed from 1,2-phenylenediacetic acid and 1,3-bis(4-pyridyl)propane flexible ligands

    International Nuclear Information System (INIS)

    Xin Lingyun; Liu Guangzhen; Wang Liya

    2011-01-01

    The hydrothermal reactions of Cd, Zn, or Cu(II) acetate salts with H 2 PHDA and BPP flexible ligands afford three new coordination polymers, including [Cd(PHDA)(BPP)(H 2 O)] n (1), [Zn(PHDA)(BPP)] n (2), and [Cu 2 (PHDA) 2 (BPP)] n (3) (H 2 PHDA=1,2-phenylenediacetic acid, BPP=1,3-bis(4-pyridyl)propane). The single-crystal X-ray diffractions reveal that all three complexes feature various metal carboxylate subunits extended further by the BPP ligands to form a diverse range of structures, displaying a remarked structural sensitivity to metal(II) cation. Complex 1 containing PHDA-bridged binuclear cadmium generates 1D double-stranded chain, complex 2 results in 2D→2D interpenetrated (4,4) grids, and complex 3 displays a 3D self-penetrated framework with 4 8 6 6 8 rob topology. In addition, fluorescent analyses show that both 1 and 2 exhibit intense blue-violet photoluminescence in the solid state. - Graphical Abstract: We show diverse supramolecular frameworks based on the same ligands (PHDA and BPP) and different metal acetate salts including 1D double-stranded chain, 2D → 2D twofold interpenetrated layer, and 3D self-penetration networks. Highlights: → Three metal(II = 2 /* ROMAN ) coordination polymers were synthesized using H 2 PHDA and BPP. → The diversity of structures show a remarked sensitivity to metal(II) center. → Complexes show the enhancement of fluorescence compared to that of free ligand.

  20. Synthesis and Side Chain Liquid Crystal Polymers by Living Ring Opening Metathesis Polymerization. 5. Influence of Mesogenic Group and Interconnecting Group on the Thermotropic Behavior of the Resulting Polymers

    Science.gov (United States)

    1992-07-22

    Scheme I. The first nucleophilic displacement of halide of an n-haloalkan-l-ol with 4-cyano-4’-hydroxybiphenyl employed potassium carbonate in...21 𔃼 polysiloxanes, 23.24 and polyacrylates . 2- All these polymers exhibit an odd-even effect. If one considers the total number of atoms between the...0.019 mol) and 4’-methoxy-4-hydroxybiphenyl (4.0g, 0.020 tool) were heated at 100°C in 40 mL of dimethylformamide in the presence of potassium carbonate

  1. Academic Education Chain Operation Model

    OpenAIRE

    Ruskov, Petko; Ruskov, Andrey

    2007-01-01

    This paper presents an approach for modelling the educational processes as a value added chain. It is an attempt to use a business approach to interpret and compile existing business and educational processes towards reference models and suggest an Academic Education Chain Operation Model. The model can be used to develop an Academic Chain Operation Reference Model.

  2. Theory of polymer blends

    International Nuclear Information System (INIS)

    Curro, J.G.; Schweizer, K.S.

    1989-01-01

    We have recently developed a new theoretical approach to the study of polymer liquids. The theory is based on the ''reference interaction site model'' (RISM theory) of Chandler and Andersen, which has been successful in describing the structure of small molecule liquids. We have recently extended our polymer RISM theory to the case of polymer blends. In the present investigation we have applied this theory to two special binary blends: (1) the athermal mixture where we isolate structural effects, and (2) the isotopic mixture in which structurally identical polymer chains interact with dissimilar attractive interactions. By studying these two special cases we are able to obtain insights into the molecular factors which control the miscibility in polymer mixtures. 18 refs., 2 figs

  3. Photoluminescence in conjugated polymers

    International Nuclear Information System (INIS)

    Furst, J.E.; Laugesen, R.; Dastoor, P.; McNeill, C.

    2002-01-01

    Full text: Conjugated polymers combine the electronic and optical properties of semiconductors with the processability of polymers. They contain a sequence of alternate single and double carbon bonds so that the overlap of unhybridised p z orbitals creates a delocalised ρ system which gives semiconducting properties with p-bonding (valence) and p* -antibonding (conduction) bands. Photoluminesence (PL) in conjugated polymers results from the radiative decay of singlet excitons confined to a single chain. The present work is the first in a series of studies in our laboratory that will characterize the optical properties of conjugated polymers. The experiment involves the illumination of thin films of conjugated polymer with UV light (I=360 nm) and observing the subsequent fluorescence using a custom-built, fluorescence spectrometer. Photoluminesence spectra provide basic information about the structure of the polymer film. A typical spectrum is shown in the accompanying figure. The position of the first peak is related to the polymer chain length and resolved multiple vibronic peaks are an indication of film structure and morphology. We will also present results related to the optical degradation of these materials when exposed to air and UV light

  4. Semi-flexible polymer engendered aggregation/dispersion of fullerene (C60) nano-particles: An atomistic investigation

    Science.gov (United States)

    Kumar, Sunil; Pattanayek, Sudip K.

    2018-06-01

    Semi flexible polymer chain has been modeled by choosing various values of persistent length (stiffness). As the polymer chain stiffness increases, the shape of polymer chain changes from globule to extended cigar to toroid like structure during cooling from a high temperature. The aggregation of fullerene nano-particles is found to depend on the morphology of polymer chain. To maximize, the number of polymer bead-nanoparticle contacts, all nano-particle have positioned inside the polymer globule. To minimize, the energy penalty, due to bending of the polymer chain, all nano-particle have positioned on the surface of the polymer's cigar and toroid morphology.

  5. The Impact of the Polymer Chain Length on the Catalytic Activity of Poly(N-vinyl-2-pyrrolidone)-supported Gold Nanoclusters.

    Science.gov (United States)

    Haesuwannakij, Setsiri; Kimura, Tetsunari; Furutani, Yuji; Okumura, Kazu; Kokubo, Ken; Sakata, Takao; Yasuda, Hidehiro; Yakiyama, Yumi; Sakurai, Hidehiro

    2017-08-29

    Poly(N-vinyl-2-pyrrolidone) (PVP) of varying molecular weight (M w  = 40-360 kDa) were employed to stabilize gold nanoclusters of varying size. The resulting Au:PVP clusters were subsequently used as catalysts for a kinetic study on the sized-dependent aerobic oxidation of 1-indanol, which was monitored by time-resolved in situ infrared spectroscopy. The obtained results suggest that the catalytic behaviour is intimately correlated to the size of the clusters, which in turn depends on the molecular weight of the PVPs. The highest catalytic activity was observed for clusters with a core size of ~7 nm, and the size of the cluster should increase with the molecular weight of the polymer in order to maintain optimal catalytic activity. Studies on the electronic and colloid structure of these clusters revealed that the negative charge density on the cluster surface also strongly depends on the molecular weight of the stabilizing polymers.

  6. Ring closure in actin polymers

    Energy Technology Data Exchange (ETDEWEB)

    Sinha, Supurna, E-mail: supurna@rri.res.in [Raman Research Institute, Bangalore 560080 (India); Chattopadhyay, Sebanti [Doon University, Dehradun 248001 (India)

    2017-03-18

    We present an analysis for the ring closure probability of semiflexible polymers within the pure bend Worm Like Chain (WLC) model. The ring closure probability predicted from our analysis can be tested against fluorescent actin cyclization experiments. We also discuss the effect of ring closure on bend angle fluctuations in actin polymers. - Highlights: • Ring closure of biopolymers. • Worm like chain model. • Predictions for experiments.

  7. Topological ferrimagnetic behaviours of coordination polymers containing manganese(II) chains with mixed azide and carboxylate bridges and alternating F/AF/AF'/AF'/AF interactions.

    Science.gov (United States)

    Wang, Yan-Qin; Liu, Hou-Ting; Qi, Yan; Gao, En-Qing

    2014-08-21

    Two Mn(ii) complexes with azide and a new zwitterionic tetracarboxylate ligand 1,2,4,5-tetrakis(4-carboxylatopyridinium-1-methylene)benzene (L(1)), {[Mn5(L(1))2(N3)8(OH)2]·12H2O}n () and {[Mn5(L(1))2(N3)8(H2O)2](ClO4)2·6H2O}n (), have been synthesized and characterized crystallographically and magnetically. and contain similar alternating chains constructed by azide and carboxylate bridges. The independent sets of bridges alternate in an ABCCB sequence between adjacent Mn(ii) ions: (EO-N3)2 double bridges (EO = end-on) (denoted as A), [(EO-N3)(OCO)2] triple bridges (denoted as B) and [(EO-N3)(OCO)] double bridges (denoted as C). The alternating chains are interlinked into 2D coordination networks by the tetrapyridinium spacers. Magnetic studies demonstrate that the magnetic coupling through the double EO azide bridges is ferromagnetic and that through mixed azide/carboxylate bridges is antiferromagnetic. The unprecedented F/AF/AF'/AF'/AF coupling sequence along the chain dictates an uncompensated ground spin state (S = 5/2 per Mn5 unit) and leads to one-dimensional topological ferrimagnetism, which features a minimum in the χT versus T plot.

  8. Inulin crystal initiation via a glucose-fructose cross-link of adjacent polymer chains: atomic force microscopy and static molecular modelling.

    Science.gov (United States)

    Cooper, Peter D; Rajapaksha, K Harinda; Barclay, Thomas G; Ginic-Markovic, Milena; Gerson, Andrea R; Petrovsky, Nikolai

    2015-03-06

    Semi-crystalline microparticles of inulin (MPI) have clinical utility as potent human vaccine adjuvants but their relevant surface structure and crystal assembly remain undefined. We show inulin crystal surfaces to resemble multi-layered, discoid radial spherulites resulting from very rapid formation of complex tertiary structures, implying directed crystal initiation. Physical and in silico molecular modelling of unit cells confirm steric feasibility of initiation by hydrogen-bonded cross-linking of terminal glucose to a fructose of another chain, mimicking bonding in sucrose crystals. A strong, chelate-like dual H-bond is proposed to compel the known antiparallel alignment of inulin chains. Such cross-linking would require one extra fructose per chain in the native inulin crystal, as observed. Completion of five H-bonded internal ring-domains would 'lock in' each new 6-fructose structural unit of each antiparallel helix pair to create a new isoform. All known properties of inulin isoforms follow readily from these concepts. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Enhanced solid-state order and field-effect hole mobility through control of nanoscale polymer aggregation

    KAUST Repository

    Chen, Mark S.

    2013-12-26

    Efficient charge carrier transport in organic field-effect transistors (OFETs) often requires thin films that display long-range order and close π-π packing that is oriented in-plane with the substrate. Although some polymers have achieved high field-effect mobility with such solid-state properties, there are currently few general strategies for controlling the orientation of π-stacking within polymer films. In order to probe structural effects on polymer-packing alignment, furan-containing diketopyrrolopyrrole (DPP) polymers with similar optoelectronic properties were synthesized with either linear hexadecyl or branched 2-butyloctyl side chains. Differences in polymer solubility were observed and attributed to variation in side-chain shape and polymer backbone curvature. Averaged field-effect hole mobilities of the polymers range from 0.19 to 1.82 cm2/V·s, where PDPP3F-C16 is the least soluble polymer and provides the highest maximum mobility of 2.25 cm2/V·s. Analysis of the films by AFM and GIXD reveal that less soluble polymers with linear side chains exhibit larger crystalline domains, pack considerably more closely, and align with a greater preference for in-plane π-π packing. Characterization of the polymer solutions prior to spin-coating shows a correlation between early onset nanoscale aggregation and the formation of films with highly oriented in-plane π-stacking. This effect is further observed when nonsolvent is added to PDPP3F-BO solutions to induce aggregation, which results in films with increased nanostructural order, in-plane π-π orientation, and field-effect hole mobilities. Since nearly all π-conjugated materials may be coaxed to aggregate, this strategy for enhancing solid-state properties and OFET performance has applicability to a wide variety of organic electronic materials. © 2013 American Chemical Society.

  10. Enhanced solid-state order and field-effect hole mobility through control of nanoscale polymer aggregation

    KAUST Repository

    Chen, Mark S.; Lee, Olivia P.; Niskala, Jeremy R.; Yiu, Alan T.; Tassone, Christopher J.; Schmidt, Kristin; Beaujuge, Pierre M.; Onishi, Seita S.; Toney, Michael F.; Zettl, Alex K.; Frechet, Jean

    2013-01-01

    Efficient charge carrier transport in organic field-effect transistors (OFETs) often requires thin films that display long-range order and close π-π packing that is oriented in-plane with the substrate. Although some polymers have achieved high field-effect mobility with such solid-state properties, there are currently few general strategies for controlling the orientation of π-stacking within polymer films. In order to probe structural effects on polymer-packing alignment, furan-containing diketopyrrolopyrrole (DPP) polymers with similar optoelectronic properties were synthesized with either linear hexadecyl or branched 2-butyloctyl side chains. Differences in polymer solubility were observed and attributed to variation in side-chain shape and polymer backbone curvature. Averaged field-effect hole mobilities of the polymers range from 0.19 to 1.82 cm2/V·s, where PDPP3F-C16 is the least soluble polymer and provides the highest maximum mobility of 2.25 cm2/V·s. Analysis of the films by AFM and GIXD reveal that less soluble polymers with linear side chains exhibit larger crystalline domains, pack considerably more closely, and align with a greater preference for in-plane π-π packing. Characterization of the polymer solutions prior to spin-coating shows a correlation between early onset nanoscale aggregation and the formation of films with highly oriented in-plane π-stacking. This effect is further observed when nonsolvent is added to PDPP3F-BO solutions to induce aggregation, which results in films with increased nanostructural order, in-plane π-π orientation, and field-effect hole mobilities. Since nearly all π-conjugated materials may be coaxed to aggregate, this strategy for enhancing solid-state properties and OFET performance has applicability to a wide variety of organic electronic materials. © 2013 American Chemical Society.

  11. Structure and Dynamics of Polymer/Polymer grafted nanoparticle composite

    Science.gov (United States)

    Archer, Lynden

    Addition of nanoparticles to polymers is a well-practiced methodology for augmenting various properties of the polymer host, including mechanical strength, thermal stability, barrier properties, dimensional stability and wear resistance. Many of these property changes are known to arise from nanoparticle-induced modification of polymer structure and chain dynamics, which are strong functions of the dispersion state of the nanoparticles' and on their relative size (D) to polymer chain dimensions (e.g. Random coil radius Rg or entanglement mesh size a) . This talk will discuss polymer nanocomposites (PNCs) comprised of Polyethylene Glycol (PEG) tethered silica nanoparticles (SiO2-PEG) dispersed in polymers as model systems for investigating phase stability and dynamics of PNCs. On the basis of small-angle X-ray Scattering, it will be shown that favorable enthalpic interactions between particle-tethered chains and a polymer host provides an important mechanism for creating PNCs in which particle aggregation is avoided. The talk will report on polymer and particle scale dynamics in these materials and will show that grafted nanoparticles well dispersed in a polymer host strongly influence the host polymer relaxation dynamics on all timescales and the polymers in turn produce dramatic changes in the nature (from diffusive to hyperdiffusive) and speed of nano particle decorrelation dynamics at the polymer entanglement threshold. A local viscosity model capable of explaining these observations is discussed and the results compared with scaling theories for NP motions in polymers This material is based on work supported by the National Science Foundation Award Nos. DMR-1609125 and CBET-1512297.

  12. Control of polymer network topology in semi-batch systems

    Science.gov (United States)

    Wang, Rui; Olsen, Bradley; Johnson, Jeremiah

    Polymer networks invariably possess topological defects: loops of different orders. Since small loops (primary loops and secondary loops) both lower the modulus of network and lead to stress concentration that causes material failure at low deformation, it is desirable to greatly reduce the loop fraction. We have shown that achieving loop fraction close to zero is extremely difficult in the batch process due to the slow decay of loop fraction with the polymer concentration and chain length. Here, we develop a modified kinetic graph theory that can model network formation reactions in semi-batch systems. We demonstrate that the loop fraction is not sensitive to the feeding policy if the reaction volume maintains constant during the network formation. However, if we initially put concentrated solution of small junction molecules in the reactor and continuously adding polymer solutions, the fractions of both primary loop and higher-order loops will be significantly reduced. There is a limiting value (nonzero) of loop fraction that can be achieved in the semi-batch system in condition of extremely slow feeding rate. This minimum loop fraction only depends on a single dimensionless variable, the product of concentration and with single chain pervaded volume, and defines an operating zone in which the loop fraction of polymer networks can be controlled through adjusting the feeding rate of the semi-batch process.

  13. Elasticity of semiflexible polymers in two dimensions

    Science.gov (United States)

    Prasad, Ashok; Hori, Yuko; Kondev, Jané

    2005-10-01

    We study theoretically the entropic elasticity of a semiflexible polymer, such as DNA, confined to two dimensions. Using the worm-like-chain model we obtain an exact analytical expression for the partition function of the polymer pulled at one end with a constant force. The force-extension relation for the polymer is computed in the long chain limit in terms of Mathieu characteristic functions. We also present applications to the interaction between a semiflexible polymer and a nematic field, and derive the nematic order parameter and average extension of the polymer in a strong field.

  14. Adsorption and flocculation by polymers and polymer mixtures.

    Science.gov (United States)

    Gregory, John; Barany, Sandor

    2011-11-14

    Polymers of various types are in widespread use as flocculants in several industries. In most cases, polymer adsorption is an essential prerequisite for flocculation and kinetic aspects are very important. The rates of polymer adsorption and of re-conformation (relaxation) of adsorbed chains are key factors that influence the performance of flocculants and their mode of action. Polyelectrolytes often tend to adopt a rather flat adsorbed configuration and in this state their action is mainly through charge effects, including 'electrostatic patch' attraction. When the relaxation rate is quite low, particle collisions may occur while the adsorbed chains are still in an extended state and flocculation by polymer bridging may occur. These effects are now well understood and supported by much experimental evidence. In recent years there has been considerable interest in the use of multi-component flocculants, especially dual-polymer systems. In the latter case, there can be significant advantages over the use of single polymers. Despite some complications, there is a broad understanding of the action of dual polymer systems. In many cases the sequence of addition of the polymers is important and the pre-adsorbed polymer can have two important effects: providing adsorption sites for the second polymer or causing a more extended adsorbed conformation as a result of 'site blocking'. Copyright © 2011 Elsevier B.V. All rights reserved.

  15. Increasing the Thermal Conductivity of Graphene-Polyamide-6,6 Nanocomposites by Surface-Grafted Polymer Chains: Calculation with Molecular Dynamics and Effective-Medium Approximation.

    Science.gov (United States)

    Gao, Yangyang; Müller-Plathe, Florian

    2016-02-25

    By employing reverse nonequilibrium molecular dynamics simulations in a full atomistic resolution, the effect of surface-grafted chains on the thermal conductivity of graphene-polyamide-6.6 (PA) nanocomposites has been investigated. The interfacial thermal conductivity perpendicular to the graphene plane is proportional to the grafting density, while it first increases and then saturates with the grafting length. Meanwhile, the intrinsic in-plane thermal conductivity of graphene drops sharply as the grafting density increases. The maximum overall thermal conductivity of nanocomposites appears at an intermediate grafting density because of these two competing effects. The thermal conductivity of the composite parallel to the graphene plane increases with the grafting density and grafting length which is attributed to better interfacial coupling between graphene and PA. There exists an optimal balance between grafting density and grafting length to obtain the highest interfacial and parallel thermal conductivity. Two empirical formulas are suggested, which quantitatively account for the effects of grafting length and density on the interfacial and parallel thermal conductivity. Combined with effective medium approximation, for ungrafted graphene in random orientation, the model overestimates the thermal conductivity at low graphene volume fraction (f 10%). For unoriented grafted graphene, the model matches the experimental results well. In short, this work provides some valuable guides to obtain the nanocomposites with high thermal conductivity by grafting chain on the surface of graphene.

  16. Integrable systems from membranes on AdS4 x S7

    International Nuclear Information System (INIS)

    Bozhilov, P.

    2008-01-01

    We describe how Neumann and Neumann-Rosochatius type integrable systems, as well as the continuous limit of the SU(2) integrable spin chain, can be obtained from membranes on AdS 4 x S 7 background, in the framework of AdS/CFT correspondence. (Abstract Copyright [2008], Wiley Periodicals, Inc.)

  17. Development of water-repellent organic–inorganic hybrid sol–gel coatings on aluminum using short chain perfluoro polymer emulsion

    International Nuclear Information System (INIS)

    Wankhede, Ruchi Grover; Morey, Shantaram; Khanna, A.S.; Birbilis, N.

    2013-01-01

    The development of an organic–inorganic sol–gel coating system (thickness ∼ 2 μm) on aluminum is reported. The coating uses glycidoxytrimethoxysilane (GPTMS) and methyltrimethoxysilane (MTMS) as silane precursors, crosslinked with hexamethylmethoxymelamine (HMMM) and followed by hydrophobic modification using a water base short chain per-fluoro emulsion (FE). Such coating resulted in enhanced hydrophobicity with a contact angle of about 120° and sliding angle of 25° for a 20 μL water droplet. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements showed reduced corrosion upon coated substrates than the bare; correlated with both a higher degree of water repellency and formation of low permeable crosslinked sol–gel network. The structure of the coatings deposited was analyzed using Fourier transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopy, revealing replacement of hydrophillic surface hydroxyls groups with low energy per-fluoro groups.

  18. Synthesis, structure and magnetic property of a two-dimensional coordination polymer decorated with sine wave-like 1D double chain

    Science.gov (United States)

    Yao, Xiao-Qiang; Li, Dan-Yang; Xiao, Guo-Bin; Ma, Heng-Chang; Lei, Zi-Qiang; Liu, Jia-Cheng

    2018-04-01

    A new compound, {[Co(BPFI)(NDC)]H2O·0.5DMF}n (1) has been synthesized under hydrothermal condition by the self-assembly of V-shaped N-containing rigid ligand BPFI with Co(II) ions in the presence of H2NDC acid, where BPFI = 2,8-di(1H-imidazole-1-yl)dibenzo[b,d]furan, H2NDC = naphthalene-1,4-dicarboxylic acid. Compound 1 was characterized by elemental analysis, single crystal X-ray diffraction, FT-IR spectroscopy and UV-visible spectra. Structural analysis reveals that compound 1 is a unique dinuclear Co-based 2D (4,4) layer structure decorated with parallel double chains. In addition, magnetic study reveals the existence of antiferromagnetic coupling interactions between the Co(II) ions within the dinuclear unit of 1.

  19. QCM-D studies on polymer behavior at interfaces

    CERN Document Server

    Liu, Guangming

    2014-01-01

    QCM-D Studies on Polymer Behavior at Interfaces reviews the applications of quartz crystal microbalance with dissipation (QCM-D) in polymer research, including the conformational change of grafted polymer chains, the grafting kinetics of polymer chains, the growth mechanism of polyelectrolyte multilayers, and the interactions between polymers and phospholipid membranes. It focuses on how QCM-D can be applied to the study of polymer behavior at various solid-liquid interfaces. Moreover, it clearly reveals the physical significance of the changes in frequency and dissipation associated with the different polymer behaviors at the interfaces.

  20. Biodegradable Polymers

    OpenAIRE

    Vroman, Isabelle; Tighzert, Lan

    2009-01-01

    Biodegradable materials are used in packaging, agriculture, medicine and other areas. In recent years there has been an increase in interest in biodegradable polymers. Two classes of biodegradable polymers can be distinguished: synthetic or natural polymers. There are polymers produced from feedstocks derived either from petroleum resources (non renewable resources) or from biological resources (renewable resources). In general natural polymers offer fewer advantages than synthetic polymers. ...

  1. Extended linear chain compounds

    CERN Document Server

    Linear chain substances span a large cross section of contemporary chemistry ranging from covalent polymers, to organic charge transfer com­ plexes to nonstoichiometric transition metal coordination complexes. Their commonality, which coalesced intense interest in the theoretical and exper­ imental solid state physics/chemistry communities, was based on the obser­ vation that these inorganic and organic polymeric substrates exhibit striking metal-like electrical and optical properties. Exploitation and extension of these systems has led to the systematic study of both the chemistry and physics of highly and poorly conducting linear chain substances. To gain a salient understanding of these complex materials rich in anomalous aniso­ tropic electrical, optical, magnetic, and mechanical properties, the conver­ gence of diverse skills and talents was required. The constructive blending of traditionally segregated disciplines such as synthetic and physical organic, inorganic, and polymer chemistry, crystallog...

  2. String Theory on AdS Spaces

    NARCIS (Netherlands)

    de Boer, J.

    2000-01-01

    In these notes we discuss various aspects of string theory in AdS spaces. We briefly review the formulation in terms of Green-Schwarz, NSR, and Berkovits variables, as well as the construction of exact conformal field theories with AdS backgrounds. Based on lectures given at the Kyoto YITP Workshop

  3. Free radical transfer in polymers

    International Nuclear Information System (INIS)

    Sonntag, C. von; Bothe, E.; Ulanski, P.

    1998-01-01

    For the present study of free-radical transfer in polymers pulse radiolysis and product studies have been carried out in aqueous solutions using thus far only the water-soluble polymers polyacrylic acid, polymethacrylic acid and polyvinyl alcohol. When OH radicals, generated in the radiolysis of N 2 O-saturated aqueous solutions, react with polymers the lifetime of the polymer radical thus created very much depends on the number of radicals per polymer chain. When there are a large number of radicals per chain their bimolecular decay may be faster than the corresponding (diffusion controlled) decay of monomeric radicals, but when the macromolecule contains only few or even just one radical their lifetime is considerably prolonged. Highly charged polymers such as polyacrylic acid at high pH attain a rod-like conformation which again favors a long lifetime of the radicals. Under such conditions, radical transfer reactions can occur. For example, in polyacrylic acid OH radicals generate two kinds of radicals side by side. The radical in β-position to the carboxylate group converts into the thermodynamically more stable α-radicals by an H-transfer reaction as can be followed by spectrophotometry. Besides radical transfer reactions β-fragmentation reactions occur causing chain scission. Such reactions can be followed in a pulse radiolysis experiment by conductometry, because counter ions are released upon chain scission. Such a process is especially effective in the case of polymethacrylic acid, where it results in a chain depolymerization. An intramolecular H-abstraction is also observed in the γ-radiolysis of polyacrylic acid with the corresponding peroxyl radicals. This causes a chain reaction to occur. The resulting hydroperoxides are unstable and decarboxylate given rise to acetylacetone-like products. In polyvinyl alcohol the peroxyl radicals in α-position to the alcohol function undergo HO 2 -elimination. This prevents a scission of the polymer chain in the

  4. "Chameleon" Macromolecules: Synthesis, Structures and Applications of Stimulus Responsive Polymers

    NARCIS (Netherlands)

    Sui, Xiaofeng

    2012-01-01

    This thesis describes the preparation and characterization of addressable responsive polymer structures and their versatile applications. Stimuli responsive polymer chains including temperature responsive poly(N-isopropylacrylamide), PNIPAM, pH responsive poly(methacrylic acid), PMAA and redox

  5. Dominant role of wormlike micelles in temperature-responsive viscoelastic properties of their mixtures with polymeric chains

    KAUST Repository

    Molchanov, Vyacheslav S.

    2013-03-01

    Temperature effects on the rheological properties of viscoelastic solutions containing entangled wormlike micelles of potassium oleate and hydrophobically modified polyacrylamide were studied in a wide range of polymer concentrations. A very pronounced drop of viscosity by four orders of magnitude was observed at heating from 20 to 78 °C both in the presence and in the absence of polymer indicating that the wormlike micelles are mainly responsible for this effect. The highly thermosensitive behavior was attributed to the shortening of micellar chains induced by heating. Although the decrease in viscosity is almost the same for both surfactant and surfactant/polymer systems, the absolute values of the viscosity in the presence of polymer are by few orders of magnitude higher, which is due to the formation of a common network of entangled polymer and micellar chains. As a result, the added polymer allows one to get highly temperature responsive system that keeps viscoelastic properties in a much wider range of temperatures, which makes it very promising for various practical applications. © 2012 Elsevier Inc.

  6. New coordination polymers from 1D chain, 2D layer to 3D framework constructed from 1,2-phenylenediacetic acid and 1,3-bis(4-pyridyl)propane flexible ligands

    Science.gov (United States)

    Xin, Ling-Yun; Liu, Guang-Zhen; Wang, Li-Ya

    2011-06-01

    The hydrothermal reactions of Cd, Zn, or Cu(II) acetate salts with H 2PHDA and BPP flexible ligands afford three new coordination polymers, including [Cd(PHDA)(BPP)(H 2O)] n(1), [Zn(PHDA)(BPP)] n(2), and [Cu 2(PHDA) 2(BPP)] n(3) (H 2PHDA=1,2-phenylenediacetic acid, BPP=1,3-bis(4-pyridyl)propane). The single-crystal X-ray diffractions reveal that all three complexes feature various metal carboxylate subunits extended further by the BPP ligands to form a diverse range of structures, displaying a remarked structural sensitivity to metal(II) cation. Complex 1 containing PHDA-bridged binuclear cadmium generates 1D double-stranded chain, complex 2 results in 2D→2D interpenetrated (4,4) grids, and complex 3 displays a 3D self-penetrated framework with 4 86 68 rob topology. In addition, fluorescent analyses show that both 1 and 2 exhibit intense blue-violet photoluminescence in the solid state.

  7. Polymer compound

    NARCIS (Netherlands)

    1995-01-01

    A Polymer compound comprising a polymer (a) that contains cyclic imidesgroups and a polymer (b) that contains monomer groups with a 2,4-diamino-1,3,5-triazine side group. According to the formula (see formula) whereby themole percentage ratio of the cyclic imides groups in the polymer compoundwith

  8. Warped AdS3 black holes

    International Nuclear Information System (INIS)

    Anninos, Dionysios; Li Wei; Padi, Megha; Song Wei; Strominger, Andrew

    2009-01-01

    Three dimensional topologically massive gravity (TMG) with a negative cosmological constant -l -2 and positive Newton constant G admits an AdS 3 vacuum solution for any value of the graviton mass μ. These are all known to be perturbatively unstable except at the recently explored chiral point μl = 1. However we show herein that for every value of μl ≠ 3 there are two other (potentially stable) vacuum solutions given by SL(2,R) x U(1)-invariant warped AdS 3 geometries, with a timelike or spacelike U(1) isometry. Critical behavior occurs at μl = 3, where the warping transitions from a stretching to a squashing, and there are a pair of warped solutions with a null U(1) isometry. For μl > 3, there are known warped black hole solutions which are asymptotic to warped AdS 3 . We show that these black holes are discrete quotients of warped AdS 3 just as BTZ black holes are discrete quotients of ordinary AdS 3 . Moreover new solutions of this type, relevant to any theory with warped AdS 3 solutions, are exhibited. Finally we note that the black hole thermodynamics is consistent with the hypothesis that, for μl > 3, the warped AdS 3 ground state of TMG is holographically dual to a 2D boundary CFT with central charges c R -formula and c L -formula.

  9. Polymer electronics

    CERN Document Server

    Hsin-Fei, Meng

    2013-01-01

    Polymer semiconductor is the only semiconductor that can be processed in solution. Electronics made by these flexible materials have many advantages such as large-area solution process, low cost, and high performance. Researchers and companies are increasingly dedicating time and money in polymer electronics. This book focuses on the fundamental materials and device physics of polymer electronics. It describes polymer light-emitting diodes, polymer field-effect transistors, organic vertical transistors, polymer solar cells, and many applications based on polymer electronics. The book also disc

  10. A conducting polymer artificial muscle with 12% linear strain

    DEFF Research Database (Denmark)

    Bay, Lasse; West, Keld; Sommer-Larsen, P.

    2003-01-01

    in a freely suspended polymer foil in response to a potential change and it includes attention to the composition of the polymer, to the synthesis conditions, and involves microstructuring of the polymer. As such, an analysis of the influence of the alkyl chain length on the properties of PPy doped with ABSs...... has shown that the obtainable strain decreases with increasing chain length for alkyl chains longer than C$-8$/....

  11. Creative industries value chain: The value chain logic in supply chain relationships

    OpenAIRE

    Emilia Madudová

    2017-01-01

    The purpose of this paper is to provide a deeper look into value chain logic in supply chain relationships in a creative industries value chains. In recent years, value has been recognized as a key factor in better understanding of consumer behavior and gaining a competitive advantage. In a value chain, added value should be defined at every step of the chain. There should be defined activity which adds value as well as the activity that subtracts any value. The total value can be then calcul...

  12. Absorption and Luminescence of Pyridine-Based Polymers

    National Research Council Canada - National Science Library

    Jessen, S

    1997-01-01

    .... The primary photoexcitations within these polymers are singlet excitons which may emit from individual chains following a random walk to lower energy segments, depending upon the excitation energy...

  13. Academic Education Chain Operation Model

    NARCIS (Netherlands)

    Ruskov, Petko; Ruskov, Andrey

    2007-01-01

    This paper presents an approach for modelling the educational processes as a value added chain. It is an attempt to use a business approach to interpret and compile existing business and educational processes towards reference models and suggest an Academic Education Chain Operation Model. The model

  14. Phase stability and dynamics of entangled polymer-nanoparticle composites.

    KAUST Repository

    Mangal, Rahul

    2015-06-05

    Nanoparticle-polymer composites, or polymer-nanoparticle composites (PNCs), exhibit unusual mechanical and dynamical features when the particle size approaches the random coil dimensions of the host polymer. Here, we harness favourable enthalpic interactions between particle-tethered and free, host polymer chains to create model PNCs, in which spherical nanoparticles are uniformly dispersed in high molecular weight entangled polymers. Investigation of the mechanical properties of these model PNCs reveals that the nanoparticles have profound effects on the host polymer motions on all timescales. On short timescales, nanoparticles slow-down local dynamics of the host polymer segments and lower the glass transition temperature. On intermediate timescales, where polymer chain motion is typically constrained by entanglements with surrounding molecules, nanoparticles provide additional constraints, which lead to an early onset of entangled polymer dynamics. Finally, on long timescales, nanoparticles produce an apparent speeding up of relaxation of their polymer host.

  15. Phase stability and dynamics of entangled polymer-nanoparticle composites.

    KAUST Repository

    Mangal, Rahul; Srivastava, Samanvaya; Archer, Lynden A

    2015-01-01

    Nanoparticle-polymer composites, or polymer-nanoparticle composites (PNCs), exhibit unusual mechanical and dynamical features when the particle size approaches the random coil dimensions of the host polymer. Here, we harness favourable enthalpic interactions between particle-tethered and free, host polymer chains to create model PNCs, in which spherical nanoparticles are uniformly dispersed in high molecular weight entangled polymers. Investigation of the mechanical properties of these model PNCs reveals that the nanoparticles have profound effects on the host polymer motions on all timescales. On short timescales, nanoparticles slow-down local dynamics of the host polymer segments and lower the glass transition temperature. On intermediate timescales, where polymer chain motion is typically constrained by entanglements with surrounding molecules, nanoparticles provide additional constraints, which lead to an early onset of entangled polymer dynamics. Finally, on long timescales, nanoparticles produce an apparent speeding up of relaxation of their polymer host.

  16. Buckling of paramagnetic chains in soft gels

    Science.gov (United States)

    Huang, Shilin; Pessot, Giorgio; Cremer, Peet; Weeber, Rudolf; Holm, Christian; Nowak, Johannes; Odenbach, Stefan; Menzel, Andreas M.; Auernhammer, Günter K.

    We study the magneto-elastic coupling behavior of paramagnetic chains in soft polymer gels exposed to external magnetic fields. To this end, a laser scanning confocal microscope is used to observe the morphology of the paramagnetic chains together with the deformation field of the surrounding gel network. The paramagnetic chains in soft polymer gels show rich morphological shape changes under oblique magnetic fields, in particular a pronounced buckling deformation. The details of the resulting morphological shapes depend on the length of the chain, the strength of the external magnetic field, and the modulus of the gel. Based on the observation that the magnetic chains are strongly coupled to the surrounding polymer network, a simplified model is developed to describe their buckling behavior. A coarse-grained molecular dynamics simulation model featuring an increased matrix stiffness on the surfaces of the particles leads to morphologies in agreement with the experimentally observed buckling effects.

  17. New theories for smectic and nematic liquid crystalline polymers

    International Nuclear Information System (INIS)

    Dowell, F.

    1987-01-01

    A summary of results from new statistical-physics theories for both backbone and side-chain liquid crystalline polymers (LCPs) and for mixtures with LCPs is presented. Thermodynamic and molecular ordering properties (including odd-even effects) have been calculated as a function of pressure, density, temperature, and molecule chemical structures (including degree of polymerization and the following properties of the chemical structures of the repeat units: lengths and shapes, intra-chain rotation energies, dipole moments, site-site polarizabilities and Lennard-Jones potentials, etc.) in nematic and multiple smectic-A LC phases and in the isotropic liquid phase. These theories can also be applied to combined LCPs. Since these theories have no ad hoc or arbitrarily adjustable parameters, these theories have been used to design new LCPs and new solvents and to predict and explain properties

  18. Falling chains

    OpenAIRE

    Wong, Chun Wa; Yasui, Kosuke

    2005-01-01

    The one-dimensional fall of a folded chain with one end suspended from a rigid support and a chain falling from a resting heap on a table is studied. Because their Lagrangians contain no explicit time dependence, the falling chains are conservative systems. Their equations of motion are shown to contain a term that enforces energy conservation when masses are transferred between subchains. We show that Cayley's 1857 energy nonconserving solution for a chain falling from a resting heap is inco...

  19. A general method for the derivation of the functional forms of the effective energy terms in coarse-grained energy functions of polymers. II. Backbone-local potentials of coarse-grained O 1 →4 -bonded polyglucose chains

    Science.gov (United States)

    Lubecka, Emilia A.; Liwo, Adam

    2017-09-01

    Based on the theory of the construction of coarse-grained force fields for polymer chains described in our recent work [A. K. Sieradzan et al., J. Chem. Phys. 146, 124106 (2017)], in this work effective coarse-grained potentials, to be used in the SUGRES-1P model of polysaccharides that is being developed in our laboratory, have been determined for the O ⋯O ⋯O virtual-bond angles (θ ) and for the dihedral angles for rotation about the O ⋯O virtual bonds (γ ) of 1 → 4 -linked glucosyl polysaccharides, for all possible combinations of [α ,β ]-[d,l]-glucose. The potentials of mean force corresponding to the virtual-bond angles and the virtual-bond dihedral angles were calculated from the free-energy surfaces of [α ,β ]-[d,l]-glucose pairs, determined by umbrella-sampling molecular-dynamics simulations with the AMBER12 force field, or combinations of the surfaces of two pairs sharing the overlapping residue, respectively, by integrating the respective Boltzmann factor over the dihedral angles λ for the rotation of the sugar units about the O ⋯O virtual bonds. Analytical expressions were subsequently fitted to the potentials of mean force. The virtual-bond-torsional potentials depend on both virtual-bond-dihedral angles and virtual-bond angles. The virtual-bond-angle potentials contain a single minimum at about θ =14 0° for all pairs except β -d-[α ,β ] -l-glucose, where the global minimum is shifted to θ =150° and a secondary minimum appears at θ =90°. The torsional potentials favor small negative γ angles for the α -d-glucose and extended negative angles γ for the β -d-glucose chains, as observed in the experimental structures of starch and cellulose, respectively. It was also demonstrated that the approximate expression derived based on Kubo's cluster-cumulant theory, whose coefficients depend on the identity of the disugar units comprising a trisugar unit that defines a torsional potential, fits simultaneously all

  20. AdS solutions through transgression

    International Nuclear Information System (INIS)

    Donos, Aristomenis; Gauntlett, Jerome P.; Kim, Nakwoo

    2008-01-01

    We present new classes of explicit supersymmetric AdS 3 solutions of type IIB supergravity with non-vanishing five-form flux and AdS 2 solutions of D = 11 supergravity with electric four-form flux. The former are dual to two-dimensional SCFTs with (0,2) supersymmetry and the latter to supersymmetric quantum mechanics with two supercharges. We also investigate more general classes of AdS 3 solutions of type IIB supergravity and AdS 2 solutions of D = 11 supergravity which in addition have non-vanishing three-form flux and magnetic four-form flux, respectively. The construction of these more general solutions makes essential use of the Chern-Simons or 'transgression' terms in the Bianchi identity or the equation of motion of the field strengths in the supergravity theories. We construct infinite new classes of explicit examples and for some of the type IIB solutions determine the central charge of the dual SCFTs. The type IIB solutions with non-vanishing three-form flux that we construct include a two-torus, and after two T-dualities and an S-duality, we obtain new AdS 3 solutions with only the NS fields being non-trivial.

  1. Polarised Black Holes in AdS

    CERN Document Server

    Costa, Miguel S.; Oliveira, Miguel; Penedones, João; Santos, Jorge E.

    2016-05-03

    We consider solutions in Einstein-Maxwell theory with a negative cosmological constant that asymptote to global $AdS_{4}$ with conformal boundary $S^{2}\\times\\mathbb{R}_{t}$. At the sphere at infinity we turn on a space-dependent electrostatic potential, which does not destroy the asymptotic $AdS$ behaviour. For simplicity we focus on the case of a dipolar electrostatic potential. We find two new geometries: (i) an $AdS$ soliton that includes the full backreaction of the electric field on the $AdS$ geometry; (ii) a polarised neutral black hole that is deformed by the electric field, accumulating opposite charges in each hemisphere. For both geometries we study boundary data such as the charge density and the stress tensor. For the black hole we also study the horizon charge density and area, and further verify a Smarr formula. Then we consider this system at finite temperature and compute the Gibbs free energy for both $AdS$ soliton and black hole phases. The corresponding phase diagram generalizes the Hawkin...

  2. How do polymers degrade?

    Science.gov (United States)

    Lyu, Suping

    2011-03-01

    Materials derived from agricultural products such as cellulose, starch, polylactide, etc. are more sustainable and environmentally benign than those derived from petroleum. However, applications of these polymers are limited by their processing properties, chemical and thermal stabilities. For example, polyethylene terephthalate fabrics last for many years under normal use conditions, but polylactide fabrics cannot due to chemical degradation. There are two primary mechanisms through which these polymers degrade: via hydrolysis and via oxidation. Both of these two mechanisms are related to combined factors such as monomer chemistry, chain configuration, chain mobility, crystallinity, and permeation to water and oxygen, and product geometry. In this talk, we will discuss how these materials degrade and how the degradation depends on these factors under application conditions. Both experimental studies and mathematical modeling will be presented.

  3. Forced reptation revealed by chain pull-out simulations

    NARCIS (Netherlands)

    Bulacu, Monica; van der Giessen, Erik

    2009-01-01

    We report computation results obtained from extensive molecular dynamics simulations of tensile disentanglement of connector chains placed at the interface between two polymer bulks. Each polymer chain (either belonging to the bulks or being a connector) is treated as a sequence of beads

  4. High cation transport polymer electrolyte

    Science.gov (United States)

    Gerald, II, Rex E.; Rathke, Jerome W [Homer Glen, IL; Klingler, Robert J [Westmont, IL

    2007-06-05

    A solid state ion conducting electrolyte and a battery incorporating same. The electrolyte includes a polymer matrix with an alkali metal salt dissolved therein, the salt having an anion with a long or branched chain having not less than 5 carbon or silicon atoms therein. The polymer is preferably a polyether and the salt anion is preferably an alkyl or silyl moiety of from 5 to about 150 carbon/silicon atoms.

  5. PHOTOREFRACTIVE POLYMERS

    NARCIS (Netherlands)

    Morichere, D; Malliaras, G.G; Krasnikov, V.V.; Bolink, H.J; Hadziioannou, G

    The use of polymers as photorefractive materials offers many advantages : flexibility in synthesis, doping, processing and low cost. The required functionalities responsible for photorefractivity, namely charge generation, transport, trapping and linear electrooptic effect are given in the polymer

  6. Photorefractive polymers

    NARCIS (Netherlands)

    Bolink, Hendrik Jan; Hadziioannou, G

    1997-01-01

    This thesis describes the synthesis and properties of photorefractive polymers. Photorefractive polymers are materials in which the refractive index can be varied by the interaction with light. Unlike in numerous other photosensitive materials, in photorefractive materials this occurs via

  7. Polymer Brushes

    NARCIS (Netherlands)

    Vos, de W.M.; Kleijn, J.M.; Keizer, de A.; Cosgrove, T.; Cohen Stuart, M.A.

    2010-01-01

    A polymer brush can be defined as a dense array of polymers end-attached to an interface that stretch out into the surrounding medium. Polymer brushes have been investigated for the past 30 years and have shown to be an extremely useful tool to control interfacial properties. This review is intended

  8. Investigation of the required length for fully developed pipe flow with drag-reducing polymer solutions

    Science.gov (United States)

    Farsiani, Yasaman; Elbing, Brian

    2015-11-01

    Adding trace amounts of long chain polymers into a liquid flow is known to reduce skin friction drag by up to 80%. While polymer drag reduction (PDR) has been successfully implemented in internal flows, diffusion and degradation have limited its external flow applications. A weakness in many previous PDR studies is that there was no characterization of the polymer being injected into the turbulent boundary layer, which can be accomplished by testing a sample in a pressure-drop tube. An implicit assumption in polymer characterization is that the flow is fully developed at the differential pressure measurement. While available data in the literature shows that the entry length to achieve fully developed flow increases with polymeric solutions, it is unclear how long is required to achieve fully developed flow for non-Newtonian turbulent flows. In the present study, the pressure-drop is measured across a 1.05 meter length section of a 1.04 cm inner diameter pipe. Differential pressure is measured with a pressure transducer for different entry lengths, flow and polymer solution properties. This presentation will present preliminary data on the required entrance length as well as characterization of polymer solution an estimate of the mean molecular weight.

  9. Primitive chain network simulations of probe rheology.

    Science.gov (United States)

    Masubuchi, Yuichi; Amamoto, Yoshifumi; Pandey, Ankita; Liu, Cheng-Yang

    2017-09-27

    Probe rheology experiments, in which the dynamics of a small amount of probe chains dissolved in immobile matrix chains is discussed, have been performed for the development of molecular theories for entangled polymer dynamics. Although probe chain dynamics in probe rheology is considered hypothetically as single chain dynamics in fixed tube-shaped confinement, it has not been fully elucidated. For instance, the end-to-end relaxation of probe chains is slower than that for monodisperse melts, unlike the conventional molecular theories. In this study, the viscoelastic and dielectric relaxations of probe chains were calculated by primitive chain network simulations. The simulations semi-quantitatively reproduced the dielectric relaxation, which reflects the effect of constraint release on the end-to-end relaxation. Fair agreement was also obtained for the viscoelastic relaxation time. However, the viscoelastic relaxation intensity was underestimated, possibly due to some flaws in the model for the inter-chain cross-correlations between probe and matrix chains.

  10. Current status of AdS instability

    CERN Multimedia

    CERN. Geneva

    2016-01-01

    arXiv:1403.6471 and thoroughly developed in arXiv:1407.6273. On the other hand the negative cosmological constant allows for the existence of stable, time-periodic, asymptotically AdS solutions of Einstein equations [arXiv:1303.3186].

  11. AdS. Klein-Gordon equation

    OpenAIRE

    Bel, Ll.

    2014-01-01

    I propose a generalization of the Klein-Gordon equation in the framework of AdS space-time and exhibit a four parameter family of solutions among which there is a two parameter family of time-dependent bound states.

  12. Improving geotechnical properties of clayey soil using polymer material

    OpenAIRE

    Karim Hussein; Al-Soudany Kawther

    2018-01-01

    This study illustrates the application of polymer material for clayey soil stabilization. The article will focus on studying the strength behavior of the clayey soils reinforced with homogenously polymer fiber. In the current research, “polypropylene” was selected as polymer material to reinforce the natural clay soil. This polymer fiber was added to the clayey soil with four different percentages of (0, 1.5, 3, and 5%) by weight of soil. Various tests with different polymer contents were per...

  13. Stochastic resonance during a polymer translocation process

    International Nuclear Information System (INIS)

    Mondal, Debasish; Muthukumar, M.

    2016-01-01

    We have studied the occurrence of stochastic resonance when a flexible polymer chain undergoes a single-file translocation through a nano-pore separating two spherical cavities, under a time-periodic external driving force. The translocation of the chain is controlled by a free energy barrier determined by chain length, pore length, pore-polymer interaction, and confinement inside the donor and receiver cavities. The external driving force is characterized by a frequency and amplitude. By combining the Fokker-Planck formalism for polymer translocation and a two-state model for stochastic resonance, we have derived analytical formulas for criteria for emergence of stochastic resonance during polymer translocation. We show that no stochastic resonance is possible if the free energy barrier for polymer translocation is purely entropic in nature. The polymer chain exhibits stochastic resonance only in the presence of an energy threshold in terms of polymer-pore interactions. Once stochastic resonance is feasible, the chain entropy controls the optimal synchronization conditions significantly.

  14. Beta-helical polymers from isocyanopeptides

    NARCIS (Netherlands)

    Cornelissen, J.J.L.M.; Donners, J.J.J.M.; Gelder, de R.; Graswinckel, W.S.; Metselaar, G.A.; Rowan, A.E.; Sommerdijk, N.A.J.M.; Nolte, R.J.M.

    2001-01-01

    Polymerization of isocyanopeptides results in the formation of high molecular mass polymers that fold in a proteinlike fashion to give helical strands in which the peptide chains are arranged in ß-sheets. The ß-helical polymers retain their structure in water and unfold in a cooperative process at

  15. Responsive gelation of hydrophobized linear polymer

    DEFF Research Database (Denmark)

    Madsen, Claus Greve; Toeth, Joachim; Jørgensen, Lene

    In this study we present the rheological properties of a physically linked polymer network, composed of linear hydrophilic chains, modified with hydrophobic moieties in each end. Solutions of the polymer in ethanol-water mixtures showed Newtonian behaviour up to about 99 % ethanol, with the highest...

  16. Lorentzian AdS, Wormholes and Holography

    CERN Document Server

    Arias, Raul E; Silva, Guillermo A

    2011-01-01

    We investigate the structure of two point functions for the QFT dual to an asymptotically Lorentzian AdS-wormhole. The bulk geometry is a solution of 5-dimensional second order Einstein Gauss Bonnet gravity and causally connects two asymptotically AdS space times. We revisit the GKPW prescription for computing two-point correlation functions for dual QFT operators O in Lorentzian signature and we propose to express the bulk fields in terms of the independent boundary values phi_0^\\pm at each of the two asymptotic AdS regions, along the way we exhibit how the ambiguity of normalizable modes in the bulk, related to initial and final states, show up in the computations. The independent boundary values are interpreted as sources for dual operators O^\\pm and we argue that, apart from the possibility of entanglement, there exists a coupling between the degrees of freedom leaving at each boundary. The AdS_(1+1) geometry is also discussed in view of its similar boundary structure. Based on the analysis, we propose a ...

  17. CLASSIFICATION OF BIODEGRADABLE POLYMERS

    Directory of Open Access Journals (Sweden)

    I. I. Karpunin

    2015-01-01

    Full Text Available The executed investigations have made it possible to ascertain that a morphological structure of starch granules mainly determine technological peculiarities of starch isolation from raw material, its modification and its later use. Morphological structure of starch granules primarily depends on type of plant starch-containing raw material which has been used for its isolation. Class of raw material exerts a strong impact on the shape and size of the granules. Linear “light” amylose chains and “heavy” amylopectin branch chains form a starch granule ultrastructure. X-ray research has proved that starch granules are characterized by presence of interlacing amorphous and crystalline regions. In this case polymer orientation using stretching of the obtained end product influences on its physical and mechanical  indices which are increasing due to polymer orientation. For the purpose of packaging orientation of polymer films can solve such important problems as significant improvement of operational properties, creation of  thermosetting film materials, improvement of qualitative indices of the recycled film.Results of the conducted research have proved the fact that it is necessary to make changes in technology in order to increase biological degradability of the recycled packaging made from polymers and improve physical and mechanical indices. In this regard film production technology presupposes usage of such substances as stark and others which are characterized by rather large presence of branch chains of molecules and interlacing amorphous and crystalline regions. Such approach makes it possible to obtain after-use package which is strong and quickly degradable by micro-organisms.

  18. Baby Skyrmions in AdS

    Energy Technology Data Exchange (ETDEWEB)

    Elliot-Ripley, Matthew; Winyard, Thomas [Department of Mathematical Sciences, Durham University,South Rd, Durham (United Kingdom)

    2015-09-01

    We study the baby Skyrme model in a pure AdS background without a mass term. The tail decays and scalings of massless radial solutions are demonstrated to take a similar form to those of the massive flat space model, with the AdS curvature playing a similar role to the flat space pion mass. We also numerically find minimal energy solutions for a range of higher topological charges and find that they form concentric ring-like solutions. Popcorn transitions (named in analogy with studies of toy models of holographic QCD) from an n layer to an n+1-layer configuration are observed at topological charges 9 and 27 and further popcorn transitions for higher charges are predicted. Finally, a point-particle approximation for the model is derived and used to successfully predict the ring structures and popcorn transitions for higher charge solitons.

  19. Supersymmetric AdS3, AdS2 and bubble solutions

    International Nuclear Information System (INIS)

    Gauntlett, Jerome P.; Waldram, Daniel; Kim, Nakwoo

    2007-01-01

    We present new supersymmetric AdS 3 solutions of type IIB supergravity and AdS 2 solutions of D = 11 supergravity. The former are dual to conformal field theories in two dimensions with N = (0, 2) supersymmetry while the latter are dual to conformal quantum mechanics with two supercharges. Our construction also includes AdS 2 solutions of D = 11 supergravity that have non-compact internal spaces which are dual to three-dimensional N = 2 superconformal field theories coupled to point-like defects. We also present some new bubble-type solutions, corresponding to BPS states in conformal theories, that preserve four supersymmetries

  20. Polymer Electrolytes

    Science.gov (United States)

    Hallinan, Daniel T.; Balsara, Nitash P.

    2013-07-01

    This review article covers applications in which polymer electrolytes are used: lithium batteries, fuel cells, and water desalination. The ideas of electrochemical potential, salt activity, and ion transport are presented in the context of these applications. Potential is defined, and we show how a cell potential measurement can be used to ascertain salt activity. The transport parameters needed to fully specify a binary electrolyte (salt + solvent) are presented. We define five fundamentally different types of homogeneous electrolytes: type I (classical liquid electrolytes), type II (gel electrolytes), type III (dry polymer electrolytes), type IV (dry single-ion-conducting polymer electrolytes), and type V (solvated single-ion-conducting polymer electrolytes). Typical values of transport parameters are provided for all types of electrolytes. Comparison among the values provides insight into the transport mechanisms occurring in polymer electrolytes. It is desirable to decouple the mechanical properties of polymer electrolyte membranes from the ionic conductivity. One way to accomplish this is through the development of microphase-separated polymers, wherein one of the microphases conducts ions while the other enhances the mechanical rigidity of the heterogeneous polymer electrolyte. We cover all three types of conducting polymer electrolyte phases (types III, IV, and V). We present a simple framework that relates the transport parameters of heterogeneous electrolytes to homogeneous analogs. We conclude by discussing electrochemical stability of electrolytes and the effects of water contamination because of their relevance to applications such as lithium ion batteries.

  1. From lattice gases to polymers

    NARCIS (Netherlands)

    Frenkel, D.

    1990-01-01

    The modification of a technique that was developed to study time correlations in lattice-gas cellular automata to facilitate the numerical simulation of chain molecules is described. As an example, the calculation of the excess chemical potential of an ideal polymer in a dense colloidal

  2. Polymer chemistry (revised edition)

    International Nuclear Information System (INIS)

    Kim, Jae Mum

    1987-02-01

    This book deals with polymer chemistry, which is divided into fourteen chapters. The contents of this book are development of polymer chemistry, conception of polymer, measurement of polymer chemistry, conception of polymer, measurement of polymer, molecule structure of polymer, thermal prosperities of solid polymer, basic theory of polymerization, radical polymerization, ion polymerization, radical polymerization, copolymerization, polymerization by step-reaction, polymer reaction, crown polymer and inorganic polymer on classification and process of creation such as polymeric sulfur and carbon fiber.

  3. Polymer Solar Cells – Non Toxic Processing and Stable Polymer Photovoltaic Materials

    DEFF Research Database (Denmark)

    Søndergaard, Roar

    The field of polymer solar cell has experienced enormous progress in the previous years, with efficiencies of small scale devices (~1 mm2) now exceeding 8%. However, if the polymer solar cell is to achieve success as a renewable energy resource, mass production of sufficiently stable and efficient...... and development of more stable materials. The field of polymer solar cells has evolved around the use of toxic and carcinogenic solvents like chloroform, benzene, toluene, chlorobenzene, dichlorobenzene and xylene. As large scale production of organic solar cells is envisaged to production volumes corresponding...... synthesis of polymers carrying water coordinating side chains which allow for processing from semi-aqueous solution. A series of different side chains were synthesized and incorporated into the final polymers as thermocleavable tertiary esters. Using a cleavable side chain induces stability to solar cells...

  4. The fishing industry - toward supply chain modelling

    DEFF Research Database (Denmark)

    Jensen, Toke Koldborg; Nielsen, Jette; Larsen, Erling P.

    Mathematical models for simulating and optimizing supply chain aspects such as distribution planning and optimal use of raw materials are widely used. However, modelling based on a holistic chain view is less studied, and food-related aspects such as quality and shelf life issues enforce additional...... requirements onto the chains. In this paper, we consider the supply chain structure of the Danish fishing industry and illustrate the potential of using mathematical models to identify quality and value-adding activities. This is a first step toward innovative supply chain modelling aimed to identify benefits...... for actors along chains in the fishing industry....

  5. Predicting AD conversion

    DEFF Research Database (Denmark)

    Liu, Yawu; Mattila, Jussi; Ruiz, Miguel �ngel Mu�oz

    2013-01-01

    To compare the accuracies of predicting AD conversion by using a decision support system (PredictAD tool) and current research criteria of prodromal AD as identified by combinations of episodic memory impairment of hippocampal type and visual assessment of medial temporal lobe atrophy (MTA) on MRI...

  6. Extrusion of polysaccharide nanocrystal reinforced polymer nanocomposites through compatibilization with poly(ethylene oxide).

    Science.gov (United States)

    Pereda, Mariana; El Kissi, Nadia; Dufresne, Alain

    2014-06-25

    Polysaccharide nanocrystals with a rodlike shape but with different dimensions and specific surface area were prepared from cotton and capim dourado cellulose, and with a plateletlike morphology from waxy maize starch granules. The rheological behavior of aqueous solutions of poly(ethylene oxide) (PEO) with different molecular weights when adding these nanoparticles was investigated evidencing specific interactions between PEO chains and nanocrystals. Because PEO also bears hydrophobic moieties, it was employed as a compatibilizing agent for the melt processing of polymer nanocomposites. The freeze-dried mixtures were used to prepare nanocomposite materials with a low density polyethylene matrix by extrusion. The thermal and mechanical behavior of ensuing nanocomposites was studied.

  7. Communication: Thermodynamic analysis of critical conditions of polymer adsorption

    International Nuclear Information System (INIS)

    Cimino, R.; Neimark, A. V.; Rasmussen, C. J.

    2013-01-01

    Polymer adsorption to solid surfaces is a ubiquitous phenomenon, which has attracted long-lasting attention. Dependent on the competition between the polymer-solid adsorption and polymer-solvent solvation interactions, a chain may assume either 3d solvated conformation when adsorption is weak or 2d adsorbed conformation when adsorption is strong. The transition between these conformations occurring upon variation of adsorption strength is quite sharp, and in the limit of “infinite” chain length, can be treated as a critical phenomenon. We suggest a novel thermodynamic definition of the critical conditions of polymer adsorption from the equality of incremental chemical potentials of adsorbed and free chains. We show with the example of freely jointed Lennard-Jones chains tethered to an adsorbing surface that this new definition provides a link between thermodynamic and geometrical features of adsorbed chains and is in line with classical scaling relationships for the fraction of adsorbed monomers, chain radii of gyration, and free energy

  8. Communication: Thermodynamic analysis of critical conditions of polymer adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Cimino, R.; Neimark, A. V., E-mail: aneimark@rutgers.edu [Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854 (United States); Rasmussen, C. J. [DuPont Central Research and Development, Corporate Center for Analytical Sciences, Macromolecular Characterization, Route 141 and Henry Clay, Wilmington, Delaware 19803 (United States)

    2013-11-28

    Polymer adsorption to solid surfaces is a ubiquitous phenomenon, which has attracted long-lasting attention. Dependent on the competition between the polymer-solid adsorption and polymer-solvent solvation interactions, a chain may assume either 3d solvated conformation when adsorption is weak or 2d adsorbed conformation when adsorption is strong. The transition between these conformations occurring upon variation of adsorption strength is quite sharp, and in the limit of “infinite” chain length, can be treated as a critical phenomenon. We suggest a novel thermodynamic definition of the critical conditions of polymer adsorption from the equality of incremental chemical potentials of adsorbed and free chains. We show with the example of freely jointed Lennard-Jones chains tethered to an adsorbing surface that this new definition provides a link between thermodynamic and geometrical features of adsorbed chains and is in line with classical scaling relationships for the fraction of adsorbed monomers, chain radii of gyration, and free energy.

  9. Winding strings in AdS3

    International Nuclear Information System (INIS)

    Herscovich, Estanislao; Minces, Pablo; Nunez, Carmen

    2006-01-01

    Correlation functions of one-unit spectral flowed states in string theory on AdS 3 are considered. We present the modified Knizhnik-Zamolodchikov and null vector equations to be satisfied by amplitudes containing states in winding sector one and study their solution corresponding to the four point function including one w = 1 field. We compute the three point function involving two one-unit spectral flowed operators and find expressions for amplitudes of three w = 1 states satisfying certain particular relations among the spins of the fields. Several consistency checks are performed

  10. Performance limitations of polymer electrolytes based on ethylene oxide polymers

    International Nuclear Information System (INIS)

    Buriez, Olivier; Han, Yong Bong; Hou, Jun; Kerr, John B.; Qiao, Jun; Sloop, Steven E.; Tian, Minmin; Wang, Shanger

    1999-01-01

    Studies of polymer electrolyte solutions for lithium-polymer batteries are described. Two different salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium trifluoromethanesulfonate (LiTf), were dissolved in a variety of polymers. The structures were all based upon the ethylene oxide unit for lithium ion solvation and both linear and comb-branch polymer architectures have been examined. Conductivity, salt diffusion coefficient and transference number measurements demonstrate the superior transport properties of the LiTFSI salt over LiTf. Data obtained on all of these polymers combined with LiTFSI salts suggest that there is a limit to the conductivity achievable at room temperature, at least for hosts containing ethylene oxide units. The apparent conductivity limit is 5 x 10-5 S/cm at 25 C. Providing that the polymer chain segment containing the ethylene oxide units is at least 5-6 units long there appears to be little influence of the polymer framework to which the solvating groups are attached. To provide adequate separator function, the mechanical properties may be disconnected from the transport properties by selection of an appropriate architecture combined with an adequately long ethylene oxide chain. For both bulk and interfacial transport of the lithium ions, conductivity data alone is insufficient to understand the processes that occur. Lithium ion transference numbers and salt diffusion coefficients also play a major role in the observed behavior and the transport properties of these polymer electrolyte solutions appear to be quite inadequate for ambient temperature performance. At present, this restricts the use of such systems to high temperature applications. Several suggestions are given to overcome these obstacles

  11. Conjugated Polymers Atypically Prepared in Water

    Science.gov (United States)

    Invernale, Michael A.; Pendergraph, Samuel A.; Yavuz, Mustafa S.; Ombaba, Matthew; Sotzing, Gregory A.

    2010-01-01

    Processability remains a fundamental issue for the implementation of conducting polymer technology. A simple synthetic route towards processable precursors to conducting polymers (main chain and side chain) was developed using commercially available materials. These soluble precursor systems were converted to conjugated polymers electrochemically in aqueous media, offering a cheaper and greener method of processing. Oxidative conversion in aqueous and organic media each produced equivalent electrochromics. The precursor method enhances the yield of the electrochromic polymer obtained over that of electrodeposition, and it relies on a less corruptible electrolyte bath. However, electrochemical conversion of the precursor polymers often relies on organic salts and solvents. The ability to achieve oxidative conversion in brine offers a less costly and a more environmentally friendly processing step. It is also beneficial for biological applications. The electrochromics obtained herein were evaluated for electronic, spectral, and morphological properties. PMID:20959869

  12. Polyphosphazine-based polymer materials

    Science.gov (United States)

    Fox, Robert V.; Avci, Recep; Groenewold, Gary S.

    2010-05-25

    Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

  13. Mechanics of responsive polymers via conformationally switchable molecules

    Science.gov (United States)

    Brighenti, Roberto; Artoni, Federico; Vernerey, Franck; Torelli, Martina; Pedrini, Alessandro; Domenichelli, Ilaria; Dalcanale, Enrico

    2018-04-01

    Active materials are those capable of giving some physical reaction under external stimuli coming from the environment such as temperature, pH, light, mechanical stress, etc. Reactive polymeric materials can be obtained through the introduction of switchable molecules in their network, i.e. molecules having two distinct stable conformations: if properly linked to the hosting polymer chains, the switching from one state to the other can promote a mechanical reaction of the material, detectable at the macroscale, and thus enables us to tune the response according to a desired functionality. In the present paper, the main aspects of the mechanical behavior of polymeric materials with embedded switchable molecules-properly linked to the polymer's chains-are presented and discussed. Starting from the micro mechanisms occurring in such active material, a continuum model is developed, providing a straightforward implementation in computational approaches. Finally, some experimental outcomes related to a switchable molecules (known as quinoxaline cavitands) added to an elastomeric PDMS under chemical stimuli, are presented and quantitatively discussed through the use of the developed mechanical framework.

  14. METHOD FOR MAKING A POLYMER, A POLYMER ARTICLE, A BIODEVICE, AND CYCLIC CARBONATE

    NARCIS (Netherlands)

    Zhong, Zhiyuan; Meng, Fenghua; Wang, Rong; Feijen, Jan

    2014-01-01

    The present invention relates to a method for making a polymer wherein during ring opening polymerisation is incorporated into the polymer chain at least one cyclic (alkyl) carbonate monomer having the formula (1) wherein Y is optional and represents the residue of a sulfhydryl reacted group, X

  15. Polymer Physics Prize Talk

    Science.gov (United States)

    Olvera de La Cruz, Monica

    Polymer electrolytes have been particularly difficult to describe theoretically given the large number of disparate length scales involved in determining their physical properties. The Debye length, the Bjerrum length, the ion size, the chain length, and the distance between the charges along their backbones determine their structure and their response to external fields. We have developed an approach that uses multi-scale calculations with the capability of demonstrating the phase behavior of polymer electrolytes and of providing a conceptual understanding of how charge dictates nano-scale structure formation. Moreover, our molecular dynamics simulations have provided an understanding of the coupling of their conformation to their dynamics, which is crucial to design self-assembling materials, as well as to explore the dynamics of complex electrolytes for energy storage and conversion applications.

  16. Luminescent lanthanide coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Ma, L.; Evans, O.R.; Foxman, B.M.; Lin, W.

    1999-12-13

    One-dimensional lanthanide coordination polymers with the formula Ln(isonicotinate){sub 3}(H{sub 2}O){sub 2} (Ln = Ce, Pr, Nd, Sm, Eu, Tb; 1a-f) were synthesized by treating nitrate or perchlorate salts of Ln(III) with 4-pyridinecarboxaldehyde under hydro(solvo)thermal conditions. Single-crystal and powder X-ray diffraction studies indicate that these lanthanide coordination polymers adopt two different structures. While Ce(III), Pr(III), and Nd(III) complexes adopt a chain structure with alternating Ln-(carboxylate){sub 2}-Ln and Ln-(carboxylate){sub 4}-Ln linkages, Sm(III), Eu(III), and Tb(III) complexes have a doubly carboxylate-bridged infinite-chain structure with one chelating carboxylate group on each metal center. In both structures, the lanthanide centers also bind to two water molecules to yield an eight-coordinate, square antiprismatic geometry. The pyridine nitrogen atoms of the isonicotinate groups do not coordinate to the metal centers in these lanthanide(III) complexes; instead, they direct the formation of Ln(III) coordination polymers via hydrogen bonding with coordinated water molecules. Photoluminescence measurements show that Tb(isonicotinate){sub 3}(H{sub 2}O){sub 2} is highly emissive at room temperature with a quantum yield of {approximately}90%. These results indicate that highly luminescent lanthanide coordination polymers can be assembled using a combination of coordination and hydrogen bonds. Crystal data for 1a: monoclinic space group P2{sub 1}/c, a = 9.712(2) {angstrom}, b = 19.833(4) {angstrom}, c = 11.616(2) {angstrom}, {beta} = 111.89(3){degree}, Z = 4. Crystal data for 1f: monoclinic space group C2/c, a = 20.253(4) {angstrom}, b = 11.584(2) {angstrom}, c = 9.839(2) {angstrom}, {beta} = 115.64(3){degree}, Z = 8.

  17. Effects of Intercalation on the Hole Mobility of Amorphous Semiconducting Polymer Blends

    KAUST Repository

    Cates, Nichole C.; Gysel, Roman; Dahl, Jeremy E. P.; Sellinger, Alan; McGehee, Michael D.

    2010-01-01

    Fullerenes have been shown to intercalate between the side chains of many crystalline and semicrystalline polymers and to affect the properties of polymer:fullerene bulk heterojunction solar cells. Here we present the first in-depth study

  18. The political attack ad

    Directory of Open Access Journals (Sweden)

    Palma Peña-Jiménez, Ph.D.

    2011-01-01

    Full Text Available During election campaigns the political spot has a clear objective: to win votes. This message is communicated to the electorate through television and Internet, and usually presents a negative approach, which includes a direct critical message against the opponent, rather than an exposition of proposals. This article is focused on the analysis of the campaign attack video ad purposely created to encourage the disapproval of the political opponent among voters. These ads focus on discrediting the opponent, many times, through the transmission of ad hominem messages, instead of disseminating the potential of the political party and the virtues and manifesto of its candidate. The article reviews the development of the attack ad since its first appearance, which in Spain dates back to 1996, when the famous Doberman ad was broadcast, and examines the most memorable campaign attack ads.

  19. CHAIN 2

    International Nuclear Information System (INIS)

    Bailey, D.

    1998-04-01

    The Second Processing Chain (CHAIN2) consists of a suite of ten programs which together provide a full local analysis of the bulk plasma physics within the JET Tokamak. In discussing these ten computational models this report is intended to fulfil two broad purposes. Firstly it is meant to be used as a reference source for any user of CHAIN2 data, and secondly it provides a basic User Manual sufficient to instruct anyone in running the CHAIN2 suite of codes. In the main report text each module is described in terms of its underlying physics and any associated assumptions or limitations, whilst deliberate emphasis is put on highlighting the physics and mathematics of the calculations required in deriving each individual datatype in the standard module PPF output. In fact each datatype of the CHAIN2 PPF output listed in Appendix D is cross referenced to the point in the main text where its evaluation is discussed. An effort is made not only to give the equation used to derive a particular data profile but also to explicitly define which external data sources are involved in the computational calculation

  20. Quantum spectral curve for the η-deformed AdS5 × S5 superstring

    Science.gov (United States)

    Klabbers, Rob; van Tongeren, Stijn J.

    2017-12-01

    The spectral problem for the AdS5 ×S5 superstring and its dual planar maximally supersymmetric Yang-Mills theory can be efficiently solved through a set of functional equations known as the quantum spectral curve. We discuss how the same concepts apply to the η-deformed AdS5 ×S5 superstring, an integrable deformation of the AdS5 ×S5 superstring with quantum group symmetry. This model can be viewed as a trigonometric version of the AdS5 ×S5 superstring, like the relation between the XXZ and XXX spin chains, or the sausage and the S2 sigma models for instance. We derive the quantum spectral curve for the η-deformed string by reformulating the corresponding ground-state thermodynamic Bethe ansatz equations as an analytic Y system, and map this to an analytic T system which upon suitable gauge fixing leads to a Pμ system - the quantum spectral curve. We then discuss constraints on the asymptotics of this system to single out particular excited states. At the spectral level the η-deformed string and its quantum spectral curve interpolate between the AdS5 ×S5 superstring and a superstring on "mirror" AdS5 ×S5, reflecting a more general relationship between the spectral and thermodynamic data of the η-deformed string. In particular, the spectral problem of the mirror AdS5 ×S5 string, and the thermodynamics of the undeformed AdS5 ×S5 string, are described by a second rational limit of our trigonometric quantum spectral curve, distinct from the regular undeformed limit.

  1. Gamma radiation-initiated polymerization of styrene at high pressure. II. Chain termination

    International Nuclear Information System (INIS)

    Moore, P.W.; Clouston, J.G.; Chaplin, R.P.

    1981-01-01

    The pressure dependence of the termination rate constant k/sub t/ for the free radical polymerization of monomers such as styrene is a function of polymer chain length, chain stiffness, and monomer viscosity, all of which influence the rate of segmental diffusion of an active radical chain end out of the coiled polymer chain to a position in which it can react with a proximate radical. Although k/sub t/ is not sensitive to changes in chain length, the large increase in molecular weight is responsible for a significant reduction in k/sub t/ at high pressures. For most of the common vinyl polymers, which exhibit some degree of chain stiffness, k/sub t/is inversely proportional to a fractional power of the monomer viscosity because it depends in part on the resistance of chain segments to movement and in part on the influence of viscosity in controlling diffusion of the chain ends. The fractional exponent appears to increase with pressure and this is interpreted as evidence that the polymer chains become more flexible in a more viscous solvent. Because the fractional exponent is higher for more flexible chains, the value of the activation volume for chain termination is an indication of the degree of flexibility of the polymer chains, provided that the monomer is a good solvent for the polymer and that chain transfer is negligible

  2. Polymer Nanocomposites

    Indian Academy of Sciences (India)

    methods for the synthesis of polymer nanocomposites. In this article we .... ers, raw materials recovery, drug delivery and anticorrosion .... region giving rise to dose-packed absorption bands called an IR ... using quaternary ammonium salts.

  3. Modular Assembly of Hierarchically Structured Polymers

    Science.gov (United States)

    Leophairatana, Porakrit

    mechanism. Post-ATRP Glaser coupling was also influenced by the ATRP synthesis ligand used. The order of ligand activity for catalyzing Glaser coupling was: linear bidentate > tridentate > tetradentate. Glaser coupling can also occur for alkynes held under CuAAC reaction conditions but again can be eliminated by adding appropriate reducing agents. With the strategy presented in Chapter 3, alkyne-terminated polymers of high-functionality were produced without the need for alkyne protecting groups. These "click" functional building blocks were employed to investigate the overall efficiency of the CuAAC "click" coupling reactions between alkyne- and azide-terminated macromonomers as discussed in Chapter 4. Quantitative convolution modeling of the entire molecular weight distribution post-CuAAC indicates a CuAAC efficiency of about 94% and an azide substitution efficiency of >99%. However, incomplete functionality of the azide-terminated macromonomer (˜92%) proves to be the largest factor compromising the overall efficacy of the coupling reactions, and is attributed primarily to the loss of bromine functionality during synthesis by ATRP. To address this issue, we discuss in Chapter 6 the development of a new set of molecular building blocks consisting of alkyne functional substrates and heterobifunctional degradable linkers that allow the growth and subsequent detachment of polymers from the solid substrate. Complex polymeric structures are created by progressive cycles of CuAAC and deprotection reactions that add building blocks to the growing polymer chain ends. We demonstrate that these building blocks were completely stable under both CuAAC and deprotection reaction conditions. Since the desired product is covalently bound to the solid surface, the unreacted monomers/macromonomers and by-products (i.e. non-functional building blocks) can be easily separated from the product via removal of the polymer-tethered solid substrate in one step. Chapter 5 discusses how MAHP was

  4. Crescimento e composição mineral do porta-enxerto tangerineira cleópatra cultivado em substrato acrescido de polímero hidrorretentor Growth and mineral composition of the cleópatra mandarin rootstock growing on substratum added with hidroretentive polymers

    Directory of Open Access Journals (Sweden)

    Marcelo Vichiato

    2004-08-01

    Full Text Available Os efeitos de polímero hidrorretentor acrescido ao substrato foi avaliado na fase inicial de produção do porta-enxerto tangerineira 'Cleópatra' cultivado em tubetes plásticos com substrato comercial à base de casca de Pinus compostada e parcialmente fertilizado. Foi utilizado o delineamento experimental de blocos casualizados com três repetições, sendo os tratamentos seis doses do hidrorretentor (0, 4, 8, 12, 16 e 32 mg.dm-3 incorporado ao substrato, com 60 plantas úteis por parcela. Avaliaram-se o Índice de Velocidade de Emergência (IVE, altura de planta, peso da matéria seca total e seus teores de N, P, K, Ca, Mg, S, B, Cu, Mn, Zn e Fe, e valores de pH do substrato ao final do período experimental. A incorporação do hidrorretentor ao substrato de cultivo promoveu elevação nos valores do pH do substrato, decréscimos no IVE, no crescimento e no peso da matéria seca total, não havendo alteração expressiva no estado nutricional dos porta-enxertos aos 150 dias pós-semeadura.The effects of hidroretentive polymers added to the substratum was evaluated in the initial phase of production of 'Cleópatra' mandarin rootstock. They were cultivated in container seedlings with commercial pine bark substratum composted and partially fertilized. The randomized blocks experimental design was used with three replications, being the treatments six doses of the hydroretentive polymer (0, 4, 8, 12, 16 and 32 mg.dm-3 incorporated to the substratum. The Index of Emergency Speed (IVE, plant height, weight of the matter total drought and their tenors of N, P, K, Ca, Mg, S, B, Cu, Mn, Zn and Fe, and values of pH substratum were evaluated. The use of incorporated hydroretentive polymer to the cultivation substratum increased the values of pH of the substratum, decreases in IVE, the growth and the weight of the total dry matter, not having expressive alteration in the nutritional state of the rootstocks.

  5. Liquid crystalline order in polymers

    CERN Document Server

    Blumstein, Alexandre

    1978-01-01

    Liquid Crystalline Order in Polymers examines the topic of liquid crystalline order in systems containing rigid synthetic macromolecular chains. Each chapter of the book provides a review of one important area of the field. Chapter 1 discusses scattering in polymer systems with liquid crystalline order. It also introduces the field of liquid crystals. Chapter 2 treats the origin of liquid crystalline order in macromolecules by describing the in-depth study of conformation of such macromolecules in their unassociated state. The chapters that follow describe successively the liquid crystalli

  6. Polymer in a pore: Effect of confinement on the free energy barrier

    Science.gov (United States)

    Kumar, Sanjiv; Kumar, Sanjay

    2018-06-01

    We investigate the transfer of a polymer chain from cis- side to trans- side through two types of pores: cone-shaped channel and flat-channel. Using the exact enumeration technique, we obtain the free energy landscapes of a polymer chain for such systems. We have also calculated the free-energy barrier of a polymer chain attached to the edge of the pore. The model system allows us to calculate the force required to pull polymer from the pore and stall-force to confine polymer within the pore.

  7. Twinning of Polymer Crystals Suppressed by Entropy

    Directory of Open Access Journals (Sweden)

    Nikos Ch. Karayiannis

    2014-09-01

    Full Text Available We propose an entropic argument as partial explanation of the observed scarcity of twinned structures in crystalline samples of synthetic organic polymeric materials. Polymeric molecules possess a much larger number of conformational degrees of freedom than low molecular weight substances. The preferred conformations of polymer chains in the bulk of a single crystal are often incompatible with the conformations imposed by the symmetry of a growth twin, both at the composition surfaces and in the twin axis. We calculate the differences in conformational entropy between chains in single crystals and chains in twinned crystals, and find that the reduction in chain conformational entropy in the twin is sufficient to make the single crystal the stable thermodynamic phase. The formation of cyclic twins in molecular dynamics simulations of chains of hard spheres must thus be attributed to kinetic factors. In more realistic polymers this entropic contribution to the free energy can be canceled or dominated by nonbonded and torsional energetics.

  8. AdS2 holographic dictionary

    International Nuclear Information System (INIS)

    Cvetič, Mirjam; Papadimitriou, Ioannis

    2016-01-01

    We construct the holographic dictionary for both running and constant dilaton solutions of the two dimensional Einstein-Maxwell-Dilaton theory that is obtained by a circle reduction from Einstein-Hilbert gravity with negative cosmological constant in three dimensions. This specific model ensures that the dual theory has a well defined ultraviolet completion in terms of a two dimensional conformal field theory, but our results apply qualitatively to a wider class of two dimensional dilaton gravity theories. For each type of solutions we perform holographic renormalization, compute the exact renormalized one-point functions in the presence of arbitrary sources, and derive the asymptotic symmetries and the corresponding conserved charges. In both cases we find that the scalar operator dual to the dilaton plays a crucial role in the description of the dynamics. Its source gives rise to a matter conformal anomaly for the running dilaton solutions, while its expectation value is the only non trivial observable for constant dilaton solutions. The role of this operator has been largely overlooked in the literature. We further show that the only non trivial conserved charges for running dilaton solutions are the mass and the electric charge, while for constant dilaton solutions only the electric charge is non zero. However, by uplifting the solutions to three dimensions we show that constant dilaton solutions can support non trivial extended symmetry algebras, including the one found by Compère, Song and Strominger http://dx.doi.org/10.1007/JHEP05(2013)152, in agreement with the results of Castro and Song http://arxiv.org/abs/1411.1948. Finally, we demonstrate that any solution of this specific dilaton gravity model can be uplifted to a family of asymptotically AdS 2 ×S 2 or conformally AdS 2 ×S 2 solutions of the STU model in four dimensions, including non extremal black holes. The four dimensional solutions obtained by uplifting the running dilaton solutions coincide

  9. Radiation induced solid-state polymerization of long-chain acrylates containing fluorocarbon chain

    International Nuclear Information System (INIS)

    Shibasaki, Y.; Zhu, Zhi-Qin

    1995-01-01

    γ-Ray irradiation post-polymerizations of long-chain acrylates containing fluorocarbon chain, H(CF 2 ) 10 CH 2 OCOCH=CH 2 and H(CF 2 ) 8 CH 2 OCOCH=CH 2 , were investigated and also the structures and thermal properties of comb-like polymers obtained were studied. It was found that these monomers exhibited very high polymerizability at wide temperature ranges around the melting points. Because the fluorocarbon chains are less flexible and thicker than the hydrocarbon chains, it can be expected that the aggregation force among the monomer molecules is strong and the conformational freedom of functional group for polymerization is large. According to the DSC and the X-ray diffraction measurements of the comb-like polymers obtained, the fluorocarbon chains are aggregated in a mode of hexagonal packing in the lamellar crystals. This situation can be considered as an optimum condition for the γ-ray irradiation post-polymerization. (author)

  10. Thermo-cleavable polymers: Materials with enhanced photochemical stability

    DEFF Research Database (Denmark)

    Manceau, Matthieu; Petersen, Martin Helgesen; Krebs, Frederik C

    2010-01-01

    Photochemical stability of three thermo-cleavable polymers was investigated as thin films under atmospheric conditions. A significant increase in lifetime was observed once the side-chain was cleaved emphasizing the detrimental effect of solubilizing groups on the photochemical stability of conju......Photochemical stability of three thermo-cleavable polymers was investigated as thin films under atmospheric conditions. A significant increase in lifetime was observed once the side-chain was cleaved emphasizing the detrimental effect of solubilizing groups on the photochemical stability...... of conjugated polymers. In addition to their ease of processing, thermo-cleavable polymers thus also offer a greater intrinsic stability under illumination....

  11. Heavy Chain Diseases

    Science.gov (United States)

    ... of heavy chain produced: Alpha Gamma Mu Alpha Heavy Chain Disease Alpha heavy chain disease (IgA heavy ... the disease or lead to a remission. Gamma Heavy Chain Disease Gamma heavy chain disease (IgG heavy ...

  12. Novel ceramic-polymer composite membranes for the separation of hazardous liquid waste. 1998 annual progress report

    International Nuclear Information System (INIS)

    Cohen, Y.

    1998-01-01

    'This report summarizes the work progress over the last 1.75 years of a 3 year project. The objectives of the project have been to develop a new class of ceramic-supported polymeric membranes that could be tailored-designed for a wide-range of applications in remediation and pollution prevention. To date, a new class of chemically-modified ceramic membranes was developed for the treatment of oil-in-water emulsions and for the pervaporation removal of volatile organics from aqueous systems. These new ceramic-supported polymer (CSP) membranes are fabricated by modifying the pore surface of a ceramic membrane support by a graft polymerization process (Chaimberg and Cohen, 1994). The graft polymerization process consists of activating the membrane surface with alkoxy vinyl silanes onto which vinyl monomers are added via free-radical graft polymerization resulting in a thin surface layer of terminally anchored polymer chains. Reaction conditions are selected based on knowledge of the graft polymerization kinetics for the specific polymer/substrate system. The resultant ceramic-supported polymer (CSP) membrane is a composite structure in which mechanical strength is provided by the ceramic support and the selectivity is determined by the covalently bonded polymer brush layer. Thus, one of the unique attributes of the CSP membrane is that it can be used in environments where the polymer layer is swollen (or even completely miscible) in the mixture to be separated (Castro et al., 1993). It is important to note that the above modification process is carried out under mild conditions (e.g., temperature of about 70 C) and is well suited for large scale commercial application. In a series of studies, the applicability of a polyvinylpyrrolidone CSP membrane was demonstrated for the treatment of oil-in-water emulsion under a variety of flow conditions (Castro et al.,1996). Improved membrane performance was achieved due to minimization of surface adsorption of the oil components

  13. Complexity of the AdS soliton

    Science.gov (United States)

    Reynolds, Alan P.; Ross, Simon F.

    2018-05-01

    We consider the holographic complexity conjectures in the context of the AdS soliton, which is the holographic dual of the ground state of a field theory on a torus with antiperiodic boundary conditions for fermions on one cycle. The complexity is a non-trivial function of the size of the circle with antiperiodic boundary conditions, which sets an IR scale in the dual geometry. We find qualitative differences between the calculations of complexity from spatial volume and action (CV and CA). In the CV calculation, the complexity for antiperiodic boundary conditions is smaller than for periodic, and decreases monotonically with increasing IR scale. In the CA calculation, the complexity for antiperiodic boundary conditions is larger than for periodic, and initially increases with increasing IR scale, eventually decreasing to zero as the IR scale becomes of order the UV cutoff. We compare these results to a simple calculation for free fermions on a lattice, where we find the complexity for antiperiodic boundary conditions is larger than for periodic.

  14. AdS2 models in an embedding superspace

    International Nuclear Information System (INIS)

    McKeon, D.G.C.; Sherry, T.N.

    2003-01-01

    An embedding superspace, whose bosonic part is the flat (2+1)-dimensional embedding space for AdS 2 , is introduced. Superfields and several supersymmetric models are examined in the embedded AdS 2 superspace

  15. Interest of neutron scattering for the investigation of liquid-crystalline polymers

    International Nuclear Information System (INIS)

    Noirez, L.

    1994-01-01

    Small-angle Neutron scattering is the unique method which allows the determination of polymer conformation in the bulk state. This method has been applied to several kinds of liquid crystalline polymers. Results concerning side-chain liquid-crystal polymer, main-chain liquid-crystal polymer and combined liquid-crystal polymers, are reported. It is shown that the polymer conformation is largely dependent on the insertion site of the liquid crystal molecule and of the structure of the meso-phase. (author). 11 refs

  16. A constitutive law for degrading bioresorbable polymers.

    Science.gov (United States)

    Samami, Hassan; Pan, Jingzhe

    2016-06-01

    This paper presents a constitutive law that predicts the changes in elastic moduli, Poisson's ratio and ultimate tensile strength of bioresorbable polymers due to biodegradation. During biodegradation, long polymer chains are cleaved by hydrolysis reaction. For semi-crystalline polymers, the chain scissions also lead to crystallisation. Treating each scission as a cavity and each new crystal as a solid inclusion, a degrading semi-crystalline polymer can be modelled as a continuum solid containing randomly distributed cavities and crystal inclusions. The effective elastic properties of a degrading polymer are calculated using existing theories for such solid and the tensile strength of the degrading polymer is predicted using scaling relations that were developed for porous materials. The theoretical model for elastic properties and the scaling law for strength form a complete constitutive relation for the degrading polymers. It is shown that the constitutive law can capture the trend of the experimental data in the literature for a range of biodegradable polymers fairly well. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Mobile ad hoc networking

    CERN Document Server

    John Wiley & Sons

    2004-01-01

    "Assimilating the most up-to-date information on research and development activities in this rapidly growing area, Mobile Ad Hoc Networking covers physical, data link, network, and transport layers, as well as application, security, simulation, and power management issues in sensor, local area, personal, and mobile ad hoc networks. Each of the book's sixteen chapters has been written by a top expert and discusses in-depth the most important topics in the field. Mobile Ad Hoc Networking is an excellent reference and guide for professionals seeking an in-depth examination of topics that also provides a comprehensive overview of the current state-of-the-art."--Jacket.

  18. Osmotic load from glucose polymers.

    Science.gov (United States)

    Koo, W W; Poh, D; Leong, M; Tam, Y K; Succop, P; Checkland, E G

    1991-01-01

    Glucose polymer is a carbohydrate source with variable chain lengths of glucose units which may result in variable osmolality. The osmolality of two commercial glucose polymers was measured in reconstituted powder infant formulas, and the change in osmolality of infant milk formulas at the same increases in energy density (67 kcal/dL to 81 and 97 kcal/dL) from the use of additional milk powder or glucose polymers was compared. All samples were prepared from powders (to nearest 0.1 mg), and osmolality was measured by freezing point depression. For both glucose polymers the within-batch variability of the measured osmolality was less than 3.5%, and between-batch variability of the measured osmolality was less than 9.6%. The measured osmolality varies linearly with energy density (p less than 0.001) and was highest in infant formula reconstituted from milk powder alone. However, there exist significant differences in the measured osmolality between different glucose polymer preparations. At high energy densities (greater than or equal to 97 kcal/dL), infant milk formulas prepared with milk powder alone or with the addition of certain glucose polymer preparation may have high osmolality (greater than or equal to 450 mosm/kg) and theoretically predispose the infant to complications of hyperosmotic feeds.

  19. Mesoscale simulation of semiflexible chains. I. Endpoint distribution and chain dynamics

    Science.gov (United States)

    Groot, Robert D.

    2013-06-01

    The endpoint distribution and dynamics of semiflexible fibers are studied by numerical simulation. A brief overview is given over the analytical theory of flexible and semiflexible polymers. In particular, a closed expression is given for the relaxation spectrum of wormlike chains, which determines polymer diffusion and rheology. Next a simulation model for wormlike chains with full hydrodynamic interaction is described, and relations for the bending and torsion modulus are given. Two methods are introduced to include torsion stiffness into the model. The model is validated by simulating single chains in a heat bath, and comparing the endpoint distribution of the chains with established Monte Carlo results. It is concluded that torsion stiffness leads to a slightly shorter effective persistence length for a given bending stiffness. To further validate the simulation model, polymer diffusion is studied for fixed persistence length and varying polymer length N. The diffusion constant shows crossover from Rouse (D ∝ N-1) to reptation behaviour (D ∝ N-2). The terminal relaxation time obtained from the monomer displacement is consistent with the theory of wormlike chains. The probability for chain crossing has also been studied. This probability is so low that it does not influence the present results.

  20. Hyperbranched polymers from polymerization in solid state

    International Nuclear Information System (INIS)

    Tomaz, Vivian A.; Silva, Rafael; Muniz, Edvani C.; Rubira, Adley F.

    2009-01-01

    The macroscopic properties of polymers are directly related to the chemical characteristics of the monomeric units and also with the geometric arrangement of polymer chains. Thus, polymers were synthesized from two well-known chelators EDTA and EDA. We evaluated the conditions for the polymerization of the precursors in the solid state. The polymerization was carried out varying the proportions of reagents, aiming the polymers with different degrees of chain branching and the materials were characterized by FTIR. The materials obtained from the best condition for synthesis were purified by size-exclusion chromatography of and were subjected to characterization by FTIR and NMR of 1 H and 13 C. The content of end groups in these samples was determined by back titration. (author)

  1. AdS3: the NHEK generation

    International Nuclear Information System (INIS)

    Bena, Iosif; Heurtier, Lucien; Puhm, Andrea

    2016-01-01

    It was argued in http://dx.doi.org/10.1007/JHEP03(2013)028 that the five-dimensional near-horizon extremal Kerr (NHEK) geometry can be embedded in String Theory as the infrared region of an infinite family of non-supersymmetric geometries that have D1, D5, momentum and KK monopole charges. We show that there exists a method to embed these geometries into asymptotically-AdS 3 ×S 3 /ℤ N solutions, and hence to obtain infinite families of flows whose infrared is NHEK. This indicates that the CFT dual to the NHEK geometry is the IR fixed point of a Renormalization Group flow from a known local UV CFT and opens the door to its explicit construction.

  2. Hadronization at the AdS wall

    International Nuclear Information System (INIS)

    Evans, Nick; French, James; Threlfall, Ed; Jensen, Kristan

    2010-01-01

    We describe hadronization events, using the AdS/CFT Correspondence, which display many of the qualitative features expected in QCD. In particular we study the motion of strings with separating end points in a back-reacted hard wall geometry. The solutions show the development of a linear QCD-like string. The end points oscillate in the absence of string breaking. We introduce string breaking by hand and evolve the new state forward in time to observe the separation of two string segments. A kink associated with this breaking evolves to the end points of the string inducing rho meson production. We explicitly compute the rho meson production at the end point.

  3. Mussel inspired preparation of MoS{sub 2} based polymer nanocomposites: The case of polyPEGMA

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying; Liu, Xinhua; Huang, Qiang; Xu, Dazhuang; Mao, Liucheng; Huang, Hongye; Deng, Fengjie [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

    2016-11-30

    Graphical abstract: A facile and universal strategy has been developed for surface modification of MoS{sub 2} nanosheets via combination of mussel inspired chemistry and chain transfer free radical polymerization. - Highlights: • Fabrication of MoS{sub 2}-PDA-PPEGMA polymer nanocomposites through mussel inspired chemistry. • MoS{sub 2}-PDA- PPEGMA polymer nanocomposites showed enhanced stability in water. • The experimental conditions are rather mild. • The strategy described in this work is also useful for fabrication of many other MoS{sub 2} based polymer nanocomposites. - Abstract: In this work, we report a facile strategy to prepare PEGylated MoS{sub 2} nanosheets through the combination of mussel inspired chemistry and Michael addition reaction. The MoS{sub 2} nanosheets were obtained from lithium intercalation and exfoliation method. Meanwhile, the amino-contained poly((polyethylene glycol) methyl ether methacrylate) (PPEGMA) were obtained via chain transfer free radical polymerization using cysteamine hydrochloride as the chain transfer agents and PEGMA as the monomer. To introduce PPEGMA on MoS{sub 2} nanosheets, polydopamine (PDA) thin films were first coated on the surface of MoS{sub 2} nanosheets through self polymerization of dopamine as the ad-layers, which can react with amino-terminated PPEGMA through Michael addition reaction. The structure, morphology and chemical compositions of MoS{sub 2} nanosheets and MoS{sub 2}-PDA-PPEGMA have been characterized by various characterization techniques. The results demonstrated that the amino-terminated PPEGMA can be successfully immobilized on MoS{sub 2} nanosheets via PDA thin films as the ad-layers. More importantly, the strategy described in this work could also be utilized for surface immobilization of various polymers on many other materials and surfaces because of the universal adhesion of PDA and the good monomer applicability of chain transfer free radical polymerization. Taken together, we

  4. Influence of molar mass, dispersity, and type and location of hydrophobic side chain moieties on the critical micellar concentration and stability of amphiphilic HPMA-based polymer drug carriers

    Czech Academy of Sciences Publication Activity Database

    Filippov, Sergey K.; Vishnevetskaya, N. S.; Niebuur, B.-J.; Koziolová, Eva; Lomkova, Ekaterina A.; Chytil, Petr; Etrych, Tomáš; Papadakis, C. M.

    2017-01-01

    Roč. 295, č. 8 (2017), s. 1313-1325 ISSN 0303-402X R&D Projects: GA MZd(CZ) NV16-28600A; GA ČR(CZ) GC15-10527J Institutional support: RVO:61389013 Keywords : drug delivery * HPMA copolymers * fluorescence correlation spectroscopy Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 1.723, year: 2016

  5. Polymer Brush Grafted Nanoparticles and Their Impact on the Morphology Evolution of Polymer Blend Films

    Science.gov (United States)

    Chung, Hyun-Joong; Ohno, Kohji; Composto, Russell

    2013-03-01

    We present an novel pathway to control the location of nanoparticles (NPs) in phase-separating polymer blend films containing poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN). Because hydrophobic polymer phases have a small interfacial energy, ~1 mJ/m2, subtle changes in the NP surface functionality can be used to guide NPs to either the interface between immiscible polymers or into one of the phases. Based on this idea, we designed a class of NPs grafted with PMMA brushes. These PMMA brushes were grown from the NP surface by atom transfer radical polymerization (ATRP), which results in chains terminated with chlorine atoms. The chain end can be substituted with protons (H) by dehalogenation. As a result, the NPs are strongly segregated at the interface when grafted PMMA chains are short (Mn =1.8K) and the end group is Cl, whereas NPs partition into PMMA-rich phase when chains are long (Mn =160K) and/or when chains are terminated with hydrogen. The Cl end groups and shorter chain length cause an increase in surface energy for the NPs. The increase in surface energy of short-chained NPs can be attributed to (i) an extended brush conformation (entropic) and/or (ii) a high density of ``unfavorable'' end groups (enthalpic). Finally, the impact of NPs on the morphological evolution of the polymer blend films will be discussed. Ref: H.-J.Chung et al., ACS Macro Lett. 1(1), 252-256 (2012).

  6. Approaches for Making High Performance Polymer Materials from Commodity Polymers

    Institute of Scientific and Technical Information of China (English)

    Xu Xi

    2004-01-01

    A brief surrey of ongoing research work done for improving and enhancing the properties of commodity polymers by the author and author's colleagues is given in this paper. A series of high performance polymers and polymer nanomaterials were successfully prepared through irradiation and stress-induced reactions of polymers and hydrogen bonding. The methods proposed are viable, easy in operation, clean and efficient.1. The effect of irradiation source (UV light, electron beam, γ -ray and microwave), irradiation dose, irradiation time and atmosphere etc. on molecular structure of polyolefine during irradiation was studied. The basic rules of dominating oxidation, degradation and cross-linking reactions were mastered. Under the controlled conditions, cross-linking reactions are prevented, some oxygen containing groups are introduced on the molecular chain of polyolefine to facilitate the interface compatibility of their blends. A series of high performance polymer materials: u-HDPE/PA6,u-HDPE/CaCO3, u-iPP/STC, γ-HDPE/STC, γ-LLDPE/ATH, e-HDPE, e-LLDPE and m-HDPEfilled system were prepared (u- ultraviolet light irradiated, γ- γ-ray irradiated, e- electron beam irradiated, m- microwave irradiated)2. The effect of ultrasonic irradiation, jet and pan-milling on structure and changes in properties of polymers were studied. Imposition of critical stress on polymer chain can cause the scission of bonds to form macroradicals. The macroradicals formed in this way may recombine or react with monomer or other radicals to form linear, branched or cross-linked polymers or copolymers. About 20 kinds of block/graft copolymers have been synthesized from polymer-polymer or polymer-monomer through ultrasonic irradiation.Through jet-milling, the molecular weight of PVC is decreased somewhat, the intensity of its crystalline absorption bonds becomes indistinct. The processability, the yield strength, strength at break and elongation at break of PVC get increased quite a lot after

  7. Polymer electronics

    CERN Document Server

    Geoghegan, Mark

    2013-01-01

    Polymer electronics is the science behind many important new developments in technology, such as the flexible electronic display (e-ink) and many new developments in transistor technology. Solar cells, light-emitting diodes, and transistors are all areas where plastic electronics is likely to, or is already having, a serious impact on our daily lives. With polymer transistors and light-emitting diodes now being commercialised, there is a clear need for a pedagogic text thatdiscusses the subject in a clear and concise fashion suitable for senior undergraduate and graduate students. The content

  8. New method for preparing a liquid crystal polymer that exhibits linearly polarized white fluorescence

    International Nuclear Information System (INIS)

    Zheng Shijun; Kun, Wang; Kobayashi, Takaomi

    2011-01-01

    With the aim of developing a single-chain white-light-emitting polymer, liquid crystal (LC) polymers with a shish-kebab-type moiety on their cross-conjugated (p-phenylene)s-poly(p-phenylenevinylene)s main chain were synthesized by Gilch polymerization. They were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and polarizing optical microscopy (POM). 1 H-NMR indicated that the polymers had a shish-kebab structure, which strongly suppressed the formation of structural defects in the polymers. DSC revealed that the polymers had thermotropic LC properties, indicating that the LC polymers were enantiotropic. XRD showed that the polymers had a mesophase, which implies that they were in a smectic LC phase. A polymer with 'kebabs' of 2,5-bis(4'-alkoxyphenyl)benzene was combined with an aligned polyimide film with orientated microgrooves. The polymer main chain was aligned due to the orientation of the 'kebabs' of the uniform cross-conjugated structure. It lay between the kebabs and the 'shish' of the polymer main chains. The aligned polymer main chain emitted yellow light while and the oriented LC side chains emitted blue light emission. These two emissions resulted in linearly polarized white fluorescence.

  9. Dynamic viscosity of polymer solutions

    Energy Technology Data Exchange (ETDEWEB)

    Peterlin, A

    1982-03-01

    The dynamic viscosity investigation of solutions of long chain polymers in very viscous solvents has definitely shown the existence of the low and high frequency plateau with the gradual transition between them. In both extreme cases the extrapolation of the measured Newtonian viscosities of the plateaus to the infinite dilution yields the limiting intrinsic viscosities. Such a behavior is expected from the dynamic intrinsic viscosity of the necklace model of the linear polymer with finite internal viscosity. The plateau at low frequency shows up in any model of polymer solution. This work shows the constant dynamic intrinsic viscosity in both extreme cases is well reproducible by the necklace model with the internal viscosity acting only between the beads on the same link. 20 references.

  10. Biodegradability of PP/HMSPP and natural and synthetic polymers blends in function of gamma irradiation degradation

    International Nuclear Information System (INIS)

    Cardoso, Elisabeth C.L.; Scagliusi, Sandra R.; Lima, Luis F.C.P.; Bueno, Nelson R.; Brant, Antonio J.C.; Parra, Duclerc F.; Lugão, Ademar B.

    2014-01-01

    Polymers are used for numerous applications in different industrial segments, generating enormous quantities of discarding in the environment. Polymeric materials composites account for an estimated from 20 to 30% total volume of solid waste. Polypropylene (PP) undergoes crosslinking and extensive main chain scissions when submitted to ionizing irradiation; as one of the most widely used linear hydrocarbon polymers, PP, made from cheap petrochemical feed stocks, shows easy processing leading it to a comprehensive list of finished products. Consequently, there is accumulation in the environment, at 25 million tons per year rate, since polymeric products are not easily consumed by microorganisms. PP polymers are very bio-resistant due to involvement of only carbon atoms in main chain with no hydrolysable functional group. Several possibilities have been considered to minimize the environmental impact caused by non-degradable plastics, subjecting them to: physical, chemical and biological degradation or combination of all these due to the presence of moisture, air, temperature, light, high energy radiation or microorganisms. There are three main classes of biodegradable polymers: synthetic polymers, natural polymers and blends of polymers in which one or more components are readily consumed by microorganisms. This work aims to biodegradability investigation of a PP/HMSPP (high melt strength polypropylene) blended with sugarcane bagasse, PHB (poly-hydroxy-butyrate) and PLA (poly-lactic acid), both synthetic polymers, at a 10% level, subjected to gamma radiation at 50, 100, 150 and 200 kGy doses. Characterization will comprise IR, DSC, TGA, OIT and Laboratory Soil Burial Test (LSBT). - Highlights: • Polymeric materials composites account for an estimated from 20 to 30% total volume of solid waste. • Landfills will not be enough for an estimated accumulation of 25 million tons per year of plastics. • Incorporation of natural/synthetic polymers in PP/HMSPP to reduce

  11. Antioxidant effect of green tea on polymer gel dosimeter

    International Nuclear Information System (INIS)

    Samuel, E J J; Sathiyaraj, P; Deena, T; Kumar, D S

    2015-01-01

    Extract from Green Tea (GTE) acts as an antioxidant in acrylamide based polymer gel dosimeter. In this work, PAGAT gel was used for investigation of antioxidant effect of GTE.PAGAT was called PAGTEG (Polyacrylamide green tea extract gel dosimeter) after adding GTE. Free radicals in water cause pre polymerization of polymer gel before irradiation. Polyphenols from GTE are highly effective to absorb the free radicals in water. THPC is used as an antioxidant in polymer gel dosimeter but here we were replaced it by GTE and investigated its effect by spectrophotometer. GTE added PAGAT samples response was lower compared to THPC added sample. To increase the sensitivity of the PAGTEG, sugar was added. This study confirmed that THPC was a good antioxidant for polymer gel dosimeter. However, GTE also can be used as an antioxidant in polymer gel if use less quantity (GTE) and add sugar as sensitivity enhancer

  12. Enhanced Nanotribology and Optimal Self-lubrication in Novel Polymer-Metal Composites

    Science.gov (United States)

    Seam, Alisha; Brostow, Witold; Olea-Mejia, Oscar

    2006-10-01

    Cheaper to produce, light-weight polymeric materials with improved micro and nano-scale tribological characteristics ar gradually replacing the heavier metals in gears, cams, ball-bearings, chains, and other critical machine components which operate under high stress, experience substantial sliding friction and wear, and require external lubrication regimes. Application of such high-performance synthetic materials in a whole range of machinery, manufacturing, aerospace and transportation industries would produce far reaching economic, energy conservation and environmental benefits. This paper devises and investigates a novel and previously untested method of developing self-lubricating and wear-resistant polymer based materials (PBMs) by blending a polymer with small proportions of a metallic additive. Tribological experiments establish that as increasing proportions of the metallic additive Iron (Fe) are added to the polymeric base polyethylene (PE), the friction and wear of the resulting composite (PE-Fe) experiences significant decline until an optimal value of 3 to 5 % Iron and then stabilize. Theoretical analysis reveals this phenomenon to likely be a result of the nano-structural formation of a lubricating oxide layer on surface of the polymer-metal composite. Furthermore, the oxide layer prevented significant degradation of the viscoelastic scratch-recovery of the base polymer, even with 10 percent metal additive (Fe) in the composite samples.

  13. Multiscale mechanics of the lateral pressure effect on enhancing the load transfer between polymer coated CNTs.

    Science.gov (United States)

    Yazdandoost, Fatemeh; Mirzaeifar, Reza; Qin, Zhao; Buehler, Markus J

    2017-05-04

    While individual carbon nanotubes (CNTs) are known as one of the strongest fibers ever known, even the strongest fabricated macroscale CNT yarns and fibers are still significantly weaker than individual nanotubes. The loss in mechanical properties is mainly because the deformation mechanism of CNT fibers is highly governed by the weak shear strength corresponding to sliding of nanotubes on each other. Adding polymer coating to the bundles, and twisting the CNT yarns to enhance the intertube interactions are both efficient methods to improve the mechanical properties of macroscale yarns. Here, we perform molecular dynamics (MD) simulations to unravel the unknown deformation mechanism in the intertube polymer chains and also local deformations of the CNTs at the atomistic scale. Our results show that the lateral pressure can have both beneficial and adverse effects on shear strength of polymer coated CNTs, depending on the local deformations at the atomistic scale. In this paper we also introduce a bottom-up bridging strategy between a full atomistic model and a coarse-grained (CG) model. Our trained CG model is capable of incorporating the atomistic scale local deformations of each CNT to the larger scale collect behavior of bundles, which enables the model to accurately predict the effect of lateral pressure on larger CNT bundles and yarns. The developed multiscale CG model is implemented to study the effect of lateral pressure on the shear strength of straight polymer coated CNT yarns, and also the effect of twisting on the pull-out force of bundles in spun CNT yarns.

  14. A method for the computation of turbulent polymeric liquids including hydrodynamic interactions and chain entanglements

    Energy Technology Data Exchange (ETDEWEB)

    Kivotides, Demosthenes, E-mail: demosthenes.kivotides@strath.ac.uk

    2017-02-12

    An asymptotically exact method for the direct computation of turbulent polymeric liquids that includes (a) fully resolved, creeping microflow fields due to hydrodynamic interactions between chains, (b) exact account of (subfilter) residual stresses, (c) polymer Brownian motion, and (d) direct calculation of chain entanglements, is formulated. Although developed in the context of polymeric fluids, the method is equally applicable to turbulent colloidal dispersions and aerosols. - Highlights: • An asymptotically exact method for the computation of polymer and colloidal fluids is developed. • The method is valid for all flow inertia and all polymer volume fractions. • The method models entanglements and hydrodynamic interactions between polymer chains.

  15. Bioinspired phospholipid polymer biomaterials for making high performance artificial organs

    Directory of Open Access Journals (Sweden)

    K Ishihara

    2000-01-01

    Full Text Available Novel polymer biomaterials, which can be used in contact with blood, are prepared with strong inspiration from the surface structure of biomembrane. That is, the polymers with a phospholipid polar group in the side chain, 2-methacrylooyloxyethyl phosphorylcholine (MPC polymers were synthesized. The MPC polymers can inhibit surface-induced clot formation effectively, when they are in contact with blood even in the absence of an anticoagulant. This phenomenon was due to the reduction of plasma protein and suppression of denaturation of adsorbed proteins, that is the MPC polymers interact with blood components very mildly. As the molecular structure of the MPC polymer was easily designed by changing the monomer units and their composition, it could be applied to surface modification of artificial organs and biomedical devices for improving blood and tissue compatibility. Thus, the MPC polymers are useful polymer biomaterials for manufacturing high performance artificial organs and biomedical devices to provide safe medical treatments.

  16. Role of polymer matrix on photo-sensitivity of CdSe polymer nanocomposites

    Science.gov (United States)

    Kaur, Ramneek; Tripathi, S. K.

    2018-04-01

    This paper reports the effect of three different polymer matrices (PVP, PMMA and PVK) and Ag doping on the photo-sensitivity of CdSe polymer nanocomposites. The results reveal that the photoconductivity is high for linear chain polymer nanocomposites as compared to aromatic ones with decreasing trend as: CdSe-PMMA > CdSe-PVP > CdSe-PVK. The large substituents or branches along the polymer backbone hinder the stacking sequences in CdSe-PVK nanocomposites resulting in lowest photoconductivity. On contrary, CdSe-PVK nanocomposite exhibit highest photosensitivity. The reason behind it is the low value of dark conductivity in CdSe-PVK nanocomposite and photoconductive PVK matrix. With Ag doping, no considerable effect on the value of photosensitivity has been observed. The obtained results indicate that the photo-conducting properties of these polymer nanocomposites can be tuned by using different polymer matrices.

  17. Fundamental radiation effect on polymers energy transfer from radiation to polymer

    International Nuclear Information System (INIS)

    Seguchi, T.

    2007-01-01

    Polymer modification as cross-link, chain scission, and graft-polymerization by radiation is initiated by the quantum energy transferred from radiation to polymers. The active species for chemical reactions are produced through ionization or activation of polymer molecules for any radiation source. The energy transfer occurs mainly by ionic interaction between radiation and polymer molecule, and the contribution from the collision interaction is miner. The radiation of electromagnetic wave as X-ray or γ-ray generates the energetic electron which induces ionic interaction with polymer molecule. The energy loss profile along the penetration to polymer material is much different among the radiation sources of EB, γ-ray, and ion beams in the macroscopic mechanism. In this article, the behavior of single event, that is, the event induced by one electron, γ-ray, ion, and neutron is described by the macroscopic mechanism and by the microscopic mechanism. (authors)

  18. Polymer physics

    CERN Document Server

    Gedde, Ulf W

    1999-01-01

    This book is the result of my teaching efforts during the last ten years at the Royal Institute of Technology. The purpose is to present the subject of polymer physics for undergraduate and graduate students, to focus the fundamental aspects of the subject and to show the link between experiments and theory. The intention is not to present a compilation of the currently available literature on the subject. Very few reference citations have thus been made. Each chapter has essentially the same structure: starling with an introduction, continuing with the actual subject, summarizing the chapter in 30D-500 words, and finally presenting problems and a list of relevant references for the reader. The solutions to the problems presented in Chapters 1-12 are given in Chapter 13. The theme of the book is essentially polymer science, with the exclusion of that part dealing directly with chemical reactions. The fundamentals in polymer science, including some basic polymer chemistry, are presented as an introduction in t...

  19. Antimicrobial polymers.

    Science.gov (United States)

    Jain, Anjali; Duvvuri, L Sailaja; Farah, Shady; Beyth, Nurit; Domb, Abraham J; Khan, Wahid

    2014-12-01

    Better health is basic requirement of human being, but the rapid growth of harmful pathogens and their serious health effects pose a significant challenge to modern science. Infections by pathogenic microorganisms are of great concern in many fields such as medical devices, drugs, hospital surfaces/furniture, dental restoration, surgery equipment, health care products, and hygienic applications (e.g., water purification systems, textiles, food packaging and storage, major or domestic appliances etc.) Antimicrobial polymers are the materials having the capability to kill/inhibit the growth of microbes on their surface or surrounding environment. Recently, they gained considerable interest for both academic research and industry and were found to be better than their small molecular counterparts in terms of enhanced efficacy, reduced toxicity, minimized environmental problems, resistance, and prolonged lifetime. Hence, efforts have focused on the development of antimicrobial polymers with all desired characters for optimum activity. In this Review, an overview of different antimicrobial polymers, their mechanism of action, factors affecting antimicrobial activity, and application in various fields are given. Recent advances and the current clinical status of these polymers are also discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Selective Template Wetting Routes to Hierarchical Polymer Films: Polymer Nanotubes from Phase-Separated Films via Solvent Annealing.

    Science.gov (United States)

    Ko, Hao-Wen; Cheng, Ming-Hsiang; Chi, Mu-Huan; Chang, Chun-Wei; Chen, Jiun-Tai

    2016-03-01

    We demonstrate a novel wetting method to prepare hierarchical polymer films with polymer nanotubes on selective regions. This strategy is based on the selective wetting abilities of polymer chains, annealed in different solvent vapors, into the nanopores of porous templates. Phase-separated films of polystyrene (PS) and poly(methyl methacrylate) (PMMA), two commonly used polymers, are prepared as a model system. After anodic aluminum oxide (AAO) templates are placed on the films, the samples are annealed in vapors of acetic acid, in which the PMMA chains are swollen and wet the nanopores of the AAO templates selectively. As a result, hierarchical polymer films containing PMMA nanotubes can be obtained after the AAO templates are removed. The distribution of the PMMA nanotubes of the hierarchical polymer films can also be controlled by changing the compositions of the polymer blends. This work not only presents a novel method to fabricate hierarchical polymer films with polymer nanotubes on selective regions, but also gives a deeper understanding in the selective wetting ability of polymer chains in solvent vapors.